CN1041958A - 聚硅氮烷组合物催化聚合控制方法 - Google Patents
聚硅氮烷组合物催化聚合控制方法 Download PDFInfo
- Publication number
- CN1041958A CN1041958A CN89107838A CN89107838A CN1041958A CN 1041958 A CN1041958 A CN 1041958A CN 89107838 A CN89107838 A CN 89107838A CN 89107838 A CN89107838 A CN 89107838A CN 1041958 A CN1041958 A CN 1041958A
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- CN
- China
- Prior art keywords
- polysilazane
- polymerization
- ion exchange
- sicl
- acid
- Prior art date
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- 229920001709 polysilazane Polymers 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title claims description 6
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000005342 ion exchange Methods 0.000 claims abstract description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229920005990 polystyrene resin Polymers 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 2
- 238000004220 aggregation Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000002685 polymerization catalyst Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 27
- 229910021529 ammonia Inorganic materials 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000012429 reaction media Substances 0.000 description 6
- -1 Organosilyl compound Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 150000001367 organochlorosilanes Chemical class 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 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
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 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 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 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 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 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 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- HELRVTDMRCSFHH-UHFFFAOYSA-N CN([Si](C)(C)C)[SiH3].C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound CN([Si](C)(C)C)[SiH3].C1(=CC=CC=C1)C1=CC=CC=C1 HELRVTDMRCSFHH-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- RAGKMIALHLWVAZ-UHFFFAOYSA-N N-[bis(ethenyl)-phenylsilyl]-N-dimethylsilylaniline Chemical compound C=1C=CC=CC=1[Si](C=C)(C=C)N([SiH](C)C)C1=CC=CC=C1 RAGKMIALHLWVAZ-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 1
- UDWMDYGDGBKDJC-UHFFFAOYSA-N [dimethyl-(triphenylsilylamino)silyl]benzene Chemical compound C1(=CC=CC=C1)[Si](N[Si](C)(C)C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 UDWMDYGDGBKDJC-UHFFFAOYSA-N 0.000 description 1
