Excellent c2c3c4 terpolymer based cast films and c2c3c4 terpolymers

Abstract

A cast film made from a terpolymer is provided as well as a terpolymer containing units derived from propylene, ethylene, and 1-butene.

Description

Technical Field

[0001] This invention relates to cast films made of polypropylene terpolymers and the polypropylene terpolymers themselves. Background Technology

[0002] Optimization of cast films based on polypropylene (PP) copolymers is a multidimensional problem. Numerous attempts have been made to optimize materials suitable for the film. WO 2002 / 057342 A1 describes a biaxially oriented polypropylene (BOPP) film made from a copolymer derived from a Ziegler-Natta catalyst, the copolymer containing at least 0.8 wt% ethylene, preferably 0.8-1.5 wt%. Although PP terpolymers are mentioned presciently, these materials are not disclosed in this application. Cast films made from the aforementioned PP copolymers exhibit undesirable high haze. WO 2009 / 019169 A1 describes a process for preparing a PP terpolymer suitable for blown film production derived from a Ziegler-Natta catalyst, the copolymer containing at least 8 wt% comonomers, the comonomer units being derived from ethylene and C4-C8 α-olefins using a 1,3-diether internal donor catalyst. According to WO 2009 / 019169 A1, an optimal performance balance can be observed when ethylene content is below 2.5 wt% combined with 1-butene content above 10 wt%, or when ethylene content is above 2.5 wt%, 1-butene content should be below 10 wt%. A composition with ethylene content of 1.2 wt% and 11.3 wt% 1-butene content (i.e., a C4 / C2 (wt / wt) ratio of 9.4) can achieve a SIT as low as 107.4 °C and a haze of 0.2% (1 mm plaque). However, these membranes exhibit unacceptably high levels of n-hexane (C6) extractables above 2.8 wt%. US 6,388,040 relates to BOPP membranes, a completely different type of membrane made from compositions with different melting temperatures.

[0003] EP 3192817A1 discloses a method for providing a ternary polymer comprising units derived from 1-butene using a crosslinked metallocene compound. EP 3192817 A1 defines an ultrawide range of structural units, namely, 4 mol%-45 mol% of structural units derived from 1-butene and 4 mol%-45 mol% of structural units derived from ethylene, citing examples of 12.8 mol% ethylene and 21.1 mol% 1-butene. Although EP 3192817 A1 proposes the concept of a membrane, a membrane is not actually disclosed in that application.

[0004] WO 2013 / 174778 discloses a propylene-based terpolymer of C2, C3, and C4 monomer units prepared using a Ziegler-Natta catalyst. According to WO 2013 / 174778, the Silt Intake (SIT) is below 110 °C, such as 106 °C. However, at 25 °C, the XCS is relatively high in the range of 5-15 wt%, and the disclosed membrane has a hexane (C6) extractable (FDA) level of 1.8 or higher, which is unacceptably high.

[0005] Therefore, there remains a need for a PP-based terpolymer cast film with a low sealing onset temperature (e.g., well below 120°C), low haze (e.g., below 6.0%), and exceptionally low hexane extractables (FDA) (e.g., below 0.75 wt%). Simultaneously, the film should possess sufficient melt flow rate and high drop-weight impact resistance.

[0006] These aspects are addressed in this invention. This invention is based on the discovery that by carefully setting the amount of ethylene units, the amount of 1-butene units, their total amount, and 2.1 regioinversions, a favorable combination of low n-alkane extractability, low haze, good processability, and good sealing properties can be obtained. Summary of the Invention

[0007] Therefore, the present invention provides a cast film made of an ethylene-propylene-1-butene terpolymer, comprising:

[0008] a) The amount of ethylene-derived units relative to the total amount of the terpolymer is 0.2-2.4 mol%.

[0009] b) The amount of propylene-derived units relative to the total amount of the terpolymer is 91.0-95.9 mol%; and

[0010] c) The amount of 1-butene-derived units relative to the total amount of the terpolymer is 3.9-6.6 mol%; and

[0011] d) Wherein, the units derived from ethylene, the units derived from propylene, and the units derived from 1-butene total 100 mol%.

[0012] e) The total amount of units derived from ethylene and units derived from 1-butene is 4.5–8.5 mol%.

[0013] f) by 13 The amount of 2.1 region inversion determined by C-NMR analysis (as described in the experimental section) was 0.20–0.60 mol%.

[0014] g) The melt flow rate MFR2 (230℃ / 2.16kg) measured according to ISO 1133 is 8-14.5g / 10min, and

[0015] h) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following equation:

[0016] Tm≥[150–1.6×(defect)–0.12×(defect)] 2 ]℃,

[0017] Wherein, "defect" represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regio inversion, all values ​​are in mol% and

[0018] Therefore, the cast film has a sealing initiation temperature (SIT) below 117°C (determined by the method described in the experimental section).

[0019] The present invention also provides an ethylene-propylene-1-butene terpolymer, comprising:

[0020] a) The amount of ethylene-derived units relative to the total amount of the terpolymer is 0.2-2.4 mol%.

[0021] b) The amount of propylene-derived units relative to the total amount of the terpolymer is 91.0-95.9 mol%; and

[0022] c) The amount of 1-butene-derived units is 3.9-6.6 mol% relative to the total amount of the terpolymer;

[0023] d) Wherein, the units derived from ethylene, the units derived from propylene, and the units derived from 1-butene total 100 mol-%, and

[0024] e) The total amount of ethylene-derived units and 1-butene-derived units is 4.5-8.5 mol%, and

[0025] f) by 13 The amount of 2.1 region inversion determined by C-NMR analysis (as described in the experimental section) was 0.20–0.60 mol%; and

[0026] g) The melt flow rate MFR2 (230℃ / 2.16kg) measured according to ISO 1133 is 8-14.5g / 10min, and

[0027] h) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following equation:

[0028] Tm≥[150–1.6×(defect)–0.12×(defect)] 2 ]℃,

[0029] Wherein, "defect" represents the sum of monomers derived from ethylene, monomers derived from 1-butene, and 2,1-regio inversion; all values ​​are in mol% and

[0030] Advantageous variants of the cast film and the ethylene-propylene-1-butene terpolymer are specified in the dependent claims.

[0031] In another aspect, the present invention relates to a composition comprising the ethylene-propylene-1-butene terpolymer of the present invention in an amount of at least 97 wt%.

[0032] definition

[0033] Regional defects in propylene polymers can be classified into three different types: 2,1-erythro (2,1e), 2,1-threo (2,1t), and 3,1 defects. A detailed description of the structure and formation mechanism of regional defects in polypropylene can be found in Chemical Reviews 2000, 100(4), pp. 1316-1327. These defects are... 13 The measurements were performed using C nuclear magnetic resonance spectroscopy, as detailed below.

