thermoplastic polymer composition

专利摘要:
THERMOPLASTIC POLYMER COMPOSITION. The present invention relates to a compound forming & structure of Formula (C). The invention also provides a thermoplastic polymer composition comprising a polyolefin polymer and a compound conforming to the structure of Formula (C) as a nucleating agent. (Ç)
公开号:BR112016006288B1
申请号:R112016006288-4
申请日:2014-09-23
公开日:2020-11-24
发明作者:John W. Miley；Sanjeev K. Dey；Eduardo Torres；Haihu Qin
申请人:Milliken & Company；
IPC主号:

专利说明:

TECHNICAL FIELD OF THE INVENTION
[0001] This application relates to nucleating agents for thermoplastic polymers, thermoplastic polymer compositions comprising such nucleating agents, articles made of such thermoplastic polymer compositions, and methods for preparing and molding such thermoplastic polymer compositions. BACKGROUND
[0002] Various nucleating agents for thermoplastic polymers are known in the art. These nucleating agents generally work by forming the nuclei or providing sites for the formation and / or growth of crystals in the thermoplastic polymer when it solidifies from a molten state. The nuclei or sites provided by the nucleating agent allow the crystals to form within the cooling polymer at a higher temperature and / or at a faster rate than the crystals will form in the virgin, non-nucleated thermoplastic polymer. These effects can then allow processing of a nucleated thermoplastic polymer composition at cycle times that are shorter than the virgin, non-nucleated thermoplastic polymer.
[0003] While the polymer nucleating agents can function in a similar way, not all nucleating agents are created equal. For example, a particular nucleating agent can be very effective in increasing the recrystallization temperature of the peak polymer of a thermoplastic polymer, however, the rapid rate of crystallization induced by such a nucleating agent can cause incompatible shrinkage of a molded part It is produced from a thermoplastic polymer composition containing the nucleating agent. Such a nucleating agent can likewise be ineffective in increasing the hardness of the molded part to a desirable degree. Likewise, while nucleating agents for polyethylene polymers are known in the art, relatively few of these nucleating agents have been shown to improve the physical properties of the polyethylene polymer to any commercially significant degree.
[0004] Given the complicated interrelationships of these properties and the fact that many nucleating agents exhibit less than ideal behavior in at least one respect, a need remains for nucleating agents that are capable of producing thermoplastic polymer compositions that exhibit a more desirable combination of the high peak polymer recirstallization temperature, adjustable shrinkage, and high hardness. Applicants believe that the nucleating agents and thermoplastic polymer compositions described in the present application satisfy such a need. BRIEF SUMMARY OF THE INVENTION
[0005] As noted above, the present application generally relates to nucleating agents, thermoplastic polymer compositions comprising such nucleating agents, articles (e.g., molded articles) made of such thermoplastic polymer compositions, and methods for preparing and molding such thermoplastic polymer compositions. The nucleating agents and thermoplastic polymer compositions according to the invention are believed to be particularly well suited for the production of thermoplastic polymer articles (e.g., molded thermoplastic polymer articles) exhibiting a desirable combination of physical properties. In particular, articles produced using the invention's nucleating agents and thermoplastic polymer compositions are believed to exhibit a desirable combination of a higher peak polymer recrystallization temperature and improved physical properties (for example, tear strength) in compared to articles made of non-nucleated thermoplastic polymer. Applicants believe that this combination of physical properties indicates that the nucleating agents and thermoplastic polymer compositions according to the invention are well suited for use in the production of thermoplastic polymer articles.
[0006] In a first embodiment, the invention provides a thermoplastic polymer composition comprising: (a) a polyolefin polymer; and (b) a nucleating agent, the nucleating agent comprising a compound conforming to the structure of Formula (I)
wherein R1 is selected from the group consisting of hydroxy, halogens, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups, ne zero or a positive integer from 1 to 4; L is a bonding group comprising two or more atoms and at least one double bond between two atoms in the bonding group; see a positive integer from 1 to 3; R2 e: (i) selected from the group consisting of alkyl groups, substituted alkyl groups, cycloalkyl groups, substituted cycloalkyl groups, aryl groups, substituted aryl groups, heteroaryl groups, and substituted heteroaryl groups when L and a divalent linking group eve 1, (ii) selected from the group consisting of alkanodiyl groups, substituted alkanodiyl groups, cycloalkanodiyl groups, substituted cycloalkanodiyl groups, arenodiyl groups, substituted arenodiyl groups, heteroarenodiyl groups, and substituted heteroarenodiyl groups when L is a trivalent linking group eve 1, (iii) selected from the group consisting of alkanediyl groups, substituted alkanodiyl groups, cycloalkanodiyl groups, substituted cycloalkanodiyl groups, groups arenodiyl, substituted arenodiyl groups, heteroarenodiyl groups, and substituted heteroarenodiyl groups when L is a divalent linking group eve 2, and (iv) selected from of the group consisting of alkanotriyl groups, substituted alkanotriyl groups, cycloalkanotriyl groups, substituted cycloalkanotriyl groups, arenotriyl groups, substituted arenotriyl groups, heteroarenotriyl groups, and substituted heteroarenotriyl groups when L is a divalent linking group and v is 3; x will be a positive integer; each Mi will be a metal cation; y will be the Valencia of the cation; z will be a positive integer; b will be zero or a positive integer; when b is a positive integer, each Q! it will be a negatively charged contrion and it will be the Valencia of the negatively charged contrion; and the values of v, x, y, z, a, and b satisfy the equation (vx) + (ab) = yz; wherein the cyclic moiety of the cycloalkyl group or substituted cycloalkyl group comprises no more than two ring structures fused together when L is a divalent bonding group, v is 1, and R2 is a cycloalkyl group or a substituted cycloalkyl group.
[0007] In a second embodiment, the invention provides a compound conforming to the structure of Formula (C)
in which R10i is selected from the group consisting of a cyclopentyl group and porgbes conforming to the structure of Formula (Cl); Formula (Cl) and
R105 is selected from the group consisting of hydrogen and halogen; x is a positive integer; each Mi and a metal cation; yea Valencia of the cation; z is a positive integer; be zero or a positive integer; when b is a positive integer, each Q1 will be a negatively charged counterion and the area of the negatively charged counter ion; and the values of x, y, z, a, and b satisfy the equation x + (ab) = yz.
[0008] In a third embodiment, the invention provides a compound conforming to the structure of Formula (CX)
wherein Rm is selected from the group consisting of a cyclopentyl group and pores conforming to the Formula structure (CXI); R112 is selected from the group consisting of hydrogen and hydroxy; Formula (CXI) and
R115 is selected from the group consisting of hydrogen, a halogen, methoxy, and phenyl; x is a positive integer; each h / h and a metal cation; yea Valencia of the cation; z is a positive integer; be zero or a positive integer; when b is a positive integer, each Q1 will be a negatively charged contrion and a will be the Valencia of the negatively charged contrion; and the values of x, y, z, a, and b satisfy the equation x + (ab) = yz; provided that if R115 is hydrogen, then R112 is hydrogen, x is 1, M1 is a lithium cation, y is 1, z is 1, eb is zero; and as long as if R115 is a methoxy group, then R112 is a hydroxy group.
[0009] In a fourth embodiment, the invention provides a compound conforming to the structure of Formula (CXX) (CXX)
where x is a positive integer; each MT and a cation of a metal selected from the group consisting of alkali metals, alkaline earth metals, and zinc; yea Valencia of the cation; z is a positive integer; be zero or a positive integer; when b is a positive integer, each Ch will be a negatively charged contrion and a will be the Valencia of the negatively charged contrion; and the values of x, y, z, a, and b satisfy the equation x + (ab) = yz. DETAILED DESCRIPTION OF THE INVENTION
[0010] The following definitions are provided to define various terms used throughout this application.
[0011] As used herein, the term "substituted alkyl groups" refers to univalent functional groups derived from substituted alkanes by removal of a hydrogen atom from an alkane carbon atom. In this definition, the term "substituted alkanes" refers to compounds derived from unbranched and branched acyclic hydrocarbons in which (1) one or more of the hydrogen atoms in the hydrocarbon is replaced with a non-hydrogen atom (for example, an atom halogen) or a non-alkyl functional group (for example, a hydroxy group, aryl group, or heteroaryl group) and / or (2) the hydrocarbon carbon-carbon chain is interrupted by an oxygen atom (as in a ether), a nitrogen atom (as in an amine), or a sulfur atom (as in a sulfide).
[0012] As used herein, the term "substituted cycloalkyl groups" refers to univalent functional groups derived from cycloalkanes substituted by removing a hydrogen atom from a cycloalkane carbon atom. In this definition, the term "substituted cycloalkanes" refers to compounds derived from saturated monocyclic and polycyclic hydrocarbons (with or without side chains) in which (1) one or more of the hydrocarbon hydrogen atoms are replaced with an atom of non-hydrogen (for example, a halogen atom) or a non-alkyl functional group (for example, a hydroxy group, aryl group, or heteroaryl group) and / or (2) the hydrocarbon carbon-carbon chain is interrupted by a oxygen atom, nitrogen atom, or sulfur atom.
[0013] As used herein, the term "substituted alkoxy groups" refers to univalent functional groups derived from hydroxyalkanes substituted by removal of a hydrogen atom from a hydroxy group. In this definition, the term "substituted hydroxyalkanes" refers to compounds having one or more hydroxy groups attached to a substituted alkane, and the term "substituted alkane" is defined as and above in the definition of substituted alkyl groups.
[0014] As used herein, the term "substituted aryl groups" refers to univalent functional groups derived from arenes substituted by removing a hydrogen atom from a carbon atom in the ring. In this definition, the term "substituted arenes" refers to compounds derived from monocyclic and polycyclic aromatic hydrocarbons in which one or more of the hydrocarbon hydrogen atoms are replaced with a non-hydrogen atom (for example, a halogen atom) or a non-alkyl functional group (for example, a hydroxy group).
[0015] As used herein, the term "substituted heteroaryl groups" refers to univalent functional groups derived from substituted heteroarenes by removal of a hydrogen atom from an atom in the ring. In this definition, the term "substituted heteroarenes" refers to compounds derived from monocyclic and polycyclic aromatic hydrocarbons in which (1) one or more of the hydrocarbon's hydrogen atoms are replaced with a non-hydrogen atom (for example, a hydrogen atom) halogen) or a non-alkyl functional group (for example, a hydroxy group) and (2) at least one methyl group (-C =) of the hydrocarbon is replaced by a trivalent heteroatom and / or at least one vinylidene group (-CH = CH-) of the hydrocarbon and replaced by a divalent heteroatom.
[0016] As used herein, the term "alkanediyl groups" refers to divalent functional groups derived from alkanes by removing two hydrogen atoms from the alkane. These hydrogen atoms can be removed from the same carbon atom in the alkane (as in ethane-1,1-diyl) or from different carbon atoms (as in ethane-1,2-diyl).
[0017] As used herein, the term "substituted alkanediyl groups" refers to divalent functional groups derived from alkanes substituted by removing two hydrogen atoms from the alkane. These hydrogen atoms can be removed from the same carbon atom in the substituted alkane (as in 2-fluoroethane-1,1-diyl) or from different carbon atoms (as in 1-fluoroethane-1,2-di -ila). In this definition, the term "substituted alkanes" has the same meaning as mentioned above in the definition of substituted alkyl groups in this definition.
[0018] As used herein, the term "cycloalkanodiyl groups" refers to divalent functional groups derived from cycloalkanes by removing two hydrogen atoms from the cycloalkane. These hydrogen atoms can be removed from the same carbon atom in the cycloalkane or from different carbon atoms.
[0019] As used herein, the term "substituted cycloalkanodiyl groups" refers to divalent functional groups derived from cycloalkanes substituted by the removal of two hydrogen atoms from the alkane. In this definition, the term "substituted cycloalkanes" has the same meaning as mentioned above in the definition of substituted cycloalkyl groups.
[0020] As used herein, the term "arenodiyl groups" refers to divalent functional groups derived from arenes (monocyclic and polycyclic aromatic hydrocarbons) by removing two hydrogen atoms from ring carbon atoms.
[0021] As used herein, the term "substituted arenodiyl groups" refers to divalent functional groups derived from arenes substituted by removing two hydrogen atoms from ring carbon atoms. In this definition, the term "substituted arenes" refers to compounds derived from monocyclic and polycyclic aromatic hydrocarbons in which one or more of the hydrocarbon hydrogen atoms are replaced with a non-hydrogen atom (for example, a halogen atom) or a group non-alkyl functional (e.g., a hydroxy group).
[0022] As used herein, the term "heteroarenodiyl groups" refers to divalent functional groups derived from heteroarenes by removing two hydrogen atoms from ring atoms. In this definition, the term "heteroarenes" refers to compounds derived from monocyclic and polycyclic aromatic hydrocarbons in which at least one methyl group (-C =) of the hydrocarbon is replaced by a trivalent heteroatom and / or at least one vinylidene group (- CH = CH-) of the hydrocarbon and is replaced by a divalent heteroatom.
[0023] As used herein, the term "substituted heteroarenodiyl groups" refers to divalent functional groups derived from heteroarenes substituted by removing two hydrogen atoms from ring atoms. In this definition, the term "substituted heteroarenes" has the same meaning as mentioned above in the definition of substituted heteroaryl groups.
[0024] As used herein, the term "alkanotriyl groups" refers to trivalent functional groups derived from alkanes by removing three hydrogen atoms from the alkane. These hydrogen atoms can be removed from the same carbon atom in the alkane or from different carbon atoms.
[0025] As used herein, the term "substituted alkanotriyl groups" refers to trivalent functional groups derived from alkanes substituted by removing three hydrogen atoms from the alkane. These hydrogen atoms can be removed from the same carbon atom in the substituted alkane or from different carbon atoms. The term "substituted alkanes" has the same meaning as mentioned above in the definition of substituted alkyl groups in this definition.
[0026] As used herein, the term "cycloalkanotriyl groups" refers to trivalent functional groups derived from cycloalkanes by removing three hydrogen atoms from the cycloalkane.
[0027] As used herein, the term "substituted cycloalkanotriyl groups" refers to trivalent functional groups derived from cycloalkanes substituted by removing three hydrogen atoms from the alkane. In this definition, the term "substituted cycloalkanes" has the same meaning as mentioned above in the definition of substituted cycloalkyl groups.
[0028] As used herein, the term "arenotriyl groups" refers to trivalent functional groups derived from arenes (monocyclic and polycyclic aromatic hydrocarbons) by removing three hydrogen atoms from ring carbon atoms.
[0029] As used herein, the term "substituted arenotriyl groups" refers to trivalent functional groups derived from arenes substituted by removing three hydrogen atoms from ring carbon atoms. In this definition, the term "substituted arenes" has the same meaning as mentioned above in the definition of substituted sandstone groups.
[0030] As used herein, the term "heteroarenotriyl groups" refers to trivalent functional groups derived from heteroarenes by removing three hydrogen atoms from ring atoms. In this definition, the term "heteroarenes" has the same meaning as mentioned above in the definition of heteroarenodiyl groups.
[0031] As used herein, the term "substituted heteroarenotriyl groups" refers to trivalent functional groups derived from heteroarenes substituted by removing three hydrogen atoms from ring atoms. In this definition, the term "substituted heteroarenes" has the same meaning as mentioned above in the definition of substituted heteroaryl groups.
[0032] In a first embodiment, the invention provides a thermoplastic polymer composition comprising a thermoplastic polymer and a nucleating agent. The thermoplastic polymer of the thermoplastic polymer composition can be any suitable thermoplastic polymer. When used herein, the term "thermoplastic polymer" is used to refer to a polymeric material that will melt on exposure to sufficient heat to form a flowable liquid and will return to a solidified state on sufficient cooling. In their solidified state, such thermoplastic polymers exhibit crystalline or semi-crystalline morphology. Suitable thermoplastic polymers include, but are not limited to, polyolefins (for example, polyethylenes, polypropylenes, polybutylenes, and any combinations thereof), polyamides (for example, synthetic fiber), polyurethanes, polyesters (for example, polyethylene terephthalate), and the like, as well as any combinations thereof. These thermoplastic polymers can be in the form of powder, fluff, flake, prill, or pellet made from newly produced polymer, recycled polymer, post-consumer residues, or post-industrial residues.
[0033] In certain embodiments, the thermoplastic polymer can be a polyolefin, such as a polypropylene, a polyethylene, a polybutylene, a poly (4-methyl-1-pentene), and a poly (cyclohexane vinyl). In a preferred embodiment, the thermoplastic polymer is a polyolefin selected from the group consisting of polypropylene homopolymers (for example, atypical polypropylene, isotactic polypropylene, and syndiotactic polypropylene), polypropylene copolymers (for example, randomized polypropylene copolymers), copolymers polypropylene, polyethylene, polyethylene copolymers, polybutylene, poly (4-methyl-1-pentene), and mixtures thereof. Suitable polypropylene copolymers include, but are not limited to, randomized copolymers made from the polymerization of propylene in the presence of a comonomer selected from the group consisting of ethylene, but1-ene (i.e., 1-butene), and hex-1- ene (i.e., 1-hexene). In such randomized polypropylene copolymers, the comonomer can be present in any suitable amount, but it is typically present in an amount less than about 10% by weight (e.g., about 1 to about 7% by weight). Suitable polypropylene impact copolymers include, but are not limited to, those produced by the addition of a copolymer selected from the group consisting of ethylene-propylene rubber (EPR), ethylene-propylene-diene monomer (EPDM), polyethylene, and plastomers for a polypropylene homopolymer or randomized polypropylene copolymer. In such polypropylene impact copolymers, the copolymer can be present in any suitable amount, but is typically present in an amount of about 5 to about 25% by weight.
[0034] In another preferred embodiment, the thermoplastic polymer can be a polyethylene. Suitable polyethylenes include, but are not limited to, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, and combinations thereof. In certain preferred embodiments, the thermoplastic polymer is selected from the group consisting of linear low density polyethylene, high density polyethylene, and mixtures thereof. In another preferred embodiment, the thermoplastic polymer is a high density polyethylene.
[0035] High density polyethylene polymers suitable for use in the invention generally have a density greater than about 0.940 g / cm3. There is no upper limit to the proper density of the polymer, however, high density polyethylene polymers typically have a density that is less than about 0.980 g / cm3 (for example, less than about 0.975 g / cm3).
[0036] High density polyethylene polymers suitable for use in the invention can be homopolymers or copolymers of ethylene with one or more α-olefins. Suitable α-Olefins include, but are not limited to, 1-butene, 1-hexene, 1-octene, 1-decene, and 4-methyl-1-pentene. The comonomer can be present in the copolymer in any suitable amount, such as an amount of about 5% by weight or less (for example, about 3% by mol or less). As will be understood by those of ordinary skill in the art, the amount of comonomer suitable for the copolymer is largely driven by the end use for the copolymer, and the properties of the polymer required or desired for that end use.
[0037] High density polyethylene polymers suitable for use in the invention can be produced by any suitable process. For example, the polymers can be produced by a free radical process using very high pressures as described, for example, in US Patent No. 2,816,883 (Larchar et al.), However, the polymers are typically produced in a catalytic process "low pressure". In this context, the term "low pressure" is used to denote processes performed at pressures less than 6.9 MPa (for example, 1,000 psig), as well as 1.4-6.9 MPa (200-1000 psig). Examples of suitable low-pressure catalytic processes include, but are not limited to, solution polymerization processes (i.e., processes in which the polymerization is carried out using a solvent for the polymer), suspension polymerization processes (i.e., processes for suspension) in which the polymerization is carried out using a liquid hydrocarbon in which the polymer does not dissolve or swell), gas phase polymerization processes (for example, processes in which the polymerization is carried out without the use of a liquid medium or diluent), or an organized reactor polymerization process. Suitable gas phase polymerization processes likewise include so-called "condensed mode" or "super-condensed mode" in which an Ifquidr hydrocarbon is introduced into the fluidized bed to increase the absorption of the heat it produces during the polymerization process In these condensed and super-condensed processes, Ifquido hydrocarbon is typically condensed in the recycling stream and used again in the reactor. Organized reactor processes can use a combination of suspension process reactors (tanks or vane) that are connected in series, in parallel, or a combination of series or parallels so that the catalyst (eg, chromium catalyst) is exposed to more than one set of reaction condipbes. Organized reactor processes can likewise be carried out by combining two series blades, combining one or more tanks and series blades, using series multiple gas phase reactors, or an array the alpha gas phase. Because of their ability to expose the catalyst to different sets of reactor condipbes, organized reactor processes are often used to produce multimodal polymers, such as those discussed below. Suitable processes likewise include those in which a prepolymerization step is carried out. In this prepolymerization step, the catalyst is typically exposed to the cocatalyst and ethylene under moderate conditions in a smaller, separate reactor, and the polymerization reaction is allowed to proceed until the catalyst comprises a relatively small amount (for example, about 5% at about 30% of the total weight) of the resulting composition. This pre-polymerized catalyst is then presented to the wide reactor in which the polymerization is to be carried out.
[0038] High density polyethylene polymers suitable for use in the invention can be produced using any suitable catalyst or combination of catalysts. Suitable catalysts include transition metal catalysts, such as supported reduced molybdenum oxide, cobalt molybdate in alumina, chromium oxide, and transition metal halides. Chromium oxide catalysts are typically produced by saturating a chromium compound over a porous high-surface area oxide vehicle, such as silica, and then calcining it in dry air at 500-90013. This converts the chromium to a hexavalent surface chromate ester or dichromate ester. Chromium oxide catalysts can be used in conjunction with metal alkyl cocatalysts, such as alkyl boron, alkyl aluminum, alkyl zinc, and alkyl lithium. Chromium oxide supports include silica, silica-titania, silica-aluminum, aluminum, and aluminum phosphates. Other examples of chromium oxide catalysts include those catalysts produced by depositing a lower valiant organochrome compound, such as Cr ° bis (arene), Or2 * and Or3 * ali, stabilized beta alkyls of Or2 * and Cr4 +, and bis (cyclopentadienyl) Or2 *, on a chromium oxide catalyst, such as those described above. Suitable transition metal catalysts also include supported chromium catalysts such as those based on chromocene or a silylchromate (e.g., bi (trisphenylsilyl) chromate). These chromium catalysts can be supported on any suitable high surface area support such as those described above for chromium oxide catalysts, with silica typically being used. The supported chromium catalysts can be used in the same way together with coca-talisators, such as the metal alkyl cocatalysts listed above for chromium oxide catalysts. Suitable transition metal halide catalysts include titanium (III) halides (eg titanium (III) chloride), titanium (IV) halides (eg titanium (IV) chloride), vanadium halides, halides zirconia, and combinations thereof. These transition metal halides are often supported in a high surface solid, like magnesium chloride. The transiption metal halide catalysts are typically used in conjunction with an aluminum alkyl cocatalyst, such as trimethyl aluminum (i.e., AI (CH3) 3) or triethyl aluminum (i.e., AI (C2H5) 3). These transiption metal halides can likewise be used in organized reactor processes. Suitable catalysts likewise include metallocene catalysts, such as cyclopentadienyl titanium halides (eg cyclopentadienyl titanium chlorides), cyclopentadienyl zirconium halides (eg cyclopentadienylzirconium chloride), cyclopentadienyl chloride halide halides (e.g. ), and combinations thereof. Metallocene catalysts based on transiption metals complexed with indenyl or fluorenyl binders are likewise known and can be used to produce the high density polyethylene polymers suitable for use in the invention. Catalysts typically contain multiple linkers, and the linkers can be substituted with several groups (e.g., n-butyl group) or linked with bridge groups, such as —CH2CH2— or> SiPh2. Metallocene catalysts are typically used in conjunction with a cocatalyst, such as methylaluminoxane (i.e., (AI (CH3) xOy) n. Other cocatalysts include those described in US Patent No. 5,919,983 (Rosen et al.), US Patent No. 6,107,230 (McDaniel et al.), US Patent No. 6,632,894 (McDaniel et aL), and US Patent No. 6,300,271 (McDaniel et al). Another "single site" catalysts suitable for use in High density polyethylene products include diimine complexes, such as those described in US Patent No. 5,891,963 (Brookhart et al.).
[0039] High density polyethylene polymers suitable for use in the invention can have any suitable molecular weight (e.g., weighted average molecular weight). For example, the weighted average molecular weight of high density polyethylene can be from 20,000 g / mol to about 1,000,000 g / mol or more. As will be understood by those of ordinary skill in the art, the appropriate weighted average molecular weight of high density polyethylene will depend, at least in part, on the particular application or end use for which the polymer is intended. For example, a high density polyethylene polymer intended for blow molding applications can have a weighted average molecular weight of about 100,000 g / mol to about 1,000,000 g / mol. A high density polyethylene polymer intended for tube applications or film applications can have a weighted average molecular weight of about 100,000 g / mol to about 500,000 g / mol. A high density polyethylene polymer intended for injection molding applications can have a weighted average molecular weight of about 20,000 g / mol to about 80,000 g / mol. A high density polyethylene polymer intended for wire insulation applications, cable insulation applications, tape applications, or filament applications can have a weighted average molecular weight of about 80,000 g / mol to about 400,000 g / mol . A high density polyethylene polymer intended for rotational molding applications can have a weighted average molecular weight of about 50,000 g / mol to about 150,000 g / mol.
[0040] High density polyethylene polymers suitable for use in the invention can likewise have suitable polydispersity, which is defined as the value obtained by dividing the weighted average molecular weight of the polymer by the numerical average molecular weight of the polymer. For example, the high density polyethylene polymer can have a polydispersity greater than 2 to about 100. As understood by those skilled in the art, the polydispersity of the polymer is heavily influenced by the catalyst system used to produce the polymer, with the metallocene and other "single site" catalysts generally producing polymers with relatively low polydispersity and narrow molecular weight distributions, and the other transition metal catalysts (for example, chromium catalysts) producing the polymers with higher polydispersity and molecular weight distributions broader. High density polyethylene polymers suitable for use in the invention can likewise have a multimodal (e.g., bimodal) molecular weight distribution. For example, the polymer can have a first fraction having a relatively low molecular weight and a second fraction having a relatively high molecular weight. The difference between the weighted average molecular weight of the fractions in the polymer can be any suitable amount. In reality, it is not necessary for the difference between the weighted average molecular weights to be quite large because two fragments of different molecular weight can be solved using gel permeation chromatography (GPC). However, in certain multimodal polymers, the difference between the weighted average molecular weights of the fractions can be quite large because two or more distinct peaks can be solved from the GPC curve for the polymer. In this context, the term "distinct" does not necessarily mean that the portions of the GPC curve corresponding to each fraction do not overlap, however, and it is intended to indicate only that a distinct peak for each fraction can be solved from the GPC curve for the polymer. Multimodal polymers suitable for use in the invention can be produced using any suitable process. As noted above, multimodal polymers can be produced using the organized reactor processes. A suitable example would be an organized solution process incorporating a series of agitated tanks. Alternatively, multimodal polymers can be produced in a single reactor using a combination of catalysts each of which is designed to produce a polymer having a different weighted average molecular weight.
[0041] High density polyethylene polymers suitable for use in the invention can have any suitable fusion index. For example, the high density polyethylene polymer can have a melting index of about 0.01 dg / min to about 40 dg / min. As with the weighted average molecular weight, those of ordinary skill in the art understand that the appropriate melting index for the high density polyethylene polymer will depend, at least in part, on the particular application or end use for which the polymer is intended . Thus, for example, a high density polyethylene polymer intended for blow molding applications can have a melting index of about 0.01 dg / min to about 1 dg / min. A high density polyethylene polymer intended for blown film acpIics may have a melting index of about 0.5 dg / min to about 3 dg / min. A high density polyethylene polymer intended for melt film applications can have a melt index of about 2 dg / min to about 10 dg / min. A high density polyethylene polymer intended for tube applications can have a melting index of about 2 dg / min to about 40 dg / min. A high density polyethylene polymer intended for injection molding applications can have a melt index of about 2 dg / min to about 80 dg / min. A high density polyethylene polymer intended for rotational molding orders can have a melting index of about 0.5 dg / min to about 10 dg / min. A high density polyethylene polymer intended for tape applications can have a melting index of about 0.2 dg / min to about 4 dg / min. A high density polyethylene polymer intended for filament applications can have a melt index of about 1 dg / min to about 20 dg / min. The melting index of the polymer is measured using ASTM Standard D1238-04c.
[0042] High density polyethylene polymers suitable for use in the invention generally do not contain high amounts of long chain branching. The term "long chain branch" is used to refer to branches that are attached to the polymer chain and are of sufficient length to affect the polymer rheology (for example, branches of about 130 carbons or more in length). If desired for the application in which the polymer is to be used, the high density polyethylene polymer may contain small amounts of long chain branching. However, high density polyethylene polymers suitable for use in the invention typically contain very small long chain branching (for example, less than about 1 long chain branch per 10,000 carbons, less than about 0.5 long chain branching per 10,000 carbons, less than about 0.1 long chain branch per 10,000 carbons, or less than about 0.01 long chain branch per 10,000 carbons).
[0043] Medium density polyethylene polymers suitable for use in the invention generally have a density of about 0.926 g / cm3 to about 0.940 g / cm3. The term "medium density polyethylene" is used to refer to ethylene polymers having a density between that of high density polyethylene and linear low density polyethylene and contains relatively short branches, at least in comparison to the long branches present in low density polyethylene polymers produced by the free radical polymerization of ethylene under high pressures.
