CN103059275B - A kind of TGIC curing transparent polyester resin for powder coating and preparation method thereof - Google Patents
A kind of TGIC curing transparent polyester resin for powder coating and preparation method thereof Download PDFInfo
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- CN103059275B CN103059275B CN201210579830.5A CN201210579830A CN103059275B CN 103059275 B CN103059275 B CN 103059275B CN 201210579830 A CN201210579830 A CN 201210579830A CN 103059275 B CN103059275 B CN 103059275B
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Abstract
The invention discloses a kind of TGIC curing transparent polyester resin for powder coating, acid number is 29-36mgKOH/g, viscosity 3800 ~ 6300mPa ﹒ s, number-average molecular weight 4500 ~ 7000, second-order transition temperature 60 ~ 68 DEG C, degree of crystallinity is lower than 2%, and it is formed through melt polymerization by following main component: polyvalent alcohol 30 ~ 40%, polyprotonic acid 45 ~ 65%, acidolysis agent 4 ~ 15%, catalyzer 0.03 ~ 0.15%.The invention also discloses the preparation method of this vibrin.This resin has the very high transparency, and the powder coating prepared with it can substitute Acrylic transparent powder paint and polyester epoxy mixed type clear applications in many-sided field.
Description
Technical field
The present invention relates to vibrin and preparation method thereof, be specifically related to a kind of TGIC curing transparent vibrin used for powder coating and preparation method thereof.
Background technology
Powder coating substitutes organic solvent type coatings just gradually with advantages such as its economy, environmental protection, efficient and performance are remarkable, become the important development direction in coating industry, high-clarity powder coating is also progressively substituting the face cap optical coating that organic clear lacquer becomes environmental protection more.
The film that different sorts coating is formed can present different visual effect, is because can there are transmission, absorption, scattering three kinds of phenomenons when visible ray (380 ~ 780nm) irradiates on film.If the optical throughput of incidence is by all transmissions of non-selectivity ground, be then visually a kind of desirable water white transparency; If the optical throughput of incidence is all absorbed by non-selectivity ground, be then visually a kind of desirable ater; If the optical throughput of incidence is by all scatterings (complete reflected diffusion) of non-selectivity ground, be then visually a kind of desirable pure white; And when incident optical throughput is by part transmission selectively, absorption, scattering, visually just define various colour and transparent color.In general, the transparency of film is relevant to the refractive index of its color stuffing size of particles and resin system.If pigment particle size is enough little and have identical refractive index with resin, then their scattered lights hardly, seem to be exactly transparent.
At present, scientific research and market Application comparison have Acrylic transparent powder paint widely, be applied to the aspect such as car surface and component thereof because its transparency is high, weather resistance is excellent, disclosed in CN1528842A and CN101260271A, transparent powder paint is all Acrylic transparent powder paint.But simultaneously oleic series transparent powder poor anti jamming capability, production and manufacturing environment requires strict, is easily polluted, and production cost and the high shortcoming of material cost make it apply and be subject to certain limitation.The more transparent powder paint of another kind of application is polyester epoxy mixed type transparent powder paint, disclosed in CN101161744A a kind of epoxy/polyester type transparent powder paint preparation method disclosed in transparent powder paint, but make it can only be applied to the surperficial Lacquer finish of indoor product due to shortcomings such as its weather resistance differences.At present, the vibrin of general TGIC solidification is after being prepared into transparent powder paint, and its transparency is lower, can not meet the problem of the service requirements of high-clarity.And also do not relate to the report of the study on the synthesis of TGIC curing transparent polyester resin for powder coating both at home and abroad.
Summary of the invention
First object of the present invention is to provide a kind of TGIC curing transparent polyester resin for powder coating, this resin has very high transparency after using TGIC solidification, and the powder coating prepared with it can substitute Acrylic transparent powder paint and polyester epoxy mixed type transparent powder paint is applied to many-sided field.
Second object of the present invention is to provide the preparation method of above-mentioned vibrin.
