MODIFIED HETEROPHASIC POLYOLEFIN COMPOSITION AND METHOD OF PREPARATION

专利摘要:
modified heterophasic polyolefin composition. The present invention relates to a method of creating a modified heterophasic polyolefin composition whereby a polyolefin composition having at least two phases is processed with a free radical generator, such as a peroxide, and a compatibilizing agent characterized by at least one nitroxide radical and at least one unsaturated bond capable of undergoing a radical addition reaction. modified heterophasic polyolefin compositions with increased pour rates, impact strength, and clarity, which incorporate the compatibilizing agent, are also included within the scope of the invention.
公开号:BR112016020830B1
申请号:R112016020830-7
申请日:2015-03-09
公开日:2021-08-17
发明作者:Joseph J. Peterson；Scott R. Trenor；Jason D. Sprinkle
申请人:Milliken & Company；
IPC主号:

专利说明:

Technical Field of the Invention
[0001] The present invention relates to a heterophasic polyolefin composition that has a flow rate as well as high impact strength and greater clarity. Of particular interest are impact-modified polypropylene copolymers. Background of the Invention
[0002] The melt flow rate (MFR) of a polymeric resin is a function of its molecular weight. In general, increasing the pour rate allows the resin to be processed at lower temperatures and fill complex geometries. Several prior art methods of increasing the pour rate involve melt mixing the resin in an extruder with a compound capable of generating free radicals, such as a peroxide. When this is done, the weight average molecular weight of the polymer is reduced and the MFR is increased. Increasing the pour rate by decreasing the molecular weight of the polyolefin polymer, however, has in many cases been shown to have a detrimental effect on the strength of the modified polymer.
[0003] Mestanza et al. - US 6,020,437 describes a method for improving the rheological properties of polypropylene polymers by melt blending polypropylene with (a) a functional compound having at least 2 acrylate groups, (b) a compound of thiouram sulfide, and (c) a compound capable of generating free radicals.
[0004] Bertin et al. - US 6,620,892 describes a method of modifying a polypropylene copolymer or homopolymer resin to increase melt flow while preserving the strength of the polymeric resin, by melt blending the resin, a radical stable free selected from nitroxyl radicals comprising at least one =NO group, and a peroxide compound (trigger), in the absence of a functional monomer.
[0005] Onoi et al. - US 7,019,086, Ashiura et al. - US 7,196,144, and Ashiura et al. - US 7,772,325, all assigned to Yokohama Rubber Co., Ltd., describe methods for modifying an elastomer to improve its binding capacity by reacting the elastomer with a compound capable of forming a stable free radical, in the presence of a free radical initiator, such as a peroxide. Examples of such stable free radical compounds include nitroxide radicals, hydrazyl radicals, aryloxy radicals and trityl radicals.
[0006] Caronia et al. - Publication US 2007/0145625 - describe a process for crosslinking a polymer after it has been formed into an article. The free radical crosslinkable polymer is based on hydrocarbons. The free radical crosslinking agent can be selected from (i) stable organic free radicals derived from hindered amine, (ii) iniferters, (iii) organometallic compounds, (iv) aryl azooxy radicals, and (v) nitro compounds, preferably a bis-TEMPO or 4-hydroxy-TEMPO.
[0007] Horst et al. - US 8,618,224 B2 describes a viscosity breaking process for polypropylene, polypropylene copolymers and polypropylene blends. The breakdown of polymer viscosity is conducted, for example, in an extruder, in the presence of an initiator (eg peroxide) and a "chain transfer agent". Suitable chain transfer agents are thiols, disulfides, phosphorous acid esters, phosphines, organic iodides, organic chlorides, propionic acid esters, aldehydes and tertiary amines.
[0008] Pham et al. - EP 1 391 482 B1 - describe a polyolefin composition comprising a reactively modified heterophasic copolymer obtained by fusing the heterophasic copolymer with an organic peroxide and a bifunctionally unsaturated monomer, such as butadiene. Invention Summary
[0009] Heterophasic polyolefin compositions, such as polypropylene impact copolymers, provide high impact strength, especially at subambient temperatures. Heterophasic polyolefin compositions are useful in a wide range of household and industrial items, including automotive parts, appliances, lids, closures and containers. A disadvantage of heterophasic polyolefin compositions in general and polypropylene impact copolymers in particular, however, has been their relatively low melt rate. Conventional methods of increasing the MFR of polymers, such as peroxide-initiated viscosity-breaking techniques, dramatically reduce their impact performance.
[00010] It has been found that, in certain heterophasic polyolefin systems, the incorporation of a compatibilizing agent characterized by (i) at least one nitroxide radical or a portion capable of producing at least one nitroxide radical while being melt blended with the heterophasic polyolefin polymer composition; and (ii) at least one unsaturated bond capable of undergoing a radical addition reaction, can improve the detrimental effect on impact strength and, in some cases, even improve the impact strength of heterophasic polyolefin polymers, when such Polymers are subjected to viscosity-breaking techniques.
[00011] Polymer compositions of interest typically have an MFR of less than 200 g/10 min. With the present invention it is possible to (i) increase the MFR, minimizing the reduction in impact strength of the polymer composition that normally accompanies the increase in MFR and/or (ii) improve the impact strength, while maintaining or increasing the MFR. In certain embodiments of the invention it is possible to increase the MFR and improve the impact strength of the polymer composition. Furthermore, the compatibilizers of the invention have been found to dramatically increase the clarity of heterophasic polyolefin compositions. Brief Description of Drawings
[00012] Figure 1 is a bar graph showing the change in MFR of a propylene impact copolymer, with 500 ppm of an organic peroxide, at different loading levels of the compatibilizing agent.
[00013] Figure 2 is a bar graph showing the change in MFR of a propylene impact copolymer, with 1000 ppm of an organic peroxide, at different loading levels of the compatibilizing agent.
[00014] Figure 3 is a bar graph showing the change in Izod Impact Strength (23° C) of a propylene impact copolymer, with 500 ppm of an organic peroxide, at various loading levels of the compatibilizing agent .
[00015] Figure 4 is a bar graph showing the change in Izod Impact Strength (23° C) of a propylene impact copolymer, with 1000 ppm of an organic peroxide, at various loading levels of the compatibilizing agent .
[00016] Figure 5 is a graph of Izod Impact Strength (23°C) versus MFR of a propylene impact copolymer, in which both Examples 1-6 and Comparative Examples C1-C6 are represented.
[00017] Figure 6 is a graph of gel permeation chromatography curves indicating the molecular weight distribution (retention time increases as the molecular weight decreases) for the unmodified heterophasic polyolefin resin, the resin treated with only peroxide, and the modified resins of Examples 1 and 2.
[00018] Figure 7 is a graph of gel permeation chromatography curves indicating the molecular weight distribution (retention time increases as the molecular weight decreases) for the unmodified heterophasic polyolefin resin, the resin treated with only peroxide, and the resins of Comparative Examples C1 and C2.
[00019] Figure 8 is a graph of gel permeation chromatography curves indicating the molecular weight distribution (retention time increases as the molecular weight decreases) for the modified heterophasic resin of Example 2 and the resin of Comparative Example two.
[00020] Figure 9 is a graph of gel permeation chromatography curves indicating the molecular weight distribution (retention time increases as the molecular weight decreases) for the unmodified (non-heterophasic) polyolefin resin, the resin treated with only peroxide, and the resins of Comparative Examples C7 and C8. Detailed Description of the Invention
[00021] Without limiting the scope of the invention, the preferred modalities and characteristics are presented below. All United States patents, which are cited in the specification, are hereby incorporated by reference. Unless otherwise noted, conditions are 25°C, 1 atmosphere pressure and 50% relative humidity, concentrations are expressed by weight, molecular weight is based on weight average molecular weight, and hydrocarbons aliphatic and radicals thereof are one to twelve carbon atoms in length. The term "polymer", as used in the present patent application, denotes a material that has a weight average molecular weight (Mw) of at least 5,000. The term "copolymer" is used in its broadest sense to include polymers containing two or more different monomeric units, such as terpolymers, and unless otherwise indicated, includes random, block, and statistical copolymers. The concentration of ethylene or propylene in a particular phase or heterophase composition is based on the weight of reacted ethylene units or propylene units relative to the total weight of polyolefin polymer in the phase or heterophase composition, respectively, excluding any charges or other non-polyolefin additives. The concentration of each phase in the general heterogeneous polymer composition is based on the total weight of polyolefin polymers in the heterophase composition, excluding any fillers or other additives or non-polyolefin polymers. Polymers
[00022] The subject heterophasic polyolefin polymers that can be advantageously modified according to the present invention are characterized by at least two distinct phases - a propylene polymer phase comprising propylene polymers selected from polypropylene homopolymers and copolymers of propylene and up to 50% by weight of ethylene and/or C4-C10 α-olefins and an ethylene polymer phase comprising ethylene polymers selected from ethylene homopolymers and copolymers of ethylene and C3-C10 α-olefins. The ethylene content of the ethylene polymer phase is at least 8% by weight. When the ethylene phase is a copolymer of ethylene and C3-C10 α-olefins, the ethylene content of the ethylene phase can range from 8 to 90% by weight. In one embodiment of the invention, the ethylene content of the ethylene phase is at least 50% by weight. Both the propylene polymer phase and the ethylene polymer phase can form the continuous phase and the other will form the discrete or dispersed phase. For example, the ethylene polymer phase can be the discontinuous phase and the polypropylene polymer phase can be the continuous phase. In one embodiment of the invention, the propylene content of the propylene polymer phase is greater than the propylene content of the ethylene polymer phase.
[00023] The relative concentrations of the propylene polymer phase and the ethylene polymer phase can vary within a wide range. By way of example, the ethylene polymer phase may comprise from 5 to 80% by weight of the total propylene polymer and ethylene polymer in the composition and the propylene polymer phase may comprise from 20 to 95% by weight of the total of propylene polymer and ethylene polymer in the composition.
[00024] In various embodiments of the invention, (i) the ethylene content can range from 5 to 75 by weight, or even 5 to 60 by weight, based on the total content of propylene polymer and ethylene polymer in the heterophasic composition , (ii) the ethylene polymer phase can be an ethylene-propylene or ethylene-octene elastomer, and/or (iii) the propylene content of the propylene polymer phase can be 80% by weight or greater.
