Excellent blown film based on C2C3C4 terpolymer and C2C3C4 terpolymer

Abstract

Blown films made from terpolymers and terpolymers containing units derived from propylene, units derived from ethylene and units derived from 1-butene.

Description

Technical Field

[0001] The present invention relates to blown films made from polypropylene terpolymers and to the polypropylene terpolymers themselves. Background Art

[0002] Optimizing blown films based on polypropylene (PP) copolymers is a multi-dimensional problem. Numerous attempts have been made to optimize materials suitable for film production. WO 2002 / 057342 A1 describes a biaxially oriented PP (BOPP) film made from a Ziegler-Natta catalyst-derived copolymer containing at least 0.8 wt. % ethylene, particularly 0.8-1.5 wt. %. Although PP terpolymers are mentioned prophetically, these materials are not disclosed in this application. Cast films made from PP copolymers exhibit undesirably high haze. WO 2009 / 019169 A1 describes a process for producing a Ziegler-Natta catalyst-derived PP terpolymer suitable for blown film production using a 1,3-diether internal donor catalyst, the PP terpolymer containing at least 8 wt. % total comonomer, wherein the comonomer units are derived from ethylene and C4-C8 α-olefins. According to WO 2009 / 019169 A1, the best balance of properties is observed when an ethylene content of less than 2.5 wt% is combined with a 1-butene content of greater than 10 wt%. Thus, when the ethylene content is greater than 2.5 wt%, the 1-butene content should be less than 10 wt%. A composition with an ethylene content of 1.2 wt% and a 1-butene content of 11.3 wt% (i.e., a C4 / C2 (w / w) ratio of 9.4) has a SIT (seal initiation temperature) as low as 107.4°C and a haze of 0.2% (1 mm plate). However, the film contains unacceptably high levels of hexane (C6) extractables, exceeding 2.8 wt%. US 6,388,040 relates to BOPP films, i.e., completely different types of films made from compositions with different melting temperatures.

[0003] EP3192817 A1 discloses a method for producing a terpolymer containing units derived from 1-butene using a crosslinked metallocene compound. EP3192817 A1 defines an extremely wide range of structural units derived from 1-butene (i.e., 4 mol% to 45 mol%) and structural units derived from ethylene (4 mol% to 45 mol%) (e.g., 12.8 mol% ethylene and 21.1 mol% 1-butene). Although EP3192817 A1 suggests some membrane concepts, these membranes are not actually disclosed in the application.

[0004] Therefore, there is still a need for a blown film based on PP terpolymers having a low seal initiation temperature (e.g., less than 120° C.), low haze (e.g., less than 6.0%), and especially low hexane extractables (e.g., less than 0.75 wt. %). At the same time, the film should have a sufficient melt flow rate and high dart impact.

[0005] The present invention relates to these aspects and is based on the discovery that careful selection of the amounts of ethylene and 1-butene units, their total amount, the 2.1 regioinversions, the molar ratio of units derived from 1-butene to units derived from ethylene, and the total amount of defects can provide an advantageous combination of low hexane extractables, low haze, good dart drop impact, and good sealing properties. Summary of the Invention

[0006] To this end, the present invention provides a blown film made from an ethylene-propylene-1-butene terpolymer, the terpolymer comprising:

[0007] a) units derived from ethylene, wherein the amount of units derived from ethylene is 0.8 to 2.8 mol% relative to the total amount of the terpolymer;

[0008] b) units derived from propylene, the amount of units derived from propylene being 91.6 to 95.8 mol% relative to the total amount of the terpolymer; and

[0009] c) units derived from 1-butene, with the amount of the units derived from 1-butene being 3.4 to 5.6 mol% relative to the total amount of the terpolymer.

[0010] d) The total of the units derived from ethylene, the units derived from propylene and the units derived from 1-butene is 100 mol%,

[0011] e) the total amount of units derived from ethylene and units derived from 1-butene is 4.5 to 8.0 mol%,

[0012] f) a molar ratio of units derived from 1-butene to units derived from ethylene of 1.5 to 5.0;

[0013] g) By 13 The amount of 2.1 regioinversion determined by C-NMR analysis (as described in the experimental section) was 0.20–0.45 mol %;

[0014] h) a melt flow rate MFR2 (230°C / 2.16 kg) determined according to ISO 1133 in the range of 1.5 to 4.5 g / 10 min, and

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

[0016] Tm<[150–1.6×(defect)–0.14×(defect) 2 ]℃,

[0017] wherein "defects" represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regioinversions, all values ​​being expressed in mol %, and

[0018] The seal initiation temperature (SIT) of the blown film (determined by the method described in the experimental part) was less than 117°C.

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

[0020] a) units derived from ethylene, wherein the amount of units derived from ethylene is 0.8 to 2.8 mol% relative to the terpolymer;

[0021] b) units derived from propylene, wherein the amount of units derived from propylene is 91.6 to 95.8 mol% relative to the total amount of the terpolymer;

[0022] c) units derived from 1-butene, with the amount of the units derived from 1-butene being 3.4 to 5.6 mol% relative to the total amount of the terpolymer.

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

[0024] e) the total amount of units derived from ethylene and units derived from 1-butene is 4.5 to 8.0 mol%,

[0025] f) a molar ratio of units derived from 1-butene to units derived from ethylene in the range of 1.5 to 5.0;

[0026] g) By 13 The amount of 2.1 regioinversion determined by C-NMR analysis (as described in the experimental section) was 0.20–0.45 mol %;

[0027] h) a melt flow rate MFR2 (230°C / 2.16 kg) determined according to ISO 1133 in the range of 1.5 to 4.5 g / 10 min, and

[0028] i) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following formula:

[0029] Tm<[150–1.6×(defect)–0.14×(defect)2]℃,

[0030] Here, "defects" represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regioinversions, and all values ​​are expressed in mol%.

[0031] Advantageous variants of the blown film and the ethylene-propylene-1-butene terpolymer are specified in the dependent claims.

[0032] In yet 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%. DETAILED DESCRIPTION

[0033] definition

[0034] Regio-defects in propylene polymers can be of three different types, namely, 2,1-erythro (2,1e), 2,1-threo (2,1t) and 3,1 defects. A detailed description of the structure and formation mechanism of regio-defects in polypropylene can be found, for example, in Chemical Reviews 2000, 100(4), pp. 1316-1327. These defects are described in more detail below. 13 Determined by C-NMR spectroscopy.

[0035] The term "2,1 regio defect" or "2,1 regio inversion" as used herein defines the sum of 2,1-erythro regio defects and 2,1-threo regio defects.

[0036] "Terpolymers" herein refer to polymers made from the monomers ethylene, propylene, and 1-butene, whereby these monomers can be found in the polymer chain. The content of units derived from these comonomers totals 100 mol%. Pseudo-terpolymers made from a mixture of two copolymers are not included in the term "terpolymers" herein. Pseudo-terpolymers can be identified by coupled TREF-IR, coupled TREF-NMR, or similar methods. By definition, the terpolymers of the present invention are not mixtures of two copolymers.

[0037] The term "defects" refers to the sum of units derived from ethylene, units derived from 1-butene and 2.1 regioinversions, all values ​​being expressed in mol%.

[0038] When the term "comprising" is used in this description and the claims, it does not exclude other, unspecified elements of major or minor functional importance. For the purposes of the present 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 is also to be understood as disclosing a group that preferably consists only of these embodiments.

[0039] Whenever the terms "including" or "having" are used, these terms are meant to be equivalent to "comprising" as defined above.

[0040] When used in general terms such as "a", "an" or the like, they include the plural form of the noun unless expressly stated otherwise.

