阅读说明：本技术 一种户外高玻璃化温度热固性粉末涂料用聚酯树脂制备方法 (A kind of open air high glass transition temperature thermosetting powder coating preparation method of polyester resin ) 是由 范士堂 董洪志 于 2019-08-20 设计创作，主要内容包括：户外高玻璃化温度热固性粉末涂料用聚酯树脂制备方法,采用回收的聚萘二甲酸乙二酯PEN废料,PEN废料粉碎后与多元醇、多元酸、环氧树脂、催化剂单丁基氧化锡、热稳定剂1010进行酯交换反应和酯化反应,减压缩聚反应结束后向物料中加二甲苯进行回流脱水,降温后加入聚丙烯酸树脂和混合型二元酸二甲酯溶剂进行稀释,稀释至合适黏度后加入固化促进剂,经过滤除去杂质即得到聚酯树脂。本发明通过先期对聚酯树脂进行环氧改性,通过接枝反应的方式明显增进柔韧性改善T弯性能,同时增加交联密度增强耐腐蚀性能,本方法制备的聚酯树脂具有较高的玻璃化温度,同时拥有较好的光泽、抗冲击性、优良的流平,满足粉末涂料生产过程中对聚酯玻璃化的要求。(Outdoor high glass transition temperature thermosetting powder coating preparation method of polyester resin, using the polyethylene naphthalate PEN waste material of recycling, ester exchange reaction and esterification are carried out with polyalcohol, polyacid, epoxy resin, catalyst Mono-n-butyltin, heat stabilizer 1010 after the crushing of PEN waste material, depressurization condensation reaction adds dimethylbenzene to carry out reflux dewatering after terminating into material, polyacrylic resin is added after cooling and mixed type dibasic acid dimethyl ester solvent is diluted, curing accelerator is added after being diluted to suitable viscosity, impurity is removed by filtration and obtains polyester resin.The present invention is epoxy-modified by carrying out in advance to polyester resin, flexibility is significantly enhanced by way of graft reaction improves the curved performance of T, increase crosslink density enhancing corrosion resistance simultaneously, the polyester resin glass transition temperature with higher of this method preparation, possess preferable gloss, impact resistance, excellent levelling simultaneously, meets the requirement in powdery paints production process to polyester fiberglass.)

1. a kind of open air high glass transition temperature thermosetting powder coating preparation method of polyester resin, it is characterized in that using recycling Polyethylene naphthalate PEN waste material, PEN waste material crush after with polyalcohol, polyacid, epoxy resin, catalyst monobutyl oxygen Change tin, heat stabilizer 1010 carries out ester exchange reaction and esterification, after ester exchange reaction and esterification, isophthalic is added The reaction was continued for dioctyl phthalate, carries out depressurization condensation reaction after reaction, and depressurization condensation reaction adds dimethylbenzene into material after terminating Reflux dewatering is carried out, until acid value 10mgKOH/g is hereinafter, addition polyacrylic resin and mixed type dibasic acid dimethyl ester are molten after cooling Agent is diluted, and discharging adds curing accelerator after being diluted to suitable viscosity, and impurity is removed by filtration and obtains polyester resin, Polyalcohol additional amount accounts for the 150%~300% of PEN mass；Mono-n-butyltin accounts for the 0.3%~0.8% of PEN mass；Epoxy Resin accounts for the 40%~120% of PEN mass；Polyacid accounts for the 200%~650% of PEN mass；Heat stabilizer 1010 accounts for PEN matter The 0.3%~0.8% of amount；M-phthalic acid accounts for the 40%~120% of PEN mass；Polyacrylic resin accounts for the 40% of PEN mass ~80%；Mixed type dibasic acid dimethyl ester solvent accounts for the 40%~80% of PEN mass；Curing accelerator accounts for the 0.8% of PEN mass ~3%.

2. open air high glass transition temperature thermosetting powder coating preparation method of polyester resin according to claim 1, It is characterized in that polyalcohol is ethylene glycol, diethylene glycol (DEG), triethylene glycol, neopentyl glycol, 2- methyl-1,3-propanediol, 1,3-PD, the third two Alcohol, butanediol, special pentanediol and trimethylolpropane it is one or more.

3. open air high glass transition temperature thermosetting powder coating preparation method of polyester resin according to claim 1, It is characterized in that polyacid is one kind or more of M-phthalic acid, p-phthalic acid, stearic acid, adipic acid, maleic acid and adipic acid Kind.

4. open air high glass transition temperature thermosetting powder coating preparation method of polyester resin according to claim 1, It is characterized in transesterification and esterification reaction temperature is 180 DEG C~250 DEG C；Transesterification and esterification termination condition are as follows: sampling analysis Acid value is 10 ± 5mgKOH/g, and viscosity is 3 ± 2cSt, and viscosimeter test temperature is 200 ± 5 DEG C.

