CN101948561A - Organic/inorganic silicon hybrid resin for coating and preparation method thereof - Google Patents
Organic/inorganic silicon hybrid resin for coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic/inorganic silicon hybrid resin for coating and a preparation method thereof. The hybrid resin has an organic/inorganic hybrid structure formed by grafting inorganic SiO2 particles onto the main chain of an organic polymer resin. The preparation method comprises: preparing SiO2 sol with a proper particle size by using a sol-gel process or dispersing a commercial nano SiO2 powder material in an organic solvent to form sol; and modifying the surface of the nano SiO2 by using organo-siloxane to provide reactivity for the nano SiO2, so that the nano SiO2 and a polymerizing monomer can copolymerize to form the hybrid resin for coating. In the hybrid resin, the inorganic component SiO2 is kept on a nano scale. The hybrid resin can be used as a film forming resin for preparing organic and inorganic hybrid coating and nano coating, so that the coating have the high mechanical performance and high weather resistance of inorganic materials and the high flexibility, attractive appearance and other prosperities of organic materials.
Description
Technical field
The present invention relates to a kind of coating organic/inorganic sila resin and preparation method thereof, this resin can make the hybridized nanometer coating that has inorganic materials and organic polymer advantage concurrently as filmogen.
Background technology
Hybrid coating is the very popular field of Recent study.Hybrid coating principal feature is to have a base-material composition that two or more belongs to organism and inorganics respectively, and key wherein is whether inorganic components participates in the granularity of interaction of film forming curing, inorganic components and organic moiety (chemical bond or weak interaction etc.) and inorganic components and dispersion state etc.For other performance (as outward appearance, stability or the like) that does not influence coating, inorganic components usually is in nanometer dimension, so hybrid coating belongs to the category of nano paint again.Inorganic ceramic paint has very excellent weathering resistance, high rigidity and scuff resistance, but its processing film-forming properties is relatively poor, and is crisp and be prone to crackle.It is good that organic binder is easily processed snappiness, but its chemicals-resistant, weathering resistance and mechanical property have certain limitation, though can be by suitably improving its performance as increasing modes such as cross-linking density, but the raising degree is limited and might influence other performance, can cause filming and shrinks sticking power variation or the like as improving cross-linking density.If can the advantage of organic materials and inorganic materials is fully inclusive and equitable, just can obtain high performance coating, the motivating force of Here it is hybrid coating origin.
Generally speaking, hybrid systems roughly can be divided into following four classes: (1) inorganic matrix: a spot of organic materials joins in a large amount of inorganic matrixes, be embedded in simply wherein after the mixing, epoxy zinc rich primer common in the engineering machinery coating can be considered as this hybrid systems; (2) organic substrate: almost any common coating that contains inorganic color stuffing all is considered to such system, but this is a simple definition only, and this system is limited to the coating that those inorganic materials combine with organic constituent securely in the adherent mode in fact; (3) IPN (interpenetrating polymer networks system): organic and inorganic polymer network structure forms separately separately, but slightly bonds together.What contain collosol-gelatum system in the polymkeric substance is exactly the coating of this type; (4) real hybrid systems: organic and inorganic two kinds of systems interconnect with chemical bond and form real molecular hybrid.Be to improve the hybrid form that coating performance all can't be gone beyond by additive method in other words to greatest extent.
