CN1587299A - Process for preparing organic-inorganic hybridized resin and its coating material - Google Patents
Process for preparing organic-inorganic hybridized resin and its coating material Download PDFInfo
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- CN1587299A CN1587299A CN 200410053255 CN200410053255A CN1587299A CN 1587299 A CN1587299 A CN 1587299A CN 200410053255 CN200410053255 CN 200410053255 CN 200410053255 A CN200410053255 A CN 200410053255A CN 1587299 A CN1587299 A CN 1587299A
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Abstract
The present invention relates to chemical and building material technology, the preparation process of hybridized organic-inorganic resin with high performance and its protective coating material. Silane as precursor with different organic functional groups is hydrolyzed and polycondensated under certain condition to obtain hybridized organic-inorganic resin and coating material with certain molecular weight and capable of being hybridized in nanometer range and cured at normal temperature. The coating material has the features of high transparency, high attachment, high hardness, high weather resistance, etc. and may be used in various protecting and decorating surface of metal, stone, concrete, etc.
Description
Technical field
The present invention relates to chemical industry, building materials field, relate to the preparation method of a kind of high performance organic-inorganic hybrid resin and supercoat thereof, coated material can be used for the decoration protection of metal, stone material, glass, plastics etc.
Background technology
Coated material is a kind of material that is coated in other body surface, plays decoration, protects or give object new effects such as function.Traditional coated material has two kinds of organic coating and inorganic materials, and its relative merits are respectively arranged.Develop rapidly along with science and technology, people are more and more higher to the requirement of coated material, the material of single composition preparation is difficult to dealing with various requirements simultaneously, this just requires to develop a kind of film forming properties excellence that both had, the coated material that has high rigidity, high-weatherability and high dirt resistance again, make coated material have the advantage of organic materials and inorganic materials concurrently, can overcome both deficiencies again, this also is one of main direction of present coated material development.
Summary of the invention
The purpose of this invention is to provide the organic-inorganic hybrid resin of a kind of normal temperature solidified film forming, excellent performance and the preparation method of coated material thereof, it can be used for the decoration protection of different substrate materials.
Organic-inorganic hybridized coatings mainly is divided into two classes, and a class is to be the hybrid inorganic-organic coating of organic phase with the polymkeric substance, and this type coating material organic content is higher, and film-forming properties is better, but weathering resistance and thermostability are relatively poor; Another kind of is the hybrid coating of full siloxanes, and this type coating material molecule amount is less, and inorganic content is higher, and hardness is big, and is thermally-stabilised good, but film forming speed is slow, needs the hot setting film forming.The organic-inorganic hybrid resin and the coated material of the present invention's preparation; normal temperature solidified film forming; have excellent properties such as excellent hardness, resistance to soiling, weathering resistance, the transparency, toughness, can be widely used in the surface protection and the decoration of automobile, aluminium-plastic panel, marble, grouan, ornamental brick, mosaic, ancient building, historical relic, glass, plastics, metal etc.
The organic-inorganic hybrid resin that the present invention proposes is by the silane precursor that contains different organo-functional groups, water, solvent, an acidic catalyst is formed, specifically consist of: (1) contains hydrogen base alkoxyl group, alkyl alkoxy, the aromatic base alkoxyl group, the thiazolinyl alkoxyl group, any of epoxy group(ing) alkoxyl group or several silane precursor, consumption is the 15-40wt% of resin total amount, as methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, phenyltrimethoxysila,e, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl dipropoxy silane, the trimethylammonium methoxy silane, trimethylethoxysilane, tetraethoxy, phenyltrimethoxysila,e, the phenyl methyl diethoxy silane, vinyltrimethoxy silane, vinyl propyl group dimethoxy silane, the dodecyl Trimethoxy silane, the dodecyl triethoxyl silane, the hexadecyl Trimethoxy silane, the hexadecyl triethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, 3-glycidyl ether oxygen propyl trimethoxy silicane etc.(2) low-molecular-weight monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, tetravalent alcohol, ketones solvent, aromatic solvent, ether solvent, aliphatic ester kind solvent etc., consumption is the 30-70wt% of resin total amount; As methyl alcohol, ethanol, Virahol, 1,4-butyleneglycol, ethylene glycol, propylene glycol, butyleneglycol, polyoxyethylene glycol, polypropylene glycol, polypropylene dibasic alcohol, polyether glycol, polyester polyol, polycaprolactone dibasic alcohol, acetone, methyl ethyl ketone, Methyl amyl ketone, benzene,toluene,xylene, ether, tetrahydrofuran (THF), vinyl acetic monomer, N-BUTYL ACETATE etc.(3) an acidic catalyst is organic acid, mineral acid or Lewis acid, consumption is the 0.01-2wt% of resin total amount, as acetic acid, p-methyl benzenesulfonic acid, vinylformic acid, methacrylic acid, oxalic acid, hydrochloric acid, nitric acid, citric acid, oxalic acid, dodecyl sodium sulfonate, Witco 1298 Soft Acid etc.
