CN1066395C - 含有烯烃聚合物组合物的膜材料的片材制品 - Google Patents
含有烯烃聚合物组合物的膜材料的片材制品 Download PDFInfo
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- CN1066395C CN1066395C CN98118521A CN98118521A CN1066395C CN 1066395 C CN1066395 C CN 1066395C CN 98118521 A CN98118521 A CN 98118521A CN 98118521 A CN98118521 A CN 98118521A CN 1066395 C CN1066395 C CN 1066395C
- Authority
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- Prior art keywords
- olefin
- weight
- ethene
- alpha
- propylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 75
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000004711 α-olefin Substances 0.000 claims abstract description 48
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 43
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920001577 copolymer Polymers 0.000 claims abstract description 33
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000005977 Ethylene Substances 0.000 claims abstract description 10
- 150000001993 dienes Chemical class 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 210000002469 basement membrane Anatomy 0.000 claims 2
- 210000004379 membrane Anatomy 0.000 claims 1
- 239000008096 xylene Substances 0.000 abstract description 12
- 229920005606 polypropylene copolymer Polymers 0.000 abstract description 3
- 229920001384 propylene homopolymer Polymers 0.000 abstract 1
- 239000010408 film Substances 0.000 description 37
- 229920000642 polymer Polymers 0.000 description 18
- 239000000178 monomer Substances 0.000 description 16
- -1 propylene-ethylene Chemical group 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229920001169 thermoplastic Polymers 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004416 thermosoftening plastic Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 235000011147 magnesium chloride Nutrition 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- 206010003084 Areflexia Diseases 