polypropylene composition

专利摘要:
  It is an innovative polypropylene composition that provides an excellent balance between mechanical properties, optical behavior and low extractable quantities combined with good retort capability.
公开号:BR112020003650A2
申请号:R112020003650-1
申请日:2018-08-30
公开日:2020-09-01
发明作者:Markus Gahleitner；Jingbo Wang；Klaus Bernreitner；Peter Niedersüss
申请人:Borealis Ag；
IPC主号:

专利说明:

[0001] [0001] The present invention relates to an innovative polypropylene composition that provides an excellent balance between mechanical properties, optical behavior and low amounts of extractable substances combined with good retort capability.
[0002] [0002] The present invention additionally relates to the use of the polypropylene composition and articles made from it.
[0003] [0003] Polymers, like polypropylene, are increasingly used in different complex applications. There is an increasing trend in the use of polypropylene in many applications across the packaging industry.
[0004] [0004] For all such applications, it is a continuous request from the industry to have products on hand that show better mechanical performance (such as rigidity and / or impact resistance), better optical behavior and smaller quantities of extractable substances at the same time.
[0005] [0005] The demands can be challenging, since many polymer properties are directly or indirectly interrelated, that is, the improvement of a specific property can only be carried out at the expense of another property.
[0006] [0006] For example, polypropylene films are often used in the packaging industry for consumer-related articles with good “transparency” properties in the content of packaged goods. There is a growing trend in the use of such polypropylene films in the medical packaging industry. In these technical areas,
[0007] [0007] In the field of some food applications, such as retort bags or some medical applications, a sterilization treatment is necessary.
[0008] [0008] The most common sterilization procedures consist of the use of heat (steam), radiation (beta radiation, electrons or gamma radiation) or chemicals (usually ethylene oxide). Steam sterilization is usually performed in a temperature range of about 120 ° C to 130 ° C. Thus, the material must have sufficient thermal stability, such as a melting temperature significantly higher than the usual steam sterilization temperature of about 120 ° C to 130 ° C.
[0009] [0009] Obviously, the treatment of a polymer under sterilization conditions highlighted above can impair its final properties, especially the optical properties, such as transparency, that is, low opacity.
[0010] [0010] In addition, certain regulations must be complied with regarding the use of such materials in food contact applications, thus, compliance with food regulations in terms of extractable components resp. soluble, as soluble in hexane is essential in advanced packaging applications.
[0011] [0011] A higher content of extractable components resp. soluble, as soluble in hexane is also undesirable in the field of medical packaging.
[0012] [0012] In the food packaging industry, it has become quite common to use plastic containers, especially bags containing sterilized or pre-cooked food. Retort bags offer many advantages over rigid metal packaging, such as faster sterilization / cooking times, less shelf space, easier disposal, improved food taste, etc. Typical bags have a multilayer structure with polyolefins, such as polyethylene or polypropylene, adhesives, barrier and outer layers. It is desired that the polyolefin material gives rigidity as well as high impact resistance to the final packaging material.
[0013] [0013] In addition, in the medical packaging industry, the polymer used must provide sufficient rigidity as well as high impact resistance to the final packaging material. In the case of medical applications, softness rather than stiffness is a key requirement.
[0014] [0014] Heterophasic propylene copolymers (HECOs) are known to be a generally suitable class of base polymers applicable to the applications described above.
[0015] [0015] However, there is still a desire to improve the overall performance of such materials. Heterophasic propylene polymers (HECOs) are polymers that have a matrix phase and a dispersed phase. The matrix phase is often a propylene homopolymer and the dispersed phase is usually an ethylene / α-olefin copolymer.
[0016] [0016] The stiffness of such heterophasic propylene copolymers (HECOs) can, for example, be improved by increasing the crystallinity and / or the relative amount of homopolymer contained in the composition. As a consequence, the material becomes brittle, thereby resulting in poor impact properties and / or worse optical properties.
[0017] [0017] Heterophasic propylene copolymers have, in general, good impact resistance over a wide temperature range, but this usually accompanies very low transparency. Impact resistance is mainly influenced by the amount of rubber, its molecular weight and its composition. It is generally known that, in addition to the amount of rubber, its molecular weight, respectively, intrinsic viscosity as well as the comonomer content affects mechanical and optical performance. As explained, for example, in the document by Gahleitner et al., J.Appl.Polym.Sci. 130 (2013) 3028-3037, the increase in the amount of rubber is the only direct parameter in this context. The relative comonomer content in the rubber phase affects the phase structure as well as the impact resistance of complex shapes, and the molecular weight of the rubber phase has a highly non-linear effect on the impact resistance in addition to depending on the geometry. All three parameters also define the quantity of extractable substances.
[0018] [0018] Document W02004055101 refers to a flat film for thermoforming with high toughness, high rigidity and high transparency, comprising a polyolefin composition of an alpha-nucleating agent. The optical properties, especially opacity, are as high as the values determined for components extractable with hexane through the FDA method (C6FDA).
[0019] [0019] EP1661935 refers to a molten film or blown film comprising 80 to 95% by weight of a polypropylene matrix (A) with an MFR of 1 to 30 g / 10 min being a homopolymer or a copolymer, which has a comonomer content of less than 3% by weight, 5 to 20% by weight of an ethylene-propylene (EPR) rubber (B) with at least 55% by weight of propylene and having an intrinsic (IV) viscosity of 1 at 2.5 dl / g and 0.0001 at 1% by weight of a nucleating agent. These materials are very soft and show high relative amounts for components extractable with hexane through the FDA method (C6FDA).
[0020] [0020] EP2585527 B1 discloses a polyolefin composition comprising (weight percentage): A) from 1.0% to 9.5%; of a copolymer of propylene and 1-hexene wherein said copolymer comprises from 0.1 to 5% of recurrent units derived from 1-hexene; and B) from 80.5% to 99% of a heterophasic polypropylene composition comprising: B1) from 50% to 85% of a propylene homopolymer, said propylene polymer being insoluble in xylene at room temperature in an amount greater than 85% having a polydiversity index that varies from 3 to 10; and a Fusion Index of 0.5 to 10 dg / min; and B2) from 5% to 50% of a copolymer of ethylene and propylene having a content of ethylene-derived units ranging from 30% to 70%, said polymer composition having a Melt Index of 0.05 to 10 dg / min. The disclosed composition is suitable for producing pipe systems and sheets. The optical properties as well as values for extractable components are not mentioned, but, in view of the high ethylene content of (B2) and its respective high intrinsic viscosity of resp. of molecular weight indicated both in the description and in the examples, it is possible to deduce very high levels of opacity for the inventive compositions.
[0021] [0021] Although much development work has been done in this field, there is still a need to further improve and thus design materials that have an improved balance between mechanical properties, optical behavior and the quantities of low extractable substances combined with good capacity retort, that is, sufficient thermal stability to enable sterilization treatment without negatively affecting optical properties.
[0022] [0022] The present invention is based on the observation that the needs discussed above for heat sealing applications can be met by a specific design of a polypropylene composition. Summary of the Invention
[0023] [0023] Thus, the present invention relates to a polypropylene composition comprising a mixture of (A) 85.0 to 95.0% by weight of a heterophasic propylene copolymer (HECO) comprising (A-1) 80.0 to 90.0% by weight of a matrix (M) being a propylene homopolymer (H-PP) with an MFR2 (230 ° C, 2.16 kg, ISO1133) of 0.8 to 10.0 g / 10 min and (A-2) 10.0 to 20.0% by weight of a propylene-ethylene elastomeric copolymer (EPC) dispersed in said matrix (M), said heterophasic propylene copolymer which has a C2 content of the soluble fraction cold in xylene (XCS) from 15.0 to 30.0% by weight and an intrinsic viscosity (iV); determined according to DIN ISO 1628/1 in decal to
[0024] [0024] It was surprisingly found that such compositions have an optimized or improved balance between mechanical properties, beneficial optical properties, low amounts of extractable substances and sufficient thermal stability to enable sterilization treatment, whereby the optical properties are maintained at a high level before and after sterilization.
[0025] [0025] In one embodiment of the present invention, the heterophasic propylene copolymer (HECO) (A) is obtainable, preferably obtained in the presence of Ziegler-Natta catalyst and the random propylene-hexene copolymer (B) is obtainable, from preferably obtained in the presence of a metallocene catalyst.
[0026] [0026] In an additional embodiment, the invention is related to the use of the composition defined above to prepare articles and the articles themselves. Detailed Description
[0027] [0027] In the following, the individual components are defined in more detail.
[0028] [0028] The polypropylene composition of the present inventions comprises a mixture of (A) a heterophasic propylene copolymer (HECO) and (B) a random propylene hexene copolymer Component heterophasic propylene copolymer (HECO) (THE)
[0029] [0029] The particular heterophasic polypropylene composition of the present invention comprises at least (A-1) the matrix (M) with a polypropylene (H-PP) homopolymer (A-2) being the elastomeric propylene-ethylene (EPC) copolymer dispersed in said matrix (M) as defined in more detail below.
[0030] [0030] Optionally, it can comprise component (A-3) being a crystalline ethylene copolymer (CEC) and / or (A-4) a nucleating agent.
[0031] [0031] The term "heterophasic polypropylene composition" used in this document denotes compositions consisting of a polypropylene homopolymer matrix resin and an elastomeric propylene-ethylene copolymer dispersed in said matrix resin and, optionally, an ethylene copolymer crystalline (CEC) and, optionally, a nucleating agent.
[0032] [0032] In the present invention, the term "matrix" should be interpreted in its commonly accepted meaning, that is, it refers to a continuous phase (in the present invention, a continuous polymer phase) in which distinct or isolated particles as rubber particles can be dispersed. The propylene homopolymer is present in such an amount that it forms a continuous phase that can act as a matrix. Ad Component (A-1):
[0033] [0033] The component (A-1) of the particular heterophasic polypropylene copolymer is a propylene homopolymer that forms the matrix of the heterophasic polypropylene copolymer.
[0034] [0034] The term homopolymer used in the present invention refers to a polypropylene that consists substantially, that is, at least 97.0% by weight, preferably at least 98.0% by weight, more preferably, in at least 99.0% by weight, even more preferably, at least 99.8% by weight of propylene units. In a preferred embodiment, only propylene units in the propylene homopolymer are detectable.
[0035] [0035] The propylene homopolymer matrix has a melt flow rate MFR2 (ISO 1133; 230 ° C; 2.16 kg) in the range of 0.8 to 10.0 g / 10 min, preferably at range of 1.0 to 8.0 g / 10 min, more preferably, in the range of 1.5 to 5.0 g / 10 min, even more preferably, in the range of 2.0 to 4.5 g / 10 min 10 min The matrix MFR2 is called the matrix fusion flow rate (MFRm).
[0036] [0036] The propylene homopolymer has a melting temperature Tm1 determined by DSC analysis according to ISO 11357.
[0037] [0037] Preferably, the Tm1 of the propylene homopolymer is in the range of 160 ° C to 170 ° C, more preferably, in the range of 161 ° C to 169 ° C, even more preferably, in the range of 162 ° C to 168 ° C
[0038] [0038] The polypropylene homopolymer can comprise or consist of a single fraction of polypropylene homopolymer (= unimodal), but it can also comprise a mixture of different polypropylene homopolymer fractions.
[0039] [0039] In cases where the polypropylene homopolymer comprises different fractions, it is understood that the polypropylene homopolymer is bimodal or multimodal.
[0040] [0040] These fractions can have different average molecular weight or different molecular weight distribution.
[0041] [0041] It is preferable that the polypropylene homopolymer can be bimodal or multimodal in view of the molecular weight or the molecular weight distribution.
[0042] [0042] It is alternatively preferred that the polypropylene homopolymer can be unimodal in view of the average molecular weight and / or the molecular weight distribution.
[0043] [0043] Thus, in one embodiment or the present invention, the matrix (M) is unimodal, whereas, in another embodiment, the matrix (M) is bimodal and consists of two fractions of propylene homopolymer (H-PP- 1) and (H-PP-2). Ad Component (A-2):
[0044] [0044] Component (A-2) is a propylene-ethylene elastomeric copolymer (EPC), which is a copolymer of propylene and ethylene being dispersed in said matrix (M) (i.e., dispersed phase).
[0045] [0045] The component (A-2) of the particular heterophasic polypropylene copolymer is the so-called ethylene-propylene rubber phase.
[0046] [0046] The term "ethylene-propylene rubber phase" denotes material that is dispersed essentially in the matrix and is soluble in p-xylene under the conditions described as XCS.
[0047] [0047] The terms “propylene-ethylene elastomeric copolymer (EPC)”, “fraction of the cold-soluble heterophasic propylene copolymer in Xylene (XCS)”, “dispersed phase” and “ethylene-propylene rubber” must be interpreted in their commonly accepted meaning, that is, they denote the same, that is, they are interchangeable.
[0048] [0048] Thus, the amount of propylene-ethylene elastomeric copolymer (EPC) constitutes the amount of the cold soluble xylene fraction (XCS) of the heterophasic propylene copolymer, which is in the range of 10.0 to 20.0% in weight in view of the heterophasic propylene copolymer, preferably in the range of 10.5 to 18.0% by weight and, more preferably, in the range of 11.0 to 17.0% by weight.
[0049] [0049] The intrinsic viscosity (iV) measured according to ISO 1628-1 (at 135 ° C in decaline) of the XCS fraction is in the range of more than 1.2 to 2.6 dl / g, preferably in the range of 1.4 to 2.4 dl / g, more preferably in the range of 1.6 to 2.2 dl / g.
[0050] [0050] The ethylene comonomer content of the XCS fraction is in the range of 15.0 to 30.0% by weight, preferably in the range of 20.0 to 30.0% by weight and more preferably, in range from 25.0 to 28.0% by weight.
[0051] [0051] The elastomeric propylene-ethylene (EPC) copolymer can be synthesized in the later stage (or in the later stages) of a multistage process, after the polypropylene homopolymer (A-1) has been synthesized.
[0052] [0052] Alternatively, the propylene-ethylene elastomeric copolymer (EPC) can be polymerized separately and mixed with the polypropylene homopolymer (A-1) in a separate melt blending step.
[0053] [0053] It is preferred that the incorporation of the polypropylene homopolymer (A-2) in the polypropylene homopolymer (A-2)
[0054] [0054] Like the propylene homopolymer matrix, the dispersed phase can be unimodal or multimodal, like bimodal.
[0055] [0055] In one embodiment, the dispersed phase is unimodal. More particularly, the dispersed phase is preferably unimodal taking into account the intrinsic viscosity and / or the comonomer distribution. Regarding the definition of unimodal and multimodal, as bimodal, it is presented in the definition above.
[0056] [0056] Preferably, the dispersed unimodal phase is made in a reaction state, more preferably, in a gas phase reactor and comprises, respectively, consists of a fraction of propylene-ethylene copolymer (EPC). Ad component (A-3)
[0057] [0057] As component (A-3), a crystalline ethylene copolymer with an α-olefin having 3-10 carbon atoms is optionally present.
[0058] [0058] α-olefins with 3-10 carbon atoms are, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.
[0059] [0059] The crystalline ethylene copolymer is a sub-reaction product obtained by preparing the heterophasic polypropylene composition. Such a crystalline ethylene copolymer is present as an inclusion in the amorphous phase due to thermodynamic reactions.
[0060] [0060] The crystalline ethylene copolymer has a melting temperature Tm2 and a melting enthalpy Hm2, as determined by DSC analysis according to ISO 11357.
[0061] [0061] Preferably, Tm2 of the crystalline ethylene copolymer is within the range of 105 ° C to 130 ° C, more preferably within the range of 110 ° C to 127 ° C and, most preferably, within the range of 112 ° C to 124 ° C.
[0062] [0062] Preferably, Hm2 of the crystalline ethylene copolymer is less than 2.0 J / g, more preferably, less than 1.0 J / g and, most preferably, less than 0.5 J / g. Ad component (A-4)
[0063] [0063] As an optional component (A-4), a nucleating agent (NA) to promote the α phase of the isotactic polypropylene may be present.
[0064] Preferably, the nucleating agent is a polymeric nucleating agent, more preferably, a vinylcycloalkane polymer and / or a vinylalkane polymer.
[0065] [0065] Said polymeric nucleating agent can be introduced into the composition by mixing with a main batch (MB) together with, for example, a carrier polymer or during the polymerization of the heterophasic propylene copolymer (HECO), preferably the polymeric nucleating agent is introduced into the composition by prepolymerizing the catalyst used to prepare part or all of the heterophasic propylene copolymer (HECO).
[0066] [0066] Any known polymeric nucleating agent can be employed, including vinyl alkane and vinyl cycloalkane polymers.
[0067] [0067] A preferred example of such a polymeric nucleating agent is a vinyl polymer, such as a vinyl polymer derived from monomers of the formula CH2 = CH-CHR1R2 in which R1 and R2 together with the carbon atom to which they are attached form a ring optionally substituted saturated or unsaturated or aromatic or a fused ring system, wherein the ring or a fused ring fraction contains four to 20 carbon atoms, preferably a saturated or unsaturated or aromatic ring or a fused ring system of 5 to 12 members or independently represent a straight or branched C4-C30 alkane, C4-C20 cycloalkane or C4-C20 aromatic ring. Preferably, R1 and R2, together with atom C, to which they are attached to, form a five or six membered aromatic or unsaturated or saturated ring or independently represent a lower alkyl group comprising 1 to 4 carbon atoms . Preferred vinyl compounds for the preparation of a polymeric nucleating agent to be used according to the present invention are, in particular, cycloalkane vinyl, in particular, cyclohexane vinyl (VCH), cyclopentane vinyl, and 2-methyl vinyl cyclohexane, 3-methyl-1-butene, 3-ethyl-1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene or mixtures thereof. VCH is a particularly preferred monomer.
[0068] [0068] In the case where the nucleating agent is incorporated into the polypropylene composition in the form of a main batch (MB), said polymeric nucleating agent, which is preferably alpha-nucleating agent, most preferably, a vinylcycloalkane, such as vinylcyclohexane (VCH), polymer and / or vinylalkane polymer, preferably vinylcyclohexane (VCH), as defined above or below, is preferably present in an amount of not more than 500 ppm , more preferably, from 1 to
[0069] [0069] It is preferred that the nucleating agent is introduced into the polypropylene composition during the polymerization process of the heterophasic propylene copolymer (HECO). The nucleating agent is preferably introduced into the heterophasic propylene copolymer (HECO) by first polymerizing the vinyl compound defined above, preferably vinylcycloalkane, as defined above or below, in the presence of a catalyst system comprising a solid catalyst component, preferably a solid Ziegler Natta catalyst component, an optional external donor cocatalyst, and the reaction mixture obtained from the vinyl compound polymer, preferably vinyl cyclohexane (VCH) polymer, and the catalyst system is then used to produce the heterophasic propylene copolymer. The above incorporation of the polymeric nucleating agent into the heterophasic propylene copolymer during the polymerization of said heterophasic propylene copolymer is called BNT technology in the present document as described below.
[0070] [0070] The said reaction mixture obtained is, in the present document, called interchangeably below, as a modified catalyst system.
[0071] [0071] Preferably, the polymeric nucleating agent is vinylcyclohexane polymer (VCH) which is introduced into the heterophasic propylene copolymer (HECO) by BNT technology.
[0072] [0072] More preferably, in this preferred embodiment, the amount of polymeric nucleating agent, such as vinylcyclohexane (VCH), polymer and / or vinylalkane polymer, more preferably, vinylcyclohexane polymer (VCH), in the heterophasic propylene copolymer (HECO) is not more than 500 ppm, more preferably from 1 to 200 ppm, most preferably 5 to 100 ppm.
