CN1127756A - 作为氢化硅烷化催化剂的三氮烯氧化物——过渡金属配合物 - Google Patents
作为氢化硅烷化催化剂的三氮烯氧化物——过渡金属配合物 Download PDFInfo
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- CN1127756A CN1127756A CN95108153A CN95108153A CN1127756A CN 1127756 A CN1127756 A CN 1127756A CN 95108153 A CN95108153 A CN 95108153A CN 95108153 A CN95108153 A CN 95108153A CN 1127756 A CN1127756 A CN 1127756A
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- China
- Prior art keywords
- general formula
- triazene
- organopolysiloxane
- carbon
- oxide compound
- 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.)
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- AYNNSCRYTDRFCP-UHFFFAOYSA-N triazene Chemical compound NN=N AYNNSCRYTDRFCP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 17
- 238000006459 hydrosilylation reaction Methods 0.000 title description 4
- 239000003054 catalyst Substances 0.000 title description 2
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 84
- 229910052697 platinum Inorganic materials 0.000 claims description 44
- 229920001296 polysiloxane Polymers 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- -1 nitrous acid ester Chemical class 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 150000001721 carbon Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 6
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- AANHHCGCDDWNAL-UHFFFAOYSA-N 1,1'-biphenyl ethylphosphonic acid Chemical compound C1(=CC=CC=C1)C1=CC=CC=C1.C(C)P(O)(O)=O AANHHCGCDDWNAL-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 235000019439 ethyl acetate Nutrition 0.000 claims description 2
- IDNUEBSJWINEMI-UHFFFAOYSA-N ethyl nitrate Chemical compound CCO[N+]([O-])=O IDNUEBSJWINEMI-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 125000006023 1-pentenyl group Chemical group 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- DBAMUTGXJAWDEA-UHFFFAOYSA-N Butynol Chemical compound CCC#CO DBAMUTGXJAWDEA-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 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 2