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002083 X-ray spectrum Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229960002380 dibutyl phthalate Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 229920002397 thermoplastic olefin Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229940099259 vaseline Drugs 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- 125000005274 4-hydroxybenzoic acid group Chemical group 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 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
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
-
- 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]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
-
- 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
- Y10T428/31913—Monoolefin polymer
Abstract
本发明揭示了含烯烃组合物的膜或薄片,包括:a.约10-50α份具有等规度大于80的丙烯均聚物,或是一种丙烯和乙烯、和/或是另一种α-烯烃的共聚物,这种共聚物含有超过80%的丙烯和等规度大于80;b.约5-20份的半结晶共聚物组分,该共聚物在室温或环境温度下不溶于二甲苯;c.约40-80份的乙烯和丙烯和/或其他α-烯烃且选择带有少量二烯烃的共聚物组分,该共聚物组分含低于40%,乙烯和/或其他α-烯烃,在室温下溶于二甲苯,有1.5-4dl/g的特性粘度。
Description
本发明专利申请是申请日为1991年9月21日申请号为91109368.0,名称为“含有烯烃聚合物组合物的膜材料”的发明专利申请的分案申请。
本发明涉及热塑性塑料膜,薄片和层压片及由其构成的复合挤出材料,由一种烯烃聚合物组合物和另一种烯烃聚合物掺和构成的膜、薄片。
在许多膜的应用中,诸如食品、化学品、危险品的包装,医药应用,工业应用都要求膜具有可靠的性能。用在食品包装方面,例如,膜必须具有高抗穿刺性,高透明和光泽度,减少气体和蒸汽的渗透性。用来制造放置化学品、危险性废物的容器的膜必须具有高抗穿刺性,高拉伸强度,高抗撕性和抗化学腐蚀性。用于医药的膜,如血袋,必须具有高抗穿刺性,低模量,高抗撕性和高压消毒性。
膜由乙烯聚合物制成,例如HDPE和LLDPE,和丙烯聚合物,如丙烯结晶均聚物及丙烯和乙烯的无规共聚物,不提供这种合适性能的组合物。
本发明已完成了克服这些聚合物缺点的发明意图,通过丙烯结晶聚合物和8至25%的在一种立体有择Ziegler-Natta型催化剂存在下顺序聚合形成的橡胶态丙烯-乙烯的共聚物的变相混和物来制备。然而,这种多相组合物的膜,尚需承受形成鱼眼,抗撕强度不足或形成粗糙表面的处理。
从此后,就需要一种具有较低的挠曲模量,高透明度、良好的抗撕强度,和其他所有合适性能的聚合物材料。
应用于本发明的全部组成分和百分比除非特别指出以外均以重量来计,室温或常温为25℃。
本发明提供了一种具有合适性能,含有多相烯烃聚合组合物的热塑性塑料,其中包括:
(a)约10-50份具有等规度大于80的丙烯均聚物,或选自于包括ⅰ)丙烯和乙烯ⅱ)丙烯、乙烯和CH2=CHRα-烯烃,其中R为C2-8的直链或支链烷基ⅲ)丙烯和一种如(a)(ⅱ)中的α-烯烃组成的组的共聚物,所述共聚物具有大于80%的丙烯且具有大于80等规度。
