CA2052402C - Olefin polymer films - Google Patents
Olefin polymer filmsInfo
- Publication number
- CA2052402C CA2052402C CA 2052402 CA2052402A CA2052402C CA 2052402 C CA2052402 C CA 2052402C CA 2052402 CA2052402 CA 2052402 CA 2052402 A CA2052402 A CA 2052402A CA 2052402 C CA2052402 C CA 2052402C
- Authority
- CA
- Canada
- Prior art keywords
- ethylene
- olefin
- propylene
- alpha
- sheet
- 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 - Fee Related
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 51
- 239000005977 Ethylene Substances 0.000 claims abstract description 97
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000004711 α-olefin Substances 0.000 claims abstract description 81
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 51
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008096 xylene Substances 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 229920005606 polypropylene copolymer Polymers 0.000 claims abstract description 12
- 150000001993 dienes Chemical class 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 31
- -1 propylene, ethylene Chemical group 0.000 claims description 25
- 150000001336 alkenes Chemical class 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims description 8
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000009863 impact test Methods 0.000 claims description 5
- 229920001897 terpolymer Polymers 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229920005684 linear copolymer Polymers 0.000 claims description 3
- 229920001384 propylene homopolymer Polymers 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 12
- 239000010408 film Substances 0.000 description 47
- 238000006116 polymerization reaction Methods 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 229910010066 TiC14 Inorganic materials 0.000 description 8
- 238000013019 agitation Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 7
- 229920005604 random copolymer Polymers 0.000 description 6
- 239000008279 sol Substances 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 5
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Natural products CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000012815 thermoplastic material Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 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
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000004806 packaging method and process Methods 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
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229920002397 thermoplastic olefin Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 229940099259 vaseline Drugs 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 101001034845 Mus musculus Interferon-induced transmembrane protein 3 Proteins 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 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
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-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
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000007664 blowing Methods 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
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000011326 mechanical measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 238000005453 pelletization Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-M phloretate Chemical compound OC1=CC=C(CCC([O-])=O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-M 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 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
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000000087 stabilizing 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
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
Classifications
-
- 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
- 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
- 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
Disclosed are films or sheets comprising an olefin polymer composition which is comprised of (a) from about 10 to 50 parts of a propylene homo-polymer having an isotactic index greater than 80, or a copolymer of propylene with ethylene and/or an another alpha-olefin, containing over 80% propylene and having an isotactic index greater than 80;
(b) from about 5 to 20 parts of a semi-crystalline copolymer fraction, which copolymer is insoluble in xylene at room or ambient temperature; and c) from about 40 to 80 parts of a copolymer fraction of ethylene with propylene and/or another alpha-olefin, and optionally with minor amounts of a diene, said copolymer fraction containing less than 40% ethylene and/or other alpha-olefin, being soluble in xylene at room temperature, and having an intrinsic viscosity from 1.5 to 4 dl/g.
Coextruded films or sheets and laminates wherein at least one layer is a film or sheet as described above, and films or sheets of blends of the olefin polymer composition and another olefin polymer are also disclosed.
(b) from about 5 to 20 parts of a semi-crystalline copolymer fraction, which copolymer is insoluble in xylene at room or ambient temperature; and c) from about 40 to 80 parts of a copolymer fraction of ethylene with propylene and/or another alpha-olefin, and optionally with minor amounts of a diene, said copolymer fraction containing less than 40% ethylene and/or other alpha-olefin, being soluble in xylene at room temperature, and having an intrinsic viscosity from 1.5 to 4 dl/g.
Coextruded films or sheets and laminates wherein at least one layer is a film or sheet as described above, and films or sheets of blends of the olefin polymer composition and another olefin polymer are also disclosed.
Description
578s This invention relates to thermoplastic films, sheets and laminates and coextruded materials formed therefrom, and films and sheets formed from blends of an olefin polymer composition with other olefin polymer materials.
In many film applications, such as packaging of foodstuffs, chemical and hazardous materials and in medical applications, the industry requires films having certain properties. In the packaging of foodstuffs, for example, the films must have high puncture resistance, high clarity and gloss, and reduced permeability to gases and/or vapors. The films used to manufacture containers for chemicals and hazardous waste materials must have a high puncture resistance, high elongation strength, high tear resistance and chemical resistance. Films used in medical applications, such as blood bags, must have a high puncture resistance, low modulus, high tear resistance and auto-clavability.
Films made from ethylene polymers, e.g., HDPE and LLDPE, and propylene polymers, such as crystalline homopolymers of propylene and random copolymers of propylene and ethylene, do not provide such a combination of desirable properties.
Attempts have been made to overcome the shortcomings of these polymers by preparing heterophasic mixtures of crystalline propylene polymers and 8 to 25% of an elastomeric propylene-ethylene copolymer by sequential polymerization in the presence of a stereospecific Ziegler-Natta type catalyst. However, films of such heterophasic compositions are subject to the formation of fisheyes, inadequate tear strength or the formation of rough surfaces.
~`
Hence, there is a need for a polymer material which has a lower fle~ural modulus, high clarity, good tear strength, as well as all of the other desirable properties.
All parts and percentages used in this application are by weight unless otherwise specified. Ambient or room temperature is approximately 25C.
mis invention provides a th~rmnrl~tic film or sheet having the desired properties comprising a heterophasic olefin polymer composition which is comprised of (a) from about 10 to 50 parts of a propylene homopolymer having an isotactic inde~ greater than 80, or a copolymer selected from the group consisting of (i) propylene and ethylene, (ii) propylene, ethylene and a CH2-CHR alpha-olefin, where R is a C2 8 straight or branched alkyl, and (iii) propylene and an alpha-olefin as defined in (a) (ii), the copolymer containing over 80% propylene and having an isotactic index greater than 80;
(b) from about 5 to 20 parts of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of about 20 to 60% wherein the copolymer is selected from the group consisting of (i) ethylene and propylene containing over 55% ethylene, (ii) ethylene, propylene, and an alpha-olefin as defined in (a) (ii) containing from 1 to 10% of the alpha-olefin and over 55% of both ethylene and alpha-olefin, and (iii) ethylene and an alpha-olefin as defined in (a) (ii) containing over 55% of the - alpha-olefin, which copolymer is insoluble in xylene at room or ambient temperature; and (c) from about 40 to 80 parts of a copolymer fraction is selected from the group consisting of a copolymer of (i) ethylene and propylene wherein the copolymer contains from 20% to less than 40% ethylene 20524 ~2 27651-20 and, (ii) ethylene, propylene, and an alpha-olefin as defined in (a) (ii) wherein the alpha-olefin is present in an amount of 1 to 10% and the amount of ethylene and alpha-olefin present is from 20% to less than 40%, and (iii) ethylene and an alpha-olefin as defined in (a) (ii) containing from 20% to less than 40% of the alpha-olefin, and optionally with 0.5 to 10% of a diene, the copolymer fraction being soluble in xylene at ambient temperature, and having an intrinsic viscosity of from 1.5 to 4.0 dl/g;
with the total of the (b) and (c) fractions, based on the total olefin polymer composition, being from about 50% to 90%, and the weight ratio of (b)/(c) being less than 0.4.
In another embodiment, this invention provides film or sheet articles comprising a film or sheet of the hetero-phasic olefin polymer composition applied to at least one surface of a thermoplastic base film or sheet or a base film or sheet of a metallic substrate.
In yet another embodiment, films or sheets made from blends of the olefin polymer composition and a thermoplastic material are provided.
Component (a) is preferably present in an amount from 10 to 40 parts, most preferably from 20 to 35 parts. When (a) is a propylene homopolymer, the isotactic index is preferably from about 85 to 98. When (a) is a copolymer, the amount of propylene in the copolymer is preferably from about 90 to 99%.
Component (b) is preferably present in an amount from 7 to 15 parts. Typically the crystallinity is about 20 to 60%
~.~
2~52~ 02 27651-20 by differential scanning calorimetry (DSC). Generally, the ethylene or said alpha-olefin content or the combination of ethylene and said alpha-olefin when both are used is over 55%
up to 98%r preferably from 80 to 95%.
Component (c) is preferably present in an amount from 50 to 70 parts. The ethylene or said alpha-olefin content or ethylene and said alpha-olefin content of component (c) -3a-. ~
20s2402 is preferably from 20 to 38%, most preferably from 25 to 38%. When component (c) is a terpolymer, the said alpha-olefin is typically present in an amount from 1 to 10%, preferably 1 to 5%. The preferred intrinsic viscosity of is from 1.7 to 3 dl/g.
The total amount of (b) and (c), based on the total olefin polymer composition is preferably from 65 to 80% and the weight ratio of (b)/(c) is preferably from 0.1 to about 0.3.
The total amount of ethylene units or said alpha-olefin units, or of ethylene and said alpha-olefin units when both are present, in the olefin polymer composition is from about 15% to about 3S%.
The compositions have at least one melt peak, deter-mined by DSC, present at temperatures higher than 120C,and at least one peak, relative to the vitreous transition, present at temperatures from -10C and -35C.
In addition, these compositions have a flexural modulus of less than 150 MPa, generally from 20 and 100 MPa; a tensile strength at yield of from 10 to 20 MPa, elongation at break over 400%; a tension set, at 75%
strain, from 20% to 50%; a Shore D hardness from 20 and 35;
and do not break (no brittle impact failure) when an IZOD
impact test is conducted at -50C.
Preferably the haze values are less than 40%, most preferably less than 35%.
Copolymer and terpolymers of propylene and ethylene or an alpha-olefin or of propylene, ethylene and an alpha-olefin are preferred as component (a), and copolymers of propylene with ethylene or an alpha-olefin are most preferred as component (a) since they provide the compositions with higher clarity.
Suitable alpha-olefins of the formula CH2-CHR
include butene-l, pentene-l, 4-methylpentene-1, hexene-l, and octene-l. When used to prepare component (a) they are 2~S~4~2 present in such quantities that the isotactic index of the resulting polymer is not less than 80%.
When a diene is present during the preparation of components (b) and (c), it is typically a butadiene, 1,4-hexadiene, 1,5-hexadiene, ethylidene norbornene diene monomer and is typically present in amount from 0.5 to 10%, preferably 1 to 5%.
The compositions can be prepared with a polymerization process comprising at least two stages, where in the first stage the propylene or propylene and ethylene or said alpha-olefin or propylene, ethylene or said alpha-olefin are polymerized to form component (a), and in the following stages the mixtures ethylene and propylene or said alpha-olefin or ethylene, propylene and said alpha-olefin, and optionally a diene, are polymerized to form components (b) and (c).
The polymerization can be conducted in liquid phase, gas phase, or liquid-gas phase using separate reactors, all of which can be done either by batch or continuously. For example, it is possible to carry out the polymerization of component (a) using liquid propylene as diluent, and the polymerization of components (b) and (c) in gas phase, without intermediate stages except for the partial degas-sing of the propylene. This is the preferred method.
