Propylene / ethylene / 1-butene terpolymer composition with multimodal base polymer

Abstract

A propylene / ethylene / 1-butene terpolymer composition comprising a) a multimodal base polymer (TP) in an amount of from 95 to 99.9 wt%, relative to the total weight of the propylene / ethylene / 1-butene terpolymer composition, said multimodal base polymer (TP) having the following properties: i. A melt flow rate (MFR2), determined according to ISO 1133 at 230 DEG C and a load of 2.16 kg, in the range of from 3 to 12 g / 10 min; ii. A content of 2, 1-region defects, determined according to quantitative 13C-NMR spectroscopy, in the range of 0.1 to 1.0 mol%; iii. An ethylene content (C2) determined according to the 13C-NMR spectrum in the range of 1.0 to 4.0 mol%; and iv. A 1-butene content (C4), determined according to 13C-NMR spectroscopy, in the range of 3.0 to 10.0 mol%; v. A xylene cold soluble content (XCS), determined according to ISO 16152, in the range of 0 to 3.0 wt%; wherein the multimodal base polymer (TP) comprises: a1) from 50 wt% to 80 wt%, relative to the total weight of the multimodal base polymer (TP), of a first terpolymer fraction (TP1) having a melt flow rate (MFR2), determined according to ISO 1133 at 230 DEG C and a load of 2.16 kg, in the range of from 1 to 10 g / 10 min; and a2) from 20 wt% to 50 wt%, relative to the total weight of the multimodal base polymer (TP), of a second terpolymer fraction (TP2) having a melt flow rate (MFR2), determined according to ISO 1133 at 230 DEG C and a load of 2.16 kg, in the range of from 5 to 30 g / 10 min; b) 0.1 to 5 wt%, relative to the total weight of the propylene / ethylene / 1-butene terpolymer composition, of an additive selected from the group consisting solely of antioxidants, anti-blocking agents, UV stabilizers, scratch resistances, release agents, lubricants, antistatic agents, pigments and mixtures thereof; wherein the propylene / ethylene / 1-butene terpolymer is substantially free of an acid scavenger.

Description

Technical Field

[0001] The present invention relates to a propylene / ethylene / 1-butene terpolymer composition, and a film, more particularly a cast film, comprising the propylene / ethylene / 1-butene composition. Background Art

[0002] Packaging films based on propylene / ethylene / 1-butene terpolymers are currently used in multilayer structures, where each layer serves a different purpose. Films made from propylene / ethylene / 1-butene terpolymers have been shown to be suitable as sealant layers in such multilayer structures, for example as biaxially oriented polypropylene (BOPP) or cast films.

[0003] Before the film is produced, different types of additives are added to the base polymer to obtain the desired properties and make them suitable for the final application. Acid scavengers or antacids are one of the most commonly used additives in the polymer industry ("Holzner, A. and Chmil, K. "Acid Scavengers" in Plastics Additives Handbook, 6th edition, pages 515-516, Chapter 4"). They are included in the additive mixture to reduce the acidity of the polymer matrix, which may occur due to catalyst residues (e.g., from Ziegler-Natta catalysts), or to indirectly affect the crystallization behavior, or sometimes as a slip agent (stearate salts exhibit this behavior). However, a common problem in polymer design is that sometimes they interact with antioxidants from the additive mixture, resulting in stability fluctuations, which then result in uneven films with different properties distributed along the thickness. In addition, when used as acid scavengers, stearates generally tend to migrate to the surface, making them less attractive for packaging applications.

[0004] US 6,388,040 B1 relates to metallocene-catalyzed ethylene / propylene / C4-C 20 An alpha-olefin terpolymer wherein the total comonomer content is in the range of 0.01 mol% to 15 mol%, and the amount of 2,1-propylene and 1,3-propylene units is in the range of 0 to 1 mol%. The terpolymers disclosed herein are also characterized in that the weight average molecular weight (Mw) is in the range of 40,000 to 1,000,000, the amount of the component eluting in o-dichlorobenzene at a temperature not higher than 40°C is not more than 10 wt% of the total weight of the terpolymer, and the amount of the component eluting in o-dichlorobenzene within the range of ±10°C of the elution peak temperature is not less than 75 wt%, based on the weight of the component eluting at a temperature higher than 0°C. However, the terpolymers of US 6,388,040 B1 are produced in a single reactor, which means that they are not multimodal.

[0005] EP 2 173 471 B1 relates to a process for producing propylene terpolymers having ethylene and C4-C8 alpha-olefin comonomers and propylene terpolymers produced by such a process. The terpolymers of EP 2 173 471 B1 contain at least 8 wt% of comonomers relative to the total weight of the terpolymer. However, the disclosed terpolymers are produced using a Ziegler-Natta catalyst.

[0006] US 7794845 B2 discloses a multilayer polypropylene film having a base layer A, a surface layer B and a metal layer M deposited on the surface layer B, wherein the surface layer B is made of a polypropylene copolymer having an amount of C4-C 10 α-Olefins The base polymer used for the surface layer B is mixed with an acid scavenger (hydrotalcite in the present embodiment and calcium stearate in the comparative example) and other additives.

[0007] It is therefore an object of the present invention to provide a polypropylene terpolymer with good processing properties suitable for packaging applications. Such a terpolymer should also be suitable for the manufacture of films having good sealing properties in terms of low seal initiation temperature (SIT) and high hot tack (HTF), good optical properties in terms of low haze and high clarity, good mechanical properties, uniform thickness distribution on the film, and stability in terms of extended oxygen induction time (OIT). A balance of all properties is intended to be obtained with the polypropylene terpolymer according to the present invention without the need to include acid scavengers in the formulation.

[0008] The present invention achieves the above objectives with the propylene / ethylene / 1-butene terpolymers described herein having a multimodal polymer design with certain levels of 2,1-regiodefects and comonomer content. Summary of the invention

[0009] The present invention relates to a propylene / ethylene / 1-butene terpolymer composition comprising

[0010] a) a multimodal base polymer (TP) in an amount of 95 to 99.9 wt% relative to the total weight of the propylene / ethylene / 1-butene terpolymer composition, said multimodal base polymer (TP) having the following properties:

[0011] i. a melt flow rate (MFR2) measured according to ISO 1133 at 230°C and 2.16 kg load in the range of 3 to 12 g / 10 min;

[0012] ii. In the range of 0.1 to 1.0 mol% according to the quantitative 13The content of 2,1-regio defects determined by C-NMR spectroscopy;

[0013] iii. In the range of 1.0 to 4.0 mol% according to 13 Ethylene content (C2) determined by C-NMR spectroscopy;

[0014] as well as

[0015] iv. In the range of 3.0 to 10.0 mol% according to 13 1-Butene content (C4) determined by C-NMR spectroscopy;

[0016] v. a xylene cold soluble content (XCS) determined according to ISO 16152 in the range of 0 to 3.0 wt%;

[0017] wherein the multimodal base polymer (TP) comprises:

[0018] a1) 50 to 80 wt% of a first terpolymer fraction (TP1), relative to the total weight of the multimodal base polymer (TP), having a melt flow rate (MFR2) in the range of 1 to 10 g / 10 min, measured according to ISO 1133 at 230 °C and 2.16 kg load; and

[0019] a2) 20 to 50 wt% of a second terpolymer fraction (TP2), relative to the total weight of the multimodal base polymer (TP), having a melt flow rate (MFR2) in the range of 5 to 30 g / 10 min, measured according to ISO 1133 at 230 °C and 2.16 kg load;

[0020] b) 0.1 to 5 wt% of an additive, relative to the total weight of the propylene / ethylene / 1-butene terpolymer composition, selected from the group consisting solely of antioxidants, antiblocking agents, UV stabilizers, antiscratch agents, mold release agents, lubricants, antistatic agents, pigments, and mixtures thereof;

[0021] The propylene / ethylene / 1-butene terpolymer contains substantially no acid scavenger.