[00025] The present invention is particularly useful in modifying impact copolymers of polypropylene. The impact copolymer can be characterized by a continuous phase comprising polypropylene polymers selected from polypropylene homopolymers and propylene copolymers and up to 50% by weight of ethylene and/or C4-C10 α-olefins and a discontinuous phase comprising polymers of elastomeric ethylene selected from ethylene/C3-C10 α-olefin monomers and the ethylene polymers have an ethylene content of 8 to 90% by weight.
[00026] In various embodiments of the invention directed to propylene impact copolymers, (i) the ethylene content of the discontinuous phase can be from 8 to 80% by weight, (ii) the ethylene content of the heterophasic composition can be 5 at 30% by weight, based on the total propylene polymers and ethylene polymers in the composition; (iii) the propylene content of the continuous phase can be 80% by weight or more and/or (iv) the discontinuous phase can be 5 to 35% by weight of the total propylene polymers and ethylene polymers in the composition.
[00027] Examples of heterophasic polyolefin polymers that can be modified are impact copolymers characterized by a relatively rigid polypropylene homopolymer matrix (continuous phase) and a finely dispersed phase of ethylene-propylene rubber particles (EPR). Polypropylene impact copolymer can be made in a two-stage process, where the polypropylene homopolymer is polymerized first and the ethylene-propylene rubber is polymerized in a second stage. Alternatively, the impact copolymer can be made in three or more stages, as is known in the art. Suitable processes can be found in the following references: US 5,639,822 and US 7,649,052 B2. Examples of processes suitable for making impact copolymers from polypropylene are Spheripol®, Unipol®, Mitsui process, Novolen process, Spherizone®, Catalloy®, Chisso process, Innovene®, Borstar®, and the Sinopec process. These processes could use Ziegler-Natta or metallocene catalysts, homogeneous or heterogeneous, to carry out the polymerization.
[00028] The heterophasic polyolefin polymer composition can be formed by melt blending two or more polymer compositions, which form at least two distinct phases in the solid state. By way of example, the heterophasic polyolefin composition can comprise three distinct phases. The heterophasic polyolefin polymer composition can result from the melt blending of two or more types of recycled polyolefin compositions. Thus, the phrase "providing a heterophasic polyolefin polymer composition", as used herein, includes employing a polyolefin polymer composition in the process that is already heterophasic, as well as melt blending two or more polyolefin polymer compositions during the process, where the two or more polyolefin polymer compositions form a heterophasic system. For example, the heterophasic polyolefin polymer can be prepared by melt blending a polypropylene homopolymer and an ethylene/α-olefin copolymer, such as an ethylene/butene elastomer. Examples of suitable copolymers would be Engage™, Exact®, Vistamaxx®, Versify™, INFUSE™, Nordel™, Vistalon®, Exxelor™, and Affinity™. Furthermore, it can be understood that the miscibility of the polyolefin polymer components that form the heterophase system may vary when the composition is heated above the melting point of the continuous phase in the system, however, the system will form two or more phases when it cools and solidifies. Examples of heterophasic polyolefin polymer compositions can be found in US 8,207,272 B2 and EP 1 391 482 B1.
[00029] In an embodiment of the invention, the heterophasic polyolefin polymer to be modified does not have any polyolefin constituents with unsaturated bonds, in particular, both the propylene polymers in the propylene phase and the ethylene polymers in the ethylene phase are free of unsaturated bonds.
[00030] In another embodiment of the invention, in addition to the propylene polymer and ethylene polymer components, the heterophase system may include an elastomer, such as elastomeric ethylene copolymers, elastomeric propylene copolymers, styrene block copolymers, such as such as styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene (SEPS) and styrene-isoprene-styrene (SIS), plastomers, ethylene-propylene-diene terpolymers , LLDPE, LDPE, VLDPE, polybutadiene, polyisoprene, natural rubber, and amorphous polyolefins. Rubbers can be virgin or recycled. Processing method to form the modified composition
[00031] The heterophasic polyolefin polymer composition is modified by mixing the polymer composition with a compatibilization agent in the presence of free radicals, which have been generated in the composition.
[00032] In an embodiment of the invention, the heterophasic polyolefin polymer composition is modified by melt mixing the polymer composition with a compatibilization agent in the presence of free radicals, which have been generated in the composition. The melt blending step is conducted under conditions such that the composition is heated above the melting temperature of the main polyolefin component of the composition and blended while in a molten state. Examples of suitable melt blending processes include melt blending, such as in an extruder, injection molding, and blending in a Banbury mixer or kneader. By way of example, the mixture can be melt blended at a temperature of 160°C to 300°C. In particular, propylene impact copolymers can be melt blended at a temperature of 180°C to 290°C. polymer composition (propylene polymer phase and ethylene polymer phase), the compatibilizing agent and an organic peroxide can be melt blended in an extruder at a temperature above the melting temperature of all polyolefin polymers in the composition .
[00033] In another embodiment of the invention, the polymer can be dissolved in a solvent and the compatibilizing agent added to the polymer solution, and the radicals generated in the solution. In another embodiment of the invention, the compatibilizing agent could be combined with the polymer in the solid state and free radicals could be generated during solid state shear spraying as described in Macromolecules, "Ester Functionalization of Polypropylene via Controlled Decomposition of Benzoil Peroxide during Solid-State Shear Pulverization" - vol. 46, p. 7834 to 7844 (2013).
[00034] Conventional processing equipment can be used to mix the propylene polymers, ethylene polymers and the compatibilizer together in a single step, in the presence of free radicals that are either added to the mixture, such as an organic peroxide, or generated on site, such as by shear, UV light, etc. However, it is also possible to mix various combinations of components in multiple steps and in various sequences, and subsequently subject the mixture to conditions where the compatibilizing agent reacts with the polyolefin polymers, as described herein.
[00035] For example, the compatibilization agent and/or the free radical generator (when a chemical compound is used) can be added to the polymer in the form of a concentrated composition or compositions. Suitable concentrated compositions may comprise the compatibilizing agent and/or the free radical generator in the carrier resin. The compatibilizing agent and/or free radical generator may be present in the concentrated composition in an amount from approximately 1% by weight to approximately 80% by weight based on the total weight of the composition. Any suitable carrier resin can be used in the concentrated compositions, as can any suitable thermoplastic polymer. For example, the carrier resin for the concentrate compositions can be a polyolefin polymer, such as a polypropylene impact copolymer, a polyethylene homopolymer, a linear low density polyethylene polymer, a polyolefin wax, or blends of such polymers. . The carrier resin can also be a propylene polymer or an ethylene polymer that is the same or similar to the propylene polymer or ethylene polymer present in the heterophasic polyolefin polymer composition. Such a concentrated composition would allow the end user to manipulate the ratio of propylene polymer(s) to ethylene polymer(s) present in the heterophasic polyolefin polymer composition. This may be preferred when the end user needs to modify the propylene to ethylene ratio of a commercial grade resin in order to achieve the desired set of properties (eg impact balance and stiffness). Compatibility agents
[00036] The compatibilizing agent is an organic compound characterized by: (i) at least one nitroxide radical or a portion capable of producing at least one nitroxide radical while being melt blended with the heterophasic polyolefin polymer composition; and (ii) at least one unsaturated bond capable of undergoing a radical addition reaction. Of particular utility are compatibilizers that have an unsaturated carbon-carbon bond, such as a double bond.
[00037] It is believed that in the presence of a free radical, the nitroxide radical functionality of the compatibilization agent and the unsaturated bond functionality react with and bind to the propylene polymers and ethylene polymers present in the composition. Thus, according to the method of the present invention, it is possible to provide a modified composition comprising propylene polymers bonded to ethylene polymers by the compatibilizing agent. In particular, it is believed that the nitroxide moiety functionality preferentially reacts with and binds the propylene polymers in the composition, and the unsaturated binding functionality preferentially reacts with and binds the ethylene polymers in the composition. The modification accounts for the higher molecular weight components, i.e., larger than the unmodified composition or the peroxide-only modified heterophasic polyolefin composition, which were observed when the compatibilizing agent in question is provided in the mixture. The resulting structure compensates for the downward shift in average molecular weight caused by the breaking of polymer chains as the MFR is modified. Additionally, it is believed that the presence of higher molecular weight species in the composition, comprising polypropylene polymers and ethylene polymers bonded together by the compatibilizer, affects the interface between the phases of the heterophasic composition, thus dramatically improving the properties optical, as measured by clarity.
[00038] Examples of nitroxide compounds that can be used in the present invention, as the compounds are synthesized or modified to contain at least one unsaturated bond capable of undergoing a radical addition reaction, can be found in Synthetic Chemistry of Stable Nitroxides, LB Volodarski et al., CRC Press, Inc. (1994). The nitroxide compound can be a 5- or 6-membered heterocyclic compound, which can incorporate nitrogen into the ring structure. For example, the compatibilizing agent can be based on 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), such as:
where R is selected from unsaturated groups capable of undergoing free radical addition, for example an aliphatic alkenyl group or substituted alkenyl aromatic group such as phenyl. In particular, the alkenyl group can be from C1 to C10, more preferably C1 to C8, C1 to C6, or C1 to C4. Specific compounds useful in the present invention are 4-methacryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl, ("TEMPO-Methacrylate"), 4-acryloyloxy-2,2,6,6-tetramethylpiperidin-1- oxyl "TEMPO-acrylate"), 4-((4-vinylbenzyl)oxy)-2,2,6,6-tetramethylpiperidin-1-oxyl ("TEMPO-styrene"), 4,4'-((bicyclo[2.2] .1] hept-5-ene-2,3-diylbis(oxy))bis(2,2,6,6-tetramethylpiperidin-1-oxyl) ("Norbornene"), and N-tert-Butyl-α-phenylnitrone ("Nitrone").