[0044] Medium density polyethylene polymers suitable for use in the invention are generally copolymers of ethylene and at least one α-olefin, such as 1-butene, 1-hexene, 1-octene, 1-decene, and 4 -methyl-1-pentene. The α-olefin comonomer can be present in any suitable amount, however, it is typically present in an amount less than about 8% by weight (for example, less than about 5% by mol). As will be understood by those of ordinary skill in the art, the amount of the suitable comonomer for the copolymer is largely driven by the end use for the copolymer, and the required or desired polymer properties dictated by that end use.
[0045] Medium density polyethylene polymers suitable for use in the invention can be produced by any suitable process. Medium density polyethylene polymers are typically produced in "low pressure" catalytic processes such as any of the processes described above with respect to high density polyethylene polymers suitable for use in the invention such as high density polyethylene polymers. Examples of suitable processes include, but are not limited to, gas phase polymerization processes, solution polymerization processes, suspension polymerization processes, and organized reactor processes. Suitable organized reactor processes can incorporate any suitable combination of the gas phase, solution, and suspension polymerization processes described above. As with high density polyethylene polymers, organized reactor processes are often used to produce multimodal polymers.
[0046] Medium density polyethylene polymers suitable for use in the invention can be produced using any suitable catalyst or combination of catalysts. For example, polymers can be produced using Ziegler catalysts, such as halides or transition metal esters (for example, titanium) used in combination with organo aluminum compounds (for example, triethyl aluminum). These Ziegler catalysts can be supported on, for example, magnesium chloride, silica, alumina, or magnesium oxide. Medium density polyethylene polymers suitable for use in the invention can likewise be produced using so-called "dual Ziegler catalysts", which contain a kind of catalyst for dimerizing ethylene in 1-butene (for example, a combination of a titanium and triethyl aluminum ester) and another catalyst for copolymerization of ethylene, and the generated 1-butene (for example, supporting titanium chloride in magnesium chloride). The medium density polyethylene polymers suitable for use in the invention can likewise be produced using chromium oxide catalysts, such as those produced by depositing a chromium compound on a silica-titania support, oxidizing the resulting catalyst in a mixture of oxygen and air, and then reducing the catalyst with carbon monoxide These chromium oxide catalysts are typically used in conjunction with cocatalysts such as trialkylboro or trialkyl aluminum compounds. The chromium oxide catalysts can be used in the same way together with a Ziegler catalyst, as well as a catalyst based on titanium halide or titanium ester. Medium density polyethylene polymers suitable for use in the invention can likewise be produced using supported chrome catalysts such as those described above in the discussion of suitable catalysts for preparing high density polyethylene. Medium density polyethylene polymers suitable for use in the invention can likewise be produced using metallocene catalysts. Several different types of metallocene catalysts can be used. For example, the metallocene catalyst can confer a bis (metallocene) complex of zirconium, titanium, or hafnium with two rings of cyclopentadienyl and methylaluminoxane. As with the catalysts used in the production of high density polyethylene, the binders can be replaced with various groups (e.g., non-butyl group) or linked with bridge groups. Another class of metallocene catalysts that can be used is composed of zirconium or titanium bis (metallocene) complexes and anions of perfluorinated boronaromatic compounds. A third class of metallocene catalysts that can be used is referred to as constrained geometry catalysts and contains derivatives of titanium or zirconium monocyclopentadienyl in which one of the carbon atoms in the cyclopentadienyl ring is attached to the metal atom by a bridge group. These complexes are activated by reacting them with methyl luminoxane or forming ionic complexes with non-coordinating anions, such as B (C6F5) 4 'or B (C6F5) 3CH3'. A fourth class of metallocene catalysts that can be used are the metallocene-based complexes of a transition metal, such as titanium, containing a cyclopentadienyl linker in combination with another linker, such as a phosphinimine or -O-SiR3. This class of metallocene catalyst is activated in the same way with methylaluminoxane or a boron compound. Other catalysts suitable for use in the preparation of medium density polyethylene suitable for use in the invention include, but are not limited to, the catalysts described in U.S. Patent No. 6,649,558.
[0047] Medium density polyethylene polymers suitable for use in the invention may have any suitable compositional uniformity which is a term used to describe the uniformity of branching in the polymer copolymer molecules. Many commercially available medium density polyethylene polymers have a relatively low compositional uniformity in which the high molecular weight fraction of the polymer contains relatively little of the α-olefin comonomer and has relatively small branching while a low molecular weight fraction of the polymer contains a relatively high amount of the α-olefin comonomer and have a relatively large amount of branching. Alternatively, another set of medium density polyethylene polymers has a relatively low compositional uniformity in which the high molecular weight fraction of the polymer contains a relatively high amount of the α-olefin comonomer while a low molecular weight fraction of the polymer contains relatively little of the α-olefin comonomer. The compositional uniformity of the polymer can be measured using any suitable method, such as the fractionation of the temperature rise elution.
[0048] Medium density polyethylene polymers suitable for use in the invention can have any suitable molecular weight. For example, the polymer can have a weighted average molecular weight of about 50,000 g / mol to about 200,000 g / mol. As will be understood by those of ordinary skill in the art, the appropriate weighted average molecular weight of the medium density polyethylene will depend, at least in part, on the particular application or end use for which the polymer is intended.
[0049] Medium density polyethylene polymers suitable for use in the invention may likewise have any suitable polydispersity. Many commercially available medium density polyethylene polymers have a polydispersity of about 2 to about 30. The medium density polyethylene polymers suitable for use in the invention can likewise have a multimodal (e.g., bimodal) molecular weight distribution . For example, the polymer can have a first fraction having a relatively low molecular weight and a second fraction having a relatively high molecular weight. As with high density polyethylene polymers suitable for use in the invention, the difference between the weighted average molecular weight of the fractions in the multimodal medium density polyethylene polymer can be any suitable amount. In reality, there is no need for the difference between the weighted average molecular weights to be large enough by the fact that two different molecular weight frapbes can be solved using gel permeation chromatography (GPC). However, in certain multimodal polymers, the difference between the weighted average molecular weights of the frapbes can be large enough because two or more distinct peaks can be solved from the GPC curve for the polymer. In this context, the term "distinct" does not necessarily mean that the portions of the GPC curve that correspond to each fraction do not overlap, however, it is only intended to indicate that a distinct peak for each fraction can be solved from the GPC curve for the polymer. Multimodal polymers suitable for use in the invention can be produced using any suitable process. As noted above, multimodal pollers can be produced using the organized reactor processes. A suitable example would be an organized solution process incorporating a series of agitated tanks. Alternatively, multimodal polymers can be produced in a single reactor using a combination of catalysts each of which are designed to produce a polymer having a different weighted average molecular weight.
[0050] Medium density polyethylene polymers suitable for use in the invention may have any suitable fusion index. For example, the medium density polyethylene polymer can have a melting index of about 0.01 dg / min to about 200 dg / min. As with the weighted average molecular weight, those of ordinary skill in the art will understand that the suitable melting index for the medium density polyethylene polymer will depend, at least in part, on the particular application or end use to which the polymer is intended. Thus, for example, a medium density polyethylene polymer intended for blow molding applications or tube applications can have a melting index of about 0.01 dg / min to about 1 dg / min. A medium density polyethylene polymer intended for blown film applications can have a melting index of about 0.5 dg / min to about 3 dg / min. A medium density polyethylene polymer intended for melt film applications can have a melting index of about 2 dg / min to about 10 dg / min. A medium density polyethylene polymer intended for injection molding applications can have a melt index of about 6 dg / min to about 200 dg / min. A medium density polyethylene polymer intended for rotational molding applications can have a melting index of about 4 dg / min to about 7 dg / min. A medium density polyethylene polymer intended for wire and cable insulation applications can have a melt index of about 0.5 dg / min to about 3 dg / min. The melting index of the polymer is measured using ASTM Standard D1238-04c.
[0051] Medium density polyethylene polymers suitable for use in the invention generally do not contain a significant amount of long chain branching. For example, medium density polyethylene polymers suitable for use in the invention generally contain less than about 0.1 long chain branch per 10,000 carbon atoms (for example, less than about 0.002 long chain branch per 100 units of carbon). ethylene) or less than about 0.01 long chain branch per 10,000 carbon atoms.
[0052] Linear low density polyethylene polymers suitable for use in the invention generally have a density of 0.925 g / cm3 or less (for example, about 0.910 g / cm3 to about 0.925 g / cm3). The term "linear low density polyethylene" is used to refer to lower density ethylene polymers having relatively short ramifications, at least in comparison to the long ramifications present in low density polyethylene polymers produced by free radical polymerization ethylene at high pressure.
[0053] Linear low density polyethylene polymers suitable for use in the invention are generally copolymers of ethylene and at least one α-olefin, such as 1-butene, 1-hexene, 1octene, 1-decene, and 4- methyl-1-pentene. The α-olefin chondomer can be present in any suitable amount, however, it is typically present in an amount less than about 6 mol% (e.g., about 2 mol% to about 5 mol%). As will be understood by those of ordinary skill in the art, the amount of comonomer suitable for the copolymer is largely driven by the end use for the copolymer, and the required or desired polymer properties dictated by that end use.
[0054] Linear low density polyethylene polymers suitable for use in the invention can be produced by any suitable process. As linear low density polyethylene polymers are typically produced in "low pressure" catalytic processes such as any of the processes described above with respect to high density polyethylene polymers suitable for use in the invention such as high density polyethylene polymers. Suitable processes include, but are not limited to, gas phase polymerization processes, solution polymerization processes, suspension polymerization processes, and organized reactor processes. Suitable organized reactor processes can incorporate any suitable combination of the gas phase, solution, and suspension polymerization processes described above. As with high density polyethylene polymers, organized reactor processes are often used to produce multimodal polymers.
[0055] Linear low density polyethylene polymers suitable for use in the invention can be produced using any suitable catalyst or combination of catalysts. For example, polymers can be produced using Ziegler catalysts, such as halides or transiption metal esters (for example, titanium) used in combination with organo aluminum compounds (for example, triethyl aluminum). These Ziegler catalysts can be supported on, for example, magnesium chloride, silica, alumina, or magnesium oxide. Linear low density polyethylene polymers suitable for use in the invention can likewise be produced using so-called “dual Ziegler catalysts”, which contain a kind of catalyst for dimerizing ethylene in 1-butene (for example, a combination of a titanium and triethyl aluminum ester) and another catalyst for copolymerization of ethylene, and the 1-butene generated (e.g., titanium chloride supported on magnesium chloride). Linear low density polyethylene polymers suitable for use in the invention can likewise be produced using chromium oxide catalysts, such as those produced by depositing a chromium compound on a silica-titania support, oxidizing the resulting catalyst in a mixture of oxygen and air, and then reducing the catalyst with carbon monoxide. These chromium oxide catalysts are typically used in conjunction with such cocatalysts as trialkylboro or trialkyl aluminum compounds. Chromium oxide catalysts can be used in the same way together with a Ziegler catalyst, as well as a catalyst based on titanium ester or titanium halide. Linear low density polyethylene polymers suitable for use in the invention can likewise be produced using chromium catalysts such as those described above in the discussion of suitable catalysts for preparing high density polyethylene. Linear low density polyethylene suitable for use in the invention can likewise be produced using metallocene catalysts. Several different types of metallocene catalysts can be used. For example, the metallocene catalyst may contain a bis (metallocene) complex of zirconium, titanium, or hafnium with two rings of cyclopentadienyl and methylaluminoxane. As with the catalysts used in the production of high density polyethylene, the binders can be substituted with various groups (e.g., non-butyl group) or linked with bridge groups. Another class of metallocene catalysts that can be used is composed of zirconium or titanium bis (metallocene) complexes and anions of perfluorinated boronaromatic compounds. A third class of metallocene catalysts that can be used is referred to as constrained geometry catalysts and contains derivatives of titanium or zirconium monocyclopentadienyl in which one of the carbon atoms in the cyclopentadienyl ring is attached to the metal atom by a bridge group. These complexes are activated by reacting them with methylaluminoxane or forming ionic complexes with non-coordinating anions, such as B (C6F5) 4or B (C6F5) 3CH3-. A fourth class of metallocene catalysts that can be used and the metallocene-based complexes of a transition metal, such as titanium, containing a cyclopentadienyl linker in combination with another linker, such as a phosphinimine or -OSiR3. This class of metallocene catalyst is likewise activated with methylaluminoxane or a boron compound. Other catalysts suitable for use in the preparation of linear low density polyethylene suitable for use in the invention include, however, are not limited to, catalysts described in U.S. Patent No. 6,649,558.
[0056] Linear low density polyethylene polymers suitable for use in the invention may have any suitable compositional uniformity which is a term used to describe the uniformity of branching in the polymer copolymer molecules. Many commercially available linear low density polyethylene polymers have a relatively low compositional uniformity in which the high molecular weight fraction of the polymer contains relatively little of the α-olefin comonomer and has relatively small branching while a low molecular weight fraction of the polymer contains a relatively high amount of the α-olefin comonomer and have a relatively large amount of branching. Alternatively, another set of linear low density polyethylene polymers has a relatively low compositional uniformity in which the high molecular weight fraction of the polymer contains a relatively high amount of the aolefin comonomer while a low molecular weight fraction of the polymer contains relatively little. a-olefin comonomer. The compositional uniformity of the polymer can be measured using any suitable method, such as elution fractionation of the temperature rise.
[0057] Linear low density polyethylene polymers suitable for use in the invention can have any suitable molecular weight. For example, the polymer can have a weighted average molecular weight of about 20,000 g / mol to about 250,000 g / mol. As will be understood by those of ordinary skill in the art, the appropriate weighted average molecular weight of linear low density polyethylene will depend, at least in part, on the particular application or end use to which the polymer is intended.
[0058] Linear low density polyethylene polymers suitable for use in the invention can likewise have any suitable polydispersity. Many commercially available linear low density polyethylene polymers have a relatively narrow molecular weight distribution and thus relatively low polydispersity, such as about 2 to about 5 (for example, about 2.5 to about 4.5 or about 3.5 to about 4.5). Linear low density polyethylene polymers suitable for use in the invention can likewise have a multimodal (e.g., bimodal) molecular weight distribution. For example, the polymer can have a first fraction having a relatively low molecular weight and a second fraction having a relatively high molecular weight. As with high density polyethylene polymers suitable for use in the invention, the difference between the weighted average molecular weight of the fractions in the multimodal linear low density polyethylene polymer can be any suitable amount. In reality, it is not necessary for the difference between the weighted average molecular weights to be large enough by the fact that two distinct molecular weight fractions can be solved using gel permeation chromatography (GPC). However, in certain multimodal polymers, the difference between the weighted average molecular weights of the fractions can be large enough by the fact that two or more distinct peaks can be solved from the GPC curve for the polymer. In this context, the term "distinct" does not necessarily mean that the portions of the GPC curve corresponding to each fraction do not overlap, however, and it is only intended to indicate that a distinct peak for each fraction can be solved from the GPC curve for the polymer. Multimodal polymers suitable for use in the invention can be produced using any suitable process. As noted above, multimodal polymers can be produced using any organized reactor process. A suitable example would be an organized solution process that incorporates a series of agitated tanks. Alternatively, multimodal polymers can be produced in a single reactor using a combination of catalysts each of which is designed to produce a polymer having a different weighted average molecular weight.
[0059] Linear low density polyethylene polymers suitable for use in the invention may have any suitable melting index. For example, the linear low density polyethylene polymer can have a melting index of about 0.01 dg / min to about 200 dg / min. As with the weighted average molecular weight, those of ordinary skill in the art understand that the suitable melting index for the linear low density polyethylene polymer will depend, at least in part, on the particular application or end use to which the polymer is intended. . Thus, for example, a linear low density polyethylene polymer intended for blow molding applications or tube applications can have a melting index of about 0.01 dg / min to about 1 dg / min. A linear low density polyethylene polymer intended for blown film applications can have a melting index of about 0.5 dg / min to about 3 dg / min. A linear low density polyethylene polymer intended for melt film applications can have a melt index of about 2 dg / min to about 10 dg / min. A linear low density polyethylene polymer intended for injection molding applications can have a melt index of about 6 dg / min to about 200 dg / min. A linear low density polyethylene polymer intended for rotational molding applications can have a melt index of about 4 dg / min to about 7 dg / min. A linear low density polyethylene polymer intended for cable and wire insulation applications can have a melt index of about 0.5 dg / min to about 3 dg / min. The melting index of the polymer is measured using ASTM Standard D1238-04c.
[0060] Linear low density polyethylene polymers suitable for use in the invention generally do not contain a significant amount of long chain branching. For example, linear low density polyethylene polymers suitable for use in the invention generally contain less than about 0.1 long chain branch per 10,000 carbon atoms (for example, less than about 0.002 long chain branch per 100 units ethylene) or less than about 0.01 long chain branch per 10,000 carbon atoms.
[0061] Low density polyethylene polymers suitable for use in the invention generally have a density less than 0.935 g / cm3 and, in comparison to high density polyethylene, medium density polyethylene and linear low density polyethylene, have a relatively small amount. large branch of long chain in the polymer.
[0062] Low density polyethylene polymers suitable for use in the invention may be ethylene homopolymers or ethylene copolymers and a polar comonomer. Suitable polar comonomers include, however, are not limited to, vinyl acetate, methyl acrylate, ethyl acrylate, and acyclic acid. These comonomers can be present in any suitable amount, with comonomer contents as high as 20% by weight being used for certain applications. Since it will be understood by those skilled in the art, the amount of comonomer suitable for the polymer is largely driven by the end use for the polymer, and the required or desired polymer properties dictated by that end use.
[0063] Low density polyethylene polymers suitable for use in the invention can be produced using any suitable process, however, typically the polymers are produced by polymerization initiated by high-pressure ethylene free radical (e.g. about 81 to about 276 MPa) and high temperature (for example, about 130 to about 330'C). Any suitable free radical initiator can be used in such processes, with peroxides and oxygen being the most common. The free radical polymerization mechanism of the PA origin is short chain branching in the polymer and likewise the relatively high degree of long chain branching that distinguishes low density polyethylene from other ethylene pollutants (for example, high polyethylene) density and linear low density polyethylene). The polymerization reaction is typically carried out in an autoclave reactor (for example, a stirred autoclave reactor), a tubular reactor, or a combination of such restores positioned in series.
[0064] Low density polyethylene polymers suitable for use in the invention can have any suitable molecular weight. For example, the polymer can have a weighted average molecular weight of about 30,000 g / mol to about 500,000 g / mol. As will be understood by those of ordinary skill in the art, the appropriate weighted average molecular weight of low density polyethylene will depend, at least in part, on the particular application or end use to which the polymer is intended. For example, a low density polyethylene polymer intended for blow molding applications can have a weighted average molecular weight of about 80,000 g / mol to about 200,000 g / mol. A low density polyethylene polymer intended for tube applications can have a weighted average molecular weight of about 80,000 g / mol to about 200,000 g / mol. A low density polyethylene polymer intended for injection molding applications can have a weighted average molecular weight of about 30,000 g / mol to about 80,000 g / mol. A low density polyethylene polymer intended for film applications can have a weighted average molecular weight of about 60,000 g / mol to about 500,000 g / mol.
[0065] Low density polyethylene polymers suitable for use in the invention can have any suitable melting index. For example, the low density polyethylene polymer can have a melting index of about 0.2 to about 100 dg / min. As noted above, the melt index of the polymer is measured using ASTM Standard D1238-04C.
[0066] As noted above, one of the main distinctions between low density polyethylene and other ethylene polymers is a relatively high degree of long chain branches within the polymer. Low density polyethylene polymers suitable for use in the invention can exhibit any suitable amount of long chain branching, such as about 0.01 or more long chain branches per 10,000 carbon atoms, about 0.1 or more branches long-chain per 10,000 carbon atoms, about 0.5 or more long-chain branches per 10,000 carbon atoms, about 1 or more long-chain branches per 10,000 carbon atoms, or about 4 or more chain branches long for 10,000 carbon atoms. While there is no strict limit on the maximum extent of the long chain branching that may be present in the low density polyethylene polymers suitable for use in the invention, the long chain branching in many low density polyethylene polymers is less than about 100 long chain ramifications per 10,000 carbon atoms.
The thermoplastic polymer composition likewise comprises a nucleating agent. When used herein, the term "nucleating agent" is used to refer to compounds or additives that form nuclei or provide sites for the formation and / or growth of crystals in a polymer when it solidifies from a molten state. In a first embodiment, the nucleating agent comprises a compound conforming to the structure of Formu la (I)
In the structure of Formula (I), it is selected from the group consisting of hydroxy, halogen, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups. The variable is zero or a positive integer from 1 to 4. L and a linking group comprising two or more atoms and at least one double bond between two atoms in the linking group. The variable sees a positive integer from 1 to 3. R2 is: (i) selected from the group consisting of alkyl groups, substituted alkyl groups, cycloalkyl groups, substituted cycloalkyl groups, aryl groups, substituted aryl groups, heteroaryl groups, and heteroaryl groups substituted when L and a divalent linking group eve 1, (ii) selected from the group consisting of alkanodiyl groups, substituted alkanodiyl groups, cycloalkanodiyl groups, substituted cycloalkanodiyl groups, arenodiyl groups , substituted arenodiyl groups, heteroarenodiyl groups, and substituted heteroarenodiyl groups when L and a trivalent linking group eve 1, (iii) selected from the group consisting of alkanodiyl groups, substituted alkanodiyl groups, cycloalkanedi groups -yl, substituted cycloalkanodiyl groups, arenodiyl groups, substituted arenodiyl groups, heteroarenodiyl groups, and heteroarenodiyl groups substituted when L and a group of l divalent bond eve 2, and (iv) selected from the group consisting of alkanotriyl groups, substituted alkanotriyl groups, cycloalkanothriyl groups, substituted cycloalkanothriyl groups, arenotriyl groups, substituted arenotriyl groups. heteroarenotriyl, and substituted heteroarenotriyl groups when L is a divalent linking group eve 3. The variable x is a positive integer. Each Mi is a metal cation; the Valencia y variable of the cation; and the variable is a positive integer. The variable is zero or a positive integer. When b is a positive integer, each Qi will be a negatively charged contrion, and a will be the Valencia of the negatively charged contrion. The values of v, x, y, z, a, and b satisfy the equation (vx) + (ab) = yz. In the structure of Formula (I), the cyclical portion of the cycloalkyl group or substituted cycloalkyl group comprises no more than two ring structures fused together when L is a divalent bonding group, v is 1, and R2 is a cycloalkyl group or a group substituted cycloalkyl.
[0068] In a preferred embodiment, R1 is a halogen or hydroxy, with n = 1 which is particularly preferred. In a more specific embodiment, it cannot be 1, R-i can be hydroxy and attached to the aryl ring in the ortho position with respect to the carboxylate group. In another preferred embodiment, n and 0, meaning that the aryl ring substituted by carboxylate is not substituted with groups R-j.
[0069] L is a bonding group comprising two or more atoms and at least one double bond between the two atoms in the bonding group. With at least one double bond between the two atoms in the bonding group, two of the atoms in the bonding group are hybridized by sp2, and the sum of the bonding angles around at least one of these atoms is approximately 360 degrees. The presence of the double bond within the group of preference restricts the rotation of the molecule around the double bond and, while not wishing to be bound by any particular theory, it is believed that it keeps the compound in a configuration that is most favorable for the nucleation of the polymer . In a series of preferred modalities, L is selected from the group consisting of portions conforming to the structure of one of the Formulas (LA) (LF) below
As can be seen from these structures, suitable linking groups comprise at least two atoms and a double bond between two atoms in the linking group. With each of these L groups, any suitable end of the linking group can be attached to the carboxylate-substituted aryl ring, and the other end (s) can be attached to the R2 group. In a preferred embodiment, L is a portion that selects from the group consisting of portions conforming to the structure of Formulas (LA) and (LD). In a particularly preferred embodiment, L is a portion conforming to the Formula (LA) structure. In such a mode, the portions may have the nitrogen atom attached to the aryl ring replaced by carboxylate or the R2 group.
[0070] The R2 group can be a monovalent, divalent, or trivalent moiety. The Valencia of R2 depends on the Valencia of the linking group L, and the number of aryl rings replaced by carboxylate in the compound. Thus, when L is a divalent linking group, v will be 1, and R2 can be selected from the group consisting of portions conforming to the structure of one of the Formulas (AA) (AG) below. The Formula (AA) structure and
In the Formula (AA) structure, the variable is zero or a positive integer from 1 to 5, and each R10 is selected independently from the group consisting of halogen, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups. The structure of Formula (AB) and (AB)
In the formula (AB) structure, the variable is zero or a positive integer from 1 to 10, and each R13 is selected independently from the group consisting of halogen, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups. The structure of Formula (AC) and (CA)
In the Formula (AC) structure, the variable e is zero or a positive integer from 1 to 8, and each R15 is selected independently from the group consisting of halogen, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups. The structure of Formula (AD) and (AD)
In the Formula (AD) structure, the variable g is zero or a positive integer from 1 to 6, and each R20 is selected independently from the group consisting of halogen, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups. The Formula (AE) structure and
In the Formula (AE) structure, the variable is zero or a positive integer from 1 to 4, and each R25 is independently selected from the group consisting of halogen, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups. The Formula (AF) structure and
In the Formula (AF) structure, the variables Xi, X2, X3, X4, and X5 are independently selected from the group consisting of a carbon atom and a nitrogen atom, provided that at least one and no more than three among Xi, X2, X3, X4, and X5 are nitrogen atoms; t is zero or a positive integer equal to 5-X where X is the number of nitrogen atoms; and each R27 is independently selected from the group consisting of halogen, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups. The structure of Formula (AG) and (AG)
In the Formula (AG) structure, variable X6 is selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, and a secondary amine group, X7, X8, and X9 are independently selected from the group consisting of a carbon atom and a nitrogen atom, at least one and no more than three of X6, X7, X8, and X9 are non-carbon atoms; u is zero or a positive integer equal to 4-Y where Y and the number of non-carbon atoms in the ring structure; and each R29 is independently selected from the group consisting of halogen, cyano groups, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups. When L is a trivalent linking group, ve 1, and R2 can be selected from the group consisting of portions conforming to the structure of one of the Formulas (AH) - (AJ) below. The structure of Formula (AH) and (AH)
In the formula (AH) structure, the variable k is zero or a positive integer from 1 to 8, and each R30 is selected independently from the group consisting of halogen, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups. The structure of Formula (Al) and (Al)
In the structure of Formula (Al), the variable m is zero or a positive integer from 1 to 4, and each R35 is independently selected from the group consisting of halogen, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups. The structure of Formula (AJ) and (AJ)
In the Formula (AJ) structure, the variable p is zero or a positive integer from 1 to 3, p 'and zero or a positive integer from 1 to 3, and each R40 and R45 is selected independently from the group consisting of halogen, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups. When L is a divalent ligation group, ve 2, and R2 can be selected from the group consisting of porphytes conforming to the Formula (BA) structure below

