CN102181059B - Carboxyl-containing siloxane and high-temperature-resistant epoxy resin compound prepared from same and preparation method thereof - Google Patents
Carboxyl-containing siloxane and high-temperature-resistant epoxy resin compound prepared from same and preparation method thereof Download PDFInfo
- Publication number
- CN102181059B CN102181059B CN201110132948.9A CN201110132948A CN102181059B CN 102181059 B CN102181059 B CN 102181059B CN 201110132948 A CN201110132948 A CN 201110132948A CN 102181059 B CN102181059 B CN 102181059B
- Authority
- CN
- China
- Prior art keywords
- carboxyl
- siloxanes
- epoxy resin
- phthalic acid
- chloropropyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title abstract description 19
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 title description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 11
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- -1 carboxyl siloxanes Chemical class 0.000 claims description 103
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000004593 Epoxy Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000002798 polar solvent Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000031709 bromination Effects 0.000 claims description 5
- 238000005893 bromination reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- BPIPAYFDIOQQNN-UHFFFAOYSA-N [O]C(=O)c1ccc(cc1)C(O)=O Chemical compound [O]C(=O)c1ccc(cc1)C(O)=O BPIPAYFDIOQQNN-UHFFFAOYSA-N 0.000 claims description 2
- HQTRCJVIHPTNAF-UHFFFAOYSA-N [O]C(=O)c1ccccc1C(O)=O Chemical compound [O]C(=O)c1ccccc1C(O)=O HQTRCJVIHPTNAF-UHFFFAOYSA-N 0.000 claims description 2
- ACMRDDIMJKWQNA-UHFFFAOYSA-N benzoic acid;carbon dioxide Chemical compound O=C=O.OC(=O)C1=CC=CC=C1 ACMRDDIMJKWQNA-UHFFFAOYSA-N 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract 2
- 150000002739 metals Chemical class 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 235000011167 hydrochloric acid Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229940106691 bisphenol a Drugs 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- DTOOTUYZFDDTBD-UHFFFAOYSA-N 3-chloropropylsilane Chemical compound [SiH3]CCCCl DTOOTUYZFDDTBD-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229940043232 butyl acetate Drugs 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000006166 lysate Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000003022 phthalic acids Chemical class 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 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
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OFQCQIGMURIECL-UHFFFAOYSA-N 2-[2-(diethylamino)ethyl]-2',6'-dimethylspiro[isoquinoline-4,4'-oxane]-1,3-dione;phosphoric acid Chemical compound OP(O)(O)=O.O=C1N(CCN(CC)CC)C(=O)C2=CC=CC=C2C21CC(C)OC(C)C2 OFQCQIGMURIECL-UHFFFAOYSA-N 0.000 description 1
- KEZMLECYELSZDC-UHFFFAOYSA-N 3-chloropropyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(OCC)CCCCl KEZMLECYELSZDC-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- YAVVGPBYBUYPSR-UHFFFAOYSA-N benzene;oxygen Chemical compound [O].C1=CC=CC=C1 YAVVGPBYBUYPSR-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- GBSIYTILHVLXDE-UHFFFAOYSA-N dichloro-(4-chlorobutyl)-methylsilane Chemical compound C[Si](Cl)(Cl)CCCCCl GBSIYTILHVLXDE-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical group CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- KISVAASFGZJBCY-UHFFFAOYSA-N methyl undecenate Chemical compound COC(=O)CCCCCCCCC=C KISVAASFGZJBCY-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention discloses carboxyl-containing siloxane, which is polymethyl-[3-(carboxyl oxyphenylcarbamoyl) propyl] siloxane. In the structural formula of the carboxyl-containing siloxane, two or more phthalic acid monoester bonds are formed among polymer molecular chains, and the number-average molecular weight of the carboxyl-containing siloxane is 870-1,270. A composition formula of a copolymer consisting of the carboxyl-containing siloxane and epoxy resin consists of 100 parts of carboxyl-containing siloxane, 50-120 parts of epoxy resin and 0-5 parts of silane coupling agent. The copolymer consisting of the carboxyl-containing siloxane and the epoxy resin with high heat resistance and better flexibility as well as high adhesive property with materials such as metals and the like by curing the materials at the temperature between 100 DEG C and 200 DEG C for 1-8 hours. The invention discloses a preparation method of the carboxyl-containing siloxane.
