JPH069779A - Silicone-polyimide copolymer and its manufacturing process - Google Patents
Silicone-polyimide copolymer and its manufacturing processInfo
- Publication number
- JPH069779A JPH069779A JP6138393A JP6138393A JPH069779A JP H069779 A JPH069779 A JP H069779A JP 6138393 A JP6138393 A JP 6138393A JP 6138393 A JP6138393 A JP 6138393A JP H069779 A JPH069779 A JP H069779A
- Authority
- JP
- Japan
- Prior art keywords
- chemical
- formula
- chemical formula
- group
- terminated
- 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.)
- Granted
Links
- 239000004642 Polyimide Substances 0.000 title claims abstract description 68
- 229920001721 polyimide Polymers 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000009833 condensation Methods 0.000 claims abstract description 35
- 230000005494 condensation Effects 0.000 claims abstract description 35
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 8
- 239000000126 substance Substances 0.000 claims description 162
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052990 silicon hydride Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 claims 1
- -1 2-20C alkylene Chemical group 0.000 abstract description 22
- 239000000565 sealant Substances 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 52
- 239000003054 catalyst Substances 0.000 description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 239000000945 filler Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 239000004697 Polyetherimide Substances 0.000 description 7
- 229920001601 polyetherimide Polymers 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
- 229910000071 diazene Inorganic materials 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 3
- CHWKGJOTGCSFNF-UHFFFAOYSA-N norbornene anhydride Chemical compound C1CC2C3C(=O)OC(=O)C3=C1C2 CHWKGJOTGCSFNF-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920005573 silicon-containing polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- SGEWZUYVXQESSB-UHFFFAOYSA-N 3-methylheptane-1,7-diamine Chemical compound NCCC(C)CCCCN SGEWZUYVXQESSB-UHFFFAOYSA-N 0.000 description 2
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 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
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- YYZUSRORWSJGET-UHFFFAOYSA-N ethyl octanoate Chemical compound CCCCCCCC(=O)OCC YYZUSRORWSJGET-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- OVSGBKZKXUMMHS-VGKOASNMSA-L (z)-4-oxopent-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O OVSGBKZKXUMMHS-VGKOASNMSA-L 0.000 description 1
- MPJJRYGVHNTASI-SUKNRPLKSA-L (z)-4-oxopent-2-en-2-olate;propane-1,3-diolate;titanium(4+) Chemical compound [Ti+4].[O-]CCC[O-].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O MPJJRYGVHNTASI-SUKNRPLKSA-L 0.000 description 1
- QMTFKWDCWOTPGJ-KVVVOXFISA-N (z)-octadec-9-enoic acid;tin Chemical compound [Sn].CCCCCCCC\C=C/CCCCCCCC(O)=O QMTFKWDCWOTPGJ-KVVVOXFISA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- BUZMJVBOGDBMGI-UHFFFAOYSA-N 1-phenylpropylbenzene Chemical compound C=1C=CC=CC=1C(CC)C1=CC=CC=C1 BUZMJVBOGDBMGI-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- XGKKWUNSNDTGDS-UHFFFAOYSA-N 2,5-dimethylheptane-1,7-diamine Chemical compound NCC(C)CCC(C)CCN XGKKWUNSNDTGDS-UHFFFAOYSA-N 0.000 description 1
- YXOKJIRTNWHPFS-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diamine Chemical compound NCC(C)CCC(C)CN YXOKJIRTNWHPFS-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- VIAWXLFFSHQNAO-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]butan-1-ol Chemical compound CCC(CO)N(CCO)CCO VIAWXLFFSHQNAO-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- SMSVUYQRWYTTLI-UHFFFAOYSA-L 2-ethylhexanoate;iron(2+) Chemical compound [Fe+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O SMSVUYQRWYTTLI-UHFFFAOYSA-L 0.000 description 1
- FHRAKXJVEOBCBQ-UHFFFAOYSA-L 2-ethylhexanoate;manganese(2+) Chemical compound [Mn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O FHRAKXJVEOBCBQ-UHFFFAOYSA-L 0.000 description 1
- KUQVFOOAIOMQOT-UHFFFAOYSA-N 2-methylpropyltin Chemical compound CC(C)C[Sn] KUQVFOOAIOMQOT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- QPIOXOJERGNNMX-UHFFFAOYSA-N 3-(3-aminopropylsulfanyl)propan-1-amine Chemical compound NCCCSCCCN QPIOXOJERGNNMX-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- POTQBGGWSWSMCX-UHFFFAOYSA-N 3-[2-(3-aminopropoxy)ethoxy]propan-1-amine Chemical compound NCCCOCCOCCCN POTQBGGWSWSMCX-UHFFFAOYSA-N 0.000 description 1
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- PXKPPXIGPAIWDZ-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propanenitrile Chemical compound C[Si](Cl)(Cl)CCC#N PXKPPXIGPAIWDZ-UHFFFAOYSA-N 0.000 description 1
- JYZKYCYHXBQTCY-UHFFFAOYSA-N 3-methoxycarbonylbicyclo[2.2.1]hept-5-ene-2-carboxylic acid Chemical compound C1C2C=CC1C(C(=O)OC)C2C(O)=O JYZKYCYHXBQTCY-UHFFFAOYSA-N 0.000 description 1
- YEEIWUUBRYZFEH-UHFFFAOYSA-N 3-methoxyhexane-1,6-diamine Chemical compound NCCC(OC)CCCN YEEIWUUBRYZFEH-UHFFFAOYSA-N 0.000 description 1
- ZWIBGDOHXGXHEV-UHFFFAOYSA-N 4,4-dimethylheptane-1,7-diamine Chemical compound NCCCC(C)(C)CCCN ZWIBGDOHXGXHEV-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- NJWZAJNQKJUEKC-UHFFFAOYSA-N 4-[4-[2-[4-[(1,3-dioxo-2-benzofuran-4-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C=1C=C(OC=2C=3C(=O)OC(=O)C=3C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC2=C1C(=O)OC2=O NJWZAJNQKJUEKC-UHFFFAOYSA-N 0.000 description 1
- IPDXWXPSCKSIII-UHFFFAOYSA-N 4-propan-2-ylbenzene-1,3-diamine Chemical compound CC(C)C1=CC=C(N)C=C1N IPDXWXPSCKSIII-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- PIVQQUNOTICCSA-UHFFFAOYSA-N ANTU Chemical compound C1=CC=C2C(NC(=S)N)=CC=CC2=C1 PIVQQUNOTICCSA-UHFFFAOYSA-N 0.000 description 1
- MKUWNMKVSHFQJR-UHFFFAOYSA-H COC(=O)[Sn+2]C1=CC=CC=C1.COC(=O)[Sn+2]C1=CC=CC=C1.COC(=O)[Sn+2]C1=CC=CC=C1.[O-]C(=O)CCCCCCC([O-])=O.[O-]C(=O)CCCCCCC([O-])=O.[O-]C(=O)CCCCCCC([O-])=O Chemical compound COC(=O)[Sn+2]C1=CC=CC=C1.COC(=O)[Sn+2]C1=CC=CC=C1.COC(=O)[Sn+2]C1=CC=CC=C1.[O-]C(=O)CCCCCCC([O-])=O.[O-]C(=O)CCCCCCC([O-])=O.[O-]C(=O)CCCCCCC([O-])=O MKUWNMKVSHFQJR-UHFFFAOYSA-H 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- LHFURYICKMKJHJ-UHFFFAOYSA-L [benzoyloxy(dibutyl)stannyl] benzoate Chemical compound CCCC[Sn+2]CCCC.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 LHFURYICKMKJHJ-UHFFFAOYSA-L 0.000 description 1
- HAAANJSJNWKVMX-UHFFFAOYSA-L [butanoyloxy(dimethyl)stannyl] butanoate Chemical compound CCCC(=O)O[Sn](C)(C)OC(=O)CCC HAAANJSJNWKVMX-UHFFFAOYSA-L 0.000 description 1
- HSULLSUSGAHAOJ-UHFFFAOYSA-N acetic acid;hexan-1-amine Chemical compound CC([O-])=O.CCCCCC[NH3+] HSULLSUSGAHAOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- FWYSSOIRLVHQNC-UHFFFAOYSA-M benzyl(trimethyl)azanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)CC1=CC=CC=C1 FWYSSOIRLVHQNC-UHFFFAOYSA-M 0.000 description 1
- IHWUGQBRUYYZNM-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-3,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(=O)O)=CC1C2 IHWUGQBRUYYZNM-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- BNGNANCNFVQZBM-UHFFFAOYSA-N cobalt;ethyl hexanoate Chemical compound [Co].CCCCCC(=O)OCC BNGNANCNFVQZBM-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- VSZOJLRQTJSWCI-UHFFFAOYSA-N cyclohexane-1,4-diamine;octadecane-1,12-diamine Chemical compound NC1CCC(N)CC1.CCCCCCC(N)CCCCCCCCCCCN VSZOJLRQTJSWCI-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- HZPATAHVYQSNOF-UHFFFAOYSA-N dichloro-(3-fluoropropyl)-methylsilane Chemical compound C[Si](Cl)(Cl)CCCF HZPATAHVYQSNOF-UHFFFAOYSA-N 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 description 1
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 1
- CBLAIDIBZHTGLV-UHFFFAOYSA-N dodecane-2,11-diamine Chemical compound CC(N)CCCCCCCCC(C)N CBLAIDIBZHTGLV-UHFFFAOYSA-N 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 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
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LSZKGNJKKQYFLR-UHFFFAOYSA-J tri(butanoyloxy)stannyl butanoate Chemical compound [Sn+4].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O LSZKGNJKKQYFLR-UHFFFAOYSA-J 0.000 description 1
- CPRPKIMXLHBUGA-UHFFFAOYSA-N triethyltin Chemical compound CC[Sn](CC)CC CPRPKIMXLHBUGA-UHFFFAOYSA-N 0.000 description 1
- DVYQCRRVXOXJSA-UHFFFAOYSA-N tris(2-ethylhexoxy)-methylsilane Chemical compound CCCCC(CC)CO[Si](C)(OCC(CC)CCCC)OCC(CC)CCCC DVYQCRRVXOXJSA-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/72—4,7-Endo-alkylene-iso-indoles
- C07D209/76—4,7-Endo-alkylene-iso-indoles with oxygen atoms in positions 1 and 3
-
- 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
- C07F7/0896—Compounds with a Si-H 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- 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
- C08G77/48—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 at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/54—Nitrogen-containing linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、シラノール終端ポリジ
オルガノシロキサン−ポリイミド共重合体およびその製
造方法に関する。さらに詳しくは、本発明は、ノルボル
ネン終端ポリイミドのヒドロシラン化およびそれに続く
生成水素化珪素終端ポリイミドのシラノール終端ポリジ
オルガノシロキサンとの反応に関する。TECHNICAL FIELD The present invention relates to a silanol-terminated polydiorganosiloxane-polyimide copolymer and a method for producing the same. More particularly, the present invention relates to hydrosilation of norbornene terminated polyimides and subsequent reaction of the resulting silicon hydride terminated polyimides with silanol terminated polydiorganosiloxanes.