[0071] In the Formula (BA) structure, the variable q is zero or a positive integer from 1 to 4, r zero or a positive integer from 1 to 4, and each R50 and R55 is independently selected from the group consisting of in halogen, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups. When L is a divalent linking group, v will be 3, and R2 can be selected from the group consisting of porphytes conforming to the Formula (CA) structure below (CA)
In the Formula (CA) structure, the variable is zero or a positive integer from 1 to 3, and each R60 is selected independently from the group consisting of halogen, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, aryl groups, and substituted aryl groups.
[0074] In a series of preferred modalities, L is a divalent β-linking group, v and 1, and R2 is a portion conforming to the Formula (AA) structure. Within this series of preferred modalities, the variable is preferably zero or 1. If set to 1, the group R10 is preferably attached to the aryl ring at the position to link to the group L. In addition, if 1, the group R10 and preferably a halogen (for example, bromine), an alkoxy group (for example, a methoxy group), or an aryl group (for example, a phenyl group).
[0075] In a series of preferred modalities, L is a divalent linking group, v and 1, and R2 is a portion conforming to the Formula (AC) structure. Within this series of preferred embodiments, the variable d is preferably zero or 1, with zero being particularly preferred.
[0076] As noted above, M1 is a metal cation. Suitable metal cations include, but are not limited to, alkali metal cations (for example, sodium), alkaline earth metal cations (for example, calcium), transition metal cations (for example, zinc), and group 13 metal (for example, aluminum). When used herein, the term "transition metal" is used to refer to those elements in block d of the periodic table of elements that correspond to groups 3 to 12 in the periodic table of elements. In a preferred embodiment, IV ^ is a metal cation selected from the group consisting of lithium, sodium, magnesium, aluminum, potassium, calcium, and zinc. In another modality he preferred, M1 and a cation de litio. In those modalities in which the compound contains more than one cation of metal M1f each IVh can be the same or different.
[0077] In a series of preferred embodiments, the nucleating agent may comprise a compound conforming to the structure of one of Formulas (IA). (IM) below



[0078] The composition may comprise one or more metal salt compounds conforming to the structure of Formula (I). For example, the composition may comprise any suitable combination of the compounds conforming to the (IA) (IM) structures described above. More specifically, the composition can comprise a compound conforming to the Formula (IA) structure and the compound conforming to the Formula (IL) structure. In another specific embodiment, the composition may comprise a compound conforming to the Formula (IB) structure and a compound conforming to the Formula (IL) structure. In yet another specific embodiment, the composition may comprise a compound conforming to the Formula (IC) structure and a compound conforming to the Formula (IL) structure. Mixtures of these compounds can be used to produce compositions that exhibit a desired combination of properties, with one compound providing a benefit and another compound providing an additional benefit.
[0079] Formula (I) metal salt compounds, and the more specific structures covered by Formula (I) can be synthesized using any suitable technique, many of which will be readily apparent to those of ordinary skill in the art. For example, if the acid used in preparing the compound is commercially available, the compound can be prepared by reacting the acid with a suitable base (for example, a base comprising the desired metal cation and a Bronsted base) in a medium. (for example, an aqueous medium). If the acid to be used in the preparation of the metal salt compound is not commercially available, the acid can be synthesized, for example, using any of the techniques illustrated below in the examples. Once the desired acid is obtained, the compound can be produced as described above (for example, by reacting the acid with a suitable base in an appropriate medium).
The metal salt compounds of Formula (I), and the more specific structures covered by Formula (I) can be produced in various forms of particle sizes. In general, these salt compounds form crystalline layered structures in which the metal ions are present in galleries that are interspersed between alternating layers of organic surfaces. As a result, flat platelet particles are often produced in which the nucleation surfaces are exposed at the top and bottom of the particles, rather than at the edges. The aspect ratio of these platelet-like particles is typically defined as the diameter, or amplitude, versus the thickness. Elongated platelets, or "slat-like" crystals, are another possible particle morphology with these metal salt compounds. In these elongated structures, the aspect ratio is typically defined as the length-to-width relationship. Aspect ratio 2 : 1 to 50: 1 are possible Particles with aspect ratios can align in the melted polymer flow fields so that the flat surfaces are parallel to the machine, or flow, direction and parallel to the cross, or cross direction. Nucleation surfaces are exposed alone in the normal direction of polymer fusion during part manufacturing (excesses would result when the platelet-shaped particles had an insufficient aspect ratio for piano recording, and swirling in the results of the polymer flow direction). Preferred particle orientations, or "registration", combined with specific crystallographic interactions with polyethylene during the nucleation event, can to create targeted lamellar growth that can result in unique and beneficial orientations of polyethylene crystals within the articles produced.
[0081] The particles of the nucleating agent discussed above can be of any suitable size. Preferably, the particles of the nucleating agent are small enough that they are not visible in a finished article made of the thermoplastic polymer composition. Thus, in a preferred embodiment, the particles of the nucleating agent are preferably less than 25 microns in diameter, more preferably less than 20 microns in diameter, and preferably less than 15 microns in diameter.
The nucleating agent can be present in the thermoplastic polymer composition in any suitable amount. The nucleating agent can be present in the thermoplastic polymer composition in an amount of about 50 parts per million (ppm) or more, about 100 ppm or more, about 250 ppm or more, or about 500 ppm or more, based on the total weight of the thermoplastic polymer composition. The nucleating agent is typically present in the thermoplastic polymer composition in an amount of about 10,000 ppm or less, about 7,500 ppm or less, about 5,000 ppm or less, about 4,000 ppm or less, or about 3,000 ppm or less, based on the total weight of the thermoplastic polymer composition. Thus, in certain embodiments of the thermoplastic polymer composition, the nucleating agent is present in the thermoplastic polymer composition in an amount of about 50, about 10,000 ppm, about 100 to about 7,500 ppm (for example, about 100 to about 5,000 ppm), about 250 to about 5,000 ppm (for example, about 250 to about 4,000 ppm or about 250 to about 3,000 ppm), or about 500 to about 5,000 ppm (for example for example, about 500 to about 4,000 ppm or about 500 to about 3,000 ppm), based on the total weight of the polymer composition.
The inventive thermoplastic polymer composition can be supplied in the same way in the form of a master batch composition designed for addition or reduction into a virgin thermoplastic polymer. In such an embodiment, the thermoplastic polymer composition will generally contain a higher amount of the nucleating agent compared to a thermoplastic polymer composition intended for use in forming a fabrication article without further dilution or adipation to a virgin thermoplastic polymer. For example, the nucleating agent can be present in such a thermoplastic polymer composition in an amount of about 1% by weight to about 10% by weight (for example, about 1% by weight to about 5% by weight). weight or about 2% by weight to about 4% by weight), based on the total weight of the thermoplastic polymer composition.
[0084] The thermoplastic polymer composition of the invention may contain other polymer additives in addition to the above-mentioned nucleating agent. Suitable additional polymer additives include, but are not limited to, antioxidants (for example, phenolic antioxidants, phosphite antioxidants, and combinations thereof), anti-blocking agents (for example, amorphous silica and diatomaceous earth), pigments (for example, pigments organic and inorganic pigments) and other dyes (for example, dyes and polymer dyes), fillers and reinforcing agents (for example, glass, glass fibers, talc, calcium carbonate, and fibrillar magnesium oxysulfate monocrystals), agents nucleation agents, clarifying agents, acid recoverers (for example, metal salts of fatty acids, such as stearic acid metal salts, and dihydrotalcite), polymer process additives (for example, process process agents) fluoropolymer polymer), polymer crosslinking agents, gliding agents (for example, fatty acid amide compounds derived from the reaction between a fatty acid and ammonia or a containing compound the amine), fatty acid ester compounds (e.g., fatty acid ester compounds derived from the reaction between a fatty acid and a hydroxyl-containing compound, such as glycerol, diglycerol, and combinations thereof), and combinations of the foregoing.
[0085] As noted above, the thermoplastic polymer composition of the invention can center other nucleating agents in addition to these compounds to conform to the structure of Formula (I). Suitable nucleating agents include, but are not limited to, 2,2'-methylene-bis- (4,6-di-tert-butylphenyl) phosphate salts (for example, 2,2'-methylene-bis- (4, Sodium 6-di-tert-butylphenyl) phosphate or 2,2'-methylene-bis (4,6-di-tert-butylphenyl) aluminum phosphate), bicycles [2.2.1] heptane2,3-dicarboxylate salts ( for example, disodium bicycles [2.2.1] heptane-2,3-dicarboxylate or calcium bicycles [2.2.1] heptane-2,3 dicarboxylate), cyclohexane-1,2 dicarboxylate salts (eg, cycle calcium-hexane-1,2-dicarboxylate, monobasic aluminum cyclohexane-1,2-dicarboxylate, dilute cyclohexane-1,2-dicarboxylate, or strontium cyclohexane-1,2 dicarboxylate), salts glycerolate (for example, zinc glycerolate), phthalate salts (for example, calcium phthalate), phenylphosphonic acid salts (for example, calcium phenylphosphonate), and combinations thereof. For the bicycles [2.2.1] heptane-2,3-dicarboxylate salts, and the cyclohexane-1,2 dicarboxylate salts, the carboxylate moieties can be arranged in the cis or trans configuration, with the cis configuration being preferred. .
[0086] As noted above, the thermoplastic polymer composition of the invention can likewise confer a clarifying agent. Suitable clarifying agents include, but are not limited to, trisamides and acetal compounds which are the condensation product of a polyhydric alcohol and an aromatic aldehyde. Suitable trisamide clarifying agents include, but are not limited to, benzene-1,3,5-tricarboxylic acid amide derivatives, N- (3,5-bis-formylamino-phenyl) -formamide derivative (e.g. A / - [3,5bis- (2,2-dimethyl-propionylamino) -phenyl] -2,2-dimethyl-propionamide), 2-carbamoyl-malonamide derivatives (e.g. / V, / V-bis- ( 2-methyl-cyclohexyl) -2- (2-methyl-cyclohexylcarbamoyl) -malonamide), and combinations thereof. As noted above, the clarifying agent can be an acetal compound which is the condensation product of a polyhydric alcohol and an aromatic aldehyde. Suitable polyhydric alcohols include acyclic polyols such as xylitol and sorbitol, as well as deoxy acyclic polyols (for example, 1,2,3-trideoxynonitol or 1,2,3-trideoxinon -1-enitol). Suitable aromatic aldehydes typically contain a single aldehyde group with the remaining posipbes in the aromatic ring being unsubstituted or substituted. Consequently, suitable aromatic aldehydes include benzaldehyde and substituted benzaldehydes (for example, 3,4-dimethyl-benzaldehyde or 4-propyl-benzaldehyde). The acetal compound produced by the aforementioned reaction can be a mono-acetal, di-acetal, or tri-acetal compound (i.e., a compound containing one, two, or three acetal groups, respectively), with the di-compounds -acetal being preferred. Suitable acetal-based clarifying agents include, but are not limited to, the clarifying agents described in U.S. Patent Nos. 5,049,605; 7,157,510; and 7,262,236.
[0087] The thermoplastic polymer composition of the invention can be produced by any suitable method or process. For example, the thermoplastic polymer composition can be produced by simply mixing the individual components of the thermoplastic polymer composition (for example, thermoplastic polymer, nucleating agent, and other additives, if any). The thermoplastic polymer composition can likewise be produced by mixing the individual components under high shear or high intensity mixing conditions. The thermoplastic polymer composition of the invention can be provided in any form suitable for use in another process for producing a fabrication article from the thermoplastic polymer composition. For example, thermoplastic polymer compositions can be provided in the form of a powder (e.g., free flowing powder), flake, pellet, prill, tablet, chipboard, and the like.
[0088] The thermoplastic polymer composition of the invention is believed to be useful in the production of manufacturing thermoplastic polymer articles. The thermoplastic polymer composition of the invention can be formed into a desired fabrication thermoplastic polymer article by any suitable technique, such as injection molding (e.g., thin-wall injection molding, multi-component molding, supermolding, or 2K molding), blow molding (for example, extrusion blow molding, injection blow molding, or injection extension blow molding), extrusion (for example, fiber extrusion, tape extrusion (eg tape) (extrusion), sheet extrusion, film extrusion, cast film extrusion, tube extrusion, extrusion coating, or foam extrusion), thermoforming, rotational molding, film blowing (blown film), film casting (cast film) ), compression molding, extrusion compression molding, extrusion compression blow molding, and the like. Thermoplastic polymer articles made using the invention's thermoplastic polymer composition can be comprised of multiple layers (e.g., melted or multi-layer blown films or articles molded by multi-layer injection), with one or any suitable number of the multiple layers containing a thermoplastic polymer composition of the invention.
[0089] The thermoplastic polymer composition of the invention can be used to produce any suitable article of manufacture. Suitable articles of manufacture include, but are not limited to, medical devices (for example, pre-filled syringes for retort applications, intravenous delivery containers, and blood collection mechanism), food packaging, liquid containers (for example, containers for drinks, medicines, personal care compositions, shampoos, and the like), apparel case (apparel = clothing), microwave items, files, cabinet doors, mechanical parts, car parts, sheets, pipes, tubes, rotationally molded parts, blow molded parts, films, fibers, and the like.
[0090] Adipation of the heterogeneous nucleating agents described above has been demonstrated constantly to nuclear the thermoplastic polymer (for example, polyolefin, as such as polyethylene), as observed, for example, through an increase in the temperature of the recrystallization of the peak polymer of the polymer. In addition, the adipation of the nucleating agent has been observed to favorably improve certain physical properties of the thermoplastic polymer, such as fog, resistance to tearing (any resistance to absolute tearing or to the balance between tearing resistance in the machine and transversal directions), hardness, and barrier properties. When the thermoplastic polymer composition is used to produce an article, the physical property effects of the nucleating agent on the polymer can be improved by manipulating the characteristic process time (T) and / or by selecting a polymer that exhibits a time of appropriate medium relaxation (X). In this context, the characteristic process time (T) is the time during which the polymer is melted and subjected to stress, which results in the stress (e.g., extensional melting stress) in the polymer's melting. The average relaxation time (X) is a characteristic of the polymer and is a measure of the time that makes melting the polymer relieve stress. The average relaxation time (X) is dependent, inter alia, on the molecular weight of the polymer, the molecular weight distribution of the polymer, and the degree of branching in the polymer. For example, it is known that X is proportional to the molecular weight of the polymer, with higher molecular weights leading to longer relaxation times. In addition, most commercial polyolefins are more or less polydispersed, with the degree of polydispersity typically indicated by Mw / Mn as determined by GPC. This polydispersity inherently produces a series of molecular weight-dependent relaxation times, however many techniques can measure only a single average relaxation time by such polydispersed systems. The polydispersity of the polymer, and the relaxation series dependent on molecular weight and / or average relaxation time, can also be intentionally extended or manipulated by making the mixtures bimodal, as described above.
Many thermoplastic polymers, such as polyethylene, crystallize by chain doubling, producing crystalline lamellae interspersed with an amorphous phase. In processes where the polymer is melted and subjected to relatively small stress, the polymer chains in the polymer melt are not well aligned, and the polymer melt (for example, polyethylene melt) cools until sufficient chain alignment occurs for spontaneously start the growth of crystalline lamellae. When this spontaneous lamellae growth occurs, the nucleation density is relatively low, and the growing lamellae also shift before meeting each other. This allows the lamellae to begin to change their direction or to widen, with the extreme of the widening being the formation of full spherulitis. Because of the relatively long time, this causes autonucleation to occur under these conditions, a nucleating agent (such as that described in this application) added to the polymer fusion will have the opportunity to control a greater proportion of the lamella growth. And with a greater proportion of the lamellae that are formed by the nucleating agent, the nucleating agent will effectively influence the physical properties of the polymer and article.
[0092] One hundred processes, such as blowing on film, can grant significant extensional tension to the melting of the polymer in the direction of the machine (i.e., the direction in which the molten polymer exits the die). The resulting stress causes the polymer chains to unwind from their alternate entropic coil, resulting in prolonged polymer chain alignments towards the machine. If this orientation persists when the polymer fusion cools, some of these long, aligned chain segments can crystallize from the fusion to form relatively long fibrils. Fibrils are very effective in nucleating the growth of chain doubling lamellae. The lamellae form and start to grow perpendicular to the axis of the fibril and more or less radially around the fibrils. Since the density of nucleation is higher, the growing lamellae can meet each other before the significant enlargement begins. This process is referred to here as "stress-induced fibril autonucleation". Under certain conditions as described below, this stress-induced fibril autonucleation may become prominent in the polymer (for example, a polyethylene polymer). Thus, any heterogeneous nucleating agent will have to compete with this stress-induced fibril autonucleation, making the nucleating agent less effective to favorably influence the physical properties of the polymer, and the article. The effects of X and T on stress-induced fibril autonucleation, and the effectiveness of nucleating agents are described below.
[0093] Assuming a constant T, a shorter X means that greater stress relaxation occurs and less polymer chain orientation (for example, polymer chain orientation induced by the extensional stress in polymer fusion) remains at the end Under such conditions, stress-induced fibril autonucleation will be less prominent in the polymer, and a nucleating agent will be more effective in controlling lamella growth and influencing the physical properties of the polymer, and the article. At the same T, a longer X means that less stress relaxation occurs and more orientation of the polymer chain remains at the end of T. Under this series of conditions, stress-induced fibril autonucleation will be more prominent in the polymer, and an agent nucleation will be less effective in controlling lamella growth and influencing the physical properties of the polymer and the article.
[0094] In assessing the effects of X and T on stress-induced fibril autonucleation, and the effectiveness of heterogeneous nucleating agents (such as those described here) in, for example, blown film processes, can be instructive consider the ratio of X to T (X / T), which will be referred to below as the "Manufacturing Time Ratio" (FTR). The FTR is similar to and approximately analogous to the number of Deborah (De). As illustrated by the previous discussion, a lower FTR means that less stress-induced fibril autonucleation will occur in the polymer, making it a more effective nucleating agent in influencing physical properties. And a higher FTR means that more stress-induced fibril autonucleation will occur in the polymer, making a nucleating agent less effective in influencing physical properties. Since the times of most commercial processes can only be varied within a relatively narrow window, the most viable option to change the FTR to improve or optimize the effect of the nucleating agent and to change X, which is done by varying the properties of the polymer. More specifically, for a given process, the effect of the nucleating agent can be optimized to achieve the desired result by varying the properties of the polymer and X to better compare the time of process T. Thus, if the person cannot reach the desired degree of nucleation effects (e.g., improved barrier properties or increased tear strength) using a given nucleating agent and polymer in one process, one can improve the results by selecting a different polymer having a shorter A. For example, one can select a bimodal polymer containing a first fraction having a relatively low Melt index (which is typically indicative of a higher molecular weight and therefore a longer A) and a second fraction having a relatively Melt index high (which is typically indicative of a lower molecular weight and therefore a shorter A). In this system, the fraction of the highest Fusion index can provide an A for the entire polymer which results in the least stress-induced fibril autonucleation and improved response to the heterogeneous nu-cleaging agent. Alternatively, the nucleating agent can only nuclear the fraction of the highest Fusion index (due to the shorter A displayed by the fraction), letting the fraction of the lowest Fusion index go through stress-induced fibril autonucleation in much the same way as if no nucleating agent was present. Regardless of the mechanism at work, the end result is that the nucleating agent controls the lamella growth in the polymer more and shows an increased influence on the physical properties of the polymer. While the previous example describes the use of bimodal polymers, the same effects can be obtained using the multimodal polymers and physical mixtures of the distinct polymers because each of these alternatives likewise provides a means of reducing A. In addition, similar improvements can be obtained by selecting a polymer having a more limited molecular weight distribution (as indicated by a lower melt flow relationship). A more limited molecular weight distribution typically indicates the absence of a higher molecular weight "syrup" or fraction in the polymer that could increase X for the polymer. Likewise, similar improvements can be obtained by selecting a polymer having lower long chain branching, since long chain branching can result in the fusion entanglement that can increase X.
[0096] In a second embodiment, the invention provides a compound conforming to the structure of Formula (C)
In the Formula (C) structure, R10i is selected from the group consisting of a cyclopentyl group and portions conforming to the Formula (Cl) structure. The structure of Formula (Cl) and
In the structure of (Cl), R10s is selected from the group consisting of hydrogen and halogen. The variable x is a positive integer; each Mi and a metal cation; yea Valencia of the cation; eze a positive integer. The variable is zero or a positive integer. When b is a positive integer, each Q1 will be a negatively charged contrion and a will be the Valencia of the negatively charged contrion. The values of x, y, z, a, and b satisfy the equation x + (ab) = yz. M1 can be any of the cations described above as being suitable for the compound conforming to the Formula (I) structure, including those cations noted to be preferred for the Formula (I) structure. In a preferred embodiment, IVh is a cation of a metal selected from the group consisting of alkali metals and alkaline earth metals. In another preferred embodiment, M1 is a cation of a metal selected from the group consisting of alkali metals. In a preferred embodiment, M1 is a lithium cation. Ch, if present, can be any of the anions described above as being suitable for the compound conforming to the structure of Formula (I), including those anions noted to be preferred for the structure of Formula (I).
[0098] In a preferred embodiment, R10i and a cyclopentyl group. The cyclopentyl group can be unsubstituted or substituted. The substituted cyclopentyl group can conform to the Formula (AC) structure above. Preferably, the cyclopentyl group is unsubstituted. In a more specific embodiment, R10i is a cyclopentyl group, the variable x is 1, IVh is a lithium cation, y is 1, z and 1, and b is zero.
[0099] In another preferred embodiment, R10i is a portion conforming to the Formula (Cl) structure. In a more specific embodiment, R10i is a portion conforming to the structure of Formula (Cl), and R105 is hydrogen. In another specific embodiment, R10i is a portion conforming to the structure of Formula (Cl), R-105 and hydrogen, x and 1, M-i and a lithium cation, y and 1, z and 1, and b and zero. In another specific embodiment, R10i is a portion conforming to the structure of Formula (Cl), and R105 is a halogen, preferably bromine. In a more specific embodiment, R10i is a portion conforming to the structure of Formula (Cl), R105 and bromine, x and 1, M-i and a lithium cation, y 1, z and 1, e and zero.
[00100] In a series of additional embodiments, the compound of this second embodiment can be used as a nucleating agent for a thermoplastic polymer as described above in the first embodiment of the invention. In particular, these additional embodiments include thermoplastic polymer compositions comprising a thermoplastic polymer, preferably a polyolefin polymer (for example, a polyethylene polymer), and one or more of the specific compounds described in the preceding paragraphs.
[00101] In a third embodiment, the invention provides a compound conforming to the structure of Formula (CX) (CX)

