CN101475731B - Epoxy resin composite material added with modified polysiloxane and preparation thereof - Google Patents
Epoxy resin composite material added with modified polysiloxane and preparation thereof Download PDFInfo
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- CN101475731B CN101475731B CN2009100364399A CN200910036439A CN101475731B CN 101475731 B CN101475731 B CN 101475731B CN 2009100364399 A CN2009100364399 A CN 2009100364399A CN 200910036439 A CN200910036439 A CN 200910036439A CN 101475731 B CN101475731 B CN 101475731B
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- silsesquioxane
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- -1 polysiloxane Polymers 0.000 title claims abstract description 47
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 46
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 34
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000570 polyether Polymers 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 46
- 239000004593 Epoxy Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 150000002431 hydrogen Chemical class 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 229920002545 silicone oil Polymers 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 230000008023 solidification Effects 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- HZBAVWLZSLOCFR-UHFFFAOYSA-N oxosilane Chemical compound [SiH2]=O HZBAVWLZSLOCFR-UHFFFAOYSA-N 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 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 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 2
- 101150065749 Churc1 gene Proteins 0.000 claims description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- 102100038239 Protein Churchill Human genes 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- MJINPUKGRATQAC-UHFFFAOYSA-N triethoxy(prop-1-enyl)silane Chemical compound CCO[Si](OCC)(OCC)C=CC MJINPUKGRATQAC-UHFFFAOYSA-N 0.000 claims description 2
- OWUTVCVPEOXXHD-UHFFFAOYSA-N trimethoxy(prop-1-enyl)silane Chemical compound CO[Si](OC)(OC)C=CC OWUTVCVPEOXXHD-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 150000003384 small molecules Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- FTDXCHCAMNRNNY-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1 FTDXCHCAMNRNNY-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
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- Epoxy Resins (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses an epoxy resin composite material of a co-modified polysiloxane added with polyether and silsesquioxane. The composite material comprises 100 weight portions of epoxy resin, 1 to 100 weight portions of the co-modified polysiloxane of the polyether and the silsesquioxane, and 10 to 80 weight portions of curing agent. The epoxy resin composite material has excellent tensile property, high heat resistance and simple preparation method.
Description
Technical field
The present invention relates to the Resins, epoxy field, particularly a kind of epoxy resin composite material that adds modified polyorganosiloxane and preparation method thereof.
Background technology
Resins, epoxy has excellent mechanical property, high thermal resistance, erosion resistance, cementability and electrical insulating property, is widely used in fields such as automobile, building, electronics, aviation.But, lack slip between molecular chain because Resins, epoxy has formed highly cross-linked 3 D stereo reticulated structure in solidification process; The bond energy of adding C-C key, C-O key is less, and surface energy is higher, causes that the cured resin internal stress is big, property is crisp, easily cracks, thereby limited its application in some technical field.Toughness and over-all properties in order to improve Resins, epoxy enlarge its Application Areas, and Chinese scholars has been carried out a large amount of research work.
What Recent study was more is polysiloxane toughening Resins, epoxy.Polysiloxane has good flexibility and thermostability, can play epoxy resin toughened purpose, but because compatibility problem, polysiloxane is not very remarkable to the toughening effect of Resins, epoxy.People such as the Sun Xiuwu of Institute of Chemistry, Academia Sinica (CN 1279257-A) find that the polysiloxane of polyether grafting can be scattered in the Resins, epoxy well, but the inventor has done the research of polyether grafting polysiloxane toughening Resins, epoxy, finds that toughening effect is undesirable.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, a kind of good toughness, cost is low, technology is simply added polyethers and silsesquioxane comodified polysiloxane epoxy resin composite material are provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned epoxy resin composite material.
Purpose of the present invention is achieved through the following technical solutions:
A kind of epoxy resin composite material that adds polyethers and silsesquioxane comodified polysiloxane is counted by weight, comprises following component:
100 parts of Resins, epoxy
1～100 part of polyethers and silsesquioxane comodified polysiloxane
10～80 parts in solidifying agent.