【０００２】[0002]
【従来の技術】本発明以前には、室温加硫性シラノール
終端ポリジオルガノシロキサン、例えばシラノール終端
ポリジメチルシロキサンは、組成物に用いた感湿性架橋
剤の性質に基づいてワンパッケージ（一液型）またはツ
ーパッケージ（二液型）系のいずれかで入手できた。代
表的な一液系では、Ceyzeriat の米国特許第３，１３
３，８９１号に示されているように、メチルトリアセト
キシシランおよびシラノール終端ポリジメチルシロキサ
ンを用いる。Nitzscheらの米国特許第３，０６５，１９
４号に示されているような二液系では、シラノール終端
ポリジメチルシロキサンを硬化触媒、例えばエチルオル
トシリケートとジブチル錫ジラウレートとの組合せと配
合する必要がある。二液系では、硬化触媒をシラノール
終端ポリジメチルシロキサンと使用前に混合する必要が
ある。Prior to the present invention, room temperature vulcanizable silanol-terminated polydiorganosiloxanes, such as silanol-terminated polydimethylsiloxanes, were one package (one-pack) based on the nature of the moisture-sensitive crosslinker used in the composition. Or it was available in either a two-package system. A typical one-part system is Ceyzeriat US Pat. No. 3,13.
Methyltriacetoxysilane and silanol terminated polydimethylsiloxane are used, as shown in US Pat. No. 3,891. Nitzsche et al., U.S. Pat. No. 3,065,19
In a two part system such as that shown in No. 4, it is necessary to formulate a silanol terminated polydimethylsiloxane with a curing catalyst, such as a combination of ethyl orthosilicate and dibutyltin dilaurate. Two-part systems require the curing catalyst to be mixed with silanol-terminated polydimethylsiloxane before use.
【０００３】[0003]
【発明が解決しようとする課題】上述した一液型および
二液型室温加硫性組成物は一般に、得られる硬化シリコ
ーンに高い引張強さが望まれる場合、補強用充填剤、例
えばシリカ充填剤をシリコーンポリマー１００部当り５
〜３００部の量使用することを必要とする。硬化シリコ
ーン重合体の靱性を改良するために用い得るもう一つの
方法では、重合体鎖中にシルアリーレンシロキシ単位を
導入して、実質的に互に化学的に結合したジオルガノシ
ロキシ単位とシルアリーレンシロキシ単位のみよりなる
共重合体を生成する。これらの方法はシリコーン重合体
の弾性率（ｐｓｉ）を著しく高めるものの、経済的でな
く、最終生成物に望まれる高度の物理的特性を達成でき
ない。The one-part and two-part room temperature vulcanizable compositions described above generally provide reinforcing fillers, such as silica fillers, when high tensile strength is desired in the resulting cured silicone. 5 per 100 parts of silicone polymer
It is necessary to use an amount of ~ 300 parts. Another method that can be used to improve the toughness of cured silicone polymers is the introduction of silarylenesiloxy units into the polymer chain so that the diorganosiloxy units and silarylene are chemically bonded to each other substantially. A copolymer consisting only of siloxy units is produced. While these methods significantly increase the modulus (psi) of silicone polymers, they are not economical and do not achieve the high degree of physical properties desired in the final product.
【０００４】[0004]
【課題を解決するための手段】本発明は、室温もしくは
低温縮合加硫性ポリジオルガノシロキサン−ポリイミド
共重合体が、通常の室温加硫性硬化触媒で硬化したと
き、１００〜１０，０００ｐｓｉの範囲の引張強さを示
すエラストマーを生成することを見出して、なされたも
のである。これらのシラノール終端または水素化珪素終
端ポリジオルガノシロキサン−ポリイミド共重合体は、
化６５のポリイミドブロック１〜９９重量％およびこれ
と化学的に結合した化６６のポリジオルガノシロキサン
ブロック９９〜１重量％よりなる。SUMMARY OF THE INVENTION The present invention provides a room temperature or low temperature condensation vulcanizable polydiorganosiloxane-polyimide copolymer, when cured with a conventional room temperature vulcanizable curing catalyst, in the range of 100 to 10,000 psi. It was made by the discovery that it produces an elastomer exhibiting a tensile strength of. These silanol terminated or silicon hydride terminated polydiorganosiloxane-polyimide copolymers are
1 to 99% by weight of the polyimide block of Chemical formula 65 and 99 to 1% by weight of the polydiorganosiloxane block of Chemical formula 66 chemically bonded thereto.
【０００５】[0005]
【化６５】 [Chemical 65]
【０００６】[0006]
【化６６】 [Chemical formula 66]
【０００７】式中のＲは、（ａ）６〜２０個の炭素原子
を有する芳香族炭化水素基およびそのハロゲン化誘導体
基、（ｂ）２〜２０個の炭素原子を有するアルキレン基
およびシクロアルキレン基およびＣ(2-8) アルキレン終
端ポリジオルガノシロキサン、および（Ｃ）化６７（式
中のＱ′は化６８、化６９、化７０、化７１および化７
２よりなる群から選択される基であり、ｘは１〜５の整
数である）で表される二価の基よりなる群から選択され
る二価のＣ(2-20)有機基であり、Ｑは化７３および化７
４（式中のＤは化７５、化７６、化７７、化７８、化７
９および化８０から選択され、Ｒ8 は化８１、化８２、
化８３、化８４、化８５、化８６、化８７および一般
式：化８８の二価有機基から選択される二価の基であ
り、ｐは０または１に等しく、Ｘは化８９、化９０、化
９１、化９２および化９３から選択される二価の基であ
り、ｙは１〜５の整数である）から選択される四価の基
であり、Ｒ1 〜Ｒ6 は水素およびＣ(1-8) アルキル基か
ら選択され、Ｒ7 は同じまたは異なる一価Ｃ(1-13)炭化
水素基および一価置換Ｃ(1-13)炭化水素基であり、Ｙは
化９４および化９５から選択される二価の基であり、ｎ
は０〜２００に等しい整数で、ｍは１〜２０００に等し
い整数である。R in the formula is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and its halogenated derivative group, (b) an alkylene group having 2 to 20 carbon atoms and a cycloalkylene group. A group and a C (2-8) alkylene-terminated polydiorganosiloxane, and (C) Chemical Formula 67 (wherein Q ′ is Chemical Formula 68, Chemical Formula 69, Chemical Formula 70, Chemical Formula 71, and Chemical Formula 7).
A divalent C (2-20) organic group selected from the group consisting of divalent groups represented by the formula ( 2) and x is an integer of 1 to 5 ) . , Q is chemical formula 73 and chemical formula 7
4 (D in the formula is: 75, 76, 77, 78, 7
9 and formula 80, R 8 is formula 81, formula 82,
Chemical formula 83, chemical formula 84, chemical formula 85, chemical formula 86, chemical formula 87 and a divalent organic group of the general formula: chemical formula 88, p is equal to 0 or 1, and X is chemical formula 89 90, chemical formula 91, chemical formula 92 and chemical formula 93, and y is a tetravalent group selected from y), and R 1 to R 6 are hydrogen and Selected from C (1-8) alkyl groups, R 7 is the same or different monovalent C (1-13) hydrocarbon group and monovalent substituted C (1-13) hydrocarbon group, and Y is Is a divalent group selected from
Is an integer equal to 0-200 and m is an integer equal to 1-2000.
【０００８】[0008]
【化６７】 [Chemical formula 67]
【０００９】[0009]
【化６８】 [Chemical 68]
【００１０】[0010]
【化６９】 [Chemical 69]
【００１１】[0011]
【化７０】 [Chemical 70]
【００１２】[0012]
【化７１】 [Chemical 71]
【００１３】[0013]
【化７２】 [Chemical 72]
【００１４】[0014]
【化７３】 [Chemical formula 73]
【００１５】[0015]
【化７４】 [Chemical 74]
【００１６】[0016]
【化７５】 [Chemical 75]
【００１７】[0017]
【化７６】 [Chemical 76]
【００１８】[0018]
【化７７】 [Chemical 77]
【００１９】[0019]
【化７８】 [Chemical 78]
【００２０】[0020]
【化７９】 [Chemical 79]
【００２１】[0021]
【化８０】 [Chemical 80]
【００２２】[0022]
【化８１】 [Chemical 81]
【００２３】[0023]
【化８２】 [Chemical formula 82]
【００２４】[0024]
【化８３】 [Chemical 83]
【００２５】[0025]
【化８４】 [Chemical 84]
【００２６】[0026]
【化８５】 [Chemical 85]
【００２７】[0027]
【化８６】 [Chemical 86]
【００２８】[0028]
【化８７】 [Chemical 87]
【００２９】[0029]
【化８８】 [Chemical 88]
【００３０】[0030]
【化８９】 [Chemical 89]
【００３１】[0031]
【化９０】 [Chemical 90]
【００３２】[0032]
【化９１】 [Chemical Formula 91]
【００３３】[0033]
【化９２】 [Chemical Formula 92]
【００３４】[0034]
【化９３】 [Chemical formula 93]
【００３５】[0035]
【化９４】 [Chemical 94]
【００３６】[0036]
【化９５】 [Chemical 95]
【００３７】本発明に使用する水素化珪素終端ポリジオ
ルガノシロキサン−ポリイミド共重合体を製造するに
は、まず最初有機ジアミン、ノルボルネン無水物および
有機二無水物間の反応を次の反応式：化９６に従って行
うことにより、ノルボルネン終端ポリイミドを形成す
る。In order to prepare the silicon hydride-terminated polydiorganosiloxane-polyimide copolymer used in the present invention, first the reaction between the organic diamine, norbornene anhydride and organic dianhydride is carried out by the following reaction formula: According to the above procedure, a norbornene-terminated polyimide is formed.
【００３８】[0038]
【化９６】 [Chemical 96]
【００３９】ここでＱ、Ｒ、Ｒ1 〜Ｒ6 、Ｙおよびｎは
前記定義の通りである。化９６の脂肪族不飽和ポリイミ
ドを次に化９７（式中のｒは０または１で、Ｒ9 は水素
およびＲ7 から選択される）の水素化珪素でヒドロシラ
ン化して、化９８の水素化珪素終端ポリイミドを生成す
る。Here, Q, R, R 1 to R 6 , Y and n are as defined above. The aliphatic unsaturated polyimide of Formula 96 is then hydrosilanated with the silicon hydride of Formula 97 (where r is 0 or 1 and R 9 is selected from hydrogen and R 7 ) to give the hydrogenation of Formula 98. Produces a silicon-terminated polyimide.
【００４０】[0040]
【化９７】 [Chemical 97]
【００４１】[0041]
【化９８】 [Chemical 98]
【００４２】ここでＲ、Ｒ1 〜Ｒ7 、Ｙ、Ｑおよびｎは
前記定義の通りである。Here, R, R 1 to R 7 , Y, Q and n are as defined above.
