CN103881031B - A kind of photocureable coating special-purpose organic silicon resin and preparation technology thereof - Google Patents
A kind of photocureable coating special-purpose organic silicon resin and preparation technology thereof Download PDFInfo
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- CN103881031B CN103881031B CN201410058584.8A CN201410058584A CN103881031B CN 103881031 B CN103881031 B CN 103881031B CN 201410058584 A CN201410058584 A CN 201410058584A CN 103881031 B CN103881031 B CN 103881031B
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Abstract
The present invention relates to photocureable coating field, particularly a kind of organosilicon photocureable coating and preparation method thereof. Concrete preparation process of the present invention is: by basic organic silicon monomer, extraordinary organic silicon monomer, silane coupler, by certain raw material proportioning, join in organic solvent and fully mix, be added drop-wise in the water that contains ether, ketone or ester class and carry out cohydrolysis, by controlled hydrolysis temperature and hydrolysis time, make organic siliconresin prepolymer; Add extraordinary organic matter monomer, under catalyst action, block reaction and graft reaction are carried out in pressurization, heating again; Under condition of negative pressure, remove low molecule, desolvation again, until deviate from without low molecule, represent to have reacted, cooling, adds active solvent, fully dissolves.
Description
Technical field
The present invention relates to a kind of resin and preparation field thereof, particularly a kind of photocureable coating special-purpose organic silicon resin and preparation technology thereof.
Background technology
The excellent properties of organic siliconresin is generally familiar with by people, along with the change of synthetic resin composition of raw materials, can synthesize the organic siliconresin of many special performances, such as, what have can be high temperature resistant, low temperature resistant, what have can be by force and firmly, what have is all right strong and tough, and what have can radiation hardness, and what have can also high insulation etc. Although the performance of organic siliconresin is different, it is as coating resin, and its paint solidification method is more single, is all conventionally to adopt the heat cure of solvent-borne type high temperature.
This paint solidification method is traditional, easy and simple to handle, can spray, and can brush, and can flood. But last curing molding is all wanted the high temperature of 160～200 DEG C. Therefore, some occasion, for example super-huge parts, the base materials of non-refractory etc., cannot implement, and its application will be restricted, moreover this class coating generally has solvent conventionally, brings adverse influence to environment.
The developing direction of coatings industry, except invention and introducing high performance resin, also will reduce the toxicity in work progress, and solvent-free photocureable coating is also the direction of a development.
Solvent-free being not equal to do not have solvent, but in Light Curing, the common film forming of solvent and resin, no longer includes solvent evaporates, and therefore this kind solvent is called active solvent.
Photocureable coating comes out now, but resin used is generally universal, and as previously mentioned, these paint solidification methods, are all to adopt the heat cure of solvent-borne type high temperature conventionally. And the property of organic siliconresin, be incorporated in solvent-free photocureable coating, be very significant as special high performance resin, be also an important technological break-through of photocureable coating aspect.
Therefore, require synthetic one or a series of organic siliconresin, they must realize photocuring, at room temperature, in ultraviolet ray several seconds to tens of second irradiation time, organic siliconresin is realized rapidly crosslinked, becomes insoluble macromolecule membrane, and this organic siliconresin, there is good compatibility with selected active solvent.
Summary of the invention
Technical problem to be solved by this invention is: the synthetic organic siliconresin of existing process is applied on coatings industry, needs heating to solidify.
For solving this technical problem, the invention provides under a kind of room temperature, the organic siliconresin that photocureable coating is special and preparation technology thereof, with the synthetic photocureable coating special-purpose organic silicon resin of the method, both there is advantage and the characteristic of organic siliconresin, can meet again the requirement that realizes photocuring completely, and good with active solvent compatibility.
The concrete technical scheme adopting of the present invention is:
The invention provides a kind of can carrying out at normal temperatures in the coating of photocuring, the organic siliconresin that adopts.
