CN105237676A - Water-soluble organosilicon-modified acrylic resin and preparation method thereof - Google Patents
Water-soluble organosilicon-modified acrylic resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-soluble organosilicon-modified acrylic resin and a preparation method thereof. The preparation method comprises preparing an organosilicon intermediate, concretely, accurately weighing an organosilicon monomer, adding an alkali solution, performing polycondensation with stirring at room temperature, adding an acid, keeping a weak acid condition, then washing with a large amount of water, adjusting to be neutral, and dewatering under a pressure-reduced condition, so as to obtain the organosilicon intermediate; preparing the water-soluble organosilicon-modified acrylic resin, concretely, firstly adding glycidyl tertcarbonate, the organosilicon intermediate and a solvent into a flask, introducing nitrogen until the temperature reaches the reaction temperature, dropwise adding a mixed solution a, and finishing adding within 3-5 h, then dropwise adding a mixed solution b and finishing adding within 1-2 h, then replenishing an initiator every other 1 h, and performing three times of replenishing, and then keeping warm for 3 h; and adding an amine for neutralizing for 10 min, finally adding water for emulsification, adjusting pH, cooling and discharging. The prepared water-soluble organosilicon-modified acrylic resin is obviously improved in stability, water-boiling resistance and adhesive force.
Description
Technical field
The invention belongs to chemistry painting industry field, the water-soluble organic silicon being specifically related to the baking of a kind of single-component is acrylic resin modified and preparation method thereof.
Background technology
Acrylic resin is widely used in paint field because having excellent film-forming properties, the good transparency, remarkable mechanical property and the feature of environmental protection; But its molecule mostly is linear structure, lacks cross-linking set, so water tolerance, weathering resistance and heat impedance poor (i.e. hot sticky cold crisp), affect its range of application.The appearing as of organosilicon material overcomes these defects and provides a good solution.Organopolysiloxane has the performance of many excellences, as low second-order transition temperature and surface tension, and special heatproof, weathering resistance etc.Organosilicon-modified acrylate is exactly utilize the high and low temperature resistance of polysiloxane excellence and water tolerance to improve the performance of acrylate. synthesize the novel material having both the two excellent properties.
Hydroxyl acrylic ester aqueous dispersion adopts solution polymerization, adds water-dispersion, have good dispersity, hydroxy radical content high after neutralization, can form macromolecular network structure, can prepare high-gloss paint by solidification.Because system is not containing additional emulsifying agent, thus color stuffing can be disperseed preferably and excellent storage stability, both aqueous one-component polyurethane coating can be prepared with blocked isocyanate, also can prepare amino baked paint, have a wide range of applications in fields such as automotive coatings, industrial coating, plastic paint, woodwork coatings at present.Polysiloxane molecule backbone structure Si-O bond energy is very high, and molecular volume is large, and cohesive energy density(CED) is low, makes it have good high and low temperature resistance, hydrophobicity, ventilation property and weathering resistance simultaneously.
Hydroxyl acrylic ester dispersion prepared by Chinese patent CN200810164126.7 adopts first synthetic resins, then desolvation, and finally neutralization adds water-dispersion, and the product relative molecular mass obtained is moderate, narrow distribution.But the baking vanish water boiling resistance configured with aminoresin or closed isocyanic acid is poor, especially on glass without sticking power.Organic-silicon-modified hydroxyl acrylic aqueous dispersion prepared by Chinese patent CN103772597 adopts segmentation to drip, unsaturated organosilicon monomer and Acrylic Acid Monomer are in reaction process generation radical polymerization, then the aqueous polyurethane coating with bi component prepared with isocyanate curing agent, sticking power and snappiness are better, but water boiling resistance and chemical resistant properties poor.