【００４３】本発明のシラノール終端ポリジオルガノシ
ロキサン−ポリイミド共重合体は化９９（式中のＺは化
６５で示される二価の基である）を有し、これを製造す
るには、化９８の水素化珪素終端ポリイミドと化１００
のシラノール終端ポリジオルガノシロキサンとの反応を
有効量の縮合触媒（後述）の存在下で行う。ここでＲ
7 、Ｒ9 、ｒおよびｍは前記定義の通りであり、ｌは約
１〜１０4 の整数である。The silanol-terminated polydiorganosiloxane-polyimide copolymer of the present invention has the chemical formula 99 (wherein Z is a divalent group represented by the chemical formula 65). Of silicon hydride terminated polyimide
With silanol terminated polydiorganosiloxane in the presence of an effective amount of a condensation catalyst (described below). Where R
7 , R 9 , r and m are as defined above, and l is an integer of about 1-10 4 .
【００４４】[0044]
【化９９】 [Chemical 99]
【００４５】[0045]
【化１００】 化６５、化９６および化９７中のＲ1 〜Ｒ6 に含まれる
基は、例えば水素、メチル、エチル、プロピル、ブチル
などである。Ｒ7 に含まれる基は、例えばアリール基お
よびハロゲン化アリール基、具体的にはフェニル、クロ
ロフェニル、トリル、キシリル、ビフェニル、ナフチル
など；アルケニル基、具体的にはビニル、アリル、シク
ロヘキセニルなど；Ｃ(1-8) アルキル基およびハロゲン
化アルキル基、具体的にはメチル、エチル、プロピル、
ブチル、オクチルなどである。[Chemical 100] The groups contained in R 1 to R 6 in Chemical formulas 65, 96 and 97 are, for example, hydrogen, methyl, ethyl, propyl, butyl and the like. The group contained in R 7 is, for example, an aryl group or a halogenated aryl group, specifically phenyl, chlorophenyl, tolyl, xylyl, biphenyl, naphthyl, etc .; an alkenyl group, specifically vinyl, allyl, cyclohexenyl, etc .; C (1-8) alkyl group and halogenated alkyl group, specifically, methyl, ethyl, propyl,
Butyl and octyl.
【００４６】[0046]
【作用】本発明の利用によれば、重量基準で； （Ａ）１００部の化９９のシラノール終端ポリジオルガ
ノシロキサン−ポリイミド共重合体、（Ｂ）０．００２
〜１０部の硬化剤、（Ｃ）０〜５部の縮合触媒、および
（Ｄ）０〜３０００部の式（７）のシラノール終端ポリ
ジオルガノシロキサンを含む縮合加硫性組成物が提供さ
れる。According to the use of the present invention, on a weight basis: (A) 100 parts of a silanol-terminated polydiorganosiloxane-polyimide copolymer of formula 99, (B) 0.002
A condensation vulcanizable composition is provided which comprises -10 parts curing agent, (C) 0-5 parts condensation catalyst, and (D) 0-3000 parts silanol terminated polydiorganosiloxane of formula (7).
【００４７】上記縮合加硫性組成物に使用できる硬化剤
は、例えばメチルトリアセトキシシラン、メチル−トリ
ス−（２−エチルヘキサンオキシ）−シランおよび化１
０１の硬化剤である。Curing agents that can be used in the above condensation vulcanizable composition include, for example, methyltriacetoxysilane, methyl-tris- (2-ethylhexaneoxy) -silane, and
01 hardener.
【００４８】[0048]
【化１０１】 [Chemical 101]
【００４９】化１０１中のＲ7 は前記定義の通り、Ｒ10
はアルキル、アルキルエーテル、アルキルエステル、ア
ルキルケトンおよびアルキルシアノ基よりなる群から選
択されるＣ(1-8) 脂肪族有機基またはＣ(7-13)アルアル
キル基であり、Ｘはアシルオキシ、アミド、アミノ、カ
ルバマト、エノキシ、ハロ、イミダト、イソシアナト、
ケトキシマト、オキシマト、チオイソシアナトおよびウ
レイド基よりなる群から選択される加水分解により遊離
する基であり、ａは０〜４に等しい整数、ｂは０または
１に等しい整数、ａ＋ｂの和は０〜４に等しい。R 7 in Chemical Formula 101 is as defined above, R 10
Is a C (1-8) aliphatic organic group or C (7-13) aralkyl group selected from the group consisting of alkyl, alkyl ether, alkyl ester, alkyl ketone and alkyl cyano groups, and X is acyloxy, amide , Amino, carbamato, enoxy, halo, imidato, isocyanato,
A group which is liberated by hydrolysis selected from the group consisting of ketoximato, oximato, thioisocyanato and ureido groups, a is an integer equal to 0-4, b is an integer equal to 0 or 1, and the sum of a + b is 0-4. equal.
【００５０】化１０１の硬化剤のほかに、本発明の縮合
加硫性組成物には、化１０２（式中のＲ7 、Ｒ10および
ｂは前記定義の通り）のアルコキシ官能性架橋剤も使用
できる。In addition to the curing agent of Formula 101, the condensation vulcanizable composition of the present invention also includes an alkoxy-functional crosslinker of Formula 102 (wherein R 7 , R 10 and b are as defined above). Can be used.
【００５１】[0051]
【化１０２】 [Chemical 102]
【００５２】縮合触媒を用いて縮合加硫性組成物の硬化
を促進することができ、また場合によっては、化９９の
シラノール終端ポリジオルガノシロキサンと化９８の水
素化珪素終端ポリイミドとの縮合を促進することができ
る。例えば、上記シラノール終端ポリジオルガノシロキ
サン−ポリイミド共重合体１００部当り０．００１〜１
部の縮合触媒を使用することができる。縮合触媒として
は、錫化合物、例えばジブチル錫ジラウレート、ジブチ
ル錫ジアセテート、ジブチル錫ジメトキシド、カルボメ
トキシフェニル錫トリスウベレート、錫オクトエート、
イソブチル錫トリセロエート、ジメチル錫ジブチレー
ト、ジメチル錫ジネオデコネート、トリエチル錫タート
レート、ジブチル錫ジベンゾエート、錫オレエート、錫
ナフテネート、ブチル錫トリ−２−エチルヘキソエー
ト、錫ブチレートが挙げられる。好適な縮合触媒は錫化
合物であり、中でもジブチル錫ジアセテートが特に好ま
しい。A condensation catalyst can be used to accelerate the cure of the condensation vulcanizable composition and, in some cases, accelerate the condensation of the silanol-terminated polydiorganosiloxane of Formula 99 with the silicon hydride-terminated polyimide of Formula 98. can do. For example, 0.001 to 1 per 100 parts of the silanol-terminated polydiorganosiloxane-polyimide copolymer.
Some condensation catalysts can be used. As the condensation catalyst, tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimethoxide, carbomethoxyphenyltin trisuberate, tin octoate,
Examples include isobutyltin tricelloate, dimethyltin dibutyrate, dimethyltin dinedeconeate, triethyltin tartrate, dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltin tri-2-ethylhexoate, tin butyrate. Suitable condensation catalysts are tin compounds, of which dibutyltin diacetate is particularly preferred.
【００５３】チタン化合物としては、例えば１，３−プ
ロパンジオキシチタンビス（エチルアセトアセテー
ト）、１，３−プロパンジオキシチタンビス（アセチル
アセトネート）、ジイソプロポキシチタンビス（アセチ
ルアセトネート）、ナフテン酸チタン、テトラブチルチ
タネート、テトラ−２−エチルヘキシルチタネート、テ
トラフェニルチタネート、テトラオクタデシルチタネー
ト、エチルトリエタノールアミンチタネートを使用でき
る。そのほかに、Weyenberg の米国特許第３，３３４，
０６７号に示されているようなβ−ジカルボニルチタン
化合物を本発明における縮合触媒として使用できる。Examples of the titanium compound include 1,3-propanedioxytitanium bis (ethylacetoacetate), 1,3-propanedioxytitanium bis (acetylacetonate), diisopropoxytitanium bis (acetylacetonate), titanium naphthenate. , Tetrabutyl titanate, tetra-2-ethylhexyl titanate, tetraphenyl titanate, tetraoctadecyl titanate, ethyl triethanolamine titanate can be used. In addition, Weyenberg, US Pat. No. 3,334,34
A β-dicarbonyltitanium compound as shown in No. 067 can be used as the condensation catalyst in the present invention.
【００５４】ジルコニウム化合物、例えばオクタン酸ジ
ルコニウムも使用できる。Zirconium compounds such as zirconium octoate can also be used.
【００５５】金属縮合触媒のさらに他の例としては、２
−エチルオクタン酸鉛、２−エチルヘキサン酸鉄、２−
エチルヘキサン酸コバルト、２−エチルヘキサン酸マン
ガン、２−エチルヘキサン酸亜鉛、オクタン酸アンチモ
ン、ナフテン酸ビスマス、ナフテン酸亜鉛、ステアリン
酸亜鉛が挙げられる。Still another example of the metal condensation catalyst is 2
-Lead ethyl octanoate, iron 2-ethylhexanoate, 2-
Examples thereof include cobalt ethylhexanoate, manganese 2-ethylhexanoate, zinc 2-ethylhexanoate, antimony octoate, bismuth naphthenate, zinc naphthenate, and zinc stearate.
【００５６】非金属縮合触媒の例には酢酸ヘキシルアン
モニウムおよび酢酸ベンジルトリメチルアンモニウムが
ある。Examples of non-metal condensation catalysts are hexyl ammonium acetate and benzyl trimethyl ammonium acetate.
【００５７】上述した一液型縮合加硫性硬化剤に加え
て、本発明の実施にあたっては、シラノール終端ポリジ
オルガノシロキサン−ポリイミド共重合体に添加してNi
tzcheらの米国特許第３，１２７，３６３号に示されて
いるような二液型縮合加硫性組成物を形成し得る硬化剤
も使用できる。In addition to the above-mentioned one-pack type condensation vulcanizing curing agent, in the practice of the present invention, it is added to a silanol-terminated polydiorganosiloxane-polyimide copolymer to obtain Ni.
Curing agents capable of forming two-part condensation vulcanizable compositions such as those shown in U.S. Pat. No. 3,127,363 to tzche et al. can also be used.
【００５８】本発明においてノルボルネン無水物連鎖終
端用単量体と共に化９６のノルボルネン終端ポリイミド
を生成するのに使用できる有機二無水物の例には、ベン
ゾフェノン二無水物、ピロメリット酸二無水物、２，２
−ビス〔４−（３，４−ジカルボキシフェノキシ）フェ
ニル〕プロパン二無水物、２，２−ビス〔４−（２，３
−ジカルボキシフェノキシ）フェニル〕プロパン二無水
物、４−（２，３−ジカルボキシフェノキシ）−４′−
（３，４−ジカルボキシフェノキシ）ジフェニル−２，
２−プロパン二無水物および化１０３のビスノルボルナ
ンシロキサン二無水物、およびこれらの混合物がある。Examples of organic dianhydrides that can be used in the present invention to form the norbornene-terminated polyimide of formula 96 with the norbornene anhydride chain terminating monomer are benzophenone dianhydride, pyromellitic dianhydride, 2, 2
-Bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (2,3
-Dicarboxyphenoxy) phenyl] propane dianhydride, 4- (2,3-dicarboxyphenoxy) -4'-
(3,4-dicarboxyphenoxy) diphenyl-2,
2-propane dianhydride and the bisnorbornane siloxane dianhydride of Formula 103, and mixtures thereof.
