CN1220669A - 含有与单或双阴离子三齿配体连接的13族元素的新化合物,其制备方法及其作为聚合催化剂的用途 - Google Patents
含有与单或双阴离子三齿配体连接的13族元素的新化合物,其制备方法及其作为聚合催化剂的用途 Download PDFInfo
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- CN1220669A CN1220669A CN97195140A CN97195140A CN1220669A CN 1220669 A CN1220669 A CN 1220669A CN 97195140 A CN97195140 A CN 97195140A CN 97195140 A CN97195140 A CN 97195140A CN 1220669 A CN1220669 A CN 1220669A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 86
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- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003446 ligand Substances 0.000 title abstract description 5
- 229910052795 boron group element Inorganic materials 0.000 title abstract 2
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- -1 cyclic ester Chemical class 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 17
- 125000005843 halogen group Chemical group 0.000 claims description 17
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 125000002524 organometallic group Chemical group 0.000 claims description 11
- 229910016467 AlCl 4 Inorganic materials 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 7
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- 230000000379 polymerizing effect Effects 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 125000005110 aryl thio group Chemical group 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 claims description 4
- 125000005366 cycloalkylthio group Chemical group 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000002924 oxiranes Chemical class 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
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- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Chemical group 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052733 gallium Chemical group 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001924 cycloalkanes Chemical class 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000010025 steaming Methods 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 229940125904 compound 1 Drugs 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
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- 229920001577 copolymer Polymers 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- LBAQSKZHMLAFHH-UHFFFAOYSA-N ethoxyethane;hydron;chloride Chemical compound Cl.CCOCC LBAQSKZHMLAFHH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- GWYPDXLJACEENP-UHFFFAOYSA-N 1,3-cycloheptadiene Chemical compound C1CC=CC=CC1 GWYPDXLJACEENP-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- 150000004645 aluminates Chemical class 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
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- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
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- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical group C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical class C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001887 cyclopentyloxy group Chemical group C1(CCCC1)O* 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004032 porphyrins Chemical group 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 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 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及含有与单或双阴离子三齿配体连接的13族元素的新化合物,其制备方法及其作为(共)聚合催化剂的用途。