Make a lot of effort organic silicon modified aqueous acrylic dispersions face research workers in recent years, achieved many-sided achievement, not only many hydroxyl acrylic dispersion liquids industrialization.But due to the hydrolysis defect that common siloxanyl monomers is intrinsic, still there are some problems in hydroxyl acrylic dispersion liquid system, addition as organo-siloxane monomer is lower, and the distribution of hydroxyl acrylic dispersion liquid morphology of particles form and hydroxyl can't accurately control.The functionalization of following research direction mainly hydroxyl acrylic dispersion liquid, by the hydroxyl acrylic dispersion liquid of performance need design nucleocapsid structure or interpenetrating polymer networks structure, and carries out modification to it on this basis.
Summary of the invention
Not good for overcoming the acrylic resin modified stability of water-soluble organic silicon, the problem of water boiling resistance and poor adhesive force.Improve stability, resistance to crocking and the antiseptic property of the single-component baking vanish of aminoresin or the supporting preparation of blocked isocyanate.The invention provides a kind of water-soluble organic silicon acrylic resin modified and preparation method thereof.The method mainly solves the acrylic resin modified poor stability of water-soluble organic silicon in the past, and water boiling resistance and sticking power can not meet some glass substrate and metal substrate.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A kind of water-soluble organic silicon is acrylic resin modified, and the consumption of each component is remembered as follows by weight:
Described mixed solution a is made up of following monomer:
Described mixed solution b is made up of following monomer:
(methyl) vinylformic acid 32.5-65%
(methyl) acrylate 32.5-65%
Initiator 1.3-6.5%.
Further, below one or more selected by described (methyl) acrylate: (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) isobomyl acrylate fat or (methyl) ethyl propenoate.
Further, following one or more selected by described hydroxyl (methyl) acrylate: hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410 or Propylene glycol monoacrylate.
Further, described (methyl) vinylformic acid selects following one or more: acrylic or methacrylic acid.
Further, one or more selected by described initiator: Diisopropyl azodicarboxylate, benzoyl peroxide, tert-butyl hydroperoxide tert-pentyl ester, tert-butyl hydroperoxide benzoyl or peroxidation and the tertiary butyl.
Further, one or more selected by described solvent, 1-Methoxy-2-propyl acetate, propandiol butyl ether, propylene glycol monomethyl ether, butyl glycol ether or butyl.
The preparation method that water-soluble organic silicon is acrylic resin modified, comprises the following steps:
(1) preparation of silicone intermediate: accurately take organosilane monomer, add alkaline solution, polycondensation is carried out under stirring and room temperature, add acid, under making it remain on micro-sour condition (with the calibrating of PH meter), then add massive laundering, modulation is neutral, dewater at reduced pressure conditions, obtain silicone intermediate;
(2) preparation that water-soluble organic silicon is acrylic resin modified: first by tertiary carbonic acid glycidyl ester, silicone intermediate, solvent adds in four-hole boiling flask, while lead to nitrogen to temperature of reaction, drips mixing solutions a, control to dropwise at 3-5h, then drip mixing solutions b, control to dropwise at 1-2h, then add an initiator every 1h, add complete three times, insulation 3h; Add in amine and 10min, finally add water and carry out emulsification, regulate PH, cooling discharge.
Further, described organosilane monomer selects the organosilane monomer of unsaturated double-bond, the organosilane monomer of described unsaturated double-bond is following one or more: vinyltriethoxysilane, vinyl silane triisopropoxide or r-methacryloxypropyl trimethoxy silane.
Further, one or more selected by described neutralizing agent: triethylamine, N, N-dimethyl diethanolamine or trolamine.