The polymerization reactions are carried out in an inert atmosphere in the presence of an inert hydrocarbon solvent or of a liquid or gaseous monomer.
Suitable inert hydrocarbon solvents include saturated hydrocarbons, such as propane, butane, hexane and heptane.
Hydrogen can be added as needed as a chain transfer agent for control of the molecular weight.
The reaction temperature in the polymerization of component (a) and for the polymerization of components (b) and (c), can be the same or different, and is generally from 40C to 90C, preferably 50 to 80C for the polymer-ization of component (a), and 40 to 65C for the polymeri-zation of components (b) and (c).
The pressure of the polymerization of component (a), if carried out in liquid monomer, is the one which competes with the vapor pressure of the liquid propylene at the operating temperature used, eventually modified by the vapor pressure of the small quantity of inert diluent used to feed the catalyst mi~ture, and the overpressure of optional monomers and the hydrogen used as molecular weight regulator.
The pressure of the polymerization of components (b) and (c), if done in gas phase, can be from 5 to 30 atm.
The residence times relative to the two stages depend on the desired ratio between fraction (a) and (b) ~ (c), and are usually from 15 min. to 8 hours.
The catalyst used in the polymerization comprises the reaction product of 1) a solid component containing a halogen-containing titanium compound and an electron-donor compound (internal donor) supported on an activated magnesium chloride, 2) a non-halogen containing Al-trialkyl compound and 3) an electron-donor compound (e~ternal donor).
Suitable titanium compounds include those with at least one Ti-halogen bond, such as halides and alko~y halides of titanium.
In order to obtain these olefin polymer compositions in the form of flowable spherical particles having a high bulk density, the solid catalyst component must have a) a surface area smaller than 100 m2/g, preferably between 50 and 80 m2/g, b) a porosity from 0.25 to 0.4 cc/g. and c) an X-ray spectrum, where the magnesium chloride reflections appear, showing the presence of a halo between the angles 2 ~ of 33.5 and 35 and by the absence of the reflection at 2 ~ of 14.95. The symbol ~ - Bragg angle.
2~5241~:2 The solid catalyst component is prepared by forming an adduct of magnesium dichloride and an alcohol, such as ethanol, propanol, butanol and 2-ethylhexanol, containing generally 3 moles of alcohol per mole of MgC12, emulsifying the adduct, cooling the emulsion quickly to cause the adduct to solidify into spherical particles, and partially dealcoholating the particulate adduct by gradually increasing the temperature from 50C to 130C for a period of time sufficient to reduce the alcohol content from 3 moles to 1-1.5 moles per mole of MgC12. The partially dealcoholated adduct is then suspended in TiC14 at 0C, such that the concentration of adduct to TiC14 is 40-50 g/l TiC14. The mixture is then heated to a temperature of 80C to 135C for a period of about 1-2 hr.
When the temperature reaches 40C, sufficient electron donor is added so that the desired molar ratio of Mg to electron donor is obtained.
An electron-donor compound selected preferably among the alkyl, cycloalkyl, and aryl phthalates, such as for example diisobutyl, di-n-butyl, and di-n-octyl phthalate, is added to the TiC14.
When the heat treatment period has ended, the excess hot TiC14 is separated by filtration or sedimentation, and the treatment with TiC14 is repeated one or more times. The solid is then washed with a suitable inert hydrocarbon compound, such as hexane or heptane, and dried.
The solid catalyst component typically has the following characteristics:
Surface area: less than 100 m2/9, preferably between 50 and 80 m2/g Porosity: 0.25 - 0.4 cc/g Pore volume distribution: 50% of the pores have a radius greater than 100 angstroms.
X-ray spectrum: where the Mg chloride reflections appear, showing a halo with ma~imum intensity between angles of 2 ~ of 33.5 and 35, and where the reflection at 2 ~ of 14.95 is absent.
The catalyst is obtained by mi~ing the solid catalyst component with a trialkyl aluminum compound, preferably triethyl aluminum and triisobutyl aluminum, and an electron-donor compound.
Various electron donor compounds are known in the art. The preferred electron donor compounds are those silane compounds having the formula R'RnSi(OR)2 where R' and R" may be the same or different and are Cl 18 normal or branched alkyl, C5 18 cycloalkyl, or C6_18 aryl radicals, and R is a Cl 4 alkyl radical.
Typical silane compounds which may be used include diphenyldimetho~ysilane, dicyclohe~yldimetho~ysilane, methyl-t-butyldimetho~ysilane, diisopropyldimetho~ysilane, dicyclopentyldimetho~ysilane, cyclohe~ylmethyldimetho~y-silane and phenyltrimetho~ysilane.
The Al/Ti ratio is typically between 10 and 200 and the Al/silane molar ratio between 1/1 and 1/100.
The catalysts may be precontacted with small quantities of olefin monomer (prepolymerization~, main-taining the catalyst in suspension in a hydrocarbon solvent and polymerizing at a temperature from room temperature to 60OC for a time sufficient to produce a quantity of polymer from 0.5 to 3 times the weight of the catalyst.
20~2~02 This prepolymerization also can be done in li~uid or gaseous monomer to produce, in this case, a quantity of polymer up to 1000 times the catalyst weight.
The content and amount of catalyst residue in the thermoplastic olefin polymers of this invention is sufficiently small so as to make the removal of catalyst residue, typically referred to as deashing, unnecessary.
The thermoplastic olefin polymers prepared with the aforementioned catalyst are in spheroidal particle form, and the particles have a diameter from 0.5 to 7 mm.
Unless otherwise specified, the following analytical methods are used to characterize the supported catalyst component, the heterophasic olefin polymer compositions, films prepared therefrom and comparative film materials.
15 Properties Method Melt Flow Rate, g/10 min. ASTM-D 1238, condition L
Ethylene, wt % I. R. Spectroscopy Intrinsic viscosity Determined in tetrahydro-naphthalene at 135C
20 Xylene solubles, wt % See description below.
Fle~ural modulus at 23C Using a device for dynamic-and Vitreous transition mechanical measurements of temperature DMTA of Polymer Laboratories at a frequency measure of 1 Hz and a scanning temperature of 2C/min. A
sample plaque (40~10x2 mm) of the polymer to be analyzed is cut from a pressure molded sheet prepared with a Carver press at 200C with 10 tons of pressure for 10 minutes and then cooling the sheet at 15C/min.
35 Notched IZOD impact ASTM-D 256 Haze ASTM-D 1003 2~35~02 ProPerties Method Tension set at 75% ASTM-D 412 Tensile Strength at yield ASTM-D 638 and at break 5 Elongation at yield and ASTM-D 638 at break Surface area B.E.T.
Porosity B.E.T.
Bulk density DIN-53194 Elemendorf tear ASTM-D 1922-78 Trouser tear ASTM-D 1938-85 Gloss ASTM-D 523 Coefficient of friction ASTM-D 1894 Moisture vapor transmission ASTM-E 96 Dart impact strength ASTM D 4272-83 Unless otherwise specified, the samples of the olefin polymer composition to be subjected to the various physical-mechanical analyses are molded by use of a Negri ~ Bossi 90 injection press, after stabilizing the material with 0.1%
Irganox 1010 tetrakis[methylene 3,5-di-tert-butyl-4-hy-dro~yhydrocinnamate)] methane and 0.1% BHT (2,6-di-tert-butyl-p-cresol), and pelletizing it with a single screw Bandera extruder (cylinder diameter 30 mm) at 210C. The analytical conditions are as follows:
temperature of the melt 250C
temperature of the mold 60C
injection time 20 sec cooling time 25 sec.
The samples to be subjected to the Haze analysis are molded into 75x75xl mm plaques using a GBF F 235/90 injection press under the following conditions:
i~ t~d~ -m~Rk temperature of the melt 260C
temperature of the mold 40OC
injection time 20 sec cooling time 10 sec.
The samples of the film materials were 1 mil in thickness and were cut from the film sheet in the size provided in the particular ASTM test method being used.
The weight percentage of the 8um of the (b) and (c) fractions, indicated by % (b) + (c), is calculated by determining the weight of the mixture fed during the second stage, and comparing it with the weight of the final product.
The weight percentage (%) of the (a), (b), and (c) fractions described herein are determined as follows:
% (a) = 100% - t(b) + (c)]
% (c) - Sf-PaSa where Sf and Sa are the percentage by weight of the portion soluble in xylene of the final product and the polypropylene fraction (a), respectively; Pa is the weight ratio between said fraction and the final product.
% (b) , 100 - % (a) - % (c) The percentage by weight of ethylene or said alpha-olefin or ethylene and said alpha-olefin contained in copolymer fraction (c) soluble in xylene is calculated using the following formula:
wt.% ethylene and/or said (Cf - Ca) . X
alpha-olefin in fraction (c) ~ 1 - X
where: 0 Cf , % ethylene and/or said alpha-olefin in the xylene solubles of the final product;
Ca - % ethylene and/or said alpha-olefin in the xylene solubles of fraction (a);
X - Sz . Pa/Sf 2~52~02 The intrinsic viscosity of fraction (c), (I.V.(c)), is calculated using the following formula:
(I.V.(c)) , (I.V.sf - I.V.(a) X)/(l-X) where I.V.Sf is the intrinsic viscosity of the ~ylene soluble fraction of the final composition and I.V.(a) is the intrinsic viscosity of the xylene soluble portion of fraction (a).
The weight percent of olefin polymer composition soluble in xylene at room temperature is determined by dissolving 2.5 g of the polymer in 250 ml of xylene in a vessel equipped with a stirrer which is heated at 135C
with agitation for 20 minutes. The solution is cooled to 25C while continuing the agitation, and then left to stand without agitation for 30 minutes so that the solids can settle. The solids are filtered with filter paper, the remaining solution is evaporated by treating it with a nitrogen stream, and the solid residue is vacuum dried at 80C until a constant weight is reached. The percent by weight of polymer insoluble in xylene at room temperature is the isotactic index of the polymer. The value obtained in this manner corresponds substantially to the isotactic index determined via extraction with boiling n-heptane, which by definition constitutes the isotactic inde~ of the polymer.
E~amples illustrative of the heterophasic olefin polymer composition, physical properties thereof, a process for preparing same, a film based on said olefin polymer composition and a method of preparing said film are set forth below.
