CN101906114A - 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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- CN101906114A CN101906114A CN 201010215782 CN201010215782A CN101906114A CN 101906114 A CN101906114 A CN 101906114A CN 201010215782 CN201010215782 CN 201010215782 CN 201010215782 A CN201010215782 A CN 201010215782A CN 101906114 A CN101906114 A CN 101906114A
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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 advantages such as fast, the low organic volatile of solvent-free or low solvent, curing speed and film performance be good with it replace traditional solvent based coating just gradually.Ultraviolet light polymerization has radically curing and two kinds of mechanism of cationic curing, wherein the radical photoinitiator cure applications is 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, make its application be subjected to certain restriction.Compare with radically curing, cationic curing then can remedy above-mentioned defective, and the cationic curing volumetric shrinkage is little, and cured film is to the strong adhesion of various base materials; There is not 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, the fire retardant that R and D have environment friendly has been subjected to paying 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, the gained material has excellent flame-retardant performance.But it adopts thermofixation, exists energy consumption height, curing speed slow, and can discharge volatile organic matter shortcomings such as (VOC).
U.S.'s " organic coating progress " (Progress in Organic Coatings, 2009,65:263-268) reported phosphorated trifunctional cycloaliphatic epoxy resin and preparation method thereof, and this phosphorated trifunctional cycloaliphatic epoxy resin mixed with commercialization difunctionality cycloaliphatic epoxy resin (UVR-6110), obtain phosphorated 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 heavy-gravity siloxane polymer, but there are the problem of dispersed and interface compatibility in this additive flame retardant and resin, and heavy addition can cause resin thermal property and the bigger 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, different additions have been compared in the resin to the influence of flame retardant properties with the reactive flame retardant of diglycidyl methylphenyl siloxane monomer as bisphenol A epoxide resin system (DGEBA).But because it adopts the thermofixation mode, compare with the ultraviolet light polymerization mode and exist energy consumption height, curing speed slow, and can discharge volatile organic matter shortcomings such as (VOC).
Chinese patent CN101481458A has reported a kind of flame retardant resistance cycloaliphatic epoxy resin and preparation method thereof, earlier with halogenated silanes and the condensation of alicyclic olefin alkylol cpd, again with double bond epoxidation, obtains siliceous liquid alicyclic epoxy resin.Because employed halogenated silanes has intensive corrodibility in this method, and condensation reaction is fierce and complicated, need to remove 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 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,, adopt cation photocuring to obtain siliceous flame retardant coating to overcome the above-mentioned defective of prior art.
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 a 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 5, ice alkane-2-base, R fall in the 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, in the presence of catalyzer, mix to methoxy base peak disappearance in the proton nmr spectra; Or, use monohydroxy olefin(e) compound and methoxy silane (1～6) * n in molar ratio earlier: 1, mix in the proton nmr spectra methoxy base peak and disappear in the presence of catalyzer, the siliceous olefin(e) compound that will obtain then is added drop-wise in the organic solution of organic peroxide acid and carries out epoxidation reaction; Wherein the number n of silica carbon bond is 2～4 integer in the molecule.
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 rings [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) ethanol or 2-[2-(three rings [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 rings [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) ethanol 2-[2-(three rings [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, N, dinethylformamide, 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, though its phosphorous-containing monomers has given cured film very high oxygen index, but its heat curing process energy consumption height, the polyphosphoric acid that produces during the phosphonium flame retardant burning has corrosive nature to metal; And the cation photocuring silicon-containing compound among the present invention has been owing to introduced element silicon and contained the ultraviolet light polymerization group, and energy consumption is low when solidifying by contrast, 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) Bao Dao phosphorated trifunctional cycloaliphatic epoxy resin and cation photocuring fire retardant material thereof, the polyphosphoric acid that produces during its burning has corrosive nature to metal; And the cation photocuring silicon-containing compound among 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 heavy addition 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) Bao Dao thermoset diglycidyl methylphenyl siloxane monomer 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 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 is adopted among the preparation method of the present invention is a pH neutrality, does not have corrodibility, side reaction is few, the productive rate height, 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, the flame retarding efficiency height.
Description of drawings
Fig. 1 is the infrared spectrum of preparation product among the embodiment 1.
Fig. 2 is the nucleus magnetic hydrogen spectrum of preparation product among the embodiment 1.
Fig. 3 is the nuclear-magnetism carbon spectrum of preparation product among the embodiment 1.
Embodiment
Describe the 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 below 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 a round-bottomed flask, disappear at 100 ℃ of reactions methoxy base peak in proton nmr spectra under the whipped state; After excessive 3-tetrahydrobenzene-1-methyl alcohol is removed in decompression, add 80mL dilution with toluene reaction solution, use 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash then successively, with the organic phase anhydrous sodium sulfate drying, resulting transparent liquid is siliceous alkene after the underpressure distillation at last.