Compared with prior art, the invention has the beneficial effects as follows:
Water-soluble organic silicon of the present invention is acrylic resin modified and preparation method thereof, comprise the following steps: the preparation of silicone intermediate: accurately take organosilane monomer, add alkaline solution, under stirring and room temperature, carry out polycondensation, add acid, under making it remain on micro-sour condition (with the calibrating of PH meter), then massive laundering is added, modulation is neutral, dewaters at reduced pressure conditions, obtains silicone intermediate; The preparation that water-soluble organic silicon is acrylic resin modified: first by tertiary carbonic acid glycidyl ester, silicone intermediate, solvent adds in flask, while lead to nitrogen to temperature of reaction, drips mixing solutions a, control to dropwise at 3-5h, then drip mixing solutions b, control to dropwise at 1-2h, then add an initiator every 1h, add complete three times, insulation 3h; Add in amine and 10min, finally add water and carry out emulsification, regulate PH, cooling discharge.The prepared acrylic resin modified stability of water-soluble organic silicon, water boiling resistance and sticking power significantly improve.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
Embodiment 1:
The preparation of unsaturated silane coupling agent intermediate: get 60g vinyltriethoxysilane, add the sodium hydroxide solution that 6g massfraction is 5%, at room temperature constantly stir, stop after 3-5h stirring, add a certain amount of hydrochloric acid and be neutralized to PH=6-7, then underpressure distillation, removes unnecessary moisture, for subsequent use.
With stirring, in the reactor of the experimental installation of heating and cooling, add above-mentioned 6g intermediate, 60g propandiol butyl ether, 120g tertiary monocarboxylic acid glyceryl ester, while lead to nitrogen limit to be heated to 150 degree, after reaching steady temperature, start to drip butyl acrylate 70g, vinylbenzene 52g, methyl methacrylate 43g, Rocryl 410 60g, vinylformic acid 10g, the mixture of t-butylperbenzoate 6g, dropwises at 3-5h.Methyl methacrylate 20g is dripped, butyl acrylate 40g, vinylformic acid 12g after 0.5h, 2g peroxidation acetic acid tert-pentyl ester mixture, dropwises at 1-2h, insulation 1h, then add initiator 2g, continue insulation, 0.5h continues to add initiator, after having added, be warming up to 155 degree of insulation 3-5h, be cooled to 80 degree, add 18.9gN, N-dimethylethanolamine, start after 0.5h to add emulsifying water, modulation is admittedly containing 35-40%, then cooling discharge.
Table 1 performance test
Embodiment 2:
The preparation of unsaturated silane coupling agent intermediate: get 60g vinyl silane triisopropoxide, add the sodium hydroxide solution that 6g massfraction is 5%, at room temperature constantly stir, stop after 3-5h stirring, add a certain amount of hydrochloric acid and be neutralized to PH=6-7, then underpressure distillation, removes unnecessary moisture, for subsequent use.
With stirring, in the reactor of the experimental installation of heating and cooling, add above-mentioned 6g intermediate, 120g butyl, 70g tertiary monocarboxylic acid glyceryl ester, while lead to nitrogen limit to be heated to 150 degree, after reaching steady temperature, start to drip butyl acrylate 90g, vinylbenzene 73g, methyl methacrylate 32g, Propylene glycol monoacrylate 50g, vinylformic acid 8g, the mixture of t-butylperbenzoate 6g, dropwises at 3-5h.Methyl methacrylate 10g is dripped, butyl acrylate 40g, vinylformic acid 16g after 0.5h, the mixture of 2g peroxidation acetic acid tert-pentyl ester, dropwises at 1-2h, insulation 1h, then add initiator 2g, continue insulation, 0.5h continues to add initiator, after having added, be warming up to 155 degree of insulation 3-5h, be cooled to 80 degree, add 18.9g triethylamine, start after 0.5h to add emulsifying water, modulation is admittedly containing 35-40%, then cooling discharge.
Table 2 performance test
Embodiment 3:
The preparation of unsaturated silane coupling agent intermediate: get 60g vinyltriethoxysilane, add the sodium hydroxide solution that 6g massfraction is 5%, at room temperature constantly stir, stop after 3-5h stirring, add a certain amount of hydrochloric acid and be neutralized to PH=6-7, then underpressure distillation, removes unnecessary moisture, for subsequent use.
