CN104854141B - 用于烯烃聚合的催化剂组分 - Google Patents
用于烯烃聚合的催化剂组分 Download PDFInfo
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- CN104854141B CN104854141B CN201380027480.4A CN201380027480A CN104854141B CN 104854141 B CN104854141 B CN 104854141B CN 201380027480 A CN201380027480 A CN 201380027480A CN 104854141 B CN104854141 B CN 104854141B
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- China
- Prior art keywords
- diethyl
- polymerization
- ethyl
- diacetate
- phenylene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 24
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 6
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 4
- -1 2 ' - (5, 5, 8, 8-tetramethyl-5, 6, 7, 8-tetrahydronaphthalene-2, 3-diyl) diacetate Chemical compound 0.000 claims description 29
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- RMSWGPQKGMRESA-UHFFFAOYSA-N (2-acetyloxy-4-chlorophenyl) acetate Chemical compound CC(=O)OC1=CC=C(Cl)C=C1OC(C)=O RMSWGPQKGMRESA-UHFFFAOYSA-N 0.000 claims description 2
- DOYAQCPJOMFNGV-UHFFFAOYSA-N (2-acetyloxy-4-propan-2-ylphenyl) acetate Chemical compound CC(C)c1ccc(OC(C)=O)c(OC(C)=O)c1 DOYAQCPJOMFNGV-UHFFFAOYSA-N 0.000 claims description 2
- ASXCXYNHCRSLLJ-UHFFFAOYSA-N (2-acetyloxy-4-propylphenyl) acetate Chemical compound CCCC1=CC=C(OC(C)=O)C(OC(C)=O)=C1 ASXCXYNHCRSLLJ-UHFFFAOYSA-N 0.000 claims description 2
- NBDHUKNVZPIOEW-UHFFFAOYSA-N (2-acetyloxy-4-tert-butylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C(C)(C)C)C=C1OC(C)=O NBDHUKNVZPIOEW-UHFFFAOYSA-N 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 9
- 125000005843 halogen group Chemical group 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 4
- BLZACQAMMBPOGV-UHFFFAOYSA-N 2-methylpropyl 2-[2-[2-(2-methylpropoxy)-2-oxoethyl]phenyl]acetate Chemical compound CC(C)COC(=O)Cc1ccccc1CC(=O)OCC(C)C BLZACQAMMBPOGV-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 13
- 239000010936 titanium Substances 0.000 description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000003609 titanium compounds Chemical class 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 235000011147 magnesium chloride Nutrition 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 229910003074 TiCl4 Inorganic materials 0.000 description 4
- FBSAITBEAPNWJG-UHFFFAOYSA-N (2-acetyloxyphenyl) acetate Chemical compound CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 125000006657 (C1-C10) hydrocarbyl group Chemical group 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical class OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BFEGGNJXZABRTM-UHFFFAOYSA-N (2-acetyloxy-3,5-dimethylphenyl) acetate Chemical compound C(C)(=O)OC1=C(C(=CC(=C1)C)C)OC(C)=O BFEGGNJXZABRTM-UHFFFAOYSA-N 0.000 description 1
- UPVHEMQZTSKJJD-UHFFFAOYSA-N (2-acetyloxy-3,5-ditert-butylphenyl) acetate Chemical compound C(C)(=O)OC1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)OC(C)=O UPVHEMQZTSKJJD-UHFFFAOYSA-N 0.000 description 1
