CN1447813A - 晚过渡金属配合物,它们作为催化剂的用途和由其得到的聚合物 - Google Patents
晚过渡金属配合物,它们作为催化剂的用途和由其得到的聚合物 Download PDFInfo
- Publication number
- CN1447813A CN1447813A CN01814321A CN01814321A CN1447813A CN 1447813 A CN1447813 A CN 1447813A CN 01814321 A CN01814321 A CN 01814321A CN 01814321 A CN01814321 A CN 01814321A CN 1447813 A CN1447813 A CN 1447813A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- composition
- carbon monoxide
- alkene
- metal complexes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 229920000642 polymer Polymers 0.000 title abstract description 8
- 150000003624 transition metals Chemical class 0.000 title description 9
- 229910052723 transition metal Inorganic materials 0.000 title description 8
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 150000004678 hydrides Chemical group 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- -1 acyclic aliphatic olefins Chemical class 0.000 claims description 20
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 7
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 125000005574 norbornylene group Chemical group 0.000 claims description 5
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 claims description 5
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 claims description 2
- 150000004820 halides Chemical group 0.000 abstract description 2
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- 150000001242 acetic acid derivatives Chemical group 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 150000001642 boronic acid derivatives Chemical group 0.000 abstract 1
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 abstract 1
- 150000007944 thiolates Chemical class 0.000 abstract 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical group [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000010949 copper Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VPHISGYUXZPVPB-UHFFFAOYSA-N 1-ethyl-2-(2-phenylphenyl)benzimidazole Chemical group C(C)N1C(=NC2=C1C=CC=C2)C1=C(C=CC=C1)C1=CC=CC=C1 VPHISGYUXZPVPB-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical class O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- WCZAXBXVDLKQGV-UHFFFAOYSA-N n,n-dimethyl-2-(7-oxobenzo[c]fluoren-5-yl)oxyethanamine oxide Chemical compound C12=CC=CC=C2C(OCC[N+](C)([O-])C)=CC2=C1C1=CC=CC=C1C2=O WCZAXBXVDLKQGV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- YGGMQWSJXSNGDT-UHFFFAOYSA-N (4-fluorophenyl)boron Chemical compound [B]C1=CC=C(F)C=C1 YGGMQWSJXSNGDT-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920004449 Halon® Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 244000197975 Solidago virgaurea Species 0.000 description 1
- 235000000914 Solidago virgaurea Nutrition 0.000 description 1
- RLAFITVGYPWJQO-UHFFFAOYSA-N [2-(trifluoromethyl)phenyl]boron Chemical compound [B]C1=CC=CC=C1C(F)(F)F RLAFITVGYPWJQO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 description 1
- 229960003132 halothane Drugs 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical compound [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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Abstract
本发明提供了一种在与活化助催化剂一起使用时得到新催化剂组合物的新金属配合物。本发明还涉及一种采用该催化剂组合物生产包含极性单体基团的聚合物和共聚物的聚合反应方法。更具体地说,本发明包括一种具有结构式LMXZn的组合物,其中X选自卤化物,氢化物,三氟甲磺酸根,乙酸盐,硼酸根,C1-12烷基,C1-12烷氧基,C3-12环烷基,C3-12环烷氧基,芳基,硫醇根,一氧化碳,氰酸根,烯烃,和其中可插入单体的任何其它部分。M选自Cu,Ag,和Au。L是具有两个以上氮原子的含氮双齿配体。Z是中性配位的配体且n等于0,1,或2。
Description
本发明领域
本发明涉及一种晚过渡金属聚合反应催化剂配合物及其在由烯烃或极性单体形成聚合物和由烯烃和极性单体形成共聚物中的应用。
背景
聚合物和共聚物可通过使用过渡金属催化剂技术由烯烃单体形成。Ziegler-Natta催化剂已使用多年,而近年来金属茂催化剂在某些场合中是优选的,因为通过金属茂催化制成的聚烯烃通常具有优异的性能。最熟知的金属茂技术采用包含早过渡金属原子如Ti和Zr的催化剂。
即使通过这些金属茂催化剂形成的聚烯烃相对通过常规Ziegler-Natta催化剂制成的聚烯烃具有某些增强性能,可以进一步提高可润湿性和粘附性之类的性能。据信包括在烯烃聚合物或共聚物中的极性单体可提高这些,并可能提高其它的性能。遗憾地,极性单体往往毒化早过渡金属催化剂。
某些晚过渡金属配合物如包含钯和镍的那些在引入某些极性单体时更具宽容性。但这些催化剂组合物大多数昂贵并得到高度支链聚合物(如,85-150个支链/1000个碳原子)。另外,官能度不在链中而是在支链的末端。因此它们将极性单体内容物限制为约15mol%或更低。这些组合物的其它缺点在于,它们仅引入有限数目的极性单体如丙烯酸烷基酯和乙烯基酮。
最近,已制造出新型晚转变有机金属催化剂以解决前述问题。更具体地,U.S.Pat.No.6,037,297(Stibrany等人,在此作为参考并入本发明)披露了具有假四面体几何的包含族11金属(Cu,Ag和Au)的催化剂组合物,它可用于形成具有烃基极性官能度的聚合物和共聚物。
但仍然需要开发可用于聚合反应工艺的其它族11金属配合物。理想地,这些晚过渡金属配合物应该能够形成不是高度支链的,具有聚合物链官能度并能够引入更加多样的极性单体的包含极性单体的烯烃聚合物和共聚物。
发明内容