Description
Technical field
The present invention relates to contain the high-temperature-resistant epoxy resin composition of carboxyl siloxanes and its composition.
Background technology
Siloxanes and polysiloxane are the special organic polymer synthetic materialss of a kind of performance, have very important status in modern synthetic materials.Siloxanes and polysiloxane have the character of many uniquenesses, such as thermostability, oxidation-resistance, snappiness, lower surface tension, gas permeability, excellent electric property, hydrophobic nature, biologically inert, and moisture resistance etc., these characteristics make siloxanes and polysiloxane obtain using very widely.But its mechanical property is relatively poor, and sticking power is relatively poor, the more high drawbacks limit of production cost its use in specific application area.Main chain or side-chain radical to siloxanes carry out modification, or are used with other polymkeric substance, can overcome some shortcomings of self, improve over-all properties, to adapt to the requirement of industrial application.
Containing the carboxyl siloxanes is a kind of of modified siloxane, has certain purposes, its preparation method has multiple, as the people such as A.Bachrach with the polydimethylsiloxane addition on the two keys of the C=C of unsaturated acid, amine or alcohol, prepare have carboxyl, the polymkeric substance of amino or hydroxyl.These polymkeric substance can with the functional group reactions that is fit in the drug molecule, can be as the carrier of some medicines [referring to BACHRACH A, ZILKHA A. Eur Polym J, 1984,20 (5): 493-500.]; Open the bright grade of pier under Red copper oxide/Tetramethyl Ethylene Diamine catalysis, ethyl propenoate or vinyl cyanide and dimethyl dichlorosilane (DMCS) are carried out addition reaction of silicon with hydrogen, generate corresponding ester group chlorosilane, rear and octamethylcyclotetrasiloxane (D4) copolymerization of hydrolysis, make Carboxyl Modified Polydimethylsiloxane through concentrated hydrochloric acid hydrolysis again, they also carry out the addition of silicon hydrogen with containing hydrogen silicone oil with the 1-methyl undecylenate, then carry out letex polymerization with D4 and obtain the silicone oil of carboxyl emulsion, be used for fabric finishing agent [referring to: a pier is bright, Yan Weilong. organosilicon material and application, 1999, (6): 7-10; It is bright to open pier, Jiang Xiqun, Yang Changzheng. Chinese invention patent, ZL 200410041395.6]; Peace autumn wind etc. with reaction preparation carboxyl siloxanes such as succinyl oxides, is used for the mellowing [referring to peace autumn wind, Lee Lim Saeng, Huang Liangxian, etc. functional polymer, 2001,14(2), 163-168] of fabric with aminosiloxane.
Aspect organosilicon-epoxide resin alloy or copolymerization system, research emphasis is abundant high strength and adhesion property in conjunction with organosilyl resistance to elevated temperatures and toughness and Resins, epoxy, to obtain having the high temperature resistant cured product of certain toughness, be used for high temperature resistant linking agent and coating etc.Because the consistency of organosilicon and Resins, epoxy is very poor, need add during blending modification method the 3rd component [referring to Cheng Bin, Shang Xiaoqin. thermosetting resin, 1991,5(3): 7; Chu Jiurong. the polymer circular, 1999,6(2): 66]; The polysiloxane that contains alkane (benzene) oxygen base with the Resins, epoxy reaction obtain having good heat resistance, toughness and sticking power contain organosilyl Resins, epoxy, and the poor-performing of water-fast, the acid of the Si-O-C key that wherein contains or alkali; The silane that contains phenolic group reacts with bisphenol A type epoxy resin, with amine or anhydride-cured, can obtain the good cured resin of thermotolerance, water tolerance and toughness, but the silane preparation that contains phenolic group is difficult; The sily oxide and the same bisphenol-a reaction of polysiloxane that contain chloromethyl or chloropropyl, same epichlorohydrin reaction again can obtain containing organosilyl Resins, epoxy [referring to US Patent No. 2997458; Chinese patent ZL 200510041071.7], wherein, two chloropropyl silane end-cappers preparations are complicated, can produce certain by product simultaneously in epoxidation process.