【００５９】[0059]
【化１０３】 [Chemical 103]
【００６０】シラノール終端ポリジオルガノシロキサン
−ポリイミド共重合体のポリイミドブロックを形成する
のに使用できる有機ジアミンは、例えば、ｏ−フェニレ
ンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレン
ジアミン、４，４′−ジアミノジフェニルプロパン、
４，４′−ジアミノジフェニルメタン（通例４，４′−
メチレンジアニリンと称される）、４，４′−ジアミノ
ジフェニルスルフィド（通例４，４′−チオジアニリン
と称される）、４，４′−ジアミノジフェニルエーテル
（通例４，４′−オキシジアニリンと称される）、１，
５−ジアミノナフタレン、３，３′−ジメチルベンジジ
ン、３，３′−ジメトキシベンジジン２，４−ビス（β
−アミノ−ｔ−ブチル）トルエン、１，３−ジアミノ−
４−イソプロピルベンゼン、１，２−ビス（３−アミノ
プロポキシ）エタン、ベンジジン、ｍ−キシリレンジア
ミン、ｐ−キシリレンジアミン、２，４−ジアミノトル
エン、２，６−ジアミノトルエン、ビス（４−アミノシ
クロヘキシル）メタン、３−メチルヘプタメチレンジア
ミン、４，４ジメチルヘプタメチレンジアミン、２，１
１−ドデカンジアミン２，２−ジメチルプロピレンジア
ミン、オクタメチレンジアミン、３−メトキシヘキサメ
チレンジアミン、２，５−ジメチルヘキサメチレンジア
ミン、２，５−ジメチルヘプタメチレンジアミン、３−
メチルヘプタメチレンジアミン、５−メチルノナメチレ
ンジアミン、１，４−シクロヘキサンジアミン１，１２
−オクタデカンジアミン、ビス（３−アミノプロピル）
スルフィド、Ｎ−メチル−ビス（３−アミノプロピル）
アミン、ヘキサメチレンジアミン、ヘプタメチレンジア
ミン、ノナメチレンジアミン、デカメチレンジアミン、
ビス（３−アミノプロピル）テトラメチルジシロキサ
ン、ビス（４−アミノプチル）テトラメチルジシロキサ
ン、およびこれらジアミンの混合物である。Organic diamines that can be used to form the polyimide block of the silanol terminated polydiorganosiloxane-polyimide copolymer include, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diamino. Diphenylpropane,
4,4'-diaminodiphenylmethane (usually 4,4'-
Methylenedianiline), 4,4'-diaminodiphenyl sulfide (usually called 4,4'-thiodianiline), 4,4'-diaminodiphenyl ether (usually called 4,4'-oxydianiline) ), 1,
5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine 2,4-bis (β
-Amino-t-butyl) toluene, 1,3-diamino-
4-isopropylbenzene, 1,2-bis (3-aminopropoxy) ethane, benzidine, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, bis (4- Aminocyclohexyl) methane, 3-methylheptamethylenediamine, 4,4 dimethylheptamethylenediamine, 2,1
1-dodecanediamine 2,2-dimethylpropylenediamine, octamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-
Methylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-cyclohexanediamine 1,12
-Octadecanediamine, bis (3-aminopropyl)
Sulfide, N-methyl-bis (3-aminopropyl)
Amine, hexamethylenediamine, heptamethylenediamine, nonamethylenediamine, decamethylenediamine,
Bis (3-aminopropyl) tetramethyldisiloxane, bis (4-aminoptyl) tetramethyldisiloxane, and mixtures of these diamines.
【００６１】本発明において、脂肪族不飽和ノルボルネ
ン基を有するポリイミド中に水素化珪素官能基を導入す
るのに使用できる化９７の水素化珪素の例には、ジオル
ガノシラン、具体的にはジメチルシラン、ジフェニルシ
ラン、１，１，３，３−テトラメチルジシロキサンなど
がある。An example of a silicon hydride of formula 97 which can be used in the present invention to introduce a silicon hydride functional group into a polyimide having an aliphatic unsaturated norbornene group is a diorganosilane, specifically dimethyl. Examples include silane, diphenylsilane, and 1,1,3,3-tetramethyldisiloxane.
【００６２】化９９のシラノール終端ポリジオルガノシ
ロキサン−ポリイミド共重合体を製造するのに上記水素
化珪素終端ポリイミドと組合せて使用できる化１００の
シラノール終端ポリジオルガノシロキサンは、粘度が約
２５℃で測定して約１０〜４００，０００センチポアズ
の範囲、特に約１０００〜２５０，０００センチポアズ
の範囲にあるのが好ましい。これらのシラノール終端流
体を製造するには、比較的高い分子量のオルガノポリシ
ロキサン、例えばジメチルポリシロキサンを鉱酸または
塩基触媒の存在下水で処理する。ジオルガノハロシラ
ン、例えばジメチルジクロロシラン、ジフェニルジクロ
ロシラン、メチルビニルジクロロシラン、メチルフルオ
ロプロピルジクロロシラン、メチルシアノエチルジクロ
ロシランまたはこれらの混合物の加水分解により、低分
子量重合体を生成することができる。その後の平衡化に
よりそれより高分子量のオルガノポリシロキサンとす
る。オルガノポリシロキサンは加圧下で水蒸気（スチー
ム）で処理するか、または米国特許第２，６０７，７９
２号および英国特許第８３５，７９０号に記載された他
の方法で処理することもできる。The silanol-terminated polydiorganosiloxane of formula 100 which can be used in combination with the above silicon hydride terminated polyimide to prepare the silanol-terminated polydiorganosiloxane-polyimide copolymer of formula 99 has a viscosity measured at about 25 ° C. Preferably in the range of about 10 to 400,000 centipoise, especially about 1000 to 250,000 centipoise. To produce these silanol terminated fluids, relatively high molecular weight organopolysiloxanes such as dimethylpolysiloxane are treated with water in the presence of a mineral acid or base catalyst. Hydrolysis of diorganohalosilanes such as dimethyldichlorosilane, diphenyldichlorosilane, methylvinyldichlorosilane, methylfluoropropyldichlorosilane, methylcyanoethyldichlorosilane or mixtures thereof can produce low molecular weight polymers. Subsequent equilibration yields a higher molecular weight organopolysiloxane. Organopolysiloxanes may be treated with steam under pressure or as described in US Pat. No. 2,607,79.
It can also be processed by other methods described in No. 2 and British Patent No. 835,790.
【００６３】化９９のシラノール終端ポリジオルガノシ
ロキサン−ポリイミド共重合体をつくるのに使用できる
縮合触媒の例には、白金触媒、具体的にはKarstedtの米
国特許第３，７７５，４４２号、Ashby の米国特許第
３，１５９，６０１号および第３，１５９，６６２号お
よびLamoreaux の米国特許第３，２２０，９７２号に示
されているような不飽和シロキサンの白金錯体がある。
白金触媒の有効量は、硬化性ヒドロシラン化混合物の重
量に基づいて約１０-4〜０．１重量％の白金である。Examples of condensation catalysts that can be used to form the silanol-terminated polydiorganosiloxane-polyimide copolymer of Formula 99 include platinum catalysts, specifically Karstedt US Pat. No. 3,775,442, Ashby. There are unsaturated siloxane platinum complexes such as those shown in US Pat. Nos. 3,159,601 and 3,159,662 and Lamoreaux US Pat. No. 3,220,972.
An effective amount of platinum catalyst is about 10 -4 to 0.1 wt% platinum, based on the weight of the curable hydrosilation mixture.
【００６４】前記室温加硫性組成物には種々の充填剤お
よび顔料を導入することができる。例えば、二酸化チタ
ン、珪酸ジルコニウム、シリカエーロゲル、酸化鉄、珪
藻土、ヒュームドシリカ、カーボンブラック、沈降シリ
カ、ガラス繊維、ポリ塩化ビニル、石英粉末、炭酸カル
シウムなどを使用できる。充填剤の使用量は、目的とす
る用途に応じて広い限度内で変え得ることが明らかであ
る。例えば、シーラント用途では、本発明の硬化性組成
物を充填剤なしで使用することができる。他の用途、例
えば本発明の硬化性組成物を結合剤の製造に用いる場
合、重量基準でポリジオルガノシロキサン−ポリイミド
共重合体１００部当り７００部以上のように多量の充填
剤を使用することができる。このような用途では、充填
剤はその主成分を、好ましくは平均粒度が約１〜１０ミ
クロンの範囲にある増量剤、例えば石英粉末、ポリ塩化
ビニルまたはこれらの混合物とすることができる。Various fillers and pigments may be incorporated into the room temperature vulcanizable composition. For example, titanium dioxide, zirconium silicate, silica aerogel, iron oxide, diatomaceous earth, fumed silica, carbon black, precipitated silica, glass fiber, polyvinyl chloride, quartz powder, calcium carbonate and the like can be used. It is clear that the amount of filler used can be varied within wide limits depending on the intended use. For example, in sealant applications, the curable compositions of the present invention can be used without fillers. For other uses, such as when the curable composition of the present invention is used to make a binder, it is possible to use a large amount of filler, such as 700 parts by weight or more per 100 parts by weight of polydiorganosiloxane-polyimide copolymer. it can. In such applications, the filler can be a major component, preferably a bulking agent having an average particle size in the range of about 1 to 10 microns, such as quartz powder, polyvinyl chloride or mixtures thereof.
【００６５】前記縮合加硫性組成物は建築用シーラント
およびコーキングコンパウンドとして用いることもでき
る。従って、充填剤の正確な量は、オルガノポリシロキ
サン組成物を用いようとする用途、使用充填剤のタイプ
（即ち充填剤の密度および粒度）などの因子に依存す
る。シラノール終端オルガノポリシロキサン１００部当
り５〜３００部の割合の充填剤（約３５部以下の補強用
充填剤、例えばヒュームドシリカ充填剤を含み得る）を
用いるのが好ましい。The condensation vulcanizable composition can also be used as a building sealant and caulking compound. Therefore, the exact amount of filler will depend on such factors as the application for which the organopolysiloxane composition is intended to be used, the type of filler used (ie, filler density and particle size). It is preferred to use from 5 to 300 parts of filler per 100 parts of silanol-terminated organopolysiloxane (which may include up to about 35 parts of reinforcing filler, such as fumed silica filler).
【００６６】化９８の水素化珪素終端ポリイミドを、室
温加硫性オルガノポリシロキサン組成物に接着促進剤と
して用いることができる。化９９のシラノール終端ポリ
ジオルガノシロキサン−ポリイミド共重合体を、前述し
た通りの室温加硫性オルガノポリシロキサン組成物に耐
衝撃性改良剤として用いることができる。The silicon hydride terminated polyimide of Formula 98 can be used as an adhesion promoter in room temperature vulcanizable organopolysiloxane compositions. The silanol-terminated polydiorganosiloxane-polyimide copolymer of Chemical Formula 99 can be used as an impact modifier in the room temperature vulcanizable organopolysiloxane composition as described above.