Inorganics and organism are inconsistent, and it is very difficult wanting both are formed all stable in the lump system of a mixing.Being seen in methods maximum in bibliographical information has: physical blending method, sol-gel method, situ aggregation method or the like.The physical blending method has simple to operate, and technology is simple, industrial feasibility height.Blending method can be with the nanoparticle of various forms, again by different methods (mechanical stirring, ultrasonic wave) thus itself and organic resin blend are obtained hybridization coating.It is that the dispersion of nanoparticle is with stable that but there is the most key problem in the physical blending method.Nano-powder is the degree that is difficult to be distributed to primary particle by general coating material production dispersion grinding equipment commonly used, and the existence of big particle diameter coacervate not only influences the outward appearance (gloss, the transparency and paint film smooth or the like) of paint film and also can influence the validity that it improves the paint film over-all properties.Situ aggregation method is used original position and is filled and make nanoparticle homodisperse in monomer, then polymerization in situ under certain condition and form matrix material.The particle filled composite of the matrix material of this method preparation is uniformly dispersed, and particle is not easy to reunite, and has kept the nano-scale characteristic of particle preferably.Because it requires under the state of polymer melt or solution and do not add the people, avoided therefore and the degraded that produces guarantees the stable of various fundamental propertys.Sol-gel method is a kind of method of using in the nanoparticle preparation the earliest, and beginning to use from the eighties in 20th century becomes the method that present use the most extensively prepares hybrid coating so far.Its specific practice is that precursors such as siloxanes or metal-salt (water-soluble salt or oil soluble alkoxide) are formed homogeneous solution in the water-soluble or organic solvent, and solute generation hydrolysis reaction generates nanoparticle and also forms colloidal sol, and colloidal sol is transformed into gel through evaporation drying.In this process, usually introduce simultaneously some organic reaction functional groups, these organic reaction functional groups have following function: (1) changes the polarity of silica particle surface, make silica particle surface become hydrophobicity by wetting ability, the consistency of increase and organic solvent or organic monomer utilizes organic segmental steric effect to make the silicon dioxide granule stable dispersion simultaneously; (2) in particle surface grafting amino, epoxy group(ing), vinyl-functional, these functional groups can form chemical bond with organic prepolymer or polymerization single polymerization monomer generation polymerization, thereby strengthen the interaction between silicon dioxide granule and the organic phase.Sol-gel method is realized running through mutually of inorganic and organic phase, inorganic network wherein just is meant the network that is formed by silane oxygen end hydrolytic condensation, organic phase is that wherein silane oxygen key has switch to replace with other or forms with other organic polymers, increase along with organic phase, the elasticity of material, stretchiness also increase thereupon, and the thickness that can apply also can suitably increase.Situ aggregation method and sol-gel method can be so that inorganic SiO
2Link to each other with organic network by chemical bond, form micro phase separation structure, this structure makes hybridization coating have splendid outward appearance, stability and over-all properties.
Generally speaking, hybrid coating combines the good characteristic of organic polymer and inorganic materials, has good mechanical performance, resistance to elevated temperatures and good snappiness.In addition, hybrid material can make the performance of material produce abundant variation with the structure of molecular level controlled substance.Therefore hybrid coating is of many uses, has huge application potential, has become the research focus of current paint field.Along with the Application and Development of people to the further investigation of hybridization coating composition, preparation, structure and performance and new function hybridization coating, hybridization coating will be brought into play bigger effect.
Summary of the invention
An object of the present invention is to provide a kind of coating organic/inorganic sila resin, this resin combines the good characteristic of organic polymer and inorganic materials, has good mechanical performance, resistance to elevated temperatures and good snappiness.
Another object of the present invention is that the preparation method of a kind of this coating with organic/inorganic sila resin will be provided.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of coating organic-inorganic sila resin, it is by inorganic SiO
2Particle grafted hybrid compound that form on the organic fluoropolymer resin main chain, that represent by following general formula:
Wherein, R
1Expression: H, CH
3, C
2H
5, C
4H
9, CH
2CH
2OH, CH
2CH (CH
3) OH or CH
2CH
2N (CH
3)
2, R
2Expression: H, Cl or F, R
3Expression: Cl, F, OOCCH
3Or Ph, R
4Expression: H or CH
3, R
5Expression: inorganic SiO
2Particle, L represents: Si ≡, CH
2CH
2CH
2Si ≡ or OCH
2CH
2(OH) CH
2OCH
2CH
2CH
2Si ≡; M, p are positive integer, and n is a natural number.
Wherein the inorganic silicon dioxide nano particle average particle size range be 20～300nm, inorganic SiO
2The grafting number of particle is relevant with the organic polymer segmental polymerization degree with the consumption of nanoparticle.
A kind of method for preparing above-mentioned coating with organic-inorganic sila resin provided by the invention comprises the steps: (1), nanometer SiO
2The preparation of colloidal sol: adopting sol-gel method, is presoma with the ortho-silicate, and presoma hydrolytic condensation in the mixed solvent of water and alcohol obtains nanometer SiO under the condition of the existence of acid or alkaline catalysts
2Colloidal sol, and add organic solvent and remove water and alcohol in the mixed solvent by component distillation, perhaps, with commercially available nanometer SiO
2Powder forms nanometer SiO by ultrasonic dispersing in organic solvent
2Colloidal sol; (2), nanometer SiO
2The surface modification of particle: the organo-siloxane that will have reactive organo-functional group joins above-mentioned nanometer SiO
2In the colloidal sol, vigorous stirring reaction pair nanometer SiO under 30～80 ℃ temperature
2Particle carries out surface modification, makes it further to participate in polyreaction; (3), reactive SiO
2Particle and monomer copolymerization: with prepared surface-modified nano SiO
2Colloidal sol and vinyl monomer mix, and add radical initiator, and copolymerization obtains the organic/inorganic sila resin of homogeneous under 60～120 ℃ of temperature.