The method for preparing organic-inorganic hybrid resin that the present invention proposes is in the reactor that agitator, thermometer, prolong are housed, add one or more silane precursor, partial solvent, a small amount of an acidic catalyst, according to silane precursor species difference, control differential responses temperature, dripped remaining an acidic catalyst, water and residual solvent at 0-100 ℃ of scope 1-5 hour, at 0-100 ℃ of ageing 1-24 hour, prepare hybrid resin.An acidic catalyst, solvent generally add 1/6 to 9/10 earlier in the preparation process before reaction, and remaining and water drips in reaction.An acidic catalyst can be mineral acid, organic acid or Lewis acid etc. in the reaction.
The preparation of the organic-inorganic hybrid resin coated material that the present invention proposes is by organic-inorganic hybrid resin directly or add behind the linking agent at normal temperature or be heated to 50-100 ℃ of film forming and make; Or add color stuffing, water, auxiliary agent etc. and make.Specifically consist of: (1) contains any or several organic-inorganic hybrid resin of the present invention preparation, and consumption is the 20-100wt% of coated material total amount.(2) contain linking agents such as any epoxy compounds, aminated compounds, nitrogen-containing heterocycle compound, consumption is the 0-7wt% of coated material total amount.As trolamine, quadrol, polyethylene polyamine, the butyl diethanolamine, terpolycyantoamino-formaldehyde resin, bisphenol A epoxide resin, ethylene glycol diglycidylether, the sorbyl alcohol polyglycidyl ether, glycerine polyglycidyl ether and trimethylolpropane polyglycidylether, aziridine, methylaziridine, the ethyl aziridine, the phenyl aziridine, two functional group's aziridine, the trifunctional aziridine, the Desmodur DA (aliphatics) of Bayer A.G, DesmodurXP-7007 (aliphatics), Desmodur XO-671 (aliphatics), Desmodur XO-672 (aromatic series) etc.(3) contain coating at least a color stuffing commonly used, consumption is the 0-50wt% of coated material total amount, as titanium dioxide, lithopone, zinc sulphide, ferric oxide, kaolin, pure aluminium silicate, talcum powder, silica powder, lime carbonate, wollastonite, sericite etc.(4) contain coating at least a auxiliary agent commonly used, consumption is the 0-10wt% of coated material total amount, as wetting dispersing agent, defoamer, thickening material, flow agent, catalyzer etc.(5) contain water, consumption is the 0-30wt% of coated material total amount.
The preparation of above-mentioned organic-inorganic hybridized coatings be organic-inorganic hybrid resin directly or add behind the linking agent in room temperature or be heated to 50-100 ℃ of preparation; Or with in an amount of auxiliary agent, the color stuffing adding suitable quantity of water, high speed dispersion stirred 15-30 minute, and adding organic-inorganic hybrid resin, residue auxiliary agent etc. prepares and gets.
The present invention's reaction conditions preferably is as follows:
The method for preparing organic-inorganic hybrid resin that the present invention proposes is that silane precursor adopts one or more in hydrogen base organoalkoxysilane, alkylalkoxy silane, aromatic base organoalkoxysilane, alkenyl alkoxy silane, the epoxy group(ing) organoalkoxysilane.
