CN102124037B - 制备顺式1,4-聚二烯用催化剂 - Google Patents
制备顺式1,4-聚二烯用催化剂 Download PDFInfo
- Publication number
- CN102124037B CN102124037B CN200980132392.4A CN200980132392A CN102124037B CN 102124037 B CN102124037 B CN 102124037B CN 200980132392 A CN200980132392 A CN 200980132392A CN 102124037 B CN102124037 B CN 102124037B
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- Prior art keywords
- compound
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- aluminium
- neodymium
- nickel
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- 239000003054 catalyst Substances 0.000 title abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 124
- 150000001875 compounds Chemical class 0.000 claims abstract description 73
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 55
- 150000002367 halogens Chemical class 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 239000002168 alkylating agent Substances 0.000 claims abstract description 36
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 26
- 125000005843 halogen group Chemical group 0.000 claims abstract description 24
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 23
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 150000003624 transition metals Chemical class 0.000 claims abstract description 13
- -1 phospho Chemical class 0.000 claims description 116
- 229910052782 aluminium Inorganic materials 0.000 claims description 113
- 239000004411 aluminium Substances 0.000 claims description 103
- 229910052779 Neodymium Inorganic materials 0.000 claims description 88
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 87
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 67
- 239000000178 monomer Substances 0.000 claims description 57
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 42
- 150000002736 metal compounds Chemical class 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 34
- 229910052759 nickel Inorganic materials 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 29
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical group FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 238000005660 chlorination reaction Methods 0.000 claims description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 21
- 230000003197 catalytic effect Effects 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 14
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 claims description 14
- 229910015900 BF3 Inorganic materials 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 125000000304 alkynyl group Chemical group 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000004703 alkoxides Chemical class 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 11
- 150000002576 ketones Chemical class 0.000 claims description 11
- 150000002899 organoaluminium compounds Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 230000031709 bromination Effects 0.000 claims description 10
- 238000005893 bromination reaction Methods 0.000 claims description 10
- 150000002901 organomagnesium compounds Chemical class 0.000 claims description 10
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 9
- 230000029936 alkylation Effects 0.000 claims description 9
- 238000005804 alkylation reaction Methods 0.000 claims description 9
- UVPKUTPZWFHAHY-UHFFFAOYSA-L 2-ethylhexanoate;nickel(2+) Chemical compound [Ni+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O UVPKUTPZWFHAHY-UHFFFAOYSA-L 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- 230000026030 halogenation Effects 0.000 claims description 7
- 238000005658 halogenation reaction Methods 0.000 claims description 7
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 5
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 claims description 5
