CN1304448C - 聚合物膜 - Google Patents
聚合物膜 Download PDFInfo
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- CN1304448C CN1304448C CNB038032392A CN03803239A CN1304448C CN 1304448 C CN1304448 C CN 1304448C CN B038032392 A CNB038032392 A CN B038032392A CN 03803239 A CN03803239 A CN 03803239A CN 1304448 C CN1304448 C CN 1304448C
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- ethene
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- olefin
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- 229920006254 polymer film Polymers 0.000 title 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000004711 α-olefin Substances 0.000 claims abstract description 44
- -1 polyethylene Polymers 0.000 claims abstract description 39
- 239000004698 Polyethylene Substances 0.000 claims abstract description 35
- 229920000573 polyethylene Polymers 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims description 55
- 229920000642 polymer Polymers 0.000 claims description 47
- 229920001577 copolymer Polymers 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 21
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 21
- 239000004702 low-density polyethylene Substances 0.000 claims description 18
- 238000007789 sealing Methods 0.000 claims description 18
- 229920001897 terpolymer Polymers 0.000 claims description 18
- 229920006158 high molecular weight polymer Polymers 0.000 claims description 17
- 229920001684 low density polyethylene Polymers 0.000 claims description 17
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 235000013305 food Nutrition 0.000 claims description 5
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- 238000002360 preparation method Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 abstract description 18
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 239000005977 Ethylene Substances 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 25