Described Resins, epoxy comprises bisphenol A type epoxy resin, novolac epoxy or cycloaliphatic epoxy resin.
Described solidifying agent comprises amine curing agent, acid anhydride type curing agent, imidazoles, polymer performed polymer, latent curing agent or functional solidifying agent; Preferably right, to '-diaminodiphenylmethane, phenol phenol resins or urethane.
The preparation method of the epoxy resin composite material of described interpolation polyethers and silsesquioxane comodified polysiloxane, be polyethers and silsesquioxane comodified polysiloxane with 100 parts by weight of epoxy resin and 1～100 weight part, high-speed stirring is carried out compound in the presence of toluene, the solidifying agent that adds 10～80 weight parts again, fully behind the mixing, with vacuum tightness is the vacuum drying oven of 133～1000Pa, under 30～120 ℃, take out solvent and bubble, pour the mould of preheating into, descended 0～6 hour by 80 ℃～90 ℃, 140 ℃～160 ℃ were descended 2～4 hours, 180 ℃～200 ℃ following 2～4 hours program Solidifications obtain epoxy resin composite material at last.
Above-mentioned polyethers and silsesquioxane comodified polysiloxane are counted by weight, comprise following component:
100 parts of containing hydrogen silicone oils
1～200 part of polyethers
1～100 part of silsesquioxane
20～500 parts of organic solvents
0.001～0.02 part of Platinic chloride
10～100 parts of end-capping reagents.
Described containing hydrogen silicone oil, molecular weight are 1000～30000, and hydrogen content is 0.1～1.6wt%.
Described polyethers is an allyl polyether, and general formula is: CH
2=CHCH
2(C
2H
4O)
a(C
3H
6O)
bR; A=1～40 wherein, b=0～20; R is hydrogen, amino, epoxy group(ing), methyl, ethyl, propyl group, sec.-propyl or benzyl.The preferred allyl polyethenoxy polyethenoxy ether of allyl polyether (F6), epoxy-capped allyl polyether or amino-terminated allyl polyether.
Described organic solvent is toluene, Virahol or butyl ether, preferred toluene.
Described end-capping reagent is methyl alcohol, ethanol, n-propyl alcohol or propyl carbinol.
The preparation method of above-mentioned polyethers and silsesquioxane comodified polysiloxane, comprise the steps: that Platinic chloride with 0.001～0.02 weight part is as catalyzer, under 60～120 ℃, the organic solvent of the polyethers of the containing hydrogen silicone oil of 100 weight parts, 1～200 weight part, the silsesquioxane of 1～100 weight part and 20～500 weight parts carried out addition reaction of silicon with hydrogen 2～10 hours; End-capping reagent with 10～100 weight parts carried out end capping 1～5 hour then, obtained polyethers and silsesquioxane comodified polysiloxane.
Preferred 90～110 ℃ of described addition reaction of silicon with hydrogen temperature.
The preparation method of above-mentioned silsesquioxane is: the dibutyl tin dilaurate with 0.01～3 weight part is a catalyzer, under 50～120 ℃, the organic solvent of the distilled water of the silane coupling agent of 100 weight parts, 1～100 weight part and 10～500 weight parts is hydrolyzed, condensation reaction 3～8 hours, obtains silsesquioxane.
Described silane coupling agent is vinyl triacetyl oxosilane, vinyltrimethoxy silane, vinyltriethoxysilane, propenyl triethoxyl silane, the propenyl Trimethoxy silane, one or more mixtures in amine propyl-triethoxysilicane (KH550), glycidoxy-propyltrimethoxy silane (KH560) or γ-(methacryloxy) propyl trimethoxy silicane (KH570).
The organic solvent that is adopted in the preparation of silsesquioxane comprises tetrahydrofuran (THF), dioxane, butanone or butyl ether, preferred tetrahydrofuran (THF).
Preferred 20～50 weight parts of the consumption of described distilled water.
