CN1274736A - Preparation of water-thinned paint with hydrolysis-resisting alkyd resin - Google Patents
Preparation of water-thinned paint with hydrolysis-resisting alkyd resin Download PDFInfo
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- CN1274736A CN1274736A CN 00115590 CN00115590A CN1274736A CN 1274736 A CN1274736 A CN 1274736A CN 00115590 CN00115590 CN 00115590 CN 00115590 A CN00115590 A CN 00115590A CN 1274736 A CN1274736 A CN 1274736A
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Abstract
Polymer containing 2-6 carboxyl groiups and with a 500-5000 molecular weight is used to replace phthalic anhydride or m-phthalic acid synthesizing alkyd resin, which is then compounded to obtain paint. The paint of the present invention has excellent hydrolysis resistance and can meet the requirement of building paint for storage period. It forms hard paint film with adjustable gloss, has excellent application performance and may be used widely in inner and outer wall of building, bridge, etc.
Description
The invention belongs to chemical technology field, is a kind of preparation method of water-reducible coating of Synolac of hydrolysis.
Synolac was succeeded in developing in nineteen twenty-seven, because the special performance of Synolac has obtained development extremely rapidly, the eighties, external Synolac consumption accounted for 40% of all full resin, and especially the North America consumption is bigger, and 27% ratio is also arranged in China.But along with the rise of whole world environment protection upsurge, coating more and more is subjected to attention highly to the pollution of environment, so oil soluble coating is progressively replaced by water-borne coatings, the output of oil soluble Synolac also descends year by year.So many in the world research institutions begin the research work of Synolac Water-borne modification.Prepare water-soluble or aqueous-dispersing alkyd resin is technical not so difficult, but it is exactly the hydrolytic resistance extreme difference that this resinoid has a very large weakness, the quality guaranteed period of conventional waterborne alkyd resin is all in half a year, and the quality guaranteed period that is used for building coating wishes more than 2 years.So on building coating, Water-borne Alkyd Coatings is very limited.In order to overcome above-mentioned shortcoming, many in the world major companies (as AMOCO company) begin to carry out the research of Synolac hydrolytic resistance, mainly be with hydrolytic resistance preferably the monomer m-phthalic acid replace the more cheap Tetra hydro Phthalic anhydride of price, and obtained certain effect, but still there is certain problem in hydrolytic resistance.Now also there are some vinyl monomers of human and Synolac copolymerization to obtain vinylbenzene or acrylate modified resin, but owing to the unsaturated double-bond of oils in this type of polymerization is affected the drying property of resin by mass consumption.At present, the work of this respect is still an emphasis research direction of water-borne coatings.
The objective of the invention is to propose a kind of preparation method with alkyd resin coating of good anti-hydrolytic performance.
The preparation method of the hydrolytic resistance Synolac that the present invention proposes is that the polymkeric substance with controlled architecture that will have certain carboxyl-content replaces traditional Tetra hydro Phthalic anhydride or m-phthalic acid, synthetic alkyd resin, and its step is as follows:
With the preparation of atomic radical transfer polymerization or active free radical polymerization contain 2-6 carboxyl, molecular weight is the polymkeric substance of 500-5000.Here polymkeric substance can be the polymkeric substance that is obtained by one or several polymerization such as vinylbenzene, acrylate, methacrylic ester, vinyl cyanide, toxilic acid and acid anhydrides thereof, vinylformic acid and acid anhydrides thereof, methacrylic acid and acid anhydrides, fumaric acid etc.
2. prepare glyceryl monoacetate with alcoholysis method or acid hydrolyzation, raw materials used is common polyvalent alcohol (for example: glycerine, TriMethylolPropane(TMP), tetramethylolmethane etc.), plant oil (as soya-bean oil, tung oil, Toenol 1140, Semen Ricini oil, Chinese catalpa oil, perilla oil, hemp wet goods).
3. with the carboxylic polymkeric substance of step 1 preparation and the glyceryl monoacetate for preparing by step 2; by 85: 15-20: 80 weight proportion, synthetic alkyd resin is reflected under the nitrogen protection and carries out; temperature of reaction system is controlled at 180-250 ℃, reaction times 0.5-8 hour.Follow the tracks of reaction process with volumetry in the reaction process, reach between the acid number 5-100 that needs up to reaction, the oil content of gained Synolac is between the 15-80.