[0034] The term “2,1 region defect” or “2,1 region inversion” used in this invention defines the sum of 2,1-Erythian region defects and 2,1-Soviet region defects.

[0035] The "terpolymer" of this invention refers to a polymer made from monomers ethylene, propylene, and 1-butene, which can be found in the polymer chain. The total amount of units derived from these monomers reaches 100 mol%. According to this invention, pseudo-terpolymers made from mixtures of two copolymers are not within the scope of the "terpolymer" of this invention. Pseudo-terpolymers can be identified by combined TREF-IR, combined TREF-NMR, or similar methods. By definition, the terpolymer of this invention is not a mixture of two copolymers.

[0036] The term “defect” refers to the sum of monomers derived from ethylene, monomers derived from butene, and 2.1 regio inversion, all values ​​are in mol%.

[0037] When the term "comprising" is used in this specification and claims, it does not exclude other unspecified elements of primary or secondary functional importance. For the purposes of this invention, the term "consisting of" is considered a preferred embodiment of the term "comprising." If a group is defined below as comprising at least a certain number of embodiments, this should also be understood as disclosing a group that preferably consists only of these embodiments.

[0038] When using terms such as "including" or "having," these terms have the same meaning as "included" as defined above.

[0039] When a noun is preceded by a generic word such as “one” or “a kind”, it includes the plural form of the noun unless otherwise specified.

[0040] Bimodality of 1-butene-derived units refers to the terpolymer being obtainable in two reactors connected in series at a split ratio of 40:60 to 60:40, operated such that the intermediate terpolymer produced in the first reactor differs from the final terpolymer by at least 20% in the content of 1-butene-derived units, all contents considered being weight percentages based on the first reactor. For example, 5.0 wt% (first reactor) and 6.1 wt% (final reactor) meet the requirements.

[0041] Bimodal molecular weight refers to the fact that terpolymers can be obtained in two reactors connected in series with a ratio of 40:60 to 60:40.

[0042] Terpolymers and Compositions

[0043] The amount of regio reversal depends to some extent on the content of comonomers; that is, the higher the comonomer content, the lower the amount of regio reversal in 2.1. Furthermore, the choice of polymerization temperature also affects the amount of regio reversal in 2.1; the higher the polymerization temperature, the more favorable it is for reducing the content of regio reversal in 2.1.

[0044] In another preferred aspect, the units derived from 1-butene in the terpolymer are bimodal. As outlined in the definition section above, this means that there are two polymers with different 1-butene contents. It goes without saying that the bimodal nature of the 1-butene content can be achieved by using two or more reactors in series or other measures such as parallel reactor devices and subsequently mixing them, for example, in a solution.

[0045] In another preferred aspect, the terpolymer has a bimodal molecular weight. As outlined in the definition section, this again implies the presence of two polymers with different melt flow rates. The same measures as described above, along with the use of a chain transfer agent (typically hydrogen), will be suitable for this purpose.

[0046] The compositions of the present invention comprise 97 wt% of a terpolymer. Preferably, the compositions of the present invention consist of the terpolymer described herein and additives. The additives are preferably selected from slip agents, antiblocking agents, UV stabilizers, antistatic agents, acid scavengers, α-nucleating agents, antioxidants, and mixtures thereof. These additives are well known to those skilled in the art.

[0047] The slip agent migrates to the surface and acts as a lubricant between polymers and between the polymer and the metal roller, thereby reducing the coefficient of friction (CoF). Examples include fatty acid amides, such as erucamide (CAS No. 112-84-5), oleamide (CAS No. 301-02-0), stearamide (CAS No. 124-26-5), or combinations thereof.

[0048] Examples of commonly used antioxidants in this field include stereohindered phenols (such as CAS No. 6683-19-8, also known as Irganox 1010 FF from BASF). TM (Sales), phosphorus-based antioxidants (such as CAS No. 31570-04-4, also known as Clariant's Hostanox PAR 24(FF)). TM Or BASF's Irgafos 168(FF) TM (For sale), sulfur-based antioxidants (such as CAS No. 693-36-7, as BASF's Irganox PS-802FL) TM (For sale), nitrogen-based antioxidants (such as 4,4'-bis(1,1'-dimethylbenzyl)diphenylamine) or mixtures of antioxidants.

[0049] Acid scavengers are also well known in the art. Examples include calcium stearate (CAS No. 1592-23-0), zinc stearate (CAS No. 557-05-1), sodium stearate, magnesium oxide and zinc oxide, synthetic hydrotalcite (e.g., SHT, CAS No. 11097-59-9), lactates and lactyl lactates.

[0050] Common anti-blocking agents include natural silica, such as diatomaceous earth.

[0051] (Such as CAS No.60676-86-0(SuperfFloss TM )), CAS No.60676-86-0(SuperFloss E TM (or CAS No. 60676-86-0 (Celite 499)) TMSynthetic silica (such as CAS No. 7631-86-9, CAS No. 7631-86-9, CAS No. 7631-86-9, CAS No. 7631-86-9, CAS No. 7631-86-9, CAS No. 112926-00-8, CAS No. 7631-86-9 or CAS No. 7631-86-9), silicates (such as aluminum silicate, kaolin, CAS No. 1318-74-7, sodium aluminum silicate CAS No. 1344-00-9, calcined kaolin CAS No. 92704-41-1, aluminum silicate CAS No. 1327-36-2 or calcium silicate ... CAS No. 7631-86-9, CAS No. 7631-86-9, CAS No. 7631-86-9, CAS No. 7631-86-9, CAS No. 7631-86-9, CAS No. 7631-86-9, CAS No. 7631-86-9, No. 1344-95-2), synthetic zeolites (such as hydrated calcium aluminosilicate sodium CAS No. 1344-01-0, CAS No. 1344-01-0, or hydrated calcium aluminosilicate sodium CAS No. 1344-01-0).

[0052] Suitable UV stabilizers include, for example, bis(2,2,6,6-tetramethyl-4-piperidinyl)-sebate (CAS No. 52829-07-9, Tinuvin 770); 2-hydroxy-4-n-octyloxybenzophenone (CAS No. 1843-05-6, Chimassorb 81).

[0053] α-Nucleating agents, such as sodium benzoate (CAS No. 532-32-1); a mixture of aluminum hydroxybis[2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate] and lithium myristate (commercially available as AdekastabNA-21 from Adeka Palmarole, France) or 1,3:2,4-bis(3,4-dimethylbenzyl)sorbitol (CAS No. 135861-56-2, commercially available as Millad 3988 from Milliken, USA).

[0054] Suitable antistatic agents include, for example, glyceryl esters (CAS No. 97593-29-8), amine ethoxylates (CAS No. 71786-60-2 or 61791-31-9), or acetamides (CAS No. 204-393-1).

[0055] Most preferably, the content of these additives is 0.01-2.0 wt% of the total weight of the polymer composition.