- 2~52~02 Solid Catalyst Co~pQne~t A) Preparation of MgC12/Alcohol Adduct Under an inert atmosphere, 28.4 g anhydrous MgC12, 49.5 g of an anhydrous ethanol, 100 ml of ROL OB/30 vaseline oil and 100 ml of silicone oil having a viscosity of 350 cs are introduced into a reaction vessel equipped with a stirrer and heated at 120C with an oil bath and stirred until the MgC12 is dissolved. The hot reaction mi~ture is then transferred under inert atmosphere to a 1500 ml vessel equipped with an Ultra Turrax~T-45 N stirrer and a heating jacket and containing 150 ml of vaseline oil and 150 ml of silicone oil. The temperature is maintained at 120C with stirring for 3 minutes at 3,000 rpm. The mixture is then discharged into a 2 liter vessel equipped with a stirrer containing 1,000 ml of anhydrous n-heptane cooled at 0C with a dry ice/isopar bath and stirred at a tip speed of 6 m/sec for about 20 minutes while maintaining the temperature at 0C. The adduct particles thus formed are recovered by filtering, are washed 3 times at room temperature with 500 ml aliquots of anhydrous hexane and gradually heated by increasing the temperature from 50C to 100C under nitrogen for a period of time sufficient to reduce the alcohol content from 3 moles to 1.5 moles per mole of MgC12. The adduct has a surface area of 9.1 m2/g and a bulk density of 0.564 g/cc.
B) Solid Catalyst Component Preparation The adduct (25 g) is transferred under nitrogen into a reaction vessel equipped with a stirrer and containing 625 ml of TiC14 at 0C under agitation. It is then heated to 100C in 1 hr. When the temperature reaches 40C, diisobutylphthalate is added in an amount such that the k molar ratio of Mg to diisobutylphthalate is 8. The contents of the vessel are heated at 100C for 2 hours with agitation, the agitation is stopped and the solids are allowed to settle. The hot liquid is removed by siphon.
550 ml of TiC14 is added to the solids in the vessel and the mixture heated at 120C for 1 hr. with agitation. The agitation is stopped and the solids are allowed to settle.
The hot liquid is then removed by siphon. The solids are washed 6 times at 60C with 200 ml aliquots of anhydrous hexane, and then 3 times at room temperature. The solids, after being vacuum dried, have a porosity of 0.261 cc/g, a surface area of 66.5 m2~g and a bulk density of 0.44 g/cc.
Examples 1-3 These examples illustrate the heterophasic olefin polymer composition and a method for preparing the polymers.
General Operatin~ Conditions The polymerization runs are conducted under nitrogen in a 22 liter stainless steel autoclave equipped with a helicoid magnetic stirrer and operated at about 90 rpm.
All temperatures, pressures and concentrations of olefin monomers and hydrogen, when present, are constant unless otherwise indicated. The concentration of hydrogen and of the relative monomers is analyzed continuously in gas phase with a process gas chromatograph and fed in order to maintain constant the desired concentration of same.
The polymerization is a batch process conducted in two stages. The first stage comprising the polymerization of the relevant monomer or monomers in liquid propylene and the second stage the copolymerization of ethylene and propylene in gas phase.
In the first stage, the following ingredients in the order in which they are listed are fed into the autoclave at 20C over a period of about 10 minutes: 16 1 of liquid 20~Z402 propylene, appropriate quantities of ethylene and hydrogen, and the catalyst system consisting of 1) the solid catalyst component (about 0.15g) prepared as described above, and 2) a mixture of 75 ml of triethyl aluminum (TEAL) at a 10%
concentration in he~ane and an appropriate quantity of - cyclohexylmethyldimethoxysilane (CMMS) electron donor such that the Al/CMMS molar ratio is 7.5. The catalyst system is pressure fed into the autoclave with propylene.
The temperature is brought to the desired level in about 10 minutes and maintained constant throughout the entire polymerization reaction period. After the established reaction time has passed, essentially all of the unreacted monomer(s) is/are eliminated by degassing at 60C at essentially atmospheric pressure.
In the second stage, the polymer product (a) of the first stage, after taking a sample for the various analyses, is brought to the established temperature for the second stage. Propylene and ethylene are then fed into the autoclave at the ratio and in the quantities established in order to achieve the pressure and the gas phase composition desired. During the polymerization the pressure and gas phase composition are maintained by feeding the propylene and ethylene mixture established by way of instruments which regulate or measure or both regulate and measure the flow rate. The length of the feed varied according to the catalyst system employed and the amount of components b) and c) desired in the particular heterophasic olefin polymer product.
At the end of the second stage polymerization reaction the powder is discharged, stabilized and then oven dried under a nitrogen stream at 60C.
The ingredients and relative operating conditions are set forth in Table IA and the tests results are set forth in Table IB.
- 2~52402 Table lA
~am~les 1 2 3 1st Phase Temperature, C 70 70 70 Pressure, atm. 31 31 31 Time, min. 30 20 30 H2 in gas phase, mol %0.58 0.10 0.30 Ethylene in gas phase, mol % 1.45 2.60 2.50 Ethylene in pol., wt. %3.0 4.3 4.1 Intrinsic Visc., dl/g 2.18 3.09 2.31 Xylene Sol. (Sa), wt. %9.4 9.0 10.7 Ethylene in Xylene Sol.
(Ca), wt. % 11 16 17 Intrinsic Visc. Xylene Sol.(I.V.a), dl/g 1.15 1.39 1.19 2nd Phase Temperature, C 50 50 50 Pressure, atm. 11.3 11.5 11.3 Time, min. 335 500 250 H2 in gas phase, mol %2.23 3.0 2.05 Ethylene in gas phase,15.9 16.9 22.54 mol %
20~2402 Table lB
Examples 1 2 3 Final Product Yield, Kg Pol/g Cat 1116.3 9.9 Comonomer, wt. % 24.6 22.7 29.0 Bipolymer (b)~(c), wt. %70 67 71.8 Intrinsic Visc., dl/g 2.05 2.3 2.34-Xyl. Sol. (Sf), wt. % 63.4 60.5 63.5 Ethylene Xyl. Sol., wt. %
(Cf) 30.2 27.0 34.8 Intrinsic Vis. Xyl. Sol.
I.V.Sf, dl/g 1.83 2.02 2.12 Fraction (b), wt. % 9.45 9.37 11.34 Fraction (c), wt. % 60.55 57.63 60.46 Ethylene frac. (b), wt. %51.9 57.1 53.7 Ethylene frac. (c), wt. %31.I 27.6 35.7 Intrinsicc Vis. frac. (c) (I.V. ), dl/g 1.86 2.05 2.18 Melt Index, C 150 147 145 Flexural modulus, MPa 30 77 82 R.C.I. IZOD at -50C, J/mNBl NB NB
Shore D hardness 24 25 20 Tension Set at 75%, % 41 28 36 Tensile strength, MPa 13.8 15.8 15.4 Tensile strength at yield, 5.0 5.8 4.6 MPa Elongation at break, % 517 925 940 Haze, % 31 34 35 Vitreous transition2,C-25(P) -23(P) -28(P) NB . no break (P) , main peak 20~2402 Examples 4 These examples illustrate a film material of the heterophasic olefin polymer composition and a method for preparing the same.
An air quenched blown film of the heterophasic olefin polymer composition of Example 2 stabilized with 0.25 parts per hundred parts of the olefin polymer composition (pph) octadecyl-3,5-bis(l,l-dimethylethyl)-4-hydroxybenzene propanoate, 0.05 pph tetrakis[methylene(3,5-di-tert-b~tyl-f ~10 4-hydroxyhydrocinnamate)~ methane, 0.06 pph Sandostab P-EPQ
composition, the main component of which is tetrakis(2,4-di-tert-butylphenyl)-4-4'-biphenylene diphosphonite and 0.05 calcium stearate is prepared by charging the composition into a single screw extruder, extruding it through a circular die and blowing it into a film form with a sufficient amount of air to provide a film of 1 mil thickness using the following equipment and processing conditions:
Screw: Compression ratio 3:1 to 4:1.
Polyolefin barrier type L/D
ratio - 24:1 to 30:1.
Blow up ratio - 2.5 to 4.1.
Die gap: 40 mils for a thickness of 0.5 to 5 mils.
Extruder barrel profile: 380 to 430F going from zone 1 to zone 6.
Adapter and die temperatures: 450F except upper and lower die zones which are 460F.
Screw speed: 20 rpm.
Pressure: 3000 psi.
The properties of the resulting film are set forth in Table 2 below.
k Table 2 Resins Properties Example 2 HDPEl LLDPE2 Yield Strength 1347/1126 3757/3145 1799/1739 (MD/CD3),psi Break Strength (MD/CD), 3096/16433960/3216 2092/1898 pSi Elongation at yield65/40 30/7 80/17 (MD/CD~, %
Elongation at break361/417 120/350 317/425 (MD/CD), %
Elemendorf tear, No tear 10/282 350/790 (MD/CD), g/ply Trouser tear, (MD/CD) 152/530 147/1026 503/758 Haze 65.7 76.8 8.7 Gloss 6 10 70 Coefficient of 1.22/0.8150.241/0.1920.688/0.650 friction (static/
kinetic) Moisture vapor trans- 1.340 1.300 mission rates at 100F & 100 relative humidity, g/100 sq.
in/24 hrs.
Dart impact strength, 0.980 0.720 1.020 ft-lb/mil 1 Quantum LR 732 HDPE having a density of 0.953 g/cc3.
2 Dowlex 2045 LLDPE containing hexene-l and having a density of 0.920 g/cc3.
In many film applications, such as packaging of foodstuffs, chemical and hazardous materials and in medical applications, the industry requires films having certain properties. In the packaging of foodstuffs, for example, the films must have high puncture resistance, high clarity and gloss, and reduced permeability to gases and/or vapors. The films used to manufacture containers for chemicals and hazardous waste materials must have a high puncture resistance, high elongation strength, high tear resistance and chemical resistance. Films used in medical applications, such as blood bags, must have a high puncture resistance, low modulus, high tear resistance and auto-clavability.
Films made from ethylene polymers, e.g., HDPE and LLDPE, and propylene polymers, such as crystalline homopolymers of propylene and random copolymers of propylene and ethylene, do not provide such a combination of desirable properties.
Attempts have been made to overcome the shortcomings of these polymers by preparing heterophasic mixtures of crystalline propylene polymers and 8 to 25% of an elastomeric propylene-ethylene copolymer by sequential polymerization in the presence of a stereospecific Ziegler-Natta type catalyst. However, films of such heterophasic compositions are subject to the formation of fisheyes, inadequate tear strength or the formation of rough surfaces.
~`
Hence, there is a need for a polymer material which has a lower fle~ural modulus, high clarity, good tear strength, as well as all of the other desirable properties.