The present invention adds in the epoxy resin composite material of polyethers and silsesquioxane comodified polysiloxane can also add filler, dyestuff, pigment, thixotropic agent, photoinitiators, potential catalyst, inhibitor, solvent, tensio-active agent, flow control agent, stablizer, help thinner, tackifier, fire retardant or other toughner processed.
Polyethers for preparing among the present invention and silsesquioxane comodified polysiloxane, the introducing of polyethers has solved the problem of polysiloxane and epoxy resin compatibility difference, make modification polysiloxane can be scattered in very equably in the epoxy resin-base; The introducing of silsesquioxane makes polysiloxane intensity be improved, and has remedied the defective that tensile strength descends when using the polyether grafting polysiloxane modified epoxy resin.Polysiloxane and silsesquioxane all have extraordinary thermostability, have solved blending toughening in the past, the problem that resistance toheat descends.And introduce contain participate in epoxy resin cure the silsesquioxane of active group, as the silsesquioxane of vinyl silicane coupling agent with the silane coupling agent hydridization that contains amino or epoxy group(ing), improve the consistency and the bonding force of polysiloxane and Resins, epoxy, further improved the resistance toheat of polyethers and silsesquioxane comodified polysiloxane/epoxy resin composite material.
The present invention compared with prior art has following advantage and effect:
(1) the epoxy resin composite material good toughness of the present invention preparation has excellent tensile properties, high thermotolerance.
(2) raw material sources of the present invention are convenient, low price.
(3) preparation method of the present invention is simple.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
With 100g KH570,43.5g tetrahydrofuran (THF), 21.7g distilled water, the 1g dibutyl tin laurate is put in the there-necked flask, under vigorous stirring, be warmed up to 70 ℃ of back flow reaction 5 hours, remove small-molecule substance under reduced pressure with Rotary Evaporators, obtaining the silsesquioxane of KH570 hydridization, is 3060 by GPC test number-average molecular weight.
With the 100g containing hydrogen silicone oil, the silsesquioxane of 5g KH570 hydridization, 100g allyl polyethenoxy polyethenoxy ether (F6) is dissolved in the 240ml toluene, logical N
2Protection; under agitation; be heated to 70 ℃; under this temperature, drip the isopropyl alcohol solution of chloroplatinic acid of 0.6mL 0.025g/mL, after stirring evenly; be warmed up to 120 ℃ of following back flow reaction 2 hours; carry out end capping 4 hours with the 50g n-propyl alcohol, remove small-molecule substances such as solvent under reduced pressure, obtain polyethers and silsesquioxane comodified polysiloxane.
With 10g E-51 Resins, epoxy and 0.5g polyethers and silsesquioxane comodified polysiloxane, high-speed stirring is carried out compound in the presence of toluene, it is right to add 2.54g again, right '-diaminodiphenylmethane (DDM), behind the mixing, be the vacuum drying oven of 133～1000Pa fully with vacuum tightness, under 80 ℃, take out solvent and bubble, pour the mould of preheating into,, obtain epoxy resin composite material at last by 80 ℃ following 5.5 hours, 150 ℃ following 2 hours, 180 ℃ following 2 hours program Solidifications.The elongation at break of gained matrix material is 16.9%, and tensile strength is 52.2MPa, 160 ℃ of Tg.
Embodiment 2
With 20g KH570,80g KH560,48.0g tetrahydrofuran (THF), 22.7g distilled water, the 1g dibutyl tin laurate is put in the there-necked flask, under vigorous stirring, is warmed up to 70 ℃ of back flow reaction 5 hours, remove small-molecule substance under reduced pressure with Rotary Evaporators, obtain KH570 and the KH560 silsesquioxane of hydridization altogether.
