CN108779307B - 丙烯聚合物组合物 - Google Patents
丙烯聚合物组合物 Download PDFInfo
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- CN108779307B CN108779307B CN201780019040.2A CN201780019040A CN108779307B CN 108779307 B CN108779307 B CN 108779307B CN 201780019040 A CN201780019040 A CN 201780019040A CN 108779307 B CN108779307 B CN 108779307B
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- propylene
- xylene
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- polymerization
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- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 229920001155 polypropylene Polymers 0.000 title claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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
- 239000005977 Ethylene Substances 0.000 claims abstract description 19
- 229920001384 propylene homopolymer Polymers 0.000 claims abstract description 5
- 229920005606 polypropylene copolymer Polymers 0.000 claims abstract description 4
- 239000000155 melt Substances 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 17
- 238000006116 polymerization reaction Methods 0.000 description 39
- 150000001875 compounds Chemical class 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VFIOZKTXVHLWRA-UHFFFAOYSA-N (2-ethylpiperidin-1-yl)-dimethoxy-(1,1,1-trifluoropropan-2-yl)silane Chemical compound CCC1CCCCN1[Si](OC)(OC)C(C)C(F)(F)F VFIOZKTXVHLWRA-UHFFFAOYSA-N 0.000 description 1
- QPFMBZIOSGYJDE-QDNHWIQGSA-N 1,1,2,2-tetrachlorethane-d2 Chemical compound [2H]C(Cl)(Cl)C([2H])(Cl)Cl QPFMBZIOSGYJDE-QDNHWIQGSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- HRAQMGWTPNOILP-UHFFFAOYSA-N 4-Ethoxy ethylbenzoate Chemical compound CCOC(=O)C1=CC=C(OCC)C=C1 HRAQMGWTPNOILP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(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 JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 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