- 125000002704 decyl 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])* 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl 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 description 2
- 238000001035 drying Methods 0.000 description 2
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 2
- 150000002443 hydroxylamines Chemical class 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- 229960002238 methylpentynol Drugs 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
本发明提供了一种在三氮烯氧化物——过渡金属配合物存在下,使具有Si键合的氢原子的有机硅化合物与具有脂族重键的有机化合进行反应的方法,其中,通过在50℃-250℃下进行加热和/或光辐照使三氮烯氧化物——过渡金属配合物活化。
Description
本发明涉及一种在三氮烯氧化物(triazene oxide)-过渡金属配合物存在下进行氢化硅烷化反应的方法,本发明还涉及含有三氮烯氧化物-过渡金属配合物的可交联有机多分子硅醚组合物,三氮烯氧化物-铂配合物,及制备三氮烯氧化物-铂配合物的方法。
在例如以下的两篇文献[R.L.Dutta,R.Sharma;J.Sci,Ind.Res.,40(11)(1981)715和D.N.Purohit等;Rev.Anal.Chem.,11(3-4),269(1992)]中描述了三氮烯氧化物-过渡金属配合物。但这些文献并未描述三氮烯氧化物-铂配合物。
众所周知,通过催化剂,特别是铂化合物可以促进Si键合的氢向脂族重键的加成,即所谓的氢化硅烷化反应。该过程例如可参见US-A-3,814,730。这些催化剂的活化能较低,常常必须在加成-交联体系中进行抑制。
本发明的目的是提供一类催化剂,它们具有较高的活化能,因此,在加成-交联体系中无需进行抑制,它们在活化后能促进Si键合的氢向脂族重键的加成。
本发明提供了一种在通式(I)的三氮烯氧化物-过渡金属配合物存在下,使具有Si键合的氢原子的有机硅化合物与具有脂族重键的有机化合物进行反应的方法,其中式(I)的配合物为:
M(ANNNOR1)aXb (I)其中
M为Pt,Pd,Rh,Ru,Os或Ir;
R1为一价的、每个基具有1-18个碳原子的、取代或未取代的烃基、通式-SiR2 C(OR2)3-C的基团或A;
R2在每种状态下可相同或不同,为每个基具有1-8个碳原子的烷基;
G为CH或N;
Q为S、O或NH;
R3为一价、具有1-12个碳原子的、取代或未取代的烃基,或下式的基团:-F、-Cl、-Br、-I、-H、-NH2、-NR2 2、-NO2、-OH、-OR2、-SH、-CN、-COOH、-COCl、-CONH2、-COR2、-CHO、-SO2NHR2、-SO3H、-SO2Cl、-R4SiR2 C(OR2)3-C,
R4为具有1-8个碳原子的二价烃基;
R2可相同或不同,为具有1-8个碳原子的烷基;
X可相同或不同,为一种配位体,选自:Cl、Br、I、NH3、P(C2H5)3、P(C6H5)3、H、CO、1,5-环辛二烯、吡啶、联吡啶、乙酸酯、丙酮酸酯、苯腈、乙二胺、乙腈、2,5-降冰片二烯、硝酸酯、亚硝酸酯、H2O、苯、二苯基膦酰乙烷、1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷、乙烯和二苯基乙炔;
a为1、2、3或4;
b为0或1-6的整数;
c为0、1、2或3;
其中,通过在50℃-250℃下进行加热和/或光辐照使三氮烯氧化物-过渡金属配合物活化。
R1的实例为:烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、叔戊基、己基如正己基和环己基、庚基如正庚基、辛基如正辛基和异辛基如2,2,4-三甲基戊基、壬基如正壬基、癸基如正癸基、十二烷基如正十二烷基、十八烷基如正十八烷基;环烷基如环己基;链烯基如乙烯基、1-丙烯基、1-丁烯基、2-丁烯基、烯丙基、异丁烯基、1-戊烯基和2-甲基-1-丁烯基;链炔基如乙炔基、炔丙基、1-丙炔基、1-丁炔基;芳烷基如苄基和α-和β-苯乙基。优选的是烷基。