【００６７】前記縮合加硫性ポリジオルガノシロキサン
−ポリイミド共重合体組成物は、硬化剤、縮合触媒およ
び所望に応じて架橋剤を化９９のシラノール終端ポリジ
オルガノシロキサン−ポリイミド共重合体（以下、「シ
ラノール−ポリイミド共重合体」と称する）と混合する
ことによって製造できる。The condensation vulcanizable polydiorganosiloxane-polyimide copolymer composition comprises a silanol-terminated polydiorganosiloxane-polyimide copolymer (hereinafter referred to as "99") containing a curing agent, a condensation catalyst and, if desired, a crosslinking agent. It can be produced by mixing with a silanol-polyimide copolymer ").
【００６８】前記縮合加硫性組成物には、前述した通り
の硬化剤を有効量使用することができ、この有効量は、
一液系が望ましいか二液系が望ましいか、あるいは使用
硬化剤が酸性副生物を発生するか実質的に中性の副生物
を発生するかによって変わる。例えば、アシルオキシ硬
化剤、例えばメチルトリアセトキシシランを用いる場合
には、シラノール−ポリイミド共重合体１００部当り
０．００２〜１０部のメチルトリアセトキシシランを用
いれば、良好な結果が得られる。化１０１で示されるよ
うな硬化剤をシラノール−ポリイミド共重合体１００部
当り０．００２〜１０部の硬化剤の割合で使用すること
ができる。化１０２で示されるような架橋剤も化１０１
の硬化剤と組合せて、シラノール−ポリイミド共重合体
１００部当り０〜１０部の架橋剤の割合で使用すること
ができる。縮合触媒も前述した通りの割合で使用するこ
とができる。An effective amount of the curing agent as described above can be used in the condensation vulcanizable composition.
It depends on whether a one-part system is desired or a two-part system is desired, or whether the curing agent used produces acidic or substantially neutral by-products. For example, when an acyloxy curing agent such as methyltriacetoxysilane is used, good results are obtained by using 0.002 to 10 parts of methyltriacetoxysilane per 100 parts of silanol-polyimide copolymer. The curing agent represented by Chemical formula 101 can be used in the proportion of 0.002 to 10 parts of the curing agent per 100 parts of the silanol-polyimide copolymer. The cross-linking agent as shown in Chemical formula 102 is also
Can be used in a proportion of 0 to 10 parts of crosslinking agent per 100 parts of silanol-polyimide copolymer. The condensation catalyst can also be used in the ratio as described above.
【００６９】前述したように、上記縮合加硫性組成物は
種々の充填剤、顔料および増量剤と組合せることもで
き、これらの充填剤、顔料および増量剤を所望に応じて
硬化剤、縮合触媒などの導入前に、または導入と同時
に、または導入後にシリコーン−ポリイミド共重合体中
に導入することができる。As mentioned above, the condensation vulcanizable composition can also be combined with various fillers, pigments and extenders, and these fillers, pigments and extenders can optionally be mixed with curing agents, condensation agents and condensation agents. It can be introduced into the silicone-polyimide copolymer before, simultaneously with, or after the introduction of the catalyst and the like.
【００７０】化９６のノルボルネン終端ポリイミドの合
成は、慣例の方法により、ほぼ等モル量の有機ジアミン
および有機二無水物を、ポリイミドを所望の分子量に生
成するのに十分な有効量の連鎖停止用ノルボルネン無水
物と共に使用することによって行うことができる。ノル
ボルネン終端ポリイミドの重合中、有機溶剤、例えばｏ
−ジクロロベンゼンを使用でき、また１４０〜２００℃
の範囲の温度を使用できる。反応を不活性雰囲気中で、
例えば窒素中で行って、望ましくない副反応を最小限に
抑えることができる。反応時間は、反応物質の性質、望
ましいポリイミドの分子量などに応じて、３０分以下か
ら３時間まで変えることができる。The synthesis of the norbornene-terminated polyimide of Formula 96 is carried out by conventional methods to produce approximately equimolar amounts of organic diamine and organic dianhydride in an effective amount to terminate the chain to a desired molecular weight of the polyimide. It can be done by using with norbornene anhydride. During the polymerization of norbornene-terminated polyimide, organic solvents such as o
-Dichlorobenzene can be used and 140-200 ° C
Temperatures in the range of can be used. The reaction in an inert atmosphere,
For example, it can be carried out under nitrogen to minimize unwanted side reactions. The reaction time can vary from less than 30 minutes to 3 hours depending on the nature of the reactants, the desired molecular weight of the polyimide, and the like.
【００７１】化９８の水素化珪素終端ポリイミドは、化
９６のノルボルネン終端ポリイミドと化９７の適当な水
素化珪素、例えば二水素シラン、二水素ジシロキサンと
の反応を、有効量の白金触媒の存在下で行うことによっ
て合成できる。有効量の白金触媒はノルボルネン終端ポ
リイミド、水素化珪素および不活性有機溶剤よりなるヒ
ドロシラン化反応混合物１部当り約１０-6〜１０-3部の
白金であり、不活性有機溶剤は固形分が１０〜５０重量
％の混合物を生成するのに十分な量使用することができ
る。適当な不活性有機溶剤として、例えばクロロベンゼ
ンおよびｏ−ジクロロベンゼンを使用することができ
る。ヒドロシラン化反応を実質的に無水の条件下で、１
５〜９０℃の範囲の温度で行うのが好ましい。The silicon hydride-terminated polyimide of formula 98 is prepared by reacting the norbornene-terminated polyimide of formula 96 with a suitable silicon hydride of formula 97 such as dihydrogensilane or dihydrogendisiloxane in the presence of an effective amount of platinum catalyst. It can be synthesized by carrying out below. An effective amount of platinum catalyst is about 10 -6 to 10 -3 parts of platinum per part of hydrosilation reaction mixture consisting of norbornene terminated polyimide, silicon hydride and an inert organic solvent, the inert organic solvent having a solid content of 10 parts. Sufficient to produce -50% by weight of the mixture can be used. Suitable inert organic solvents are, for example, chlorobenzene and o-dichlorobenzene. The hydrosilation reaction is conducted under substantially anhydrous conditions, 1
It is preferably carried out at a temperature in the range of 5 to 90 ° C.
【００７２】シラノール−ポリイミド共重合体の製造
は、化９８の水素化珪素終端ポリイミドと化１００のシ
ラノール終端ポリジオルガノシロキサンとの反応を、１
５〜１５０℃の範囲内の温度で、有効量の共重合触媒の
存在下で行うことによって達成できる。適当な共重合触
媒として、例えばアミン、アルカリ金属フッ化物、コロ
イドニッケル、塩化亜鉛、白金またはロジウム錯体、ジ
ブチル錫ジアセテートなどを、反応物質の相互溶解性に
応じて、反応を促進する中性溶剤、例えばジクロロメタ
ン、クロロベンゼン、ｏ−ジクロロベンゼンなどと共
に、またはかゝる溶剤なしで使用することができる。The silanol-polyimide copolymer is prepared by reacting the silicon hydride-terminated polyimide of Chemical Formula 98 with the silanol-terminated polydiorganosiloxane of Chemical Formula 1
It can be achieved by carrying out at a temperature in the range of 5-150 ° C. in the presence of an effective amount of copolymerization catalyst. Suitable copolymerization catalysts include, for example, amines, alkali metal fluorides, colloidal nickel, zinc chloride, platinum or rhodium complexes, dibutyltin diacetate, etc., depending on the mutual solubility of the reactants, neutral solvents that accelerate the reaction. , With dichloromethane, chlorobenzene, o-dichlorobenzene, etc., or without such a solvent.
【００７３】縮合加硫性シリコーン−ポリイミド組成物
は、前述した通りの化１００のシラノール終端ポリジオ
ルガノシロキサンと配合することもできる。配合は実質
的に無水の条件下で約１５〜２００℃またはそれ以上の
範囲の温度で行うことができる。こうして得られる硬化
されたシリコーン−ポリイミド共重合体は、高い強度、
高性能の耐熱性エラストマーを必要とする各種用途に使
用することができる。The condensation vulcanizable silicone-polyimide composition can also be blended with a silanol terminated polydiorganosiloxane of formula 100 as described above. The compounding can be carried out under substantially anhydrous conditions at temperatures in the range of about 15 to 200 ° C or higher. The cured silicone-polyimide copolymer thus obtained has high strength,
It can be used in various applications requiring a high-performance heat-resistant elastomer.
【００７４】[0074]
【実施例】当業者が本発明を容易に実施できるようにす
るために、以下に本発明の実施例を限定としてではな
く、例示として示す。「部」はすべて重量基準である。EXAMPLES In order that those skilled in the art may readily practice the present invention, the following examples of the present invention are given by way of illustration and not limitation. All "parts" are by weight.
【００７５】[0075]
【実施例１】１３．６８ｇの５−ノルボルネン−２，３
−ジカルボン酸無水物および４３．３３ｇの２，２−ビ
ス〔４−（３，４−ジカルボキシフェノキシ）フェニ
ル〕プロパン二無水物の混合物を、１３．５１ｇのｍ−
フェニレンジアミンおよび１００ｍｌのｏ−ジクロロベ
ンゼンの溶液に窒素中で１０分間にわたって添加した。
得られた溶液を２時間加熱還流し、この間水を連続的に
共沸除去した。得られた溶液を４００ｍｌのメタノール
に注ぎ、激しくかきまぜた。生成物を沈澱させ、濾過
し、メタノールで洗い、乾燥した。製造方法に基づい
て、生成物は化１０４を有した。Example 1 13.68 g of 5-norbornene-2,3
-A mixture of dicarboxylic anhydride and 43.33 g of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 13.51 g of m-
A solution of phenylenediamine and 100 ml of o-dichlorobenzene was added over 10 minutes under nitrogen.
The resulting solution was heated under reflux for 2 hours, during which water was continuously azeotropically removed. The resulting solution was poured into 400 ml of methanol and stirred vigorously. The product was precipitated, filtered, washed with methanol and dried. Based on the method of manufacture, the product had Formula 104.
【００７６】[0076]
【化１０４】 [Chemical 104]
【００７７】６４．８ｇの上記ノルボルネン終端ポリエ
ーテルイミドが得られ、収率は９７％であった。64.8 g of the above norbornene-terminated polyetherimide was obtained with a yield of 97%.