[00039] The concentration of the compatibilization agent in the composition can be varied to satisfy the end user's goals. For example, the concentration can be varied so as to achieve a desired increase in the MFR of the polymer composition with a minimal decrease (or potentially even an increase) in polymer strength, in particular impact strength. In a preferred embodiment, the compatibilizing agent may be present in an amount of approximately 10 ppm or more, approximately 50 ppm or more, approximately 100 ppm or more, approximately 150 ppm or more, or approximately 200 ppm or more, based on total weight of polymer composition. In another preferred embodiment, the compatibilizing agent may be present in an amount of approximately 5% by weight (50,000 ppm) or less, approximately 4% by weight (40,000 ppm) or less, approximately 3% by weight (30,000 ppm) or less, approximately 2% by weight (20,000 ppm) or less, approximately 1% by weight (10,000 ppm) or less, or approximately 0.5% by weight (5,000 ppm) or less, based on the total weight of the polymer composition . Thus, in certain preferred embodiments, the compatibilizing agent may be present in an amount of from approximately 10 to approximately 50,000 ppm, from approximately 100 to approximately 10,000 ppm, or from approximately 200 to approximately 5,000 ppm, based on the total weight of the polymer composition. .
[00040] When a chemical free radical generator is employed (as discussed below), the concentration of the compatibilizing agent in the polymer composition may additionally or alternatively be expressed in terms of a relationship between the amount of the compatibilizing agent and the amount of chemical free radical generator. In order to normalize this relationship for differences in the molecular weight of the compatibilizing agents and the number of peroxide bonds in chemical free radical generators, the relationship is generally expressed as a ratio of the number of moles of the compatibilizing agent present in the composition to the molar equivalents of peroxide bonds (OO bonds) present from the addition of the chemical free radical generator. Preferably, the ratio (i.e., the ratio of moles of compatibilizing agent to mole equivalents of peroxide linkages) is about 1:10 or more, about 1:5 or more, about 3:10 or more, about 2 :5 or more, about 1:2 or more, about 3:5 or more, about 7:10 or more, about 4:5 or more, about 9:10 or more, or about 1:1 or more. In another preferred embodiment, the ratio is approximately 10:1 or less, approximately 5:1 or less, approximately 10:3 or less, approximately 5:2 or less, approximately 2:1 or less, approximately 5:3 or less , approximately 10:7 or less, approximately 5:4 or less, approximately 10:9 or less, or approximately 1:1 or less. Thus, in a number of preferred embodiments, the compatibilizing agent can be present in the composition in a ratio of moles of compatibilizing agent to molar equivalents of peroxide linkages of from approximately 1:10 to approximately 10:1, approximately 1:5 to approximately 5:1, approximately 1:4 to approximately 4:1, approximately 3:10 to approximately 10:3, approximately 2:5 to approximately 5:2, or approximately 1:2 to approximately 2:1. Free Radical Generator
[00041] A free radical generator is employed in the present invention to cause polymer chain scission and thus positively affect the MFR of the heterophasic polyolefin polymer composition, while generating sufficient free radicals to promote the reaction of the compatibilizing agent with the polyolefin polymers in the composition. The free radical generator can be a chemical compound, such as an organic peroxide or a bis-azo compound, or free radicals can be generated by applying ultrasound, shear, an electron beam (eg β-rays), light (eg, UV light), heat and radiation (eg, y-rays and X-rays), to the reaction system, or combinations of the above.
[00042] Organic peroxides that have one or more O-O functionalities are of particular use in the present invention. Examples of such organic peroxides include: 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexine-3,3,6, 6,9.9- pentamethyl-3-(ethyl acetate)-1,2,4,5- tetraoxy cyclononane, t-butyl hydroperoxide, hydrogen peroxide, dicumyl peroxide, t-butyl peroxy isopropyl carbonate, di-t-butyl peroxide, p-chlorobenzoyl peroxide, dibenzoyl diperoxide, t-butyl-cumyl peroxide; t-butyl hydroxyethyl peroxide, di-t-amyl peroxide and 2,5-dimethyl-hexene-2,5-diperisononanoate, acetylcyclohexanesulfonyl peroxide, di-isopropyl peroxydicarbonate, tert-amyl perneodecanoate, tert-butyl-perneodecanoate, tert- butylperpivalate, tert-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis-(2-methylbenzoyl)peroxide, disuccinoyl peroxide, diacetyl peroxide, dibenzoyl peroxide, tert- butyl-per-2-ethyl-hexanoate, bis(4-chlorobenzoyl)peroxide, tert-butyl perisobutyrate, tert-butyl permaleate, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1 ,1-bis(tert-butylperoxy)cyclohexane, tert-butyl peroxy-isopropyl carbonate, tert-butyl perisononaoate, 2,5-dimethyl-2,5-dibenzoate, tert-butyl peracetate, tert-amyl perbenzoate, tert- butyl-perbenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)propane, dicumyl peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxide, 3-tert -butylperoxy-3-phenyl ft alide, di-tert-amyl peroxide, α,α'-bis(tert-butylperoxy-isopropyl)benzene, 3,5-bis(tert-butylperoxy)-3,5-dimethyl-1,2-dioxolane, di-tert -butyl peroxide, 2,5-dimethyl-hexine 2,5-di-tert-butyl peroxide, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane, p-menthane hydroperoxide , pinane hydroperoxide, diisopropylbenzene mono-α-hydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide.
[00043] Organic peroxide can be present in the polymer composition in any suitable amount. The proper amount of organic peroxide will depend on several factors, such as the particular polymer that is used in the composition, the starting MFR of the polymer, and the desired change in MFR of the polymer. In a preferred embodiment, the organic peroxide can be present in the polymer composition in an amount of approximately 10 ppm or more, approximately 50 ppm or more, or approximately 100 ppm or more, based on the total weight of the polymer composition. In another preferred embodiment, the organic peroxide may be present in the polymer composition in an amount of approximately 2% by weight (20,000 ppm) or less, approximately 1% by weight (10,000 ppm) or less, approximately 0.5% by weight (5,000 ppm) or less, approximately 0.4% by weight (4000 ppm) or less, approximately 0.3% by weight (3,000 ppm) or less, approximately 0.2% by weight (2,000 ppm) or less, or approximately 0.1% by weight (1,000 ppm) or less, based on the total weight of the polymer composition. Thus, in a number of preferred embodiments, the organic peroxide may be present in the polymer composition in an amount of from approximately 10 to approximately 20,000 ppm, from approximately 50 to approximately 5,000 ppm, from approximately 100 to approximately 2,000 ppm, or approximately 100 to approximately approximately 1,000 ppm, based on the total weight of the polymer composition. The amount of organic peroxide can also be expressed in terms of a molar ratio of the compatibilizing agent and peroxide bonding, as described above.
[00044] Suitable bis-azo compounds can also be employed as a source of free radicals. Such azo compounds are, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis (4- methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-dimethyl azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile, 2,2'-azo-bis-(2,4,4-trimethylpentane), 2,2'-azobis(2-methyl-propane), 2, 2'-azobis (N,N'-dimethyleneisobutyramidine) as free base or hydrochloride, 2,2'-azobis (2-amidinopropane) as free base or hydrochloride, 2,2'-azobis {2-methyl-N-[1 ,1-bis(hydroxymethyl)ethyl]propionamide} or 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}.
[00045] Other chemical compounds useful as free radical initiators include 2,3-dimethyl-2,3-diphenylbutane and sterically hindered hydroxylamine ester.
[00046] The various radical generators can be used independently or in combination. Additions
[00047] The heterophasic polyolefin composition of the present invention is compatible with several types of additives conventionally used in thermoplastic compositions, including stabilizers, UV absorbers, hindered amine light stabilizers (HALS), antioxidants, flame retardants, acid neutralizers , slip agents, anti-blocking agents, anti-static agents, anti-scratch agents, processing aids, blowing agents, dyes, opacifiers, clarifiers, and/or nucleating agents. By way of further example, the composition may comprise fillers such as calcium carbonate, talc, glass fibers, glass beads, inorganic crystals such as Hyperform® HPR-803i available from Milliken Chemical, USA, magnesium oxysulfate, calcium sulfate crystals, calcium carbonate crystals, mica, wollastonite, clays such as montmorillonite, and filler of biological or natural origin. Additives can comprise up to 75% by weight of the total components of the modified heterophasic polyolefin composition. Examples
[00048] The following examples further illustrate the subject described above, but, of course, they should not be interpreted as limiting its scope in any way. The following methods, unless otherwise indicated, were used to determine the properties described in the following examples.
[00049] Each of the compositions was mixed by blending the components in a closed container for approximately one minute. The compositions were then melt blended in a Prism TSE-16-TC co-rotating, parallel, twin screw extruder with a screw diameter of 16 mm and a length/diameter ratio of 25:1. The extruder barrel temperature rose from approximately 195°C to approximately 215°C, and the screw speed was set at approximately 500 rpm. The extrudate (in the form of a wire) for each polypropylene copolymer composition was cooled in a water bath and subsequently pelleted.
[00050] The pelletized compositions were then used to form bars by injection molding the compositions in a 7 ton Nissei HM7 injection molder having a 14 mm diameter screw. The injection molder drum temperature was approximately 215°C to 230°C, and the mold temperature was approximately 25°C. The resulting bars measured approximately 80 mm in length, approximately 10 mm in width, and approximately 4.0 mm mm thick.
[00051] The melt flow rate (MFR) was determined in the pelletized compositions according to (ASTM D1238) at 230°C with a load of 2.16 kg for polypropylene.
[00052] The notched Izod impact strength for the bars was measured according to the ISO 180/A method. Notched Izod impact strength was measured at +23°C on bars that were conditioned either at +23°C or -30°C.
[00053] The molecular weight distribution (MWD), as well as the weight average of said distribution, Mw, was determined using gel permeation chromatography (GPC), also called size exclusion chromatography (SEC). All measurements were performed using the Agilent PL-GPC 220 GPC/SEC system containing (3) Mixed-B LS 300 x 7.5 mm PLgel 10μm columns, a refractive index detector, viscometer and light scattering detector 15° and 90° (at 160°C) with trichlorobenzene inhibited with 125 ppm butylhydroxytoluene as mobile phase, a column temperature of 160°C and a sample concentration of approximately 1 mg/ml. In the examples listed below, a 15° light scattering detector is chosen to measure the concentration. Gel permeation chromatography is a separation technique in which molecules are separated based on volume or hydrodynamic molecular size. With proper column calibration or through the use of molecular weight sensitive detectors, such as light scattering or viscometry, the molecular weight distribution and statistical molecular weight averages can be obtained. In gel permeation chromatography, molecules pass through a column via a combination of transport to and through beads along with beads in the column. The time required for a molecule to pass through the column is reduced with increasing molecular weight. The amount of polymer that leaves the column in a given time is measured with various detectors. More details in depth description of instrumentation and detectors can be found in the chapter entitled "Composition, Molar Mass and Molar Mass Distribution" in Characterization and Analysis of Polymers by Ron Clavier (2008).
[00054] Solubles in xylene were determined by a modified ASTM D5492-10 and are a measure of the amount of rubber present in heterophasic polypropylene copolymers. Approximately 0.6 g of polymer was weighed and placed in a round bottom flask along with a stir bar. 50 ml of xylene was added to the polymer in the vial. The polymer/xylene mixture was heated to reflux temperature while under vigorous stirring. Once the reflux temperature was reached, the solution was stirred for another 30 min, then cooled to room temperature. The resulting polymer/xylene mixture was gently agitated to disperse any precipitated polymer gel, then poured through a No. 4 filter paper, both the filtrate containing the soluble fraction and the filtrate containing the insoluble fraction were collected. A 10 ml aliquot of the filtrate was obtained with a Class A pipette and transferred to a weighed container. The vessel containing the filtrate was then placed on a temperature-controlled hot plate maintaining a temperature of 155°C to evaporate the xylene. Once most of the xylene had evaporated, the vessel was transferred to a vacuum oven set at a temperature of 80 ±10°C. The pressure was reduced to less than 13.3 kPa and the sample was dried for approximately 2 hours or until a constant weight has been reached. The mass of the container was then subtracted giving the mass of residual soluble polymer. The percentage of soluble polymer in the original sample was calculated as follows: SS = ((Vbo/Vb1*(W2-W1))/W0)*100; where: Ss = soluble fraction of the sample; Vbo = original solvent volume, ml; Vb1 = volume of the aliquot used for soluble determination, mL; W2 = mass of container and soluble, g; W1 = mass of container, g; and W0 = mass of the original sample, g. EXAMPLES 1-6
[00055] The following examples demonstrate the modification of a heterophasic polyolefin composition and performance improvements achieved, according to the method of the present invention.
[00056] The compatibilization agent was mixed by melting in batches to a heterophasic polypropylene copolymer according to the general formulation shown in Table 1. Table 1 - Heterophasic polypropylene copolymer formulations
Irganox® 1010 is available from BASF Irgafos® 168 is available from BASF Varox DBPH is an organic peroxide available from RT Vanderbilt Company
[00057] Each of the compositions listed in Table 2 was mixed, extruded and injection molded according to the procedure above. The bars were then subjected to the pour rate and Izod impact test described above, and evaluated using the 15° light scattering detector signal during the Gel Permeation Chromatography (GPC) test. Table 2 - Performance in medium impact heterophasic polypropylene copolymer.