取代的烃基R1的实例为:卤代烷基如3,3,3-三氟正丙基、2,2,2,2′,2′,2′-六氟异丙基、七氟异丙基、3-氯正丙基、2-乙基溴和3-丙基溴;羟基烷基如:HOCH2CH2OCH2CH2-、HOCH2CH2-、CH3CH2CH(OH)CH2-;氨烷基如氨甲基和氮乙基;羧基烷基如-(CH2)7COOH、-(CH2)8COOH和-CH2COCH2CH2COOH及它们的酯和酰胺-(CH2)7COOCH3、-(CH2)7COOC2H5、-(CH2)7CONH2、-(CH2)8COOCH3、-(CH2)8COOC2H5、-(CH2)8CONH2、基团-CH(COOC2H5)2;取代的芳烷基如取代的苄基和取代的α-和β-苯乙基。
R2的实例为由基团R1所给出的烷基。
R3的实例为由基团R1给出的、具有1-12个碳原子的、取代或未取代的烃基。
烃基R4的实例为直链或支链亚烷基如亚甲基、亚乙基、亚丙基、2-甲基亚丙基和亚丁基。
R3为芳基或杂芳基A的取代基,例如当A为芳族六元环如苯基时,R3可位于邻、间或对位。
催化剂的实例为:PtANNNOR1 aXb,其中a=2或4,b=2、1或0,PdANNNOR1 aXb,其中a=1或2,b=0或1,RuANNNOR1 aXb,其中a=1、2、3或4,b=0、1、2、或3,RhANNNOR1 aXb,其中a=1、2或3,b=0、1或2,OsANNNOR1 aXb,其中a=3或4,b=0、1、2或3,IrANNNOR1 aXb,其中a=1,2,3或4,b=0,1,2、或3,其中,X、A和R1定义同上。
优选的三氮烯氧化物-过渡金属配合物的实例为:Pt[C6H5NNNOCH3]4、Pt[p-CN-C6H4NNNOC6H11]4、Pt[p-H3COC6H4NNNOC6H11]4、Pt[p-CH3(CH2)x-C6H4NNNOCH3]4、1,5-环辛二烯·Pt[p-CN-C6H4NNNOC6H11]2、1,5-环辛二烯.Pt[p-CH3O-C6H4NNNOCH3]2、[(C6H5)3P]3Rh[p-CN-C6H4NNNOC6H11]、Pd[p-CH3(CH2)x-C6H4NNNOCH3]2,其中x为1、3、5、7、11、或17,特别是1、5、7或11,上述的铂的三氮烯配合物是特别优选的。
当三氮烯氧物-过渡金属配合物用作催化剂时,活化温度取决于通式ANNNOR1的三氮烯氧化物配位体和各配合物的金属原子M。优选采用紫外光来对本发明的催化剂进行活化。有多种可商购的紫外灯可发射200-400nm的紫外光。可通过在50℃-250℃下进行加热以及再用光、优选紫外光进行辐照来活化本发明的催化剂。
就本发明而言,具有脂族重键的有机化合物包括具有环脂族重键的有机化合物。
通式(I)的三氮烯氧化物-铂配合物可用于所有使用催化剂以促进Si键合的氢向脂族重键加成的可交联的有机多分子硅醚组合物中。
相应地,本发明还提供了一种可交联的有机多分子硅醚组合物,它包括:
(1)具有包含脂族碳-碳重键的基团的有机多分子硅醚,
(2)具有Si键合的氢原子的有机多分子硅醚,或者代换有机多分子硅醚(1)和(2)的
(3)既具有包含脂族碳-碳重键的基团又具有Si键合的氢原子的有机多分子硅醚,
(4)作为催化剂的通式(I)的三氮烯氧化物-铂配合物。
就本发明而言,具有脂族碳-碳重键的基团包括具有环脂族碳-碳重键的基团。
本发明中所使用的具有含脂族碳-碳重键基团的有机多分子硅醚(1)优选为包含通式(II)的单元的直链或支链有机多分子硅醚 其中
R5为一价的、不含脂族碳-碳重键的、具有1-18个碳原子的取代或未取代的烃基;
R6为一价的、具有脂族碳-碳重键的、具有2-8个碳原子的烃基;
n为0、1、2或3;
m为0、1或2;
n+m的总和为0,1,2,或3;
条件是:每一个分子中至少包含2个R6基团。
有机多分子硅醚(1)在25℃时的平均粘度优选为100-10,000mPa·s。
烃基R5的实例为由R1给出的一价的、不含脂族碳-碳重键的、具有1-18个碳原子的取代或未取代的烃基;
R6的实例为:链烯基如乙烯基、5-己烯基、1-丙烯基、烯丙基、1-丁烯基和1-戊烯基;链炔基如乙炔基、炔丙基和1-丙炔基。
本发明中所使用的具有Si键合的氢原子的有机多分子硅醚(2)优选为包含通式(III)的单元的直链、环状或支链有机多分子硅醚 其中
R5定义同式(II);
e为0、1、2或3;
f为0、1或2;
e+f的总和为0,1,2,或3;
条件是:每一个分子中平均至少包含2个Si键合的氢原子。
有机多分子硅醚(2)在25℃时的平均粘度优选为10-1,000mPa·s。
R5和R6定义同式(II);
k为0、1、2或3;
l为0、1或2;
p为0、1或2;
条件是:每一分子中至少包含2个R6基团和平均至少2个Si键合的氢原子。