- 230000002902 bimodal effect Effects 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229920000092 linear low density polyethylene Polymers 0.000 description 8
- 239000004707 linear low-density polyethylene Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
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- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- BLDFSDCBQJUWFG-UHFFFAOYSA-N 2-(methylamino)-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(NC)C(O)C1=CC=CC=C1 BLDFSDCBQJUWFG-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229920001179 medium density polyethylene Polymers 0.000 description 3
- 239000004701 medium-density polyethylene Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
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- 239000000523 sample Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ALSOCDGAZNNNME-UHFFFAOYSA-N ethene;hex-1-ene Chemical group C=C.CCCCC=C ALSOCDGAZNNNME-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RQFCIQWKZMYMFA-UHFFFAOYSA-L [Cl-].[Cl-].C(CCC)[Hf+2](C1C=CC=C1)C1C=CC=C1 Chemical compound [Cl-].[Cl-].C(CCC)[Hf+2](C1C=CC=C1)C1C=CC=C1 RQFCIQWKZMYMFA-UHFFFAOYSA-L 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002035 hexane extract Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
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Abstract
本发明提供了一种聚乙烯膜,该聚乙烯通过单点催化剂催化的聚合反应而制得并且包含至少两种C4-12α-烯烃(优选1-丁烯和1-己烯)作为乙烯的共聚单体。
Description
本发明涉及聚乙烯膜,特别是可热封的膜,以用于例如产品包装。
聚乙烯(PE)膜、尤其线性低密度聚乙烯(LLDPE)膜广泛应用于包装产品,例如食品、液体(比如洗涤剂再装物)等等。在这些应用中,膜的密封性能特别重要。为解决该问题,已知的是在PE中引入共聚单体,以便给聚合物提供熔点较低的组分,因而提高膜的热粘性能。关于这一点已知的是,与引入丁烯-乙烯共聚物的LLDPE相比,在LLDPE中引入己烯-乙烯共聚物可提供更优良的密封性能,并且与引入己烯-乙烯共聚物的LLDPE相比,引入辛烯-乙烯共聚物可提供更好的性能。
然而使用较高级的α-烯烃共聚单体,也就是使用C4或更高级的α-烯烃,将会增加聚合物产品的成本,而且引入共聚单体的效率通常随着共聚单体中碳含量的增加而降低,也就是说己烯的引入效率比丁烯低,辛烯的引入效率比己烯低,如此类推。
现在我们意外地发现,通过引入两种不同的α-烯烃共聚单体可以制备出这样的聚乙烯膜产品,它比采用任一种共聚单体作为唯一共聚单体而制得的聚乙烯具有更优良的密封性能。
因而从一方面来看本发明提供了一种聚乙烯膜,该聚乙烯通过单点催化剂催化的聚合反应而制得并且包含作为乙烯的共聚单体的至少两种C4-12α-烯烃,优选至少两种选自丁-1-烯、己-1-烯、4-甲基-1-戊烯、庚-1-烯、辛-1-烯和癸-1-烯的α-烯烃,特别是丁-1-烯和己-1-烯。