[00102] In the structure of (CX), Rm is selected from the group consisting of a cyclopentyl group and portions conforming to the structure of Formula (CXI); and R112 is selected from the group consisting of hydrogen and hydroxy. The Formula (CXI) structure and

[00103] In the structure of (CXI), R115 is selected from the group consisting of hydrogen, a halogen, methoxy, and phenyl. The variable x is a positive integer; each M-i and a metal cation; yea Valencia of the cation; and z is a positive integer. Variable b is zero or a positive integer. When b is a positive integer, each Q! it will be a negatively charged contrion and it will be the Valencia of the negatively charged contrion. The values of x, y, z, a, and b satisfy the equation x + (ab) = yz. In addition, if R115 is hydrogen, then R112 is hydrogen, x is 1, M-i is a lithium cation, y is 1, z is 1, and b is zero. Likewise, R115 is a methoxy group, then R112 and a hydroxy group.
[00104] M1 can be any of the cations described above as being suitable for the compound conforming to the structure of Formula (I), including those cations noted to be preferred for the structure of Formula (I). In a preferred embodiment, MT is a cation of a metal selected from the group consisting of alkali metals and alkaline earth metals. In another preferred embodiment, M-i is a cation of a metal selected from the group consisting of alkali metals. In a preferred embodiment, M-i is a lithium cation. If present, it can be any of the anions described above as being suitable for the compound conforming to the structure of Formula (I), including those anions noted to be preferred for the structure of Formula (I).
[00105] In a preferred embodiment, Rm and a cyclopentyl group. The cyclopentyl group can be unsubstituted or substituted. The substituted cyclopentyl group can conform to the Formula (AC) structure above. Preferably, the cyclopentyl group is unsubstituted. In a more specific embodiment, Rm is a cyclopentyl group, the variable x and 1, M-i and a lithium cation, y and 1, z and 1, and b ezero.
[00106] In another preferred embodiment, Rm is a portion conforming to the Formula (CXI) structure. In a more specific embodiment, Rm is a portion conforming to the structure of Formula (CXI), and R115 is hydrogen. In another more specific embodiment, Rm is a portion conforming to the structure of Formula (CXI), and R115 is a methoxy group. In yet another specific embodiment, Rm is a portion conforming to the structure of Formula (CXI), R115 and a methoxy group, x and 1, M-i and a lithium cation, y and 1, z and 1, and b and zero. In another more specific embodiment, Rm is a portion conforming to the structure of Formula (CXI), and R115 is a halogen, preferably chlorine. In still a more specific embodiment, Rm is a portion conforming to the structure of Formula (CXI), R115 is a halogen, preferably chlorine, and R112 is hydrogen. In another more specific modality, Rm is a portion conforming to the structure of Formula (CXI), R115 and chlorine, R112 and hydrogen, and MT is a cation of a metal selected from the group consisting of alkali metals, preferably sodium . In a more specific embodiment, Rm is a portion conforming to the structure of Formula (CXI), R115 and chlorine, R112 and hydrogen, x and 1, IVh a sodium cation, y and 1, z and 1, and b and zero.
[00107] In a series of additional embodiments, the compound of this third embodiment can be used as a nucleating agent for a thermoplastic polymer as described above in the first embodiment of the invention. In particular, these additional embodiments include thermoplastic polymer compositions comprising a thermoplastic polymer, preferably a polyolefin polymer (for example, a polyethylene polymer) and one or more of the specific compounds described in the preceding paragraphs.
[00108] In a fourth embodiment, the invention provides a compound conforming to the structure of Formula (CXX)

[00109] In the structure of (CXX), the variable x is a positive integer. Each M1 is a cation of a metal selected from the group consisting of alkali metals, alkaline earth metals, and zinc; yea Valencia of the cation; and z is a positive integer. Variable b is zero or a positive integer. When b is a positive integer, each QT will be a negatively charged contrion and a will be the Valencia of the negatively charged contrion. The values of x, y, z, a, and b satisfy the equation x + (ab) = yz.
[00110] In a preferred embodiment, M-i is a cation of a metal selected from the group consisting of alkali metals and alkaline earth metals. In another preferred embodiment, M-i is a cation of a metal selected from the group consisting of alkali metals. In a more specific mode, M1 is a cation of lithium. In another specific embodiment, x and 1, M-i and a cation of lithium, ye1, ze1, ebe zero.
[00111] In a series of additional embodiments, the compound of this quantum embodiment can be used as a nucleating agent for a thermoplastic polymer as described above in the first embodiment of the invention. In particular, these additional embodiments include thermoplastic polymer compositions comprising a thermoplastic polymer, preferably a polyolefin polymer (for example, a polyethylene polymer), and, one or more of the specific compounds described in the preceding paragraphs.
[00112] In another embodiment, the invention provides an additive composition comprising a nucleating agent as described above and an acid recovery compound. The nucleating agent present in the composition can be any one or more of the nucleating agent compounds described above, as well as a compound conforming to the structure of Formula (I), a compound conforming to the structure of Formula (C ), a compound conforming to the structure of Formula (CX), a compound conforming to the structure of Formula (CXX), or any suitable mixture of such compounds. Preferably, the nucleating agent in the additive composition is selected from the group consisting of compounds conforming to the Formula (CX) structure. More preferably, the nucleating agent is a compound conforming to the Formula (CX) structure wherein R112 is hydrogen, Rm is a portion conforming to the Formula (CXI) structure, and R115 is a halogen. In a more specific preferred embodiment, the nucleating agent is a compound conforming to the Formula (CX) structure wherein R112 is hydrogen, Rm and a portion conforming to the Formula (CXI) structure, R115 and chlorine , Mi and a sodium cation, x and 1, y 1, z and 1, e and 0.
[00113] Preferably, the acid recoverer is selected from the group consisting of metal salts of fatty acids and synthetic hydrotalcite compounds. Suitable metal salts of fatty acids include, but are not limited to, the metal salts of C12-C22 fatty acids, such as stearic acid. In a preferred embodiment, the acid stove is selected from the group consisting of zinc, potassium, and stearic acid lanthanode. Suitable synthetic hydrotalcite compounds include, but are not limited to, DHT-4A acid recoverer sold by Kyowa Chemical Industry Co., Ltd.
[00114] The nucleating agent, and the acid recoverer can be present in the additive composition in any suitable amount. For example, the nucleating agent, and the acid recoverer can be present in the additive composition in a ratio (nucleating agent for acid recoverer) of about 10: 1 to about 1:10 based on the weight of the nucleation, and in the acid recoverer in the composition. More preferably, the nucleating agent, and the acid recoverer are present in the additive composition in a ratio (nucleating agent for acid recoverer) from about 4: 1 to about 1: 4, about 3: 1 to about from 1: 3, about 1: 1 to about 1: 4, or about 1: 1 to about 1: 3 based on the weight of the nucleating agent, and the acid recoverer in the additive composition.
[00115] Surprisingly, it has been found that the nucleating agent, and the acid recoverer interact synergistically when the additive composition described above is added to a termoplastic polymer. In particular, it has been found that the addition of the acid recoverer can improve the performance of the nucleating agent. For example, the addition of both the nucleating agent and the acid recovery can improve the physical property enhancements to the polymer in addition to those perceived when the nucleating agent is used alone. Likewise, the addition of the acid recoverer can allow the person to achieve a desired level of physical property enhancements to the polymer using less nucleating agent than would be required if the nucleating agent were added alone. This synergy is considered especially surprising given the fact that the acid stove has not been observed to nuclear the polymer itself. For example, the addition of the acid stove alone does not have an appreciable effect on the physical properties of the polymer.
[00116] The additive composition described above is intended for incorporation into a thermoplastic polymer, such as the polyethylene and polypropylene polymers described earlier in this application. In particular, it is believed that the additive composition is particularly effective when used in a high density polyethylene polymer. In these polymers, the addition of the additive composition was observed by significantly decreasing the shrinkage of the machine direction which is indicative of the increased machine direction orientation of the crystalline lamellae and significantly improving the hardness and thermal deflection temperature of the polymer.
[00117] The following examples also illustrate the subject described above, however, of course, they should not be interpreted in any way as limiting the scope of the same. PREPARATION EXAMPLE EX1
[00118] This example demonstrates the preparation of methyl ester of 4-chlorocarbonyl-benzoic acid having the following structure

[00119] In a 4 L boiler with a mechanical stirrer, reflux condenser, addition funnel, thermometer, water bath and heat plate, 438 g of dimethyl terephthalate (DMT) and 2700 ml of toluene were added. The boiler was heated to about 650 to dissolve the entire DMT. After dissolution, a solution of potassium hydroxide (144.54 g in 700 ml of methanol) was added dropwise over 45 minutes. The reaction was stirred at 650 ° C for three hours, and then the reaction cooled to room temperature overnight. The solid was collected after filtration and washed with 3750 ml of toluene at 800. The product was filtered again and dried in the oven at 1100. The yield was 465.9 g (95.3%).
[00120] In a flask with a rounded base with three 2 L necks with a mechanical stirrer, addition funnel, water bath, thermometer, nitrogen sweep and thermal plate, 130.31 g of the product made in the previous step and 1000 mL of toluene were added. Then, 48 ml of thionyl chloride were added dropwise. After completion of the addition, the mixture was heated to 670 ° C for three hours. The reaction cooled to room temperature and was stirred overnight. The contents were filtered to collect the filtrate. The excess solvent was removed by vacuum and 86.52 g of product was obtained (73% yield). PREPARATION EXAMPLE EX2
[00121] This example demonstrates the synthesis of N-cyclopentyltereftalamic acid having the following structure

[00122] A 2 L rounded base flask was loaded with 15.44 g of sodium bicarbonate, 15.75 g of cyclopentyl amine, 0.5 g of triethylamine and 200 ml of tetrahydrofuran (THF). The flask was cooled in an ice bath, and then a 4-chlorocarbonyl-benzoic acid methyl ester solution (36.78 g in about 100 ml of THF) was added dropwise to the flask. After the addition, the mixture was heated to reflux. The reaction was monitored with infrared spectroscopy (IR) until the peak at 1780 cm'1 had disappeared. Then, the mixture was poured into about 2 L of water and stirred for approximately 20 minutes. The solid product was collected after filtration and dried in the oven at 1000 ° C.
[00123] In a flask with a rounded base with three 2 L necks, 21 grams of the product made in the previous step and 150 mL of methanol were added. The mixture was heated to reflux and potassium hydroxide (4.76 g, pre-dissolved in methanol) was added. The reaction was monitored with IR until the peak at 1720 cm-1 disappeared. Then, 400 ml of water was added, and any insoluble impurities were filtered off. The pH of the filtrate was adjusted to about 2 and a precipitate formed. The solid product was filtered and dried in an oven at 100'C. PREPARATION EXAMPLE EX3
[00124] This example demonstrates the production of the potassium salt of N-cyclopentyl-terephthalamic acid having the following structure

[00125] In a beaker, 10 g of N-cyclopentyl-terephthalamic acid was added to 50 ml of H2O. Then, 2.41 g of potassium hydroxide was dissolved in a separate beaker containing about 20 mL of H2O. The potassium hydroxide solution was added to the N-cyclopentyl-terephthalamic acid suspension, and most of the solid dissolved. To remove any undissolved material, the mixture was filtered. The filtrate was collected, and the water was evaporated to produce the product. The product was dried overnight in an oven at 110’C. PREPARATION EXAMPLE EX4
[00126] This example demonstrates the production of N-phenyltereftalamic acid having the following structure

[00127] In a flask with a rounded base with three 1 L necks with magnetic stirrer, addition funnel, ice bath, nitrogen sweep, purifier and heat plate, 93.13 g of aniline, 42.30 g of bicarbonate of sodium, 0.5 g of triethylamine and 300 ml of tetrahydrofuran (THF) were added. The mixture was cooled to below 10 ° C, and then a solution of 100 g of 4-chlorocarbonyl-benzoic acid methyl ester in 100 ml of tetrahydrofuran was added dropwise. The temperature was maintained at about 10X3 during the addition. After addition, the mixture was heated to reflux and monitored until completion of the IR reaction (peak disappearance at 1780 cm -1). After completion, the reaction was diluted to 2 L with cold deionized water (DI) and stirred for approximately 20 minutes. The solid product was filtered and dried in an oven at 110 ° C. After drying, 105.6 g of product (82.2% yield) were obtained.
[00128] In a 1 L Erlenmeyer flask with magnetic stir bar and stir plate, 15.94 g of the product made in the previous step and 200 ml of methanol were added. Then, potassium hydroxide (3.87 g) which was pre-dissolved in methanol was added. The reaction was monitored by IR (peak disappearance at about 1720 cm -1). Upon completion, the reaction was diluted with 400 ml of water. The solid impurities were removed by filtration, and the pH of the filtration was adjusted to about 2. A product precipitated in this step and was collected by filtration. The product was washed with further washing with DI water until neutral, and the product was dried in an oven at 100 ° C. After drying, 14.47 g of the product (95% yield) were obtained. PREPARATION EXAMPLE EX5
[00129] This example demonstrates the production of the lithium salt of N-phenyl-terephthalamic acid having the following structure.

[00130] In a 500 mL Erlenmeyer flask with a magnetic stir bar and stirring plate, 13.3 g of N-phenyl terthalamic acid and 200 ml of water were added. The mixture was heated to near boiling, and then an aqueous solution of lithium hydroxide (containing 1.49 g of anhydrous lithium hydroxide) was added. The reaction was monitored by IR (disappearance of the peak at 1677 cm -1). After completion, the reaction was cooled and filtered to collect the product. The product was dried in an oven at 110 * 0 and 11.56 g of product were obtained. PREPARATION EXAMPLE EX6
[00131] This example demonstrates the production of 4- (4-bromobenzoylamino) benzoic acid having the following structure

[00132] In a flask with a rounded base with three 1 L necks, 40 g of 4-aminobenzoic acid and 400 ml of dioxane were added. The mixture was stirred until the acid had dissolved. Then, 4-bromobenzoyl chloride solution (32.04 g in 100 ml dioxane) was added dropwise to the reaction. After addition, the reaction was stirred overnight, and then filtered to collect the solid. The solid was washed with boiling water, and then cold DI water until the pH was neutral. After drying, the product was obtained in 99.6% yield. EXAMPLE OF PREPARATION EX7
[00133] This example demonstrates the production of the 4- (4-bromo-benzoylamino) benzoic acid potassium salt having the following structure

[00134] In a beaker, 25 g of 4- (4-bromo-benzoylamino) benzoic acid and 200 ml of DI water were added. The mixture was stirred until a uniform suspension was formed. Then, a potassium hydroxide solution (4.4 g in 100 ml of water) was added. The reaction was stirred overnight, and the pH dropped to 10.6. The solid product was filtered and dried in an oven at 11 ° C. PREPARATION EXAMPLE EX8
[00135] This example demonstrates the production of the 4- (4-bromo-benzoylamino) benzoic acid lithium salt having the following structure

[00136] In a beaker, 3 grams of 4- (4-bromo-benzoylamino) benzoic acid were dispersed in about 50 ml of water with stirring. Then, a solution of lithium hydroxide monohydrate (0.39 g in 50 ml H2O) was added to the suspension. The reaction was stirred overnight, and then the solid was collected by filtration. The filtrate was washed with DI water, and then dried in an oven at 110 €. PREPARATION EXAMPLE EX9
[00137] This example demonstrates the production of the calcium salt of 4- (4-bromo-benzoylamino) benzoic acid having the following structure

[00138] In a beaker, 3 grams of 4- (4-bromo-benzoylamino) benzoic acid were dispersed in about 50 ml of stirred water. Then, a solution of calcium hydroxide (0.35 g in 50 ml of water) was added to the suspension. The reaction was stirred over the weekend, and then filtered to collect the resulting solid. The filtrate was washed with DI water, and then dried in a black oven. PREPARATION EXAMPLE EX10
[00139] This example demonstrates the production of 4- (cyclopropanecarbonyl-amino) -benzoic acid having the following structure

[00140] In a flask with three necks, 20.3 g of sodium carbonate were dispersed in 80 ml of THF under N2. While stirring, 13.1 g of 4-aminobenzoic acid dispersion (in 15 ml of THF) and 10.0 g of carbonyl cyclopropane chloride solution (in 15 ml of THF) were added dropwise separately . The reaction was stirred overnight. Then, 10.15 g of sodium carbonate was added, and the mixture was stirred for another 3 hours. Then, the THF was evaporated, and the reaction mixture was transferred to a 1 L beaker and diluted with 600 ml of water. The pH was adjusted to about 2 with hydrochloric acid to form the product as a precipitate. The mixture was filtered to collect the precipitate, and the precipitate was dried in a vacuum oven. PREPARATION EXAMPLE EX11
[00141] This example demonstrates the production of the 4- (cyclopropanecarbonyl-amino) -benzoic acid lithium salt having the following structure

[00142] In a beaker, 5 grams of 4- (cyclopropanecarbonylamino) benzoic acid were dispersed in 20 ml of water, and then 1.13 g of lithium hydroxide monohydrate was added. After stirring for 20 minutes, the reaction was concentrated in vacuo to obtain the product. The product was dried, and the yield was about 2.59 g. PREPARATION EXAMPLE EX12
[00143] This example demonstrates the production of 4- (cyclopropanecarbonyl-amino) -benzoic acid sodium salt having the following structure

[00144] In a beaker, 20 grams of 4- (cyclopropanecarbonyl-amino) -benzoic acid were mixed with 80 ml of water, and then 8.58 g of sodium hydroxide solution (50% in water) was added. After stirring for 20 minutes, the reaction was concentrated in vacuo to obtain the product. PREPARATION EXAMPLE EX13
[00145] This example demonstrates the production of the lithium salt of 4-stilbenocarboxylic acid having the following structure

[00146] In a beaker, 1 gram of 4-stilbenecarboxylic acid (a mixture of trans and cis isomers) was dispersed in 25 ml of water. Then, 0.19 g of lithium hydroxide monohydrate was dissolved in 25 ml of water, and then added to the acid suspension. The reaction was stirred overnight. The solid product was collected by filtration, washed three times with water, and then dried in an oven at 1100 ° C. PREPARATION EXAMPLE EX14
[00147] This example demonstrates the production of 4- (1,3-dioxooctahydro-isoindol-2-yl) -2-hydroxy-benzoic acid having the following structure

[00148] In a flask with four necks of 500 mL with rounded base equipped with temperature probe, heating mantle, shaker and condenser, 21.20 g of hexahydrophthalic anhydride and 50 ml of acetic acid were loaded. At 70X3, the mixture was stirred until uniform, and then 21.7 g of 4 aminosalicylic acid and 100 ml of acetic acid were loaded. After heating under reflux for 6 hours, the contents were poured into ice cold H2O DI and filtered in vacuo to collect the solid. After washing with H2O DI and drying, 33.07 g of product were obtained. PREPARATION EXAMPLE EX15
[00149] This example demonstrates the production of 4- (1,3-dioxo-octahydro-isoindol-2-yl) -2-hydroxy-benzoic acid zinc salt having the following structure

[00150] In a beaker, 4- (1,3-dioxo-octahydro-isoindol-2-yl) 2-hydroxy-benzoic acid and suspend in about 100-150 ml of water with a magnetic stirrer. Then, a 25% sodium hydroxide solution was added slowly until the pH stabilized at 12.5, and the solution was clear. Then, an equivalent of zinc chloride was added (used 1eq instead of 0.5, because the metal ions can also coordinate with the meta hydroxy group). The products precipitated, and the mixture was filtered to collect the product. PREPARATION EXAMPLE EX16
[00151] This example demonstrates the production of 4- (2,2dimethyl-propionylamino) -benzoic acid having the following structure

[00152] In a flask with rounded base with three bottlenecks with suspended agitation, temperature probe, dry ice bath and reflux condenser, 25 g of 4-aminobenzoic acid, 15.12 g of calcined soda and 200 ml of THF. added. Under stirring, 21.98 g of pivaloyl chloride were added dropwise over 1-1.5 hour. Then, 22.68 g of calcined soda was added, and the mixture was heated to 40X3 to bring the reaction to completion. The resulting mixture was diluted with 2 L of H2O DI. The pH of the mixture was adjusted to 2.37 with concentrated hydrochloric acid, and then the mixture was filtered to collect the product. PREPARATION EXAMPLE EX17
[00153] This example demonstrates the production of 4- (2,2-dimethyl-propionylamino) -benzoic acid potassium salt having the following structure

[00154] In a beaker, 4- (2,2-dimethyl-propionylamino) -benzoic acid was suspended in about 100-150 ml of water with a magnetic stirrer. Then, a 25% solution of potassium hydroxide was added slowly until the pH stabilized at 12.5, and the solution was clear. The water was extracted, and the product was obtained. PREPARATION EXAMPLE EX18
[00155] This example demonstrates the production of the 4- (2,2-dimethyl-propionylamino) -benzoic acid calcium salt having the following structure.