Above-mentioned sol-gel method prepares nanometer SiO
2The presoma that colloidal sol adopted is selected from one or more in the oligomer of original quanmethyl silicate, tetraethyl orthosilicate, orthosilicic acid four butyl esters or above-mentioned substance; Described acid catalyst is formic acid, acetate, propionic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or oxalic acid, and described alkaline catalysts is ammoniacal liquor, potassium hydroxide or sodium hydroxide.
The organo-siloxane of above-mentioned employing has the organo-functional group that can react, and it is selected from gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, γ-(glycidoxy) propyl-triethoxysilicane or the gamma-amino propyl trimethoxy silicane one or more.
The used vinyl monomer of above-mentioned copolyreaction is selected from vinyl acetate, vinylchlorid, vinylidene chloride, vinylidene fluoride, vinyl toluene, vinylbenzene, methacrylic acid, vinylformic acid, methyl methacrylate, methyl acrylate, Jia Jibingxisuanyizhi, ethyl propenoate, butyl methacrylate, butyl acrylate, methacrylic acid 2-ethylhexyl, 2-EHA, methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxypropyl acrylate, vinylformic acid 2-hydroxypropyl acrylate, methacrylic acid 4-hydroxy butyl ester, vinylformic acid 4-hydroxy butyl ester, methacrylic acid N, N-dimethylamino ethyl ester vinylformic acid N, the N-dimethylamino ethyl ester, in isobornyl methacrylate or the isobornyl acrylate one or more.
Of the present invention at nanometer SiO
2Add organic solvent azeotropic in the colloidal sol and distill water and the alcohol of removing in the reaction product.Above-mentioned organic solvent can adopt butylacetate, also can adopt isobutyl acetate, butanols, isopropylcarbinol, methyl iso-butyl ketone (MIBK), pimelinketone, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, tirethylene glycol monobutyl ether, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, diacetone alcohol or the like.
Radical initiator can adopt azo-initiator and superoxide, azo-initiator has Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate, peroxide initiator has tert-butyl peroxide, the dicumyl peroxide base, benzoyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester, di-cyclohexylperoxy dicarbonate.
Utilize commercially available nanometer SiO
2Powder preparing nanometer SiO
2The organic solvent that colloidal sol adopted can be a butylacetate, also can adopt isobutyl acetate, butanols, isopropylcarbinol, methyl iso-butyl ketone (MIBK), pimelinketone, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, tirethylene glycol monobutyl ether, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, diacetone alcohol or the like.
The invention has the beneficial effects as follows: coating disclosed by the invention combines the good characteristic of organic polymer and inorganic materials with organic-inorganic sila resin, has good mechanical performance, resistance to elevated temperatures and good snappiness.In addition, hybrid material can make the performance of material produce abundant variation with the structure of molecular level controlled substance.Therefore hybrid coating is of many uses, has huge application potential, has become the research focus of current paint field.Along with the Application and Development of people to the further investigation of hybridization coating composition, preparation, structure and performance and new function hybridization coating, hybridization coating will be brought into play bigger effect.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is inorganic SiO of the present invention
2The schematic arrangement of particle.
Embodiment
For better explanation the present invention, below in conjunction with embodiment the present invention is introduced further and sets forth, but the present invention's scope required for protection is not limited to the represented scope of embodiment.
Embodiment 1
Reacting nano SiO
2The preparation of colloidal sol:
In being housed, the four-hole round-bottomed flask of prolong, agitator, thermometer and constant pressure funnel adds 62.4 parts of tetraethyl orthosilicates (TEOS) and 60 parts of ethanol, mix, be warming up to 30 ℃, under condition of stirring, slowly drip the mixed solution of 21.6 parts of deionized waters, 64.2 parts of ethanol and an amount of commercially available strong aqua by dropping funnel, speed is dripped in control makes mixed solution dropwise in 2h, continue 30 ℃ of stirring reaction 24h of constant temperature, obtain being blue opalescent translucent SiO
2Colloidal sol.