- 150000002798 neodymium compounds Chemical class 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001398 aluminium Chemical class 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 4
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 4
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 claims description 3
- VSCPNUIRAFSXSV-UHFFFAOYSA-N carbamic acid;neodymium Chemical compound [Nd].NC(O)=O VSCPNUIRAFSXSV-UHFFFAOYSA-N 0.000 claims description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000071 diazene Inorganic materials 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 3
- 239000012433 hydrogen halide Substances 0.000 claims description 3
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 claims description 3
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 claims description 3
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 claims description 3
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 claims description 3
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 claims description 3
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 claims description 3
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 claims description 3
- SCEZYJKGDJPHQO-UHFFFAOYSA-M magnesium;methanidylbenzene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C1=CC=CC=C1 SCEZYJKGDJPHQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 claims description 3
- OFDISMSWWNOGFW-UHFFFAOYSA-N 1-(4-ethoxy-3-fluorophenyl)ethanamine Chemical compound CCOC1=CC=C(C(C)N)C=C1F OFDISMSWWNOGFW-UHFFFAOYSA-N 0.000 claims description 2
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 claims description 2
- DSPXASHHKFVPCL-UHFFFAOYSA-N 1-isocyanocyclohexene Chemical compound [C-]#[N+]C1=CCCCC1 DSPXASHHKFVPCL-UHFFFAOYSA-N 0.000 claims description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- CIJHBFKEUTYXGP-UHFFFAOYSA-M C[Mg+].I(=O)(=O)[O-] Chemical compound C[Mg+].I(=O)(=O)[O-] CIJHBFKEUTYXGP-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 claims description 2
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims description 2
- WVJIOUJYLKKXMK-UHFFFAOYSA-N [Ni].C1=CC=CC1 Chemical compound [Ni].C1=CC=CC1 WVJIOUJYLKKXMK-UHFFFAOYSA-N 0.000 claims description 2
- ZBVTWYBFBVZMKE-UHFFFAOYSA-N [P]=O.[Br] Chemical compound [P]=O.[Br] ZBVTWYBFBVZMKE-UHFFFAOYSA-N 0.000 claims description 2
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 claims description 2
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 claims description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 2
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- JMBNQWNFNACVCB-UHFFFAOYSA-N arsenic tribromide Chemical compound Br[As](Br)Br JMBNQWNFNACVCB-UHFFFAOYSA-N 0.000 claims description 2
- OEYOHULQRFXULB-UHFFFAOYSA-N arsenic trichloride Chemical compound Cl[As](Cl)Cl OEYOHULQRFXULB-UHFFFAOYSA-N 0.000 claims description 2
- IKIBSPLDJGAHPX-UHFFFAOYSA-N arsenic triiodide Chemical compound I[As](I)I IKIBSPLDJGAHPX-UHFFFAOYSA-N 0.000 claims description 2
- AQIHMSVIAGNIDM-UHFFFAOYSA-N benzoyl bromide Chemical compound BrC(=O)C1=CC=CC=C1 AQIHMSVIAGNIDM-UHFFFAOYSA-N 0.000 claims description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 2
- 229940073608 benzyl chloride Drugs 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 2
- PIMYDFDXAUVLON-UHFFFAOYSA-M chloro(triethyl)stannane Chemical compound CC[Sn](Cl)(CC)CC PIMYDFDXAUVLON-UHFFFAOYSA-M 0.000 claims description 2
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical class CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- QPADTPIHSPAZLQ-UHFFFAOYSA-N ethyl 5-nitronaphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OCC)=CC=CC2=C1[N+]([O-])=O QPADTPIHSPAZLQ-UHFFFAOYSA-N 0.000 claims description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-AHCXROLUSA-N indium-111 Chemical compound [111In] APFVFJFRJDLVQX-AHCXROLUSA-N 0.000 claims description 2