Summary of the invention
This patent provides to contain the siloxanes of chloropropyl and a kind of carboxyl siloxanes that contains of phthalic acid reaction preparation, and provide a kind of described carboxyl siloxanes that contains with the composite formula of Resins, epoxy, have excellent thermotolerance and flexility preferably after composition solidifies, have good adhesiveproperties with the material such as metal.
Basic thought of the present invention is: in non-proton property polar solvent, the siloxanes by containing chloropropyl and excessive phthalic acid carry out condensation reaction and prepare a kind of carboxyl siloxanes that contains.Thisly contain the carboxyl siloxanes and bisphenol A type epoxy resin can react and crosslinking curing, form and have excellent thermotolerance and the cross-linked resin of flexility preferably, have good adhesiveproperties with the material such as metal.
Technical scheme of the present invention is as follows:
A kind of carboxyl siloxanes that contains, it is poly-methyl-[3-(carboxyl benzene carbonyl oxygen base) propyl group] siloxanes, it has following structural formula:
Be contain two or more phthalic acid monoester bond in the middle of the polymer molecular chain contain the carboxyl siloxanes, its number-average molecular weight is 870-1270.
The above-mentioned carboxyl siloxanes that contains, described carboxyl benzene carbonyl oxygen base are the mixtures of 2-carboxyl phenyl carbonyl oxygen base, 3-carboxyl phenyl carbonyl oxygen base or 4-carboxyl phenyl carbonyl oxygen base or above-mentioned both or three's arbitrary proportion.
A kind ofly prepare the above-mentioned method that contains the carboxyl siloxanes, it comprises the following steps:
(1) in aprotic polar solvent, in the presence of the organic amine acid binding agent, chloropropyl siloxanes hydrolyzate and phthalic acid are carried out condensation reaction under the phase-transfer catalyst effect, what obtain containing in the middle of the molecular chain two or more phthalic acid monoester bond contains the carboxyl siloxanes, temperature of reaction is 140～150 ℃, reaction times is 8～20h, and wherein, the amount of substance of phthalic acid is 2～3 times of chloropropyl amount of substance in the chloropropyl siloxanes;
(2) reaction mixture with step (1) gained carries out suction filtration, organic ammonium salt except the dereaction generation, rotary evaporation goes out aprotic polar solvent, and then with the acidifying of gained mixture, washing, drying, use again suitable organic solvent dissolution product, suction filtration, dried filtrate is revolved and is obtained the described carboxyl siloxanes that contains after steaming desolventizing.
The reaction formula of above-mentioned method for making is as follows:
Above-mentioned preparation contains the method for carboxyl siloxanes, described solvent is aprotic polar solvent, it can increase speed of response, this aprotic polar solvent can be N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) etc., its consumption to be making system become the homogeneous phase solution state to be advisable under temperature of reaction, are 3.2～5.6 times of phthalic acid quality.
Above-mentioned preparation contains the method for carboxyl siloxanes, and the described organic amine acid binding agent of step 1 is triethylamine or tri-n-butylamine, and its consumption is 1.3 times of amount of substance of chloropropyl in the chloropropyl siloxanes hydrolyzate.
Above-mentioned preparation contains the method for carboxyl siloxanes, and the described phthalic acid of step 1 can be terephthalic acid, phthalic acid or m-phthalic acid, or the mixture of the arbitrary proportion of their two kinds or three kinds.The reactive behavior of these phthalic acids does not have obvious difference.
Above-mentioned preparation contains the method for carboxyl siloxanes, and the described phase-transfer catalyst of step 1 is bromination tetra-n-butyl ammonium, and its consumption is 0.17～1% of reactant (comprising solvent) total mass.
Above-mentioned preparation contains the method for carboxyl siloxanes, and the described organic solvent of step 2 can be ethyl acetate or butylacetate.
In the step of above-mentioned method for making (1), described chloropropyl siloxanes hydrolyzate can be through containing chloropropyl silane hydrolyzate and get, namely under a small amount of hydrochloric acid catalysis, gamma-chloropropylmethyldimethoxysilane, γ-chloropropyl methyldiethoxysilane or γ-chloropropyl dimethyl dichlorosilane (DMCS) or above both mixture are hydrolyzed.Reaction mixture with gained separates with separating funnel again, and extremely neutral with distilled water and sodium bicarbonate aqueous solution washing again, underpressure distillation desolvation after the drying makes chloropropyl siloxanes hydrolyzate.
