CN101717564A - Preparation method of aqueous hyperbranched polyester resin for paint - Google Patents
Preparation method of aqueous hyperbranched polyester resin for paint Download PDFInfo
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- CN101717564A CN101717564A CN200910198203A CN200910198203A CN101717564A CN 101717564 A CN101717564 A CN 101717564A CN 200910198203 A CN200910198203 A CN 200910198203A CN 200910198203 A CN200910198203 A CN 200910198203A CN 101717564 A CN101717564 A CN 101717564A
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Abstract
The invention discloses a preparation method of aqueous hyperbranched polyester resin for paint, comprising the specific steps: firstly, divalent alcohol or polyalcohol performs esterification reaction with dimethylolpropionic acid and long-chain fatty acid to prepare hydroxyl-terminated hyperbranched polyester resin prepolymer; the prepared hydroxyl-terminated hyperbranched polyester resin prepolymer and a proper amount of anhydride react at the temperature of 110-170 DEG C until acid value does not change; when temperature is lowered to 80 DEG C, cosolvent, neutralizer and aqueous amino resin are added to be fully stirred evenly; a proper amount of deionized water is added to obtain aqueous hyperbranched polyester resin which can be used for preparing aqueous baking finish. The method of the invention has wide raw material source, low cost, simple synthetic method, simple technology, favorable controllability, favorable product dissolubility and low manufacturing cost. The invention is suitable for preparing aqueous baking finish and has wide application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of aqueous hyperbranched polyester resin for paint.
Background technology
Hyperbranched polymer is the highly branched polymkeric substance with three-dimensional spherical three-dimensional arrangement of a class.Have excellent physics-chem characteristic because of its particular structure, and synthesis technique is simple, is just becoming new research focus in the synthetic chemistry, at numerous areas such as biological medicine, manufactured goods, coating great application prospect is arranged.Hyperbranched polymer has the active end group of One's name is legion, can obtain the various performances of wanting by modification, and is applied to various fields.
Chen Mengru, imperial space, Jin Yangzhi etc. prepare the aqueous hyperbranched polyester of the photocuring that contains photosensitive group with hyper-branched polyester terminal grafted propylene acyl group and carboxyl and photosensitive group.Teng Qiu, Liming Tang etc. uses TriMethylolPropane(TMP), dimethylol propionic acid to synthesize hyper-branched polyester, and carries out terminal groups modification with adjacent phthalic anhydride, and polymer-modified have a good hydrophilicity.Wang XX, Lai G Q, usefulness cis-butenedioic anhydride modifications such as Jiang Zh J are that nuclear and DMPA are branched monomer synthetic two generations HBPE with TMP, obtain water-soluble polyester, use it for the preparation of pure-acrylic emulsion, find that the introducing of the water-soluble HBPE of end acrylic not only can improve the Calcium ion stability of pure-acrylic emulsion, also can improve the hardness of latex film.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of aqueous hyperbranched polyester resin for paint.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of aqueous hyperbranched polyester resin for paint, this method may further comprise the steps:
A. with neopentyl glycol (NPG) or polyvalent alcohol and acid, under inert atmosphere, carry out esterification at 140 ℃～170 ℃, the reaction times is 4～6 hours, obtains superbrnaching end-hydroxy polyester resin prepolymer; Described acid is dimethylol propionic acid (DMPA) and longer chain fatty acid; The quality of described alcohol with the ratio of the total mass of acid is: 1: (2～50), and the quality of longer chain fatty acid accounts for the 8%-15% of the total mass of acid in the described acid;
B. the prepolymer that step a is obtained is cooled to 110 ℃, adds the acid anhydrides through dissolution with solvents; The consumption of acid anhydrides is 4%～6% of a prepolymer total mass; Slough solvent in reaction under 110 ℃～170 ℃ after 4 hours; Be cooled to 50～60 ℃, 10%～12% the aminoresin that adds 25%～35% the solubility promoter account for the prepolymer total mass, accounts for 8%～12% neutralizing agent of prepolymer total mass and account for the prepolymer total mass, back adding appropriate amount of deionized water to the solid content that stirs is 20%-40%, stir, obtain aqueous hyperbranched polyester resin for paint.
Above-mentioned polyvalent alcohol is tetramethylolmethane (PER) or TriMethylolPropane(TMP) (TMP).
Above-mentioned longer chain fatty acid is behenic acid or ricinolic acid.