- 229940055742 indium-111 Drugs 0.000 claims description 2
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 claims description 2
- 229940050176 methyl chloride Drugs 0.000 claims description 2
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- KWKDMHWAAVTQSZ-UHFFFAOYSA-N neodymium phosphoric acid Chemical compound [Nd].P(O)(O)(O)=O KWKDMHWAAVTQSZ-UHFFFAOYSA-N 0.000 claims description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 2
- VBLNFWKVZVKXPH-UHFFFAOYSA-L nickel(2+);2,2,2-trifluoroacetate Chemical compound [Ni+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F VBLNFWKVZVKXPH-UHFFFAOYSA-L 0.000 claims description 2
- GAIQJSWQJOZOMI-UHFFFAOYSA-L nickel(2+);dibenzoate Chemical compound [Ni+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAIQJSWQJOZOMI-UHFFFAOYSA-L 0.000 claims description 2
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- HSXSCKMVXBELIK-UHFFFAOYSA-N tetracosan-12-ylphosphonic acid Chemical class CCCCCCCCCCCCC(P(O)(O)=O)CCCCCCCCCCC HSXSCKMVXBELIK-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种制备顺式1,4-聚二烯用聚合催化剂组合物。该催化剂组合物包含(a)含金属化合物,所述金属是过渡金属或镧系金属;(b)卡宾;(c)烷基化剂,和可选的(d)含卤素化合物,条件是当含金属化合物和烷基化剂均不含有不稳定卤素原子时必须存在含卤素化合物。还提供一种聚二烯的生产方法,其包含在该聚合催化剂组合物存在下使共轭二烯反应。
Description
技术领域
本发明公开内容涉及制备顺式1,4-聚二烯用催化剂组合物。
背景技术
已知配位催化剂体系(齐格勒-纳塔型催化剂)可以用于将共轭二烯聚合为顺式1,4-聚二烯,例如,聚合1,3-丁二烯以形成顺式-1,4-聚丁二烯。这种配位催化剂体系可以基于过渡金属如钛、钴和镍,或镧系金属如钕。
通过配位催化剂体系生产的顺式1,4-聚二烯能够具有宽的分子量分布。因为具有窄的分子量分布的聚合物可以提供某些的优点如更高的耐磨耗性、更低的滞后和更好的拉伸性能,所期望的是开发能够生产具有更窄的分子量分布的顺式1,4-聚二烯的配位催化剂体系。
联合拥有(commonly owned)的2008年11月13日提交的美国专利申请序列号12/270,424,公开了镍基催化剂组合物,其包含(a)镍的N-杂环卡宾配合物,(b)有机铝化合物,(c)含氟化合物,和(d)可选的醇。该催化剂组合物可以生产顺式1,4-聚二烯,例如,具有窄的分子量分布和低乙烯基含量的高顺式1,4-聚丁二烯。然而,镍的N-杂环卡宾配合物必须在将其加入催化剂组合物之前制备。仍然存在对不需要在催化剂组合物之外(即,制备之前)制备的卡宾配合物的催化剂组合物的需求。
这里使用的“乙烯基含量”是指在聚合物链上乙烯基侧基的量,其源于1,2-加成而不是1,4-加成。
“过渡金属”是在IUPAC版周期表中的第3-12族的那些。
“镧系金属”是在周期表上57-71的元素。
发明内容
本发明公开内容提供一种聚合催化剂组合物,其包含:
(a)含金属化合物,所述金属选自由过渡金属和镧系金属组成的组;
(b)卡宾;
(c)烷基化剂;和可选的
(d)包括一种以上不稳定卤素原子的含卤素化合物,条件是当含金属化合物和烷基化剂均不含有不稳定卤素原子时必须存在含卤素化合物。
还提供一种聚二烯的生产方法,其包含在聚合催化剂组合物存在下使共轭二烯反应,所述聚合催化剂组合物包含:
(a)含金属化合物,所述金属选自由过渡金属和镧系金属组成的组;
(b)卡宾;
(c)烷基化剂;和可选的
(d)包含一种以上不稳定卤素原子的含卤素化合物,条件是当含金属化合物和烷基化剂均不含有不稳定卤素原子时必须存在含卤素化合物。
在优选实施方案中,共轭二烯是1,3-丁二烯。
具体实施方式
本发明公开内容目的在于聚合催化剂组合物,其包含(a)含金属化合物,所述金属选自由过渡金属和镧系金属组成的组;(b)卡宾;(c)烷基化剂;和可选的(d)包括一种以上不稳定卤素原子的含卤素化合物,其条件是当含金属化合物和烷基化剂均 不含有不稳定卤素原子时必须存在含卤素化合物。
通常,含金属化合物可以是任何起到用于二烯聚合的齐格勒-纳塔型催化剂作用的化合物。这样的化合物为本领域技术人员所熟知,包括含过渡金属如钛、钴和镍的化合物;和含镧系金属如镧、钕、铈、镨、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥和钕镨混合物的化合物。
在具有过渡金属的含金属化合物中优选含有镍的那些。含镍的化合物可以是任何镍盐或含有约1-20个碳原子的有机酸的镍盐。含镍化合物的一些代表性实例包括但不限于,苯甲酸镍、乙酸镍、环烷酸镍、辛酸镍、新癸酸镍、双(α-呋喃二肟)镍、棕榈酸镍、硬脂酸镍、乙酰丙酮酸镍、水杨醛镍、双(环戊二烯)镍、双(水杨醛)乙二亚胺镍、环戊二烯基-亚硝酰基镍、双(η3-烯丙基)镍、双(π-环辛-1,5-二烯)镍、双(η3-烯丙基镍三氟乙酸酯)、四羰基镍、硼酰化镍及其混合物。其它适合的含镍化合物包括但不限于,羧酸硼酸镍(nickel carboxylate borates),如具有式(RCOONiO)3B的那些,其中R是氢原子或烃基例如但不限于烷基、环烷基、取代环烷基、链烯基、环烯基、取代环烯基、芳基、取代芳基、芳烷基、烷芳基、烯丙基和炔基,其中各基团优选含有1个碳原子或形成该基团适当的最小碳原子数直至约20个碳原子。这些烃基可以含有杂原子例如但不限于氮、氧、硅、硫和磷原子。羧酸硼酸镍的具体实例包括新癸酸硼酸镍、己酸硼酸镍、环烷酸硼酸镍、硬脂酸硼酸镍、辛酸硼酸镍、2-乙基己酸硼酸镍及其混合物。
优选的含镍化合物是羧酸的镍盐或镍的有机配合物。环烷酸镍、辛酸镍和新癸酸镍是高度优选的含镍化合物。通常被称为辛酸镍的2-乙基己酸镍,是由于经济因素最常使用的含镍化合物。
适合的含钴化合物包括但不限于,苯甲酸钴、乙酸钴、环烷酸钴、双(α-呋喃二肟)钴、辛酸钴、棕榈酸钴、硬脂酸钴、乙酰丙酮钴、双(水杨醛乙二亚胺)钴、水杨醛钴和八羰基二钴。
至于具有镧系金属的含金属化合物,镧系原子可以处于各种氧化态,包括但不限于0、+2、+3和+4氧化态。优选三价镧系化合物,其中镧系原子处于+3氧化态。适合的镧系化合物包括但不限于,镧系元素羧酸盐、镧系元素有机磷酸盐、镧系元素有机膦酸盐、镧系元素有机次膦酸盐(organophosphinate)、镧系元素氨基甲酸盐、镧系元素二硫代氨基甲酸盐、镧系元素黄原酸盐、镧系元素β-二酮酸盐(lanthanide β-diketonate)、烷氧化或芳氧化镧系元素、镧系元素卤化物、镧系元素假卤化物、卤氧化镧系元素和有机镧系元素化合物。在具有镧系金属的含金属化合物中优选含有钕的那些。
适合的羧酸钕包括甲酸钕、乙酸钕、乙酸钕、丙烯酸钕、甲基丙烯酸钕、戊酸钕、葡萄糖酸钕、柠檬酸钕、富马酸钕、乳酸钕、马来酸钕、草酸钕、2-乙基己酸钕、新癸酸钕、环烷酸钕、硬脂酸钕、油酸钕、苯甲酸钕和吡啶甲酸钕。