Description
已知某些单和双阴离子三齿配体可作为过渡金属的配体。因此,(Ph2PCH2SiMe2)2N-衍生物可用于制备铱配合物(Fryzuk等,Angew.Chem.Ed.Engl.(1990),29,73),[(Me3SiNCH2CH2)2NSiMe3]2-衍生物可用于制备二氯化锆配合物(Cloke等,J.Chem.Soc.,Dalton Trans.(1995),25)。含有[(O2CCH2)2NCH3]2-配体的硼衍生物也是已知的(Contrepas等,有机金属化学杂志(J.Organomer.Chem.)(1986),307,1)。此外,对含有[NH(CH2CH2O)2]2-配体的铝衍生物也有记载(Mehrotra等,印度化学会志(J.India Chem.Soc.)(1962),39,677-82)。
含有13族元素的Lewis酸在有机合成中的用途(Yamamoto,H.,合成方法中的有机金属(Organometallics in Synthesis);Schlosser,M.编;John Wiley and Sons Ltd.:West Sussex,England,1994,第7章)以及作为杂环聚合催化剂的用途(Inoue,Acc.Chem.Res.(1996)29,39)也是已知的。Inoue等证实,含有卟啉型配体的催化剂能够生产出多分子性指数接近于1的聚合物(化学会志,化学通讯(J.Chem.Soe.,Chem.Commun.)(1985),1148;化学通讯(Chem.Lett.)(1987),991;Makromol.Chem.(1981)182,1073)。此外,这些催化剂还可用于制备交替或嵌段共聚物(Inoue等,美国化学会志(J.Am.Chem.Soc.)(1983)105,1304;美国化学会志(J.Am.Chem.Soc.)(1985)107,1385;大分子(Macromolecules)(1984)17,2217)。这两种特性是由于生成了活性聚合物。
但是,这些催化体系使用昂贵且不易得到的卟啉配体,从而增加了成本。此外,为了增加活性,需要加入Lewis酸,结果增加了催化体系的复杂性(Inoue等,大分子(Macromolecules)(1994)27,2013;大分子(Macromoleeules)(1995)28,651)。
因此,所需解决的问题是寻找比现有技术中的催化体系更有效、更易于合成且更经济的催化体系。
本发明涉及含有与单或双阴离子三齿配体连接的13族元素的新化合物,其制备方法及其尤其是作为聚合催化剂的用途。
芳基、烷氧基、环烷氧基、芳氧基、烷硫基、环烷硫基
或芳硫基,所述基团是取代(被一个或多个相同或不同的
取代基取代)或未取代的,并且其中所述的取代基是卤原
子、烷基、硝基或氰基;A和B 彼此独立地表示含有2-4个碳原子的碳链,所述碳链被
如下取代(被一个或多个相同或不同的取代基取代)或未
取代的基团之一视具体情况而定地取代:烷基、环烷基
或芳基,其中所述的取代基是卤原子、烷基、硝基或氰
基;L1,L2和L3 彼此独立地表示式-E15(R15)-的基团,其中
E15是15族元素,
R15表示氢原子;如下取代(被一个或多个相同或不同的
取代基取代)或未取代的基团之一:烷基、环烷基或芳
基,其中所述的取代基是卤原子、烷基、硝基或氰基;
式RR′R″E14-的基团,其中E14-是14族元素,R、R′
和R″彼此独立地表示氢原子或如下取代(被一个或多个
相同或不同的取代基取代)或未取代的基团之一:烷
基、环烷基、芳基、烷氧基、环烷氧基、芳氧基、烷硫
基、环烷硫基或芳硫基,其中所述的取代基是卤原子、
烷基、硝基或氰基;或式SO2R′15的基团,其中R′15表
示卤原子、烷基、卤代烷基或被一个或多个选自烷基、
卤代烷基和卤素的取代基视具体情况而定取代的芳基;X1 - 表示不与元素M配位的非配位阴离子;R1 表示氢原子;式RR′R″E14-的基团,其中E14、R、R′
和R″的定义同上;或如下取代(被一个或多个相同或不
同的取代基取代)或未取代的基团之一:烷基、环烷基或
芳基,其中所述取代基是卤原子、烷基、硝基或氰基。
在上述定义中,术语卤素表示氟、氯、溴或碘原子,优选氯。术语烷基优选表示含有1-6个碳原子的直链或支链烷基,特别是含有1-4个碳原子的烷基,例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基和叔丁基。
术语卤代烷基优选表示其中烷基如上所定义并且被一个或多个上述卤原子取代的基团,例如溴乙基、三氟甲基、三氟乙基或五氟乙基。烷氧基可对应于其中烷基如上所定义的基团。优选甲氧基、乙氧基、异丙氧基或叔丁氧基。烷硫基优选表示其中烷基如上所定义的基团,例如甲硫基或乙硫基。
环烷基选自饱和或不饱和的单环烷基。饱和的单环烷基可以选自含有3-7个碳原子的基团,例如环丙基、环丁基、环戊基、环己基或环庚基。不饱和的环烷基可以选自环丁烯、环戊烯、环己烯、环庚二烯、环己二烯基团。环烷氧基可对应于其中的环烷基如上所定义的基团。优选环丙氧基、环戊氧基或环己氧基。环烷硫基可对应于其中环烷基如上所定义的基团如环己硫基。
芳基可以是单环或多环类型的。单环芳基可以选自被一个或多个烷基视具体情况而定取代的苯基,例如甲苯基、二甲苯基、基、异丙苯基。多环芳基可以选自萘基、蒽基、菲基。芳氧基可对应于其中芳基如上所定义的基团。优选苯氧基、2,4,6-三叔丁基苯氧基、甲苯氧基或氧基。芳硫基优选是指其中的芳基如上所定义的基团,例如苯硫基。
X1 -阴离子可以选自不与M配位的非配位阴离子,例如四氟硼酸根、四苯基硼酸根、四氯铝酸根、六氟磷酸根、六氟锑酸根、三氟甲磺酸根或高氯酸根阴离子。
更具体地,本发明涉及上述通式1和2的化合物,其特征在于,M表示硼、铝或镓;RM表示氢原子;卤原子、特别是氯;或甲基;A和B彼此独立地表示含有2-4个碳原子的碳链,特别是含有2个碳原子的碳链;L1和L2彼此独立地表示式-E15(R15)-的基团,其中E15是氮或磷原子,R15表示式RR′R″E14-的基团,其中E14-表示碳或硅原子,R、R′和R″彼此独立地表示氢原子或烷基;R15尤其是代表异丙基和Me3Si;L3表示式-E15(R15)-的基团,其中E15是氮或磷原子,R15表示烷基、特别是甲基,或式RR′R′E14-的基团,其中E14-表示硅原子,R、R′和R″彼此独立地表示烷基、特别是甲基;R1表示氢原子。
更具体地讲,本发明涉及实施例中描述的化合物,特别是下式化合物:-[(Me3SiNCH2CH2)2NSiMe3]AlCl;-[(Me3SiNCH2CH2)2NMe]AlCl;-[(Me3SiNCH2CH2)2NMe]AlH;-[(Me3SiNCH2CH2)2NMe]AlCH3;-[(Me3SiNCH2CH2)2NSiMe3]GaCl;-{[((CH3)2CHNCH2CH2)((CH3)2CHNHCH2CH2)NMe]AlCl}{AlCl4};-{[(Me3SiNCH2CH2)(Me3SiNHCH2CH2)NSiMe3]AlCl}{AlCl4}.