4. will neutralize with alkali by the Synolac of step 3 preparation, add entry, add siccative, filler, pigment and other auxiliary agent again, mix well, promptly make waterborne alkyd resin coating.The solid content of this coating is between 10-70%, and the pH value is 7-10.Wherein, siccative can be organic metal salts such as calcium, cobalt, lead.Filler, pigment, auxiliary agent etc. are similar with common coating.
In the above-mentioned steps 1, the process that the atom Group Transfer polymerization prepares carboxylic polymkeric substance is as follows: with 1 part of monomer (mol of unit, for example with 100mol as 1 part) and the initiator of monomeric 0.001-5%, the metal halide of 0.001-5%, the complexing agent of 0.001-5% put into reaction flask, reaction is 2-24 hour under 50-130 ℃ of temperature, promptly obtains the polymkeric substance of setting structure.Wherein, monomer can be one or several of vinylbenzene, acrylate, methacrylic ester, vinyl cyanide, toxilic acid and acid anhydrides thereof, vinylformic acid and acid anhydrides thereof, methacrylic acid and acid anhydrides, fumaric acid etc.Initiator can be a kind of of AIBN, BPO, persulphate, tetracol phenixin, bromobenzyl, ∝-bromine ethylbenzene, 2 bromopropionic acid ester etc.Metal halide can be a kind of of cuprous bromide, cuprous chloride, ferrous bromide, iron protochloride etc.5-methyl-diethyl triamine etc. that complexing agent can be a connection arsenic pyridine or derivatives thereof, N, N, N ', N ", N " a kind of.
In the above-mentioned steps 1, the process that active free radical polymerization prepares carboxylic polymkeric substance is as follows: with 1 part of monomer (mol of unit, for example with 100mol as 1 part) and the initiator of monomeric 0.001-10%, the free and stable base of 0.001-5% put into reaction flask, at 50-130 ℃ of thermotonus 4-48 hour, promptly obtain the polymkeric substance of setting structure.Wherein, monomeric kind as described above; Initiator is a kind of of AIBN, BPO, DCPO, persulphate etc.; Stabilized radical can be 2,2,6,6-tetramethylpiperidinol nitroxyl free radical (TEMPOL), 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical (TEMPO) a kind of.
In the above-mentioned steps 2, raw material is put into reaction flask by proportioning, the reacting by heating system is to 180-210 ℃ under the nitrogen atmosphere, add alcoholysis catalysts, reheat kept 25-35 minute to 240-260 ℃, check the solubleness of reactant then, when arriving suitable solubleness, stopped reaction promptly obtains glyceryl monoacetate.Check general per ten minutes and get sample one time, check the dissolving situation of reactant, when the 1ml sample is dissolvable in water in the methyl alcohol about 3ml till.
In the above-mentioned steps 4, used alkali can be ammoniacal liquor, triethylamine, N, N-dimethylethanolamine, 2-amino-2-methyl propyl alcohol, N-ethylmorpholine etc.
In the step 1-3 process of the present invention, the reaction flask of use all has the entry and exit of thermometer, agitator, condenser and nitrogen.Thermometer is used for measuring the temperature of reaction process, so that the control heating condition, agitator is used for the stirring to reactant, and condenser is used for the pyritous reaction product is cooled down.
Can be made into the waterborne alkyd resin coating of 0VOC or low VOC with the resin of the inventive method preparation, this coating can be widely used in building inside and outside wall, bridge, the every field of industry and people's lives.This coating has good anti-hydrolytic performance, can satisfy building coating fully to the requirement of storage period, and hardness of paint film is good, and glossiness can be regulated, and workability is good.
Embodiment 1, adds 52.2g methyl methacrylate, 37.5g butyl acrylate in the reaction flask that has thermometer, agitator, condenser and nitrogen inlet and outlet; 10.3g methacrylic acid, 3.8mL2-bromo-propionic acid ester, 5.0g cuprous bromide; 7.3mL N; N, N ', N "; N "-5-methyl-diethyl triamine; under stirring and nitrogen protection, reaction system is heated to 110 ℃ of temperature, reacted 12 hours, can obtain the polymkeric substance-product (I) of the band carboxyl of narrow distribution.
In the reaction flask that has thermometer, agitator, condenser and nitrogen inlet and outlet, add the 15.8g TriMethylolPropane(TMP); 51.8g soya-bean oil; reacting by heating system to 204 ℃ under nitrogen atmosphere then; add 0.026gFASCAT4100; continue to be heated to 250 ℃ and protect 30 minutes, sampling in per ten minutes is once checked the dissolving situation of reactant then; stopped reaction when the 1mL sample is dissolvable in water in the methyl alcohol of 3mL obtains glyceryl monoacetate-product (II).