本发明提供了一种可与活化助催化剂一起用于生产聚合物和共聚物的晚过渡金属配合物。另外,与U.S.Pat.No.6,037,297的发明类似,本发明可用于生产包含极性单体的聚合物和共聚物。
在一个实施方案中,本发明是一种具有结构式LMXZn的组合物,其中X选自卤化物,氢化物,三氟甲磺酸根,乙酸根,硼酸根,C1-12烷基,C1-12烷氧基,C3-12环烷基,C3-12环烷氧基,芳基,硫醇根,一氧化碳,氰酸根,烯烃,和其中可插入单体的任何其它部分。M选自Cu,Ag,和Au。L是具有两个以上氮原子的含氮双齿配体。Z是中性配位的配体和n等于0,1,或2。
在另一实施方案中,本发明是包含以下物质的反应产物的催化剂组合物:上述具有结构式LMXZn的金属配合物,和活化助催化剂。本发明的该实施方案尤其可用于聚合反应化学。
在另一实施方案中,本发明提供了一种使用该组合物生产包含极性单体单元的聚合物和共聚物的方法。该方法包括将单体在聚合反应条件下与包含具有定义如上的结构式LMXZn的组合物,和活化助催化剂的催化剂组合物接触。视需要,氧化剂也可在该工艺过程中使用。
本发明的这些和其它特点,方面和优点可根据以下描述和所附权利要求书更好地理解。
发明的详细说明
本发明涉及一种在与活化助催化剂一起使用时提供新型催化剂组合物的新型金属配合物。本发明还提供了一种采用该催化剂组合物的聚合反应方法。一般来说,本发明方法生产包含极性单体基团的聚合物和共聚物。
在一个实施方案中,本发明包括一种具有结构式LMXZn的组合物,其中X选自卤化物,氢化物,三氟甲磺酸根,乙酸根,硼酸根,C1-C12烷基,C1-C12烷氧基,C3-C12环烷基,C3-C12环烷氧基,芳基,硫醇根,一氧化碳,氰酸根,烯烃,和其中可插入单体的任何其它部分;M选自Cu,Ag,和Au;L是具有两个以上氮原子的含氮双齿配体;Z是中性配位的配体;其中n等于0,1,或2。
本发明金属配合物的几何构型可以是假四面体或三角平面的,这取决于n的值(即,n可等于0,1或2)。本领域熟练技术人员应该理解,尽管术语″假四面体″用于描述金属配合物的几何结构,它不排除纯″四面体″几何排列。前缀″假″在整个说明书中用于最准确地描述本文所述的非限定性实施方案。本领域熟练技术人员同样应该理解,术语″三角平面″还包括近似三角平面的几何构型。
如果金属组合物与活化助催化剂如甲基铝氧烷(即,″MAO″)反应,形成一种催化剂组合物。因此,在另一实施方案中,本发明是一种包含以下物质的反应产物的催化剂组合物:(a)在一个实施方案中,本发明包括一种具有结构式LMXZn的组合物,其中X选自卤化物,氢化物,三氟甲磺酸根,乙酸根,硼酸根,C1-C12烷基,C1-C12烷氧基,C3-C12环烷基,C3-C12环烷氧基,芳基,硫醇根,一氧化碳,氰酸根,烯烃,和其中可插入单体的任何其它部分;M选自Cu,Ag,和Au;L是具有两个以上氮原子的含氮双齿配体;Z是中性配位的配体;其中n等于0,1,或2;和(b)活化助催化剂。
另外,通过控制温度,催化剂加载量,配体结构,和停留时间,可调节产物选择性以生产高选择性的各个聚合物和共聚物。因此,在另一实施方案中,本发明提供了一种用于生产聚合物和共聚物的方法。
理想地,Z是弱配位的和足够不稳定的以允许催化剂的活化。在一个优选的实施方案组合物中,对于每次出现的Z,每个Z独立地选自二乙基醚,四氢呋喃,乙腈,苄腈,二噁烷,丙酮,2-丁酮,苯基异氰酸酯,乙烯,一氧化碳,1-己烯,和降冰片烯。
本发明的其它优选的实施方案是一种如上所述具有结构式LMXZn的配合物,其中L是表示为下式的含氮双齿配体:
其中R1独立地选自氢,C1-C12直链或支链烷基,C3-C12环烷基,芳基,和三氟乙烷;
R2和R3独立地选自氢,C1-C12直链或支链烷基,C3-C12环烷基,C1-C12烷氧基,F,Cl,SO3,C1-C12全氟烷基,和N(CH3)2;
R选自未取代的C1-C12烷基,C3-C12环烷基;甲氧基;氨基;卤代;C1-C12卤代烷基取代的烷基;最高12个碳原子的环烷基,C1-C40芳基;和C1-C40烷基芳基。
X选自卤素,氢化物,三氟甲磺酸根,乙酸根,三氟乙酸根,全氟四苯基硼酸根,四氟硼酸根,C1-C12烷基,C1-C12烷氧基,C3-C12环烷基,C3-C12环烷氧基,芳基,和其中可插入单体的任何其它部分如共价或离子键接到M上的原子,或原子团;Z是中性配位的配体;其中n等于0,1,或2。在一个优选的实施方案中,对于每次出现的Z,每个Z独立地选自二乙基醚,四氢呋喃,乙腈,苄腈,二噁烷,丙酮,2-丁酮,苯基异氰酸酯,乙烯,一氧化碳,1-己烯,和降冰片烯。
简便起见,所给出的一些键没有末端;这些键由甲基封端。
Cu优选用于M。在X的选项中,卤素是优选的。X的合适的非卤化物选项包括,但不限于,三氟甲磺酸根,三氟乙酸根,全氟四苯基硼酸根,或四氟硼酸根,氢化物,烷基基团或其中可插入单体的任何其它配体如共价或离子键接到M上的原子,或原子团。