本发明的目的还在于以上所定义的通式1和2化合物的制备方法,其特征在于,将式Ⅰ化合物
(L1-A-L3-B-L2)2-,2Y+ (Ⅰ)其中L1、A、L3、B和L2具有上述含义,Y表示有机金属基团、金属或氢原子,与式Ⅱ化合物反应,
RMMZ1Z2 (Ⅱ)其中RM和M具有上述含义,Z1和Z2彼此独立地表示离去基团,从而得到式1化合物,所述式1化合物可与式(Ⅲ)化合物反应,
R1X1 (Ⅲ)其中R1和X1具有上述含义,得到相应的式2化合物。
用于制备式1化合物的通式Ⅰ化合物和通式Ⅱ化合物之间的反应可以在惰性气氛如氟利昂或氩气氛下、在非质子传递溶剂中、在-60至+50℃的温度范围内进行。当进行从相应的式1化合物制备式2化合物的反应时,将化合物1在惰性气氛和室温下与式Ⅲ化合物于非质子传递介质中反应。
MX′3 (Ⅴ)其中M具有上述含义并且X′表示以上定义的卤原子、烷基或烷氧基,从而得到相应的化合物2。
从相应的通式Ⅳ化合物制备通式2化合物的反应可以在惰性气氛如氟利昂或氩气氛下、在室温下和式Ⅴ化合物于非质子传递介质中进行。化合物2还可以根据本领域技术人员已知的另一种方法,通过除去13族元素的配位阴离子而从式Ⅳ化合物制得。
无论使用的是何种制备方法,所制得的化合物1和2均用常规的纯化方法进行纯化。还可从化合物Ⅳ在其最后使用的介质中就地制得化合物2。
式Ⅳ化合物可通过将式Ⅵ化合物
(R1L1-A-L3-B-L2)-,Y1 +(Ⅵ)其中R1、L1、A、L3、B和L2具有上述含义,Y1表示有机金属基团、金属或氢原子,与式Ⅶ化合物反应制得,
RMMZ3 (Ⅶ)其中RM、M和X具有上述含义,Z3表示离去基团。反应可以在惰性气氛如氟利昂或氩气氛下、在非质子传递溶剂中、在-60至+50℃的温度范围内进行。
式Ⅳ化合物还可以通过将以上所定义的式1化合物与式(Ⅷ)的化合物R1X反应制得,其中的R1和X具有上述含义。反应可以在惰性气氛如氟利昂或氩气氛下、在非质子传递溶剂中、在-60至+50℃的温度范围内进行。
作为非质子传递溶剂,可以使用芳烃如苯、甲苯;脂肪烃如戊烷、庚烷、己烷、环己烷;醚如乙醚、二噁烷、四氢呋喃、乙基叔丁基醚。
在化合物Ⅰ和Ⅵ中,Y和Y1彼此独立地表示有机金属基团、金属或氢原子。有机金属基团可以是式RM1或R3M2的化合物,其中R表示如上定义的烷基、环烷基、芳基、烷氧基、环烷氧基或芳氧基,M1是锌或汞原子,M2是锡或铅原子;优选所述有机金属基团选自ZnMe、SnMe3、SnBu3或PbMe3。金属可以是选自锂、钠或钾的碱金属,或是碱土金属如镁。
在化合物Ⅱ和Ⅶ中,Z1、Z2和Z3彼此独立地表示离去基团,例如以上所定义的卤原子、烷基、环烷基、烷氧基、芳基或芳氧基,或是甲磺酰氧基、苯磺酰氧基、对甲苯磺酰氧基。
在化合物Ⅳ中,X表示与元素M配位的配位阴离子。阴离子X可以是卤素或硫族元素类型的阴离子。优选X表示氯或溴原子。
式Ⅰ的原料化合物和式Ⅵ化合物是已知化合物或可以从已知化合物制得。合成这些化合物时,可以提到如下参考文献:Cloke等,J.Chem.Soc.,Dalton Trans.(1995),25;Wilkinson和Stone,有机金属化学大全(Comprehensive Organometallic Chemistry)(1982)第1卷,557。
式Ⅲ和Ⅷ化合物可购买到或可以通过本领域技术人员已知的方法制得。
式Ⅳ化合物是新的。因此,本发明还涉及新的工业产物、以上所定义的式Ⅳ化合物。
本发明还涉及以上所定义的式1和2化合物在(共)聚合反应、即聚合或共聚反应中作为催化剂的用途。式1和2化合物特别适用于杂环化合物的聚合反应。所述杂环可以含有一个或多个15族和/或16族的杂原子,并且可以是3-8元环。相应于上式的杂环的例子可以是,环氧化物、硫代环氧化物、环状的酯或硫酯如内酯、内酰胺和酸酐。式1和2化合物还特别适用于环状酯的(共)聚合。环状酯的例子是,乳酸和/或乙醇酸的聚合物环状酯。依据是将单体在反应开始时一同引入还是在反应过程中依次引入而制得无规或嵌段共聚物。
本发明的目的还在于制备聚合物或共聚物的方法,该方法包括将一种或多种单体、聚合催化剂和聚合溶剂相接触,其特征在于所述聚合催化剂选自本发明的化合物。
反应溶剂可以是催化反应所用的底物或多种底物之一。也可以使用不干扰催化反应的溶剂。所述溶剂的例子是,饱和或芳香烃、醚、脂肪族或芳香族卤化物。
反应在室温至约150℃的温度范围内进行;最优选在40至100℃的温度范围内进行。反应时间为1至300小时,优选4至72小时。
通常通过向反应介质中加入质子溶剂如醇或非质子传递溶剂如四氢呋喃,并随后离心除去元素M的化合物来回收产物。
该(共)聚合方法特别适用于制备环状酯的(共)聚合物、特别是乳酸和/或乙醇酸的聚合物环状酯。所制得的产物如乙醇酸乳酸共聚物可以被生物降解,特别适于在缓释治疗组合物中用作载体。该方法还特别适用于环氧化物、特别是环氧丙烷的聚合。所制得的聚合物可用于合成有机液晶或用作半透膜。
提供以下实施例是为了说明上述方法,不应理解为是对本发明范围的限定。实施例1:[(Me3SiNCH2CH2)2NSiMe3]AlCl
化合物1,其中M=Al;RM=Cl;A=B=-CH2CH2-;