[00156] In a beaker, 4- (2,2-Dimethyl-propionylamino) -benzoic acid was suspended in about 100-150 ml of water with a magnetic stirrer. Then, a 25% solution of potassium hydroxide was added slowly until the pH stabilized at 12.5, and the solution was clear. Then, an equivalent of calcium chloride was added. The product precipitated, and the mixture was filtered to collect the product. PREPARATION EXAMPLE EX19
[00157] This example demonstrates the production of N-4-methoxybenzoyl aminosalicylic acid having the following structure

[00158] A flask with a rounded base with three bottlenecks was equipped with suspended agitation, temperature probe, dry ice bath and reflux condenser. Then, 12.36 g of 4 aminosalicylic acid, 16.75 g of calcined soda and 500 ml of tetrahydrofuran were loaded into the flask. The mixture was cooled below 10Â ° C, and then 14.85 g of 4-methoxybenzoyl chloride were added dropwise over 1 -1.5 hour. The resulting mixture was diluted with 2 L of water and filtered to collect the product. PREPARATION EXAMPLE EX20
[00159] This example demonstrates the production of N-4-methoxybenzoyl aminosalicylic acid having the following structure

[00160] In a beaker, N-4-methoxybenzoyl aminosalicylic acid was suspended in about 100-150 ml of water with a magnetic stirrer. Then, a 25% potassium hydroxide solution was added slowly until the pH stabilized at 12.5, and the solution was clear. The water was extracted, and the product was obtained. EX21 PREPARATION EXAMPLE
[00161] This example demonstrates the production of the lithium salt of N-4-methoxybenzoyl aminosalicylic acid having the following structure

[00162] In a beaker, N-4-methoxybenzoyl aminosalicylic acid was suspended in about 100-150 ml of water with a magnetic stirrer. Then, a 25% lithium hydroxide solution was added slowly until the pH stabilized at 12.5, and the solution was clear. The water was extracted, and the product was obtained. PREPARATION EXAMPLE EX22
[00163] This example demonstrates the production of the sodium salt of N-4-methoxybenzoyl aminosalicylic acid having the following structure

[00164] In a beaker, N-4-methoxybenzoyl aminosalicylic acid was suspended in about 100-150 ml of water with a magnetic stirrer. Then, a 25% sodium hydroxide solution was added slowly until the pH stabilized at 12.5, and the solution was clear. The water was extracted, and the product was obtained. PREPARATION EXAMPLE EX23
[00165] This example demonstrates the production of 4- (cyclobutanocarbonyl-amino) -benzoic acid having the following structure

[00166] In a flask, 20.3 g of sodium carbonate, 6.3 g of 4-aminobenzoic acid and 80 ml of THF were added. Then, 5 g of cyclobutanocarbonyl chloride (diluted in 15 ml of THF) was added. The reaction was stirred under nitrogen for the weekend, and the THF evaporated. The mixture was transferred to a 1 L beaker and dissolved with 400 ml of water. The solution was acidified with hydrochloric acid until the pH was about 2, and the product precipitated. The product was collected by filtration, then washed with water and dried. EX24 PREPARATION EXAMPLE
[00167] This example demonstrates the production of 4- (cyclobutanocarbonyl-amino) -benzoic acid potassium salt having the following structure

[00168] In a beaker, 4- (Cyclobutanocarbonyl-amino) -benzoic acid was suspended in about 100-150 ml of water with a magnetic stir bar. Then, a 25% sodium hydroxide solution was added to raise the solution pH to about 12.5. A clear solution was obtained, and then the water was extracted to collect the product as a well. EX25 PREPARATION EXAMPLE
[00169] This example demonstrates the production of 4- (1,3-dioxo1,3-dihydro-isoindol-2-yl) -benzoic acid having the following structure

[00170] In a flask with four necks with a rounded base of 500 ml equipped with a temperature probe, heating mantle, stirrer and condenser, 25.03 g of phthalic anhydride and 87 ml of acetic acid were loaded. At 7013, the reaction was stirred until a clear solution was obtained. Then, 24.37 g of 4aminobenzoic acid was charged, and the mixture was heated to reflux for 2 hours. Then, an additional 50 ml of acetic acid was added. The contents were poured into H2O DL. The product was collected by filtration, and then washed with H2O DI. After drying, 43.345 g of product were obtained (96% yield). PREPARATION EXAMPLE EX26
[00171] This example demonstrates the production of 4- (1,3-dioxo-1,3-dihydro-isoindol-2-yl) -benzoic acid lithium salt having the following structure

[00172] In a 1000 ml beaker equipped with a stirrer, 5.03 g of 4- (1,3-Dioxo-1,3-dihydro-isoindol-2-yl) -benzoic acid and 100 ml of H2O DI were loaded. Lithium hydroxide was loaded into the beaker, and the mixture was stirred until all the acid was in the solution. If the acid was not completely dissolved, lithium hydroxide in 0.1 g increments was added until the acid was completely dissolved. Rotary evaporation was used to recover the product. PREPARATION EXAMPLE EX27
[00173] This example demonstrates the production of 4- (1,3-dioxo-1,3-dihydro-isoindol-2-yl) -benzoic acid sodium salt having the following structure

[00174] In a 1000 ml beaker equipped with a suspense stirrer, 4- (1,3-dioxo-1,3-dihydro-isoindol-2-yl) -benzoic acid and 100 ml of H2O DI were added. The solution was stirred, and a 25% sodium hydroxide solution was added slowly until all of the acid was in the solution. The water was removed by rotary evaporation to recover the product. PREPARATION EXAMPLE EX28
[00175] This example demonstrates the production of N-cyclobutyl-terephthalamic acid methyl ester having the following structure

[00176] In a flask with a rounded base with three bottlenecks, 14.8 g of sodium carbonate and 50 ml of tetrahydrofuran were added. 5 g of cyclobutylamine was then added. Then, 11.59 g of carbonyl chloride 4-methylbenzoate (diluted in 30 ml of tetrahydrofuran) were added dropwise. The reaction was stirred overnight at room temperature. The reaction mixture was then transferred to a beaker and mixed with 200 ml of water. The mixture was acidified with 1M hydrochloric acid. Then, the mixture was transferred to a separatory funnel and extracted with ethyl acetate three times (80 ml each). The organic phase was concentrated to collect the product.
[00177] The product obtained in the previous step was mixed with 200 ml of water, and then heated to 800. A 50% solution of sodium hydroxide was added during the heating course to maintain the pH above 12. After 4 hours, the reaction was acidified to a pH of about 2, and the product precipitated. The product was filtered off. PREPARATION EXAMPLE EX29
[00178] This example demonstrates the production of the lithium salt of N-cyclobutyl-terephthalamic acid having the following structure

[00179] In a beaker, 300 mg of N-cyclobutyl-terephthalamic acid was dispersed in about 40 ml of water. Lithium hydroxide was added slowly until the pH was approximately 12. Then, the solution was concentrated to obtain the desired product. PREPARATION EXAMPLE EX30
[00180] This example demonstrates the production of N-cyclopropyltereftalamic acid having the following structure

[00181] In a flask, 9.3 g of sodium carbonate, 5 g of cyclopropylamine, and 80 ml of tetrahydrofuran were added. Then, 16.43 g of methyl ester of 4-chlorocarbonyl-benzoic acid were diluted in 30 ml of THF, and then added dropwise to the reaction. The reaction was stirred overnight. The product was from the mixture with 400 ml of water. The product was collected and dried, about 18 grams were obtained.
[00182] In a flask, 18 g of the product obtained in the previous step were mixed with 200 ml of water, and then heated to 800. A 50% solution of sodium hydroxide was added during the heating course to maintain the pH above 12. After 4 hours, the reaction was acidified to a pH of about 2, and the product precipitated. The solution was filtered to obtain the product. PREPARATION EXAMPLE EX31
[00183] This example demonstrates the production of the lithium salt of N-cyclopropyl-terephthalamic acid having the following structure

[00184] In a beaker, 2.46 g of wet N-cyclopropyl-terephthalamic acid was mixed with 100 ml of water, and then lithium hydroxide monohydrate was added until the pH was 12. The reaction was stirred for 20 minutes and concentrated to produce the product. PREPARATION EXAMPLE EX32
[00185] This example demonstrates the production of the N-cyclopropyl-terephthalamic acid calcium salt having the following structure

[00186] In a beaker, 2.51 g of N-Cyclopropyl-terephthalamic acid were mixed with 50 ml of water. Then, a 50% sodium hydroxide solution was added until the pH was 12. The reaction was stirred for 20 minutes. Then, 3.52 g of calcium chloride dihydrate was added to the solution to form the product. The product was collected by filtration and dried in an oven. PREPARATION EXAMPLE EX33
[00187] This example demonstrates the production of the zinc salt of N-cyclobutyl-terephthalamic acid having the following structure

[00188] In a beaker, 2.51 g of N-cyclopropyl-terephthalamic acid were mixed with 50 ml of water. Then, a 50% solution of sodium hydroxide was added until the pH was 12. The reaction was stirred for 20 minutes. Then, 3.27 g of zinc chloride was added to the solution to form the product. The product was collected by filtration and dried in an oven. PREPARATION EXAMPLE EX34
[00189] This example demonstrates the production of 4- (4-met6xibenzoylamino) benzoic acid having the following structure

[00190] In a bottle with three 1 L necks equipped with a suspense stirrer, temperature probe, dry ice bath and a reflux condenser, 25 g of 4-aminobenzoic acid, 45.39 g of calcined soda and 200 mL of tetrahydrofuran were added. With stirring, 31.10 g of 4-methoxybenzoyl chloride were added dropwise over a period of 1-1.5 hours. The temperature was kept below 10 ° C during the addition. After completion of the reaction, the mixture was diluted with 2 L of water. The pH was lowered to about 2 with hydrochloric acid to precipitate the product. The product was collected by filtration and dried in an oven. PREPARATION EXAMPLE EX35
[00191] This example demonstrates the production of the 4- (4-methoxy-benzoylamino) benzoic acid sodium salt having the following structure

[00192] In a beaker, 24 g of 4- (4-metdxi-benzoylamino) benzoic acid were mixed with 200 ml of water. Then, a 50% sodium hydroxide solution was added slowly until a stable pH value of 12 was obtained. The solution was concentrated in vacuo to provide the 4- (4-methoxy-benzoylamino) benzoic acid sodium salt. PREPARATION EXAMPLE EX36
[00193] This example demonstrates the production of the 4- (4-methoxy-benzoylamino) benzoic acid lithium salt having the following structure

[00194] In a beaker, 6 g of 4- (4-methoxy-benzoylamino) benzoic acid were mixed with 100 ml of water and lithium hydroxide monohydrate was added slowly until the pH stabilized at 12. The reaction was stirred for 20 minutes, and then it was concentrated in vacuo to provide the product. PREPARATION EXAMPLE EX37
[00195] This example demonstrates the production of N-cycloeptiltereftalamico acid having the following structure

[00196] A flask with a rounded base of 1 L was loaded with 9.3 g of sodium bicarbonate, 5 g of cycloheptylamine and 80 ml of tetrahydrofuran (THF). The flask was cooled with an ice bath. Then, a methyl ester solution of 4-chlorocarbonyl-benzoic acid (8.32 g in about 30 ml of THF) was added dropwise to the vial. After adipation, the reaction was heated to reflux. The reaction was monitored with IR until the peak at 1780 cm-1 disappeared. Then, the mixture was poured into about 400 ml of water and stirred for about 20 minutes. The product was collected by filtration and dried in an oven at 10013 ° C.
[00197] In a flask, 9.1 g of the product from the previous step were mixed with 200 ml of water. A 50% NaOH solution was added until the pH was around 12. The reaction was heated to 800 ° C, stirred for 4 hours, and the pH was maintained at 12 ° C during the reaction. After thin layer chromatography showed completion of the reaction, the pH was adjusted to 2 to precipitate the product. The product was filtered and washed. PREPARATION EXAMPLE EX38
[00198] This example demonstrates the production of the sodium salt of N-cycloeptyl-terephthalamic acid having the following structure

[00199] In a flask, 8.8 g of N-Cycloeptyl-terephthalamic acid were mixed with 200 ml of water and a 50% solution of sodium hydroxide was added slowly until the pH stabilized at 12. For another 20 minutes , the solution was stirred, and then it was concentrated in vacuo to produce the product. PREPARATION EXAMPLE EX39
[00200] This example demonstrates the production of 4- (1,3-Dioxo1H, 3H-benzo [de] isoquinolin-2-yl) -2-hydroxy-benzoic acid having the following structure

[00201] In a flask with a rounded base with four 500 mL necks equipped with a temperature probe, heating mantle, stirrer and condenser, 17.95 g of naphthalic anhydride and 87 ml of acetic acid were loaded. The mixture was heated to 70 ° C and stirred until a clear solution was obtained. The solution turned a light amber color. Then, 14.58 g of 4-aminosalicylic acid were added to the solution. After heating to reflux for 6 hours, the reaction mixture was poured into water. The product was collected by filtration, and then washed with water. After drying, 22.18 g of product was obtained as a brown powder. EX40 PREPARATION EXAMPLE
[00202] This example demonstrates the production of 4- (1,3-dioxo-1H, 3H-benzo [de] isoquinolin-2-yl) -2-hydroxy-benzoic acid sodium salt having the following structure

[00203] In a beaker, 4- (1,3-Dioxo-1H, 3H-benzo [de] isoquinolin-2-yl) -2-hydroxy-benzoic acid was mixed with 200 ml of water. Then, a 50% solution of sodium hydroxide was added slowly until a stable pH value of 12 was obtained. The solution was concentrated in vacuo to produce 4- (1,3doxo-1H, 3H-benzo [de] isoquinolin-2-yl) -2-hydroxy-benzoic acid sodium salt. PREPARATION EXAMPLE EX41
[00204] This example demonstrates the production of the 4- (1,3-Dioxo-1 H, 3H-benzo [de] isoquinolin-2-yl) -2-hydroxy-benzoic acid potassium salt having the following structure

[00205] In a beaker, 4- (1,3-Dioxo-1H, 3H-benzo [de] isoquinolin-2-yl) -2-hydroxy-benzoic acid was mixed with 200 ml of water. Then, potassium hydroxide was added slowly until a stable pH value of 12 was obtained. The solution was concentrated in vacuo providing the 4- (1,3-dioxo-1H, 3Hbenzo [de] isoquinolin-2-yl) -2-hydroxy-benzoic acid potassium salt. PREPARATION EXAMPLE EX42
[00206] This example demonstrates the production of N- (3,4-dimethyl-phenyl) -tereftalamic acid having the following structure

[00207] The product was prepared in a manner similar to that used in PREPARATION EXAMPLE EX37 using 3,4-dimethyl aniline in place of cycloeptylamine. PREPARATION EXAMPLE EX43
This example demonstrates the production of the potassium salt of N- (3,4-Dimethyl-phenyl) -tereftalamic acid having the following structure

[00209] In a beaker, N- (3,4-Dimethyl-phenyl) -tereftalamic acid was mixed with 200 ml of water. Then, potassium hydroxide was added slowly until a stable pH of 12 and a clear solution were obtained. The solution was concentrated in vacuo, providing the desired product. PREPARATION EXAMPLE EX44
[00210] This example demonstrates the production of the lithium salt of N- (3,4-Dimethyl-phenyl) -tereftalamic acid having the following structure

[00211] In a beaker, N- (3,4-Dimethyl-phenyl) -tereftalamic acid was mixed with 200 ml of water. Then, lithium hydroxide monohydrate was added slowly until a stable pH value of 12 was obtained. The solution was concentrated in vacuo, providing the desired product. PREPARATION EXAMPLE EX45
[00212] This example demonstrates the production of 4-benzoylamino benzoic acid having the following structure

[00213] In a 1 L beaker with mechanical agitation, 27.4 g of 4-aminobenzoic acid (0.2 mol) were mixed in 300 ml of H2O DI. Then, 21.2 g (0.2 mol) of sodium carbonate was added until the pH value had become 9.1 and all the 4-amino benzoic acid had dissolved in the water.
[00214] Then, 56.24 g (0.4 mol) of benzoyl chloride was added dropwise to the beaker at room temperature. The reaction was stirred overnight. A solid formed during the reaction, and the pH stabilized at 4.0. The pH was also lowered to about 2 with hydrochloric acid. The product was collected by filtration and washed with hot water to remove excess benzoic acid. The solid product was dried in an oven at 1100 and 44.21 g of the product were obtained (yield 96.7%). PREPARATION EXAMPLE EX46
[00215] This example demonstrates the production of the lithium salt of 4-benzoyl benzoic acid having the following structure

[00216] In a 500 ml beaker, 44.21 g of 4-benzoamidobenzoic acid were mixed with about 250 ml of water. Then, 7.69 g of lithium hydroxide monohydrate (dissolved in about 100 ml of water) was added. The reaction was stirred overnight, and the pH was neutral. The solid product was collected by filtration and dried in an oven at 110X3, 39.7 g of material were obtained (yield 88%). PREPARATION EXAMPLE 47
[00217] This example demonstrates the production of the magnesium salt of 4-benzoyl benzoic acid having the following structure

[00218] In a 500 ml beaker, 30 g of 4-benzoamidobenzoic acid were mixed with about 250 ml of water. Then, 6.98 g of potassium hydroxide (dissolved in about 50 ml of water) were added. The resulting mixture was stirred overnight. All solids dissolved, and the pH value was neutral. Then, 25.3 g of magnesium chloride hexahydrate in about 100 ml of water were added. The product precipitated immediately. The mixture was stirred an additional hour after addition, and then filtered to collect the product. The product was washed with DI water and dried in an oven at 1100 ° C. PREPARATION EXAMPLE EX48
[00219] This example demonstrates the production of 4-N-cyclohexyl-amidobenzoic acid having the following structure

[00220] In a 2 L rounded flask equipped with an ice bath, 3.83 g of sodium bicarbonate, 4.53 g of cyclohexylamine, 0.5 g of triethylamine and 200 ml of tetrahydrofuran . Then, 9.06 g of 4-carbomethoxybenzoyl chloride (dissolved in 9.70 g of tetrahydrofuran) were added dropwise over one hour to the flask. After adipation, the reaction was gently heated to reflux. IR was monitored for completion of the reaction (the disappearance of the peak at 1780 cm -1). After completion, the reaction was diluted with 2 L of H2O, stirred 20-30 min, and then filtered to collect the solid as the product. The product was dried in an oven at 11013; 11.31 g of product were obtained.
[00221] In a flask with a rounded base with three 2 L necks, 11.31 g of the product made in the previous step and 150 ml of methanol were added. Then, 2.72 g of potassium hydroxide (dissolved in methanol) was added dropwise to the flask. After completion of the addition, the reaction was heated to reflux. IR was monitored for completion of the reaction (disappearance of the peak at 1720 cm -1). After the reaction, 750 ml of water was added and filtered to remove any insoluble impurities. The pH of the filtrate was adjusted to about 2 with hydrochloric acid to precipitate the product. The mixture was filtered to collect the product, and the product was washed with DI water. The product was dried in an oven at 1100 ° C. PREPARATION EXAMPLE EX49
[00222] This example demonstrates the production of the potassium salt of 4-N-cyclohexyl-amidobenzoic acid having the following structure

[00223] In a beaker, 6 g of 4-N-cyclohexyl-amidobenzoic acid were dispersed in 50 ml of H2O. Then, 1.36 g of potassium hydroxide was dissolved in another beaker with about 20 ml of H2O, and then added to the suspension. Most of the material dissolved, and the residual insoluble solid was removed by filtration. H2O was extracted from the filtrate to collect the product. The product was dried overnight in an oven at 1100 ° C. EX50 PREPARATION EXAMPLE
[00224] This example demonstrates the production of the aluminum salt of 4-N-cyclohexyl-amidobenzoic acid having the following structure

[00225] 1 gram of the potassium salt of 4-N-cyclohexyl-amidobenzoic acid was dissolved in a beaker with about 25 mL of H2O. In another beaker, 0.78 g of aluminum sulphate octadecahydrate was dissolved with about 15 ml of H2O. The two solutions were mixed and a precipitate formed immediately. The solid was collected by suction filtration and dried overnight in an oven at 11013 ° C. PREPARATION EXAMPLE EX51
[00226] This example demonstrates the production of 4- (1,3-dioxo1H, 3H-benzo [de] isoquinolin-2-yl) -benzoic acid having the following structure

[00227] In a flask with a rounded base with four 1 L necks equipped with a temperature probe, heating mantle, stirrer and condenser, 25 g of naphthalic anhydride and 80 ml of acetic acid were loaded. After the formation of a dark reddish orange solution, 17.31 g of 4-aminobenzoic acid were added, and the reaction was heated to reflux overnight. The reaction mixture was poured in excess amount of DI water to precipitate the product. The product was collected by filtration, washed with more DI water, and then dried in an oven. PREPARATION EXAMPLE EX52
[00228] This example demonstrates the production of 4- (1,3-dioxo-1H, 3H-benzo [de] isoquinolin-2-yl) -benzoic acid lithium salt having the following structure

[00229] In a 1000 mL beaker equipped with a suspense stirrer, 5.09 g of 4- (1,3-dioxo-1H, 3H-benzo [de] isoquinolin-2-yl) -benzoic acid and 100 ml of H2O DL The reaction was stirred, and the pH was adjusted with lithium hydroxide until all of the acid was in solution. Water was removed by rotary evaporation. 5.231 g of the product were obtained. EX53 PREPARATION EXAMPLE
[00230] This example demonstrates the production of the lithium salt of N-benzyl-terephthalamic acid having the following structure

[00231] In a round neck flask with three necks equipped with a condenser and adipation funnel, 6.345 g of sodium bicarbonate, 8.09 g of benzylamine, 0.5 g of triethylamine and 350 ml of tetrahydrofuran . The mixing temperature was cooled to below 100 ° C. Then, 15 g of carbomethoxybenzoyl chloride (dissolved in about 150 ml of tetrahydrofuran) was added dropwise over one hour. After adipation, the mixture was gently heated to reflux. The reaction was monitored until completion with IR (peak disappearance at 1780cm-1). Upon completion, the mixture was diluted with about 2L of DI water and stirred for 20-30 min. The product was collected by filtration and dried in a 10013 oven. 18.68 grams of material were obtained (yield 91.84%)
[00232] 2.12 g of the product from the previous step and 300 ml of DI water were added to a 2 L beaker. Then, 1.89 g of a 10% lithium hydroxide solution was added and stirred until the reaction was complete (peak disappearance at 1720 cm -1 in IR). Then, all the water was removed by rotary evaporation to collect the product; 1.94 g of the product was obtained (yield 94.37%). PREPARATION EXAMPLE EX54
[00233] This example demonstrates the production of the lithium salt of N-pyridin-2-yl-terephthalamic acid having the following structure

[00234] In a round-bottomed flask with three 250 ml necks equipped with suspended agitation, temperature probe, ice bath and reflux condenser, 4.71 g of 3-aminopyridine, 4.2 g of sodium bicarbonate, about 0.1 g of triethylamine and 50 ml of tetrahydrofuran were added. The temperature was cooled to below 1013 ° C, and then 9.9 grams of carbomethoxybenzoyl chloride (a solution in 20 ml of tetrahydrofuran) was added dropwise over 1-1.5 hour. The reaction was stirred overnight, and then heated to reflux for about 2 hours. Then, 500 ml of DI water was used to dilute the reaction, and the resulting mixture was stirred for 20-30 minutes. The solid product was collected by filtration and dried in an oven at 110 ° C.
[00235] In a 250 ml beaker equipped with a magnetic stir bar, 2.56 g of the product made in the previous step, 0.42 g of lithium hydroxide monohydrate and 50 ml of DI water were added. The beaker was heated to 9013 until the pH was below 10. The solid product was collected by filtration and all water was removed by evaporation. EX55 PREPARATION EXAMPLE
[00236] This example demonstrates the production of N- (2-chlorophenyl) -tereftalamic acid having the following structure

[00237] In a flask with a rounded base of 2 L, 6.34 g of sodium bicarbonate, 9.63 g of 2-chloroaniline, 0.5 g of triethylamine and 200 ml of tetrahydrofuran were added. After the reaction was cooled with an ice bath, 15 g of carbomethoxybenzoyl chloride (dissolved in about 100 ml of THF) was added dropwise to the flask. After the addition, the reaction was heated to reflux. IR was monitored for completion (peak disappearance at 1780 cm-1). Upon completion, the solution was diluted with 2 L of H2O DI and stirred 20-30 min. The solid product was collected by filtration and dried in an oven at 1100 ° C.
[00238] In a flask with a rounded base with three 2 L necks, 20.12 g of the product from the previous step and 150 mL of methanol were added. The reaction was heated to reflux. Upon heating, 3.90 g of potassium (dissolved in methanol) was added dropwise to the reaction. IR was monitored for completion (peak disappearance at 1720 cm-1). Upon completion, the solution was diluted with excess H2O. Filtration was used to remove any residual solid, and then HCI was added to the filtrate until the pH value was about 2. The product precipitated in this step was collected by filtration, and then dried in an oven at 11013 ° C. PREPARATION EXAMPLE EX56
[00239] This example demonstrates the production of the lithium salt of N- (2-chloro-phenyl) -tereftalamic acid having the following structure

[00240] In a beaker, 1 gram of N- (2-Chloro-phenyl) -tereftalamic acid was suspended in about 20 ml of water, and then 0.1527 g of lithium hydroxide monohydrate was added. The reaction was stirred until the pH dropped below 10. The solid product was collected by filtration. PREPARATION EXAMPLE EX57
[00241] This example demonstrates the production of the potassium salt of N- (2-chloro-phenyl) -tereftalamic acid having the following structure

[00242] In a beaker, 12 grams of N- (2-Chloro-phenyl) terephthalamic acid were suspended in about 200 ml of water, and then 2.448 g of potassium hydroxide were added. The reaction was stirred until the pH dropped below 10. The product was collected after rotary evaporation to remove excess water. PREPARATION EXAMPLE EX58
[00243] This example demonstrates the production of N- (3,5-dicyano-4-methyl-thiophen-2-yl) -tereftalamic acid having the following structure

[00244] In a bottle with a rounded base with three bottlenecks equipped with suspended agitation, temperature probe, dry ice bath and reflux condenser, 12.32 g of 5-amino-3-methylthiophene -2,4-dicarbonitrile, 6 , 27 g of calcined soda and 200 ml of tetrahydrofuran were added. The temperature was lowered to below 10 ° C, and then 30 grams of a solution of carbomethoxybenzoyl chloride (50% solution in tetrahydrofuran) was added dropwise over 1-1.5 hour. After adipation, the mixture was heated to about 40 ° C until the reaction was complete (monitored by IR, the peak at 1780 cm -1 disappeared). Then, the reaction was diluted with about 2 L of DI water and filtered to collect the product.
[00245] In a 32 oz jar equipped with a magnetic stir bar, 17.4 g of the product made in the previous step were dissolved in 300 ml of methanol. And then, 30.05 g of a potassium hydroxide solution (10% in methanol) was added. The reaction was monitored by IR. After completion of the reaction, the mixture was diluted with 1 liter of water. The mixture was filtered to remove any insoluble impurity, and the filtrate was acidified with hydrochloric acid until the pH was about 2. The product precipitated in this step. The mixture was filtered to collect the product. The product is washed with DI water and dried. PREPARATION EXAMPLE EX59
[00246] This example demonstrates the production of the sodium salt of N- (3,5-dicyano-4-methyl-thiophen-2-yl) -tereftalamic acid having the following structure