All parts and percentages used in this application are by weight unless otherwise specified. Ambient or room temperature is approximately 25C.
mis invention provides a th~rmnrl~tic film or sheet having the desired properties comprising a heterophasic olefin polymer composition which is comprised of (a) from about 10 to 50 parts of a propylene homopolymer having an isotactic inde~ greater than 80, or a copolymer selected from the group consisting of (i) propylene and ethylene, (ii) propylene, ethylene and a CH2-CHR alpha-olefin, where R is a C2 8 straight or branched alkyl, and (iii) propylene and an alpha-olefin as defined in (a) (ii), the copolymer containing over 80% propylene and having an isotactic index greater than 80;
(b) from about 5 to 20 parts of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of about 20 to 60% wherein the copolymer is selected from the group consisting of (i) ethylene and propylene containing over 55% ethylene, (ii) ethylene, propylene, and an alpha-olefin as defined in (a) (ii) containing from 1 to 10% of the alpha-olefin and over 55% of both ethylene and alpha-olefin, and (iii) ethylene and an alpha-olefin as defined in (a) (ii) containing over 55% of the - alpha-olefin, which copolymer is insoluble in xylene at room or ambient temperature; and (c) from about 40 to 80 parts of a copolymer fraction is selected from the group consisting of a copolymer of (i) ethylene and propylene wherein the copolymer contains from 20% to less than 40% ethylene 20524 ~2 27651-20 and, (ii) ethylene, propylene, and an alpha-olefin as defined in (a) (ii) wherein the alpha-olefin is present in an amount of 1 to 10% and the amount of ethylene and alpha-olefin present is from 20% to less than 40%, and (iii) ethylene and an alpha-olefin as defined in (a) (ii) containing from 20% to less than 40% of the alpha-olefin, and optionally with 0.5 to 10% of a diene, the copolymer fraction being soluble in xylene at ambient temperature, and having an intrinsic viscosity of from 1.5 to 4.0 dl/g;
with the total of the (b) and (c) fractions, based on the total olefin polymer composition, being from about 50% to 90%, and the weight ratio of (b)/(c) being less than 0.4.
In another embodiment, this invention provides film or sheet articles comprising a film or sheet of the hetero-phasic olefin polymer composition applied to at least one surface of a thermoplastic base film or sheet or a base film or sheet of a metallic substrate.
In yet another embodiment, films or sheets made from blends of the olefin polymer composition and a thermoplastic material are provided.
Component (a) is preferably present in an amount from 10 to 40 parts, most preferably from 20 to 35 parts. When (a) is a propylene homopolymer, the isotactic index is preferably from about 85 to 98. When (a) is a copolymer, the amount of propylene in the copolymer is preferably from about 90 to 99%.
Component (b) is preferably present in an amount from 7 to 15 parts. Typically the crystallinity is about 20 to 60%
~.~
2~52~ 02 27651-20 by differential scanning calorimetry (DSC). Generally, the ethylene or said alpha-olefin content or the combination of ethylene and said alpha-olefin when both are used is over 55%
up to 98%r preferably from 80 to 95%.
Component (c) is preferably present in an amount from 50 to 70 parts. The ethylene or said alpha-olefin content or ethylene and said alpha-olefin content of component (c) -3a-. ~
20s2402 is preferably from 20 to 38%, most preferably from 25 to 38%. When component (c) is a terpolymer, the said alpha-olefin is typically present in an amount from 1 to 10%, preferably 1 to 5%. The preferred intrinsic viscosity of is from 1.7 to 3 dl/g.
The total amount of (b) and (c), based on the total olefin polymer composition is preferably from 65 to 80% and the weight ratio of (b)/(c) is preferably from 0.1 to about 0.3.
The total amount of ethylene units or said alpha-olefin units, or of ethylene and said alpha-olefin units when both are present, in the olefin polymer composition is from about 15% to about 3S%.
The compositions have at least one melt peak, deter-mined by DSC, present at temperatures higher than 120C,and at least one peak, relative to the vitreous transition, present at temperatures from -10C and -35C.
In addition, these compositions have a flexural modulus of less than 150 MPa, generally from 20 and 100 MPa; a tensile strength at yield of from 10 to 20 MPa, elongation at break over 400%; a tension set, at 75%
strain, from 20% to 50%; a Shore D hardness from 20 and 35;
and do not break (no brittle impact failure) when an IZOD
impact test is conducted at -50C.
Preferably the haze values are less than 40%, most preferably less than 35%.
Copolymer and terpolymers of propylene and ethylene or an alpha-olefin or of propylene, ethylene and an alpha-olefin are preferred as component (a), and copolymers of propylene with ethylene or an alpha-olefin are most preferred as component (a) since they provide the compositions with higher clarity.
Suitable alpha-olefins of the formula CH2-CHR
include butene-l, pentene-l, 4-methylpentene-1, hexene-l, and octene-l. When used to prepare component (a) they are 2~S~4~2 present in such quantities that the isotactic index of the resulting polymer is not less than 80%.
When a diene is present during the preparation of components (b) and (c), it is typically a butadiene, 1,4-hexadiene, 1,5-hexadiene, ethylidene norbornene diene monomer and is typically present in amount from 0.5 to 10%, preferably 1 to 5%.
The compositions can be prepared with a polymerization process comprising at least two stages, where in the first stage the propylene or propylene and ethylene or said alpha-olefin or propylene, ethylene or said alpha-olefin are polymerized to form component (a), and in the following stages the mixtures ethylene and propylene or said alpha-olefin or ethylene, propylene and said alpha-olefin, and optionally a diene, are polymerized to form components (b) and (c).
The polymerization can be conducted in liquid phase, gas phase, or liquid-gas phase using separate reactors, all of which can be done either by batch or continuously. For example, it is possible to carry out the polymerization of component (a) using liquid propylene as diluent, and the polymerization of components (b) and (c) in gas phase, without intermediate stages except for the partial degas-sing of the propylene. This is the preferred method.
The polymerization reactions are carried out in an inert atmosphere in the presence of an inert hydrocarbon solvent or of a liquid or gaseous monomer.
Suitable inert hydrocarbon solvents include saturated hydrocarbons, such as propane, butane, hexane and heptane.
Hydrogen can be added as needed as a chain transfer agent for control of the molecular weight.
The reaction temperature in the polymerization of component (a) and for the polymerization of components (b) and (c), can be the same or different, and is generally from 40C to 90C, preferably 50 to 80C for the polymer-ization of component (a), and 40 to 65C for the polymeri-zation of components (b) and (c).
The pressure of the polymerization of component (a), if carried out in liquid monomer, is the one which competes with the vapor pressure of the liquid propylene at the operating temperature used, eventually modified by the vapor pressure of the small quantity of inert diluent used to feed the catalyst mi~ture, and the overpressure of optional monomers and the hydrogen used as molecular weight regulator.
The pressure of the polymerization of components (b) and (c), if done in gas phase, can be from 5 to 30 atm.
The residence times relative to the two stages depend on the desired ratio between fraction (a) and (b) ~ (c), and are usually from 15 min. to 8 hours.
The catalyst used in the polymerization comprises the reaction product of 1) a solid component containing a halogen-containing titanium compound and an electron-donor compound (internal donor) supported on an activated magnesium chloride, 2) a non-halogen containing Al-trialkyl compound and 3) an electron-donor compound (e~ternal donor).
Suitable titanium compounds include those with at least one Ti-halogen bond, such as halides and alko~y halides of titanium.
In order to obtain these olefin polymer compositions in the form of flowable spherical particles having a high bulk density, the solid catalyst component must have a) a surface area smaller than 100 m2/g, preferably between 50 and 80 m2/g, b) a porosity from 0.25 to 0.4 cc/g. and c) an X-ray spectrum, where the magnesium chloride reflections appear, showing the presence of a halo between the angles 2 ~ of 33.5 and 35 and by the absence of the reflection at 2 ~ of 14.95. The symbol ~ - Bragg angle.
2~5241~:2 The solid catalyst component is prepared by forming an adduct of magnesium dichloride and an alcohol, such as ethanol, propanol, butanol and 2-ethylhexanol, containing generally 3 moles of alcohol per mole of MgC12, emulsifying the adduct, cooling the emulsion quickly to cause the adduct to solidify into spherical particles, and partially dealcoholating the particulate adduct by gradually increasing the temperature from 50C to 130C for a period of time sufficient to reduce the alcohol content from 3 moles to 1-1.5 moles per mole of MgC12. The partially dealcoholated adduct is then suspended in TiC14 at 0C, such that the concentration of adduct to TiC14 is 40-50 g/l TiC14. The mixture is then heated to a temperature of 80C to 135C for a period of about 1-2 hr.
When the temperature reaches 40C, sufficient electron donor is added so that the desired molar ratio of Mg to electron donor is obtained.
An electron-donor compound selected preferably among the alkyl, cycloalkyl, and aryl phthalates, such as for example diisobutyl, di-n-butyl, and di-n-octyl phthalate, is added to the TiC14.
When the heat treatment period has ended, the excess hot TiC14 is separated by filtration or sedimentation, and the treatment with TiC14 is repeated one or more times. The solid is then washed with a suitable inert hydrocarbon compound, such as hexane or heptane, and dried.
The solid catalyst component typically has the following characteristics:
Surface area: less than 100 m2/9, preferably between 50 and 80 m2/g Porosity: 0.25 - 0.4 cc/g Pore volume distribution: 50% of the pores have a radius greater than 100 angstroms.
X-ray spectrum: where the Mg chloride reflections appear, showing a halo with ma~imum intensity between angles of 2 ~ of 33.5 and 35, and where the reflection at 2 ~ of 14.95 is absent.
The catalyst is obtained by mi~ing the solid catalyst component with a trialkyl aluminum compound, preferably triethyl aluminum and triisobutyl aluminum, and an electron-donor compound.
Various electron donor compounds are known in the art. The preferred electron donor compounds are those silane compounds having the formula R'RnSi(OR)2 where R' and R" may be the same or different and are Cl 18 normal or branched alkyl, C5 18 cycloalkyl, or C6_18 aryl radicals, and R is a Cl 4 alkyl radical.
Typical silane compounds which may be used include diphenyldimetho~ysilane, dicyclohe~yldimetho~ysilane, methyl-t-butyldimetho~ysilane, diisopropyldimetho~ysilane, dicyclopentyldimetho~ysilane, cyclohe~ylmethyldimetho~y-silane and phenyltrimetho~ysilane.
The Al/Ti ratio is typically between 10 and 200 and the Al/silane molar ratio between 1/1 and 1/100.
The catalysts may be precontacted with small quantities of olefin monomer (prepolymerization~, main-taining the catalyst in suspension in a hydrocarbon solvent and polymerizing at a temperature from room temperature to 60OC for a time sufficient to produce a quantity of polymer from 0.5 to 3 times the weight of the catalyst.
20~2~02 This prepolymerization also can be done in li~uid or gaseous monomer to produce, in this case, a quantity of polymer up to 1000 times the catalyst weight.
The content and amount of catalyst residue in the thermoplastic olefin polymers of this invention is sufficiently small so as to make the removal of catalyst residue, typically referred to as deashing, unnecessary.
The thermoplastic olefin polymers prepared with the aforementioned catalyst are in spheroidal particle form, and the particles have a diameter from 0.5 to 7 mm.
Unless otherwise specified, the following analytical methods are used to characterize the supported catalyst component, the heterophasic olefin polymer compositions, films prepared therefrom and comparative film materials.