(b)约5-20份的具有约20至60%结晶度的半结晶状的基本上线性的共聚物组分,其中选自于包括ⅰ)含有大于55%乙烯的乙烯和丙烯ⅱ)乙烯、丙烯和一种α-烯烃如(a)中(ⅱ)规定的含有1至10%的α-烯烃和大于55%的乙烯与α-烯烃ⅲ)乙烯和一种α-烯烃如(a)中(ⅱ)规定的含大于55%所说的α-烯烃的组的共聚物,该共聚物在室温下不溶于二甲苯。
(c)约40-80份的共聚物组分是选自于包括ⅰ)乙烯和丙烯其中共聚物含有20%至40%以下的乙烯,ⅱ)乙烯丙烯和α-烯烃如(a)中ⅱ)-烯烃存在量是1至10%且乙烯和α-烯烃的量为20%至40%以下,ⅲ)乙烯和α-烯烃如(a)(ⅲ)所规定,的含有20%至40%以下的α-烯烃,且可选择性含有0.5至10%的二烯烃的组。所述的共聚物在室温下溶于二甲苯,且具1.5至4dl/g的特性粘度。
以聚烯烃组合物总量为基准,(b)和(c)的总量约为50%至90%,(b)/(c)的重量比为小于0.4。
在另一实施例中,本发明提供了含有一层应用于至少一个热塑性膜物质或一金属基体表面的多相烯烃聚合物组合物构成的膜。
还有一实施例本发明提供了由烯烃聚合物组合物和热塑性塑料掺和组成的膜。
组成(a)存在量较佳地为10至40份,最佳为20至35份。当(a)为丙烯均聚物时,等规度较佳地为约85至98,当(a)是共聚物时,共聚物中丙烯的量较佳地为约90至99%。
组成(b)存在量较佳地为7至15份,典型的结晶度经差示扫描量热法(DSC)测试为约20至60%。一般地,乙烯或所述的α-烯烃含量或乙烯和所说的α-烯烃的组合物,在使用时,两者的量为大于55%-98%,较佳地为80-95%。
组成(c)存在量较佳地为50-70份。
乙烯或所述的α-烯烃的含量或组成(c)的乙烯和α-烯烃含量较佳地为20至38%,最佳为25至38%,当组成(c)是三元共聚物时,所述的α-烯烃存在量典型地为1至10%,较佳地为1至5%,可取的特性粘度为1.7至3dl/g。
以烯烃聚合物组合物为基准,(b)和(c)的总量较佳地为65至80%,且(d)/(c)的重量比率较佳地为0.1至约0.3。
烯烃聚合物组合物中乙烯单元或所述的α-烯烃单元或乙烯和所述的α-烯烃单元(当两者存在时)的总量约为15%至35%。
该组合物至少有一个最大熔融值,经差示扫描量热法测定,出现在高于120℃的温度,且至少一个最大值关系到玻璃化转变时,出现在-10℃和-35℃的温度。
此外,这些组合物有一个小于150MPa的挠曲模量,一般地为20至100MPa;拉伸强度值为10至20MPa,断裂伸长大于400%;75%应变下的拉伸变定为20%至50%,肖氏D硬度20至25;且当悬臂梁式冲击试验在-50℃时进行,也不断裂(无脆性冲击破坏)。
混浊度值较佳地为小于40%,最佳为小于35%。
丙烯和乙烯或一种α-烯烃,或丙烯、乙烯和一种α-烯烃的共聚物,和三元共聚物较佳如组成(a)所示;丙烯和乙烯或一种α-烯烃的共聚物由于提供了高透明度的组合物而最好如组成(a)所示。
分子式CH2=CHR的适宜的α-烯烃包括,丁烯-1,戊烯-1,4-甲基戊烯-1,己烯-1和辛烯-1。当被用来制备组成(a)时,它们以这样的量出现以至所提共聚物的等规度不少于80%。
当一种二烯烃出现在组成(b)和(c)的制备过程中,典型的为一种丁二烯,1,4-己二烯,1,5-己二烯,乙烯基降冰片二烯单体且典型地量为0.5至10%,较佳地为1至5%。
用聚合法制备这些组合物至少包括二步,第一步,丙烯或丙烯和乙烯或所述的α-烯烃或丙烯、乙烯或所述的α-烯烃被聚合成组成(a),在第二步中,乙烯和丙烯,或所述的α-烯烃或乙烯、丙烯和所说α-烯烃,和任意选择的一种二烯的混合物被聚合形成组成(b)和(c)。
该聚合反应可以在液相,气相,或气一液相应用分开的反应器进行,所有这些反应可以是分批进行或连续进行。例如,组成(a)聚合反应可能在用液态丙烯作稀释剂的情况下进行,而组成(b)和(c)的聚合反应除丙烯的部分排气外没有中间步骤而在气相中发生。
该聚合反应发生在有惰性碳氢化合物溶剂或液态或气态单体存在的惰性气氛中。
适宜的惰性碳氢化合物溶剂包括饱和碳氢化合物,诸如,丙烷,丁烷,己烷和庚烷。
氢气作为链转移剂可以根据需要加入以控制分子量。
组成(a)和组成(b),组成(c)的聚合反应的反应温度,可以相同或不同,一般地为40℃-90℃,对于组成(a)的聚合反应较佳地为50至80℃,对于组成(b)和(c)的聚合反应较佳地为40-65℃。
组成(a)的聚合反应的反应压力如果是在液态单体中反应,则是一个与所用操作温度下液态丙烯蒸汽压对抗的压力,最终通过少量用来馈送催化剂混合物的惰性稀释剂的蒸汽压和任意选择的单体及作分子量调节剂的氢气的余压来进行调整。