Above-mentioned acid anhydrides is Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride or MALEIC ANHYDRIDE.
Above-mentioned solvent is pimelinketone or N-BUTYL ACETATE.
Above-mentioned neutralizing agent is potassium hydroxide, triethylamine or ammoniacal liquor.
Above-mentioned solubility promoter is propyl carbinol, ethylene glycol ethyl ether, butyl glycol ether, diethylene glycol ether, Diethylene Glycol butyl ether or propylene-glycol ethyl ether.
The reaction mechanism of foundation of the present invention is:
The inventive method raw material sources are extensive, low price, and simple synthetic method, technology is simple, and controllability is good, and the product solvability is good, and preparation cost is low.Be suitable for preparing water-based stoving paint, have a wide range of applications.
Concrete embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment one: DMPA, the 0.8g of the NPG of 2.08g and 80.4g added benzene methanesulfonic acid be equipped with in the there-necked flask of agitator, prolong, thermometer, water trap, add an amount of dimethylbenzene as reflux solvent, be warming up to 120 ℃ of fusions, start stirring, be warming up to 140 ℃ of isothermal reactions.Acid number drops to below 10, obtains product, and its second-order transition temperature is 52.3 ℃.Be cooled to 110 ℃ then, add with 10ml N-BUTYL ACETATE dissolved Tetra hydro Phthalic anhydride 3.06g, react about 4 hours after, underpressure distillation removes and desolvates, be cooled to 70 ℃, add 20g ethylene glycol ethyl ether, butyl glycol ether mixed solvent and 4.53g triethylamine and stirred 5 minutes, get the 10g product, add the aminoresin of 2g and an amount of water then, stir, film on sheet tin, 170 ℃ of baking 30min obtain smooth surface, hard filming.Hardness of film is 3H, and sticking power is 1 grade.
Embodiment two: the TMP of 2.64g and DMPA, the adding of the 0.6g vitriol oil of 57.32g are equipped with in the there-necked flask of agitator, prolong, thermometer, water trap, add an amount of dimethylbenzene as reflux solvent, be warming up to 120 ℃ of fusions, start stirring, be warming up to 160 ℃ of isothermal reactions.Acid number drops to below 10, obtains product, and its second-order transition temperature is 39.5 ℃.Be cooled to 110 ℃ then, add with 10ml pimelinketone dissolved trimellitic acid 1,2-anhydride 3.06g, react about 4 hours after, underpressure distillation removes and desolvates, be cooled to 70 ℃, add 20g diethylene glycol ether, Diethylene Glycol butyl ether mixed solvent and 2.44g ammoniacal liquor and stirred 5 minutes, get the 10g product, add the aminoresin of 2g and an amount of water then, stir, film on sheet tin, 180 ℃ of baking 15min obtain smooth surface, hard filming.Hardness of film is 4H, and sticking power is 2 grades.
Embodiment three: the PER of 2.62g and DMPA, the 0.4g of 38.17g are equipped with in the there-necked flask of agitator, prolong, thermometer, water trap benzene methanesulfonic acid, the adding of 4g ricinolic acid, start stirring, slowly be warming up to 160 ℃ of fusions, isothermal reaction 1h, vacuumize reaction 2h, get lipid acid terminal groups modification hyper-branched polyester, its second-order transition temperature is 40.8 ℃.Be cooled to 110 ℃ then, add with 10ml N-BUTYL ACETATE dissolved Tetra hydro Phthalic anhydride 1.75g, react about 4 hours after, underpressure distillation removes and desolvates, be cooled to 70 ℃, add 20g propyl carbinol and 2.23g triethylamine and stirred 5 minutes, get the 10g product, add the aminoresin of 2g and an amount of water then, stir, film on sheet tin, 180 ℃ of baking 15min obtain smooth surface, hard filming.Hardness of film is 4H, and sticking power is 1 grade.
Embodiment four: the NPG of 2.10g and DMPA, the 0.87g of 81.98g are equipped with in the there-necked flask of agitator, prolong, thermometer, water trap benzene methanesulfonic acid, the adding of 8.13g behenic acid, start stirring, slowly be warming up to 150 ℃ of fusions, isothermal reaction 1h, vacuumize reaction 2h, get lipid acid terminal groups modification hyper-branched polyester, its second-order transition temperature is 50.2 ℃.Be cooled to 110 ℃ then, add with 10ml N-BUTYL ACETATE dissolved trimellitic acid 1,2-anhydride 23.97g, react about 4 hours after, underpressure distillation removes and desolvates, be cooled to 70 ℃, add 30g propylene-glycol ethyl ether and 2.85g sodium hydroxide and stirred 5 minutes, get the 10g product, add the aminoresin of 2g and an amount of water then, stir, film on sheet tin, 180 ℃ of baking 15min obtain smooth surface, hard filming.Hardness of film is 5H, and sticking power is 1 grade.