[00247] In a beaker, N- (3,5-Dicyano-4-methyl-thiophen-2-yl) terephthalamic acid was mixed with 200 ml of water. Then, a solution of 25% sodium hydroxide was added slowly until a stable pH value of 12 was obtained. The solution was concentrated in vacuo, providing the desired product. EX60 PREPARATION EXAMPLE
[00248] This example demonstrates the production of the lithium salt of N- (3,5-dicyano-4-methyl-thiophen-2-yl) -tereftalamic acid having the following structure

[00249] In a beaker, N- (3,5-Dicyano-4-methyl-thiophen-2-yl) terephthalamic acid was mixed with 200 ml of water. Then, lithium hydroxide monohydrate was added slowly until a stable pH value of 12 was obtained. The solution was concentrated in vacuo, providing the desired product. PREPARATION EXAMPLE EX61
[00250] This example demonstrates the production of the zinc salt of N- (3,5-dicyano-4-methyl-thiophen-2-yl) -tereftalamic acid having the following structure

[00251] In a beaker, N- (3,5-Dicyano-4-methyl-thiophen-2-yl) terephthalamic acid was mixed with 200 ml of water. Then, a 25% potassium hydroxide solution was added slowly until a stable pH value of 12 was obtained. An equivalent of zinc chloride (dissolved in water) was then added to the solution, and the product precipitated. The product was collected by filtration and washed with DL water PREPARATION EXAMPLE EX62
[00252] This example demonstrates the production of the lithium salt of N-Pyridin-3-yl-terephthalamic acid having the following structure

[00253] In a 250 ml three-necked flask equipped with suspended agitation, temperature probe, ice bath and reflux condenser, 4.71 g of 3-aminopyridine, 4.2 g of sodium bicarbonate, about 0 , 1 g of triethylamine and 50 ml of tetrahydrofuran were added. The temperature was lowered to below 1013, and then 9.9 grams of carbomethoxybenzoyl chloride (a solution in 20 ml of tetrahydrofuran) was added dropwise over 1-1.5 hour. The reaction was stirred overnight, and then heated to reflux for about 2 hours. Then, the reaction was diluted with about 500 ml of DI water and stirred for 20-30 minutes. The solid product was collected by filtration and dried in an oven at 110 'C.
[00254] In a 250 ml beaker equipped with a magnetic stir bar, 2.56 g of the product made in the previous step, 0.42 g of lithium hydroxide monohydrate and 75 ml of DI water were added. The beaker was heated to 90X3 until the pH was below 10. All solids were removed by filtration, and the filtrate was collected. The product was collected after the excess water was removed by evaporation. PREPARATION EXAMPLE EX63
[00255] This example demonstrates the production of N- (2-Met6xiphenyl) -tereftalamic acid having the following structure

[00256] In a three-necked flask equipped with suspended agitation, temperature probe, dry ice bath and reflux condenser, 7.44 g of o-anisidine, 5.01 g of calcined soda and 200 ml of tetrahydrofuran have been added. The temperature was lowered to below 10'C, and then 25 grams of a solution of carbomethoxybenzoyl chloride (48% in tetrahydrofuran) was added dropwise over 1-1.5 hour. After adipation, the reaction was heated to about 40 ° C until the reaction was complete (monitored by IR, the peak at 1780 cm -1 disappeared). Then, the mixture was diluted with about 2 L of DI water, and the product was collected by filtration. magnetics, 13.95 g of the product made in the previous step were dissolved in 300 ml of methanol. Then, 27.5 g of potassium hydroxide solution (10% in methanol) was added. The reaction was monitored by IR. After completion of the reaction, the mixture was diluted with about 1 L of water. Insoluble impurities were removed by filtration. The filtrate was acidified with hydrochloric acid until the pH was about 2. The product precipitated in this step. The product was collected by filtration, washed with DI water and dried.
[00257] In a 32 oz jar equipped with a stir bar EX64 PREPARATION EXAMPLE
[00258] This example demonstrates the production of the potassium salt of N- (2-met6xi-phenyl) -tereftalamic acid having the following structure

[00259] In a beaker, N- (2-methoxy-phenyl) -tereftalamic acid was mixed with 200 ml of water. Then, a 25% solution of potassium hydroxide was added slowly until a stable pH value of 12 was obtained. The solution was concentrated in vacuo to produce the desired product. PREPARATION EXAMPLE EX65
[00260] This example demonstrates the production of the magnesium salt of 4-N-phenyl-terephthalamic acid having the following structure

[00261] In a 250 ml beaker equipped with a magnetic stir bar and stir plate, 10 g of 4-N-phenylamidobenzoic acid and 50 ml of water were added. The reaction was heated to close to boiling and 1.5 g of magnesium oxide was added. IR was used to monitor the reaction until completion, and the product was collected by filtration. PREPARATION EXAMPLE EX66
[00262] This example demonstrates the production of the 4-N- (3,4-dichlorophenyl) amidobenzoic acid lithium salt having the following structure

[00263] In a flask with rounded base with three 1 L necks, equipped with magnetic stirring, adipation funnel, ice bath, nitrogen inlet and a thermal plate, 12.48 g of 3,4-dichloroaniline, 6, 34 g of sodium bicarbonate, 0.5 g of triethylamine and 200 ml of tetrahydrofuran were added. The temperature was lowered to below 100 ° C, and then 15 grams of carbomethoxybenzoyl chloride (a solution in 100 ml of tetrahydrofuran) was added dropwise over 1-1.5 hour. After adipation, the reaction was heated to about 4013 ° C until the reaction was completed (monitored by IR, the peak at 1780 cm -1 disappeared). Then, the reaction was diluted with about 2 L of DI water, and the product was collected by filtration. 23.87 g of product were obtained (yield: 97.5%).
[00264] In a 250 ml beaker, 3 g of the product from the previous step were mixed with 50 ml of water. The mixture was heated to near boiling, and 2.22 grams of a 10% lithium hydroxide solution was added. The reaction was monitored until completion by IR. The reaction mixture was evaporated to near dryness, and the product was collected by filtration. 1.92 g of the product was obtained (yield 65.6%). PREPARATION EXAMPLE EX67
[00265] This example demonstrates the production of the 4-N- (2,6-diisopropylphenyl) amidobenzoic acid calcium salt having the following structure

[00266] In a round-bottomed flask with three 1 L necks equipped with a magnetic stirrer, adipation funnel, ice bath, nitrogen sweeper, purifier and heat plate, 14.73 g of 2,6-diisopropylaniline, 6 , 34 g of sodium bicarbonate, 0.5 g of triethylamine and 200 ml of tetrahydrofuran were loaded. The mixture was cooled to below 10'C, and then 15 g of carbomethoxybenzoyl chloride (dissolved in 100 ml of tetrahydrofuran) was added dropwise over 1-1.5 hour. After the addition, the reaction was slowly heated to reflux. After the reaction was completed (peak disappearance at 1780 cm -1 in IR), it was diluted with cold DI water and stirred for 20-30 minutes. The product was collected by filtration and dried in an oven at 1100 ° C.
[00267] In a 600 ml beaker, 13.79 grams of the product from the previous step were mixed in 200 ml of water. The mixture was heated to near boiling, and 22.8 grams of a 10% potassium hydroxide solution was added. After completion of the reaction was monitored by IR, 6.72 g of calcium chloride dihydrate (dissolved to form 10% solution) was added. The product precipitated and was collected by filtration. PREPARATION EXAMPLE EX68
[00268] This example demonstrates the production of 4-benzoylamino-2-hydroxy-benzoic acid having the following structure
suspended, temperature probe, dry ice bath and a reflux condenser, 25 g of 4-aminosalicylic acid, 5.01 g of calcined soda and 200 ml of tetrahydrofuran were added and stirred. The temperature was lowered to below 1013, and 7.32 g of benzoyl chloride was added dropwise over 1-1.5 hour. After addition, the flask was gently heated to 40 ° C. After the completion of the reaction (monitored by IR when the peak at 1780 cm -1 disappears), the reaction mixture was diluted with 300 ml of water. The organic layer was separated. After drying the solvent, about 16 grams of product were obtained.
[00269] In a bottle with three necks equipped with agitation PREPARATION EXAMPLE EX69
[00270] This example demonstrates the production of the 4-benzoylamino-2-hydroxy-benzoic acid lithium salt having the following structure

[00271] In a beaker, 3 grams of 4-Benzoylamino-2-hydroxy-benzoic acid were mixed with 20 ml of water. Then, 1.05 g of lithium hydroxide monohydrate was added. The mixture was stirred for 20 minutes, and then the reaction mixture was concentrated in vacuo to provide the desired lithium salt. PREPARATION EXAMPLE EX70
[00272] This example demonstrates the production of the 4-benzoylamino-2-hydroxy-benzoic acid calcium salt having the following structure

[00273] In a beaker, 3 grams of 4-Benzoylamino-2-hydroxy-benzoic acid were mixed with 20 ml of water. Then, 2.51 g of a 50% sodium hydroxide solution was added. After the solution became clear, a solution containing 3.53 g of calcium chloride dehydrate was added. The product precipitated and was collected by filtration. PREPARATION EXAMPLE EX71
[00274] This example demonstrates the production of 4 - [(biphenyl-4carbonyl) -amino] -benzoic acid having the following structure

[00275] In a flask with a rounded base with three 5 L necks, 316.5 g of 4-aminobenzoic acid were dissolved in about 3 L of dioxane. Then, 250 grams of biphenyl-4-carbonyl chloride (dissolved in about 150 ml of dioxane) were added dropwise over 1 hour. The reaction was stirred overnight and filtered to collect the solid. The solid was washed with boiling DI water, and then cold DI water until the pH of the water was almost neutral. The washed solid was then dried in a vacuum oven. PREPARATION EXAMPLE EX72
[00276] This example demonstrates the production of the lithium salt of 4 - [(biphenyl-4-carbonyl) -amino] -benzoic acid having the following structure

[00277] In a beaker, 364.62 g of 4 - [(biphenyl-4-carbonyl) amino] -benzoic acid were suspended in about 3 L of water. Then, a solution of lithium hydroxide monohydrate (41.96 g in about 500 ml of water) was added to the suspension. The reaction was stirred overnight, and the pH became 7.5. The solid product was collected by filtration, washed with water and dried in an oven at 11 ° C. 334.7 g of the product were obtained (90% yield). EX73 PREPARATION EXAMPLE
[00278] This example demonstrates the production of 4- (benzylidene-amino) -benzoic acid having the following structure

[00279] In a flask with a rounded base with three 500 ml necks, equipped with a condenser, heating mantle, magnetic stirring and two buffers, 10 grams of 4-aminobenzoic acid, 7.75 g of benzaldehyde and 200 ml of ethanol have been added. The reaction mixture was heated to reflux for 6 hours. The product crystallized out of the solution after the solution was cooled to room temperature. The product was collected by filtration. The additional product was recovered by concentrating the filtrate. 15.41 g of the product were obtained (yield: 94%). EX74 PREPARATION EXAMPLE
[00280] This example demonstrates the production of 4- (benzylidene-amino) -benzoic acid lithium salt having the following structure

[00281] In a 2 L beaker, 15.41 of 4 (benzylidene-amino) -benzoic acid were dissolved in 200 ml of water. The mixture was gently heated and stirred on a thermal plate, until a clear solution was obtained. Then, 2.85 g of lithium hydroxide monohydrate was added slowly. The solution became slightly cloudy. After the completion of the reaction, it was cooled, and the water was evaporated. A yellow solid was collected. The product was washed with acetone, and then dried in an oven at 110 'C. EX75 PREPARATION EXAMPLE
[00282] This example demonstrates the production of 4-chlorophenylamido-benzoic acid having the following structure

[00283] In a 5 L flask, 274.3 g of 4-aminobenzoic acid (2 mol) and 2800 ml of acetone were added. The reaction was stirred until a uniform suspension was formed. Then, 175 g of 4-chlorobenzoyl chloride were added dropwise to the 5 L flask, while the contents were being stirred. The reaction was stirred overnight, and then filtered to collect the solid. The product was rinsed with about 500 ml of acetone, and then three times with water (500 ml each time). After washing, the solid was moved to a 4 L beaker and suspended in about 2 L of boiling water for one hour. The solid product was collected by filtration and washed with more boiling water until the water became colorless. PREPARATION EXAMPLE EX76
[00284] This example demonstrates the production of the sodium salt of 4-chlorophenylamido-benzoic acid having the following structure

[00285] In a 2 L beaker, equipped with a mechanical stirrer, 400 ml of water and 27.5 g of 4-chlorophenylamido-benzoic acid were added. In another beaker, 8.4 grams of NaOH (50% solution) was diluted in 100 ml of water. The NaOH solution was added to the 4-chlorophenyl starch-benzoic acid suspension, and the mixture was stirred overnight. The product was collected by filtration. The product was washed with DI water until the pH of the water was below 10, and the product was then dried in an oven at 1100 ° C. EX77 PREPARATION EXAMPLE
[00286] This example demonstrates the production of 4- (4-fluorobenzoylamino) -benzoic acid having the following structure

[00287] In a 4 L beaker, 21.27 g of 4-aminobenzoic acid and 1 L of H2O DI were added. Then, 33.38 g of sodium carbonate were added. Then, 100 g of 4 fluorobenzoyl chloride was added dropwise to the flask (over about 45 min -1 h), and the reaction was stirred overnight. The solid product was collected by vacuum filtration and washed with boiling water to remove excess 4-fluorobenzoic acid. The product was dried overnight in a vacuum oven. 59.08 g of product were obtained. PREPARATION EXAMPLE EX78
[00288] This example demonstrates the production of 4- (4-fluoro-benzoylamino) -benzoic acid lithium salt having the following structure

[00289] In a beaker, 10 grams of 4- (4-fluoro-benzoylamino) benzoic acid were suspended in 100 ml of DI water. Then, 1.62 g of lithium hydroxide monohydrate was dissolved first in 25 ml of DI water, and then added to the acid suspension. The reaction was stirred overnight, and the product was collected by evaporation of water. PREPARATION EXAMPLE EX79
[00290] This example demonstrates the production of 4-benzoylamino-2,3,4,5-tetrafluoro-benzoic acid having the following structure

[00291] In a 250 ml flask equipped with a stirrer, 3.37 g of 4-amino-2,3,4,5-tetrafluroro benzoic acid, 1,06 g of sodium carbonate and 20 ml of water were added . Then, 6.8 g of 4-benzoyl chloride were added dropwise to the flask (over about 45 min 1h). The pH was recorded below 1 the next morning. The solid product was collected by filtration, washed with DI water 5 times, and then dried in an oven at 110 'C. PREPARATION EXAMPLE EX80
[00292] This example demonstrates the production of the 4- (4-fluoro-benzoylamino) -benzoic acid lithium salt having the following structure

[00293] In a 250 ml beaker, 2 grams of 4-Benzoylamino-2,3,4,5-tetrafluoro-benzoic acid and 20 ml of DI water were added. Then, 0.27 g of lithium hydroxide monohydrate was dissolved first in 10 ml of DI water, and then added to the acid suspension. The reaction was stirred overnight, and the product was collected by evaporation of water. PREPARATION EXAMPLE EX81
[00294] This example demonstrates the production of benzene-1,3,5-tricarboxylic acid tris- (4-carboxybenzene) amide having the following structure

[00295] In a flask with a rounded base with three bottlenecks, 21.2 g of sodium carbonate and 100 ml of tetrahydrofuran were added. Then, 13.75 g of 4-aminobenzoic acid and 8 g of 1,3,5-benzene tricarbonyl trichloride were each separately diluted in 15 ml of THF and added simultaneously to the reaction via two adipation funnels. The reaction was stirred overnight at room temperature. About 80 ml of tetrahydrofuran was added to compensate for evaporation during the reactions and an additional 10.6 grams of sodium carbonate was added. Three hours later, the reaction was transferred to a 1 L beaker with 600 ml of water. The pH was adjusted to about 2 with hydrochloric acid. The product precipitated and was collected by filtration. The product was then partially dried in a vacuum oven at 40 ° C. About 35 grams of wet product were obtained. PREPARATION EXAMPLE EX82
[00296] This example demonstrates the production of the sodium salt of tris (4-carboxybenzene) benzene-1,3,5-tricarboxylic acid amide having the following structure

[00297] In a beaker, 32 grams of benzene-1,3,5-tricarboxylic acid tris- (4-carboxybenzene) amide were mixed with 200 ml of water. Then, a 50% solution of sodium hydroxide was added slowly to the mixture until the pH was 12. The mixture was stirred for 20 minutes, and then it was concentrated in vacuo to produce the product. EX83 PREPARATION EXAMPLE
[00298] This example demonstrates the production of biphenyl-4,4'-dicarboxylic acid bis- (4-carboxybenzene) amide having the following structure

[00299] In a flask with a rounded base with three bottlenecks, 5.67 g of sodium carbonate and about 40 ml of tetrahydrofuran were added. Then 4.9 g of 4-aminobenzoic acid and 5.0 g of 4,4'-biphenyldicarbonyl chloride were each separately diluted in 15 ml of THF, and then added simultaneously to the reaction by means of two funnels. addiction. The reaction was stirred overnight at room temperature. Then, the reaction was transferred to a 1 L beaker with 600 ml of water. The pH was adjusted to about 2 with hydrochloric acid. The product precipitated and was collected by filtration. The product was dried in a vacuum oven at 50 ° C. PREPARATION EXAMPLE EX84
This example demonstrates the production of the sodium salt of biphenyl-4,4'-dicarboxylic acid bis (4-carboxybenzene) amide having the following structure

[00301] In a beaker, 12 grams of biphenyl-4,4'-dicarboxylic acid (bis- (4-carboxybenzene) amide were mixed with 100 ml of water, followed by a 50% sodium hydroxide solution the mixture was added slowly until the pH was 12.5 The mixture was stirred for 20 minutes, and then it was concentrated in vacuo to produce the product. EX85 PREPARATION EXAMPLE
[00302] This example demonstrates the production of 4- (4-methylbenzoylamino) benzoic acid having the following structure

[00303] In a flask with a rounded base with three 5 L necks, 274 g of 4-aminobenzoic acid and 3000 ml of acetone were added. The mixture was stirred to form a clear solution. Then, 154.5 g of 4-methylbenzoyl chloride were added dropwise to the reaction. After the addition, the reaction was stirred overnight, and then filtered to collect the solid. The solid was washed with boiling water, and then cold DI water until the pH of the water was neutral. The product was dried at 1100 ° C. EX86 PREPARATION EXAMPLE
[00304] This example demonstrates the production of 4- (4-methyl-benzoylamino) benzoic acid lithium salt having the following structure

[00305] In a beaker, 25.5 g of 4- (4-methyl-benzoylamino) benzoic acid and 200 ml of DI water were added. The mixture was stirred until a uniform suspension was formed. Then, 4.2 g of lithium hydroxide monohydrate was added. The reaction was stirred overnight, and the pH dropped to 10. The solid product was filtered and then dried in an oven at 110'C. PREPARATION EXAMPLE EX87
[00306] This example demonstrates the production of the lithium salt of N-cyclopentyl-terephthalamic acid having the following structure
were added to 100 mL of H2O. Then, 4.2 g of lithium hydroxide monohydrate was dissolved in a separate beaker containing about 50 ml of H2O. The lithium hydroxide solution was added to the N-cyclopentyl-terephthalamic acid suspension and was stirred until the pH value was almost neutral. The product was partially soluble in water. The water was removed by evaporation to produce the product. The product was dried overnight in an oven at 110 ° C.
[00307] In a beaker, 23.3 g of N-cyclopentyl-terephthalamic acid EX88 PREPARATION EXAMPLE
[00308] This example demonstrates the production of the 4- (cyclopentanocarbonyl-amino) -benzoic acid lithium salt having the following structure

[00309] In a round-bottomed flask of 2 1-liter necks, 40 grams of 4-aminobenzoic acid were dissolved in about 400 ml of dioxane. Then, 19.35 g of cyclopentanecarbonyl chloride were added dropwise to the solution. The reaction intermediate, 4- (cyclopentanecarbonyl-amino) -benzoic acid, formed as a white solid in the step and was collected by filtration. After washing the product with about 200 ml of dioxane and then with about 1 liter of boiling water, the reaction intermediate was dried in an oven at 110 ° C. The yield at this stage was about 27.7 g (81%).
[00310] The 27.7 grams of 4- (cyclopentanecarbonyl-amino) benzoic acid were suspended in about 277 ml of water. Then, 5 grams of lithium hydroxide monohydrate was added. The mixture was stirred overnight, and the pH became about 7. After evaporating the excess water, the final product (the lithium salt of 4- (cyclopentanecarbonyl-amino) -benzoic acid) was collected as a white solid and dried in an oven at 110 ° C. EXAMPLE T1
[00311] Various additives from the Preparation Examples above were individually sprayed and mixed with a high density polyethylene polymer having a density of approximately 0.952 g / cm3 and a melt flow index of approximately 19 dg / minute (ExxonMobil ™ HDPE HD 6719). Then, the mixture was injection molded into bars or melted into thin films. The peak polymer recrystallization temperature (Tc) for each thermoplastic polymer composition was measured using a differential scanning calorimeter (MettlerToledo DSC822 differential scanning calorimeter). In particular, a sample was taken from the target part and heated at a rate of 2013 / minute from a temperature of 60X3 for 220X3, held at 220X3 for two minutes, and cooled at a rate of approximately 10X3 / minute at a temperature of 60X3. The temperature at which the peak polymer crystal reform took place (which corresponds to the peak polymer recrystallization temperature) was recorded for each sample and reported in Table 1 below.
[00312] Comparative example CTCEX1 and the high density polyethylene polymer having a density of approximately 0.952 g / cm3 and a melt flow index of approximately 19 dg / minute (ExxonMobil ™ HDPE HD 6719) which was molded by injection into bars of sample. Comparative example CTCEX2 and CTCEX3 are the same high density polyethylene polymer containing 1000 ppm sodium benzoate and aluminum bis [4-1 (1,1-dimethylethyl) benzoate] aluminum (AI-pTBBA), respectively. Comparative example CTCEX4 and the same high density polyethylene polymer melted into a film. Examples TCEX1 to example TCEX56 are the melted film of high density polyethylene polymer containing 1500 ppm of Preparation Examples as described in this application. Table 1. Recrystallization temperature of the peak polymer (Tc) of various additives in PE.



[00313] From Table 1, it is clear that all metal salt compounds of the invention can increase the recrystallization temperature (Tc) of the polyethylene to some extent. While Tc is not the only important factor when choosing a suitable nucleator for a semicrystalline thermoplastic polymer, the improvement in Tc is very desirable since it improves the rate of crystallization during the process, shortens the cycle time, and improves production efficiency . Manufacture of Nucleated Blown Films
[00314] For all examples of blown films, the used polyethylene resins were ground first to about a 35 mesh well. Then 1000 ppm Irganox 10i0, 800 ppm Irgafos 168, 1000 ppm DHT4-A, and the inventive nucleating agent were added to the resin and mixed in a Henschel high intensity mixer for about 2 minutes with a blade speed of about 2100 rpm. The samples were then composed by melting in an MPM helix extruder with a 38 mm diameter helix. The barrel temperature of the extruder was increased from 160 to 190 <C. The extrudate in the form of filaments, was cooled in a water bath and then subsequently pelleted.
[00315] The films were produced in a blown film line on a pilot scale, with a 4-in monolayer matrix, using a 2 mm matrix opening. The line included a Future Design dual flap air ring with cooled air. The extruder had a 55 mm diameter helix with a 24: 1 length-to-width ratio. The barrel temperature of the extruder was increased from 190 to 220X3. Nucleated Polyethylene Blown Film Test
[00316] The% fog of the parts was measured using a meter BYK Gardner Harze, according to ASTM D1023. The clarity of the parts was measured using a BYK Gardner Harze meter. Permeation, measured as Water Vapor Transmission Rate, was measured using an Illinois Instruments 7000 Water Vapor Permeation Analyzer, according to ASTM E398. The tear resistance was measured using a ProTear tear analyzer according to ASTM D1922. The rapid motion drop impact test was performed using a Dynisco Model D2085AB-P fast motion drop polymer analyzer according to ASTM D1709. The film tensile test was performed using an MTS Q-Test-5 instrument, according to ASTM D882.
[00317] The peak polymer (Tc) recrystallization temperature for thermoplastic polymer compositions was measured using a differential scanning calorimeter (Mettler-Toledo DSC822 differential scanning calorimeter). In particular, a compression-molded plate was prepared from the pellets, and a sample was taken from the plate and heated at a rate of 20X3 / minute from a temperature of 60X3 for 220X3, held at 220X3 for two minutes, and cooled at a rate of approximately 10X3 / minute at a temperature of 60X3. The temperature at which the reform of the peak polymer crystal occurred (which corresponds to the recrystallization temperature of the peak polymer) was recorded for each sample. EXAMPLE F1
[00318] This example demonstrates some of the physical properties exhibited by a high density polyethylene polymer that has been nucleated with a nucleating agent according to the invention. The polymer compositions were prepared by composing (as described above) 2000 ppm EX5 in a commercially available high density polyethylene polymer (Sclair® 19G from Nova Chemicals) having a density of approximately 0.962 g / cm3 and a flow index melting rate of approximately 1.2 dg / minute. The polymer composition pellet formed then was used to produce the blown films (3 mil thick) using the following arrangement: 10i, 6 mm (4 in) die, 2.0 mm die opening, BUR 2.3, DDR 11.4, and production 30 kg / h. The recrystallization temperature of the peak polymer, permeation, resistance to tearing, impact of the fall in rapid movement, 1% secant module, and optical properties of the resulting films were measured and are reported in Tables F1 to F4. EXAMPLE F2
[00319] Example F2 was prepared in the same way as the example F1 except EX46 that was used in place of EX5. EXAMPLE F3
[00320] Example F3 was prepared in the same way as the example F1 except EX76 that was used in place of EX5. COMPARATIVE EXAMPLE CF1
[00321] Comparative example CF1 was prepared in the same way as example F1 except that no nucleating agent was used. Table F1. Peak polymer recrystallization temperature (Tc), vapor permeation, and impact of the fast moving drop of comparative example CF1 and examples F1, F2, and F3.
Table F2. Fog and clarity of comparative example CF1 and examples F1, F2, and F3.
Table F3. Secant module at 1% of comparative example CF1 and examples F1, F2, and F3.
Table F4. Tear resistance of comparative example CF1 and examples F1, F2, and F3.