With stirring, in the reactor of the experimental installation of heating and cooling, add above-mentioned 6g intermediate, 90g propandiol butyl ether, 90g tertiary monocarboxylic acid glyceryl ester, while lead to nitrogen limit to be heated to 150 degree, after reaching steady temperature, start to drip butyl acrylate 70g, vinylbenzene 43g, isobomyl acrylate fat 52g, hydroxyethyl methylacrylate 60g, methacrylic acid 10g, the mixture of t-butylperbenzoate 6g, dropwises at 3-5h.Methyl methacrylate 20g is dripped, butyl acrylate 40g, vinylformic acid 12g after 0.5h, the mixture of 2g peroxidation acetic acid tert-pentyl ester, dropwises at 1-2h, insulation 1h, then add initiator 2g, continue insulation, 0.5h continues to add initiator, after having added, be warming up to 155 degree of insulation 3-5h, be cooled to 80 degree, add 18.9gN, N-dimethylethanolamine, start after 0.5h to add emulsifying water, modulation is admittedly containing 35-40%, then cooling discharge.
Table 3 performance test
Embodiment 4:
The preparation of unsaturated silane coupling agent intermediate: get 60gr-methacryloxypropyl trimethoxy silane, add the sodium hydroxide solution that 6g massfraction is 5%, at room temperature constantly stir, stop after 3-5h stirring, add a certain amount of hydrochloric acid and be neutralized to PH=6-7, then underpressure distillation, removes unnecessary moisture, for subsequent use.[0035] with stirring, in the reactor of the experimental installation of heating and cooling, above-mentioned 6g intermediate is added, 90g propandiol butyl ether, 90g tertiary monocarboxylic acid glyceryl ester, while lead to nitrogen limit to be heated to 150 degree, after reaching steady temperature, start to drip butyl acrylate 70g, vinylbenzene 43g, methyl methacrylate 52g, Propylene glycol monoacrylate 60g, vinylformic acid 10g, the mixture of t-butylperbenzoate 6g, dropwises at 3-5h.Methyl methacrylate 20g is dripped, butyl acrylate 40g, vinylformic acid 12g after 0.5h, the mixture of 2g peroxidation acetic acid tert-pentyl ester, dropwises at 1-2h, insulation 1h, then add initiator 2g, continue insulation, 0.5h continues to add initiator, after having added, be warming up to 155 degree of insulation 3-5h, be cooled to 80 degree, add 18.9g trolamine, start after 0.5h to add emulsifying water, modulation is admittedly containing 35-40%, then cooling discharge.
Table 4 performance test
Embodiment 5:
The preparation of unsaturated silane coupling agent intermediate: get 60g vinyltrimethoxy silane, add the sodium hydroxide solution that 6g massfraction is 5%, at room temperature constantly stir, stop after 3-5h stirring, add a certain amount of hydrochloric acid and be neutralized to PH=6-7, then underpressure distillation, removes unnecessary moisture, for subsequent use.
With stirring, in the reactor of the experimental installation of heating and cooling, add above-mentioned 6g intermediate, 100g 1-Methoxy-2-propyl acetate, 70g tertiary monocarboxylic acid glyceryl ester, while lead to nitrogen limit to be heated to 150 degree, after reaching steady temperature, start to drip butyl acrylate 100g, vinylbenzene 21g, methacrylic acid iso-borneol fat 75g, Rocryl 410 45g, vinylformic acid 14g, the mixture of t-butylperbenzoate 6g, dropwises at 3-5h.Methyl methacrylate 10g is dripped, butyl acrylate 50g, vinylformic acid 16g after 0.5h, the mixture of 2g peroxidation acetic acid tert-pentyl ester, dropwises at 1-2h, insulation 1h, then add initiator 2g, continue insulation, 0.5h continues to add initiator, after having added, be warming up to 155 degree of insulation 3-5h, be cooled to 80 degree, add 21.9gN, N-dimethylethanolamine, start after 0.5h to add emulsifying water, modulation is admittedly containing 35-40%, then cooling discharge.