[0056] In the most general embodiment, the ethylene-propylene-1-butene terpolymer comprises:

[0057] a) The amount of ethylene-derived units relative to the total amount of the terpolymer is 0.2-2.4 mol%.

[0058] b) The amount of propylene-derived units relative to the total amount of the terpolymer is 91.0-95.9 mol%; and

[0059] c) The amount of 1-butene-derived units is 3.9-6.6 mol% relative to the total amount of the terpolymer;

[0060] d) The total amount of units derived from ethylene, propylene, and 1-butene is 100 mol-%, and

[0061] e) The total amount of ethylene-derived units and 1-butene-derived units is 4.5-8.5 mol%, and

[0062] f) by 13 The amount of 2.1 region inversion determined by C-NMR analysis (as described in the experimental section) was 0.20–0.60 mol%; and

[0063] g) The melt flow rate MFR2 (230℃ / 2.16kg) measured according to ISO 1133 is 8-14.5g / 10min, and

[0064] h) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following equation:

[0065] Tm≥[150–1.6×(defect)–0.12×(defect)] 2 ]℃,

[0066] Wherein, “defect” represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regio inversion, and all values ​​are in mol%.

[0067] In a preferred embodiment, the ethylene-propylene-1-butene terpolymer has:

[0068] a) The amount of ethylene-derived units relative to the total amount of the terpolymer is 0.2-1.2 mol%; and

[0069] b) The amount of propylene-derived units relative to the total amount of the terpolymer is 93.6-95.3 mol%; and

[0070] c) The amount of 1-butene-derived units is 4.5-5.2 mol% relative to the total amount of the terpolymer;

[0071] d) The total amount of units derived from ethylene, propylene, and 1-butene is 100 mol-%, and

[0072] e) The total amount of units derived from ethylene and units derived from 1-butene is 4.8–6.5 mol%, and

[0073] f) by 13 The amount of 2.1 region inversion determined by C-NMR analysis (as described in the experimental section) was 0.36–0.55 mol-%.

[0074] g) The melt flow rate MFR2 (230℃ / 2.16kg) measured according to ISO 1133 is 10⁻¹⁴.5 g / 10 min, and

[0075] h) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following equation:

[0076] Tm≥[150–1.6×(defect)–0.12×(defect)] 2 ]℃,

[0077] Wherein, “defect” represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regio inversion, and all values ​​are in mol%.

[0078] catalyst

[0079] Many catalysts are suitable for this invention.

[0080] Generally, the catalyst system used in this invention can be prepared as described in WO 2018 / 122134 A1. The catalyst can be used in supported or unsupported form, preferably in a supported form. The particulate support material used is preferably an organic or inorganic material, such as silica, alumina, or zirconium oxide, or a mixed oxide, such as silica-alumina, particularly silica, alumina, or silica-alumina. Silica support is preferred. Those skilled in the art understand the procedures required for supporting metallocene catalysts.

[0081] Particularly preferred is that the carrier is a porous material, so that the complex can be loaded into the pores of the carrier, for example using methods similar to those described in WO 94 / 14856 (Mobil), WO 95 / 12622 (Borealis) and WO 2006 / 097497.

[0082] The average particle size of silica supports is typically 10-100 micrometers. However, it has been found that a particularly advantageous average particle size of 15-80 μm, preferably 18-50 μm, can be achieved.

[0083] The average pore size of the silica carrier material can range from 10 to 100 nm, and the pore volume can be 1 to 3 mL / g.

[0084] Suitable support materials include ES757 manufactured and sold by PQ, Sylopol 948 manufactured and sold by Grace, or SUNSPERA DM-L-303 silica manufactured by AGC Si-Tech. The support can be calcined before use in catalyst preparation to achieve the optimal silanol content.

[0085] The use of these carriers is common practice in this field.

[0086] The preferred complex used in this invention is formula (II') or (II).

[0087]

[0088] Where M represents zirconium or hafnium;

[0089] Each X is an independent hydrogen atom, halogen atom, or carbon atom. 1-6 -alkoxy group, C 1-6 -alkyl, phenyl or benzyl;

[0090] L is a divalent bridging group selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, and -R'2Ge-, where each R' is independently a hydrogen atom and C is a carbon atom. 1-20 -alkyl, C 3-10 -cycloalkyl, tri(C 1-20 -alkyl)silyl, C 6-20 -Aryl, C 7-20 -Arylalkyl or C 7-20 -alkylaryl;

[0091] Each R 2 Or R 2' C 1-10 -alkyl;

[0092] R 5' C 1-10 -alkyl or Z'R 3' Group;

[0093] R 6 It is hydrogen or C 1-10 -alkyl;

[0094] R 6' C 1-10 -alkyl or C 6-10 -Aryl; preferably tertiary alkyl;

[0095] R 7 For hydrogen, C 1-6 -alkyl or Zr 3 Group, R 7' It is hydrogen;

[0096] Z and Z' are independently O or S;

[0097] R 3' C can be optionally substituted with one or more halogen groups. 1-10 -alkyl or C 6-10 -Aryl;

[0098] R 3 C 1-10 -alkyl;

[0099] Each n is independently between 0 and 4, for example, 0, 1, or 2;

[0100] Each R 1 Independently for C 1-20 - Hydrocarbon group, such as C 1-10 -alkyl.

[0101] Other preferred complexes used in this invention are of formula (III') or (III):

[0102]

[0103] M represents zirconium or hafnium;

[0104] Each X is independently a hydrogen atom, a halogen atom, or a carbon atom. 1-6 -alkoxy group, C 1-6 -alkyl, phenyl or benzyl;

[0105] L is a divalent bridging group selected from -R'2C- or -R'2Si-, where each R' is independently a hydrogen atom, C is a carbon atom, and C is a carbon atom. 1-20 -alkyl or C 3-10 -cycloalkyl;

[0106] R 6 It is a hydrogen atom or a carbon atom. 1-10 -alkyl;

[0107] R 6' It is C 1-10 -alkyl or C 6-10 -aryl, preferably tertiary alkyl;

[0108] R 7 It is hydrogen, C 1-6 -alkyl or OC 1-6 -alkyl; Z' is O or S;

[0109] R 3' It is a C that is optionally substituted by one or more halogenated groups. 1-10-alkyl or C 6-10 -Aryl;

[0110] n is independently 0 to 4, for example 0, 1, or 2; and each R1 is independently C. 1-10 -alkyl.