Condition of cure was 170 ℃ of 30min or 180 ℃ of 15min when aqueous hyperbranched vibrin of the present invention prepared water-based stoving paint.
Claims (7)
1. the preparation method of an aqueous hyperbranched polyester resin for paint is characterized in that this method may further comprise the steps:
A. with neopentyl glycol or polyvalent alcohol and acid, under inert atmosphere, carry out esterification at 140 ℃～170 ℃, the reaction times is 4～6 hours, obtains superbrnaching end-hydroxy polyester resin prepolymer; Described acid is dimethylol propionic acid and longer chain fatty acid; The quality of described alcohol with the ratio of the total mass of acid is: 1: (2～50), and the quality of longer chain fatty acid accounts for the 8%-15% of the total mass of acid in the described acid;
B. the prepolymer that step a is obtained is cooled to 110 ℃, adds the acid anhydrides through dissolution with solvents; The consumption of acid anhydrides is 4%～6% of a prepolymer total mass; Under 110 ℃～170 ℃, react to acid number and no longer change, slough solvent; Be cooled to 50～60 ℃, 10%～12% the aminoresin that adds 25%～35% the solubility promoter account for the prepolymer total mass, accounts for 8%～12% neutralizing agent of prepolymer total mass and account for the prepolymer total mass, back adding appropriate amount of deionized water to the solid content that stirs is 20%-40%, stir, obtain aqueous hyperbranched polyester resin for paint.
2. the preparation method of aqueous hyperbranched polyester resin for paint according to claim 1 is characterized in that described polyvalent alcohol is tetramethylolmethane or TriMethylolPropane(TMP).
3. the preparation method of aqueous hyperbranched polyester resin for paint according to claim 1 is characterized in that described longer chain fatty acid is behenic acid or ricinolic acid.
4. the preparation method of aqueous hyperbranched polyester resin for paint according to claim 1 is characterized in that described acid anhydrides is Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride or MALEIC ANHYDRIDE.
5. the preparation method of aqueous hyperbranched polyester resin for paint according to claim 1 is characterized in that described solvent is pimelinketone or N-BUTYL ACETATE.
6. the preparation method of aqueous hyperbranched polyester resin for paint according to claim 1 is characterized in that described neutralizing agent is potassium hydroxide, triethylamine or ammoniacal liquor.
7. the preparation method of aqueous hyperbranched polyester resin for paint according to claim 1 is characterized in that described solubility promoter is propyl carbinol, ethylene glycol ethyl ether, butyl glycol ether, diethylene glycol ether, Diethylene Glycol butyl ether or propylene-glycol ethyl ether.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408820A (en) * | 2011-07-29 | 2012-04-11 | 哈尔滨理工大学 | Preparation method of water-soluble low-contact-angle half-inorganic silicon sheet varnish |
| CN102690504A (en) * | 2011-03-24 | 2012-09-26 | 东丽纤维研究所（中国）有限公司 | Polyester and production method thereof |
| CN102943386A (en) * | 2012-09-11 | 2013-02-27 | 江苏宝泽高分子材料股份有限公司 | Water-based PU net-shaped crack coating agent for artificial leather |
| CN103113569A (en) * | 2013-01-13 | 2013-05-22 | 株洲时代电气绝缘有限责任公司 | Hyper-branched unsaturated resin and application thereof |
| CN104231235A (en) * | 2014-09-28 | 2014-12-24 | 江门市恒光新材料有限公司 | Preparation method of hyperbranched polyester with flexible long chain |
| CN105694014A (en) * | 2014-11-27 | 2016-06-22 | 合众（佛山）化工有限公司 | Method for preparing hyperbranched waterborne polyester resin |
| CN106700048A (en) * | 2016-12-12 | 2017-05-24 | 衡阳山泰化工有限公司 | Terminal hydroxyl branched polyester resin and preparation method thereof |