The preparation method of above-mentioned photocureable coating special-purpose organic silicon resin is that concrete technology is as follows:
A, preparation starting monomer
Starting monomer comprises organic silicon monomer (wherein, organic silicon monomer comprises basic organic silicon monomer and extraordinary organic silicon monomer) and extraordinary organic matter monomer,
Basic organic silicon monomer is two or more the organic silicon monomer material blends in dimethyldichlorosilane, diphenyl dichlorosilane, Trichloromethyl silane and a phenyl trichlorosilane,
Wherein, dimethyldichlorosilane, this is the substantially linear skeleton of polysiloxanes,
Diphenyl dichlorosilane, this is the linear material of polysiloxanes, is again high temperature resistant, the main contributions person of shielding property and raising and solvent and polymer-polymer miscibility,
Trichloromethyl silane, this is the main component of organic siliconresin cross-linked structure,
One phenyl trichlorosilane, this is the main component of organic siliconresin cross-linked structure,
For above-mentioned 4 kinds of basic organic silicon monomers, Trichloromethyl silane and a phenyl trichlorosilane, in formula of the present invention, be must have, and all the other two kinds of monomers, can add as required or not add,
Extraordinary organic silicon monomer is (as the triethoxysilane containing epoxy radicals containing the organic silicon monomer (methyl ethylene dichlorosilane) of two key groups, the organic silicon monomer (methyl hydrogen dichlorosilane) that contains active hydrogen and silane coupler; containing the triethoxysilane of ester group; and the triethoxysilane of amino-contained, acryloyl group etc.) in more than a kind organic silicon monomer material
As preferably: in total organic silicon monomer, the organic group R number on silicon atom and the ratio of silicon atom number, R/Si is between 1.0～1.6, and phenyl number accounts for 15～60% of total R number, and extraordinary organic silicon monomer quality accounts for 10～40% of organic silicon monomer gross mass,
Further: in total organic silicon monomer, the organic group R number on silicon atom and the ratio of silicon atom number, R/Si is between 1.1～1.4, and phenyl number accounts for 20～40% of total R number, and extraordinary organic silicon monomer quality accounts for 10～25% of organic silicon monomer gross mass,
Extraordinary organic matter monomer is the polyfunctional group organic compound that contains two keys, as the mixture of one or more monomers in methacrylic acid, acrylic acid, methyl acrylate, methyl methacrylate, hydroxypropyl acrylate, hydroxy-ethyl acrylate, two hydroxy acrylate, acrylic acid ethylene glycol, maleic anhydride and fumaric acid anhydride;
B, by ready basic organic silicon monomer and extraordinary organic silicon monomer in steps A, join in organic solvent and fully after mixing, obtain organic silicon monomer mixed liquor, the organic silicon monomer mixed liquor obtaining is added drop-wise in the water that contains ether, ketone or ester, carry out cohydrolysis, make organic siliconresin prepolymer system
Wherein, organic solvent is boiling point lower than the water-fast organic solvent of 120 DEG C, and organic solvent quality equals monomer mass (0.8-1.2 times that organic solvent quality is monomer mass) substantially,
Ketone, ether or ester are respectively butanone, cyclohexanone; Butyl ether; Ethyl acetate, this kind solvent has good compatibility with monomer, reacts mitigation, prevents into ring and crosslinked,
In this step, organic silicon monomer mixed liquor is added drop-wise in the water that contains ether, ketone or ester, carries out cohydrolysis, be specially, hydrolysis temperature is controlled at below 25 DEG C, preferably 5-10 DEG C, and time for adding is controlled at 3-5 hours. In order to make reaction more abundant, after dropwising, can also continue to react 15-30 minutes,
The quality of water is the more than 1.5 times of organic silicon monomer gross mass, and preferably 2-3 times, the quality of ketone, ether or ester is water quality 1/3-1/2;
C, in the organic siliconresin prepolymer system obtaining in step B, add extraordinary organic matter monomer, under catalyst action, heating, compressive reaction (block reaction and graft reaction), then under condition of negative pressure, remove low molecule, desolvation, until while deviating from without low molecule, represent to have prepared, obtain photocureable coating special-purpose organic silicon resin
In step C, specifically, add after extraordinary organic matter monomer, catalyst, heating, compressive reaction a period of time, stop heating, compressive reaction, be adjusted into condition of negative pressure (vacuumizing), remove after low molecule, solvent, reheat again, compressive reaction a period of time, carry out negative pressure again and remove low molecule, solvent, so cycling, until when deviate from without low molecule, be enough to represent to have prepared
The catalyst of block and graft reaction is the salt of transition metal, mainly contains PtCl6, lithium acetate, zinc acetate, zinc octoate, cobalt naphthenate etc., object is that the functional group reactions on organic silicon monomer and silicon atom is completed,
The consumption of catalyst is 0.1%-1% of total overall reaction monomer (organic silicon monomer and extraordinary organic matter monomer) gross mass,
In step C, the quality of the extraordinary organic matter monomer adding, is 15～35% of organic silicon monomer gross mass.