[0073] [0073] Regarding the BNT technology, reference is made to international applications WO 99/24478, WO 99/24479 and, particularly, WO 00/68315. According to this technology, a catalyst system, preferably a Ziegler-Natta pro-catalyst, can be modified by polymerizing a vinyl compound in the presence of the catalyst system, which comprises, in particular, the Ziegler-Natta pro-catalyst , an external donor and a cocatalyst, in which the vinyl compound has the formula: CH2 = CH-CHR1R2 as defined above.
[0074] [0074] The polymerized vinyl compound acts as an alpha-nucleating agent. The weight ratio between vinyl compound and solid catalyst component in the catalyst modification step is preferably up to 5 (5: 1), preferably up to 3 (3: 1), most preferably 0 , 5 (1: 2) to 2 (2: 1). The most preferred vinyl compound is vinylcyclohexane (VCH).
[0075] [0075] When a nucleating agent is introduced into the heterophasic propylene copolymer (HECO) during the polymerization process, the amount of nucleating agent present in the heterophasic propylene copolymer is preferably not more than 500 ppm, even more preferably, it is 0.025 to 200 ppm, even more preferably, it is 1 to 100 ppm and, most preferably, it is 5 to 100 ppm, based on the heterophasic propylene copolymer and the nucleating agent, preferably based on weight total of the heterophasic propylene copolymer including all additives.
[0076] [0076] The use of the polymeric nucleating agent according to the present invention enables the preparation of heterophasic propylene copolymer (HECO) which has highly satisfactory mechanical properties, that is, for improved stiffness ⁄ impact balance, so that it is not The compositions according to the present invention are required to contain low molecular weight nucleating agents, in particular, expensive particle nucleating agents such as organophosphates or soluble nucleating agents such as sorbitol or nonitol derived nucleating agents. Ad heterophasic propylene copolymer
[0077] [0077] The heterophasic polypropylene (HECO) copolymer of the present invention is characterized by a total melt flow rate (MFRt) (ISO 1133; 230 ° C; 2.16 kg) in the range of 1.0 to 8.0 g / 10 min, preferably in the range of 1.5 to 6.5 g / 10 min and, more preferably, in the range of 2.0 to 5.5 g / 10 min.
[0078] [0078] It is also observed that the total content of the ethylene comonomers in the heterophasic propylene copolymer (HECO) is quite moderate.
[0079] Consequently, it is preferable that the heterophasic propylene copolymer (HECO) has a total ethylene content of the comonomer in the range of 1.8 to 6.5% by weight, preferably in the range of 2.0 to 6, 0% by weight, more preferably in the range of 2.5 to 5.0% by weight and, even more preferably, in the range of 3.0 to 4.6% by weight.
[0080] [0080] The heterophasic propylene copolymer (HECO) of the present invention is composed of components (A-1) and (A-2) and optional components (A-3) and / or (A-4).
[0081] [0081] The component (A-1) is present in an amount of 80.0 to 90.0% by weight, preferably from 82.0 to 90.0% by weight and, more preferably, from 83, 0 to 90.0% by weight
[0082] [0082] The component (A-2) is present in an amount of 10.0 to 20.0% by weight, preferably from 10.0 to 18.0% by weight and, more preferably, from 10, 0 to 17.0% by weight.
[0083] [0083] The component (A-3) is present in an amount of 0.0 to 4.0% by weight, preferably from 0.0 to 2.0% by weight and, more preferably, from 0, 0 to 1.5% by weight.
[0084] [0084] The component (A-4) is present in an amount of 0.0 to 0.1% by weight, preferably from 0.0 to
[0085] [0085] If the component (A-4) is added in the form of a main batch (MB), the quantity of main batch containing the component (A-4) is up to 10.0% by weight with respect to the entire copolymer heterophasic propylene (HECO), preferably up to 5.0% by weight and, more preferably, in the range of 1.5 to 3.5% by weight based on the entire heterophasic propylene copolymer (HECO).
[0086] [0086] The sum of fractions (A-1), (A-2), (A-3) and (A-4) is 100% by weight or less depending on the presence of fractions or additives or additional components. The weight percent (% by weight) ranges, as used herein, define the amount of each of the fractions or components based on the total heterophasic propylene copolymer (HECO) according to the present invention. All fractions, components and additives together provide a sum of 100% by weight.
[0087] [0087] The heterophasic propylene copolymer (HECO) according to the present invention, separated from the polymeric components and the nucleating agent (A-4), optionally in the form of a main lot (MB), can also comprise non-components polymeric, for example, additives for different purposes.
[0088] [0088] The following additional additives are: process and hot stabilizers, pigments and other coloring agents allowing retention of transparency, antioxidants, antistatic agents, gliding agents, anti-blocking agents, UV stabilizers and acid scavengers.
[0089] [0089] Depending on the type of additive, they can be added in an amount of 0.001 to 2.0% by weight, based on the weight of the heterophasic propylene copolymer (HECO).
[0090] [0090] The heterophasic propylene copolymer (HECO) of the present invention comprises a matrix which is a propylene homopolymer (A-1) and dispersed therein an ethylene propylene rubber (A-2). Thus, the matrix contains dispersed inclusions (finely) that are not part of the matrix and said inclusions contain the ethylene propylene copolymer (A-2). The term inclusion indicates that the matrix and the inclusion form different phases in the heterophasic propylene copolymer (HECO). The presence of second phases or so-called inclusions is, for example, visible by high resolution microscopy, such as electron microscopy or atomic force microscopy or by dynamic-mechanical thermal analysis (DMTA). Specifically, in DMTA, the presence of a multi-phase structure can be identified by the presence of at least two distinct glass transition temperatures.
[0091] [0091] Thus, the heterophasic polypropylene composition of the present invention exhibits at least two glass transitions (Tg) in DMTA at significantly different temperatures. One Tg in relation to the component (a) of propylene homopolymer (a) is located in the range of - 5.0 to 5.0 ° C, another Tg in relation to the propylene rubber and ethylene (b) is located in the range from -55 to - 35 ° C. Preparation of the heterophasic propylene copolymer (HECO)
[0092] [0092] The heterophasic propylene copolymer (HECO) according to the present invention can be prepared by any suitable process, including, in particular, blending processes, such as mechanical blending, including mixing and fusion blending, and any combinations of them, as well as blending in place during the polymerization process. They can be performed by methods known to the skilled person, including batch processes and continuous processes. The heterophasic propylene copolymer (HECO) according to the invention is preferably prepared by a sequential polymerization process, as described below, in the presence of a catalyst system comprising a Ziegler-Natta (ZN-C) Catalyst, a cocatalyst (Co) and, optionally, an external donor (ED), as described below.
[0093] [0093] The term "sequential polymerization system" according to this invention indicates that the heterophasic propylene copolymer (HECO) is produced in at least two polymerization reactors connected in series. Consequently, the present polymerization system comprises at least one first polymerization reactor (R1), a second polymerization reactor (R2), optionally a third polymerization reactor (R3) and, optionally, still a fourth polymerization reactor (R4 ). The term "polymerization reactor" should indicate that the main polymerization occurs. Preferably, at least one of the two polymerization reactors (R1) and (R2) is a gas phase reactor (GPR). Most preferably, the second polymerization reactor (R2), the optional third polymerization reactor (R3) and the optional fourth polymerization reactor (R4) are gas-phase reactors
[0094] [0094] Consequently, the first polymerization reactor (R1) is preferably a slurry reactor (SR) and can be any simple or continuous agitated batch tank reactor or cycle reactor that operates in bulk or slurry . Bulk means polymerization in a reaction medium that comprises at least 60% (w / w) monomer. According to the present invention, the slurry reactor (SR) is preferably a cycle reactor (LR) (by mass).
[0095] [0095] In this first polymerization reactor (R1), matrix polypropylene (H-PP) or part thereof, that is, a first fraction of propylene homopolymer (H-PP-1), is produced.
[0096] [0096] Preferably, this propylene homopolymer of the first polymerization reactor (R1), more preferably the polymer slurry of the cycle reactor (LR) containing the matrix (M) or part thereof, that is, a first fraction of propylene homopolymer (H-PP-1), is fed into the second polymerization reactor (R2), that is, in the gas phase reactor (first) (GPR1), without an instant vaporization step between the stages.
[0097] [0097] This type of direct feed is described in documents EP 887379 A, EP 887380 A, EP 887381 A and EP
[0098] [0098] "Direct feed" means a process in which the content of the first polymerization reactor (R1), that is, the cycle reactor (LR), the polymer slurry comprising the propylene homopolymer matrix ( H-PP) or part of it, that is, a first fraction of propylene homopolymer (H-PP-1), is taken directly to the gas phase reactor of the next stage.
[0099] [0099] Alternatively, the propylene homopolymer of the first polymerization reactor (R1), preferably polymer slurry from the cycle reactor (LR) containing the propylene homopolymer matrix, can be directed to an instant vaporization step or through an additional concentration step before being fed into the second polymerization reactor (R2), that is, the 1st gas phase reactor (GPR1). Consequently, this "indirect feed" refers to a process in which the contents of the first polymerization reactor (R1), the cycle reactor (LR), that is, the polymer slurry, is fed into the second polymerization reactor ( R2), in the (first) gas phase reactor (GPR1), by means of a reaction medium separation unit and the reaction medium as a separation unit gas.
[0100] [0100] More specifically, the second polymerization reactor (R2) and any subsequent reactor, for example, the third (R3) or fourth polymerization reactor (R4) are preferably gas phase reactors (GPRs). Such gas phase reactors (GPR) can be any fluidized bed or mechanically mixed reactors. Preferably, gas phase reactors (GPRs)
[0101] [0101] Thus, in a preferred embodiment, the first polymerization reactor (R1) is a slurry reactor (SR), as a cycle reactor (LR), while the second polymerization reactor (R2) and the third reactor of optional polymerization (R3), and the fourth optional polymerization reactor (R4) are gas phase reactors (GPRs).
[0102] [0102] Consequently, for the present process, at least two, preferably two, polymerization reactors (R1), and (R2) or three polymerization reactors (R1), (R2) and (R3), or even four reactors polymerization (R1), (R2), R (3) and (R4), namely a slurry reactor (SR), as a cycle reactor (LR) and a (first) gas phase reactor (GPR1) , a second optional gas phase reactor (GPR2) and, optionally, a third gas phase reactor (GPR3) connected in series are used.
[0103] [0103] Before the slurry reactor (SR), a prepolymerization reactor is positioned.
[0104] [0104] As the process also includes a prepolymerization step, the entire Ziegler-Natta catalyst (ZN-C) is fed into the prepolymerization reactor. Subsequently, the prepolymerization product containing the Ziegler-Natta catalyst (ZN-C) is transferred to the first polymerization reactor (R1).
[0105] [0105] Especially good results are achieved if the temperature in the reactors is carefully chosen.
[0106] [0106] Consequently, it is preferred that the operating temperature in the first polymerization reactor (R1) is in the range of 62 to 85 ° C, more preferably, in the range of 65 to 82 ° C, even more preferably, in the range from 67 to 80 ° C.
[0107] [0107] Alternatively or in addition to the previous paragraph, it is preferable that the operating temperature in the second polymerization reactor (R2) and the optional third reactor (R3) and the optional fourth reactor (R4) is in the range of 75 to 95 More preferably in the range of 78 to 92 ° C.
[0108] [0108] Preferably, the operating temperature in the second polymerization reactor (R2) is equal to or greater than the operating temperature in the first polymerization reactor (R1). Consequently, it is preferred that the operating temperature (a) in the first polymerization reactor (R1) is in the range of 62 to 85 ° C, more preferably, in the range of 65 to 82 ° C, even more preferably, in the range from 67 to 80 ° C, such as 70 to 80 ° C; and (b) in the second polymerization reactor (R2) is in the range of 75 to 95 ° C, more preferably in the range of 78 to 92 ° C, even more preferably in the range of 78 to 88 ° C, with the condition that the operating temperature in the second polymerization reactor (R2) is equal to or greater than the operating temperature in the first polymerization reactor (R1).
[0109] [0109] Typically, the pressure in the first polymerization reactor (R1), preferably in the cycle reactor (LR), is in the range of 2 to 8 MPa (20 to 80 bar), preferably 3 to 7 MPa ( 30 to 70 bar), such as 3.5 to 6.5 MPa (35 to 65 bar), while the pressure in the second polymerization reactor (R2), that is, in the (first) gas phase reactor (GPR1), and in any subsequent reactor, such as in the third polymerization reactor (R3), for example, in the second gas phase reactor (GPR2), or in a fourth polymerization reactor (R4), for example, in the third gas phase reactor (GPR3) ) is in the range of 0.5 to 5 MPa (5 to 50 bar), preferably 1.5 to 4 MPa (15 to 40 bar).
[0110] [0110] Preferably, hydrogen is added to each polymerization reactor in order to control the molecular weight, that is, the MFR2 melt flow rate.
[0111] [0111] Preferably, the average residence time is longer in the polymerization reactors (R1) and (R2). In general, the average residence time (t) is defined as the ratio between the reaction volume (VR) and the reactor volumetric efflux rate (Qo) (ie VR / Qo), that is, t = VR / Qo [tau = VR / Qo]. In this case of a cycle reactor, the reaction volume (VR) is equal to the reactor volume.
[0112] [0112] Consequently, the average residence time (t) in the first polymerization reactor (R1) is preferably at least 5 min, more preferably in the 15 to 80 min range, even more preferably in the range 20 to 60 min, as in the 24 to 50 min range, and / or the average residence time (t) in the second polymerization reactor (R2) is preferably at least 70 min, more preferably in the range from 70 to 220 min, even more preferably, in the 80 to 210 min range, even more preferably, in the 90 to 200 min range, as in the 90 to 190 min range. Preferably, the average residence time (t) in the third polymerization reactor (R3) or in the fourth polymerization reactor (R4) - if present- is preferably at least 30 min, more preferably in the range of 30 at 120 min, even more preferably, in the 40 to 100 min range, as in the 50 to 90 min range.
[0113] [0113] As mentioned above, the preparation of the heterophasic propylene copolymer (HECO) comprises, in addition to the (main) polymerization of the propylene polymer in at least two polymerization reactors (R1, R2 and R3, R4 optional) before it, one prepolymerization in a prepolymerization reactor (PR) upstream to the first polymerization reactor (R1).
[0114] [0114] In the prepolymerization (PR) reactor, a polypropylene (Pre-PP) is produced. Prepolymerization is carried out in the presence of the Ziegler-Natta catalyst (ZN-C). According to this modality, the Ziegler-Natta catalyst (ZN-C), the cocatalyst (Co), and the external donor (ED) are all introduced in the prepolymerization stage. However, this should not exclude the option that, at a later stage, for example, additional cocatalyst (Co) and / or external donor (ED) are added in the polymerization process, for example, in the first reactor (R1). In one embodiment, the Ziegler-Natta catalyst (ZN-C), the cocatalyst (Co), and the external donor (ED) are only added to the prepolymerization (PR) reactor.
[0115] [0115] The prepolymerization reaction is typically conducted at a temperature of 10 to 60 ° C, preferably 15 to 50 ° C and, more preferably, 20 to 45 ° C.
[0116] [0116] The pressure in the prepolymerization reactor is not critical, but it must be high enough to keep the reaction mixture in the liquid phase. Thus, the pressure can be 2 to 10 MPa (20 to 100 bar), for example, 3 to 7 MPa (30 to 70 bar).
[0117] [0117] In a preferred embodiment, prepolymerization is conducted as bulk polymerization in liquid propylene, that is, the liquid phase comprises mainly propylene, with optionally inert components dissolved in it. In addition, according to the present invention, an ethylene feed can be employed during prepolymerization as mentioned above.
[0118] [0118] It is possible to add other components also to the prepolymerization stage. Thus, hydrogen can be added in the prepolymerization stage to control the molecular weight of polypropylene (Pre-PP), as is known in the art. In addition, antistatic additive can be used to prevent particles from adhering to each other or to the reactor walls.
[0119] [0119] Precise control of prepolymerization conditions and reaction parameters is inherent to technical aptitude.
[0120] [0120] Due to the process conditions defined above in the prepolymerization, a mixture (Ml) of the Ziegler-Natta catalyst (ZN-C) and the polypropylene (Pre-PP) produced in the prepolymerization (PR) reactor is obtained . Preferably, the Ziegler-Natta (ZN-C) catalyst is (finely) dispersed in the polypropylene (Pre-PP). In other words, the Ziegler-Natta (ZN-C) catalyst particles
[0121] [0121] Consequently, the heterophasic propylene copolymer (HECO) is preferably produced in a process that comprises polymerization of propylene in at least two subsequent polymerization steps in the presence of a Ziegler-Natta catalyst, in which: a) No first polymerization reactor (R1), that is, in a cycle reactor (LR), propylene is polymerized by obtaining a first fraction of propylene homopolymer (H-PP-1) or the propylene homopolymer matrix (M) , transferring said first propylene homopolymer fraction (H-PP-1) or propylene homopolymer matrix (M) to a second polymerization reactor (R2), c) in the second polymerization reactor (R2), a second fraction propylene homopolymer (H-PP-2), which together with the first propylene homopolymer fraction (H-PP-1) forms the propylene homopolymer (M) matrix or the propylene copolymer fraction (EPC) in the presence of the propylene (M) homopolymer matrix produced in the ante above a) through which c) if, in the first and second polymerization reactors, the propylene homopolymer matrix (M) is produced, in a third polymerization reactor (R3), the propylene copolymer fraction ( EPC) in the presence of the propylene homopolymer matrix (M) produced in the previous steps a) and b) is produced.
[0122] [0122] In another preferred process, a prepolymerization step is also included before the reaction in the first polymerization reactor (R1).
[0123] [0123] In such a prepolymerization step, before the reaction in the first polymerization reactor (R1), a mixture (MI) of the Ziegler-Natta catalyst (ZN-C) and the polypropylene (Pre-PP) produced in the reactor prepolymerization (PR) is obtained. Preferably, the Ziegler-Natta (ZN-C) catalyst is (finely) dispersed in the polypropylene (Pre-PP). Subsequent to prepolymerization, the mixture (MI) of the Ziegler-Natta catalyst (ZN-C) and polypropylene (Pre-PP) produced in the prepolymerization reactor (PR) is transferred to the first reactor (R1). Typically, the total amount of polypropylene (Pre-PP) in the final heterophasic propylene copolymer (HECO) is, instead, low and typically no more than 5.0% by weight, more preferably, no more than 4.0 % by weight, even more preferably, in the range of 0.5 to 4.0% by weight, as in the range of 1.0 to 3.0% by weight.
[0124] [0124] A preferred multistage process is a "gas cycle phase" process, as developed by Borealis (known as BORSTAR® technology) and is described, for example, in patent literature, as in EP 0 887 379, WO 92/12182 WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
[0125] [0125] An additional gaseous-slurry process is the Basell Spheripol® process.
[0126] [0126] The catalyst components are preferably all introduced in the prepolymerization step. However, when the solid catalyst component (i) and the cocatalyst (ii) can be fed separately, it is possible that only a part of the cocatalyst is introduced in the prepolymerization stage and the remaining part in subsequent polymerization stages. In addition, in such cases, it is necessary to introduce a lot of cocatalyst in the prepolymerization stage so that a sufficient polymerization reaction is obtained in it.
[0127] [0127] It is possible to add other components to the prepolymerization stage as well. Thus, hydrogen can be added to the prepolymerization stage to control the molecular weight of the prepolymer, as is known in the art. In addition, antistatic additive can be used to prevent particles from adhering to each other or to the reactor walls.
[0128] [0128] Precise control of prepolymerization conditions and reaction parameters is within the skill of the technique.
[0129] [0129] According to the invention, the heterophasic polypropylene composition is obtained by a multi-stage polymerization process, as described above, in the presence of a catalyst system.
[0130] [0130] In the process described above, a Ziegler-Natta (ZN-C) catalyst for the preparation of the heterophasic polypropylene composition is applied. This Ziegler-Natta (ZN-C) catalyst can be any stereo-specific Ziegler-Natta (ZN-C) catalyst for polymerization of propylene, which preferably has the ability to catalyze the polymerization and copolymerization of propylene and comonomers at a pressure from 500 to 10000 kPa, in particular, 2500 to 8000 kPa, and at a temperature of 40 to 110 ° C, in particular, from 60 to 110 ° C.
