CN102690418A - Organosilicon modified epoxy resin and preparation method thereof - Google Patents
Organosilicon modified epoxy resin and preparation method thereof Download PDFInfo
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- CN102690418A CN102690418A CN2012101672558A CN201210167255A CN102690418A CN 102690418 A CN102690418 A CN 102690418A CN 2012101672558 A CN2012101672558 A CN 2012101672558A CN 201210167255 A CN201210167255 A CN 201210167255A CN 102690418 A CN102690418 A CN 102690418A
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- organopolysiloxane
- epoxy resin
- organosilicon
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 30
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 32
- -1 polysiloxane Polymers 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 27
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 26
- 239000011230 binding agent Substances 0.000 claims description 22
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- 239000011550 stock solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 13
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 10
- 229960001124 trientine Drugs 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 8
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- GTPDFCLBTFKHNH-UHFFFAOYSA-N chloro(phenyl)silicon Chemical compound Cl[Si]C1=CC=CC=C1 GTPDFCLBTFKHNH-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- CMPPMAWHJGPAHS-UHFFFAOYSA-N Cl[SiH3].CC=C Chemical compound Cl[SiH3].CC=C CMPPMAWHJGPAHS-UHFFFAOYSA-N 0.000 claims description 6
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 claims description 6
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims description 5
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 150000004756 silanes Chemical class 0.000 claims description 3
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 abstract description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 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 description 2
- 239000000126 substance Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VIJMMQUAJQEELS-UHFFFAOYSA-N n,n-bis(ethenyl)ethenamine Chemical compound C=CN(C=C)C=C VIJMMQUAJQEELS-UHFFFAOYSA-N 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Epoxy Resins (AREA)
Abstract
The invention relates to an organosilicon modified epoxy resin which is characterized by being made of polysiloxane and epichlorohydrin, wherein the weight percentage of the polysiloxane to the epichlorohydrin is 100:20-100. The organosilicon modified epoxy resin is high in flexibility and resistant to high and low temperature, ultraviolet and aging.
Description
Technical field
The present invention relates to a kind of preparation method of organosilicon epoxy resin, especially a kind of modifying epoxy resin by organosilicon with good ageing-resistant performance and preparation method thereof belongs to the polymer-function material field.
Technical background
Epoxy resin is a kind of important thermosetting resin kind; Because it not only has excellent physical and mechanical properties, electrical insulation capability, resistance to chemical corrosion and heat-resisting and adhesiveproperties; And have the characteristics that shrinking percentage is low, hardness is high, wear resistance is good again, be widely used in industrial circles such as chemical industry, water conservancy, traffic, machinery, electronics, household electrical appliances, automobile and aerospace at present.But common epoxy resin internal stress is big, and snappiness is relatively poor, generally all contains fragrant ehter bond in the normally used bisphenol A epoxide resin, and cured article is prone to the degraded chain rupture behind sun exposure, be not suitable for the work condition environment of having relatively high expectations to ageing-resistant.
Summary of the invention
The object of the invention: be intended to propose a kind of high-and low-temperature resistance, anti-ultraviolet, ageing-resistant modifying epoxy resin by organosilicon and preparation method thereof.
This modifying epoxy resin by organosilicon proposed by the invention is characterized in that: it is formulated by organopolysiloxane and epoxy chloropropane; And by organopolysiloxane: epoxy chloropropane is the weight percent preparation of 100:20 ~ 100.
Described organopolysiloxane is with formulated as a kind of in terepthaloyl moietie, methyl alcohol or the ethanol of auxiliary agent or more than one mixed aid by the mixture more than three kinds or three kinds in methyl chlorosilane, phenyl chlorosilane, methyl ethylene chlorosilane, ethyl trichlorosilane, propyltrichlorosilan, the vinyl trichloro silane.
Need to adopt acid binding agent in the building-up process of said organopolysiloxane, described acid binding agent is a triethylamine, quadrol, hexanediamine, a kind of in the triethylene tetramine or two kinds, and two or more mixtures; The consumption of said acid binding agent is the % of organopolysiloxane synthetic system gross weight.
Need in the building-up process of said organopolysiloxane to adopt catalyzer, the catalyzer that is adopted is a kind of or mixture more than three kinds and three kinds in aluminum chloride, iron trichloride, tosic acid, the TBAH; Said catalyst consumption is 0.5 ~ 1.5% of an organopolysiloxane synthetic system gross weight.
Need to adopt solvent in the building-up process of said organopolysiloxane; Described solvent is a kind of or two kinds and the two or more mixture in toluene, YLENE, ethylene glycol ethyl ether, the diethylene glycol ether, and used solvent load is 1-5 a times of organopolysiloxane reactant gross weight.
In the building-up process of described organopolysiloxane, temperature of reaction is 10 ℃-180 ℃.
This modifying epoxy resin by organosilicon, its preparation method is following:
At first, get auxiliary agent according to preparation program, acid binding agent, solvent joins and is mixed with stock solution in the clean container;
Secondly, according to preparation program a certain amount of multiple monomeric silanes, catalyzer and solvent are added together in the three-necked bottle of 500ml and heat to 80 ℃; And slowly drip the stock solution that a last step is prepared, be controlled at and accomplished dropping in 1-1.5 hour; Mixing solutions after will dropwising subsequently is through heating reflux reaction 2 hours, the mixture of ZGK 5;
Its three, without processing, be cooled to 60-70 ℃ after question response is accomplished, will carry out dropwise reaction according to the epoxy chloropropane that preparation program is selected for use, after dropwising in 1-1.5 hour, carrying out 3 hours stopped reaction of heating reflux reaction once more;
At last, after cooling is handled naturally, in reaction system, add 120-150ml water, washing removes amine salt, the underpressure distillation solvent that dereaction generated, and obtains the modifying epoxy resin by organosilicon product.
Modifying epoxy resin by organosilicon according to above technical scheme proposes not only has high-low temperature resistant, the characteristics that ageing-resistant performance is good, and also preparation technology is simple.
Embodiment
Further specify the present invention through embodiment below, but the present invention never only is confined to these embodiment.
This modifying epoxy resin by organosilicon is characterized in that: it is formulated by organopolysiloxane and epoxy chloropropane; And by organopolysiloxane: epoxy chloropropane is the weight percent preparation of 100:20 ~ 100.
Described organopolysiloxane is with formulated as a kind of in terepthaloyl moietie, methyl alcohol or the ethanol of auxiliary agent or more than one mixed aid by the mixture more than three kinds and three kinds in methyl chlorosilane, phenyl chlorosilane, methyl ethylene chlorosilane, ethyl trichlorosilane, propyltrichlorosilan, the vinyl trichloro silane.
Need to adopt acid binding agent in the building-up process of said organopolysiloxane, described acid binding agent is a triethylamine, quadrol, hexanediamine, a kind of in the triethylene tetramine or two kinds, and two or more mixtures; The consumption of said acid binding agent is the 1-7% of organopolysiloxane synthetic system gross weight.
Need in the building-up process of said organopolysiloxane to adopt catalyzer, the catalyzer that is adopted is a kind of or two kinds and the two or more mixture in aluminum chloride, iron trichloride, tosic acid, the TBAH; Said catalyst consumption is 0.5 ~ 1.5% of an organopolysiloxane synthetic system gross weight.
Need to adopt solvent in the building-up process of said organopolysiloxane; Described solvent is a kind of or two kinds and the two or more mixture in toluene, YLENE, ethylene glycol ethyl ether, the diethylene glycol ether, and used solvent load is 1-5 a times of organopolysiloxane reactant gross weight.
In the building-up process of described organopolysiloxane, temperature of reaction is 10 ℃-180 ℃.
This modifying epoxy resin by organosilicon, its preparation method is following:
At first, get auxiliary agent according to preparation program, acid binding agent, solvent joins and is mixed with stock solution in the clean container;
Secondly, according to preparation program a certain amount of multiple monomeric silanes, catalyzer and solvent are added together in the three-necked bottle of 500ml and heat to 80 ℃; And slowly drip the stock solution that a last step is prepared, be controlled at and accomplished dropping in 1-1.5 hour; Mixing solutions after will dropwising subsequently is through heating reflux reaction 2 hours, the mixture of ZGK 5;
Its three, without processing, be cooled to 60-70 ℃ after question response is accomplished, will carry out dropwise reaction according to the epoxy chloropropane that preparation program is selected for use, after dropwising in 1-1.5 hour, carrying out 3 hours stopped reaction of heating reflux reaction once more;
At last, after cooling is handled naturally, in reaction system, add 120-150ml water, washing removes amine salt, the underpressure distillation solvent that dereaction generated, and obtains the modifying epoxy resin by organosilicon product.
Embodiment 1
At first, get auxiliary agent terepthaloyl moietie 35.6g according to preparation program, acid binding agent triethylamine 28g, solvent ethylene glycol ether 56.3g joins and is mixed with stock solution in the clean container.
Secondly, according to preparation program with methyl chlorosilane 20.8g, phenyl chlorosilane 24g, propyltrichlorosilan 23.6g, catalyzer TBAH 0.8g, solvent toluene 68g adds together in the three-necked bottle of 500ml and heats to 80 ℃; And slowly drip the stock solution that a last step is prepared, be controlled at and accomplished dropping in 1-1.5 hour; Mixing solutions after will dropwising subsequently is through heating reflux reaction 2 hours, the mixture of ZGK 5.
Its three, without processing, be cooled to 60-70 ℃ after question response is accomplished, will carry out dropwise reaction according to the 47g epoxy chloropropane that preparation program is selected for use, after dropwising in 1-1.5 hour, carrying out 3 hours stopped reaction of heating reflux reaction once more.
At last, after cooling is handled naturally, in reaction system, add 120ml water, washing removes amine salt, the underpressure distillation solvent that dereaction generated, and obtains the modifying epoxy resin by organosilicon product.
Above products obtained therefrom technical indicator:
Viscosity: 8000-15000mPa.s
Epoxy equivalent (weight): 680-750g/mol
The auxiliary agent terepthaloyl moietie of in above-mentioned embodiment, being selected for use also can be used methyl alcohol, ethanol or terepthaloyl moietie and methyl alcohol, alcoholic acid mixture replacing.The acid binding agent of being selected for use also can be selected quadrol for use except that triethylamine, hexanediamine, a kind of in the triethylene tetramine or two kinds, and two or more mixtures.The catalyzer of being selected for use also can be selected in aluminum chloride, iron trichloride, the tosic acid any for use except that TBAH, perhaps be two or more mixture of TBAH, aluminum chloride, iron trichloride, tosic acid.The solvent of being selected for use also can be a kind of or two kinds and the two or more mixtures in YLENE, ethylene glycol ethyl ether, the diethylene glycol ether except that toluene.
Embodiment 2
At first, get auxiliary agent terepthaloyl moietie 31.2g according to preparation program, acid binding agent triethylene tetramine 15g, solvent ethylene glycol ether 46.2g joins and is mixed with stock solution in the clean container.
Secondly, press preparation program with phenyl chlorosilane 27g, methyl ethylene chlorosilane 31g, ethyl trichlorosilane 24.5g, catalyzer TBAH 0.9g, solvent toluene 120g joins together in the three-necked bottle of 500ml and heats to 80 ℃; And slowly drip the stock solution that a last step is prepared, be controlled at and accomplished dropping in 1-1.5 hour; Subsequently, with the mixing solutions heating reflux reaction after dropwising 2 hours, obtain the mixture of ZGK 5.
Its three, without processing, be cooled to 60-70 ℃ after question response is accomplished, will carry out dropwise reaction according to the 54g epoxy chloropropane that allocation plan is selected for use, after dropwising in 1-1.5 hour once more reflux handle, back flow reaction is stopped reaction after 3 hours.
At last, after cooling is handled naturally, in the reaction system thing, add 150ml water, washing removes the amine salt that dereaction generated, and the underpressure distillation solvent obtains the modifying epoxy resin by organosilicon product.
Above products obtained therefrom technical indicator:
Viscosity: 8000-15000mPa.s;
Epoxy equivalent (weight): 710-760g/mol.
The auxiliary agent terepthaloyl moietie of in above-mentioned embodiment, being selected for use also can be used methyl alcohol, ethanol or terepthaloyl moietie and methyl alcohol, alcoholic acid mixture replacing.The acid binding agent of being selected for use also can be selected quadrol for use except that triethylene amine, hexanediamine, a kind of in the triethylamine or two kinds, and two or more mixtures.The catalyzer of being selected for use also can be selected in aluminum chloride, iron trichloride, the tosic acid any for use except that TBAH, perhaps be two or more mixture of TBAH, aluminum chloride, iron trichloride, tosic acid.The solvent of being selected for use also can be a kind of or two kinds and the two or more mixtures in YLENE, toluene, the diethylene glycol ether except that ethylene glycol ethyl ether.
Embodiment 3
At first, get auxiliary agent according to preparation program and get terepthaloyl moietie 25g, methyl alcohol 9.8g, acid binding agent triethylamine 27.3g, solvent xylene 65g joins and is mixed with stock solution in the clean container.
Secondly; According to preparation program with methyl chlorosilane 29.8g, propyltrichlorosilan 33.6g, catalyzer TBAH 0.75g; Solvent toluene 68g; Join together in the three-necked bottle of 500ml and heat to 80 ℃, and slowly drip the stock solution that a last step is prepared, be controlled at and accomplished dropping in 1-1.5 hour; To dropwise the post-heating back flow reaction subsequently 2 hours, get the mixture of ZGK 5.
Its three, without processing, be cooled to 60-70 ℃ after question response is accomplished, will carry out dropwise reaction according to the 44g epoxy chloropropane that preparation program is selected for use, dropwising the post-heating reflow treatment through 1-1.5 hour, back flow reaction is stopped reaction after 3 hours.
At last, after cooling is handled naturally, in reaction system, add 120ml water, washing removes the amine salt that dereaction generated, and the underpressure distillation solvent obtains the modifying epoxy resin by organosilicon product.
Above products obtained therefrom technical indicator:
Viscosity: 7000-12000mPa.s;
Epoxy equivalent (weight): 650-730g/mol.
The auxiliary agent of in above-mentioned embodiment, being selected for use also can be with ethanol or terepthaloyl moietie and methyl alcohol, alcoholic acid mixture replacing except that terepthaloyl moietie, methyl alcohol.The acid binding agent of being selected for use also can be selected quadrol for use except that triethylamine, hexanediamine, a kind of in the triethylene tetramine or two kinds, and two or more mixtures.The catalyzer of being selected for use also can be selected in aluminum chloride, iron trichloride, the tosic acid any for use except that TBAH, perhaps be two or more mixture of TBAH, aluminum chloride, iron trichloride, tosic acid.The solvent of being selected for use also can be a kind of or two kinds and the two or more mixtures in YLENE, ethylene glycol ethyl ether, the diethylene glycol ether except that toluene.
Embodiment 4
At first, get auxiliary agent terepthaloyl moietie 45g according to preparation program, acid binding agent triethylene tetramine 11g, solvent ethylene glycol ether 55g joins and is mixed with stock solution in the clean container.
Secondly, press preparation program with phenyl chlorosilane 22g, methyl ethylene chlorosilane 37.5g, ethyl trichlorosilane 30.5g, catalyzer TBAH 1.0g, solvent toluene 150g joins together in the three-necked bottle of 500ml and heats to 80 ℃; And slowly drip the stock solution that a last step is prepared, be controlled at and accomplished dropping in 1-1.5 hour; Subsequently, with the mixing solutions heating reflux reaction after dropwising 2 hours, obtain the mixture of ZGK 5.
With its three, without processing, be cooled to 60-70 ℃ after question response is accomplished, will carry out dropwise reaction according to the 135g epoxy chloropropane that allocation plan is selected for use, after dropwising in 1-1.5 hour once more reflux handle, back flow reaction is stopped reaction after 3 hours.
At last, after cooling is handled naturally, in the reaction system thing, add 200ml water, washing removes the amine salt that dereaction generated, and the underpressure distillation solvent obtains the modifying epoxy resin by organosilicon product.
Above products obtained therefrom technical indicator:
Viscosity: 8000-15000mPa.s;
Epoxy equivalent (weight): 350-400g/mol.
The auxiliary agent of in above-mentioned embodiment, being selected for use also can be with ethanol or terepthaloyl moietie and methyl alcohol, alcoholic acid mixture replacing except that terepthaloyl moietie, methyl alcohol.The acid binding agent of being selected for use also can be selected quadrol for use except that triethylamine, hexanediamine, a kind of in the triethylene tetramine or two kinds, and two or more mixtures.The catalyzer of being selected for use also can be selected in aluminum chloride, iron trichloride, the tosic acid any for use except that TBAH, perhaps be two or more mixture of TBAH, aluminum chloride, iron trichloride, tosic acid.The solvent of being selected for use also can be a kind of or two kinds and the two or more mixtures in YLENE, ethylene glycol ethyl ether, the diethylene glycol ether except that toluene.
Embodiment 5
At first, get auxiliary agent terepthaloyl moietie 28g according to preparation program, acid binding agent triethylene tetramine 11g, solvent ethylene glycol ether 50g joins and is mixed with stock solution in the clean container.
Secondly, press preparation program with phenyl chlorosilane 17g, methyl ethylene chlorosilane 25.8g, propyltrichlorosilan 23g, catalyzer TBAH 0.5g, solvent toluene 120g joins together in the three-necked bottle of 500ml and heats to 80 ℃; And slowly drip the stock solution that a last step is prepared, be controlled at and accomplished dropping in 1-1.5 hour; Subsequently, with the mixing solutions heating reflux reaction after dropwising 2 hours, obtain the mixture of ZGK 5.
Its three, without processing, be cooled to 60-70 ℃ after question response is accomplished, will carry out dropwise reaction according to the 13.2g epoxy chloropropane that preparation program is selected for use, after dropwising in 1-1.5 hour once more reflux handle, back flow reaction is stopped reaction after 3 hours.
At last, after cooling is handled naturally, in the reaction system thing, add 120ml water, washing removes the amine salt that dereaction generated, and the underpressure distillation solvent obtains the modifying epoxy resin by organosilicon product.
Above products obtained therefrom technical indicator:
Viscosity: 8000-15000mPa.s;
Epoxy equivalent (weight): 860-920g/mol.
The auxiliary agent of in above-mentioned embodiment, being selected for use also can be with ethanol or terepthaloyl moietie and methyl alcohol, alcoholic acid mixture replacing except that terepthaloyl moietie, methyl alcohol.The acid binding agent of being selected for use also can be selected quadrol for use except that triethylamine, hexanediamine, a kind of in the triethylene tetramine or two kinds, and two or more mixtures.The catalyzer of being selected for use also can be selected in aluminum chloride, iron trichloride, the tosic acid any for use except that TBAH, perhaps be two or more mixture of TBAH, aluminum chloride, iron trichloride, tosic acid.The solvent of being selected for use also can be a kind of or two kinds and the two or more mixtures in YLENE, ethylene glycol ethyl ether, the diethylene glycol ether except that toluene.
The present invention is not limited to the method described in the embodiment; Its description is illustrative; And it is nonrestrictive; Authority of the present invention is limited claim, based on present technique field personnel according to the present invention can change, technology and the product relevant that method such as reorganization obtains with the present invention, all within protection scope of the present invention.
Claims (7)
1. modifying epoxy resin by organosilicon, it is characterized in that: it is formulated by organopolysiloxane and epoxy chloropropane; And by organopolysiloxane: epoxy chloropropane is the weight percent preparation of 100:20 ~ 100.
2. a kind of modifying epoxy resin by organosilicon as claimed in claim 1 is characterized in that: described organopolysiloxane is with formulated as a kind of in terepthaloyl moietie, methyl alcohol or the ethanol of auxiliary agent or more than one mixed aid by the mixture more than three kinds or three kinds in methyl chlorosilane, phenyl chlorosilane, methyl ethylene chlorosilane, ethyl trichlorosilane, propyltrichlorosilan, the vinyl trichloro silane.
3. according to claim 1 or claim 2 a kind of modifying epoxy resin by organosilicon; It is characterized in that: need to adopt acid binding agent in the building-up process of said organopolysiloxane; Described acid binding agent is a triethylamine, quadrol, hexanediamine; A kind of in the triethylene tetramine or two kinds, and two or more mixtures; The consumption of said acid binding agent is the 1-7% of organopolysiloxane synthetic system gross weight.
4. like claim 1 or 2 or 3 described a kind of modifying epoxy resin by organosilicon; It is characterized in that: need in the building-up process of said organopolysiloxane to adopt catalyzer, the catalyzer that is adopted is a kind of or two kinds and the two or more mixture in aluminum chloride, iron trichloride, tosic acid, the TBAH; Said catalyst consumption is 0.5 ~ 1.5% of an organopolysiloxane synthetic system gross weight.
5. according to claim 1 or 2 or 3 or 4 described a kind of modifying epoxy resin by organosilicon; It is characterized in that: need to adopt solvent in the building-up process of said organopolysiloxane; Described solvent is a kind of or two kinds and the two or more mixture in toluene, YLENE, ethylene glycol ethyl ether, the diethylene glycol ether, and used solvent load is 1-5 a times of organopolysiloxane reactant gross weight.
6. a kind of modifying epoxy resin by organosilicon as claimed in claim 1 is characterized in that: in the building-up process of described organopolysiloxane, temperature of reaction is 10 ℃-180 ℃.
7. like the described a kind of modifying epoxy resin by organosilicon of claim 1-6, its preparation method is following:
At first, get auxiliary agent according to allocation plan, acid binding agent, solvent joins and is mixed with stock solution in the clean container;
Secondly, according to allocation plan a certain amount of multiple monomeric silanes, catalyzer and solvent are added together in the three-necked bottle of 500ml and heat to 80 ℃; And slowly drip the stock solution that a last step is prepared, be controlled at and accomplished dropping in 1-1.5 hour; Mixing solutions after will dropwising subsequently is through heating reflux reaction 2 hours, the mixture of ZGK 5;
Its three, without processing, be cooled to 60-70 ℃ after question response is accomplished, will carry out dropwise reaction according to the epoxy chloropropane that preparation program is selected for use, after dropwising in 1-1.5 hour, carrying out 3 hours stopped reaction of heating reflux reaction once more;
At last, after cooling is handled naturally, in reaction system, add 120-150ml water, washing removes amine salt, the underpressure distillation solvent that dereaction generated, and obtains the modifying epoxy resin by organosilicon product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101672558A CN102690418A (en) | 2012-05-25 | 2012-05-25 | Organosilicon modified epoxy resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101672558A CN102690418A (en) | 2012-05-25 | 2012-05-25 | Organosilicon modified epoxy resin and preparation method thereof |
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| Publication Number | Publication Date |
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| CN102690418A true CN102690418A (en) | 2012-09-26 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104492399A (en) * | 2014-12-23 | 2015-04-08 | 江南大学 | Preparation method of functional resin modified porous material and application of material to heavy metal ion adsorption |
| CN104277225B (en) * | 2014-10-08 | 2017-01-25 | 江苏苏博特新材料股份有限公司 | Organic silicon resin capable of promoting sliding-resistant coefficient, as well as preparation method and applications thereof |
| CN106700996A (en) * | 2016-12-23 | 2017-05-24 | 上海回天新材料有限公司 | Two-component epoxy structure adhesive and application thereof |
| CN113025160A (en) * | 2021-03-12 | 2021-06-25 | 东莞市德聚胶接技术有限公司 | High-temperature-resistant electromagnetic shielding coating and application thereof |
| CN113789122A (en) * | 2021-10-14 | 2021-12-14 | 江苏乐离新材料科技有限公司 | Polyvinyl alcohol resin organic silicon modified water-soluble equipment protective film solution and preparation method thereof |
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| CN104277225B (en) * | 2014-10-08 | 2017-01-25 | 江苏苏博特新材料股份有限公司 | Organic silicon resin capable of promoting sliding-resistant coefficient, as well as preparation method and applications thereof |
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| CN113025160A (en) * | 2021-03-12 | 2021-06-25 | 东莞市德聚胶接技术有限公司 | High-temperature-resistant electromagnetic shielding coating and application thereof |
| CN113025160B (en) * | 2021-03-12 | 2021-11-23 | 东莞市德聚胶接技术有限公司 | High-temperature-resistant electromagnetic shielding coating and application thereof |
| CN113789122A (en) * | 2021-10-14 | 2021-12-14 | 江苏乐离新材料科技有限公司 | Polyvinyl alcohol resin organic silicon modified water-soluble equipment protective film solution and preparation method thereof |
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