[00322] From the data in Tables F1-F4, it is clear that all additives, EX5, EX46, and EX76 increased the recrystallization temperature of the peak polymer, decreased the haze, and increased the clarity. In addition, EX5 and EX46 increased the resistance to tearing the machine direction, impact of the fall in rapid motion, and vapor permeation. EX76 also increased the tear resistance of the machine. Most importantly, EX76 generated balanced resistance to tearing in the machine and transversal directions, improved barrier property (proven by the lower permeation number), and improved the hardness of the machine direction (1% secant module). EXAMPLE F4
[00323] This example demonstrates some of the physical properties exhibited by a linear low density polyethylene polymer that has been nucleated with a nucleating agent according to the invention. The polymer compositions were prepared by composing (as described above) 2000 ppm EX5 in a commercially available linear low density polyethylene polymer (ExxonMobil ™ LLDPE LL 1001.32) having a density of approximately 0.918 g / cm3 and a melt flow index of approximately 1.0 dg / minute. The polymer composition pellet formed was then used to produce the blown films (2 mil thick) using the following arrangement: 10i, 6 mm (4 in) die, 2.0 mm die opening, BUR 2.35, DDR 17, and production 30 kg / h. The recrystallization temperature of the peak polymer, permeation, impact of the fall in rapid motion, 1% secant module, and tear resistance were measured and are reported in Tables F5 and F6. EXAMPLE F5
[00324] Example F5 was prepared in the same way as example F4 except EX46 that was used in place of EX5. EXAMPLE F6
[00325] Example F6 was prepared in the same way as example F4 except EX76 that was used in place of EX5. COMPARATIVE EXAMPLE CF2
[00326] COMPARATIVE EXAMPLE CF2 was prepared in the same manner as example F4 except that no nucleating agent was used. Table F5. Peak polymer recrystallization temperature (Tc), vapor permeation, and impact of the fast moving drop of comparative example CF2 and samples F4, F5, and F6.
Table F6. Secant module at 1% and resistance to tearing of the comparative sample CF2 and samples F4, F5, and F6.

[00327] From the data in Tables F5 and F6, it is clear that the additives, EX5, EX46, and EX76 increased the recrystallization temperature of the peak polymer. EX5 and EX46 significantly increased the resistance to tearing the machine direction and EX76 increased the machine direction module. All three nucleation agents of the invention increase the resistance to impact in rapid movement slightly. EXAMPLE F7
[00328] This example demonstrates some of the physical properties exhibited by a linear low density polyethylene polymer that has been nucleated with a nucleating agent according to the invention. Polymer compositions were prepared by composing (as described above) 2000 ppm EX46 in a commercially available, linear low density polyethylene polymer (Dowlex ™ 2056G) having a density of approximately 0.922 g / cm3 and a flow rate of melting at approximately 1.0 dg / minute. The polymer composition pellet formed then was used to produce the blown films (1 mil thick) using the following arrangement: 10i, 6 mm (4 in) die, 2.0 mm die opening, BUR 2.38, DDR 33, and production 22 kg / h. The recrystallization temperature of the peak polymer, permeation, impact of the fall in rapid motion, 1% secant module, and tear resistance were measured and are reported in Tables F7 and F8. COMPARATIVE EXAMPLE CF3
[00329] Comparative example CF3 was prepared in the same way as example F7 except that no nucleating agent was used. Table F7. Peak polymer recrystallization temperature (Tc), vapor permeation, and impact of the rapid moving drop of comparative sample CF3 and samples F7.
Table F8. Secant module at 1% and resistance to tearing of the comparative sample CF3 and samples F7.

[00330] From the data in Tables F7 and F8, it is clear that the additive EX46 increased the recrystallization temperature of the peak polymer, increased the resistance to tearing of the machine direction, and impact of the fall in rapid motion. EXAMPLE F8
[00331] This example demonstrates some of the physical properties exhibited by a linear low density polyethylene polymer that has been nucleated with a nucleating agent according to the invention. Polymer compositions were prepared by composing (as described above) 2000 ppm EX76 in a commercially available, linear low density polyethylene polymer (Dowlex ™ 2056G) having a density of approximately 0.922 g / cm3 and a flow rate of melting at approximately 1.0 dg / minute. The formed polymer composition pellet was then used to produce the blown pellets (3 mil thick) using the following arrangement: 10i, 6 mm (4 in) die, 2.0 mm die opening, BUR 2.38, DDR 11, and production 23 kg / h. The recrystallization temperature of the peak polymer, permeation, impact of the fall in rapid movement, impact of the fall in rapid movement, secant module at 1%, and resistance to tearing were measured and are reported in Tables F9 and F10. COMPARATIVE EXAMPLE CF4
[00332] Comparative example CF4 was prepared in the same way as example F8 except that no nucleating agent was used. Table F9. Recrystallization temperature of the peak polymer (Tc) and impact of the fast moving drop of the comparative sample CF4 and samples F8.
Table F10. Secant module at 1% and resistance to tearing of the comparative sample CF4 and samples F8.

[00333] From the data in Tables F9 and F10, it is clear that additive EX76 increased the crystalline peak temperature, impact of the fall in rapid movement, and secant module at 1% MD. Likewise, it provides a balanced tearing resistance in the machine and transversal directions. EXAMPLE F9
[00334] This example demonstrates some of the physical properties exhibited by a linear low density polyethylene polymer that has been nucleated with a nucleating agent according to the invention. Polymer compositions were prepared by composing (as described above) 2000 ppm EX5 in a commercially available, linear low density polyethylene polymer (Dow Elite ™ 5100G) having a density of approximately 0.922 g / cm3 and a flow index melting rate of approximately 0.85 dg / minute. The polymer composition pellet formed then was used to produce the blown films (2 and 3 mil thick) using the following arrangement: 10i, 6 mm (4 in) die, 2.0 mm die opening , BUR 2.38, DDR 16.5 and 11 respectively for films of 2 thousand and 3 thousand, and production 30 kg / h. The recrystallization temperature of the peak polymer, permeation, 1% secant module, and tear strength were measured and are reported in Tables F11 and F12. EXAMPLE F10
[00335] Example F10 was prepared in the same way as example F9 except EX46 that was used in place of EX5. EXAMPLE F11
[00336] Example F11 was prepared in the same way as example F9 except EX76 that was used in place of EX5. COMPARATIVE EXAMPLE CF5
[00337] Comparative example CF1 was prepared in the same way as example F9 except that no nucleating agent was used. Table F11. Recrystallization temperature of the peak polymer (Tc) and vapor permeation of the comparative sample CF1 and samples F9, F10, and F11.
Table F12. Tear resistance of comparative sample CF1 and samples F9, F10, and F11.

[00338] From the data in Tables F11-F12, it is clear that the additives, EX5, EX46, and EX76 increased the recrystallization temperature of the peak polymer. In addition, EX5 and EX46 increased the resistance to tearing the machine direction, especially when the film was 3 mil thick. EX76 increased the tensile module in the direction of the machine and generated more balanced resistance to tearing in the machine and transversals directions. EX5 and EX46 increased permeation while EX76 reduced permeation. Injection Molded Nuclear Polyethylene Fabrication
[00339] In the following injection molding examples, the polyethylene resins used were first ground to a 35 mesh well. Then, the inventive nucleating agent was added to the resin and mixed in a Henschel high intensity mixer for about 2 minutes with a blade speed of about 2100 rpm. The samples were then composed by melting in a DeltaPlast helix extruder, with a 25 mm diameter helix and a 30: 1 length-to-diameter ratio. The barrel temperature of the extruder was increased from 160 to 190'C, and the helix speed was set at about 130 rpm. The extrudate in the form of a filament, was cooled in a water bath and then subsequently pelleted.
[00340] The plates and bars were formed by injection molding in a 40 ton Arburg injection molder with a 25.4 mm helix in diameter. The barrel temperature of the injection molder was 23013 unless otherwise specified, and the mold temperature was controlled at 2513.
[00341] Unless otherwise specified, the injection speed for the plates was 2.4 cc / sec, and their dimensions are about 60 mm in length, 60 mm in width and 2 mm in thickness. These plates were used to measure the recrystallization temperature, bidirectional hardness, and multi-axial impact resistance.
[00342] Unless otherwise specified, the injection speed for the bars was 15 cc / sec, and their dimensions are about 127 mm long, 12.7 mm wide and 3.3 mm thick. These bars were used to measure the 1% secant module, HDT and Izod impact strength. Nuclear Polyethylene Test
[00343] The flexural properties test (reported as a bidirectional module) was performed on the aforementioned plates using an MTS Q-Test-5 instrument with a distance of 32 mm, a fixed deflection rate of 8.53 mm / minute, and a nominal sample width of 50.8 mm. The samples were prepared by cutting the square sections (approximately 50mm X 50mm) from the center of the plates to obtain an isotropic sample. In addition to testing the samples by the machine / flow direction as usual (labeled "Cross Direction" in the results table), the samples were likewise tested by flexing in the cross-flow direction to measure the hardness in that direction as well ( labeled "Machine Direction" in the results table) to examine the bidirectional hardness of the plates.
[00344] The multi-axial impact test was carried out on the pre-laid plates using an Instron Ceast 9350 analyzer according to ISO 6603 standard, using a speed of 2.2 m / sec and a chamber temperature of -30 * 0. The flexural module test (reported as a 1% secant module) was performed on the aforementioned bars using an MTS Qtest / 5 instrument, according to ASTM D790, procedure B. The thermal deflection temperature was performed on the aforementioned bars using a Ceast instrument HDT 3 VICAT, according to ASTM D648-07, method B. The Izod impact test was performed on the aforementioned bars, using a Tinius-Olsen 892T instrument, according to ASTM D256, method A.
[00345] The recrystallization temperature of the peak polymer (Tc) for the thermoplastic polymer compositions was measured using a differential scanning calorimeter (Mettler-Toledo DSC822 differential scanning calorimeter). In particular, a sample was taken from the target part and heated at a rate of 20X3 / minute from a temperature of GO'C for 22013, held at 220X3 for two minutes, and cooled at a rate of approximately 10X3 / minute to a 60X3 temperature. The temperature at which the peak polymer crystal reform took place (which corresponds to the peak polymer recrystallization temperature) was recorded for each sample. EXAMPLE 11-13
[00346] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer that has been nucleated with nucleating agents according to the invention. The polymer compositions were prepared by composing (as described above) Preparation Example EX5 and different acid recoverers in a commercially available high density polyethylene (Dowlex ™ IP 40) having a density of approximately 0.954 g / cm3 and an index melt flow rate of approximately 40 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets. The polymer composition pellet formed was then molded by injection into test plates and bars.
[00347] The formulation information for Examples 11 to I3 and Comparative Example CI1 is listed in table 11. The peak polymer (Tc) recrystallization temperature, multi-axial impact at temperatures of -30X) and bidirectional module (measured in plates), and 1% secant module and thermal deflection temperature (measured in bars) are reported in Tables I2 and I3 below Table 11: Formulation information for Samples CI1, 11.12 and I3.
Table 12: Multi-axial impact at -30X3 temperature and bidirectional sample module CI1,11, I2 and I3.
Table I3: 1% secant module, thermal deflection temperature, and recrystallization temperature of the CI peak polymer 1,1,11,12, and I3.
EXAMPLE I4-I6
[00348] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer that has been nucleated with nucleating agents according to the invention. The polymer compositions were prepared by composing (as described above) Preparation Example EX46 and different acid recoveries in commercially available high density polyethylene (Dowlex ™ IP 40) having a density of approximately 0.954 g / cm3 and an index of melting flow of approximately 40 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets. The polymer composition pellet formed was then molded by injection into test plates and bars. The formulation information for Examples I4 to I6 and Comparative Example CI2 is listed in Table I4. The recrystallization temperature of the peak polymer (Tc), multi-axial impact at -301C and bidirectional module (measured in plates), and 1% secant module and thermal deflection temperature (measured in bars) are reported in Table I5 and I6 below. Table I4: Formulation information for Samples CI2, I4.15 and I6.
Table 15: Multi-axial impact at -30X3 temperature and bidirectional sample module CI2,14, 15 and 16
Table 16: 1% secant module, recrystallization temperature of the peak polymer, and deflection temperature
EXAMPLE I7
[00349] This example demonstrates some of the physical properties exhibited by a high density polyethylene polymer which has been cleaved with nucleating agents according to the invention. The polymer compositions were prepared by composing (as described above) Preparation Example EX76 in a commercially available high density polyethylene (Dowlex ™ IP 40) having a density of approximately 0.954 g / cm3 and a flow rate of melting at approximately 40 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets. The polymer composition pellet formed was then injection molded into test plates and bars. The formulation information for Example I7 and Comparative Example CI3 is listed in Table I7. The recrystallization temperature of the peak polymer (Tc), multi-axial impact at -30'C and bidirectional module (measured in plates), and 1% secant module and thermal deflection temperature (measured in bars) were measured and reported in Table I8 and I9 below. Table I7: Formulation information for Samples CI3 and I7.
Table 18: Multi-axial impact at -SOX} temperature and bidirectional module of samples CI3 and 17
Table 19: 1% secant module, thermal deflection temperature, and recrystallization temperature of the CI3 and I7 peak polymer.
EXAMPLE 18-110
[00350] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer that has been nucleated with nucleating agents according to the invention. The polymer compositions were prepared by composing (as described above) Preparation Example EX5 and different acid recoverers in a commercially available high density polyethylene (ExxonMobil ™ HDPE HD 6719) having a density of approximately 0.952 g / cm3 and a melting flow index of approximately 19 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets. The polymer composition pellet formed was then molded by injection into test plates and bars. The formulation information for Examples I8 to 110 and Comparative Example CI4 is listed in Table 110. The recrystallization temperature of the peak polymer, multi-axial impact at -3013 temperature and bidirectional module (measured in plates), and secant module at 1% and thermal deflection temperature (measured in bars) were measured and are reported in Table 111 and 112 below. Table 110: Formulation information for Samples CI4,18,19 and 110.
Table 111: Multi-axial impact at -3013 and bidirectional sample module CI4,18,19 and 110.
Table 112: 1% secant module, thermal deflection temperature, and recrystallization temperature of the CI peak polymer 4,18,19 and 110.
EXAMPLE 111-112
[00351] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer that has been nucleated with nucleating agents according to the invention. The polymer compositions were prepared by composing (as described above) Preparation Examples EX46 and EX76 in a commercially available high density polyethylene (ExxonMobil ™ HDPE HD 6719) having a density of approximately 0.952 g / cm3 and a flow index melting rate of approximately 19 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets. The polymer composition pellet formed was then molded by injection into test plates and bars. In this example, the plates were molded at 15 cc / sec, and the bars at 40 cc / sec, keeping the other process conditions equal to those described above. The formulation information for Examples 111 and 112 and Comparative Example CI5 is listed in Table 113. The recrystallization temperature of the peak polymer, multi-axial impact at -3013 temperature and bidirectional module (measured in plates), and secant module at 1%, izod impact at -30X3, and thermal distortion temperature (measured in bars) were measured and are reported in Table 114 and 115 below. Table 113: Formulation information for Samples CI5,111 and 112.
Table 114: Multi-axial impact at -30 * 0 and bidirectional module of sample CI5, 111 and 11 2. Plates molded at 15 cc / sec
Table 115: Secant module at 1%, recrystallization temperature of the peak polymer, and thermal deflection temperature of CI5,111 and 112. Bars molded at 40 cc / sec
EXAMPLE 113-115
[00352] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer that has been nucleated with nucleating agents according to the invention. The polymer compositions were prepared by composing Preparation Examples EX5, EX46 and EX76 in a commercially available high density polyethylene (LyondellBasell Hostalen® ACP 6541A UV) having a density of approximately 0.954 g / cm3 and a melt flow index approximately 1.5 dg / minute. The resin was first poured, mixed with the additives, and then composed and extruded to form the pellets. The polymer composition pellet formed was then injection molded into test plates and bars. In this example, the plates were molded at 220X3 and 20 cc / sec, and the bars were molded at 220X3 and 40 cc / sec, keeping the other process conditions the same as described above. The formulation information for Examples 113, 114, 115 and Comparative Example CI6 is listed in Table 116. The recrystallization temperature of the peak polymer, multi-axial impact at -30X3 temperature and bidirectional module (measured in plates), and 1% secant module, Izod impact, and thermal deflection temperature (measured in bars) were measured and are reported in Table 117 and 118 below. Table 116: Formulation information for Samples CI6, 113, 114 and 115.
Table 117: Multi-axial impact at -3013 and bidirectional sample module CI6, 113, 114 and 115.
Table 118: 1% secant module, recrystallization temperature of the peak polymer, and thermal deflection temperature of CI6,113, 114 and 115.
Manufacture of Deli Cups Molded by Injection of Thin Wall Nu-Cleared
[00353] The polyethylene resins used were first ground to a 35 mesh well. The inventive nucleating agent was added to the resin and mixed in a Henschel high intensity mixer for about 2 minutes with a blade speed of about 2100 rpm. The samples were then composed cast in an extruder with an MPM helix, with a 38 mm diameter helix. The temperature of the extruder barrel has been increased from 160 to 190 ° C. The extrudate in the form of filaments, was cooled in a water bath and then subsequently pelleted. Deli glasses with a volumetric capacity of 16 oz. were produced in a Husky S-90 RS40 / 32 injection molder, 90 ton press and high speed / accumulator assisted injection unit using a single cavity mold. The injection molder has an alternative helix of 32 mm in diameter, with a length to diameter ratio of 25: 1. The temperature of the extruder barrel was between 190 and 21013 depending on the melting index of the resin, with the hot runner temperatures similarly set at around 21013. The mold temperature was set at around 1213. The dimensions of the Deli cups they are approximately 117 mm in diameter and 76 mm in height. Nucleated Polyethylene Deli Cup Test
[00354] The% haze of the parts was measured on the side wall using a meter BYK Gardner Hazer, according to ASTM D1023. The clarity of the parts was measured on the side wall using a BYK Gardner Hazer meter. The top load of the parts was measured using an MTS Q-Test-5 instrument according to ASTM D 2659. The recrystallization temperature of the peak polymer (Tc) for the thermoplastic polymer compositions was measured using a differential scanning calorimeter ( differential scanning calorimeter (Mettler-Toledo DSC822). In particular, a compression-molded plate was prepared from the pellets and a sample was taken from the plate and heated at a rate of 20'C / minute from a temperature of 60'C during 22013, maintained at 22013 for two minutes, and cooled at a rate of approximately 1013 / minute to a temperature of 6013. The temperature at which the reform of the peak polymer crystal occurred (which corresponds to the recrystallization temperature of the peak polymer) was recorded for each sample. EXAMPLE 116-118
[00355] These examples demonstrate some of the physical properties exhibited by high density polyethylene polymer articles (Deli cups) that have been produced using a composition containing a nucleating agent according to the invention. The polyethylene articles were prepared by composing (as described above) the Repair Examples EX5, EX46, and EX76 in a commercially available high density polyethylene (Dowlex IP 40) having a density of approximately 0.954 g / cm3 and an index of melting flow of approximately 40 dg / minute. The resin was first poured, mixed with the additives, and then composed and extruded to form the pellets as described above. The polymer composition pellet formed was then processed by thin-wall injection molding (TWIM) to form the polyethylene articles. In this example, Deli cups were produced using a refill time of 0.21 seconds. The formulation information for Examples 116, 117, 118 and Comparative Example CI7 is listed in Table 119. Peak recrystallization time (measured on a compression molded plate produced with the pellets), clarity, fog, and charge top of the deli cups were measured and reported in Table I20 below. Table 119: Formulation information for Samples CI7 and 116 to 118. All compositions contain 1000 ppm of organoxoxide and 800 ppm of Irgafos 168.
Table I20. Selected physical properties of Comparative Samples CH 7 and sample 116 to 118.
Manufacturing of Nuclear Injection Molded Food Storage Container
[00356] The used polyethylene resins were first ground to a 35 mesh well. The inventive nucleating agents were added to the resin and mixed in a Henschel high intensity mixer for about 2 minutes with a blade speed of about 2100 rpm. The samples were then composed by melting in an extruder with an MPM helix, with a 38 mm diameter helix. The barrel temperature of the extruder was increased from 160 to 190 * 0. The extrudate in the form of filaments, was cooled in a water bath and then subsequently pelleted. The reusable food storage containers weighing approximately 62 g were produced in a Husky S-90 RS40 / 32 injection molder, 90 ton press and accumulator assisted / high speed injection unit using a single mold cavity. The injection molder has an alternative helix of 32 mm in diameter, with a length to diameter ratio of 25: 1. The barrel temperature of the extruder was between 190 and 220X3 depending on the melting index of the resin, with the hot runner temperatures similarly fixed at about 220X3. The mold temperature was set at about 12X3. The dimensions of the food storage containers are 190.5 mm X 98.4 mm X 76.2 mm, and the wall thickness is about 1 mm. Testing of nu-cleared polyethylene food storage containers
[00357] The% haze of the parts was measured on the side wall using a meter BYK Gardner Harze, according to ASTM D1023. The clarity of the parts was measured on the side wall using a BYK Gardner Harze meter. The top load of the parts was measured using an MTS Q-Test-5 instrument in accordance with ASTM D 2659. The recrystallization temperature of the peak polymer (Tc) for thermoplastic polymer compositions was measured using a differential scanning calorimeter ( differential scanning calorimeter (Mettler-Toledo DSC822). In particular, a compression molded plate was prepared from the pellets and a sample was taken from the plate and heated at a rate of 20X3 / minute from a temperature of 60X3 for 220X3, held at 220X3 for two minutes, and cooled at a rate of approximately 10X3 / minute at a temperature of 60X3. The temperature at which the peak polymer crystal reform took place (which corresponds to the peak polymer recrystallization temperature) was recorded for each sample. EXAMPLE H1-H3
[00358] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer article (food storage container) that has been nucleated with nucleating agents according to the invention. Polyethylene articles were prepared by composing Preparation Examples EX5, EX46, and EX76 in a commercially available high density polyethylene (ExxonMobil ™ HDPE HD 6719) having a density of approximately 0.952 g / cm3 and a melt flow index approximately 19 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets as described above. The formed polymer composition pellet was then processed by injection molding (IM) to form the polyethylene articles. In this example, household utensils were produced using a supply time of 2.8 seconds. The formulation information for Examples H1, H2, H3 and Comparative Example CH1 is listed in Table TH1. Peak recrystallization time (measured on a compression molded plate produced with the pellets), lightness, fog, and top load were measured and are reported in Table TH2 below. Table TH1: Formulation information for Samples CH1 and H1 to H3. All compositions contain 1000 ppm Irganox1010 and 800 ppm Irgafos 168.