【００７８】２２．０ｇの上記ノルボルネン終端ポリエ
ーテルイミド、４．０ｇの１，１，３，３−テトラメチ
ルジシロキサンおよび４０ｍｌの乾燥クロロベンンゼン
の混合物に、Karstedtの米国特許第３，７７５，４４２
号に従って調整した５％白金触媒５滴を窒素雰囲気中で
添加した。溶液をかきまぜ７０℃に約１２時間加熱し
た。得られた混合物に室温でカーボンブラックを加え、
溶液を３０分間かきまぜた。次に混合物を濾過し、濾液
を２００ｍｌの乾燥ジエチルエーテルに激しくかきまぜ
ながら注いだ。沈澱が得られ、これを濾過し、ジエチル
エーテルで洗い、乾燥した。製造方法に基づいて、収率
９８％で得られた沈澱は化１０５の水素化珪素終端ポリ
エーテルイミドであった。To a mixture of 22.0 g of the above norbornene-terminated polyetherimide, 4.0 g of 1,1,3,3-tetramethyldisiloxane and 40 ml of dry chlorobenzene, Karstedt US Pat. 442
5 drops of 5% platinum catalyst prepared according to No. 5 was added in a nitrogen atmosphere. The solution was stirred and heated to 70 ° C. for about 12 hours. Add carbon black to the resulting mixture at room temperature,
The solution was stirred for 30 minutes. The mixture was then filtered and the filtrate was poured into 200 ml dry diethyl ether with vigorous stirring. A precipitate was obtained, which was filtered, washed with diethyl ether and dried. Based on the method of preparation, the precipitate obtained in 98% yield was the silicon hydride terminated polyetherimide of Formula 105.
【００７９】[0079]
【化１０５】 [Chemical 105]
【００８０】生成物の同定をＮＭＲおよびＩＲ分析によ
りさらに確認した。The identity of the product was further confirmed by NMR and IR analysis.
【００８１】５．５８ｇの上記水素化珪素終端ポリエー
テルイミド、３４．０２ｇのシラノール終端ポリジメチ
ルシロキサン（シラノール含量０．３１重量％）および
３０ｍｌの乾燥ジクロロメタンの混合物に、上記Karste
dt触媒の５％溶液１滴を窒素中で加えた。得られた溶液
を８０℃に３時間加熱した。赤外分析により、得られる
混合物に水素化珪素が存在しないことを確かめた。混合
物から溶剤を蒸発させて、粘度１４６，２００センチポ
アズの不透明残留物を得た。製造方法に基づいて、この
不透明残留物は化１０６のシラノール終端ポリジメチル
シロキサン−ポリエーテルイミドブロック共重合体であ
った。To a mixture of 5.58 g of the above silicon hydride terminated polyetherimide, 34.02 g of silanol terminated polydimethylsiloxane (silanol content 0.31% by weight) and 30 ml of dry dichloromethane was added the above Karste.
One drop of a 5% solution of dt catalyst was added under nitrogen. The resulting solution was heated to 80 ° C. for 3 hours. Infrared analysis confirmed the absence of silicon hydride in the resulting mixture. The solvent was evaporated from the mixture to give an opaque residue with a viscosity of 146,200 centipoise. Based on the method of preparation, the opaque residue was a silanol terminated polydimethylsiloxane-polyetherimide block copolymer of Formula 106.
【００８２】[0082]
【化１０６】 [Chemical formula 106]
【００８３】但し、ｘは３以上の整数である。However, x is an integer of 3 or more.
【００８４】実質的に無水の条件下で上記シラノール終
端シリコーン−ポリエーテルイミド共重合体に１．０グ
ラムモルのメチルトリメトキシシランを混合し、次いで
０．１ｇのジブチル錫ジアセテートおよび０．３ｇのジ
ブチルアミンを添加した。得られた混合物を湿度５８％
の環境下で１週間放置した。かくして不粘着性の硬化さ
れたブロック共重合体が得られ、これは引張強さ１４６
ｐｓｉおよび伸び６３０％を示した。The silanol-terminated silicone-polyetherimide copolymer was mixed under substantially anhydrous conditions with 1.0 gram mol of methyltrimethoxysilane, followed by 0.1 g dibutyltin diacetate and 0.3 g. Dibutylamine was added. The resulting mixture has a humidity of 58%
It was left for 1 week under the environment. A tack free cured block copolymer is thus obtained, which has a tensile strength of 146
It exhibited psi and an elongation of 630%.
【００８５】上記手順を、上記シラノール終端ポリジメ
チルシロキサン−ポリエーテルイミドブロック共重合体
の代りに粘度１４６，０００センチポアズ（２５℃）の
シラノール終端ポリジメチルシロキサンを用いて、繰返
した。引張強さ４９ｐｓｉおよび伸び３００％を示す硬
化生成物を得た。The above procedure was repeated using a silanol-terminated polydimethylsiloxane having a viscosity of 146,000 centipoise (25 ° C.) instead of the silanol-terminated polydimethylsiloxane-polyetherimide block copolymer. A cured product having a tensile strength of 49 psi and an elongation of 300% was obtained.
【００８６】[0086]
【実施例２】９．９１ｇ（０．０５モル）のメチレンジ
アニリン、１９．６２ｇ（０．０１モル）の５−ノルボ
ルネン−２，３−ジカルボン酸モノメチルエステルおよ
び１００ｍｌの乾燥メタノールの混合物をＮ2 中で２時
間還流した。溶剤を除去した後、残留物をオーブン内で
Ｎ2 中で１５０℃に２時間加熱した。得られた白色固形
物をＣＨ2 Ｃｌ2 に溶解し、４００ｍｌのメタノールに
注ぎ、激しくかきまぜた。製造方法に基づいて、ビス
（ノルボルネンイミド）が得られ、これを濾過し、メタ
ノールで洗い、乾燥した。化１０７のビスイミドが収率
９８％で得られた。EXAMPLE 2 A mixture of 9.91 g (0.05 mol) of methylene dianiline, 19.62 g (0.01 mol) of 5-norbornene-2,3-dicarboxylic acid monomethyl ester and 100 ml of dry methanol was added to N2. It was refluxed for 2 hours in 2. After removing the solvent, the residue was heated in an oven at 150 ° C. for 2 hours under N 2 . The white solid obtained was dissolved in CH 2 Cl 2 , poured into 400 ml of methanol and stirred vigorously. Based on the method of preparation, bis (norbornene imide) was obtained, which was filtered, washed with methanol and dried. The bisimide of Chemical formula 107 was obtained with a yield of 98%.
【００８７】[0087]
【化１０７】 [Chemical formula 107]
【００８８】窒素中で、１００ｍｌの乾燥クロロベンゼ
ンおよび５．２６ｇ（１×１０-2モル）の上記ビス（ノ
ルボルネンイミド）の溶液に、４ｇ（３×１０-2モル）
の１，１，３，３−テトラメチルジシロキサンおよびKa
rstedtの米国特許第３，７１５，３３４号に示されたＰ
ｔ触媒の５％溶液５滴を加えた。得られた溶液を６０〜
８０℃に１夜加熱した。過剰な１，１，３，３−テトラ
メチルジシロキサンを除去した後、溶液にカーボンブラ
ックを加えた。混合物を１時間かきまぜ、次いで濾過し
た。製造方法に基づいて、化１０８の水素化珪素終端ビ
スイミドが得られた。To a solution of 100 ml of dry chlorobenzene and 5.26 g (1 × 10 -2 mol) of the above bis (norbornene imide) under nitrogen, 4 g (3 × 10 -2 mol).
1,1,3,3-tetramethyldisiloxane and Ka
P shown in U.S. Pat. No. 3,715,334 to rstedt
5 drops of a 5% solution of t catalyst were added. 60 ~
Heated to 80 ° C. overnight. After removing excess 1,1,3,3-tetramethyldisiloxane, carbon black was added to the solution. The mixture was stirred for 1 hour and then filtered. Based on the production method, a silicon hydride terminated bisimide of Chemical formula 108 was obtained.
【００８９】[0089]
【化１０８】 [Chemical 108]
【００９０】上記水素化珪素終端ビスイミドを１５．２
３ｇのシラノール終端ポリジメチルシロキサン（ＯＨ含
量２．６重量％）および３ｍｇのＣｌＲｈ（ＰＰｈ3 ）
（但し、ｐｈはフェニル基）と混合し、次いで８０℃に
２時間加熱した。溶剤を除去すると、透明で非常に粘稠
な残留物が得られた。製造方法に基づいて、この残留物
は化１０９のシラノール終端ビスイミドシロキサンであ
った。The above silicon hydride-terminated bisimide was added to 15.2
3 g silanol-terminated polydimethylsiloxane (OH content 2.6% by weight) and 3 mg ClRh (PPh 3 ).
(However, ph is a phenyl group), Then, it heated at 80 degreeC for 2 hours. Removal of the solvent gave a clear, very viscous residue. Based on the method of preparation, this residue was a silanol-terminated bisimide siloxane of Formula 109.
【００９１】[0091]
【化１０９】 [Chemical 109]
【００９２】但し、ｙは１１以上の整数である。続いて
残留物を０．１ｇのメチルトリアセトキシシランと混合
し、次いでＢｕ2 Ｓｎ（ＯＡｃ）2 を添加した。得られ
た混合物を湿度５８％の環境下で１週間放置した。硬化
した材料は、靱性および伸びが著しく改良された透明な
ゴムであった。However, y is an integer of 11 or more. The residue was subsequently mixed with 0.1 g of methyltriacetoxysilane and then Bu 2 Sn (OAc) 2 was added. The obtained mixture was left for one week in an environment of 58% humidity. The cured material was a clear rubber with significantly improved toughness and elongation.
【００９３】[0093]
【実施例３】ノルボルネン終端ビスイミドを製造するた
めに、１７４ｇのイソホロンジアミンおよび３２８ｇの
ノルボルネンジカルボン酸無水物を１８００ｍｌのＮ−
メチルピロリドンおよび６００ｍｌのトルエンに溶解し
た。反応混合物を１２時間にわたって加熱して水を除去
した。次に混合物を加熱してトルエンおよびＮ−メチル
ピロリドンの一部を除去した。残留物を４０％イソプロ
パノール中に注いだ。かくして得られたベージュ色の固
形物を濾過により収集し、乾燥した。EXAMPLE 3 To prepare a norbornene-terminated bisimide, 174 g isophoronediamine and 328 g norbornene dicarboxylic acid anhydride were added to 1800 ml N-.
Dissolved in methylpyrrolidone and 600 ml toluene. The reaction mixture was heated for 12 hours to remove water. The mixture was then heated to remove toluene and some of the N-methylpyrrolidone. The residue was poured into 40% isopropanol. The beige solid thus obtained was collected by filtration and dried.
【００９４】４６．２ｇの上記イソホロンノルボルネン
終端ジイミド、２０ｐｐｍの白金触媒および２００ｍｌ
のクロロベンゼンの溶液を３２．６ｇのテトラメチルジ
シロキサンで８０〜１００℃で６時間処理して、イソホ
ロンジイミドジヒドロシロキサンを生成した。約７３ｇ
のジイミドヒドロシロキサンを、平均約３個の化学的に
結合したシロキシ単位を有するシラノール終端ポリジメ
チルシロキサン流体と、約１：１および１：２のモル比
で、白金触媒の存在下、５０〜６０℃の温度で縮合し
て、化９９の範囲内のシラノール終端ポリジオルガノシ
ロキサン−ポリイミド共重合体を生成した。46.2 g of the above isophorone norbornene terminated diimide, 20 ppm platinum catalyst and 200 ml
Was treated with 32.6 g of tetramethyldisiloxane at 80-100 ° C. for 6 hours to produce isophorone diimidedihydrosiloxane. About 73g
Of the diimide hydrosiloxane with a silanol-terminated polydimethylsiloxane fluid having an average of about 3 chemically bonded siloxy units in a molar ratio of about 1: 1 and 1: 2 in the presence of a platinum catalyst of 50-60. Condensation at a temperature of ° C produced a silanol terminated polydiorganosiloxane-polyimide copolymer within the range of 99.