First object of the present invention is achieved through the following technical solutions: a kind of TGIC curing transparent polyester resin for powder coating, its acid number is 29-36mgKOH/g, viscosity 3800 ~ 6300mPa ﹒ s, number-average molecular weight 4500 ~ 7000, second-order transition temperature 60 ~ 68 DEG C, degree of crystallinity is lower than 2%, and it is formed through melt polymerization by the main component of following mass percent:
Polyvalent alcohol 30 ~ 40%, polyprotonic acid 45 ~ 65%, acidolysis agent 4 ~ 15%, catalyzer 0.03 ~ 0.15%.
Described polyvalent alcohol is one or both the mixing in neopentyl glycol, TriMethylolPropane(TMP), methyl propanediol.
The present invention can do following improvement: at described polyvalent alcohol be one or both mixing in neopentyl glycol, TriMethylolPropane(TMP), methyl propanediol basis on, add 2-ethyl-2-butyl 1, ammediol, its mass percent in polyvalent alcohol is greater than zero and is less than or equal to 20%.
Described polyprotonic acid is one or both the mixing in terephthalic acid, m-phthalic acid, hexanodioic acid.
The present invention can do following improvement: at described polyprotonic acid be one or both mixing in terephthalic acid, m-phthalic acid, hexanodioic acid basis on, add 1,4-cyclohexane cyclohexanedimethanodibasic, its mass percent in polyprotonic acid is greater than zero and is less than or equal to 13%.
Described catalyzer comprises Mono-n-butyltin or non-butyl tin oxide compound.Described non-butyl tin oxide compound comprises single tin octylate, triphenyltin, Tricyclohexyltin and stannous oxalate etc.
Second object of the present invention is realized by following technical scheme: the preparation method of above-mentioned vibrin, in a kettle., add polyvalent alcohol and be warming up to 80 ~ 100 DEG C of heating and melting, after adding polyprotonic acid and catalyzer, logical nitrogen temperature to 170 ~ 185 DEG C start esterification, and distill water outlet, controlling heat-up rate makes distillation column top temperature be no more than 100 DEG C, be warming up to 228 ~ 240 DEG C of esterifying polycondensation reaction 10 ~ 14h, when level of response reaches more than 95%, when acid number reaches 10 ~ 15mgKOH/g, add acidolysis agent, then after 235 ~ 240 DEG C of insulation 3 ~ 5h, acid number reaches 43 ~ 47mgKOH/g, vacuumize polycondensation 1 ~ 4h, obtain for TGIC curing transparent polyester resin for powder coating.The acid number of TGIC curing transparent polyester resin for powder coating of the present invention is 29-36mgKOH/g, viscosity 3800 ~ 6300mPa ﹒ s, and number-average molecular weight 4500 ~ 7000, second-order transition temperature 60 ~ 68 DEG C, degree of crystallinity is lower than 2%.
the present invention compared with prior art has the following advantages:
(1) transparent powder paint vibrin of the present invention is by changing macromolecular chain segment structure, reduces high molecular degree of crystallinity, makes it to form more homogeneous amorphous silicon carbonfilms, thus have the very high transparency.The film mist degree of the TGIC curing transparent powder coating adopting vibrin of the present invention to make is less than 2%, relative light transmission is greater than 98%, the height of its transparency visible, Acrylic transparent powder paint can be substituted and polyester epoxy mixed type transparent powder paint is applied to many-side, as aspects such as furniture decoration, automobile component, five metals household electrical appliances.
(2) the TGIC curing transparent powder coating adopting the vibrin of the present invention's synthesis to make has excellent levelling property, and easily process, immunity from interference is strong, and steady quality, economical, alternative acrylic acid or the like transparent powder paint is applied to the aspect such as automobile aluminum wheel hub and surperficial Lacquer finish.
Accompanying drawing explanation
Fig. 1 is the degree of crystallinity test spectrogram of the XRD of comparative example 1.
Fig. 2 is the degree of crystallinity test spectrogram of the XRD of the embodiment of the present invention 4.
Embodiment
Set forth content of the present invention in further detail by the following examples, but following embodiment is just for setting forth content of the present invention, instead of restriction, therefore any change in the implication suitable with claims of the present invention and scope, all should think to be included in the scope of claims.
