CN102942585A - Succinic anhydride group containing cyclic organosiloxane, preparation thereof, organosiloxane composition and thermosetting resin composition - Google Patents
Succinic anhydride group containing cyclic organosiloxane, preparation thereof, organosiloxane composition and thermosetting resin composition Download PDFInfo
- Publication number
- CN102942585A CN102942585A CN2012103983585A CN201210398358A CN102942585A CN 102942585 A CN102942585 A CN 102942585A CN 2012103983585 A CN2012103983585 A CN 2012103983585A CN 201210398358 A CN201210398358 A CN 201210398358A CN 102942585 A CN102942585 A CN 102942585A
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- CN
- China
- Prior art keywords
- group
- succinyl oxide
- carbonatoms
- integer
- alkyl
- Prior art date
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- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 125000005375 organosiloxane group Chemical group 0.000 title claims description 44
- 239000011342 resin composition Substances 0.000 title claims description 20
- 238000002360 preparation method Methods 0.000 title claims description 16
- 229920001187 thermosetting polymer Polymers 0.000 title 1
- -1 sulfydryl Chemical group 0.000 claims abstract description 92
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 50
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 43
- 125000005843 halogen group Chemical group 0.000 claims abstract description 31
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 24
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 24
- 229920000570 polyether Polymers 0.000 claims abstract description 24
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 23
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 23
- 125000001424 substituent group Chemical group 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 72
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 68
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 68
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 59
- 125000004122 cyclic group Chemical group 0.000 claims description 58
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 229910052799 carbon Inorganic materials 0.000 claims description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 31
- 229910052697 platinum Inorganic materials 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 27
- 239000011737 fluorine Substances 0.000 claims description 25
- 229920000728 polyester Polymers 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000004643 cyanate ester Substances 0.000 claims description 22
- 150000003553 thiiranes Chemical group 0.000 claims description 22
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000005864 Sulphur Substances 0.000 claims description 14
- 229920001721 polyimide Polymers 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- 239000009719 polyimide resin Substances 0.000 claims description 9
- WQJONRMBVKFKOB-UHFFFAOYSA-N cyanatosulfanyl cyanate Chemical compound N#COSOC#N WQJONRMBVKFKOB-UHFFFAOYSA-N 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical group O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920006122 polyamide resin Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 abstract 2
- 229940014800 succinic anhydride Drugs 0.000 abstract 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 abstract 1
- 239000007767 bonding agent Substances 0.000 abstract 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract 1
- 125000001730 thiiranyl group Chemical group 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 238000006884 silylation reaction Methods 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000007788 liquid Substances 0.000 description 18
- 238000001723 curing Methods 0.000 description 16
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 description 16
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 15
- 150000008065 acid anhydrides Chemical class 0.000 description 14
- 150000008064 anhydrides Chemical group 0.000 description 14
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 229940017219 methyl propionate Drugs 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 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 5
- 125000000962 organic group Chemical group 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- MAMMVUWCKMOLSG-UHFFFAOYSA-N Cyclohexyl propionate Chemical compound CCC(=O)OC1CCCCC1 MAMMVUWCKMOLSG-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009432 framing Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 description 4
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000001808 coupling effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 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 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 2
- LTVRSJBNXLZFGT-UHFFFAOYSA-N 2-silylethenone Chemical compound [SiH3]C=C=O LTVRSJBNXLZFGT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 0 C*N(*C)C(*)(*)CO* Chemical compound C*N(*C)C(*)(*)CO* 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CEQGYPPMTKWBIU-UHFFFAOYSA-N Octyl propanoate Chemical compound CCCCCCCCOC(=O)CC CEQGYPPMTKWBIU-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 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
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- HUOYUOXEIKDMFT-UHFFFAOYSA-N decyl propionate Chemical compound CCCCCCCCCCOC(=O)CC HUOYUOXEIKDMFT-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- GOKKOFHHJFGZHW-UHFFFAOYSA-N hexyl propanoate Chemical compound CCCCCCOC(=O)CC GOKKOFHHJFGZHW-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 239000003607 modifier 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- DFATXMYLKPCSCX-UHFFFAOYSA-N CC(CC(O1)=O)C1=O Chemical compound CC(CC(O1)=O)C1=O DFATXMYLKPCSCX-UHFFFAOYSA-N 0.000 description 1
- ASKAQQFJYDXSGQ-UHFFFAOYSA-N C[Si](C)(C=C)O[Si](C)(C)C=C.Cl Chemical compound C[Si](C)(C=C)O[Si](C)(C)C=C.Cl ASKAQQFJYDXSGQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004821 Contact adhesive Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XWHJQTQOUDOZGR-UHFFFAOYSA-N hex-1-enyl(trimethoxy)silane Chemical compound CCCCC=C[Si](OC)(OC)OC XWHJQTQOUDOZGR-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002632 lipids Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- BHANWPPOZXXMCR-UHFFFAOYSA-N trichloro(hex-1-enyl)silane Chemical compound CCCCC=C[Si](Cl)(Cl)Cl BHANWPPOZXXMCR-UHFFFAOYSA-N 0.000 description 1
- YVRYYVDHGQKMMU-BQYQJAHWSA-N trichloro-[(e)-oct-1-enyl]silane Chemical compound CCCCCC\C=C\[Si](Cl)(Cl)Cl YVRYYVDHGQKMMU-BQYQJAHWSA-N 0.000 description 1
- DVFZJTWMDGYBCD-UHFFFAOYSA-N triethoxy(hex-1-enyl)silane Chemical compound CCCCC=C[Si](OCC)(OCC)OCC DVFZJTWMDGYBCD-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- ZYMHKOVQDOFPHH-UHFFFAOYSA-N trimethoxy(oct-1-enyl)silane Chemical compound CCCCCCC=C[Si](OC)(OC)OC ZYMHKOVQDOFPHH-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
Classifications
-
- 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
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The formula (1) represents the succinic anhydride group containing cyclic organosiloxane. (R1 is alkyl or aryl group, R2 is hydrogen atom or Halogen atom, alkyl selected from the substituent group of vinyl, epoxy group, thiirane groups,(methyl)acryloyl group, sulfydryl, isocyanate group, hydrolytic silicyl, succinic anhydride, perfluoroalkyl group, polyether,and fluorolink. The R2 using the hydrolytic silicyl as the substituent group is more than one, and the R 2 using the succinic anhydride as the substituent group are more than two. N is an integer in a range of from 3 to 6. In the invention, one molecule is provided with more than two succinic anhydrides, therefore the composition containing the organic perssad or the functional group having the reaction, the composition can be used as the bonding agent. In addition, the hydrolytic silicyl is also provided, therefore the silane coupling agent effect is expectable, and the composition is a material having no prior art.
Description
Technical field
The present invention relates in 1 molecule take annular siloxane as main framing, contain water-disintegrable silyl and 2 above succinyl oxide bases more than 1 cyclic organic siloxane, its preparation method, contain this cyclic organic siloxane and contain the organosiloxane composition of trapping agent of thing and the hot curing resin composition that contains above-mentioned cyclic organic siloxane as the change that contains active hydrogen of anhydride group stablizer.
Background technology
The compound that has 2 above anhydride group in 1 molecule is as the constituent material of polyimide, but the compound that has 3 above anhydride group in 1 molecule is unknown.By using the above acid anhydrides of 3 officials energy, can increase the cross-linking density of resin tremendously, therefore expect the raising of the physical strength of gained synthetic resin.In addition, 2 officials can acid anhydrides situation under, for example have water-disintegrable silyl and except as the tackiness agent in the resin, can also expect that it is as the effect of silane connection agent as the compound of other organic group.
Silane coupling agent with acid anhydrides residue and water-disintegrable silyl, can enumerate pressure sensitive adhesion power adjusting agent (patent documentation 1: Japanese kokai publication hei 8-302320 communique) in the contact adhesive composition, TOHKEMY 2006-22158 communique) etc. based on the linking agent of the solidification compound of Resins, epoxy (patent documentation 2: as representative purposes, in addition, also be used for the various fields such as polyimide resin properties-correcting agent, but be the silane coupling agent that in 1 molecule, has 1 water-disintegrable silyl and 1 anhydride group only in this case, can't expect aforesaid adhesive effect.
In general, organic oligosiloxane (hereinafter referred to as siloxane oligomer) of silane coupling agent partial hydrolysis condensation gained, it is the material that in structure, has a plurality of organic groups and water-disintegrable silyl, but be in this situation with water-disintegrable organic group of anhydride-functional base at organic group, when silyl partly is hydrolyzed condensation, anhydride group is also reacted, so aforementioned techniques can't use, and requires it to have ageing stability.