L1=L2=L3=NSiMe3
将3.26g(9.6mmol)[(Me3SiNCH2CH2)2NSiMe3]2-,2Li+和100ml四氢呋喃依次加入到装有磁力搅拌器和氩气吹扫的Schlenk管中。将反应混合物冷却至-40℃,然后加入1.33g(10mmol)三氯化铝的100ml四氢呋喃溶液。使反应混合物恢复至室温,然后室温搅拌18小时。蒸除溶剂。将残余物于80℃下真空(0.05乇)升华。以白色晶体的形式分离得到所需化合物。通过X-射线衍射鉴定化合物(图1和表1)。熔点10-13℃。实施例2:[(Me3SiNCH2CH2)2NMe]AlCl
化合物1,其中M=Al;RM=Cl;A=B=-CH2CH2-;
L1=L2=NSiMe3;L3=NMe
根据上述方法制备该化合物。通过X-射线衍射鉴定化合物(图2和表1)。熔点130℃(分解)。实施例3:[(Me3SiNCH2CH2)2NMe]AlH
化合物1,其中M=Al;RM=H;A=B=-CH2CH2-;
L1=L2=NSiMe3;L3=NMe
将2.30g(8.8mmol)(Me3SiNHCH2CH2)2NMe和50ml四氢呋喃依次加入到装有磁力搅拌器和氩气吹扫的Schlenk管中。将反应混合物冷却至-40℃,然后加入0.33g(8.8mmol)LiAlH4的70ml四氢呋喃悬浮液。观察到有气体溢出。使反应混合物恢复至室温,然后将其室温搅拌18小时。过滤后,蒸除溶剂,然后将残余物于90℃下真空(0.05乇)升华。以白色晶体的形式分离得到所需化合物。通过X-射线衍射鉴定化合物(图3和表1)。熔点15℃。实施例4:[(Me3SiNCH2CH2)2NMe]AlCH3
化合物1,其中M=Al;RM=CH3;A=B=-CH2CH2-;
L1=L2=NSiMe3;L3=NMe
将3.53g(8.8mmol)(Me3SiNHCH2CH2)2NMe和50ml四氢呋喃依次加入到装有磁力搅拌器和氩气吹扫的Schlenk管中。将反应混合物冷却至-60℃,然后加入6.7ml 2M AlMe3的甲苯溶液。使反应混合物恢复至室温,然后加热至100℃,历时12小时。蒸除溶剂,然后将残余物于70℃下真空(0.05乇)升华。以白色晶体的形式分离得到所需化合物。通过X-射线衍射鉴定化合物(图4和表1)。熔点67℃。实施例5:[(Me3SiNCH2CH2)2NSiMe3]GaCl
化合物1,其中M=Ga;RM=Cl;A=B=-CH2CH2-;
L1=L2=L3=NSiMe3
氩气氛下,将1.34g(4.0mmol)[(Me3SiNCH2CH2)2NSiMe3]2-,2Li+和50ml四氢呋喃依次加入到装有磁力搅拌器的Schlenk管中。将反应混合物冷却至-40℃,然后加入0.33g(8.8mmol)GaCl3的50ml四氢呋喃溶液。使反应混合物恢复至室温,然后室温搅拌18小时。观察到有沉淀生成。过滤后,蒸除溶剂。将残余物于90℃下真空(0.05乇)升华。以白色晶体的形式分离得到所需化合物。通过多核磁共振鉴定化合物。熔点62℃。NMR 1H(C6D6;400MHz):0.18(s,SiCH3,9H);0.46(s,SiCH3,18H);1.98(ddd,J=122;5.0;5.0Hz;CH2,2H);2.44(ddd,J=12.2;7.4;5.2Hz;CH2,2H);2.94(ddd,J=12.2;5.0;5.0Hz;CH2,2H);3.00(ddd,J=12.2;7.4;5.0Hz;CH2,2H).NMR 13C{1H}(C6D6;100.63MHz):1.42(SiCH3);1.82(SiCH3);44.20(CH2);54.21(CH2).NMR 29Si(C6D6;79.49MHz):-3.70;-3.05.实施例6:{[((CH3)2CHNCH2CH2)((CH3)2CHNHCH2CH2)NMe]AlCl}{AlCl4}
化合物2,其中M=Al;RM=Cl;R1=H;A=B=-CH2CH2-;
L1=L2=NCH(CH3)2;L3=NMe;X1 -=AlCl4 -
氩气氛下,将1.03g(3.2mmol)[Me2CHNCH2CH2)2NCH3]AlCl和30ml甲苯依次加入到装有磁力搅拌器的Schlenk管中。将反应混合物冷却至-40℃,然后加入3.2mmol盐酸乙醚溶液。使反应混合物恢复至室温,然后将其室温搅拌18小时。蒸除溶剂至体积为5ml,然后置于-30℃下。以白色晶体的形式分离得到式(Ⅳ)化合物。将该化合物通过X-射线衍射鉴定(图5和表1;熔点160℃(分解))。加入1当量三氯化铝的甲苯悬浮液制得所需化合物。实施例7:{[(Me3SiNCH2CH2)(Me3SiNHCH2CH2)NSiMe3]AlCl}{AlCl4}
化合物2,其中M=Al;RM=Cl;R1=H;A=B=-CH2CH2-;
L1=L2=L3=NSiMe3;X1-=AlCl4 -