Table 5 performance test
Last it is noted that these are only the preferred embodiments of the present invention; be not limited to the present invention; although with reference to embodiment to invention has been detailed description; for a person skilled in the art; it still can be modified to the technical scheme described in foregoing embodiments; or equivalent replacement is carried out to wherein portion of techniques feature; but it is within the spirit and principles in the present invention all; any amendment of doing, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a water-soluble organic silicon is acrylic resin modified, it is characterized in that: the consumption of each component is remembered as follows by weight:
Described mixed solution a is made up of following monomer:
Described mixed solution b is made up of following monomer:
(methyl) vinylformic acid 32.5-65%
(methyl) acrylate 32.5-65%
Initiator 1.3-6.5%.
2. a kind of water-soluble organic silicon is acrylic resin modified according to claim 1, it is characterized in that: below one or more selected by described (methyl) acrylate: (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) isobomyl acrylate fat or (methyl) ethyl propenoate.
3. a kind of water-soluble organic silicon is acrylic resin modified according to claim 1, it is characterized in that: below one or more selected by described hydroxyl (methyl) acrylate: hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410 or Propylene glycol monoacrylate.
4. a kind of water-soluble organic silicon is acrylic resin modified according to claim 1, it is characterized in that: described (methyl) vinylformic acid selects below one or more: acrylic or methacrylic acid.
5. a kind of water-soluble organic silicon is acrylic resin modified according to claim 1; it is characterized in that: one or more selected by described initiator: Diisopropyl azodicarboxylate; benzoyl peroxide, tert-butyl hydroperoxide tert-pentyl ester, tert-butyl hydroperoxide benzoyl or peroxidation and the tertiary butyl.
6. a kind of water-soluble organic silicon is acrylic resin modified according to claim 1, it is characterized in that: one or more selected by described solvent, 1-Methoxy-2-propyl acetate, propandiol butyl ether, propylene glycol monomethyl ether, butyl glycol ether or butyl.
7. the preparation method that a kind of water-soluble organic silicon is acrylic resin modified according to claim 1, is characterized in that: comprise the following steps:
(1) preparation of silicone intermediate: accurately take organosilane monomer, add alkaline solution, polycondensation is carried out under stirring and room temperature, add acid, under making it remain on micro-sour condition (with the calibrating of PH meter), then add massive laundering, modulation is neutral, dewater at reduced pressure conditions, obtain silicone intermediate;
(2) preparation that water-soluble organic silicon is acrylic resin modified: first by tertiary carbonic acid glycidyl ester, silicone intermediate, solvent adds in four-hole boiling flask, while lead to nitrogen to temperature of reaction, drips mixing solutions a, control to dropwise at 3-5h, then drip mixing solutions b, control to dropwise at 1-2h, then add an initiator every 1h, add complete three times, insulation 3h; Add in amine and 10min, finally add water and carry out emulsification, regulate PH, cooling discharge.
8. the preparation method that a kind of water-soluble organic silicon is acrylic resin modified according to claim 7, it is characterized in that: described organosilane monomer selects the organosilane monomer of unsaturated double-bond, the organosilane monomer of described unsaturated double-bond is following one or more: vinyltriethoxysilane, vinyl silane triisopropoxide or r-methacryloxypropyl trimethoxy silane.
9. the preparation method that a kind of water-soluble organic silicon is acrylic resin modified according to claim 7, is characterized in that: one or more selected by described neutralizing agent: triethylamine, N, N-dimethyl diethanolamine or trolamine.