[0041] The bimodality of the units derived from 1-butene means that the terpolymer can be obtained in two reactors connected in series with a split ratio of 40:60 to 60:40. The reactors are therefore operated in such a way that the intermediate terpolymer produced in the first reactor differs from the final terpolymer in terms of the content of units derived from 1-butene by at least 20%, all contents being expressed as weight percentages, with the first reactor value serving as the reference. For example, 5.0 wt% (first reactor product) and 6.1 wt% (final product) meet the requirements.

[0042] The bimodality of the molecular weight means that the terpolymer can be obtained in two reactors in series with a split ratio of 40:60 to 60:40, whereby the reactors are operated in such a way that the intermediate terpolymer produced in the first reactor differs from the final terpolymer in terms of melt flow rate (ISO 1133, 2.16 kg load, 230° C.) by at least 20%, e.g. 1.5 g / 10 min (first reactor product) and 1.8 g / 10 min (final product).

[0043] Terpolymers and compositions

[0044] The amount of regioinversion depends to some extent on the amount of comonomer, i.e. the higher the amount of comonomer, the lower the amount of 2.1 regioinversion. In addition, the 2.1 regioinversion can be influenced by the choice of polymerization temperature: higher polymerization temperatures favor lower amounts of 2.1 regioinversion.

[0045] In another preferred aspect, the terpolymer is bimodal with respect to the units derived from 1-butene. As outlined above in the definition section, this means that two polymers are present, which differ in their 1-butene content. It goes without saying that bimodality in 1-butene content can be achieved by using two or more reactors in series or by other measures such as a parallel reactor arrangement and subsequent mixing (e.g., mixing in solution).

[0046] In another preferred aspect, the terpolymer is bimodal in molecular weight. As outlined in the definition section, this also means the presence of two polymers that differ in melt flow rate. The same measures as above and the use of a chain transfer agent (typically hydrogen) will apply to this purpose.

[0047] The composition of the present invention comprises the terpolymer in an amount of 97 wt %. Preferably, the composition of the present invention comprises the terpolymer as described herein and additives. The additives are preferably selected from the group consisting of slip agents, antiblocking agents, UV stabilizers, antistatic agents, acid scavengers, α-nucleating agents, antioxidants, and mixtures thereof. Such additives are well known to those skilled in the art.

[0048] Slip agents migrate to the surface and act as lubricants between polymers and between polymers and metal rollers, reducing the coefficient of friction (CoF). Examples are 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.

[0049] Examples of antioxidants commonly used in the art are sterically hindered phenols (e.g., CAS No. 6683-19-8, also marketed by BASF as Irganox 1010FF TM Phosphorus antioxidants (such as CAS No. 31570-04-4, also sold by Clariant as Hostanox PAR 24 (FF) TM Sold or sold by BASF as Irgafos 168 (FF) TM Sold), sulfur antioxidants (such as CAS No. 693-36-7, sold by BASF as Irganox PS-802FL TM sold), nitrogen-based antioxidants (such as 4,4'-bis(1,1'-dimethylbenzyl)diphenylamine), or antioxidant blends.

[0050] Acid scavengers are also well known in the art. Examples are 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 lactylates.

[0051] Common anti-adhesion agents include natural silica, such as diatomaceous earth (CAS No. 60676-86-0 (SuperFloss TM), CAS No.60676-86-0(SuperFloss E TM ) or CAS No.60676-86-0(Celite499 TM )), synthetic 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.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.1344-95-2), synthetic zeolite (such as hydrated sodium calcium aluminosilicate CAS No. No.1344-01-0, CAS No.1344-01-0 or hydrated sodium calcium aluminosilicate CAS No.1344-01-0).

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

[0053] In addition, an α-nucleating agent may be added, such as sodium benzoate (CAS No. 532-32-1); a mixture of bis[2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate]hydroxyaluminum and lithium myristate (commercially available as Adekastab NA-21 from Adeka Palmarole (France)); or 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (CAS No. 135861-56-2, commercially available as Millad 3988 (product of Milliken Company, USA)).

[0054] Suitable antistatic agents are, for example, glycerol esters (CAS No. 97593-29-8) or ethoxylated amines (CAS No. 71786-60-2 or 61791-31-9) or ethoxylated amides (CAS No. 204-393-1).

[0055] Most preferably, these additives are present in the range of 0.01 to 2.0 wt %, based on the total weight of the polymer composition.

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

[0057] a) units derived from ethylene, the amount of units derived from ethylene being 0.8 to 2.8 mol% relative to the total amount of the terpolymer; and

[0058] b) units derived from propylene, the amount of units derived from propylene being 91.6 to 95.8 mol% relative to the total amount of the terpolymer; and

[0059] c) units derived from 1-butene, with the amount of the units derived from 1-butene being 3.4 to 5.6 mol% relative to the total amount of the terpolymer.

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

[0061] e) the total amount of units derived from ethylene and units derived from 1-butene is 4.5 to 8.0 mol%, and

[0062] f) a molar ratio of units derived from 1-butene to units derived from ethylene in the range of 1.5 to 5.0;

[0063] g) By 13 The amount of 2.1 regio inversion determined by C-NMR analysis (as described in the experimental section) was 0.20–0.45 mol %;

[0064] h) a melt flow rate MFR2 (230°C / 2.16 kg) determined according to ISO 1133 in the range of 1.5 to 4.5 g / 10 min, and

[0065] i) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following formula:

[0066] Tm<[150–1.6×(defect)–0.14×(defect)2]℃,

[0067] Here, "defects" represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regioinversions, and all values ​​are expressed in mol%.

[0068] In a preferred embodiment, the ethylene-propylene-1-butene terpolymer has:

[0069] a) units derived from ethylene, the amount of units derived from ethylene being 1.3 to 2.4 mol% relative to the total amount of the terpolymer; and

[0070] b) units derived from propylene, the amount of units derived from propylene being 92.2 to 94.1 mol% relative to the total amount of the terpolymer; and

[0071] c) units derived from 1-butene, with the amount of the units derived from 1-butene being 4.6 to 5.4 mol% relative to the total amount of the terpolymer.

[0072] d) the total of units derived from ethylene, units derived from propylene and units derived from 1-butene is 100 mol%, and

[0073] e) the total amount of units derived from ethylene and units derived from 1-butene is 5.8 to 7.5 mol%, and

[0074] f) a molar ratio of units derived from 1-butene to units derived from ethylene of from 1.6 to 4.5; and

[0075] g) By 13 The amount of 2.1 regio inversion determined by C-NMR analysis (as described in the experimental section) is 0.20-0.40 mol%; and

[0076] h) a melt flow rate MFR2 (230°C / 2.16 kg) determined according to ISO 1133 in the range of 1.5 to 4.5 g / 10 min, and

[0077] i) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following formula:

[0078] Tm<[150–1.6×(defect)–0.14×(defect)2]℃,

[0079] Here, "defects" represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regioinversions, and all values ​​are expressed in mol%.

[0080] catalyst

[0081] A wide variety of catalysts may be suitable for use in the present invention.

[0082] Typically, the catalyst system used in the present invention can be manufactured as described in WO 2018 / 122134A1. The catalyst can be used in a 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), in particular silica, alumina or silica-alumina. Silica support is preferably used. Those skilled in the art are aware of the procedures required for supporting metallocene catalysts.

[0083] Particularly preferably, the support is a porous material and the complex can be loaded into the pores of the support, for example using methods similar to those described in WO 94 / 14856 (Mobil), WO 95 / 12622 (Borealis) and WO 2006 / 097497.

[0084] The average particle size of the silica support can generally be from 10 to 100 μm. However, it has been shown that particular advantages are achieved if the average particle size of the support is from 15 to 80 μm, preferably from 18 to 50 μm.

[0085] The average pore size of the silica support may be in the range of 10 to 100 nm, and the pore volume may be 1 to 3 mL / g.