氩气氛下,将0.19g(0.5mmol)[(Me3SiNCH2CH2)2NSiMe3]AlCl、4ml甲苯和1mmol盐酸乙醚溶液依次加入到装有磁力搅拌器的Schlenk管中。观察到有沉淀形成。然后室温下加入89mg(0.67mmol)三氯化铝的3ml甲苯悬浮液。反应化合物再次变为均相;将其室温搅拌1小时。蒸除溶剂至体积为0.5ml,然后室温放置。以白色晶体的形式分离得到所需化合物。将该化合物通过X-射线衍射进行鉴定(图6和表1)。实施例8:环氧丙烷的聚合
氩气氛下,将0.15g(0.4mmol)[(Me3SiNCH2CH2)2NSiMe3]AlCl和4.5ml(63mmol)环氧丙烷依次加入到装有磁力搅拌器的Schlenk管中。将反应混合物于30℃下搅拌144小时,蒸除过量的环氧丙烷,然后加入20ml甲醇。离心后,回收液相并蒸除溶剂。得到0.55g低聚物和聚合物的混合物。将该混合物通过碳和质子核磁共振(NMR)进行鉴定。通过GPC(凝胶渗透色谱)进行分析,用质量为194-22000的聚乙二醇(PEG)标准物进行校准并外推更高的分子量,分析结果表明,该样品由平均分子量为798道尔顿的低聚物和具有相似分子量(Mw/Mn=1.69)并且Mw=106904道尔顿的聚合物组成。实施例9:环氧丙烷的聚合
操作条件与实施例8相同,所不同的是使用手性阳离子{[(Me3SiNCH2CH2)(Me3SiNHCH2CH2)NSiMe3]AlCl}{AlCl4}作为催化剂。离心后,回收液相并蒸除溶剂。得到2.17g聚合物的混合物。将该聚合物通过碳和质子NMR进行鉴定。通过GPC进行分析,用质量为194-22000的聚乙二醇(PEG)标准物进行校准,分析结果表明,该样品为相似分子量(Mw/Mn=1,17)并且Mw=1446道尔顿的聚合物的混合物。实施例10:D,L-丙交酯的聚合
氩气氛下,将0.05g(0.17mmol)[(Me3SiNCH2CH2)2NMe]AlH、1.15g D,L-丙交酯和30ml甲苯依次加入到装有磁力搅拌器的Schlenk管中。将反应混合物于80℃下搅拌120小时。蒸除溶剂,然后加入20mlTHF。离心后,回收液相并蒸除溶剂。得到1.04g D,L-丙交酯(32%)和聚合物(68%)的混合物。将该混合物通过碳和质子NMR进行鉴定。通过GPC进行分析,用质量为194-22000的聚乙二醇(PEG)标准物进行校准并外推更高的分子量,分析结果表明,所述聚合物为相似分子量(Mw/Mn=1,61)并且Mw=21659道尔顿的大分子的混合物。实施例11:D,L-丙交酯和乙交酯混合物的聚合
氩气氛下,将0.08g(0.17mmol){[(Me3SiNCH2CH2)(Me3SiNHCH2CH2)NSiMe3]AlCl}{AlCl4}、0.17g(3mmol)环氧丙烷依次加入到装有磁力搅拌器的Schlenk管中。将反应混合物于30℃下搅拌1.5小时,然后蒸除环氧丙烷。依次加入1.15g D,L-丙交酯、0.93g乙交酯和30ml苯。将反应混合物于80℃搅拌240小时。蒸除溶剂,然后加入20mlTHF。离心后,回收液相并蒸除溶剂。得到1.47g共聚物的混合物。将该混合物通过碳和质子NMR进行鉴定。通过GPC进行分析,用质量为194-22000的聚乙二醇(PEG)标准物进行校准并外推更高的分子量,分析结果表明,该样品为Mw=1962的共聚物的混合物(Mw/Mn=1,98)。表1:实施例1-4和6-7化合物选定的键的长度(埃)和键角(度)
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例6 | 实施例7 | |
Al(1)-Cl(1) | 2.144(1) | 2.148(3) | - | - | 2.2584(14) | 2.103(2) |
Al(1)-Cl(2) | - | - | - | - | 2.2056(14) | - |
Al(1)-C(7) | - | - | - | 1.963(3) | - | - |
Al(1)-N(1) | 1.811(1) | 1.816(3) | 1.833(2) | 1.837(2) | 1.819(3) | 1.947(3) |
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例6 | 实施例7 | |
Al(1)-N(2) | 1,998(1) | 1,991(3) | 2,016(3) | 2,018(2) | 2,103(3) | 1,963(3) |
Al(1)-N(3) | 1,803(1) | - | - | - | 2,041(3) | 1,782(3) |
Al(1)-N(1a) | - | 1,816(3) | 1,833(3) | 1,837(2) | - | - |
N(1)-Al(1)-N(2) | 92,8(1)° | 91.1(1)° | 89,76(8)° | 89,77(7)° | 82,99(13)° | 91,8(1)° |
N(1a)-Al(1)-N(2) | - | 91,9(1)° | 89,76(8)° | 89,77(7)° | - | - |
N(1a)-Al(1)-N(1) | - | 126,3(1)° | 125,47(14)° | 122,35(12)° | - | - |