15 Properties Method Melt Flow Rate, g/10 min. ASTM-D 1238, condition L
Ethylene, wt % I. R. Spectroscopy Intrinsic viscosity Determined in tetrahydro-naphthalene at 135C
20 Xylene solubles, wt % See description below.
Fle~ural modulus at 23C Using a device for dynamic-and Vitreous transition mechanical measurements of temperature DMTA of Polymer Laboratories at a frequency measure of 1 Hz and a scanning temperature of 2C/min. A
sample plaque (40~10x2 mm) of the polymer to be analyzed is cut from a pressure molded sheet prepared with a Carver press at 200C with 10 tons of pressure for 10 minutes and then cooling the sheet at 15C/min.
35 Notched IZOD impact ASTM-D 256 Haze ASTM-D 1003 2~35~02 ProPerties Method Tension set at 75% ASTM-D 412 Tensile Strength at yield ASTM-D 638 and at break 5 Elongation at yield and ASTM-D 638 at break Surface area B.E.T.
Porosity B.E.T.
Bulk density DIN-53194 Elemendorf tear ASTM-D 1922-78 Trouser tear ASTM-D 1938-85 Gloss ASTM-D 523 Coefficient of friction ASTM-D 1894 Moisture vapor transmission ASTM-E 96 Dart impact strength ASTM D 4272-83 Unless otherwise specified, the samples of the olefin polymer composition to be subjected to the various physical-mechanical analyses are molded by use of a Negri ~ Bossi 90 injection press, after stabilizing the material with 0.1%
Irganox 1010 tetrakis[methylene 3,5-di-tert-butyl-4-hy-dro~yhydrocinnamate)] methane and 0.1% BHT (2,6-di-tert-butyl-p-cresol), and pelletizing it with a single screw Bandera extruder (cylinder diameter 30 mm) at 210C. The analytical conditions are as follows:
temperature of the melt 250C
temperature of the mold 60C
injection time 20 sec cooling time 25 sec.
The samples to be subjected to the Haze analysis are molded into 75x75xl mm plaques using a GBF F 235/90 injection press under the following conditions:
i~ t~d~ -m~Rk temperature of the melt 260C
temperature of the mold 40OC
injection time 20 sec cooling time 10 sec.
The samples of the film materials were 1 mil in thickness and were cut from the film sheet in the size provided in the particular ASTM test method being used.
The weight percentage of the 8um of the (b) and (c) fractions, indicated by % (b) + (c), is calculated by determining the weight of the mixture fed during the second stage, and comparing it with the weight of the final product.
The weight percentage (%) of the (a), (b), and (c) fractions described herein are determined as follows:
% (a) = 100% - t(b) + (c)]
% (c) - Sf-PaSa where Sf and Sa are the percentage by weight of the portion soluble in xylene of the final product and the polypropylene fraction (a), respectively; Pa is the weight ratio between said fraction and the final product.
% (b) , 100 - % (a) - % (c) The percentage by weight of ethylene or said alpha-olefin or ethylene and said alpha-olefin contained in copolymer fraction (c) soluble in xylene is calculated using the following formula:
wt.% ethylene and/or said (Cf - Ca) . X
alpha-olefin in fraction (c) ~ 1 - X
where: 0 Cf , % ethylene and/or said alpha-olefin in the xylene solubles of the final product;
Ca - % ethylene and/or said alpha-olefin in the xylene solubles of fraction (a);
X - Sz . Pa/Sf 2~52~02 The intrinsic viscosity of fraction (c), (I.V.(c)), is calculated using the following formula:
(I.V.(c)) , (I.V.sf - I.V.(a) X)/(l-X) where I.V.Sf is the intrinsic viscosity of the ~ylene soluble fraction of the final composition and I.V.(a) is the intrinsic viscosity of the xylene soluble portion of fraction (a).
The weight percent of olefin polymer composition soluble in xylene at room temperature is determined by dissolving 2.5 g of the polymer in 250 ml of xylene in a vessel equipped with a stirrer which is heated at 135C
with agitation for 20 minutes. The solution is cooled to 25C while continuing the agitation, and then left to stand without agitation for 30 minutes so that the solids can settle. The solids are filtered with filter paper, the remaining solution is evaporated by treating it with a nitrogen stream, and the solid residue is vacuum dried at 80C until a constant weight is reached. The percent by weight of polymer insoluble in xylene at room temperature is the isotactic index of the polymer. The value obtained in this manner corresponds substantially to the isotactic index determined via extraction with boiling n-heptane, which by definition constitutes the isotactic inde~ of the polymer.
E~amples illustrative of the heterophasic olefin polymer composition, physical properties thereof, a process for preparing same, a film based on said olefin polymer composition and a method of preparing said film are set forth below.
- 2~52~02 Solid Catalyst Co~pQne~t A) Preparation of MgC12/Alcohol Adduct Under an inert atmosphere, 28.4 g anhydrous MgC12, 49.5 g of an anhydrous ethanol, 100 ml of ROL OB/30 vaseline oil and 100 ml of silicone oil having a viscosity of 350 cs are introduced into a reaction vessel equipped with a stirrer and heated at 120C with an oil bath and stirred until the MgC12 is dissolved. The hot reaction mi~ture is then transferred under inert atmosphere to a 1500 ml vessel equipped with an Ultra Turrax~T-45 N stirrer and a heating jacket and containing 150 ml of vaseline oil and 150 ml of silicone oil. The temperature is maintained at 120C with stirring for 3 minutes at 3,000 rpm. The mixture is then discharged into a 2 liter vessel equipped with a stirrer containing 1,000 ml of anhydrous n-heptane cooled at 0C with a dry ice/isopar bath and stirred at a tip speed of 6 m/sec for about 20 minutes while maintaining the temperature at 0C. The adduct particles thus formed are recovered by filtering, are washed 3 times at room temperature with 500 ml aliquots of anhydrous hexane and gradually heated by increasing the temperature from 50C to 100C under nitrogen for a period of time sufficient to reduce the alcohol content from 3 moles to 1.5 moles per mole of MgC12. The adduct has a surface area of 9.1 m2/g and a bulk density of 0.564 g/cc.
B) Solid Catalyst Component Preparation The adduct (25 g) is transferred under nitrogen into a reaction vessel equipped with a stirrer and containing 625 ml of TiC14 at 0C under agitation. It is then heated to 100C in 1 hr. When the temperature reaches 40C, diisobutylphthalate is added in an amount such that the k molar ratio of Mg to diisobutylphthalate is 8. The contents of the vessel are heated at 100C for 2 hours with agitation, the agitation is stopped and the solids are allowed to settle. The hot liquid is removed by siphon.
550 ml of TiC14 is added to the solids in the vessel and the mixture heated at 120C for 1 hr. with agitation. The agitation is stopped and the solids are allowed to settle.
The hot liquid is then removed by siphon. The solids are washed 6 times at 60C with 200 ml aliquots of anhydrous hexane, and then 3 times at room temperature. The solids, after being vacuum dried, have a porosity of 0.261 cc/g, a surface area of 66.5 m2~g and a bulk density of 0.44 g/cc.
Examples 1-3 These examples illustrate the heterophasic olefin polymer composition and a method for preparing the polymers.
General Operatin~ Conditions The polymerization runs are conducted under nitrogen in a 22 liter stainless steel autoclave equipped with a helicoid magnetic stirrer and operated at about 90 rpm.
All temperatures, pressures and concentrations of olefin monomers and hydrogen, when present, are constant unless otherwise indicated. The concentration of hydrogen and of the relative monomers is analyzed continuously in gas phase with a process gas chromatograph and fed in order to maintain constant the desired concentration of same.
The polymerization is a batch process conducted in two stages. The first stage comprising the polymerization of the relevant monomer or monomers in liquid propylene and the second stage the copolymerization of ethylene and propylene in gas phase.
In the first stage, the following ingredients in the order in which they are listed are fed into the autoclave at 20C over a period of about 10 minutes: 16 1 of liquid 20~Z402 propylene, appropriate quantities of ethylene and hydrogen, and the catalyst system consisting of 1) the solid catalyst component (about 0.15g) prepared as described above, and 2) a mixture of 75 ml of triethyl aluminum (TEAL) at a 10%
concentration in he~ane and an appropriate quantity of - cyclohexylmethyldimethoxysilane (CMMS) electron donor such that the Al/CMMS molar ratio is 7.5. The catalyst system is pressure fed into the autoclave with propylene.
The temperature is brought to the desired level in about 10 minutes and maintained constant throughout the entire polymerization reaction period. After the established reaction time has passed, essentially all of the unreacted monomer(s) is/are eliminated by degassing at 60C at essentially atmospheric pressure.
In the second stage, the polymer product (a) of the first stage, after taking a sample for the various analyses, is brought to the established temperature for the second stage. Propylene and ethylene are then fed into the autoclave at the ratio and in the quantities established in order to achieve the pressure and the gas phase composition desired. During the polymerization the pressure and gas phase composition are maintained by feeding the propylene and ethylene mixture established by way of instruments which regulate or measure or both regulate and measure the flow rate. The length of the feed varied according to the catalyst system employed and the amount of components b) and c) desired in the particular heterophasic olefin polymer product.
At the end of the second stage polymerization reaction the powder is discharged, stabilized and then oven dried under a nitrogen stream at 60C.
The ingredients and relative operating conditions are set forth in Table IA and the tests results are set forth in Table IB.
- 2~52402 Table lA
~am~les 1 2 3 1st Phase Temperature, C 70 70 70 Pressure, atm. 31 31 31 Time, min. 30 20 30 H2 in gas phase, mol %0.58 0.10 0.30 Ethylene in gas phase, mol % 1.45 2.60 2.50 Ethylene in pol., wt. %3.0 4.3 4.1 Intrinsic Visc., dl/g 2.18 3.09 2.31 Xylene Sol. (Sa), wt. %9.4 9.0 10.7 Ethylene in Xylene Sol.
(Ca), wt. % 11 16 17 Intrinsic Visc. Xylene Sol.(I.V.a), dl/g 1.15 1.39 1.19 2nd Phase Temperature, C 50 50 50 Pressure, atm. 11.3 11.5 11.3 Time, min. 335 500 250 H2 in gas phase, mol %2.23 3.0 2.05 Ethylene in gas phase,15.9 16.9 22.54 mol %
20~2402 Table lB
Examples 1 2 3 Final Product Yield, Kg Pol/g Cat 1116.3 9.9 Comonomer, wt. % 24.6 22.7 29.0 Bipolymer (b)~(c), wt. %70 67 71.8 Intrinsic Visc., dl/g 2.05 2.3 2.34-Xyl. Sol. (Sf), wt. % 63.4 60.5 63.5 Ethylene Xyl. Sol., wt. %
(Cf) 30.2 27.0 34.8 Intrinsic Vis. Xyl. Sol.