By the organic siliconresin of preparing by above-mentioned steps, be made into photocureable coating, concrete operations are: under normal temperature, in above-mentioned organic siliconresin, add active solvent, fully dissolve,
Active solvent is methyl styrene, vinyltoluene, allyl acrylate or styrene, and in the photocureable coating being made into, solid content is 45-55%(mass fraction).
The invention has the beneficial effects as follows:
The present invention, by regulating the formula of organic silicon monomer, has designed and has had organosilicon special property, and had the organic siliconresin prepolymer of good compatibility. By extraordinary organic silicon monomer cohydrolysis with it, make to there is active group on the main chain of organic siliconresin prepolymer, can carry out grafting and the block polymerization effect of next stage.
Under the effect of extraordinary catalyst, there is the organic monomer of two keys, a part is with the functional group grafting on silicon atom in silicones prepolymer, and a part is reacted with the end group of organic siliconresin prepolymer, forms the block copolymer with two keys.
Synthetic like this organic siliconresin polymer all has a considerable amount of pairs of key groups on main chain and side chain, be beneficial under ultraviolet radiation with active solvent in two keys form radical copolymerizations or ionic combined polymerization, thereby reach the object of photocuring.
Synthesizing of this photocuring special-purpose organic silicon resin; the market and the market demand that meets photocureable coating of photocureable coating are not only greatly opened up; make to have increased in photocureable coating the silicones of high performance heat resistant; and make the market of organic siliconresin to nontoxic solvent-free direction exploitation; for photocureable coating industry has been made contribution; photocureable coating adapts to the requirement that low-carbon (LC) is nontoxic, energy-saving and cost-reducing solvent-free volatilization and waste, protection of the environment, for chemistry painting industry industry is made significant contribution.
Detailed description of the invention
Embodiment 1
A, raw material are by mass:
B, above-mentioned raw materials is joined in 180g toluene, fully mix, mixed liquor is dropped in 400g water and 200g cyclohexanone mixed liquor and is hydrolyzed, hydrolysis temperature is controlled at 5-7 DEG C, within 5 hours, is added dropwise to complete, and obtains organic siliconresin prepolymer system;
C, in the organic siliconresin prepolymer system obtaining in step B, be added dropwise to the mixture of 15g methyl methacrylate and 15g hydroxy-ethyl acrylate, set reaction pressure 0.15MPa, then add 1gPtCl6Catalyst, 180 DEG C of reactions,
Vacuum removal solvent and low-boiling-point substance, until while deviating from without low molecule, represent prepare, lower the temperature, and obtains photocureable coating special-purpose organic silicon resin,
The organic siliconresin of preparing by above-mentioned steps is cooled to 100 DEG C, adds vinyltoluene, being made into solid content is 50%(mass fraction) photocureable coating.
The photocureable coating making in the present embodiment, the key technical indexes is as follows:
Outward appearance: light yellow transparent liquid
Solid content: 50%
Period of storage: half a year above (25 DEG C of preservations)
Ultraviolet curing process:
Utilize the photocureable coating in the present embodiment, add 0.5%(initator to account for the mass percent of photocureable coating) styrax be initator, ultraviolet ray (wavelength is 300nm) is irradiated 20 seconds, rapidly crosslinked film forming, and without unnecessary dissolvent residual, functional (film forming thickness is set according to the requirement of following each performance test standard respectively) of film.
Adhesion property meets GB/T1720-79(89) 1 grade
Heat resistance meets GB/T1735-89 " paint film Heat-tolerance Determination method "
Chemical-resistance meets GB/T1763-89 " paint film chemical reagent resistance determination method "
Wet-hot aging performance meets 1 grade of GB/T1740-91 " paint film wet-heat resisting determination method "
Petrol-resistance can meet GB/T1734-93 " paint film petrol-resistance determination method "
Embodiment 2
A, raw material are by mass:
B, above-mentioned raw materials is joined in 160g toluene, fully mix, mixed liquor is dropped in 400g water and 200g butyl ether mixed liquor and is hydrolyzed, hydrolysis temperature is controlled at 9-10 DEG C, within 3 hours, be added dropwise to complete, in order to make reaction more abundant, after dropwising, continue reaction 15 minutes, obtain organic siliconresin prepolymer system;
C, in the organic siliconresin prepolymer system obtaining in step B, be added dropwise to the mixture of 15g methyl methacrylate and 15g fumaric acid anhydride, set reaction pressure 0.05MPa, then add 0.7g zinc acetate catalyst, 170 DEG C of reactions,
Vacuum removal solvent and low molecule, until while deviating from without low molecule, represent prepare, lower the temperature, and obtains photocureable coating special-purpose organic silicon resin,
The organic siliconresin of preparing by above-mentioned steps is cooled to 100 DEG C, adds styrene, being made into solid content is 45%(mass fraction) photocureable coating.