Be warming up to 60 ℃, add 7.5 parts of gamma-methyl allyl acyloxypropyl trimethoxysilanes (MAPTMS), constant temperature stirs and continues reaction 6h.At nanometer SiO
2Adding high boiling solvent component distillation is removed water and the alcohol in the reaction product in the colloidal sol, product is transferred in the single necked round bottom flask after removing by filter a spot of solid micelle, add an amount of butylacetate, ethanol is removed in underpressure distillation and residual moisture content obtains organic solvent dispersive reacting nano SiO
2Colloidal sol, the about 75nm of its median size, dispersity 0.24 (dynamic light scattering method measurement), moisture content≤0.5%, SiO
2The about 10wt% of content.
Embodiment 2
Reacting nano SiO
2The preparation of colloidal sol:
In being housed, the four-hole round-bottomed flask of prolong, agitator, thermometer and constant pressure funnel adds 62.4 parts of tetraethyl orthosilicates (TEOS) and 60 parts of ethanol, mix, be warming up to 30 ℃, under condition of stirring, slowly drip the mixed solution of 21.6 parts of deionized waters, 64.2 parts of ethanol and an amount of commercially available strong aqua by dropping funnel, speed is dripped in control makes mixed solution dropwise in 2h, continue 30 ℃ of stirring reaction 24h of constant temperature, obtain being blue opalescent translucent SiO
2Colloidal sol.
Be warming up to 60 ℃, add 5.7 parts of vinyltriethoxysilanes (VTES), constant temperature stirs and continues reaction 6h.At nanometer SiO
2Adding high boiling solvent component distillation is removed water and the alcohol in the reaction product in the colloidal sol, product is transferred in the single necked round bottom flask after removing by filter a spot of solid micelle, add an amount of butylacetate, ethanol is removed in underpressure distillation and residual moisture content obtains organic solvent dispersive reacting nano SiO
2Colloidal sol, the about 68nm of its median size, dispersity 0.26 (dynamic light scattering method measurement), moisture content≤0.5%, SiO
2The about 10wt% of content.
Embodiment 3
Reacting nano SiO
2The preparation of colloidal sol:
Take by weighing 10 parts of nanometer SiO
2Powder (primary particle diameter 30nm) and an amount of butylacetate make nanometer SiO by ultrasonic wave or high speed dispersion
2Colloidal sol is with SiO
2Colloidal sol joins in the four-hole round-bottomed flask that prolong, agitator, thermometer and constant pressure funnel are housed, vigorous stirring also is warming up to 60 ℃, add 5.2g gamma-methyl allyl acyloxypropyl trimethoxysilane (MAPTMS) by dropping funnel, isothermal reaction 6h obtains organic solvent dispersive reacting nano SiO
2Colloidal sol, the about 128nm of its median size, dispersity 0.37 (dynamic light scattering method measurement), moisture content≤0.5%, SiO
2The about 10wt% of content.
Embodiment 4
The preparation of hybrid resin
In the reaction flask that agitator, prolong, thermometer, nitrogen conduit and dropping funnel are housed, add the prepared reacting nano SiO of 3.5 parts and 100 parts embodiment of 1-Methoxy-2-propyl acetate 1
2Colloidal sol mixes, and is warming up to 85 ℃.20 parts of methyl methacrylates, 40 parts of vinylbenzene, 20 parts of butyl acrylates and 20 parts of hydroxyethyl methylacrylates and 2.5 parts of azo-initiators are mixed form monomer solution and slowly drip by dropping funnel, 4h drips, and remains 85 ℃ of stirring and constant temperature in the dropping process.Dropwise the back and wash dropping funnels with 4 parts of 1-Methoxy-2-propyl acetates, constant temperature 30min, add part initiator solution (0.2 part of initiator is dissolved in 12 parts of 1-Methoxy-2-propyl acetates) then, continue isothermal reaction 2h, obtain organic/inorganic sila resin solution.Organic/inorganic sila resin solution solid content 47.8%, monomer conversion is about 95.5%, and GPC tests its molecular weight number-average molecular weight Mn=12300, molecular weight distribution PDI=2.35.