[00058] Referring to Figure 1, the MFR data from Table 2 for the unmodified resin, the resin with 500 ppm organic peroxide only, and three levels of compatibilizing agent loading (Examples 1-3) are presented in the format of bar graph. Referring to Figure 2, the MFR data from Table 2 for the unmodified resin, the resin with 1000 ppm organic peroxide only, and three levels of compatibilizing agent loading (Examples 4-6) are presented in graph format. bars.
[00059] Referring to Figure 3, the Izod Impact Strength (23° C) data from Table 2 for the unmodified resin, the resin with 500 ppm organic peroxide only, and three levels of compatibilizing agent loading (Examples 1-3) are displayed in bar graph format. Referring to Figure 4, the Izod Impact Strength (23°C) data from Table 2 for the unmodified resin, the resin with 1000 ppm organic peroxide only, and three levels of compatibilizing agent loading (Examples 4-6 ) are displayed in bar graph format. COMPARATIVE EXAMPLES C1-C6
[00060] The following comparative examples demonstrate the modification of a heterophasic polyolefin composition that employs a nitroxide compound, which does not have an unsaturated bond capable of undergoing a radical addition reaction.
[00061] The nitroxide was mixed by batch melting of a heterophasic polypropylene copolymer according to the general formulation shown in Table 1, except that the molar equivalents of 4-hydroxy-TEMPO were replaced by the compatibilizing agent, ie, TEMPO -methacrylate. Each of the compositions listed in Table 3 were mixed, extruded and injection molded according to the above procedure. The bars were then subjected to the pour rate and Izod impact test described above, and evaluated using the 15° light scattering detector signal during the Gel Permeation Chromatography (GPC) test. Table 3 - Performance in medium impact heterophasic propylene copolymer


[00062] The results obtained for Examples 1-6 and Comparative Examples C1-C6 are graphically represented together in Figure 5, showing the change in Izod Impact Strength (23°C) versus MFR for each of the compositions as well. such as unmodified resin and resin containing 500ppm and 1000ppm peroxide only. Comparative examples containing 4-hydroxy-TEMPO and examples of the invention containing TEMPO-methacrylate have similar pour rates when added at equal molar loadings. (See Ex. 1 vs. Comp. Ex. C1; Ex. 2 vs. Comp. C2; Ex. 3 vs. Comp. C3; Ex. 4 vs. Comp. C4; Ex. 5 vs. Comp. C5; Ex. 6 vs. Comp. Comp. C6). When similar comparisons are made for the Izod Impact Strength, however, the examples of the invention have surprisingly higher impact strength when added at equal loads.
[00063] As can be seen in Figure 5, when the combined properties of MFR and Izod Impact Strength are taken into account, the compatibilization agent of the present invention allows the production of modified heterophase polyolefin resins that occupy a distinct area in the graph from nitroxide compounds that do not include an unsaturated bond capable of undergoing a radical addition reaction. In fact, as shown in Figures 3-5, the method of the present invention makes it possible to provide a heterophasic modified polyolefin resin that has both a better MFR and a better Izod Impact resistance, relative to the unmodified resin.
[00064] The resulting change in polymer molecular weight is shown in Figure 6, based on GPC data for the unmodified resin, resin blended with 500 ppm organic peroxide only and Examples 1 and 2. When peroxide is added to polypropylene, molecular weight is reduced as indicated by peak shift for longer retention times and there is a relative decrease in signal at retention times less than approximately 16 minutes. Compositions of the invention show a shift back to shorter retention times (higher molecular weights) and a pronounced peak at retention time of approximately 15 minutes, not seen in the unmodified resin or the peroxide-modified heterophasic resin. This peak indicates the formation of a modified polymer with a higher molecular weight than either the unmodified resin or the peroxide modified heterophasic resin. Referring to Figure 7, the GPC data for Comparative Examples C1 and C2 are presented, along with the data for the unmodified resin and the resin with 500 ppm organic peroxide only. When peroxide is added to the heterophasic impact polypropylene copolymer, the molecular weight is reduced, as indicated by the shift to longer retention times. Comparative compositions containing 4-hydroxy-TEMPO show a shift back to shorter retention times (higher molecular weights) as they neutralize the peroxide, but do not show the peak as seen with Examples 1 and 2.
[00065] Figure 8 shows a direct comparison of Example 2 of the invention (TEMPO-methacrylate) and Comparative Example C2 (4-hydroxy-TEMPO), which contain equal charges of peroxide and equal molar charges of the derivatives of TEMPO. The difference in structure of the resulting polymer for the compositions of the invention and comparative compositions is evident. This example shows the need for the unsaturated bond capable of undergoing a radical addition reaction in the nitroxide-based compatibilizer of the present invention, in order to obtain an increase in molecular weight over the unmodified or modified heterophasic polypropylene copolymer with peroxide only. COMPARATIVE EXAMPLES C7-C8
[00066] The following examples demonstrate the combination of a compatibilizing agent that meets the specifications of the present invention (TEMPO-methacrylate), with a polypropylene homopolymer composition, which is a non-heterophasic polyolefin composition, and therefore out of scope of the present invention.
[00067] Comparative compounds were mixed in batches of polypropylene homopolymer compositions according to the general formulation shown in Table 4. Table 4 - Polypropylene homopolymer compositions.
Irganox® 1010 is available from BASF Irgafos® 168 is available from BASF Varox DBPH is available from RT Vanderbilt Company
[00068] Each of the polypropylene homopolymer compositions shown in Table 5 was blended, extruded, and pelletized according to the above procedure. The pellets were then run-rate and evaluated using the 15° light scattering detector signal during the Gel Permeation Chromatography (GPC) test. Table 5 - Performance in polypropylene homopolymer.