[0086] Examples of suitable support materials are ES757 manufactured and sold by PQ, Sylopol 948 manufactured and sold by Grace, or SUNSPERA DM-L-303 silica manufactured and sold by AGC Si-Tech. The support can optionally be calcined before use in the catalyst preparation to achieve an optimal silanol group content.

[0087] The use of these vectors is routine in the art.

[0088] Preferred complexes for use in the present invention have formula (II') or (II):

[0089]

[0090] Wherein, M is zirconium or hafnium;

[0091] Each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkoxy, C 1-6 -alkyl, phenyl or benzyl;

[0092] L is a divalent bridging group selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom, C 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;

[0093] R 2 or R 2 'Each is C 1-10 -alkyl;

[0094] R5 ' for C 1-10 Alkyl or Z'R 3 'group;

[0095] R 6 is hydrogen or C 1-10 -alkyl;

[0096] R 6 ' for C 1-10 -alkyl or C 6-10 - aryl, preferably tertiary alkyl;

[0097] R 7 For hydrogen, C 1-6 -alkyl or ZR 3 group, and R 7 ' is hydrogen;

[0098] Z and Z' are independently O or S;

[0099] R 3 ' for C 1-10 -alkyl or C optionally substituted by one or more halogens 6-10 -aryl;

[0100] R 3 C 1-10 -alkyl;

[0101] Each n is independently 0 to 4, for example 0, 1 or 2;

[0102] Each R 1 Independently C 1-20 -hydrocarbyl, for example C 1-10 -alkyl.

[0103] More preferred complexes for use in the present invention have formula (III') or (III):

[0104]

[0105] Wherein, M is zirconium or hafnium;

[0106] Each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkoxy, C 1-6 -alkyl, phenyl or benzyl;

[0107] L is a divalent bridging group selected from -R'2C- or -R'2Si-, wherein each R' is independently a hydrogen atom, C 1-20 -alkyl or C 3-10 -cycloalkyl;

[0108] R 6 is hydrogen or C 1-10 -alkyl;

[0109] R 6 ' for C 1-10 -alkyl or C 6-10 - aryl, preferably tertiary alkyl;

[0110] R 7 For hydrogen, C 1-6 -alkyl or OC 1-6 -alkyl; Z' is O or S;

[0111] R 3 ' for C 1-10 -alkyl or C optionally substituted by one or more halogens 6-10 -aryl;

[0112] n is independently 0 to 4, for example, 0, 1 or 2;

[0113] Each R 1 Independently C 1-10 -alkyl.

[0114] Particularly preferred complexes for use in the present invention have the formula (IV') or (IV):

[0115]

[0116] Wherein, M is zirconium or hafnium;

[0117] Each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkoxy, C 1-6 -alkyl, phenyl or benzyl;

[0118] Each R' is independently a hydrogen atom, C 1-20 -alkyl or C 3-7 -cycloalkyl;

[0119] R 6 is hydrogen or C 1-10 -alkyl;

[0120] R 6 ' for C 1-10 -alkyl or C 6-10 - aryl, preferably tertiary alkyl;

[0121] R 7 For hydrogen, C 1-6 -alkyl or OC 1-6 -alkyl; Z' is O or S;

[0122] R 3 ' for C 1-10 -alkyl or C optionally substituted by one or more halogens 6-10 -aryl; n is independently 0, 1 or 2; each R1 Independently C 3-8 -alkyl.

[0123] Most preferably, the complex used in the present invention has formula (V') or (V):

[0124]

[0125] wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkoxy, C 1-6 -alkyl, phenyl or benzyl;

[0126] R' is independently C 1-6 -alkyl or C 3-10 -cycloalkyl;

[0127] R 1 Independently C 3-8 -alkyl;

[0128] R 6 is hydrogen or C 3-8 -alkyl;

[0129] R 6 ' for C 3-8 -alkyl or C 6-10 -aryl, preferably tertiary C 4-8 -alkyl;

[0130] R 3 ' for C 1-6 -alkyl or C optionally substituted by one or more halogens 6-10 -aryl; n is independently 0, 1 or 2.

[0131] Specific compounds of the present invention include:

[0132]

[0133]

[0134] Most preferably, rac-trans-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2 is used.

[0135] The ligands required for forming the complexes of the present invention and the catalysts of the present invention can be synthesized by any method, and a skilled organic chemist will be able to devise various synthetic schemes for making the necessary ligand materials. For example, WO2007 / 116034 discloses the necessary chemical reactions. Synthetic schemes can also be found generally in WO2002 / 02576, WO2011 / 135004, WO2012 / 084961, WO2012 / 001052, WO2011 / 076780, WO2013 / 007650, WO2015 / 158790, and WO2018 / 122134. The Examples section also provides sufficient guidance for the skilled person.

[0136] co-catalyst

[0137] It is well known in the art that a cocatalyst is generally required to form active catalytic species. Cocatalysts comprising one or more compounds of Group 13 metals (e.g., organoaluminum compounds) or boron-containing cocatalysts or combinations thereof for activating metallocene catalysts are suitable for use in the present invention.

[0138] In a preferred embodiment of the present invention, a cocatalyst system comprising a boron-containing cocatalyst (eg, a borate cocatalyst) and an aluminoxane cocatalyst is used.

[0139] Thus, the single site polymerization catalyst system used in the present invention may comprise (i) the complex as defined above and an aluminoxane cocatalyst.

[0140] The aluminoxane cocatalyst may be one of formula (VI):

[0141]

[0142] wherein n is 6 to 20, and R has the following meanings.

[0143] Aluminoxanes are formed during the partial hydrolysis of organoaluminum compounds such as compounds having the formula AlR3, AlR2Y and Al2R3Y3, where R can be, for example, C1-C 10 -alkyl (preferably C1-C5-alkyl), or C3-C 10 -cycloalkyl, C7-C 12 -Arylalkyl or C7-C 12 -alkylaryl and / or phenyl or naphthyl, Y can be hydrogen, halogen (preferably chlorine or bromine), or C1-C 10 - alkoxy group (preferably methoxy or ethoxy group). The oxygen-containing aluminoxane obtained is usually not a pure compound but a mixture of oligomers of formula (VI).

[0144] A preferred aluminoxane is methylaluminoxane (MAO).

[0145] Since the aluminoxanes used as cocatalysts according to the invention are not pure compounds due to the way they are prepared, the molarity of the aluminoxane solutions hereinafter is based on their aluminum content.

[0146] According to the invention, it is also possible to use cocatalysts containing boron.

[0147] Boron-containing cocatalysts of interest include cocatalysts of formula (VII):

[0148] BY3(VII),

[0149] Wherein, Y is the same or different and is a hydrogen atom, an alkyl group having 1 to about 20 carbon atoms, an aryl group having 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 radical and 6 to 20 carbon atoms in the aryl radical), or fluorine, chlorine, bromine, or iodine. Preferred examples of Y include fluorine, trifluoromethyl, and aromatic fluorinated groups such as p-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl, and 3,5-bis(trifluoromethyl)phenyl. Preferred options are trifluoroborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(pentafluorophenyl)borane, tris(3,5-difluorophenyl)borane and / or tris(3,4,5-trifluorophenyl)borane.

[0150] Tris(pentafluorophenyl)borane is particularly preferred.

[0151] Preferably, however, as boron-containing cocatalysts, borates, ie compounds containing borate, are used.

[0152] These compounds typically contain anions of the formula:

[0153] (Z)4B - (VIII),

[0154] Wherein, Z is an optionally substituted phenyl derivative, wherein the substituent is a halo-C 1-6 - an alkyl or halogen group. Preferred options are fluoromethyl or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

[0155] Such ionic cocatalysts preferably contain a weakly coordinating anion, such as tetrakis(pentafluorophenyl)borate or tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. Suitable counterions are protonated amines or aniline derivatives, such as methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylanilinium or p-nitro-N,N-dimethylanilinium.