Embodiment 5
The preparation of hybrid resin
In the reaction flask that agitator, prolong, thermometer, nitrogen conduit and dropping funnel are housed, add the prepared reacting nano SiO of 3.5 parts and 100 parts embodiment of 1-Methoxy-2-propyl acetate 2
2Colloidal sol mixes, and is warming up to 85 ℃.20 parts of methyl methacrylates, 40 parts of vinylbenzene, 20 parts of butyl acrylates and 20 parts of hydroxyethyl methylacrylates and 2.5 parts of azo-initiators are mixed form monomer solution and slowly drip by dropping funnel, 4h drips, and remains 85 ℃ of stirring and constant temperature in the dropping process.Dropwise the back and wash dropping funnels with 4 parts of 1-Methoxy-2-propyl acetates, constant temperature 30min, add part initiator solution (0.2 part of initiator is dissolved in 12 parts of 1-Methoxy-2-propyl acetates) then, continue isothermal reaction 2h, obtain organic/inorganic sila resin solution.Organic/inorganic sila resin solution solid content 48.2%, monomer conversion is about 96.4%, and GPC tests its molecular weight number-average molecular weight Mn=13100, molecular weight distribution PDI=2.27.
Embodiment 6
The preparation of hybrid resin
In the reaction flask that agitator, prolong, thermometer, nitrogen conduit and dropping funnel are housed, add the prepared reacting nano SiO of 3.5 parts and 100 parts embodiment of 1-Methoxy-2-propyl acetate 3
2Colloidal sol mixes, and is warming up to 85 ℃.20 parts of methyl methacrylates, 40 parts of vinylbenzene, 20 parts of butyl acrylates and 20 parts of hydroxyethyl methylacrylates and 2.5 parts of azo-initiators are mixed form monomer solution and slowly drip by dropping funnel, 4h drips, and remains 85 ℃ of stirring and constant temperature in the dropping process.Dropwise the back and wash dropping funnels with 4 parts of 1-Methoxy-2-propyl acetates, constant temperature 30min, add part initiator solution (0.2 part of initiator is dissolved in 12 parts of 1-Methoxy-2-propyl acetates) then, continue isothermal reaction 2h, obtain organic/inorganic sila resin solution.Organic/inorganic sila resin solution solid content 47.9%, monomer conversion is about 95.8%, and GPC tests its molecular weight number-average molecular weight Mn=11400, molecular weight distribution PDI=2.44.
Comparative Examples
In the reaction flask that agitator, prolong, thermometer, nitrogen conduit and dropping funnel are housed, add 35 parts of 1-Methoxy-2-propyl acetates and 35 parts of butylacetates, be warming up to 85 ℃, stirring and refluxing.20 parts of methyl methacrylates, 40 parts of vinylbenzene, 20 parts of butyl acrylates and 20 parts of hydroxyethyl methylacrylates and 2.5 parts of azo-initiators are mixed form monomer solution and slowly drip by dropping funnel, 4h drips, and remains 85 ℃ of stirring and constant temperature in the dropping process.Dropwise the back and wash dropping funnels with 2 parts of 1-Methoxy-2-propyl acetates and 2 parts of butylacetates, add part initiator solution (0.2 part of initiator is dissolved in the mixed solvent of 12 parts of 1-Methoxy-2-propyl acetates and 12 parts of butylacetates) behind the constant temperature 30min, continue isothermal reaction 2h, obtain acrylic resin soln.This resin solution solid content 48.8%, monomer conversion is about 97.6%, and GPC tests its molecular weight number-average molecular weight Mn=11800, molecular weight distribution PDI=2.13.
Application examples 1
Dual-component polyurethane varnish
With Comparative Examples acrylic resin and organic/inorganic sila resin and the two component Polyurethane varnish of polyisocyanate curing agent preparation, can be coated on by the mode of brushing, dip-coating, showering or spraying through on the tinplate of sand papering, levelling, 80 ℃ of baking 30min film-formings, the test paint film property.Prescription and film performance such as table 1.
Table 1 hybrid dual-component polyurethane varnish performance
Annotate: GB/T 6739-1996 is pressed in hardness test, and GB/T9286-1998 is pressed in the sticking power test, and gloss is pressed GB/T 9754-1998 standard and carried out; Zero expression is no abnormal by the test panel face.
Application examples 2
The single-component baking vanish
With Comparative Examples acrylic resin and organic/inorganic sila resin and aminoresin configuration single-component baking varnish, can be coated on by the mode of brushing, dip-coating, showering or spraying through on the tinplate of sand papering, 150 ℃ of baking 30min film-formings behind the levelling, the test paint film property.Prescription and film performance such as table 2.
Table 2 hybrid single-component baking vanish performance
Annotate: GB/T 6739-1996 is pressed in hardness test, and GB/T9286-1998 is pressed in the sticking power test, and gloss is pressed GB/T 9754-1998 standard and carried out; Zero expression is no abnormal by the test panel face.
