CN103739830B - Polyester resin for TGIC cured high-toughness powder coating and preparation method thereof - Google Patents
Polyester resin for TGIC cured high-toughness powder coating and preparation method thereof Download PDFInfo
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- CN103739830B CN103739830B CN201310494885.0A CN201310494885A CN103739830B CN 103739830 B CN103739830 B CN 103739830B CN 201310494885 A CN201310494885 A CN 201310494885A CN 103739830 B CN103739830 B CN 103739830B
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Abstract
The invention discloses a polyester resin for a TGIC cured high-toughness powder coating. The polyester resin is obtained by a melting condensation polymerization reaction of the following raw materials in percentage by weight: 32-40% of a dihydric alcohol, 52-60% of an aromatic dibasic acid, 0.4-1.6% of a polyhydric alcohol, 2-8% of a fatty dibasic acid, and 0.01-0.15% of an esterification catalyst. The invention also discloses a preparation method of the polyester resin. The prepared polyester resin has an appropriate glass transition temperature, is suitable for a TGIC curing system; and a coating layer of the prepared powder coating has excellent flexibility, and also has excellent mechanical properties under conditions of the room temperature and the low temperature of about -10 DEG C.
Description
Technical field
The present invention relates to a kind of polyester resin, particularly relate to a kind of TGIC and solidify high tenacity polyester resin for powder coating, the invention still further relates to the preparation method of this polyester resin.
Background technology
Powdery paints have solvent-free, utilization rate is high and the advantage of high comprehensive performance, is an important development field of environmental protection coating material.One basic function of coating is to realize the protection to ground, keeps being coated with the intact premise being to realize protective effect of layer function.
The shock resistance of the coating that powder paint obtains along with temperature decline and decline, use ambient temperature relatively low time, due to the decline of main component organic polymer mobility, the shock resistance of coating is also decreased obviously.Significantly example is that some powdery paints coating shock resistances when summer are fine, once often occurs situation about just can not recoiled by 50cm to winter.Even it addition, under normal temperature environment, some need the application in secondary operations field also the pliability of powdery paints to be proposed higher requirement.For adapting to these requirements using environment, expand the application of powdery paints, it is necessary to synthesize a kind of pliability excellence and still there is under lower temperature environments the polyester resin for powder coating of preferable mechanical performance.At present, on domestic market, pliability exsertile polyester resin product is less appears in the newspapers, and the outdoor product being suitable for TGIC curing system is the most less.
CN 102417589 A discloses a kind of high levelling low temperature curing polyester resin, and this resin introduces the long-chain fat race monomers such as a large amount of ethylene glycol and diethylene glycol, therefore can speculate that this resin also should have preferable pliability.But owing to ethylene glycol and diethylene glycol are the poor monomer of weatherability, this resin does not possess outdoor use value, is not suitable as TGIC curing system polyester resin.Additionally, for realizing the high levelling under low temperature curing conditions, the number equal relative molecular mass resin of this resin can not be too big, macroscopically shows as final viscosity relatively low, this glass transition temperature that certainly will have influence on this resin and the mechanical performance of corresponding powdery paints.The resinous acid value of final synthesis is at 45 ~ 55 mgKOH/g
Between, use as 60:40 mixed polyester resin, little to synthesis TGIC solidification high tenacity polyester resin for powder coating reference.It is the polyester resin of 30 ~ 50mgKOH/g that CN 102627755 A discloses a kind of acid number, this resin have employed the aliphatic polybasic acids such as aliphatic polyol and adipic acid such as substantial amounts of hexanediol, resin has splendid pliability, but this resin is semi-crystalline polyester resin, there is the problem that powdery paints manufactures difficulty, and prepare coating surface hardness relatively low, be difficult at present in actual production widely apply.
Summary of the invention
An object of the present invention is to provide a kind of TGIC and solidifies high tenacity polyester resin for powder coating, this polyester resin has suitable glass transition temperature, the powdery paints of preparation has the pliability of excellence, at normal temperatures and all has the mechanical performance of excellence under about-10 DEG C cryogenic conditions.
The two of the purpose of the present invention are to provide the preparation method of above-mentioned polyester resin.
First purpose of the present invention is achieved through the following technical solutions: a kind of TGIC solidifies high tenacity polyester resin for powder coating, this polyester resin acid number is 31～37mgKOH/g, hydroxyl value is less than 10mgKOH/g, glass transition temperature is 60～65 DEG C, melt viscosity is 6000～9000mPa.s, and it is obtained through melt polycondensation reaction by the raw material of following percentage by weight:
Dihydroxylic alcohols
32～40%
Aromatic dibasic acid 52～60%
Polyhydric alcohol
0.4～1.6%
Binary acid 2～8%
Esterification catalyst 0.01～0.15%.