【００９５】シラノール終端ジメチルシロキサン２モル
対ジイミドヒドロシロキサン１モルの比を有する混合物
からつくった２０ｇのシラノール終端ポリジメチルシロ
キサン−ポリイミド共重合体、１００ｇのシラノール終
端ポリジメチルシロキサン（粘度１２０〜１８０，００
０センチポアズ）、４ｇのメチルトリメトキシシシラ
ン、０．５ｇのジヘキシルアミンおよび０．３ｇのジブ
チル錫ジアセテートから無水条件下で縮合硬化性の混合
物を製造した。20 g of silanol-terminated polydimethylsiloxane-polyimide copolymer made from a mixture having a ratio of 2 mol silanol-terminated dimethylsiloxane to 1 mol diimidehydrosiloxane, 100 g silanol-terminated polydimethylsiloxane (viscosity 120-180,00).
0 centipoise), a condensation curable mixture was prepared under anhydrous conditions from 4 g of methyltrimethoxysisilane, 0.5 g of dihexylamine and 0.3 g of dibutyltin diacetate.
【００９６】このＲＴＶ組成物は、空気にさらしたとこ
ろ、１０〜１６分以内に硬化した。試験片を製作して硬
さ（ショアＡ）、伸び（％）および引張強さ（ｐｓｉ）
を測定した。次の結果を得た。The RTV composition cured within 10-16 minutes when exposed to air. Hardness (Shore A), Elongation (%) and Tensile Strength (psi)
Was measured. The following results were obtained.
【００９７】硬さ １７ 伸び ３７２ 引張強さ １４３Hardness 17 Elongation 372 Tensile Strength 143
【００９８】本発明のシラノール終端ポリジオルガノシ
ロキサン−ポリイミド共重合体を含まないこと以外は、
上記手順を繰返してＲＴＶ組成物をつくった。次の結果
を得た。Except that the silanol-terminated polydiorganosiloxane-polyimide copolymer of the present invention is not included.
The above procedure was repeated to make an RTV composition. The following results were obtained.
【００９９】硬さ ９ 伸び ３２８ 引張強さ ５３Hardness 9 Elongation 328 Tensile strength 53
【０１００】これらの結果は、シラノール終端ポリジメ
チルシロキサン−ポリイミド共重合体が慣用の室温加硫
性オルガノポリシロキサン組成物に優れた物理的特性を
与えることを示している。These results show that the silanol terminated polydimethylsiloxane-polyimide copolymer provides excellent physical properties to conventional room temperature vulcanizable organopolysiloxane compositions.
【０１０１】[0101]
【実施例４】実施例３の手順を繰返した。但し、本例で
は、水素化珪素終端ジイミドとシラノール終端ポリジメ
チルシロキサンとの１：１モル比の混合物から製造した
シラノール終端ポリジメチルシロキサン−ポリイミド共
重合体を使用した。このシラノール終端ポリジメチルシ
ロキサン−ポリイミドをさらに実施例３の室温加硫性組
成物の成分と配合した。但し、本例では粘度２０〜５
０，０００センチポアズのシラノール終端ポリジメチル
シロキサンを使用した。そのほかに、オクタメチルシク
ロテトラシロキサンおよびジシラザンで処理したヒュー
ムドシリカを上記混合物にそれぞれ全混合物の重量に基
づいて５重量％および１０重量％の割合で添加した。こ
れらの混合物を実施例３に記載した通りに大気条件下で
硬化させ、下記の結果を得た。「５％充填剤」および
「１０％充填剤」は上述した充填剤含有組成物を意味
し、ショアＡ硬さ、伸びおよび引張強さは前記定義の通
りである。Example 4 The procedure of Example 3 was repeated. However, in this example, a silanol terminated polydimethylsiloxane-polyimide copolymer prepared from a mixture of a silicon hydride terminated diimide and a silanol terminated polydimethylsiloxane in a 1: 1 molar ratio was used. This silanol terminated polydimethylsiloxane-polyimide was further compounded with the components of the room temperature vulcanizable composition of Example 3. However, in this example, the viscosity is 20 to 5
A 10,000 centipoise silanol terminated polydimethylsiloxane was used. In addition, fumed silica treated with octamethylcyclotetrasiloxane and disilazane was added to the above mixture in proportions of 5% and 10% by weight, respectively, based on the weight of the total mixture. These mixtures were cured under atmospheric conditions as described in Example 3 with the following results. "5% filler" and "10% filler" mean the filler-containing composition described above, and the Shore A hardness, elongation and tensile strength are as defined above.
【０１０２】 [0102]
【０１０３】シラノール終端ポリジメチルシロキサン−
ポリイミド共重合体を配合処方に用いないことを除いて
は、上記手順を繰返した。次の結果を得た。Silanol-terminated polydimethylsiloxane-
The above procedure was repeated, except that the polyimide copolymer was not used in the formulation. The following results were obtained.
【０１０４】 [0104]
【０１０５】これらの結果は、本発明のシラノール終端
ポリジメチルシロキサン−ポリイミド共重合体を導入し
た結果として、硬化した室温加硫性オルガノポリシロキ
サン組成物に著しく増加した靱性が付与されることを示
している。These results indicate that the cured room temperature vulcanizable organopolysiloxane composition is provided with significantly increased toughness as a result of the introduction of the silanol-terminated polydimethylsiloxane-polyimide copolymer of the present invention. ing.
【０１０６】上記実施例は本発明の範囲内の室温加硫性
および低温加硫性組成物を含む極めて多数の縮合加硫性
シリコーン−ポリイミド共重合体の数例を示しただけで
あるが、本発明は、シラノール終端ポリジオルガノシロ
キサン−ポリイミド共重合体を、化１０１で示されるよ
うな硬化剤および所望に応じて化１０２で示されるよう
な架橋剤と組合わせて、またさらに縮合触媒と組合わせ
て使用することにより得られるもっと広い範囲の縮合加
硫性組成物に関与することを理解すべきである。さらに
本発明は、硬化状態で高い強度のシリコーン−ポリイミ
ド共重合体に転化し得る縮合加硫性組成物を製造するの
に有用な材料である、化９８の水素化珪素終端ポリイミ
ドおよび化９９のシラノール−ポリイミド共重合体にも
関与する。Although the above examples only show a few examples of a very large number of condensation vulcanizable silicone-polyimide copolymers containing room temperature vulcanizable and low temperature vulcanizable compositions within the scope of the present invention, The present invention provides a silanol-terminated polydiorganosiloxane-polyimide copolymer in combination with a curing agent as shown in Formula 101 and optionally a crosslinker as shown in Formula 102, and further in combination with a condensation catalyst. It should be understood that it is responsible for the broader range of condensation vulcanizable compositions that can be obtained when used together. The present invention further provides a silicon hydride-terminated polyimide of Chemical Formula 98 and a chemical formula 99 which are useful materials for producing a condensation vulcanizable composition that can be converted to a high strength silicone-polyimide copolymer in the cured state. It is also involved in silanol-polyimide copolymers.
Claims (4)
素基およびそのハロゲン化誘導基、（ｂ）２〜２０個の
炭素原子を有するアルキレン基およびシクロアルキレン
基およびＣ(2-8) アルキレン終端ポリジオルガノシロキ
サン、および（ｃ）次の化３： 【化３】 （化３中のＱ′は化４、化５、化６、化７および化８よ
りなる群から選択され、ｘは１〜５の整数である） 【化４】 【化５】 【化６】 【化７】 【化８】 で表される二価の基よりなる群から選択される二価のＣ
(2-20)有機基で、 Ｑは、化９および化１０ 【化９】 【化１０】 （式中のＤは化１１、化１２、化１３、化１４、化１
５、および化１６から選択され、 【化１１】 【化１２】 【化１３】 【化１４】 【化１５】 【化１６】 Ｒ8 は化１７、化１８、化１９、化２０、化２１、化２
２、化２３および一般式化２４： 【化１７】 【化１８】 【化１９】 【化２０】 【化２１】 【化２２】 【化２３】 【化２４】 の二価有機基から選択される二価の基であり、ｐは０ま
たは１に等しく、Ｘは次の化２５、化２６、化２７、化
２８および化２９： 【化２５】 【化２６】 【化２７】 【化２８】 【化２９】 の二価の基から選択され、ｙは１〜５の整数である）か
ら選択される四価の基であり、 Ｒ1 〜Ｒ6 は水素およびＣ(1-8) アルキル基から選択さ
れ、 Ｒ7 は同じまたは異なる一価Ｃ(1-13)炭化水素基および
一価置換Ｃ(1-13)炭化水素基であり、 Ｒ9 は水素およびＲ7 から選択され、 Ｙは化３０および化３１から選択される二価の基であ
り、 【化３０】 【化３１】 ｎは０〜２００に等しい整数で、 ｒは０または１に等しい整数で、 ｍは１〜２０００に等しい整数で、 ｌは約１〜１０4 の値を有する整数である〕で表される
シラノール終端ポリジオルガノシロキサンポリイミド。1. The following chemical formula 1: [Z in the chemical formula 1 is the following chemical formula 2: Wherein R is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative thereof, (b) an alkylene group having 2 to 20 carbon atoms, and A cycloalkylene group and a C (2-8) alkylene-terminated polydiorganosiloxane, and (c) the following chemical formula 3: (Q 'in Chemical formula 3 is selected from the group consisting of Chemical formula 4, Chemical formula 5, Chemical formula 6, Chemical formula 7, and Chemical formula 8 and x is an integer of 1 to 5) [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] A divalent C selected from the group consisting of divalent groups represented by
(2-20) an organic group, Q is a chemical formula 9 or a chemical formula 10 [Chemical 10] (D in the formula is expressed in Chemical formula 11, Chemical formula 12, Chemical formula 13, Chemical formula 14, Chemical formula 1
5 and chemical formula 16, [Chemical 12] [Chemical 13] [Chemical 14] [Chemical 15] [Chemical 16] R 8 is chemical formula 17, chemical formula 18, chemical formula 19, chemical formula 20, chemical formula 21, chemical formula 2
2, Chemical Formula 23 and General Formula 24: [Chemical 18] [Chemical 19] [Chemical 20] [Chemical 21] [Chemical formula 22] [Chemical formula 23] [Chemical formula 24] Is a divalent group selected from the divalent organic groups of, p is equal to 0 or 1, and X is of the following formulas 25, 26, 27, 28 and 29: [Chemical formula 26] [Chemical 27] [Chemical 28] [Chemical 29] Is a tetravalent group selected from the group consisting of divalent groups, wherein y is an integer of 1 to 5), R 1 to R 6 are selected from hydrogen and a C (1-8) alkyl group, R 7 is the same or different monovalent C (1-13) hydrocarbon group and monovalent substituted C (1-13) hydrocarbon group, R 9 is selected from hydrogen and R 7 , and Y is A divalent group selected from 31 [Chemical 31] n is an integer equal to 0 to 200, r is an integer equal to 0 or 1, m is an integer equal to 1 to 2000, and l is an integer having a value of about 1 to 10 4 ] Terminated polydiorganosiloxane polyimide.