Table 1 is the embodiment of TGIC curing transparent polyester resin for powder coating, the wherein basic recipe that synthesizes for weather resistant vibrin of comparative example 1, as comparative example of the present invention, under nitrogen protection, having heating unit, the neopentyl glycol of proportional quantity listed by table 1 is added in the vibrin synthesis reaction vessel of agitator and distillation column, methyl propanediol, TriMethylolPropane(TMP) heated and stirred adds terephthalic acid after dissolving successively, hexanodioic acid, m-phthalic acid and Monobutyltin catalyzer, progressively be warming up to about 180 DEG C start esterification and have water to distillate, progressively be warmed up to 240 DEG C afterwards, esterifying polycondensation reacts 13 hours, esterification yield reaches more than 95%, when acid number reaches 10 ~ 15mgKOH/g, add acidolysis agent m-phthalic acid, hexanodioic acid or 1, 4-cyclohexane cyclohexanedimethanodibasic, vacuumize polycondensation 2h when 240 DEG C of acidolysis reaction 5h acid numbers reach 43 ~ 47mgKOH/g and obtain vibrin acid number 29 ~ 36mgKOH/g, viscosity 3800 ~ 6300Pa ﹒ s, number-average molecular weight 4500 ~ 7000m, second-order transition temperature 60 ~ 68 DEG C, degree of crystallinity is lower than 2%.
The properties of transparency of the vibrin synthesized by the present invention need be embodied by the transparency of the transparent powder coating made.By the auxiliary agent Homogeneous phase mixing such as vibrin, TGIC, flow agent that the inventive method is synthesized, melt extruded by Φ 30 twin screw extruder, compressing tablet, fragmentation, pulverize and sieve and make powder coating, see experimental example B ~ E.Experimental example A is powder coating prepared by the vibrin of comparative example 1, and experimental example F is existing Acrylic transparent powder paint.Two kinds of detection methods are adopted: (1), by powder paint on the totally transparent glass panel through waste heat, compare spray coating powder paint by eye-observation after 180 ~ 200 DEG C/10 ~ 20min solidifies after, the sharpness of mirror image and pure mirror image evaluates the quality of the transparency in detection of the present invention.(2) cloud caused due to light diffusion due to the inside of the transparent or semitransparent material of a. or surface or the degree of cloudy appearance represent with the percentage of the optical throughput of diffusion with the ratio of the optical throughput of permeable material, are referred to as mist degree.B. the efficiency through light of display equipment etc. is to represent through the optical throughput of transparent or semitransparent body and the percentage of its incident flux, to be referred to as transmittance.Mist degree and transmittance have also become the index weighing transparent substance transparency, therefore, this detection method be exactly by powder paint on the totally transparent normal glass plate through waste heat, after 180 ~ 200 DEG C/10 ~ 20min solidifies, the test mist degree of spray coating plate and transparency, and with do not spray normal glass plate and contrast and evaluate transparent quality.
Can be illustrated by above-described embodiment, vibrin synthesized by the present invention, transparent powder paint coating obtained after being solidified by TGIC, the transparent powder paint coating prepared relative to the normal polyester resin of comparative example 1 has the advantage that mirror image is clear, mist degree is low and transparence is high, can clear display by Lacquer finish background color feature, can the surperficial Lacquer finish aspect of widespread use outdoor weatherability object.
Claims (6)
1. a TGIC curing transparent polyester resin for powder coating, it is characterized in that, its acid number is 29-36mgKOH/g, viscosity 3800 ~ 6300mPa ﹒ s, number-average molecular weight 4500 ~ 7000, second-order transition temperature 62 ~ 68 DEG C, degree of crystallinity is lower than 2%, it is formed through melt polymerization by following main component: polyvalent alcohol 30 ~ 40%, polyprotonic acid 45 ~ 65%, acidolysis agent 4 ~ 15%, catalyzer 0.03 ~ 0.15%, described polyvalent alcohol is neopentyl glycol, one or both mixing in TriMethylolPropane(TMP) and methyl propanediol, described polyprotonic acid is terephthalic acid, one or both mixing in m-phthalic acid and hexanodioic acid,
Described vibrin is prepared by following methods and obtains: in a kettle., add polyvalent alcohol and be warming up to 80 ~ 100 DEG C of heating and melting, after adding polyprotonic acid and catalyzer, logical nitrogen temperature to 170 ~ 185 DEG C start esterification, and distill water outlet, controlling heat-up rate makes distillation column top temperature be no more than 100 DEG C, be warming up to 228 ~ 240 DEG C of esterifying polycondensation reaction 10 ~ 14h, when level of response reaches more than 95%, when acid number reaches 10 ~ 15mgKOH/g, add acidolysis agent, then after 235 ~ 240 DEG C of insulation 3 ~ 5h, acid number reaches 43 ~ 47mgKOH/g, vacuumize polycondensation 1 ~ 4h, obtain for TGIC curing transparent polyester resin for powder coating.