如果反应在气相中进行,组成(b)和(c)的聚合反应的反应压力可以是0.5至3MPa(5至30atm)。停留时间关系到组成(a)和(b)+(c)之间的所需比率为基础的二步反应,通常为15分钟至8小时。
用于聚合反应的催化剂由下列组成的反应产物:1)一个包含一含卤素的钛化合物和一个载附在活性的氯化镁上的电子给予体化合物(内部给予体)的固体组成。2)一个不含卤素包含三烷基铝的化合物。3)一种电子给予体化合物(外部给予体)。
适宜的钛化合物包括有至少一个钛-卤键的如钛的卤素化合物和烷氧基卤化物。
为了这些得到具有高松密度流动的球形颗粒形状的烯烃聚合物组合物,固体催化剂组成必须具有a)一个表面积小于100m2/g,较佳地为50至80m2/g,b)孔隙率为0.25至0.4cc/gc)氯化镁反射显示的X-射线光谱图显示在光环在2v为33.5°和35°的之间,而2v为14.95°的无反射,符号2v为布喇格角。
固体催化剂组成由二氯化镁和醇,诸如,乙醇,丙醇,丁醇和2-乙基己醇,形成加合物制备的通常每mole二氧化镁包含3mole醇,乳化加合物,快速冷却乳化物,使加合物固化成球形颗粒,粒子化的加合物部分脱醇一般地是通过逐步地提高温度从50℃到130℃保持足够长一段时间以减小醇含量满足每mol MgCl2 3mol至1-1.5mol。这部分脱醇的加合物在0℃时悬浮在ToCl4,加合物在TiCl4的浓度是40-50g/lTiCl4,然后加热混和物在80℃至135℃保持1-2小时。当温度到达40℃时,集合了足够多的电子给予体可以达到镁对电子组予体的所要求的摩尔比。
加入于TiCl4中的一个电子给予体组合物较佳地选自于烷基,环烷基,芳香邻苯二甲酸酯,诸如二异丁基,二-n-丁基,和二-n-辛基邻苯二甲酸酯之中。
当升温阶段结束时,过热的TiCl4通过过滤或沉积法分离开,并重复用TiCl4处理一次或多次。然后用合适的惰性碳氢化合物如乙烷或庚烷或其他合乎要求的烃来洗涤固体,并烘干。
固体催化剂组成典型地具有下列性质:
表面积: 小于100m2/g,
较佳地在50-80m2/g之间
孔隙率: 0.25-0.4cc/g
孔体积分配:50%的孔半径大于100A
X-射线光谱:氯化镁反射显示,在2v为33.5°和35°的之间有最强光环的反射角,在2v为14.95°的角度无反射
该催化剂是通过固体催化剂组成和一种三烷铝化合物,较好的是三乙基铝和三异丁基铝,和一种电子给予体化合物互相混合而得到的。
现有技术已经知道各种电子给予体化合物,较佳的电子组予体化合物是具有R'R″Si(OR)2分子式的硅烷化合物,其中R'和R″可相同或不同且是C1-18烷基或带支链的烷基,C5-18环烷基,或是C6-18芳基,R是一种C1-4的烷基。
所用的典型的硅烷化合物包括二苯基二苯氧基硅烷,二环己基,二甲氧基硅烷,甲基特丁基二甲氧基硅烷,二异丙基二甲氧基硅烷,二环戊基二甲氧基硅烷,环己基甲基二甲氧基硅烷,苯基三甲氧基硅烷。
Al/Ti的比值典型在于10和200之间且A/硅烷的摩尔比在1/1和1/100之间。
催化剂可以用少量的烯烃单体预先处理(预聚合),将催化剂悬浮在一种碳氢化合物溶剂中在室温到60℃范围温度下聚合足够的时间而生成是催化剂0.5-3倍重量的聚合物。
该预聚合物反应也可以在液态或气态单体中进行,假如是这样的话,将生成催化剂1000倍重量的聚合物。
本发明中热塑性烯烃聚合物催化剂残渣的量和含量足够小以致于要除去催化剂残渣即一般的除灰,被认为是没有必要。
用前面提到的催化剂制备的热塑性烯烃聚合物为圆颗粒状,颗粒的直径为0.5-7mm。
除非另外的说明,下述分析方法被用来表示所支持的催化组成、多相烯烃聚合组合物从那里制得的膜和相应的膜材料的特征。性质 方法熔融流动速率,g/10min ASTM-D1238条件L乙烯,wt% 红外光谱特性粘度 以135℃时在四氢化萘中测定二甲苯可溶性,wt% 参见下面描述的方法23(℃时的挠曲膜量和玻璃 使用在1Hz和2℃/min的扫描温度化转变温度 采用聚合物实验的DMTA的动态力学测试装置,用Carver在1×104千克(10吨)压力和200℃下压制10分钟,然后在15℃/min下冷却该薄片制得压模板,从该板上切割供分析用聚合物样品试板(40×10×2mm)。悬臂梁式缺口冲击 ASTM-D 256强度浊度 ASTM-D 100375%的拉伸变定 ASTM-D 412断裂时和屈服时 ASTM-D 638的拉伸强度屈服和断裂时的伸长 ASTM-D 638率表面积 B.E.F孔隙率 B.E.F松密度 DIN-53194埃尔曼多夫撕裂 ASTM-D 1922-78裤型撕裂 ASTM-D 1938-85光泽度 ASTM-D 523摩擦系数 ASTM-D 1894透湿气量 ASTM-E 96落镖冲击强度 ASTM-D 4272-83