[0131] [0131] Preferably, the Ziegler-Natta (ZN-C) catalyst comprises a high performance Ziegler-Natta type catalyst including an internal donor component, which can be used at high polymerization temperatures of 80 ° C or more.
[0132] [0132] Such a high performance Ziegler-Natta (ZN-C) catalyst can comprise a succinate, a diether, a phthalate, etc., or mixtures thereof as an internal donor (ID), and are known in the art.
[0133] [0133] Additionally, the solid catalyst can be supported on suitable external supports, for example, on silica or MgCl2, or it can be free of any external support material, such as silica or MgCl2, but the catalyst can be self-supporting.
[0134] [0134] Thus, examples of useful solid catalysts are, that is, those disclosed, for example, in WO-A-2003/000757, WO-A-2003/000754, WO-A-2004/029112, WO2007 / 137853 and WO2015 / 197354. These catalysts are solid spherical catalysts with compact structure and little surface area of the particles. In addition, these catalysts are presented by a uniform distribution of catalytically active sites across the catalyst particles. The catalysts are prepared by the emulsion-solidification method, in which no external support is required. The dispersed phase in the form of liquid droplets of the emulsion forms the catalyst part, which is transformed into solid catalyst particles during the solidification step.
[0135] [0135] The Ziegler-Natta (ZN-C) catalyst can be further defined by the way it is obtained.
[0136] [0136] Consequently, in one embodiment of the present invention, the Ziegler-Natta (ZN-C) catalyst is preferably obtained by a process comprising steps from a) to 1) providing a solution of at least one alkoxy compound of Group 2 metal (Ax) which is the reaction product of a Group 2 metal compound and a monohydric alcohol (A) which comprises, in addition to the chemical hydroxyl fraction, at least one chemical ether fraction, optionally, in an organic liquid reaction medium; or a2) a solution of at least one Group 2 metal alkoxy compound (Ax ') which is the reaction product of a Group 2 metal compound and a mixture of monohydric alcohol (A) and an alcohol monohydric (B) of formula ROH, optionally, in an organic liquid reaction medium; or a3) providing a solution of a mixture of the Group 2 alkoxy compound (Ax) and a Group 2 metal alkoxy compound (Bx) which is the reaction product of a Group 2 metal compound and the mono- water (B), optionally, in an organic liquid reaction medium; or a4) provide a solution of Group 2 alkoxide of formula M (OR1) n (OR2) mX2-nm or mixture of Group 2 M (OR1) n'X2-n 'and M (OR2) m'X2- m ', where M is a Group 2 metal, X is halogen, R1 and R2 are different alkyl groups from C2 to C16 carbon atoms, and 0 <n <2, 0 <m <2 and n + m + (2 -nm) = 2, provided that both n and m ≠ 0, 0 <n '<2 and 0 <m' <2; and b) adding said solution from step a) to at least one transition metal compound from Groups 4 to 6 and c) obtaining the solid catalyst component particles, and adding an internal non-phthalic donor, in any step prior to the step ç).
[0137] [0137] The internal donor or precursor of the same is preferably added to the solution in step a).
[0138] [0138] According to the above procedure, the Ziegler-Natta catalyst can be obtained by means of precipitation method or by emulsion (liquid / liquid two-phase system) - solidification method depending on physical conditions, especially temperature used in steps b) and c).
[0139] [0139] In both methods (precipitation or emulsion-solidification), the catalyst chemistry is the same.
[0140] [0140] In precipitation, the combination of the solution method from step a) with at least one transition metal compound in step b) is performed and the entire reaction mixture is maintained at least at 50 ° C, more preferably, in the temperature range of 55 ° C to 110 ° C, more preferably in the range of 70 ° C to 100 ° C, to maintain complete precipitation of the component catalyst in the form of solid particles (step c).
[0141] [0141] In the solidification-emulsion method in step b), the solution from step a) is typically added to at least one transition metal compound at a lower temperature, such as from -10 to below 50 ° C, preferably , from -5 to 30 ° C. During stirring the emulsion, the temperature is typically maintained at -10 to below 40 ° C, preferably from -5 to 30 ° C. The droplets of the dispersed phase of the emulsion form the active catalyst composition. The solidification (step c) of the droplets is suitably carried out by heating the emulsion to a temperature of 70 to 150 ° C, preferably to 80 to 110 ° C.
[0142] [0142] The catalyst prepared by the solidification-emulsion method is preferably used in the present invention.
[0143] [0143] In a preferred embodiment, in step a), the solution of a2) or a3) is used, that is, a solution of (Ax ') or a solution of a mixture of (Ax) and (Bx).
[0144] [0144] Preferably, the Group 2 metal is magnesium.
[0145] [0145] The magnesium alkoxy compounds (Ax), (Ax ') and (Bx) can be prepared on site in the first stage of the catalyst preparation process, step a), by reacting the magnesium compound with alcohol ( or alcohols), as described above, or said magnesium alkoxy compounds may be separately prepared magnesium alkoxy compounds or they may still be commercially available as magnesium alkoxy compounds ready and used in this way in the catalyst preparation process. of the invention.
[0146] [0146] Illustrative examples of alcohols (A) are monoethers of dihydric alcohols (glycol monoethers). Preferred alcohols (A) are glycolic monoethers of C2 to C4, wherein the ether moieties comprise from 2 to 18 carbon atoms, preferably from 4 to 12 carbon atoms in this document. Preferred examples are 2- (2-ethylhexyloxy) ethanol, 2-butyloxy ethanol, 2-hexyloxy ethanol and 1,3-propylene glycol-monobutyl ether, 3-butoxy-2-propanol, with 2- (2-ethyl -hexyloxy) ethanol and 1,3-propylene glycol-monobutyl ether, where 3-butoxy-2-propanol is particularly preferred.
[0147] [0147] Illustrative monohydric alcohols (B) are of the formula ROH, with R being a straight or branched chain C6-C10 alkyl residue. The most preferred monohydric alcohol is 2-ethyl-1-hexanol or octanol.
[0148] [0148] Preferably, a mixture of Mg (Ax) and (Bx) alkoxy compounds or mixture of alcohols (A) and (B), respectively, are used and employed in a mol ratio of Bx: Ax or B : A from 8: 1 to 2: 1, more preferably, 5: 1 to 3: 1.
[0149] [0149] The magnesium alkoxy compound can be an alcohol reaction product (alcohols) as defined above, and a magnesium compound selected from dialkyl magnesium, alkyl magnesium alkoxides, magnesium dialcoxides, magnesium alkoxide halides alkyl magnesium halides. Alkyl groups can be a similar or different C1-C20 alkyl, preferably C2-C10 alkyl. Typical alkyl-alkoxy magnesium compounds, when used, are ethyl magnesium butoxide, butyl magnesium pentoxide, octyl magnesium butoxide and octyl magnesium octoxide. Preferably, dialkyl magnesium is used. The most preferred dialkyl magnesium is butyl octyl magnesium or butyl ethyl magnesium.
[0150] [0150] It is also possible that the magnesium compound can react, in addition to alcohol (A) and alcohol (B), also with a polyhydric alcohol (C) of the formula R ”(OH) m to obtain the said magnesium alkoxide compounds.
[0151] [0151] The magnesium alkoxy compounds of step a) are thus selected from the group consisting of magnesium dialoxides, magnesium diaryloxides, magnesium alkoxide halides, magnesium aryloxide halides, alkyl magnesium alkoxides, alkoxides aryl magnesium and alkyl magnesium aryloxides. In addition, a mixture of magnesium dihalide and a magnesium dialoxide can be used.
[0152] [0152] The solvents to be used for the preparation of the present catalyst can be selected from linear, branched and cyclic aromatic and aliphatic hydrocarbon chains with 5 to 20 carbon atoms, more preferably 5 to 12 carbon atoms, or mixtures of the same. Suitable solvents include benzene, toluene, cumene, xylol, pentane, hexane, heptane, octane and nonane. Hexanes and pentanes are particularly preferred.
[0153] [0153] The Mg compound is typically supplied as a 10 to 50% by weight solution in a solvent, as indicated above. The typical commercially available Mg compound, especially dialkyl magnesium solutions are solutions of 20 to 40% by weight in toluene or heptanes.
[0154] [0154] The reaction for the preparation of the magnesium alkoxy compound can be carried out at a temperature of 40 ° to 70 ° C. The most suitable temperature is selected depending on the Mg and alcohol compound (or alcohols) used.
[0155] [0155] The transition metal compound of Groups 4 to 6 is preferably a titanium compound, more preferably a titanium halide, such as TiCI4.
[0156] [0156] The internal non-phthalic donor used in the preparation of the catalyst according to this embodiment of the invention is preferably selected from non-phthalic (di) carboxylic (di) esters, 1,3-diethers, derivatives and mixtures thereof. Especially preferred donors are diesters of monounsaturated dicarboxylic acids, in particular esters that belong to a group comprising malonates, maleates, succinates, citraconates, glutarates, cyclohexene-1,2-dicarboxylates and benzoates, and any derivatives and / or mixtures of the same. Preferred examples are, for example, substituted maleates and citraconates, most preferably citraconates.
[0157] [0157] In the emulsion method, the two-phase liquid-liquid system can be formed by simple stirring and, optionally, add (still) solvent (or solvents) and additives, such as the turbulence minimizing agent (TMA) and / or emulsifying agents and / or emulsion stabilizers, such as surfactants, which are used in a manner known in the art to facilitate the formation of and / or stabilize the emulsion. Preferably surfactants are acrylic or methacrylic polymers. Particular preference is given to C12 to C20 unbranched (meth) acrylates such as poly (hexadecyl) -methacrylate and poly (octadecyl) -methacrylate and mixtures thereof. The turbulence-minimizing agent (TMA), if used, is preferably selected from alpha-olefin polymers of alpha-olefin monomers with 6 to 20 carbon atoms, such as polyoctene, polynonene,
[0158] [0158] The solid particulate product obtained by precipitation or solidification-emulsion method may be washed at least once, preferably at least twice, most preferably, at least three times with an aromatic and / or aliphatic hydrocarbon, preferably with toluene, heptane or pentane. The catalyst can also be dried, as by evaporation or nitrogen washing, or it can be a slurry to an oily liquid without any drying step.
[0159] [0159] The Ziegler-Natta catalyst finally obtained is desirable in the form of particles that, in general, have a range of average particle size from 5 to 200 µm, preferably 10 to 100. The particles are compact with low porosity and have a surface area below 20 g / m2, more preferably below 10 g / m2. Typically, the amount of Ti is 1 to 6% by weight, Mg from 10 to 20% by weight and donor from 10 to 40% by weight of the catalyst composition.
[0160] [0160] The detailed description of the preparation of such catalysts is disclosed, for example, in WO 2012/007430, EP2610271, EP 261027 and EP2610272.
[0161] [0161] The Ziegler-Natta (ZN-C) catalyst is preferably used in association with an alkyl aluminum (Co) cocatalyst and, optionally, external donors (ED).
[0162] [0162] As an additional component in the present polymerization process, an external donor (ED) is preferably present. Suitable external donors include certain silanes, ethers, esters, amines, ketones, heterocyclic compounds and mixtures thereof. It is especially preferable to use a silane. It is more preferable to use silanes of the general formula RapRbqSi (ORc) (4 ∙ p ∙ q) where Ra, Rb and Rc denote a hydrocarbon radical, in particular, an alkyl or cycloalkyl group, and where p and q are numbers ranging from 0 to 3 with their sum of p + q equal to or less than 3. Ra, Rb and Rc can be chosen independently of each other and can be the same or different. Specific examples of such silanes are (tert-butyl) 2Si (OCH3) 2, (cyclohexyl) (methyl) Si (OCH3) 2, (phenyl) 2Si (OCH3) 2 and (cyclopentyl) 2Si (OCH3) 2 or da general formula Si (OCH2CH3) 3 (NR3R4) where R3 and R4 can be the same or different from a representation of a hydrocarbon group having 1 to 12 carbon atoms. R3 and R4 are independently selected from the group consisting of linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, branched aliphatic hydrocarbon group having 1 to 12 carbon atoms and cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms carbon. In particular, it is preferable that R3 and R4 are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl, iso-pentyl, tert- butyl, tert-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
[0163] [0163] Most preferably, both R3 and R4 are equal, even more preferably, both R3 and R4 are an ethyl group.
[0164] [0164] External donors (ED) that are especially preferred are the donor of dicyclopentyl dimethoxy silane (donor D) or the donor of cycloheximethyl dimethoxy silane (Donor C).
[0165] [0165] In addition to the Ziegler-Natta catalyst (ZN-C) and the optional external donor (ED), a cocatalyst (Co) can be used. The cocatalyst (Co) is preferably a compound of group 13 of the periodic table (IUPAC), for example, organo aluminum, as an aluminum compound, such as alkyl aluminum, aluminum halide or alkyl aluminum halide compound. Consequently, in a specific modality, the cocatalyst (Co) is a trialkylaluminium, such as triethylaluminium (TEAL), dialkyl aluminum chloride or alkyl aluminum dichloride or mixtures thereof. In a specific modality, the cocatalyst (Co) is triethyl aluminum (TEAL).
[0166] [0166] Preferably, the ratio between the cocatalyst (Co) and the external donor (ED) [Co / ED] and / or the ratio between the cocatalyst (Co) and the transition metal (TM) [Co / TM] must be carefully chosen.
[0167] [0167] Consequently, (a) the molar ratio between cocatalyst (Co) and external donor (ED) [Co / ED] should be in the range of 5 to 45, preferably in the range of 5 to 35, more preferably , is in the range of 5 to 25; and, optionally, (b) the molar ratio between cocatalyst (Co) and titanium compound (TC) [Co / TC] should be in the range above 80 to 500, preferably in the range of 100 to 350, still more preferably, be in the range of 120 to 300.
[0168] [0168] The heterophasic polypropylene (HECO) composition according to this invention is preferably produced in the presence of (a) a Ziegler-Natta (ZN-C) catalyst comprising an internal donor (ID), (b) optionally, a cocatalyst (Co), and (c) optionally, an external donor (ED).
[0169] [0169] As mentioned above, the Ziegler-Natta (ZN-C) catalyst is optionally modified by the so-called BNT technology during the prepolymerization step described above in order to introduce the polymeric nucleating agent.
[0170] [0170] Such a polymeric nucleating agent is, as described above, a vinyl polymer, such as vinyl polymer derived from monomers of the formula CH2 = CH-CHR1R2 as described above.
[0171] [0171] The weight ratio between vinyl compound and polymerization catalyst in the polymerization catalyst modification step is preferably 0.3 or more to 40, such as 0.4 to 20 or, more preferably, 0, 5 to 15, such as 0.5 to 2.0.
[0172] [0172] The polymerization of the vinyl compound, for example, VCH, can be done in any inert fluid that does not dissolve the polymer formed (for example, polyVCH). It is important to ensure that the viscosity of the final polymerized composite catalyst / vinyl inert fluid mixture is high enough to prevent the catalyst particles from settling during storage and transportation.
[0173] [0173] The viscosity adjustment of the mixture can be done either before or after the polymerization of the vinyl compound. It is, for example, possible to carry out the polymerization in a low viscosity oil and, after the polymerization of the vinyl compound, the viscosity can be adjusted by adding a highly viscous substance. Such a highly viscous substance can be a "wax", such as an oil or a mixture of an oil with a highly viscous or solid substance (oil-grease). The viscosity of such a viscous substance is, in general, 1,000 to 15,000 cP at room temperature. The advantage of using wax is that the catalyst storage and feed in the process is improved. Since no washing, drying, screening and transfer are required, the catalyst activity is maintained.
[0174] [0174] The weight ratio between the oil and the highly viscous or solid polymer is preferably less than 5:
[0175] [0175] In addition to viscous substances, liquid hydrocarbons, such as isobutane, propane, pentane and hexane, can also be used as a medium in the modification step.
[0176] [0176] Polypropylenes produced with a catalyst modified with polymerized vinyl compounds do not essentially contain free (unreacted) vinyl compounds. This means that the vinyl compounds must be completely reacted in the catalyst modification step. For this purpose, the weight ratio between the (added) vinyl compound and the catalyst should be in the range of 0.05 to 10, preferably less than 3, more preferably, about 0.1 to 2.0 and in particular
[0177] [0177] Additionally, the reaction time of the catalyst modification by polymerization of a vinyl compound must be sufficient to allow complete reaction of the vinyl monomer, that is, the polymerization is continued until the amount of unreacted vinyl compounds in the reaction mixture (including the polymerization medium and the reagents) is less than 0.5% by weight, in particular less than 2000 ppm by weight (shown by analysis). Thus, when the prepolymerized catalyst contains a maximum of about 0.1% by weight of vinyl compound, the final content of vinyl compound in the polypropylene will be below the limit of determination using the GC-MS method (< 0.01 ppm by weight). In general, when operating on an industrial scale, a polymerization time of at least 30 minutes is required, preferably the polymerization time is at least 1 hour and, in particular, at least 5 hours. Polymerization times even in the range of 6 to 50 hours can be used. The modification can be carried out at temperatures of 10 to 60 ° C, preferably 15 to 55 ° C.
[0178] [0178] The general conditions for the modification of the catalyst are also disclosed in WO 00/6831, incorporated in this document for reference in relation to the modification of the polymerization catalyst. Preferred embodiments, as described earlier in the present application, with respect to the vinyl compound also apply with respect to the polymerization catalyst of the present invention and the preferred polypropylene composition according to the present invention.
[0179] [0179] Suitable means for the modification step include, in addition to oils, also inert organic solvents with low viscosity, such as pentane and heptane. In addition, small amounts of hydrogen can be used during modification.
[0180] [0180] Therefore, a process for the production of a heterophasic propylene copolymer (HECO) of the present invention is also an objective of the present invention. Such a process comprises polymerizing propylene in at least 2 subsequent polymerization steps in the presence of a) a Ziegler-Natta catalyst comprising compounds (TC) of a transition metal from Groups 4 to 6 of IUPAC, a Group 2 metal compound and an internal donor, b) a cocatalyst (Co), and c) optionally, an external donor (ED). Component propylene hexene random copolymer (B)
[0181] [0181] The propylene-hexene random copolymer has a hexene content in the range of 2.0 to 10.0% by weight, preferably in the range of 2.5 to 8.0% by weight and, more preferably , in the range of 3.0 to 6.0% by weight.
[0182] [0182] The MFR2 (230 ° C, 2.16 kg, ISO1133) of the random propylene-hexene copolymer is in the range of 1.0 to 20.0 g / 10 min, preferably in the range of 5.0 and 20.0 g / 10 min, more preferably in the range of 8.0 to 20.0 g / 10 min and even more preferably, in the range of 10.0 to 20.0 g / 10 min.
[0183] [0183] The melting temperature Tm of the random propylene-hexene copolymer is in the range of 120 ° C to 140 ° C, preferably in the range of 120 ° C to 135 ° C and, more preferably, in the range of 125 ° C to 135 ° C.
[0184] [0184] Preferably, the random propylene-hexene copolymer has a molecular weight distribution (Mw / Mn) in the range of 2.0 to 5.0 and, more preferably, in the range of 2.5 to 4.5 .
[0185] [0185] In addition to or alternatively to the molecular weight distribution (Mw / Mn), as defined in the previous paragraph, the random propylene-hexene copolymer preferably has an average molecular weight Mw in the range of 120 to 500 kg / mol, with more preferably, in the range of 130 to 400 kg / mol, as in the range of 135 to 300 kg / mol.
[0186] [0186] Also preferably, the random propylene-hexene copolymer has a low amount of cold soluble xylene fraction (XCS) of less than 3.0% by weight, more preferably in the range of 0.2 to 2 , 5% by weight.
[0187] [0187] The propylene-hexene random copolymer, as described above, is preferably obtainable in the presence of a metallocene catalyst.
[0188] [0188] The metallocene catalyst can be a supported catalyst using conventional supports or it can be free of an external carrier. By free of an external carrier it is understood that the catalyst does not contain an external support, such as an inorganic support, for example, silica or alumina or an organic polymeric support material.
[0189] [0189] Preferably, metallocene catalysts are used that are free of an external carrier.
[0190] [0190] More preferably, the metallocene catalyst comprises (i) a complex of formula (I):
[0191] [0191] Each X is independently a sigma donor linker.
[0192] [0192] Thus, each X can be the same or different, and is preferably a hydrogen atom, a halogen atom, a linear or branched, cyclic or acyclic C1-20-alkyl or alkoxy group, a C6- 20-aryl, a C7-20-alkylaryl group or a C7-20-arylalkyl group; optionally containing one or more heteroatoms from Groups 14-16 of the periodic table.
[0193] [0193] The term halogen includes fluorine, chlorine, bromine and iodine, preferably chlorine groups. The term hetero atoms belonging to groups 14-16 of the periodic table includes, for example, Si, N, O or S.