- BUEPLEYBAVCXJE-UHFFFAOYSA-N [ethenyl-methyl-(trimethylsilylamino)silyl]ethene Chemical compound C(=C)[Si](N[Si](C)(C)C)(C=C)C BUEPLEYBAVCXJE-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- TVRFAOJPBXYIRM-UHFFFAOYSA-N bis(chloromethyl)-dimethylsilane Chemical compound ClC[Si](C)(C)CCl TVRFAOJPBXYIRM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- OOCUOKHIVGWCTJ-UHFFFAOYSA-N chloromethyl(trimethyl)silane Chemical compound C[Si](C)(C)CCl OOCUOKHIVGWCTJ-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920005565 cyclic polymer Polymers 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical class Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
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Abstract
本发明涉及含有效催化量聚合催化剂的聚硅氮烷组合物聚合控制方法，其特征是聚合过之中或之后将组合物与至少一种离子交换物质，特别是离子交换树脂接触。
Description
本发明涉及聚硅氮烷制法，该聚硅氮烷选自有机聚硅氮烷和/或有机聚（二甲硅烷基）硅氮烷，其物理化学性质能加以控制，这种聚硅氮烷可用于制取氮化硅和/或碳化硅陶瓷产品和制品，例如制成纤维状。
有机聚硅氮烷和有机聚（二甲硅烷基）硅氮烷，以下统称聚硅氮烷，为已知产品，形态呈单体，低聚物和高聚物，可为环状或直链，还可呈聚合树脂。这些聚硅氮烷可按各种方法用各种初始产品制得。
这些聚硅氮烷可成形并可以Si3N4，SiC或其混合物形态得以热解。还可抽丝成连续纤维，再热解呈陶瓷纤维。
还可制成薄片，模制品，并可用作陶瓷纤维或碳纤维的粘结剂和作多孔陶瓷品的烧结粘结剂。聚硅氮烷的这种可成形性是其主要优点。
为制成优良的陶瓷母体，聚硅氮烷热解后应高收率地得到陶瓷材料。为此必须使聚硅氮烷在热解过程中具有良好的热稳定性，这可由高分子量和/或室温下的高粘性，直至固态而达到。
但是，一种或多种有机氯硅烷氨解的普通法得到的单体或低聚物并不是良好的母体，因为其沸点低。因此，热解夹带有蒸馏，除非在高压下进行，并且陶瓷收率特别低。所以说迫切需要建立起达到足以克服该问题的分子量的大分子链。
为此，已提出用催化剂将硅氮烷聚合而得其热解后陶瓷收率大大提高的产品。
该聚合还可得到室温下为固态，高温下可熔并且具有潜在可抽丝性的聚硅氮烷。
不过，该聚合反应尽管可提高聚硅氮烷的分子量，但也还有许多固有的缺点，主要是到目前为止，当聚合过程中形成的聚硅氮烷达到了适于后续转化的物理-化学性能时还不可能控制和停止聚合反应。
因此，为控制聚硅氮烷的聚合程度，可控制其熔融温度并因而控制其成形温度，该温度应处于该聚合物开始降解温度以下。
另一方面，不可忽略的残余量催化剂仍存于成形后得到的聚硅氮烷中，因此，即使在所说聚合步骤之后，聚硅氮烷还可在室温下和/或在后续处理和/或成形时连续变化。这主要是由于聚合物熔点不可控制地升高而造成的，而这有碍于达到工业生产水平（聚合物存料的管理，用于进行其转化的材料的调节）。
因此本发明目的之一是提出聚硅氮烷催化聚合反应的减少方法，用以控制聚硅氮烷的物理化学性能（如粘度，熔点等），目的是促进和控制其后续转化。
这一目的可用含催化有效量聚合催化剂的聚硅氮烷组合物聚合控制方法达到，该法特征是聚合过程之中或之后将组合物与至少一种离子交换物质接触。
一般来说，采用该法即经济并可重复地随意控制聚硅氮烷的聚合，目的是得到物理化学性能特别适宜于其任何特殊应用，特别是制成成形陶瓷产品，如纤维的聚合物。
但本发明其它优点，特征和各方面还需参见以下详述和非限制性具体实例。
适宜于按本发明方法聚合的有机聚硅氮烷，为已知并易于制得的产品;可采用下述化合物的任意反应产品：（a）至少一种下式（Ⅰ）的有机卤代硅烷：
RaX4-aSi （Ⅰ）
其中X为卤素，一般为氯，而R相同或不同，选自氢，直链或支链且必要时可卤代烷基，环烷基，芳基如苯基和萘基，芳烷基或烷芳基，烯基如乙烯基或烯丙基，炔基如乙炔基或丙炔基，a为0，1，2或3，和（b）带至少一个NH2或NH的有机或有机甲硅烷基化合物如氨，伯或仲胺，甲硅烷基胺，酰胺，肼，酰肼等。
式（Ⅰ）中，烷基R可举出甲基，乙基，丙基，丁基，戊基，己基，庚基和辛基;环烷基R可举出环戊基，环己基和环庚基;芳烷基R可举出苯甲基和苯乙基;烷芳基R可举出甲苯基和二甲苯基。
作为例子，可单独或混合使用的有机卤代硅烷可举出：
CH3HSiCl2，H2SiCl2，（CH3）2HSiCl，HSiCl3
（CH3）2SiCl2，（CH3）3SiCl，CH3SiCl3，SiCl4
（CH3）2Si（CH2Cl）2，（CH3）3SiCH2Cl，CH3Si（CH2Cl）3
（C6H5）2SiCl2，（C6H5）（CH3）SiCl2，C6H5SiCl3
（CH3）（CH3CH2）SiCl2，（CH3）（CH2＝CH）SiCl2
（CH3）2（CH2＝CH）SiCl，（C6H5）2（CH2＝CH）SiCl
（C6H5）（CH2＝CH）SiCl2，CH3（C6H5）（CH2＝CH）SiCl.