[0156] Preferred ionic compounds that can be used in the present invention include:

[0157] Tributylammonium tetrakis(pentafluorophenyl)borate,

[0158] Tributylammonium tetrakis(trifluoromethylphenyl)borate,

[0159] Tributylammonium tetrakis(4-fluorophenyl)borate,

[0160] N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate,

[0161] N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate,

[0162] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

[0163] N,N-di(propyl)ammonium tetrakis(pentafluorophenyl)borate,

[0164] Di(cyclohexyl)ammonium tetrakis(pentafluorophenyl)borate,

[0165] triphenylcarbonium tetrakis(pentafluorophenyl)borate,

[0166] Or ferrocenium tetrakis(pentafluorophenyl)borate.

[0167] Preferably triphenylcarbonium tetrakis(pentafluorophenyl)borate,

[0168] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

[0169] N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, or

[0170] N,N-Dimethylbenzylammonium tetrakis(pentafluorophenyl)borate.

[0171] 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).

[0172] Suitable amounts of co-catalyst are well known to those skilled in the art.

[0173] Preferably, the amount of cocatalyst is chosen so as to achieve the molar ratios defined below.

[0174] The molar ratio of the feed amount of boron (B) to the metal ion (M) of the metallocene (preferably zirconium), i.e., Boron / M, can be in the range of 0.1:1 to 10:1 mol / mol, preferably in the range of 0.3:1 to 7:1 mol / mol, and especially in the range of 0.3:1 to 5:1 mol / mol.

[0175] More preferably, the molar ratio of the feed amount of boron (B) to the metal ion (M) of the metallocene (preferably zirconium), ie, boron / M, is 0.3:1 to 3:1.

[0176] The molar ratio of Al from aluminoxane to the metal ion (M) of the metallocene (preferably zirconium), i.e., Al / M, may be in the range of 1:1 to 2000:1 mol / mol, preferably in the range of 10:1 to 1000:1 mol / mol, and more preferably in the range of 50:1 to 600:1 mol / mol.

[0177] Other suitable catalyst systems are described in WO2019179959, which is incorporated herein by reference. In the broadest aspect, the catalyst complex satisfies the following structure.

[0178]

[0179] in,

[0180] Mt is Hf or Zr;

[0181] Each X is a σ-ligand,

[0182] Each R 1 are independently the same or may be different, and are CH2-R 7 group, where R 7 H, straight chain or branched chain C 1-6 Alkyl, C 3-8 Cycloalkyl, C 6-10 Aryl,

[0183] Each R 2 are independently -CH=, -CY=, -CH2-, -CHY- or -CY2- groups, wherein Y is C 1-10 Hydrocarbyl, n is 2-6,

[0184] Each R 3 and R 4 are independently the same or may be different and are H, linear or branched C 1-6 Alkyl, OY group, C 7-20 Arylalkyl, C 7-20Alkyl aryl or C 6-20 Aryl, each phenyl group has at least one R 3 and at least one R 4 are not hydrogen, optionally, two adjacent R 3 or R 4 The groups may be part of a ring containing the phenyl carbon to which they are attached,

[0185] R 5 Straight chain or branched C 1-6 Alkyl, C 7-20 Arylalkyl, C 7-20 Alkyl aryl or C6-C 20 Aryl,

[0186] R 6 C(R 8 )3 groups, wherein R 8 Straight chain or branched C 1-6 alkyl,

[0187] Each R is independently C1-C 20 Hydrocarbon, C6-C 20 Aryl, C7-C 20 Arylalkyl or C7-C 20 Alkylaryl.

[0188] As specific metallocene catalyst complexes, the following three embodiments may be mentioned, abbreviated as MC1, MC2 and MC3.

[0189]

[0190] Rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride (MC-1)

[0191] Rac-anti-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 (MC-2)

[0192] Rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-ditert-butyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride (MC-3)

[0193] Also included are their corresponding dimethyl zirconium analogs.

[0194] The polymer composition of the present invention can be compounded and granulated using any of the various compounding and blending machines and methods well known and commonly used in the resin compounding field. In order to blend the individual components of the present composition, conventional compounding or blending equipment can be used, such as a Banbury mixer, a two-roll rubber mixer, a Buss co-kneader or a twin-screw extruder. The composition recovered from the extruder / mixer is generally in the form of particles. These particles are then further processed and formed into blown film of the present invention. The composition of the present invention preferably comprises a terpolymer as described herein in an amount of at least 97wt%. More preferably, the composition of the present invention consists of a terpolymer as described herein in an amount of at least 97wt% and additives. Preferred additives for this purpose have been further described above.

[0195] Blown film

[0196] The blown film of the present invention is made from the ethylene-propylene-1-butene terpolymer as described above. All preferred aspects also apply to the blown film.

[0197] As briefly summarized above, the present invention relates to a blown film made from an ethylene-propylene-1-butene terpolymer, the terpolymer comprising:

[0198] a) units derived from ethylene, the amount of units derived from ethylene being 0.8 to 2.8 mol% relative to the total amount of the terpolymer; and

[0199] b) units derived from propylene, the amount of units derived from propylene being 91.6 to 95.8 mol% relative to the total amount of the terpolymer; and

[0200] c) units derived from 1-butene, with the amount of the units derived from 1-butene being 3.4 to 5.6 mol% relative to the total amount of the terpolymer.

[0201] d) the total of units derived from ethylene, units derived from propylene and units derived from 1-butene is 100 mol%, and

[0202] e) the total amount of units derived from ethylene and units derived from 1-butene is 4.5 to 8.0 mol%,

[0203] f) a molar ratio of units derived from 1-butene to units derived from ethylene of from 1.5 to 5.0; and

[0204] g) By 13 The amount of 2.1 regio inversion determined by C-NMR analysis (as described in the experimental section) was 0.20–0.45 mol %;

[0205] h) a melt flow rate MFR2 (230°C / 2.16 kg) determined according to ISO 1133 in the range of 1.5 to 4.5 g / 10 min, and

[0206] i) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following formula:

[0207] Tm<[150–1.6×(defect)–0.14×(defect)2]℃,

[0208] where "defects" represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regioinversions, all values ​​are expressed in mol%, and

[0209] The seal initiation temperature (SIT) of the blown film (determined by the method described in the experimental part) was less than 117°C.

[0210] Such films can be made on blown film lines known in the art, such as air-cooled or water-cooled blown film lines, including multi-layer coextrusion lines.

[0211] The "blown film made of ethylene-propylene-1-butene terpolymer" of the present invention means that at least one layer (of the film) comprises ethylene-propylene-1-butene terpolymer, preferably consists of the ethylene-propylene-1-butene terpolymer composition of the present invention.

[0212] Blown films can be advantageously produced using a single-screw extruder that combines a monolip cooling ring and an internal bubble cooling system (IBC), the extruder having a barrel diameter of about 70 mm and a circular cross-section die of about 200 mm (wherein the die gap is about 1 mm). The melt temperature can be selected between 200 and 215°C. In the die, the temperature of the cooling air is 15°C to 20°C. As a typical blow up ratio (BUR), 2.5:1 to 3.5:1 can be used. The film thickness can be easily adjusted by the ratio between the extruder output, the take-off speed and the blow up ratio (BUR).

[0213] A Collin blown film line can be used, having a screw diameter of 30 millimeters (mm), an L / D of about 30, a die diameter of about 60 mm, a die gap of about 1.5 mm, and a double-lip cooling ring. A manufacturing temperature of about 190° C. and a blow-up ratio of about 2.5 can be recommended.

[0214] The blown film of the present invention is preferably made of an ethylene-propylene-1-butene terpolymer having units derived from ethylene in an amount of 1.3 to 2.4 mol% relative to the total amount of the terpolymer.

[0215] In another preferred aspect, the blown film of the present invention is preferably made of an ethylene-propylene-1-butene terpolymer having units derived from 1-butene in an amount of 4.6 to 5.4 mol% relative to the total amount of the terpolymer.