[0022] The present invention also relates to films, more preferably cast films, comprising the propylene / ethylene / 1-butene terpolymer composition disclosed herein. DETAILED DESCRIPTION

[0023] All terms used herein should be understood to have the ordinary meaning known to those skilled in the art. For greater precision, the following terms will have the meanings described below.

[0024] Propylene terpolymers are copolymers of propylene monomer units, wherein the copolymer is selected from ethylene and C4-C8 alpha-olefins. Terpolymers generally contain two or more different types of comonomers.

[0025] A multimodal polymer is a polymer having two or more fractions that differ from each other in at least one property, such as weight average molecular weight or comonomer content. The molecular weight distribution curve (a plot of polymer weight fraction against molecular weight) of such a multimodal polymer exhibits two or more maxima, depending on the morphology, or such a curve is significantly broadened compared to the curves for the individual fractions. When a polymer comprises two different fractions, it is called "bimodal".

[0026] 1) Propylene / ethylene / 1-butene terpolymer composition

[0027] The propylene / ethylene / 1-butene terpolymer composition according to the present invention comprises the multimodal base polymer (TP) in an amount of 95 to 99.9 wt% relative to the total weight of the propylene / ethylene / 1-butene terpolymer composition and the additives in an amount of 0.1 to 5 wt% relative to the total weight of the propylene / ethylene / 1-butene terpolymer composition.

[0028] The propylene / ethylene / 1-butene terpolymer composition preferably has a melt flow rate (MFR2) measured according to ISO 1133 at 230°C and 2.16 kg load of 1 to 20 g / 10 min, more preferably 5 to 15 g / 10 min, most preferably 8 to 12 g / 10 min.

[0029] The propylene / ethylene / 1-butene terpolymer composition preferably has a crystallization enthalpy measured according to DSC analysis of 50 to 70 J / g, more preferably 55 to 68 J / g, most preferably 60 to 65 J / g.

[0030] The propylene / ethylene / 1-butene terpolymer composition preferably has a crystallization temperature as measured by DSC analysis of 70 to 95°C, more preferably 75 to 92°C, most preferably 80 to 90°C.

[0031] The propylene / ethylene / 1-butene terpolymer composition preferably has a heat of fusion as measured by DSC analysis of 55 to 75 J / g, more preferably 60 to 73 J / g, most preferably 62 to 69 J / g.

[0032] The propylene / ethylene / 1-butene terpolymer composition preferably has a melting point as measured by DSC analysis in the range of 110 to 135°C, more preferably 115 to 130°C, most preferably 120 to 128°C.

[0033] The propylene / ethylene / 1-butene terpolymer composition preferably has an oxygen induction time measured at 180° C. according to ISO 11357-6 in the range of 10 to 30 minutes, more preferably 15 to 28 minutes, most preferably 20 to 26 minutes.

[0034] The propylene / ethylene / 1-butene terpolymer composition preferably has an oxygen induction time measured at 190° C. according to ISO 11357-6 in the range of 3 to 20 minutes, more preferably 5 to 15 minutes, most preferably 7 to 13 minutes.

[0035] Multimodal base polymer (TP)

[0036] The amount of multimodal base polymer (TP) according to this invention is typically 95 to 99.9 wt%, preferably 97 to 99.8 wt%, relative to the total weight of the propylene / ethylene / 1-butene terpolymer composition.

[0037] The multimodal base polymer (TP) comprises at least two parts:

[0038] - a first terpolymer part (TP1), and

[0039] - Second terpolymer part (TP2).

[0040] In a preferred embodiment the multimodal base polymer (TP) according to the invention consists of a first terpolymer fraction (TP1) and a second terpolymer fraction (TP2). In other words, it is preferred that the multimodal base polymer (TP) is bimodal.

[0041] The multimodal base polymer (TP) has a melt flow rate (MFR2) measured according to ISO 1133 at 230°C and 2.16 kg load of 3 to 12 g / 10 min, most preferably 5 to 9 g / 10 min.

[0042] The multimodal base polymer (TP) has a quantitative 13 The content of 2,1-regio defects was determined by C-NMR spectroscopy.

[0043] The multimodal base polymer (TP) has a molecular weight in the range of 1.0 to 4.0 mol%, preferably 1.5 to 3.5 mol%, more preferably 2.0 to 3.0 mol%, most preferably 2.5 to 2.8 mol%. 13 Ethylene content (C2) determined by C-NMR spectroscopy.

[0044] The multimodal base polymer (TP) has a molecular weight in the range of 3.0 to 10.0 mol%, preferably 3.5 to 9.0 mol%, more preferably 4.0 to 8.0 mol%, most preferably 4.5 to 7.0 mol%. 13 1-Butene content (C4) determined by C-NMR spectroscopy.

[0045] The multimodal base polymer (TP) has a xylene cold soluble content (XCS) determined according to ISO 16152 in the range of 0 to 3.0 wt%, preferably 1.0 to 2.8 wt%, more preferably 1.5 to 2.5 wt%.

[0046] The multimodal base polymer (TP) preferably has an ethylene / 1-butene ratio in the range of 0.1 to 0.9, more preferably 0.2 to 0.7, most preferably 0.3 to 0.6, wherein the ethylene / 1-butene ratio is calculated by dividing the amount of ethylene in mol% by the amount of 1-butene in mol%.

[0047] First terpolymer part (TP1)

[0048] The amount of the first terpolymer fraction (TP1) is typically 50-80 wt%, preferably 55 to 75 wt%, most preferably 58 to 70 wt%, relative to the total weight of the multimodal base polymer (TP).

[0049] The first terpolymer part (TP1) has a melt flow rate (MFR2) determined according to ISO 1133 at 230°C and 2.16 kg load in the range of 1 to 10 g / 10 min, preferably 2 to 8 g / 10 min, most preferably 3 to 6 g / 10 min.

[0050] The first terpolymer fraction (TP1) preferably has a ratio according to 13 Ethylene content (C2) determined by C-NMR spectroscopy.

[0051] The first terpolymer fraction (TP1) preferably has a ratio according to 13 1-Butene content (C4) determined by C-NMR spectroscopy.

[0052] The first terpolymer fraction (TP1) preferably has a xylene cold soluble content (XCS) determined according to ISO 16152 in the range of 0.1 to 5.0 wt%, more preferably 0.3 to 3.0 wt%, most preferably 0.5 to 1.0 wt%.

[0053] Second terpolymer part (TP2)

[0054] The amount of the second terpolymer fraction (TP2) is typically from 20 to 50 wt%, preferably from 25 to 45 wt%, most preferably from 30 to 42 wt%, relative to the total weight of the multimodal base polymer (TP).

[0055] The second terpolymer fraction (TP2) has a melt flow rate (MFR2) determined according to ISO 1133 at 230°C and 2.16 kg load in the range of 5 to 30 g / 10 min, preferably 10 to 27 g / 10 min, most preferably 15 to 23 g / 10 min.