The photocureable coating making in the present embodiment, the key technical indexes is as follows:
Outward appearance: light yellow transparent liquid
Solid content: 45%
Period of storage: half a year above (25 DEG C of preservations)
Ultraviolet curing process:
Utilize the photocureable coating in the present embodiment, add 0.8%(initator to account for the mass percent of photocureable coating) benzophenone be initator, ultraviolet ray (wavelength is 240nm) is irradiated 20 seconds, rapidly crosslinked film forming, and without unnecessary dissolvent residual, functional (film forming thickness is set according to the requirement of following each performance test standard respectively) of film.
Adhesion property meets GB/T1720-79(89) 1 grade
Heat resistance meets GB/T1735-89 " paint film Heat-tolerance Determination method "
Chemical-resistance meets GB/T1763-89 " paint film chemical reagent resistance determination method "
Wet-hot aging performance meets 1 grade of GB/T1740-91 " paint film wet-heat resisting determination method "
Petrol-resistance can meet GB/T1734-93 " paint film petrol-resistance determination method "
Embodiment 3
A, raw material are by mass:
B, above-mentioned raw materials is joined in 200g toluene, fully mix, mixed liquor is dropped in 400g water and 200g ethyl acetate mixed liquor and is hydrolyzed, hydrolysis temperature is controlled at 7-9 DEG C, within 4 hours, be added dropwise to complete, in order to make reaction more abundant, after dropwising, continue reaction 30 minutes, obtain organic siliconresin prepolymer system;
C, in the organic siliconresin prepolymer system obtaining in step B, be added dropwise to the mixture of 5g methyl methacrylate, 15g fumaric acid anhydride and 10g methacrylic acid, set reaction pressure 0.05MPa, then add 0.6g cobalt naphthenate catalyst, 180 DEG C of reactions,
Vacuum removal solvent and low molecule, until while deviating from without low molecule, represent prepare, lower the temperature, and obtains photocureable coating special-purpose organic silicon resin,
The organic siliconresin of preparing by above-mentioned steps is cooled to 100 DEG C, adds styrene and ethyl acrylate mixture (both mass ratioes are 1:1), being made into solid content is 55%(mass fraction) photocureable coating.
The photocureable coating making in the present embodiment, the key technical indexes is as follows:
Outward appearance: yellow transparent liquid
Solid content: 55%
Period of storage: half a year above (25 DEG C of preservations)
Ultraviolet curing process:
Utilize the photocureable coating in the present embodiment, add 1%(initator to account for the mass percent of photocureable coating) benzoin isopropyl ether be initator, ultraviolet ray (wavelength is 200nm) is irradiated 25 seconds, rapidly crosslinked film forming, and without unnecessary dissolvent residual, functional (film forming thickness is set according to the requirement of following each performance test standard respectively) of film.
Adhesion property meets GB/T1720-79(89) 1 grade
Heat resistance meets GB/T1735-89 " paint film Heat-tolerance Determination method "
Chemical-resistance meets GB/T1763-89 " paint film chemical reagent resistance determination method "
Wet-hot aging performance meets 1 grade of GB/T1740-91 " paint film wet-heat resisting determination method "
Petrol-resistance can meet GB/T1734-93 " paint film petrol-resistance determination method ".
Claims (7)
1. a preparation method for photocureable coating special-purpose organic silicon resin, is characterized in that:
Described photocureable coating can carry out photocuring at normal temperatures;
Described preparation method is as follows:
A, preparation starting monomer
Starting monomer comprises organic silicon monomer and extraordinary organic matter monomer, wherein, organic silicon monomer comprise basic organic silicon monomer andExtraordinary organic silicon monomer,
Basic organic silicon monomer is dimethyldichlorosilane, diphenyl dichlorosilane, Trichloromethyl silane and a phenyl trichlorine siliconTwo or more organic silicon monomer material blends in alkane,
Extraordinary organic silicon monomer is containing the organic silicon monomer of two key groups, organic containing organic silicon monomer and the silane coupler of active hydrogenMore than a kind organic silicon monomer material in silicon monomer,
Organic silicon monomer containing two key groups is methyl ethylene dichlorosilane,
Organic silicon monomer containing active hydrogen is methyl hydrogen dichlorosilane,
Extraordinary organic matter monomer be methacrylic acid, acrylic acid, methyl acrylate, methyl methacrylate, hydroxypropyl acrylate,One or more in hydroxy-ethyl acrylate, two hydroxy acrylate, acrylic acid ethylene glycol, maleic anhydride and fumaric acid anhydrideThe mixture of monomer;
B, by ready basic organic silicon monomer and extraordinary organic silicon monomer in steps A, join in organic solvent fully mixedAfter closing, obtain organic silicon monomer mixed liquor, the organic silicon monomer mixed liquor obtaining is added drop-wise in the water that contains ether, ketone or ester, enterRow cohydrolysis, makes organic siliconresin prepolymer system;
C, in the organic siliconresin prepolymer system obtaining in step B, add extraordinary organic matter monomer, under catalyst action,Heating, compressive reaction, then under condition of negative pressure, remove low molecule, desolvation, until while deviating from without low molecule, represent to makeStandby completing, obtains photocureable coating special-purpose organic silicon resin.