Reaction equation is as follows:
Wherein, R be-Cl ,-OCH
3,-OCH
2CH
3
The chloropropyl siloxanes hydrolyzate that makes may be ring texture, and the structural unit number is mainly 3～5, also might be the linear body of molecular weight, and its structure does not affect further reaction and invention effect, is referred to as chloropropyl siloxanes hydrolyzate here.
The reaction of step (1) is chloropropyl and the phthalic acid reaction in the chloropropyl siloxane structure unit, in order to make more unreacted carboxyl groups is arranged in the reaction product, when feeding intake, make carboxyl excessive, the control phthalic acid with the ratio of the amount of substance of chloropropyl between 2:1～3:1.
In the step (2) of above-mentioned method for making, when product is separated, remove by filter first the organic amine salt hydrochlorate of generation, then use the Rotary Evaporators removal of solvent under reduced pressure.Be that about 5% hydrochloric acid carries out acidifying to the gained mixture with massfraction again, to remove the organic amine with the carboxyl combination, then be washed with distilled water to neutrality (the water pH=6 after the washing～7), at 100 ℃ of lower baking 1h, add ethyl acetate or butylacetate lysate, after suction filtration is removed insolubles, add anhydrous Na
2SO
4Drying is filtered, and the desolventizing of filtrate rotary evaporation obtains the described carboxyl siloxanes that contains.
Contain carboxyl of the present invention containing in the carboxyl siloxanes, can react with the epoxy group(ing) in the Resins, epoxy and obtain crosslinking curing, and the resin after crosslinked has excellent thermotolerance and flexility preferably, has good adhesiveproperties with the material such as metal.
The above-mentioned composite formula that contains carboxyl siloxanes and epoxy resin copolymer is: contain 100 parts of carboxyl siloxanes, 50～120 parts of Resins, epoxy and 0～5 part of composition of silane coupling agent, they solidify 1～8h under 100～200 ℃ of conditions, namely get have excellent thermotolerance and preferably flexility, and the material such as metal have a good adhesiveproperties contain carboxyl siloxanes and epoxy resin copolymer cross-linked resin.
The above-mentioned composite formula that contains carboxyl siloxanes and epoxy resin copolymer, described Resins, epoxy can be bisphenol A type epoxy resins, and its oxirane value is between the 0.2-0.6, and preferred oxirane value is between the 0.3-0.55.
The above-mentioned composite formula that contains carboxyl siloxanes and epoxy resin copolymer, described silane coupling agent can be 3-aminopropyl triethoxysilane (KH-550) or 3-(2, the 3-glycidoxy) propyl trimethoxy silicane (KH-560), they play the tackifier effect.
Technological merit of the present invention is:
Method for making of the present invention with some be simple and easy to raw material, prepared through conventional reaction and to have contained the carboxyl siloxanes, need not to use the expensive pair of raw material such as chloropropyl silane end-cappers.
Method for making of the present invention is to introduce the aromatic acid group through the condensation esterification on the side chain of siloxanes, and carboxyl can be with Resins, epoxy generation crosslinking reaction.Because product is the siloxanes of many carboxyl functional groups, so product is during with epoxy resin cure, and the consumption of Resins, epoxy can be regulated in wider scope according to requirements.
Have benefited from the chemical structure that contains the carboxyl siloxanes and the character of the method for the invention preparation, such as part annular siloxane structure, aromatic ester groups etc., and effectively combine the fundamental property of Resins, epoxy, have excellent thermotolerance and flexility preferably after composition solidifies, have good adhesiveproperties with the material such as metal.
The range of application of composition of the present invention is very extensive, as can being used in the application places of ordinary epoxy resin, as is applied to many Application Areass such as seal gum, printed circuit board (PCB) or moulding material, electronic encapsulation material and epoxypaint.In addition, the composition of this siloxanes and Resins, epoxy has good flexility and adhesiveproperties and the excellent resistance to elevated temperatures good to metallic aluminium, stainless steel etc., therefore also be specially adapted to the occasion that those all have higher requirements to flexility and adhesiveproperties simultaneously, or some use under hot environment.
Description of drawings
Fig. 1: thermogravimetric (TG) curve of the cross-linked resin after embodiment 5 compositions solidify under the nitrogen atmosphere.
