CN102492125B - Preparation method of copolyester for metal powder coating - Google Patents
Preparation method of copolyester for metal powder coating Download PDFInfo
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- CN102492125B CN102492125B CN 201110390510 CN201110390510A CN102492125B CN 102492125 B CN102492125 B CN 102492125B CN 201110390510 CN201110390510 CN 201110390510 CN 201110390510 A CN201110390510 A CN 201110390510A CN 102492125 B CN102492125 B CN 102492125B
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- terephthalic acid
- dibasic alcohol
- hydroxyethylation
- tetrabutyl titanate
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Abstract
The invention relates to a preparation method of a copolyester for a metal powder coating, mainly comprising the following steps of: (1) carrying out transesterification reaction between terephthalic acid, isophthalic acid, hydroxyethyl bisphenol A and C2-C6 dihydric alcohol under the action of a tetrabutyl titanate/butylhydroxyoxo-stannane catalyst; and (2) adding a stabilizer triphenyl phosphite into the product obtained from Step (1) at atmospheric pressure and carrying out decompressing copolycondensation at 230-250 DEG C and at 80-130 Pa to obtain the copolyester. The obtained copolyester has advantages of steaming and boiling resistance, acid and alkali resistance and strong adhesive force. The coating provided by the invention can be applied in the field of metal can coating.
Description
Technical field
The present invention relates to can be used as the preparation method of a kind of metal powder coating with copolyesters.The objective of the invention is to obtain the copolyesters of anti-boiling, acid and alkali-resistance, strong adhesive force, make coating can be applied to fields such as metal can coating.
Background technology
Powder coating is a kind of 100% solids component that contains, and carries out application with powder morphology, then the coating of heating and melting levelling or film-forming.The VOC content of powder coating is low, removes easily, crosses the recyclable utilization again of coating of spray; Filming after the construction does not produce pin hole basically, usually than the easy construction of liquid coating, and the good endurance of filming of formation.Powder coating is coating new variety, the new technology that begins to grow up the sixties in 20th century, have save the energy and resource, minimizing environmental pollution, technology easy, easily realize automatization, coating is sturdy and durable, nuisanceless, labor productivity is high, the recyclable characteristics such as use again of powder.
Metal powder coating is the trend of this powder coating development in several years, and it is meant the various powder coating that contain metallic pigment (as: copper bronze, silver-colored aluminium powder etc.), because metal powder coating can be showed a kind of bright, luxurious decorative effect, is widely used.Vibrin has been taken into account the advantage of epoxy, vinylformic acid and urethane resin, its paint coatings has ornamental preferably and weathering resistance, it is a kind of main raw material of making powder coating, for example, Chinese patent CN2007100938.0 has proposed a kind of method for preparing metal powder coating with vibrin as main raw material; European patent EP 525871 has prepared a kind of polyester that is applicable to outdoor durable coating system; Japanese Patent JP96-12751 has invented a kind of can gloss varnish based on vibrin.At present still useless hydroxyethylation dihydroxyphenyl propane is as the product of the conjugated polyester resin of main polyester raw material, and the introducing of hydroxyethylation dihydroxyphenyl propane has improved the hardness and the thermotolerance of coating, has also improved the resistance to acids and bases and the water tolerance of coating simultaneously.The present invention proposes following scheme, hydroxyethylation is bisphenol A modified as the raw material synthetic copolyester, obtain the required vibrin of high-performance metal powder coating.
Summary of the invention
The purpose of this invention is to provide a kind of metal powder coating and synthesized anti-boiling with the preparation method of copolyesters, the cohesive strength height, acid and alkali-resistance, and have the copolyesters of good hardness, snappiness and sticking power, its whole fusing point satisfies the needs of association area between 130～150 ℃.
Method of the present invention comprises the steps:
(1) terephthalic acid, m-phthalic acid, hydroxyethylation dihydroxyphenyl propane, C
2～C
6Dibasic alcohol carries out transesterification reaction under tetrabutyl titanate/butyl stannonic acid catalyst action, temperature of reaction is 180～210 ℃, is 90 of theoretical amount～92% o'clock until the quantity of distillate of water, and esterification finishes.
(2) under normal pressure, the stablizer triphenyl phosphite is added the product of step (1), at 230～250 ℃, 80～130Pa decompression copolycondensation down, the time is 1.0～2.0 hours, obtains the copolyesters product.