[0194] [0194] More preferably, each X is independently a hydrogen atom, a halogen atom, a linear or branched C1-6-alkyl or C1-6-alkoxy group, a phenyl or benzyl group.
[0195] [0195] Even more preferably, each X is independently a halogen atom, a C1-4-
[0196] [0196] Most preferably, each X is independently chlorine, benzyl or a methyl group.
[0197] [0197] Preferably, both groups X are the same.
[0198] [0198] The most preferred options for both groups X are two chlorides, two methyls or two benzyl groups.
[0199] [0199] L is a bridge of formula - (ER82) y-, with y being 1 or 2, E being C or Si, and each R8 is independently a C1-C20-hydrocarbyl or tri (C1-C20-alkyl) silyl , or L is an alkylene group, such as methylene or ethylene.
[0200] [0200] Thus, the - (ER82) y- bridge is a methylene or ethylene binder or L is a bridge of the formula - SiR82-, where each R8 is independently a C1-C20-hydrocarbyl or tri (C1-C20- alkyl) silyl.
[0201] [0201] The term C1-20-hydrocarbyl group includes C1-20-alkyl, C2-20-alkenyl, C2-20-alkynyl, C3-20-cycloalkyl, C3-20-cycloalkenyl, C6-20-aryl groups, groups C7-20-alkylaryl or C7-20-arylalkyl groups or, obviously, mixtures of these groups such as cycloalkyl substituted by alkyl. Unless stated otherwise, the preferred C1-20-hydrocarbyl groups are C1-20-alkyl, C4-20-cycloalkyl, C5-20-cycloalkyl-alkyl groups, C7-20-alkylaryl groups, C7-20-arylalkyl groups or C6-20-aryl groups.
[0202] [0202] If L is an alkylene linking group, ethylene and methylene are preferred.
[0203] [0203] It is preferred if R8 is a C1-C10-hydrocarbyl, such as methyl, ethyl, propyl, isopropyl, tert-butyl,
[0204] [0204] Alkylene binders are preferably methylene or ethylene.
[0205] [0205] L is most preferably -Si (CH3) 2-.
[0206] [0206] Ar and Ar 'are each independently a C6-C10-aryl or C5-C10-heteroaryl group optionally substituted by 1 to 3 groups R1 or R1', respectively.
[0207] [0207] Preferably, Ar and Ar 'are each independently a C6-C10-aryl group and, more preferably, both Ar and Ar' are phenyl.
[0208] [0208] In a preferred embodiment, each of the groups Ar and Ar 'is replaced independently by 1 or 2 groups R1 or R1' R1 and R1 'are each independently the same or may be different and are a C1- group C6-linear or branched alkyl, C7-20 arylalkyl group, C7-20 alkylaryl group or C6-20 aryl group.
[0209] [0209] Preferably, R1 and R1 'are each independently the same or may be different and are a linear or branched C1-C6-alkyl group or C6-20 aryl groups, more preferably a C1-C4-alkyl group linear or branched.
[0210] [0210] More preferably, each R1 and each R1 'are independently methyl, ethyl, isopropyl or tert-butyl,
[0211] [0211] Preferably, each R1 is equal and each R1 'is equal.
[0212] [0212] The total of two substituents of R1 and R1 'is ideally 2, 3 or 4.
[0213] [0213] For the preferred case where Ar and Ar 'are phenyl, the ring is preferably replaced by a group R1 or R1' in the position for (position 4 or 4 ') if there is only one substituent on the phenyl ring .
[0214] [0214] When there are 2 substituents on the ring, the ring is preferably replaced by groups R1 or R1 'in the ortho positions (positions 3 and 5 or 3' and 5 ').
[0215] [0215] Ideally, no phenyl ring will comprise two branched substituents. If a phenyl ring contains two substituents, then it is preferred if R1 or R1 'is C1-4 linear alkyl, for example, methyl.
[0216] [0216] If a phenyl ring contains a substituent, then it is preferred that R1 or R1 'is a branched C4-6 alkyl, for example, tert-butyl.
[0217] [0217] R2 and R2 'are the same or are different and are a CH2-R9 group, with R9 being H or a linear or branched C1-6-alkyl group, such as methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, sec-butyl and tert-butyl or C3-8 cycloalkyl group (for example, cyclohexyl), C6-10 aryl group (for example, phenyl).
[0218] [0218] Preferably, R2 and R2 'are the same and are a CH2-R9 group, with R9 being H or a linear or branched C1-C4-alkyl group, more preferably, R2 and R2' are the same and are a CH2 group -R9, with R9 being H or a linear or branched C1-C3-alkyl group. More preferably, both R2 and
[0219] [0219] Each R3 is a -CH2-, -CHRx- or C (Rx) 2- group in which Rx is C1-4 alkyl and where m is 2-6.
[0220] [0220] R3 is preferably -CH2-. The subscript m is preferably 2 to 4, like 3 (thus forming a 5-membered ring).
[0221] [0221] R5 is a C1-C6-alkyl group, C7-20 arylalkyl group, C7-20 alkylaryl group or linear or branched C6-C2o-aryl group.
[0222] [0222] R5 is preferably a C1-C6-alkyl group or C6-20 linear or branched aryl group, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, preferably a linear C1-C4-alkyl group, more preferably a C1-C2-alkyl group and, more preferably, methyl.
[0223] [0223] R6 is a C (R10) 3 group, with R10 being a straight or branched C1-C6 alkyl group, whereby each R10 can be the same or different. Preferably, each R10 is the same or different with R10 being a linear or branched C1-C4-alkyl group, more preferably, with R10 being the same and being a C1- C2-alkyl group. More preferably, R6 is a tert-butyl group, therefore, all R10 groups are methyl.
[0224] [0224] R7 and R7 'are the same or different and are H or a linear or branched C1-C6-alkyl group. Preferably, R7 and R7 'are the same or different and are H or a linear or branched C1-C4-alkyl group, and more preferably H or a C1-C2-alkyl group. In some embodiments, one of R7 or R7 'is H and the other is a straight or branched C1-C6-alkyl, preferably a C1- group
[0225] [0225] The term C1-20 hydrocarbyl group includes C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-20 cycloalkyl, C3-20 cycloalkenyl, C6-20 aryl groups, C7-20 alkylaryl groups or C7 groups -20 arylalkyl or, obviously, mixtures of these groups, such as cycloalkyl substituted by alkyl.
[0226] [0226] Unless otherwise stated, the preferred C1-20 hydrocarbyl groups are C1-20-alkyl, C4-20 cycloalkyl, C5-20 cycloalkyl-alkyl groups, C7-20 alkylaryl groups, C7-20 arylalkyl groups C6-20 aryl, especially C1-10 alkyl groups, C6-10 aryl groups or C7-12 arylalkyl groups, for example, C1-8 alkyl groups. Especially preferred hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-6-cycloalkyl, cyclohexylmethyl, phenyl or benzyl.
[0227] [0227] The term halo includes fluorine, chlorine, bromine and iodine groups, especially chlorine groups, when referring to the definition of the complex.
[0228] [0228] The oxidation state of the metal ion is managed by the nature of the metal ion in question and the stability of the individual oxidation states of the metal ion.
[0229] [0229] It will be noted that, in the complexes of the invention, the metal ion M is coordinated by ligands X in order to satisfy the valence of the metal ion and fill its coordination sites. The nature of these σ-ligands can vary considerably.
[0230] [0230] In an even more preferred embodiment, the invention provides a complex of formula (II) in which M is Hf or Zr; X is a sigma donor linker, preferably each X is independently a hydrogen atom, a halogen atom, a C1-6 alkoxy group, a C1-6 alkyl, a phenyl or benzyl group; L is an alkylene bridge or a bridge of the formula - SiR82-, wherein each R8 is independently a C1-C6-alkyl, C3-8 cycloalkyl or C6-aryl group; each n is independently 1 or 2; R1 and R1 'are each independently the same or may be different and are a linear or branched C1-C6-alkyl group; R2 and R2 'are the same and are different and are a group a CH2-R9 group, with R9 being H or a linear or branched C1-6-alkyl group; R5 is a straight or branched C1-C6-alkyl group; and R6 is a C (R10) 3 group, with R10 being a straight or branched C1-C6 alkyl group.
[0231] [0231] In any of formulas (I) to (II), it is preferred if the 4-position substituent on the indenyl or indacenyl ring is a 3,5-dimethylphenyl- or 4-tBu-phenyl group.
[0232] [0232] In formula (II), it is preferred that, if n = 2, then both groups R1 are equal.
[0233] [0233] In formula (II), it is preferred that, if n = 2, then both groups R1 'are equal.
[0234] [0234] In formula (II), it is preferred that, if n = 2, then the R1 groups are in the 3,5 position.
[0235] [0235] In formula (II), it is preferred that, if n = 2, then the groups R1 'are in the 3,5 position.
[0236] [0236] In formula (II), it is preferable that, if n = 1, then R1 is in position 4.
[0237] [0237] In formula (II), it is preferred that, if n = 1, then R1 'is in position 4.
[0238] [0238] Particular complexes of the invention include: Antirremic-dimethylsilanediyl dichloride [2-methyl-4- (4-tert-butylphenyl) -5,6,7-trihydro-s-indacen-1-yl] [2- methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl zirconium or dimethyl, Anti-racemic-dimethylsilanedi-yl dichloride [2-iso-butyl-4- (4-tert-butylphenyl) ) -5,6,7-trihydro-s-indacen-1-
[0239] [0239] The catalyst preferably used to produce the random propylene-hexene copolymer used in the invention is in the form of solid particles. As mentioned above, it can be supported on a conventional carrier known by an element skilled in the art. Preferably, the catalyst used is free of an external carrier.
[0240] [0240] Ideally, the catalyst is obtainable by a process in which (a) a liquid / liquid emulsion system is formed, said liquid / liquid emulsion system comprising a solution of the catalyst components (i) and (ii) dispersed in a solvent for the purpose of forming dispersed droplets; and (b) solid particles are formed by solidifying said dispersed droplets.
[0241] [0241] The binders required to form the complexes and therefore the catalysts of the invention can be synthesized by any process and the skilled organic chemist would be able to design various synthetic protocols for the manufacture of the necessary binder materials. For example, WO2007 / 116034 discloses the required chemistry. Synthetic protocols can, in general, also be found in documents W02002 / 02576, WO2011 / 135004, WO2012 / 084961, WO2012 / 001052, WO2011 / 076780 and WO2015 / 158790. The examples section also provides the versed element with sufficient direction.
[0242] [0242] For example, the following general synthetic scheme can be used: Scheme 1
[0243] [0243] The reagents suitable for this transformation are determined in the examples section.
[0244] [0244] While this scheme refers to specific compounds, the general principles shown here apply to all metallocenes described above. If the ligands are asymmetric, a conventional reaction with SiMe2Cl2 cannot be carried out to connect two ligands as it leads to symmetrical products. Instead, each ligand should be attached to the bridge gradually with control over the reaction stoichiometry. Cocatalyst
[0245] [0245] In order to form an active catalytic species, it is usually necessary to employ a cocatalyst as is well known in the art. Cocatalysts that comprise one or more Group 13 metal compounds, such as organoaluminum compounds or borates used to activate metallocene catalysts are suitable for use in the present invention.
[0246] [0246] Suitable amounts of cocatalyst will be well known by the versed element. Manufacturing
[0247] [0247] The catalyst used to manufacture the heterophasic copolymers of the invention is ideally supplied in the form of solid particles, but not supported, that is, no external carrier is used. In order to supply the catalyst of the invention in solid form, but without using an external carrier, it is preferred if a liquid / liquid emulsion system is used. The process involves forming the dispersing catalyst components (i) and (ii) in a solvent, and solidifying said dispersed droplets to form solid particles.
[0248] [0248] In particular, the method involves preparing a solution of one or more catalyst components; dispersing said solution in a solvent to form an emulsion in which said one or more catalyst components are present in the droplets of the dispersed phase; immobilizing the catalyst components in the dispersed droplets, in the absence of an external porous particle support, to form solid particles comprising said catalyst, and optionally recovering said particles.
[0249] [0249] This process makes it possible to manufacture active catalytic particles with improved morphology,
[0250] [0250] The use of unsupported heterogeneous catalysts (ie "self-supporting" catalysts) may have, as a disadvantage, a tendency to dissolve to some extent in the polymerization media, that is, some active catalyst components can leach the catalyst particles during slurry polymerization, whereby the original good catalyst morphology can be lost. These leachate catalyst components are very active, possibly causing problems during polymerization. Therefore, the amount of leachate components can be minimized, that is, all catalyst components must be maintained in a heterogeneous manner.
[0251] [0251] Additionally, self-supporting catalysts generate, due to the high number of species catalytically in the catalyst system, high temperatures at the beginning of the polymerization, which can cause melting of the product material. Both effects, that is, the partial dissolution of the catalyst system and the generation of heat, can cause fouling, lamination and deterioration of the morphology of the polymeric material.
[0252] [0252] In order to minimize the possible problems associated with high activity and leaching, it is preferable to "prepolymerize" the catalyst before using it in the polymerization process. It should be noted that prepolymerization in this regard is part of the catalyst preparation process, which is a step performed after a solid catalyst is formed. This catalyst prepolymerization step is not part of the actual polymerization configuration, which can comprise a conventional process prepolymerization step as well. After the catalyst prepolymerization step, a solid catalyst is obtained and used in the polymerization.
[0253] [0253] The "prepolymerization" of catalyst occurs after the solidification step of the liquid / liquid emulsion process described earlier in this document. Prepolymerization can take place by known methods described in the art, such as that method described in WO 2010/052263, WO 2010/052260 or WO 2010/052264. Preferred embodiments of that aspect of the invention are described in the present document.
[0254] [0254] As monomers in the catalyst prepolymerization step, preferably alpha-olefins are used. The preferred C2-C10 olefins, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene 1-decene, styrene and vinyl cycle -hexene, are used. The most preferred alpha-olefins are ethylene and propylene.
[0255] [0255] The prepolymerization of catalyst can be carried out in gas phase and in an inert diluent, typically, oil or fluorinated hydrocarbon, preferably in fluorinated hydrocarbons or fluorinated hydrocarbon mixture. Preferably, perfluorinated hydrocarbons are used. The melting point of such (per) fluorinated hydrocarbons is typically in the range of 0 ° C to 140 ° C, preferably 30 ° C to 120 ° C, as 50 ° C to 110 ° C.
[0256] [0256] When catalyst prepolymerization is done in fluorinated hydrocarbons, the temperature for the prepolymerization step is below 70 ° C, for example, in the range of -30 ° C to 70 ° C, preferably from 0 ° C to 65 ° C and, more preferably, in the range of 20 ° C to 55 ° C.
[0257] [0257] The pressure contained in the prepolymerization vessel is preferably greater than the atmospheric pressure to minimize eventual leaching of air and / or moisture in the catalyst vessel. Preferably, the pressure is in the range of at least 0.1 MPa to 1.5 MPa (1 to 15 bar), preferably 0.2 to 1.0 MPa (2 to 10 bar). The prepolymerization vessel is preferably kept in an inert atmosphere such as under nitrogen or argon or similar atmosphere.
[0258] [0258] Prepolymerization is continued until the degree of prepolymerization defined as polymer matrix weight / solid catalyst weight before the prepolymerization step is reached. The degree is less than 25, preferably 0.5 to 10.0, more preferably 1.0 to 8.0, most preferably 2.0 to 6.0.
[0259] [0259] The use of the catalyst prepolymerization step offers the advantage of minimizing the leaching of catalyst components and thus local overheating.
[0260] [0260] After prepolymerization, the catalyst can be isolated and stored.
[0261] [0261] The propylene-hexene random copolymer can be produced in a single polymerization step comprising a single polymerization reactor (R1) or in a sequential polymerization process comprising at least two polymerization reactors (R1) and (R2), whereby, in the first polymerization reactor (R1), a first fraction of propylene copolymer (R-PP1) is produced, which is subsequently transferred to the second polymerization reactor (R2). In the second polymerization reactor (R2), a second fraction of propylene copolymer (R-PP2) is produced in the presence of the first fraction of propylene copolymer (R-PP1).
[0262] [0262] Polymerization processes that are suitable for producing the random propylene-hexene copolymer generally comprise one or two polymerization stages and each stage can be carried out in solution, slurry, fluidized bed, in bulk or in phase gaseous.
[0263] [0263] The term "polymerization reactor" is defined as described above for Component (A).
[0264] [0264] The term "sequential polymerization process" is defined as described above for Component (A).
[0265] [0265] The first, respectively the only, polymerization reactor (R1) is preferably a slurry reactor and can be any continuous or simple agitated batch tank reactor or cycle reactor that operates in bulk or slurry fluid. Bulk means polymerization in a reaction medium that comprises at least 60% (w / w) monomer. According to the present invention, the slurry reactor is preferably a cycle reactor (in bulk).
[0266] [0266] In the case where a “sequential polymerization process” is applied to the second polymerization reactor (R2) and the optional third polymerization reactor (R3), they are gas phase reactors (GPRs), that is, a first gas phase reactor (GPR1) and a second gas phase reactor (GPR2). A gas phase reactor (GPR) according to this invention is preferably a fluidized bed reactor, a fast fluidized bed reactor or a sedimented bed reactor or any combination thereof.
[0267] [0267] A preferred multistage process is a "gas cycle phase" process, as developed by Borealis (known as BORSTAR® technology) described, for example, in patent literature, as in EP 0 887 379, WO 92 / 12182 WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or WO 00/68315.
[0268] [0268] An additional gaseous-slurry process is the Basell Spheripol® process.
[0269] [0269] The propylene-hexene random copolymer can be unimodal or multimodal, such as bimodal, in view of the comonomer and / or MFR2 content.
[0270] [0270] If the random propylene-hexene copolymer is unimodal, it is preferably produced in a single polymerization step in a polymerization reactor (R1). Alternatively, a random propylene-hexene copolymer can be produced in a sequential polymerization process with the use of polymerization conditions in all reactors.
[0271] [0271] If the random propylene-hexene copolymer is multimodal, it is preferably produced in a sequential polymerization process using different polymerization conditions (amount of comonomer, amount of hydrogen, etc.) in the reactors .
[0272] [0272] Preferably, the random propylene-hexene copolymer used in accordance with the present invention is unimodal.
[0273] [0273] The propylene-hexene random copolymer as defined in the present invention can contain up to 5.0% by weight of additives, such as α-nucleating agents and antioxidants, as well as non-stick agents and anti-blocking agents. Preferably, the additive content (without α-nucleating agents) is below 3.0% by weight, as below 1.0% by weight. Composition of polypropylene
[0274] [0274] The polypropylene composition according to this invention can be obtained by mixing (melting) the individual fractions, i.e., heterophasic propylene copolymer (HECO) (A) and random propylene-hexene copolymer (B). During melt mixing, suitable additives can be added. For mixing, a conventional compounding or blending apparatus, for example, a Banbury mixer, a 2-cylinder rubber mill, Buss co-mixer, a single screw extruder with special mixing segments or double screw extruder can be used . The polymeric composition recovered from the extruder is usually in the form of pellets.
[0275] [0275] In the blend for the polypropylene composition according to this invention, component (A) is present in an amount of about 85.0 to 95.0% by weight and component (B) is present in an amount of about
[0276] [0276] Preferably, component (A) is present in an amount of 87.0 to 93.0% by weight and, more preferably, in an amount of 88.0 to 92.0% by weight.
[0277] [0277] Thus, component (B) is preferably present in an amount of 7.0 to 13.0% by weight and, more preferably, in an amount of 8.0 to 12.0% by weight .
[0278] [0278] The total melt flow rate, ie the MFR2 melt flow rate (230 ° C) measured according to ISO 1133 of the polypropylene composition, is in the range of 1.0 to 15.0 g / 10 min, preferably in a range of 1.2 g / 10 min to 10.0 g / 10 min, more preferably, in a range of 1.5 g / 10 min to 8.0 g / 10 min and, even more preferably, in a range of 2.0 to 6.0 g / 10 min.
[0279] [0279] It is observed that the inventive polypropylene composition has a melting temperature in the range of 155 ° C to 170 ° C, preferably in the range of 160 ° C to 169 ° C, and, more preferably, in the range from 162 ° C to 168 ° C.
[0280] [0280] Additionally, it is observed that the inventive polypropylene composition has a crystallization temperature of more than 120 ° C, preferably in the range of 121 ° C to 135 ° C and, more preferably, in the range of 122 ° C to 132 ° C.
[0281] [0281] The polypropylene composition according to the present invention has a total hexene content of 0.1 to 1.5% by weight, preferably in the range of 0.2 to 1.2% by weight and, with more preferably, in the range of 0.3 to 1.0% by weight.
[0282] [0282] The polypropylene composition according to the present invention has a total ethylene content of 1.5 to 6.2
[0283] [0283] Additionally, the inventive polypropylene composition is characterized by a low level of soluble in hexane. Thus, the inventive polypropylene composition has a hexane-soluble value determined according to the FDA method (federal registration, title 21, Chapter 1, part 177, section 1520, s. Annex B) in cast films of ≤ 100 µm 3.0% by weight, preferably below 2.0% by weight, more preferably below 1.8% by weight and, even more preferably, below 1.6% by weight.