除非另外特别说明,要经受有关各种物理动力学分析的烯烃聚合物组合物的样品通过采用Negr和Bossi 90注压机,在用0.1%伊尔加偌克斯1010四〔亚甲基3,5-二-叔-丁基-4-羟基氢化肉桂酸酯〕甲烷稳定,用单个螺杆Banderq挤塑机(机简直径30mm)在210℃时造粒后进行成形。分析情况如下:
熔融温度250℃
成形温度60℃
注塑时间20秒
冷却时间25秒
要经受混浊度测试分析的样品,依靠应用GBF-235/90注塑料机在下述状态下模塑成形为75×75×1mm的试片;
熔融温度260℃
成形温度40℃
注塑时间20秒
冷却时间10秒
膜的样品厚度为1m;1且是从以所用的特殊的ASTM测试法为条件的膜片上按一定尺寸割取下来的。
(b)和(c)的总量的重百分比,表示为%(b)+(c),是通过第二步步骤中混和物重量和最后产物重量相比计算得出的。
(a),(b)和(c)的重量百分比在这儿所表示的如下边所确定的:
%(a)=100%-〔(b)+(c)〕
%(c)=Sf-PaSa其中Sf和Sa分别为最终产物和聚丙烯组分(a)溶解在二甲苯中部分的重量百分比;Pa是所述组分与最终产物的重量比值。
%(b)=100-%(a)-%(c)包含溶解在二甲苯中的共聚物组分(c)中的乙烯或所述α-烯烃或乙烯和所述α-烯烃的重量百分率用下式计算:
组份(c)中乙烯和/或
所述α-烯烃的
其中:
Cf=存在于最终产物的二甲苯可溶物中的乙烯和/或所述的α-烯烃的百分率。
Ca=存在于组分(a)的二甲苯可溶物中的乙烯和/或所述的α-烯烃的百分率。
X=Sz·Pa/Sf
组分(c)的特性粘度(I.V.cc)如下式计算:
(I.V.cc)=(I.V.sf-I.V.(a)·X)/(1-X)其中I.V.sf是最终组合物的二甲苯可溶物的特性粘度,I.V.(a)是组分(a)的二甲苯或溶物部分的特性粘度。
室温下溶解在二甲苯中烯烃聚合物组合物的重量百分率是通过在带有搅拌的容器中将聚合物2.5g溶于250ml的二甲苯,加热到135℃并搅拌20分钟测得的。继续搅拌溶液冷却到25℃,然后停止搅拌放置30分钟而得到固体物质。该固体颗粒用滤纸过滤,蒸发余下的滤液并通氮气气流处理,固体残渣在80℃下真空干燥,直到达到恒重,室温下不溶于二甲苯的聚合物的重量百分比是该聚合物的等规度。用这种方法得到的值实质上相当于用沸腾的正庚烷萃取测得的,这是用来定义确定聚合物的等规度的方法。
用作说明多相烯烃聚合组合物的例子,其物理性质,相同制备的方法,以所述烯烃聚合物为基的膜和制备所述膜的方法的实例公布于下面的内容。
固体催化剂组成
A)MgCl2/乙醇加合物的制备
在一种惰性气体下,将28.4g无水MgCl2,49.5g无水乙醇,100ml αOL OB/30凡士林油和100ml有3.5×108m2/s(350厘沲)粘度的硅油加入一带有搅拌装置的反应器中,油浴加热到120℃并搅拌直到MgCl2溶解。将该热反应混和物在惰性气体下转移至l500ml带有Ultra Turrax T-45N搅拌器和加热夹套并含有150ml凡士林油和150ml硅油的容器中。保持温度120℃情况下,以转速3,000rpm搅拌3分钟,然后将混和物移装在一个带搅拌装置的含有1000ml的无水正庚烷的2升容器中,用干冰/isopar浴冷却至0℃,且保持0℃时的温度以6m/s的端点速度搅拌20分钟,加合物粒子形成后经过过滤,用等分500ml无水己烷的在室温下洗涤三次,然后在通氮气下足够长的时间里升高温度从50℃-100℃逐步加热以将每摩尔MgCl2中乙醇含量从3mol减少到1.5mol的处理步骤。加合物具有9.1m2/g表面积和0.564g/cc的松密度。
B)固体催化剂成分的制备
将加合物(25g)在氮气下移入一个搅拌装置内含625ml TiCl4的反应器中0℃下搅拌。然后在1小时内加热到100℃,当温度到达40℃时加入一定量的邻苯二甲酸二异丁基酯使得镁对邻苯二甲酸二异丁基酯的摩尔比为8。容器中的内容物被加热到100℃并搅拌2小时停止搅拌,澄清固体颗粒。热的液体用虹吸法移出,在容器的固体颗粒中加入550ml TiCl4,在120℃加热混和物搅拌1小时,停止搅拌并澄清固体颗粒,然后用虹吸法移出热液体。等分200ml的无水己烷在60℃下洗涤固体颗粒6次,在室温下洗涤3次。经真空干燥后,固体颗粒的孔障率为0.26lcc/g,表面积66.5m2/g松密度0.44g/cc。