Described C
2～C
6Dibasic alcohol is selected from ethylene glycol, 2-methyl isophthalic acid, ammediol, 1, more than one in 2-propylene glycol, 1,4 cyclohexanedimethanol;
The mol ratio of diprotic acid and dibasic alcohol is 1.0: 1.6～1.9;
Described diprotic acid is meant terephthalic acid and m-phthalic acid, and described dibasic alcohol is meant hydroxyethylation dihydroxyphenyl propane and C
2～C
6Dibasic alcohol;
The mol ratio of described terephthalic acid and m-phthalic acid is 9: 1～7: 3;
Described hydroxyethylation dihydroxyphenyl propane and C
2～C
6The mol ratio of dibasic alcohol is 1: 10～20.
Described catalyzer is tetrabutyl titanate and butyl stannonic acid, and the mass ratio of the quality of catalyzer and terephthalic acid is respectively:
Butyl stannonic acid: terephthalic acid=0.1～0.3: 100;
Tetrabutyl titanate: terephthalic acid=0.005～0.02: 100.
Described stablizer triphenyl phosphite add-on is 0.05%～0.1% (massfraction) of terephthalic acid
Compared with prior art, innovative point of the present invention is: the present invention adds the hydroxyethylation dihydroxyphenyl propane and carries out copolymerization, the copolyesters of gained has big, the anti-boiling of viscosity intensity, acid and alkali-resistance, the characteristics that processibility is good, second-order transition temperature is between 70 ℃～80 ℃, guaranteed the plentiful and smooth light of coating, whole fusing point meets the requirement of association area between 130 ℃～150 ℃.
Embodiment
Embodiment 1
Have in the polymerization reaction kettle of water distilling apparatus at 2.0L, add terephthalic acid (244.28g), m-phthalic acid (24.92g), ethylene glycol (97.29g), 2-methyl isophthalic acid, ammediol (102.74g), hydroxyethylation dihydroxyphenyl propane (44.89g), butyl stannonic acid (0.45g) and tetrabutyl titanate (0.07g), when temperature reaches 180 ℃ in the heating, begin to have water to distillate, continue to be warming up to 210 ℃, treat that distilled water reaches 92% o'clock of theoretical amount, esterification finishes.Add triphenyl phosphite 0.12g again, be warming up to 240 ℃, system pressure remains on 80Pa, and reaction 1h gets copolyesters product P 1.
Embodiment 2
Have in the polymerization reaction kettle of water distilling apparatus at 2.0L, add terephthalic acid (199.36g) m-phthalic acid (49.84g), ethylene glycol (51.36g) 2-methyl isophthalic acid, ammediol (154.11g) hydroxyethylation dihydroxyphenyl propane (89.78g), butyl stannonic acid (0.44g) and tetrabutyl titanate (0.08g), when heating reaches 183 ℃, begin to have water to distillate, continue to be warming up to 200 ℃, treat that distilled water reaches 90% o'clock of theoretical amount, transesterification reaction finishes.Add triphenyl phosphite 0.11g again, be warming up to 230 ℃, system pressure remains on 110Pa, and reaction 1.5h gets copolyesters product P 2.
Embodiment 3
Have in the polymerization reaction kettle of water distilling apparatus at 2.0L, add terephthalic acid (174.44g) m-phthalic acid (74.76g), ethylene glycol (85.60g), 2-methyl isophthalic acid, ammediol (116.80g), hydroxyethylation dihydroxyphenyl propane (59.54g), butyl stannonic acid (0.44g) and tetrabutyl titanate (0.08g), when being heated to 180 ℃, begin to have water to distillate, continue to be warming up to 210 ℃, treat that distilled water reaches 92% o'clock of theoretical amount, esterification finishes.Add triphenyl phosphite 0.1g again, be warming up to 250 ℃, system pressure is 100Pa, and reaction 1.3h gets copolyesters product P 3.
Embodiment 4
Have in the polymerization reaction kettle of water distilling apparatus at 2.0L, add terephthalic acid (186.90g), m-phthalic acid (62.30g), ethylene glycol (75.42), 1, ammediol (115.58g) hydroxyethylation dihydroxyphenyl propane (64.89g), butyl stannonic acid (0.45g) and tetrabutyl titanate (0.10g), begin to have water to distillate when being heated to 180 ℃, continue to be warming up to 210 ℃, treat that distilled water reaches 90% o'clock of theoretical amount, esterification finishes.Add triphenyl phosphite 0.08g again, be warming up to 240 ℃, system pressure 130Pa reaction 2h gets copolyesters product P 4.