[0216] Furthermore, preferably, the blown film of the present invention is made of an ethylene-propylene-1-butene terpolymer, and the total amount of the units derived from ethylene and the units derived from 1-butene of the terpolymer is 5.8 to 7.5 mol%.

[0217] In a further preferred aspect, the blown film of the present invention is made of an ethylene-propylene-1-butene terpolymer, wherein the molar ratio of units derived from 1-butene to units derived from ethylene is in the range of 1.6 to 4.5.

[0218] Furthermore, preferably, the blown film of the present invention is made of an ethylene-propylene-1-butene terpolymer, which is obtained by 13 The amount of 2.1 regio inversion determined by C-NMR analysis (as described in the experimental section) was 0.20-0.40 mol%.

[0219] In a particularly preferred embodiment, the blown film of the present invention is made from an ethylene-propylene-1-butene terpolymer comprising:

[0220] a) units derived from ethylene, the amount of units derived from ethylene being 1.3 to 2.4 mol% relative to the total amount of the terpolymer; and

[0221] b) units derived from propylene, the amount of units derived from propylene being 92.2 to 94.1 mol% relative to the total amount of the terpolymer; and

[0222] c) units derived from 1-butene, with the amount of the units derived from 1-butene being 4.6 to 5.4 mol% relative to the total amount of the terpolymer.

[0223] d) the total of units derived from ethylene, units derived from propylene and units derived from 1-butene is 100 mol%, and

[0224] e) the total amount of units derived from ethylene and units derived from 1-butene is 5.8 to 7.5 mol%, and

[0225] f) a molar ratio of units derived from 1-butene to units derived from ethylene of from 1.6 to 4.5; and

[0226] g) By 13 The amount of 2.1 regio inversion determined by C-NMR analysis (as described in the experimental section) is 0.20-0.40 mol%; and

[0227] h) a melt flow rate MFR2 (230°C / 2.16 kg) determined according to ISO 1133 in the range of 1.5 to 4.5 g / 10 min, and

[0228] i) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following formula:

[0229] Tm<[150–1.6×(defect)–0.14×(defect)2]℃,

[0230] where "defects" represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regioinversions, all values ​​are expressed in mol%, and

[0231] The seal initiation temperature (SIT) of the blown film (determined by the method described in the experimental part) is less than 112°C, in particular 105-111°C.

[0232] The blown film of the present invention is preferably made of an ethylene-propylene-1-butene terpolymer having a flexural modulus of 600 to 900 MPa, preferably 600 to 800 MPa, as measured according to ISO 178.

[0233] In another aspect, the blown film of the present invention is preferably made from an ethylene-propylene-1-butene terpolymer that is bimodal in butene content and / or bimodal in molecular weight.

[0234] The advantageous properties of the blown films of the present invention can be understood when taking into account the optomechanical properties (OMA) in the machine direction (MD), which are typically determined on a 50 μm thick test film, where the OMA (for a 50 μm thick film) is:

[0235]

[0236] Wherein, the tensile modulus in the longitudinal direction is determined as described in the experimental section;

[0237] DDI is determined according to ASTM D1709, using Method A.

[0238] The haze is measured on a test film having a thickness of 50 μm according to ASTM D1003-00.

[0239] The films of the present invention have an optomechanical performance (OMA) of at least 7,000, preferably at least 9,000, and most preferably at least 10,000.

[0240] It should be noted that the film thickness is not limited to 50 microns. For ease of comparison, only 50 micron thick films were used as test samples. Typically and preferably, the blown film of the present invention is made of an ethylene-propylene-1-butene terpolymer having a hexane solubility (FDA) of 0.70 wt % or less.

[0241] Experimental part

[0242] A. Measurement Method

[0243] Unless defined otherwise, the following definitions of terms and determination methods apply to the above general description of the invention and the following examples.

[0244] a) MFR2 (230° C.) is determined according to ISO 1133 (230° C., 2.16 kg load).

[0245] b) Quantification of microstructure by nuclear magnetic resonance (NMR) spectroscopy

[0246] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers.

[0247] A Bruker Avance 111 500 NMR spectrometer was used to analyze 1 H and 13 For C, the operation was carried out at 500.13 MHz and 125.76 MHz, respectively, and quantitative data were recorded in the molten state. 13 C{ 1 H} NMR spectroscopy. For all aerodynamic characteristics, nitrogen was used at 180 °C. 13 All spectra were recorded using a C-optimized 7 mm magic-angle spinning (MAS) probe. Approximately 200 mg of material was packed into a 7 mm outer diameter zirconium oxide MAS rotor, which was spun at 4 kHz. This setup was chosen primarily for the high sensitivity required for rapid identification and precise quantification {klimke06, parkinson07, castignolles09}. Standard single-pulse stimulation was employed using NOEs with a short recycle delay of 3 s {pollard04, klimke06} and an RS-HEPT decoupling scheme {fillip05, griffin07}. A total of 1024 (1 k) transients were acquired for each spectrum.

[0248] Quantitative 13 C{ 1 H} NMR spectra were processed and integrated, and the relevant quantitative properties were determined from the integration. All chemical shifts were internally referenced to the isotactic methyl pentad (mmmm) at 21.85 ppm.

[0249] For polypropylene homopolymer, all chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.

[0250] The characteristic signal {brandolini01} corresponding to the incorporation of 1-butene was observed and the comonomer content was quantified.

[0251] The amount of isolated 1-butene incorporated into the PBP sequence was quantified by calculating the number of reporter sites per comonomer using the integration of the αB2 site at 43.6 ppm:

[0252] B=I αB2 / 2

[0253] The amount of continuously incorporated 1-butene in the PBBP sequence was quantified by calculating the number of reporter sites per comonomer using the integration of the ααB2B2 sites at 40.5 ppm:

[0254] BB=2×I ααB2B2

[0255] When BB is present, the value of B must be corrected for the effect of the αB2 site generated by BB:

[0256] B=(I αB2 / 2)–BB / 2

[0257] The total 1-butene content was calculated based on the sum of isolated 1-butene and continuously incorporated 1-butene:

[0258] B 总 =B+BB

[0259] The characteristic signal {brandolini01} corresponding to the incorporation of ethylene was observed and the comonomer content was quantified.

[0260] The amount of isolated ethylene incorporated into the PEP sequence was quantified using the integration of the Sββ site at 24.3 ppm to calculate the number of reporter sites per comonomer:

[0261] E=I Sββ

[0262] If a characteristic signal corresponding to the continuous incorporation of ethylene in the PEE sequence is observed, quantification is performed using the Sβδ site at 27.0 ppm:

[0263] EE=I Sβδ

[0264] Characteristic signals corresponding to regio defects {resconi00} were observed. The presence of isolated 2,1-erythro regio defects was indicated by the presence of two methyl sites at 17.7 and 17.2 ppm, a methylene site at 42.4 ppm, and confirmed by other characteristic sites. The presence of 2,1 regio defects adjacent to ethylene units was indicated by two inequivalent Sαβ signals at 34.8 and 34.4 ppm, respectively, and a Tγγ signal at 33.7 ppm.