用于合成上述有机聚硅氮烷的带至少一个NH2或NH的化合物可举出：氨，甲基胺，二甲基胺，乙基胺，环丙基胺，肼，甲基肼，乙二胺，四亚甲基二胺，六亚甲基二胺，苯胺，甲基苯胺，二苯基胺，甲苯胺，胍，氨基胍，尿素，六甲基二硅氮烷，二苯基四甲基二硅氮烷，四苯基二甲基二硅氮烷，四甲基二乙烯基二硅氮烷，二甲基二苯基二乙烯基二硅氮烷和四甲基二硅氮烷。
反应后所得聚硅氮烷包括：
1.下式的线性聚合物：
其中R定义同式（Ⅰ）;p和p′为1-1000，一般为3-300的整数。
式（Ⅱ）聚合物可将二有机聚硅烷与氨接触而得，而式（Ⅲ）2可将氨与三有机氯硅烷或二有机二氯硅烷和三有机氯硅烷的混合物反应而得（参见FR-A-1086932，US-A-2564674）。
一般来说，有机卤代硅烷与有机胺反应见于US-A-3853567和3892583，而有机卤代硅烷与二硅氮烷反应见于BE-A-888787。
2.下式的环状聚合物：
其中n为3-10，一般n＝3，4，而R定义同上式（Ⅰ）（参见BG-A-881178）。
3.由选自R3SiNH0.5，R2SiNH，RSiNH1.5，Si（NH）2的单元构成的树脂聚合物。
可将相应有机氯硅烷或其混合物与氨接触而有效地制得，接触优选在有机溶剂中进行（参见FR-A-1379243，FR-A-1392853和FR-A-1393728）。
适于按本发明方法聚合的有机聚（二甲硅烷基）硅氮烷一般为已知并易于制成的产品。特别是可将以下化合物反应而得：（a）带至少一个NH2或NH的有机或有机甲硅烷基化合物如氨，伯或仲胺，甲硅烷基胺，酰胺，肼和酰肼等，（b）至少一种下式有机卤代二硅烷：
其中R相同或不同，定义同上述，b为0，1，2或3，c为0，1或2，X为卤素，一般为氯。
式（Ⅴ）化合物例子可举出：
（CH3）2ClSiSi（CH3）2Cl，（CH3）2ClSiSiCH3Cl2
CH3Cl2SiSiCH3Cl2
用于合成聚（二甲硅烷基）硅氮烷的带至少一个NH2或NH的化合物例子可举出与有机卤代甲硅烷氨基分解时的化合物相同。
一般来说，卤代二硅烷在必要时存在卤代硅烷的情况下与氨反应见于EP-A-75826。卤代二硅烷与二硅氮烷反应已见于FR-A-2497812。
最后，如EP-A-75826所述，可将前述胺衍生物与上述式（Ⅰ）和（Ⅴ）的卤代产品的混合物反应而制成有机聚（二甲硅烷基）硅氮烷-硅氮烷。
用氨制成的初始聚硅氮烷一般称为氨解产物并且用上述胺化合物1制成的初始聚硅氮烷称为氨基分解产物，如上述产物，可进行催化处理，从而按初始氨基分解产物的性质而引发聚合和/或共聚和/或分子重排，目的是改善其热解时的性能。
本说明书中所用聚合一词应理解为定义了一种上述用氨基分解产物催化处理时进行的完全转化的一般方式。
为此，可采用各种催化剂。
重要的一类催化剂包括酸催化剂，但并不排除其它催化剂，但仅仅是用得少而已。
作为例子，还可用酸性稀土，方法见于日本专利申请公开No.77/160446。也可用Lewis酸，如一元羧酸金属盐，特别是铁，锌，锰，铅，钙，锆，锡，钴或铈的环烷酸盐或辛酸盐，全部应用条件已见于例如US 3007886，或者无机酸金属盐，特别是铜，银，金，锌，镉，汞，铁，钴或镍的硫酸盐，硝酸盐或氯化物，应用条件特别见于US 3187030。
本发明还特别适于各种强酸聚合的氨基分解产物，酸选自高氯酸HClO4和三氟甲烷磺酸，应用方式已见于例如法国专利申请No.2577933，为本发明专利申请人的申请。按照所用初始氨基分解产物和催化剂的性质，可直接或以有机溶剂中的溶液聚合。
如上所述，到目前为止提出的问题是各种聚合反应难于减少并加以控制。
而且，在采用三氟甲烷磺酸作为催化剂的更特殊情况下，可出人意料地发现甚至在大量放出这种聚合固有的氨的情况下还在继续进行聚合反应，甚至还可认为，向反应介质中加碱应能够阻止阳离子型聚合（酸性催化剂）。
因此，为控制该聚合反应，按本发明，将该反应介质与离子交换物质接触。
当然这种接触可保证聚合进行的程度达到相当于得到其物理化学性能符合后续要求的硅氮烷聚合物。
接触可按各种已知方法进行。
按照本发明方法第一方案，直接将细粉碎状态（粉）离子交换物质引入反应介质中而进行接触;聚合物产品可用各种适当方法，特别是过滤而从混合物中分出。
按照另一方面，让反应介质横穿过（浸有）离子交换物质的膜或筛;这项技术可避免后续进行分离步骤。
该接触步骤的参数包括离子交换物质量和质量，接触时间和温度，这些参数相互关联。
当然，离子交换物质的性质，即其阴离子和/或阳离子性质，是根据氨基分解产物聚合用催化剂的性质选择的。
因此，更精确地说，若采用前述酸性催化剂，则所用离子交换物质为阴离子型。
可用于本发明方法的特别重要和优选的一类离子交换物质为离子交换树脂。
离子交换树脂基本上为合成产品，为本专业人员已知。为此，可参考例如“Techniques de l′ Ingenieur”的摘录文章，参考号J2860a，题为“Operation Chimiques Unitaires，Echange d′ ions”。
在用酸性催化剂进行聚合的情况下，主要用于本发明方法的阴离子交换树脂为聚苯乙烯树脂和聚丙烯酸树脂。