有机多分子硅醚(3)的实例为那些包含SiO4/2、R5 3SiO1/2、R5 2R6SiO1/2和R5 2HSiO1/2单元的有机多分子硅醚,所谓的MQ树脂,其中这些树脂中可包含T单元(R5SiO3/2)和D单元(R5 2SiO)。
有机多分子硅醚(3)在25℃时的平均粘度优选为100-100,000mPa·s或为分子量为5,000-50,000g/mol的固体。
以有机多分子硅醚(1)和(2)的总重量或有机多分子硅醚(3)的总重量计,通式(I)的三氮烯氧化物-过渡金属配合物的用量优选为1-1,000ppm(重量,百万重量分之一),优选为10-100ppm(重量),在每种情况下是分别以过渡金属元素Pt、Pd、Ru、Rh、Os和Ir来计算的。
在可交联的有机多分子硅醚组合物中也可使用抑制剂。抑制剂的实例为:1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷、苯并三唑、二烷基甲酰胺、烷基硫脲、甲基乙基酮肟、在1012mbar(abs.)下沸点至少为25℃且至少具有一个脂族三键的有机化合物或有机硅化合物如1-乙炔基环己-1-醇、2-甲基-3-丁炔-2-醇、3-甲基-1-戊炔-3-醇、2,5-二甲基-3-己炔-2,5-二醇和3,5-二甲基-1-己炔-3-醇,以及包含马来酸二烯丙酯和乙酸乙烯酯的混合物和马来酸单酯的抑制剂。
具有Si键合氢原子的有机硅化合物的实例为每分子中具有一个Si键合氢原子的硅烷,如三氯硅烷、二甲基氯硅烷、二甲基乙氧基硅烷、甲基二乙氧基硅烷、甲基二氯硅烷和三乙氧基硅烷;以及每分子中至少具有一个Si键合氢原子的有机聚硅氧烷,如α,ω-二氢[二甲基聚硅氧烷]、四甲基二硅氧烷、四甲基环四硅氧烷、包含三甲基硅氧烷和甲基氢化硅氧烷单元的共聚物、包含三甲基硅氧烷、二甲基硅氧烷和甲基氢化硅氧烷单元的共聚物、以及三甲基甲硅烷氧基氢硅烷。
具有脂族重键的有机化合物的实例为具有脂族碳-碳双键的化合物,如苯乙烯、烯丙基缩水甘油基醚、烯丙基腈、乙酸烯丙酯、烯丙基琥珀酸酐、乙二醇单烯丙基醚、甲基丙烯酸烯丙酯、烯丙胺和环己烯,及具有脂族碳-碳三键的化合物,如乙炔和丁炔醇(butynol)。
本发明还提供了一种通式(VII)的三氮烯氧化物-铂配合物,
Pt(ANNNOR1)aXb (VII)其中,A、R1、X、a和b同通式(I)的定义。
例如,在文献[R.L.Dutta,R.Sharma;J.Sci.Ind.Res.,40(11)(1981)715]中描述了除铂的三氮烯配合物之外的过渡金属的三氮烯配合物的制备方法以及三氮烯氢氧化物的制备方法。
本发明还提供了一种制备通式(VII)的三氮烯氧化物-铂配合物的方法,包括在碱存在下,使通式(VIII)的三氮烯氢氧化物
ANNNOHR1 (VIII)与通式(IX)的铂化合物反应,
PtXd (IX)其中A、R1和X同通式(I)的定义,d为1-6的整数。
可用于制备三氮烯氧化物-铂配合物的、通式ANNNOHR1的三氮烯氢氧化物配位体的优选实例为:C6H5NNNOHCH3、C6H5NNNOHC6H5、p-CH3O-C6H4NNNOHCH3、o-CH3O-C6H4NNNOHCH3、p-CN-C6H4NNNOH(CH2)xCH3、p-NO2-C6H4NNNOHC6H11、p-(CH3)2N-C6H4NNNOH(CH2)xCH3,特另优选p-CN-C6H4NNNOHC6H11、p-Cl-C6H4NNNOHC6H11和p-CH3(CH2)xC6H4NNNOHCH3,其中,X为1、3、5、7、11或17,优选1、5、7或11。
用于制备三氮烯氧化物-铂配合物的、通式PtXd的铂化合物的实例为:PtCl2、PtI2、[(C6H5)3P]2PtCl2、[(C2H5)3P]2PtCl2、PtCI4、Pt(H2NCH2CH2NH2)Cl2、Pt(NH3)2Cl2、PtBr2、PtI2、H2PtCl6、1,5-环辛二烯·PtCl2、(1,5-环辛二烯)2Pt、1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷铂配合物(例如,Pt2[1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷]3)、双(二苯基乙炔基)Pt,其中,优选为PtCl4、1,5-环辛二烯·PtCl2、PtI2、1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷铂配合物。
用于制备三氮烯氧化物-铂配合物的碱的实例为:正丁基锂、三乙胺、哌啶、吡啶、NaOCH3和NaNH2,优选为正丁基锂和三乙胺。
三氮烯氧化物-铂配合物的制备过程优选是在有机溶剂如正己烷、甲苯、二氯甲烷、氯仿、丙酮或四氢呋喃的存在下进行,但也可在水与有机溶剂如甲醇、乙醇、异丙醇或四氢呋喃的混合物存在下进行该过程。