[0056] The second terpolymer fraction (TP2) preferably has a ratio according to 13 Ethylene content (C2) determined by C-NMR spectroscopy.

[0057] The second terpolymer fraction (TP2) preferably has a ratio according to 13 1-Butene content (C4) determined by C-NMR spectroscopy.

[0058] additive

[0059] The propylene / ethylene / 1-butene terpolymer composition further comprises 0.1 to 5 wt%, preferably 0.15 to 3 wt% of additives relative to the total weight of the propylene / ethylene / 1-butene terpolymer composition.

[0060] The additives are selected from the group consisting of antioxidants, antiblocking agents, UV stabilizers, antiscratch agents, release agents, lubricants, antistatic agents, pigments and mixtures thereof. Such additives are well known and well described, for example in Hans Zweifel's "Plastic Additives Handbook", pages 871 to 873, 5th edition, 2001.

[0061] The propylene / ethylene / 1-butene terpolymer is substantially free of acid scavengers. Acid scavengers or antacids are one of the most commonly used additives in the polymer industry ("Holzner, A. and Chmil, K. Plastics Additives Handbook, 6th edition, Chapter 4 "Acid Scavengers" on pages 515-516) and are used to reduce the acidity of the polymer matrix. The presence of acid scavengers and other additives, especially antioxidants, often leads to stability fluctuations because it interacts with the antioxidant. Such fluctuations can result in non-uniform films with varying properties along the thickness distribution. Examples of acid scavengers include calcium stearate (commercially available from Baerlocher GmbH as "Ceasit", CAS No.: 1592-23-0), zinc stearate (commercially available from Baelocher GmbH as "Zincum", CAS No.: 557-05-1), magnesium oxide (CAS No.: 1309-48-4), synthetic hydrotalcite (SHT, commercially available from Kisuma / Kyowa as "DHT 4A" or "DHT-4C", CAS No.: 11097-59-9).

[0062] Then, preferably the additive is selected from the group consisting only of one or more antioxidants and antiblocking agents.

[0063] The antioxidant may be any antioxidant known to those skilled in the art. For example, it may be selected from the group consisting of:

[0064] - sterically hindered phenols ("Phenolic AO"), for example 2,6-di-tert-butyl-4-methylphenol (commercially available as "Ionol CP" from Raschig, CAS No. 128-37-0), 3-(3',5'-di-tert-butyl-4-hydroxyphenyl)pentaerythritol tetrapropionate (commercially available as "Irganox 1010" from BASF or as "Kinox

[0065] 10G", CAS No. 6683-19-8), 3-(3',5'-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl (commercially available as "Irganox 1076" from BASF, CAS No. 2082-79-3), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)benzene (commercially available as "Irganox 1330" from BASF, CAS No. 1709-70-2), calcium (3,5-di-tert-butyl-4-hydroxybenzyl monoethylphosphonate) (commercially available as "Irganox 1425" from BASF, CAS No. 65140-91-2), 1,3,5-tris(3',5'-di-tert-butyl-4-hydroxybenzyl) isocyanurate (commercially available as "Irganox 3114" is commercially available, CAS number:

[0066] 27676-62-6);

[0067] - phosphorus-based, for example tris(2,4-di-tert-butylbenzene)phosphite (marketed by BASF as "Irgafos 168FF"

[0068] Commercially available, CAS number: 31570-04-4), tetrakis-(2,4-di-tert-butylphenyl)-4,4'-biphenylene-diphosphonite (commercially available as "Hostanox P-EPQ" by Clariant, CAS number: 38613-77-3);

[0069] - alkyl radical scavengers;

[0070] - sulfur-based, for example distearyl thiodipropionate (commercially available as "Irganox PS-802" from BASF, CAS No.: 693-36-7), didodecyl thiodipropionate (commercially available as "Irganox PS-800" from BASF, CAS No.: 123-28-4);

[0071] - aromatic amines;

[0072] -Hindered amine stabilizer

[0073] and mixtures thereof.

[0074] The anti-blocking agent may be any anti-blocking agent known to those skilled in the art. For example, it may be selected from the group consisting of natural silica, synthetic silica (commercially available as "Gasil AB 725" by PQ Corporation, CAS No. 7631-86-9), silicates such as sodium calcium aluminosilicate, hydrates (commercially available as "Siltom JC-30" by Mizusawa Ind. Chem.), and mixtures thereof.

[0075] The propylene / ethylene / 1-butene terpolymer composition preferably has an antioxidant level of less than 0.3 wt%, more preferably 0.05 to 0.25 wt%, most preferably 0.08 to 0.2 wt% relative to the total weight of the propylene / ethylene / 1-butene terpolymer composition.

[0076] 2) Production of multimodal propylene / ethylene / 1-butene terpolymer compositions

[0077] The multimodal propylene / ethylene / 1-butene terpolymer composition is preferably produced according to a process having the following steps:

[0078] a) mixing the multimodal base polymer (TP) as described herein and additives in an intensive mixer, and

[0079] b) The above ingredients were mixed in a co-rotating twin screw extruder.

[0080] Process for the preparation of a multimodal base polymer (TP)

[0081] The multimodal base polymer (TP) according to the present invention is polymerized according to a process having the following steps:

[0082] a) polymerizing propylene, ethylene and 1-butene comonomer units in a first reactor in the presence of a single site catalyst (SSc) to produce a first terpolymer fraction (TP1),

[0083] b) transferring the product of the first reactor to a second reactor,

[0084] c) polymerizing propylene, ethylene and 1-butene comonomer units in a second reactor in the presence of the above single site catalyst (SSc) to produce a mixture comprising a first terpolymer fraction (TP1) and a second terpolymer fraction (TP2); and

[0085] d) removing said mixture comprising the first terpolymer fraction (TP1) and the second terpolymer fraction (TP2).

[0086] In a preferred embodiment, as given in step a), a prepolymerization is carried out prior to the polymerization. In this optional step, propylene, ethylene and 1-butene are prepolymerized in the presence of a single site catalyst (SSc).

[0087] The first reactor is preferably a slurry reactor, more preferably a loop reactor, and the second reactor is preferably a gas phase reactor. This process involving multi-step polymerization was developed by Borealis A / S in Denmark (called technology) and is described in detail in the patent literature, for example in WO92 / 12182 or EP-A-0887379.

[0088] The operating temperature of the first reactor is preferably in the range of 55 to 85°C, while the pressure is preferably in the range of 20 to 80. In the second reactor, on the other hand, the temperature is preferably in the range of 70 to 100°C, while the pressure is preferably in the range of 10 to 50 bar.

[0089] It is also preferred to use hydrogen as a chain control agent in at least one or both reactors and then control the molecular weight of the fractions produced in the above reactors, which results in control of the melt flow rate.

[0090] catalyst

[0091] The single site catalyst (SSc) according to the present invention can be any supported metallocene catalyst suitable for producing isotactic polypropylene. Preferably, the single site catalyst (SSc) comprises a metallocene complex, a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst, and a silica support.