The method for preparing organic-inorganic hybrid resin that the present invention proposes is that to adopt molecular weight be in the monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, tetravalent alcohol, ketones solvent, aromatic solvent, ether solvent, aliphatic ester kind solvent of 30-1000 one or more to solvent.
The method for preparing organic-inorganic hybrid resin that the present invention proposes is that an acidic catalyst adopts organic acid, mineral acid or Lewis acid.
The method for preparing the organic-inorganic hybrid resin coated material that the present invention proposes is that linking agent adopts any in epoxy compounds, aminated compounds, the nitrogen-containing heterocycle compound.
The method for preparing the organic-inorganic hybrid resin coated material that the present invention proposes is that color stuffing adopts one or more in titanium dioxide or titanium dioxide and existing other color stuffing.
The method for preparing the organic-inorganic hybrid resin coated material that the present invention proposes is that auxiliary agent adopts one or more of wetting dispersing agent, defoamer, thickening material, flow agent, catalyzer.
The organic-inorganic hybrid resin molecular weight of the present invention's preparation is in 1000-10000 scope, normal temperature solidified film forming; good, the strong adhesion of the coated material transparency, hardness height, weathering resistance and the resistance to soiling of preparation are good, can be used for the covering with paint and the protection of substrate surfaces such as metal, stone material, concrete, masonry, glass, plastics.
The present invention adopts following analysis and characterization method to measure the physical and chemical performance of resin and coated material: the molecular weight and the molecular weight distribution that adopt the Breeze 1515 gel chromatographs test resin of Waters company; The NEXUS470 that adopts Nicolet company to produce tests the infrared spectra of resin and coated material; The DSX300 type nuclear magnetic resonance spectrometer that adopts German Bruker company is in the sample
29Si has carried out nuclear magnetic resonance research; Adopt the thermostability of the TGA7 thermal gravimetric analyzer mensuration material of Perkin Elmer Instruments company; Adopt the SPA-300HV atomic force microscope observation coatingsurface pattern of NSK SII company; Adopt the weathering resistance of the accelerated aging test case mensuration material of U.S. Q-Pannel Lab Products company; Employingization lattice method is measured the sticking power of material etc.
The organic-inorganic hybrid resin and the coated material of the present invention's preparation, have the following advantages: the resin of preparation has certain molecular weight, and molecular weight ranges is 1000-10000, and hybrid inorganic-organic is a hydridization in nano-scale range; The normal temperature solidified film forming of coated material of preparation has performances such as the excellent transparency, hardness, resistance to soiling, weathering resistance, toughness, and coating hardness can reach 2-3H, and weathering resistance can reach 10-20.
The organic-inorganic hybrid resin and the coated material of the present invention's preparation; can be applied to metallic surfaces such as automobile, aluminium-plastic panel; stone surfaces such as marble, grouan, ornamental brick, mosaic, artifact, ancient building, and the protection and the decoration on surfaces such as concrete, glass, plastics.
Embodiment
Example 1:
In the reactor that agitator, thermometer, prolong, dropping funnel are housed, add methyltrimethoxy silane 75 grams, vinyltriethoxysilane 27 grams, ethanol 130 grams, hydrochloric acid 0.2 gram, in 0 ℃ of ice bath, stirred 10 minutes, ethanol 100 grams, hydrochloric acid 0.3 gram, water 135 grams are mixed and are placed on dropping funnel, dripped at 0 ℃ of ice bath 2-3 hour, be warming up to 10 ℃, stir ageing 3-5 hour, discharging obtains organic-inorganic hybrid resin.The above-mentioned resin that makes 85 grams, water 10 grams, 1 gram butyl diethanolamine, 0.5 flow agent are mixed stirring 10 minutes, and the drying at room temperature film forming makes transparent organic-inorganic hybridized coatings.