Embodiment
Below by some specific embodiments the specific embodiment of the invention is further elaborated.
Synthesizing of embodiment 1. chloropropyl siloxanes hydrolyzates
In 1000 ml four-necked bottles, add 200 ml distilled water, adding several concentrated hydrochloric acids in the four-necked bottle, to make pH value of water solution be 2, stir lower, by dropping funnel to the mixing solutions that wherein drips 200 ml gamma-chloropropylmethyldimethoxysilanes and 200 ml ether, dropping is finished about 30 min, dropwise in stirring at room and react 2 h, be warmed up to again 40 ℃ and continue reaction 2.5 h.Reaction is left standstill after finishing, and tells organic layer, uses respectively 20ml extracted with diethyl ether water layer twice, and merges with organic layer.Organic layer washs to neutrality with distilled water and sodium bicarbonate, uses an amount of anhydrous Na again
2SO
4Drying, placement is spent the night.Dried organic layer is filtered, and filtrate is transferred in the 500 ml round-bottomed flasks, and heating steams ether, obtains having the chloropropyl siloxanes hydrolyzate of certain viscosity, and quality is 155.20 g.
Through the Switzerland DPX300 of BRUKER company type nmr determination, chloropropyl siloxanes hydrolyzate compound
1H NMR is: chemical shift δ: 3.55 ppm(8H ,-CH
2-Cl), 1.84 ppm(8H ,-CH
2-), 0.72 ppm(8H ,-CH
2-Si), 0.17 ppm(12H, Si-CH
3), prove chloropropyl siloxanes hydrolyzate.
Embodiment 2. contains the preparation I of carboxyl siloxanes
Add 99.68 g terephthalic acids, 320 g DMFs, 30.36 g triethylamines in 1000 ml four-necked bottles, heated and stirred is to fully dissolving.Be warming up to 130 ℃, add 5 g bromination tetra-n-butyl ammoniums, after stirring, drip 27.33 g chloropropyl siloxanes hydrolyzates with dropping funnel, at 140～150 ℃ of lower reaction 8 h.After having reacted, remove by filter the organic ammonium salt of generation, then removing most DMF solvents with Rotary Evaporators decompression, is that 5% hydrochloric acid carries out acidifying to the gained mixture with concentration again, to remove the organic amine with the carboxyl combination, then be washed with distilled water to neutrality (the water pH=6 after the washing～7), at 100 ℃ of lower baking 1h, add 300 mL acetic acid ethyl dissolution products, after suction filtration is removed insolubles, add anhydrous Na
2SO
4Dried filtrate, last rotary evaporation desolventizing obtains containing carboxyl siloxanes 30.91g, and its number-average molecular weight is 920.
Through the Switzerland DPX300 of BRUKER company type nmr determination, compound: δ: 8.00ppm(16H, m, Ph-H), 4.19ppm(8H, s ,-CH
2-O-), 1.74ppm(8H, s ,-CH
2-), 0.62ppm(8H, s ,-CH
2-Si), 0.10ppm(12H, s, Si-CH
3), prove and contain the carboxyl siloxanes
Use the 0.1mol/L standard solution of sodium hydroxide, titration makes contains the carboxyl siloxanes, and the carboxyl-content that records product is 0.34mol/100g.
Embodiment 3. contains the preparation II of carboxyl siloxanes
Add 120 g m-phthalic acids, 450 g methyl-sulphoxides, 30.36g triethylamine in the 1000ml four-necked bottle, heated and stirred is to fully dissolving.Be warming up to 130 ℃, add 3 g bromination tetra-n-butyl ammoniums, after stirring, drip 27.33 g chloropropyl siloxanes hydrolyzates with dropping funnel, at 140～150 ℃ of lower reaction 10 h.After having reacted, remove by filter the organic ammonium salt of generation, then remove most methyl-sulphoxides with the Rotary Evaporators decompression, be that 5% hydrochloric acid carries out acidifying to the gained mixture with concentration again, to remove the organic amine with the carboxyl combination, then be washed with distilled water to neutrality (the water pH=6 after the washing～7), at 100 ℃ of lower baking 1h, add the butylacetate lysate of 350mL, after suction filtration is removed insolubles, add anhydrous Na
2SO
4Dried filtrate, last rotary evaporation desolventizing obtains containing carboxyl siloxanes 25.54 g, and its number-average molecular weight is 870.