N(1)-Al(1)-N(3) | 124,4(1)° | - | - | - | 115,28(14)° | 114,8(1)° |
N(2)-Al(1)-N(3) | 92,8(1)° | - | - | - | 81,98(12)° | 95,0(1)° |
Cl(1)-Al(1)-N(1) | 113,1(1)° | 113,7(1)° | - | - | 100,09(12)° | 109,4(1)° |
Cl(1)-Al(1)-N(2) | 116,5(1)° | 112,7(1)° | - | - | 171,58(9)° | 117,9(1)° |
Cl(1)-Al(1)-N(3) | 113,1(1)° | - | - | - | 89,63(10)° | 123,0(1)° |
Cl(1)-Al(1)-N(1a) | - | 113,7(1)° | - | - | - | - |
Cl(2)-Al(1)-N(1) | - | - | - | - | 121,84(11)° | - |
Cl(2)-Al(1)-N(2) | - | - | - | - | 91,12(5)° | - |
Cl(2)-Al(1)-N(3) | - | - | - | - | 121,03(10)° | - |
C(7)-Al(1)-N(1) | - | - | - | 116,08(6)° | - | - |
C(7)-Al(1)-N(1) | - | - | - | 116,08(6)° | - | - |
C(7)-Al(1)-N(1) | - | - | - | 114,69(13)° | - | - |
Claims (12)
一:烷基、环烷基、芳基、烷氧基、环烷氧基、芳氧
基、烷硫基、环烷硫基或芳硫基,其中所述取代基
是卤原子、烷基、硝基或氰基;A和B 彼此独立地表示含有2-4个碳原子的碳链,所述碳链
被如下取代或未取代的基团之一视具体情况而定地
取代:烷基、环烷基或芳基,其中所述的取代基是卤
原子、烷基、硝基或氰基;L1,L2和L3 彼此独立地表示式-E15(R15)-的基团,其中
E15是15族元素,
R15表示氢原子;如下取代或未取代的基团之一:烷
基、环烷基或芳基,其中所述取代基是卤原子、烷
基、硝基或氰基;式RR′R″E14-的基团,其中E14-
是14族元素,R、R′和R″彼此独立地表示氢原子
或如下取代或未取代的基团之一:烷基、环烷基、芳
基、烷氧基、环烷氧基、芳氧基、烷硫基、环烷硫
基或芳硫基,其中所述取代基是卤原子、烷基、硝
基或氰基;或式SO2R′15的基团,其中R′15表示卤原
子、烷基、卤代烷基或被一个或多个选自烷基、卤
代烷基和卤素的取代基视具体情况而定取代的芳
基;X1 - 表示不与元素M配位的非配位阴离子;R1 表示氢原子;式RR′R″E14-的基团,其中E14、R、
R′和R″的定义同上;或如下取代或未取代的基团之
一:烷基、环烷基或芳基,其中所述取代基是卤原
子、烷基、硝基或氰基。
2.权利要求1的通式1和2化合物,其特征在于M表示硼、铝或镓原子;RM表示氢原子;卤原子、特别是氯;或甲基;A和B彼此独立地表示含有2-4个碳原子的碳链,特别是含有2个碳原子的碳链;L1和L2彼此独立地表示式-E15(R15)-的基团,其中E15是氮或磷原子,R15表示式RR′R″E14-的基团,其中E14-表示碳或硅原子,R、R′和R″彼此独立地表示氢原子或烷基;L3表示式-E15(R15)-的基团,其中E15是氮或磷原子,R15表示烷基或式RR′R″E14-的基团,其中E14-表示硅原子,R、R′和R″彼此独立地表示烷基;并且R1表示氢原子。
3.权利要求2的通式1和2化合物,其特征在于RM表示氢原子、氯原子或甲基;A和B彼此独立地表示含有2个碳原子的碳链;L1和L2彼此独立地表示异丙基氨基或Me3SiN;L3表示甲氨基或Me3SiN。
4.权利要求1-3中任一项的通式1化合物,其中该化合物具有如下结构式:-[(Me3SiNCH2CH2)2NSiMe3]AlCl;-[(Me3SiNCH2CH2)2NMe]AlCl;-[(Me3SiNCH2CH2)2NMe]AlH;-[(Me3SiNCH2CH2)2NMe]AlCH3;-[(Me3SiNCH2CH2)2NSiMe3]GaCl;-{[((CH3)2CHNCH2CH2)((CH3)2CHNHCH2CH2)NMe]AlCl}(AlCl4};-{[(Me3SiNCH2CH2)(Me3SiNHCH2CH2)NSiMe3]AlCl}{AlCl4}.
7.权利要求1-4中任一项的式1或2化合物作为(共)聚合反应催化剂的用途。
8.权利要求7的用途,其中包括杂环化合物、特别是环氧化物如环氧丙烷的(共)聚合。
9.权利要求7的用途,其中包括用于环状酯、特别是乳酸和/或乙醇酸聚合物环状酯的(共)聚合。
10.制备聚合物或共聚物的方法,该方法包括将一种或多种单体、聚合催化剂和聚合溶剂在室温至150℃的温度下接触1-300小时,其特征在于所述聚合催化剂选自权利要求1-4的化合物。