[0111] Other preferred complexes used in this invention are of formula (IV') or (IV):

[0112]

[0113] M is zirconium or hafnium;

[0114] Each X is independently a hydrogen atom, a halogen atom, or a C atom. 1-6 -alkoxy group, C 1-6 -alkyl, phenyl or benzyl;

[0115] Each R' is independently a hydrogen atom, C 1-20 -alkyl or C 3-7 -cycloalkyl;

[0116] R 6 It is a hydrogen atom or a carbon atom. 1-10 -alkyl;

[0117] R 6' C 1-10 -alkyl or C 6-10 -aryl, preferably tertiary alkyl;

[0118] R 7 For hydrogen, C 1-6 -alkyl or OC 1-6 -alkyl; Z' is O or S;

[0119] R 3' C is a C that can be optionally substituted with one or more halogen groups. 1-10 -alkyl or C 6-10 -Aryl;

[0120] n is independently 0, 1, or 2; and each R 1 Independent is C 3-8 -alkyl.

[0121] Most preferably, the complex used in this invention is of formula (V') or (V):

[0122]

[0123] Where each X is independently a hydrogen atom, a halogen atom, or a carbon atom. 1-6 -alkoxy group, C 1-6 -alkyl, phenyl or benzyl;

[0124] R' independently for C 1-6-alkyl or C 3-10 -cycloalkyl;

[0125] R 1 Independently for C 3-8 -alkyl;

[0126] R 6 Is it hydrogen or C? 3-8 -alkyl;

[0127] R 6' It is C 3-8 -alkyl or C 6-10 -Aromatic, preferably tert-C 4-8 -alkyl;

[0128] R 3' It is a C that can be optionally substituted with one or more halogen groups. 1-6 -alkyl or C 6-10 -Aryl; and n is independently 0, 1 or 2.

[0129] The specific compounds of this invention include:

[0130]

[0131] The optimal choice is rac-antiMe2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2.

[0132] The ligands required to form the complexes and catalysts of this invention can be synthesized by any method, and skilled organic chemists can design various synthetic schemes to produce the necessary ligand materials. For example, WO 2007 / 116034 discloses the necessary chemical methods. Synthetic schemes can also generally be found in WO 2002 / 02576, WO 2011 / 135004, WO 2012 / 084961, WO2012 / 001052, WO 2011 / 076780, WO 2013 / 007650, WO 2015 / 158790, and WO 2018 / 122134. The examples section also provides sufficient guidance for those skilled in the art.

[0133] co-catalyst

[0134] To form an active catalyst, a co-catalyst well known in the art is typically required. Co-catalysts comprising one or more Group 13 metal compounds (such as organoaluminum compounds) or boron-containing co-catalysts, or combinations thereof, for activating metallocene catalysts are suitable for this invention.

[0135] In a preferred embodiment of the invention, a cocatalyst system comprising a boron-containing cocatalyst (e.g., a borate cocatalyst) and an aluminoxane cocatalyst is used.

[0136] Therefore, the unit site polymerization catalyst system used in this invention may include (i) a complex and an aluminoxane cocatalyst as defined above.

[0137] The aluminum oxane catalyst can be one of formula (VI):

[0138]

[0139] Where n is between 6 and 20, and R has the following meaning.

[0140] Aluminoxanes are formed during the partial hydrolysis of organoaluminum compounds, such as those of the formula AlR3, AlR2Y, and Al2R3Y3, where R can be, for example, C1-C2. 10 -alkyl, preferably C1-C5-alkyl, or C3-C 10 -Cycloalkyl, C7-C 12 -arylalkyl or -alkylaryl and / or phenyl or naphthyl, Y can be hydrogen, halogen, preferably chlorine or bromine, or C1-C 10 -alkoxy, preferably methoxy or ethoxy. The resulting oxygen-containing alumina is generally not a pure compound, but a mixture of oligomers of formula (VI).

[0141] The preferred aluminum oxane is methylaluminoxane (MAO).

[0142] The aluminoxanes of the present invention used as cocatalysts are not pure compounds due to their preparation method; therefore, the molar number of aluminoxane solutions mentioned below is based on their aluminum content.

[0143] According to the present invention, a boron-containing cocatalyst may also be used.

[0144] Boron-containing catalysts include those of formula (VII).

[0145] BY3(VII)

[0146] Wherein Y may be the same or different, and is a hydrogen atom, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 15 carbon atoms, an alkylaryl group, an aralkyl group, a haloalkyl group, or a haloaryl group (each alkyl group containing 1 to 10 carbon atoms, and the aryl group containing 6 to 20 carbon atoms), or fluorine, chlorine, bromine, or iodine. Preferred examples of Y are fluorine, trifluoromethyl, or aromatic fluorinated groups, such as p-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl, and 3,5-di(trifluoromethyl)phenyl. Trifluoroborane, tri(4-fluorophenyl)borane, tri(3,5-difluorophenyl)borane, tri(4-fluoromethylphenyl)borane, tri(2,4,6-trifluorophenyl)borane, tri(pentafluorophenyl)borane, tri(3,5-difluorophenyl)borane, and / or tri(3,4,5-trifluorophenyl)borane are preferred.

[0147] Tris(pentafluorophenyl)borane is particularly preferred.

[0148] However, borates, i.e. compounds containing borates, are preferred as boron-containing cocatalysts.

[0149] These compounds typically contain anions as shown in the following formula:

[0150] (Z)4B - (VIII)

[0151] Wherein Z is a phenyl derivative that can be optionally substituted, and the substituent is a halogenated-C. 1-6 -Alkyl or halogen group. Preferably fluorine or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

[0152] These ionic cocatalysts preferably contain a weakly coordinating anion, such as tetra(pentafluorophenyl)borate or tetra(3,5-di(trifluoromethyl)phenyl)borate. Suitable counterions are protonated amines or aniline derivatives, such as methylammonium, phenylammonium, dimethylammonium, diethylammonium, N-methylphenylammonium, diphenylammonium, N,N,N-dimethylphenylammonium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylphenylammonium, or p-nitro-N,N-dimethylphenylammonium.

[0153] Preferred ionic compounds that can be used according to the present invention include:

[0154] Tributyltetra(pentafluorophenyl)ammonium borate,

[0155] Tributyltetra(trifluoromethylphenyl)ammonium borate,

[0156] Tributyltetra(4-fluorophenyl)ammonium borate,

[0157] N,N-Dimethylcyclohexyltetra(pentafluorophenyl)borate ammonium,

[0158] N,N-Dimethylbenzyltetra(pentafluorophenyl)borate ammonium,

[0159] N,N-Dimethylphenyltetra(pentafluorophenyl)borate ammonium,

[0160] N,N-Di(propyl)tetra(pentafluorophenyl)borate ammonium,

[0161] Ammonium di(cyclohexyl)tetra(pentafluorophenyl)borate

[0162] Triphenylbenzyltetra(pentafluorophenyl)ammonium borate,

[0163] Or ferrocene tetra(pentafluorophenyl)borate.

[0164] Preferred is triphenylcarbium tetra(pentafluorophenyl)borate,

[0165] N,N-Dimethylphenyltetra(pentafluorophenyl)borate ammonium,

[0166] N,N-Dimethylcyclohexyltetra(pentafluorophenyl)borate ammonium or

[0167] N,N-Dimethylbenzyltetra(pentafluorophenyl)borate ammonium.