[0265] The integration of the methylene sites at 42.4 ppm was used (I e9 ), isolated 2,1-erythro regiodefects (P 21e孤立 ) is quantified:

[0266] P 21e孤立 =I e9

[0267] If present, the methine site at 33.7 ppm (I Τγγ ), the amount of 2,1 regional defects adjacent to ethylene (P E21 ) for quantification:

[0268] P E21 =I Tγγ

[0269] The total ethylene content was then calculated based on the sum of ethylene from isolated, continuously incorporated, and adjacent 2,1 regio defects:

[0270] E 总 =E+EE+P E21

[0271] 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 21e孤立 , accounting for the three missing propylene units from the isolated 2,1-erythro regiodefect), the amount of propylene was quantified:

[0272] P 总 =I Sαα +3×P 21e孤立 +B+0.5×BB+E+0.5×EE+2×P E21

[0273] The total mole fraction of 1-butene and ethylene in the polymer is then calculated as:

[0274] fB=B 总 / (E 总 +P 总 +B 总 )

[0275] fE=E 总 / (E 总 +P 总 +B 总 )

[0276] The mole percentage of comonomer incorporation is calculated based on the mole fraction:

[0277] B [mol%] = 100 × fB

[0278] E[mol%]=100×fE

[0279] The weight percent of comonomer incorporation is calculated based on the mole fraction:

[0280] B[wt%]=100×(fB×56.11) / ((fE×28.05)+(fB×56.11)+((1-(fE+fB))×42.08))

[0281] E[wt%]=100×(fE×28.05) / ((fE×28.05)+(fB×56.11)+((1-(fE+fB))×42.08))

[0282] The mole percentage of isolated 2,1-erythro regiodefects relative to all propylene was quantified:

[0283] [21e]mol%=100×P 21e孤立 / P 总

[0284] The mole percentage of 2,1 regio defects adjacent to ethylene was quantified relative to all propylene:

[0285] [E21]mol%=100×P E21 / P 总

[0286] The total amount of defects in the 2,1 region is quantified as follows:

[0287]

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

[0288] The characteristic signal {resconi00} corresponding to other types of regional defects (2,1-threo, 3,1 insertion) was not observed.

[0289] Literature (mentioned above):

[0290]

[0291] c)DSC analysis, melting temperature (Tm) and crystallization temperature (Tc):

[0292] The measurements were performed on 5-7 mg samples using a TA Instrument Q2000 Differential Scanning Calorimeter (DSC). The DSC was run in the temperature range of -30°C to +225°C according to ISO 11357 / Part 3 / Method C2, using a heating / cooling / heating cycle and a scan rate of 10°C / min. The crystallization temperature (Tc) and the enthalpy of crystallization (Hc) were determined from the cooling step, while the melting temperature (Tm) and the enthalpy of melting (Hm) were determined from the second heating step.

[0293] d) Blown film

[0294] All film properties (except hexane solubles) were measured on 50 μm thick monolayer blown films produced on a Collin 30 lab-scale blown film line.

[0295] The line has a 30 millimeter (mm) screw diameter, an L / D of 30, a 60 mm die diameter, a 1.5 mm die gap, and a double-lip cooling ring. Film samples were produced at 215°C with an average thickness of 50 μm, a blow-up ratio of 2.5:1, and an output rate of approximately 8 kilograms per hour (kg / h).

[0296] e) Haze

[0297] Measured according to ASTM D1003-00 on blown test films with a thickness of 50 μm.

[0298] f) Hot tack

[0299] Hot tack was measured on a J&B hot tack tester using 50 μm thick films produced on a single-layer blown film line according to ASTM F1921-12 - Method B. All film test samples were produced in a standard atmosphere for conditioning and testing at 23°C (±2°C) and 50% (±10%) relative humidity.

[0300] The minimum conditioning time of the test samples in the standard atmosphere before the start of the test is at least 16 hours. The minimum storage time between the extrusion of the film sample and the start of the test is at least 88 hours.

[0301] The strength of the heat seal formed in the film was determined by a hot tack test immediately after the seal was made and before it cooled to ambient temperature.The hot tack test was performed under the following conditions.

[0302] Film sample width: 25.4mm

[0303] Sealing strip length: 50mm

[0304] Sealing strip width: 5mm

[0305] Sealing strip shape: flat

[0306] Sealing pressure: 0.3N / mm 2

[0307] Sealing time: 0.5 seconds

[0308] Cooldown: 99 seconds

[0309] Peeling speed: 200mm / s

[0310] Starting temperature: 90°C

[0311] End temperature: 140℃

[0312] Increments: 10°C

[0313] Hot tack is measured as a function of temperature within the temperature range specified above at the specified temperature increments. At each temperature, at least three samples are tested. The output of this method is a hot tack curve, i.e., a force versus temperature curve.

[0314] The hot tack force (HTF) is evaluated from this curve as the maximum force (maximum peak) in the failure mode "peel".

[0315] g) Sealing initiation temperature (SIT); sealing termination temperature (SET)

[0316] Sealing start temperature (SIT); sealing end temperature (SET), sealing range:

[0317] This method determines the sealing temperature range (sealing range) of polypropylene films (particularly blown or cast films) according to ASTM F1921-12. The sealing pressure, cooling time and peel speed were varied as described below.

[0318] The sealing temperature range is the temperature range within which the film can be sealed according to the following given conditions.

[0319] The lower limit (heat seal initiation temperature (SIT)) is the sealing temperature at which a seal strength > 5 N is achieved. The upper limit (seal end temperature (SET)) is reached when the film sticks to the sealing device.

[0320] The sealing range was determined on a J&B Universal Sealer Model 3000 using a blown film with a thickness of 50 μm and the following parameters:

[0321] Sample width: 25.4mm

[0322] Sealing pressure: 0.1N / mm 2

[0323] Sealing time: 0.1 seconds

[0324] Cooldown: 99 seconds

[0325] Peeling speed: 10mm / s

[0326] Starting temperature: 80°C

[0327] End temperature: 150℃

[0328] Increment: 10℃

[0329] At each seal bar temperature, the samples were sealed A to A and the seal strength (force) was measured at each step.

[0330] The temperature at which the sealing strength reaches 5N was measured.

[0331] h) Hexane (C6) extractables

[0332] The hexane extractable fraction was determined according to the FDA method (Federal Register, Title 21, Chapter 1, Part 177, Section 1520, see Appendix B).

[0333] The measurement was performed according to FDA Part 177, Section 1520, wherein 1 g of a 100 μm thick polymer film was added to 400 ml of hexane at 50°C and stirred for 2 hours using a reflux cooler. After 2 hours, the mixture was immediately filtered through filter paper. The precipitate was collected in an aluminum receiver, and the remaining hexane was evaporated on a steam bath under a stream of N2. The amount of hexane solubles was determined by the following formula: ((sample weight (wt) + crucible weight (wt)) - (crucible weight (wt))) / (sample weight (wt)) × 100%.

[0334] The films used in the tests were produced on a Collin cast film laboratory line with a melt temperature of 230°C, an output rate of 8 kg / h and a chill roll temperature of 40°C.

[0335] i) Tensile modulus

[0336] The tensile modulus in the longitudinal and transverse directions of the blown films with a thickness of 50 μm produced by the above method was determined according to ISO 527-3 at 23° C. The test was carried out at a crosshead speed of 1 mm / min.

[0337] j) Dart drop strength (DDI), also known as dart drop impact, was tested using ASTM D1709-Method A (alternative test technique). A dart with a 38 mm diameter hemispherical head was dropped from a height of 0.66 m onto the film clamped above the hole. Groups of 20 samples were tested consecutively. Each group used a weight, and the weight was increased (or decreased) in uniform increments. The weight that caused 50% of the samples to fail was calculated and recorded.

[0338] k) Optomechanical performance (OMA)

[0339] Optomechanical performance (OMA) is understood as the ratio of mechanical (especially impact and bending) performance to optical performance (ie haze), wherein the mechanical performance is targeted to be as high as possible, while the optical performance is desired to be as low as possible.

[0340] The photomechanical properties are determined according to the following formula:

[0341]

[0342] Here, the tensile modulus was measured in the machine direction (MD) and the transverse direction (TD) [MPa], and the DDI (g) and the haze were measured as described above.

[0343] l) Flexural modulus

[0344] Measured according to ISO 178 at 23°C on 80×10×4 mm2 plastics injection molded according to EN ISO 1873-2 3 The flexural modulus of the test bars in 3-point bending.