| CN106957413A (en) * | 2017-03-22 | 2017-07-18 | 上海展辰涂料有限公司 | A kind of quick-drying, easily polishing, low VOC PU woodenware priming paint hyperbranched alkyd resin and preparation method thereof |
| CN106995675A (en) * | 2017-03-20 | 2017-08-01 | 苏州瀚海新材料有限公司 | A kind of adhesive and preparation method and application |
| CN107109205A (en) * | 2014-12-30 | 2017-08-29 | 佐治亚-太平洋化工品有限公司 | The coating proppant and its application method of the coating containing super branched polyurethane |
| CN110790870A (en) * | 2018-08-01 | 2020-02-14 | 恒昌涂料（惠阳）有限公司 | Modified hydroxyl acrylic resin, preparation method and modified hydroxyl acrylic ester coating |
| CN111777927A (en) * | 2020-07-16 | 2020-10-16 | 进彩涂料科技(上海)有限公司 | High-hardness paper tape abrasion-resistant household appliance color plate coating and preparation method thereof |
| CN112831257A (en) * | 2020-12-30 | 2021-05-25 | 浙江淋泉材料技术有限公司 | Metal planing groove bending baking coating, preparation method and spraying baking process |
| CN114907552A (en) * | 2022-05-25 | 2022-08-16 | 广东润昌南星新材料有限公司 | Hyperbranched alkyd resin and preparation method and application thereof |
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2009
- 2009-11-03 CN CN200910198203A patent/CN101717564A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690504A (en) * | 2011-03-24 | 2012-09-26 | 东丽纤维研究所（中国）有限公司 | Polyester and production method thereof |
| CN102408820A (en) * | 2011-07-29 | 2012-04-11 | 哈尔滨理工大学 | Preparation method of water-soluble low-contact-angle half-inorganic silicon sheet varnish |
| CN102943386A (en) * | 2012-09-11 | 2013-02-27 | 江苏宝泽高分子材料股份有限公司 | Water-based PU net-shaped crack coating agent for artificial leather |
| CN103113569A (en) * | 2013-01-13 | 2013-05-22 | 株洲时代电气绝缘有限责任公司 | Hyper-branched unsaturated resin and application thereof |
| CN103113569B (en) * | 2013-01-13 | 2015-04-22 | 株洲时代电气绝缘有限责任公司 | Hyper-branched unsaturated resin and application thereof |
| CN104231235A (en) * | 2014-09-28 | 2014-12-24 | 江门市恒光新材料有限公司 | Preparation method of hyperbranched polyester with flexible long chain |
| CN105694014B (en) * | 2014-11-27 | 2017-09-08 | 合众（佛山）化工有限公司 | A kind of preparation method of hyperbranched aqueous polyester resin |
| CN105694014A (en) * | 2014-11-27 | 2016-06-22 | 合众（佛山）化工有限公司 | Method for preparing hyperbranched waterborne polyester resin |
| CN107109205A (en) * | 2014-12-30 | 2017-08-29 | 佐治亚-太平洋化工品有限公司 | The coating proppant and its application method of the coating containing super branched polyurethane |
| CN106700048A (en) * | 2016-12-12 | 2017-05-24 | 衡阳山泰化工有限公司 | Terminal hydroxyl branched polyester resin and preparation method thereof |
| CN106995675A (en) * | 2017-03-20 | 2017-08-01 | 苏州瀚海新材料有限公司 | A kind of adhesive and preparation method and application |
| CN106957413A (en) * | 2017-03-22 | 2017-07-18 | 上海展辰涂料有限公司 | A kind of quick-drying, easily polishing, low VOC PU woodenware priming paint hyperbranched alkyd resin and preparation method thereof |
| CN110790870A (en) * | 2018-08-01 | 2020-02-14 | 恒昌涂料（惠阳）有限公司 | Modified hydroxyl acrylic resin, preparation method and modified hydroxyl acrylic ester coating |
| CN111777927A (en) * | 2020-07-16 | 2020-10-16 | 进彩涂料科技(上海)有限公司 | High-hardness paper tape abrasion-resistant household appliance color plate coating and preparation method thereof |
| CN112831257A (en) * | 2020-12-30 | 2021-05-25 | 浙江淋泉材料技术有限公司 | Metal planing groove bending baking coating, preparation method and spraying baking process |
| CN114907552A (en) * | 2022-05-25 | 2022-08-16 | 广东润昌南星新材料有限公司 | Hyperbranched alkyd resin and preparation method and application thereof |
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Open date: 20100602 |