[0168] According to the present invention, it is particularly preferred to use an aluminoxane cocatalyst (such as MAO) together with a boron-containing cocatalyst (such as a borate cocatalyst).

[0169] The appropriate dosage of the catalyst is well known to technicians.

[0170] The amount of catalyst should ideally be selected to achieve the molar ratio defined below.

[0171] The molar ratio (boron / M) of the feed amount of boron (B) to metal ions (M) (preferably zirconium) in the metallocene can be in the range of 0.1:1 to 10:1 mol / mol, preferably 0.3:1-7:1, and particularly preferably 0.3:1-5:1 mol / mol.

[0172] More preferably, the molar ratio (boron / M) of the feed amount of boron (B) to metal ions (M) (preferably zirconium) in the metallocene is 0.3:1 to 3:1.

[0173] The molar ratio (Al / M) of Al in the aluminoxane to metal ions (M) (preferably zirconium) in the metallocene can be in the range of 1:1-2000:1 mol / mol, preferably 10:1-1000:1, and more preferably 50:1-600:1 mol / mol.

[0174] Other suitable catalyst systems are described in WO2019179959, which are incorporated herein by reference. In the broadest sense, catalyst complexes have the following structures.

[0175]

[0176] in

[0177] Mt is either Hf or Zr

[0178] Each X is a σ ligand;

[0179] Each R 1 Independently identical or different, CH2-R 7 Group, wherein R 7 Is it H or straight chain or branched chain C? 1-6 -alkyl, C 3-8 cycloalkyl, C 6-10 Aryl,

[0180] Each R 2 Independently, it is a -CH=, -CY=, -CH2-, -CHY-, or -CY2- group, where Y is C. 1-10 Hydrocarbon group, n is 2-6,

[0181] Each R 3 and R 4 Independently identical or different, being hydrogen, straight-chain or branched C1-C6-alkyl, OY group or C 7-20 Aryl alkyl, C 7-20 alkylaryl or C 6-20 Aryl, each phenyl group has at least one R 3 And at least one R 4 Not hydrogen, and optionally, two adjacent R 3 Or R 4 The groups can be part of the ring containing the phenyl carbon to which these groups are bonded.

[0182] R 5 It is a straight-chain or branched C1-C6-alkyl, C 7-20 Aryl alkyl, C 7-20 Alkyl or C6-C 20 Aryl,

[0183] R 6 It is C(R) 8 )3 groups, of which R 8 It is a straight-chain or branched C1-C6 alkyl group.

[0184] Each R is independently C1-C 20 -Hydrocarbon group, C6-C 20 -Aryl, C7-C 20 -Aryl or C7-C 20 -alkylaryl.

[0185] As specific metallocene catalyst complexes, the following three examples can be mentioned, abbreviated as MC1, MC2 and MC3.

[0186]

[0187] rac-trans-dimethylsilanediyl[2-methyl-4,8-bis-(4<'>tert-butylphenyl)-1,5,6,7-tetrahydro-s-inden-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride (MC-1)

[0188] rac-trans-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-inden-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride (MC-2)

[0189] rac-trans-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-inden-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride (MC-3)

[0190] This also includes the corresponding dimethylzirconium analogues.

[0191] The polymer compositions according to the invention can be compounded and granulated using various compounding and blending equipment and methods known and commonly used in the field of resin blending. Conventional compounding or blending equipment, such as Banbury mixers, twin-roll rubber mills, Buss-co-kneaders, or twin-screw extruders, can be used to compound the various components of the compositions of the invention. The composition recovered from the extruder / mixer is typically in granular form. These granules are then further processed to form the cast film of the invention. Preferably, the compositions of the invention contain the terpolymer described herein in a content of at least 97 wt%. More preferably, the compositions of the invention consist of at least 97 wt% of the terpolymer described herein and additives. Preferred additives for this purpose have been specifically described above.

[0192] Cast film

[0193] The cast film of the present invention is made from the above-mentioned ethylene-propylene-1-butene terpolymer. All preferred aspects also apply to the cast film.

[0194] As briefly summarized above, the present invention relates to a cast film made of an ethylene-propylene-1-butene ternary polymer, the ternary polymer comprising:

[0195] a) The amount of ethylene-derived units relative to the total amount of the terpolymer is 0.2-2.4 mol%; and

[0196] b) The amount of propylene-derived units relative to the total amount of the terpolymer is 91.0-95.9 mol%; and

[0197] c) The amount of 1-butene-derived units is 3.9-6.6 mol% relative to the total amount of the terpolymer;

[0198] d) The total amount of units derived from ethylene, propylene, and 1-butene is 100 mol-%, and

[0199] e) The total amount of ethylene-derived units and 1-butene-derived units is 4.5-8.5 mol%, and

[0200] f) by 13 The amount of 2.1 region inversion determined by C-NMR analysis (as described in the experimental section) was 0.20–0.60 mol%; and

[0201] g) The melt flow rate MFR2 (230℃ / 2.16kg) measured according to ISO 1133 is 8-14.5g / 10min, and

[0202] h) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following equation:

[0203] Tm≥[150–1.6×(defect)–0.12×(defect)] 2 ]℃,

[0204] Wherein, “defect” represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regio inversion; all values ​​are in mol% and

[0205] The sealing start temperature (SIT) of the cast film (determined by the method described in the experimental section) is below 117°C.

[0206] The membrane of the present invention can be obtained by converting the polymer composition of the present invention into a membrane using conventional membrane technology, such as casting film technology.

[0207] The molten polymer is preferably extruded through a slit die onto cooling rollers, where it is cooled into a solid film. Typically, the polymer is first compressed and liquefied in an extruder (preferably a single-screw extruder), and all additives may have been added to the polymer or introduced at this stage via masterbatch. The melt is then passed through a flat die (slit die), and the extruded film is demolded on one or more release rollers, cooled, and solidified. Maintaining the temperature of the take-up rollers, which cool and solidify the extruded film, at 10-50°C (preferably 15-40°C) has been shown to be particularly advantageous. To improve film quality, auxiliary devices such as air knives and / or vacuum chambers can be used.

[0208] The cast film of the present invention is preferably made from the following ethylene-propylene-1-butene terpolymer: in which the content of ethylene-derived units relative to the total amount of the terpolymer is 0.2-1.2 mol%.

[0209] In another preferred aspect, the cast film of the present invention is preferably made of an ethylene-propylene-1-butene terpolymer, wherein the content of 1-butene-derived units in the terpolymer is 4.5-5.2 mol relative to the total amount of the terpolymer.

[0210] The cast film of the present invention is preferably made of the following ethylene-propylene-1-butene terpolymer, wherein the total amount of ethylene-derived units and 1-butene-derived units is 4.8-6.5 mol.