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZQAWBRRSQKDOEL-UHFFFAOYSA-J chloro(diethyl)alumane;trichlorotitanium Chemical compound Cl[Ti](Cl)Cl.CC[Al](Cl)CC ZQAWBRRSQKDOEL-UHFFFAOYSA-J 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- VJYNTADJZPKUAF-UHFFFAOYSA-N diethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](C)(OCC)CCC(F)(F)F VJYNTADJZPKUAF-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- BTJCEVZMRIJBSM-UHFFFAOYSA-N dimethoxy-methyl-(1,1,1-trifluoropropan-2-yl)silane Chemical compound CO[Si](C)(OC)C(C)C(F)(F)F BTJCEVZMRIJBSM-UHFFFAOYSA-N 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 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
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C08F297/083—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 the monomers being ethylene or propylene
-
- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
- C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/651—Pretreating with non-metals or metal-free compounds
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
一种丙烯组合物，其包含(重量百分比)：A)70％至95％的丙烯均聚物，其多分散指数(P.I.)值为4.6至10，在25℃下不溶于二甲苯的部分高于90％，和MFR(根据ISO 1133，条件L，即230℃和2.16kg载荷的熔体流动速率)为47至90g/10min；B)5％至30％丙烯的共聚物，其含有40％至34.5％包括端值的乙烯衍生单元；该组合物在25℃下可溶于二甲苯的部分的特性粘度为3至5dl/g。
Description
技术领域
本发明涉及一种丙烯聚合物组合物，其具有最佳的平衡性能，特别是在0°时改善的冲击强度。
背景技术
众所周知，全同立构聚丙烯具有卓越的优异性能组合，这使其适用于非常多的用途。为了改善所述性能，丙烯有规立构均聚方法中已引入了一个或多个共聚步骤，或均聚物基质中已引入或一种或多种单体。
WO 05/014713涉及一种多相聚烯烃组合物，其包含(重量百分比)：
1)65-95％的结晶丙烯聚合物，其选自丙烯均聚物和丙烯与0.1-10％的α-烯烃的无规聚合物，α-烯烃选自乙烯、C4-C10α-烯烃及其混合物，所述聚合物在环境温度下不溶于二甲苯的量超过85％，且多分散指数为4至13、优选为4.5至12、更优选为5-9，特性粘度值超过2.2dl/g、优选为2.2至4.5dl/g；和
2)5-35％的弹性烯烃聚合物，其为乙烯与C3-C10α-烯烃和任选的二烯的聚合物，其中乙烯含量为15-85％，特性粘度值至少为1.4dl/g，优选为2.5至5dl/g。
发明内容
申请人发现，通过使用特定种类的丙烯组合物，可以实现改善的性能，特别是在0℃下的冲击强度方面。
本发明的目的是提供一种丙烯聚合物组合物，其包含：
A)60wt％至75wt％的丙烯均聚物，其多分散指数(P.I.)值为4.3至4.9，在25℃下不溶于二甲苯的部分高于95％，和MFR(根据ISO 1133，条件L，即230℃和2.16kg载荷的熔体流动速率)范围为20至75g/10min；
B)25wt％至40wt％的共聚物，其为丙烯与46.0wt％至49.0wt％乙烯衍生单元的共聚物；
该组合物在25℃下可溶于二甲苯的部分的特性粘度为2.2至2.9dl/g；且关系式：
10.7+1.3×MFRa-17.7×P.I.-29.3×IV+4.9×Xs (I)
在40和66之间；其中，