适合的有机磷酸钕包括二丁基磷酸钕、二戊基磷酸钕、二己基磷酸钕、二庚基磷酸钕、二辛基磷酸钕、双(1-甲基庚基)磷酸钕、双(2-乙基己基)磷酸钕、二癸基磷酸钕、二-十二烷基磷酸钕、二-十八烷基磷酸钕、二油烯基磷酸钕、联苯基磷酸钕、双(对-壬基苯基)磷酸钕、丁基(2-乙基己基)磷酸钕、(1-甲基庚基)(2-乙基己基)磷酸钕、和(2-乙基己基)(对-壬基苯基)磷酸钕。
适合的有机膦酸钕包括丁基膦酸钕、戊基膦酸钕、己基膦酸钕、庚基膦酸钕、辛基膦酸钕、(1-甲基庚基)膦酸钕、(2-乙基己基)膦酸钕、癸基膦酸钕、十二烷基膦酸钕、十八烷基膦酸钕、油烯基膦酸钕、苯基膦酸钕、(对-壬基苯基)膦酸钕、丁基 丁基膦酸钕、戊基戊基膦酸钕、己基己基膦酸钕、庚基庚基膦酸钕、辛基辛基磷酸钕、(1-甲基庚基)(1-甲基庚基)膦酸钕、(2-乙基己基)(2-乙基己基)膦酸钕、癸基癸基膦酸钕、十二烷基十二烷基膦酸钕、十八烷基十八烷基膦酸钕、油烯基油烯基膦酸钕、苯基苯基膦酸钕、(对-壬基苯基)(对-壬基苯基)膦酸钕、丁基(2-乙基己基)膦酸钕、(2-乙基己基)丁基膦酸钕、(1-甲基庚基)(2-乙基己基)膦酸钕、(2-乙基己基)(1-甲基庚基)膦酸钕、(2-乙基己基)(对-壬基苯基)膦酸钕和(对-壬基苯基)(2-乙基己基)膦酸钕。
适合的有机次膦酸钕包括二丁基次膦酸钕、二戊基次膦酸钕、二己基次膦酸钕、二庚基次膦酸钕、二辛基次膦酸钕、双(1-甲基庚基)次膦酸钕、双(2-乙基己基)次膦酸钕、二癸基次膦酸钕、二-十二烷基次膦酸钕、二-十八烷基次膦酸钕、二油烯基次膦酸钕、二苯基次膦酸钕、双(对-壬基苯基)次膦酸钕、丁基(2-乙基己基)次膦酸钕、(1-甲基庚基)(2-乙基己基)次膦酸钕和(2-乙基己基)(对-壬基苯基)次膦酸钕。
适合的氨基甲酸钕包括二甲基氨基甲酸钕、二乙基氨基甲酸钕、二异丙基氨基甲酸钕、二丁基氨基甲酸钕和二苄基氨基甲酸钕。
适合的二硫代氨基甲酸钕包括二甲基二硫代氨基甲酸钕、二乙基二硫代氨基甲酸钕、二异丙基二硫代氨基甲酸钕、二丁基二硫代氨基甲酸钕和二苄基二硫代氨基甲酸钕。
适合的黄原酸钕包括甲基黄原酸钕、乙基黄原酸钕、异丙基黄原酸钕、丁基黄原酸钕和苄基黄原酸钕。
适合的β-二酮酸钕包括乙酰基丙酮酸钕、三氟乙酰基丙酮酸钕、六氟乙酰基丙酮酸钕、苯甲酰基丙酮酸钕和2,2,6,6-四甲基-3,5-庚烷二酮酸钕。
适合的烷氧化或芳氧化钕包括甲醇钕、乙醇钕、异丙醇钕、2-乙基己醇钕、苯酚钕、壬基苯酚钕和萘酚钕。
适合的卤化钕包括氟化钕、氯化钕、溴化钕和碘化钕。适合的假卤化钕包括氰化钕、氰酸钕、硫代氰酸钕、叠氮钕和亚铁氰化钕。适合的卤氧化钕包括氟氧化钕、氯氧化钕和溴氧化钕。在使用卤化钕、卤氧化钕或含有不稳定卤素原子的其它钕化合物的场合下,含钕化合物可以用作镧系化合物和含卤素化合物两者。路易斯碱如四氢呋喃(THF)可以作为这类钕化合物在惰性有机溶剂中的溶解助剂使用。
术语有机镧系化合物指任何含有至少一个镧系元素-碳键的镧系化合物。这些化合物主要是含有环戊二烯基(Cp)、取代环戊二烯基、烯丙基和取代烯丙基配体的那些,但并不排除其它的。适合的有机镧系化合物包括Cp3Ln、Cp2LnR、Cp2LnCl、CpLnCl2、CpLn(环辛四烯)、(C5Me5)2LnR、LnR3、Ln(烯丙基)3、和Ln(烯丙基)2Cl,其中Ln表示镧系原子并且R表示烃基。
卡宾用作催化剂组合物的组分(b)。优选,卡宾是N-杂环卡宾。适合的N-杂环卡宾包括但不限于,具有根据式I或II结构的那些:
其中R1和R2选自由C1-C12烷基、C2-C12烯基、C2-C12炔基、苯基、烷基-取代苯基及其混合组成的组,并且可以全部相同或全部分别地选择,但是不能是H;以及R3和R4选自由H、C1-C12烷基、C2-C12烯基、C2-C12炔基、苯基、烷基-取代苯基及其混合组成的组,并且可以全部相同或全部分别地选择。
适合的N-杂环卡宾包括但不限于,1,3-二异丙基-4,5-二甲基咪唑-2-叉基(imidazol-2-ylidene)、1,3-双-(2,4,6-三甲基苯基)-咪唑-2-叉基、1,3-双-(2,6-二异丙基苯基)-咪唑-2-叉基(由式IV表示)、1,3-二环己基咪唑-2-叉基、1,3-二-叔丁基咪唑-2-叉基、1,3-二金刚烷基咪唑-2-叉基、1,3-双-(2,6-二异丙基苯基)-4,5-二氢化咪唑-2-叉基(由式III表示)及其混合物。根据式III和IV的卡宾可以通过公开在B.R.Dible,M.S.Sigman,J.Am.Chem.Soc.,2003,125,872中的方法制备,在此以其全部内容引入以作参考。此外,许多根据式I-IV的卡宾可以从供应商如Strem Chemicals,Inc.和Sigma-Aldrich Co.商购可得。
在一个特别优选的实施方案中,N-杂环卡宾可以具有根据式III或IV的结构:
各种烷基化剂或其混合物可以用作催化剂组合物的组分(c)。烷基化剂(也可以称作烃基化剂)是可以将烃基转移至另一金属的有机金属化合物。典型地,这些试剂是正电性金属如第1、2和3族金属(第IA、IIA和IIIA族的金属)的有机金属化合物。优选烷基化剂包括有机铝和有机镁化合物。在烷基化剂包括不稳定卤素原子的场合下,烷基化剂也可以起到含卤素化合物的作用。
术语“有机铝化合物”指任何含有至少一个铝-碳键的铝化合物。优选可溶于烃溶剂的有机铝化合物。可以利用的有机铝 化合物的优选类由通式AlR5 nX3-n表示,其中各R5可以相同或不同,是经由碳原子连接至铝原子的单价有机基团;其中各X可以相同或不同,是氢原子、卤素原子、羧酸酯基、烷氧化物基团(alkoxide group)或芳氧化物基团(aryloxide group);其中n是1至3的整数。优选各R5是烃基例如,但不限于,烷基、环烷基、取代环烷基、烯基、环烯基、取代环烯基、芳基、取代芳基、芳烷基、烷芳基、烯丙基和炔基,其中各基团优选含有1个碳原子或形成该基团适当的最小碳原子数直至约20个碳原子。这些烃基可以含有杂原子例如,但不限于,氮、氧、硼、硅、硫和磷原子。
适合的有机铝化合物包括但不限于,三烃基铝、氢化二烃基铝、二氢化烃基铝、二烃基铝羧酸盐、烃基铝双(羧酸盐)、烷氧化二烃基铝、二烷氧化烃基铝、卤化二烃基铝、二卤化烃基铝、芳氧化二烃基铝和二芳氧化烃基铝化合物。优选三烃基铝、氢化二烃基铝和二氢化烃基铝化合物。
适合的三烃基铝化合物包括三甲基铝、三乙基铝、三异丁基铝、三正丙基铝、三异丙基铝、三正丁基铝、三叔丁基铝、三正戊基铝、三新戊基铝、三正己基铝、三正辛基铝、三(2-乙基己基)铝、三环己基铝、三(1-甲基环戊基)铝、三苯基铝、三对甲苯基铝、三(2,6-二甲基苯基)铝、三苄基铝、二乙基苯基铝、二乙基对甲苯基铝、二乙基苄基铝、乙基二苯基铝、乙基二对甲苯基铝和乙基二苄基铝。
适合的氢化二烃基铝化合物包括氢化二乙基铝、氢化二正丙基铝、氢化二异丙基铝、氢化二正丁基铝、氢化二异丁基铝、氢化二正辛基铝、氢化二苯基铝、氢化二对甲苯基铝、氢化二苄基铝、氢化苯基乙基铝、氢化苯基正丙基铝、氢化苯基异丙基铝、氢化苯基正丁基铝、氢化苯基异丁基铝、氢化苯基正辛 基铝、氢化对甲苯基乙基铝、氢化对甲苯基正丙基铝、氢化对甲苯基异丙基铝、氢化对甲苯基正丁基铝、氢化对甲苯基异丁基铝、氢化对甲苯基正辛基铝、氢化苄基乙基铝、氢化苄基正丙基铝、氢化苄基异丙基铝、氢化苄基正丁基铝、氢化苄基异丁基铝和氢化苄基正辛基铝。
适合的二氢化烃基铝包括二氢化乙基铝、二氢化正丙基铝、二氢化异丙基铝、二氢化正丁基铝、二氢化异丁基铝和二氢化正辛基铝。
适合的氯化二烃基铝化合物包括氯化二乙基铝、氯化二丙基铝、氯化二正丙基铝、氯化二异丙基铝、氯化二正丁基铝、氯化二异丁基铝、氯化二正辛基铝、氯化二苯基铝、氯化二对甲苯基铝、氯化二苄基铝、氯化苯基乙基铝、氯化苯基正丙基铝、氯化苯基异丙基铝、氯化苯基正丁基铝、氯化苯基异丁基铝、氯化苯基正辛基铝、氯化对甲苯基乙基铝、氯化对甲苯基正丙基铝、氯化对甲苯基异丙基铝、氯化对甲苯基正丁基铝、氯化对甲苯基异丁基铝、氯化对甲苯基正辛基铝、氯化苄基乙基铝、氯化苄基正丙基铝、氯化苄基异丙基铝、氯化苄基正丁基铝、氯化苄基异丁基铝和氯化苄基正辛基铝。
适合的二氯化烃基铝包括二氯化乙基铝、二氯化正丙基铝、二氯化异丙基铝、二氯化正丁基铝、二氯化异丁基铝和二氯化正辛基铝。
其它的有机铝化合物包括己酸二甲基铝、辛酸二乙基铝、2-乙基己酸二异丁基铝、新癸酸二甲基铝、硬脂酸二乙基铝、油酸二异丁基铝、甲基铝双(己酸盐)、乙基铝双(辛酸盐)、异丁基铝双(2-乙基己酸盐)、甲基铝双(新癸酸盐)、乙基铝双(硬脂酸盐)、异丁基铝双(油酸盐)、二甲基铝甲醇盐、二乙基铝甲醇盐、二异丁基铝甲醇盐、二甲基铝乙醇盐、二乙基铝乙醇盐、 二异丁基铝乙醇盐、二甲基铝苯酚盐、二乙基铝苯酚盐、二异丁基铝苯酚盐、甲基铝二甲醇盐、乙基铝二甲醇盐、异丁基铝二甲醇盐、甲基铝二乙醇盐、乙基铝二乙醇盐、异丁基铝二乙醇盐、甲基铝二苯酚盐、乙基铝二苯酚盐和异丁基铝二苯酚盐等,及其混合物。