Example 2:
In the reactor that agitator, thermometer, prolong, dropping funnel are housed, add Union carbide A-162 95 grams, tetraethoxy 20 grams, 3-glycidyl ether oxygen propyl trimethoxy silicane 67 grams, N-BUTYL ACETATE 70 grams, tosic acid 1 gram, be heated to 50-60 ℃, N-BUTYL ACETATE 100 grams, tosic acid 3 grams, water 120 grams are mixed and are placed on dropping funnel, in 4 hours, drip, insulated and stirred ageing 24 hours, discharging obtains organic-inorganic hybrid resin.With titanium dioxide 70 gram, talcum powder 20 grams, coarse whiting 10 grams, kaolin 10 grams, water 40 grams, dispersion agent 1 gram, defoamer 2 grams, the above-mentioned resin that makes 320 gram high speed dispersion 20 minutes, the drying at room temperature film forming made the organic-inorganic hybridized coatings of opacifying power 〉=90%.
Example 3:
In the reactor that agitator, thermometer, prolong, dropping funnel are housed, add phenyl triethoxysilane 55 grams, vinyl propyl group dimethoxy silane 30 grams, dimethylbenzene 170 grams, acetic acid 1 gram, be heated to 70-90 ℃, dimethylbenzene 130 grams, acetic acid 8 grams, water 100 grams are mixed and are placed on dropping funnel, dripped at 2-3 hour,, stir ageing 12 hours temperature to 60 ℃, discharging obtains organic-inorganic hybrid resin.The direct drying at room temperature film forming of the above-mentioned resin that makes is made transparent organic-inorganic hybridized coatings.
Example 4:
Agitator is being housed, thermometer, prolong, in the reactor of dropping funnel, add hydrogen ethyl triethoxy silicane alkane 15 grams, hexadecyl triethoxyl silane 20 grams, dimethyldiethoxysilane 42 grams, Methyl amyl ketone and polypropylene glycol mixture (1: 1) 190 grams, Witco 1298 Soft Acid 1 gram, be heated to 40-60 ℃, with Methyl amyl ketone and polypropylene glycol mixture (1: 1) 140 grams, Witco 1298 Soft Acid 0.1 gram, water 50 grams mix and are placed on dropping funnel, dripped at 2-3 hour, be warming up to 90 ℃, stir ageing 3 hours, discharging obtains organic-inorganic hybrid resin.With titanium dioxide 20 gram, wollastonite 20 grams, coarse whiting 5 grams, ferric oxide 6 grams, dispersion agent 1 gram, defoamer 1 gram, the above-mentioned resin that makes 460 gram high speed dispersion 30 minutes, add terpolycyantoamino-formaldehyde resin 13 grams, flow agent 1 gram, thickening material 2 grams, 1 hour drying and forming-film of 100 ℃ of heating makes organic-inorganic hybridized coatings russet.
Claims (10)
1. the preparation method of an organic-inorganic hybrid resin, its feature is as follows:
Organic-inorganic hybrid resin be by the silane precursor that contains different organo-functional groups in the presence of water, solvent, an acidic catalyst, hydrolysis under certain condition, condensation and get, the composition of above-mentioned each reactant is:
Form weight percent wt%
Silane precursor 15-40
Water 5-35
Solvent 30-70
An acidic catalyst 0.01-2,
Concrete preparation method is: add silane precursor, partial solvent and an acidic catalyst in reactor earlier, in 0-100 ℃, 1-5 hour scope, drip water, residual solvent and an acidic catalyst, dropwise, promptly got organic-inorganic hybrid resin at 0-100 ℃ of ageing 1-24 hour.
2. the preparation method of organic-inorganic hybrid resin coated material according to claim 1, it is characterized in that directly or after adding linking agent obtaining transparent coating material at normal temperature or 50-100 ℃ of following film forming of heating by organic-inorganic hybrid resin, or add color stuffing, water, auxiliary agent and obtain coated material with opacifying power, the composition of above-mentioned each reactant is:
Form weight percent wt%
Organic-inorganic hybrid resin 20-100
Water 0-30
Linking agent 0-7
Color stuffing 0-50
Auxiliary agent 0-10.
3. the preparation method of organic-inorganic hybrid resin coated material according to claim 2, it is characterized in that an amount of auxiliary agent, color stuffing are added in the suitable quantity of water, high speed dispersion stirred 15-30 minute, added the organic-inorganic hybridized coatings that the organic-inorganic hybrid resin preparation has certain opacifying power.