In said components, described dihydroxylic alcohols is neopentyl glycol, 2-methyl isophthalic acid, ammediol, hexanediol and 2, the mixture of one or more of 2-dimethyl-3-hydracrylic acid DOPCP (HPHP)；Described aromatic dibasic acid is one or both the mixture in p-phthalic acid and M-phthalic acid；Described polyhydric alcohol is the mixture of one or more in trimethylolpropane, 1,3,5-tri-(2-ethoxy) cyanuric acid and trimethylolethane；Described fat unit diacid is the mixture of one or more in adipic acid, decanedioic acid, Azelaic Acid, dodecanedioic acid and 1,4 cyclohexanedicarboxylic acid；Described esterification catalyst is organic tin compound, especially includes Mono-n-butyltin, Dibutyltin oxide.
The preparation method of above-mentioned TGIC solidification high tenacity polyester used for powder coating tree is: in a kettle., adds the dihydroxylic alcohols of proportional quantity, is heated to material melting；Then being sequentially added into aromatic dibasic acid and esterification catalyst, logical nitrogen continues temperature reaction, starts to generate and distillate to 180 DEG C of esterification water；Then 250 DEG C it are gradually heating to, after the esterification water of coreaction 5～10 hours to 95% is discharged, acid number reaches 10～20mgKOH/g, add acidolysis agent, reaction 2～4h, acid number reaches 40～50mgKOH/g, evacuation polycondensation about 2～4h, acid number reaches 31～37mgKOH/g, i.e. stopped reaction obtains TGIC and solidifies high tenacity polyester resin for powder coating；Wherein, described acidolysis agent is one or both the mixing in aromatic dibasic acid and binary acid.
Polyester resin prepared by the inventive method is unformed terminal carboxyl polyester resin, and acid number is 31～37mgKOH/g, and hydroxyl value is less than 10mgKOH/g, and glass transition temperature is 60～65 DEG C, and melt viscosity is 6000～9000mPa.s.The polyester resin of the present invention has suitable glass transition temperature, it is suitable for TGIC curing system, the coating of the powdery paints of preparation at normal temperatures and all has the mechanical performance of excellence under about-10 DEG C cryogenic conditions, have excellent pliability and shock resistance and good weatherability.
The polyester resin using present invention synthesis is prepared the step of weather-resistant powder paint and is: mix after being weighed up in proportion with firming agent TGIC, filler, pigment and other auxiliary agents respectively by the polyester resin of synthesis, melt extrudes, cools down and crush, pulverize and sieve and make powdery paints.Color stuffing includes that titanium dioxide, barium sulfate, calcium carbonate, Ciba are green etc., and other auxiliary agents include Benzoinum, levelling agent etc..
Detailed description of the invention
A part of specific embodiment is set forth below, and the present invention will be described, and table 1 is the embodiment of polyester resin, A～E is comparative example F of different monomers and process combination.In 10 liters of reactors, add the neopentyl glycol of proportional quantity listed by table 1,2,2-dimethyl-3-hydracrylic acid DOPCP, trimethylolpropane, 1,3,5-tri-(2-ethoxy) cyanuric acid, be heated to material melting；It is subsequently adding p-phthalic acid, monobutyltin oxide, logical nitrogen continues temperature reaction, and about 180 DEG C esterification water start to generate and distillate, are then gradually heating to 250 DEG C, after the esterification water of coreaction 5～10 hours to 95% is discharged, acid number reaches 10～20mgKOH/g, adds acidolysis agent M-phthalic acid, adipic acid, dodecanedioic acid, reacts 2～4h, acid number reaches 40～50mgKOH/g, evacuation polycondensation about 2～4h, acid number reaches 31～37mgKOH/g, gets final product stopped reaction.
Acid number: 31～37mgKOH/g；Vitrification point: 60～65 DEG C；Softening point: 100～110 DEG C；200 DEG C of melt viscosities (ICI bores plate viscometer): 6000～9000mPa s.