在本发明的金属配合物中,尤其优选的实施方案是具有2,2′-二[2-(1-烷基苯并咪唑-2-基)]联苯的那些,其中烷基是C1-C20,和X是氯化物。
一般来说,铜作为金属和氯作为X以及C1-C20作为R1的2,2'-二[2-(1-烷基苯并咪唑-2-基)]联苯配体具有以下结构:特定金属配合物的优选实施方案包括,但不限于以下:[(2,2′-二[2-(1-乙基苯并咪唑-2-基)]联苯)(乙腈)铜(I)](四氟硼酸根)和(2,2′-二[2-(1-乙基苯并咪唑-2-基)]联苯)氯化铜(I)
有利地,本发明的催化剂在用于形成完全或部分由烯属单体合成的聚合物和共聚物时不被包含烃基极性官能团的化合物所毒化。因此,本发明催化剂可用于制备由烯属单体形成的聚合物和共聚物,如聚乙烯;由包含烃基极性官能团的单体形成的聚合物和共聚物如聚(甲基丙烯酸甲酯);和衍生自烯烃和包含烃基极性官能团的单体的共聚物如聚(乙烯-甲基丙烯酸甲酯)。
与以上定义的金属配合物结合使用的活化助催化剂包括,但是不限于,包含Al-O键的铝化合物如烷基铝氧烷如甲基铝氧烷(″MAO″),异丁基改性的甲基铝氧烷(″MMAO″);″干″[即,无溶剂和无Me3Al(″TMA″)]MAO;烷基铝;卤化铝;卤化烷基铝;非以上列举的其它Lewis酸;而且前述的混合物也可与烷基化剂,如甲基氯化镁和甲基锂结合使用。这些Lewis酸的例子是对应于结构式:R″″3B,或R3″″Al的那些化合物,其中R″″独立地分别选自氢,甲硅烷基,烃基,卤代烃基,醇盐,芳基氧化物,酰胺或其组合,所述R″″具有最高30个非氢原子。
本领域熟练技术人员可以理解,优选的Lewis酸的以上结构式表示经验结构式,而且许多Lewis酸在溶液或固体状态下存在为二聚体或高级低聚物。可用于本发明催化剂组合物的其它Lewis酸对本领域熟练技术人员是显然的。
这些助催化剂的其它例子包括族13元素配合物的盐。合适的助催化剂的这些和其它例子以及它们在有机金属聚合反应中的应用讨论于U.S.Pat.No.5,198,401和PCT专利文件PCT/US97/10418和PCT/US96/09764,在此都作为参考并入本发明。。
优选的活化助催化剂包括三甲基铝,三异丁基铝,甲基铝氧烷,烷基改性的铝氧烷,″干″铝氧烷,氯乙基铝,二氯乙基铝,三乙基硼,三甲基硼,三苯基硼和卤化,尤其氟化,三芳基硼和铝化合物,碳硼烷和卤化碳硼烷。
最优选的活化助催化剂包括三乙基铝,甲基铝氧烷,和氟-取代的芳基硼烷和硼酸盐如三(4-氟苯基)硼,三(2,4-二氟苯基硼),三(3,5-二(三氟甲基-苯基)硼,三(五氟苯基)硼,五氟苯基-二苯基硼,和二(五氟苯基)苯基硼和四(五氟苯基)硼酸盐。这些氟-取代的芳基硼烷可容易根据例如公开于Marks,等人,J.Am.Chem.Soc.,113,3623-3625(1991)的技术合成。氟化四芳基硼酸盐或铝酸盐和全氟四萘基硼酸盐或铝酸盐也是本领域熟知的。
催化剂可通过形成以上定义的金属配合物LMXZn,并根据需要将活化助催化剂与其在稀释剂中结合而使用。视需要,氧化剂也可与助催化剂结合使用。氧化剂可包括,但是不限于:NOBF4;1,4-苯醌;四氯-1,4-苯醌;AgClO4;Ag(C6F5)4B;二茂铁(C6F5)4B;(3,5(CF3)2(C6H4)B)Cp2Fe+;和(3,5(CF3)2(C6H4)B)Cp2 *Fe+。制备可在根据需要一种或多种可加成聚合的单体的存在下进行。优选,催化剂在-100℃至300℃,优选0℃至250℃,最优选0℃至100℃的温度下制备。合适的溶剂包括液体或超临界气体如CO2,直和支链-链烃如异丁烷,丁烷,戊烷,己烷,庚烷,辛烷,和其混合物,环状和脂环族烃如环己烷,环庚烷,甲基环己烷,甲基环庚烷,卤化烃如氯苯,和二氯苯全氟化C4-10烷烃和芳族和烷基-取代的芳族化合物如苯,甲苯和二甲苯。合适的溶剂还包括可用作单体或共聚单体的液体烯烃,包括乙烯,丙烯,丁二烯,1-己烯,3-甲基-1-戊烯,4-甲基-1-戊烯,1-辛烯,1-癸烯,和4-乙烯基环己烷,(包括单独或混合形式的所有的异构体)。其它溶剂包括茴香醚,甲基氯,二氯乙烯,2-吡咯烷酮和N-甲基吡咯烷酮。优选的溶剂是脂族烃和芳族烃,如甲苯。
如果活化助催化剂用于形成催化剂组合物,金属配合物与活化助催化剂的当量比率优选为1∶0.5-1∶104,更优选1∶0.75-1∶103。在大多数聚合反应中,所采用的催化剂:可聚合化合物的当量比率是10-12∶-10-1∶1,更优选10-9∶1-10-4∶1。
可与本发明催化剂一起用于形成均聚物和共聚物的烯烃单体包括,但不限于,烯属不饱和单体,非共轭二烯,和低聚物,和更高分子量,乙烯基-封端的大分子单体。例子包括C2-20烯烃,乙烯基环己烷,四氟乙烯,和其混合物。优选的单体包括C2-10α-烯烃尤其乙烯,丙烯,异丁烯,1-丁烯,1-己烯,4-甲基-1-戊烯,和1-辛烯或其混合物。