MFRa是组分A)的熔体流动速率(根据ISO 1133，条件L，即230℃和2.16kg载荷的熔体流动速率)
P.I.是组分A)的多分散指数；
IV是在25℃下可溶于二甲苯的部分的特性粘度；和
Xs是在25℃下可溶于二甲苯的部分。
并且其中A+B的量等于100wt％。
具体实施方式
本发明的目的是提供一种丙烯聚合物组合物，其包含：
A)60wt％至75wt％，优选62wt％至72wt％，更优选63wt％至71wt％的丙烯均聚物，其多分散指数(P.I.)值为4.3至4.9，优选为4.4至4.9，在25℃下不溶于二甲苯的部分高于95％，更优选高于97wt％，和MFR(根据ISO 1133，条件L，即230℃和2.16kg载荷的熔体流动速率)范围为20至75g/10min，特别是25至70g/10min；
B)25wt％至40wt％，优选28wt％至38wt％，更优选29wt％至37wt％的共聚物，其为丙烯与46.0wt％至49.0wt％，优选47.0wt％至48.5wt％乙烯衍生单元的共聚物；
该组合物在25℃下可溶于二甲苯的部分的特性粘度在2.2和2.9dl/g之间，优选为在2.4和2.9dl/g之间，并且在25℃下可溶于二甲苯的部分，Xs，在25.0wt％和34.0wt％之间；优选为26.5wt％和32.5wt％之间；并且其中以下关系式(I)：
10.7+1.3×MFRa-17.7×P.I.-29.3×IV+4.9×Xs(I) (I)
的结果在40和66之间，优选在45和60之间；更优选地在50和55之间；其中
MFRa是组分A)的熔体流动速率(根据ISO 1133，条件L，即230℃和2.16kg载荷的熔体流动速率)
P.I.是组分A)的多分散指数；
IV是在25℃下可溶于二甲苯的部分的特性粘度；和
Xs是组合物在25℃下可溶于二甲苯的部分；
并且其中A+B的量等于100wt％。
从以上定义可以明显看出，术语“共聚物”限于仅含有丙烯和乙烯的聚合物。
本发明的丙烯组合物在0℃下显示出高的IZOD值，其高于40KJ/m2，优选高于45KJ/m2。这是由于关系式(I)导致的各种特征的特定平衡。鉴于这些值，本发明的丙烯组合物特别适用于注塑制品，特别是在低温下使用的注塑容器。
本发明的丙烯聚合物组合物通过至少两个阶段的顺序聚合制备，随后的每个聚合阶段在前一个聚合反应中形成的聚合材料的存在下进行，其中共聚物(A)通常在至少一个第一聚合阶段制备，共聚物(B)通常在至少一个第二聚合阶段制备。
优选地，每个聚合阶段在高度立体定向的多相齐格勒-纳塔催化剂存在下进行。适用于制备本发明的丙烯聚合物组合物的齐格勒-纳塔催化剂包含固体催化剂组分，该固体催化剂组分包含至少一种具有至少一个钛-卤键的钛化合物和至少一种电子给体化合物(内给体)，两者均负载在氯化镁上。齐格勒-纳塔催化剂体系进一步包含有机铝化合物作为必要的助催化剂和任选的外电子给体化合物。
在欧洲专利EP45977、EP361494、EP728769、EP 1272533和国际专利申请W000163261中描述了合适的催化剂体系。
优选地，固体催化剂组分包含Mg、Ti、卤素和选自式(I)的琥珀酸酯的电子给体：
其中基团R1和R2彼此相同或不同，为C1-C20直链或支链烷基、烯基、环烷基、芳基、芳烷基或烷芳基，任选地含有属于元素周期表第15-17族的杂原子；基团R3至R6彼此相同或不同，为氢或C1-C2直链或支链烷基、烯基、环烷基、芳基、芳烷基或烷芳基，任选地含有杂原子，以及结合至相同碳原子的基团R3至R6可以连接在一起形成环。
R1和R2优选为C1-C8烷基、环烷基、芳基、芳烷基和烷芳基。
特别优选的是其中R1和R2选自伯烷基，特别是支链伯烷基的化合物。合适的R1和R2基团的实例是甲基、乙基、正丙基、正丁基、异丁基、新戊基、2-乙基己基。特别优选的是乙基、异丁基和新戊基。
由式(I)描述的优选的一组化合物是其中R3至R5为氢且R6为具有3至10个碳原子的支链烷基、环烷基、芳基、芳烷基和烷芳基。式(I)中的另一组优选化合物是其中R3至R6中的至少两个基团不同于氢并且选自C1-C20直链或支链烷基、烯基、环烷基、芳基、芳烷基或烷芳基，任选地含有属于族的杂原子。
特别优选的是其中两个不同于氢的基团与相同碳原子连接的化合物。此外，化合物中连接至不同碳原子的至少两个不同于氢的基团，特别优选R3和R5或R4和R6。