I.V.Sf, dl/g 1.83 2.02 2.12 Fraction (b), wt. % 9.45 9.37 11.34 Fraction (c), wt. % 60.55 57.63 60.46 Ethylene frac. (b), wt. %51.9 57.1 53.7 Ethylene frac. (c), wt. %31.I 27.6 35.7 Intrinsicc Vis. frac. (c) (I.V. ), dl/g 1.86 2.05 2.18 Melt Index, C 150 147 145 Flexural modulus, MPa 30 77 82 R.C.I. IZOD at -50C, J/mNBl NB NB
Shore D hardness 24 25 20 Tension Set at 75%, % 41 28 36 Tensile strength, MPa 13.8 15.8 15.4 Tensile strength at yield, 5.0 5.8 4.6 MPa Elongation at break, % 517 925 940 Haze, % 31 34 35 Vitreous transition2,C-25(P) -23(P) -28(P) NB . no break (P) , main peak 20~2402 Examples 4 These examples illustrate a film material of the heterophasic olefin polymer composition and a method for preparing the same.
An air quenched blown film of the heterophasic olefin polymer composition of Example 2 stabilized with 0.25 parts per hundred parts of the olefin polymer composition (pph) octadecyl-3,5-bis(l,l-dimethylethyl)-4-hydroxybenzene propanoate, 0.05 pph tetrakis[methylene(3,5-di-tert-b~tyl-f ~10 4-hydroxyhydrocinnamate)~ methane, 0.06 pph Sandostab P-EPQ
composition, the main component of which is tetrakis(2,4-di-tert-butylphenyl)-4-4'-biphenylene diphosphonite and 0.05 calcium stearate is prepared by charging the composition into a single screw extruder, extruding it through a circular die and blowing it into a film form with a sufficient amount of air to provide a film of 1 mil thickness using the following equipment and processing conditions:
Screw: Compression ratio 3:1 to 4:1.
Polyolefin barrier type L/D
ratio - 24:1 to 30:1.
Blow up ratio - 2.5 to 4.1.
Die gap: 40 mils for a thickness of 0.5 to 5 mils.
Extruder barrel profile: 380 to 430F going from zone 1 to zone 6.
Adapter and die temperatures: 450F except upper and lower die zones which are 460F.
Screw speed: 20 rpm.
Pressure: 3000 psi.
The properties of the resulting film are set forth in Table 2 below.
k Table 2 Resins Properties Example 2 HDPEl LLDPE2 Yield Strength 1347/1126 3757/3145 1799/1739 (MD/CD3),psi Break Strength (MD/CD), 3096/16433960/3216 2092/1898 pSi Elongation at yield65/40 30/7 80/17 (MD/CD~, %
Elongation at break361/417 120/350 317/425 (MD/CD), %
Elemendorf tear, No tear 10/282 350/790 (MD/CD), g/ply Trouser tear, (MD/CD) 152/530 147/1026 503/758 Haze 65.7 76.8 8.7 Gloss 6 10 70 Coefficient of 1.22/0.8150.241/0.1920.688/0.650 friction (static/
kinetic) Moisture vapor trans- 1.340 1.300 mission rates at 100F & 100 relative humidity, g/100 sq.
in/24 hrs.
Dart impact strength, 0.980 0.720 1.020 ft-lb/mil 1 Quantum LR 732 HDPE having a density of 0.953 g/cc3.
2 Dowlex 2045 LLDPE containing hexene-l and having a density of 0.920 g/cc3.
3 MD/CD ~ machine direction/cross direction.
From the above Table one can see that the olefin polymer composition of this invention provides an air quenched blown film with improved elongation at break and Elemendorf tear properties and a better balance of properties. Further, polymer materials, the major portion of which comprise propylene units, generally do not run well, if at all, on air quenched blown film equipment.
Example 5 This example illustrates an cast film material of the heterophasic olefin polymer composition, of a coextruded film of the heterophasic olefin polymer composition and a random copolymer of propylene and ethylene and a method for preparing same.
A cast film of the heterophasic olefin polymer composition of Example 2 stabilized as set forth in Example 4 is prepared by charging the composition into an extruder, extruding it through a flat film die and quenching onto a chill roll to produce a film of 1 mil thickness using the following equipment and processing conditions:
0 Screw design: Compression ratio: 4:1 to 3:1 Feed zone depth: 0.435 to 0.490" (3.5"
extruder with 3.5:1 compression ratio) Metering zone depth: 0.125 to 0.140" for 3.5"
extruder 5 Die: Convention center-fed coathanger manifold.
Extruder operating conditions:
Melt temperature: 430-500F
E~truder Barrel: 350-420F going from zone 1 to zone 6.
Adapter and die temperatures: 420F
A coe~truded film 1.25 mils thick comprising a film layer of the heterophasic olefin polymer composition of Example 2 stabilized as set forth in Example 4 as the center layer, and two film layers of Pro-fa ~SA 861 propylene-ethylene random copolymer with an ethylene ~t~ k content of 3.0%, one layer of said copolymer on each surface of the center layer is prepared by the cast film technique.
The properties of the resulting film are set forth in Table 3 below.
Tahle 3 Resi~
Properties Ex. 2 Coesl p-E Co2 Yield Strength 118S/865 1095/817 2523/2452 (MD/CD3), psi Break Strength (MD/CD), 3899/1708 3637/1693 4120/3363 psi Elongation at yield 34/19 32/22 15/10 (MD/CD), %
Elongation at break~450/>550 ,530/,550 522/584 (MD/CD), %
Elemendorf tear, 192/No 657/544 49/102 (MD/CD), g/ply Tear Haze 49.0 5.2 2.3 Gloss 20.0 57.0 78.1 1 Propylene-ethylene random copolymer/Heterophasic olefin polymer composition of E~. 2/Propylene-ethylene random copolymer.
2 Pro-fa~ 861 propylene-ethylene random copolymer with an ethylene content of 3.0%.
3 MD/CD . machine direction/cross direction.
From the above Table one can see that the olefin polymer composition of this invention provides an cast film and a coextruded cast filme with improved elongation at yield and Elemendorf tear properties.
2~402 Various types of film materials of conventional thickness and thin films less than 20 mils thick to as thin as about 0.5 mils can be prepared using the heterophasic olefin polymer composition described herein as well as heavy film materials, typically referred to as sheets, from 20 to 100 mils thick. For e~ample, it can be used to prepare cast films, uniaxially and biaxially oriented films and extruded or calendared sheets. In addition, a layer comprising the heterophasic olefin polymer composition can be applied to, e.g. by lamination or coextrusion techniques, at least one surface of a thermoplastic film material or a metallic sheet or foil substrate. Typical thermoplastic materials include crystalline homopolymers of a C2 10 alpha-olefin monomer, such as propylene or ethylene, or copolymers of propylene with ethylene or with a C4 10 alpha-olefin monomers or of propylene with both ethylene and a C4 10 alpha-olefin monomers, provided that, when the comonomer is ethylene, the maximum polymerized ethylene content is about 10%, preferably about 4%, and when the comonomer is a C4 10 olefin, the maximum polymerized content thereof is about 20%, preferably about 16%, and when both ethylene and an alpha-olefin are used the ma~imum polymerized content of both is 30%, preferably 20%, as well as polyesters, polyamides, ethylene-vinyl alcohol copolymers and ethylene-vinyl acetate copolymers.
Aluminum is a suitable metallic substrate.
In addition, film materials can be prepared from blends of from about 5 to 45% of the heterophasic olefin polymer composition described herein with from about 95 to 55% of a crystalline homopolymer of a C2 10 alpha-olefin monomer or copolymer of propylene with ethylene or with a C4 10 alpha-olefin monomer or of propylene, ethylene and a C4 10 alpha-olefin monomer, said copolymer having the ma~imum polymerized content of ethylene or alpha-olefin or both as described in the preceding paragraph. Preferably the amount of the heterophasic olefin polymer composition present in such blends is from 10 to 30%.
The olefin polymer composition of this invention is such that one can achieve the proper balance of properties in the resulting product when a film layer of same is the material applied to at least one surface of another thermoplastic material or to a metallic substrate and when it is blended with another thermoplastic material and the blend is used to make film materials.
Other features, advantages and embodiments of the invention disclosed herein will be readily apparent to those exercising ordinary skill after reading the foregoing disclosures. In this regard, while specific embodiments of the invention have been described in considerable detail, variations and modifications of these embodiments can be effected without departing from the spirit and scope of the invention as described and claimed.
From the above Table one can see that the olefin polymer composition of this invention provides an air quenched blown film with improved elongation at break and Elemendorf tear properties and a better balance of properties. Further, polymer materials, the major portion of which comprise propylene units, generally do not run well, if at all, on air quenched blown film equipment.
Example 5 This example illustrates an cast film material of the heterophasic olefin polymer composition, of a coextruded film of the heterophasic olefin polymer composition and a random copolymer of propylene and ethylene and a method for preparing same.
A cast film of the heterophasic olefin polymer composition of Example 2 stabilized as set forth in Example 4 is prepared by charging the composition into an extruder, extruding it through a flat film die and quenching onto a chill roll to produce a film of 1 mil thickness using the following equipment and processing conditions:
0 Screw design: Compression ratio: 4:1 to 3:1 Feed zone depth: 0.435 to 0.490" (3.5"
extruder with 3.5:1 compression ratio) Metering zone depth: 0.125 to 0.140" for 3.5"
extruder 5 Die: Convention center-fed coathanger manifold.
Extruder operating conditions:
Melt temperature: 430-500F
E~truder Barrel: 350-420F going from zone 1 to zone 6.
Adapter and die temperatures: 420F
A coe~truded film 1.25 mils thick comprising a film layer of the heterophasic olefin polymer composition of Example 2 stabilized as set forth in Example 4 as the center layer, and two film layers of Pro-fa ~SA 861 propylene-ethylene random copolymer with an ethylene ~t~ k content of 3.0%, one layer of said copolymer on each surface of the center layer is prepared by the cast film technique.
The properties of the resulting film are set forth in Table 3 below.
Tahle 3 Resi~
Properties Ex. 2 Coesl p-E Co2 Yield Strength 118S/865 1095/817 2523/2452 (MD/CD3), psi Break Strength (MD/CD), 3899/1708 3637/1693 4120/3363 psi Elongation at yield 34/19 32/22 15/10 (MD/CD), %
Elongation at break~450/>550 ,530/,550 522/584 (MD/CD), %
Elemendorf tear, 192/No 657/544 49/102 (MD/CD), g/ply Tear Haze 49.0 5.2 2.3 Gloss 20.0 57.0 78.1 1 Propylene-ethylene random copolymer/Heterophasic olefin polymer composition of E~. 2/Propylene-ethylene random copolymer.