With the 100g containing hydrogen silicone oil, 10g KH570 and KH560 be the silsesquioxane of hydridization altogether, and the end capped allyl polyether of 100g epoxy group(ing) (available from Yangzhou Group Co.,Ltd in morning) is dissolved in the 300ml toluene, logical N
2Protection; under agitation; be heated to 70 ℃; under this temperature, drip the isopropyl alcohol solution of chloroplatinic acid of 0.6mL 0.025g/mL, after stirring evenly; be warmed up to 110 ℃ of following back flow reaction 4 hours; carry out end capping 1 hour with 10g methyl alcohol, remove small-molecule substances such as solvent under reduced pressure, obtain polyethers and silsesquioxane comodified polysiloxane.
With 10g novolac epoxy and 1.5g polyethers and silsesquioxane comodified polysiloxane, high-speed stirring is carried out compound in the presence of toluene, it is right to add 2.66g again, right '-diaminodiphenylmethane (DDM), behind the mixing, be the vacuum drying oven of 133～1000Pa fully with vacuum tightness, under 80 ℃, take out solvent and bubble, pour the mould of preheating into,, obtain epoxy resin composite material at last by 90 ℃ following 3 hours, 150 ℃ following 2 hours, 200 times 2 hours program Solidifications.The elongation at break of gained matrix material is 25.86%, and tensile strength is 68.25MPa, 166 ℃ of Tg.
Embodiment 3
With the 20g vinyltriethoxysilane, 80g KH560,48.0g tetrahydrofuran (THF), 24.0g distilled water, the 1g dibutyl tin laurate is put in the there-necked flask, under vigorous stirring, is warmed up to 70 ℃ of back flow reaction 5 hours, remove small-molecule substance under reduced pressure with Rotary Evaporators, obtain vinyltriethoxysilane and the KH560 silsesquioxane of hydridization altogether.
With the 100g containing hydrogen silicone oil, 10g vinyltriethoxysilane and KH560 be the silsesquioxane of hydridization altogether, and the end capped allyl polyether of 100g epoxy group(ing) is dissolved in the 300ml toluene, logical N
2Protection; under agitation; be heated to 70 ℃; under this temperature, drip the isopropyl alcohol solution of chloroplatinic acid of 0.6mL 0.025g/mL, after stirring evenly; be warmed up to 100 ℃ of following back flow reaction 8 hours; carry out end capping 3 hours with ethanol, remove small-molecule substances such as solvent under reduced pressure, obtain polyethers and silsesquioxane comodified polysiloxane.
With 10g novolac epoxy and 1.5g polyethers and silsesquioxane comodified polysiloxane, high-speed stirring is carried out compound in the presence of toluene, it is right to add 2.66g again, right '-diaminodiphenylmethane (DDM), behind the mixing, be the vacuum drying oven of 133～1000Pa fully with vacuum tightness, under 80 ℃, take out solvent and bubble, pour the mould of preheating into,, obtain epoxy resin composite material at last by 90 ℃ following 3 hours, 150 ℃ following 2 hours, 200 times 2 hours program Solidifications.The elongation at break of gained matrix material is 24.87%, and tensile strength is 66.13MPa, 168 ℃ of Tg.
Embodiment 4
With 20g vinyl triacetyl oxosilane, 80g KH550,50.0g tetrahydrofuran (THF), 24.5g distilled water, the 1g dibutyl tin laurate is put in the there-necked flask, under vigorous stirring, is warmed up to 70 ℃ of back flow reaction 5 hours, remove small-molecule substance under reduced pressure with Rotary Evaporators, obtain vinyl triacetyl oxosilane and the KH550 silsesquioxane of hydridization altogether.
With the 100g containing hydrogen silicone oil, 5g vinyl triacetyl oxosilane and KH550 be the silsesquioxane of hydridization altogether, and the amino-terminated allyl polyether of 100g is dissolved in the 210ml toluene, logical N
2Protection; under agitation; be heated to 70 ℃; under this temperature, drip the isopropyl alcohol solution of chloroplatinic acid of 0.6mL 0.025g/mL, after stirring evenly; be warmed up to 60 ℃ of following back flow reaction 10 hours; carry out end capping 5 hours with propyl carbinol, remove small-molecule substances such as solvent under reduced pressure, obtain polyethers and silsesquioxane comodified polysiloxane solution.