根据优选的方法，固体催化剂组分可以通过使式Ti(OR)n-yXy的钛化合物，其中n是钛的化合价，y是1和n之间的数，优选TiC4，与衍生自式MgCl2·pROH的加合物的氯化镁反应来制备，其中p为0.1至6，优选为2至3.5，R为具有1-18个碳原子的烃基。通过在与加合物不混溶的惰性烃存在下混合醇和氯化镁，在加合物的熔融温度(100-130”C)的搅拌条件下操作，可以适当地制备球形加合物。然后，乳液快速淬火，从而使加合物以球形颗粒的形式固化。根据该方法制备的球形加合物的实例描述于US4,399,054和US 4,469,648中。这样得到的加合物可直接与Ti化合物反应或它可以预先经受热控制的脱醇(80-130℃)，以获得其中醇的摩尔数通常低于3，优选在0.1和2.5之间的加合物。与Ti化合物的反应可以按如下进行：将加合物(脱醇或照此)悬浮在冷的TiCl4(通常为0℃)中；将混合物加热至80-130℃并在此温度下保持0.5-2小时。采用Tic4的处理可以进行一次或多次。内部供体可以在采用TiCl4处理期间加入，并且采用电子给体化合物的处理可以重复一次或多次。通常，式(I)的琥珀酸酯以相对于MgCl2的摩尔比为0.01至1，优选为0.05至0.5使用。球形催化剂组分的制备描述于例如欧洲专利申请EP-A-395083和国际专利申请WO98144001中。根据上述方法得到的固体催化剂组分的表面积(通过BET法)通常为20至500m21g，优选为50至400m21g，总孔隙率(通过BET法)高于0.2cm31g，优选为0.2至0.6cm31g。由半径高达10.000A的孔引起的孔隙率(Hg法)通常为0.3至1.5cm31g，优选为0.45至1cm31g。
有机铝化合物优选为选自三烷基铝化合物的烷基-Al，诸如例如三乙基铝、三异丁基铝、三正丁基铝、三正己基铝、三正辛基铝。还可以使用三烷基铝与烷基铝卤化物、烷基铝氢化物或烷基铝倍半氯化物如AlEt2Cl和Al2Et3Cl3的混合物。
优选的外电子给体化合物包括硅化合物、醚、诸如4-乙氧基苯甲酸乙酯的酯、胺、杂环化合物，特别是2，2，6，6-四甲基哌啶、酮和1，3-二醚。另一类优选的外给体化合物是式Ra 5Rb 6Si(OR7)c的硅化合物，其中a和b是0至2的整数，c是1至3的整数，并且(a+b+c)总和是4；R5、R6和R7是具有1-18个碳原子的烷基、环烷基或芳基，任选地含有杂原子。特别优选的是甲基环己基二甲氧基硅烷、二苯基二甲氧基硅烷、甲基-叔丁基二甲氧基硅烷、二环戊基二甲氧基硅烷、2-乙基哌啶基-2-叔丁基二甲氧基硅烷和1，1，1-三氟丙基-2-乙基哌啶基-二甲氧基硅烷和1，1，1-三氟丙基-甲基二甲氧基硅烷(1，1，1，三氟丙基-甲基二乙氧基硅烷)。外电子给体化合物的用量使得有机铝化合物与所述电子给体化合物之间的摩尔比为0.1-500。
聚合方法可以在气相和/或液相中，在连续或间歇反应器，例如流化床或淤浆反应器中进行。例如，可以使用液体丙烯作为稀释剂进行丙烯聚合物(A)在液相中的聚合，而以获得丙烯共聚物部分(B)的共聚阶段在气相中进行，除了单体的部分脱气之外没有中间阶段。或者，所有顺序聚合阶段可以在气相中进行。聚合步骤的反应时间、温度和压力并不重要，但是制备部分(A)和(B)的温度可以相同或不同，通常为50℃至120℃。如果聚合在气相中进行，则聚合压力优选为0.5至12MPa。催化体系可与少量烯烃预接触(预聚合)。通过使用已知的调节剂如氢来调节丙烯聚合物组合物的分子量。
根据优选的实施方案，丙烯聚合物(A)通过在至少两个互连聚合区中进行的气相聚合方法制备。所述聚合方法描述于WO 00/02929中。
该方法在第一和第二互连聚合区中进行，在催化剂体系存在下将丙烯和乙烯或丙烯和α-烯烃加入其中，并从中排出所产生的聚合物。生长的聚合物颗粒在快速流化条件下流过所述第一聚合区(提升管)，离开所述第一聚合区并进入所述第二聚合区(下降管)，它们在重力作用下以致密形式流过，离开所述第二聚合区并重新引入所述第一聚合区，从而在两个聚合区之间建立聚合物循环。通常，第一聚合区中快速流化的条件通过将单体气体混合物进料到将生长的聚合物重新引入所述第一聚合区的点以下来建立的。进入第一聚合区的输送气体的速度高于操作条件下的输送速度，通常在2和15m/s之间。在第二聚合区中，聚合物在重力作用下以致密形式流动，达到高固体密度值，接近聚合物的堆积密度；因此，可以沿流动方向获得正的压力增益，从而可以在没有机械装置的帮助下将聚合物重新引入第一反应区中。以这种方式，建立“回路”循环，其由两个聚合区之间的压力平衡和引入系统的压头损失限定。任选地，一种或多种惰性气体，例如氮气或脂族烃，保持在聚合区中，其量使得惰性气体的分压之和优选为气体总压力的5％和80％之间。操作参数诸如例如温度是气相烯烃聚合过程中常用的温度，例如在50℃和120℃之间。该方法可在0.5和10MPa之间，优选1.5和6MPa之间的操作压力下进行。优选地，在所述第一聚合区的任何点将各种催化剂组分进料到第一聚合区。然而，它们也可以在第二聚合区的任何点进料。本领域已知的分子量调节剂，特别是氢，可用于调节生长的聚合物的分子量。