11.权利要求10的方法,其特征在于所述单体选自环氧化物、特别是环氧丙烷,或环状酯、特别是乳酸和/或乙醇酸的聚合物环状酯。
12.作为新的工业产品的权利要求6所述的式Ⅳ化合物。
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EP (1) | EP1027357B1 (zh) |
JP (1) | JP4117028B2 (zh) |
CN (1) | CN1091110C (zh) |
AT (1) | ATE215543T1 (zh) |
AU (1) | AU724206B2 (zh) |
BR (1) | BR9708967A (zh) |
CA (1) | CA2253416C (zh) |
CZ (1) | CZ293097B6 (zh) |
DE (1) | DE69711718T2 (zh) |
ES (1) | ES2174254T3 (zh) |
HU (1) | HU225537B1 (zh) |
IL (1) | IL126682A (zh) |
NO (1) | NO318098B1 (zh) |
NZ (1) | NZ332678A (zh) |
PL (1) | PL187099B1 (zh) |
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US5889128A (en) | 1997-04-11 | 1999-03-30 | Massachusetts Institute Of Technology | Living olefin polymerization processes |
US6271325B1 (en) * | 1999-05-17 | 2001-08-07 | Univation Technologies, Llc | Method of polymerization |
EP1063239A1 (fr) * | 1999-06-25 | 2000-12-27 | Societe De Conseils De Recherches Et D'applications Scientifiques (S.C.R.A.S.) | Nouveaux composés possédant un lanthanide et un ligand tridentate, leur procédé de préparation et leur application notamment comme catalyseurs de polymérisation |
EP1063238A1 (fr) * | 1999-06-25 | 2000-12-27 | Societe De Conseils De Recherches Et D'applications Scientifiques (S.C.R.A.S.) | Nouveaux composés possédant un élément du groupe 11 ou 12 et un ligand tridentate, leur procédé de préparation et leur application notamment comme catalyseurs de polymérisation |
US6300439B1 (en) | 1999-11-08 | 2001-10-09 | Univation Technologies, Llc | Group 15 containing transition metal catalyst compounds, catalyst systems and their use in a polymerization process |
US6380328B1 (en) | 1999-12-10 | 2002-04-30 | Univation Technologies, Llc | Catalyst systems and their use in a polymerization process |
US6265505B1 (en) | 1999-11-18 | 2001-07-24 | Univation Technologies, Llc | Catalyst system and its use in a polymerization process |
US6300438B1 (en) | 1999-10-22 | 2001-10-09 | Univation Technolgies, Llc | Hafnium transition metal catalyst compounds, catalyst systems and their use in a polymerization process |
US6624107B2 (en) | 1999-10-22 | 2003-09-23 | Univation Technologies, Llc | Transition metal catalyst compounds having deuterium substituted ligand and catalyst systems thereof |