实施例1-3
这些实例描述了多相烯烃聚合组合物和制备聚合物的方法。
一般操作条件
聚合反应试验在通氮气的带有磁性螺旋搅拌器的22升不锈钢高压釜内进行,操作转速约90rpm。
全部温度、压力和烯烃单体以及氢气的浓度需要时均是恒定的,除非另外指出。氢气和相关单体的浓度连续地用气相色谱法在气相中分析检查以保持所规定的相同浓度不变。
聚合反应是包含二阶段的分批实验方法。第一步包括在液态丙烯中相关的单体或多个单体的聚合反应,第二步是在气相中乙烯和丙烯的共聚反应。
第一步反应中,将下列单子上所列出的组成成分在20℃下,约10分钟的时间内倒入高压釜内;161液态丙烯,适量的乙烯和氢气和由1)如上所述制备出的固体催化剂组成(约0.15g),2)一种由75ml10%浓度存在于己烷中的三乙基铝和适量的具有Al/CMMs摩尔比为7.5的环己基甲基二甲氧基硅油(CMMS)电子给予体组成的混和物,组成的催化剂体系。该催化剂体系用丙烯压入高压釜。
温度约在10分钟后升到所要求的水平并保持温度在整个聚合反应的反应阶段不变。当确定的反应时间结束后,本质上讲所有未反应的单体已经通过排气系统在60℃,实际的气压下排除。
在第二步中,第一步的聚合物(a)在抽取供各种分析用的样品之后,升温到确定温度准备第二步反应。然后加入高压釜以一定比率和规定量的丙烯和乙烯以达到要求的压力和气相组合物,在聚合反应过程中压力和气相组合物加入依靠仪器调节或测量或调节和测量其流速而达到规定值的丙烯和乙烯的混合物。进料长度根据使用的催化剂体系和在特殊的多相烯烃聚合物产物中要求的组成(b)和(c)的量而改变。
在第二步聚合反应结束时,粉末被除去,稳定,然后在60℃下氮气流下烘干。其成分和相关操作条件列于后面的表ⅠA,测验结果列子后面的表ⅠB。
表ⅠA
实例 1 2 3
第一相
温度,℃ 70 70 70
压力,MPa(atm) 3.14(31) 3.14(31) 3.14(31)
时间.min 30 20 30
气相中氢气含量,mol% 0.58 0.10 0.30
气相中乙烯含量,mol% 1.45 2.60 2.50
聚合物中乙烯量,wt·% 3.0 4.3 4.1
特性粘度,dl/g 2.18 3.09 2.31
二甲苯可溶物(Sa),wt% 9.4 9.0 10.7
二甲苯可溶物中乙烯含量 11 16 17
(Ca),wt%
二甲苯可溶物特性粘度 1.15 1.39 1.19
(I.V.a)dl/g
第二相
温度,℃ 50 50 50
压力,MPa(atm) 1.14 1.16 1.14
(11.3) (11.5) (11.3)
时间,min 335 500 250
气相中氢气,mol% 2.23 3.0 2.05
气相中乙烯含量,mol% 15.9 16.9 22.54
表ⅠB实施例 1 2 3最终产物产率,Kg Pol/g Cat 11 16.3 9.9共聚单体,wt.% 24.6 22.7 29.0二聚合物(b)+(c),wt.% 70 67 71.8特性粘度,dl/g 2.05 2.3 2.34二甲苯可溶物(Sr),wt.% 63.4 60.5 63.5二甲苯可溶物中乙烯量.,wt.%(C1) 30.2 27.0 34.8二甲苯可溶物的 1.83 2.02 2.12特性粘度I.V.Sf’dl/g组份(b),wt% 9.45 9.37 11.34组份(c)wt.% 60.55 57.63 60.46乙烯成份(b),wt.% 51.9 57.1 53.7乙烯成分(c),wt.% 31.1 27.6 35.7组份(c)的特性粘度(c) 1.86 2.05 2.18(I.V.C)dl/g熔融指数,℃ 150 147 145挠曲模量,MPa 30 77 82在-50℃时R..C.I悬臂式 NB1 NB NB中击强度J/m肖尔D硬度 24 25 2075%拉伸变定,% 41 28 36拉伸强度,MPa 13.8 15.8 15.4屈服时的拉 5.0 5.8 4.6伸强度MPa断裂伸长% 517 925 940混浊度% 31 34 35玻璃化转变温度℃ -25(P)-23(P)-28(P)
-75 -119 -81
-128 -121 -125
1.NB=无断裂
2.(P)=主峰