适合的有机铝化合物的另一类是铝氧烷。铝氧烷包含可以由通式表示的低聚线型铝氧烷:
和可以由通式表示的低聚环状铝氧烷:
其中x是1-约100的整数,优选约10-约50;y是2-约100的整数,优选约3-约20;和其中各R6可以相同或不同,是经由碳原子连接至铝原子的单价有机基团。优选各R6是烃基,例如但不限于烷基、环烷基、取代环烷基、链烯基、环烯基、取代环烯基、芳基、取代芳基、芳烷基、烷芳基、烯丙基和炔基,其中各基团优选含有1个碳原子或形成该基团适当的最小碳原子数直至约20个碳原子。这些烃基可以含有杂原子,例如但不限于氮、氧、硼、硅、硫和磷原子。应当注意,用于本申请的铝氧烷的摩尔数指铝原子的摩尔数而不是低聚铝氧烷分子的摩尔数。该惯例通常用在利用铝氧烷的催化剂技术领域。
铝氧烷可以通过三烃基铝化合物与水反应制备。该反应可以根据已知的方法进行,例如(1)其中将三烃基铝化合物溶解在有机溶剂中,然后与水接触的方法,(2)其中三烃基铝化合物与包含于如金属盐的结晶水或吸附于无机或有机化合物的水反应的方法,和(3)其中三烃基铝化合物与存在于将要聚合的单体或单体溶液中的水反应的方法。
适合的铝氧烷化合物包括甲基铝氧烷(MAO)、改性的甲基铝氧烷(MMAO)、乙基铝氧烷、正丙基铝氧烷、异丙基铝氧烷、丁基铝氧烷、异丁基铝氧烷、正戊基铝氧烷、新戊基铝氧烷、正己基铝氧烷、正辛基铝氧烷、2-乙基己基铝氧烷、环己基铝氧烷、1-甲基环戊基铝氧烷、苯基铝氧烷和2,6-二甲基苯基铝氧烷等,及其混合物。由于其可得性以及其在脂族和脂环族烃溶剂中的溶解性,因此异丁基铝氧烷是特别有用的。可以通过使用该领域技术人员所熟知的技术借助用C2-C12烃基、优选用异丁基取代甲基铝氧烷中约20-80%的甲基形成改性的甲基铝氧烷。
铝氧烷可以单独或与其它的有机铝化合物组合使用。在一个优选实施方案中,甲基铝氧烷和氢化二异丁基铝组合使用。
术语“有机镁化合物”指任何含有至少一个镁-碳键的镁化合物。优选可溶于烃溶剂的有机镁化合物。可以利用的有机镁化合物的优选类由通式MgR7 2表示,其中各R7可以相同或不同,是单价有机基团,条件是该基团经由碳原子连接至镁原子。优选各R7是烃基,例如但不限于烷基、环烷基、取代环烷基、链烯基、环烯基、取代环烯基、芳基、烯丙基、取代芳基、芳烷基、烷芳基和炔基,其中各基团优选含有1个碳原子或形成该基团适当的最小碳原子数直至约20个碳原子。这些烃基可以含有杂原子,例如但不限于氮、氧、硅、硫和磷原子。
可以利用的适合的二烃基镁化合物的一些具体实例包括二乙基镁、二正丙基镁、二异丙基镁、二丁基镁、二己基镁、二苯基镁、二苄基镁及其混合物。由于其可得性以及其在脂族和脂环族烃溶剂中的溶解性,二丁基镁是特别有用的。
可以用作成分(c)的有机镁化合物的另一类由通式R8MgX表示,其中R8是单价有机基团,条件是该基团经由碳原子连接至镁原子,并且X是氢原子、卤素原子、羧酸酯基、烷氧化物基团或芳氧化物基团。在烷基化剂是包括不稳定卤素原子的有机镁化合物的场合下,有机镁化合物可以充当烷基化剂和含卤素化合物两者。优选R8是烃基,例如但不限于烷基、环烷基、取代环烷基、链烯基、环烯基、取代环烯基、芳基、烯丙基、取代芳基、芳烷基、烷芳基和炔基,其中各基团优选含有1个碳原子或形成该基团适当的最小碳原子数直至约20个碳原子。这些烃基可以含有杂原子,例如但不限于氮、氧、硼、硅、硫和磷原子。优选X是羧酸酯基、烷氧化物基团或芳氧化物基团,其中各基团优选含有1-20个碳原子。
由通式R8MgX表示的有机镁化合物的一些适合的类型包括但不限于,氢化烃基镁、卤化烃基镁、羧酸烃基镁、烃基镁醇盐、烃基镁酚盐及其混合物。
由通式R8MgX表示的适合的有机镁化合物的一些具体实例包括氢化甲基镁、氢化乙基镁、氢化丁基镁、氢化己基镁、氢化苯基镁、氢化苄基镁、氯化甲基镁、氯化乙基镁、氯化丁基镁、氯化己基镁、氯化苯基镁、氯化苄基镁、溴化甲基镁、溴化乙基镁、溴化丁基镁、溴化己基镁、溴化苯基镁、溴化苄基镁、己酸甲基镁、己酸乙基镁、己酸丁基镁、己酸己基镁、己酸苯基镁、己酸苄基镁、甲基镁乙醇盐、乙基镁乙醇盐、丁基镁乙醇盐、己基镁乙醇盐、苯基镁乙醇盐、苄基镁乙醇盐、 甲基镁苯酚盐、乙基镁苯酚盐、丁基镁苯酚盐、己基镁苯酚盐、苯基镁苯酚盐和苄基镁苯酚盐等,及其混合物。
含有一种以上不稳定卤素原子的各种化合物或其混合物可以用作催化剂组合物的成分(d)。这些化合物可以简单地称为含卤素化合物。卤素原子的实例包括但不限于,氟、氯、溴和碘。也可以将两种以上卤素原子组合使用。优选可溶于烃溶剂的含卤素化合物。然而,不溶于烃的含卤素化合物可以悬浮在低聚反应介质中以形成催化活性种类,因此是有用的。
含卤素化合物的可用类型包括但不限于,卤素单质、混合的卤素、卤化氢、有机卤化物、无机卤化物、金属卤化物、有机金属卤化物及其混合物。
适合的卤素单质包括氟、氯、溴和碘。适合的混合的卤素的一些具体实例包括单氯化碘、单溴化碘、三氯化碘和五氟化碘。
适合的卤化氢包括氟化氢、氯化氢、溴化氢和碘化氢。
适合的有机卤化物包括叔丁基氯、叔丁基溴、烯丙基氯、烯丙基溴、苄基氯、苄基溴、氯-二苯基甲烷、溴-二苯基甲烷、三苯基甲基氯、三苯基甲基溴、苄叉基氯化物、苄叉基溴化物、甲基三氯硅烷、苯基三氯硅烷、二甲基二氯硅烷、二苯基二氯硅烷、三甲基氯硅烷、苯甲酰氯、苯甲酰溴、丙酰氯、丙酰溴、氯代甲酸甲酯和溴代甲酸甲酯。
适合的无机卤化物包括三氯化磷、三溴化磷、五氯化磷、氯氧化磷、溴氧化磷、三氟化硼、三氯化硼、三溴化硼、四氟化硅、四氯化硅、四溴化硅、四碘化硅、三氯化砷、三溴化砷、三碘化砷、四氯化硒、四溴化硒、四氯化碲、四溴化碲和四碘化碲。
适合的金属卤化物包括四氯化锡、四溴化锡、三氯化铝、 三溴化铝、三氯化锑、五氯化锑、三溴化锑、三碘化铝、三氟化铝、三氯化镓、三溴化镓、三碘化镓、三氟化镓、三氯化铟、三溴化铟、三碘化铟、三氟化铟、四氯化钛、四溴化钛、四碘化钛、二氯化锌、二溴化锌、二碘化锌和二氟化锌。
适合的有机金属卤化物包括氯化二甲基铝、氯化二乙基铝、溴化二甲基铝、溴化二乙基铝、氟化二甲基铝、氟化二乙基铝、二氯化甲基铝、二氯化乙基铝、二溴化甲基铝、二溴化乙基铝、二氟化甲基铝、二氟化乙基铝、倍半氯化甲基铝、倍半氯化乙基铝、倍半氯化异丁基铝、氯化甲基镁、溴化甲基镁、碘化甲基镁、氯化乙基镁、溴化乙基镁、氯化丁基镁、溴化丁基镁、氯化苯基镁、溴化苯基镁、氯化苄基镁、氯化三甲基锡、溴化三甲基锡、氯化三乙基锡、溴化三乙基锡、二氯化二-叔丁基锡、二溴化-二-叔丁基锡、二氯化二丁基锡、二溴化二丁基锡、氯化三丁基锡和溴化三丁基锡。
如果催化剂组合物的组分(a)中的含金属化合物含有过渡金属,期望含卤素化合物是含氟化合物。适合的含氟化合物包括但不限于,氟化氢、三氟化硼、四氟化硅、三氟化铝、三氟化铟、二氟化锌、氟化二甲基铝、氟化二乙基铝和二氟化甲基铝。优选含氟化合物包括氟化氢、三氟化硼、以及与由一元醇、酚、水、含氧无机酸、水、醛、酯、醚、酮和腈组成的类中的一个络合的氟化氢和三氟化硼。
酮的子集可以由式R9COR10定义,其中R9和R10表示含有1-约30个碳原子的烷基、环烷基、芳基、烷芳基和芳烷基;R9和R10可以相同或不同。这些酮表示具有通过双键连接至氧的碳原子类别的化合物。用于本发明公开内容的三氟化硼和氟化氢配合物的制备的代表性而非详尽的酮是丙酮、甲乙酮、二丁基酮、甲基异丁基酮、乙基辛基酮、2,4-戊二酮、丁基环庚酮、苯乙 酮、戊基苯基酮、丁基苯基酮、二苯甲酮、苯基甲苯基酮和醌等。典型的酮的配合物是三氟化硼.苯乙酮和三氟化硼.二苯甲酮,也可以是氟化氢.苯乙酮和氟化氢.二苯甲酮和氟化氢。
醛的子集可以由式R11--CHO定义,其中R11表示含有1-约30个碳原子的烷基、环烷基、芳基、烷芳基和芳烷基。该醛具有通过双键连接至氧原子的碳原子。代表性而非详尽的醛是丁醛、茴香醛、肉桂醛、异丁醛、庚醛、十二醛、苯甲醛、苯乙醛、甲基苯甲醛、间-硝基苯甲醛、对-硝基苯甲醛和间-羟基苯甲醛(hydrobenzaldehyde)等。例如,可以由醛形成的典型的配合物是三氟化硼-苯甲醛、三氟化硼-甲基苯甲醛、氟化氢-苯甲醛和氟化氢-甲基苯甲醛。
酯的子集可以由式R12-COOR13表示,其中R12和R13表示含有1-约30个碳原子的烷基、环烷基、芳基、烷芳基和芳烷基。该酯含有通过双键连接至氧原子的碳原子。代表性而非详尽的酯是丁酸乙酯、辛酸乙酯、己酸异丙酯、乙酸戊酯、丙酸己酯、乙酸十六酯、苯甲酸乙酯、苯甲酸戊酯、乙酸苯酯、丁酸苯酯和苯甲酸苯酯等。例如,由该酯形成的典型的配合物是三氟化硼-苯甲酸乙酯和三氟化硼-乙酸苯酯;也可以是氟化氢-苯甲酸乙酯和氟化氢-乙酸苯酯。