本发明的膜尤其适于用作可热封的膜;例如5或7层共挤出的层状膜,例如用于食品包装和医疗包装应用。它们也可用于密封性能和机械性能的结合很重要的工业FFS(成型灌装和封口)。
许多情形下,在要密封的膜和制品之间形成密封,当其尚温热时使该密封处于载荷下。这意味着,对于确保即使是在冷却之前形成牢固的密封而言,密封层的热粘性能至关重要。所有可热封的膜都具有一个范围(window),在这个范围内进行热合,也就是说在该范围内密封层变得部分熔融。传统上该热合范围(sealing window)具有相当窄的含义,也即热封过程中的温度控制很严格。本发明的膜可具有较宽的热合范围,因而可以在较低温度下进行密封操作并且使得热封过程中的温度控制变得不那么重要。在较低温度下操作的好处在于,要密封的制品不会暴露于高温下,不进行密封的膜的其它层同样不会暴露在高温下。由于较低的温度显然更容易获得和维持,因此还带来了经济上的优势。
本发明的膜用聚乙烯通常是两种或多种聚乙烯的混合物,例如通过共混或者通过两段或多段聚合反应而制得的聚乙烯。作为构成成分的聚乙烯可以是均聚物、共聚物、三元共聚物或者四种或更多种共聚单体的聚合物;不过,优选至少一种聚合物是三元共聚物或者至少两种聚合物是共聚物,特别是其中一种单体也即主组分是乙烯而一种或两种共聚单体也即少量组分是C4和/或C6α-烯烃。尤其优选的是在两段或多段聚合中制得聚合物,其中,在初期阶段加入低级α-烯烃共聚单体,在其后的阶段加入高级α-烯烃。尽管如此,但是仍落入本发明范围的是,在两段聚合反应中制备聚合物,其中在第一阶段制得乙烯均聚物,在第二阶段制得乙烯三元共聚物,或者反过来,其中在第一阶段制得乙烯与高级α-烯烃共聚单体的共聚物,在第二阶段制得乙烯与低级α-烯烃共聚单体的共聚物。同样地,可以在第一阶段制得乙烯共聚物并在第二阶段制得乙烯三元共聚物,反之亦然。
此处所用的乙烯的“均聚物”这种表达是指基本上由乙烯构成的聚乙烯,也就是由至少98wt%、优选至少99wt%、更优选至少99.5wt%且最优选至少99.8wt%的乙烯构成的聚乙烯。
本发明聚合物膜的乙烯聚合物采用所谓的单点催化剂制备,例如包含金属的催化剂,该金属配位有一个或多个η-键合配体。这种η-键合的金属通常称之为茂金属,这些金属一般是Zr、Hf或Ti,特别是Zr或Hf。η-键合配体通常是η5-环状配体,也就是任选带有稠合或侧接取代基的均环或杂环的环戊二烯基基团。这些茂金属催化剂大约二十年以来已普遍描述在科技和专利文献中。这些茂金属催化剂经常与催化剂活化剂或助催化剂一起使用,催化剂活化剂或助催化剂例如甲基铝氧烷之类的铝氧烷,同样它们也已广泛记载在文献中。
本发明膜用聚合物优选为双峰或多峰聚合物,也就是说,其分子量曲线不是单一峰,而是包括两个或多个中心点位于不同平均分子量的峰(它们可能是可辨别的,也可能是不可辨别的)的结合,这是由于该聚合物包含两种或更多种单独制备的组分。在该实施方案中,优选较高分子量组分对应于高级α-烯烃共聚单体的共聚物(或三元共聚物等等),优选较低分子量组分对应于乙烯均聚物或低级α-烯烃共聚单体的共聚物(或三元共聚物等等)。这些双峰乙烯聚合物可以通过例如两段或多段聚合反应而制备,或者通过在一个聚合阶段中使用两种或多种不同的聚合催化剂而制备。不过,优选它们是在两段聚合反应中采用相同催化剂例如茂金属催化剂而制得的,特别是在回路反应器内进行於浆聚合,接着在气相反应器内进行气相聚合。回路反应器-气相反应器体系由Borealis A/S(丹麦)在市场上作为BORSTAR反应器体系出售。
优选地,低分子量聚合物级分在连续操作的回路反应器内进行制备,该回路反应器中乙烯在如上所述的聚合催化剂和诸如氢之类链转移剂的存在下进行聚合。稀释剂通常是惰性脂族烃,优选异丁烷和丙烷。优选加C4至C12α-烯烃共聚单体以控制低分子量共聚物级分的密度。
优选如此选择氢气浓度,以使得低分子量共聚物级分具有所希望的熔体流动速率。更优选氢与乙烯的摩尔比为0.1至1.5mol/kmol,最优选0.2至1.0mol/kmol。
若低分子量共聚物级分的目标密度超过955kg/m3,则有利的是采用丙烷稀释剂在所谓的超临界条件下运转回路反应器,其中操作温度超过反应混合物的临界温度,并且操作压力超过反应混合物的临界压力。那么优选的温度范围是90至110℃,优选的压力范围是50至80巴。
间歇地或连续地从回路反应器内移走於浆,并将其输送到分离单元,在分离单元中至少链转移剂(例如氢)从聚合物中分离出来。然后将含有活性催化剂的聚合物导入气相反应器,在气相反应器中在另外加入的乙烯、共聚单体和任选的链转移剂的存在下进行聚合,以制备出高分子量共聚物级分。从气相反应器内间歇地或连续地取出聚合物,并且从聚合物中分离出残留的烃。从气相反应器收集的聚合物即是双峰三元共聚物。