优选在0℃-50℃、大气压及隔绝光线的条件下,进行三氮烯氧化物-铂配合物的制备过程。在反应后,优选将有机溶剂或有机溶剂与水的混合物除去。
在下述实施例中,除非另有说明:a)所有的量均指重量;b)所有的压力为0.10MPa(abs,);c)所有的温度为20℃。
实施例1-6的实验均在绝对隔绝光线的条件下进行。用于实施例1-6的三氮烯氢氧化物的合成方法
将0.1mol的苯胺衍生物溶解于300ml的10%盐酸水溶液中并将其冷却至0℃。
在搅拌下,将溶解在40ml水中的0.1mol亚硝酸钠缓慢加入,随后在0℃下搅拌混合物1小时,再与20g的活性炭混合并在0℃下继续搅拌10分钟,过滤。
在0℃及搅拌下,向溶解于600ml水中的0.1mol羟胺衍生物和0.6mol碳酸钠的混合物中缓慢地滴加上面得到的滤液。从水溶液中沉淀出相应的三氮烯氢氧化物,过滤后仔细地用水对沉淀进行洗涤。
在高真空下用五氧化磷对黄色的三氮烯氢氧化物进行干燥至恒重。收率为理论值的50-80%。
表1苯胺衍生物 羟胺衍生物 三氮烯氢氧化物 实施例4-NC-C6H4-NH2 H-NC6H11(OH)·HCl 4-NC-C6H4-N3C6H11(OH) 1C6H5-NH2 H-NCH3(OH)·HCl C6H5N3CH3(OH) 2+54-CH3(CH2)3-C6H4-NH2 H-NCH3(OH)·HCl 4-CH3(CH2)3C6H4N3CH3(OH) 4+64-CH3O-C6H4-NH2 H-NCH3(OH)·HCl 4-CH3O-C6H4N3CH3(OH) 3
所有下述实施例均是在隔绝水分下进行的。
实施例1-6:三氮烯氧化物-过渡金属配合物的制备
实施列1
将0.7g(2.9mmol)的1-[4-氰基苯基]-3-环己基-3-羟基三氮-1-烯溶解于20g(434.1mmol)的乙醇中。
随后将得到的溶液与0.6g(3.2mmol)的30%的氢氧化钾的甲醇溶液混合并在室温下搅拌半个小时。然后向其中缓慢加入悬浮于10g(217.1mmol)乙醇中的0.54g(1.4mmol)的环辛-1,4-二烯铂二氯化物,将混合物搅拌2小时,得到浅米色固体沉淀。分离出固体后,用10g乙醇洗涤,并将其溶解于30g(325.6mmol)的甲苯中。将溶液过滤,在高真空及室温下蒸出溶剂。得到的残余物为0.8g的黄色固体,铂含量为28%(重量)(收率为理论值的82%;以纯铂计)。
将0.3g(0.43mmol铂)的双[1-(4-氰基苯基)-3-环己基-3-氧三氮-1-烯]铂-环辛-1,4-二烯配合物溶解于8.1g(87.9mmol)的甲苯中。该溶液含有1%(重量)的纯铂,为1号催化剂(cat.1)。
实施例2
将2g(13.2mmol)的1-苯基-3-甲基-3-羟基-三氮-1-烯溶解于7g(97.1mmol)的四氢呋喃中。将溶液冷却至0℃后,搅拌下缓慢滴加10ml(16mmol的丁基锂)的1.6M丁基锂正己烷溶液,在此过程中温度控制在不超过5℃。再将反应混合物搅拌半个小时。随后,在0℃、搅拌下缓慢加入1.11g(3.3mmol)四氯化铂在15g(208.0mmol)四氢呋喃中的溶液,将反应混合物搅拌1小时。将溶液过滤后,在高真空及室温下蒸出溶剂。得到的残余物吸收于50g(1.563mol)甲醇中。从甲醇溶液中沉淀出固体,通过过滤将其分离出来。在高真空及室温下将暗黄色粉末干燥至恒重。得到0.84g产物,其中铂含量为33.8%(重量)(收率为理论值的44.1%;以纯铂计)。
将0.3g(0.52mmol铂)的四[1-苯基-3-甲基-3-氧三氮-1-烯]铂配合物溶解于9.84g(136.5mmol)的四氢呋喃中。该溶液含有1%(重量)的纯铂,为2号催化剂(cat.2)。
实施例3
将3g(16.6mmol)的1-(4-甲氧基苯基)-3-甲基-3-羟基三氮-1-烯溶解于10g(138.7mmol)的四氢呋喃中。将溶液冷却至0℃后,搅拌下缓慢滴加12.5ml(20.0mmol的丁基锂)的1.6M丁基锂正己烷溶液,在此过程中温度保持在不超过5℃。再将反应混合物搅拌半个小时。随后,搅拌下缓慢加入1.4g(4.15mmol)四氯化铂在17g(235.8mmol)四氢呋喃中的溶液,将反应溶液搅拌1小时。将溶液过滤后,在高真空及室温下蒸出溶剂;得到的残余物吸收于50g(499.2mmol)甲基·异丁基酮中。从溶液中沉淀出固体,通过过滤将其分离出来。分别用20g(625mmol)的甲醇洗涤固体两次,然后在高真空及室温下将其干燥至恒重。得到1.45g褐色粉末,其中铂含量为30.4%(重量)(收率为理论值的54.4%;以纯铂计)。
将0.3g(0.47mmol铂)的四[1-(4-甲氧基苯基)-3-甲基-3-氧三氮-1-烯]铂配合物溶解于8.82g(122.3mmol)的四氢呋喃中。该溶液含有1%(重量)的纯铂,为3号催化剂(cat.3)。