[00069] The resulting change in polymer molecular weight is shown in Figure 9 for Comparative Examples C7-C8, along with the unmodified non-heterophasic polypropylene homopolymer resin and the resin with 500 ppm organic peroxide only. When peroxide is added to the polypropylene homopolymer, the molecular weight is reduced as indicated by the shift to longer retention times. Comparative compositions containing TEMPO-methacrylate show a shift back to shorter retention times (higher molecular weights) as TEMPO-methacrylate neutralizes the peroxide, but do not show the peak as seen with Examples 1 and 2, thus demonstrating the need for the heterophasic nature of polypropylene to achieve the objectives of the present invention. EXAMPLES 7-16 and Comparative Examples C9-C12
[00070] The following examples demonstrate the production of compositions and performance improvements achieved by incorporating nitroxide compounds having an unsaturated bond capable of undergoing a radical addition reaction relative to nitroxide compounds that do not have an unsaturated bond. The compounds of the invention and comparative compounds were melt blended in batches of heterophasic polypropylene copolymer compositions according to the general formulation shown in Table 6 and the results are shown in Table 7. Table 6 - Polypropylene copolymer formulations
Irganox® 1010 is available from BASF Irgafos® 168 is available from BASF Varox DBPH is available from RT Vanderbilt Company
[00071] Each of the heterophasic polypropylene copolymer compositions was blended, extruded and injection molded according to the above procedure. The bars were then subjected to the pour rate and Izod impact test described above. The data for the examples of the invention and comparative examples are presented in Table 7. Table 7 - Invention and Comparative Performance


COMPARATIVE EXAMPLES C13-C24
[00072] The following comparative examples demonstrate the modification of a non-heterophasic ethylene/propylene copolymer resin with (a) nitroxide compounds having an unsaturated bond capable of undergoing a radical addition reaction (compatibilization agents of the present invention) ; or (b) nitroxide compounds that do not have an unsaturated bond.
[00073] A random ethylene/propylene copolymer with a pour rate of 11 dg/min having an ethylene content of approximately 4.0% and marketed under the name Pro-Fax SA849S from LyondellBasell Industries was used as the base resin in the formulation, as described in Table 8, below. The polyolefin composition is not heterophasic. Table 8

Irganox® 1010 is available from BASF Irgafos® 168 is available from BASF Varox DBPH is available from RT Vanderbilt Company
[00074] Each of the polypropylene copolymer compositions was blended, extruded and injection molded according to the above procedure. The bars were then subjected to the pour rate and Izod impact test described above. The resulting changes in Izod pour and impact rate at 23°C are listed in Table 9, and clearly show that in the absence of a heterophasic polypropylene system, there is no advantage of the inventive compatibilizer (Comparative Examples C13-C18) on the other nitroxide compounds that do not have an unsaturated bond (Comparative Examples C19-C24) in this type of non-heterophasic resin, despite the ethylene content of the resin. Table 9 - Compatibilization agent and nitroxides with a saturated bond in a non-heterophasic polyolefin

EXAMPLE 17
[00075] The following examples demonstrate the production of a heterophasic modified polyolefin composition created by melt blending a polypropylene homopolymer, a polyolefin elastomer, an organic peroxide and the compatibilizing agent of the present invention. In particular, a 2 dg/min polypropylene homopolymer (Total Petrochemicals 3276), 20% by weight of a polyolefin elastomer (Engage™ 7467 by The Dow Chemical Company), an organic peroxide (Varox DBPH available from RT Vanderbilt Company) and TEMPO-methacrylate (Sigma-Aldrich) were melt blended and tested. The results were compared to the heterophasic polyolefin composition created when the peroxide alone was present and when neither the peroxide nor the compatibilizing agent was present.
[00076] The loadings of the initiator and TEMPO-methacrylate are listed in Table 10. Each of the polymer blend compositions was blended, extruded and injection molded according to the procedure above. The bars were then subjected to the pour rate and Izod impact test described above. Table 10 - Heterophasic Polyolefin Composition Formed During Melt Mixing

[00077] The blend of polypropylene homopolymer and polyolefin elastomer without either the peroxide or the compatibilizing agent, exhibits Izod impact behavior at 23°C without breakage, but has an undesirably low pour rate. When peroxide is added to the blend, the pour rate increases substantially, but the resistance to Izod Impact at 23°C is undesirably reduced from no break at 83 J/m. Surprisingly, when TEMPO-methacrylate is added at a load of 828 ppm, as demonstrated in Example 17, the pour rate remains high, the Izod Impact strength at 23°C exhibits no-break behavior and the Izod Impact at -30 °C increases significantly. Example 17 of the invention achieves a desirable balance of high pour rate and high Izod impact strength performance. EXAMPLE 18
[00078] The following examples demonstrate the production of compositions according to the invention and performance improvements achieved through the incorporation of TEMPO-methacrylate (Sigma-Aldrich) in certain polymer blends. The polymer blends consisted of a 12 dg/min polypropylene homopolymer (LyondellBasell Pro-Fax 6301), 20% by weight of an olefin block copolymer (INFUSE™ 9817 by The Dow Chemical Company), and optionally a peroxide ( Varox DBPH) and/or TEMPO-methacrylate. The peroxide and TEMPO-methacrylate loadings are listed in Table 11 with the blend balance being the polypropylene homopolymer at 12 dg/min. Table 11 - Polymer blend formulations
Irganox® 1010 is available from BASF Irgafos® 168 is available from BASF DHT-4A is available from Kyowa Chemical Industry Co., Ltd Varox DBPH is available from RT Vanderbilt Company
[00079] Each of the polymer blend compositions was blended, extruded and injection molded according to the procedure above. The bars were then subjected to the pour rate and Izod impact test described above. The results are reported in Table 12 below. Table 12 - Polymer Blends Using Olefin Block Copolymers

[00080] The unmodified blend of polypropylene homopolymer and olefin block copolymer without additives has a high Izod impact performance at 23°C but an undesirably low pour rate. The addition of peroxide to the polymer blend increases the pour rate to a desirable level, but the Izod impacts at 23°C and -30°C significantly decrease. Example 18 of the invention demonstrates that when 828 ppm of TEMPO-methacrylate is added to the composition with 1000 ppm of peroxide, the pour rate remains at a high level and the Izod impact at 23°C and -30°C increases substantially. EXAMPLES 19-24
[00081] The following examples demonstrate the production of compositions and performance improvements achieved by incorporating TEMPO-methacrylate into a high impact heterophasic polypropylene copolymer according to the invention. The resin used for these samples was an 18 MFR high impact heterophasic polypropylene copolymer, Pro-Fax SG702 (LyondellBasell Industries), which was approximately 25% soluble in xylene. The compositions consisted of the ingredients listed in Table 13. Table 13 - High impact heterophasic polypropylene copolymer
Irganox® 1010 is available from BASF Irgafos® 168 is available from BASF Varox DBPH is available from RT Vanderbilt Company
[00082] Each of the compositions was mixed by blending the components in a closed container for approximately one minute. The compositions were then melt melt blended in a Prism TSE-16-TC co-rotating, fully interwoven, parallel twin-screw extruder with a screw diameter of 16 mm and a length/diameter ratio of 25:1. The extruder barrel temperature rose from approximately 195°C to approximately 215°C, and the screw speed was set at approximately 500 rpm. The extrudate (in the form of a wire) for each polypropylene copolymer composition was cooled in a water bath and subsequently pelleted.
[00083] The pelletized compositions were then used to form bars by injection molding the compositions in a 40 ton Arburg injection molder having a 25.4mm diameter screw. The injection molder drum temperature was approximately 200°C to 220°C, and the mold temperature was approximately 25°C. The resulting bars measured approximately 127 mm in length, approximately 12.7 mm in width, and approximately 3.2mm thick. The bars were then subjected to the impact tests described below.
[00084] Notched Charpy impact strength for the bars was measured according to ASTM method D6110-10. Notched Charpy impact strength was measured at +23°C on bars that were conditioned at either +23°C or at -30°C. The pour rate (MFR) was determined in accordance with (ASTM D1238) at 230 ° C with a load of 2.16 kg for polypropylene. The resulting change in pour rate and Charpy impact at 23°C and at -30°C is listed in Table 14. Table 14 - High Impact Heterophasic Polypropylene Copolymer Performance

[00085] The compositions resulting from the addition of 500 and 1,000 ppm of organic peroxide alone (without compatibilizing agent) demonstrate that as the peroxide is added to the high impact polypropylene copolymer, the flow rate increases significantly, but the impact Charpy at 23°C and -30°C decreases undesirably. The addition of TEMPO-methacrylate with 500 ppm peroxide demonstrated in Examples 19 - 21 of the invention shows how the pour rate can be increased with minimal decreases in Charpy impact performance at 23°C and better Charpy impact performance at -30 °C. The use of the TEMPO-methacrylate with 1000 ppm peroxide shown in examples 22 - 24 of the invention demonstrates further increases in the pour rate, while the Charpy impact performance at 23°C and -30°C is also increased. EXAMPLES 25-26
[00086] The following examples demonstrate the production of compositions and performance improvements achieved, according to the invention, through the incorporation of TEMPO-methacrylate in a polymer blend where the polypropylene homopolymer is a minor component, that is, the phase discrete in the heterophasic composition. The polymer blends of the present invention consisted of 75% by weight of a polyolefin elastomer (Engage™ 8842 from The Dow Chemical Company), 2 dg/min of polypropylene homopolymer (Total Petrochemicals 3276), 1000 ppm of a peroxide organic (Varox DBPH available from RT Vanderbilt Company) and TEMPO-methacrylate. The peroxide and TEMPO-methacrylate loadings are listed in Table 15, with the balance of the blend being the polyolefin elastomer and polypropylene homopolymer. The results were compared to the heterophasic polyolefin composition created when the peroxide alone was present and when neither the peroxide nor the compatibilizing agent was present.
[00087] Each of the compositions was mixed by blending the components in a closed container for approximately one minute. The compositions were then melt blended in a Prism TSE-16-TC co-rotating, fully interwoven, parallel twin-screw extruder with a screw diameter of 16 mm and a length/diameter ratio of 25:1. The extruder barrel temperature rose from approximately 195°C to approximately 215°C, and the screw speed was set at approximately 500 rpm. The extrudate (in the form of a wire) for each polyolefin blend composition was cooled in a water bath and subsequently pelleted. The pelletized compositions were then compression molded in a 12 ton Carver Press at a plate temperature of 230°C and a holding pressure of approximately 6 tons for approximately 4 minutes on a sheet that was approximately 15.24 cm (6'') in width, 15.24 cm (6'') in length and 0.119 cm (0.047'') in thickness. ASTM Type IV dog bone specimens were then cut from these compression molded sheets. Tensile properties for ASTM Type IV dog bones were measured according to the ASTM D638 method using an MTS Q-Test-5 with a velocity of 0.846 cm/s (20.0 in/min). Table 15 - Performance of polyolefin blends