With 10g novolac epoxy and 1.5g polyethers and silsesquioxane comodified polysiloxane, high-speed stirring is carried out compound in the presence of toluene, add 6.3g resol again, fully behind the mixing, with vacuum tightness is the vacuum drying oven of 133～1000Pa, takes out solvent and bubble under 80 ℃, pours the mould of preheating into, by 150 ℃ of following 2 hours, 200 ℃ following 2 hours program Solidifications, obtain epoxy resin composite material at last.The elongation at break of gained matrix material is 19.35%, and tensile strength is 59.23MPa, 170 ℃ of Tg.
Test case 1
The various performances of the epoxy resin composite material of the interpolation polyethers of the epoxy resin composite material of the polyether-modified polysiloxane of existing interpolation and the present invention's preparation and silsesquioxane comodified polysiloxane are compared, and the result is as shown in table 1.
Table 1
In the table 1, E-51 is an E-51 Resins, epoxy.Polysiloxane 1 is a polyethers F6 modified polyorganosiloxane, is by 100 parts of containing hydrogen silicone oils, 100 parts of polyethers F6, and 200 parts of toluene, 0.005 part of Platinic chloride 110 ℃ of down reactions 4 hours, carried out end capping 2 hours with n-propyl alcohol again and prepares.Polysiloxane 2 is the silsesquioxane comodified polysiloxane of polyethers F6 and KH570 hydridization, be by 100 parts of containing hydrogen silicone oils, 100 parts of polyethers F6, the silsesquioxane of 5 parts of KH570 hydridization, 200 parts of toluene, 0.0025 part Platinic chloride at 120 ℃ of following back flow reaction 2h, carries out end capping with n-propyl alcohol again and prepared in 4 hours.
Sample 1,2,3,4 solidifying agent that adopted are right, to '-diaminodiphenylmethane (DDM), its consumption calculates according to the mol ratio of epoxy group(ing) and amino hydrogen at 1: 1; All by 80 ℃/5.5h+150 ℃/2h+180 ℃/2h program Solidification.
Elongation at break and tensile strength are measured with electronic universal tester by GB1040-1992, and sample is a dumb-bell shape; Second-order transition temperature (Tg): after sample solidified, grinding powder was with the Perkin-Elmer DSC-2C type differential scanning calorimeter test that U.S. PE company produces, N
2Atmosphere, temperature rise rate are 20 ℃/min.
From table 1 data as can be seen, the sample 3 of the present invention preparation, sample 4 are keeping having better tensile property under the prerequisite of certain resistance toheat.
Test case 2
The sample of the present invention's preparation and the performance of existing novolac epoxy are compared, and the result is as shown in table 2.
Table 2
In the table 2, polysiloxane 3 is by 100 parts of containing hydrogen silicone oils, 10 parts of KH570, KH560 are total to the silsesquioxane (wherein the weight ratio of KH570 and KH560 is 20/80) of hydridization, 100 parts of end capped allyl polyethers of epoxy group(ing), 200 parts of toluene, 0.015 part Platinic chloride, 110 ℃ of following back flow reaction 4 hours were carried out end capping 1 hour with 10g methyl alcohol and the polyethers and the silsesquioxane comodified polysiloxane that obtain again.
Sample 5,6,7 all by 80 ℃/5.5h+150 ℃/2h+180 ℃/2h program Solidification, and used solidifying agent is right, to '-diaminodiphenylmethane (DDM), its consumption calculates according to the mol ratio of epoxy group(ing) and amino hydrogen at 1: 1.
Elongation at break and tensile strength are measured with electronic universal tester by GB1040-1992, and sample is a dumb-bell shape; Second-order transition temperature (Tg): after sample solidified, grinding powder was with the Perkin-Elmer DSC-2C type differential scanning calorimeter test that U.S. PE company produces, N
2Atmosphere, temperature rise rate are 20 ℃/min.