- SQIKJFTVOYUNMT-UHFFFAOYSA-N (2-acetyloxy-4,5-dimethylphenyl) acetate Chemical compound C(C)(=O)OC1=C(C=C(C(=C1)C)C)OC(C)=O SQIKJFTVOYUNMT-UHFFFAOYSA-N 0.000 description 1
- GJZLJBJUIBIUQV-UHFFFAOYSA-N (2-acetyloxy-4-butylphenyl) acetate Chemical compound CCCCC1=CC=C(OC(C)=O)C(OC(C)=O)=C1 GJZLJBJUIBIUQV-UHFFFAOYSA-N 0.000 description 1
- ZOXATXRUISPBNC-UHFFFAOYSA-N (2-acetyloxy-4-ethylphenyl) acetate Chemical compound CCC1=CC=C(OC(C)=O)C(OC(C)=O)=C1 ZOXATXRUISPBNC-UHFFFAOYSA-N 0.000 description 1
- AOPKLCBVSXXATF-UHFFFAOYSA-N (2-acetyloxy-4-methylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C)C=C1OC(C)=O AOPKLCBVSXXATF-UHFFFAOYSA-N 0.000 description 1
- RTNUFARDHKRTRJ-UHFFFAOYSA-N (2-propanoyloxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC=CC=C1OC(=O)CC RTNUFARDHKRTRJ-UHFFFAOYSA-N 0.000 description 1
- 125000006658 (C1-C15) hydrocarbyl group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- UVGKQRAGAYVWQV-UHFFFAOYSA-N 2,3-dimethylbutan-2-yl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C(C)C UVGKQRAGAYVWQV-UHFFFAOYSA-N 0.000 description 1
- CKQJKQXELPQTSS-UHFFFAOYSA-N 2-ethoxypropanal Chemical compound CCOC(C)C=O CKQJKQXELPQTSS-UHFFFAOYSA-N 0.000 description 1
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 102100038463 Ubiquitin carboxyl-terminal hydrolase 4 Human genes 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 238000006653 Ziegler-Natta catalysis Methods 0.000 description 1
- DYGIJVPTAIGBLI-UHFFFAOYSA-N [2-acetyloxy-4-(2-methylpropyl)phenyl] acetate Chemical compound CC(C)CC1=CC=C(OC(C)=O)C(OC(C)=O)=C1 DYGIJVPTAIGBLI-UHFFFAOYSA-N 0.000 description 1
- RTQCAYKHUMWCEM-UHFFFAOYSA-N [Mg].ClO Chemical compound [Mg].ClO RTQCAYKHUMWCEM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- TWPUGUHHZJAPQQ-UHFFFAOYSA-N butyl 2-(3-butoxy-3-oxopropyl)benzoate Chemical compound CCCCOC(=O)CCc1ccccc1C(=O)OCCCC TWPUGUHHZJAPQQ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- MAWOHFOSAIXURX-UHFFFAOYSA-N cyclopentylcyclopentane Chemical group C1CCCC1C1CCCC1 MAWOHFOSAIXURX-UHFFFAOYSA-N 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- FRLLYEZNQRZALB-UHFFFAOYSA-N ethyl 2-(1-ethoxy-1-oxoheptan-3-yl)benzoate Chemical compound CCCCC(CC(=O)OCC)c1ccccc1C(=O)OCC FRLLYEZNQRZALB-UHFFFAOYSA-N 0.000 description 1
- QUTXCWPDAHWUTF-UHFFFAOYSA-N ethyl 2-(1-ethoxy-1-oxopentan-3-yl)benzoate Chemical compound CCOC(=O)CC(CC)c1ccccc1C(=O)OCC QUTXCWPDAHWUTF-UHFFFAOYSA-N 0.000 description 1
- KWCWQGPLOFUNNZ-UHFFFAOYSA-N ethyl 2-(1-ethoxy-4,4-dimethyl-1-oxopentan-3-yl)benzoate Chemical compound CCOC(=O)CC(c1ccccc1C(=O)OCC)C(C)(C)C KWCWQGPLOFUNNZ-UHFFFAOYSA-N 0.000 description 1
- ZUTKFSGFQAYHKU-UHFFFAOYSA-N ethyl 2-(1-ethoxy-4-methyl-1-oxopentan-3-yl)benzoate Chemical compound CCOC(=O)CC(C(C)C)c1ccccc1C(=O)OCC ZUTKFSGFQAYHKU-UHFFFAOYSA-N 0.000 description 1
- FSSPFFNKKHOMOY-UHFFFAOYSA-N ethyl 2-(1-ethoxy-5-methyl-1-oxohexan-3-yl)benzoate Chemical compound CCOC(=O)CC(CC(C)C)c1ccccc1C(=O)OCC FSSPFFNKKHOMOY-UHFFFAOYSA-N 0.000 description 1