Can the performance of powdery paints by making embody by the performance of the polyester resin of the inventive method synthesis.Mix after the polyester resin A F that the present invention synthesizes is weighed up in the ratio in table 2 with TGIC, levelling agent, titanium dioxide, barium sulfate, Benzoinum, pigment etc. respectively, with the melted extrusion respectively of screw extruder, tabletting, crush, then sheet stock is pulverized and sieved and make powdery paints (see embodiment 1-5 and comparative example 6).Powdery paints uses electrostatic gun to be sprayed on the metallic plate of surface treated (phosphatization), through 200 DEG C/6～10min solidifications, then carries out various performance test, and wherein, impact property at normal temperatures and is tested at-10 DEG C respectively, and the performance test results is as shown in table 2.
From table 1～2, the pliability that the glass transition temperature of polyester resin prepared by the inventive method is suitably excellent, the coating of the powdery paints of preparation at normal temperatures and all has the mechanical performance of excellence under about-10 DEG C cryogenic conditions.
Claims (3)
1. a TGIC solidifies high tenacity polyester resin for powder coating, it is characterized in that, this polyester resin acid number is 31～37mgKOH/g, hydroxyl value is less than 10mgKOH/g, glass transition temperature is 60～65 DEG C, melt viscosity is 6000～9000mPa s but is not 6000mPa s, and it is obtained through melt polycondensation reaction by the composition of following percentage by weight:
Dihydroxylic alcohols
32～40%
Aromatic dibasic acid 52～60%
Polyhydric alcohol
0.4～1.6%
Binary acid 2～8%
Esterification catalyst 0.01～0.15%；
Described dihydroxylic alcohols is neopentyl glycol, 2-methyl isophthalic acid, ammediol, hexanediol and 2, the mixture of one or more of 2-dimethyl-3-hydracrylic acid DOPCP, described aromatic dibasic acid is p-phthalic acid and M-phthalic acid, described polyhydric alcohol is trimethylolpropane or 1,3,5-tri-(2-ethoxy) cyanuric acid, the interpolation when reaction carries out acidolysis of described binary acid；
Described melt polycondensation preparation method is:
In a kettle., add dihydroxylic alcohols and polyhydric alcohol, be heated to material melting；Then being sequentially added into aromatic dibasic acid p-phthalic acid and esterification catalyst, logical nitrogen continues temperature reaction, starts to generate and distillate to 180 DEG C of esterification water；Then 250 DEG C it are gradually heating to, after the esterification water of coreaction 5～10 hours to 95% is discharged, acid number reaches 10～20mgKOH/g, add acidolysis agent, reaction 2～4h, acid number reaches 40～50mgKOH/g, evacuation polycondensation 2～4h, acid number reaches 31～37mgKOH/g, i.e. stopped reaction obtains TGIC and solidifies high tenacity polyester resin for powder coating；Wherein, described acidolysis agent is the mixing of aromatic dibasic acid M-phthalic acid and binary acid, and described binary acid is the mixture of one or more in adipic acid, decanedioic acid, Azelaic Acid and dodecanedioic acid.
TGIC the most according to claim 1 solidifies high tenacity polyester resin for powder coating, it is characterized in that, described esterification catalyst is Mono-n-butyltin or Dibutyltin oxide.
3. the preparation method of the TGIC solidification high tenacity polyester resin for powder coating described in claim 1, is characterized in that, in a kettle., add dihydroxylic alcohols and polyhydric alcohol, be heated to material melting；Then being sequentially added into aromatic dibasic acid p-phthalic acid and esterification catalyst, logical nitrogen continues temperature reaction, starts to generate and distillate to 180 DEG C of esterification water；Then 250 DEG C it are gradually heating to, after the esterification water of coreaction 5～10 hours to 95% is discharged, acid number reaches 10～20mgKOH/g, add acidolysis agent, reaction 2～4h, acid number reaches 40～50mgKOH/g, evacuation polycondensation 2～4h, acid number reaches 31～37mgKOH/g, i.e. stopped reaction obtains TGIC and solidifies high tenacity polyester resin for powder coating；Wherein, described acidolysis agent is the mixing of aromatic dibasic acid M-phthalic acid and binary acid.