Use the 0.1mol/L standard solution of sodium hydroxide, titration makes contains the carboxyl siloxanes, and the carboxyl-content that records product is 0.31mol/100g.
Embodiment 4. contains the preparation III of carboxyl siloxanes
Add 80 g phthalic acids, 450 g N,N-dimethylacetamide, 30.36g triethylamine in the 1000ml four-necked bottle, heated and stirred is to fully dissolving.Be warming up to 130 ℃, add 1 g bromination tetra-n-butyl ammonium, after stirring, drip 27.33 g chloropropyl siloxanes hydrolyzates with dropping funnel, at 140～150 ℃ of lower reaction 20 h.Repeat embodiment 2 operations, obtain containing carboxyl siloxanes 24.24g, its number-average molecular weight is 1270, and the carboxyl-content of product is 0.29mol/100g.
Embodiment 5. application experiments 1.
In clean tetrafluoroethylene mould, take by weighing in proportion that embodiment 2 obtains contain the carboxyl siloxanes, (blue star Wuxi resin processing plant produces WSR618 type Resins, epoxy, oxirane value 0.51), and an amount of solvent DMF, stir and make its whole dissolvings, take a morsel, thin and be coated in equably the end on the stainless steel substrates surface of crossing and cleaning up with ethanol (or acetone) with sand papering, the alignment of the cemented surface of two stainless steel substrates, compress, clamp with iron clamp.The residue sample is retained in the tetrafluoroethylene mould.Baking oven is put in above-mentioned stainless steel test piece and tetrafluoroethylene mould, first at 150 ℃ of lower 1h that solidify, at 180 ℃ of lower 4h that solidify, taken out after the cooling again.Sample in the tetrafluoroethylene mould is cut the making dumbbell plate.Carry out performance test.Prescription and correlated performance see Table one.
Resin carries out thermogravimetric (TG) analysis after solidifying in the tetrafluoroethylene mould, and thermogravimetric curve is seen accompanying drawing 1 as a result.As can be seen from Figure 1, in the analytic process, composition of the present invention does not almost have mass loss in 0～350 ℃, and during temperature to 700 ℃, mass loss rate is 35.88%, has good resistance toheat.
Embodiment 6～14.
Application experiment 2～10.
Change composite formula, repeat embodiment 5, prescription and correlated performance see Table one.
Table one contains prescription and the performance of carboxyl siloxanes and composition epoxy resin
Claims (10)
1. one kind contains the carboxyl siloxanes, it is characterized in that: it is poly-methyl-[3-(carboxyl benzene carbonyl oxygen base) propyl group] siloxanes, and it has following structural formula:
Be contain two or more phthalic acid monoester bond in the middle of the polymer molecular chain contain the carboxyl siloxanes, its number-average molecular weight is 870-1270.
2. the carboxyl siloxanes that contains according to claim 1 is characterized in that: described carboxyl benzene carbonyl oxygen base is the mixture of 2-carboxyl phenyl carbonyl oxygen base, 3-carboxyl phenyl carbonyl oxygen base or 4-carboxyl phenyl carbonyl oxygen base or above-mentioned both or three's arbitrary proportion.
3. one kind prepares the method that contains the carboxyl siloxanes claimed in claim 1, it is characterized in that it comprises the following steps:
(1) in aprotic polar solvent, in the presence of the organic amine acid binding agent, chloropropyl siloxanes hydrolyzate and phthalic acid are carried out condensation reaction under the phase-transfer catalyst effect, what obtain containing in the middle of the molecular chain two or more phthalic acid monoester bond contains the carboxyl siloxanes, temperature of reaction is 140～150 ℃, reaction times is 8～20h, and wherein, the amount of substance of phthalic acid is 2～3 times of chloropropyl amount of substance in the chloropropyl siloxanes;
(2) reaction mixture with step (1) gained carries out suction filtration, organic ammonium salt except the dereaction generation, rotary evaporation goes out aprotic polar solvent, and then with the acidifying of gained mixture, washing, drying, use again the organic solvent dissolution product, suction filtration, dried filtrate is revolved and is obtained the described carboxyl siloxanes that contains after steaming desolventizing.