2 Pro-fa~ 861 propylene-ethylene random copolymer with an ethylene content of 3.0%.
3 MD/CD . machine direction/cross direction.
From the above Table one can see that the olefin polymer composition of this invention provides an cast film and a coextruded cast filme with improved elongation at yield and Elemendorf tear properties.
2~402 Various types of film materials of conventional thickness and thin films less than 20 mils thick to as thin as about 0.5 mils can be prepared using the heterophasic olefin polymer composition described herein as well as heavy film materials, typically referred to as sheets, from 20 to 100 mils thick. For e~ample, it can be used to prepare cast films, uniaxially and biaxially oriented films and extruded or calendared sheets. In addition, a layer comprising the heterophasic olefin polymer composition can be applied to, e.g. by lamination or coextrusion techniques, at least one surface of a thermoplastic film material or a metallic sheet or foil substrate. Typical thermoplastic materials include crystalline homopolymers of a C2 10 alpha-olefin monomer, such as propylene or ethylene, or copolymers of propylene with ethylene or with a C4 10 alpha-olefin monomers or of propylene with both ethylene and a C4 10 alpha-olefin monomers, provided that, when the comonomer is ethylene, the maximum polymerized ethylene content is about 10%, preferably about 4%, and when the comonomer is a C4 10 olefin, the maximum polymerized content thereof is about 20%, preferably about 16%, and when both ethylene and an alpha-olefin are used the ma~imum polymerized content of both is 30%, preferably 20%, as well as polyesters, polyamides, ethylene-vinyl alcohol copolymers and ethylene-vinyl acetate copolymers.
Aluminum is a suitable metallic substrate.
In addition, film materials can be prepared from blends of from about 5 to 45% of the heterophasic olefin polymer composition described herein with from about 95 to 55% of a crystalline homopolymer of a C2 10 alpha-olefin monomer or copolymer of propylene with ethylene or with a C4 10 alpha-olefin monomer or of propylene, ethylene and a C4 10 alpha-olefin monomer, said copolymer having the ma~imum polymerized content of ethylene or alpha-olefin or both as described in the preceding paragraph. Preferably the amount of the heterophasic olefin polymer composition present in such blends is from 10 to 30%.
The olefin polymer composition of this invention is such that one can achieve the proper balance of properties in the resulting product when a film layer of same is the material applied to at least one surface of another thermoplastic material or to a metallic substrate and when it is blended with another thermoplastic material and the blend is used to make film materials.
Other features, advantages and embodiments of the invention disclosed herein will be readily apparent to those exercising ordinary skill after reading the foregoing disclosures. In this regard, while specific embodiments of the invention have been described in considerable detail, variations and modifications of these embodiments can be effected without departing from the spirit and scope of the invention as described and claimed.
Claims (24)
1. A thermoplastic film or sheet made of a heterophasic olefin polymer composition which is comprised of:
(a) from about 10 to 50 parts of a propylene homo-polymer having an isotactic index greater than 80, or a copolymer selected from the group consisting of (i) propylene and ethylene, (ii) propylene, ethylene and a CH2=CHR alpha-olefin, where R is a C2-8 straight or branched alkyl, and (iii) propylene and an alpha-olefin as defined in (ii), the copolymer containing over 80% propylene and having an isotactic index greater than 80;
(b) from about 5 to 20 parts of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of about 20 to 60% wherein the copolymer is selected from the group consisting of (i) ethylene and propylene containing over 55%
ethylene, (ii) ethylene, propylene, and an alpha-olefin as defined in (a) (ii) containing from 1 to 10% of the alpha-olefin and over 55% of both ethylene and alpha-olefin, and (iii) ethylene and an alpha-olefin as defined in (a) (ii) containing over 55% of the alpha-olefin, which copolymer is insoluble in xylene at room or ambient temperature; and (c) from about 40 to 80 parts of a copolymer fraction wherein the copolymer is selected from the group consisting of (i) ethylene and propylene containing from 20% to less than 40% ethylene, (ii) ethylene, propylene, and an alpha-olefin as defined in (a) (ii) wherein the alpha-olefin is present in an amount of 1 to 10% and the amount of ethylene and alpha-olefin present is from 20% to less than 40%, and (iii) ethylene and an alpha-olefin as defined in (a) (ii) containing from 20% to less than 40% of the alpha-olefin, and optionally with 0.5 to 10% of a diene, said copolymer fraction being soluble in xylene at ambient temperature, and having an intrinsic viscosity of from 1.5 to 4.0 dl/g with the total of the (b) and (c) fractions, based on the total olefin polymer composition, being from about 50% to 90%, and the weight ratio of (b)/(c) being less than 0.4.
(a) from about 10 to 50 parts of a propylene homo-polymer having an isotactic index greater than 80, or a copolymer selected from the group consisting of (i) propylene and ethylene, (ii) propylene, ethylene and a CH2=CHR alpha-olefin, where R is a C2-8 straight or branched alkyl, and (iii) propylene and an alpha-olefin as defined in (ii), the copolymer containing over 80% propylene and having an isotactic index greater than 80;
(b) from about 5 to 20 parts of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of about 20 to 60% wherein the copolymer is selected from the group consisting of (i) ethylene and propylene containing over 55%
ethylene, (ii) ethylene, propylene, and an alpha-olefin as defined in (a) (ii) containing from 1 to 10% of the alpha-olefin and over 55% of both ethylene and alpha-olefin, and (iii) ethylene and an alpha-olefin as defined in (a) (ii) containing over 55% of the alpha-olefin, which copolymer is insoluble in xylene at room or ambient temperature; and (c) from about 40 to 80 parts of a copolymer fraction wherein the copolymer is selected from the group consisting of (i) ethylene and propylene containing from 20% to less than 40% ethylene, (ii) ethylene, propylene, and an alpha-olefin as defined in (a) (ii) wherein the alpha-olefin is present in an amount of 1 to 10% and the amount of ethylene and alpha-olefin present is from 20% to less than 40%, and (iii) ethylene and an alpha-olefin as defined in (a) (ii) containing from 20% to less than 40% of the alpha-olefin, and optionally with 0.5 to 10% of a diene, said copolymer fraction being soluble in xylene at ambient temperature, and having an intrinsic viscosity of from 1.5 to 4.0 dl/g with the total of the (b) and (c) fractions, based on the total olefin polymer composition, being from about 50% to 90%, and the weight ratio of (b)/(c) being less than 0.4.
2. The film or sheet of claim 1, wherein component (a) is a copolymer of propylene and ethylene.
3. The film or sheet of claim 1, wherein component (c) is a copolymer of propylene and ethylene.
4. The film or sheet of claim 1, wherein component (c) is a terpolymer of propylene, ethylene and butene-1.
5. The film or sheet of claim 1, wherein component (a) is a copolymer of propylene and butene-1.
6. The film or sheet of claim 3, wherein component (a) is a copolymer of propylene and butene-1.
7. The film or sheet of claim 4, wherein component (a) is a copolymer of propylene and butene-1.
8. The film or sheet of claim 5, wherein the total content of copolymerized ethylene in the heterophasic olefin polymer composition is from 15% to 35% by weight.
9. The film or sheet of claim 6, wherein the total content of copolymerized ethylene in the heterophasic olefin polymer composition is from 15% to 35% by weight.
10. The film or sheet of claim 7, wherein the total content of copolymerized ethylene in the heterophasic olefin polymer composition is from 15% to 35% by weight.
11. A film or sheet article comprising:
a thermoplastic base film or sheet of a crystalline homopolymer of a C2-10 alpha-olefin monomer or of a copolymer selected from the group consisting of (i) propylene with ethylene, (ii) propylene with ethylene and a C4-10 alpha-olefin monomer, and (iii) propylene with a C4-10 alpha-olefin monomer, provided that, when the comonomer is ethylene, the maximum polymerized ethylene content is about 10%, when the comonomer is a C4-10 olefin, the maximum polymerized content thereof is about 20%, and when both ethylene and a C4-10 olefin are used, the maximum polymerized content thereof is about 30%; and, applied to at least one surface of the base film or sheet, the film or sheet of claim 1.
a thermoplastic base film or sheet of a crystalline homopolymer of a C2-10 alpha-olefin monomer or of a copolymer selected from the group consisting of (i) propylene with ethylene, (ii) propylene with ethylene and a C4-10 alpha-olefin monomer, and (iii) propylene with a C4-10 alpha-olefin monomer, provided that, when the comonomer is ethylene, the maximum polymerized ethylene content is about 10%, when the comonomer is a C4-10 olefin, the maximum polymerized content thereof is about 20%, and when both ethylene and a C4-10 olefin are used, the maximum polymerized content thereof is about 30%; and, applied to at least one surface of the base film or sheet, the film or sheet of claim 1.
12. A film or sheet article comprising:
a thermoplastic base film or sheet of a crystalline homopolymer of a C2-10 alpha-olefin monomer or of a copolymer selected from the group consisting of (i) propylene with ethylene, (ii) propylene with ethylene and a C4-10 alpha-olefin monomer, and (iii) propylene with a C4-10 alpha-olefin monomer, provided that, when the comonomer is ethylene, the maximum polymerized ethylene content is about 10%, when the comonomer is a C4-10 olefin, the maximum polymerized content thereof is about 20%, and when both ethylene and a C4-10 olefin are used, the maximum polymerized content thereof is about 30%; and, applied to at least one surface of the base film or sheet, the film or sheet of claim 6.
a thermoplastic base film or sheet of a crystalline homopolymer of a C2-10 alpha-olefin monomer or of a copolymer selected from the group consisting of (i) propylene with ethylene, (ii) propylene with ethylene and a C4-10 alpha-olefin monomer, and (iii) propylene with a C4-10 alpha-olefin monomer, provided that, when the comonomer is ethylene, the maximum polymerized ethylene content is about 10%, when the comonomer is a C4-10 olefin, the maximum polymerized content thereof is about 20%, and when both ethylene and a C4-10 olefin are used, the maximum polymerized content thereof is about 30%; and, applied to at least one surface of the base film or sheet, the film or sheet of claim 6.
13. A film or sheet article comprising:
a thermoplastic base film or sheet of a crystalline homopolymer of a C2-10 alpha-olefin monomer or of a copolymer selected from the group consisting of (i) propylene with ethylene, (ii) propylene with ethylene and a C4-10 alpha-olefin monomer, and (iii) propylene with a C4-10 alpha-olefin monomer, provided that, when the comonomer is ethylene, the maximum polymerized ethylene content is about 10%, when the comonomer is a C4-10 olefin, the maximum polymerized content thereof is about 20%, and when both ethylene and a C4-10 olefin are used, the maximum polymerized content thereof is about 30%; and applied to at least one surface of the base film or sheet, the film or sheet of claim 7.
a thermoplastic base film or sheet of a crystalline homopolymer of a C2-10 alpha-olefin monomer or of a copolymer selected from the group consisting of (i) propylene with ethylene, (ii) propylene with ethylene and a C4-10 alpha-olefin monomer, and (iii) propylene with a C4-10 alpha-olefin monomer, provided that, when the comonomer is ethylene, the maximum polymerized ethylene content is about 10%, when the comonomer is a C4-10 olefin, the maximum polymerized content thereof is about 20%, and when both ethylene and a C4-10 olefin are used, the maximum polymerized content thereof is about 30%; and applied to at least one surface of the base film or sheet, the film or sheet of claim 7.