[0211] Preferably, the cast film of the present invention is made of such an ethylene-propylene-1-butene terpolymer, according to... 13 C-NMR analysis (as described in the experimental section) showed that the terpolymer had 0.36-0.55 mol% of 2.1 regioinversion.

[0212] In a particularly preferred embodiment, the cast film of the present invention is made of an ethylene-propylene-1-butene terpolymer comprising:

[0213] a) The amount of ethylene-derived units relative to the total amount of the terpolymer is 0.2-1.2 mol%.

[0214] b) The amount of propylene-derived units relative to the total amount of the terpolymer is 93.6-95.3 mol%; and

[0215] c) The amount of 1-butene-derived units is 4.5-5.2 mol% relative to the total amount of the terpolymer;

[0216] d) The total percentage of units derived from ethylene, propylene, and 1-butene is 100 mol%, and

[0217] e) The total amount of units derived from ethylene and units derived from 1-butene is 4.8–6.5 mol%, and

[0218] f) by 13 The amount of 2.1 region inversion determined by C-NMR analysis (as described in the experimental section) was 0.36–0.55 mol-%.

[0219] g) The melt flow rate MFR2 (230℃ / 2.16kg) measured according to ISO 1133 is 10⁻¹⁴.5 g / 10 min, and

[0220] h) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following equation:

[0221] Tm≥[150–1.6×(defect)–0.12×(defect)] 2 ]℃,

[0222] Wherein, "defect" represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regio inversion; all values ​​are in mol%.

[0223] The sealing start temperature (SIT) of the cast film (determined by the method described in the experimental section) is below 112°C, preferably 105 to 111°C.

[0224] The cast film of the present invention preferably has a tensile modulus of 200-800 MPa, more preferably 400-700 MPa, and more preferably 520-620 MPa, measured in the mechanical direction (preferably also in the transverse direction) of a film with a thickness of 50 μm at 23°C according to ISO 527-3.

[0225] In another aspect, the cast film of the present invention is preferably made of the following ethylene-propylene-1-butene terpolymer, wherein the butene content of the terpolymer is bimodal and / or the molecular weight is bimodal.

[0226] It is worth noting that the membrane thickness is not limited to 50 μm. The 50 μm thick membrane was used as a test sample only for ease of comparison.

[0227] In a preferred embodiment, the cast film of the present invention is made of the following ethylene-propylene-1-butene terpolymer having a hexane solubility (FDA) of 0.80 wt% or less, preferably 0.70 wt% or less, more preferably 0.65 wt% or less, such as in the range of 0.65-0.01 wt%.

[0228] Furthermore, the preferred casting film of the present invention has a xylene cold soluble (XCS) fraction determined according to ISO 16152 in the range of 0.5 to 22.0 wt%. In another preferred embodiment, the casting film of the present invention has a xylene cold soluble (XCS) fraction determined according to ISO 16152 of 0.5-5.0 wt%, more preferably 0.6-2.5 wt%, and even more preferably 1.0-2.0 wt%.

[0229] The cast film of the present invention preferably has a haze of less than 3.0% as measured according to ASTM D1003-00 on a film with a thickness of 50 μm, more preferably 0.1-0.9%, and more preferably 0.2%-0.5%. Detailed Implementation

[0230] A. Measurement Method

[0231] Unless otherwise defined, the following terms and methods of determination apply to the above general description of the invention and the following embodiments.

[0232] a) MFR2 (230°C) was measured according to ISO 1133 (230°C, 2.16 kg load).

[0233] b) Quantitative analysis of microstructure using nuclear magnetic resonance spectroscopy

[0234] Quantitative nuclear magnetic resonance (NMR) spectroscopy is used to quantify the comonomer content in polymers.

[0235] Quantitative 13 C{ 1 ¹H NMR spectroscopy was performed using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz in the molten state. 1 H and 13 Recorded using C. All spectra were recorded using... 13 A C-optimized 7mm magic angle rotation (MAS) probe was used for recording at 180°C, with nitrogen used for all gas atmospheres. Approximately 200 mg of material was loaded into a 7mm outer diameter zirconia MAS rotor and rotated at a frequency of 4 kHz. This setup was chosen primarily to achieve the high sensitivity required for rapid identification and accurate quantification. Standard single-pulse excitation was employed, utilizing a 3-second short-cycle delay NOE and an RS-HEPT decoupling scheme. A total of 1024 (1k) transients were obtained for each spectrum.

[0236] Quantitative 13 C{1 The H NMR spectra were processed and integrated, and the relevant quantitative properties were determined based on the integration. All chemical shifts were internally referenced to the methyl isotactic pentatonic group (mmmm) at 21.85 ppm.

[0237] The characteristic signal {brandolini01} corresponding to the incorporation of 1-butene was observed, and the copolymer content was quantified.

[0238] The amount of isolated 1-butene incorporated into the PBP sequence was quantified using the integral at the αB2 site at 43.6 ppm, where the integral represents the number of reporter sites per monomer.

[0239] B = I αB2 / 2

[0240] The amount of 1-butene sequentially incorporated into the PBBP sequence was quantified using the integral at the ααB2B2 site at 40.5 ppm, where the integral represents the number of reporter sites for each comonomer.

[0241] BB = 2 * I ααB2B2

[0242] In the presence of BB, the B value must be corrected for the effect of BB on the αB2 site:

[0243] B = (I αB2 / 2)–BB / 2

[0244] The total amount of 1-butene is calculated based on the sum of isolated and continuous incorporation of 1-butene:

[0245] B 总和 =B+BB

[0246] The characteristic signal {brandolini01} corresponding to the incorporation of ethylene was observed, and the amount of comonomer was quantified.

[0247] The amount of isolated ethylene incorporated into the PEP sequence was quantified using the integral at the Sββ site at 24.3 ppm, where the integral represents the number of reporter sites per monomer.

[0248] E = I S ββ

[0249] If a characteristic signal corresponding to the continuous incorporation of ethylene is observed in the PEE sequence, quantification is performed using the Sβδ site at 27.0 ppm:

[0250] EE = I S βδ

[0251] Characteristic signals {resconi00} corresponding to regional defects were observed. Two methyl sites at 17.7 and 17.2 ppm and a methylene site at 42.4 ppm indicate the presence of isolated 2,1-erythrode regional defects, which is confirmed by other characteristic sites. 2,1-erythrode defects adjacent to ethylene units are indicated by two dissimilar Sαβ signals at 34.8 ppm and 34.4 ppm, and a Tγγ signal at 33.7 ppm.