如此选择气相反应器内的条件,以使得乙烯聚合物具有所希望的性能。优选反应器内的温度为70至100℃,压力为10至40巴。氢与乙烯的摩尔比优选是0至1mol/kmol,更优选0至0.5mol/kmol,α-烯烃共聚单体与乙烯的摩尔比优选是1至100mol/kmol,更优选是5至50mol/kmol且最优选是5至30mol/kmol。
本发明的膜可采用常规生产膜的技术来进行制造。该膜通常是10至1000微米厚,尤其20至100微米厚。具体的厚度根据将要用膜包装的产品的特性和其期望的后续处理条件来进行选择。
然而该膜优选是挤出的膜,特别优选的吹胀比为2∶1至4∶1。
如果需要的话,该膜可以是多层膜,例如层压或共挤出得到的膜。
多层膜中,其它层可包含拥有所希望的性能和加工性能的任何膜等级聚合物树脂。这些聚合物的实例包括:阻隔层PA(聚酰胺)和EVA;乙烯的极性共聚物,例如乙烯与乙烯醇的共聚物或者乙烯与丙烯酸酯单体的共聚物;粘合剂层,例如含离子键的聚合物,乙烯与丙烯酸乙酯的共聚物,等等;刚性HDPE;高压方法制得的LDPE树脂;通过乙烯与α-烯烃共聚单体在齐格勒、铬或茂金属催化剂存在下进行的聚合而制得的LLDPE树脂;以及MDPE树脂。不过,多层膜优选具有至少一个密封层,优选为外层,它是含有至少两种其它α-烯烃共聚单体的双峰乙烯聚合物。
从另一方面考虑,本发明还提供了一种用于生产膜的聚乙烯组合物,所述组合物包含一种聚乙烯,该聚乙烯通过单点催化剂催化的聚合反应而制得并且具有作为乙烯的共聚单体的至少两种C4-12α-烯烃,优选至少两种选自丁-1-烯、己-1-烯、4-甲基-1-戊烯、庚-1-烯、辛-1-烯和癸-1-烯的α-烯烃,特别是丁-1-烯和己-1-烯。
从另一方面考虑,本发明提供了一种用聚乙烯热封膜包装的产品(例如食品、诸如洗涤剂之类的液体等等),该聚乙烯通过单点催化剂催化的聚合反应而制得并且其包含作为乙烯的共聚单体的至少两种C4-12α-烯烃,优选至少两种选自丁-1-烯、己-1-烯、4-甲基-1-戊烯、庚-1-烯、辛-1-烯和癸-1-烯的α-烯烃,特别是丁-1-烯和己-1-烯。
本发明的膜优选要么是双峰三元共聚物,该双峰三元共聚物包含
a)乙烯的低分子量均聚物和
b)乙烯、1-丁烯和C6-C12α-烯烃的高分子量三元共聚物,要么是双峰聚合物,该双峰聚合物包含
a)低分子量聚合物,它是乙烯与C4-C12α-烯烃的二元共聚物,和
b)高分子量聚合物,如果a)的低分子量聚合物是乙烯与C6-C12α-烯烃的二元共聚物,则该高分子量聚合物是乙烯与1-丁烯的二元共聚物,或者该高分子量聚合物是乙烯、1-丁烯和C6-C12α-烯烃的三元共聚物。
在优选实施方案中,本发明提供了一种双峰型聚合物膜,它具有较窄的分子量分布(MWD)和极好的密封性能、良好的加工性能、低渗透性和低含量的可提取物。MWD优选为2.5至10,尤其是3.0至8.0。
这里聚合物形态(modality)是表示其分子量分布(MWD)曲线的形式,也就是体现聚合物的重量级分作为其分子量的函数。如果聚合物在连续方法中制得,也即通过利用串联反应器并且在各个反应器中采用不同条件而制得,那么在不同反应器内制得的不同聚合物级分将各自具有它们自己的分子量分布,这些分子量分布可能彼此的差别相当大。
所得最终聚合物的分子量分布曲线可以看上去是聚合物级分之分子量分布曲线的叠合,因此与单独级分的曲线相比它们将显示出两个或多个明显不同的最大值或者它们至少明显变宽。显示出这种分子量分布曲线的聚合物分别称为双峰或多峰聚合物。
多峰聚合物尤其双峰聚合物可以按照例如EP-0517868B1或WO-A-96/18662中描述的几种方法来进行制备。
多峰聚乙烯优选以多步反应顺序在多段工艺方法中制得,例如EP-0517868B1或WO-A-96/18662中所述。这些文献的内容在此作为参考文献引入。
该方法中,第一步,乙烯在回路反应器内在惰性低沸点烃介质的液相中进行聚合。然后从回路反应器排放出反应混合物,并且从反应混合物中至少除去惰性烃介质,将聚合物输送至一个或多个气相反应器,在该气相反应器中在气态乙烯的存在下继续进行聚合。相比于不能通过例如聚合物的混合而获得的不同聚合物级分的分布,按照该工艺方法制得的多峰聚合物具有优良的均匀性。
用于制备乙烯聚合物的催化剂可以是单点催化剂,比如使用WO97/28170、WO 00/34341和WO 00/40620中所公开的那些催化剂之一种。这些公开出版物的内容在此引入作为参考。