[0092] In particular, it is preferred that the single site catalyst (SSc) comprises

[0093] (i) Metallocene complex of general formula (I)

[0094]

[0095] wherein each X is independently a σ-donor ligand, L is a divalent linker selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or a C1-C ... 20 - a hydrocarbon group, or optionally two R' groups taken together to form a ring,

[0096] Each R 1 are independently the same or may be different and are hydrogen, linear or branched C1-C6 alkyl, C 7-20 Arylalkyl, C 7-20 Alkyl aryl or C 6-20 Aryl or OY group, where Y is C 1-10 The hydrocarbon group and optionally two adjacent R1 groups may be part of a ring including the phenyl carbon to which they are bonded, each R2 is independently the same or may be different and is CH2-R 8 Group, where R 8 It is H or straight chain or branched chain C 1-6 Alkyl, C 3-8 Cycloalkyl, C 6-10 Aryl,

[0097] R 3It is a straight chain or branched C1-C6 alkyl group, C 7-20 Arylalkyl, C 7-20 -alkylaryl or C6-C 20 Aryl, R 4 is C(R 9 )3 groups, wherein R 9 is a linear or branched C1-C6 alkyl group,

[0098] R 5 is hydrogen or an aliphatic C1-C12 radical optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table 20 Hydrocarbon; R 6 is hydrogen or an aliphatic C1-C12 radical optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table 20 Hydrocarbyl; or

[0099] R 5 and R 6 can be joined together to form a 5-membered saturated carbocyclic ring, which is optionally substituted by n groups R 10 substitution, n is 0 to 4;

[0100] Each R 10 are the same or different and can be C1-C 20 A hydrocarbon group or a C1-C ... 20 Hydrocarbon;

[0101] R 7 is H or optionally substituted by 1 to 3 groups R 11 Substituted straight-chain or branched C1-C6-alkyl or aryl or heteroaryl having 6 to 20 carbon atoms, each R 11 are independently the same or may be different and are hydrogen, linear or branched C1-C6 alkyl, C 7-20 Arylalkyl, C 7-20 Alkyl aryl or C 6-20 Aryl or OY group, where Y is C 1-10 Hydrocarbon,

[0102] (ii) a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst, and

[0103] (iii) Silica support.

[0104] The term "σ-donor ligand" is well known to those skilled in the art, i.e., a group that binds to a metal via a σ bond. Thus, the anionic ligand "X" can independently be a halogen or selected from the group consisting of R', OR', SiR'3, OSiR'3, OSO2CF3, OCOR', SR', NR'2 or PR'2, wherein R' is independently hydrogen, a linear or branched, cyclic or acyclic C1 to C20 Alkyl, C2 to C 20 Alkenyl, C2 to C 20 Alkynyl, C3 to C 12 Cycloalkyl, C6 to C 20 Aryl, C7 to C 20 Arylalkyl, C7 to C 20 Alkyl aryl, C8 to C 20 Arylalkenyl, wherein the R' group may optionally contain one or more heteroatoms belonging to Groups 14 to 16. In a preferred embodiment, the anionic ligands "X" are the same, or are halogen, such as Cl, or are methyl or benzyl.

[0105] Preferred monovalent anionic ligands are halogens, especially chloride (Cl).

[0106] Preferred complexes of metallocene catalysts include:

[0107] Racemic-dimethylsilanediylbis[2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene

[0108] -1-yl] zirconium dichloride,

[0109] Racemic-trans-dimethylsilanediyl[2-methyl-4-(4′-tert-butylphenyl)-inden-1-yl][2-methyl-4-(4′-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0110] Racemic-trans-dimethylsilanediyl[2-methyl-4-(4′-tert-butylphenyl)-inden-1-yl][2-methyl-4-phenyl

[0111] -5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0112] Racemic-trans-dimethylsilanediyl[2-methyl-4-(3',5'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride,

[0113] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-(4′-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacene

[0114] -1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0115] Racemic-trans dimethylsilanediyl [2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl] [2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride, racemic-trans dimethylsilanediyl [2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl] [2-methyl-4-(3',5'-5-di-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride.

[0116] Particularly preferred is rac-trans-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride.

[0117] The ligands required to form the complex and the catalyst of the present invention can be synthesized by any method, and a skilled organic chemist can design various synthesis schemes to make the necessary ligand materials. For example, WO2007 / 116034 discloses the necessary chemical substances. Synthesis schemes can also be generally found in WO 2002 / 02576, WO 2011 / 135004, WO 2012 / 084961, WO2012 / 001052, WO 2011 / 076780, WO 2015 / 158790 and WO 2018 / 122134. With particular reference to WO2019 / 179959, the most preferred catalyst of the present invention is described.

[0118] Catalyst

[0119] In order to form an active catalytic species, it is usually necessary to use a promoter as is known in the art.

[0120] According to the present invention, a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst is used in combination with the metallocene catalyst complex defined above.

[0121] The aluminoxane cocatalyst may be one of formula (II):

[0122]

[0123] wherein n is generally 6 to 20 and R has the following meanings.

[0124] Aluminoxanes are formed upon partial hydrolysis of organoaluminum compounds, such as those of the formula AlR3, AlR2Y, and Al2R3Y3, wherein R can be, for example, C1-C 10Alkyl, preferably C1-C5 alkyl, or C3-C 10 Cycloalkyl, C7-C 12 Arylalkyl or alkylaryl and / or phenyl or naphthyl, and wherein Y can be hydrogen, halogen, preferably chlorine or bromine, or C1-C 10 The alkoxy group is preferably a methoxy group or an ethoxy group. The oxygen-containing aluminoxane obtained is usually not a pure compound but a mixture of oligomers of the formula (II).

[0125] A preferred aluminoxane is methylaluminoxane (MAO).Since the aluminoxanes used as cocatalysts according to the invention are not pure compounds due to the way they are prepared, the molar concentrations of the aluminoxane solutions given below are based on their aluminum content.

[0126] According to the present invention, a boron-containing cocatalyst may also be used instead of the aluminoxane cocatalyst, or the aluminoxane cocatalyst may be used in combination with the boron-containing cocatalyst.

[0127] Those skilled in the art will appreciate that when a boron-based cocatalyst is used, the complex is usually pre-alkylated by reaction with an alkyl aluminum compound such as TIBA. This process is well known and any suitable aluminum alkyl may be used, such as Al(C1-C6 alkyl). Preferred aluminum alkyl compounds are triethylaluminum, triisobutylaluminum, triisohexylaluminum, tri-n-octylaluminum and triisooctylaluminum.

[0128] Alternatively, when a borate cocatalyst is used, the metallocene catalyst complex is in its alkylated form, for example a dimethyl or dibenzyl metallocene catalyst complex may be used.

[0129] Boron-based cocatalysts of interest include those of formula (III)

[0130] BY3(III)

[0131] wherein Y is the same or different and is a hydrogen atom, an alkyl group of 1 to about 20 carbon atoms, an aryl group of 6 to about 15 carbon atoms, an alkylaryl group, an arylalkyl group, a haloalkyl group, or a haloaryl group (each having 1 to 10 carbon atoms in the alkyl group, 6 to 20 carbon atoms in the aryl group, or fluorine, chlorine, bromine, or iodine). Preferred options are trifluoroborane, triphenylborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(pentafluorophenyl)borane, tris(tolyl)borane, tris(3,5-dimethylphenyl)borane, tris(3,5-difluorophenyl)borane, and / or

[0132] or tris(3,4,5-trifluorophenyl)borane.

[0133] Tris(pentafluorophenyl)borane is particularly preferred.