In the reaction flask that has thermometer, agitator, water separator, nitrogen inlet and outlet, add 50g product (I) and 50g product (II), under nitrogen protection, reaction system is heated to 210 ℃, reacted 1 hour.Follow the tracks of reaction process with volumetry then, be reached for 35 o'clock stopped reaction, promptly obtain needed resin up to the reaction system acid number.
In the above-mentioned gained resin of 50.7g, add 2.61g N, the N-dimethylethanolamine, 50g water adds 1.22g Hydrocure II5% Cobalt, 1.22g Hydrochem5% Calcium then, 0.61g Hy-drochem12% Zirconium, 0.21g EXKIN#2 and 0.31g BYK301 stirred 1 hour, can make waterborne alkyd resin coating, the solid content of this coating is 51%, and the pH value is about 8.
Embodiment 2, add 52.2g methyl methacrylate, 37.5g butyl methacrylate in having thermometer, agitator, condenser and nitrogen inlet and outlet reaction flask; 5.1g methacrylic acid, 7.9mL2-bromo-propionic acid ester, 9.8g cuprous bromide; 15.0mL N; N, N ', N "; N "-5-methyl-diethyl triamine; under stirring and nitrogen protection, reaction system is heated to 110 ℃ of temperature, reacted 10 hours, can obtain the polymkeric substance-product (I) of the band carboxyl of narrow distribution.
The preparation method of glyceryl monoacetate-product (II) is with example 1.
In the reaction flask that has thermometer, agitator, water separator and nitrogen inlet and outlet, add 40g product (I) and 50g product (II), under nitrogen protection, reaction system is heated to 220 ℃, reacted 1 hour.Follow the tracks of reaction process with volumetry then, be reached for 35 o'clock stopped reaction, promptly obtain needed resin up to the reaction system acid number.
In the above-mentioned gained resin of 50.0g, add 2.6gN, N-dimethylethanolamine, 70g water, 25.0gTiO
2Add 1.31g Hydrocure II5% Cobalt then, 1.35g Hydrochem 5% Calcium, 0.60gHydrochem 12% Zirconium, 0.25g EXKIN#2 and 0.33g BYK301, stirred 1 hour, can make waterborne alkyd resin coating, the solid content of this coating is 55%, and the pH value is about 8.
Embodiment 3; in the reaction flask that has thermometer, agitator, condenser and nitrogen inlet and outlet, add 50g vinylbenzene; the 37g butyl acrylate; 8.0g vinylformic acid; 3.0g AIBN and 3.1gTEMPOL; under stirring and nitrogen protection, reaction system is heated to 95 ℃ of temperature, reacted 36 hours, can obtain the polymkeric substance-product (I) of the band carboxyl of narrow distribution.
The preparation method of glyceryl monoacetate-product (II) is with example 1.
In the reaction flask that has thermometer, agitator, water separator and nitrogen inlet and outlet, add 45g product (I) and 50g product (II), under nitrogen protection, reaction system is heated to 220 ℃, reacted 1 hour.Follow the tracks of reaction process with volumetry in reaction process, reaching acid number up to reaction is 30 o'clock, and stopped reaction promptly obtains needed resin.
In the above-mentioned institute of 50.0g resin, add 2.5gN, N-dimethylethanolamine, 70g water, 25.0gTiO
2Add 1.35g Hydrocure II5% Cobalt then, 1.20g Hydrochem 5% Calcium, 0.65gHydrochem 12% Zirconium, 0.20g EXKIN#2 and 0.30g BYK301 stirred 1 hour, can make waterborne alkyd resin coating, the solid content of this coating is 55%, and the pH value is about 8.