Embodiment 5
Have in the polymerization reaction kettle of water distilling apparatus at 2.0L, add terephthalic acid (186.90g), m-phthalic acid (62.30g), ethylene glycol (85.42g), 1, ammediol (110.58g), hydroxyethylation dihydroxyphenyl propane (48.9g), butyl stannonic acid (0.45g) and tetrabutyl titanate (0.09g), begin to have water to distillate when being heated to 180 ℃, continue to be warming up to 200 ℃, treat that distilled water reaches 90% o'clock of theoretical amount, esterification finishes.Add triphenyl phosphite 0.08g again, be warming up to 230 ℃, system pressure 80Pa reaction 2h gets copolyesters product P 5.
Embodiment 6
Have in the polymerization reaction kettle of water distilling apparatus at 2.0L, add terephthalic acid (181.90g), m-phthalic acid (62.30g), ethylene glycol (78.42), 1, ammediol (115.58g) hydroxyethylation dihydroxyphenyl propane (48.5g), butyl stannonic acid (0.45g) and tetrabutyl titanate (0.09g), begin to have water to distillate when being heated to 180 ℃, continue to be warming up to 205 ℃, treat that distilled water reaches 90% o'clock of theoretical amount, esterification finishes.Add triphenyl phosphite 0.08g again, be warming up to 238 ℃, system pressure 120Pa reaction 2h gets copolyesters product P 6.
Embodiment 7
Have in the polymerization reaction kettle of water distilling apparatus at 2.0L, add terephthalic acid (180.90g), m-phthalic acid (60.30g), ethylene glycol (71.42), 1, ammediol (105.58g), hydroxyethylation dihydroxyphenyl propane (54.89g), butyl stannonic acid (0.45g) and tetrabutyl titanate (0.09g), begin to have water to distillate when being heated to 180 ℃, continue to be warming up to 200 ℃, treat that distilled water reaches 90% o'clock of theoretical amount, esterification finishes.Add triphenyl phosphite 0.08g again, be warming up to 245 ℃, system pressure 100Pa reaction 2h gets copolyesters product P 7.
With the copolyesters product of gained in the foregoing description respectively according to standard GB/T4608, GB/T3682, GB/T19466-2, GB/T 9274 first methods, GB/T 5237.4 and 9286 pairs of micro-fusing points of GB/T, second-order transition temperature, melting index, resistance to acids and bases, boiling resistance, go back sticking power and test, the result is referring to table 1, wherein the technical requirements by resistance to acids and bases and boiling resistance test is: smooth surface, do not have obvious bubble, do not have serious loss of gloss.The sticking power test specification is dried adhering to ,≤1 grade.
The pairing performance of each product of table 1
Claims (4)
1. the preparation method of a metal powder coating usefulness copolyesters is characterized in that comprising the steps: (1) terephthalic acid, m-phthalic acid, hydroxyethylation dihydroxyphenyl propane, C
2～C
6Dibasic alcohol carries out esterification under tetrabutyl titanate and butyl stannonic acid catalyst action, temperature is 180～210 ℃, is 90 of theoretical amount～92% o'clock until the quantity of distillate of water, and esterification finishes; (2) the stablizer triphenyl phosphite is added the product of step (1) under normal pressure, at 230～250 ℃, 80～130Pa decompression copolycondensation 1.0～2.0 hours down obtains the copolyesters product;
The mol ratio of diprotic acid and dibasic alcohol is 1.0: 1.6～1.9;
Described diprotic acid is meant terephthalic acid and m-phthalic acid, and described dibasic alcohol is meant hydroxyethylation dihydroxyphenyl propane and C
2～C
6Dibasic alcohol;
The mol ratio of described terephthalic acid and m-phthalic acid is 9: 1～7: 3;
Described hydroxyethylation dihydroxyphenyl propane and C
2～C
6The mol ratio of dibasic alcohol is 1: 10～20.
2. method according to claim 1 is characterized in that, described C
2～C
6Dibasic alcohol is selected from ethylene glycol, 2-methyl isophthalic acid, ammediol, 1, more than one in the 2-propylene glycol.