The above-mentioned just preferred embodiment of the invention, is utilized commercially available nanometer SiO at used vinyl monomer, organic solvent, the radical initiator of presoma, catalyzer, organo-siloxane, the copolyreaction under the constant situation of preparation condition in the foregoing description
2Powder preparing nanometer SiO
2The organic solvent that colloidal sol adopted can be replaced with following material, as one or more replacements in the oligomer of the also available original quanmethyl silicate of presoma, orthosilicic acid four butyl esters or original quanmethyl silicate, tetraethyl orthosilicate, orthosilicic acid four butyl esters; Catalyzer usable acid catalyzer such as formic acid, acetate, propionic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid etc. or replacements such as alkaline catalysts such as potassium hydroxide, sodium hydroxide; Organo-siloxane can use gamma-methyl allyl acyloxypropyl triethoxyl silane, vinyltrimethoxy silane, γ-(glycidoxy) propyl-triethoxysilicane or gamma-amino propyl trimethoxy silicane to replace, and perhaps replaces with two or more the mixture that is selected from gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, γ-(glycidoxy) propyl-triethoxysilicane or the gamma-amino propyl trimethoxy silicane; The used vinyl monomer of copolyreaction is also available in the foregoing description: vinyl acetate, vinylchlorid, vinylidene chloride, vinylidene fluoride, (methyl) vinylformic acid, (methyl) ethyl propenoate, (methyl) 2-EHA, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) vinylformic acid N, one or more replacements in N-dimethylamino ethyl ester or (methyl) isobornyl acrylate; Organic solvent can be used isobutyl acetate, butanols, isopropylcarbinol, methyl iso-butyl ketone (MIBK), pimelinketone, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, tirethylene glycol monobutyl ether, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, replacement butylacetates such as diacetone alcohol (need to prove, when hybrid resin will be applied to double-component polyurethane paint, preferably without alcoholic solvent); Radical initiator can be used 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate, tert-butyl peroxide, dicumyl peroxide base, benzoyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester, di-cyclohexylperoxy dicarbonate is replaced Diisopropyl azodicarboxylate; Utilize commercially available nanometer SiO
2Powder preparing nanometer SiO
2The organic solvent that colloidal sol adopted can be used isobutyl acetate, butanols, isopropylcarbinol, methyl iso-butyl ketone (MIBK), pimelinketone, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, tirethylene glycol monobutyl ether, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, replacement butylacetates such as diacetone alcohol are (when hybrid resin will be applied to double-component polyurethane paint, can not use alcoholic solvent) or the like, do not enumerate one by one at this.
Claims (7)
1. a coating is with organic-inorganic sila resin, and it is characterized in that: it is by inorganic SiO
2Particle grafted hybrid compound that form on the organic fluoropolymer resin main chain, that represent by following general formula:
Wherein, R
1Expression: H, CH
3, C
2H
5, C
4H
9, CH
2CH
2OH, CH
2CH (CH
3) OH or CH
2CH
2N (CH
3)
2, R
2Expression: H, Cl or F, R
3Expression: Cl, F, OOCCH
3Or Ph, R
4Expression: H or CH
3, R
5Expression: inorganic SiO
2Particle, L represents: Si ≡, CH
2CH
2CH
2Si ≡ or OCH
2CH
2(OH) CH
2OCH
2CH
2CH
2Si ≡; M, p are positive integer, and n is a natural number.
2. a kind of coating according to claim 1 is characterized in that with organic-inorganic sila resin: wherein the inorganic silicon dioxide nano particle average particle size range be 20～300nm.
3. a coating as claimed in claim 1 is with the preparation method of organic-inorganic sila resin, and it is characterized in that: it comprises the steps: (1), nanometer SiO
2The preparation of colloidal sol: adopting sol-gel method, is presoma with the ortho-silicate, and presoma hydrolytic condensation in the mixed solvent of water and alcohol obtains nanometer SiO under the condition of the existence of acid or alkaline catalysts
2Colloidal sol adds organic solvent and removes water and alcohol in the mixed solvent by component distillation, perhaps, and with commercially available nanometer SiO
2Powder forms nanometer SiO by ultrasonic dispersing in organic solvent
2Colloidal sol; (2), nanometer SiO
2The surface modification of particle: the organo-siloxane that will have reactive organo-functional group joins above-mentioned nanometer SiO
2In the colloidal sol, vigorous stirring reaction pair nanometer SiO under 30～80 ℃ temperature
2Particle carries out surface modification, makes it further to participate in polyreaction; (3), reactive SiO
2Particle and monomer copolymerization: with prepared surface-modified nano SiO
2Colloidal sol and vinyl monomer mix, and add radical initiator, and copolymerization obtains the organic/inorganic sila resin of homogeneous under 60～120 ℃ of temperature.