In the flask that mechanical stirring, thermometer and constant pressure funnel are housed, add 62.1g (0.36mol) metachloroperbenzoic acid and 200mL methylene dichloride, mix the back and drip the siliceous alkene that above-mentioned reaction makes, remove white solid at 24 hours after-filtration of 25 ℃ of reactions, gained filtrate is used saturated aqueous sodium thiosulfate, 10% sodium bicarbonate and distilled water wash successively, with the organic phase anhydrous sodium sulfate drying, resulting transparent liquid is product after the underpressure distillation at last.
Above-mentioned products therefrom is carried out the infrared spectrum analysis, Fig. 1 be in the present embodiment preparation product infrared spectrum, from this infrared spectrum as seen at 808cm
-1There is tangible 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 the nucleus magnetic hydrogen spectrum and the nuclear-magnetism carbon spectrums of preparation product in the present embodiment.The fignal center at 51.2ppm and 52.2ppm place had further proved the epoxide group existence during the fignal center of 3.03-3.26ppm and nuclear-magnetism carbon were composed 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 a round-bottomed flask, disappear at 100 ℃ of reactions methoxy base peak in proton nmr spectra under the whipped state; Add 80mL dilution with toluene reaction solution then earlier, use 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash more successively, at last with the organic phase anhydrous sodium sulfate drying, the transparent liquid that underpressure distillation obtains is siliceous alkene.
In the flask that mechanical stirring, thermometer and constant pressure funnel are housed, add 62.1g (0.36mol) metachloroperbenzoic acid and 160mL methylene dichloride and 40mLN, the mixed solvent that dinethylformamide is formed, mix the back and drip the siliceous alkene that above-mentioned reaction 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, resulting transparent liquid is product after the underpressure distillation at last.
To this products therefrom carry out nuclear magnetic spectrogram analyze after as can be known, the present embodiment product is three (5, ice alkane-2-methoxyl group falls in the 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 a round-bottomed flask, vacuumize under the whipped state in 50 ℃ of reactions methoxy base peak disappearance in proton nmr spectra; Add 80mL dilution with toluene reaction solution then earlier, use 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash more successively, at last with the organic phase anhydrous sodium sulfate drying, the transparent liquid that obtains after the underpressure distillation is siliceous alkene.
In the flask that mechanical stirring, thermometer and constant pressure funnel are housed, add 82.8g (0.48mol) metachloroperbenzoic acid and 250mL methylene dichloride, mix the back and drip the siliceous alkene that above-mentioned reaction makes, remove white solid at 24 hours after-filtration of 25 ℃ of reactions, gained filtrate is used saturated aqueous sodium thiosulfate, 10% sodium bicarbonate and distilled water wash successively, with the organic phase anhydrous sodium sulfate drying, resulting transparent liquid is product after the underpressure distillation 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 rings [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 a round-bottomed flask, disappear at 100 ℃ of reactions methoxy base peak in proton nmr spectra under the whipped state; Add 80mL dilution with toluene reaction solution then earlier, use 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash more successively, at last with the organic phase anhydrous sodium sulfate drying, resulting transparent liquid is siliceous alkene after the underpressure distillation.
In the flask that mechanical stirring, thermometer and constant pressure funnel are housed, add 41.4g (0.24mol) metachloroperbenzoic acid and 200mL methylene dichloride, mix the back and drip the siliceous alkene that above-mentioned reaction makes, remove white solid at 24 hours after-filtration of 25 ℃ of reactions, gained filtrate is used saturated aqueous sodium thiosulfate, 10% sodium bicarbonate and distilled water wash successively, with the organic phase anhydrous sodium sulfate drying, resulting transparent liquid is product after the underpressure distillation 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 a round-bottomed flask, vacuumize under the whipped state in 60 ℃ of reactions methoxy base peak disappearance in proton nmr spectra; Add 80mL dilution with toluene reaction solution then earlier, using 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash successively, at last with the organic phase anhydrous sodium sulfate drying, resulting transparent liquid is product after the underpressure distillation.
To this products therefrom carry out nuclear magnetic spectrogram analyze after as can be known, the present embodiment product is four (3-ethyl trimethylene oxide-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 a round-bottomed flask, and the following 80 ℃ of reactions of whipped state methoxy base peak in proton nmr spectra disappears; Add 80mL dilution with toluene reaction solution then earlier, use 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash more successively, at last with the organic phase anhydrous sodium sulfate drying, resulting transparent liquid is product after the underpressure distillation.
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 a round-bottomed flask, disappear at 100 ℃ of reactions methoxy base peak in proton nmr spectra under the whipped state; Add 80mL dilution with toluene reaction solution then earlier, use 5% aqueous tartaric acid solution, 5% sodium bicarbonate aqueous solution and distilled water wash more successively, at last with the organic phase anhydrous sodium sulfate drying, resulting transparent liquid is product after the underpressure distillation.