[0345] m) Xylene cold solubles (XCS)

[0346] The xylene solubles (XS) fraction, as defined and described herein, is determined according to ISO 16152 as follows: 2.0 g of polymer are dissolved in 250 ml of p-xylene at 135° C. with stirring. After 30 minutes, the solution is allowed to cool at ambient temperature for 15 minutes and then allowed to stand at 25±0.5° C. for 30 minutes. The solution is filtered through filter paper and placed into two 100 ml flasks. The solution from the first 100 ml container is evaporated in a stream of nitrogen, and the residue is dried under vacuum at 90° C. until a constant weight is reached. The xylene solubles fraction (in percentage) can then be determined as follows:

[0347] XS% = (100 x m x V0) / (m0 x v); m0 = initial polymer amount (g); m = weight of residue (g); V0 = initial volume (ml); v = volume of analyzed sample (ml).

[0348] B. Examples

[0349] Preparation of the first catalyst system (#1)

[0350] Metallocene (MC1) (rac-trans-dimethylsilanediyl(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride) was synthesized as described in WO 2013 / 007650.

[0351] Preparation of MAO-silica support

[0352] A steel reactor equipped with a mechanical stirrer and a filter screen was purged with nitrogen and the reactor temperature was set to 20°C. Then, DM-L-303 grade silica (7.4 kg) from AGC Si-Tech, pre-calcined at 600°C, was added from the feed bucket and subsequently carefully pressurized and decompressed with nitrogen using a manual valve. Then, toluene (32 kg) was added. The mixture was stirred for 15 minutes. Then, a 30 wt% solution of MAO from Lanxess in toluene (17.5 kg) was added over 70 minutes through the feed line on the reactor top. Then, the reaction mixture was heated to 90°C and stirred at 90°C for another 2 hours. The slurry was allowed to settle and the mother liquor was filtered off. At 90°C, the MAO-treated support was washed twice with toluene (32 kg), then settled and filtered. The reactor was cooled to 60°C and the solid was washed with heptane (32.2 kg). Finally, the MAO-treated SiO2 was dried at 60°C under nitrogen flow for 2 hours and then stirred under vacuum (-0.5 bar, gauge) for 5 hours. The MAO-treated support was collected as a free-flowing white powder containing 12.6% aluminum (by weight).

[0353] Catalyst system manufacturing

[0354] At 20°C, 30 wt% MAO in toluene (2.2 kg) was added via burette to a nitrogen-sealed steel reactor. Toluene (7 kg) was then added with stirring. Metallocene MC1 (286 g) was added from a metal cylinder, followed by a 1 kg toluene rinse. The mixture was stirred at 20°C for 60 minutes. Trityl tetrakis(pentafluorophenyl)borate (336 g) was then added from a metal cylinder, followed by a 1 kg toluene rinse. The mixture was stirred at room temperature for 1 hour. The resulting solution was added over 1 hour to a stirred cake of MAO-silica support prepared as described above. The cake was allowed to stand for 12 hours, then dried at 60°C under a stream of N2 for 2 hours and then dried under vacuum (-0.5 bar gauge) with stirring for an additional 5 hours. The dried catalyst was sampled and found to be a pink, free-flowing powder containing 13.9 wt% aluminum and 0.26 wt% zirconium (Zr).

[0355] Preparation of the Second Catalyst System (#2)

[0356] The catalyst used was 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.

[0357] The metallocene complex is prepared according to the method for preparing MC-2 in WO2019 / 179959.

[0358]

[0359] Preparation of MAO-silica support

[0360] A steel reactor equipped with a mechanical stirrer and filter was purged with nitrogen and the reactor temperature was set to 20°C. Next, DM-L-303 grade silica (5.0 kg) from AGC Si-Tech, pre-calcined at 600°C, was added from a feed bucket and then carefully pressurized and depressurized with nitrogen using a manual valve. Then, toluene (22 kg) was added. The mixture was stirred for 15 minutes. Next, a 30 wt% solution of MAO from Lanxess in toluene (9.0 kg) was added over 70 minutes through the feed line on the top of the reactor. The reaction mixture was then heated to 90°C and stirred at 90°C for another 2 hours. The slurry was allowed to settle and the mother liquor was filtered off. At 90°C, the catalyst was washed twice with toluene (22 kg), then settled and filtered. The reactor was cooled to 60°C and the MAO-treated support was collected with heptane as a free-flowing white powder containing 12.2% aluminum (by weight).

[0361] Catalyst manufacturing

[0362] At 20°C, 30 wt% MAO in toluene (0.7 kg) was added via burette to a nitrogen-sealed steel reactor. Toluene (5.4 kg) was then added with stirring. The above catalyst (93 g) was added from a metal cylinder, followed by a 1 kg toluene rinse. The mixture was stirred at 20°C for 60 minutes. Trityl tetrakis(pentafluorophenyl)borate (91 g) was then added from a metal cylinder, followed by a 1 kg toluene rinse. The mixture was stirred at room temperature for 1 hour. The resulting solution was added over 1 hour to a stirred cake of MAO-silica support prepared as described above. The cake was allowed to stand for 12 hours, then dried at 60°C under a stream of N2 for 2 hours, and then dried under vacuum (-0.5 bar gauge) with stirring for an additional 5 hours. The dried catalyst was sampled and found to be a pink, free-flowing powder containing 13.9% aluminum and 0.11% zirconium (Zr).

[0363] Preparation of the third catalyst system (#3)

[0364] First, under atmospheric pressure, in a reactor, under inert conditions, 0.1 mol of MgCl2×3EtOH was suspended in 250 ml of decane. The solution was cooled to a temperature of -15°C and 300 ml of cold TiCl4 was added while maintaining the temperature at that level. The temperature of the slurry was then slowly raised to 20°C. At this temperature, 0.02 mol of dioctyl phthalate (DOP) was added to the slurry. After the addition of the phthalate, the temperature was raised to 135°C within 90 minutes and the slurry was allowed to stand for 60 minutes. Then, another 300 ml of TiCl4 was added and the temperature was maintained at 135°C for 120 minutes. Thereafter, the catalyst was filtered from the liquid and washed six times with 300 ml of heptane at 80°C. The solid catalyst component was then filtered and dried.

[0365] The catalyst and its production concept are generally described in, for example, patent publications EP 491566, EP 591224 and EP 586390. The catalyst is used together with triethylaluminium (TEAL) as cocatalyst and dicyclopentyldimethoxysilane (D-donor) as donor.

[0366] Polymerization and granulation

[0367] Terpolymers IE1-IE4 were produced in a Borstar pilot plant consisting of a prepolymerization reactor, a loop reactor, and a gas phase reactor (GPR) connected in series. Polymerization conditions and polymer characterization results are shown in Table 1. IE1-IE3 were produced using the aforementioned catalyst system No. 1 (#1), while IE4 was produced using catalyst system No. 2 (#2).

[0368] All examples were compounded in a co-rotating twin-screw extruder Coperion ZSK 57 at 220° C. with 0.1 wt % of an antiblocking agent (synthetic silica; CAS No. 7631-86-9); 0.05 wt % of an antioxidant (Irgafos 168FF, CAS No. 31570-04-4, BASF); 0.1 wt % of a sterically hindered phenol (Irganox 1010FF, CAS No. 6683-19-8, BASF); and 0.04 wt % of DHT-4A (CAS No. 11097-59-9, Kisuma Chemicals).

[0369] Table 1: Polymerization process conditions of Example (IE) and Comparative Example (CE)

[0370]

[0371]

[0372] *From US 6 388 040

[0373] It can be seen that for a given amount of total defects, the melting temperature can be made lower by carefully setting the amount of units derived from ethylene, the total amount of units derived from ethylene and units derived from butene, and the ratio of units derived from butene to units derived from ethylene, and controlling the 2.1 zone inversion.