[0252] Using the integral of the methylene site at 42.4 ppm (I e9 ) for isolated 2,1-erythian region inversion (P 孤立21e Quantitative analysis:

[0253] P 孤立21e =I e9

[0254] If present, use the value at 33.7 ppm (I Tγγ The methyl site at position ) corresponds to ethylene (P) E21 Quantitative analysis of defects in adjacent 2,1 regions:

[0255] P E21 =I Tγγ

[0256] Then, the total ethylene content is calculated based on the sum of isolated, continuously incorporated ethylene and ethylene adjacent to defects in region 2,1:

[0257] E total =E + EE + P E21

[0258] The amount of propylene is based on the Sαα methylene site at 46.7 ppm (including all other propylene units not covered by Sαα, e.g., a factor of 3*P representing the three propylene units missing from an isolated 2,1-erythroline region defect). 孤立21e Quantitative analysis:

[0259] P 总和 =I Sαα +3*P 孤立21e +B+0.5*BB+E+0.5*EE+2*P E21

[0260] The total mole fractions of 1-butene and ethylene in the polymer are then calculated using the following formula:

[0261] fB = B 总和 / (E 总和 +P 总和 +B 总和 )

[0262] fE=E总和 / (E 总和 +P 总和 +B 总和 )

[0263] Calculate the molar percentage of the comonomer based on the molar fraction:

[0264] B[mol%]=100*fB

[0265] E[mol%]=100*fE

[0266] Calculate the weight percentage of comonomer added based on mole fraction:

[0267] B[wt.-%]=100*(fB*56.11) / ((fE*28.05)+(fB*56.11)+((1-(fE+fB))*42.08))

[0268] E[wt.-%]=100*(fE*28.05) / ((fE*28.05)+(fB*56.11)+((1-(fE+fB))*42.08))

[0269] Quantification of the molar percentage of isolated 2,1-erythroide region defects relative to all propylene:

[0270] [21e]mol% = 100*P 21e孤立 / P 总和

[0271] The molar percentage of defects in the 2,1 region adjacent to ethylene relative to all propylene was quantified:

[0272] [E21]mol% = 100*P E21 / P 总和

[0273] The total quantity of defects 2,1 is quantified as follows:

[0274]

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

[0275] No characteristic signal {resconi00} corresponding to other types of regional defects (2,1-Su type, 3,1 insertion) was observed.

[0276] References (mentioned above):

[0277]

[0278] c) DSC analysis, melting temperature (Tm) and crystallization temperature (Tc):

[0279] Samples ranging from 5 to 7 mg were measured using a TA Instruments Q2000 differential scanning calorimeter (DSC). DSC was performed in heating / cooling / heating cycles at a scan rate of 10 °C / min within a temperature range of -30 °C to +225 °C, according to ISO 11357 / Part 3 / Method C2. Crystallization temperature (Tc) and enthalpy of crystallization (Hc) were determined by the cooling step, while melting temperature (Tm) and enthalpy of fusion (Hm) were determined by the second heating step.

[0280] d) Cast film

[0281] The properties of the cast film (except for hexane solubility and tensile modulus) were determined on cast films produced by a single-screw extruder in a production line with a barrel diameter of 30 mm, a 200*0.5 mm die, and equipped with cooling and winding rollers. The melt temperature in the die was 260 °C. The temperature of the cooling and winding rollers was maintained at 15 °C, and the film thickness was 50 μm.

[0282] e) Haze

[0283] The thickness of the cast film was measured according to ASTM D1003-00.

[0284] g) Sealing start temperature (SIT); Sealing end temperature (SET);

[0285] Sealing start temperature (SIT), sealing end temperature (SET), and sealing range: The method described above determines the sealing temperature range (sealing range) of polypropylene film (particularly blown or cast film) according to ASTM F1921-12. Sealing pressure, cooling time, and peel speed may be modified as described below.

[0286] The sealing temperature range refers to the temperature range under which the membrane can be sealed according to the following conditions.

[0287] The lower limit (heat sealing initiation temperature (SIT)) refers to the sealing temperature at which a seal strength greater than 5N is achieved. The upper limit (seal sealing end temperature (SET)) is reached when the membrane adheres to the sealing device.

[0288] The sealing range was determined using a 50μm thick cast film on a J&B 3000 universal sealing machine. Specific parameters are as follows:

[0289] Sample width: 25.4mm

[0290] Sealing pressure: 0.1 N / mm 2

[0291] Sealing time: 0.1s

[0292] Cooldown time: 99s

[0293] Peeling speed: 10mm / s

[0294] Starting temperature: 80℃

[0295] Finishing temperature: 150℃

[0296] Increment: 10℃

[0297] The samples were sealed from side to side at various sealing temperatures, and the sealing strength (force) was measured at each step.

[0298] Determine the temperature at which the seal strength reaches 5N.

[0299] h) Hexane (C6) extractables

[0300] Hexane extractables were determined according to FDA methods (Federal Register, Title 21, Chapter 1, Part 177, Section 1520, Annex B).

[0301] The determination was performed according to FDA Section 177.1520. 1 g of a 100 μm thick polymer membrane was added to 400 ml of n-hexane, and the mixture was stirred at 50°C using a reflux condenser for 2 hours. After 2 hours, the mixture was immediately filtered through filter paper. The precipitate was collected in an aluminum container, and the remaining n-hexane was evaporated in a vapor bath under a nitrogen stream. The amount of n-hexane dissolved was determined by the following formula: ((sample weight + crucible weight) - (crucible weight)) / (sample weight) x 100%.

[0302] The film used in the experiment was produced on the Collin cast film production line with a melting temperature of 230℃, a production capacity of 8kg / h, and a cold roll temperature of 40℃.

[0303] i) Tensile modulus

[0304] The tensile modulus in the machine direction and transverse direction was determined according to ISO 527-3 at 23°C for the aforementioned 50μm thick cast film sample produced by a single-layer casting film production line. In this production line, the melting temperature was 220°C and the cold rolling temperature was 20°C. The test was conducted at a crosshead speed of 1 mm / min.

[0305] m) Cold-soluble xylene (XCS)

[0306] The xylene solubility (XS) fraction defined and described in this invention was determined according to ISO 16152 as follows: 2.0 g of polymer was dissolved in 250 ml of p-xylene with stirring at 135 °C. After 30 minutes, the solution was cooled to room temperature for 15 minutes, and then precipitated at 25 ± 0.5 °C for 30 minutes. The solution was filtered through filter paper into two 100 ml flasks. The solution from the first 100 ml container was evaporated under a nitrogen stream, and the residue was dried under vacuum at 90 °C until a fixed weight was achieved. The soluble fraction (percentage) of xylene can be determined by the following formula:

[0307] XS%=(100*m*V0) / (m0*v); m0=initial polymer amount (g); m=residue weight (g); V0=initial volume (ml); V=analytical sample volume (ml).

[0308] B. Example

[0309] Preparation of the catalyst system used in Examples IE1-IE3

[0310] Metallocene (MC1) (rac-trans-dimethylsilyldiyl(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride) was synthesized according to the method described in WO 2013 / 007650.