[0134] However, preference is given to using borates, i.e. compounds containing borate 3+ ions. Such ionic promoters preferably contain non-coordinating anions, such as tetrakis(pentafluorophenyl)borate and tetraphenylborate. Suitable counterions are protonated amines or aniline derivatives, such as methylammonium, aniline, dimethylammonium, diethylammonium, N-methylaniline, diphenylammonium, N,N-dimethylaniline, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridine, p-bromo-N,N-dimethylaniline or p-nitro-N,N-dimethylaniline.

[0135] Surprisingly, it has been found that certain boron co-catalysts are particularly preferred. Therefore, preferred borates used in the present invention contain trityl ions. Therefore, it is particularly preferred to use N,N-dimethylammonium-tetrakis(pentafluorophenyl)borate and Ph3CB(PhF5)4 and the like.

[0136] Preferred cocatalysts are aluminoxanes, more preferably methylaluminoxane, combinations of aluminoxanes with aluminum alkyls, boron or borate cocatalysts, and combinations of aluminoxanes and boron-based cocatalysts.

[0137] The catalyst system of the present invention is used in a supported form. The particle support material used is silicon dioxide or a mixed oxide, such as silicon dioxide-alumina, in particular silicon dioxide. Preferably, a silicon dioxide support is used. Those skilled in the art know the steps required for supporting the metallocene catalyst.

[0138] In a preferred embodiment, the catalyst system corresponds to ICS3 of WO 2020 / 239598 A1.

[0139] 3) Membrane

[0140] The present invention also relates to a film comprising a propylene / ethylene / 1-terpolymer composition, preferably in an amount of at least 80 wt%, more preferably in an amount of at least 90 wt%, more preferably in an amount of at least 95 wt%. Most preferably, the film consists of a propylene / ethylene / 1-terpolymer composition.

[0141] The film according to the present invention is preferably a cast film. The thickness of the cast film is preferably in the range of 5 to 100 μm, more preferably 10 to 80 μm, most preferably 20 to 60 μm.

[0142] The film, more preferably cast film, preferably has a sealing initiation temperature (SIT) measured according to the method described in the "Measurement Methods" section herein for 50 μm cast film of preferably 100 to 115°C, more preferably 101 to 110°C, most preferably 102 to 108°C.

[0143] The film, more preferably cast film, preferably has a hot tack measured according to ASTM F1921-12 method B on 50 μm cast film in the range of 1.0 to 5.0 N, more preferably 1.5 to 4.0 N, most preferably 2.4 to 3.5 N.

[0144] The film, more preferably a cast film, preferably has a haze value measured according to ASTM D1003 on 50 μm cast film in the range of 0 to 2.0%, more preferably 0.1 to 1.0%, most preferably 0.2 to 0.65%.

[0145] The film, more preferably the cast film, preferably has a transparency value measured according to ASTM D1003 on 50 μm cast film in the range of 90 to 100%, more preferably 92 to 100%, most preferably 94 to 100%.

[0146] The film, more preferably a cast film, preferably has a tensile modulus in the machine direction (MD), measured according to ISO 527-3 on 50 μm cast films, in the range of 300 to 700 MPa, more preferably 400 to 600 MPa, most preferably 450 to 550 MPa.

[0147] Example

[0148] A. Measurement Method

[0149] A1- Quantification of microstructure by NMR spectroscopy

[0150] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers as well as the amount of 2,1-regio defects.

[0151] A Bruker Avance III 400 MHz NMR spectrometer was used to analyze the 1 H and 13 C was operated at 500.13 and 125.76 MHz and quantitative data were recorded in the molten state. 13 C{ 1 H}NMR spectra. All spectra were obtained using 13 The spectra were recorded at 180 °C using a C-optimized 7 mm magic angle spinning (MAS) probe head with nitrogen used for all pneumatics. Approximately 200 mg of material was loaded into a 7 mm outer diameter zirconium oxide MAS rotor and spun at 4 kHz. This setup was chosen primarily for the high sensitivity required for rapid identification and accurate quantification {klimke06, parkinson07, castignolles09}. Standard single pulse excitation was used, utilizing NOE {pollard04, klimke06} with a short recycle delay of 3 s and an RS-HEPT decoupling scheme {fillip05, griffin07}. A total of 1024 (1k) transients were acquired for each spectrum.

[0152] Quantitative 13 C{1H} NMR spectra were processed, integrated, and the relevant quantitative properties were determined from the integration. All chemical shifts were internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.

[0153] A characteristic signal {brandolini01} corresponding to the incorporation of 1-butene was observed and the comonomer content was quantified.

[0154] The amount of isolated 1-butene incorporated into the PBP sequence was quantified using the integration of the αB2 site at 43.6 ppm and taking into account the number of reporter sites per comonomer:

[0155] B=I αB2 / 2

[0156] The amount of continuously incorporated 1-butene in the PBBP sequence was quantified using the integration of the ααB2B2 sites at 40.5 ppm and taking into account the number of reporter sites per comonomer:

[0157] BB=2 * I ααB2B2

[0158] In the presence of BB, the B value must be corrected for the effect of the αB2 site generated by the BB:

[0159] B=(I αB2 / 2)-BB / 2

[0160] The total 1-butene content was calculated based on the sum of separated and continuously incorporated 1-butene:

[0161] B 总计 =B+BB

[0162] A characteristic signal {brandolini01} corresponding to the incorporation of ethylene was observed and the comonomer content was quantified.

[0163] The amount of isolated ethylene incorporated into the PEP sequence was quantified using the integration of the Sββ site at 24.3 ppm and taking into account the number of reporter sites per comonomer:

[0164] E=I Sββ

[0165] If a characteristic signal corresponding to the continuous incorporation of ethylene in the PEE train is observed, the Sβδ site at 27.0 ppm is used for quantification:

[0166] EE=I Sβδ

[0167] Characteristic signals {resconi00} corresponding to regio defects were observed. The presence of two methyl sites at 17.7 and 17.2 ppm, the presence of a methylene site at 42.4 ppm, and confirmation of other characteristic sites indicated the presence of isolated 2,1-erythro regio defects. The presence of 2,1 regio defects adjacent to ethylene units was indicated by two inequivalent Sαβ signals at 34.8 ppm and 34.4 ppm, respectively, and a Tγγ signal at 33.7 ppm.

[0168] Using the methylene site integration at 42.4 ppm (I e9 ) to quantify the isolated 2,1-erythro regio-defects (P 21e分离的 ) amount:

[0169] P 21e分离的 =I e9

[0170] If present, the methylene site at 33.7 ppm (I Tγγ ) Quantify adjacent ethylene (PE 21 ) of the 2,1 area defect:

[0171] PE 21 =I Tγγ

[0172] The total ethylene content was then calculated based on the sum of ethylene from isolated, continuously incorporated and adjacent 2,1 regio defects:

[0173] E 总计 =E+EE+PE 21

[0174] Based on the Sαα methylene site at 46.7 ppm (including all additional propylene units not covered by Sαα, e.g., factor 3 * P21 e分离的 The amount of propylene is quantified by accounting for three missing propylene units from an isolated 2,1-erythro regio defect:

[0175] P 总计 =I Sαα +3 * P 21e分离的 +B+0.5 * BB+E+0.5 * EE+2 * PE 21

[0176] The total mole fraction of 1-butene and ethylene in the polymer is then calculated as:

[0177] fB=B 总计 / (E 总计 +P总计 +B 总计 )

[0178] fE=E 总计 / (E 总计 +P 总计 +B 总计 )

[0179] The mole percentage of comonomer incorporation is calculated from the mole fraction:

[0180] B [mol%] = 100 * f

[0181] E[mol%]=100 * f

[0182] The weight percent of comonomer incorporation is calculated from the mole fraction:

[0183] B [wt.-%] = 100 * (fB * 56.11) / ((fE * 28.05)+(fB * 56.11)+((1-

[0184] (fE+fB)) * 42.08))

[0185] E[wt.-%]=100 * (fE * 28.05) / ((fE * 28.05)+(fB * 56.11)+((1-

[0186] (fE+fB)) * 42.08))

[0187] Quantify the mole percentage of isolated 2,1-erythro regio defects relative to total propylene:

[0188] [21e]mol%=100 * P 21e分离的 / P 总计

[0189] Quantify the mole percentage of 2,1 regio defects adjacent to ethylene relative to total propylene:

[0190] [E21]mol%=100 * PE 21 / P 总计

[0191] 2.1 The total amount of defects is quantified as follows:

[0192]

[21] mol%=[21e]+[E21]

[0193] No characteristic signals {resconi00} corresponding to other types of regional defects (2,1-threo, 3,1 insertion) were observed.