[0284] [0284] The amount of cold soluble xylene fraction (XCS) of the present polypropylene composition is in the range of 8.0 to 21.0% by weight (determined at 25 ° C according to ISO 16152; 2005), preferably, in the range of 10.0 to 19.0% by weight and, more preferably, in the range of 11.0 to 17.0% by weight.
[0285] [0285] In one embodiment of the present invention, the polypropylene composition has i) a flexural modulus according to ISO 178 in the range 1000 to 1800 MPa, ii) impact resistance by Charpy NIS +23 ° C notch according to ISO 179 1eA in the range of 25 to 75 kJ / m2, and iii) impact resistance per notch of Charpy NIS -20 ° C according to ISO 179 1eA in the range of 1.5 to 5.0 kJ / m2 .
[0286] [0286] Preferably, the flexural modulus measured according to ISO 178 in the range of 1100 to 1600 MPa, more preferably, in the range of 1200 to 1500 MPa.
[0287] [0287] Charpy notch impact resistance NIS +23 ° C according to ISO 179 1eA is preferably in the range of 28 to 65 kJ / m2, more preferably in the range of 31 to 55 kJ / m2 .
[0288] [0288] Charpy notch impact resistance NIS -20 ° C according to ISO 179 1eA is preferably in the range of 1.7 to 4.8 kJ / m2.2, more preferably in the range of 1.9 to 4.6 kJ / m2.
[0289] [0289] In addition, the propylene composition according to the present invention has an opacity according to ASTM D 1003-00 measured on a 1 mm thick injection molded specimen of ≤ 50.0%, preferably at range of 10.0 to 50.0% and, more preferably, in the range of 15.0 to 45.0%.
[0290] [0290] The polypropylene composition as defined in the present invention can contain up to 5.0% by weight of additives, such as α-nucleating agents and antioxidants, as well as non-stick agents and anti-blocking agents. Preferably, the additive content (without α-nucleating agents) is below 3.0% by weight, as below 1.0% by weight.
[0291] [0291] The present invention is further directed to a process for the preparation of the polypropylene composition as defined above, the process comprising the steps of (i) preparing a heterophasic propylene copolymer (A) in the presence of a Ziegler-Natta catalyst ( ii) prepare a random propylene-hexene copolymer (B) by polymerizing propylene and hexene in the presence of a metallocene catalyst (iii) mixing said heterophasic propylene copolymer (A) with the random propylene-hexene copolymer (B) for obtaining a mixture of (A) and (B) and (iv) extruding said mixture to obtain the mixture of (A) and (B). applications
[0292] [0292] The present invention is directed not only to the present polypropylene composition, but also to the use of the polypropylene composition to prepare articles and articles comprising the polypropylene composition.
[0293] [0293] Suitable articles are films for flexible packaging systems, such as bags or pouches, for food and pharmaceutical packaging and for medical articles in general.
[0294] [0294] In one embodiment, the present invention is also related to non-oriented films and film layers of multi-layered film constructions comprising the inventive polypropylene composition. Consequently, the present invention is also directed to non-oriented films, such as molten films or blown films, for example, air-cooled blown films, comprising at least 90% by weight, preferably comprising at least 95% by weight, even with more preferably, comprising at least 99% by weight, of the present polypropylene composition.
[0295] [0295] It has been found that such a polypropylene composition according to the present invention provides the film material made from it with an optimized or improved balance between mechanical properties, beneficial optical properties, low amounts of extractable substances and sufficient thermal stability to enable sterilization treatment, whereby optical properties are maintained at a high level before and after sterilization.
[0296] [0296] Thus, the films, respectively articles, according to the present invention comprising the polypropylene composition defined above are suitable to be sterilized without adversely affecting the optical properties.
[0297] [0297] Therefore, the present invention is also directed to a sterilizable or sterile article, preferably to a sterilizable or sterile film, such as a sterilizable or sterile film. More preferably, the invention is directed to containers, that is, bags, especially, to sterilizable or steam-sterilized containers, that is, bags, preferably comprising, more preferably, consisting of the film as defined herein. The container is, in particular, a pouch. Said additional container, i.e., pouch, was preferably subjected to a steam sterilization treatment in a temperature range of about 120 ° C to 130 ° C.
[0298] [0298] In addition, such a non-oriented film comprising the inventive polypropylene composition should preferably have an opacity (prior to sterilization) determined on a 50 µm molten film (opacity b.s.) Below 10.0%, more preferably, below 9.0% and, even more preferably, below 8.0%.
[0299] [0299] The films according to the invention additionally have an opacity value (determined in the melted film of 50 µm) after sterilization (opacity) at 121 ° C for 30 min below 15.0%, preferably , below 12.0% and, even more preferably, below 8.0%.
[0300] [0300] Thus, it is preferable that an unoriented film comprising the inventive polypropylene composition shows only a very limited increase in opacity after sterilization at 121 ° C for 30 min. A ∆ (opacity), defined as ∆ (opacity) = (opacity.s. - opacityb.s.) ⁄ opacityb.s. * 100%, therefore, is preferably below 10%, more preferably below 5%.
[0301] [0301] In an embodiment of the present invention, such non-oriented films have a machine-driven tensile module (DM) determined in accordance with ISO 527-3 in a 50 µm molten film in a range of 750 to 1500 MPa, preferably in the range of 800 to 1400 MPa and, more preferably, in the range of 850 to 1300 MPa.
[0302] [0302] A multilayered film construction comprising at least one layer comprising the inventive polypropylene composition is preferably produced by multilayer coextrusion followed by film casting or film blowing. In that case, at least one of the outermost layers of said multilayer film construction which serves as the sealing layer (or sealing layers) must comprise the inventive polypropylene composition as defined above. The inventive multilayer film construction should preferably have a thickness in the range of 30 to 500 µm,
[0303] [0303] Films and / or multi-layered film constructions according to the present invention should preferably be used for flexible packaging systems, such as bags or pouches, as packaging for food and pharmaceuticals or medical articles in general.
[0304] [0304] In a case where a film is produced by fused film technology, the fused polypropylene composition is extruded through a slit extrusion die on a cooling roll to cool the polypropylene composition for a solid film. Typically, the polypropylene composition is first compressed and liquefied in an extruder, and it is possible that any additives are already added to the polypropylene composition or introduced at this stage through a main batch. Then, the fused material is forced through a flat film matrix (slit matrix), and the extruded film is removed on one or more one or more removal rolls during which it cools and solidifies. It has been particularly favorable to maintain the withdrawal roll or rollers, whereby the extruded film is cooled and solidified, at a temperature of 10 ° C to 50 ° C, preferably from 15 ° C to 40 ° C.
[0305] [0305] In the blown film process, the fused polypropylene composition is extruded through an annular matrix and blown into a tubular film by forming a bubble that collapses between the strangulation cylinders after solidification. Blow extrusion can preferably be carried out at a temperature in the range of 160 ° C to 240 ° C, and cooled by water or, preferably, by blowing gas (in general, air) at a temperature of 10 ° C to 50 ° C to provide a freezing line height of 0.5 to 8 times the diameter of the die. The explosion rate should generally be in the range of 1.5 to 4, like 2 to 4, preferably 2.5 to 3.5. Methods
[0306] [0306] The fraction soluble in xylene at room temperature (XCS,% by weight): The quantity of the polymer soluble in xylene is determined at 25 ° C according to ISO 16152; 2005;
[0307] [0307] Intrinsic viscosity (XCS IV)
[0308] [0308] The intrinsic viscosity (IV of XCS) is measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135 ° C) in the fraction soluble in xylene (XCS).
[0309] [0309] MFR2 (230 ° C) is measured according to ISO 1133 (230 ° C, 2.16 kg load)
[0310] [0310] The melt flow rate is measured as the MFR2 according to ISO 1133 15 (230 ° C, 2.16 kg load) for polypropylene. MFR is an indication of the flow capacity, and therefore processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. Comonomer determination by NMR spectroscopy (C2 determination)
[0311] [0311] Quantitative nuclear magnetic resonance (NMR) spectroscopy was also used to quantify the comonomer content and the comonomer sequence distribution of the polymers.
[0312] [0312] With characteristic signs corresponding to 2.1 erythro regiodefects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, HN, Macromolecules 1984, 17, 1950, and in WJ, Wang and S. Zhu, Macromolecules 2000, 33 1157) correction for the influence of regiodefects on certain properties was necessary. The characteristic signs that correspond to other types of regiodefects were not observed.
[0313] [0313] The comonomer fraction was quantified using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) through the integration of multiple signals across the spectral region in the 13C {1H} spectra. This method was chosen for its robust nature and the ability to be responsible for the presence of regiodefects when necessary. The integral regions were slightly adjusted to increase the applicability throughout the range of comonomer content found. For systems where only ethylene isolated in PPEPP sequences was observed, the method of Wang et. al. has been modified to reduce the influence of non-zero integrals from locations that are known to not be present. This approach reduced the overestimation of ethylene content for such systems and was achieved by reducing the number of sites used to determine the absolute ethylene content for: E = 0.5 (Sββ + Sβγ + Sβδ + 0.5 (Sαβ + Sαγ ))
[0314] [0314] Using this set of locations, the corresponding integral equation becomes: E = 0.5 (Ih + Ig + 0.5 (lC + ID)) using the same notation used in the article by Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157). The equations used for absolute propylene content have not been modified.
[0315] [0315] The molar percent comonomer incorporation was calculated from the mol fraction: E [mol%] = 100 * fE
[0316] [0316] The comonomer incorporation in weight percent was calculated from the mol fraction: E [% by weight] = 100 * (fE * 28.06) ⁄ ((fE * 28.06) + ((1 -fE) * 42.08))
[0317] [0317] The comonomer sequence distribution at the triad level was determined using the method of analysis by Kakugo et al. (Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T. Macromolecules 15 (1982) 1150). This method was chosen for its robust nature and slightly adjusted integration regions to increase the applicability to a wide range of comonomer content. Comonomer determination: hexene content - 13C NMR spectroscopy
[0318] [0318] The quantitative 13C {1H} NMR spectra were recorded in the fused state using a Bruker Avance III 500 NMR spectrometer that operates at 500.13 and 125.76 MHz for 1H and 13C, respectively. All spectra were recorded using a 7 mm magic angle rotation (MAS) probe head optimized by 13C at 180 ° C with the use of nitrogen gas for all tires. Approximately 200 mg of material was packed in a MAS zirconia rotor with an outside diameter of 7 mm and rotated at 4 kHz. This configuration was chosen mainly due to the high sensitivity required for rapid identification and accurate quantification (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006; 207: 382., Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2007; 208: 2128., Castignolles, P., Graf, R. , Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373). Standard single pulse excitation was employed with the use of NOE in short 3 s recycling delays (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M. , Macromol. Chem. Phys. 2006; 207: 382., Pollard, M., Klimke, K., Graf, R., Spiess, HW, Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37: 813.). and the RS-HEPT decoupling scheme (Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176,239., Griffin, JM, Tripon, C., Samoson, A., Filip, C., and Brown, SP, Mag. Res. In Chem. 2007 45, S1, S198). A total of 16384 (16k) variables were acquired by spectra.
[0319] [0319] The quantitative spectra of 13C {1H} NMR were processed, integrated and the relevant quantitative properties determined from the integrals. All chemical deviations are internally related to the methyl isotactic penile (mmmm) at 21.85 ppm.
[0320] [0320] The characteristic signs corresponding to the incorporation of 1-hexene were observed and the comonomer content quantified as follows.
[0321] [0321] The amount of 1-hexene incorporated in isolated PHP sequences was quantified using the integral of αB4 sites at 44.2 ppm considering the number of reporting sites per comonomer: H = lαB4 ⁄ 2
[0322] [0322] The amount of 1-hexene incorporated in consecutive double PHHP sequences was quantified using the ααB4 site integral at 41.7 ppm considering the number of reporting sites per comonomer: HH = 2 * lααB4
[0323] [0323] When double consecutive incorporation was observed, the amount of 1-hexene incorporated in isolated PHP sequences needed to be compensated due to the overlap of the signals αB4 and αB4B4 at 44.4 ppm: H = (lαB4 - 2 * lααB4) ⁄ two
[0324] [0324] The content of total 1-hexene was calculated based on the sum of 1-hexene isolated and consecutively incorporated: Htotal = H + HH
[0325] [0325] When there were no indicative sites of consecutive incorporation, the comonomer content of total 1-hexene was calculated only in that quantity: Htotal = H
[0326] [0326] The characteristic signs of regiodefects of
[0327] [0327] The presence of 2.1 erythro regiodefects was indicated by the presence of the methyl sites Pαβ (21e8) and Pαγ (21e6) at 17.7 and 17.2 ppm and confirmed by other characteristic signs.
[0328] [0328] The total amount of secondary inserted propene (2,1-erythro) was quantified based on the αα21e9 methylene site at 42.4 ppm: P21 = Iαα21e9
[0329] [0329] The total amount of secondary inserted propene (1.2) was quantified based on the main Sαα methylene sites at 46.7 ppm and compensating for the relative amount of 2,1-erythro, αB4 methylene unit and ααB4B4 methylene of propylene not counted (note that H and HH count the number of hexene monomers per sequence, not by number of sequences): P12 = lsαα + 2 * P21 + H + HH / 2
[0330] [0330] The total amount of propene was quantified as the sum of primary (1,2) and secondary (2,1-erythro) inserted propene: Ptotal = P12 + P21 = Isαα + 3 * Iαα21e9 + (lαB4 - 2 * lααB4 ) / 2 + lααB4
[0331] [0331] More simply: Ptotal = Isαα + 3 * Iαα21e9 + 0,5 * lαB4
[0332] [0332] The total mol fraction of 1-hexene in the polymer was then calculated as: fH = Htotal ⁄ (Htotal + Ptotal)
[0333] [0333] The complete integral equation for the mole fraction of 1-hexene in the polymer was:
[0334] [0334] The incorporation of total comonomer of 1-hexene in mol percentage was calculated from the mol fraction in the usual way: H [mol%] = 100 * fH
[0335] [0335] The incorporation of total comonomer of 1-hexene in percentage by weight was calculated from the mole fraction in the standard way: H [% by weight] = 100 * (fH * 84.16) / ((fH * 84 , 16) + ((1 - fH) * 42,08)) DSC analysis, melting temperature (Tm) and crystallization temperature (Tc):
[0336] [0336] measured with a TA Instrument Q2000 differential scanning calorimetry (DSC) in samples of 5 to 7 mg. DSC is performed according to ISO 11357 ⁄ part 3 / method C2 in a heat / cold / heat cycle with a scan rate of 10 ° C / min in the temperature range from -30 ° C to +225 ° C.
[0337] [0337] The temperature of crystallization and the heat of crystallization (Hc) are determined from the cooling step, while the temperature of fusion and the heat of fusion (Hf) are determined from the second heating step. The hexane-soluble fraction
[0338] [0338] The amount of polymer extractable with hexane according to the FDA method (federal registration, title 21,
[0339] [0339] The amount of hexane-soluble polymer is determined according to the FDA method (federal registration, title 21, Chapter 1, part 177, section 1520, s. Annex B) of the film samples as described above. The extraction was carried out at a temperature of 50 ° C and an extraction time of 2 hours.
[0340] [0340] Flexural Module: The flexural module was determined in 3 point flexion according to ISO 178 in test bars of 80x10x4 mm3 injection molded at 23 ° C according to EN ISO 1873-2.
[0341] [0341] Charpy's notch impact resistance (NIS) was determined according to ISO 179 1eA at 23 °, and at -20 ° C using an injection molded 80x10x4 mm3 test bar according to EN ISO 1873-2.
[0342] [0342] The opacity determined according to ASTM D1003- 00 on 60x60x1 mm3 injection molded plates according to EN ISO 1873-2 using a melting temperature of 200 ° C and in 50 µm thick cast films produced in a monolayer cast film according to a melting temperature of 220 ° C and a cooling roll temperature of 20 ° C. Traction Module
[0343] [0343] The machine-driven traction module (DM) was determined according to ISO 527-3 in cast films with a thickness of 50 µm at a crossbar speed of 100 mm / min.
[0344] [0344] Steam sterilization was performed on a Systec D series machine (Systec Inc., USA). The samples were heated to a heating rate of 5 ° C / min starting at 23 ° C. After being kept for 30 min at 121 ° C, they were immediately removed from the steam sterilizer and stored at room temperature until they were further processed. Examples: Component (A)
[0345] [0345] The catalyst used in the polymerization process for the heterophasic propylene copolymer (HECO) of the inventive example (IE1) and CE1 and CE2 was prepared as described below and was used in conjunction with triethyl aluminum (TEA) as a cocatalyst and dicyclopentyl dimethoxy silane (donor D) as donor. 1a) Preparation of catalyst
[0346] [0346] 3.4 liters of 2-ethylhexanol and 810 ml of propylene glycol butyl monoether in a 4/1 molar ratio were added to a 20 l reactor. Then, 7.8 liters of a 20% toluene solution of BEM (butyl ethyl magnesium) supplied by Crompton GmbH were added to the well-stirred alcohol mixture. During the addition, the temperature was maintained at 10 ° C. After the addition, the temperature of the reaction mixture was increased to 60 ° C and the mixture was continued at that temperature for 30 minutes. Finally, after cooling to room temperature, the obtained Mg alkoxide was transferred to a storage vessel.
[0347] [0347] 21.2 g of Mg alkoxide prepared above was mixed with 4.0 ml of bis (2-ethylhexyl) citraconate for 5 min. After mixing, the Mg complex obtained was used immediately in the preparation of the catalyst component.
[0348] [0348] 19.5 ml of titanium tetrachloride were placed in a 300 ml reactor equipped with a mechanical stirrer at 25 ° C. The mixing speed was adjusted to 170 rpm. 26.0 g of Mg complex prepared above were added for 30 minutes, maintaining the temperature at 25 ° C. 3.0 ml of Viscoplex 1-254 and 1.0 ml of a toluene solution with 2 mg Necadd 447 was added. Then, 24.0 ml of heptane was added to form an emulsion. The mixing was continued for 30 minutes at 25 ° C. Then, the reactor temperature was increased to 90 ° C for 30 minutes. The reaction mixture was stirred for an additional 30 minutes at 90 ° C. Subsequently, stirring was stopped and the reaction mixture was left to stand for 15 minutes at 90 ° C.
[0349] [0349] The solid material was washed 5 times: The washings were done at 80 ° C under agitation for 30 min at 170 rpm. After stirring was stopped, the reaction mixture was left to stand for 20-30 minutes and followed by siphoning.
[0350] [0350] Wash 1: The wash was done with a mixture of 100 ml of toluene and 1 ml of donor
[0351] [0351] Wash 2: The wash was done with a mixture of 30 ml of TiCl4 and 1 ml of donor.
[0352] [0352] Wash 3: The wash was done with 100 ml of toluene.
[0353] [0353] Wash 4: The wash was done with 60 ml of heptane.
[0354] [0354] Wash 5: The wash was done with 60 ml of heptane under 10 minutes of agitation.
[0355] [0355] Subsequently, the stirring was stopped and the reaction mixture was left to stand for 10 minutes, decreasing the temperature to 70 ° C with siphoning, and followed by homogenization of N2 for 20 minutes to yield an air-sensitive powder. 1b) VCH modification of the catalyst
[0356] [0356] 35 ml of mineral oil (Liquid Paraffin PL68) was added to a 125 ml stainless steel reactor per 0.82 g of triethyl aluminum (TEAL) and 0.33 g of dicyclopentyl dimethoxy silane (donor D) under conditions inert at room temperature. After 10 minutes, 5.0 g of the catalyst prepared in 1a (Ti content of 1.4% by weight) was added and, after an additional 20 minutes, 5.0 g of vinyl cyclohexane (VCH) was added. The temperature was raised to 60 ° C for 30 minutes and was maintained like this for 20 hours. Finally, the temperature was lowered to 20 ° C and the concentration of unreacted HCV in the oil / catalyst mixture was analyzed and found to be 120 ppm by weight.
[0357] [0357] Component (A) was produced in a Borstar pilot plant with a prepolymerization reactor, a slurry cycle reactor and two gas phase reactors.
[0358] [0358] The solid catalyst was used in all cases together with triethyl aluminum (TEAL) as a cocatalyst and dicyclo-pentyl-dimethoxysilane (donor D) as a donor. The aluminum to donor ratio was 5 mol / mol, the TEAL / Ti ratio was 90 mol / mol.
[0359] [0359] Polymerization data is shown in Table