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| CN105367767B (en) * | 2015-12-07 | 2017-06-23 | 浙江传化天松新材料有限公司 | Hydroxy polyester resin and preparation method thereof in high-flexibility saturation used for powder coating |
| CN106928820B (en) * | 2017-04-18 | 2019-05-07 | 安徽桑瑞斯环保新材料有限公司 | A kind of preparation process of coiled material Weather-resisting powder coating |
| CN107151315B (en) * | 2017-05-24 | 2019-03-01 | 黄山市向荣新材料有限公司 | A kind of polyester resin for powder coating with autocatalytic activity, preparation method and the powdery paints comprising it |
| CN107177033B (en) * | 2017-07-14 | 2019-01-04 | 黄山市徽州康佳化工有限责任公司 | A kind of powdery paints Self-leveling polyester resin, preparation method and the powder paint compositions containing it |
| CN107602826A (en) * | 2017-08-18 | 2018-01-19 | 帝兴树脂(昆山)有限公司 | The polyester resin for powder coating of TGIC solidifications and the powder paint compositions comprising polyester resin |
| CN108753125A (en) * | 2018-05-23 | 2018-11-06 | 上海新泊地化工技术服务有限公司 | A kind of high adhesion force high temperature resistance polyester powdery paints and preparation method thereof |
| CN109161311A (en) * | 2018-08-23 | 2019-01-08 | 黄山佳杰新材料科技有限公司 | High adhesion force Heat Resistant Powder Coatings polyester resin and preparation method thereof |
| CN109180922B (en) * | 2018-09-07 | 2021-06-22 | 安徽恒隆新材料有限公司 | Low-temperature curing type polyester resin and preparation method and application thereof |
| CN110305569B (en) * | 2019-07-17 | 2021-04-30 | 浙江光华科技股份有限公司 | Polyester resin based on phenyl succinic anhydride and preparation method thereof |
| CN110790909B (en) * | 2019-10-30 | 2022-03-15 | 擎天材料科技有限公司 | Polyester resin and preparation method thereof |
| CN111138642A (en) * | 2019-12-27 | 2020-05-12 | 广东银洋环保新材料有限公司 | Polyester resin for microwave oven inner layer powder coating, preparation method of polyester resin and powder coating |
| CN111518460B (en) * | 2020-05-12 | 2021-09-28 | 帝兴树脂(昆山)有限公司 | Low gloss powder coatings with good flexibility |
| CN112961334B (en) * | 2021-04-25 | 2022-08-12 | 山东尚核电力科技有限公司 | Polyester resin for corrosion-resistant weather-resistant high-storage-performance powder coating |
| CN113980560B (en) * | 2021-12-16 | 2023-04-18 | 安徽美佳新材料股份有限公司 | Powder coating special for coil steel and preparation method thereof |
| CN114350234A (en) * | 2021-12-27 | 2022-04-15 | 广东西敦千江粉漆科学研究有限公司 | High-toughness bending-resistant powder coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408550A (en) * | 2011-11-14 | 2012-04-11 | 广州擎天实业有限公司 | Carboxyl-terminated polyester resin for super weather-proof powder coating and preparation method thereof |
| CN102443148A (en) * | 2011-10-20 | 2012-05-09 | 广州擎天实业有限公司 | Polyester resin for rapid curing of weather-durable powdery paint by beta-hydroxyalkylamide and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059275B (en) * | 2012-12-28 | 2015-09-30 | 广州擎天材料科技有限公司 | A kind of TGIC curing transparent polyester resin for powder coating and preparation method thereof |
-
2013
- 2013-10-21 CN CN201310494885.0A patent/CN103739830B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443148A (en) * | 2011-10-20 | 2012-05-09 | 广州擎天实业有限公司 | Polyester resin for rapid curing of weather-durable powdery paint by beta-hydroxyalkylamide and preparation method thereof |
| CN102408550A (en) * | 2011-11-14 | 2012-04-11 | 广州擎天实业有限公司 | Carboxyl-terminated polyester resin for super weather-proof powder coating and preparation method thereof |
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Address after: 510860 Yufeng Road, Shiling Town, Huadu District, Guangzhou City, Guangdong Province Co-patentee after: China Electrical Appliance Research Institute Co., Ltd. Patentee after: Guangzhou Kinte Industrial Co., Ltd. Address before: 510860 Yufeng Road, Shiling Town, Huadu District, Guangzhou City, Guangdong Province Co-patentee before: China National Electric Apparatus Research Institute Co., Ltd. Patentee before: Guangzhou Kinte Industrial Co., Ltd. |
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Address after: No.5 Lisha East Road, Shatian Town, Dongguan City, Guangdong Province 523000 Co-patentee after: China Electrical Appliance Research Institute Co.,Ltd. Patentee after: Qingtian Material Technology Co., Ltd Address before: Shiling Town, Huadu District, Guangzhou City, Guangdong province 510860 Yufeng Road No. 16 Co-patentee before: China Electrical Appliance Research Institute Co.,Ltd. Patentee before: GUANGZHOU KINTE INDUSTRIAL Co.,Ltd. |
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