Claims (4)
1. the preparation method of a hydrolytic resistance phthalic resin coating is characterized in that concrete steps are as follows:
(1) with the preparation of atomic radical transfer polymerization or active free radical polymerization contain 2-6 carboxyl, molecular weight is the polymkeric substance of 500-5000, this polymkeric substance is the polymkeric substance that one or more polymerizations by vinylbenzene, acrylate, methacrylic ester, vinyl cyanide, toxilic acid and acid anhydrides thereof, vinylformic acid and acid anhydrides thereof, methacrylic acid and monomers such as acid anhydrides, fumaric acid thereof obtain;
(2) prepare glyceryl monoacetate with alcoholysis method or acid hydrolyzation, raw materials used is common polyvalent alcohol and vegetables oil;
(3) will press 85 by the carboxylic polymkeric substance of step (1) preparation with by the glyceryl monoacetate of step (2) preparation: 15-20: 80 weight proportion synthetic alkyd resin; be reflected under the nitrogen protection and carry out; temperature of reaction system is controlled at 180-250 ℃; reaction times 0.5-8 hour; follow the tracks of reaction process with volumetry; reaction is reached between the acid number 5-100 that needs, and gained Synolac oil content is between the 15-80.
(4) will neutralize with alkali by the Synolac of step (3) preparation, add entry, add siccative, filler, the relevant auxiliary agent of pigment again, mix well, promptly get waterborne alkyd resin coating with other.
2. the preparation method of phthalic resin coating according to claim 1, it is characterized in that in the step (1), with 1 part of monomer, the complexing agent of the initiator of monomeric 0.001-5%, the metal halide of 0.001-5%, 0.001-5% is put into reaction flask, reaction is 2-24 hour under 50-130 ℃ of temperature, obtains the polymkeric substance of setting structure; Wherein, monomer is one or more of vinylbenzene, acrylate, methacrylic ester, vinyl cyanide, toxilic acid and acid anhydrides thereof, vinylformic acid and acid anhydrides thereof, methacrylic acid and acid anhydrides thereof, fumaric acid; Initiator is a kind of of AIBN, BPO, persulphate, tetracol phenixin, bromobenzyl, ∝-bromine ethylbenzene, 2 bromopropionic acid fat etc.; Metal halide is a kind of of cuprous bromide, cuprous chloride, ferrous bromide, iron protochloride; Complexing agent for connection arsenic pyridine or and derivative, N, N, N ', N " 5-methyl-diethyl triamine a kind of.
3. the preparation method of phthalic resin coating according to claim 1, it is characterized in that in the step (1), with 1 part of monomer, the initiator of monomeric 0.001-10%, the stabilized radical of 0.001-5% are put into reaction flask, at 50 1 130 ℃ of thermotonus 4-48 hours, obtain the polymkeric substance of setting structure; Wherein, monomer is identical with monomer scope in the claim 2, and initiator is a kind of of AIBN, BPO, DCPO, persulphate, and stabilized radical is 2,2,6,6-tetramethylpiperidinol nitroxyl free radical, 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical a kind of.
4. the preparation method of phthalic resin coating according to claim 1, it is characterized in that in the step (2), raw material is put into reaction flask by proportioning, and the reacting by heating system adds alcohol catalyst to 180-210 ℃ under the nitrogen atmosphere, reheat is to 240-260 ℃, kept 25-35 minute, and then, checked the dissolving situation of reactant, stopped reaction when suitable solubleness obtains glyceryl monoacetate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 00115590 CN1274736A (en) | 2000-05-06 | 2000-05-06 | Preparation of water-thinned paint with hydrolysis-resisting alkyd resin |
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| CN 00115590 CN1274736A (en) | 2000-05-06 | 2000-05-06 | Preparation of water-thinned paint with hydrolysis-resisting alkyd resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453610C (en) * | 2002-04-12 | 2009-01-21 | 特殊材料分析有限责任公司 | Acrylate-functionalized alkyd compositions for fast-dry coatings |
| CN1957048B (en) * | 2004-05-25 | 2010-10-13 | 阿克佐诺贝尔国际涂料股份有限公司 | Coating composition comprising a vinyl modified alkyd resin |
| CN101407698B (en) * | 2007-10-09 | 2012-01-25 | 上海涂料有限公司技术中心 | Composite drier for aqueous air drying type coating |
-
2000
- 2000-05-06 CN CN 00115590 patent/CN1274736A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453610C (en) * | 2002-04-12 | 2009-01-21 | 特殊材料分析有限责任公司 | Acrylate-functionalized alkyd compositions for fast-dry coatings |
| CN1957048B (en) * | 2004-05-25 | 2010-10-13 | 阿克佐诺贝尔国际涂料股份有限公司 | Coating composition comprising a vinyl modified alkyd resin |
| CN101407698B (en) * | 2007-10-09 | 2012-01-25 | 上海涂料有限公司技术中心 | Composite drier for aqueous air drying type coating |
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