实施列4
将3g(14.5mmol)的1-(4-丁基苯基)-3-甲基-3-羟基三氮-1-烯溶解于10g(138.7mmol)的四氢呋喃中。将溶液冷却至0℃后,搅拌下缓慢滴加10.9ml(17.4mmol的丁基锂)的1.6M丁基锂正己烷溶液,在此过程中温度保持在不超过5℃。再将反应混合物搅拌半个小时。随后,搅拌下缓慢加入1.22g(3.6mmol)四氯化铂在15g(208.0mmol)四氢呋喃中的溶液,将反应混合物搅拌1小时。将溶液过滤后,在高真空及室温下蒸出溶剂;得到的残余物吸收于50g(1.563mol)甲醇中。从甲醇溶液中沉淀出固体,通过过滤将其分离出来。在高真空及室温下将其干燥至恒重。得到0.72g黄色粉末,其中铂含量为30.8%(重量)(收率为理论值的31.6%;以纯铂计)。
将0.3g(0.47mmol铂)的四[1-(4-丁基苯基)-3-甲基-3-氧三氮-1-烯]铂配合物溶解于8.94g(97.0mmol)的甲苯中。该溶液含有1%(重量)的纯铂,为4号催化剂(cat.4)。
实施例5
将0.2g(1.3mmol)的1-苯基-3-甲基-3-羟基-三氮-1-烯溶解于2g(27.7mmol)的四氢呋喃中。将溶液冷却至0℃后,搅拌下缓慢滴加1.0ml(1.6mmol的丁基锂)的1.6M丁基锂正己烷溶液,在此过程中温度保持在不超过5℃。再将反应混合物搅拌半个小时。
随后,在0℃及搅拌下缓慢加入1.2g(1.3mmol)三(三苯基膦)铑氯化物在10g(138.7mmol)四氢呋喃中的溶液,将反应溶液搅拌1小时。将溶液过滤后,在高真空及室温下蒸出溶剂。得到的残余物吸收于50g(1.22mol)乙腈中。从溶液中沉淀出固体,通过过滤将其分离出来。在高真空及室温下将其干燥至恒重。得到0.31g浅褐色粉末,(收率为理论值的22.9%)。
将0.1g(0.096mmol铑)的(1-苯基-3-甲基-3-氧三氮-1-烯)三(三苯基膦)铑配合物溶解于0.89g(7.5mmol)的氯仿中。该溶液含有1%(重量)的纯铑,为5号催化剂(cat.5)。
实施例6
在50℃下,将0.8g(4.5mmol)的二氯化钯溶解于50g的5%的盐酸水溶液中(68.6mmol氯化氢)。随后,用5.5g(67.0mmol)乙酸钠将pH值调节至约3。之后,在搅拌及60℃下将1.87g(9.0mmol)1-(4-丁基苯基)-3-甲基-3-羟基三氮-1-烯溶解于250g(5.43mol)的乙醇中的溶液加入。一经加入即产生沉淀,随着乙醇溶液的加入到上述溶液中,沉淀量不断增加。在60℃下进一步搅拌混合物1小时,再将固体通过过滤分离出来,并其将吸收在70g(0.76mol)的甲苯中。将溶液过滤后,在高真空及室温下蒸出溶剂,将得到的紫色粉末干燥至恒重。得到2.1g产物,其铂含量为17.8%(重量)(收率为理论值的78.1%;以纯铂计)。
将0.3g(0.5mmol纯钯)的双[1-(4-丁基苯基)-3-甲基-3-氧三氮-1-烯]钯配合物溶解于5.04g(54.7mmol)的甲苯中。该溶液含有1%(重量)的纯钯,为6号催化剂(cat.6)。
实施例7
将0.083g实施例1制得的1号催化剂加至在25℃下粘度为500mPa·s的8gα,ω-二乙烯基二甲基聚硅氧烷中。向该反应混合物中加入0.2g的一种共聚物,从而使混合物以元素计算含100ppm(重量)的铂,该共聚物包含三甲基硅氧烷和甲基氢化硅氧烷单元,其25℃下的粘度为33mPa·s,并含1.12%(重量)的Si键合的氢。
在50℃下加热4.5分钟后,可实现完全交联。得到一种不溶于有机溶剂的透明产物。
实施例8
重复实施例7的过程,只是用0.083g实施例4制得的4号催化剂代替0.083g1号催化剂。在120℃下2分钟后,可实现完全交联。得到一种不溶于有机溶剂的透明产物。
实施例9
重复实施例7的过程,只是用25℃下粘度为1000mPa·s的α,ω-二乙烯基二甲基聚硅氧烷代替25℃下粘度为500mPa·s的α,ω-二乙烯基二甲基聚硅氧烷,用0.083g实施例2制得的2号催化剂代替0.083g1号催化剂。
在120℃下2分钟后,可实现完全交联。得到一种不溶于有机溶剂的透明产物。
实施例10
将0.083g实施例1制得的1号催化剂与0.75g的一种有机多分子硅醚树脂混合,该有机多分子硅醚树脂包含SiO2、三甲基硅氧烷、二甲基乙烯基硅氧烷和甲基苯基硅氧烷单元,25℃下的粘度为1600mPa·s,它包含7.6%(重量)的Si键合的乙烯基基团。向混合物中加入7.45g的一种有机多分子硅醚树脂,该树脂包含SiO2、三甲基硅氧烷、二甲基氢化硅氧烷和甲基苯基硅氧烷单元,25℃下的粘度为2000mPa·s,它包含0.2%(重量)的Si键合的氢,从而使混合物包含100ppm(重量)的铂。