4. a kind of coating according to claim 3 preparation method of organic-inorganic sila resin, it is characterized in that: sol-gel method prepares nanometer SiO
2The presoma that colloidal sol adopted is selected from one or more in the oligomer of original quanmethyl silicate, tetraethyl orthosilicate, orthosilicic acid four butyl esters or above-mentioned substance; Described acid catalyst is formic acid, acetate, propionic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or oxalic acid, and described alkaline catalysts is ammoniacal liquor, potassium hydroxide or sodium hydroxide.
5. a kind of coating according to claim 3 preparation method of organic-inorganic sila resin, it is characterized in that: the organo-siloxane that is adopted has the organo-functional group that can react, and it is selected from gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, γ-(glycidoxy) propyl-triethoxysilicane or the gamma-amino propyl trimethoxy silicane one or more.
6. a kind of coating according to claim 3 preparation method of organic-inorganic sila resin, it is characterized in that: the used vinyl monomer of copolyreaction is selected from vinyl acetate, vinylchlorid, vinylidene chloride, vinylidene fluoride, (methyl) vinylbenzene, (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) vinylformic acid N, one or more in N-dimethylamino ethyl ester or (methyl) isobornyl acrylate.
7. a kind of coating according to claim 3 preparation method of organic-inorganic sila resin, it is characterized in that: radical initiator is azo-initiator or superoxide.
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| CN102649835A (en) * | 2012-04-26 | 2012-08-29 | 华南理工大学 | Organic-inorganic hybrid high-silicon-content acrylic ester emulsion and preparation method thereof |
| CN102766403A (en) * | 2012-07-13 | 2012-11-07 | 太仓富勒姆纳米新材料科技有限公司 | Acrylic-modified organosilicon nano paint and preparation method thereof |
| CN102911530A (en) * | 2012-11-07 | 2013-02-06 | 北京化工大学 | Preparation method capable of realizing chemical blending of modified nano silicon dioxide particles in acrylate monomer |
| CN103113534A (en) * | 2013-01-21 | 2013-05-22 | 中山大桥化工集团有限公司 | Preparation method of photo-curing organic-inorganic hybrid prepolymer and application thereof |
| CN103497622A (en) * | 2013-09-29 | 2014-01-08 | 合肥华清金属表面处理有限责任公司 | Environment-friendly interpenetrating network anticorrosive coating containing inorganic particles and preparation method thereof |
| CN103965778A (en) * | 2014-05-23 | 2014-08-06 | 泉州三欣新材料科技有限公司 | Ordinary temperature curing high-hardness organic-inorganic hybrid coating as well as preparation and use method thereof |
| WO2015018154A1 (en) * | 2013-08-08 | 2015-02-12 | 京东方科技集团股份有限公司 | Modified nano-silica and preparation method therefor, pigment dispersion, and photosensitive resin composition |
| CN104530328A (en) * | 2014-12-26 | 2015-04-22 | 中昊北方涂料工业研究设计院有限公司 | Method for preparing self-extinction resin |
| CN105801779A (en) * | 2016-04-05 | 2016-07-27 | 四川理工学院 | Modified nano-silica sol containing rich hydrophilic groups and preparation method of modified nano-silica sol |
| CN107141937A (en) * | 2017-06-06 | 2017-09-08 | 常德金德镭射科技股份有限公司 | A kind of preparation method of polymolecularity antimildew and antibacterial coated film |
| WO2020133034A1 (en) * | 2018-12-27 | 2020-07-02 | Kemira Oyj | Polymer and methods for manufacturing it |
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| CN113388273A (en) * | 2021-06-11 | 2021-09-14 | 广东轻工职业技术学院 | Fluorinated silica nanoparticles and applications |
| CN113512357A (en) * | 2021-08-03 | 2021-10-19 | 浙江华德新材料有限公司 | Inorganic nano continuous aldehyde-removing material and preparation method thereof |
| CN114806303A (en) * | 2022-05-31 | 2022-07-29 | 东风商用车有限公司 | Varnish suitable for one-time spraying film forming of vehicle body and preparation method thereof |