EXAMPLE H4-H6
[00359] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer article (food storage container) that was made with a resin nucleated with a nucleating agent according to the invention. Polyethylene articles were prepared by composing Preparation Examples EX5, EX46, and EX76 in a commercially available high density polyethylene (Dow ™ HDPE DMDA-8965 NT 7) having a density of approximately 0.954 g / cm3 and a flow index melting rate of approximately 66 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets as described above. The polymer composition pellet formed then was processed by injection molding (IM) to form the polyethylene articles. In this example, household utensils were produced using a supply time of 3.0 seconds. The formulation information for Examples H4, H5, H6 and Comparative Example CH2 is listed in Table TH3. Peak recrystallization time (measured on a compression molded plate produced with the pellets), clarity, haze, and top load were measured and are reported in Table TH4 below. Table TH3: Formulation information for Samples CH2 and H4 to H6. All compositions contain 1000 ppm of organoxoxide and 800 ppm of Irgafos 168.
Table TH4. Selected physical properties of Comparative Samples CH2 and H4 to H6.
EXAMPLE H7-H9
[00360] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer article (food storage container) that was produced using a resin nucleated with a nucleating agent according to the invention. Polyethylene articles were prepared by composing Preparation Examples EX5, EX46, and EX76 in a commercially available linear low density polyethylene (ExxonMobil ™ LLDPE LL 6100.17) having a density of approximately 0.925 g / cm3 and a melt flow index approximately 20 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets as described above. The polymer composition pellet formed then was processed by injection molding (IM) to form the polyethylene articles. In this example, household utensils were produced using a refill time of 2.7 seconds. The formulation information for Examples H7, H8, H9 and Comparative Example CH3 is listed in Table TH5. Peak recrystallization time (measured on a compression molded plate produced with the pellets), lightness, fog, and top load were measured and are reported in Table TH6 below. Table TH5: Formulation information for Samples CH3 and H7 to H9. All compositions contain 1000 ppm of organoxoxide and 800 ppm of Irgafos 168.
Table TH6. Selected physical properties of comparative tests CH3 and H7 to H9.
EXAMPLE H10-H12
[00361] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer article (food storage container) that was made with a resin nucleated with a nucleating agent according to the invention. Polyethylene articles were prepared by composing Preparation Examples EX5, EX46, and EX76 in a commercially available linear low density polyethylene (Dowlex ™ 2517) having a density of approximately 0.919 g / cm3 and a melt flow index of approximately 25 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets as described above. The polymer composition pellet formed then was processed by injection molding (IM) to form the polyethylene articles. In this example, household utensils were produced using a refill time of 2.5 seconds. The formulation information for Examples H10, H11, H12 and Comparative Example CH4 is listed in Table TH7. Peak recrystallization time (measured on a compression molded plate produced with the pellets), lightness, fog, and top load were measured and are reported in Table TH8 below. Table TH7: Formulation information for Sample CH4 and H10 to H12. All compositions contain 1000 ppm of organoxoxide and 800 ppm of Irgafos 168.
Table TH8. Selected physical properties of Comparative Samples CH4 and H10a H12.
Nuclear Polypropylene Forming
[00362] The different additives were added to the polypropylene-based resin and mixed in a high intensity Henschel mixer for about 2 minutes with a blade speed of about 2100 rpm. The samples were then composed by melting in a DeltaPlast helix extruder, with a 25 mm diameter helix and a 30: 1 length-to-diameter ratio. The barrel temperature of the extruder was increased from 190 to 230 * 0, and the screw speed was set at about 130 rpm. The extrudate in the form of a filament, was cooled in a water bath and then subsequently pelleted.
[00363] The plates and bars were formed by injection molding in a 40 ton Arburg injection molder with a 25.4 mm helix in diameter. The barrel temperature of the injection molder was 230 * C, and the mold temperature was controlled to 25 * C. The injection speed for the plates was 2.4 cc / sec, and its dimensions are about 60 mm long, 60 mm wide and 2 mm thick. These plates were used to measure the recrystallization temperature, bidirectional hardness. The injection speed for the bars was 15 cc / sec, and its dimensions are about 127 mm long, 12.7 mm wide and 3.3 mm thick. These bars were used to measure the 1% secant module, HDT and Izod impact strength. Nucleated Polypropylene Test
[00364] The flexural properties test (reported as a bidirectional module) was performed on the aforementioned plates using an MTS Q-Test-5 instrument with a distance of 32 mm, a fixed deflection rate of 8.53 mm / minute, and a nominal sample width of 50.8 mm. The samples were prepared by cutting the square shafts (approximately 50mm x 50mm) from the center of the plates to obtain an isotropic sample. In addition to testing the samples by the machine / flow direction as usual (labeled "Transversal Direction" in the results table), the samples were likewise tested by flexing in the cross-flow direction to measure the hardness in that direction as well ( labeled "Machine Direction" in the results table) to examine the bidirectional hardness of the plates.
[00365] The flexural module test (reported as 1% secant module) was performed on the above-mentioned bars using an MTS Qtest / 5 instrument, according to ASTM D790, procedure B. The thermal deflection temperature was performed on the bars aforementioned using a Ceast HDT 3 VICAT instrument, according to ASTM D648-07, method B. The Izod impact test was performed on the aforementioned bars, using a Tinius-Olsen 892T instrument, according to ASTM D256, method A. The recrystallization temperature of the peak polymer (Tc) for the thermoplastic polymer compositions was measured using a differential scanning calorimeter (Mettler-Toledo DSC822 differential scanning calorimeter). This was accomplished by heating a sample of approximately 5 milligrams obtained from the target plates at 20'C / minute SO'C for 220'C, maintaining at 220'C for 2 minutes, cooling the plates at a rate of about 20'C / minute again at SO'C, and recorded at the temperature at which peak polymer crystal reform occurs (Tc). EXAMPLE P1-P6
[00366] These examples demonstrate some of the physical properties exhibited by a polypropylene polymer that has been nucleated with nucleating agents according to the invention. The polymer compositions were prepared by composing Preparation Examples EX5, EX46, EX9, EX8, EX36 and EX76 in a commercially available polypropylene homopolymer (LyondellBasell Pro-fax ™ 6301) having a melt flow index of approximately 12 dg /minute. The resin was first mixed with the inventive nucleating agent with antioxidant and acid recoverers, then the mixture was compounded and extruded to form the pellets. The formed pellet was molded by injection into test plates and bars as described above. The formulation information for Examples P1 to P6 and Comparative Example CP1 is listed in Table P1. The recrystallization temperature of the peak polymer, bidirectional module, Izod impact, and thermal deflection temperature were measured and reported in Table P2 and P3 below. Table P1: Formula Information for Samples CP1 and P1 to P6. All compositions contain 500 ppm Irganox 10 10, 1000 ppm Irgafos 168, and 800 ppm calcium stearate.
Table P2: Bidirectional module of comparative example CP1 and examples P1 to P6
Table P3: Recrystallization temperature of the peak polymer, Izod impact at room temperature, and thermal deflection temperature of comparative example CP1 and examples P1 to P6
EXAMPLE P7-P12
[00367] These examples demonstrate some of the physical properties exhibited by a polypropylene polymer that has been nucleated with a nucleating agent according to the invention. Polymer compositions were prepared by composing Preparation Examples EX5, EX46, EX9, EX8, EX36 and EX76 in a commercially available polypropylene homopolymer (LyondellBasell Pro-fax ™ 6301) having a melt flow index of approximately 12 dg /minute. The resin was first mixed with the nucleating agents of the invention with antioxidant and acid recoverers, then the mixture was compounded and extruded to form the pellets. The formed pellet was molded by injection into test plates and bars as described above. The formulation information for Examples P7 to P12 and Comparative Example CP2 is listed in Table P4. The recrystallization temperature of the peak polymer, bidirectional module, Izod impact, and thermal deflection temperature were measured and reported in Table P5 and P6 below. Table P4: Formulation information for Samples CP2 and P7 to P12. All compositions contain 500 ppm Irganox 10 10, 1000 ppm Irgafos 168, and 500 ppm DHT-4A.
Table P5: Bidirectional module of comparative example CP2 and examples P7 to P12
Table P6: Recrystallization temperature of the peak polymer, Izod impact at room temperature, and thermal deflection temperature of comparative example CP2 and examples P7 to P12
EXAMPLE P13-P18
[00368] These examples demonstrate some of the physical properties exhibited by a polypropylene polymer that has been nucleated with a nucleating agent according to the invention. The polymer compositions were prepared by composing Preparation Examples EX5, EX46, EX9, EX8, EX36 and EX76 in a commercially available impact polypropylene copolymer (LyondellBasell Profax ™ SD375S) having a melt flow index of approximately 18 dg /minute.
[00369] The resin was first mixed with the nucleating agents of the invention with antioxidant and acid recoverers, then the mixture was compounded and extruded to form the pellets. The formed pellet was molded by injection into test plates and bars as described above. Information on the formulation for Examples P13 to P18 and Comparative Example CP3 is listed in Table P7. The recrystallization temperature of the peak polymer, bidirectional module, Izod impact, and thermal deflection temperature were measured and reported in Table P8 and P9 below. Table P7: Formulation information for Samples CP3 and P13 to P18. All compositions contain 500 ppm Irganox 10i0, 1000 ppm Irgafos 168, and 800 ppm calcium stearate.
Table P8: Bidirectional module of comparative example CP3 and examples P13aP18
Table P9: Recrystallization temperature of the peak polymer, and has thermal deflection temperature of comparative example CP3 and examples P13aP18
EXAMPLE P19-P24
[00370] These examples demonstrate some of the physical properties exhibited by a polypropylene polymer that has been nucleated with a nucleating agent according to the invention. Polymer compositions were prepared by composing Preparation Examples EX5, EX46, EX9, EX8, EX36 and EX76 in a commercially available impact polypropylene copolymer (LyondellBasell Pro-fax ™ SD375S) having a melt flow index of approximately 18 dg / minute.
[00371] The resin was first mixed with the nucleating agents of the invention with antioxidants and acid recoverers, then the mixture was compounded and extruded to form the pellets. The formed pellet was molded by injection into test plates and bars as described above. The formulation information for Examples P19 to P24 and Comparative Example CP4 is listed in Table P10. The recrystallization temperature of the peak polymer, bidirectional module, Izod impact, and thermal deflection temperature were measured and reported in Table P11 and P12 below. Table P10: Formulation information for Samples CP4 and P19 to P24. All compositions contain 500 ppm Irganox 1010, 1000 ppm Irgafos 168, and 500 ppm DHT-4A.
Table P11: Bidirectional module of comparative example CP4 and examples P19 to P24
Table P12: Recrystallization temperature of the peak polymer, and thermal deflection temperature of comparative example CP4 and examples P19 to P24
Manufacturing of Nucleated Polyethylene by Injection Molding
[00372] In the following injection molding examples, polyethylene resins were prepared as described above with respect to the previous injection molding examples. The plates and bars were formed by injection molding in a 40 ton Arburg injection molder with a 25.4 mm helix in diameter. The barrel temperature of the injection molder was between 190 and 23013 depending on the melting index of the resin, and the temperature of the mold was controlled at 2513.
[00373] Unless otherwise specified, the injection speed for the plates was 15 cc / sec, and their dimensions were approximately 60 mm in length, 60 mm in width and 2 mm in thickness. These plates were used to measure bidirectional shrinkage, recrystallization temperature, and bidirectional hardness.
[00374] Unless otherwise specified, the injection speed for the bars was 40 cc / sec, and their dimensions were approximately 127 mm in length, 12.7 mm in width and 3.3 mm in thickness. These bars were used to measure 1% secant module and HDT. Nuclear Polyethylene Test
[00375] Shrinkage is measured on the plates, also in the direction of the machine (MD), and in the transversal direction (TD), after 48 hours of aging in ambient conditions according to ASTM D955. The percent shrinkage for each address using the following equation is calculated:

[00376] The flexural properties test (reported as a bidirectional module) was performed on the aforementioned plates using an MTS Q-Test-5 instrument with a distance of 32 mm, a fixed deflection rate of 8.53 mm / minute, and a nominal sample width of 50.8 mm. The samples were prepared by cutting the square sections (approximately 50mm X 50mm) from the center of the plates to obtain an isotropic size sample. In addition to testing the samples by the machine / flow direction as usual (labeled "Transversal Direction" in the results table), the samples were likewise tested by flexing in the direction perpendicular to the flow direction to measure the hardness in that direction (labeled “Machine Direction” in the results table) to examine the bidirectional hardness of the plates.
[00377] The peak polymer (Tc) recrystallization temperature for thermoplastic polymer compositions was measured using a differential scanning calorimeter (Mettler-Toledo DSC822 differential scanning calorimeter). In particular, a sample was taken from the target part and heated at a rate of 20'C / minute from a temperature of 60C to 220'C, maintained at 220'C for two minutes, and cooled at a rate of approximately 10C / minute at a temperature of OO'C. The temperature at which the peak polymer crystal reform took place (which corresponds to the peak polymer recrystallization temperature) was recorded for each sample. EXAMPLES Q1-Q12
[00378] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer that has been nucleated with a mixture of EX76 and an acid recoverer, specifically zinc stearate (ZnSt) or a synthetic dihydrotalcite compound (DHT-4A ). The polymer compositions were prepared by composing (as described above) Preparation Example EX76 and different acid recoverers in a commercially available high density polyethylene (Nova Sclair® 19G) having a density of approximately 0.960 g / cm3 and an index melt flow rate of approximately 1.2 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets. The polymer composition pellet formed was then molded by injection into test plates and bars.
[00379] The formulation information for Examples Q1 to Q12 and Comparative Example CQ1 is listed in table Q1. The recrystallization temperature of the peak polymer (Tc), bidirectional module (measured in plates), and 1% secant module and thermal deflection temperature (measured in bars) is reported in Tables Q2 and Q3 below. Table Q1: Formulation information for Samples CQ1 and Q1 to Q12.

Table Q2: Bidirectional module and bidirectional shrinkage of samples CQ1 and Q1 to Q12.

[00380] EX76 without ZnSt or DHT-4A provides some guidance for the growth of the machine direction crystal (MD) since it is proven by the decrease in the shrinkage of the MD. When DHT-4A is used as the acid recoverer in a 3: 1 ratio of EX76 to DHT-4A, a stronger MD orientation (lower MD than TD shrinkage) is present in 1,500 ppm loads of the mixture . When ZnSt is used as the acid recover, the strong MD orientation is evident in mix loads as low as 500 ppm. This is evident from the lower MD shrinkage, the higher MD hardness, and a decrease in TD hardness. Table Q3: 1% secant module, thermal deflection temperature, and recrystallization temperature of the CQ1 and Q1 to Q12 peak polymer.

[00381] As can be seen from Table Q3, mixtures of EX76 with an acid stove had the same effect on Tc as EX76 alone. The hardness and HDT measurements in flex bars confirmed that the use of EX76 together with ZnSt or DHT-4A significantly improves the performance of EX76 when compared to EX76 alone. When a mixture of the nucleating agent and acid recoverer is used, lower loads of the nucleating agent (EX76) may grant similar or better properties than the higher loads of the EX76 alone. EXAMPLES R1-R9
[00382] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer that has been nucleated with mixtures of EX76 and ZnSt in different relapses. The polymer compositions were prepared by composing (as described above) Preparation Example EX76 and ZnSt in a commercially available high density polyethylene (Nova Sclair® 19G) having a density of approximately 0.960 g / cm3 and a flow rate of melting at approximately 1.2 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets. The polymer composition pellet formed was then molded by injection into test plates and bars.
[00383] The formulation information for Examples R1 to R9 and Comparative Examples CR1 and CR2 is listed in table R1. The temperature of the recruiter is the peak polymer (Tc), bidirectional module (measured in plates), and 1% secant module and thermal deflection temperature (measured in bars) is reported in Tables R2 and R3 below. Table R1: Formulation information for Samples CR1, CR2, and R1 to R9.
Table R2: Bidirectional module and bidirectional shrinkage of samples CR1, CR2, and R1 to R9.

[00384] The data for Sample CR2 shows that the addition of ZnSt alone does not have a significant effect on the bidirectional hardness or shrinkage of this resin. This is an evidence that ZnSt does not nucleate the resin. Samples R1 and R2 show that EX76 without ZnSt provides guidance for MD crystal growth (decreasing MD shrinkage compared to CR1 and CR2). When ZnSt is used in conjunction with EX76, a much stronger MD orientation (very low MD shrinkage) is observed. This is even true with a 1: 4 ratio mixture, where EX76 is only present at 125 ppm in the resin.
[00385] When EX76 and ZnSt are used together, a very high MD hardness and a decrease in TD hardness are observed, which is indicative of a very strong MD orientation. The MD hardness granted by all mixtures is higher than the MD hardness of EX76 alone at both 1,000 ppm and 2,000 ppm. This is surprising since the resins composed with the mixtures contain less EX76. The highest MD hardness is obtained with mixtures of EX76 and ZnSt that have ratios ranging from 4: 1, 3: 1, 2: 1 and 1: 1. However, even in 1: 3 and 1: 4 ratios (which refer to EX76 loads of 250 ppm and 125 ppm, with ZnSt at 750 ppm and 875 ppm respectively), MD hardness is similar or slightly higher than EX76 alone at 2,000 ppm. Table R3: 1% secant module, thermal deflection temperature, and recrystallization temperature of the peak polymer of CR1, CR2, and R1 to R9.


[00386] As can be seen from the data in Table R3, EX76 increased the Tc of the resin. Mixtures other than EX76 with ZnSt did not improve Tc over that observed with EX76 alone. Indeed, Tc decreased slightly when the amount of EX76 decreased.
[00387] The hardness and HDT measurements in flex bars confirmed the synergy between EX76 and ZnSt. Mixtures having 4: 1, 3: 1, 2: 1, 1: 1 and 1: 2 ratios (EX76: ZnSt) gave much higher hardness and HDT than EX76 alone. And the mixtures of EX76 with ZnSt in 1: 3 and 1: 4 ratios gave hardness and HDT values similar to those of EX76 alone. This means that someone could use a resin containing a mixture of EX76 at 125 ppm and ZnSt at 875 ppm and still obtain similar performance to a resin containing EX76 alone at 2,000 ppm. EXAMPLES S1-S5
[00388] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer that has been nucleated with mixtures of EX76 and ZnSt in different ratios. The polymer compositions were prepared by composing (as described above) Preparation Example EX76 and different acid recoveries in a commercially available high density polyethylene (Dow HDPE DMDA-8007 NT7) having a density of approximately 0.967 g / cm3 and a melt flow index of approximately 8.3 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets. The polymer composition pellet formed was then molded by injection into test plates and bars.
[00389] The formulation information for Examples S1 to S5 and Comparative Examples CS1 and CS2 are listed in table S1. The recrystallization temperature of the peak polymer (Tc), bidirectional module (measured in plates), and 1% secant module and thermal deflection temperature (measured in bars) are reported in Tables S2 and S3 below. Table S1: Formulation information for Samples CS1, CS2, and S1 to S5.
Table S2: Bidirectional module and bidirectional shrinkage of samples CS1, CS2, and S1 to S5.

[00390] The data for Sample CS2 shows that the adipation of ZnSt alone does not have a significant effect on the bidirectional hardness or shrinkage of this resin. These observations confirm that ZnSt does not nucleate the resin. Data for Samples S1 and S2 show that EX76 alone provides guidance for MD crystal growth (decreasing MD shrinkage compared to CS1 and CS2). When ZnSt and EX76 are used together, a much stronger MD orientation (very low MD shrinkage) is observed. This is true for all tested mixtures.
[00391] When a mixture of EX76 and ZnSt is used, a very high MD hardness and a decrease in TD hardness are observed, which is indicative of a very strong MD orientation. The hardness of MD given by any of the mixtures in a total load of 1,000 ppm is higher than that given by EX76 alone, even in a load of 2,000 ppm. These results are consistent with those observed with lower melt flow index polyethylene resins. Table S3: 1% secant module, thermal deflection temperature, and recrystallization temperature of the peak polymer of CS1, CS2, and S1 to S5.

[00392] As can be seen from the data in Table S3, EX76 increased the Tc of the resin. Mixtures other than EX76 with ZnSt did not improve Tc over that observed with EX76 alone. In fact, Tc decreased slightly when the amount of EX76 decreased.
[00393] The hardness and HDT measurements in flex bars confirmed the synergy between EX76 and ZnSt. Mixtures in 3: 1, 2: 1 and 1: 1 ratios (EX76: ZnSt) gave hardness and HDT values much higher than EX76 alone. EXAMPLES T1-T5
[00394] These examples demonstrate some of the physical properties exhibited by a high density polyethylene polymer that has been nucleated with mixtures of EX76 and ZnSt in different relapses. The polymer compositions were prepared by composing (as described above) Preparation Example EX76 and different acid recoveries in a commercially available high density polyethylene (Dowlex ™ IP40) having a density of approximately 0.952 g / cm3 and an index of melting flow of approximately 40 dg / minute. The resin was first ground, mixed with the additives, and then composed and extruded to form the pellets. The polymer composition pellet formed was then injection molded into test plates and bars.
[00395] The formulation information for Examples T1 to T5 and Comparative Example CT1 and CT2 is listed in table T1. The recrystallization temperature of the peak polymer (Tc), bidirectional module (measured in plates), and 1% secant module and thermal deflection temperature (measured in bars) is reported in Tables T2 and T3 below. Table T1: Formulation information for Samples CT1, CT2, and T1 to T5.
Table T2: Bidirectional module and bidirectional shrinkage of samples CT1, CT2, and T1 to T5.

[00396] The data for Sample CT2 shows that the adipation of ZnSt alone does not have a significant effect on the bidirectional hardness or shrinkage of this resin. This is an evidence that ZnSt does not nucleate the resin. Samples T1 and T2 show that EX76 alone provides guidance for MD crystal growth (decreasing MD shrinkage compared to CT1 and CT2). When ZnSt and EX76 are used together, a much stronger MD orientation (very low MD shrinkage) is present. This is true for all the different mixing relays tested.
[00397] When EX76 and ZnSt are used together, a very high MD hardness and a decrease in TD hardness are observed, which is indicative of a very strong MD orientation. The MD hardness granted for all mixtures is higher than the MD hardness of EX76 alone at 1,000 and 2,000 ppm loads. These results are consistent with those observed with other HDPE resins. Table T3: Secant module at 1%, thermal deflection temperature, and recrystallization temperature of the peak polymer (Tc) of CT1, CT2, and T1 to T5.

[00398] As can be seen from the data in Table T3, EX76 increased the Tc of the resin. Mixtures other than EX76 with ZnSt did not improve Tc over that seen with EX76 alone.
[00399] The measurement of hardness and HDT in flex bars confirm the synergy between EX76 and ZnSt. Mixtures having 3: 1, 2: 1 and 1: 1 ratios gave much higher hardness and HDT values than EX76 alone.
[00400] All references, including publications, patent applications, and patents, cited here are hereby incorporated by reference into the same extension as if each referendum were individually and specifically indicated to be incorporated by reference and were mentioned in its entirety here.
[00401] The use of the terms "one" and "one" and "o / a" and similar referents in the context of describing the subject of this application (especially in the context of the following claims) should be interpreted to cover both the singular and the plural , unless otherwise indicated here or clearly contradicted by the context. The terms "comprising", "having", "including" and "containing" are to be interpreted as open terms (i.e., meaning "including, but not limited to,") unless otherwise noted. The recitation of the ranges of values here is only intended to serve as a shorthand method of referring individually to each separate value that is included in the range, unless otherwise indicated here, and each separate value is incorporated in the specification as if it were listed individually here. All methods described here can be performed in any appropriate order unless otherwise indicated here or otherwise clearly contradicted by the context. The use of any and all examples, or exemplary language (for example, "tai como") provided here, is intended only to better illuminate the subject of the application and does not represent a limitation on the scope of the subject unless otherwise claimed . No language in the specification should be interpreted as indicating any element not claimed as essential to the practice of the subject described here.
[00402] Preferred embodiments of the subject of this application are described here, including the best way known to the inventors to carry out the claimed subject. Variances of these preferred embodiments may be evident from those of ordinary skill in the art by reading the foregoing description. The inventors expect skilled technicians to employ such variances where appropriate, and the inventors intend that the subject described here be practiced in another way than as specifically described here. Consequently, this description includes all modifications and equivalents of the subject listed in the appended claims so far as permitted by applicable law. In addition, any combination of the elements described above in all possible variations thereof is covered by the present description unless otherwise indicated here or otherwise clearly contradicted by the context.

权利要求:
Claims (13)
[0001]
1. Compound conforming to the structure of Formula (C) (C)
[0002]
2. Compound according to claim 1, characterized by the fact that IVh is a cation of a metal selected from the group consisting of alkali metals and alkaline earth metals.
[0003]
3. Compound according to claim 2, characterized by the fact that h / h and a cation of a metal selected from the group consisting of alkali metals.
[0004]
4. Compound according to claim 3, characterized by the fact that M1 is a cation de lithium.
[0005]
5. Compound according to any one of claims 1-4, characterized by the fact that R10i is a cyclopentyl group.
[0006]
6. Compound according to claim 5, characterized by the fact that x and 1, IVh is a cation of lithium, y and 1, z and 1, and b and zero.
[0007]
7. Compound according to any of c 1-4, characterized by the fact that R10i is a portion conforming to the structure of Formula (Cl).
[0008]
A compound according to claim 7, characterized by the fact that R105 is hydrogen.
[0009]
9. Compound according to claim 8, characterized by the fact that x and 1, IVh is a cation of lithium, y and 1, z and 1, and b and zero.
[0010]
A compound according to claim 7, characterized by the fact that R105 is a halogen.
[0011]
11. Compound according to claim 10, characterized by the fact that R105 and bromine.
[0012]
12. Compound according to claim 11, characterized by the fact that x and 1, M1 is a cation of lithium, y and 1, z and 1, and b and zero.
[0013]
13. Composition, characterized in that it comprises a polyolefin polymer and the compound as defined in any of claims 1-12.

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法律状态:
2019-12-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-08-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/09/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361881212P| true| 2013-09-23|2013-09-23|

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US61/881,212|2013-09-23|

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US14/492,531|US9200142B2|2013-09-23|2014-09-22|Thermoplastic polymer composition|

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US14/492,531|2014-09-22|

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PCT/US2014/056919|WO2015042562A1|2013-09-23|2014-09-23|Thermoplastic polymer composition|

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