[0360] [0360] Component (A) was stabilized by melt mixing in a 200 - 230 ° C twin screw extruder with 0.2 wt% Irganox B225 (1: 1 blend of Irganox 1010 (Pentaeritritiltetrakis ( 3- (3 ', 5'- di-terc.butyl-4-hydroxytoluyl) -propionate, CAS No. 6683-19-8, and tris (2,4-di-t-butylphenyl) phosphate) phosphite), CAS No. 31570- 04-4, from BASF AG, Germany) 0.1% by weight of calcium stearate (CAS No. 1592-23-0, available commercially from Faci, Italy). Table 2: properties of component (A) Final product IE1 total MFR2 [g / 10 min] 3.0 total C2 content [% by weight] 4.2 XCS [% by weight] 14.0 C2 XCS [ % by weight] 27.0 XCS intrinsic viscosity [dl / g] 1.9 τm (DSC) [° C] 167 Tc (DSC) [° C] 128 Component (B) Catalyst: Metallocene synthesis MC-1 4 -Bromo-2,6-dimethylaniline
[0361] [0361] 159.8 g (1.0 mol) of bromine were slowly added (over 2 h) to a stirred solution of 121.2 g (1.0 mol) of 2,6-dimethylaniline in 500 ml of methanol. The resulting dark red solution was stirred overnight at room temperature, then poured into a cold solution of 140 g (2.5 mol) of potassium hydroxide in 1100 ml of water. The organic layer was separated, the aqueous layer was extracted with 500 ml of diethyl ether. The combined organic extract was washed with 1000 ml of water, dried over K2CO3, and evaporated in vacuo to generate 202.1 g of 4-bromo-2,6-dimethylaniline (approximately 90% purity) as a dark red oil which crystallized at room temperature. This material was used additionally without further purification.
[0362] [0362] 1H NMR (CDCl3): δ 7.04 (s, 2H), 3.53 (s l., 2H), 2.13 (s, 6H). 1-Bromo-3,5-dimethylbenzene
[0363] [0363] 97 ml (1.82 mol) of 96% sulfuric acid were gradually added to a solution of 134.7 g (approximately 673 mmol) of 4-bromo-2,6-dimethylaniline (prepared above, purity approximately 90 %) in 1400 ml of 95% ethanol cooled to -10 ° C, at such a rate to keep the reaction temperature below 7 ° C. After the addition was completed, the solution was stirred at room temperature for 1 h. Then, the reaction mixture was cooled in an ice bath, and a solution of 72.5 g (1.05 mol) of sodium nitrite in 150 ml of water was gradually added over approximately 1 h. The formed solution was stirred at the same temperature for 30 min. Then, the cooling bath was removed, and 18 g of copper powder was added. Upon completion of the rapid evolution, additional portions of nitrogen were added
[0364] [0364] 1H NMR (CDCl3): δ 7.12 (s, 2H), 6.89 (s, 1H), 2.27 (s, 6H). 13C {1H} NMR (CDCl3): δ 139.81, 129.04, 128.61, 122.04, 20.99. Boronic (3,5-dimethylphenyl) acid
[0365] [0365] A solution of 3,5-dimethylphenylmagnesium bromide obtained from a solution of 190.3 g (1.03 mol) of 1-bromo-3,5-dimethylbenzene in 1000 ml of THF and 32 g (1 , 32 mol, 28% excess) of magnesium chips were cooled to -78 ° C, and 104 g (1.0 mol) of trimethylborate were added in one portion. The resulting heterogeneous mixture was stirred overnight at room temperature. The boronic ester was hydrolyzed by carefully adding 1200 ml of 2M HCl. 500 ml of diethyl ether was added, the organic layer was separated, and the aqueous layer was further extracted with 2x500 ml of diethyl ether. The combined organic extract was dried in
[0366] [0366] Anal. calc. for C8H11BO2: C, 64.06; H, 7.39. Found: C, 64.38; H, 7.72.
[0367] [0367] 1H NMR (DMSO-d6): δ 7.38 (s, 2H), 7.00 (s, 1H), 3.44 (very l., 2H), 2.24 (s, 6H) . 2-methyl-4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butyl-indan-1-one
[0368] [0368] A mixture of 49.14 g (157.9 mmol) of 2-methyl-4-bromo-5-methoxy-6-tert-butylindan-1-one, 29.6 g (197, 4 mmol, 1.25 eq.) Of (3,5-dimethylphenyl) boronic acid, 45.2 g (427 mmol) of Na2CO3, 1.87 g (8.3 mmol, 5 mol%) of Pd ( OAc) 2, 4.36 g (16.6 mmol, 10 mol%) of PPh3, 200 ml of water, and 500 ml of 1,2-dimethoxyethane for 6.5 h. DME was evaporated on a rotary evaporator, 600 ml of water and 700 ml of dichloromethane were added to the residue. The organic layer was separated, and the aqueous layer was further extracted with 200 ml of dichloromethane. The combined extract was dried over K2CO3 and then evaporated to dryness to generate a black oil. The crude product by flash chromatography on silica gel 60 (40-63 µm, hexane-dichloromethane = 1: 1, vol, then 1: 3, vol) to generate 48.43 g (91%) of 2-methyl- 4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butylindan-1-one as a brownish oil.
[0369] [0369] Anal. calc. for C23H28O2: C, 82.10; H, 8.39. Found: C, 82.39; H, 8.52.
[0370] [0370] 1H NMR (CDCl3): δ 7.73 (s, 1H), 7.02 (s, 3H), 7.01 (s, 3H), 3.32 (s, 3H), 3.13 ( dd, J = 17.5 Hz, J = 7.8 Hz, 1H), 2.68-2.57 (m, 1H), 2.44 (dd, J = 17.5 Hz, J = 3.9 Hz), 2.36 (s, 6H), 1.42 (s, 9H), 1.25 (d, J = 7.5 Hz, 3H). 13C {1H} NMR (CDCl3): δ 208.90, 163.50, 152.90, 143.32, 138.08, 136.26, 132.68, 130.84, 129.08, 127.18, 121.30, 60.52, 42.17, 35.37, 34.34, 30.52, 21.38, 16.40. 2-methyl-5-tert-butyl-6-methoxy-7- (3,5-dimethylphenyl) -1H- indene
[0371] [0371] 8.2 g (217 mmol) of NaBH4 was added to a solution of 48.43 g (143.9 mmol) of 2-methyl-4- (3,5-dimethylphenyl) -5-methoxy-6- tert-butylindan-1-one in 300 ml of THF cooled to 5 ° C. Then, 150 ml of methanol was gradually added to this mixture or vigorous stirring for approximately 7 h at 5 ° C. The resulting mixture was evaporated to dryness, and the residue was partitioned between 500 ml of dichloromethane and 500 ml of 2M HCl. The organic layer was separated, the aqueous layer was further extracted with 100 ml of dichloromethane. The combined organic extract was evaporated to dryness to generate a slightly yellow oil. To a solution of this oil in 600 ml of toluene, 400 mg of TsOH were added, this mixture was refluxed with Dean-Stark's head for 10 min and then cooled to room temperature using a water bath. The formed solution was washed with 10% Na2CO3, the organic layer was separated, the aqueous layer was extracted with 150 ml of dichloromethane. The combined organic extract was dried over K2CO3 and then passed through a short layer of silica gel 60 (40-63 µm). The silica gel layer was washed further in 100 ml of dichloromethane. The combined organic eluate was evaporated to dryness, and the resulting oil was vacuum dried at elevated temperature. This procedure generated 45.34 g (98%) of 2-methyl-5-tert-butyl-6-methoxy-7- (3,5-dimethylphenyl) -1 / - / - indene which was used without further purification.
[0372] [0372] Anal. calc. for C23H28O: C, 86.20; H, 8.81. Found: C, 86.29; H, 9.07.
[0373] [0373] 1H NMR (CDCl3): δ 7.20 (s, 1H), 7.08 (s l., 1H), 6.98 (s l., 1H), 6.42 (m, 1H), 3.25 (s, 3H), 3.11 (s, 2H), 2.36 (s, 6H), 2.06 (s, 3H), 1.43 (s, 9H). 13C {1H} NMR (CDCl3): δ 154.20, 145.22, 141.78, 140.82, 140.64, 138.30, 137.64, 131.80, 128.44, 127.18, 126.85, 116.98, 60.65, 42.80, 35.12, 31.01, 21.41, 16.65. [2-methyl-4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-
[0374] [0374] To a solution of 9.0 g (28.08 mmol) of 2-methyl-5-tert-butyl-6-methoxy-7- (3,5-dimethylphenyl) -1H-indene in 150 ml of ether , cooled to -50 ° C, 11.6 ml (28.19 mmol) of nBuLi in 2.43 M hexanes were added in one portion. The resulting mixture was stirred for 6 h at room temperature, then the yellow suspension obtained was cooled to -60 ° C, and 18.1 g (140.3 mmol, 5 equiv.) Of dichlorodimethylsilane was added in one portion. The obtained solution was stirred overnight at room temperature and then filtered through a glass frit (G3). The filtrate was evaporated to dryness to generate [2-methyl-4- (3,5-dimethylphenyl) -5-methoxy-6-tert-Butyl-1H-inden-1-yl] (chlorine) dimethylsilane as an oil slightly yellowish which was used additionally without further purification.
[0375] [0375] 1H NMR (CDCl3): δ 7.38 (s, 1H), 7.08 (s, 2H), 6.98 (s, 1H), 6.43 (s, 1H), 3.53 ( s, 1H), 3.25 (s, 3H), 2.37 (s, 6H), 2.19 (s, 3H), 1.43 (s, 9H), 0.43 (s, 3H), 0.17 (s, 3H). 13C {1H} NMR (CDCl3): δ 155.78, 145.88, 143.73, 137.98, 137.56, 137.49, 136.74, 128.32, 127.86, 127.55, 126.64, 120.86, 60.46, 49.99, 35.15, 31.16, 21.41, 17.55, 1.11, -0.58. 1-methoxy-2-methyl-4- (3,5-Dimethylphenyl) -1,2,3,5,6,7-hexahydro-s-indacene
[0376] [0376] To a mixture of 2.0 g (2.56 mmol, 1.8 mol% of NiCl2 (PPh3) IPr and 40.0 g (142.3 mmol) of 4-bromo-1-methoxy were added -2-methyl-1,2,3,5,6,7-hexahydro-s-indacene, 200 ml (200 mmol, 1.4 eq) of 1,0 M 3,5-dimethylphenylmagnesium bromide in The resulting solution was refluxed for 3 h, then cooled to room temperature, and 400 ml of water was added followed by 500 ml of 1.0 M HCl solution. In addition, this mixture was extracted with 600 ml of dichloromethane, the organic layer was separated, and the aqueous layer was extracted with 2x100 ml of dichloromethane.The combined organic extract was evaporated to dryness to generate a slightly greenish oil. The product was isolated by flash chromatography on silica gel 60 ( 40-63 µm; eluent: hexanes-dichloromethane = 2: 1, vol, then 1: 2, vol. This procedure generated 43.02 g (99%) of 1-methoxy-2-methyl-4- (3 , 5-dimethylphenyl) -1,2,3,5,6,7-hexahydro-s-indacene as a colorless thick oil as a mixture of and two diastereoisomers.
[0377] [0377] Anal. calc. for C22H26O: C, 86.23; H, 8.55. Found: C, 86.07; H, 8.82.
[0378] [0378] 1H NMR (CDCl3), Sin isomer: δ 7.21 (s, 1H), 6.94 (s l., 1H), 6.90 (s l., 2H), 4.48 (d, J = 5.5 Hz, 1H), 3.43 (s, 3H), 2.94 (t, J = 7.5 Hz, 2H), 2.87-2.65 (m, 3H), 2, 63-
[0379] [0379] To the solution of 43.02 g (140.4 mmol) 1-methoxy-2-methyl-4- (3,5-dimethylphenyl) - 1,2,3,5,6,7-hexahydro- s- indacene in 600 ml of toluene, 200 mg of TsOH were added, and the resulting solution was refluxed using Dean-Stark's head for 15 min. After cooling to room temperature, the reaction mixture was washed with 200 ml of 10% NaHCO3. The organic layer was separated, and the aqueous layer was further extracted with 300 ml of dichloromethane. The combined organic extract was evaporated to dryness to generate slightly orange oil. The product was isolated by flash chromatography on silica gel 60 (40-63 µm; eluent: hexanes, then hexanes-dichloromethane = 10: 1, vol). This procedure generated 35.66 g (93%) of 4- (3,5-dimethylphenyl) -6-methyl-1,2,3,5-tetrahydro-s-indacene as a slightly yellowish oil which spontaneously solidified to form a white mass.
[0380] [0380] Anal. calc. for C21H22: C, 91.92; H, 8.08. Found: C, 91.78; H, 8.25.
[0381] [0381] 1H NMR (CDCl3): δ 7.09 (s, 1H), 6.98 (s l., 2H), 6.96 (s l., 1H), 6.44 (m, 1H), 3.14 (s, 2H), 2.95 (t, J = 7.3 Hz, 2H), 2.76 (t, J = 7.3 Hz, 2H), 2.35 (s, 6H), 2.07 (s, 3H), 2.02 (quin, J = 7.3 Hz, 2H). 13C {1H} NMR (CDCl3): δ 145.46, 144.71, 142.81, 140.17, 139.80, 137.81, 137.50, 134.33, 128.35, 127.03, 126.48, 114.83, 42.00, 33.23, 32.00, 25.87, 21.38, 16.74. [2-methyl-4- (3,5-dimethylphenyl) -5-methoxy-6-tert-Butyl-1H-inden-1-yl] [2-methyl-4- (3,5-dimethylphenyl) -1, 5,6,7-tetrahydro-s-indacen-1-yl] dimethylsilane
[0382] [0382] To a solution of 7.71 g (28.1 mmol) of 4- (3,5-dimethylphenyl) -6-methyl-1,2,3,5-tetrahydro-s-indacene in a mixture 150 ml of ether and 20 ml of THF 11.6 ml (28.19 mmol) of nBuLi in 2.43 M hexanes were added in one portion at -50 ° C.
[0383] [0383] Anal. calc. for C46H54OSi: C, 84.87; H, 8.36. Found: C, 85.12; H, 8.59.
[0384] [0384] 1H NMR (CDCI3): δ 7.48 and 7.33 (2s, sum 1H), 7.26-7.18 (m, 1H), 7.16-7.07 (m, 2H), 7.04-6.95 (m, 4H), 6.51 and 6.45 (2s, sum 2H), 3.69 and 3.65 (2s, sum 2H), 3.28 and 3.26 (2s , sum 3H), 3.01-2.74 (m, 4H), 2.38 and 2.37 (2s, sum 12H), 2.20 and 2.15 (2s, sum 6H), 2.09- 1.97 (m, 2H), 1.43 and 1.42 (2s, sum 9H), -0.17, -0.18, -0.19 and -0.24 (4s, sum 6H). 13C {1H} NMR (CDCl3): δ 155.29, 147.45, 147.39, 145.99, 145.75, 143.93, 143.90, 143.72, 143.69, 142.06, 142.01, 140.08, 140.06, 139.46, 139.37, 139.26, 139.03, 139.00, 138.24, 137.50, 137.34, 137.07, 136, 99, 130.39, 128.23, 128.14, 127.92, 127.50, 127.46, 127.26, 126.12, 126.05, 125.99, 125.94, 120.55, 120.51, 118.46, 118.27, 60.49, 47.33, 46.86, 46.76, 35.14, 33.33, 33.28, 32.18, 31.26, 31, 21, 25.95, 25.91, 21.44, 17.96, 17.88, -5.27, - 5.39, - 5.50, -5.82. Anti-dimethylsilanedi-yl [2-methyl-4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl] [2-methyl-4- (3,5-dimethylphenyl) dichloride -1,5,6,7-tetrahydro-s-indacen-1-yl] zirconium
[0385] [0385] To a solution of 11.95 g (18.36 mol) of [2-methyl- 4- (3,5-dimethylphenyl) -5-methoxy-6- tert-butyl-1 H- inden-1- yl] [2-methyl-4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacen-1-yl] dimethylsilane (prepared above) in 200 ml of ether, cooled to -50 ° C, 15.1 ml (35.7 mmol) of 2.43 M nBuLi in hexanes was added in one portion.
[0386] [0386] Anti-dimethylsilanediyl dichloride [2-methyl-4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl] [2- methyl-4- (3,5 -dimethylphenyl) -1,5,6,7-tetrahydro-s-indacen-1-yl] zirconium:
[0387] [0387] Anal. calc. for C46H52Cl2OSiZr x 0.6C7H8: C, 69.59; H, 6.61. Found: C, 69.74; H, 6.68.
[0388] [0388] 1H NMR (CDCl3): δ 7.47 (s, 1H), 7.40 (s, 1H), 7.37-7.03 (m, 4H), 6.95 (s, 2H), 6.71 (s, 1H), 6.55 (s, 1H), 3.43 (s, 3H), 3.03-2.96 (m, 2H), 2.96-2.87 (m, 1H), 2.87-2.76 (m, 1H), 2.34 and 2.33 (2s, adds 12H), 2.19 and 2.18 (2s, adds 6H), 2.06-1, 94 (m, 2H), 1.38 (s, 9H), 1.28 (s, 3H), 1.27 (s, 3H). 13C {1H} NMR (CDCl3,): δ 159.73, 144.59, 143.99, 143.00, 138.26, 137.84, 137.59, 136.80, 135.35, 133.85 , 133.63, 132.95, 132.52, 128.90, 128.80, 127.40, 126.95, 126.87, 126.65, 122.89, 121.61, 121.53, 120 , 82, 117.98, 81.77, 81.31, 62.62, 35.73, 33.20, 32.12, 30.37,
[0389] [0389] Syn-dimethylsilanediyl dichloride [2-methyl-4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butylinden- 1 -yl] [2- methyl-4- (3,5-dimethylphenyl) ) -1,5,6,7-tetrahydro-s-indacen-1-yl] zirconium.
[0390] [0390] Anal. calc. for C46H52Cl2OSiZr: C, 68.11; H, 6.46. Found: C, 68.37; H, 6.65. 1H NMR (CDCl3): δ 7.51 (s, 1H), 7.39 (s, 1H), 7.36 - 6.99 (m, 4H), 6.95 (s, 2H), 6.60 (s, 1H), 6.44 (s, 1H), 3.27 (s, 3H), 2.91-2.75 (m, 4H), 2.38 and 2.34 (2s, sum 18H) , 1.99-1.87 (m, 1H), 1.87-1.74 (m, 1H), 1.42 (s, 3H), 1.36 (s, 9H), 1.19 (s , 3H). 13C {1H} NMR (CDCl3,): δ 158.74, 143.41, 142.84, 142.31, 138.30, 137.77, 137.55, 136.85, 135.87, 135.73 , 134.99, 134.75, 131.64, 128.83, 128.76, 127.97, 127.32, 126.82, 126.22, 123.91, 121.35, 121.02, 120 , 85, 118.56, 83.47, 83.08, 62.32, 35.53, 33.33, 31.96, 30.33, 26.53, 21.45 (two resonances), 18.56 , 18.43, 2.93, 2.65. Catalyst: Synthesis of catalyst:
[0391] [0391] 1H, 1 H-Perfluoro (2-methyl-3-oxa-hexan-1-ol) (CAS 26537-88-2) purchased from Unimatec, dried on activated molecular sieves (2 times) and degassed by bubbling of argon before use was used as a surfactant.
[0392] [0392] Inside the glove box, 28.8 mg of dry and degassed surfactant (in 0.2 ml of toluene) were gradually added to 5 ml of MAO. The solution was left under stirring for 10 minutes. Then, 98.7 mg of MC-1 was added to the MAO / surfactant solution. After 60 minutes of stirring, 106.0 mg of trityl tetrakis (pentafluorophenyl) borate was added.
[0393] [0393] After 60 minutes of stirring, the surfactant-MAO-metallocene borate solution was successively added to a 50 ml glass emulsification reactor containing 40 ml of PFC at -10 ° C and equipped with an upper stirrer (speed stirring = 600 rpm). A red emulsion formed immediately and was stirred for 15 minutes at -10 ° C ⁄ 600rpm. Then, the emulsion was transferred through a 2/4 teflon tube to 100 ml of the hot PFC at 90 ° C, and stirred at 600 rpm until the transfer was completed, then the speed was reduced to 300 rpm. After stirring for 15 minutes, the oil bath was removed and the stirrer was turned off. The catalyst was placed on top of the PFC and, after 35 minutes, the solvent was removed by siphon. The catalyst was placed on top of the PFC and, after 35 minutes, the solvent was removed by siphon. The remaining catalyst was dried for 2 hours at 50 ° C under argon flow. 0.60 g of a free flowing red powder were obtained. Offline prepolymerization procedure
[0394] [0394] The catalyst produced above was prepolymerized off-line according to the following procedure: The catalyst was prepolymerized according to the following procedure: The off-line prepolymerization experiment was carried out in a reactor 125 ml pressure tank equipped with gas supply lines and a stirrer and an upper stirrer. The perfluoro-1.3-dimethylcyclohexane (15 cm3) dried and degassed and the desired amount of the catalyst to be prepolymerized were loaded into the reactor in a glove box and the reactor was sealed. So,
[0395] [0395] A stirred autoclave (equipped with a tape stirrer) with a total volume of 21.2 dm3 containing 0.2 bar-g of propylene (quality 2.3; purified through columns filled with PolyMax301 T-4427B (60 ° C; Cu / CuO), MS13X-APG 1/16 and Selexsorb COS) are filled with an additional 4.45 kg of propylene and a chosen amount of 1-hexene. The amount of triethyl aluminum was 0.4 ml of TEA. After the addition of triethylaluminium (0.62 molar solution in n-heptane) using a flow of 250 g of propylene. The solution is stirred at 20 ° C and 250 rpm for at least 20 min. Subsequently, the reactor is brought up to the defined prepolymerization temperature (30 ° C) and the catalyst is injected.
[0396] [0396] The solid prepolymerized catalyst of the above is loaded in a 5 ml stainless steel flask inside the glove box. The vial is attached to the autoclave, then a second 5 ml vial containing 4 ml of n-heptane and pressurized with 1 MPa (10 bar) of N2 is added at the top. The chosen amount of H2 is dosed in the reactor through a flow controller. The chosen amount of hexene and H2 depends on the desired final properties of component (B) and can be easily adjusted by an expert in the art.
[0397] [0397] The valve between the two vials is open and the solid catalyst is in contact with heptane under N2 pressure for 2 s, and then flushed in the reactor with 250 g of propylene. The stirring speed is maintained at 250 rpm and prepolymerization is carried out for the defined time. The polymerization temperature is now increased to 75 ° C. The reactor temperature is kept constant throughout the polymerization. The polymerization time is measured from the temperature below 2 ° C of the defined polymerization temperature. When the polymerization time is 60 min, the reaction is stopped by injecting 5 ml of ethanol, cooling the reactor and cleaning the volatile components. After cleaning the reactor 3 times with N2 and a vacuum / N2 cycle, the product is removed and dried overnight in an exhaust fan.
[0398] [0398] A propylene-hexene B-1 copolymer was prepared with the following base properties:
[0399] [0399] Component (B) was stabilized in the same way as component (A) by mixing by melting in a co-rotating twin screw extruder at 200 -230 ° C with 0.2% by weight of Irganox B225 (mixture of 1 : 1 of Irganox 1010 (Pentaeritritiltetrakis (3- (3 ', 5'-di-terc.butil-4-hydroxytoluyl) -propionate, CAS No. 6683-19-8, and tris (2,4-di-t-butylphenyl ) phosphite phosphate), CAS No. 31570-04-4, from BASF AG, Germany) and 0.1% by weight of calcium stearate (CAS No. 1592-23-0, commercially available from Faci, Italy).
[0400] [0400] For Comparative Examples CE1 and CE2, the following blends were used for Component (A): CE1: HF700SA is a polypropylene homopolymer commercially available from Borealis AG, Austria, with an MFR2 (230 ° C; 2 , 16 kg) is 21.0 g / 10 min. The density is 905 kg / m3 and the melting point in DSC is 165 ° C. (Component B-2) CE2: RF365MO is a random copolymer of polypropylene-ethylene commercially available from Borealis AG, Austria, which has a MFR2 (230 ° C; 2.16 kg) of 20 g / 10 min, a content of 3.1% by weight ethylene and a DSC melting point of 151 ° C. (Component B-3)
[0401] [0401] Component (A) and Components (B) were compounded in a Coperion ZSK 18 cogiratory twin screw extruder at 220 ° C without additional additives. Table 4: Polymer blends and inventive and comparative properties CE2 CE1 IE1 Component A% by weight 90.0 90.0 90.0 Component B-1% by weight 10.0 Component B-2% by weight 10.0 Component B -3% by weight 10.0 mfr2 g / 10 min 3.6 3.6 3. 6 Tc ° C 128 129 128 Tm ° C 167 168 166 XCS% by weight 14.1 13.6 13.7 C6 FDA% by weight 1.81 1.47 1.45 Flexion Module (DM) MPa 1351 1392 1335 NIS (23 ° C) kJ / m2 38 33 36 NIS (-20 ° C) kJ / m2 2.0 2.9 2 ,1
[0402] [0402] The inventive and comparative polymer blends were converted into 50 µm thick monolayer cast films in a PM30 casting line (laboratory extruder of the type supplied by Plastik Maschinenbau GmbH., Germany). The equipment consists of an extruder, a cooling roller with an air knife and a coil.
[0403] [0403] A PP 3 zone thread with a diameter of 30 mm, 25D in length, 200 mm of die, 0.5 mm of die span is applied in combination with a groove die assembly with coating hanger.
[0404] [0404] The extrusion parameters were as follows:
[0405] [0405] Extruder temperature profile: 220 ° C / 240oC / 250oC / 260oC / 260 ° C (melting temperature 250 ° C; melting pressure 6.1 MPa (61 bar)) Extruder speed: 50 rpm Temperature cooling roll: 20 ° C Withdrawal speed: 10.2 m / min
[0406] [0406] The films were additionally steam sterilized.
[0407] [0407] Steam sterilization was performed on a Systec D series machine (Systec Inc., USA). The samples were heated to a heating rate of 5 ° C / min starting at 23 ° C. After being kept for 30 min at 121 ° C, they were immediately removed from the steam sterilizer and stored at room temperature until they were further processed.
[0408] [0408] In Table 5, the optical parameters (opacity before sterilization, b.s. and after sterilization, a.s.) as well as tensile modulus (DM) measured in the 50 µm cast films can be seen. Table 5 CE2 CE1 IE1 DM MPa Traction Module 915 1007 1025 Opacity b.s. % 8 9 7 Opacity a.s.% 8 10 7 Δ (Opacity)% 0 11 0
[0409] [0409] From the tables above, it can be clearly seen that the inventive polymer blends are characterized by an excellent balance between mechanical performance, optical elements and those soluble in hexane.
[0410] [0410] Compared to a random or homo ZN-PP copolymer, the following advantages can be seen: • C6 FDA: IE has the same level as ZN-PPH, but much lower than the level for the ZN random copolymer • Properties film mechanics: IE generates the same balance of stiffness ⁄ impact as with ZN-PPH, but much better than the random copolymer of ZN • Optics: Opacity is lower for IE, before and after sterilization, which is observed as a important benefit for this type of application.