醚的子集可以由式R14--O-R14定义,其中各R14独立的表示含有1-约30个碳原子的烷基、环烷基、芳基、烷芳基和芳烷基。代表性而非详尽的醚是乙氧基丁烷、乙氧基辛烷、异丙氧基己烷、丙氧基乙烷、乙氧基苯和戊氧基苯等。
腈的子集可以由式R15CN表示,其中R15表示烷基、环烷基、芳基、烷芳基和芳烷基。该腈含有通过三键连接至氮原子的碳原子。代表性而非详尽的腈的子集是乙腈、丁腈、丙烯腈、苯基氰、苄基氰和苯乙腈等。例如,由亚硝酸盐制备的典型的配 合物是三氟化硼.苯基氰和氟化氢.苯基氰。
上述类别化合物的一元醇子集可以象征地描述为R16OH,其中R16表示含有1-30个碳原子的烷基、环烷基和芳烷基。代表性而非详尽的醇组是甲醇、乙醇、正丙醇、异丙醇、正丁醇和苯甲醇等。例如,由上述组形成的典型的配合物如下:BF3甲醇、BF3乙醇、BF3丁醇、BF3正己醇、HF甲醇、HF丁醇和HF己醇。
上述类别化合物的酚子集可以象征地描述为PHI-OH,其中PHI表示苯型基团。代表性而非详尽的酚组是苯酚、对甲苯酚、间苯二酚、萘酚和氢醌等。例如,由上述苯酚子集形成的典型的配合物如下:BF32-苯酚、BF3对甲苯酚、HF对甲苯酚和HF苯酚。
含氧无机酸子集中的许多成员将与BF3和HF络合。代表性而非详尽的无机酸子集是磷酸、硫酸和硝酸等。例如,由该无机酸子集形成的配合物的实例是BF3100%磷酸、BF385%磷酸和HF100%磷酸。
尽管自成一个子集,水形成至少两种水合配合物。它们是BF3.H2O和BF3.2H2O。
当无法商购可得时,许多三氟化硼配合物可以通过直接将三氟化硼气体(在常温和常压下的无色气体)与用作络合剂的化合物也就是电子供体化合物接触容易地形成。该接触是用结合有灵敏的称量装置的反应设备实现的,以便获得期望的BF3和电子供体化合物之间的摩尔比。反应是在惰性气氛下进行的。反应环境可以仅由反应组分BF3气体和电子供体化合物组成,或适当时,反应可以在惰性有机稀释剂的介质中进行。当电子供体化合物作为固体存在并且必须放入溶液或悬浮液以确保与BF3气体充分接触时,这最后的条件通常是必须的。
各种三氟化硼配合物在其保存期限稳定性上变化显著。一些,例如BF3·异丙醇,在室温下日光中是相当不稳定的。其它的,例如BF3·苯酚在室温下相当稳定并且具有相对长的保存期限。在特别是BF3配合物具有不稳定保存期限的场合下,期望其尽可能接近聚合的时间制备。
氟化氢配合物通常具有低蒸气压并且不像氟化氢那样发烟。氟化氢在19.7℃沸腾,而40重量%氟化氢二乙醚共沸物在74℃沸腾。当络合氟化氢时,氟化氢的腐蚀性降低。氟化氢配合物可以溶于溶剂并由此可以作为溶液处理和注入体系。能够利用的溶剂可以是烷基、烷芳基、芳烷基或芳基烃。例如甲苯是合适的溶剂体系。
BF3和HF配合物可以通过将适量的络合剂例如酮、醚、酯、醇、腈或水溶于适合的溶剂中,以及适量的氟化氢溶于适合的溶剂中,并混合两种溶剂体系来制备。除了水以外,络合剂的混合可以在没有水蒸汽下进行。另一个可行方法是将氟化氢或络合剂之一溶于适合的溶剂中,并将另一个组分加入。还有另一个混合方法是将络合剂溶于溶剂中并鼓泡气态氟化氢通过该体系直到络合剂与氟化氢反应。浓度可以通过重量的增加或化学滴定测定。期望的络合剂的量可以在依赖于反应体系的条件、络合剂的氢键强度、络合剂的尺寸的范围内,或其可以为氟化氢配合物与氟化氢加上络合剂之间的平衡。
任何一种催化剂组分的最佳浓度依赖于各其它的催化剂组分浓度。此外,使用的催化剂浓度依赖于如纯度、期望的速率和温度等的因素及其它因素。虽然聚合在催化剂浓度和摩尔比的宽范围内进行,但具有最期望性质的聚合物在更窄的范围内获得。
在一个实施方案中,含金属化合物以约0.01mmol金属/100g 单体至约0.4mmol金属/100g单体的催化量存在,优选以约0.02mmol金属/100g单体至约0.2mmol金属/100g单体的催化量存在。卡宾可以以约0.01mmol卡宾/100g单体至约0.4mmol卡宾/100g单体的催化量存在,优选以约0.02mmol卡宾/100g单体至约0.2mmol卡宾/100g单体的催化量存在。烷基化剂可以以约0.15mmol烷基化金属/100g单体至约20.0mmol烷基化金属/100g单体的催化量存在,优选以约0.30mmol烷基化金属/100g单体至约6.0mmol烷基化金属/100g单体的催化量存在(术语“烷基化金属”指在烷基化剂中的金属)。含卤素化合物可以以约0.01mmol卤素/100g单体至约12.0mmol卤素/100g单体的催化量存在,优选以约0.04mmol卤素/100g单体至约6.0mmol卤素/100g单体的催化量存在。
催化剂组合物可以通过将含金属化合物、卡宾、烷基化剂和可选的含卤素化合物组合或混合来形成。
尽管认为活性催化剂物种由该组合产生,但是无法以任何大的确定度知道各种成分或组分之间的相互作用或反应的程度。因此,使用术语“催化剂组合物”以涵盖所述成分的简单混合物、通过物理或化学的吸引力导致的各种成分的配合物、所述成分的化学反应产物、或前述的组合。
本发明公开内容的催化剂组合物可以通过使用以下方法中之一形成。
第一,催化剂组合物可以通过将催化剂成分以阶梯式或同时方式加入含单体和溶剂的溶液中或者仅本体单体中而原位形成。当以阶梯式加入催化剂成分时,其中添加催化剂成分的顺序不是关键的。然而优选首先添加含金属化合物,接着是烷基化剂,接着是卡宾,接着是含卤素化合物。
第二,催化剂成分可以在通常为约-20℃至约80℃的适当温 度下在聚合体系外预混合,然后将所得催化剂组合物加入单体溶液。
第三,催化剂组合物可以在至少一种共轭二烯单体存在下预形成。也就是说,催化剂成分是在通常为约-20℃至约80℃的适当温度下在少量共轭二烯单体存在下预混合。用于预形成催化剂的共轭二烯单体的量可以在基于每摩尔含金属化合物为约1至约500摩尔,更优选基于每摩尔含金属化合物为约5至约250摩尔,甚至更优选基于每摩尔含金属化合物为约10至约100摩尔的范围内。然后将所得催化剂组合物加入至其余要聚合的共轭二烯单体。预形成催化剂可以通过将催化剂成分和至少一种共轭二烯单体以阶梯式或同时方式之一加入来形成。当以阶梯式加入催化剂成分和共轭二烯单体时,其中添加催化剂成分和共轭二烯单体的顺序不是关键的。然而优选首先加入共轭二烯单体,接着是含金属化合物,接着是烷基化剂,接着是卡宾,接着是含卤素化合物。
第四,催化剂组合物可以通过使用两阶段步骤形成。第一阶段包括将烷基化剂与含金属化合物和卡宾在没有共轭二烯单体的情况下,或在少量共轭二烯单体存在下,在通常约-20℃至约80℃的适当温度下组合。在第二阶段,如有必要,将上述反应混合物和剩余催化剂组分(即,含卤素化合物)以阶梯式或同时方式添加至剩余要聚合的共轭二烯单体。
在任何上述形成催化剂组合物的步骤中,期望含金属化合物和卡宾在至少一种所述共轭二烯、所述烷基化剂或如果存在的所述含卤素化合物的存在下组合。换句话说,期望含金属化合物和卡宾不与自身组合。
当催化剂组合物溶液或一种以上催化剂成分的溶液如上述方法阐述的在聚合体系外制备时,优选使用有机溶剂或载体。 有机溶剂可以用来溶解催化剂组合物或成分,或该溶剂可以仅仅充当催化剂组合物或成分可以悬浮其中的载体。优选有机溶剂是对催化剂组合物惰性的。有用的溶剂包括烃熔剂如芳烃、脂族羟和脂环族烃。芳烃溶剂的非限制性实例包括苯、甲苯、二甲苯、乙苯、二乙基苯和均三甲苯等。脂族烃溶剂的非限制性实例包括正戊烷、正己烷、正庚烷、正辛烷、正壬烷、正癸烷、异戊烷、异己烷、异戊烷、异辛烷、2,2-二甲基丁烷、石油醚、煤油和石油溶剂油等。以及脂环族烃熔剂的非限制性实例包括环戊烷、环己烷、甲基环戌烷和甲基环己烷等。也可以使用上述烃的商购混合物。由于环境原因,高度优选脂族和脂环族溶剂。
优选聚合在作为稀释剂的有机溶剂中进行。在一个实施方案中,使用溶液聚合体系,该溶液聚合体系是要聚合的单体和形成的聚合物可溶于聚合介质的体系。可选择地,通过选择形成的聚合物不溶于其中的溶剂,可以使用沉淀聚合体系。在这两种情况下,要聚合的单体处于凝聚相(condensed phase)中。此外,优选催化剂成分是可溶或悬浮在有机溶剂之内。换句话说,优选催化剂成分不浸渍在催化剂载体上。
在进行这些聚合中,优选将可用于制备催化剂组合物的有机溶剂的量之外的有机溶剂的量添加至聚合体系。额外的有机溶剂可以相同或不同于用于制备催化剂组合物的有机溶剂。优选选择相对于用于催化聚合的催化剂组合物是惰性的有机溶剂。以上已经阐明示例性的烃熔剂。当使用溶剂时,要聚合的单体的浓度不限于任何特别的量。然而优选,在聚合开始时存在于聚合介质中的单体浓度应当是在聚合介质和单体的组合重量的约3重量%-约80重量%,更优选约5重量%-约50重量%,甚至更优选约10重量%-约30重量%的范围内。
聚合也可以通过本体聚合进行,所述本体聚合指没有使用任何单独的溶剂的聚合环境。本体聚合可以在浓缩液相中或在气相中实施。