キサンポリイミドが次の化３２： 【化３２】 （式中のｘは３以上の整数である）のシラノール終端ポ
リジメチルシロキサン−ポリイミド共重合体である請求
項１に記載のポリイミド。2. The silanol-terminated polydiorganosiloxane polyimide is represented by the following formula: The polyimide according to claim 1, which is a silanol-terminated polydimethylsiloxane-polyimide copolymer (wherein x is an integer of 3 or more).
族炭化水素基およびそのハロゲン化誘導基、（ｂ）２〜
２０個の炭素原子を有するアルキレン基およびシクロア
ルキレン基およびＣ(2-8) アルキレン終端ポリジオルガ
ノシロキサン、および（ｃ）次の化３４： 【化３４】 （式中のＱ′は化３５、化３６、化３７、化３８および
化３９よりなる群から選択され、ｘは１〜５の整数であ
る） 【化３５】 【化３６】 【化３７】 【化３８】 【化３９】 で表される二価の基よりなる群から選択される二価のＣ
(2-20)有機基で、Ｑは化４０および化４１ 【化４０】 【化４１】 （式中のＤは化４２、化４３、化４４、化４５、化４６
および化４７から選択され、 【化４２】 【化４３】 【化４４】 【化４５】 【化４６】 【化４７】 Ｒ8 は化４８、化４９、化５０、化５１、化５２、化５
３、化５４および一般式化５５： 【化４８】 【化４９】 【化５０】 【化５１】 【化５２】 【化５３】 【化５４】 【化５５】 の二価有機基から選択される二価の基であり、ｐは０ま
たは１に等しく、Ｘは次の化５６、化５７、化５８、化
５９および化６０： 【化５６】 【化５７】 【化５８】 【化５９】 【化６０】 の二価の基から選択され、ｙは１〜５の整数である）か
ら選択される四価の基であり、 Ｒ1 〜Ｒ6 は水素およびＣ(1-8) アルキル基から選択さ
れ、 Ｒ7 は同じまたは異なる一価Ｃ(1-13)炭化水素基および
一価置換Ｃ(1-13)炭化水素基であり、 Ｒ9 は水素およびＲ7 から選択され、 Ｙは化６１および化６２から選択される二価の基であ
り、 【化６１】 【化６２】 ｎは０〜２００に等しい整数で、 ｒは０または１に等しい整数である〕で表される水素化
珪素終端ポリイミドと、 次の化６３： 【化６３】 （Ｒ7 は同じまたは異なる一価Ｃ(1-13)炭化水素基およ
び一価置換Ｃ(1-13)炭化水素基であり、 ｍは１〜２０００に等しい整数である）のシラノール終
端ポリジオルガノシロキサンとの反応を有効量の縮合接
触の存在下で行うことからなるシラノール終端ポリジオ
ルガノシロキサン−ポリイミド共重合体の製法。3. The following chemical formula 33: [Wherein R is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative thereof, (b) 2
Alkylene and cycloalkylene groups having 20 carbon atoms and C (2-8) alkylene-terminated polydiorganosiloxane, and (c) (Q ′ in the formula is selected from the group consisting of: 35, 36, 37, 38 and 39, and x is an integer of 1 to 5) [Chemical 36] [Chemical 37] [Chemical 38] [Chemical Formula 39] A divalent C selected from the group consisting of divalent groups represented by
(2-20) an organic group, Q is a chemical formula 40 and a chemical formula 41 [Chemical 41] (In the formula, D is a chemical formula 42, a chemical formula 43, a chemical formula 44, a chemical formula 45, a chemical formula 46
And are selected from the following: [Chemical 43] [Chemical 44] [Chemical formula 45] [Chemical formula 46] [Chemical 47] R 8 is chemical formula 48, chemical formula 49, chemical formula 50, chemical formula 51, chemical formula 52, chemical formula 5
3, Chemical Formula 54 and General Formula 55: [Chemical 49] [Chemical 50] [Chemical 51] [Chemical 52] [Chemical 53] [Chemical 54] [Chemical 55] Is a divalent group selected from the group consisting of divalent organic groups, wherein p is equal to 0 or 1, and X is the following formula 56, formula 57, formula 58, formula 59 and formula 60: [Chemical 57] [Chemical 58] [Chemical 59] [Chemical 60] Is a tetravalent group selected from the group consisting of divalent groups, wherein y is an integer of 1 to 5), R 1 to R 6 are selected from hydrogen and a C (1-8) alkyl group, R 7 is the same or different monovalent C (1-13) hydrocarbon group and monovalent substituted C (1-13) hydrocarbon group, R 9 is selected from hydrogen and R 7 , and Y is A divalent group selected from 62 [Chemical formula 62] n is an integer equal to 0 to 200, r is an integer equal to 0 or 1], and a silicon hydride terminated polyimide represented by the following formula: (Wherein R 7 is the same or different monovalent C (1-13) hydrocarbon group and monovalent substituted C (1-13) hydrocarbon group, and m is an integer equal to 1 to 2000), a silanol-terminated polydiorgano A method of making a silanol terminated polydiorganosiloxane-polyimide copolymer comprising reacting with a siloxane in the presence of an effective amount of condensation contact.
６４： 【化６４】 で表される請求項３に記載の製法。4. The silicon hydride terminated polyimide has the following chemical formula: embedded image The method according to claim 3, which is represented by:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US44268282A | 1982-11-18 | 1982-11-18 | |
| US442682 | 1982-11-18 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58216385A Division JPH0655888B2 (en) | 1982-11-18 | 1983-11-18 | Condensation vulcanizable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH069779A true JPH069779A (en) | 1994-01-18 |
| JPH0784523B2 JPH0784523B2 (en) | 1995-09-13 |
Family
ID=23757722
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58216385A Expired - Lifetime JPH0655888B2 (en) | 1982-11-18 | 1983-11-18 | Condensation vulcanizable composition |
| JP6138393A Expired - Lifetime JPH0784523B2 (en) | 1982-11-18 | 1993-02-26 | Silicon hydride terminated polyimide and method for producing the same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58216385A Expired - Lifetime JPH0655888B2 (en) | 1982-11-18 | 1983-11-18 | Condensation vulcanizable composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JPH0655888B2 (en) |
| CA (1) | CA1204760A (en) |
| DE (1) | DE3341700A1 (en) |
| FR (1) | FR2536405B1 (en) |
| GB (1) | GB2131038B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4472565A (en) * | 1982-11-18 | 1984-09-18 | General Electric Company | Silicone-polyimide copolymers, condensation vulcanizable compositions obtained therefrom, and methods for making |
| US4517342A (en) * | 1983-06-23 | 1985-05-14 | General Electric Company | Heat curable compositions |
| GB8410766D0 (en) * | 1983-06-23 | 1984-06-06 | Gen Electric | Curable silicone-polyimide block copolymers |
| US4533737A (en) * | 1984-04-02 | 1985-08-06 | General Electric Company | Silicon functionalized norbornane carboxyimide and methods for making |
| DE3423608A1 (en) * | 1984-06-27 | 1986-01-02 | Th. Goldschmidt Ag, 4300 Essen | FLUORALKYLSILANES OR -SILOXANES, THEIR PRODUCTION AND USE |
| US4941729A (en) * | 1989-01-27 | 1990-07-17 | At&T Bell Laboratories | Building cables which include non-halogenated plastic materials |
| US5024506A (en) * | 1989-01-27 | 1991-06-18 | At&T Bell Laboratories | Plenum cables which include non-halogenated plastic materials |
| US4969706A (en) * | 1989-04-25 | 1990-11-13 | At&T Bell Laboratories | Plenum cable which includes halogenated and non-halogenated plastic materials |
| US5021585A (en) * | 1989-06-14 | 1991-06-04 | Hughes Aircraft Company | Aromatic polyimide silanol compounds, precursors and polymers thereof |
| WO1994013669A1 (en) * | 1992-12-07 | 1994-06-23 | Commonwealth Scientific And Industrial Research Organisation | Bisnadimides |
| DE19734245A1 (en) | 1997-08-07 | 1999-02-11 | Wacker Chemie Gmbh | Silicone imides |
| JP2001247819A (en) * | 2000-03-03 | 2001-09-14 | Dow Corning Toray Silicone Co Ltd | Electric insulating crosslinked film-forming organic resin composition, and method for forming electric insulating crosslinked film |
| US6737494B2 (en) * | 2001-11-09 | 2004-05-18 | General Electric Company | Synthesis and use of alkylalkoxyacyloxysilanes and blends thereof for use as a crosslinking agent in moisture curing RTV'S |
| JP2012025903A (en) * | 2010-07-27 | 2012-02-09 | Nitto Denko Corp | Composition for thermoplastic silicone resin |
| US11466126B2 (en) * | 2020-12-23 | 2022-10-11 | Momentive Performance Materials Inc. | Condensation curable composition comprising siloxane-imide base polymer |
| US11655368B2 (en) * | 2020-12-23 | 2023-05-23 | Momentive Performance Materials Inc. | Condensation curable composition comprising siloxane-imide crosslinker |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3950308A (en) * | 1973-06-07 | 1976-04-13 | Ciba-Geigy Corporation | Crosslinked polymers containing siloxane groups |
| FR2422696A1 (en) * | 1978-04-13 | 1979-11-09 | Rhone Poulenc Ind | IMIDE GROUPING POLYMERS |
| US4404350A (en) * | 1982-07-07 | 1983-09-13 | General Electric Company | Silicone-imide copolymers and method for making |
| US4381396A (en) * | 1982-07-07 | 1983-04-26 | General Electric Company | Silynorbornane anhydrides and method for making |
-
1983
- 1983-10-13 CA CA000438946A patent/CA1204760A/en not_active Expired
- 1983-11-15 FR FR8318109A patent/FR2536405B1/en not_active Expired
- 1983-11-17 GB GB08330725A patent/GB2131038B/en not_active Expired
- 1983-11-18 DE DE19833341700 patent/DE3341700A1/en not_active Withdrawn
- 1983-11-18 JP JP58216385A patent/JPH0655888B2/en not_active Expired - Lifetime
-
1993
- 1993-02-26 JP JP6138393A patent/JPH0784523B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| GB2131038B (en) | 1986-07-30 |
| JPH0784523B2 (en) | 1995-09-13 |
| CA1204760A (en) | 1986-05-20 |
| DE3341700A1 (en) | 1984-05-24 |
| JPS59131629A (en) | 1984-07-28 |
| JPH0655888B2 (en) | 1994-07-27 |
| FR2536405B1 (en) | 1987-08-28 |
| FR2536405A1 (en) | 1984-05-25 |
| GB8330725D0 (en) | 1983-12-29 |
| GB2131038A (en) | 1984-06-13 |
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