用紫外光(UVA=70mW/cm2,UVB=20mW/cm2)辐照20分钟后,可实现完全交联。得到一种浅黄色的不溶于有机溶剂的透明产物。
实施例11
重复实施例8的过程,只是用0.083g实施例3制得的的3号催化剂代替0.083g的4号催化剂。
用紫外光(UVA=70mW/cm2,UVB=20mW/cm2)辐照3分钟后,可实现完全交联。得到一种不溶于有机溶剂的透明产物。
实施例12
将0.083g实施例1制得的1号催化剂加至7.88g25℃下粘度为500mPa·s的α,ω-二乙烯基二甲基聚硅氧烷中。向反应混合物中加入0.2g的一种共聚物和0.116g(0.93mmol)的1-乙炔基-环己醇,从而使混合物以元素计算含100ppm(重量)的铂。所述的共聚物包含三甲基硅氧烷和甲基氢化硅氧烷单元,其在25℃下的粘度为33mPa·s,并含1.12%(重量)的Si键合的氢。
用紫外光(UVA=70mW/cm2,UVB=20mW/cm2)辐照15秒钟后,可实现完全交联。得到一种不溶于有机溶剂的透明产物。
实施例13
重复实施例7的过程,只是用实施例5制得的的5号催化剂代替0.083g的1号催化剂。用紫外光(UVA=70mW/cm2,UVB=20mW/cm2)辐照10分钟后,可实现完全交联。得到一种不溶于有机溶剂的透明产物。
实施例14
重复实施例10的过程,只是用0.083g实施例6制得的6号催化剂代替0.083g的1号催化剂。在170℃下30分钟后,可实现完全交联。得到一种不溶于有机溶剂浅黄色透明产物。
Claims (4)
1、一种在通式(I)的三氮烯氧化物-过渡金属配合物存在下,使具有Si键合的氢原子的有机硅化合物与具有脂族重键的有机化合物进行反应的方法,其中式(I)的配合物为:
M(ANNNOR1)aXb (I)其中
M为Pt,Pd,Rh,Ru,Os或Ir;
R1为一价的、每个基具有1-18个碳原子的、取代或未取代的烃基、通式-SiR2 C(OR2)3-C的基团或A;
R2在每种状态下可相同或不同,为每个基具有1-8个碳原子的烷基;
G为CH或N;
Q为S、O或NH;
R3为一价、具有1-12个碳原子的、取代或未取代的烃基,或下式的基团:-F、-Cl、-Br、-I、-H、-NH2、-NR2 2、-NO2、-OH、-OR2、-SH、-CH、-COOH、-COCl、-CONH2、-COR2、-CHO、-SO2NHR2、-SO3H、-SO2Cl、-R4SiR2 C(OR2)3-C′
R4为具有1-8个碳原子的二价烃基;
R2可相同或不同,为具有1-8个碳原子的烷基;
X可相同或不同,为一种配位体,选自:Cl、Br、I、NH3、P(C2H5)3、P(C6H5)3、H、CO、1,5-环辛二烯、吡啶、联吡啶、乙酸酯、丙酮酸酯、苯腈、乙二胺、乙腈、2,5-降冰片二烯、硝酸酯、亚硝酸酯、H2O、苯、二苯基膦酰乙烷、1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷、乙烯和二苯基乙炔;
a为1、2、3或4;
b为0或1-6的整数;
c为0、1、2或3;
其中,通过在50℃-250℃下进行加热和/或光辐照使三氮烯氧化物-过渡金属配合物活化。
2、一种可交联的有机多分子硅醚组合物,包括:
(1)具有包含脂族碳-碳重键的基团的有机多分子硅醚,
(2)具有Si键合的氢原子的有机多分子硅醚,或者代换有机多分子硅醚(1)和(2)的
(3)既具有包含脂族碳-碳重键的基团又具有Si键合的氢原子的有机多分子硅醚,
(4)作为催化剂的通式(I)的三氮烯氧化物-铂配合物。
3、一种通式(VII)的三氮烯氧化物-铂配合物,
Pt(ANNNOR1)aXb (VII)其中,A、R1、X、a和b同通式(I)的定义。
4、一种制备通式(VII)的三氮烯氧化物-铂配合物的方法,包括在碱存在下,使通式(VIII)的三氮烯氢氧化物
ANNNOHR1(VIII)与通式(IX)的铂化合物反应,
PtXd (IX)其中A、R1和X同通式(I)的定义,d为1-6的整数。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4423195A DE4423195A1 (de) | 1994-07-01 | 1994-07-01 | Triazenoxid-Übergangsmetall-Komplexe als Hydrosilylierungskatalysatoren |
DEP4423195.4 | 1994-07-01 |
Publications (1)
Publication Number | Publication Date |