可与本发明催化剂一起用于形成均聚物和共聚物的具有烃基极性官能团的单体是乙烯基醚和C1-C20烷基乙烯基醚如n-丁基乙烯基醚,丙烯酸酯,如C1-C24,或丙烯酸烷基酯如丙烯酸t-丁基酯,和丙烯酸月桂基酯,以及甲基丙烯酸酯如甲基丙烯酸甲酯。
一般来说,聚合反应可在本领域熟知用于Ziegler-Natta或Kaminsky-Sinn型聚合反应的条件,即,-100℃至250℃,优选0℃至250℃的温度,和大气压至2000个大气压(200Mpa)的压力下实施。合适的聚合反应条件包括已知在由铝或硼-活化化合物活化时可用于金属茂催化剂的那些条件。可根据需要采用悬浮,溶液,淤浆,气相或其它工艺条件。催化剂可被承载且这些承载的催化剂可用于本发明的聚合反应。优选的载体包括矾土,硅石,聚合物载体和中孔材料。
聚合反应通常在溶剂存在下进行。合适的溶剂包括以上描述可用于制备催化剂的那些。实际上,聚合反应可在与用于制备催化剂相同的溶剂中进行。当然,催化剂可视需要单独地在一种溶剂中制备并在另一溶剂中使用。
聚合反应进行足够时间以形成聚合物,然后将聚合物通过本领域熟知的并在有助于进一步描述本发明的以下非限定性实施例中给出的技术回收。
实施例1
[Cu(diEtBBIL)(ACN)](BF4)的制备
在氩气手套箱中,制备35mg(0.11mmol)Cu(ACN)4(BF4)在8mL乙腈中的无色溶液。然后,将50mg(0.11mmol)diEtBBIL加入该溶液并充分混合。将包含该无色溶液的烧瓶随后放入包含乙醚的密封罐中以进行蒸气扩散。在一天之后,得到外消旋-[(2,2′-二[2-(1-乙基苯并咪唑-2-基)]联苯)(乙腈)铜(I)](四氟硼酸根)的无色晶体。1HNMR(CDC13):δ=7.65(d,J=6,7Hz,2H),7.54(dd,J=7.8Hz,J=17.9Hz,4H),7.33(m,8H),6.93(d,J=7,4Hz,2H),4.47(dm,J=40.3Hz,4H),2.15(s,3H),1.66(t,J=6.8Hz,6H).X-射线结晶数据:单斜晶,P2(1),Z=4,a=16.952(3),b=15.527(3),c=12.946(2),α=90,β=111.33(3),γ=90,V=3174.15。
实施例2
Cu(I)(diEtBBIL)Cl的还原制备
将100mg量的10μ铜粉末放入具有侧臂的100mL圆底烧瓶中。然后,将2mL原甲酸三乙基酯和20mL乙腈加入烧瓶。烧瓶配有起泡器并在连续氮气流下脱气。然后,将33mg(0.19mmol)CuCl2·2H2O在有效氮气流下加入搅拌的混合物中以得到一种绿色溶液。然后,将170mg(0.38mmol)diEtBBIL加入烧瓶以得到一种黄色溶液。该混合物在氮气下搅拌72小时以上。将包含无色溶液和剩余固体的烧瓶随后过滤以得到无色滤液。溶剂在氮气流下去除以得到白色固体。将该固体在高真空下再放置1小时以得到144mg白色(2,2′-二[2-(1-乙基苯并咪唑-2-基)]联苯)氯化铜(I)。1H NMR(CDCl3):δ=8.08(m,2H),7.69(m,1H),7.53(m,3H),7.27(m,6H),6.95(dm,4H),4.38(dm,4H),1.58(m,3H),1.90(m,3H)。
实施例3
使用[Cu(I)(diEtBBIL)(ACN)](BF4)制备聚乙烯
在氩气下在玻璃套管中称出32.1mg(0.051mmol)量的Cu(diEtBBIL)(MeCN))BF4。然后,将30 mL甲苯加入套管,随后加入2.0g 30wt.%MAO(0.010mol),得到一种浅黄色淤浆。将套管放在一个密封的,用乙烯加压并加热至80℃的300mL Parr反应器中,反应在720psig下进行15小时。在该时间段结束时,将反应器冷却,通气并用5mL甲醇骤冷。随后将聚合物在150mL酸性甲醇(10%)中沉淀出。将聚合物过滤分离并在真空下在50℃下干燥一天。产率:0.8g.Tm:142℃(第二热)。13C NMR(ppm,125℃四氯乙烷):29.5(s,-CH2-CH2-);在最高约一个碳/500-1000个碳的检测限度内没有出现端基和支链点。
实施例4
使用[Cu(I)(diEtBBIL)(ACN)](BF4)制备聚(丙烯酸t-丁基酯)