双峰聚合物组合物优选包括一种低分子量共聚物级分和一种高分子量共聚物级分。如果使用二元共聚物的话,低分子量共聚物级分优选含有C4至C12α-烯烃,特别是选自1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯和1-癸烯的α-烯烃。高分子量共聚物级分的C6至C12α-烯烃优选选自1-己烯、4-甲基-1-戊烯、1-庚烯、1-辛烯和1-癸烯。
双峰聚合物的重均分子量优选是50,000至250,000g/mo1。低分子量聚合物级分的重均分子量优选为5000至100,000g/mol,更优选为10,000至70,000g/mol,而高分子量聚合物级分的重均分子量优选是50,000至500,000g/mol,更优选是100,000至300,000g/mol。
聚合物的分子量分布可按照ISO 1133在190℃下的熔体流动速率(MFR)来进行表征。熔体流动速率主要取决于平均分子量。原因在于较大分子给材料带来的流动趋势比较小分子要低。
分子量增大意味着MFR值降低。所测量的熔体流动速率是在特定温度和压力条件下以g/10mm表示的聚合物的排出量,并且熔体流动速率是聚合物粘度的一种度量方式,其对于每种类型的聚合物而言,熔体流动速率同样也主要受其分子量分布的影响,但还受其支化度等因素的影响。在2.16kg(ISO 1133)负载下测得的熔体流动速率表示为MFR2。同样,用21.6kg测得的熔体流动速率表示为MFR21。
最终的双峰聚合物优选具有0.3-5g/10min的熔体流动速率MFR2,更优选为0.4-3g/10min。低分子量聚合物级分优选具有50至1000g/10min的熔融指数MFR2,更优选50至300g/10min。
材料的熔体流动速率和密度决定了强度性能,然而只有密度对熔点、表面硬度、渗透性和吸水性具有决定作用。
最终双峰聚合物的密度优选为905-940kg/m3,更优选为905-930kg/m3。低分子量聚合物级分的密度优选为925-945kg/m3,更优选为925-940kg/m3。
本发明的双峰聚合物优选包含全部组合物的30-70wt%、更优选35-60wt%且最优选38-55wt%的低分子量共聚物级分。
聚合物中全部共聚单体的含量优选是0.1-10%mol,更优选0.5-7%mol,低分子量聚合物中共聚单体的含量优选为0-3.0%mol,更优选0-2.5%mol。高分子量聚合物中共聚单体的含量优选为0.1-10%mol,更优选0.1-7%mol。共聚单体含量可以用核磁共振(nmr)来测量。
而且,高分子量共聚物级分的分子量应当是如此,也即要使得当低分子量共聚物级分具有如上所述的熔融指数和密度时,最终双峰聚合物也具有如上所讨论的熔融指数和密度。
除了聚合物本身外,本发明的组合物和膜还可以含有本领域已知的抗氧剂、加工稳定剂、颜料和其它添加剂。此外,乙烯与两种其它α-烯烃共聚单体的双峰SSC聚合物可以与其它聚合物共混,同时保留聚合物膜适合于所需最终应用的密封和机械性能。这类可用的其它聚合物的实例包括LDPE、HDPE、MDPE、LLDPE、EMA、EBA和EVA。通常,全部聚合物的多至约50wt%可以由许多更进一步的聚合物构成,在HDPE、MDPE或LLDPE的情况下更优选多至30wt%。考虑到对可得到的膜的光学性能的重大改进,因而将LDPE包括在内特别有利。
当这些膜将要用于包装某些产品尤其食品时,特别重要的是膜应具有高透明性和光泽。若这些膜仅由SSC聚合物(也就是采用单点催化剂制得的聚合物)制成,则它们在外观上常常比较混浊和/或无光泽。这可以通过在SSC聚乙烯中掺混LDPE来解决,例如高达5wt%、更优选1-5wt%、特别是3-4wt%且尤其是约3.5wt%的掺混聚合物是LDPE。我们还意外地发现,密度较高的LDPE(例如925-932kg/m3)在这方面特别有效。这种LDPE的一个实例是从Borealis A/S以商标名Himod LDPE市购的产品,它是用管式高压工艺方法制得的。
密度较高的LDPE对PE膜光学性能的这种影响十分出乎意料,因为曾经料想的是,LDPE添加剂的密度越高,对光学性能的改进则越小。因此,从另一方面考虑,本发明提供了较高密度的LDPE(例如密度为925-932kg/m3的LDPE)在膜制造用聚乙烯组合物中作为添加剂(例如构成组合物的1-5wt%)的用途,以改进由其制得的膜的光学特性。
稳定剂的实例是受阻酚、受阻胺、磷酸盐、亚磷酸盐和亚膦酸盐(phosphonites)。
颜料的实例是炭黑、群青和二氧化钛。
其它添加剂的实例例如粘土、滑石、碳酸钙、硬脂酸钙、硬脂酸锌和抗静电剂,比如以商标名Lankrostat出售的那些商品。