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 among the embodiment 1 mixes, the salt compounded of iodine cation light initiator (Iragcure250) that adds 4% weight respectively, stirring mixes it, make the sample rod of long 14cm, wide 6.5 ± 0.5mm, thick 3mm, place 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 limiting oxygen index determination instrument.It the results are shown in the following table:
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 (10)
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 cation photocuring group, R
2And R
3Group is a methyl or phenyl.
2. the silicon oxide compound of cation ultraviolet curing group-containing as claimed in claim 1 is characterised in that described cation photocuring radicals R
1Be 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 5, ice alkane-2-base, R fall in the 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.
3. 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 or monohydroxy-3-oxygen heterocycle butane and methoxy silane (1～6) * n in molar ratio: 1, in the presence of catalyzer, mix to methoxy base peak disappearance in the proton nmr spectra; Or, use monohydroxy olefin(e) compound and methoxy silane (1～6) * n in molar ratio earlier: 1, mix in the proton nmr spectra methoxy base peak and disappear in the presence of catalyzer, the siliceous olefin(e) compound that will obtain then is added drop-wise in the organic solution of organic peroxide acid and carries out epoxidation reaction; Wherein the number n of silica carbon bond is 2～4 integer in the molecule.
4. as the preparation method of the silicon oxide compound of cation ultraviolet curing group-containing as described in the claim 3, be characterised in that described monohydroxy vinyl ethers compound is 4-hydroxybutyl vinyl ether or Diethylene Glycol mono vinyl ether.
5. as the preparation method of the silicon oxide compound of cation ultraviolet curing group-containing as described in the claim 3, be characterised in that described monohydroxy-3-oxygen heterocycle butane is 3-methyl-3-methylol trimethylene oxide or 3-ethyl-3-methylol trimethylene oxide.
6. as the preparation method of the silicon oxide compound of cation ultraviolet curing group-containing as described in the claim 3, be characterised in that described catalyzer is positive tetraethyl titanate, titanium isopropylate, tetrabutyl titanate or metatitanic acid 2-ethylhexyl.
7. as the preparation method of the silicon oxide compound of cation ultraviolet curing group-containing as described in the claim 3, be characterised in that described methoxy silane is methyl silicate, phenyltrimethoxysila,e, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxy silane, methyltrimethoxy silane or dimethyldimethoxysil,ne.
8. as the preparation method of the silicon oxide compound of cation ultraviolet curing group-containing as described in the claim 3, be characterised in that 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 rings [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) ethanol or 2-[2-(three rings [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) oxyethyl group] ethanol, their structural formula is 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 rings [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) ethanol 2-[2-(three rings [5.2.1.0] last of the ten Heavenly stems-4-alkene-8-base oxygen) oxyethyl group] ethanol.
9. as the preparation method of the silicon oxide compound of cation ultraviolet curing group-containing as described in the claim 3, be characterised in that described organic peroxide acid be Peracetic Acid, peroxide propynoic acid, benzoyl hydroperoxide, metachloroperbenzoic acid, to nitro benzoyl hydroperoxide, nitro benzoyl hydroperoxide or potassium hydrogen persulfate composite salts.
10. as the preparation method of the silicon oxide compound of cation ultraviolet curing group-containing as described in the claim 3, 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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| 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 |
| CN113620985A (en) * | 2021-08-13 | 2021-11-09 | 合肥工业大学 | Silicon-containing oxetane derivative and preparation method and application thereof |
| CN113816985A (en) * | 2021-09-15 | 2021-12-21 | 同济大学 | Twin monomer containing cationic polymerizable group and preparation method and application thereof |
| CN114133410A (en) * | 2021-12-07 | 2022-03-04 | 同济大学 | Oligomeric siloxane containing accelerant and cationic polymerizable group, preparation and application thereof |
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| CN106086990A (en) * | 2016-08-04 | 2016-11-09 | 北京工业大学 | A kind of method of the immobilized molybdenum bisuphide of porous titania thin films |
| CN106086990B (en) * | 2016-08-04 | 2019-02-01 | 北京工业大学 | A kind of method of the immobilized molybdenum disulfide of porous titania thin films |
| JP2019011296A (en) * | 2017-06-30 | 2019-01-24 | 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 |
| CN113620985A (en) * | 2021-08-13 | 2021-11-09 | 合肥工业大学 | Silicon-containing oxetane derivative and preparation method and application thereof |
| CN113816985A (en) * | 2021-09-15 | 2021-12-21 | 同济大学 | Twin monomer containing cationic polymerizable group 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 |
| CN114133410A (en) * | 2021-12-07 | 2022-03-04 | 同济大学 | Oligomeric siloxane containing accelerant and cationic polymerizable group, preparation and application thereof |
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