聚合可以以间歇法、连续法或半连续法进行。在半连续法中,单体是因需要替代已经聚合的单体而间歇地装入。在任何情况下,优选在通过使用惰性保护气体如氮、氩或氦的缺氧条件下随着温和至剧烈搅拌下进行聚合。聚合温度可以从低温如约-10℃以下至高温如约100℃以上广泛地变化,其中优选温度范围是约20℃至约90℃。可以通过外冷却、借助单体或溶剂的蒸发的冷却、或这两种方法的组合来除去聚合热。尽管使用的聚合压力可以广泛地变化,优选压力范围是约1个大气压至约10个大气压。
一旦达到期望的转化率,可以通过添加聚合停止剂以使催化剂失活来停止聚合。典型地,聚合的时间为约20分钟至约24小时,并且依赖于其它的聚合条件如温度以及催化剂的选择。典型地,使用的停止剂是质子化合物,其包括但不限于醇、羧酸、无机酸、水或其混合物。
在一个实施方案中,用于本发明公开内容的停止剂混合物包括在胺-水混合物中的无机碱。当BF3用作含卤素化合物并且水和胺的混合物用于停止聚合时,水与有机铝化合物和/或BF3反应以使催化剂组分失活,留下胺可以与三烷基硼烷反应。胺-水混合物的使用在题目为“Low Gel High Cis Polydiene(低凝胶高顺聚二烯)”的共同转让的美国专利6,596,825中详细说明了,在此将其公开内容以其全部引入以作参考。无机碱可用于中和停止和聚合反应产生的酸性副产物。通过提高体系的pH,这使得添加较少的胺并减少或消除在反应容器中的腐蚀。
该无机碱/胺/水混合物可以共同或顺序地添加。在一个实 施方案中该混合物可以顺序地添加。胺∶水的摩尔比可以是约1∶100,并且在更具体的实施方案中为约1∶500。停止剂混合物的水组分可以额外地包括醇。在一个实施方案中,醇是一种以上的甲醇、乙醇、异丙醇、丙醇和丁醇。当包含时,水∶醇的比可以为约1∶500,并且在更具体的实施方案中为约1∶50。可选择地,可以从停止剂中省略水,以致停止剂混合物仅包括胺/无机碱混合物。
适合的胺包括氨、氢氧化铵、伯胺、仲胺、叔胺、脂肪胺和芳香胺。示例性胺包括但不限于,吡啶、苯胺、苄胺、正丁胺、环己胺、二乙胺、二异丙胺、二甲胺、二苯胺、乙胺、乙二胺、己二胺、N,N-二乙基环己胺、N,N-二甲基环己胺、N,N,N′-三甲基乙二胺、N,N,N′N′-四甲基乙二胺(TMEDA),和取代吡啶如N,N-二甲基氨基吡啶(DMAP)、4-吡咯烷基吡啶和4-哌啶子基吡啶。有或者没有使用水时,TMEDA可以用作停止剂混合物的胺组分。
另一适合的停止剂混合物包括羧酸和无机碱。无机碱包括上述那些。适合的羧酸包括由下式表示的那些:
R17-COOH其中R17选自由含3-20个碳原子的取代或未取代的烷基、环烷基和芳烷基组成的组。可以用于停止剂混合物中使用的羧酸是2-乙基己酸(EHA)。羧酸的金属盐也可以添加至停止剂混合物。因此,另一适合的停止剂混合物包括EHA和EHA钙盐的混合物。与上述适合的胺类停止剂混合物一样,水可以或不可以包括在羧酸类停止剂混合物中。再次,认为无机碱是与被认为是聚合期间产生的酸副产物以及由残余水与EHA或使用的其它羧酸反应生成的任何酸性产物反应。
当使用胺和羧酸两者时,添加到反应混合物的无机碱的量 优选为足以保持反应容器中的pH为超过7。在一个实施方案中,添加无机碱的量以调节pH为约7-9。尽管不意欲限定,用于本发明公开内容的适合的量为等于来自含卤素化合物存在于反应混合物的卤素离子的摩尔当量的量。在停止剂混合物中无机碱的使用减少了有效停止聚合所必需的胺的量。
抗氧化剂如2,6-二-叔丁基-4-甲基苯酚可以与停止剂的添加一起、或在此之前、或在此之后添加。使用的抗氧化剂的量通常在聚合物产物的0.2重量%-1重量%的范围内。
当聚合已经停止时,聚合物产物可以通过利用脱溶剂的常规步骤并且干燥从聚合混合物中回收。例如,通过用醇如甲醇、乙醇或异丙醇凝固聚合混合物接着过滤,或者通过蒸汽蒸馏溶剂和未反应的单体接着过滤,可以从聚合混合物中分离聚合物。然后将分离的聚合物产物干燥以除去剩余量的溶剂和水。可选择地,聚合物可以通过直接转鼓式干燥聚合物浆料从聚合混合物中分离。
本发明公开内容的催化剂组合物显示出用于将共轭二烯聚合为高顺式-1,4-聚二烯的高催化活性。尽管一个优选实施方案以将1,3-丁二烯聚合为顺式-1,4-聚丁二烯为目标,但是也可以聚合其它的共轭二烯。可以聚合的其它的共轭二烯的一些具体实例包括异戊二烯、1,3-戊二烯、1,3-己二烯、2,3-二甲基-1,3-丁二烯、2-乙基-1,3-丁二烯、2-甲基-1,3-戊二烯、3-甲基-1,3-戊二烯、4-甲基-1,3-戊二烯和2,4-己二烯。也可以在共聚中使用两种以上共轭二烯的混合物。
利用此处公开的催化剂组合物聚合的高顺式-1,4-聚二烯典型地具有至少约90%、优选至少95%的顺式-1,4含量。高顺式-1,4-聚二烯也典型地具有在约75,000-约200,000范围内的数均分子量,约2-约4的分子量分布和小于约2%的乙烯基含量。分 子量分布是通常已知的当重均分子量除以数均分子量时得到的值。
用此处公开的催化剂组合物生产的高顺式-1,4-聚二烯有很多用途。它们可以与各种天然或合成橡胶共混以改善其性质。例如,它们可以引入至弹性体以改善拉伸性能、耐磨耗性和耐疲劳性,和以减少滞后损失。因此,顺式-1,4-聚二烯,特别是高顺式-1,4-聚丁二烯,可使用在用于轮胎胎面和轮胎胎壁的橡胶组合物中。
为了演示本发明公开内容的实施,已经制备并测试了以下实施例。然而不应当将实施例视作限定本发明的范围。权利要求将用来定义本发明。
实施例
在实施例中,除非另作说明,份和%基于重量。
在实施例中,使用以下方法测定聚合物性质。通过GPC(凝胶渗透色谱法)使用聚丁二烯标准和THF作为溶剂测定分子量。通过使溶于CS2的聚合物样品进行FTIR测定顺式-1,4、反式-1,4和乙烯基含量。
比较例:将己烷加入用氮气吹扫的干燥瓶,并在己烷中共混1,3-丁二烯(Bd),得到350g 15.0%Bd在己烷中的溶液。将以Bd溶液(19.7%Bd,2.5mL)、三异丁基铝(TIBA)溶液(0.68M,0.35mL)、辛酸镍溶液(0.050M,0.53ml)依次混合的预形成催化剂溶液装入该溶液。最后,装入三氟化硼二丁醚合物溶液(1.0M,0.59mL)。将该瓶置于65℃水浴中4小时。用含2,6-二-叔丁基-4-甲基苯酚(BHT)的异丙醇处理反应混合物以使催化剂失活,凝固和稳定聚合物。然后聚丁二烯在转鼓式干燥器中在120℃下干燥。聚合物性质示于表1中。
实施例1:将己烷加入用氮气吹扫的干燥瓶,和在己烷中共 混1,3-丁二烯(Bd),得到350g 15.0%Bd在己烷中的溶液。将以辛酸镍溶液(0.050M,0.53mL),1,3-双-(2,6-二异丙基苯基)咪唑-2-叉基(0.50M,0.53mL),TIBA溶液(0.68M,0.35mL)、Bd溶液(19.7%,2.5mL)依次混合的预形成催化溶液装入该溶液。最后,装入三氟化硼二丁醚合物溶液(1.0M,0.59mL)。将该瓶置于65℃水浴中4小时。用含2,6-二-叔丁基-4-甲基苯酚(BHT)的异丙醇处理反应混合物以使催化剂失活,凝固和稳定聚合物。然后聚丁二烯在转鼓式干燥器中在120℃下干燥。聚合物性质示于表1中。
实施例2-5:除了以如表1所示的不同次序在预形成溶液中混合催化剂组分以外,以与实施例1类似的方式进行聚合试验。
本说明书已经提供了示例性实施方案。显而易见地,基于阅读和理解前面的详细说明,其它人进行改进和修改。意欲将示例性实施方案解释为包括所有此类改进和修改,只要它们落入附加的权利要求或其相当范围的范围内。
Claims (35)
1.一种聚合催化剂组合物,其包含:
(a)含金属化合物,所述金属选自由过渡金属和镧系金属组成的组;
(b)卡宾;
(c)烷基化剂;和可选的
(d)包括一种以上不稳定卤素原子的含卤素化合物,条件是当所述含金属化合物和所述烷基化剂均不含有不稳定卤素原子时必须存在所述含卤素化合物;
其中所述卡宾包含式I或II的N-杂环卡宾:
其中R1和R2选自由C1-C12烷基、C2-C12烯基、C2-C12炔基、苯基、烷基-取代的苯基及其混合组成的组,并且可以全部相同或可以全部分别地选择,但是不能是H;
R3和R4选自由H、C1-C12烷基、C2-C12烯基、C2-C12炔基、苯基、烷基-取代的苯基及其混合组成的组,并且可以全部相同或可以全部分别地选择。
3.根据权利要求1所述的聚合催化剂组合物,其中所述含金属化合物包含镍。
4.根据权利要求1所述的聚合催化剂组合物,其中所述含金属化合物选自由苯甲酸镍、乙酸镍、环烷酸镍、辛酸镍、新癸酸镍、双(α-呋喃二肟)镍、棕榈酸镍、硬脂酸镍、乙酰丙酮酸镍、水杨醛镍、双(环戊二烯)镍、双(水杨醛)乙二亚胺镍、环戊二烯基-亚硝酰基镍、双(η3-烯丙基)镍、双(π-环辛-1,5-二烯)镍、双(η3-烯丙基镍三氟乙酸酯)、四羰基镍、硼酰化镍、新癸酸硼酸镍、己酸硼酸镍、环烷酸硼酸镍、硬脂酸硼酸镍、辛酸硼酸镍、2-乙基己酸硼酸镍及其混合物组成的组。