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| CN102649835A (en) * | 2012-04-26 | 2012-08-29 | 华南理工大学 | Organic-inorganic hybrid high-silicon-content acrylic ester emulsion and preparation method thereof |
| CN102649835B (en) * | 2012-04-26 | 2014-07-30 | 华南理工大学 | Organic-inorganic hybrid high-silicon-content acrylic ester emulsion and preparation method thereof |
| CN102766403B (en) * | 2012-07-13 | 2014-05-14 | 苏州维艾普新材料有限公司 | Acrylic-modified organosilicon nano paint and preparation method thereof |
| CN102766403A (en) * | 2012-07-13 | 2012-11-07 | 太仓富勒姆纳米新材料科技有限公司 | Acrylic-modified organosilicon nano paint and preparation method thereof |
| CN102911530A (en) * | 2012-11-07 | 2013-02-06 | 北京化工大学 | Preparation method capable of realizing chemical blending of modified nano silicon dioxide particles in acrylate monomer |
| CN103113534A (en) * | 2013-01-21 | 2013-05-22 | 中山大桥化工集团有限公司 | Preparation method of photo-curing organic-inorganic hybrid prepolymer and application thereof |
| WO2015018154A1 (en) * | 2013-08-08 | 2015-02-12 | 京东方科技集团股份有限公司 | Modified nano-silica and preparation method therefor, pigment dispersion, and photosensitive resin composition |
| US10138390B2 (en) | 2013-08-08 | 2018-11-27 | Boe Technology Group Co., Ltd. | Modified nano-silica and method for preparing the same, pigment dispersion and photosensitive resin composition |
| CN103497622A (en) * | 2013-09-29 | 2014-01-08 | 合肥华清金属表面处理有限责任公司 | Environment-friendly interpenetrating network anticorrosive coating containing inorganic particles and preparation method thereof |
| CN103497622B (en) * | 2013-09-29 | 2016-04-27 | 合肥华清金属表面处理有限责任公司 | A kind of environment-friendly type contains interpenetrating polymer network anticorrosion paint of inorganic particulate and preparation method thereof |
| CN103965778A (en) * | 2014-05-23 | 2014-08-06 | 泉州三欣新材料科技有限公司 | Ordinary temperature curing high-hardness organic-inorganic hybrid coating as well as preparation and use method thereof |
| CN103965778B (en) * | 2014-05-23 | 2016-05-11 | 泉州三欣新材料科技有限公司 | Normal temperature cure high rigidity organic-inorganic hybridization coating and preparation and application thereof |
| CN104530328A (en) * | 2014-12-26 | 2015-04-22 | 中昊北方涂料工业研究设计院有限公司 | Method for preparing self-extinction resin |
| CN104530328B (en) * | 2014-12-26 | 2018-12-21 | 中昊北方涂料工业研究设计院有限公司 | A kind of preparation method from matting resin |
| CN105801779A (en) * | 2016-04-05 | 2016-07-27 | 四川理工学院 | Modified nano-silica sol containing rich hydrophilic groups and preparation method of modified nano-silica sol |
| CN105801779B (en) * | 2016-04-05 | 2019-04-09 | 四川理工学院 | A kind of richness hydrophilic radical modified manometer silicon dioxide colloidal sol and preparation method thereof |
| CN107141937A (en) * | 2017-06-06 | 2017-09-08 | 常德金德镭射科技股份有限公司 | A kind of preparation method of polymolecularity antimildew and antibacterial coated film |
| WO2020133034A1 (en) * | 2018-12-27 | 2020-07-02 | Kemira Oyj | Polymer and methods for manufacturing it |
| CN113316594A (en) * | 2018-12-27 | 2021-08-27 | 凯米拉公司 | Polymer and method for producing same |
| CN113316594B (en) * | 2018-12-27 | 2023-10-27 | 凯米拉公司 | Polymer and method for producing same |
| CN111729824A (en) * | 2020-07-04 | 2020-10-02 | 上海灿达建材科技有限公司 | Preparation process of water-based printed ceramic aluminum decorative plate |
| CN113388273A (en) * | 2021-06-11 | 2021-09-14 | 广东轻工职业技术学院 | Fluorinated silica nanoparticles and applications |
| CN113512357A (en) * | 2021-08-03 | 2021-10-19 | 浙江华德新材料有限公司 | Inorganic nano continuous aldehyde-removing material and preparation method thereof |
| CN114806303A (en) * | 2022-05-31 | 2022-07-29 | 东风商用车有限公司 | Varnish suitable for one-time spraying film forming of vehicle body and preparation method thereof |
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