4. the preparation method of organic-inorganic hybrid resin according to claim 1 is characterized in that silane precursor is one or more in hydrogen base organoalkoxysilane, alkylalkoxy silane, aromatic base organoalkoxysilane, alkenyl alkoxy silane, the epoxy group(ing) organoalkoxysilane.
5. the preparation method of organic-inorganic hybrid resin according to claim 1 is characterized in that preparing solvent for use and is molecular weight and be in the monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, tetravalent alcohol, ketones solvent, aromatic solvent, ether solvent, aliphatic ester kind solvent of 30-1000 one or more.
6. the preparation method of organic-inorganic hybrid resin according to claim 1 is characterized in that an acidic catalyst is organic acid or mineral acid or Lewis acid.
7. the preparation method of organic-inorganic hybrid resin coated material according to claim 2 is characterized in that linking agent is any in epoxy compounds, aminated compounds, the nitrogen-containing heterocycle compound.
8. the preparation method of organic-inorganic hybrid resin coated material according to claim 2 is characterized in that color stuffing is one or more in titanium dioxide or titanium dioxide and existing other color stuffing.
9. the preparation method of organic-inorganic hybrid resin coated material according to claim 2 is characterized in that auxiliary agent is one or more of wetting dispersing agent, defoamer, thickening material, flow agent, catalyzer.
10. be used for the covering with paint and the protection of organic or inorganic material surface according to claim 2 prepared organic-inorganic hybrid resin coated material.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585694A (en) * | 2011-01-14 | 2012-07-18 | 湖南三力达化工有限公司 | Annealing rustproof water-based insulating paint for electrical sheets and preparation method for annealing rustproof water-based insulating paint |
| CN103408763A (en) * | 2013-04-08 | 2013-11-27 | 北京化工大学 | Method for preparing silicon-titanium polymers |
| CN105062292A (en) * | 2015-08-06 | 2015-11-18 | 苏州好洁清洁器具有限公司 | High-corrosion-resistance aluminum alloy pipe material |
| CN105907294A (en) * | 2016-04-14 | 2016-08-31 | 顺德职业技术学院 | Preparation method of water-borne inorganic paint and method for preparation of inorganic coating from water-borne inorganic paint |
| CN107868610A (en) * | 2017-11-11 | 2018-04-03 | 萍乡亨厚新材科技有限公司 | A kind of siliceous coating of normal temperature cure |
| CN112094585A (en) * | 2020-09-21 | 2020-12-18 | 中昊北方涂料工业研究设计院有限公司 | Ultrathin steel structure fireproof coating and preparation method thereof |
| CN114605650A (en) * | 2020-12-09 | 2022-06-10 | 财团法人工业技术研究院 | Organic-inorganic hybrid resin, coating and composite structure |
-
2004
- 2004-07-29 CN CN 200410053255 patent/CN1243039C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585694A (en) * | 2011-01-14 | 2012-07-18 | 湖南三力达化工有限公司 | Annealing rustproof water-based insulating paint for electrical sheets and preparation method for annealing rustproof water-based insulating paint |
| CN103408763A (en) * | 2013-04-08 | 2013-11-27 | 北京化工大学 | Method for preparing silicon-titanium polymers |
| CN105062292A (en) * | 2015-08-06 | 2015-11-18 | 苏州好洁清洁器具有限公司 | High-corrosion-resistance aluminum alloy pipe material |
| CN105907294A (en) * | 2016-04-14 | 2016-08-31 | 顺德职业技术学院 | Preparation method of water-borne inorganic paint and method for preparation of inorganic coating from water-borne inorganic paint |
| CN107868610A (en) * | 2017-11-11 | 2018-04-03 | 萍乡亨厚新材科技有限公司 | A kind of siliceous coating of normal temperature cure |
| CN112094585A (en) * | 2020-09-21 | 2020-12-18 | 中昊北方涂料工业研究设计院有限公司 | Ultrathin steel structure fireproof coating and preparation method thereof |
| CN114605650A (en) * | 2020-12-09 | 2022-06-10 | 财团法人工业技术研究院 | Organic-inorganic hybrid resin, coating and composite structure |
| US11618822B2 (en) | 2020-12-09 | 2023-04-04 | Industrial Technology Research Institute | Organic-inorganic hybrid resin, coating material, and composite structure |
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