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Cited By (10)
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| CN105733390A (en) * | 2016-04-20 | 2016-07-06 | 湖南省金海科技有限公司 | Water-based two-component transparent finish paint for PP plastic and preparation method of finish paint |
| CN106280626A (en) * | 2016-08-12 | 2017-01-04 | 太仓市美航涂料有限公司 | A kind of environment-friendly type high adhesion force waterborne glass coatings |
| CN107746449A (en) * | 2017-09-01 | 2018-03-02 | 佛山市高明同德化工有限公司 | A kind of organosilicon-modified acrylic grafting water borne PUA and preparation method thereof |
| CN108003271A (en) * | 2017-12-25 | 2018-05-08 | 佛山市三求光固材料股份有限公司 | A kind of alkali soluble type anti-plate photosensitive resin and preparation method and application |
| CN108912283A (en) * | 2018-07-10 | 2018-11-30 | 广东日化涂料有限公司 | A kind of aqueous silicon wax oil is acrylic resin modified |
| CN108976952A (en) * | 2018-08-06 | 2018-12-11 | 中山市明日涂料材料有限公司 | A kind of novel environment-friendly water-based glass baking varnish and preparation method thereof |
| CN110028608A (en) * | 2018-04-09 | 2019-07-19 | 鹤山市肇能新材料有限公司 | A kind of E-10 and silicone-modified water-soluble thermoset acrylic resins and preparation method thereof |
| CN110885397A (en) * | 2019-12-04 | 2020-03-17 | 东胜化学(上海)有限公司 | Organic silicon modified acrylic resin and preparation method thereof |
| CN111234134A (en) * | 2020-02-28 | 2020-06-05 | 南京长江涂料有限公司 | High-performance glycidyl versatate modified polysiloxane resin and preparation method thereof |
| CN113980179A (en) * | 2021-10-15 | 2022-01-28 | 广汉市科思诺新材料科技有限公司 | Modified water-based hydroxyl acrylic acid dispersoid and synthesis process thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105733390A (en) * | 2016-04-20 | 2016-07-06 | 湖南省金海科技有限公司 | Water-based two-component transparent finish paint for PP plastic and preparation method of finish paint |
| CN106280626A (en) * | 2016-08-12 | 2017-01-04 | 太仓市美航涂料有限公司 | A kind of environment-friendly type high adhesion force waterborne glass coatings |
| CN107746449A (en) * | 2017-09-01 | 2018-03-02 | 佛山市高明同德化工有限公司 | A kind of organosilicon-modified acrylic grafting water borne PUA and preparation method thereof |
| CN108003271A (en) * | 2017-12-25 | 2018-05-08 | 佛山市三求光固材料股份有限公司 | A kind of alkali soluble type anti-plate photosensitive resin and preparation method and application |
| CN110028608A (en) * | 2018-04-09 | 2019-07-19 | 鹤山市肇能新材料有限公司 | A kind of E-10 and silicone-modified water-soluble thermoset acrylic resins and preparation method thereof |
| CN110028608B (en) * | 2018-04-09 | 2021-09-03 | 鹤山市肇能新材料有限公司 | E-10 and siloxane modified water-soluble thermosetting acrylic resin and preparation method thereof |
| CN108912283A (en) * | 2018-07-10 | 2018-11-30 | 广东日化涂料有限公司 | A kind of aqueous silicon wax oil is acrylic resin modified |
| CN108976952A (en) * | 2018-08-06 | 2018-12-11 | 中山市明日涂料材料有限公司 | A kind of novel environment-friendly water-based glass baking varnish and preparation method thereof |
| CN110885397A (en) * | 2019-12-04 | 2020-03-17 | 东胜化学(上海)有限公司 | Organic silicon modified acrylic resin and preparation method thereof |
| CN111234134A (en) * | 2020-02-28 | 2020-06-05 | 南京长江涂料有限公司 | High-performance glycidyl versatate modified polysiloxane resin and preparation method thereof |
| CN113980179A (en) * | 2021-10-15 | 2022-01-28 | 广汉市科思诺新材料科技有限公司 | Modified water-based hydroxyl acrylic acid dispersoid and synthesis process thereof |
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Application publication date: 20160113 |