[0194] Literature (as mentioned above):

[0195] klimke06 Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382.

[0196] parkinson07 Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128.

[0197] pollard04 Pollard, M., Klimke, K., Graf, R., Spiess, HW, Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules2004;37:813.

[0198] filip05 Filip,

[0199] castignolles09 Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer 50(2009)2373.

[0200] resconi00 Resconi,L.,Cavallo,L.,Fait,A.,Piemontesi,F.,Chem.Rev.2000,100,1253.

[0201] brandolini01 AJ Brandolini, DDHills, “NMR spectra of polymers and polymer additives”, Marcel Deker Inc., 2000

[0202] Calculation of the comonomer content of the second terpolymer part (TP2):

[0203]

[0204] in

[0205] w(TP1) is the weight fraction [in wt %] of the first terpolymer part (TP1),

[0206] w(TP2) is the weight fraction [in wt %] of the second terpolymer part (TP2),

[0207] C(TP1) is the comonomer content [in mol %] of the first terpolymer part (TP1),

[0208] C(TP) is the comonomer content [in mol %] of the multimodal base polymer (TP),

[0209] C(TP2) is the calculated comonomer content [in mol %] of the second terpolymer part (TP2).

[0210] A2-Melt flow rate

[0211] The melt flow rate (MFR) is determined according to ISO 1133 and is expressed in g / 10 min. The MFR is an indicator of the fluidity of the polymer and therefore of its processability. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR2 of polypropylene is determined at a temperature of 230°C and a load of 2.16 kg.

[0212] Calculation of the melt flow rate MFR2 (230°C) of the second terpolymer part (TP2):

[0213]

[0214] in

[0215] w(TP1) is the weight fraction of the first terpolymer part (TP1) in [wt %],

[0216] w(TP2) is the weight fraction of the second terpolymer part (TP2) in [wt %],

[0217] MFR(TP) is the melt flow rate MFR2 (230°C) of the multimodal base polymer (TP) in [g / 10 min],

[0218] MFR(TP1) is the melt flow rate MFR2 (230°C) of the first terpolymer part (TP1) in [g / 10 min],

[0219] MFR(TP2) is the melt flow rate MFR2 (230°C) of the second terpolymer part (TP2) in [g / 10 min].

[0220] A3 - xylene cold soluble fraction at room temperature (XCS, wt%)

[0221] The amount of polymer soluble in xylene is determined according to ISO 16152; 5th edition; 2005-07-01 at 25°C.

[0222] A4-DSC analysis, melting temperature (T m ), heat of fusion (H f ), crystallization temperature (T c ) and crystallization enthalpy (H c )

[0223] Melting temperatures (T) were measured on 5 to 7 mg samples using a TA Instruments Q200 differential scanning calorimeter (DSC). m ), heat of fusion (H f ), crystallization enthalpy (H c ) and crystallization temperature (T c ). The DSC was run according to ISO 11357 / Part 3 / Method C2 in the temperature range of -30 to +225°C with a scan rate of 10°C / min in a hot / cold / hot cycle.

[0224] Crystallization temperature (T c ) and crystallization enthalpy (H c ) is determined by the cooling step, while the melting temperature (T m ) and heat of fusion (H f ) is determined by the second heating step.

[0225] A5-Oxidation Induction Time (OIT)

[0226] The oxidation induction time (OIT) at 180°C and 190°C was determined with a TA Instruments Q20 according to ISO 11357-6. The instrument was calibrated with indium and tin according to ISO 11357-1. The maximum error of the calibration temperature was less than 0.1K. Each polymer sample weighing 10±2 mg (cylindrical geometry with a diameter of 5 mm and a thickness of 1±0.1 mm prepared by compression molding) was placed in an open aluminum crucible and heated from 25°C to 180°C (or 190°C) at a rate of 20°C / min in nitrogen (>99.95 vol.% N2, <5 ppm O2). The sample was kept at a constant temperature and the exotherm associated with the oxidation was recorded. The oxidation induction time is the time interval between the start of the oxygen flow and the start of the oxidation reaction. Each data point presented is the average of three independent measurements.

[0227] A6-Optical properties-Haze and transparency

[0228] Haze and clarity were measured according to ASTM D1003 on 50 μm thick cast films produced on a single layer cast film line with a melt temperature of 240°C and a chill roll temperature of 20°C.

[0229] A7-Tensile Modulus (TM)

[0230] The tensile modulus in machine direction (MD) was determined according to ISO 527-3 on a 50 μm thick cast film produced on a monolayer cast film line with a melt temperature of 240° C. and a chill roll temperature of 20° C. The test was performed at a crosshead speed of 1 mm / min.

[0231] A8-Hot Tack Force (HTF)

[0232] Hot tack was measured on a J&B Hot Tack Tester according to ASTM F192-12 - Method B1 on 50 μm thick films produced on a monolayer cast film line with a melt temperature of 240°C and a chill roll temperature of 20°C.

[0233] Specimen cutter:

[0234] The specimens were cut into a width of 25 mm (± 0.5%) using a drum cutter or a strip cutter.

[0235] Testing machine:

[0236] Sealing strip length: 50mm

[0237] Sealing strip width: 5mm

[0238] Sealing strip shape: flat

[0239] Sealing strip material: Brass-Nickel

[0240] ●Sealing strip coating:

[0241] ● Roughness of sealing strip: about 1μm

[0242] Force measurement: piezoelectric force sensor

[0243] Temperature measurement: 2 independent heating systems

[0244] Thickness measuring device (accuracy according to ISO 4593:1993):

[0245] Position sensor (Heidenhain; model: ND 280)

[0246] Messtaster (Heidenhain; model: MT 1281)

[0247] Measuring surface: Flat / Polished surface

[0248] Diameter of each face: 6.5mm

[0249] Conditioning of samples / test pieces:

[0250] All specimens were prepared in a standard atmosphere for conditioning and testing at 23°C (±2°C) and 50% (±10%) relative humidity.

[0251] Before starting the test, the shortest conditioning time of the sample in the standard atmosphere: >16h.

[0252] Minimum storage time between film sample extrusion and start of testing: >88h.

[0253] Sample preparation:

[0254] Specimen type: Specimen type: Take parallel cut strips of 25mm (width) x approximately 320mm (length) across the entire specimen width.

[0255] Specimen direction: longitudinal

[0256] The specimen (film) should be free of dust, fingerprints, wrinkles, folds, shrinkage or other obvious defects. The edges of the cut specimens should be smooth and without gaps.