[00088] The composition comprising peroxide only (without compatibilizing agent) demonstrates that when the peroxide is added to a blend of polyolefins containing 75% by weight of polyolefin elastomer and polypropylene homopolymer in equilibrium, the resulting tensile strength remains unchanged and a traction modulus increases. When TEMPO-methacrylate is added to this blend, as shown in Examples 25 and 26 of the invention, the tensile strength in yield increases significantly. The tensile modulus can also be significantly increased when 552 ppm of TEMPO-methacrylate is combined with 1000 ppm of peroxide in the blend that contained 75% polyolefin elastomer, as demonstrated in Example 25. EXAMPLE 27-30 and comparative examples C25-C28
[00089] The following examples demonstrate unexpected improvements in the optical properties of heterophasic impact copolymers obtained by incorporating the compatibilizing agents of the present invention. The compounds of the invention and comparatives were mixed in batches of polypropylene copolymer compositions according to the general formulation shown in Table 16. Table 16 - Heterophasic polypropylene copolymer formulations
Irganox® 1010 is available from BASF Irgafos® 168 is available from BASF Varox DBPH is available from RT Vanderbilt Company
[00090] Each of the heterophasic polypropylene copolymer compositions was blended and extruded according to the above procedure. The pelletized compositions were then used to form discs by injection molding the compositions in a 7 ton Nissei HM7 injection molder having a 14 mm diameter screw. The injection molder drum temperature was approximately 215°C to 230°C, and the mold temperature was approximately 25°C. The resulting discs measured approximately 37mm in diameter and 1.3mm thick (50 mil) . Clarity measurements for the samples analyzed here were provided in accordance with ASTM D1003 using a haze meter such as BYK-Gardner Haze-Gard Plus on injection molded discs. Table 17 - Clarity Performance


[00091] The above examples demonstrate the changes in optical properties of a heterophasic impact copolymer modified with the nitroxide compounds of the invention having an unsaturated bond capable of undergoing a radical addition reaction, relative to a nitroxide compound without a unsaturated bond. The clarity of the unmodified impact copolymer was 11.4 and the peroxide modification only caused a decrease in clarity. Comparative Examples C25-C28 show that modification of the heterophasic polypropylene copolymer with a nitroxide which does not have the unsaturated functionality further decreases clarity. Examples 27-30 show that nitroxides with unsaturated functionality increase clarity significantly.
[00092] Without being limited to a particular theory, it is believed that the compatibilization agent, which has both a nitroxide functionality and an unsaturated bond capable of undergoing a radical addition reaction, is capable of reacting with the molecules in both phases of a heterophasic polyolefin, thus modifying the interface between the distinct phases. The modification results in a drastic and unexpected increase in clarity of the heterophasic polyolefin composition. EXAMPLE 31
[00093] The following example demonstrates the modification of a concentrate composition and performance improvements obtained in a heterophasic polyolefin composition containing the concentrate composition, according to the method of the present invention.
[00094] Three modified concentrate compositions were produced. Comparative Sample 31-MB (CS 31-MB) was made by melt blending a polypropylene copolymer with a peroxide as a viscosity breaking agent. Samples 31A-MB and 31-B-MB were made by melt blending the same polypropylene copolymer with a peroxide viscosity breaking agent and 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO-Methacrylate) as a compatibilizing agent. The general formulation for these samples is shown in Tables 18 and 19. Table 18 - Modified concentrated formulations.

[00095] Each of the compositions listed in Table 18 was blended and extruded according to the procedure above. Table 19 - Modified concentrated compositions

[00096] Three heterophasic polymeric compositions were produced by adding the modified concentrate compositions described above to a polypropylene copolymer. Comparative Sample 31A (CS 31A) was unmodified polypropylene copolymer. Comparative Sample 31B (CS 31B) was made by blending the unmodified polypropylene copolymer with Comparative Sample 31-MB (CS 31-MB) Sample 31A was made by blending the same unmodified polypropylene copolymer with the Sample 31A-MB, and Sample 31B was made by blending the same unmodified polypropylene copolymer with Sample 31B-MB. The general formulation for these samples is shown in Tables 20 and 21. Table 20 - Heterophasic polypropylene copolymer formulations with modified concentrate compositions

[00097] Each of the compositions listed in Table 20 were mixed, extruded and injection molded according to the procedures described above. The bars were then subjected to the pour rate and Izod impact test as described above. Table 21. Performance in medium impact heterophasic polypropylene copolymer


[00098] The data presented in Table 21 demonstrate that a modified concentrate composition according to the invention (for example, a modified concentrate composition obtained by melt mixing a heterophasic polymer with a viscosity breaking agent and a compatibilizing agent ) can be melt blended into an unmodified heterophasic polymer, thus significantly improving the impact strength of the heterophasic polymer. For example, the data for C.S.31B show that melt blending the concentrated composition with C.S.31-MB viscosity drop into the unmodified heterophasic polymer does not appreciably affect the impact strength of the polymer. In contrast, the data for Samples 31A and 31B show that melt blending the unmodified heterophase polymer with the modified concentrate compositions Sample 31A-MB and Sample 31B-MB increases the impact strength of the polymer by a maximum of 12%. This is particularly valuable because it demonstrates that improved heterophasic polymer compositions can be produced without directly adding the viscosity breaking agent and/or the compatibilizing agent to the target heterophasic polymer. Direct addition of these additives can be difficult in certain scenarios, such as mixing facilities and injection molding facilities. However, these facilities routinely use concentrated compositions. Therefore, such facilities can easily achieve the physical property improvements described herein through the use of a modified concentrate composition as described above. EXAMPLE 32
[00099] The following example demonstrates the modification of a concentrate and performance improvements obtained in a heterophasic polyolefin composition containing the concentrate, according to the method of the present invention.
[000100] Three modified concentrate compositions were produced. The 32-MB Comparative Sample (CS 32-MB) was made by melt blending a polypropylene homopolymer, an ethylene/octene elastomer, and a peroxide as a viscosity breaking agent. Samples 32A-MB and 32B-MB were made by melt blending the same polypropylene homopolymer and ethylene/octene elastomer with a peroxide as a viscosity breaking agent and 4-methacryloyloxy-2,2,6,6- tetramethylpiperidin-1-oxyl (TEMPO-Methacrylate) as a compatibilizing agent. The general formulation for these samples is shown in Table 22. Table 22 - Modified concentrated formulations

[000101] Each of the compositions listed in Table 22 was mixed and extruded according to the procedures described above. Table 23 - Modified concentrated compositions


[000102] Three heterophasic polymeric compositions were produced by adding the modified concentrate compositions described above to a polypropylene copolymer. Comparative Sample 32A (CS 32A) was modified polypropylene copolymer. Comparative Sample 32B (CS 32B) was made by blending unmodified polypropylene copolymer with Comparative Sample 32-MB (CS 32-MB). Sample 32A was made by blending the same unmodified polypropylene copolymer with Sample 32A-MB, and Sample 32B was made by blending the same unmodified polypropylene copolymer with Sample 32B-MB. The general formulation for these samples is shown in Tables 24 and 25. Table 24 - Heterophasic polypropylene copolymer formulations with modified concentrates

[000103] Each of the compositions listed in Table 24 was mixed, extruded and injection molded according to the procedures described above. The bars were then subjected to the pour rate and Izod impact test as described above. Table 25 - Performance in medium impact heterophasic polypropylene copolymer

[000104] The data presented in Table 25 demonstrate that a modified concentrate according to the invention (for example, a modified concentrate obtained by melt blending a heterophasic polymer with a viscosity breaking agent and a compatibilizing agent) can be melt blended into an unmodified heterophasic polymer, thereby significantly improving the impact strength of the heterophasic polymer. For example, the data for C.S. 32B shows that melt blending the C.S. 32-MB broken viscosity concentrate into the unmodified heterophasic polymer does not appreciably affect the impact strength of the polymer. In contrast, the data for Samples 32A and 32B show that melt blending the unmodified heterophase polymer with the modified concentrate compositions Sample 32A-MB and Sample 32B-MB significantly increases the impact strength of the polymer. In fact, the impact strength of the polymer was increased to the point where the part did not completely fracture during the Izod impact test and therefore a value for the impact strength could not be measured. Such a result is particularly valuable because it demonstrates that improved heterophasic polymer compositions can be produced by directly adding the viscosity breaking agent and/or the compatibilizing agent to the target heterophasic polymer. Direct addition of these additives can be difficult in certain scenarios, such as mixing facilities and injection molding facilities. However, these facilities routinely use concentrated compositions. Therefore, such facilities can easily achieve the physical property improvements described herein through the use of a modified concentrate composition as described above. applications
[000105] The heterophasic polyolefin composition of the present invention can be used in conventional polymer processing applications, including but not limited to injection molding, thin wall injection molding, single screw mixing, twin screw mixing, blending Banbury, co-kneader mixing, two-roll milling, sheet extrusion, fiber extrusion, film extrusion, tube extrusion, profile extrusion, extrusion coating, extrusion blow molding, injection and blow molding, molding by stretch blow and injection, compression molding, compression and extrusion molding, blow and compression forming, stretch blow and compression forming, thermoforming, and rotational molding. Thermoplastic polymer articles made using the thermoplastic polymer composition of the present invention can be composed of multiple layers, with one or any suitable number of multilayers containing a thermoplastic polymer composition of the present invention. By way of example, typical end-use products include containers, packaging, automotive parts, jars, expanded or foam items, appliance parts, closures, cups, furniture, housewares, battery boxes, crates, pallets, films, sheets , fibers, tubes and rotationally molded parts.
[000106] All references, including publications, patent applications and patents cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and are presented in their entirety herein.
[000107] The use of the terms "a", "an' and "the", "a" and similar referents in the context of the description of the subject matter of this application (especially in the context of the following claims) is to be understood as covering both the singular and the plural, unless otherwise indicated herein or clearly contradicted by the context. The terms "comprising", "having", "including" and "containing" are to be interpreted as open terms (ie meaning "including, but not limited to"), unless otherwise indicated. The citation of ranges of values cited herein is merely intended to serve as an abbreviation method of referring individually to each separate value that falls within the range, unless stated herein otherwise indicated, and each separate value is incorporated into the specification as if it were individually cited herein. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or otherwise clearly contradicted by it context. The use of any and all examples, or exemplary language (eg, "as") provided herein, is only intended to further illuminate the subject of the application and does not constitute a limitation on the scope of the subject, unless otherwise claimed. No language in the specification should be understood to indicate any element not claimed to be essential to the practice of the subject described herein.
[000108] Preferred embodiments of the subject matter of this application are described herein, including the best mode known to the inventors for carrying out the claimed subject matter. Variations of these preferred embodiments may become apparent to those skilled in the art upon reading the foregoing description. The inventors expect those skilled in the art to employ such variations as the case may be, and the inventors intend that the subject matter described herein be practiced other than as specifically described herein. Thus, this description includes all modifications and equivalents to the subject matter cited in the appended claims, as permitted by applicable law. Furthermore, any combination of the elements described above in all possible variations thereof is encompassed by the present description, unless otherwise indicated herein or otherwise clearly contradicted by the context.