实施例4
这些实施例描述了多相烯烃聚合物组合物的膜材料及其制备方法。
实施例2经空气淬冷的多相烯烃聚合物组合物的膜用这些来稳定:每100份的烯烃聚合物组合物(pph)用0.25份的十八烷基-3,5-双(1,1-二甲基乙基)-4-羟基苯丙酸酯,0.05pph四〔亚甲-基(3,5-二-叔-丁基-4-羟基氢化肉桂酸酯)〕甲烷,0.06pph Sandostab P-EPQ组合物,其主要成份是四(2,4-二-异丁基苯基)-4-4'-亚联苯双磷酸酯和0.05硬脂酸钙,是通过将组合物装入一单螺杆挤塑机,挤压通过一圆口模头,吹入一带足够空气的成膜装置来制备的,运用下述的装置和操作条件可以制出2.54×10-5m(1mil)厚的膜。螺杆 压缩比3∶1-4∶1
聚烯烃阻流销型L/D比=24∶1-
30∶1吹胀率=2.5-4.1
模隙调节1.01×10-3m(40mils)
对于1.27×10-5-1.27×10-4m
(0.5-5mils)的厚度。挤塑机机筒外形: 从段1-段6为
193-221℃(380-430F)注嘴接头和模口温度: 232℃(450F),除较高或较低模
口段为238℃(460F)螺杆转速 20rpm压力 20.68MPa(3000Psi)
产物膜的性质列于下面的表2
表2
树脂性能 实施例2 HDPE1 LLDPR2屈服强度 9.287/7.763 25.90/21.68 12.06/11.99(MD/CD3),MPa (1347/1126) (3757/3145) (1749/1739)(Psi)断裂强度 3096/1643 3960/3216 2092/1898(MD/CD)屈伸时伸长 65/40 30/7 80/17(MD/CD),%断裂时伸长 361/417 120/350 317/425(MD/CD),%埃尔曼多夫断裂 Notear 10/282 350/790(MD/CD),g/Ply裤型撕裂(MD/ 152/530 147/1026 503/758CD)混浊度 65.7 76.8 8.7光泽度 6 10 70摩擦系数 1.22/0.815 0.241/0.192 0.688/0.650(静态/动态)透湿气性值在 1.340 1.300 -38℃(100F)和100模湿气下落镖冲击强度 0.98 0.72 1.020
1.Quantun LR732HDPE具有0.953g/cc3密度
2.Dowlex 2045LLDPE包含己烯-1和0.920g/cc3的密度
3.MD/CD=机器纵向/横向
从上表中可以看出一点,本发明的烯烃聚合物组合物提供了一种具有改进的断裂伸长和埃尔曼多夫撕裂性能和较好的其他余下性能的空气淬冷膜。进一步说,聚合物,包括丙烯单元的较大部分,一般地使用并不好,如全部在空气淬冷吹塑膜装置上操作。
实施例5
本实施例描述了一种多相烯烃聚合组成物的流涎薄膜、多相烯烃聚合物的共挤塑薄膜和丙烯和乙烯的无规共聚物,及制备方法。
按实施例4方法稳定的实施例2中多相烯烃聚合物组合物的流涎薄膜是通过将组合物装入一挤塑机,挤塑通过一平膜模头,并在骤冷辊上淬冷来制备的,按下述装置和操作条件可制出0.0254mm(1mil)厚度的膜。螺杆设计 压缩比:4∶1-3∶1
进料段深度:11.05-12.45mm(0.435-0.490″)
(压缩比为3.5∶1的88.9mm(3.5″)挤塑机)
计量段深度:3.175-3.556mm(0.125-0.140″)
对于88.9mm(3.5″)挤塑机模头 常用中心进料衣架型多支管料道。挤塑机操作条件:
熔融温度:221-260℃(430-500下)
挤塑机机筒:段1到段6为177-216℃(350-420F)
注嘴接头和模口温度:216℃(420下)。
0.0318mm(1.25mils)厚的共挤塑薄膜包括一层作为中心层的如实施例4方法稳定的实施例2中的多相烯烃聚合物组合物的膜,二层含3.0%乙烯成份的Pro-fax SA861丙烯-乙烯为规共聚物的膜、一层在中心层的第一面上的所述共聚物,这种共挤塑薄膜由流涎薄膜技术制备。
所得膜的性能列于下表3
表3