[0311] The catalysts used in Examples IE1-IE3 were prepared from MC1 according to the method described in detail in WO2015 / 011135A1 (WO2015 / 011135A1 describes the preparation of catalyst 3 from metallocene complex MC1 and methylaluminoxane (MAO) and borate), but the surfactant was 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-1-propanol.

[0312] Preparation of catalyst systems for comparative examples CE1-CE2

[0313] For comparative examples CE1 and CE2, Ziegler-Natta catalyst, sold by Lyondell Basell under the trademark Avant ZN180, was used. TEAL was used as the co-catalyst at a feed rate of 150 g / t C3, and dicyclopentyldimethoxysilane (=donor D, CAS No. 126990-35-0) was used as the external donor at a feed rate of 40 g / t C3.

[0314] Polymerization and Granulation

[0315] Terpolymers IE1-IE3 were produced at a Borstar pilot plant, which consisted of a prepolymerization reactor, a circulating reactor, and a gas-phase reactor connected in series. The polymerization conditions and polymer characterization results are shown in Table 1. IE1-IE3 were prepared using the aforementioned metallocene catalyst system, while CE1-CE2 were prepared using the aforementioned Zn catalyst system.

[0316] Table 1: Polymerization process conditions for IEs and CEs.

[0317]

[0318]

[0319]

[0320] nm = Not tested.

[0321] It can be seen that carefully setting the amount of ethylene-derived units, the total amount of ethylene and butene-derived units, and controlling the reversal of region 2.1 can result in a relatively low melting temperature for a given number of total defects. Simultaneously, the hexane solubility is also very low.

[0322] The obtained polymer was compounded with 1500 ppm of antioxidant (Irganox B215, commercially available from BASF) and 500 ppm of calcium stearate in a co-rotating twin-screw extruder (Cooperion ZSK 57) at 220 °C. The final MFR2 of the final composition was achieved by viscous cracking in a twin-screw extruder using an appropriate amount (350 ppm) of (tert-butylperoxy)-2,5-dimethylhexane (Trigonox 101, commercially available from AkzoNobel). The properties of the cast film made from the trimer are shown in Table 2 below.

[0323] Table 2: Properties of Polymer Composition and Cast Film

[0324] IE1 IE2 IE3 CE1 CE2 Membrane type cast cast cast cast cast TM / MD MPa 614 536 452 574 430 Haze ％ 0.22 0.49 0.30 0.54 0.65 Clarity ％ 99.8 99.8 99.8 99.3 99.0 Sealing start temperature ℃ 111 106 103 117 112

[0325] As can be seen from Table 2, the membranes made from the materials containing the terpolymers (IE1-IE3) of the present invention have a lower sealing initiation temperature compared to comparative examples CE1 and CE2. Furthermore, the membranes of the present invention exhibit very good mechanical and optical properties.

Claims

1. Cast film made from an ethylene-propylene-1-butene terpolymer, wherein, The ethylene-propylene-1 -butene terpolymer comprises: a) units derived from ethylene in an amount of 0.2 to 1.2 mol-%, relative to the total amount of the terpolymer; b) units derived from propylene in an amount of 93.6 to 95.3 mol-%, relative to the total amount of the terpolymer; and c) units derived from 1 -butene in an amount of 4.5 to 5.2 mol-%, relative to the total amount of the terpolymer; d) wherein the units derived from ethylene, the units derived from propylene and the units derived from 1 -butene add up to 100 mol-%; e) the total amount of units derived from ethylene and units derived from 1 -butene is 4.8 to 6.5 mol-%; g) a melt flow rate MFR2measured according to ISO 1133 at 230 °C and 2.16 kg is in the range of 10 to 14.5 g / 10 min; f) Based on the description in the experimental section, by 13 The amount of 2.1 region inversion determined by C-NMR analysis was 0.36-0.55 mol%. h) the melting temperature Tmmeasured by differential scanning calorimetry DSC fulfils the following formula: Tm≥ [150 - 1.6 x (defects) - 0.12 x (defects)2] °C, wherein "defects" denotes the sum of units derived from ethylene, units derived from 1 -butene and 2.1 regio-inversions, all values in mol-%, the seal initiation temperature SIT of the cast film determined by the method described in the experimental part is below 112 °C. the seal initiation temperature SIT of the cast film determined by the method described in the experimental part is in the range of 105 to 11 1 °C.

2. The cast film according to claim 1, characterized in that the tensile modulus determined according to ISO 527-3 at 23 °C on a sample cast film having a thickness of 50 pm in the machine direction MD is in the range of 200 to 800 MPa.

3. The cast film according to claim 1, characterized in that the tensile modulus determined according to ISO 527-3 at 23 °C on a sample cast film having a thickness of 50 pm in the machine direction MD is in the range of 520 to 620 MPa.

4. The cast film according to claim 1, characterized in that the xylene cold soluble XCS fraction determined according to ISO 16152 is in the range of 0.5 to 5.0 wt-%.

5. The cast film according to any one of claims 1-4, wherein, The ethylene-propylene-1 -butene terpolymer comprises:

6. An ethylene-propylene-1-butene terpolymer wherein, a) units derived from ethylene in an amount of 0.2 to 1.2 mol-%, relative to the total amount of the terpolymer; b) units derived from propylene in an amount of 93.6 to 95.3 mol-%, relative to the total amount of the terpolymer; and c) units derived from 1 -butene in an amount of 4.5 to 5.2 mol-%, relative to the total amount of the terpolymer; d) wherein the units derived from ethylene, the units derived from propylene and the units derived from 1 -butene add up to 100 mol-%; e) the total amount of units derived from ethylene and units derived from 1 -butene is 4.8 to 6.5 mol-%; g) a melt flow rate MFR2measured according to ISO 1133 at 230 °C and 2.16 kg is in the range of 10 to 14.5 g / 10 min; h) the melting temperature Tmmeasured by differential scanning calorimetry DSC fulfils the following formula: f) Based on the description in the experimental section, by 13 The amount of 2.1 region inversion determined by C-NMR analysis was 0.36-0.55 mol%. Tm≥ [150 - 1.6 x (defects) - 0.12 x (defects)2] °C, wherein "defects" denotes the sum of units derived from ethylene, units derived from 1 -butene and 2.1 regio-inversions, all values in mol-%, Tm ≥ [150–1.6 × (defect)–0.12 × (defect)²]℃, Wherein, "defect" refers to the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regio inversion, and all values ​​are in mol%.

7. A composition wherein, The composition comprises the ethylene-propylene-1-butene terpolymer of claim 6, wherein the amount of the terpolymer is at least 97 wt% relative to the total amount of the composition.

8. The composition of claim 7, wherein, The composition comprises the ethylene-propylene-1-butene terpolymer of claim 6 and additives.

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