权利要求:
Claims (15)
[1]
1. Polypropylene composition characterized by a mixture of (A) 85.0 to 95.0% by weight of a heterophasic propylene copolymer (HECO) comprising (A-1) 80.0 to 90.0% by weight of a matrix (M) being a propylene homopolymer (H-PP) with an MFR2 (230 ° C, 2.16 kg, ISO1133) of 0.8-10.0 g / 10 min and (A-2) 10 , 0 to 20.0% by weight of an elastomeric propylene copolymer (EPC) dispersed in said matrix (M), said heterophasic propylene copolymer which has a C2 content of the xylene cold soluble fraction (XCS) of 15 , 0 to 30.0% by weight and an intrinsic viscosity (iV); determined in accordance with DIN ISO 1628/1 in decalin at 135 ° C) of the XCS fraction of 1.2 to 2.6 dl / g (B) 5.0 to 15.0% by weight of a random propylene copolymer -hexene with a hexene content in the range of 2.0 to 10.0% by weight and an MFR2 (230 ° C, 2.16 kg, ISO1133) in a range of 1.0 to 20.0 g / 10 min and (C) optionally, an alpha-nucleating agent.
[2]
2. Polypropylene composition according to claim 1, the composition being characterized by having a total hexene content of 0.1 to 1.5% by weight and an MFR2 (230 ° C, 2.16 kg, IS01133) from 1.0 to 15.0 g / 10 min.
[3]
3. Polypropylene composition according to claim 1 or 2, the composition being characterized by having a soluble hexane value (C6FDA) of ≤ 3.0% by weight.
[4]
4. Polypropylene composition according to any one of the preceding claims, the composition being characterized by having a total hexene content of about 0.1 to 1.5% by weight and a total ethylene content of about 1, 5 to 6.2% by weight.
[5]
5. Polypropylene composition, according to any one of the preceding claims, the composition being characterized by still having (i) a Flexing Module according to ISO 178 in a range of 1000 to 1800 MPa, (ii) an impact resistance per notch of Charpy NIS + 23 ° C according to ISO 179 in the range of 25 to 75 kJ / m2 and iii) impact resistance per notch of Charpy NIS - 20 ° C according to ISO 179 1eA in the range of 1, 5 to 5.0 kJ / m2.
[6]
6. Polypropylene composition according to any one of the preceding claims, the composition being characterized by still having an opacity according to ASTM D 1003-00 measured on a 1 mm thick injection molded specimen of ≤ 50.0% .
[7]
7. Process for preparing the polypropylene composition as defined in any one of the preceding claims, the process being characterized by comprising the steps of (i) preparing a heterophasic propylene copolymer (HECO) (A) in the presence of a Ziegler-Natta catalyst (ii) preparing a random propylene-hexene copolymer (B) by polymerizing propylene and hexene in the presence of a single catalyst from the site (iii) mixing said heterophasic propylene copolymer
(HECO) (A) with the random propylene-hexene copolymer (B) to obtain a mixture of (A) and (B) and (iv) extrude said mixture to obtain the mixture of (A) and (B).
[8]
Use of a polypropylene composition as defined in claims 1 to 6, or prepared according to claim 7, characterized in that it is for the production of articles.
[9]
Use of a polypropylene composition as defined in claims 1 a, or prepared according to claim 6, characterized in that it is for the production of sterile articles.
[10]
An article characterized in that it comprises the polypropylene composition as defined in any one of claims 1 to 6, or prepared according to claim 7.
[11]
11. Article according to claim 10, the article being characterized by being an unoriented film comprising more than 90% of the blend according to any of the preceding claims 1 to 6, or prepared according to claim 7, where the film is a cast film or a blown film.
[12]
12. Film according to claim 11, the film being characterized by having undergone a sterilization treatment.
[13]
13. Film according to any one of the preceding claims 11 to 12, the film being characterized in that, a) before the sterilization treatment, it has an opacity (bs) determined in a 50 µm molten film below 10.0% and , b) after sterilization treatment at 121 ° C for 30 min, have an opacity value (as) (determined in the 50 µm cast film) below 15.0.
[14]
14. Film according to claim 13, the film being characterized by having a value ∆ (opacity) defined as ∆ (opacity) = (opacity (as) - opacity (bs)) / opacity (bs) * 100%, below 10%.
[15]
15. Film according to any one of the preceding claims 11 to 14, the film being characterized by having a machine-driven traction module (DM) determined according to ISO 527-3 in a 50 µm cast film in the range 750 to 1500 MPa.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112020003650A2|2020-09-01|polypropylene composition