树脂性能 实施例2 Coex1 P-ECo2屈服强度 8.170/5.964 7.550/5.633 17.40/16.90(MD/CD3),MPa(Psi)(1185/865) (1095/817) (2523/2452)断裂强度 26.88/11.78 25.08/11.67 28.40/23.19(MD/CD),MPa(Psi) (3899/1708) (3637/1 693) (4120/3363)屈伸时伸长 34/19 32/22 15/10(MD/CD),%断裂时伸长 450/550 530/550 522/584(MD/CD),%埃尔曼多夫断裂 192/No 657/544 49/102(MD/CD),g/ply 撕裂混浊度 49.0 5.2 2.3光泽度 20.0 57.0 78.1
1.丙烯-乙烯无规共聚/实施例2的多相烯烃聚合物组合物/丙烯-乙烯无规共聚物。
2.含3.0%乙烯成份的Pro-fax 861丙烯-乙烯无规共聚物。
3.MD/CD=机器纵向/横向。
从上表可以看出本发明的烯烃聚合物组合物提供了具有改进的屈服伸长和埃尔曼多夫撕裂性能的一种流涎薄膜和一种共挤出流涎薄膜。
各种类型的常规厚度的膜材和厚度小于0.508mm(20mils)到约0.0127mm(0.5mils)薄的薄膜能用这儿描述的多相烯烃聚合物组合物以及片材重膜材料典型地如从0.508至2.54mm(20至100mils)厚度来制备。例如,它可以用来制备流涎薄膜,单轴和双轴定向膜和挤塑或压延片。另外,可以将含有多相烯烃聚合物组合物的层,例如,使用层压或共挤压技术涂敷到至少热塑性膜材料或金属片或箔基料的一个表面。典型的热塑性材料包括一种C2-10α-烯烃单体,如丙烯或乙烯的结晶性均聚物或丙烯和乙烯或和一种C4-10α-烯烃单体的共聚物,或丙烯既和乙烯又和一种C4-10α-烯烃单体的共聚物,假如,当共聚单体是乙烯,其最大聚合含量约为10%,较佳地约为4%,当共聚单体是C4-10烯烃时,其最大的聚合含量约为20%,较好地约为16%,当既用乙烯又用α-烯烃时它们的最大聚合含量为30%,较佳地为20%,以及聚酯、聚酰胺、乙烯-乙烯醇共聚物和乙烯-醋酸乙烯酯共聚物。铝是合适的金属基料。
另外,膜材料可以从本文所述的约5-45%的多相烯烃聚合物组合物和约95-55%的C2-10α-烯烃单体的结晶均聚物或丙烯和乙烯或和C4-10α-烯烃单体的共聚物掺和制备,所述共聚物具有乙烯或α-烯烃或全如前文所述的最大聚合含量,较佳地,存在于这种共混料中的多相烯烃聚合物组合物含量为10-30%。
本发明的烯烃聚合物组合物是一可以达到最终产物的性能适当平衡的物质当相同的一层膜是被涂敷到至少另一种热塑性材料或一种金属基料的材料的一个表面且当它是和其他热塑性材料混和时该共混料用来制造膜材料。
在这儿所揭示的本发明的其他特性,优点和实施例对于那些具有一般技能的人阅读完前面的揭示是容易且明显能掌握。从这点上,当本发明的特殊实施例已经在重要细节里叙述,这些实施例的变更和修改可以在不脱离本发明作用描述和权项的精神和范围下进行。
Claims (1)
1.一种片材制品,其特征在于至少含有一层丙烯和乙烯结晶共聚物的基膜,其中以共聚物的总重量为基准,聚合乙烯的含量为30重量%,在该基膜的至少一个表面涂覆一层膜材料,所述膜材料由烯烃聚合物组合物制成,所述组合物含有:
(a)10-50重量份等规度大于80的丙烯均聚物,或选自ⅰ)丙烯和乙烯,ⅱ)丙烯、乙烯和CH2=CHR α-烯烃,其中R为C2-8的直链或支链烷基,ⅲ)丙烯和一种如ⅱ)中所定义的α-烯烃的共聚物,所述共聚物含有大于80重量%的丙烯且等规度大于80;
(b)5-20重量份结晶度为20-60%的半结晶的基本上线型的共聚物组分,所述共聚物选自ⅰ)乙烯含量大于55重量%的乙烯和丙烯,ⅱ)乙烯、丙烯和一种如(a)ⅱ)中所定义的α-烯烃,含有1-10重量%的α-烯烃和大于55重量%的乙烯和α-烯烃,以及ⅲ)乙烯和一种如(a)ⅱ)中所定义的α-烯烃,含有大于55重量%所述的α-烯烃,该共聚物在室温下不溶于二甲苯;以及
(c)40-80重量份共聚物组分,所述共聚物选自ⅰ)含有20重量%到少于40重量%乙烯的乙烯和丙烯,ⅱ)乙烯、丙烯和如(a)ⅱ)中所定义的α-烯烃,其中α-烯烃的含量为1-10重量%,且乙烯和α-烯烃的含量为20重量%到少于40重量%,以及ⅲ)乙烯和如(a)ⅱ)中所定义的α-烯烃,含有20重量%到少于40重量%所述的α-烯烃,且可选择性地含有0.5至10重量%的二烯烃,所述共聚物组分在环境温度下溶于二甲苯,且特性粘度为1.5至4.0dl/g;
以烯烃聚合物组合物总重量为基准,(b)和(c)组份的总量为50重量%至90重量%,(b)/(c)的重量比小于0.4。
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