In No. 4013023 communique of Japanese Patent (patent documentation 3), the technology that the compound that will have fluoro-alkyl and anhydride group on the annular siloxane skeleton is used for bonding auxiliary agent is disclosed.Yet, in this communique, in molecule, only have the compound of 1 anhydride group, do not contain water-disintegrable silyl, so it does not have the effect as coupling agent, thereby can't expect adhesive effect and coupling effect.
No. 2682359 communique of Japanese Patent (patent documentation 4) discloses relevantly has the technology of the compound of anhydride group in chain, branched siloxane backbone, and No. 2546104 communique of Japanese Patent (patent documentation 5) discloses the relevant technology that has the compound of anhydride group at the annular siloxane skeleton.Yet, because they all are used as the solidifying agent of Resins, epoxy etc., therefore anhydride group must have unsaturated lipid ring type skeleton, although the reactivity of acid anhydride structure itself is identical, but the ring skeleton can cause the high viscosity (solidification) of material, therefore can't expect as above-mentioned coupling agent and even the tackiness agent of resin.In addition, because the organo-siloxane of gained is residual in the ring skeleton unsaturated link(age) arranged, therefore described position becomes the starting point of oxidation, thermolysis easily, for example, when being used as the tackiness agent of resin combination, have the problem of the declines such as heat-resisting discolouration that make this resin.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 8-302320 communique
Patent documentation 2: TOHKEMY 2006-22158 communique
Patent documentation 3: No. 4013023 communique of Japanese Patent
Patent documentation 4: No. 2682359 communique of Japanese Patent
Patent documentation 5: No. 2546104 communique of Japanese Patent
Brief summary of the invention
The problem that invention will solve
The present invention In view of the foregoing carries out, its purpose is to be provided at the cyclic organic siloxane, its preparation method that contain water-disintegrable silyl and 2 above succinyl oxide bases more than 1 in 1 molecule take annular siloxane as main framing, contain this cyclic organic siloxane and suppress the stablizer of this organo-siloxane rheological parameters' change with time, the hot curing resin composition of having given the organosiloxane composition of ageing stability and comprise this cyclic organic siloxane in constituent.
For the method for dealing with problems
In order to achieve the above object, the inventor has carried out positive research repeatedly, found that the represented compound of following formula (1) that carries out the hydrosilylation gained by the succinyl oxide that makes the cyclic organohydrogensiloxanes that has a plurality of hydrogenation silyls in 1 molecule, has the compound that contains water-disintegrable silyl of carbon-to-carbon unsaturated bond and have a carbon-to-carbon unsaturated bond in the presence of platinum and/or platinum complex can be used for addressing the above problem, and finish the present invention thus.
Therefore, the invention provides the cyclic organic siloxane that contains the succinyl oxide base, its preparation method, organosiloxane composition and the hot curing resin composition shown in following.
[1]
By the represented cyclic organic siloxane that contains the succinyl oxide base of following general formula (1).
(in the formula, R
1Be 1～10 alkyl or aryl independently of one another for carbonatoms, R
2Be 1～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another; this substituting group is selected from halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) cyanate ester based, water-disintegrable silyl, succinyl oxide base, perfluoroalkyl, polyether-based and holo-fluorine polyester, wherein take water-disintegrable silyl as substituent R
2Be more than 1, take the succinyl oxide base as substituent R
2Be more than 2.N is 3～6 integer.)
[2]
Such as [1] the described cyclic organic siloxane that contains the succinyl oxide base, it is represented by following general formula (2).
(in the formula, R
1With above-mentioned same, R
4Be 1～4 alkyl independently of one another for carbonatoms, R
5The carbonatoms that can insert Sauerstoffatom for halogen atom, centre independently of one another is that 1～20 alkoxyl group or carbonatoms are 6～10 aryloxy, R
6Be 1～10 alkyl for hydrogen atom maybe can have the carbonatoms of getting the shape base independently of one another; this substituting group is selected from that halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) are cyanate ester based, perfluoroalkyl, polyether-based and holo-fluorine polyester; k is 2～6 integer; m is 2～10 integer, and x is 1～3 integer.P 〉=2, q 〉=1, r 〉=0, p+q+r is 3～6 integer.)
[3]
Such as [2] the described cyclic organic siloxane that contains the succinyl oxide base, it is characterized in that being represented by following general formula (3).
(in the formula, p ' 〉=2, q ' 〉=1, p '+q ' is 3～6 integer.)
[4]
Such as [2] the described cyclic organic siloxane that contains the succinyl oxide base, it is characterized in that annular siloxane is cyclotetrasiloxane.
[5]
By the preparation method of the represented cyclic organic siloxane that contains the succinyl oxide base of following general formula (1), the succinyl oxide that it is characterized in that making the cyclic organohydrogensiloxanes that has at least 3 Si-H bases in 1 molecule, has the compound that contains water-disintegrable silyl of carbon-to-carbon unsaturated bond and have a carbon-to-carbon unsaturated bond carries out hydrosilylation in the presence of platinum and/or platinum complex.
(in the formula, R
1Be 1～10 alkyl or aryl independently of one another for carbonatoms, R
2Be 1～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another; this substituting group is selected from halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) cyanate ester based, water-disintegrable silyl, succinyl oxide base, perfluoroalkyl, polyether-based and holo-fluorine polyester, wherein take water-disintegrable silyl as substituent R
2Be more than 1, take the succinyl oxide base as substituent R
2Be more than 2.N is 3～6 integer.)
[6]
Such as [5] the described preparation method who contains the cyclic organic siloxane of succinyl oxide base; it is characterized in that; make and have part Si-H base contained in the cyclic organohydrogensiloxanes of at least 3 Si-H bases in 1 molecule; with the compound that contains water-disintegrable silyl with carbon-to-carbon unsaturated bond and as required be used as the substituent halogen atom that is selected from; vinyl; epoxy group(ing); thiiranes group; (methyl) acryl; sulfydryl; different (sulphur) is cyanate ester based; perfluoroalkyl; at least a replacement or unsubstituted unsaturated hydrocarbon compound in polyether-based and the holo-fluorine polyester carry out hydrosilylation reactions in the presence of platinum and/or platinum complex, then make Si-H base remaining in the cyclic organohydrogensiloxanes of gained carry out hydrosilylation reactions with the succinyl oxide that contains carbon-to-carbon unsaturated bond.
[7]
Such as [6] the described preparation method who contains the cyclic organic siloxane of succinyl oxide base, the compound that contains water-disintegrable silyl that it is characterized in that having carbon-to-carbon unsaturated bond is represented by following formula,
(in the formula, R
1With above-mentioned same, R
4Be 1～4 alkyl independently of one another for carbonatoms, R
5The carbonatoms that can insert Sauerstoffatom for halogen atom, centre independently of one another is that 1～20 alkoxyl group or carbonatoms are 6～10 aryloxy, and m1 is 0～8 integer, and x is 1～3 integer.)
The unsaturated hydrocarbon compound that adds as required is represented by following formula,
CH
2＝CH-R
6a
(in the formula, R
6aBe 1～8 alkyl for hydrogen atom maybe can have substituent carbonatoms, and this substituting group is selected from that halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) are cyanate ester based, perfluoroalkyl, polyether-based and holo-fluorine polyester.)
The succinyl oxide that contains carbon-to-carbon unsaturated bond is represented by following formula,
(in the formula, k1 is 0～4 integer.)
And obtain by the represented cyclic organic siloxane that contains the succinyl oxide base of following general formula (2),
(in the formula, R
1, R
4, R
5, x as mentioned above.R
6Be 3～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another; this substituting group is selected from that halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) are cyanate ester based, perfluoroalkyl, polyether-based and holo-fluorine polyester; k is 2～6 integer; m is 2～10 integer, and x is 1～3 integer.P 〉=2, q 〉=1, r 〉=0, p+q+r is 3～6 integer.)
[8]
Such as [7] the described preparation method who contains the cyclic organic siloxane of succinyl oxide base, the compound that contains water-disintegrable silyl that it is characterized in that having carbon-to-carbon unsaturated bond is vinyltrimethoxy silane, the succinyl oxide that contains carbon-to-carbon unsaturated bond is the allyl group succinyl oxide, and obtains by the represented cyclic organic siloxane that contains the succinyl oxide base of following general formula (3).
(in the formula, p ' 〉=2, q ' 〉=1, p '+q ' is 3～6 integer.)
[9]
Organosiloxane composition, its contain just like each described cyclic organic siloxane that contains the succinyl oxide base of [1]～[4] and as the trapping agent of the compound that contains active hydrogen by the represented α of following general formula (4)-silyl aliphatic ester compound.
(in the formula, R
7For the carbonatoms that the carbonatoms that does not replace or replace is 1～20 alkyl, the carbonatoms that do not replace or replace is 5～20 cycloalkyl or do not replace or replace is 6～20 aryl, R
8Be hydrogen atom or methyl, R
9The carbonatoms that is independently not replacement or replacement is 1～4 alkyl, R
10Be 1～4 alkyl independently for the carbonatoms of not getting shape or replacement.Y is 1～3 integer.)
[10]
Contain the hot curing resin composition by the represented cyclic organic siloxane that contains the succinyl oxide base of following general formula (1).
(in the formula, R
1Be 1～10 alkyl or aryl independently of one another for carbonatoms, R
2Be 1～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another; this is got the shape base and is selected from halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) cyanate ester based, water-disintegrable silyl, succinyl oxide base, perfluoroalkyl, polyether-based and holo-fluorine polyester, wherein take water-disintegrable silyl as substituent R
2Be more than 1, take the succinyl oxide base as substituent R
2Be more than 2.N is 3～6 integer.)
[11]
Such as [10] described hot curing resin composition, the organopolysiloxane that wherein contains the succinyl oxide base is represented by following general formula (2).
(in the formula, R
1With above-mentioned same, R
4Be 1～4 alkyl independently of one another for carbonatoms, R
5The carbonatoms that can insert Sauerstoffatom for halogen atom, centre independently of one another is that 1～20 alkoxyl group or carbonatoms are 6～10 aryloxy, R
6Be 1～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another; this substituting group is selected from that halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) are cyanate ester based, perfluoroalkyl, polyether-based and holo-fluorine polyester; k is 2～6 integer; m is 2～10 integer, and x is 1～3 integer.P 〉=2, q 〉=1, r 〉=0, p+q+r is 3～6 integer.)
[12]
Such as [11] described hot curing resin composition, the organopolysiloxane that wherein contains the succinyl oxide base is represented by following general formula (3).
(in the formula, p ' 〉=2, q ' 〉=1, p '+q ' is 3～6 integer.)
[13]
Such as each described hot curing resin composition of [10]～[12], wherein above-mentioned hot curing resin composition contains polyamide resin or polyimide resin.
The invention effect
Cyclic organic siloxane of the present invention, owing in 1 molecule, have 2 above succinyl oxide bases, therefore modulation with contain and this functional group when having the composition of compound of reactive organic group (for example amine, hydroxyl), can show the function as tackiness agent, in addition, owing to also comprise water-disintegrable silyl, therefore can also expect the effect as silane coupling agent, cyclic organic siloxane of the present invention is the material that there is no at present example.In addition, by with stablizer coexistence, in any case, the present invention can preserve steadily in the long term at room temperature (25 ℃) and high temperature (30～100 ℃, preferred 40～80 ℃).
Embodiment
Below, the present invention is specifically described.
[cyclic organic siloxane]
Cyclic organic siloxane of the present invention, if with the annular siloxane structure as main framing, and contain in 1 molecule that water-disintegrable silyl and 2 above succinyl oxide bases get final product more than 1, and more preferably contain 3 above succinyl oxide bases.The detailed construction of this organo-siloxane is the annular siloxane shown in the following general formula (1), and except water-disintegrable silyl and succinyl oxide base, can also have following cited organic functional base.
(in the formula, R
1Be 1～10 alkyl or aryl independently of one another for carbonatoms, R
2Be 1～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another; and this substituting group is selected from halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) cyanate ester based, water-disintegrable silyl, succinyl oxide base, perfluoroalkyl, polyether-based and holo-fluorine polyester, wherein take this water-disintegrable silyl as substituent R
2Be more than 1, take the succinyl oxide base as substituent R
2Be more than 2.N is 3～6 integer.The arrangement of each repeating unit is arbitrarily.)
Herein, so-called anhydride group among the present invention refers to remove 1 atomic group residual behind hydrogen atom that carbon atom is combined from acid anhydrides.In the present invention, anhydride group is the succinyl oxide base.
In the general formula (1) of above-mentioned organo-siloxane, n represents the unit number of siloxanes, and as long as n is 3～6 scope, though then exist distribute also no problem, but more preferably Thermodynamically stable, make n=4 (the siloxanes tetramer of raw material siloxanes easily; Cyclotetrasiloxane).
In the general formula of above-mentioned organo-siloxane, as R
1Carbonatoms be 1～10 alkyl, aryl, can be straight chain shape, branched, ring-type, as alkyl, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl, cyclopentyl, hexyl, cyclohexyl, octyl group, decyl etc. typically, as aryl, can enumerate phenyl, naphthyl etc.In addition, R
2Hydrogen atom, can to have substituent carbonatoms be 1～10, is in particular 1～6 alkyl, the alkyl of main structure and aforementioned R
1Alkyl same; and as substituting group, can enumerate the holo-fluorine polyesters such as the polyether-based such as the perfluoroalkyls such as the halogen atoms such as chlorine atom, fluorine atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) cyanate ester based, water-disintegrable silyl, succinyl oxide base, trifluoromethyl, pentafluoroethyl group, seven fluoropropyls, nine fluorine butyl, ten trifluoro hexyls, 17 fluorine octyl groups, poly-(ethylene oxide) base, poly-(propylene oxide) base, poly-(hexafluoro ethylene oxide) base.
Organo-siloxane of the present invention except the succinyl oxide base, also must contain water-disintegrable silyl.By containing water-disintegrable silyl, this organo-siloxane has the function as silane coupling agent.Water-disintegrable silyl, so long as have the water-disintegrable atom of 1 valency that directly is connected on the Siliciumatom (by generating the atom of silanol group with the water reaction) and directly be connected at least a silyl in the 1 valency hydrolization group (by reacting the group that generates silanol group with water) on the Siliciumatom, just be not particularly limited.Can only there be 1 in water-disintegrable silyl in aforementioned organo-siloxane, also can exist more than 2, exists under the situation more than 2, and it can be of the same race, also can be not of the same race.As the concrete structure of the organo-siloxane with water-disintegrable silyl and succinyl oxide base, can be by following general formula (2)
(in the formula, R
1With above-mentioned same, R
4Be 1～4 alkyl independently of one another for carbonatoms, R
5The carbonatoms that can insert Sauerstoffatom for halogen atom, centre independently of one another is 1～20, is in particular 1～6 alkoxyl group or carbonatoms and is 6～10 aryloxy, R
6Be 1～10 for hydrogen atom maybe can have substituent carbonatoms independently of one another; be in particular 1～6 alkyl; and this substituting group is selected from, and halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) are cyanate ester based, perfluoroalkyl, polyether-based and holo-fluorine polyester; k is 2～6 integer; m is 2～10; be in particular 2～8 integer, x is 1～3 integer.P 〉=2, q 〉=1, r 〉=0, p+q+r is 3～6 integer.The arrangement of each repeating unit is arbitrarily.) expression.
As the details of water-disintegrable silyl structure, R
4Can be straight chain shape or branched, specifically can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-etc., and consider from the easy manufacture view of raw material, be preferably methyl.R
5By reacting the group that generates silanol group with water, specifically (for example can enumerate alkoxyl group, the ethylene glycol monoalkyl ether bases such as the halogen atoms such as chlorine atom, bromine atoms, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, phenoxy group, the ethylene glycol monobutyl ether base) alkoxyl group that replaced by Sauerstoffatom of part carbon atom etc. such as, but be not limited thereto the group of giving an example in the place.Wherein, from raw material make easily, water-disintegrable balance considers, is preferably methoxyl group, oxyethyl group.In addition, as R
6Substituent halogen atom, perfluoroalkyl, polyether-based, holo-fluorine polyester can be enumerated R in the above-mentioned general formula (1)
2Illustrated same substituting group.
As the object lesson of the represented organo-siloxane of above-mentioned general formula (2), for example, can enumerate the represented material of following formula (3).
(in the formula, p ' 〉=2, q ' 〉=1, p '+q ' is 3～6 integer.The arrangement of each repeating unit is arbitrarily.)
As organo-siloxane of the present invention, more particularly, can enumerate 1,3,5-three (succinyl oxide propyl group)-7-trimethoxysilyl octyl group tetramethyl-ring tetrasiloxane, 1,3,5-three (succinyl oxide propyl group)-7-trimethoxysilylethylgroup group tetramethyl-ring tetrasiloxane, 1,3-two (succinyl oxide propyl group)-5,7-two (trimethoxysilylethylgroup group) tetramethyl-ring tetrasiloxane, 1,5-two (succinyl oxide propyl group)-3,7-two (trimethoxysilylethylgroup group) tetramethyl-ring tetrasiloxane etc.
Organo-siloxane of the present invention can carry out hydrosilylation by the succinyl oxide that makes the cyclic organohydrogensiloxanes that has at least 3 Si-H bases in 1 molecule, has the compound that contains water-disintegrable silyl of carbon-to-carbon unsaturated bond and have a carbon-to-carbon unsaturated bond and make in the presence of platinum and/or platinum complex.When importing water-disintegrable silyl and other organic functional base as required, by making the unsaturated compound that contains these organic functional bases and the part Si-H base in the above-mentioned organohydrogensiloxanes carry out hydrosilylation, then make Si-H base remaining in the cyclic organohydrogensiloxanes of gained carry out hydrosilylation reactions with the succinyl oxide that contains carbon-to-carbon unsaturated bond, can obtain desirable compound.At this moment, the order as hydrosilylation is not particularly limited, but considers from the viewpoint of reaction efficiency, preferably makes the succinyl oxide that contains carbon-to-carbon unsaturated bond carry out in the back hydrosilylation.
Namely; preferably make and have part Si-H base contained in the cyclic organohydrogensiloxanes of at least 3 Si-H bases in 1 molecule; with the compound that contains water-disintegrable silyl with carbon-to-carbon unsaturated bond and as required be used as the substituent halogen atom that is selected from; vinyl; epoxy group(ing); thiiranes group; (methyl) acryl; sulfydryl; different (sulphur) is cyanate ester based; perfluoroalkyl; at least a replacement or unsubstituted unsaturated hydrocarbon compound in polyether-based and the holo-fluorine polyester carry out hydrosilylation reactions in the presence of platinum and/or platinum complex, then make Si-H base remaining in the cyclic organohydrogensiloxanes of gained carry out hydrosilylation reactions with the succinyl oxide that contains carbon-to-carbon unsaturated bond.
In the preparation method of organo-siloxane of the present invention, temperature of reaction is room temperature (25 ℃)～150 ℃, is preferably 40～130 ℃, and more preferably 70～120 ℃.If less than room temperature, then because reaction can't be carried out, and perhaps speed of response is very low, therefore have the situation of productivity deficiency.On the other hand, when surpassing 150 ℃, then might produce thermolysis or undesirable side reaction.
In the preparation method of organo-siloxane of the present invention, the reaction times is preferably 10 minutes～and 24 hours.The time that can fully consume raw material so long as carried out reaction gets final product, but is preferably 1～10 hour, and more preferably 2～7 hours.If less than 10 minutes, then raw material consumption may be insufficient, and surpass 24 hours, and therefore then completely consumed of raw material has and produced unnecessary operation, the situation that causes production efficiency to descend.
In the preparation method of organo-siloxane of the present invention, can use suitable reaction solvent.So long as can not produce to raw material and platinum complex non-reacted and that be used for reaction the material of catalysis toxicity, just be not particularly limited, as representative, can enumerate the ketone series solvents such as the pure series solvent such as aromatic hydrocarbons series solvent, methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, methylethylketone, mibk such as aliphatic hydrocarbon series solvent, toluene, the dimethylbenzene such as hexane, heptane.
Organohydrogensiloxanes among the present invention so long as take annular siloxane as main framing, and contains 3 above Si-H bases in 1 molecule, just be not particularly limited, and as other structure, can also have straight chain shape, the structure such as branched.But, as binder constituents the time, owing to have the situation of narrow molecular weight distribution to a certain degree, can avoid unnecessary cross-linking density to increase, therefore in order to form lower molecular weight, be necessary for annular siloxane.
As the object lesson of cyclic organohydrogensiloxanes, can enumerate 1,3,5-trimethylammonium cyclotrisiloxane, 1,3,5,7-tetramethyl-ring tetrasiloxane, 1,3,5,7-tetramethyl--1-propyl group cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-D5 etc., but be not limited thereto the material of giving an example in the place.Wherein, obtain easily the viewpoint consideration from above-mentioned reason and raw material, most preferably be 1,3,5,7-tetramethyl-ring tetrasiloxane.
Herein, in the present invention, as the compound that contains water-disintegrable silyl with carbon-to-carbon unsaturated bond, be by following formula preferably
(in the formula, R
1With above-mentioned same, R
4Be 1～4 alkyl independently of one another for carbonatoms, R
5The carbonatoms that can insert Sauerstoffatom for halogen atom, centre independently of one another is that 1～20 alkoxyl group or carbonatoms are 6～10 aryloxy, and m1 is 0～8 integer, and x is 1～3 integer.)
Represented compound, the unsaturated hydrocarbon compound that adds as required is by following formula
CH
2＝CH-R
6a
(in the formula, R
6aBe 1～8 alkyl for hydrogen atom maybe can have substituent carbonatoms, and this substituting group is selected from that halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) are cyanate ester based, perfluoroalkyl, polyether-based and holo-fluorine polyester.)
Represented compound, the succinyl oxide with carbon-to-carbon unsaturated bond are by following formula
(in the formula, k1 is 0～4 integer.)
Represented material, and obtain following general formula (2)
(in the formula, R
1, R
4, R
5, x as mentioned above.R
6Be 3～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another; and this substituting group is selected from, and halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) are cyanate ester based, perfluoroalkyl, polyether-based and holo-fluorine polyester; k is 2～6 integer; m is 2～10 integer, and x is 1～3 integer.P 〉=2, q 〉=1, r 〉=0, p+q+r is 3～6 integer.)
The represented cyclic organic siloxane that contains the succinyl oxide base.
Have the succinyl oxide of carbon-to-carbon unsaturated bond among the present invention, so long as contain the succinyl oxide of the alkene with hydrosilylation reactions, just be not particularly limited, specifically can enumerate the allyl group succinyl oxide.
In addition, raw material during as the water-disintegrable silyl of importing, so long as contain the water-disintegrable silane of the alkene with hydrosilylation reactions, just be not particularly limited, specifically can enumerate vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, hexenyl trichlorosilane, hexenyl Trimethoxy silane, hexenyl triethoxyl silane, octenyl trichlorosilane, octenyl Trimethoxy silane, octenyl triethoxyl silane etc., but be not limited thereto the material of giving an example in the place.
Importing succinyl oxide base and water-disintegrable silyl above-mentioned substituent R in addition
6The time, only have this substituent olefin(e) compound (above-mentioned CH with using
2=CH-R
6a) get final product.
The usage rate of reaction raw materials among the present invention is with respect to the base of the Si-H in 1 mole of organohydrogensiloxanes, is preferably to add up to 0.7～1.5 mole olefin(e) compound, and more preferably 0.9～1.1 mole.The olefin(e) compound that contains the succinyl oxide base and the usage rate that contains the olefin(e) compound of water-disintegrable silyl are preferably 5: 1～1: 2 ratio with molar ratio computing.
In addition, when the Si-H radix with respect to above-mentioned annular siloxane, the above-mentioned compound that contains water-disintegrable silyl with carbon-to-carbon unsaturated bond, have the succinyl oxide of carbon-to-carbon unsaturated bond and the number of the total carbon-to-carbon unsaturated bond base of the olefin(e) compound that adds as required when less, can obtain the material that R6 is hydrogen atom.
Hydrosilylation reaction catalyst among the present invention, be as the well-known platinum of known technology (Pt) and/or centered by platinum (Pt) complex compound of metal.Specifically, can enumerate Platinic chloride alcoholic solution, Platinic chloride 1,3-divinyl tetramethyl disiloxane complex compound and to this complex compound carried out neutralizing treatment compound, in Oxidation Number be 1 of Pt (II) or Pt (0), 3-divinyl tetramethyl disiloxane complex compound.Optionally viewpoint considers that the Oxidation Number of preferred center metal is Pt (IV) complex compound in addition, and is particularly preferably Pt (0), Pt (II) from the additional position.
The usage quantity of the hydrosilylation reaction catalyst among the present invention, so long as show the amount of the catalytic effect of hydrosilylation reactions, just be not particularly limited, preferably with respect to 1 mole of the total amount of olefin(e) compound, count 0.000001～1 mole with the platinum conversion, and more preferably 0.0001～0.01 mole.When less than 0.000001 mole, may not show enough catalytic effects, and when more than 1 mole because effect is saturated, therefore have production cost uprise, uneconomic may.
[organosiloxane composition]
Organosiloxane composition of the present invention comprises the cyclic organic siloxane that contains above-mentioned succinyl oxide base and water-disintegrable silyl.At this moment, in order to keep the storage stability of this organo-siloxane, preferably add the trapping agent of the compound that contains active hydrogen shown in following as stablizer.The trapping agent of the compound that contains active hydrogen among the present invention is the stablizer that contains the cyclic organic siloxane of succinyl oxide base and water-disintegrable silyl.
Herein, the compound that contains active hydrogen refers to contain the compound that has reactive hydrogen atoms group (below, be sometimes referred to as " containing active hydrogen group ") with anhydride group.As this hydrogen atoms group, for example, can enumerate hydroxyl (OH), amino (NH
2), (NH-), sulfydryl (SH) etc. for imino-.Therefore, as the compound that contains active hydrogen, for example, can enumerate the hydroxy-containing compounds such as water, alcohol, carboxylic acid; Ammonia, primary amine etc. contain aminocompound; The imido-compounds such as secondary amine; The compounds containing thiol groups such as hydrogen sulfide, mercaptan etc.As the object lesson of alcohol, can enumerate methyl alcohol, ethanol, Virahol etc.As the object lesson of carboxylic acid, can enumerate acetic acid, propionic acid, formic acid etc.As the object lesson of primary amine, can enumerate methylamine, ethamine, butylamine etc.As the object lesson of secondary amine, can enumerate dimethyl amine, diethylamide, ethylmethylamine etc.As the object lesson of mercaptan, can enumerate methyl mercaptan, ethanethio etc.
The above-mentioned compound that contains active hydrogen, when coexisting with the organo-siloxane that contains succinyl oxide base and water-disintegrable silyl, at first, this compound that contains active hydrogen becomes the initiator of this organo-siloxane rheological parameters' change with time, then the newly-generated compound that contains active hydrogen, and the rheological parameters' change with time of this organo-siloxane is chain to carry out, and then purity drop.Specifically, for example, when the compound that contains active hydrogen that becomes initiator be as atmosphere in moisture and the water that exists, and when aforementioned organo-siloxane is 1,3,5-three (succinyl oxide propyl group)-7-trimethoxysilylethylgroup group tetramethyl-ring tetrasiloxane, following reaction 1 becomes initial action, then, reaction 2 and 3 repeats, so the purity of this organo-siloxane through the time descend.
Reaction 1: by the caused methoxy methyl silylation of the moisture in atmosphere hydrolysis → methanol
Reaction 2: the ring-opening reaction of the anhydride rings that is caused by the methyl alcohol that generates → generation carboxylic acid
Reaction 3: the transesterification reaction → methanol of the carboxylic acid of generation and methoxy methyl silylation
In addition, in the present invention, contain the trapping agent of the compound of active hydrogen, thereby refer to and the material that contains active hydrogen group in this compound that contains active hydrogen is eliminated in the compound reaction that contains active hydrogen, the active hydrogen group that contains of eliminating in the compound that contains active hydrogen is called as " seizure ".
Consideration is during by the above-mentioned reaction mechanism of the caused organo-siloxane rheological parameters' change with time that contains succinyl oxide base and water-disintegrable silyl of the compound that contains active hydrogen, and it is as described below to contain the condition that the trapping agent of the compound of active hydrogen will satisfy.
Condition 1: trapping agent can catch the compound that contains active hydrogen (being the water in the atmosphere in above-mentioned concrete example) that becomes initiator
Condition 2: trapping agent can the catching reaction system in the newly-generated compound that contains active hydrogen (carboxylic acid for generating in methyl alcohol and the reaction 2 in above-mentioned concrete example)
Condition 3: trapping agent is reactive with succinyl oxide base and water-disintegrable silyl right and wrong with the seizure resultant itself that the compound reaction that contains active hydrogen generates
Condition 4: trapping agent and the reactivity that contains the compound of active hydrogen be better than succinyl oxide base and water-disintegrable silyl respectively with the reactivity of the compound that contains active hydrogen
As the trapping agent of the compound that contains active hydrogen, as long as satisfy above condition, just can be not particularly limited to use any trapping agent, but preferably can enumerate for example α-silyl aliphatic ester compound.In the present invention, α-silyl aliphatic ester compound refers to that silyl directly is connected to the ester of aliphatic carboxylic acid of the carbon atom of α position.This silyl only otherwise contain active hydrogen group, just can be arbitrarily, for example, can enumerate and does not contain the water-disintegrable silyl that contains active hydrogen group etc.As this water-disintegrable silyl, for example, preferably comprise alkoxyl group, aryloxy etc., and particularly preferably comprise alkoxyl group.
Aforementioned α-silyl aliphatic ester compound is preferably following general formula (4)
(in the formula, R
7For the carbonatoms that does not replace or replace is 1～20, be in particular 1～10 alkyl, the carbonatoms that does not replace or replace is 5～20, be in particular 6～10 cycloalkyl or the carbonatoms that do not replace or replace is 6～20, be in particular 6～10 aryl, R
8Be hydrogen atom or methyl, R
9The carbonatoms that is independently not replacement or replacement is 1～4 alkyl, R
10The carbonatoms that is independently not replacement or replacement is 1～4 alkyl.Y is 1～3 integer.)
Represented compound.
As above-mentioned R
7During for alkyl, can be the straight chain shape, also can be the branch chain.As above-mentioned R
7Object lesson, can enumerate the alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl; The cycloalkyl such as cyclopentyl, cyclohexyl, suberyl; The aryl such as phenyl, tolyl, naphthyl; The part or all of hydrogen atom that is connected with the carbon atom of these groups wherein, is preferably ethyl, octyl group by the group of the replacements such as halogen atom (fluorine atom, chlorine atom, bromine atoms, iodine atom).
As above-mentioned R
9, R
10Object lesson, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, and preferable methyl, ethyl.
As the object lesson of α-silyl aliphatic ester compound, can enumerate α-trimethoxysilyl methyl propionate, α-trimethoxysilyl ethyl propionate, α-trimethoxysilyl propyl propionate, α-trimethoxysilyl butyl propionate, α-trimethoxysilyl amyl propionate, α-trimethoxysilyl n-hexyl propionate, α-trimethoxysilyl n-octyl propionate, α-trimethoxysilyl n-decyl propionate, α-trimethoxysilyl cyclohexyl propionate, α-trimethoxysilyl isopropyl propionate, α-trimethoxysilyl phenylpropionate, α-triethoxysilyl methyl propionate, α-triethoxysilyl ethyl propionate, α-triethoxysilyl propyl propionate, α-triethoxysilyl butyl propionate, α-triethoxysilyl amyl propionate, α-triethoxysilyl n-hexyl propionate, α-triethoxysilyl n-octyl propionate, α-triethoxysilyl n-decyl propionate, α-triethoxysilyl cyclohexyl propionate, α-triethoxysilyl isopropyl propionate, α-triethoxysilyl phenylpropionate, Alpha-Methyl dimethoxy silyl methyl propionate, Alpha-Methyl dimethoxy silyl ethyl propionate, Alpha-Methyl dimethoxy silyl propyl propionate, Alpha-Methyl dimethoxy silyl butyl propionate, Alpha-Methyl dimethoxy silyl amyl propionate, Alpha-Methyl dimethoxy silyl n-hexyl propionate, Alpha-Methyl dimethoxy silyl n-octyl propionate, Alpha-Methyl dimethoxy silyl n-decyl propionate, Alpha-Methyl dimethoxy silyl cyclohexyl propionate, Alpha-Methyl dimethoxy silyl isopropyl propionate, Alpha-Methyl dimethoxy silyl phenylpropionate, Alpha-Methyl diethoxy silyl methyl propionate, Alpha-Methyl diethoxy silyl ethyl propionate, Alpha-Methyl diethoxy silyl propyl propionate, Alpha-Methyl diethoxy silyl butyl propionate, Alpha-Methyl diethoxy silyl amyl propionate, Alpha-Methyl diethoxy silyl n-hexyl propionate, Alpha-Methyl diethoxy silyl n-octyl propionate, Alpha-Methyl diethoxy silyl n-decyl propionate, Alpha-Methyl diethoxy silyl cyclohexyl propionate, Alpha-Methyl diethoxy silyl isopropyl propionate, Alpha-Methyl diethoxy silyl phenylpropionate, alpha-alpha-dimethyl methoxy methyl silylation methyl propionate, alpha-alpha-dimethyl methoxy methyl silylation ethyl propionate, alpha-alpha-dimethyl methoxy methyl silylation propyl propionate, alpha-alpha-dimethyl methoxy methyl silylation butyl propionate, alpha-alpha-dimethyl methoxy methyl silylation amyl propionate, alpha-alpha-dimethyl methoxy methyl silylation n-hexyl propionate, alpha-alpha-dimethyl methoxy methyl silylation n-octyl propionate, alpha-alpha-dimethyl methoxy methyl silylation n-decyl propionate, alpha-alpha-dimethyl methoxy methyl silylation cyclohexyl propionate, alpha-alpha-dimethyl methoxy methyl silylation isopropyl propionate, alpha-alpha-dimethyl methoxy methyl silylation phenylpropionate, alpha-alpha-dimethyl (ethoxymethyl) silylation methyl propionate, alpha-alpha-dimethyl (ethoxymethyl) silylation ethyl propionate, alpha-alpha-dimethyl (ethoxymethyl) silylation propyl propionate, alpha-alpha-dimethyl (ethoxymethyl) silylation butyl propionate, alpha-alpha-dimethyl (ethoxymethyl) silylation amyl propionate, alpha-alpha-dimethyl (ethoxymethyl) silylation n-hexyl propionate, alpha-alpha-dimethyl (ethoxymethyl) silylation n-octyl propionate, alpha-alpha-dimethyl (ethoxymethyl) silylation n-decyl propionate, alpha-alpha-dimethyl (ethoxymethyl) silylation cyclohexyl propionate, alpha-alpha-dimethyl (ethoxymethyl) silylation isopropyl propionate, alpha-alpha-dimethyl (ethoxymethyl) silylation phenylpropionate, α-trimethyl silyl methyl propionate, α-trimethyl silyl ethyl propionate, α-trimethyl silyl propyl propionate, α-trimethyl silyl butyl propionate, α-trimethyl silyl amyl propionate, α-trimethyl silyl n-hexyl propionate, α-trimethyl silyl n-octyl propionate, α-trimethyl silyl n-decyl propionate, α-trimethyl silyl cyclohexyl propionate, α-trimethyl silyl isopropyl propionate, α-trimethyl silyl phenylpropionate, α-triethylsilyl methyl propionate, α-triethylsilyl ethyl propionate, α-triethylsilyl propyl propionate, α-triethylsilyl butyl propionate, α-triethylsilyl amyl propionate, α-triethylsilyl n-hexyl propionate, α-triethylsilyl n-octyl propionate, α-triethylsilyl n-decyl propionate, α-triethylsilyl cyclohexyl propionate, α-triethylsilyl isopropyl propionate, α-triethylsilyl phenylpropionate etc.Wherein, consider from catching reaction height and the easy viewpoint that obtains of material, more preferably α-trimethoxysilyl ethyl propionate, Alpha-Methyl dimethoxy silyl n-octyl propionate.
When α-silyl aliphatic ester compound reacted with the compound that contains active hydrogen, silyl separated from the carbon atom of α position, generates the aliphatic carboxylic acid esters, who does not contain the silicoorganic compound of active hydrogen group and do not contain active hydrogen group.Because resultant does not contain active hydrogen group, therefore do not have the reactivity with the organo-siloxane that contains succinyl oxide base and water-disintegrable silyl.Specifically, for example, when the compound that contains active hydrogen is methyl alcohol, and when the trapping agent that contains the compound of active hydrogen is α-trimethoxysilyl ethyl propionate, the compound that generates by the catching reaction shown in following is tetramethoxy-silicane and ethyl propionate, and they do not have the reactivity with the organo-siloxane that contains succinyl oxide base and water-disintegrable silyl.
In addition, used α among the present invention-silyl aliphatic ester compound, can also be α-silyl aliphatic ester compound and the mixture that is in the silyl ketene acetal (silylketene acetal) of keto-enol equilibrium relationship, at this moment, the α-amount of silyl aliphatic ester compound refers to the total amount of α-silyl aliphatic ester compound and silyl ketene acetal.
The usage quantity of stablizer with respect to 100 mass parts cyclic organic siloxane of the present invention, is preferably 0.01～10 mass parts, and 0.1～5 mass parts more preferably.When this usage quantity is the scope of 0.01～10 mass parts, can unnecessarily reduced the purity of this organo-siloxane because adding stablizer, and can obtain the stabilising effect corresponding to usage quantity.
Organosiloxane composition of the present invention comprises the cyclic organic siloxane that contains succinyl oxide base and water-disintegrable silyl and above-mentioned stablizer.Said composition is owing to contain stablizer, even therefore after prolonged preservation in arbitrary situation of room temperature and high temperature, and the decline that also is difficult to produce this organo-siloxane purity, and can effectively bring into play the effect of acid anhydrides tackiness agent and coupling agent.Cyclic organic siloxane and stablizer can use separately a kind separately, also can will also use more than 2 kinds.In addition, the use level of cyclic organic siloxane (silicoorganic compound) and stablizer is with identical to the illustrated usage quantity of stabilising method of the present invention.Organosiloxane composition of the present invention can and obtain according to conventional methods with this organo-siloxane and the even mixing of this stablizer.Organosiloxane composition of the present invention is particularly useful for the purposes such as modifier, pressure sensitive adhesive, caking agent, powder handling agent.
[hot curing resin composition]
Hot curing resin composition of the present invention contains above-mentioned cyclic organic siloxane and the heat-curing resin that contains the succinyl oxide base.In the hot curing resin composition that comprises the cyclic organic siloxane that contains the succinyl oxide base of the present invention, heat-curing resin can be enumerated resol, Resins, epoxy, polyimide resin, polyamide resin, urethane resin, melamine resin, urea-formaldehyde resin, unsaturated polyester resin, Synolac, bismaleimide-triazine resin etc.Wherein, in the polyamide resin that can add as tackiness agent, polyimide resin, bring into play easily the performance of organo-siloxane of the present invention.
Particularly in the situation that forms polyimide resin composition, can be with respect to the organo-siloxane that contains the succinyl oxide base of the present invention, preferably cooperate the diamine compound such as phenylenediamine, tolylene diamine, Alkylenediamine, bisphenol A-type diamines by equivalence ratio with 0.7～1.3 ratio and obtain polyamic acid solution, then heat by ordinary method and obtain polyimide resin.
Comprise in the hot curing resin composition of the cyclic organic siloxane that contains the succinyl oxide base in the present invention, it not only can be used as above-mentioned tackiness agent, but also can be the same as with common silane coupling agent modifier.
This hot curing resin composition during as other composition, can show the coupling effect of resin-inorganic powder at the inorganic powder that add to be used for improves physical strength, and and the energy of 2 officials in the past acid anhydrides compare, can expect the raising of forming composition physical strength.
Embodiment
Below, illustrate in greater detail the present invention by using embodiment, comparative example, but the present invention is not limited to these embodiment.It is pointed out that viscosity is that the value under 25 ℃ that Brookfield viscometer measures is used in expression.In addition, in following example, part expression mass parts.
[embodiment 1]
Synthesizing of 1,3,5-three (succinyl oxide propyl group)-7-trimethoxysilyl octyl group tetramethyl-ring tetrasiloxane
In the detachable flask of the 500ml with stirrer, reflux exchanger, dropping funnel and thermometer, mix 24.0 parts of (0.1 moles) 1,3,5,7-tetramethyl-ring tetrasiloxane, 24.0 parts of toluene, platinum complex (1 of Pt (0), 3-divinyl tetramethyl disiloxane complex compound) toluene solution wherein holds the amount that is equivalent to 0.00002 mole (being scaled platinum) with respect to 1 mole of Si-H base platinum complex.Then, when being heated to interior temperature and becoming 80 ℃, dripped 23.2 parts of (0.1 mole) octenyl Trimethoxy silanes through 30 minutes.When dripping, produce reaction and heat release, because reacting liquid temperature is from 80 ℃ of climbeds, so stopped heating, make it be no more than 90 ℃ Yi Bian adjust reacting liquid temperature, continuation dropping on one side.After dripping end, heat, making interior temperature is 90 ℃, when interior temperature reaches 90 ℃, drips 42.0 parts of (0.3 mole) allyl group succinyl oxides through 30 minutes.When dripping, produce reaction and heat release, because reacting liquid temperature is from 90 ℃ of climbeds, so stopped heating, make it be no more than 110 ℃ Yi Bian adjust reacting liquid temperature, continuation dropping on one side.After drip finishing, Yi Bian heat, make interior temperature become 90 ℃, Yi Bian made the reaction solution slaking 1 hour, the then IR of assaying reaction liquid and hydrogen generating quantity, affirmation does not have the Si-H base residual.Then, remove toluene by underpressure distillation, obtaining as viscosity is 22100mPas, and specific refractory power is the title siloxanes of the light yellow transparent liquid of 1.4502 (25 ℃, lower same).
[embodiment 2]
Synthesizing of 1,3,5-three (succinyl oxide propyl group)-7-trimethoxysilylethylgroup group tetramethyl-ring tetrasiloxane
In the detachable flask of the 500ml with stirrer, reflux exchanger, dropping funnel and thermometer, mix 24.0 parts of (0.1 moles) 1,3,5, the toluene solution of 7-tetramethyl-ring tetrasiloxane, 24.0 parts of toluene, platinum complex wherein holds the amount that is equivalent to 0.00002 mole (being scaled platinum) with respect to 1 mole of Si-H base platinum complex.Then, when being heated to interior temperature and becoming 80 ℃, dripped 14.8 parts of (0.1 mole) vinyltrimethoxy silanes through 30 minutes.When dripping, produce reaction and heat release, because reacting liquid temperature is from 80 ℃ of climbeds, so stopped heating, make it be no more than 90 ℃ Yi Bian adjust reacting liquid temperature, continuation dropping on one side.After dripping end, heat, make interior temperature become 90 ℃, when interior temperature reaches 90 ℃, dripped 42.0 parts of (0.3 mole) allyl group succinyl oxides through 30 minutes.When dripping, produce reaction and heat release, because reacting liquid temperature is from 90 ℃ of climbeds, so stopped heating, make it be no more than 110 ℃ Yi Bian adjust reacting liquid temperature, continuation dropping on one side.After drip finishing, Yi Bian heat, making interior temperature is 90 ℃, Yi Bian made the reaction solution slaking 1 hour, the then IR of assaying reaction liquid and hydrogen generating quantity, affirmation does not have the Si-H base residual.Then, remove toluene by underpressure distillation, obtaining as viscosity is 20400mPas, and specific refractory power is the described siloxanes of title of 1.4706 light yellow transparent liquid.
[embodiment 3]
1,3-two (succinyl oxide propyl group)-5,7-two (trimethoxysilylethylgroup group) tetramethyl-ring tetrasiloxane and 1,5-two (succinyl oxide propyl group)-3, the mixture of 7-two (trimethoxysilylethylgroup group) tetramethyl-ring tetrasiloxane synthetic
In the detachable flask of the 500ml with stirrer, reflux exchanger, dropping funnel and thermometer, mix 24.0 parts of (0.1 moles) 1,3,5, the toluene solution of 7-tetramethyl-ring tetrasiloxane, 24.0 parts of toluene, platinum complex wherein holds the amount that is equivalent to 0.00002 mole (being scaled platinum) with respect to 1 mole of Si-H base platinum complex.Then, when being heated to interior temperature and becoming 80 ℃, dripped 29.6 parts of (0.2 mole) vinyltrimethoxy silanes through 30 minutes.When dripping, produce reaction and heat release, because reacting liquid temperature is from 80 ℃ of climbeds, so stopped heating, make it be no more than 90 ℃ Yi Bian adjust reacting liquid temperature, continuation dropping on one side.After dripping end, heat, make interior temperature become 90 ℃, when interior temperature reaches 90 ℃, dripped 28.0 parts of (0.2 mole) allyl group succinyl oxides through 30 minutes.When dripping, produce reaction and heat release, because reacting liquid temperature is from 90 ℃ of climbeds, so stopped heating, make it be no more than 110 ℃ Yi Bian adjust reacting liquid temperature, continuation dropping on one side.After drip finishing, Yi Bian heat, making interior temperature is 90 ℃, Yi Bian made the reaction solution slaking 1 hour, the then IR of assaying reaction liquid and hydrogen generating quantity, affirmation does not have the Si-H base residual.Then, remove toluene by underpressure distillation, obtaining as viscosity is 1030mPas, and specific refractory power is the title mixture of siloxanes of 1.4570 light yellow transparent liquid.
[comparative example 1]
Synthesizing of 1,3,5,7-four (succinyl oxide propyl group) tetramethyl-ring tetrasiloxane
In the detachable flask of the 500ml with stirrer, reflux exchanger, dropping funnel and thermometer, mix 24.0 parts of (0.1 moles) 1,3,5, the toluene solution of 7-tetramethyl-ring tetrasiloxane, 24.0 parts of toluene, platinum complex wherein holds the amount that is equivalent to 0.00002 mole (being scaled platinum) with respect to 1 mole of Si-H base platinum complex.Then, when being heated to interior temperature and becoming 90 ℃, dripped 56.0 parts of (0.4 mole) allyl group succinyl oxides through 30 minutes.When dripping, produce reaction and heat release, because reacting liquid temperature is from 90 ℃ of climbeds, so stopped heating, make it be no more than 110 ℃ Yi Bian adjust reacting liquid temperature, continuation dropping on one side.After drip finishing, heat on one side, when making interior temperature become 90 ℃, Yi Bian made the reaction solution slaking 1 hour, the then IR of assaying reaction liquid and hydrogen generating quantity, affirmation does not have the Si-H base residual.Then, add 24.0 parts of N-Methyl pyrrolidone, be heated to interior temperature and become 150 ℃, and remove the toluene that distillates, obtaining as viscosity is 2140mPas, and specific refractory power is the 50%N-methyl-2-pyrrolidone solution take the described siloxanes of title as principal constituent of 1.2331 light yellow transparent liquid.
[experimental example]
[storage stability test]
For the organo-siloxane of gained among the embodiment 1～3 and to the composition that has wherein added α as stablizer-trimethoxysilyl ethyl propionate, in the thermostatic bath of room temperature (25 ℃) or 50 ℃, preserved 1 month, confirm to have or not viscosity to increase.Promote the viscosimetric analysis before and after the test to the results are shown in table 1.
[table 1]
The above results confirmed under room temperature and high temperature, the organo-siloxane that contains succinyl oxide base and water-disintegrable silyl demonstrate through the time tackify behavior, and by cooperating stablizer can suppress its tackify.
[embodiment 4～9, comparative example 2～5]
The modulation of polyimide resin composition
Cooperate acid anhydrides, the diamine compound shown in the following table 2 take functional group's ratio as acid anhydrides/amino=1, thereby modulation polyamic acid solution, and under 150～200 ℃, make this polyamic acid solution dehydration, imidization, and then use solvent cut, obtain the polyimide varnish that principal constituent is 30 quality %.In addition, add the silicon sol of solvent dispersion type, form polyimide resin composition.
[table 2]
Acid anhydrides CHAH-2: cyclohexyl tetracarboxylic acid anhydride (following structure)
Amine compound AM-B: bisphenol A-type diamines (following structure)
Solvent NMP:N-methyl-2-pyrrolidone
Silicon sol ス ノ one テ Star Network ス PMA (Nissan Chemical Ind Ltd's system)
The physical property measurement of polyimide curing overlay film
The resin combination of gained in embodiment 4～9, the comparative example 2～5 is coated on the glass substrate, and making its thickness is 20 μ m, then carries out 150 ℃ * 1 hour drying, forms the polyimide curing overlay film.To the cured coating film of gained, measure it to checker fitness test and the pencil hardness (JISK5600) of glass baseplate.The results are shown in table 3.
[table 3]
The above-mentioned checker adaptation of ※ is to be illustrated on the surface of separating with 10 * 10 square behind the bonding scotch tape it to be peeled off, and residues in the square number of filming of base material.
By the above results as can be known, because organo-siloxane of the present invention has the function as multifunctional acid anhydrides, therefore its cross-linking density is higher than the resin that uses existing two sense acid anhydrides, and then overlay film hardness improves, in addition, owing to contain water-disintegrable silyl, therefore show the coupling effect with glass baseplate and silicon oxide, thereby improved adaptation and overlay film hardness.On the other hand, do not contain the multifunctional acid anhydrides of water-disintegrable silyl, although shown high rigidity, its cementability is poor, and for existing two sense acid anhydrides, does not also show sufficient hardness.