---

BR112016017227B1|2021-06-29|HETEROPHASIC PROPYLENE COPOLYMER, UNORIENTED FILM, CONTAINER, AND USE OF A HETEROPHASIC PROPYLENE COPOLYMER

---

ES2699641T3|2019-02-12|Heterophasic propylene copolymer with high melting point

---

ES2833297T3|2021-06-14|Propylene Random Copolymer for Film Applications

---

KR102270300B1|2021-06-29|polypropylene composition

---

BR112015028319B1|2021-05-18|propylene copolymer, injection molded article, thin packaging and copolymer production process

---

BR112016027190B1|2021-08-17|NUCLEATE POLYPROPYLENE COMPOSITION, USE OF NUCLEATE PROPYLENE COMPOSITION, AND, MOLDED ARTICLE

---

ES2887577T3|2021-12-23|Soft polypropylene composition with improved properties

---

RU2739399C1|2020-12-23|Polypropylene composition with low shrinkage in wide range of application temperatures

---

BR112019027563A2|2020-07-07|process for preparing a polypropylene composition

---

ES2744721T3|2020-02-26|Propylene copolymer composition with improved long-term mechanical properties

---

US20180362746A1|2018-12-20|Extruded articles with improved optical properties

---

BR112020025207A2|2021-03-09|COMPOSITION OF HETEROPHASIC POLYPROPYLENE WITH ENHANCED BALANCE OF PROPERTIES

---

BR112018001472B1|2022-01-11|COMPOSITE AND MOLDED ARTICLE

---

WO2020126516A1|2020-06-25|Polypropylene composition for film sealing layer

---

BR112020017945A2|2020-12-22|POLYPROPYLENE COMPOSITION

同族专利:

---

公开号 | 公开日

---

CN111051423B|2021-07-20|

---

CN111051423A|2020-04-21|

---

PT3456776T|2020-03-09|

---

EP3456776A1|2019-03-20|

---

RU2744581C1|2021-03-11|

---

EP3456776B1|2019-12-11|

---

WO2019052820A1|2019-03-21|

---

KR102157139B1|2020-09-17|

---

US10875993B2|2020-12-29|

---

US20200317895A1|2020-10-08|

---

PL3456776T3|2020-09-21|

---

KR20200030118A|2020-03-19|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

IT1181234B|1984-11-22|1987-09-23|Giovanni Zago|AUTOMATIC CLEANING SYSTEMS FOR VIDEO RECORDERS AND CLEANING BOXES SO MADE|

---

FR2603996A1|1986-09-17|1988-03-18|Primat Didier|OBJECTIVE-FREE OPTICAL READING DEVICE|

---

FI86867C|1990-12-28|1992-10-26|Neste Oy|FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN|

---

FI111848B|1997-06-24|2003-09-30|Borealis Tech Oy|Process and equipment for the preparation of homopolymers and copolymers of propylene|

---

FI111846B|1997-06-24|2003-09-30|Borealis Tech Oy|Process and apparatus for preparing mixtures of polypropylene|

---

FI111845B|1997-06-24|2003-09-30|Borealis Tech Oy|Process for producing propylene homopolymers and polymers with modified impact strength|

---

FI111847B|1997-06-24|2003-09-30|Borealis Tech Oy|A process for the preparation of copolymers of propylene|

---

FI980342A0|1997-11-07|1998-02-13|Borealis As|Polymerroer och -roerkopplingar|

---

FI974175A|1997-11-07|1999-05-08|Borealis As|Process for producing polypropylene|

---

IT1302123B1|1998-07-31|2000-07-31|Ennio Truono|AUTOMATIC CLEANING DEVICE FOR REFLECTORS ARRANGED IN LONG AND HIGHWAYS|

---

FI991057A0|1999-05-07|1999-05-07|Borealis As|High stiffness propylene polymers and process for their preparation|

---

EP1313746B1|2000-06-30|2005-07-27|ExxonMobil Chemical Patents Inc.|Metallocenes with a bridged 4-phenyl-indenyl-ligand for olefin polymerisation|

---

AT328912T|2001-06-20|2006-06-15|Borealis Tech Oy|Preparation of a catalyst component for olefin polymerisation|

---

BR0215768A|2002-06-25|2005-03-15|Borealis Tech Oy|Process for the preparation of a biomodal rubber polypropylene polymer composition, polymer product, use of polymer, and molded article|

---

EP1403292B1|2002-09-30|2016-04-13|Borealis Polymers Oy|Process for preparing an olefin polymerisation catalyst component with improved high temperature activity|

---

AU2003288090A1|2002-12-18|2004-07-09|Borealis Technology Oy|Flat film for thermoforming|

---

EP1484343A1|2003-06-06|2004-12-08|Universiteit Twente|Process for the catalytic polymerization of olefins, a reactor system and its use in the same process|

---

EP1669403A1|2004-12-07|2006-06-14|Borealis Technology OY|Novel propylene polymer blends|

---

ES2269021T5|2005-05-12|2012-06-27|Borealis Technology Oy|Transparent and easily breakable laminar element|

---

EP2004664B1|2006-04-12|2016-12-14|Basell Polyolefine GmbH|Metallocene compounds|

---

DK1849826T3|2006-04-26|2013-04-22|Borealis Tech Oy|Transparent polyolefin tooth that has been subjected to heat treatment|

---

ES2594859T3|2006-05-31|2016-12-23|Borealis Technology Oy|Catalyst with Al-alkoxy component|

---

EP2094780B1|2006-12-22|2010-10-20|Basell Poliolefine Italia S.R.L.|Polyolefin composition for pipe systems and sheets|

---

EP2022824A1|2007-08-08|2009-02-11|Borealis Technology Oy|Sterilisable and Tough Impact Polypropylene Composition|

---

EP2355927B1|2008-11-07|2015-03-04|Borealis AG|Solid catalyst composition|

---

ES2619729T3|2008-11-07|2017-06-26|Borealis Ag|Solid catalyst composition|

---

EP2361267B1|2008-11-07|2015-03-04|Borealis AG|Process to prepare a solid catalyst composition|

---

EP2275485B1|2009-06-22|2011-06-08|Borealis AG|Heterophasic polypropylene copolymer composition|

---

US9029284B2|2009-12-22|2015-05-12|Borealis Ag|Catalysts|

---

EP2368937A1|2010-03-22|2011-09-28|Borealis AG|Heterophasic polypropylene with excellent creep performance|

---

JP5785609B2|2010-04-28|2015-09-30|ボレアリス エージー|catalyst|

---

WO2011160953A1|2010-06-23|2011-12-29|Basell Poliolefine Italia Srl|Polyolefin composition for pipe systems and sheets|

---

BR112012032548B1|2010-06-23|2020-10-27|Basell Poliolefine Italia S.R.L.|polyolefin composition, and sheets and piping systems comprising such a polyolefin composition|

---

EP2402353B1|2010-07-01|2018-04-25|Borealis AG|Group 4 metallocenes useful as catalysts for the polymerization of olefins|

---

ES2525554T3|2010-07-13|2014-12-26|Borealis Ag|Catalyst component|

---

EP2655431A1|2010-12-22|2013-10-30|Borealis AG|Bridged metallocene catalysts|

---

ES2643158T3|2011-07-08|2017-11-21|Borealis Ag|Catalysts|

---

EP2610271B1|2011-12-30|2019-03-20|Borealis AG|Preparation of phthalate free ZN PP catalysts|

---

EP2610272B1|2011-12-30|2017-05-10|Borealis AG|Catalyst component|

---

EP3033389B1|2013-08-14|2017-10-11|Borealis AG|Propylene composition with improved impact resistance at low temperature|

---

RU2693453C2|2014-04-17|2019-07-03|Бореалис Аг|Improved catalyst system for producing polyethylene copolymers in high-temperature solution polymerisation method|

---

EP2960256B1|2014-06-27|2018-04-25|Borealis AG|Catalyst component for the preparation of nucleated polyolefins|JP2020511423A|2016-12-29|2020-04-16|ボレアリス エージー|catalyst|

---

US20210002397A1|2018-05-09|2021-01-07|Borealis Ag|Process for preparing propylene copolymers comprising c4-c12-apha olefin comonomer units|

---

EP3733720A1|2019-04-30|2020-11-04|Borealis AG|Polypropylene-polyethylene composition with improved toughness|

---

EP3733764A1|2019-04-30|2020-11-04|Borealis AG|Polypropylene-polyethylene composition with improved toughness|

---

KR20220016163A|2019-05-29|2022-02-08|보레알리스 아게|Improved process for making catalyst systems|

---

WO2020245369A1|2019-06-07|2020-12-10|Borealis Ag|Heterophasic propylene polymer composition with high toughness and stiffness|

---

CN110438814A|2019-07-26|2019-11-12|温多利遮阳材料（德州）股份有限公司|It is a kind of for improving the Textilene fabric coating of weatherability|

---

WO2021053154A1|2019-09-20|2021-03-25|Borealis Ag|Heterophasic propylene polymer composition with improved property profile|

---

EP3812404A1|2019-10-23|2021-04-28|Borealis AG|Heterophasic polypropylene composition having improved mechanical properties|

---

EP3825357A1|2019-11-25|2021-05-26|Borealis AG|Propylene composition for foaming with improved mechanical properties|

---

EP3912794A1|2020-05-18|2021-11-24|Borealis AG|Multilayer film with improved properties|

---

EP3950739A1|2020-08-05|2022-02-09|Borealis AG|Polypropylene sheet|

法律状态:
2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

---

申请号 | 申请日 | 专利标题

---

EP17190820.5|2017-09-13|

---

EP17190820.5A|EP3456776B1|2017-09-13|2017-09-13|Polypropylene composition|

---

PCT/EP2018/073308|WO2019052820A1|2017-09-13|2018-08-30|Polypropylene composition|

---