Data from table 2 as can be seen, the sample 6 and the sample 7 of the present invention preparation have excellent tensile properties, high thermotolerance.
Claims (5)
1. epoxy resin composite material that adds polyethers and silsesquioxane comodified polysiloxane is characterized in that: meter by weight comprises following component:
100 parts of Resins, epoxy
1～100 part of polyethers and silsesquioxane comodified polysiloxane
10～80 parts in solidifying agent;
Described Resins, epoxy comprises bisphenol A type epoxy resin, novolac epoxy or cycloaliphatic epoxy resin;
Described polyethers and silsesquioxane comodified polysiloxane, meter comprises following component by weight:
100 parts of containing hydrogen silicone oils
1～200 part of polyethers
1～100 part of silsesquioxane
20～500 parts of organic solvents
0.001～0.02 part of Platinic chloride
10～100 parts of end-capping reagents;
Described polyethers is an allyl polyether, and general formula is: CH
2=CHCH
2(C
2H
4O)
a(C
3H
6O)
bR; A=1～40 wherein, b=0～20; R is hydrogen, amino, epoxy group(ing), methyl, ethyl, propyl group, sec.-propyl or benzyl;
Described silsesquioxane is to adopt following method to prepare: the dibutyl tin dilaurate with 0.01～3 weight part is a catalyzer, under 50～120 ℃, the organic solvent of the distilled water of the silane coupling agent of 100 weight parts, 1～100 weight part and 10～500 weight parts is hydrolyzed, condensation reaction 3～8 hours, obtains silsesquioxane; Wherein, described silane coupling agent is vinyl triacetyl oxosilane, vinyltrimethoxy silane, vinyltriethoxysilane, propenyl triethoxyl silane, one or more mixtures in propenyl Trimethoxy silane, amine propyl-triethoxysilicane, glycidoxy-propyltrimethoxy silane or γ-(methacryloxy) propyl trimethoxy silicane.
2. epoxy resin composite material according to claim 1 is characterized in that: described solidifying agent comprises amine curing agent, acid anhydride type curing agent, imidazoles, polymer performed polymer, latent curing agent or functional solidifying agent.
3. epoxy resin composite material according to claim 1 is characterized in that: described containing hydrogen silicone oil, molecular weight are 1000～30000, and hydrogen content is 0.1～1.6wt%; Described organic solvent is toluene, Virahol or butyl ether; Described end-capping reagent is methyl alcohol, ethanol, n-propyl alcohol or propyl carbinol.
4. epoxy resin composite material according to claim 1, it is characterized in that: the preparation method of described polyethers and silsesquioxane comodified polysiloxane, comprise the steps: that Platinic chloride with 0.001～0.02 weight part is as catalyzer, under 60～120 ℃, the organic solvent of the polyethers of the containing hydrogen silicone oil of 100 weight parts, 1～200 weight part, the silsesquioxane of 1～100 weight part and 20～500 weight parts carried out addition reaction of silicon with hydrogen 2～10 hours; End-capping reagent with 10～100 weight parts carried out end capping 1～5 hour then, obtained polyethers and silsesquioxane comodified polysiloxane.
5. the preparation method of each described epoxy resin composite material in the claim 1～4, it is characterized in that comprising the steps: polyethers and silsesquioxane comodified polysiloxane with 100 parts by weight of epoxy resin and 1～100 weight part, high-speed stirring is carried out compound in the presence of toluene, the solidifying agent that adds 10～80 weight parts again, fully behind the mixing, with vacuum tightness is the vacuum drying oven of 133～1000Pa, under 30～120 ℃, take out solvent and bubble, pour the mould of preheating into, descended 0～6 hour by 80 ℃～90 ℃, 140 ℃～160 ℃ were descended 2～4 hours, 180 ℃～200 ℃ following 2～4 hours program Solidifications obtain epoxy resin composite material at last.
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