4. above-mentioned preparation contains the method for carboxyl siloxanes according to claim 3, and it is characterized in that: described aprotic polar solvent is DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO), and its consumption is 3.2～5.6 times of phthalic acid quality.
5. preparation according to claim 3 contains the method for carboxyl siloxanes, it is characterized in that: the described organic amine acid binding agent of step 1 is triethylamine or tri-n-butylamine, and its consumption is 1.3 times of amount of substance of chloropropyl in the chloropropyl siloxanes hydrolyzate.
6. preparation according to claim 3 contains the method for carboxyl siloxanes, it is characterized in that: the described phthalic acid of step 1 is terephthalic acid, phthalic acid or m-phthalic acid, or the mixture of the arbitrary proportion of their two kinds or three kinds.
7. preparation according to claim 3 contains the method for carboxyl siloxanes, it is characterized in that: the described phase-transfer catalyst of step 1 is bromination tetra-n-butyl ammonium, and its consumption is 0.17～1% of reactant total mass.
8. composition that contains carboxyl siloxanes and epoxy resin copolymer claimed in claim 1, it is characterized in that: it forms by containing 0～5 part of 100 parts of carboxyl siloxanes, 50～120 parts of Resins, epoxy and silane coupling agent, they solidify 1～8h under 100～200 ℃ of conditions, namely get have thermotolerance and with the material adhesive performance such as metal contain carboxyl siloxanes and epoxy resin copolymer.
9. the composition that contains carboxyl siloxanes and epoxy resin copolymer according to claim 8, it is characterized in that: described Resins, epoxy is bisphenol A type epoxy resin, its oxirane value is between the 0.2-0.6.
10. the composition that contains carboxyl siloxanes and epoxy resin copolymer according to claim 8, it is characterized in that: described silane coupling agent is 3-aminopropyl triethoxysilane or 3-(2, the 3-glycidoxy) propyl trimethoxy silicane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110132948.9A CN102181059B (en) | 2011-05-23 | 2011-05-23 | Carboxyl-containing siloxane and high-temperature-resistant epoxy resin compound prepared from same and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110132948.9A CN102181059B (en) | 2011-05-23 | 2011-05-23 | Carboxyl-containing siloxane and high-temperature-resistant epoxy resin compound prepared from same and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102181059A CN102181059A (en) | 2011-09-14 |
| CN102181059B true CN102181059B (en) | 2013-03-20 |
Family
ID=44567367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110132948.9A Expired - Fee Related CN102181059B (en) | 2011-05-23 | 2011-05-23 | Carboxyl-containing siloxane and high-temperature-resistant epoxy resin compound prepared from same and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102181059B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103215816B (en) * | 2012-01-20 | 2015-05-06 | 中国中化股份有限公司 | Organosilicone softening agent and preparation method |
| CN103215817B (en) * | 2012-01-20 | 2015-03-18 | 中国中化股份有限公司 | Organosilicone softening agent having block structure and preparation method |
| CN105442326B (en) * | 2015-12-29 | 2017-12-01 | 陕西科技大学 | A kind of nano combined uvioresistant organic coating finishing agent and preparation method thereof |
| CN105694044B (en) * | 2016-04-11 | 2019-10-01 | 南京大学 | A kind of polysiloxanes of carboxyl functional and preparation method thereof |
| CN106118358B (en) * | 2016-06-29 | 2019-02-12 | 广西凯威铁塔有限公司 | A kind of fire-retardant artificial tree bark and preparation method thereof |
| CN106010116B (en) * | 2016-06-29 | 2019-02-12 | 广西凯威铁塔有限公司 | A kind of anti-aging artificial tree bark and preparation method thereof |
| CN111647370A (en) * | 2020-05-25 | 2020-09-11 | 湖北航泰科技有限公司 | Adhesive film for bonding rubber materials and using method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2997458A (en) * | 1958-10-03 | 1961-08-22 | Westinghouse Electric Corp | Epoxy-substituted organosilicone compounds |
| JP3020324B2 (en) * | 1990-11-29 | 2000-03-15 | オットー・ボック・オルトペディッシェ・インデュストリエ・ベジッツ−ウント・フェアバルトゥンクス−コマンディットゲゼルシャフト | Prostheses without joints |