14. A film or sheet article comprising a base film or sheet of a metallic substrate having applied to at least one surface thereof the film or sheet of claim 1.
15. A film or sheet article comprising a base film or sheet of a metallic substrate having applied to at least one surface thereof the film or sheet of claim 6.
16. A film or sheet article comprising a base film or sheet of a metallic substrate having applied to at least one surface thereof the film or sheet of claim 7.
17. A thermoplastic film or sheet made of a blend of:
(1) from about 5 to 45% a heterophasic olefin polymer composition which is comprised of:
(a) from about 10 to 50 parts of a propylene homopolymer having an isotactic index greater than 80, or a copolymer selected from the group consisting of (i) propylene and ethylene, (ii) propylene, ethylene and a CH2=CHR alpha-olefin, where R is a C2-8 straight or branched alkyl, and (iii) propylene and an alpha-olefin as defined in (ii), said copolymer containing over 80% propylene and having an isotactic index greater than 80;
(b) from about 5 to 20 parts of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of about 20 to 60% wherein the copolymer is selected from the group consisting of (i) ethylene and propylene containing over 55% ethylene, (ii) ethylene, propylene, and an -27a-alpha-olefin as defined in (a) (ii) containing from 1 to 10% of the alpha-olefin and over 55% of both ethylene and alpha-olefin, and (iii) ethylene and an alpha-olefin as defined in (a) (ii) containing over 55% of said alpha-olefin, which copolymer is insoluble in xylene at room or ambient temperature;
and (c) from about 40 to 80 parts of a copolymer fraction wherein the copolymer is selected from the group consisting of (i) ethylene and propylene containing from 20% to less than 40% ethylene, (ii) ethylene, propylene, and an alpha-olefin as defined in (a) (ii) wherein the alpha-olefin is present in an amount of 1 to 10% and the amount of ethylene and alpha-olefin present is from 20% to less than 40%, and (iii) ethylene and an alpha-olefin as defined in (a) (ii) containing from 20% to less than 40% of said alpha-olefin, and optionally with 0.5 to 10 % of a diene, said copolymer fraction being soluble in xylene at ambient temperature, and having an intrinsic viscosity of from 1.5 to 4.0 dl/g;
with the total of the (b) and (c) fractions, based on the total olefin polymer composition, being from about 50% to 90%, and the weight ratio of (b)/(c) being less than 0.4; and (2) from about 95 to 55% of a crystalline homo-polymer of a C2-10 alpha-olefin monomer or of a copolymer selected from the group consisting of (i) propylene with ethylene, (ii) propylene with ethylene and a C4-10 alpha-olefin monomer and (iii) propylene with a C4-10 alpha-olefin monomer, provided that, when the comonomer is ethylene, the maximum polymerized ethylene content is about 10%, when the comonomer is a C4-10 alpha-olefin monomer, the maximum polymerized content is about 20% and when the comonomers are ethylene and a C4-10 alpha-olefin monomer, the maximum polymerized content of both is about 30%.
(1) from about 5 to 45% a heterophasic olefin polymer composition which is comprised of:
(a) from about 10 to 50 parts of a propylene homopolymer having an isotactic index greater than 80, or a copolymer selected from the group consisting of (i) propylene and ethylene, (ii) propylene, ethylene and a CH2=CHR alpha-olefin, where R is a C2-8 straight or branched alkyl, and (iii) propylene and an alpha-olefin as defined in (ii), said copolymer containing over 80% propylene and having an isotactic index greater than 80;
(b) from about 5 to 20 parts of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of about 20 to 60% wherein the copolymer is selected from the group consisting of (i) ethylene and propylene containing over 55% ethylene, (ii) ethylene, propylene, and an -27a-alpha-olefin as defined in (a) (ii) containing from 1 to 10% of the alpha-olefin and over 55% of both ethylene and alpha-olefin, and (iii) ethylene and an alpha-olefin as defined in (a) (ii) containing over 55% of said alpha-olefin, which copolymer is insoluble in xylene at room or ambient temperature;
and (c) from about 40 to 80 parts of a copolymer fraction wherein the copolymer is selected from the group consisting of (i) ethylene and propylene containing from 20% to less than 40% ethylene, (ii) ethylene, propylene, and an alpha-olefin as defined in (a) (ii) wherein the alpha-olefin is present in an amount of 1 to 10% and the amount of ethylene and alpha-olefin present is from 20% to less than 40%, and (iii) ethylene and an alpha-olefin as defined in (a) (ii) containing from 20% to less than 40% of said alpha-olefin, and optionally with 0.5 to 10 % of a diene, said copolymer fraction being soluble in xylene at ambient temperature, and having an intrinsic viscosity of from 1.5 to 4.0 dl/g;
with the total of the (b) and (c) fractions, based on the total olefin polymer composition, being from about 50% to 90%, and the weight ratio of (b)/(c) being less than 0.4; and (2) from about 95 to 55% of a crystalline homo-polymer of a C2-10 alpha-olefin monomer or of a copolymer selected from the group consisting of (i) propylene with ethylene, (ii) propylene with ethylene and a C4-10 alpha-olefin monomer and (iii) propylene with a C4-10 alpha-olefin monomer, provided that, when the comonomer is ethylene, the maximum polymerized ethylene content is about 10%, when the comonomer is a C4-10 alpha-olefin monomer, the maximum polymerized content is about 20% and when the comonomers are ethylene and a C4-10 alpha-olefin monomer, the maximum polymerized content of both is about 30%.
18. The film or sheet of claim 17, wherein component (1) (a) is a copolymer of propylene and ethylene and component (1) (c) is a terpolymer of propylene, ethylene and butene-1.
19. The film or sheet of claim 17, wherein component (1) (a) is a copolymer of propylene and butene-1 and component (1) (c) is a copolymer of propylene and ethylene.
20. The film or sheet of claim 19, wherein component (1) is present in an amount from 10 to 30%.
21. The film or sheet of any one of claims 1 through 10, wherein the heterophasic olefin polymer composition has at least one peak, determined by differential scanning calorimetry (DSC), present at a temperature higher than 120°C and at least one peak, relative to a vitreous transition, present at a temperature from -10°C to -35°C; and wherein the heterophasic olefin polymer composition has a flexural modulus of from 20 to 150 MPa, a tensile strength at yield of from 10 to 20 MPa, an elongation at break over 400%, a tension at 75% strain of from 20% to 50% and a Shore D hardness of from 20 to 35 and does not break when an IZOD impact test is conducted at -50°C.
22. The film or sheet article of any one of claims 11 through 13, wherein the heterophasic olefin polymer composition, of which the film or sheet applied to the base film or sheet is made, has at least one peak, determined by differential scanning calorimetry (DSC), present at a temperature higher than 120°C and at least one peak, relative to a vitreous transition, present at a temperature from -10°C to -35°C; and wherein the heterophasic olefin polymer composition has a flexural modulus of from 20 to 150 MPa, a tensile strength at yield of from 10 to 20 MPa, an elongation at break over 400%, a tension at 75%
strain of from 20% to 50% and a Shore D hardness of from 20 to 35 and does not break when an IZOD impact test is conducted at -50°C.
strain of from 20% to 50% and a Shore D hardness of from 20 to 35 and does not break when an IZOD impact test is conducted at -50°C.
23. The film or sheet article of any one of claims 14 through 16, wherein the metallic substrate is made of aluminum;
wherein the heterophasic olefin polymer composition, of which the film or sheet applied to the surface of the metallic substrate is made, has at least one peak, determined by differential scanning calorimetry (DSC), present at a tempera-ture hlgher than 120°C and at least one peak, relative to a vitreous transition, present at a temperature from -10°C to -35°C; and wherein the heterophasic olefin polymer composition has a flexural modulus of from 20 to 150 MPa, a tensile strength at yield of from 10 to 20 MPa, an elongation at break over 400%, a tension at 75% strain of from 20% to 50% and a Shore D
hardness of from 20 to 35 and does not break when an IZOD impact test is conducted at -50°C.
wherein the heterophasic olefin polymer composition, of which the film or sheet applied to the surface of the metallic substrate is made, has at least one peak, determined by differential scanning calorimetry (DSC), present at a tempera-ture hlgher than 120°C and at least one peak, relative to a vitreous transition, present at a temperature from -10°C to -35°C; and wherein the heterophasic olefin polymer composition has a flexural modulus of from 20 to 150 MPa, a tensile strength at yield of from 10 to 20 MPa, an elongation at break over 400%, a tension at 75% strain of from 20% to 50% and a Shore D
hardness of from 20 to 35 and does not break when an IZOD impact test is conducted at -50°C.
24. The film or sheet of any one of claims 17 through 20, wherein the heterophasic olefin polymer composition has at least one peak, determined by differential scanning calorimetry (DSC), present at a temperature higher than 120°C and at least one peak, relative to a vitreous transition, present at a temperature from -10°C to -35°C; and wherein the heterophasic olefin polymer composition has a flexural modulus of from 20 to 150 MPa, a tensile strength at yield of from 10 to 20 MPa, an elongation at break over 400%, a tension at 75% strain of from 20% to 50% and a Shore D hardness of from 20 to 35 and does not break when an IZOD impact test is conducted at -50°C.
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US07/749,055 US5212246A (en) | 1990-09-28 | 1991-08-27 | Olefin polymer films |
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1991
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- 1991-09-11 EP EP91115353A patent/EP0477662B1/en not_active Expired - Lifetime
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- 1991-09-11 DE DE1991607558 patent/DE69107558T2/en not_active Expired - Lifetime
- 1991-09-11 DK DK91115353T patent/DK0477662T3/en active
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- 1991-09-26 PT PT99093A patent/PT99093A/en not_active Application Discontinuation
- 1991-09-26 AU AU84793/91A patent/AU653550B2/en not_active Ceased
- 1991-09-27 CA CA 2052402 patent/CA2052402C/en not_active Expired - Fee Related
- 1991-09-27 BR BR9104180A patent/BR9104180A/en not_active IP Right Cessation
- 1991-09-27 KR KR1019910016854A patent/KR0157637B1/en not_active IP Right Cessation
- 1991-09-27 FI FI914560A patent/FI104830B/en active
- 1991-09-27 CS CS912964A patent/CS296491A3/en unknown
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1993
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1998
- 1998-02-26 KR KR1019980006046A patent/KR0157762B1/en not_active IP Right Cessation
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