在这方面，总是优选采用聚苯乙烯树脂。
最适宜于本发明方法的聚苯乙烯类阴离子树脂如下式：
其中X为卤原子，R1，R2和R3相同或不同，选自氢，烃基，必要时可取代。最常用烃基可举出必要时可卤代的直链或支链烷基，环烷基，芳基如苯基和萘基，芳烷基和烷芳基，以及烯基如乙烯基或烯丙基，炔基如乙炔基或丙炔基。
作为例子，烷基R可举出甲基，乙基，丙基，丁基，戊基，己基，庚基和辛基;环烷基R可举出环戊基，环己基和环庚基;芳烷基R可举出苯甲基和苯乙基;烷芳基R可举出甲苯基和二甲苯基。
R1，R2和R3为烷基最适宜。
树脂优选呈粉状应用，直接引入反应介质中。仅用少量树脂就够了;一般为反应介质总量为0.1-10%w，优选为0.1-4%w。
接触时间为几分钟至1-2小时。
在该步骤结束时，分出聚合的聚硅氮烷，必要时呈溶剂的溶液态，以及树脂，这可用各种已知方法进行，特别是用过滤法。
收集到聚硅氮烷，必要时除去溶剂后干燥，最后成为产品。
这类聚硅氮烷在制取至少部分含氮化硅和/或碳化硅的陶瓷产品和制品过程中具有各种特殊用途。
在最一般情况下（得到粉），在惰性或真空气氛中将聚硅氮烷加热到600-1500℃，直至聚硅氮烷完全转化成Si3N4和/或SiC。
由于其物理化学性质可灵活控制，本发明方法所得聚硅氮烷特别适于制成成形陶瓷产品，特别是纤维。聚硅氮烷可用抽丝机抽丝成纤维后热处理（热解）而得Si3N4和/或SiC纤维。这些纤维可作为陶/陶瓷，陶瓷/塑料或陶瓷/金属类复合材料的加强结构。
以下实例详述本发明。
实例1-3
这些实例说明按本发明方法聚合的聚硅氮烷的热稳定性。
A/制取初始共同氨解产物
为31双盖反应器中装有机械搅拌装置，气体入口管以及冷凝器，是其中存在1.1l异丙醚存在下，让不同比例的（CH3）2SiCl2（D式）和CH3SiCl3（T式）混合物共同氨解。D/T在异丙醚中的混合物冷至3℃并保持在该温度下引入NH3气。引入NH3的流量保持为约6ml/s气并且加料进行6小时。在反应过程中形成大量chlorydrate铵盐，这可使溶液增稠。
试验结束时，在烧结玻璃上滤出形成NH4Cl（平均孔径：10μm）。用无水溶剂多次洗涤沉淀物。收集到的溶液透明。真空蒸出溶剂（25毫巴70℃），最后的微量溶剂在70℃2毫巴下除去。所得共同氨解产物室温下为粘性液。
反应开始时引入的氯代硅烷D和T量如下：
53.6g（CH3）2SiCl2（0.36mol）和138.7g CH3SiCl3（1.06mol），T/D为75/25
78.7g（CH3）2SiCl2（0.67mol）和119.1g CH3SiCl3（0.91mol），T/D为60/40
72.1g（CH3）2SiCl2（0.61mol）和134.0g CH3SiCl3（1.3mol），T/D为55/45。
B/共同氨解产物的聚合
A中所得共同氨解产物在异丙醚中稀释至50%w。聚合催化剂为三氟甲烷磺酸。温度为70℃。聚合后，加3.0%树脂“Microionex”，为Rohm et Haas公司的产品（聚苯乙烯类阴离子树脂），室温下进行oh30。反应混合物然后在No.4玻璃料上过滤。溶剂在2mmHg下170℃清除3hoo。所得聚合物熔点Pf如下：
实例 共同氨解产物T/D Pf℃
1 55/45 ＜30
2 60/40 85
3 75/25 145
所得产品4hoo内加热到170℃仍是热稳定的。
比较例4-6
这些比较例按与上述对应试验1-3相同的操作方式进行，但并不将反应混合物与阴离子树脂接触。所得聚合物熔点Pf如下：
比较例 共同氨解产物T/D Pf℃
4 55/45 130
5 60/40 180
6 75/25 ＞240
产品4加热到170℃其熔点4hoo内变化30℃并且产品5加热到170℃其熔点4hoo内变化40℃。
这些结果表明还可得到其软化温度及其成形温度，如抽丝温度（若想得到纤维的话），均在其开始降解温度以下，对于这种产品，其开始降解温度一般为约200℃。一方面，这可在更低温度下成形，因此可节能和节省原料，另一方面，又给成形步骤中增加了灵活性和安全感。
Claims (12)
1、含有效催化量聚合催化剂的聚硅氮烷组合物聚合控制方法，其特征是聚合过程之中或之后将组合物与至少一种离子交换物质接触。
2、权利要求1的方法，其特征是所说物质为离子交换树脂。
3、权利要求1和2中任一项的方法，其特征是直接进行聚合。
4、权利要求1和2中任一项的方法，其特征是聚合在有机溶剂的溶液中进行。
5、上述权利要求中任一项的方法，其特征是采用酸性聚合催化剂。
6、权利要求5的方法，其特征是催化剂选自高氯酸和三氟甲烷磺酸。
7、权利要求5和6中任一项的方法，其特征是采用聚苯乙烯类或聚丙烯酸类阴离子交换树脂。
8、权利要求7的方法，其特征是采用聚苯乙烯类树脂。
9、权利要求8的方法，其特征是所说聚苯乙烯类树脂如下式：
其中X为卤原子，R1，R2和R3相同或不同，选自氢，以及烃基必要时可取代。
10、权利要求9的方法，其特征是R1，R2和R3为烷基。
11、用权利要求1-10中任一项所述方法制成的聚硅氮烷。