现在将通过以下非限定性实施例和所附附图进一步解释本发明,其中图1是对于由实施例2的聚合物和四种对比聚合物吹制的膜来说热粘性随温度变化绘成的曲线。
热粘性:
“热粘性”是在密封操作之后立即测量膜和层压品的热封强度的一种方法。该性能用52-D(w-4236)型DTC国际热粘测试仪来测量。
将样品切成宽度15mm。密封时间为0.5秒,延迟时间为0.1秒并且密封压力是90N。测量在不同温度下的密封,对每一测试温度取5次平行值。测试之前调整试样,使其在环境温度下放置最少24小时。
MFR
按照ISO 1133在190℃下测量MFR。负载以下标表示,也就是说,MFR2表示在2.16kg负载下进行测量,MFR21则分别表示在21.6kg负载下进行测量。
FRR
流动速率比(FRR)是在不同负载下测得的两个熔体流动速率的比值。负载以下标表示。因此,FRR21/2表示MFR21对MFR2之比。
MWD:
通过基于ISO/TC61/SC5N 5024的方法而测得重均分子量Mw和分子量分布(MWD=Mw/Mn,其中Mn等于数均分子量)。该方法与所用方法的主要差别是温度;ISO方法在室温下进行而所用方法是在140℃下。Mw与Mn之比是分布宽度的一种量度,因为它们每个均受“集群”(population)相反端的影响。
密度:
按照ISO 1183/D测量密度。
己烷可提取物:
采用ASTM D5227进行己烷提取物的测量。
氧气渗透性:
采用ASTM D3985进行氧气渗透性的测量。
水渗透性:
按照ASTM F1249测量水蒸汽传输速率。
流变性:
采用Rheometrics RDA II动态流变仪测定聚合物的流变性能。于190℃下在氮气气氛中进行测量。测量得到储能模量(G’)和损耗模量(G”)以及复数粘度(η*)的绝对值是随频率(ω)或复合模量(G*)的绝对值而变化的函数,其中:
η*=((G’2+G”2)/ù)1/2
G*=(G’2+G”2)1/2
在该方法中,绘制低剪切速率下(0.05弧度/秒)的粘度相对于高剪切速率(300弧度/秒)下的粘度变化的图线,作为衡量加工性能的量度;低剪切速率下的高粘度与高剪切速率下的低粘度结合则获得优良的加工性能。
实施例1
将134克茂金属配合物(由Witco作为TA02823供应的双(正丁基二环戊二烯基)二氯化铪,其含有0.36wt%的Hf)和9.67千克30%甲基铝氧烷(MAO)在甲苯中的溶液(由Albemarle提供)合并在一起,并且加入3.18千克干燥的精制甲苯。将由此获得的配合物溶液在2小时内通过极慢的均匀喷雾加载在17千克二氧化硅载体Sylopol 55 SJ(由Grace供应)上。将温度保持为低于30℃。配合物加料完毕后使混合物在30℃下反应3小时。
实施例2
聚合物A
体积为500dm3、连续运转的回路反应器在85℃的温度和60巴的压力下进行操作。向反应器内导入丙烷稀释剂、乙烯、1-丁烯共聚单体、氢和实施例1所述的聚合催化剂,其量使得乙烯在回路反应器液相中的浓度为5.8%摩尔,氢与乙烯之比为0.48mol/kmol,1-丁烯与乙烯之比为118mol/kmol,并且反应器中聚合物的生产率为30kg/h。由此形成的聚合物具有79g/10min的熔融指数MFR2和938kg/m3的密度。
通过采用沉降支管(settling leg)间歇地从反应器内取出淤浆,并将其直接送至在约50℃的温度和约3巴的压力下操作的闪蒸罐。
从闪蒸罐出来的聚合物粉末含有少量残留烃,将这些聚合物粉末输送至在75℃温度和20巴压力下操作的气相反应器。同样向气相反应器内加入另外的乙烯、1-己烯共聚单体和作为惰性气体的氮气,其量要使得乙烯在循环气流中的浓度为37%摩尔,1-己烯与乙烯之比为10mol/kmol,并且聚合物的生产率为37kg/h。1-丁烯和氢气的浓度如此低以至于借助用来监控气相组成的在线气相色谱仪无法检测到它们。
通过向粉末中加入0.15wt%稳定剂Irganox B561而使从气相反应器收集到的聚合物稳定。然后用由Japan Steel Works制造的CIM90P挤出机将稳定的聚合物挤出和造粒。
因此回路反应器和气相反应器的产量分成45/55。聚合物粒料的熔融指数MFR2为0.78g/10min,密度为919kg/m3,1-丁烯含量为1.4wt%,1-己烯的含量为7.1wt%,重均分子量Mw为131000g/mol,数均分子量Mn为28200g/mol并且Z均分子量Mz为333000g/mol。此外,聚合物在零剪切速率下的粘度η0为11700Pa·s而剪切稀化指数SHI0/100为3.9。
实施例3
聚合物B
重复实施例2的过程,只是将工艺条件调整为如表1所示。
聚合物粒料的熔融指数MFR2为0.76g/10min,密度为919kg/m3,1-丁烯含量为2.0wt%,1-己烯的含量为6.8wt%,重均分子量Mw为126000g/mol,数均分子量Mn为16600g/mol并且Z均分子量Mz为349000g/mol。此外,聚合物在零剪切速率下的粘度η0为12900Pa·s而剪切稀化指数SHI0/100为5.4。
表1
实施例 | 2 | 3 | 6 |
回路中的C2,mol% | 5.8 | 7.0 | 5.5 |
回路中的H2/C2,mol/kmol | 0.48 | 0.78 | 0.53 |
回路中的C4/C2,mol/kmol | 118 | 139 | 123 |
回路中的C6/C2,mol/kmol | 0 | 0 | 0 |
回路聚合物的MFR2,g/10min | 79 | 340 | 145 |
回路聚合物的密度,kg/m3 | 938 | 937 | 939 |
回路的生产率,kg/h | 30 | 30 | 30 |
气相反应器中的C2,mol% | 37 | 43 | 32 |
气相反应器中的H2/C2,mol/kmol | * | * | * |
气相反应器中的C4/C2,mol/kmol | * | * | * |
气相反应器中的C6/C2,mol/kmol | 10 | 12 | 10 |
气相反应器的生产率,kg/h | 37 | 30 | 36 |
产量分成,回路/气相反应器 | 45/55 | 50/50 | 44/56 |
*表示含量太低以至无法用GC检测到
实施例2、3和6的聚合物的特性列于下表2中。
表2
聚合物 | A | B | L |
回路的MFR2(低分子量组分)[g/10min] | 79 | 340 | 145 |
密度(低分子量组分)(kg/m3) | 938.4 | 936.6 | 939 |
分成(低分子量/高分子量) | 45/55 | 50/50 | 44/56 |
最终MFR2(g/10min) | 0.78 | 0.76 | 0.86 |
FRR21/2 | 38 | 55 | 42 |
最终密度(kg/m3) | 919 | 919 | 919 |
MWD | 4.6 | 7.6 | 5.7 |
己烷可提取物(%wt) | 0.3 | 0.8 | 0.4 |
氧气渗透性(cm3/m2.24小时) | 6425 | 5350 | - |
水渗透性(g/m2.24小时) | 9.5 | 8.4 | - |
实施例4
膜的生产
为了比较,使用实施例2和3的聚合物以及(C)LDPE(从Borealis A/S得到的FT 5230)、(D)以1-丁烯作为共聚单体的双峰型ZN-LLDPE(从Borealis得到的FB 2230)、(E)以1-丁烯作为共聚单体的ZN-LLDPE(从Borealis A/S得到的FG 5190)和(F)以1-辛烯作为共聚单体的SSC-PE(从DOW得到的Elite5400),在Reifenhauser薄膜生产线上挤出厚度为40微米的薄膜,口模直径为150mm,螺杆直径为70mm,BUR(吹胀比)为2.5∶1,口模间隙为2.0mm,口模温度为210℃。
测量薄膜的热粘性并且在图1中绘制出来。可以看出,本发明的薄膜可与采用以辛烯作为共聚单体的PE制成的那些膜相媲美,并且要优于那些采用低级烯烃共聚单体的膜。
实施例5
聚合物共混物
将实施例3的聚合物与4wt%高压釜生产的LDPE(从Borealis A/s得到的FA 5223,MFR2为1.2g/10min,密度为922kg/m3)或与4wt%高压釜生产的LDPE(从BorealisA/s得到的CA 8200,MFR2为7.5g/10min,密度为920kg/m3)掺混在一起。将所得共混物、聚合物(G)和(H)各自以及聚合物B本身用Ankutec吹膜机(30mm,LD之比为25∶1,口模直径为50mm,口模间隙为2.4mm)加工成40微米厚的薄膜。按照ASTM D2457和ASTM D1003分别评价光泽和雾度,结果列于下表3中:
表3
聚合物 | G | H | B |
光泽60(%) | 71 | 63.6 | 39.1 |
雾度(%) | 15.9 | 15.4 | 31.9 |
同样地,将实施例6的聚合物与4wt%的FA5223或4wt%密度较高的管式LDPE(从BorealisA/S得到的FA5270)或者与4wt%的CA8200掺混在一起。同样将所得共混物、聚合物(I)、(J)和(K)分别进行吹膜,并且同样评价其雾度和光泽。结果列于下表4中:
表4
聚合物 | I | J | K | L |
光泽60°(%) | 88.9 | 95.6 | 72.4 | 45.7 |