2. TGIC curing transparent polyester resin for powder coating according to claim 1, it is characterized in that, described polyvalent alcohol is on the basis of one or both mixing in neopentyl glycol, TriMethylolPropane(TMP) and methyl propanediol, add 2-ethyl-2-butyl-1, ammediol, its mass percent in polyvalent alcohol is greater than zero and is less than or equal to 20%.
3. TGIC curing transparent polyester resin for powder coating according to claim 1 and 2, it is characterized in that, at described polyprotonic acid be one or both mixing in terephthalic acid, m-phthalic acid and hexanodioic acid basis on, add 1,4-cyclohexane cyclohexanedimethanodibasic, its mass percent in polyprotonic acid is greater than zero and is less than or equal to 13%.
4. TGIC curing transparent polyester resin for powder coating according to claim 1, is characterized in that, described catalyzer is Mono-n-butyltin or non-butyl tin oxide compound.
5. TGIC curing transparent polyester resin for powder coating according to claim 4, is characterized in that, described non-butyl tin oxide compound is one or both mixing in single tin octylate, triphenyltin, Tricyclohexyltin and stannous oxalate.
6. the preparation method of the TGIC curing transparent polyester resin for powder coating described in any one of claim 1 ~ 5, it is characterized in that, in a kettle., add polyvalent alcohol and be warming up to 80 ~ 100 DEG C of heating and melting, after adding polyprotonic acid and catalyzer, logical nitrogen temperature to 170 ~ 185 DEG C start esterification, and distill water outlet, controlling heat-up rate makes distillation column top temperature be no more than 100 DEG C, be warming up to 228 ~ 240 DEG C of esterifying polycondensation reaction 10 ~ 14h, when level of response reaches more than 95%, when acid number reaches 10 ~ 15mgKOH/g, add acidolysis agent, then after 235 ~ 240 DEG C of insulation 3 ~ 5h, acid number reaches 43 ~ 47mgKOH/g, vacuumize polycondensation 1 ~ 4h, obtain for TGIC curing transparent polyester resin for powder coating.
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| CN104262594A (en) * | 2014-09-23 | 2015-01-07 | 南通顺阳化工有限公司 | Preparation method of pure polyester resin |
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| CN106543420A (en) * | 2016-10-24 | 2017-03-29 | 广州擎天材料科技有限公司 | High TGIC type polyester resin for powder coating of a kind of water boiling resistance color fastness and preparation method thereof |
| CN106750208A (en) * | 2016-12-12 | 2017-05-31 | 衡阳山泰化工有限公司 | A kind of powdery paints polyester resin special and preparation method thereof |
| CN106496532A (en) * | 2016-12-12 | 2017-03-15 | 衡阳山泰化工有限公司 | A kind of extra-weather-proof polyester resin for powder coating |
| 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 |
| CN108034337A (en) * | 2017-12-01 | 2018-05-15 | 成都信达高分子材料有限公司 | A kind of transparent powder paint |
| CN108003757A (en) * | 2017-12-01 | 2018-05-08 | 成都信达高分子材料有限公司 | A kind of noctilucent powder paint |
| CN111040603A (en) * | 2019-12-31 | 2020-04-21 | 江苏变色龙微粉技术有限公司 | Wire drawing coating for metal powder coating, preparation method thereof and wire drawing coating process |
| CN111040604A (en) * | 2019-12-31 | 2020-04-21 | 江苏变色龙微粉技术有限公司 | Wire drawing coating process suitable for powder coating |
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Address after: No.5 Lisha East Road, Shatian Town, Dongguan City, Guangdong Province 523000 Patentee after: Qingtian Material Technology Co., Ltd Address before: Shiling Town, Huadu District, Guangzhou City, Guangdong province 510860 Yufeng Road No. 16 Patentee before: GUANGZHOU KINTE INDUSTRIAL Co.,Ltd. |