[0257] Thickness measurement:

[0258] The thickness of the test specimen is measured in the sealed area.

[0259] Hot bonding – sealing process:

[0260] The test should be carried out under the same atmospheric conditions as for conditioning.

[0261] Under specified conditions of temperature, contact time and pressure, the sealing jaws are heated from two flat 5 * 50mm) to apply pressure to seal the prepared sample strip.

[0262] The specimen is folded between the sealing jaws using an automatic specimen folding device. The sealing jaws are closed and after a preset sealing time, the sealing jaws are opened and the heat seal is completed. After a selected cooling time, the lower specimen gripper moves downward. During the stretching of the specimen, a force sensor attached to the upper specimen gripper measures the forces. Afterwards, the failure mode is determined visually.

[0263] Standard test conditions:

[0264] Sealing temperature (ambient temperature -240℃)

[0265] Sealing time (thickness <25μm: 0.5s; thickness ≥25μm: 1s)

[0266] Sealing pressure (0.15N / mm 2 )

[0267] Delay time (0.2s)

[0268] Clamp separation speed (200mm / s)

[0269] Note: Parameter values ​​are freely selectable by the user.

[0270] Number of specimens: At least 3 specimens at each temperature.

[0271] If a significant deviation appears in the measured values ​​for a temperature step, make sure that this is just an outlier and test another sample (the number of samples should always be an odd number, but the total number should not exceed 7 test samples) allowing the outlier to be excluded from the measurement - deviations due to other reasons must be considered.

[0272] Temperature step / interval: 5℃↑

[0273] (In case of a sharp rise / fall between two temperature steps, 2°C↑)

[0274] The measurement was started with two temperature steps below 0.2-0.3N.

[0275] Stop measurement at the destruction mode burn-through

[0276] It also allows for a burn-through failure mode and two other failure modes - plus an additional temperature step

[0277] A typical hot tack curve may require 25 to 50 specimens per material.

[0278] result:

[0279] The output of this method is a thermotack curve. The interpretation of the thermotack curve has always relied on the relationship between the sealing force and the sealing temperature.

[0280] Hot Tack: Maximum force when failure mode is "peel". When using 3 specimens / temperature steps, two "peel" failure modes and any other failure mode (except burn-through failure mode) are also allowed.

[0281] Unlike ASTM F1921-12 Chapter 9, the test is performed after a cooling time of 200 ms. The end of the measurement described in ASTM F1921-12 Chapter 9.8 (test stop after hot tack determination) is not taken into account. The test ends after the film is thermally destroyed. In addition to the evaluation of the failure modes described in the standard, other failure modes are used.

[0282] A9-Seal Initiation Temperature (SIT)

[0283] This method is used to determine the sealing window (sealing temperature range) of a film. The procedure is similar to hot tack measurement, but in contrast to hot tack, the sealing range applies to the seal strength after cooling (delay time of 30 seconds). Sealing range = (sealing start temperature to sealing end temperature)

[0284] The results provide the user with a quantitatively useful indication of the strength of the sealed film and show the temperature range for optimum sealing.

[0285] By default, the temperature interval is set to 5°C, but it can be lowered to 1°C to represent a better curve profile when the curve shows a sharp increase or decrease in force values ​​between two temperature steps.

[0286] Unlike ASTM F1921-12, the test parameters sealing pressure, cooling time and test speed were modified. The force / temperature curve was determined until thermal failure of the membrane. In addition to the evaluation of the failure mode described in the standard, other failure modes were used.

[0287] For characterization of the material, the measured values ​​sealing range start temperature (SIT), temperature at maximum force (MAX) and sealing range end temperature (SET) were also determined.

[0288] Standard conditions:

[0289] Adjustment time: >96h

[0290] Sealing jaws size: 50x5 mm

[0291] Sealing jaws shape: flat

[0292] Sealing jaw coating: Niptef

[0293] Sealing temperature: ambient temperature -240℃

[0294] Sealing temperature interval: 5°C

[0295] Sealing time: 1 second

[0296] Delay time: 30 seconds

[0297] Sealing pressure: 0.4N / mm 2 (PE); 0.67N / mm 2 (PP)

[0298] Grip separation rate: 42 mm / sec

[0299] Sealing starting force: 5N

[0300] Sample width: 25mm

[0301] result:

[0302] The output of this method is a sealing curve.

[0303] The lower limit (Seal Initiation Temperature - SIT) is the sealing temperature at which a sealing force of 5 N is reached.

[0304] B. Examples

[0305] The catalyst used in the polymerization process of all examples is trans-dimethylsilanediyl [2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl] [2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl] zirconium dichloride, as disclosed as MC-2 in WO 5 2019 / 179959A1. The production of the supported metallocene catalyst is similar to IE2 in WO 2019 / 179959 A1.

[0306] All examples given in this application were prepared using a multimodal base polymer (TP) and the polymerization conditions are given in Table 1 below. In the loop reactor the polymer product taken off at the end of the process consisted of the first terpolymer fraction (TP1), whereas in the gas phase reactor the polymer product taken off at the end of the process consisted of both the first (TP1) and the second terpolymer fraction (TP2). Therefore, the values ​​given in the "loop reactor" section of Table 1 represent the values ​​for the first terpolymer fraction (TP1), whereas the values ​​given in the "gas phase reactor" section represent the values ​​for the first (TP1) and the second terpolymer fraction (TP2), i.e. the multimodal base polymer (TP). The single value for the second terpolymer fraction (TP2) was then calculated using the method described in the "measurement methods" section above.

[0307] Table 1: Polymerization conditions of multimodal base polymer (TP)

[0308]

[0309] The calculated values ​​for the second terpolymer fraction (TP2) are as follows:

[0310] MFR2: 19.9g / 10min

[0311] C2 content: 5.4 mol%

[0312] C4 content: 5.9 mol%

[0313] C2 / C4:0.91

[0314] The amount of 2,1-regio defects of the multimodal base polymer (TP) was determined to be 0.3 mol%.

[0315] The multimodal base polymer (TP) was then mixed with different additives in an intensive mixer and IE1, IE2, CE1 and CE2 were prepared in a co-rotating twin-screw extruder. The formulations are shown in Table 2, where antioxidant 1 (AO1) was Kinox 10G (supplied by HPL Additives), antioxidant 2 (AO2) was Irgafos 168FF (supplied by BASF), anti-blocking agent (AB) was Gasil AB 725 (supplied by PQ Corporation), acid scavenger 1 (AS1) was CEASIT-FI (supplied by Baerlocher), and acid scavenger 2 (AS2) was DHT-4A (supplied by Kisuma / Kyowa).

[0316] Table 2: Details of the propylene / ethylene / 1-butene terpolymer composition

[0317] Components CE1 CE2 IE1 IE2 TP [wt%] 99.74 99.77 99.78 99.74 AO1 [wt%] 0.06 0.06 0.06 0.08 AB [wt%] 0.1 0.1 0.1 0.1 AO2 [wt%] 0.06 0.06 0.06 0.08 AS1 [wt%] - 0.01 - - AS2 [wt%] 0.04 - - -

[0318] The properties of polymer compositions prepared according to the formulations given in Table 2 and cast films prepared from such compositions are given in Table 3 below.