12、氮化硅和/或碳化硅纤维，其特征是将权利要求11所述聚硅氮烷抽丝后在惰性或真空气氛中于600-1500℃下热解而得。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR88/13530 | 1988-10-14 | ||
| FR8813530A FR2637902B1 (fr) | 1988-10-14 | 1988-10-14 | Procede pour controler la polymerisation catalytique de compositions polysilazanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1041958A true CN1041958A (zh) | 1990-05-09 |
Family
ID=9371021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89107838A Pending CN1041958A (zh) | 1988-10-14 | 1989-10-12 | 聚硅氮烷组合物催化聚合控制方法 |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US5037933A (zh) |
| EP (1) | EP0364339A1 (zh) |
| JP (1) | JPH02169627A (zh) |
| KR (1) | KR900006409A (zh) |
| CN (1) | CN1041958A (zh) |
| AU (1) | AU4286289A (zh) |
| BR (1) | BR8905187A (zh) |
| DK (1) | DK508789A (zh) |
| FI (1) | FI894874A7 (zh) |
| FR (1) | FR2637902B1 (zh) |
| IL (1) | IL91975A0 (zh) |
| NO (1) | NO894074L (zh) |
| PT (1) | PT91993A (zh) |
| ZA (1) | ZA897771B (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4114217A1 (de) * | 1991-05-01 | 1992-11-05 | Bayer Ag | Organische silazanpolymere, verfahren zu ihrer herstellung, sowie ein verfahren zur herstellung von keramikmaterialien daraus |
| DE4114218A1 (de) * | 1991-05-01 | 1992-11-05 | Bayer Ag | Organische silazanpolymere, verfahren zu ihrer herstellung, sowie ein verfahren zur herstellung von keramikmaterialien daraus |
| EP2890729B1 (de) * | 2012-08-30 | 2020-01-01 | Clariant Finance (BVI) Limited | Verfahren zur herstellung von thermoplastischen präkeramischen polymeren |
| US9593210B1 (en) * | 2015-06-03 | 2017-03-14 | General Electric Company | Methods of preparing polysilazane resin with low halogen content |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3322722A (en) * | 1965-10-18 | 1967-05-30 | Dow Corning | Acidic interchange of siloxane bonds with silicon-bonded alkoxy and acyloxy bonds |
| DE3508219A1 (de) * | 1984-11-13 | 1986-09-11 | Licentia Patent-Verwaltungs-Gmbh, 6000 Frankfurt | Verfahren zur reinigung von siliconoel |
| FR2581386B1 (fr) * | 1985-05-06 | 1987-11-20 | Rhone Poulenc Rech | Procede de traitement de polyorganosilazanes et/ou de polyorgano(disilyl)silazanes par un traitement de polyorganosilazanes par un systeme catalytique comprenant un sel mineral ionique et un compose complexant |