5.根据权利要求1所述的聚合催化剂组合物,其中所述含金属化合物包含钕。
6.根据权利要求1所述的聚合催化剂组合物,其中所述含金属化合物选自由卤化钕、假卤化钕、卤氧化钕、有机钕化合物及其混合物组成的组。
7.根据权利要求6所述的聚合催化剂组合物,其中所述有机钕化合物包含羧酸钕、有机磷酸钕、有机膦酸钕、有机次膦酸钕、氨基甲酸钕、二硫代氨基甲酸钕、黄原酸钕、β-二酮酸钕、烷氧化或芳氧化钕。
8.根据权利要求1所述的聚合催化剂组合物,其中所述烷基化剂包含有机铝化合物、有机镁化合物或两者。
9.根据权利要求8所述的聚合催化剂组合物,其中所述有机铝化合物由通式AlR5 nX3-n表示,其中各R5可以相同或不同,其为经由碳原子连接至铝原子的单价有机基团,其中各X可以相同或不同,是氢原子、卤素原子、羧酸酯基、烷氧化物基团或芳氧化物基团,和其中n是1至3的整数。
10.根据权利要求9所述的聚合催化剂组合物,其中所述有机铝化合物选自由三甲基铝、三乙基铝、三丙基铝、三丁基铝、三异丁基铝、三己基铝、三辛基铝、氢化二异丁基铝及其混合物组成的组。
11.根据权利要求1所述的聚合催化剂组合物,其中所述含卤素化合物包含卤素单质、混合的卤素、有机卤化物、无机卤化物、有机金属卤化物及其混合物。
12.根据权利要求11所述的聚合催化剂组合物,其中所述无机卤化物包含卤化氢和金属卤化物。
13.根据权利要求5所述的聚合催化剂组合物,其中所述含卤素化合物包含单质氯、单质溴、单质碘、氯化氢、溴化氢、碘化氢、单氯化碘、单溴化碘、三氯化碘、叔丁基氯、叔丁基溴、烯丙基氯、烯丙基溴、苄基氯、苄基溴、氯二苯基甲烷、溴二苯基甲烷、三苯基甲基氯、三苯基甲基溴、苄叉基氯化物、苄叉基溴化物、甲基三氯硅烷、苯基三氯硅烷、二甲基二氯硅烷、二苯基二氯硅烷、三甲基氯硅烷、苯甲酰氯、苯甲酰溴、丙酰氯、丙酰溴、氯代甲酸甲酯、溴代甲酸甲酯、三氯化磷、三溴化磷、五氯化磷、氯氧化磷、溴氧化磷、三氯化硼、三溴化硼、四氯化硅、四溴化硅、四碘化硅、三氯化砷、三溴化砷、三碘化砷、四氯化硒、四溴化硒、四氯化碲、四溴化碲、四碘化碲、四氯化锡、四溴化锡、三氯化铝、三溴化铝、三氯化锑、五氯化锑、三溴化锑、三碘化铝、三氯化镓、三溴化镓、三碘化镓、三氯化铟、三溴化铟、三碘化铟、四氯化钛、四溴化钛、四碘化钛、二氯化锌、二溴化锌、二碘化锌、氯化二甲基铝、氯化二乙基铝、溴化二甲基铝、溴化二乙基铝、二氯化甲基铝、二氯化乙基铝、二溴化甲基铝、二溴化乙基铝、倍半氯化甲基铝、倍半氯化乙基铝、倍半氯化异丁基铝、氯化甲基镁、溴化甲基镁、碘化甲基镁、氯化乙基镁、溴化乙基镁、氯化丁基镁、溴化丁基镁、氯化苯基镁、溴化苯基镁、氯化苄基镁、氯化三甲基锡、溴化三甲基锡、氯化三乙基锡、溴化三乙基锡、二氯化二叔丁基锡、二溴化二叔丁基锡、二氯化二丁基锡、二溴化二丁基锡、氯化三丁基锡、溴化三丁基锡及其混合物。
14.根据权利要求4所述的聚合催化剂组合物,其中所述含卤素化合物包含配合物,所述配合物为三氟化硼和选自由C1-C5脂族醚、醇、酮和羧酸组成的组的化合物的配合物。
15.根据权利要求1所述的聚合催化剂组合物,其中
(a)所述含金属化合物选自由环烷酸镍、辛酸镍、新癸酸镍及其混合物组成的组;
(b)所述烷基化剂包含三乙基铝、三异丁基铝及其混合物;和
(c)所述含卤素化合物包含配合物,所述配合物为三氟化硼和选自由C1-C5脂族醚、醇、酮和羧酸组成的组的化合物的配合物。
16.一种聚合催化剂组合物,其包含:
(a)含金属化合物,所述金属选自由过渡金属和镧系金属组成的组;
(b)卡宾;
(c)烷基化剂;和可选的
(d)包括一种以上不稳定卤素原子的含卤素化合物,条件是当所述含金属化合物和所述烷基化剂均不含有不稳定卤素原子时必须存在所述含卤素化合物;
其中所述卡宾包含式I或II的N-杂环卡宾:
其中R1和R2选自由C1-C12烷基、C2-C12烯基、C2-C12炔基、苯基、烷基-取代的苯基及其混合组成的组,并且可以全部相同或全部分别地选择,但是不能是H;
R3和R4选自由H、C1-C12烷基、C2-C12烯基、C2-C12炔基、苯基、烷基-取代的苯基及其混合组成的组,并且可以全部相同或全部分别地选择;
其中所述含金属化合物和所述卡宾在至少一种所述烷基化剂和如果存在的所述含卤素化合物的存在下组合。
17.一种生产聚二烯的方法,其包含在聚合催化剂组合物存在下使共轭二烯反应,所述聚合催化剂组合物包含:
(a)含金属化合物,所述金属选自由过渡金属和镧系金属组成的组;
(b)卡宾;
(c)烷基化剂;和任选的
(d)包括一种以上不稳定卤素原子的含卤素化合物,条件是当所述含金属化合物和所述烷基化剂均不含有不稳定卤素原子时必须存在所述含卤素化合物;
其中所述卡宾包含式I或II的N-杂环卡宾:
其中R1和R2选自由C1-C12烷基、C2-C12烯基、C2-C12炔基、苯基、烷基-取代的苯基及其混合组成的组,并且可以全部相同或可以全部分别地选择,但是不能是H;
R3和R4选自由H、C1-C12烷基、C2-C12烯基、C2-C12炔基、苯基、烷基-取代的苯基及其混合组成的组,并且可以全部相同或可以全部分别地选择。
19.根据权利要求17所述的方法,其中所述聚二烯在-10℃至100℃的温度下生产。
20.根据权利要求17所述的方法,其中所述聚二烯在20分钟至24小时的时间期间内生产。
21.根据权利要求17所述的方法,其中所述聚二烯具有大于95%的顺式含量,60,000至200,000的数均分子量范围,2至4的分子量分布,和小于2%的乙烯基含量。
22.根据权利要求17所述的方法,其中所述方法在选自由芳烃、脂族烃及其混合物组成的组中的溶剂存在下进行。
23.根据权利要求22所述的方法,其中所述脂族烃包括脂环族烃。
24.根据权利要求22所述的方法,其中所述溶剂包含己烷。
25.根据权利要求17所述的方法,其中所述含金属化合物以0.01mmol金属/100g单体至0.4mmol金属/100g单体的催化量存在。
26.根据权利要求25所述的方法,其中所述含金属化合物以0.02mmol金属/100g单体至0.2mmol金属/100g单体的催化量存在。
27.根据权利要求17所述的方法,其中所述卡宾以0.01mmol卡宾/100g单体至0.4mmol卡宾/100g单体的催化量存在。
28.根据权利要求27所述的方法,其中所述卡宾以0.02mmol卡宾/100g单体至0.2mmol卡宾/100g单体的催化量存在。
29.根据权利要求17所述的方法,其中所述烷基化剂以0.15mmol烷基化金属/100g单体至20.0mmol烷基化金属/100g单体的催化量存在。
30.根据权利要求29所述的方法,其中所述烷基化剂以0.30mmol烷基化金属/100g单体至6.0mmol烷基化金属/100g单体的催化量存在。
31.根据权利要求17所述的方法,其中所述含卤素化合物以0.01mmol含卤素化合物/100g单体至12.0mmol含卤素化合物/100g单体的催化量存在。
32.根据权利要求31所述的方法,其中所述含卤素化合物以0.4mmol含卤素化合物/100g单体至6.0mmol含卤素化合物/100g单体的催化量存在。
33.根据权利要求17所述的方法,其中所述聚二烯包含聚丁二烯。
34.根据权利要求17所述的方法,其中
(a)所述含金属化合物选自由环烷酸镍、辛酸镍、新癸酸镍及其混合物组成的组;
(b)所述烷基化剂包含三乙基铝、三异丁基铝或其混合物;和
(c)所述含卤素化合物包含三氟化硼与选自由C1-C5脂族醚、醇、酮和羧酸组成的组的化合物的配合物。
35.一种生产聚二烯的方法,其包含在聚合催化剂组合物存在下使共轭二烯反应,所述聚合催化剂组合物包含:
(a)含金属化合物,所述金属选自由过渡金属和镧系金属组成的组;
(b)卡宾;
(c)烷基化剂;和可选的
(d)包括一种以上不稳定卤素原子的含卤素化合物,条件是当所述含金属化合物和所述烷基化剂均不含有不稳定卤素原子时必须存在所述含卤素化合物;
其中所述卡宾包含式I或II的N-杂环卡宾:
其中R1和R2选自由C1-C12烷基、C2-C12烯基、C2-C12炔基、苯基、烷基-取代的苯基及其混合组成的组,并且可以全部相同或可以全部分别地选择,但是不能是H;
R3和R4选自由H、C1-C12烷基、C2-C12烯基、C2-C12炔基、苯基、烷基-取代的苯基及其混合组成的组,并且可以全部相同或可以全部分别地选择;
其中所述含金属化合物和所述卡宾在至少一种所述共轭二烯、所述烷基化剂和如果存在的所述含卤素化合物的存在下组合。
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