权利要求:
Claims (21)
[0001]
1. Heterophasic polymer composition, characterized in that it comprises: (1) a propylene polymer phase (a) comprising propylene polymers selected from the group consisting of polypropylene homopolymer and propylene copolymer and < 50% by weight of ethylene and/or C4-C10 a-olefin monomers, and (2) an ethylene polymer phase (b) comprising ethylene polymers selected from the group consisting of ethylene homopolymers and ethylene copolymers and C3 monomers -C10 a-olefin, having ethylene content > 8% by weight, wherein the propylene content of step (a) is greater than the propylene content of step (b), and (3) propylene polymers bonded to ethylene polymers by a compatibilizing agent selected from organic compounds that (i) have at least one nitroxide radical or are capable of producing at least one nitroxide radical when melt blended with the propylene polymers and ethylene polymers; and (ii) has at least one unsaturated carbon-carbon bond capable of undergoing a radical addition reaction.
[0002]
2. Composition according to claim 1, characterized in that the ethylene polymers are selected from the group consisting of ethylene-propylene elastomers, ethylene-butene elastomers, ethylene-hexene elastomers, ethylene elastomers -octene and mixtures thereof.
[0003]
3. Composition according to claim 1, characterized in that the ethylene polymer comprises from 5 to 80% by weight, based on the total weight of propylene polymers and ethylene polymers in the composition.
[0004]
4. Composition according to claim 1, characterized in that the ethylene content is 5 to 60% by weight, based on the total weight of propylene polymers and ethylene polymers in the composition.
[0005]
5. Composition according to claim 1, characterized in that: the nitroxide radical of the compatibilization agent has reacted with, and is bonded to, a propylene polymer, and the unsaturated carbon-carbon bond of the compatibilization agent has reacted with, and is bound to an ethylene polymer, and the reaction is conducted in the presence of a free radical generator, and preferably the free radical generator is an organic peroxide.
[0006]
6. Heterophasic polymer composition characterized in that it comprises (1) a continuous phase (a) comprising polypropylene polymers selected from and homopolymer of polypropylenes and copolymers of propylene and <80% by weight of ethylene and/or C4-C10 α-olefins and (2) a discontinuous phase (b) comprising elastomeric ethylene copolymers selected from the group consisting of ethylene/C3-C10 α-olefin copolymers having an ethylene of 8 to 90% by weight, wherein the propylene content of the propylene polymer phase (a) is greater than the phase (b) and (3) propylene polymers bonded to ethylene polymers by a compatibilizing agent selected from organic compounds that (i) have at least one nitroxide radical or are capable of producing at least one nitroxide radical while being melt blended with the propylene polymers and ethylene polymers; and (ii) at least one unsaturated carbon-carbon bond capable of undergoing a radical addition reaction.
[0007]
7. Composition according to claim 6, characterized in that the discontinuous phase (b) comprises from 5 to 35% by weight, based on the weight of propylene polymers and ethylene copolymers in the composition.
[0008]
8. Composition according to claim 7, characterized in that the ethylene copolymer comprising the discontinuous phase has an ethylene content of 8 to 80% by weight.
[0009]
9. Composition according to claim 7, characterized in that it comprises from 5 to 30% by weight of ethylene, based on the total weight of propylene polymers and ethylene copolymers in the composition.
[0010]
10. Composition according to claim 1 or 6, characterized in that the propylene content of phase (a) is > 80% by weight.
[0011]
11. Composition according to claim 1, characterized in that the propylene content of phase (a) is > 80% by weight and phase (b) is a discontinuous phase.
[0012]
12. Composition according to claim 1 or 6, characterized in that the unsaturated carbon-carbon bond of the compatibilization agent is a double bond.
[0013]
13. Composition according to claim 1 or 6, characterized in that the compatibilization agent is selected from the group consisting of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl; 4-acryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl; 4-((4-vinylbenzyl)oxy)-2,2,6,6-tetramethylpiperidin-1-oxyl; 4,4'-((bicyclo[2.2.1]hept-5-ene-2,3-diylbis(oxy))bis(2,2,6,6-tetramethylpiperidin-1-oxyl); and N- tert-Butyl-α-phenylnitrone.
[0014]
14. Composition according to claim 1 or 6, characterized in that the compatibilization agent is present in a concentration of 10 ppm to 5% by weight, based on the total weight of the composition.
[0015]
15. Composition according to claim 6, characterized in that the compatibilization agent is present in a concentration of 10 ppm to 5% by weight, based on the total weight of the composition, the nitroxide radical of the compatibilization agent reacted with, and is bonded to a propylene polymer, and the carbon-carbon unsaturated bond of the compatibilizing agent reacted with, and is bonded to an ethylene polymer, and the reaction is conducted in the presence of a free radical generator selected from the a group consisting of organic peroxides incorporating one or more OO bonds, and the compatibilizing agent is present in a molar ratio to OO bonds of 1:10 to 10:1.
[0016]
16. Method for preparing a heterophasic polyolefin polymer composition obtained by the process characterized in that it comprises the steps of: (1) providing - a phase (a) of propylene polymer comprising propylene polymers selected from the group consisting of of homopolymer of polypropylenes and propylene copolymers < 50% by weight of ethylene and/or C4-C10 α-olefin monomers, and - an ethylene polymer phase (b) comprising ethylene polymers selected from the group consisting of homopolymers of ethylene and copolymers of ethylene and C3-C10 α-olefin monomers, having an ethylene content of > 8% by weight, (2) provide a compatibilizing agent for organic compounds in which - have at least one nitroxide radical or are capable to produce at least one nitroxide radical while being melt blended with the composition of propylene polymers and ethylene polymers; and - has at least one unsaturated carbon-carbon bond capable of undergoing a radical addition reaction; and (3) mixing phase (a), phase (b) and the compatibilization agent in the presence of carbon free radicals, where the propylene polymers are bonded to the ethylene polymers by the compatibilization agent, and where the polymer phase of propylene and the ethylene polymer phase form a heterophasic composition.
[0017]
17. Method according to claim 16, characterized in that phase (a), phase (b) and the compatibilization agent are mixed in the presence of carbon free radicals by means of melt mixing, and the composition is heterophasic at 25°C.
[0018]
18. Method according to claim 17, characterized in that phase (a) is the continuous phase and has a propylene content of > 80% by weight, and phase (b) is the discontinuous phase and the ethylene polymers are copolymers of ethylene and C3-C10 α-olefins having an ethylene content of 8 to 80% by weight.
[0019]
19. Method according to claim 17, characterized in that phase (a) and phase (b) are supplied to the mixture as a heterophasic impact copolymer obtained by operating in at least two stages of polymerization.
[0020]
20. Method according to claim 17, characterized in that - the compatibilization agent is present in the heterophasic polyolefin polymer composition in a concentration of 10 ppm to 5% by weight, based on the total weight of the composition, where - the reaction between the unsaturated carbon-carbon bond of the compatibilizing agent and the ethylene polymer is conducted in the presence of a free radical generator selected from the group consisting of organic peroxides incorporating one or more OO bonds, and - o compatibilizing agent and organic peroxide are present in a molar ratio to OO bonds of 1:10 to 10:1.
[0021]
21. Heterophasic polymer composition characterized in that it is obtainable by the method according to any one of claims 16-20.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112016020830B1|2021-08-17|MODIFIED HETEROPHASIC POLYOLEFIN COMPOSITION AND METHOD OF PREPARATION

---

JP6469862B2|2019-02-13|Modified heterophasic polyolefin composition

---

JP2010537036A|2010-12-02|Compatibilized polyolefin composition

---

CN107406640B|2020-12-08|Modified heterophasic polyolefin composition

---

US10745538B2|2020-08-18|Thermoplastic polymer compositions

---

RU2733961C1|2020-10-08|Method of producing heterophase polymer compositions

---

US9914825B2|2018-03-13|Modified heterophasic polyolefin composition

---

BR112017001140B1|2021-09-21|MODIFIED HETEROPHASIC POLYOLEFIN COMPOSITION

---

BR112017017721B1|2021-10-26|COMPOSITION OF HETEROPHASIC POLYOLEFIN AND PREPARATION PROCESS

---

BR112017017069B1|2021-09-28|HETEROPHASIC POLYMER COMPOSITION

同族专利:

---

公开号 | 公开日

---

JP6724098B2|2020-07-15|

---

KR20180112106A|2018-10-11|

---

US10400096B2|2019-09-03|

---

KR102059982B1|2019-12-27|

---

EP3116945B1|2019-05-15|

---

US20150259453A1|2015-09-17|

---

US11248114B2|2022-02-15|

---

BR112016020830A2|2017-08-15|

---

WO2015138300A1|2015-09-17|

---

JP2019031680A|2019-02-28|

---

KR20160132958A|2016-11-21|

---

CN106459488A|2017-02-22|

---

US20200199339A1|2020-06-25|

---

JP6615771B2|2019-12-04|

---

JP2017508051A|2017-03-23|

---

EP3116945A1|2017-01-18|

---

CN106459488B|2019-09-13|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3376304A|1962-03-14|1968-04-02|Mcneilab Inc|2--6-r3-6-r4-fulvenes|

---

NL293710A|1962-06-12|

---

US3379677A|1966-02-28|1968-04-23|Koppers Co Inc|Ultraviolet light stabilizers for plastic materials|

---

JPS5150265Y2|1971-04-28|1976-12-03|

---

LU84921A1|1983-07-18|1985-04-17|Cockerill Sambre Sa|CLAW EXTRACTOR|

---

DE4117144A1|1991-05-25|1992-11-26|Basf Ag|HIGHLY FLOWABLE PROPYLENE ETHYLENE COPOLYMERISATE|

---

NL9300801A|1992-05-22|1993-12-16|Ciba Geigy|3- BENZOFURAN-2-ON AS STABILIZERS.|

---

TW255902B|1992-09-23|1995-09-01|Ciba Geigy|

---

FR2736648B1|1995-07-11|1997-10-03|Solvay|PROPYLENE POLYMER, PROCESS FOR OBTAINING SAME, USE AND OBJECTS CONTAINING SAME|

---

JPH1180298A|1997-08-29|1999-03-26|Toyota Motor Corp|Polypropylene/propylene-ethylene copolymer composition and preparation thereof|

---

FR2792321B1|1999-04-19|2003-12-12|Atochem Elf Sa|PROCESS FOR PRODUCING POLYPROPYLENE RESIN WITH CONTROLLED RHEOLOGY|

---

JP4190093B2|1999-06-24|2008-12-03|株式会社Ａｄｅｋａ|Piperidine derivative polymer and polymer composition containing the same|

---

CN1250784A|1999-10-21|2000-04-19|复旦大学|Multi-block or multi-branched PMMA-PS polymer and its synthetic process|

---

DE10025727A1|2000-05-25|2002-01-03|Basell Polypropylen Gmbh|Highly flowable propylene block copolymers|

---

US6392056B1|2000-08-03|2002-05-21|Ciba Specialty Chemical Corporation|2H-benzotriazole UV absorders substituted with 1,1-diphenylalkyl groups and compositions stabilized therewith|

---

FR2814749B1|2000-10-03|2003-06-13|Atofina|COMPOSITION DELAYING TOASTING|

---

EP1211289A1|2000-11-29|2002-06-05|Borealis GmbH|Polyolefin compositions with improved properties|

---

FR2824840B1|2001-05-17|2005-05-13|Atofina|THERMAL STABILIZER OF ORGANIC PEROXIDES|

---

AT321080T|2002-04-18|2006-04-15|Borealis Gmbh|POLYPROPYLENE MIXTURE WITH IMPROVED MECHANICAL PROPERTIES|

---

DE60232409D1|2002-08-20|2009-07-02|Borealis Tech Oy|polypropylene composition|

---

JP2004182926A|2002-12-05|2004-07-02|Yokohama Rubber Co Ltd:The|Method for modifying polymer|

---

ITTO20030478A1|2003-06-25|2004-12-26|Univ Pisa|CONTROLLED RADICAL FUNCTIONALIZATION PROCEDURE|

---

BRPI0417756A|2003-12-24|2007-04-10|Dow Global Technologies Inc|improved process for preparing a fabricated crosslinked article, fabricated article, free radical crosslinkable polymer composition, power cord attachment, power cord and shoe sole|

---

JP4101242B2|2004-04-01|2008-06-18|横浜ゴム株式会社|Polymer modification method|

---

BRPI0510824B1|2004-05-21|2016-01-19|Basell Poliolefine Srl|heterophasic polyolefin composition and polymerization process for preparing said composition|

---

EP1607440A1|2004-06-18|2005-12-21|Borealis Technology OY|Modified polypropylene composition|

---

WO2007043358A1|2005-10-07|2007-04-19|Konica Minolta Opto, Inc.|Method for producing cellulose ester film, cellulose ester film, polarizing plate and liquid crystal display|

---

EP1987070B1|2006-02-24|2019-04-10|Basf Se|Viscosity breaking process for propylene polymers|

---

JP4215796B2|2006-12-13|2009-01-28|横浜ゴム株式会社|Thermoplastic elastomer composition|

---

WO2008134131A1|2007-04-25|2008-11-06|Dow Global Technologies Inc.|Process for the production of a polymer composition by mediated free radical chain growth polymerization|

---

EP2170970B1|2007-07-16|2014-09-03|Dow Global Technologies LLC|Functionalized polymers and articles prepared therefrom|

---

JP5513503B2|2008-07-23|2014-06-04|サウディベーシックインダストリーズコーポレイション|Process for preparing a modified polypropylene composition|

---

MX2011003078A|2008-09-23|2011-08-03|Dow Global Technologies Llc|Radically functionalized olefin-based polymer with reduced molecular weight change and method.|

---

AT552300T|2008-10-29|2012-04-15|Borealis Ag|SOLID COMPOSITION FOR FOOD APPLICATIONS|

---

EP2454298B1|2009-07-14|2013-05-15|Dow Global Technologies LLC|Polypropylene impact copolymers having high melt flow and izod ductility|

---

GB201000120D0|2010-01-06|2010-02-17|Dow Corning|Process for forming crosslinked and branched polymers|

---

JP4821916B1|2010-05-07|2011-11-24|横浜ゴム株式会社|Process for producing modified polymers|

---

WO2013025822A1|2011-08-16|2013-02-21|Mba Polymers, Inc.|Control of the melt flow rate of polyolefin mixtures recovered from post-consumer durable goods|

---

EP2615135A1|2012-01-13|2013-07-17|Borealis AG|Soft heterophasic polyolefin composition having low content of p-xylene solubles and hexane solubles|

---

ES2663142T3|2012-05-24|2018-04-11|Borealis Ag|Composition of soft heterophasic polyolefin that has a removable level in low C6|

---

MX365953B|2012-07-16|2019-06-20|Bostik Inc|Polypropylene impact copolymer based hot melt adhesive.|

---

BR112016020830B1|2014-03-14|2021-08-17|Milliken & Company|MODIFIED HETEROPHASIC POLYOLEFIN COMPOSITION AND METHOD OF PREPARATION|

---

JP6469862B2|2014-07-25|2019-02-13|ミリケン・アンド・カンパニーＭｉｌｌｉｋｅｎ ＆ Ｃｏｍｐａｎｙ|Modified heterophasic polyolefin composition|BR112016020830B1|2014-03-14|2021-08-17|Milliken & Company|MODIFIED HETEROPHASIC POLYOLEFIN COMPOSITION AND METHOD OF PREPARATION|

---

JP6469862B2|2014-07-25|2019-02-13|ミリケン・アンド・カンパニーＭｉｌｌｉｋｅｎ ＆ Ｃｏｍｐａｎｙ|Modified heterophasic polyolefin composition|

---

WO2016085535A1|2014-11-26|2016-06-02|Milliken & Company|Modified heterophasic polyolefin composition|

---

KR102124239B1|2015-02-10|2020-06-17|밀리켄 앤드 캄파니|Thermoplastic polymer composition|

---

EP3265514A1|2015-03-05|2018-01-10|Milliken & Company|Modified heterophasic polyolefin composition|

---

KR101958609B1|2015-09-13|2019-07-04|밀리켄 앤드 캄파니|Method for producing heterophasic polymer composition|

---

DE202015106875U1|2015-12-17|2017-03-20|Rehau Ag + Co|Thermoplastic composition|

---

EP3199586B1|2016-01-29|2020-04-29|Borealis AG|Polyolefin composition with improved thoughness|

---

EP3246358A1|2016-05-18|2017-11-22|Borealis AG|Soft and transparent propylene copolymers|

---

KR102327465B1|2017-02-21|2021-11-17|밀리켄 앤드 캄파니|Method of making a heterophasic polymer composition|

---

EP3395377A1|2017-04-28|2018-10-31|Borealis AG|Soft polypropylene composition with improved properties|

---

KR101992598B1|2017-05-10|2019-06-25|한서대학교 산학협력단|Polymer compound composition for thermoplastic resin and method of manufacturing polymer compound using the same|

---

JP2021520432A|2018-04-18|2021-08-19|ダブリュー・アール・グレース・アンド・カンパニー−コーンＷ Ｒ Ｇｒａｃｅ ＆ Ｃｏ−Ｃｏｎｎ|Impact resistant clear polypropylene copolymer composition|

---

US20200325256A1|2019-04-12|2020-10-15|Indian Oil Corporation Limited|Morphology modified heterophase propylene copolymers and their products thereof|

法律状态:
2019-12-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2021-06-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-07-20| B350| Update of information on the portal [chapter 15.35 patent gazette]|

---

2021-08-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|

---

2021-08-17| 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 09/03/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201461953261P| true| 2014-03-14|2014-03-14|

---

US61/953,261|2014-03-14|

---

PCT/US2015/019410|WO2015138300A1|2014-03-14|2015-03-09|Modified heterophasic polyolefin composition|

---