[0374] At the same time, the hexane solubility was also very low. Due to unacceptably high hexane solubility (FDA), CE2 was excluded from further evaluation.

[0375] The characteristics of the blown films made from the terpolymer are shown in Table 2 below.

[0376] Table 2: Characteristics of polymer compositions and blown film results

[0377]

[0378]

[0379] As can be seen, the blown films of the present invention have a lower seal initiation temperature, a good impact-stretch-haze balance (OMA), and reasonable hot tack. Compared to CE1 (0.4 mol% C2; C4 / C2 ratio of 11.3), the inventive examples have significantly better DDI, better haze, and significantly better SIT.

Claims

1. A blown film, the blown film being made from an ethylene-propylene-1-butene terpolymer, the terpolymer comprising: a) units derived from ethylene, the amount of units derived from ethylene being 0.8 to 2.8 mol% relative to the total amount of the terpolymer; and b) units derived from propylene, the amount of units derived from propylene being 91.6 to 95.8 mol% relative to the total amount of the terpolymer; and c) units derived from 1-butene, with the amount of the units derived from 1-butene being 3.4 to 5.6 mol% relative to the total amount of the terpolymer. d) the total of units derived from ethylene, units derived from propylene and units derived from 1-butene is 100 mol%, and e) the total amount of units derived from ethylene and units derived from 1-butene is 4.5 to 8.0 mol%, and f) a molar ratio of units derived from 1-butene to units derived from ethylene of from 1.5 to 5.0; and g) By 13 The amount of 2.1 regio inversion determined by C-NMR analysis is 0.20 to 0.45 mol%; and h) a melt flow rate MFR2 measured according to ISO 1133 at a temperature of 230° C. and a load of 2.16 kg in the range of 1.5 to 4.5 g / 10 min, and i) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following formula: Tm<[150–1.6×(defect)–0.14×(defect)2]℃, in, "Defects" means the sum of units derived from ethylene, units derived from 1-butene and 2.1 regioinversions, all values ​​are expressed in mol%, The seal initiation temperature (SIT) of the blown film is less than 117°C.

2. The blown film according to claim 1, wherein The amount of the units derived from ethylene in the ethylene-propylene-1-butene terpolymer is 1.3 to 2.4 mol% relative to the total amount of the terpolymer.

3. The blown film according to claim 1 or 2, wherein The amount of the unit derived from 1-butene in the ethylene-propylene-1-butene terpolymer is 4.6 to 5.4 mol% relative to the total amount of the terpolymer.

4. The blown film according to claim 1 or 2, wherein The total amount of the units derived from ethylene and the units derived from 1-butene in the ethylene-propylene-1-butene terpolymer is 5.8 to 7.5 mol%.

5. The blown film according to claim 1 or 2, wherein The molar ratio of the units derived from 1-butene to the units derived from ethylene is in the range of 1.6 to 4.

5.

6. The blown film according to claim 1 or 2, wherein Ethylene-propylene-1-butene terpolymer 13 The amount of 2.1 region inversion determined by C-NMR analysis was 0.20 to 0.40 mol%.

7. The blown film according to claim 1 or 2, wherein Ethylene-propylene-1-butene terpolymer contains: a) units derived from ethylene, the amount of units derived from ethylene being 1.3 to 2.4 mol% relative to the total amount of the terpolymer; and b) units derived from propylene, the amount of units derived from propylene being 92.2 to 94.1 mol% relative to the total amount of the terpolymer; and c) units derived from 1-butene, with the amount of the units derived from 1-butene being 4.6 to 5.4 mol% relative to the total amount of the terpolymer. d) the total of units derived from ethylene, units derived from propylene and units derived from 1-butene is 100 mol%, and e) the total amount of units derived from ethylene and units derived from 1-butene is 5.8 to 7.5 mol%, and f) a molar ratio of units derived from 1-butene to units derived from ethylene of from 1.6 to 4.5; as well as g) By 13 The amount of 2.1 region inversion determined by C-NMR analysis was 0.20–0.40 mol %; as well as h) a melt flow rate MFR2 measured according to ISO 1133 at a temperature of 230° C. and a load of 2.16 kg in the range of 1.5 to 4.5 g / 10 min, and i) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following formula: Tm<[150–1.6×(defect)–0.14×(defect)2]℃, where "defects" represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regioinversions, and all values ​​are expressed in mol %, The film has a seal initiation temperature (SIT) of less than 112°C.

8. The blown film according to claim 7, wherein The seal initiation temperature (SIT) of the film is 105-111°C.

9. The blown film according to claim 1 or 2, wherein The flexural modulus of the ethylene-propylene-1-butene terpolymer, measured according to ISO 178, is 600-900 MPa.

10. The blown film according to claim 1 or 2, wherein The ethylene-propylene-1-butene terpolymer is bimodal with respect to the butene content and / or bimodal with respect to the molecular weight.

11. An ethylene-propylene-1-butene terpolymer, the terpolymer comprising: a) units derived from ethylene, the amount of units derived from ethylene being 0.8 to 2.8 mol% relative to the total amount of the terpolymer; and b) units derived from propylene, the amount of units derived from propylene being 91.6 to 95.8 mol% relative to the total amount of the terpolymer; and c) units derived from 1-butene, with the amount of the units derived from 1-butene being 3.4 to 5.6 mol% relative to the total amount of the terpolymer. d) the total of units derived from ethylene, units derived from propylene and units derived from 1-butene is 100 mol%, and e) the total amount of units derived from ethylene and units derived from 1-butene is 4.5 to 8.0 mol%, and f) a molar ratio of units derived from 1-butene to units derived from ethylene in the range of 1.5 to 5.0; and g) By 13 The amount of 2.1 regio inversion determined by C-NMR analysis is 0.20 to 0.45 mol%; and h) a melt flow rate MFR2 measured according to ISO 1133 at a temperature of 230° C. and a load of 2.16 kg in the range of 1.5 to 4.5 g / 10 min, and i) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following formula: Tm<[150–1.6×(defect)–0.14×(defect)2]℃, in, "Defects" represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regio inversions, all values ​​being expressed in mol%.

12. The ethylene-propylene-1-butene terpolymer according to claim 11, wherein The terpolymer has: a) units derived from ethylene, the amount of units derived from ethylene being 1.3 to 2.4 mol% relative to the total amount of the terpolymer; and b) units derived from propylene, the amount of units derived from propylene being 92.2 to 94.1 mol% relative to the total amount of the terpolymer; and c) units derived from 1-butene, with the amount of the units derived from 1-butene being 4.6 to 5.4 mol% relative to the total amount of the terpolymer. d) the total of units derived from ethylene, units derived from propylene and units derived from 1-butene is 100 mol%, and e) the total amount of units derived from ethylene and units derived from 1-butene is 5.8 to 7.5 mol%, and f) a molar ratio of units derived from 1-butene to units derived from ethylene of 1.6 to 4.5; as well as g) By 13 The amount of 2.1 region inversion determined by C-NMR analysis was 0.20–0.40 mol %; as well as h) a melt flow rate MFR2 measured according to ISO 1133 at a temperature of 230° C. and a load of 2.16 kg in the range of 1.5 to 4.5 g / 10 min, and i) The melting temperature Tm measured by differential scanning calorimetry (DSC) satisfies the following formula: Tm<[150–1.6×(defect)–0.14×(defect)2]℃, Here, "defects" represents the sum of units derived from ethylene, units derived from 1-butene, and 2.1 regio inversions, and all values ​​are expressed in mol%.

13. A composition comprising the ethylene-propylene-1-butene terpolymer according to claim 11 or 12, wherein The amount of the terpolymer is at least 97 wt % relative to the total amount of the composition.

14. The composition according to claim 13, wherein The composition consists of the ethylene-propylene-1-butene terpolymer according to claim 11 or 12 and additives.

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