将32.1mg(0.051mmol)量的Cu(diEtBBIL)(MeCN))BF4在氩气手套箱中加入100mL圆底烧瓶。将10mL甲苯加入烧瓶,随后加入1.02g30wt.%MAO(5.3mmol),得到一种黄色淤浆。将5.9g丙烯酸t-丁基酯(从CaCl2中新蒸馏并用300ppm吩噻嗪稳定化)加入淤浆。淤浆在室温下在黑暗中搅拌18小时。在该时间段结束时,反应用5mL甲醇骤冷并随后将聚合物在150mL酸性甲醇(10%)中沉淀出。将聚合物过滤分离并在真空下在40℃下干燥一天。产率:14%。13C NMR(ppm,CDC13):28.2(s,-CH2-CH(COOC(CH3)3)-),34.3-37.6(m,-CH2-CH(COOC(CH3)3)-),42-43.5(m,-CH2-CH(COOC(CH3)3)-),80.5(m,-CH2-CH(COOC(CH3)3)-),173.2-174.1(m,-CH2-CH(COOC(CH3)3)-),39%rr,47%mr,14%mm(通过对次甲基峰进行积分)。
实施例5
使用[Cu(I)(diEtBBIL)(ACN)](BF4)制备聚乙烯
聚合反应使用一种混合物进行,该混合物通过将21.1mg(0.033mmol)[Cu(diEtBBIL)(ACN)](BF4)溶解在80ml甲苯中得到无色溶液而制成。在此之后加入100mg NOBF4(0.85mmol),仍是无色溶液。然后加入1.5ml 30%MAO,得到一种浓黄色溶液。Parr反应器用550psig乙烯加压并加热至80℃并在80℃下保持20.75小时,在此过程中压力由560psig降至540psig。将聚合反应混合物用甲醇冷却并骤冷,处理得到31mg固体聚乙烯。
实施例6
聚(丙烯酸t-丁基酯-乙烯)的制备
在氩气下在玻璃套管中称出24.1mg(0.045mmol)量的Cu(diEtBBIL)Cl。将30mL甲苯加入套管,随后加入1.98g 30wt.%MAO(0.010mol),得到一种浅黄色淤浆。然后,将10.7克丙烯酸t-丁基酯(将丙烯酸t-丁基酯从CaCl2中蒸馏,脱气并放入手套箱,随后加入约100ppm吩噻嗪)加入淤浆。将套管放在一个密封的,用乙烯加压并加热至80℃的300mL Parr反应器中,反应在840psig下进行17小时。在该时间段结束时,将反应器冷却,通气并用5mL甲醇骤冷,然后将聚合物在300mL酸性甲醇(10%)中沉淀出。将聚合物过滤分离并在真空下在60℃下干燥一天。产率是4.5g。将聚合物在THF在soxhlet萃取器中萃取以去除所有的催化剂残余物并表征。
共聚物的组成通过13C-NMR在CDCl3中确定。丙烯酸酯酯含量通过对丙烯酸酯羰基和t-丁基基团的季碳的积分值求平均值而计算。乙烯含量随后通过校正丙烯酸t-丁基酯积分的总脂族积分而得到。另外,以丙烯酸酯为中心的特征是通过对次甲基共振的三个簇积分而量化:EAE:46.5,EAA/AAE:44.2,AAA:42.2ppm。共聚物结果具有76mol%丙烯酸t-丁基酯且EAE∶EAA/AAE∶AAA=8∶38∶53。
前述实施例清楚地说明,本发明的新组合物可作为有效的聚合反应催化剂用于制备聚合物和共聚物,包括具有极性官能度的共聚物。更具体地,实施例表明如何可容易地聚合极性单体而不会毒化催化剂。另外,主链,而不是支链,包含显著量的极性单体。另外,所形成的聚合物不是高度支链的。另外,实施例表明,所形成的聚合物具有高百分比的极性单体含量(如,大于约15mol%)。最后,可以将各种各样的极性单体引入烯烃聚合物和共聚物产物。这些特点克服了以上在背景部分讨论的目前使用的大多数有机金属催化剂技术的缺点。
Claims (10)
1.一种具有结构式LMXZn的组合物,其中X选自卤化物,氢化物,三氟甲磺酸根,乙酸根,硼酸根,C1-12烷基,C1-12烷氧基,C3-12环烷基,C3-12环烷氧基,芳基,硫醇根,一氧化碳,氰酸根,烯烃,和其中可插入单体的任何其它部分;M选自Cu,Ag,和Au;L是具有两个以上氮原子的含氮双齿配体;Z是中性配位的配体;其中n等于0,1,或2。
2.根据权利要求1的组合物,其中对于每次出现的Z,每个Z独立地选自二乙基醚,四氢呋喃,乙腈,苄腈,二噁烷,丙酮,2-丁酮,苯基异氰酸酯,乙烯,一氧化碳,1-己烯,和降冰片烯。
3.一种包含以下物质的反应产物的催化剂组合物:
(a)一种具有结构式LMXZn的金属配合物,其中X选自卤化物,氢化物,三氟甲磺酸根,乙酸根,硼酸根,C1-C12烷基,C1-C12烷氧基,C3-C12环烷基,C3-C12环烷氧基,芳基,硫醇根,一氧化碳,氰酸根,烯烃,和其中可插入单体的任何其它部分;M选自Cu,Ag,和Au;L是具有两个以上氮原子的含氮双齿配体;Z是中性配位的配体;其中n等于0,1,或2;和(b)活化助催化剂。
4.根据权利要求3的组合物,其中M是Cu。
5.根据权利要求3的组合物,其中对于每次出现的Z,每个Z独立地选自二乙基醚,四氢呋喃,乙腈,苄腈,二噁烷,丙酮,2-丁酮,苯基异氰酸酯,乙烯,一氧化碳,1-己烯,和降冰片烯。
6.根据权利要求3的组合物,其中活化助催化剂是甲基铝氧烷。