2. the preparation method of photocureable coating special-purpose organic silicon resin as claimed in claim 1, is characterized in that: steps AIn, in described organic silicon monomer, the organic group R number on silicon atom and the ratio of silicon atom number, R/Si is 1.0～1.6Between, and phenyl number accounts for 15～60% of total R number, and extraordinary organic silicon monomer quality accounts for 10～40% of organic silicon monomer gross mass.
3. the preparation method of photocureable coating special-purpose organic silicon resin as claimed in claim 1, is characterized in that: step BIn, the quality of water is the more than 1.5 times of organic silicon monomer gross mass, the quality of ketone, ether or ester is water quality 1/3-1/2.
4. the preparation method of photocureable coating special-purpose organic silicon resin as claimed in claim 1, is characterized in that: steps AIn, in described organic silicon monomer, the organic group R number on silicon atom and the ratio of silicon atom number, R/Si is 1.1～1.4Between, and phenyl number accounts for 20～40% of total R number, and extraordinary organic silicon monomer quality accounts for 10～25% of organic silicon monomer gross mass.
5. the preparation method of photocureable coating special-purpose organic silicon resin as claimed in claim 1, is characterized in that: step CIn, the quality of the extraordinary organic matter monomer adding, is 15～35% of organic silicon monomer gross mass.
6. the preparation method of photocureable coating special-purpose organic silicon resin as claimed in claim 1, is characterized in that: step BIn, described organic solvent is boiling point lower than the water-fast organic solvent of 120 DEG C.
7. the preparation method of photocureable coating special-purpose organic silicon resin as claimed in claim 1, is characterized in that: step BIn, described is added drop-wise to organic silicon monomer mixed liquor in the water that contains ether, ketone or ester, carries out cohydrolysis, is specially hydrolysisTemperature is controlled at 5-10 DEG C, and time for adding is controlled at 3-5 hours.
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| CN107236449B (en) * | 2016-03-29 | 2018-06-29 | 沙河市湡久新材料有限公司 | UV curing types hard coating and weatherability hard coat film obtained by being coated with the hard coating |
| CN106432736A (en) * | 2016-10-21 | 2017-02-22 | 湖南师范大学 | Preparation method of novel UV (Ultraviolet) curable polyfunctionality functional organosilicane monomer and application of novel UV curable polyfunctionality functional organosilicane monomer in stain resisting coating |
| CN108676125B (en) * | 2018-06-05 | 2020-04-28 | 南雄市瑞晟化学工业有限公司 | Organic silicon graft modified glass ultraviolet curing resin |
| CN110183670A (en) * | 2019-06-04 | 2019-08-30 | 无锡博强高分子材料科技有限公司 | A kind of bipolarity dissaving polymer UV matt process for preparing resins and the resin |
| CN110734547B (en) * | 2019-10-25 | 2022-04-08 | 常州市嘉诺有机硅有限公司 | Method for preparing organic silicon resin through stepwise hydrolysis |
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| CN101034258A (en) * | 2006-10-25 | 2007-09-12 | 深圳市飞世尔实业有限公司 | Liquid light curing resin composition |
| CN101463222A (en) * | 2007-12-20 | 2009-06-24 | 比亚迪股份有限公司 | UV curing color coating |
| CN101555386A (en) * | 2009-05-07 | 2009-10-14 | 中国科学院广州化学研究所 | Epoxy organosilicone ultraviolet curing coating modified by (methyl) acrylic acid and preparation method thereof |
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| CN101034258A (en) * | 2006-10-25 | 2007-09-12 | 深圳市飞世尔实业有限公司 | Liquid light curing resin composition |
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