在特别优选的聚合方法的第二阶段中，丙烯/乙烯共聚物(B)在常规流化床气相反应器中在聚合材料存在下制备，催化剂体系来自前面的聚合步骤。将聚合混合物从下降管中排出到气固分离器中，然后在常规温度和压力条件下操作进料到流化床气相反应器。
本发明的丙烯聚合物组合物可进一步包含通常用于聚烯烃领域的添加剂，例如抗氧化剂、光稳定剂、成核剂、抗酸剂、着色剂和填料。
本发明的丙烯聚合物组合物的主要应用是模塑制品，特别是注塑制品的生产。包含本发明的丙烯聚合物组合物的注塑制品具有良好的柔韧性和良好的冲击性能，尤其是在低温下。
给出以下实例以说明而非限制本发明。
实例
丙烯聚合物材料的数据根据以下方法获得：
25℃下二甲苯可溶部分
二甲苯可溶部分根据ISO 16152，2005测量，但具有以下偏差(括号中为ISO 16152规定)
溶液体积为250ml(200ml)
在25℃沉淀阶段期间持续30分钟，最后10分钟，溶液通过磁力搅拌器保持搅拌(30分钟，完全没有任何搅拌)
最后的干燥步骤在70℃(100℃)的真空下完成
所述二甲苯可溶部分的含量表示为原始2.5克的百分比，然后，差值(100的不足部分)，二甲苯不溶性％
乙烯(C2)含量
丙烯/乙烯共聚物的13C NMR
在配备有冷冻探针的Bruker AV-600光谱仪上获得13C NMR光谱，在120℃下以傅里叶变换模式在160.91MHz下操作。
Sββ碳的峰(根据“Monomer Sequence Distribution in Ethylene-PropyleneRubber Measured by 13C NMR.3.Use of Reaction Probability Mode(通过13C NMR测量的乙烯-丙烯橡胶中的单体序列分布。3.反应概率模式的使用)”C.J.Carman，R.A.Harrington and C.E.Wilkes，Macromolecules，1977，10，536命名)用作29.9ppm处的内参。将样品在120℃下以8％wt/v浓度溶解在1，1，2，2-四氯乙烷-d2中。每个光谱采用90°脉冲采集，脉冲和CPD之间15秒的延迟以去除1H-13C耦合。使用9000Hz的光谱窗口将512个瞬变存储在32K数据点中。
使用以下等式，根据Kakugo(“Carbon-13NMR determination of monomersequence distribution in ethylene-propylene copolymers prepared with δ-titanium trichloride-diethylaluminum chloride(用δ-三氯化钛-二乙基氯化铝制备的乙烯-丙烯共聚物中的单体序列分布的碳-13NMR测定)”M.Kakugo，Y.Naito，K.Mizunumaand T.Miyatake，Macromolecules，1982，15，1150)进行光谱的分配，三元组分布和组成的评估：
PPP＝100Tββ/S PPE＝100Tβδ/S EPE＝100Tδδ/S
PEP＝100Sββ/S PEE＝100Sβδ/S EEE＝100(0.25Sγδ+0.5Sδδ)/S
S＝Tββ+Tβδ+Tδδ+Sββ+Sβδ+0.25Sγδ+0.5Sδδ
使用以下等式评估乙烯的摩尔百分比含量：E％mol＝100*[PEP+PEE+EEE]。乙烯的重量百分比含量使用以下等式评估：
其中P％mol是丙烯的摩尔百分比含量，而MWE和MWP分别是乙烯和丙烯的分子量。
根据Carman(C.J.Carman，R.A.Harrington and C.E.Wilkes，Macromolecules，1977；10，536)计算反应性比率r1r2的乘积为：
丙烯序列的立构规整度由PPP mmTββ(28.90-29.65ppm)与总Tββ(29.80-28.37ppm)的比率计算为mm含量。
已经在最终组合物上测量了乙烯C2含量，组分B)的乙烯含量通过使用式C2tot＝XBC2B计算，其中XB是组合物中组分B的量。
进料气体的摩尔比
通过气相色谱法测定
熔体流动速率(MFR)
根据ISO 1133(230℃，2.16Kg)测定聚合物的熔体流动速率MFR。
特性粘度
在135℃下在四氢化萘中测定
弯曲模数
根据ISO0178和根据ISO 1873-2的补充条件采用注塑成型样品测定
IZOD冲击强度
根据ISO 180/A，采用注塑成型样品，根据ISO 1873-2和根据ISO 3167，沿边缘切口(ISO 1873-2ed.1989的条件，除条件1A外)测定。