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CN1127756A true CN1127756A (zh) | 1996-07-31 |
Family
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CN95108153A Pending CN1127756A (zh) | 1994-07-01 | 1995-06-30 | 作为氢化硅烷化催化剂的三氮烯氧化物——过渡金属配合物 |
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Country | Link |
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US (1) | US5496961A (zh) |
EP (1) | EP0690067B1 (zh) |
JP (1) | JP2820640B2 (zh) |
KR (1) | KR0150097B1 (zh) |
CN (1) | CN1127756A (zh) |
AT (1) | ATE193293T1 (zh) |
CA (1) | CA2149393A1 (zh) |
DE (2) | DE4423195A1 (zh) |
FI (1) | FI953244A (zh) |
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-
1994
- 1994-07-01 DE DE4423195A patent/DE4423195A1/de not_active Withdrawn
-
1995
- 1995-05-10 US US08/437,830 patent/US5496961A/en not_active Expired - Fee Related
- 1995-05-15 CA CA002149393A patent/CA2149393A1/en not_active Abandoned
- 1995-06-22 AT AT95109673T patent/ATE193293T1/de active
- 1995-06-22 EP EP95109673A patent/EP0690067B1/de not_active Expired - Lifetime
- 1995-06-22 DE DE59508374T patent/DE59508374D1/de not_active Expired - Fee Related
- 1995-06-30 KR KR1019950018824A patent/KR0150097B1/ko not_active IP Right Cessation
- 1995-06-30 JP JP7166589A patent/JP2820640B2/ja not_active Expired - Lifetime
- 1995-06-30 CN CN95108153A patent/CN1127756A/zh active Pending
- 1995-06-30 FI FI953244A patent/FI953244A/fi unknown
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Also Published As
Publication number | Publication date |
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JPH0848778A (ja) | 1996-02-20 |
JP2820640B2 (ja) | 1998-11-05 |
EP0690067B1 (de) | 2000-05-24 |
KR0150097B1 (ko) | 1998-10-15 |
FI953244A (fi) | 1996-01-02 |
EP0690067A1 (de) | 1996-01-03 |
ATE193293T1 (de) | 2000-06-15 |
US5496961A (en) | 1996-03-05 |
FI953244A0 (fi) | 1995-06-30 |
DE4423195A1 (de) | 1996-01-04 |
KR960004358A (ko) | 1996-02-23 |
CA2149393A1 (en) | 1996-01-02 |
DE59508374D1 (de) | 2000-06-29 |
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