| CN1712425A (en) * | 2005-07-18 | 2005-12-28 | 南京大学 | Production of Redix with siloxane structural unit |
| CN101472978A (en) * | 2006-06-30 | 2009-07-01 | 博士伦公司 | Carboxylic siloxanyl monomers with pendant polymerizable groups |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0320324A (en) * | 1989-02-03 | 1991-01-29 | Sumitomo Durez Co Ltd | Silicone-modified epoxy resin |
-
2011
- 2011-05-23 CN CN201110132948.9A patent/CN102181059B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2997458A (en) * | 1958-10-03 | 1961-08-22 | Westinghouse Electric Corp | Epoxy-substituted organosilicone compounds |
| JP3020324B2 (en) * | 1990-11-29 | 2000-03-15 | オットー・ボック・オルトペディッシェ・インデュストリエ・ベジッツ−ウント・フェアバルトゥンクス−コマンディットゲゼルシャフト | Prostheses without joints |
| CN1712425A (en) * | 2005-07-18 | 2005-12-28 | 南京大学 | Production of Redix with siloxane structural unit |
| CN101472978A (en) * | 2006-06-30 | 2009-07-01 | 博士伦公司 | Carboxylic siloxanyl monomers with pendant polymerizable groups |
Non-Patent Citations (1)
| Title |
|---|
| 安秋凤 等.官能团转化法制备羧基硅油及其柔软性能研究.《功能高分子学报》.2001,第14卷(第2期),163-168. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102181059A (en) | 2011-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102181059B (en) | Carboxyl-containing siloxane and high-temperature-resistant epoxy resin compound prepared from same and preparation method thereof | |
| CN101724226B (en) | Modified hot setting resin and preparation method thereof | |
| CN101848957B (en) | Polysiloxane, method for producing the same, and method for producing cured product of the same | |
| CN102942585B (en) | Succinic anhydride group containing cyclic organosiloxane, preparation thereof, organosiloxane composition and thermosetting resin composition | |
| KR101480587B1 (en) | Novel silphenylene skeleton containing silicone type polymer compound and method for producing the same | |
| CN103665863B (en) | Containing the compositions of thermosetting resin of double-tower type epoxy silsesquioxane | |
| CN101260190B (en) | Multiple functionality degree polysiloxane coupling agent and preparation method thereof | |
| CN104829841B (en) | A kind of organosilicon macromolecule material and preparation method thereof | |
| CN111253575A (en) | Preparation method and application of high-refractive-index phenyl methyl amino silicone resin | |
| CN102584884A (en) | Benzoxazine monomer, benzoxazine precursor and low-dielectric benzoxazine resin | |
| CN102492116A (en) | Epoxy resin and polyhedral silsesquioxane nano hybrid material and its preparation method | |
| CN101475731A (en) | Epoxy resin composite material added with modified polysiloxane and preparation thereof | |
| CN101638517B (en) | Organosilicon resin composition | |
| WO2011129935A1 (en) | Copolymers and ceramic-carbonaceous solids from divinyl aromatic ether oligomers and divinyl carborane siloxane | |
| US11299593B2 (en) | Fluorosilicone resin and preparation method thereof | |
| CN113583216A (en) | Bio-based epoxy resin containing silicon-oxygen bond and preparation and application methods thereof | |
| CN105778096B (en) | The manufacturing method and application of the silicone resin of alkenyl containing benzocyclobutane | |
| JP4998702B2 (en) | Articles coated or surface-treated with a coating agent composition | |
| TWI745332B (en) | Aryl compound and its manufacturing method | |
| CN110229339A (en) | A kind of phenylethylene based siloxane resins, high refractive index LED encapsulation silicon resin composition and preparation method thereof | |
| JP2004359703A (en) | Siloxane copolymer and manufacturing method therefor, and thermosetting resin composition obtained by using the same | |
| CN107400238B (en) | Multi-arm siloxane bridged ladder-shaped polysiloxane copolymer and preparation method and application thereof | |
| CN1283695C (en) | Method for raising heat-resistance property of organic silicon resin adopting polyheadral oligo-sesqui silione | |
| CN104387590A (en) | Antenna-structure cage-type organic silicon resin, and preparation method and application thereof | |
| CN111777890A (en) | High-temperature-resistant coating adhesion promoter for titanium alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130320 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |