CN101906114B - Cation ultraviolet curing group-containing silicon oxide compound and preparation method thereof - Google Patents
Cation ultraviolet curing group-containing silicon oxide compound and preparation method thereof Download PDFInfo
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- CN101906114B CN101906114B CN 201010215782 CN201010215782A CN101906114B CN 101906114 B CN101906114 B CN 101906114B CN 201010215782 CN201010215782 CN 201010215782 CN 201010215782 A CN201010215782 A CN 201010215782A CN 101906114 B CN101906114 B CN 101906114B
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- DCEODCRHIDLCRS-UHFFFAOYSA-N C(C1CC=CCC1)O[Si](c1ccccc1)(OCC1CC=CCC1)OCC1CC=CCC1 Chemical compound C(C1CC=CCC1)O[Si](c1ccccc1)(OCC1CC=CCC1)OCC1CC=CCC1 DCEODCRHIDLCRS-UHFFFAOYSA-N 0.000 description 1
- XWCLJAHAXDPURT-OXGMQBCFSA-O C/C=C(\C=C/C=C)/[SH+](OCC1CC2OC2CC1)(OCC1CC2OC2CC1)OCC1C(C2)OC2CC1 Chemical compound C/C=C(\C=C/C=C)/[SH+](OCC1CC2OC2CC1)(OCC1CC2OC2CC1)OCC1C(C2)OC2CC1 XWCLJAHAXDPURT-OXGMQBCFSA-O 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N CO[Si](c1ccccc1)(OC)OC Chemical compound CO[Si](c1ccccc1)(OC)OC ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- VEIYJWQZNGASMA-UHFFFAOYSA-N OCC1CC=CCC1 Chemical compound OCC1CC=CCC1 VEIYJWQZNGASMA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a cation ultraviolet curing group-containing silicon oxide compound and a preparation method thereof. The preparation method is characterized by comprising the following steps of: mixing and stirring monohydroxy vinyl ether compound or monohydroxy-3-oxetane compound and methoxysilane in the presence of a catalyst in a molar ratio of (1-6)*n:1 until methoxyl group peak disappears in nuclear magnetic resonance spectroscopy; or mixing and stirring monohydroxy olefin compound and the methoxysilane in the presence of the catalyst in a molar ratio of (1-6)*n:1 until the methoxyl group peak disappears in the nuclear magnetic resonance spectroscopy, and then adding the obtained silicon olefin-containing compound dropwise into organic solution of organic peracid for performing epoxidation, wherein the number n of siloxicon bonds in molecules is an integer of 2 to 4. The preparation method has the advantages of low cost and readily available raw materials, simple and convenient preparation operation and convenient industrial production; and the obtained cation ultraviolet curing group-containing silicon oxide compound can be cured rapidly by ultraviolet irradiation; and the obtained coating has the advantages of high smoothness, high flame retardant efficiency and wide industrial application prospect.
Description
Technical field
The invention belongs to ultraviolet light polymerization material technical field, be specifically related to silicon oxide compound of cation ultraviolet curing group-containing and preparation method thereof.
Background technology
Along with the enhancing of people's environmental consciousness, ultraviolet photocureable material is fast, low VOC of solvent-free or low solvent, curing speed and the advantage such as film performance is good with it, replaces just gradually traditional solvent based coating.Ultraviolet light polymerization has radically curing and two kinds of mechanism of cationic curing, wherein radical UV curing is used comparatively extensive, but because its cured film is relatively poor to the sticking power of base material, stronger oxygen inhibition effect and distinctive mucous membrane irritation are arranged, its application is subject to certain restrictions.Compare with radically curing, cationic curing can make up defects, and the cationic curing volumetric shrinkage is little, the strong adhesion of cured film to various base materials; There is no oxygen inhibition during curing; Curing reaction is difficult for stopping, and has " dark reaction ", is applicable to the photocuring of thick film and colored paint.Therefore the research of cation photocuring has become one of " hot subject " in radiation curing field.
But to the fire-retardant occasion that particular requirement is arranged, the inflammableness of conventional resins cured film is greatly limited its application at some.Halogen-containing fire retardant commonly used can produce poisonous, fatal hydrogen halide when burning, therefore, R and D have the fire retardant of environment friendly and paid attention to widely.
European patent EP 0412425A1 and German patent DE 19856397A1 reported diglycidyl phosphonic acid ester epoxy monomer preparation and with the epoxy systems copolymerization.In printed circuit board (PCB) lamination material, use biconjugate aminophenyl ethyl phosphine oxide compound that above-mentioned system is solidified, resulting materials has good flame retardant resistance.But it adopts thermofixation, has that energy consumption is high, curing speed is slow, and can discharge the shortcomings such as volatile organic matter (VOC).
U.S.'s " organic coating progress " (Progress in Organic Coatings, 2009,65:263-268) reported phosphorous trifunctional cycloaliphatic epoxy resin and preparation method thereof, and this phosphorous trifunctional cycloaliphatic epoxy resin is mixed with commercialization difunctionality cycloaliphatic epoxy resin (UVR-6110), obtain phosphorous flame retardant resistance cation photocuring material.But the polyphosphoric acid that produces during the phosphonium flame retardant burning has corrosive nature to metal, and phosphorus-containing flame-retardant material is very restricted in the application of industry member.
The additive flame retardant resin (SFR-100) of General Electric Apparatus Co.'s exploitation is a kind of siloxane polymer of thickness, but there are the problem of dispersed and interface compatibility in this additive flame retardant and resin, and a large amount of interpolations can cause resin thermal property and the larger reduction of mechanical property.
U.S.'s " polymer science magazine " (Journal of Polymer Science:Part A:Polymer Chemistry, 2006,44:5580-5587) reported diglycidyl methylphenyl siloxane monomer and preparation method thereof, and with the reactive flame retardant of diglycidyl methylphenyl siloxane monomer as bisphenol A epoxide resin system (DGEBA), compared the impact of Different adding amount on flame retardant properties in the resin.But because it adopts the thermofixation mode, compare with the ultraviolet light polymerization mode and have that energy consumption is high, curing speed is slow, and can discharge the shortcomings such as volatile organic matter (VOC).
Chinese patent CN101481458A has reported a kind of flame retardant resistance cycloaliphatic epoxy resin and preparation method thereof, first with halogenated silanes and the condensation of alicyclic olefin alkylol cpd, then with double bond epoxidation, obtains siliceous liquid alicyclic epoxy resin.Because the halogenated silanes that uses in the method has strong corrodibility, and condensation reaction is fierce and complicated, need except acid treatment, must use a large amount of organic solvents, bring the more difficult control of processing condition, unstable product quality and palpus to solve the problems such as solvent recuperation to large-scale commercial production.
Summary of the invention
The objective of the invention is silicon oxide compound that proposes a kind of cation ultraviolet curing group-containing and preparation method thereof, to overcome the defects of prior art, adopt cation photocuring to obtain siliceous flame retardant coating.
The silicon oxide compound of cation ultraviolet curing group-containing of the present invention is characterised in that its cation photocuring group is connected with Siliciumatom by the silica carbon bond, and general molecular formula can be expressed as:
Wherein, m is 0～2 integer, and n is 2～4 integer, R
1Be cation photocuring group, R
2And R
3Group is methyl or phenyl.
Described cation photocuring radicals R
1Comprise following structure :-CH
2CH
2CH
2CH
2OCH=CH
2,-CH
2CH
2OCH
2CH
2OCH=CH
2,-CH
2C (CH
2CH
3) (CH
2OCH
2R
4)
2,-CH
2CH
2OCH
2R
4,-R
5,-CH
2R
5,-CH
2CH
2O (CO) R
5,-CH
2CH
2OR
6,-CH
2CH
2OCH
2CH
2OR
6,-CH
2R
7,-R
8Or-CH
2R
8Wherein, R
4Be epoxy group(ing), R
5Be that ice alkane-2-base, R fall in 5,6-epoxy
6Be 5-oxa-Fourth Ring [6.2.1.0.0] undecane-9-base, R
7Be 3,4-epoxy group(ing)-cyclohexyl, R
8Be 3-trimethylene oxide-3-base.
The preparation method of the silicon oxide compound of cation ultraviolet curing group-containing of the present invention, it is characterized in that: adopt monohydroxy vinyl ethers or monohydroxy-3-oxygen heterocycle butane and methoxy silane (1～6) * n in molar ratio: 1, mix to proton nmr spectra under catalyzer exists in the disappearance of methoxy base peak; Or, first use monohydroxy olefin(e) compound and methoxy silane (1～6) * n in molar ratio: 1, mix to proton nmr spectra under catalyzer exists in, the methoxy base peak disappears, and the siliceous olefin(e) compound that then will obtain is added drop-wise in the organic solution of organic peroxide acid and carries out epoxidation reaction; Wherein in molecule, the number n of silica carbon bond is 2～4 integer.
Described monohydroxy vinyl ethers compound is 4-hydroxybutyl vinyl ether or Diethylene Glycol mono vinyl ether, and their structural formula can be expressed as respectively:
4-hydroxybutyl vinyl ether Diethylene Glycol mono vinyl ether.
Described monohydroxy-3-oxygen heterocycle butane is 3-methyl-3-methylol trimethylene oxide or 3-ethyl-3-methylol trimethylene oxide, and their structural formula can be expressed as respectively:
3-methyl-3-methylol trimethylene oxide 3-ethyl-3-methylol trimethylene oxide.
Described catalyzer is positive tetraethyl titanate, titanium isopropylate, tetrabutyl titanate or metatitanic acid 2-ethylhexyl.
Described methoxy silane is methyl silicate, phenyltrimethoxysila,e, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxy silane, methyltrimethoxy silane or dimethyldimethoxysil,ne.
Described monohydroxy olefin(e) compound is 3-tetrahydrobenzene-1-methyl alcohol, ethylene glycol monoallyl ether, trimethylolpropane allyl ether, 5-norbornylene-2-alcohol, 5-norbornylene-2-methyl alcohol, 5-norbornylene-2-carboxylic acid-(2-hydroxyethyl) ester, 2-(three ring [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) ethanol or 2-[2-(three ring [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) oxyethyl group] ethanol, their structural formula can be expressed as respectively:
3-tetrahydrobenzene-1-methyl alcohol ethylene glycol monoallyl ether trimethylolpropane allyl ether
5-norbornylene-2-alcohol 5-norbornylene-2-methyl alcohol 5-norbornylene-2-carboxylic acid-(2-hydroxyethyl) ester
2-(three ring [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) ethanol 2-[2-(three ring [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) oxyethyl group] ethanol.
Described organic peroxide acid is Peracetic Acid, peroxide propynoic acid, benzoyl hydroperoxide, metachloroperbenzoic acid, to nitro benzoyl hydroperoxide, nitro benzoyl hydroperoxide or potassium hydrogen persulfate composite salts.
Described organic solvent is methylene dichloride, chloroform, tetracol phenixin, DMF, N,N-dimethylacetamide, methyl-sulphoxide or ethyl acetate.
Compare with the diglycidyl phosphonic acid ester epoxy monomer of European patent EP 0412425A1 and German patent DE 19856397A1 report, although its phosphorous-containing monomers has given cured film very high oxygen index, but its heat curing process energy consumption is high, and the polyphosphoric acid that produces during the phosphonium flame retardant burning has corrosive nature to metal; And the cation photocuring silicon-containing compound in the present invention has been owing to having introduced element silicon and having contained the ultraviolet light polymerization group, and when solidifying by contrast, energy consumption is low, speed fast, organic volatile content is lower, and its products of combustion has environment friendly.
U.S.'s " organic coating progress " (Progress in Organic Coatings, 2009,65:263-268) phosphorous trifunctional cycloaliphatic epoxy resin and the cation photocuring fire retardant material thereof of report, the polyphosphoric acid that produces during its burning has corrosive nature to metal; And the cation photocuring silicon-containing compound in the present invention belongs to silicon-series five-retardant, is a kind of generally acknowledged environmentally friendly fire retardant.
The flame-retarded resin (SFR-100) of General Electric Apparatus Co.'s exploitation is non-response type, has the problem of dispersed and interface compatibility, and a large amount of the interpolation can reduce material physical property; And can be used as reactive flame retardant, directly uses cation photocuring silicon-containing compound of the present invention, good with all the other light-cured components consistencies, and broad range of applicability.
With U.S.'s " polymer science magazine " (Journal of Polymer Science:Part A:Polymer Chemistry, 2006,44:5580-5587) the thermoset diglycidyl methylphenyl siloxane monomer of report is compared, and photocuring silicon-containing compound of the present invention has that solvent-free or low solvent, curing speed are fast, organic volatile content is lower and the advantage such as film performance is good.
The method for preparing the flame retardant resistance cycloaliphatic epoxy resin with Chinese patent CN101481458A is compared, because the raw material siloxanes that adopts in preparation method of the present invention is that pH is neutral, there is no corrodibility, side reaction is few, productive rate is high, easy control of process conditions, constant product quality during industrial production.
Preparation method's raw material of the present invention cheaply is easy to get, and preparation manipulation is easy, is convenient to suitability for industrialized production.
Adopt the silicon oxide compound of the cation ultraviolet curing group-containing of method preparation of the present invention can pass through the ultraviolet light irradiation fast setting, the solidified coating planarization of acquisition is good, and flame retarding efficiency is high.
Description of drawings
Fig. 1 is the infrared spectrum of preparation product in embodiment 1.
Fig. 2 is the nucleus magnetic hydrogen spectrum of preparation product in embodiment 1.
Fig. 3 is the nuclear-magnetism carbon spectrum of preparation product in embodiment 1.
Embodiment
The below describes preparation method and the application of flame retardant resistance in ultraviolet-curing paint thereof of the silicon oxide compound of cation ultraviolet curing group-containing of the present invention in detail with embodiment.
Embodiment 1:
19.8g (0.1mol) phenyltrimethoxysila,e, 100.8g (0.9mol) 3-tetrahydrobenzene-1-methyl alcohol and 0.28g (0.001mol) titanium isopropylate are placed in a round-bottomed flask, react until methoxy base peak disappearance in proton nmr spectra at 100 ℃ under whipped state; After excessive 3-tetrahydrobenzene-1-methyl alcohol is removed in decompression, add 80mL dilution with toluene reaction solution, then use successively 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash, with the organic phase anhydrous sodium sulfate drying, after underpressure distillation, resulting transparent liquid is siliceous alkene at last.
Add 62.1g (0.36mol) metachloroperbenzoic acid and 200mL methylene dichloride in the flask that mechanical stirring, thermometer and constant pressure funnel are housed, mix the siliceous alkene that the above-mentioned reaction of rear dropping makes, cross after 24 hours 25 ℃ of reactions and filter out white solid, gained filtrate is used saturated aqueous sodium thiosulfate, 10% sodium bicarbonate and distilled water wash successively, with the organic phase anhydrous sodium sulfate drying, after underpressure distillation, resulting transparent liquid is product at last.
Above-mentioned products therefrom is carried out the infrared spectrum analysis, Fig. 1 be in the present embodiment the preparation product infrared spectrum, from this infrared spectrum as seen at 808cm
-1There is obvious epoxide group fignal center at the place.
Above-mentioned product is carried out the nuclear magnetic spectrogram analysis, and Fig. 2 and Fig. 3 are respectively nucleus magnetic hydrogen spectrum and the nuclear-magnetism carbon spectrums of preparation product in the present embodiment.In the fignal center of 3.03-3.26ppm and nuclear-magnetism carbon spectrum, the fignal center at 51.2ppm and 52.2ppm place has further proved the epoxide group existence from nucleus magnetic hydrogen spectrum.
Hence one can see that, and the present embodiment product is three (3,4-epoxy group(ing)-cyclohexyl-1-methoxyl group) phenyl silane.
Said process can adopt reaction formula to be expressed as:
Embodiment 2:
13.6g (0.1mol) methyltrimethoxy silane, 37.3g (0.3mol) 5-norbornylene-2-methyl alcohol and 0.28g (0.001mol) titanium isopropylate are placed in a round-bottomed flask, react until methoxy base peak disappearance in proton nmr spectra at 100 ℃ under whipped state; Then first add 80mL dilution with toluene reaction solution, then use successively 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash, at last with the organic phase anhydrous sodium sulfate drying, the transparent liquid that underpressure distillation obtains is siliceous alkene.
Add 62.1g (0.36mol) metachloroperbenzoic acid and 160mL methylene dichloride and 40mLN in the flask that mechanical stirring, thermometer and constant pressure funnel are housed, the mixed solvent that dinethylformamide forms, mix the siliceous alkene that the above-mentioned reaction of rear dropping makes, 25 ℃ the reaction 24 hours after, cross and filter out white solid, gained filtrate is used saturated aqueous sodium thiosulfate, 10% sodium bicarbonate and distilled water wash successively, with the organic phase anhydrous sodium sulfate drying, after underpressure distillation, resulting transparent liquid is product at last.
To this products therefrom carry out nuclear magnetic spectrogram analyze after as can be known, the present embodiment product is three (ice alkane-2-methoxyl group falls in 5,6-epoxy) methyl-monosilane, its structural formula can be expressed as:
Embodiment 3:
15.2g (0.1mol) methyl silicate, 245g (2.4mol) ethylene glycol monoallyl ether and 0.28g (0.001mol) titanium isopropylate are placed in a round-bottomed flask, vacuumize under whipped state 50 ℃ of reactions until methoxy base peak disappearance in proton nmr spectra; Then first add 80mL dilution with toluene reaction solution, then use successively 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash, at last with the organic phase anhydrous sodium sulfate drying, the transparent liquid that obtains after underpressure distillation is siliceous alkene.
Add 82.8g (0.48mol) metachloroperbenzoic acid and 250mL methylene dichloride in the flask that mechanical stirring, thermometer and constant pressure funnel are housed, mix the siliceous alkene that the above-mentioned reaction of rear dropping makes, cross after 24 hours 25 ℃ of reactions and filter out white solid, gained filtrate is used saturated aqueous sodium thiosulfate, 10% sodium bicarbonate and distilled water wash successively, with the organic phase anhydrous sodium sulfate drying, after underpressure distillation, resulting transparent liquid is product at last.
To this products therefrom carry out nuclear magnetic spectrogram analyze after as can be known, the present embodiment product is four (2-glycidyl ether base oxethyl) silane, its structural formula can be expressed as:
Embodiment 4:
18.2g (0.1mol) aminomethyl phenyl dimethoxy silane, 38.9g (0.2mol) 2-(three ring [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) ethanol and 0.28g (0.001mol) titanium isopropylate are placed in a round-bottomed flask, under whipped state 100 ℃ of reactions until in proton nmr spectra the methoxy base peak disappear; Then first add 80mL dilution with toluene reaction solution, then use successively 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash, at last with the organic phase anhydrous sodium sulfate drying, after underpressure distillation, resulting transparent liquid is siliceous alkene.
Add 41.4g (0.24mol) metachloroperbenzoic acid and 200mL methylene dichloride in the flask that mechanical stirring, thermometer and constant pressure funnel are housed, mix the siliceous alkene that the above-mentioned reaction of rear dropping makes, cross after 24 hours 25 ℃ of reactions and filter out white solid, gained filtrate is used saturated aqueous sodium thiosulfate, 10% sodium bicarbonate and distilled water wash successively, with the organic phase anhydrous sodium sulfate drying, after underpressure distillation, resulting transparent liquid is product at last.
To this products therefrom carry out nuclear magnetic spectrogram analyze after as can be known, the present embodiment product is two [(5-oxa-Fourth Ring [6.2.1.0.0] undecane-9-yl) oxyethyl group] phenyl methyl silane, its structural formula can be expressed as:
Embodiment 5:
15.2g (0.1mol) methyl silicate, 46.46g (0.4mol) 3-ethyl-3-methylol trimethylene oxide and 0.34g (0.001mol) tetrabutyl titanate are placed in a round-bottomed flask, vacuumize under whipped state 60 ℃ of reactions until methoxy base peak disappearance in proton nmr spectra; Then first add 80mL dilution with toluene reaction solution, using successively 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash, at last with the organic phase anhydrous sodium sulfate drying, after underpressure distillation, resulting transparent liquid is product.
To this products therefrom carry out nuclear magnetic spectrogram analyze after as can be known, the present embodiment product is four (3-Ethyloxetane-3-methoxyl group) silane.
Said process can adopt reaction formula to be expressed as:
Embodiment 6:
19.8g (0.1mol) phenyltrimethoxysila,e, 122g (1.05mol) 4-hydroxybutyl vinyl ether and 0.34g (0.001mol) tetrabutyl titanate are placed in a round-bottomed flask, and the lower 80 ℃ of reactions of whipped state are until methoxy base peak disappearance in proton nmr spectra; Then first add 80mL dilution with toluene reaction solution, then use successively 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash, at last with the organic phase anhydrous sodium sulfate drying, after underpressure distillation, resulting transparent liquid is product.
To this products therefrom carry out nuclear magnetic spectrogram analyze after as can be known, the present embodiment product is three (4-vinyl ether butoxy) phenyl silane.
Said process can adopt reaction formula to be expressed as:
Embodiment 7:
24.4g (0.1mol) dimethoxydiphenylsilane, 139.3g (1.2mol) 4-hydroxybutyl vinyl ether and 0.28g (0.001mol) titanium isopropylate are placed in a round-bottomed flask, react until methoxy base peak disappearance in proton nmr spectra at 100 ℃ under whipped state; Then first add 80mL dilution with toluene reaction solution, then use successively 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash, at last with the organic phase anhydrous sodium sulfate drying, after underpressure distillation, resulting transparent liquid is product.
To this products therefrom carry out nuclear magnetic spectrogram analyze after as can be known, the present embodiment product is two (4-vinyl ether butoxy) diphenyl silane, its structural formula can be expressed as:
Embodiment 8:
Different ratios listed in cation photocuring silicon-containing compound and commercialization bisphenol A epoxide resin (EP828) according to the form below with preparation in embodiment 1 mixes, the salt compounded of iodine cation light initiator (Iragcure250) that adds respectively 4% weight, stirring mixes it, make the sample rod of long 14cm, wide 6.5 ± 0.5mm, thick 3mm, be placed in 10 centimetres of lamps apart from the place, with the medium pressure mercury lamp F300S-6 irradiation that U.S. Fusion UV Systems company produces, solidified sample is measured its oxygen index with ZRY type oxygen index measurer.The results listed in the following table for it:
The cation photocuring silicon-containing compound that adopts method of the present invention to prepare can be used as fire retardant and is applied in the coatings such as material of construction, electronic product, textiles and electric wire, is a kind of environment friendly flame retardant.
Claims (5)
1. the silicon oxide compound of a cation ultraviolet curing group-containing is characterised in that its general molecular formula is:
Wherein, m is 0～2 integer, and n is 2～4 integer, R
1Be the cation photocuring group, described cation photocuring radicals R
1Be following structure :-CH
2CH
2CH
2CH
2OCH=CH
2,-R
5,-CH
2R
5,-CH
2CH
2O (CO) R
5,-CH
2CH
2OR
6,-CH
2CH
2OCH
2CH
2OR
6Wherein, R
5Be that ice alkane-2-base, R fall in 5,6-epoxy
6Be 5-oxa-Fourth Ring [6.2.1.0.0] undecane-9-base, R
2And R
3Group is methyl or phenyl.
2. the preparation method of the silicon oxide compound of the described cation ultraviolet curing group-containing of claim 1, it is characterized in that: adopt monohydroxy vinyl ethers and methoxy silane (1～6) * n in molar ratio: 1, mix to proton nmr spectra under catalyzer exists in the disappearance of methoxy base peak, or, first use monohydroxy olefin(e) compound and methoxy silane (1～6) * n in molar ratio: 1, mix to proton nmr spectra under catalyzer exists in, the methoxy base peak disappears, the siliceous olefin(e) compound that then will obtain is added drop-wise in the organic solution of organic peroxide acid and carries out epoxidation reaction, wherein, this monohydroxy vinyl ethers is 4-hydroxybutyl vinyl ether, this methoxy silane is methyl silicate, phenyltrimethoxysila,e, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxy silane, methyltrimethoxy silane or dimethyldimethoxysil,ne, wherein in molecule, the number n of silica carbon bond is 2～4 integer, described monohydroxy olefin(e) compound is 5-norbornylene-2-alcohol, 5-norbornylene-2-methyl alcohol, 5-norbornylene-2-carboxylic acid-(2-hydroxyethyl) ester, 2-(three ring [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) ethanol or 2-[2-(three ring [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) oxyethyl group] ethanol, their structural formula is respectively:
5-norbornylene-2-alcohol 5-norbornylene-2-methyl alcohol 5-norbornylene-2-carboxylic acid-(2-hydroxyethyl) ester
2-(three ring [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) ethanol 2-[2-(three ring [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) oxyethyl group] ethanol.
3. the preparation method of the silicon oxide compound of cation ultraviolet curing group-containing as claimed in claim 2, be characterised in that described catalyzer is positive tetraethyl titanate, titanium isopropylate, tetrabutyl titanate or metatitanic acid 2-ethylhexyl.
4. the preparation method of the silicon oxide compound of cation ultraviolet curing group-containing as claimed in claim 2, be characterised in that described organic peroxide acid be Peracetic Acid, peroxide propynoic acid, benzoyl hydroperoxide, metachloroperbenzoic acid, to nitro benzoyl hydroperoxide or a nitro benzoyl hydroperoxide.
5. the preparation method of the silicon oxide compound of cation ultraviolet curing group-containing as claimed in claim 2, be characterised in that described organic solvent is methylene dichloride, chloroform, tetracol phenixin, N, dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or ethyl acetate.
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| JP6718048B2 (en) * | 2017-06-30 | 2020-07-08 | 協立化学産業株式会社 | Novel polymerizable compound and flexible resin composition |
| CN112979692A (en) * | 2021-03-01 | 2021-06-18 | 宁波公牛电器有限公司 | Modified silane compound, hand feeling coating, electrical product and preparation method |
| CN113620985B (en) * | 2021-08-13 | 2022-09-27 | 合肥工业大学 | Silicon-containing oxetane derivative and preparation method and application thereof |
| CN113816985B (en) * | 2021-09-15 | 2022-11-11 | 同济大学 | Twin monomer containing cationic polymerizable group and preparation method and application thereof |
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| CN1416447A (en) * | 2000-02-18 | 2003-05-07 | 罗狄亚化学公司 | Plastic material surface treatment with polymerisable and/or crosslinkable organic compsn. having reactive functions |
| GB2393444A (en) * | 2002-09-25 | 2004-03-31 | Coates Brothers Plc | Compositions comprising photoinitiator and oxetane compound |
| CN1930213A (en) * | 2005-02-08 | 2007-03-14 | 横滨橡胶株式会社 | Oxetane compound and hardenable composition containing the same |
| CN101481458A (en) * | 2009-01-20 | 2009-07-15 | 大连理工大学 | Flame-retardant silicon-containing liquid alicyclic epoxy resin and preparation thereof |
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