- CVRDUIRKRXFGSC-UHFFFAOYSA-N ethyl 2-(2-ethoxycarbonyl-3,3-dimethylbutyl)benzoate Chemical compound CCOC(=O)C(Cc1ccccc1C(=O)OCC)C(C)(C)C CVRDUIRKRXFGSC-UHFFFAOYSA-N 0.000 description 1
- REZQQBBKSDOBCJ-UHFFFAOYSA-N ethyl 2-(2-ethoxycarbonyl-3-methylbutyl)benzoate Chemical compound CCOC(=O)C(Cc1ccccc1C(=O)OCC)C(C)C REZQQBBKSDOBCJ-UHFFFAOYSA-N 0.000 description 1
- MDURACYNUOMXLR-UHFFFAOYSA-N ethyl 2-(3-ethoxy-2-methyl-3-oxopropyl)benzoate Chemical compound CCOC(=O)C(C)Cc1ccccc1C(=O)OCC MDURACYNUOMXLR-UHFFFAOYSA-N 0.000 description 1
- YURFQNMFRGZELU-UHFFFAOYSA-N ethyl 2-(3-ethoxy-3-oxo-1-phenylpropyl)benzoate Chemical compound CCOC(=O)CC(c1ccccc1)c1ccccc1C(=O)OCC YURFQNMFRGZELU-UHFFFAOYSA-N 0.000 description 1
- PCGUFTWEHCYMRN-UHFFFAOYSA-N ethyl 2-(3-ethoxy-3-oxopropyl)-4-methylbenzoate Chemical compound CCOC(=O)CCc1cc(C)ccc1C(=O)OCC PCGUFTWEHCYMRN-UHFFFAOYSA-N 0.000 description 1
- SJMKJIQRTVZSJK-UHFFFAOYSA-N ethyl 2-(3-ethoxy-3-oxopropyl)-4-propan-2-ylbenzoate Chemical compound CCOC(=O)CCc1cc(ccc1C(=O)OCC)C(C)C SJMKJIQRTVZSJK-UHFFFAOYSA-N 0.000 description 1
- VFQWBIABUIEKKU-UHFFFAOYSA-N ethyl 2-(3-ethoxy-3-oxopropyl)-5-(2-methylpropyl)benzoate Chemical compound CCOC(=O)CCc1ccc(CC(C)C)cc1C(=O)OCC VFQWBIABUIEKKU-UHFFFAOYSA-N 0.000 description 1
- HWZMVBPUUCFFGU-UHFFFAOYSA-N ethyl 2-(3-ethoxy-3-oxopropyl)-5-ethylbenzoate Chemical compound CCOC(=O)CCc1ccc(CC)cc1C(=O)OCC HWZMVBPUUCFFGU-UHFFFAOYSA-N 0.000 description 1
- GPMBCUYIDOUACI-UHFFFAOYSA-N ethyl 2-(3-ethoxy-3-oxopropyl)-5-methylbenzoate Chemical compound CCOC(=O)CCc1ccc(C)cc1C(=O)OCC GPMBCUYIDOUACI-UHFFFAOYSA-N 0.000 description 1
- RBQKGMZVELTTFC-UHFFFAOYSA-N ethyl 2-(3-ethoxy-3-oxopropyl)benzoate Chemical compound CCOC(=O)CCC1=CC=CC=C1C(=O)OCC RBQKGMZVELTTFC-UHFFFAOYSA-N 0.000 description 1
- MHFOZBBTPIAMSX-UHFFFAOYSA-N ethyl 2-(4-ethoxy-4-oxobutan-2-yl)benzoate Chemical compound CCOC(=O)CC(C)c1ccccc1C(=O)OCC MHFOZBBTPIAMSX-UHFFFAOYSA-N 0.000 description 1
- NFZSOJLMESIPCX-UHFFFAOYSA-N ethyl 2-[1-(3,4-dichlorophenyl)-3-ethoxy-3-oxopropyl]benzoate Chemical compound CCOC(=O)CC(c1ccc(Cl)c(Cl)c1)c1ccccc1C(=O)OCC NFZSOJLMESIPCX-UHFFFAOYSA-N 0.000 description 1
- IYHCOUWWZLQCMC-UHFFFAOYSA-N ethyl 2-[1-(3,4-dimethylphenyl)-3-ethoxy-3-oxopropyl]benzoate Chemical compound CCOC(=O)CC(c1ccc(C)c(C)c1)c1ccccc1C(=O)OCC IYHCOUWWZLQCMC-UHFFFAOYSA-N 0.000 description 1
- XUGZFSHDYIPKOP-UHFFFAOYSA-N ethyl 2-[2-(1-ethoxy-1-oxopropan-2-yl)phenyl]-3-methylbutanoate Chemical compound CCOC(=O)C(C)c1ccccc1C(C(C)C)C(=O)OCC XUGZFSHDYIPKOP-UHFFFAOYSA-N 0.000 description 1
- GTHDFYARNWTZJG-UHFFFAOYSA-N ethyl 2-[2-(2-ethoxy-2-oxoethyl)phenyl]acetate Chemical compound CCOC(=O)CC1=CC=CC=C1CC(=O)OCC GTHDFYARNWTZJG-UHFFFAOYSA-N 0.000 description 1
- ZUARNRKVQPHNNF-UHFFFAOYSA-N ethyl 2-[2-(2-oxo-2-propoxyethyl)phenyl]acetate Chemical compound CCCOC(=O)Cc1ccccc1CC(=O)OCC ZUARNRKVQPHNNF-UHFFFAOYSA-N 0.000 description 1
- RBFSNGQCQDQYPF-UHFFFAOYSA-N ethyl 3-(3-ethoxy-3-oxopropyl)naphthalene-2-carboxylate Chemical compound CCOC(=O)CCc1cc2ccccc2cc1C(=O)OCC RBFSNGQCQDQYPF-UHFFFAOYSA-N 0.000 description 1
- FPOIINHDMXYKAO-UHFFFAOYSA-N ethyl 4-chloro-2-(3-ethoxy-3-oxopropyl)benzoate Chemical compound CCOC(=O)CCc1cc(Cl)ccc1C(=O)OCC FPOIINHDMXYKAO-UHFFFAOYSA-N 0.000 description 1
- YHWCHQBKQWEFKT-UHFFFAOYSA-N ethyl 5-chloro-2-(3-ethoxy-3-oxopropyl)benzoate Chemical compound CCOC(=O)CCc1ccc(Cl)cc1C(=O)OCC YHWCHQBKQWEFKT-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- UQJJSOGPLFWORH-UHFFFAOYSA-N methyl 2-[2-(2-oxo-2-propoxyethyl)phenyl]acetate Chemical compound CCCOC(=O)Cc1ccccc1CC(=O)OC UQJJSOGPLFWORH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 239000012074 organic phase Substances 0.000 description 1
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- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
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- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 238000005303 weighing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- 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
- C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
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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
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Abstract
一种用于烯烃聚合的催化剂组分，其包含Mg、Ti和下式(I)中的电子供体化合物
其中R基团相同或彼此不同，是C1‑C15烃基，R1‑R2基团相同或彼此不同，是氢、卤素或C1‑C15烃基，任选地含有选白卤素、P、S、N和Si的杂原子，它们可稠合在一起，以形成一个或多个环；n和m是0至3的整数，条件是它们中的至少一个不为0，并且邻苯二乙酸二异丁酯被排除在外。
Description
本发明涉及用于烯烃，特别是丙烯聚合的催化剂组分，其包含载有Ti原子的二卤化镁基载体和从特定类别的苯二乙酸酯衍生物中选出的电子供体。本发明还涉及由所述组分获得的催化剂，以及它们在用于烯烃，特别是丙烯的聚合方法中的用途。
用于烯烃的立体定向聚合的催化剂组分广泛地为本领域所知。关于丙烯的聚合，最广泛的催化剂家族属于齐格勒-纳塔类，且概括地说，其包含一种固体催化剂组分，由载有钛化合物的二卤化镁和内部电子供体化合物构成，与烷基铝化合物结合使用。然而，按照惯例，当需要聚合物具有较高的结晶度时，也需要外部供体(例如，烷氧基硅烷)，以便获得较高的全同立构规整度。优选类别的内部供体之一是由邻苯二甲酸的酯构成的，而最常用的是二异丁酯。邻苯二甲酸酯用作内部供体，与作为外部供体的烷基烷氧基硅烷结合。这种催化剂体系在活性、全同立构规整度和二甲苯不溶性方面展现出良好的性能。
与使用这种催化剂体系相关联的问题之一是，邻苯二甲酸酯最近引起了关注，这是由于它们的使用与医疗问题相关联而且此类别中的一些化合物已被归类为严重健康问题的根源。
因此，已对此进行研究以探索用于制备用于丙烯聚合的催化剂组分的替代类别的内部供体。
该苯二乙酸酯类在USP 4,725,656中以一般的方式提到过，其可用于PP生产，但是没有报告任何具体的例子。另一方面，USP 4,522,930没有具体描述本发明的二酯类，但报告了包括本类中的一个成员，即邻苯二乙酸二异丁酯作为电子供体的催化剂的丙烯聚合试验。如本申请的实验部分中所示，丙烯聚合的结果对这种供体不是特别好。
因此，非常意外地发现，不同于特定的邻苯二乙酸二异丁酯，该类苯二乙酸酯衍生物在生成具有良好的活性和立体定向性的催化剂方面是有效的。
因此，本发明的目的在于一种用于烯烃聚合的催化剂组分，其包含Mg、Ti和下式(I)中的电子供体化合物
其中R基团相同或彼此不同，是C1-C15烃基，R1-R2基团相同或彼此不同，是氢、卤素或C1-C15烃基，任选地含有选自卤素、P、S、N和Si的杂原子，它们可稠合在一起，以形成一个或多个环；n和m是0至3的整数，条件是它们中的至少一个不为0，并且邻苯二乙酸二异丁酯被排除在外。
优选地，R基团选自C1-C10烃基，更优选地选自直链C1-C8烷基，诸如，甲基、乙基和正丁基。
在特别优选的实施例中，当所有的R2基团都是氢时，R基团独立地选自直链C1-C4烷基且特别是选自直链C1-C3烷基。
优选地，n+m的总和为2，更优选地，n和m都为1。
在本发明的优选方面中，基团R1选自氢和C1-C5烷基。优选地，它们不同时为烷基，更优选地，它们同时为氢。
R2基团，独立地，优选地选自氢、卤素或C1-C10烃基，任选地形成一个或多个饱和的环。更优选地，它们中的至少一个选自卤素或C1-C10烷基。优选的卤原子是Cl、Br和F，其中Cl是最优选的。在C1-C10烷基中，优选的是C1-C5支链烷基。在一个特定实施例中，R2基团中的两个连接形成与式(I)中的苯环缩合的环状基团。优选地，与苯环缩合的环状基团链中具有4至8个碳原子，且它们中的一个或多个可进一步被另外的烃基取代。
结构(I)的非限制性实例如下：
2-(2-(2-乙氧基-2-氧代乙基)苯基)乙酸丁酯、2-(2-(2-甲氧基-2-氧代乙基)苯基)乙酸丁酯、2-(2-(2-氧代-2-丙氧基乙基)苯基)乙酸丁酯、2，2’-(1，2-亚苯基)二乙酸二丁酯、2，2’-(1，2-亚苯基)二乙酸二乙酯、2，2’-(1，2-亚苯基)二乙酸二甲酯、2，2’-(1，2-亚苯基)二乙酸二丙酯、2-(2-(2-甲氧基-2-氧代乙基)苯基)乙酸乙酯、2-(2-(2-氧代-2-丙氧基乙基)苯基)乙酸乙酯、2-(2-(2-氧代-2-丙氧基乙基)苯基)乙酸甲酯、2，2’-(4-(1-苯乙基)-1，2-亚苯基)二乙酸二乙酯、2，2’-(4-(2-苯基丙烷-2-基)-1，2-亚苯基)二乙酸二乙酯、2，2’-(4-(叔丁基)-1，2-亚苯基)二乙酸二乙酯、2，2’-(4-丁基-1，2-亚苯基)二乙酸二乙酯、2，2’-(4-环己基-1，2-亚苯基)二乙酸二乙酯、2，2’-(4-环戊基-1，2-亚苯基)二乙酸二乙酯、2，2’-(4-乙基-1，2-亚苯基)二乙酸二乙酯、2，2’-(4-异丁基-1，2-亚苯基)二乙酸二乙酯、2，2’-(4-异丙基-1，2-亚苯基)二乙酸二乙酯、2，2’-(4-甲基-1，2-亚苯基)二乙酸二乙酯、2，2’-(4-丙基-1，2-亚苯基)二乙酸二乙酯、2，2’-(4-氯-1，2-亚苯基)二乙酸二乙酯、2，2’-(1，2-亚苯基)双(3-甲基丁酸二乙酯)、2，2’-(1，2-亚苯基)二丙酸二乙酯、2-(2-(1-乙氧基-1-氧代丙烷-2-基)苯基)-3-甲基丁酸乙酯、2，2’-(3，4，5，6-四甲基-1，2-亚苯基)二乙酸二乙酯、2，2’-(3，5-二-叔-丁基-1，2-亚苯基)二乙酸二乙酯、2，2’-(3，5-二异丙基-1，2-亚苯基)二乙酸二乙酯、2，2’-(3，5-二甲基-1，2-亚苯基)二乙酸二乙酯、2，2’-(4，5-二甲基-1，2-亚苯基)二乙酸二乙酯、2，2’-(5，5，8，8-四甲基-5，6，7，8-四氢化萘-2，3-二基)二乙酸二乙酯、2，2’-(5-(叔丁基)-3-甲基-1，2-亚苯基)二乙酸二乙酯、2，2’-(萘-2，3-二基)二乙酸二乙酯、2-(3-丁氧基-3-氧代丙基)苯甲酸丁酯、2-(3-乙氧基-3-氧代丙基)苯甲酸乙酯、2-(3-甲氧基-3-氧代丙基)苯甲酸甲酯、2-(2-(乙氧羰基)-3，3-二甲基丁基)苯甲酸乙酯、2-(2-(乙氧羰基)-3-甲基丁基)苯甲酸乙酯、2-(2-(乙氧羰基)-4-甲基-戊基)苯甲酸乙酯、2-(2-(乙氧羰基)丁基)苯甲酸乙酯、2-(2-(乙氧羰基)己基)苯甲酸乙酯、2-(3-乙氧基-2-甲基-3-氧代丙基)苯甲酸乙酯、2-(1-(3，4-二氯苯基)-3-乙氧基-3-氧代丙基)苯甲酸乙酯、2-(1-(3，4-二甲基苯基)-3-乙氧基-3-氧代丙基)苯甲酸乙酯、2-(1-乙氧基-1-氧代庚烷-3-基)苯甲酸乙酯、2-(1-乙氧基-1-氧代戊烷-3-基)苯甲酸乙酯、2-(1-乙氧基-4，4-二甲基-1-氧代戊烷-3-基)苯甲酸乙酯、2-(1-乙氧基-4-甲基-1-氧代戊烷-3-基)苯甲酸乙酯、2-(1-乙氧基-5-甲基-1-氧代己烷-3-基)苯甲酸乙酯、2-(3-乙氧基-3-氧代-1-苯丙基)苯甲酸乙酯、2-(4-乙氧基-4-氧代丁烷-2-基)苯甲酸乙酯、2-(3-乙氧基-3-氧代丙基)-5-乙基苯甲酸乙酯、2-(3-乙氧基-3-氧代丙基)-5-异丁基苯甲酸乙酯、2-[(3-乙氧基-3-氧代丙基)-5-异丙基苯甲酸乙酯、2-(3-乙氧基-3-氧代丙基)-5-甲基苯甲酸乙酯、5-(叔-丁基)-2-(3-乙氧基-3-氧代丙基)苯甲酸乙酯、5-氯-2-(3-乙氧基-3-氧代丙基)苯甲酸乙酯、2-(3-乙氧基-3-氧代丙基)-4-异丙基苯甲酸乙酯、2-(3-乙氧基-3-氧代丙基)-4-甲基苯甲酸乙酯、4-(叔-丁基)-2-(3-乙氧基-3-氧代丙基)苯甲酸乙酯、4-氯-2-(3-乙氧基-3-氧代丙基)苯甲酸乙酯、2-(2-(乙氧羰基)环己基)苯甲酸乙酯、3-(3-乙氧基-3-氧代丙基)-2-萘甲酸乙酯。
如上所述，除了上述电子供体外，本发明的催化剂组分还包含Ti、Mg和卤素。具体地，催化剂组分包含一种钛化合物，该钛化合物具有至少一个钛-卤键以及负载在卤化镁上的上述电子供体化合物。卤化镁优选是活化型MgCl2，活化型MgCl2是专利文献中广泛公知的齐格勒-纳塔催化剂的载体。专利USP 4,298,718和USP 4,495,338首次描述了在齐格勒-纳塔催化中使用这些化合物。从这些专利中可知，在用于烯烃聚合的催化剂组分中作为载体或助载体的活化型二卤化镁通过X射线谱表征，其中，非活性卤化物光谱中出现的最强衍射线的强度减小且由光晕所代替，该光晕的最大强度朝向相对于较强衍射线的角度更低的角度偏移。
本发明催化剂组分中所用的优选钛化合物是TiCl4和TiCl3；此外，也可以使用化学式为Ti(OR)q-yXy的卤代醇化钛，其中q是钛的化合价，y是介于1和q-1之间的数字，X是卤素，且R是具有1-10个碳原子的烃基。
固体催化剂组分的制备可以按照几种方法进行。
根据这些方法其中的一种方法，将无水状态下的二氯化镁、钛化合物和电子供体化合物在二氯化镁活化发生的条件下一起研磨。可在80-135℃的温度下用过量的TiCl4对这样得到的产物进行一次或多次处理。在此处理之后，用烃类溶剂洗涤，直至氯离子消失为止。根据另一种方法，通过共研磨无水状态下的氯化镁、钛化合物和电子供体化合物所获得的产物用卤代烃，诸如，1，2-二氯乙烷、氯苯、二氯甲烷等进行处理。该处理在40℃至卤化烃沸点的温度下进行1-4个小时。另一种方法包括在约80-120℃以及电子供体化合物存在的条件下，醇化镁或氯醇化镁(具体为根据USP4，220，554制备的氯醇化物)与过量TiCl4之间的反应。
根据优选的方法，固体催化剂组分可以通过钛化合物与加合物衍生的氯化镁反应而制得，所述钛化合物的化学式为Ti(OR)q-yXy，其中q是钛的化合价，且y是介于1和q之间的数字，优选TiCl4，所述加合物的化学式为MgCl2·pROH，其中p是0.1-6的数字，优选为2-3.5，且R是具有1-18个碳原子的烃基。加合物可通过如下步骤以球形形式适当地制备：将醇与氯化镁在与加合物不混溶的惰性烃存在的条件下进行混合，在加合物的熔化温度(100-130℃)下，在搅拌条件下操作。然后，乳状液迅速骤冷，从而使加合物固化为球形颗粒。根据此流程制备的球形加合物的实施例在USP4,399,054和USP 4,469,648中有所描述。如此获得的加合物可直接与Ti化合物发生反应，或者该加合物可预先经受热控脱醇处理(80-130℃)以获得一种加合物，其中醇的摩尔数通常低于3，优选为0.1-2.5。与Ti化合物的反应可通过将加合物(脱醇或此类处理)悬浮在冷的TiCl4(一般为0℃)中进行；将混合物加热至80-135℃并保持在该温度下0.5-2个小时。可以使用TiCl4进行一次或多次的处理。电子供体化合物可以以所需的比例在使用TiCl4进行处理期间加入。在以下专利中描述了球形催化剂组分的制备方法，例如，欧洲专利申请EP-A-395083、EP-A-553805、EP-A-553806、EPA601525以及WO98/44001。
根据上述方法得到的固体催化剂组分显示出一般介于20-500m2/g之间的表面积(通过B.E.T法)，优选为50-400m2/g，且总孔隙率(通过B.E.T法)大于0.2cm3/g，优选为0.2-0.6cm3/g。由于孔半径高达
孔隙率(Hg法)范围一般介于0.3-1.5cm3/g之间，优选为0.45-1cm3/g。
固体催化剂组分的平均粒度范围为5-120μm，更优选为10-100μm。
如上所述，可以以这些制备方法的任一种原样添加所需电子供体化合物，或可以以另外的方式通过使用适当前体而原位获得所需电子供体化合物，所述适当前体能够通过，例如，已知的化学反应，例如，醚化、烷基化、酯化、酯交换等在所需电子供体化合物中进行转化。
无论使用哪种制备方法，化学式(I)的电子供体化合物的最终量是，相对于Ti原子，它的摩尔比为0.01-3，优选为0.2-2，更优选为0.3-1.5。
根据本发明的固体催化剂组分通过根据已知方法使它们与有机铝化合物反应而被转化成用于烯烃聚合的催化剂。
具体而言，本发明的目的在于一种用于烯烃CH2＝CHR的聚合的催化剂，其中R是氢或具有1-12个碳原子的烃基，其包含通过接触以下物质得到的产物：
(i)上文所公开的固体催化剂组分和
(ii)烷基铝化合物和任选地，
(iii)外部电子供体化合物。
烷基铝化合物(ii)优选地选自三烷基铝化合物，诸如，举例而言，三乙基铝、三异丁基铝、三正丁基铝、三正己基铝、三正辛基铝。也可能使用烷基铝卤化物、烷基铝氢化物或烷基铝倍半氯化物，诸如，AlEt2Cl和Al2Et3Cl3，其可能与如上所述的三烷基铝存在于混合物中。
合适的外部电子-供体化合物(iii)包括硅化合物、醚类、酯类、胺类、杂环化合物以及尤其包括2，2，6，6-四甲基哌啶和酮类。
另一类优选的外部供体化合物是化学式为(R6)a(R7)bSi(OR8)c的硅化合物，其中a和b是0-2的整数，c是1-4的整数，且(a+b+c)总和是4；R6、R7和R8是具有1-18个碳原子且任选地含有杂原子的烷基、环烷基或芳烃基。在聚丁烯-1制备中特别优选的是硅化合物，其中R6和R7中的至少一个选自支链烷基，或具有3-10个碳原子的环烷基，且R8为C1-C10烷基，具体而言是甲基。这类优选的硅化合物实例是二异丙基二甲氧基硅烷、叔丁基三甲氧基硅烷、叔己基三甲氧基硅烷以及二环戊基二甲氧基硅烷。
电子供体化合物(c)的用量使得有机铝化合物与所述电子供体化合物(iii)的摩尔比介于0.1-500之间，优选为1-300，更优选为3-150。
因此，它构成了本发明的又一目的，一种用于烯烃CH2＝CHR的(共)聚合的方法，其中R是氢或具有1-12个碳原子的烃基，在催化剂存在下进行，所述催化剂包含以下物质之间反应的产物：
(i)本发明的固体催化剂组分；
(ii)烷基铝化合物和，
(iii)任选的电子-供体化合物(外部供体)。
丙烯与少量乙烯或化学式为CH2＝CHR的其它烯烃均聚或共聚是优选的。聚合方法可根据已知技术，例如，使用惰性烃溶剂作为稀释剂的淤浆聚合，或使用液体单体(例如，丙烯)作为反应介质的本体聚合进行。
此外，也可能在一个或多个流化床或机械搅拌床反应器中进行气相聚合过程。
聚合通常在20-120℃，优选为40-90℃的温度下进行。在本体聚合中，操作压力一般介于0.1-6MPa之间，优选为1.0-4MPa。聚合可以在一个或多个反应器中进行，所述反应器可以在相同或不同反应条件，诸如，分子量调节剂的浓度、单体浓度、温度，以及压力等下工作。
另外，为了制备尤其适合于聚合步骤的催化剂，可以在预聚合步骤中预聚合所述催化剂。所述预聚合可一般在低于100℃，优选在20℃-70℃的温度下在液体(淤浆或溶液)或气相中进行。使用少量的单体进行必要时间的预聚合步骤，以获得量为0.5-2000g聚合物/每g固体催化剂组分，优选5-500，更优选10-100g聚合物/每g固体催化剂组分。预聚合中使用的单体可以是丙烯和/或另一种具有2-10个碳原子的α-烯烃。
利用本发明的催化剂生产的聚丙烯可以用于所有通常使用聚丙烯的应用。然而，由于它是本领域中的专家所熟知的，且可容易地通过常规试验进行确定，因此可加入其他聚合物组分、添加剂(诸如，稳定剂、抗氧化剂、抗腐蚀剂、成核剂、加工助剂等)以及有机和无机填料，它们可以赋予本发明产物以特定性能。
给出以下实例是为了更好地说明而不是限制本发明。
表征
Ti的测定
固体催化剂组分中Ti含量通过“I.C.P光谱仪ARL Accuris”的电感耦合等离子体发射光谱进行确定。
在“fluxy”铂坩埚上分析称量0.1÷0.3克催化剂以及3克偏硼酸锂/四硼酸锂1/1混合物以制备样品。将坩埚放置在弱本生灯火焰上以进行燃烧步骤，然后加入数滴KI溶液后，插入到特殊装置“Claisse Fluxy”中以完全燃烧。用5％v/v的HNO3溶液收集残余物，然后通过ICP在368.52nm波长下对钛进行分析。
内部供体含量的测定
固体催化剂化合物中内部供体的含量通过气相色谱分析完成测定。将固体组分溶解在酸性水中。用乙酸乙酯对溶液进行萃取，加入内标物，且在气相色谱仪中分析有机相样品，以确定起始催化剂化合物中供体存量。
X.I.的测定
将2.5g聚合物和250ml邻二甲苯置于装有冷却器和回流冷凝器的圆底烧瓶中，并保持在氮气下。将得到的混合物加热至135℃，并持续搅拌约60分钟。最终溶液在连续搅拌的条件下冷却至0℃，然后在0℃下过滤不溶性聚合物。然后将滤液在140℃的氮气流中蒸发，达到恒重。所述二甲苯可溶馏分的含量用初始2.5克的百分比来表示，然后通过差，确定X.I.％。
熔体流动速率(MFR)
聚合物的熔体流动速率MIL根据ISO 1133(230℃，2.16Kg)来确定。
实例
用于丙烯聚合的一般流程
在70℃下用氮气流对配备有搅拌器、压力表、温度计、催化剂进料系统、单体进料线和恒温夹套的4升不锈钢高压釜吹扫1个小时。然后，在30℃下在丙烯气流下，顺序装入75ml的无水己烷、0.76g的AlEt3、0.076g的二环戊基(D供体)和0.006÷0.010g的固体催化剂组分。封闭压力釜；随后加入2.0N]的氢。然后，在搅拌条件下，1.2kg的液体丙烯进行进料。在五分钟内将温度升高至70℃，且在该温度下聚合两个小时。在聚合结束时，除去未反应的丙烯；回收聚合物，并在70℃下真空干燥三个小时。然后，将聚合物称重并用邻二甲苯分级，以确定二甲苯不溶物(X.I.)级分的量。
供体的合成
下文报道的实例中所用的内部电子供体根据下列反应方案来制备：
其中
R2：正丙基、异丙基、叔丁基。
R：乙基、正丙基、正丁基、异丁基
t-BuONa：叔丁醇钠
NBS：N-溴代丁二酰亚胺
球形加合物的制备流程
根据WO98/44009的实施例2中描述的方法(但是进行了更大规模上的操作)来制备初始量的微球状MgCl2·2.8C2H5OH。载体加合物具有约为25微米的P50，和约为56wt％的乙醇含量。
实施例1-7和比较例1
固体催化剂组分的制备。
在配备有机械搅拌器、冷却器和温度计的500mL的圆底烧瓶中，在室温下在氮气气氛下引入250mL的TiCl4。冷却至0℃后，在搅拌时，表1中所示的内部供体和10.0g的球形加合物(如上文所述那样制备)依次加入到烧瓶中。带电内部供体的量使得Mg/供体的摩尔比为6。将温度升高到100℃，并维持2个小时。之后，停止搅拌，使固体产物能够在100℃沉降并将上清液虹吸抽出。在除去上清液后，加入额外的新鲜的TiCl4直到再次达到初始液体体积。然后，在120℃下加热混合物，并在此温度下保持1个小时。再次停止搅拌，使得固体能够沉降，并将上清液虹吸抽出。
在温度梯度降至60℃时用无水己烷将固体清洗六次(6x 100mL)，并在室温下清洗一次(100mL)。然后，将所得到的固体在真空下干燥并进行分析。
在比较例1中，供体添加导致球形加合物完全溶解，因此，不能沉降，且不能以任何方式回收。
实施例8和比较例2
在配备有机械搅拌器、冷却器和温度计的500mL的圆底烧瓶中，在室温下在氮气气氛下引入250mL的TiCl4。冷却至0℃后，在搅拌时，将10.0g的球形加合物(如上文所述那样制备)加入到烧瓶中。将温度升高至40℃并保持1小时。之后，停止搅拌，使固体产物能够在40℃下沉降，并将上清液虹吸抽出。除去上清液后，加入额外的新鲜的TiCl4直到再次达到初始液体体积，然后加入内部供体。带电内部供体的量使得Mg/供体的摩尔比为6。然后，在100℃下加热混合物，并在此温度下维持2个小时。再次停止搅拌，使固体能够沉降并将上清液虹吸抽出。在除去上清液后，加入额外的新鲜的TiCl4直到再次达到初始液体体积。然后，在120℃下加热混合物，并在此温度下保持1个小时。再次停止搅拌，使得固体能够沉降，并将上清液虹吸抽出。
在温度梯度降至60℃时用无水己烷将固体清洗六次(6x 100mL)，并在室温下清洗一次(100mL)。然后，将得到的固体在真空下干燥，并进行分析。
实施例9-11
固体催化剂组分根据实施例1-7的流程来制备，不同之处在于用TiCl4进行第一次处理在120℃而不是100℃下进行。
Claims (5)
1.一种用于烯烃聚合的催化剂组分，其包含Mg、Ti和选自以下物质的电子供体化合物：
2，2′-(4-丙基-1，2-亚苯基)二乙酸二乙酯、2，2′-(4-异丙基-1，2-亚苯基)二乙酸二乙酯、2，2′-(4-(叔丁基)-1，2-亚苯基)二乙酸二乙酯、2，2′-(4-氯-1，2-亚苯基)二乙酸二乙酯和2，2′-(5，5，8，8-四甲基-5，6，7，8-四氢化萘-2，3-二基)二乙酸二乙酯。
2.一种用于烯烃CH2＝CHR的聚合的催化剂，其中R是氢或具有1-12个碳原子的烃基，其包含通过接触以下物质得到的产物：
(i)根据权利要求1所述的催化剂组分和
(ii)烷基铝化合物和任选地，
(iii)外部电子供体化合物。
3.根据权利要求2所述的催化剂，其中外部电子供体选自化学式为(R6)a(R7)bSi(OR8)c的硅化合物，其中a和b是0-2的整数，c是1-4的整数，且(a+b+c)总和是4；R6、R7和R8是具有1-18个碳原子且任选地含有杂原子的烷基、环烷基或芳烃基。
4.一种用于烯烃CH2＝CHR的聚合的方法，其中R是氢或具有1-12个碳原子的烃基，在催化剂存在下进行，所述催化剂包含以下物质之间反应的产物：
(i)根据权利要求1所述的催化剂组分；
(ii)烷基铝化合物和，
(iii)任选的作为外部供体的电子-供体化合物。
5.一种用于烯烃CH2＝CHR的共聚的方法，其中R是氢或具有1-12个碳原子的烃基，在催化剂存在下进行，所述催化剂包含以下物质之间反应的产物：
(i)根据权利要求1所述的催化剂组分；
(ii)烷基铝化合物和，
(iii)任选的作为外部供体的电子-供体化合物。
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| Application Number | Priority Date | Filing Date | Title |
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| EP12171236.8 | 2012-06-08 | ||
| EP12171236.8A EP2671894A1 (en) | 2012-06-08 | 2012-06-08 | Catalyst components for the polymerization of butene-1 |
| PCT/EP2013/061546 WO2013182585A1 (en) | 2012-06-08 | 2013-06-05 | Catalyst components for the polymerization of olefins |
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| CN201380027480.4A Active CN104854141B (zh) | 2012-06-08 | 2013-06-05 | 用于烯烃聚合的催化剂组分 |
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| EP (3) | EP2671894A1 (zh) |
| JP (1) | JP5976927B2 (zh) |
| KR (1) | KR20150027138A (zh) |
| CN (2) | CN104540858A (zh) |
| BR (2) | BR112014029395A2 (zh) |
| ES (2) | ES2634138T3 (zh) |
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| JP6216634B2 (ja) * | 2013-12-17 | 2017-10-18 | 東邦チタニウム株式会社 | オレフィン類重合用固体触媒成分、オレフィン類重合用触媒及びオレフィン類重合体の製造方法 |
| CN103897080B (zh) * | 2014-04-19 | 2016-05-04 | 山东东方宏业化工有限公司 | 高等规聚丁烯的工业化生产方法及实施该方法的装置 |
| US9738736B2 (en) * | 2014-08-12 | 2017-08-22 | W. R. Grace & Co.-Conn | Combined internal donor system for Ziegler-Natta polyolefin catalysts and methods of making and using same |
| BR112018074123B1 (pt) * | 2016-05-23 | 2022-04-05 | W.R. Grace & Co. -Conn. | Componente catalisador sólido e sistema catalisador para uso na polimerização olefínica e processo para polimerização ou copolimerização de um monômero de olefina |
| CN112649464A (zh) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | 一种聚丁烯-1可溶物含量的检测方法 |
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| US4841003A (en) * | 1982-12-24 | 1989-06-20 | Mitsui Petrochemical Industries, Ltd. | Process for producing olefin polymers |
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| SE363977B (zh) | 1968-11-21 | 1974-02-11 | Montedison Spa | |
| YU35844B (en) | 1968-11-25 | 1981-08-31 | Montedison Spa | Process for obtaining catalysts for the polymerization of olefines |
| GB1603724A (en) | 1977-05-25 | 1981-11-25 | Montedison Spa | Components and catalysts for the polymerisation of alpha-olefins |
| IT1096661B (it) | 1978-06-13 | 1985-08-26 | Montedison Spa | Procedimento per la preparazione di prodotti in forma sferoidale solidi a temperatura ambiente |
| IT1098272B (it) | 1978-08-22 | 1985-09-07 | Montedison Spa | Componenti,di catalizzatori e catalizzatori per la polimerizzazione delle alfa-olefine |
| IT1190683B (it) | 1982-02-12 | 1988-02-24 | Montedison Spa | Componenti e catalizzatori per la polimerizzazione di olefine |
| ATE38044T1 (de) | 1984-08-30 | 1988-11-15 | Mitsui Petrochemical Ind | Buten-1-polymer und seine verwendung. |
| IT1230134B (it) | 1989-04-28 | 1991-10-14 | Himont Inc | Componenti e catalizzatori per la polimerizzazione di olefine. |
| IT1262934B (it) | 1992-01-31 | 1996-07-22 | Montecatini Tecnologie Srl | Componenti e catalizzatori per la polimerizzazione di olefine |
| IT1262935B (it) | 1992-01-31 | 1996-07-22 | Montecatini Tecnologie Srl | Componenti e catalizzatori per la polimerizzazione di olefine |
| IT1256648B (it) | 1992-12-11 | 1995-12-12 | Montecatini Tecnologie Srl | Componenti e catalizzatori per la polimerizzazione delle olefine |
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| TR199802467T1 (xx) | 1997-03-29 | 2001-07-23 | Montell Technology Company B.V. | Magnezyum diklor�r-alkol ad�ktleri, bunlar�n �retimi i�in i�lem ve bunlardan elde edilen kataliz�r bile�enleri. |
| CN1140545C (zh) | 1998-03-05 | 2004-03-03 | 蒙特尔技术有限公司 | 聚丁烯-1(共)聚合物及其制备方法 |
| CN1169845C (zh) | 2002-02-07 | 2004-10-06 | 中国石油化工股份有限公司 | 用于烯烃聚合的固体催化剂组分和含该催化剂组分的催化剂及其应用 |
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| Publication number | Publication date |
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| EP2859024B1 (en) | 2016-04-27 |
| CN104854141A (zh) | 2015-08-19 |
| JP2015517604A (ja) | 2015-06-22 |
| ES2573516T3 (es) | 2016-06-08 |
| EP2859024A1 (en) | 2015-04-15 |
| WO2013182585A1 (en) | 2013-12-12 |
| US20150141595A1 (en) | 2015-05-21 |
| BR112014029728A2 (pt) | 2017-06-27 |
| KR20150027138A (ko) | 2015-03-11 |
| CN104540858A (zh) | 2015-04-22 |
| ES2634138T3 (es) | 2017-09-26 |
| BR112014029395A2 (pt) | 2017-06-27 |
| WO2013182474A1 (en) | 2013-12-12 |
| EP2671894A1 (en) | 2013-12-11 |
| EP2859026A1 (en) | 2015-04-15 |
| EP2859026B1 (en) | 2017-06-28 |
| JP5976927B2 (ja) | 2016-08-24 |
| US20150141594A1 (en) | 2015-05-21 |
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