US6417304B1 (en) | 1999-11-18 | 2002-07-09 | Univation Technologies, Llc | Method of polymerization and polymer produced therefrom |
US6274684B1 (en) | 1999-10-22 | 2001-08-14 | Univation Technologies, Llc | Catalyst composition, method of polymerization, and polymer therefrom |
US6271323B1 (en) | 1999-10-28 | 2001-08-07 | Univation Technologies, Llc | Mixed catalyst compounds, catalyst systems and their use in a polymerization process |
US6281306B1 (en) * | 1999-12-16 | 2001-08-28 | Univation Technologies, Llc | Method of polymerization |
RU2282640C2 (ru) * | 2000-05-15 | 2006-08-27 | Сосьете Де Консей Де Решерш Э Д`Аппликасьон Сьентифик (С.К.Р.А.С.) | Применение станниленов и гермиленов в качестве катализаторов полимеризации гетероциклических соединений |
JP4126231B2 (ja) * | 2001-04-10 | 2008-07-30 | ソシエテ ド コンセイユ ド ルシェルシェ エ ダアップリカーション シャンティフィック(エス.セー.エール.アー.エス.) | 環状エステルの重合触媒として亜鉛誘導体の使用 |
WO2008134118A1 (en) * | 2007-04-26 | 2008-11-06 | Dow Global Technologies Inc. | Highly active catalysts for alkylene oxide polymerization |
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NO985061L (no) | 1998-12-29 |
CA2253416C (fr) | 2006-09-19 |
EP1027357A1 (fr) | 2000-08-16 |
CZ293097B6 (cs) | 2004-02-18 |
AU724206B2 (en) | 2000-09-14 |
US6281154B1 (en) | 2001-08-28 |
AU2780197A (en) | 1997-11-26 |
HUP9902137A2 (hu) | 1999-11-29 |
DE69711718T2 (de) | 2002-10-17 |
ATE215543T1 (de) | 2002-04-15 |
BR9708967A (pt) | 1999-08-03 |
WO1997042197A1 (fr) | 1997-11-13 |
NZ332678A (en) | 1999-03-29 |
PL329626A1 (en) | 1999-03-29 |
JP2000509706A (ja) | 2000-08-02 |
CZ348198A3 (cs) | 1999-03-17 |
RU2180664C2 (ru) | 2002-03-20 |
CA2253416A1 (fr) | 1997-11-13 |
PT1027357E (pt) | 2002-07-31 |
HU225537B1 (en) | 2007-02-28 |
CN1091110C (zh) | 2002-09-18 |
HUP9902137A3 (en) | 1999-12-28 |
EP1027357B1 (fr) | 2002-04-03 |
NO318098B1 (no) | 2005-01-31 |
NO985061D0 (no) | 1998-10-30 |
PL187099B1 (pl) | 2004-05-31 |
IL126682A (en) | 2002-07-25 |
DE69711718D1 (de) | 2002-05-08 |
IL126682A0 (en) | 1999-08-17 |
JP4117028B2 (ja) | 2008-07-09 |
ES2174254T3 (es) | 2002-11-01 |
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