5. open air high glass transition temperature thermosetting powder coating preparation method of polyester resin according to claim 1, It is characterized in that epoxy resin is small-molecular-weight epoxy resin.

6. open air high glass transition temperature thermosetting powder coating preparation method of polyester resin according to claim 1, It is characterized in depressurization condensation reaction condition are as follows: reacting kettle inner pressure≤0.095Mpa, 230~250 DEG C of temperature；The decompression polycondensation React termination condition are as follows: sampling analysis viscosity reaches 40 ± 10cSt, and viscosimeter temperature is 200 ± 5 DEG C, and acid value reaches 35 ± 10mgKOH/g, hydroxyl value reach < 5mgKOH/g.

7. open air high glass transition temperature thermosetting powder coating preparation method of polyester resin according to claim 1, It is characterized in that heat stabilizer 1010 is four [β-(3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid] pentaerythritol esters.

Technical field

The present invention relates to polyester resin to prepare technical field, and in particular to a kind of open air high glass transition temperature powder thermosetting Coating preparation method of polyester resin.

Background technique

Currently, domestic thermosetting powder coating is mainly made of resin, curing agent, pigments and fillers, auxiliary agent etc., it is broadly divided into pure Polyester powder coating and mixed powder coating are mainly used in the fields such as household metal furniture, electrical accessorie, hardware component. Wherein pure polyester powdery paints are using powdery paints made of hydroxy polyester resin, because having excellent weatherability, usually quilt Referred to as Weather-resisting powder coating.

In powdery paints use process, it is frequently encountered powder conglomeration, hardened problem, especially during the broiling summer And the higher region of temperature, the problem are more notable.And to solve the problems, such as this can only by improve powdery paints in polyester used The glass transition temperature of resin.Furthermore polyester resin product uses outdoors, and Corrosion Protection is not so good as epoxy resin, in order to make up The performance shortcomings of Polyester resin lacquer, usually using polyester resin spell plus epoxy resin method, be desirably to obtain one it is comprehensive The excellent outdoor powdery paints of energy.Now widely used spelling plus Epoxy Resin Technology after being polyester resin, i.e., in polyester resin The epoxy resin of coating material production stage split a part increases attachment to reach, improves hardness, increase the purpose of corrosion-resistant.But In actual use, cold spell adds epoxy resin to have problems, such as spells the curved performance of T after adding and declines, flexibility is deteriorated, batch Between dosage fluctuate, storage layering is obvious etc..

Summary of the invention

The present invention provides a kind of outdoor high glass transition temperature thermosetting powder coating preparation method of polyester resin, with solution The undesirable and rear curved performance decline of T spelled plus epoxy resin causes of glass transition temperature certainly of the existing technology, flexibility are deteriorated The technical issues of dosage fluctuates between batch.

The technical solution adopted by the present invention to solve the technical problems is:

A kind of open air high glass transition temperature thermosetting powder coating preparation method of polyester resin, using the poly- naphthalene two of recycling Formic acid second diester PEN waste material, PEN waste material crush after with polyalcohol, polyacid, epoxy resin, catalyst Mono-n-butyltin, heat Stabilizer 1010 carries out ester exchange reaction and esterification, and after ester exchange reaction and esterification, M-phthalic acid is added The reaction was continued, carries out depressurization condensation reaction after reaction, and depressurization condensation reaction adds dimethylbenzene to be returned after terminating into material Stream dehydration, until acid value 10mgKOH/g is hereinafter, be added polyacrylic resin and the progress of mixed type dibasic acid dimethyl ester solvent after cooling Dilution, discharging adds curing accelerator after being diluted to suitable viscosity, and impurity is removed by filtration and obtains polyester resin, polyalcohol Additional amount accounts for the 150%~300% of PEN mass；Mono-n-butyltin accounts for the 0.3%~0.8% of PEN mass；Epoxy resin accounts for The 40%~120% of PEN mass；Polyacid accounts for the 200%~650% of PEN mass；Heat stabilizer 1010 accounts for PEN mass 0.3%~0.8%；M-phthalic acid accounts for the 40%~120% of PEN mass；Polyacrylic resin account for PEN mass 40%~ 80%；Mixed type dibasic acid dimethyl ester solvent accounts for the 40%~80% of PEN mass；Curing accelerator account for PEN mass 0.8%~ 3%.

Above-mentioned PEN waste material melting temperature is 170~235 DEG C, need to be ground into the particle of 5mm~10mm partial size.