| FR2584079B1 (fr) * | 1985-06-26 | 1987-08-14 | Rhone Poulenc Rech | Procede de traitement par catalyse cationique d'un polysilazane comportant en moyenne au moins deux groupes sih par molecule |
| FR2590580B1 (fr) * | 1985-11-28 | 1988-05-13 | Rhone Poulenc Spec Chim | Procede de traitement catalytique d'un polysilazane comportant en moyenne au moins deux groupes hydrocarbone a insaturation aliphatique par molecule |
-
1988
- 1988-10-14 FR FR8813530A patent/FR2637902B1/fr not_active Expired - Lifetime
-
1989
- 1989-10-04 EP EP89402740A patent/EP0364339A1/fr not_active Withdrawn
- 1989-10-11 JP JP1263165A patent/JPH02169627A/ja active Pending
- 1989-10-12 AU AU42862/89A patent/AU4286289A/en not_active Abandoned
- 1989-10-12 IL IL91975A patent/IL91975A0/xx unknown
- 1989-10-12 BR BR898905187A patent/BR8905187A/pt unknown
- 1989-10-12 CN CN89107838A patent/CN1041958A/zh active Pending
- 1989-10-12 NO NO89894074A patent/NO894074L/no unknown
- 1989-10-13 ZA ZA897771A patent/ZA897771B/xx unknown
- 1989-10-13 DK DK508789A patent/DK508789A/da not_active Application Discontinuation
- 1989-10-13 FI FI894874A patent/FI894874A7/fi not_active IP Right Cessation
- 1989-10-13 PT PT91993A patent/PT91993A/pt not_active Application Discontinuation
- 1989-10-13 KR KR1019890014663A patent/KR900006409A/ko not_active Withdrawn
- 1989-10-16 US US07/421,944 patent/US5037933A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DK508789A (da) | 1990-04-17 |
| FI894874A0 (fi) | 1989-10-13 |
| FR2637902B1 (fr) | 1992-06-12 |
| EP0364339A1 (fr) | 1990-04-18 |
| KR900006409A (ko) | 1990-05-08 |
| DK508789D0 (da) | 1989-10-13 |
| PT91993A (pt) | 1990-04-30 |
| NO894074D0 (no) | 1989-10-12 |
| AU4286289A (en) | 1990-04-26 |
| ZA897771B (en) | 1990-07-25 |
| US5037933A (en) | 1991-08-06 |
| NO894074L (no) | 1990-04-17 |
| IL91975A0 (en) | 1990-07-12 |
| JPH02169627A (ja) | 1990-06-29 |
| FR2637902A1 (fr) | 1990-04-20 |
| BR8905187A (pt) | 1990-05-15 |
| FI894874A7 (fi) | 1990-04-15 |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
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