[0319] Table 3: Properties of polymer compositions

[0320]

[0321] The inventors have found that the polymers produced by single-site catalysts according to the present invention do not require the addition of acid scavengers in the additive formulation. CE1 contains DHT4A as an acid scavenger, which is commonly used in the target application and is observed to significantly reduce OIT. On the other hand, CE2 contains calcium stearate as an acid scavenger, which appears to have little effect on OIT; however, it migrates to the surface of the film, affecting the properties of the film, such as adhesion to the metallized layer. Despite the absence of acid scavengers, these two inventive examples still provide the desired thermal properties (as seen by low SIT and high HTF), good mechanical properties (as seen from tensile modulus) and good optical properties (as seen from low haze and high transparency). Therefore, when using polymers according to the present invention produced using single-site catalysts, formulations without acid scavengers perform even better without negatively affecting sealing properties, such as hot adhesion and seal initiation temperature, optical and mechanical properties.

Claims

1. A propylene / ethylene / 1-butene terpolymer composition comprising a) a multimodal base polymer (TP) in an amount of 95 to 99.9 wt% relative to the total weight of the propylene / ethylene / 1-butene terpolymer composition, said multimodal base polymer (TP) having the following properties: i. a melt flow rate (MFR2) measured according to ISO 1133 at 230°C and 2.16 kg load in the range of 3 to 12 g / 10 min; ii. In the range of 0.1 to 1.0 mol% according to the quantitative 13 The content of 2,1-regio defects determined by C-NMR spectroscopy; iii. In the range of 1.0 to 4.0 mol% according to 13 Ethylene content (C2) determined by C-NMR spectroscopy; iv. In the range of 3.0 to 10.0 mol% according to 13 1-Butene content (C4) determined by C-NMR spectroscopy; v. a xylene cold soluble content (XCS) determined according to ISO 16152 in the range of 0 to 3.0 wt%; wherein the multimodal base polymer (TP) comprises: a1) 50 to 80 wt% of a first terpolymer fraction (TP1), relative to the total weight of the multimodal base polymer (TP), having a melt flow rate (MFR2) in the range of 1 to 10 g / 10 min, measured according to ISO 1133 at 230 °C and 2.16 kg load; and a2) 20 to 50 wt% of a second terpolymer fraction (TP2), relative to the total weight of the multimodal base polymer (TP), having a melt flow rate (MFR2) in the range of 5 to 30 g / 10 min, measured according to ISO 1133 at 230 °C and 2.16 kg load; b) 0.1 to 5 wt% of an additive, relative to the total weight of the propylene / ethylene / 1-butene terpolymer composition, selected from the group consisting solely of antioxidants, antiblocking agents, UV stabilizers, antiscratch agents, mold release agents, lubricants, antistatic agents, pigments, and mixtures thereof; The propylene / ethylene / 1-butene terpolymer contains substantially no acid scavenger.

2. The propylene / ethylene / 1-butene terpolymer composition according to claim 1, wherein the additive is selected from the group consisting of only one or more antioxidants and antiblocking agents.

3. The propylene / ethylene / 1-butene terpolymer composition according to any one of the preceding claims having an antioxidant level of less than 0.3 wt%, more preferably from 0.05 to 0.25 wt%, most preferably from 0.08 to 0.2 wt%, relative to the total weight of the propylene / ethylene / 1-butene terpolymer composition.

4. The propylene / ethylene / 1-butene terpolymer composition according to any of the preceding claims, wherein the multimodal base polymer (TP) is bimodal.

5. The propylene / ethylene / 1-butene terpolymer composition according to any one of the preceding claims, wherein the multimodal base polymer (TP) has a quantitative 13 The 2,1-regio defect content ranged from 0.2 to 0.5 mol % as determined by C-NMR spectroscopy.

6. The propylene / ethylene / 1-butene terpolymer composition according to any one of the preceding claims, wherein the multimodal base polymer (TP) has a) in the range of 1.5 to 3.5 mol%, more preferably 2.0 to 3.0 mol%, most preferably 2.5 to 2.8 mol% according to 13 Ethylene content (C2) determined by C-NMR spectroscopy, and / or b) in the range of 3.5 to 9.0 mol %, more preferably 4.0 to 8.0 mol %, most preferably 4.5 to 7.0 mol % according to 13 1-Butene content (C4) determined by C-NMR spectroscopy.

7. The propylene / ethylene / 1-butene terpolymer composition according to any of the preceding claims, wherein the multimodal base polymer (TP) has an ethylene / 1-butene amount ratio in the range of 0.1 to 0.9, more preferably 0.2 to 0.7, most preferably 0.3 to 0.6, wherein the ethylene / 1-butene amount ratio is calculated by dividing the amount of ethylene in mol% by the amount of 1-butene in mol%.

8. The propylene / ethylene / 1-butene terpolymer composition according to any one of the preceding claims, wherein the first terpolymer fraction (TP1) has a) in the range of 0.2 to 3.0 mol%, more preferably 0.5 to 2.0 mol%, most preferably 0.8 to 1.5 mol% according to 13 Ethylene content (C2) determined by C-NMR spectroscopy; and / or b) in the range of 2.0 to 7.0 mol %, more preferably 3.0 to 6.0 mol %, most preferably 4.0 to 5.0 mol % 13 1-Butene content (C4) determined by C-NMR spectroscopy.

9. The propylene / ethylene / 1-butene terpolymer composition according to any one of the preceding claims, wherein the second terpolymer fraction (TP2) has a) in the range of 3.0 to 7.5 mol %, more preferably 4.0 to 7.0 mol %, most preferably 5.0 to 6.0 mol % according to 13 Ethylene content (C2) determined by C-NMR spectroscopy; and / or b) in the range of 3.0 to 8.0 mol %, more preferably 4.0 to 7.0 mol %, most preferably 5.0 to 6.5 mol % according to 13 1-Butene content (C4) determined by C-NMR spectroscopy.

10. The propylene / ethylene / 1-butene terpolymer composition according to any one of the preceding claims, having a) an oxygen induction (OIT) time measured at 180°C according to ISO 11357-6 in the range of 10 to 30 minutes, more preferably 15 to 28 minutes, most preferably 20 to 26 minutes, and / or b) an oxygen induction (OIT) time measured according to ISO 11357-6 at 190°C in the range of 3 to 20 minutes, more preferably 5 to 15 minutes, most preferably 7 to 13 minutes.

11. A film, preferably a cast film, comprising the propylene / ethylene / 1-butene terpolymer composition according to any one of claims 1 to 10.

12. The film, preferably cast film, according to claim 11 having a sealing initiation temperature in the range of 100 to 115°C, more preferably 101 to 110°C, most preferably 102 to 108°C measured according to the method described in the experimental part on 50 μm cast film.

13. A film according to claim 11 or claim 12, preferably a cast film, having a hot tack measured according to ASTM F1921-12 - Method B on 50 μm cast film in the range of 1.0 to 5.0 N, more preferably 1.5 to 4.0 N, most preferably 2.4 to 3.5 N.

14. The film, more preferably cast film, according to any one of claims 11-13, having a haze value measured according to ASTM D1003 on 50 μm cast film in the range of 0 to 2.0%, more preferably 0.1 to 1.0%, most preferably 0.2 to 0.65%.

15. The film according to any one of claims 11-13, more preferably a cast film, having a tensile modulus in the machine direction (MD) measured according to ISO 527-3 for 50 μm cast films in the range of 300 to 700 MPa, more preferably 400 to 600 MPa, most preferably 450 to 550 MPa.

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