7.一种用于聚合选自以下的烯属单体的方法:(a)无环脂族烯烃,(b)具有烃基极性官能度的烯烃,和(c)(i)至少一种具有烃基极性官能团的烯烃和(ii)至少一种无环脂族烯烃的混合物,该方法包括,将烯属单体在聚合反应条件下与一种包含以下物质的反应产物的催化剂组合物接触:(a)一种具有结构式LMXZn的金属配合物,其中X选自卤化物,氢化物,三氟甲磺酸根,乙酸根,硼酸根,C1-C12烷基,C1-C12烷氧基,C3-C12环烷基,C3-C12环烷氧基,芳基,硫醇根,一氧化碳,氰酸根,烯烃,和其中可插入单体的任何其它部分;M选自Cu,Ag,和Au;L是具有两个以上氮原子的含氮双齿配体;Z是中性配位的配体;其中n等于0,1,或2;和(b)活化助催化剂。
8.根据权利要求7的方法,进一步包括将所述金属配合物与氧化剂接触。
9.根据权利要求7的方法,其中对于每次出现的Z,每个Z独立地选自二乙基醚,四氢呋喃,乙腈,苄腈,二噁烷,丙酮,2-丁酮,苯基异氰酸酯,乙烯,一氧化碳,1-己烯,和降冰片烯。
10.根据权利要求7的方法,其中活化助催化剂是甲基铝氧烷。
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CA (1) | CA2415856A1 (zh) |
WO (1) | WO2002016373A1 (zh) |
ZA (1) | ZA200300421B (zh) |
Families Citing this family (4)
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US6809058B2 (en) * | 2001-08-28 | 2004-10-26 | Exxonmobil Research And Engineering Company | Multi-dentate late transition metal catalyst complexes and polymerization methods using those complexes |
DE10211418A1 (de) * | 2002-03-15 | 2003-09-25 | Bayer Ag | Verfahren zur Herstellung hochreaktiver Polyisobutene |
JP4742647B2 (ja) * | 2005-03-31 | 2011-08-10 | 住友化学株式会社 | 極性モノマー−オレフィン共重合体の製造方法 |
FR2937643B1 (fr) | 2008-10-27 | 2011-10-14 | Arkema France | Nouveaux copolymeres a blocs d'olefines polaires et apolaires |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
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US3703561A (en) | 1968-03-28 | 1972-11-21 | Phillips Petroleum Co | Olefin conversion using complexes of cu,ag and au with organoaluminums |
US3558520A (en) | 1968-03-28 | 1971-01-26 | Phillips Petroleum Co | Complexes of cu,ag and au with organoaluminums as olefin reaction catalysts |
CA2091413A1 (en) | 1992-03-11 | 1993-09-12 | Anna Sommazzi | Homogeneous catalytic system and process for copolymerizing olefins with carbon monoxide |
US5556823A (en) | 1994-11-28 | 1996-09-17 | Enichem S.P.A. | Catalytic system and process for the copolymerization of olefins with carbon monoxide |
US5880241A (en) | 1995-01-24 | 1999-03-09 | E. I. Du Pont De Nemours And Company | Olefin polymers |
US5763548A (en) | 1995-03-31 | 1998-06-09 | Carnegie-Mellon University | (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization |
TW505665B (en) | 1996-08-09 | 2002-10-11 | Du Pont | Process for polymerization of olefinic monomers |
KR20000071130A (ko) | 1997-02-17 | 2000-11-25 | 타다시 마츠다 | 구리 화합물을 사용한 중합체의 제조 방법 |
US6103658A (en) * | 1997-03-10 | 2000-08-15 | Eastman Chemical Company | Olefin polymerization catalysts containing group 8-10 transition metals, processes employing such catalysts and polymers obtained therefrom |
GB9722447D0 (en) * | 1997-10-23 | 1997-12-24 | Borealis As | Process |
US6037297A (en) | 1997-12-16 | 2000-03-14 | Exxon Research And Engineering Co. | Catalyst complexes and polymers therefrom |
WO1999030822A1 (en) | 1997-12-16 | 1999-06-24 | Exxon Research And Engineering Company | Group 11 transition metal amine catalysts for olefin polymerization |
US7056983B2 (en) | 1998-04-28 | 2006-06-06 | Kaneka Corporation | Block copolymer |
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2000
- 2000-08-18 US US09/642,488 patent/US6479425B1/en not_active Expired - Fee Related
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2001
- 2001-08-03 EP EP01959448A patent/EP1311512A1/en not_active Withdrawn
- 2001-08-03 BR BR0113238-5A patent/BR0113238A/pt not_active Application Discontinuation
- 2001-08-03 WO PCT/US2001/024290 patent/WO2002016373A1/en not_active Application Discontinuation
- 2001-08-03 JP JP2002521471A patent/JP2004507466A/ja active Pending
- 2001-08-03 CA CA002415856A patent/CA2415856A1/en not_active Abandoned
- 2001-08-03 AU AU2001281004A patent/AU2001281004A1/en not_active Abandoned
- 2001-08-03 CN CN01814321A patent/CN1447813A/zh active Pending
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2002
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ZA200300421B (en) | 2003-11-07 |
CA2415856A1 (en) | 2002-02-28 |
WO2002016373A1 (en) | 2002-02-28 |
US6479425B1 (en) | 2002-11-12 |
JP2004507466A (ja) | 2004-03-11 |
BR0113238A (pt) | 2003-07-08 |
AU2001281004A1 (en) | 2002-03-04 |
US20030027714A1 (en) | 2003-02-06 |
EP1311512A1 (en) | 2003-05-21 |
US6642327B2 (en) | 2003-11-04 |
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