雾度(%) | 12.7 | 11.6 | 14.8 | 29.5 |
实施例6
聚合物L
重复实施例2的过程,只是将工艺条件调整为如表1所示。
聚合物粒料的熔融指数MFR2为0.86g/10min,密度为919kg/m3,1-丁烯含量为1.5wt%,1-己烯的含量为7.3wt%,重均分子量Mw为127000g/mol,数均分子量Mn为22200g/mol并且Z均分子量Mz为324000g/mol。此外,聚合物在零剪切速率下的粘度η0为11000Pa·s而剪切稀化指数SHI0/100为4。
Claims (19)
1.一种聚乙烯膜,该聚乙烯通过具有多于一个η5-环状配体的单点催化剂催化的聚合反应而制得,所述聚乙烯的密度为905-940kg/m3,并且包含
ai)乙烯的低分子量均聚物,和
bi)乙烯、1-丁烯和C6-12α-烯烃的高分子量三元共聚物;或者
aii)低分子量聚合物,它是乙烯与选自C4-C12α-烯烃的共聚单体的二元共聚物,和
bii)高分子量聚合物,如果aii)的低分子量聚合物是乙烯与C6-C12α-烯烃的二元共聚物,则该高分子量聚合物是乙烯与1-丁烯的二元共聚物,或者该高分子量聚合物是乙烯、1-丁烯和选自C6-C12α-烯烃的共聚单体的三元共聚物;
其中所有的组分都是由相同的催化剂制备的。
2.权利要求1的膜,其中所述共聚单体选自丁-1-烯、己-1-烯、4-甲基-1-戊烯、庚-1-烯、辛-1-烯和癸-1-烯
3.权利要求2的膜,其中所述共聚单体是丁-1-烯、己-1-烯。
4.权利要求1的膜,其中分子量较低的组分构成聚乙烯的30-70wt%。
5.权利要求1的膜,其中所述聚乙烯的共聚单体含量为0.1-10mol%。
6.权利要求1的膜,其中所述聚乙烯的密度为905-930kg/m3。
7.权利要求1的膜,其中所述聚乙烯的重均分子量为50000-250000g/mol。
8.权利要求1的膜,其中所述聚乙烯的分子量分布为3至8。
9.权利要求1的膜,其中所述聚乙烯的MFR2为0.4-3g/10min,ISO1133,190℃,2.16kg。
10.权利要求1的膜,其中所述聚乙烯与其它聚合物掺混在一起。
11.权利要求10的膜,其中所述其它聚合物是低密度聚乙烯。
12.权利要求1的膜,该膜包括许多层。
13.权利要求1的膜,该膜以2∶1至4∶1的吹胀比挤出而制得。
14.权利要求1的膜,其中所述聚乙烯包括
aii)低分子量聚合物,它是乙烯与选自C4-C12α-烯烃的共聚单体的二元共聚物,和
bii)高分子量聚合物,如果aii)的低分子量聚合物是乙烯与C6-C12α-烯烃的二元共聚物,则该高分子量聚合物是乙烯与1-丁烯的二元共聚物,或者该高分子量聚合物是乙烯、1-丁烯和选自C6-C12α-烯烃的共聚单体的三元共聚物。
15.一种用于生产膜的聚乙烯组合物,所述聚乙烯的密度为905-940kg/m3,所述组合物包含一种聚乙烯,该聚乙烯通过具有多于一个η5-环状配体的单点催化剂催化的聚合反应而制得并且包括
ai)乙烯的低分子量均聚物,和
bi)乙烯、1-丁烯和C6-12α-烯烃的高分子量三元共聚物;或者
aii)低分子量聚合物,它是乙烯与选自C4-C12α-烯烃的共聚单体的二元共聚物,和
bii)高分子量聚合物,如果aii)的低分子量聚合物是乙烯与C6-C12α-烯烃的二元共聚物,则该高分子量聚合物是乙烯与1-丁烯的二元共聚物,或者该高分子量聚合物是乙烯、1-丁烯和选自C6-C12α-烯烃的共聚单体的三元共聚物;
其中所有的组分都是由相同的催化剂制备的。
16.权利要求15的组合物,该组合物包含所述聚乙烯和其它聚合物的共混物。
17.权利要求16的组合物,其中所述其它聚合物是低密度聚乙烯。
18.一种用聚乙烯热封膜包装的产品,该聚乙烯通过一种具有多于一个η5-环状配体的单点催化剂催化的聚合反应而制得,并且所述聚乙烯的密度为905-940kg/m3,并且包含
ai)乙烯的低分子量均聚物,和
bi)乙烯、1-丁烯和C6-12α-烯烃的高分子量三元共聚物;或者
aii)低分子量聚合物,它是乙烯与选自C4-C12α-烯烃的共聚单体的二元共聚物,和
bii)高分子量聚合物,如果aii)的低分子量聚合物是乙烯与C6-C12α-烯烃的二元共聚物,则该高分子量聚合物是乙烯与1-丁烯的二元共聚物,或者该高分子量聚合物是乙烯、1-丁烯和选自C6-C12α-烯烃的共聚单体的三元共聚物;
其中所有的组分都是由相同的催化剂制备的。
19.权利要求18的产品,该产品是包装的食品或液体。
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