Claims (13)
1. by the represented cyclic organic siloxane that contains the succinyl oxide base of following general formula (1),
In the formula, R
1Be 1～10 alkyl or aryl independently of one another for carbonatoms, R
2Be 1～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another; this substituting group is selected from halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) cyanate ester based, water-disintegrable silyl, succinyl oxide base, perfluoroalkyl, polyether-based and holo-fluorine polyester, wherein take water-disintegrable silyl as substituent R
2Be more than 1, take the succinyl oxide base as substituent R
2Be more than 2; N is 3～6 integer.
2. the cyclic organic siloxane that contains the succinyl oxide base as claimed in claim 1, it is by following general formula (2) expression,
In the formula, R
1With above-mentioned same, R
4Be 1～4 alkyl independently of one another for carbonatoms, R
5The carbonatoms that can insert Sauerstoffatom for halogen atom, centre independently of one another is that 1～20 alkoxyl group or carbonatoms are 6～10 aryloxy, R
6Be 1～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another, this gets that the shape base is selected from that halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) are cyanate ester based, perfluoroalkyl, polyether-based and holo-fluorine polyester, k is 2～6 integer, m is 2～10 integer, and x is 1～3 integer; P 〉=2, q 〉=1, r 〉=0, p+q+r is 3～6 integer.
3. the cyclic organic siloxane that contains the succinyl oxide base as claimed in claim 2 is characterized in that by following general formula (3) expression,
4. the cyclic organic siloxane that contains the succinyl oxide base as claimed in claim 2 is characterized in that annular siloxane is cyclotetrasiloxane.
5. by the preparation method of the represented cyclic organic siloxane that contains the succinyl oxide base of following general formula (1), the succinyl oxide that it is characterized in that making the cyclic organohydrogensiloxanes that has at least 3 Si-H bases in 1 molecule, has the compound that contains water-disintegrable silyl of carbon-to-carbon unsaturated bond and have a carbon-to-carbon unsaturated bond carries out hydrosilylation in the presence of platinum and/or platinum complex
In the formula, R
1Be 1～10 alkyl or aryl independently of one another for carbonatoms, R
2Be 1～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another; this substituting group is selected from halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) cyanate ester based, water-disintegrable silyl, succinyl oxide base, perfluoroalkyl, polyether-based and holo-fluorine polyester, wherein take water-disintegrable silyl as substituent R
2Be more than 1, take the succinyl oxide base as substituent R
2Be more than 2; N is 3～6 integer.
6. the preparation method who contains the cyclic organic siloxane of succinyl oxide base as claimed in claim 5; it is characterized in that; make and have part Si-H base contained in the cyclic organohydrogensiloxanes of at least 3 Si-H bases in 1 molecule; with the compound that contains water-disintegrable silyl with carbon-to-carbon unsaturated bond and as required be used as the substituent halogen atom that is selected from; vinyl; epoxy group(ing); thiiranes group; (methyl) acryl; sulfydryl; different (sulphur) is cyanate ester based; perfluoroalkyl; at least a replacement or unsubstituted unsaturated hydrocarbon compound in polyether-based and the holo-fluorine polyester carry out hydrosilylation reactions in the presence of platinum and/or platinum complex, then make Si-H base remaining in the cyclic organohydrogensiloxanes of gained carry out hydrosilylation reactions with the succinyl oxide that contains carbon-to-carbon unsaturated bond.
7. the preparation method who contains the cyclic organic siloxane of succinyl oxide base as claimed in claim 6, the compound that contains water-disintegrable silyl that it is characterized in that having carbon-to-carbon unsaturated bond is represented by following formula,
In the formula, R
1With above-mentioned same, R
4Be 1～4 alkyl independently of one another for carbonatoms, R
5The carbonatoms that can insert Sauerstoffatom for halogen atom, centre independently of one another is that 1～20 alkoxyl group or carbonatoms are 6～10 aryloxy, and m1 is 0～8 integer, and x is 1～3 integer;
The unsaturated hydrocarbon compound that adds as required is represented by following formula,
CH
2＝CH-R
6a
In the formula, R
6aBe 1～8 alkyl for hydrogen atom maybe can have substituent carbonatoms, and this substituting group is selected from that halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) are cyanate ester based, perfluoroalkyl, polyether-based and holo-fluorine polyester;
The succinyl oxide that contains carbon-to-carbon unsaturated bond is represented by following formula,
In the formula, k1 is 0～4 integer;
And obtain by the represented cyclic organic siloxane that contains the succinyl oxide base of following general formula (2)
In the formula, R
1, R
4, R
5, x as mentioned above; R
6Be 3～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another, and this substituting group is selected from, and halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) are cyanate ester based, perfluoroalkyl, polyether-based and holo-fluorine polyester, k is 2～6 integer, m is 2～10 integer, and x is 1～3 integer; P 〉=2, q 〉=1, r 〉=0, p+q+r is 3～6 integer.
8. the preparation method who contains the cyclic organic siloxane of succinyl oxide base as claimed in claim 7, the compound that contains water-disintegrable silyl that it is characterized in that having carbon-to-carbon unsaturated bond is vinyltrimethoxy silane, the succinyl oxide that contains carbon-to-carbon unsaturated bond is the allyl group succinyl oxide, and obtain the represented cyclic organic siloxane that contains succinyl oxide of following general formula (3)
In the formula, p ' 〉=2, q ' 〉=1, p '+q ' is 3～6 integer.
9. organosiloxane composition, its contain just like each described cyclic organic siloxane that contains the succinyl oxide base of claim 1～4 and as the trapping agent of the compound that contains active hydrogen by the represented α of following general formula (4)-silyl aliphatic ester compound
In the formula, R
7For the carbonatoms that does not replace or replace is 1～20 alkyl, the carbonatoms that do not replace or replace is 5～20 cycloalkyl or do not get shape or the carbonatoms of replacement is 6～20 aryl, R
8Be hydrogen atom or methyl, R
9The carbonatoms that is independently not replacement or replacement is 1～4 alkyl, R
10The carbonatoms that is independently not replacement or replacement is 1～4 alkyl; Y is 1～3 integer.
10. contain the hot curing resin composition by the represented cyclic organic siloxane that contains the succinyl oxide base of following general formula (1).
In the formula, R
1Be 1～10 alkyl or aryl independently of one another for carbonatoms, R
2Be 1～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another; this substituting group is selected from halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) cyanate ester based, water-disintegrable silyl, succinyl oxide base, perfluoroalkyl, polyether-based and holo-fluorine polyester, wherein take water-disintegrable silyl as substituent R
2Be more than 1, take the succinyl oxide base as substituent R
2Be more than 2; N is 3～6 integer.
11. hot curing resin composition as claimed in claim 10 wherein contains the organopolysiloxane of succinyl oxide base by following general formula (2) expression,
In the formula, R
1With above-mentioned same, R
4Be 1～4 alkyl independently of one another for carbonatoms, R
5The carbonatoms that can insert Sauerstoffatom for halogen atom, centre independently of one another is that 1～20 alkoxyl group or carbonatoms are 6～10 aryloxy, R
6Be 1～10 alkyl for hydrogen atom maybe can have substituent carbonatoms independently of one another, this substituting group is selected from that halogen atom, vinyl, epoxy group(ing), thiiranes group, (methyl) acryl, sulfydryl, different (sulphur) are cyanate ester based, perfluoroalkyl, polyether-based and holo-fluorine polyester, k is 2～6 integer, m is 2～10 integer, and x is 1～3 integer; P 〉=2, q 〉=1, r 〉=0, p+q+r is 3～6 integer.
12. hot curing resin composition as claimed in claim 11 wherein contains the organopolysiloxane of succinyl oxide base by following general formula (3) expression,
In the formula, p ' 〉=2, q ' 〉=1, p '+q ' is 3～6 integer.
13. such as each described hot curing resin composition of claim 10～12, wherein above-mentioned hot curing resin composition contains polyamide resin or polyimide resin.
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| CN114672025A (en) * | 2022-04-20 | 2022-06-28 | 波米科技有限公司 | Heterocycle-containing POSS siloxane compound and preparation method and application thereof |
| CN115073742A (en) * | 2022-07-04 | 2022-09-20 | 山东共聚有机硅技术研究院有限公司 | Foaming carboxylated polyether silicon oil, preparation method thereof and no-clean foaming alcohol hand sanitizer containing foaming carboxylated polyether silicon oil |
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