3. method according to claim 1 is characterized in that, described catalyzer is tetrabutyl titanate and butyl stannonic acid, and the mass ratio of the quality of catalyzer and terephthalic acid is respectively:
Butyl stannonic acid: terephthalic acid=0.1～0.3: 100;
Tetrabutyl titanate: terephthalic acid=0.005～0.02: 100.
4. method according to claim 1 is characterized in that, it is 0.05%～0.1% of terephthalic acid quality that described stablizer triphenyl phosphite adds quality.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110390510 CN102492125B (en) | 2011-11-30 | 2011-11-30 | Preparation method of copolyester for metal powder coating |
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|---|---|---|---|
| CN 201110390510 CN102492125B (en) | 2011-11-30 | 2011-11-30 | Preparation method of copolyester for metal powder coating |
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| CN102492125A CN102492125A (en) | 2012-06-13 |
| CN102492125B true CN102492125B (en) | 2013-07-31 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015070459A1 (en) * | 2013-11-18 | 2015-05-21 | Ppg Packaging Coatings (Suzhou) Co., Ltd | Packaging coating composition |
| CN103641978B (en) * | 2013-12-06 | 2015-10-28 | 上海华峰超纤材料股份有限公司 | A kind of Polyurethane resin slurry and industrial application thereof |
| CN103665306B (en) * | 2013-12-06 | 2016-01-20 | 上海华峰超纤材料股份有限公司 | A kind of leather Polyurethane resin slurry and preparation method thereof |
| CN103739831B (en) * | 2014-01-16 | 2017-02-01 | 帝兴树脂(昆山)有限公司 | Preparation method of polyester resin for high temperature resistant powder coating and high temperature resistant powder coating |
| CN108047901A (en) * | 2017-12-29 | 2018-05-18 | 广西平果宝信涂料有限公司 | Enhance metal powder coating of decorative effect and preparation method thereof |
| EP3848415A4 (en) * | 2019-07-26 | 2021-10-06 | Kinte Materials Science and Technology Co., Ltd. | Polyester resin and preparation method therefor, coating, and workpiece |
| CN110408013A (en) * | 2019-08-30 | 2019-11-05 | 广东工业大学 | A kind of polyester resin for powder coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454202A (en) * | 2000-07-31 | 2003-11-05 | 株式会社爱伊斯 | Bis-beta-hydroxyethyle terephthalate |
| CN1800236A (en) * | 2004-12-31 | 2006-07-12 | 中国石化仪征化纤股份有限公司 | Highly transparent copolyester preparation method |
| CN101338023A (en) * | 2008-08-14 | 2009-01-07 | 浙江理工大学 | Low-melting-point copolyester and method for preparing same |
-
2011
- 2011-11-30 CN CN 201110390510 patent/CN102492125B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454202A (en) * | 2000-07-31 | 2003-11-05 | 株式会社爱伊斯 | Bis-beta-hydroxyethyle terephthalate |
| CN1800236A (en) * | 2004-12-31 | 2006-07-12 | 中国石化仪征化纤股份有限公司 | Highly transparent copolyester preparation method |
| CN101338023A (en) * | 2008-08-14 | 2009-01-07 | 浙江理工大学 | Low-melting-point copolyester and method for preparing same |
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Owner name: SHANGHAI TIANYANG HOLT MELT ADHESIVE MATERIALS CO. Free format text: FORMER NAME: SHANGHAI TIANYANG HOTMELT ADHESIVES CO., LTD. |
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Address after: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee after: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY Patentee after: KUNSHAN TIANYANG HOT MELT ADHESIVE Co.,Ltd. Address before: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee before: Shanghai Tianyang Hotmelt Adhesives Co.,Ltd. Patentee before: EAST CHINA University OF SCIENCE AND TECHNOLOGY Patentee before: KUNSHAN TIANYANG HOT MELT ADHESIVE Co.,Ltd. |
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Address after: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee after: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY Patentee after: Kunshan Tianyang New Material Co.,Ltd. Address before: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee before: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. Patentee before: EAST CHINA University OF SCIENCE AND TECHNOLOGY Patentee before: KUNSHAN TIANYANG HOT MELT ADHESIVE Co.,Ltd. |
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Address after: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee after: Tianyang New Material (Shanghai) Technology Co.,Ltd. Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY Patentee after: Kunshan Tianyang New Material Co.,Ltd. Address before: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee before: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. Patentee before: EAST CHINA University OF SCIENCE AND TECHNOLOGY Patentee before: Kunshan Tianyang New Material Co.,Ltd. |