多分散指数(PI)：聚合物分子量分布的测量。为了确定PI值，在低模数值下的模数分离，例如500Pa，通过使用由Rheometrics(USA)销售的RMS-800平行板流变仪模型在200℃的温度下测定，在从0.01rad/秒增加到100rad/秒的振荡频率下操作。根据模数分离值，可以使用以下等式导出PI：
PI＝54.6×(模数分离)-1.76
其中模数分离(MS)定义为：
MS＝(G′＝500Pa的频率)/(G″＝500Pa的频率)
其中G′是储能模数，G″是损耗模数。
实例1和2对比例3-5
根据欧洲专利EP728769的实例5第48-55行制备齐格勒-纳塔催化剂。三乙基铝(TEAL)用作助催化剂，二环戊基二甲氧基硅烷用作外给体。
实例的丙烯聚合物组合物在两步聚合方法中制备，其中共聚物(A)在第一聚合步骤中通过将单体和催化剂体系进料至包含两个互连聚合区、提升管和下降管的气相聚合反应器中来制备，如WO 00/02929中所述，使得提升管中氢的浓度不同于提升管中氢的浓度。
将聚合混合物从所述反应器排出，输送到气固分离器中，并将聚合的材料送入常规的气相流化床反应器中，在该反应器中生产丙烯乙烯共聚物(B)。操作条件如表1中所示。
将从第二聚合步骤离开的聚合物颗粒进行蒸汽处理以去除未反应的单体并干燥。
表1
表1续
C2乙烯；C3丙烯；H2氢
*组分B相对于A+B的量
C2 -＝乙烯C3 -＝丙烯
对于根据实例1-2和对比例3-5获得的材料，添加了以下添加剂：
| 实例1、2比较例3-5的聚合物 | wt％ | 98.988 |
| DIHYDROTALCIT-DHT 4A(KISUMA) | wt％ | 0.0400 |
| IRGAFOS 168 | wt％ | 0.0860 |
| IRGANOX 1010 | wt％ | 0.0440 |
| TALC-HM05 | wt％ | 0.8500 |
材料经过挤压和分析，其性能见表2
表2续
C2 -＝乙烯
XsIV＝在25℃下可溶于二甲苯的部分的特性粘度
通过比较本发明实例1和3以及比较例3-5，可以注意到0℃的Izod冲击强度落在比较例中，而在根据本发明的实例中类似于在23℃下测量的Izod冲击强度。
Claims (11)
1.一种丙烯聚合物组合物，其包含：
A）60 wt％至75 wt％的丙烯均聚物，其具有4.3至4.9的多分散指数值、高于95％的在25℃下二甲苯不溶部分，和范围为20至75 g/10 min的根据ISO 1133，条件L，即230℃和2.16 kg载荷的熔体流动速率；
B）25 wt％至40 wt％的共聚物，其为丙烯与46.0 wt％至49.0 wt％乙烯衍生单元的共聚物；
所述组合物具有包括在2.2和2.9 dl/g之间的在25℃下可溶于二甲苯的部分的特性粘度；且关系式：
10.7+1.3×MFRa-17.7×P.I.-29.3×IV+4.9×Xs （I）
包括在40和66之间；其中，
MFRa是组分A）的根据ISO 1133，条件L，即230℃和2.16 kg载荷的熔体流动速率；
P.I.是组分A）的多分散指数；
IV是在25℃下可溶于二甲苯的部分的特性粘度；和
Xs是在25℃下可溶于二甲苯的部分；
并且其中A+B的量等于100 wt％。
2.根据权利要求1所述的组合物，其中组分A）具有范围为25至70 g/10 min的根据ISO1133，条件L，即230℃和2.16 kg载荷的熔体流动速率。
3.根据权利要求1或2所述的组合物，其中组分B）具有47.0 wt％至48.5 wt％的乙烯衍生单元。
4.根据权利要求1或2所述的组合物，其具有包括在2.4和2.9 dl/g之间的在25℃下可溶于二甲苯的部分的特性粘度。
5.根据权利要求1或2所述的组合物，其中组分A）的范围为62 wt％至72 wt％，以及组分B）的范围为28 wt％至38 wt％。
6.根据权利要求1或2所述的组合物，其中所述关系式（I）
10.7+1.3×MFRa-17.7×P.I.-29.3×IV+4.9×Xs （I）;
的结果包括在45和60之间。
7.根据权利要求1或2所述的组合物，其中所述关系式（I）
10.7+1.3×MFRa-17.7×P.I.-29.3×IV+4.9×Xs （I）;
的结果包括在50和55之间。
8.根据权利要求1或2所述的组合物，其中组分A）的范围为63 wt％至71 wt％，以及组分B）的范围为29 wt％至37 wt％。
9.根据权利要求1或2所述的组合物，其中组分A）在25℃下不溶于二甲苯的部分高于97wt％。
10.一种用权利要求1-9中任一项所述的丙烯聚合物组合物得到的模塑制品。
11.根据权利要求10所述的模塑制品，其中所述模塑制品是注塑制品。
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