Above-mentioned polyalcohol is ethylene glycol, diethylene glycol (DEG), triethylene glycol, neopentyl glycol, 2- methyl-1,3-propanediol, 1,3- the third two Alcohol, propylene glycol, butanediol, special pentanediol and trimethylolpropane it is one or more.

Above-mentioned polyacid is the one of M-phthalic acid, p-phthalic acid, stearic acid, adipic acid, maleic acid and adipic acid Kind is a variety of.

Above-mentioned transesterification and esterification reaction temperature are 180 DEG C~250 DEG C；Transesterification and esterification termination condition are as follows: take It is 10 ± 5mgKOH/g that sample, which analyzes acid value, and viscosity is 3 ± 2cSt, and viscosimeter test temperature is 200 ± 5 DEG C.

Above-mentioned epoxy resin is small-molecular-weight epoxy resin.

Above-mentioned depressurization condensation reaction condition are as follows: reacting kettle inner pressure≤0.095Mpa, 230~250 DEG C of temperature；Described subtracts Press polycondensation reaction termination condition are as follows: sampling analysis viscosity reaches 40 ± 10cSt, and viscosimeter temperature is 200 ± 5 DEG C, and acid value reaches 35 ± 10mgKOH/g, hydroxyl value reach < 5mgKOH/g

Heat stabilizer 1010 is four [β-(3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid] pentaerythritol esters.

The method of the present invention is produced using PEN material class waste material, realizes the recycling of waste and old PEN, is reduced useless Pollution of the old PEN to environment has significant environmental benefit；And it is epoxy-modified by being carried out in advance to polyester resin, pass through The mode of graft reaction, which significantly enhances flexibility, improves the curved performance of T, while increasing crosslink density enhancing corrosion resistance, this method The polyester resin of preparation glass transition temperature with higher, while possessing preferable gloss, impact resistance, excellent levelling, it is full Requirement in the coating production process of foot-powder end to polyester fiberglass.

Specific embodiment

Example 1

The pure poly- type thermosetting powder coating preparation method of polyester resin of a kind of open air high glass transition temperature, using recycling Polyethylene naphthalate PEN waste material, PEN waste material melting temperature are 170~235 DEG C, need to be ground into the broken of 5mm~10mm partial size After material with polyalcohol, polyacid, epoxy resin, catalyst Mono-n-butyltin, heat stabilizer 1010 carry out ester exchange reaction and Esterification, polyalcohol be ethylene glycol, diethylene glycol (DEG), triethylene glycol, neopentyl glycol, 2- methyl-1,3-propanediol, 1,3-PD, Propylene glycol, butanediol, special pentanediol and trimethylolpropane it is one or more, polyacid is M-phthalic acid, essence to benzene two Formic acid, stearic acid, ethanedioic acid, maleic acid and adipic acid it is one or more, polyalcohol additional amount accounts for the 230% of PEN mass；It is single Butyl tin oxide accounts for the 0.5% of PEN mass；Polyacid accounts for the 400% of PEN mass；Epoxy resin accounts for the 80% of PEN mass；Heat Stabilizer 1010 accounts for the 0.6% of PEN mass, and transesterification and esterification reaction temperature are 180 DEG C~250 DEG C；Transesterification and esterification are anti- Answer termination condition are as follows: sampling analysis acid value is 10 ± 5mgKOH/g, and viscosity is 3 ± 2cSt, and viscosimeter test temperature is 200 ± 5 DEG C, after ester exchange reaction and esterification, M-phthalic acid is added, and the reaction was continued, and M-phthalic acid accounts for PEN mass 40%, continuation reaction temperature is 245 ± 5 DEG C after M-phthalic acid is added, and reacts termination condition are as follows: acid value is 50 ± 5mgKOH/ G, viscosity is 5 ± 2cSt, and viscosimeter test temperature is 200 ± 5 DEG C, carries out depressurization condensation reaction after reaction, depressurizes polycondensation Reaction condition are as follows: reacting kettle inner pressure control is in 0.09Mpa~0.095Mpa, and 230~250 DEG C of temperature；The decompression polycondensation React termination condition are as follows: sampling analysis viscosity reaches 40 ± 10cSt, and viscosimeter temperature is 200 ± 5 DEG C, and acid value reaches 35 ± 10mgKOH/g, hydroxyl value reach < 5mgKOH/g, and depressurization condensation reaction adds dimethylbenzene to carry out reflux dewatering after terminating into material, It is dilute to acid value 10mgKOH/g hereinafter, addition polyacrylic resin and mixed type dibasic acid dimethyl ester solvent are diluted after cooling Discharging adds curing accelerator after releasing to suitable viscosity, and polyacrylic resin accounts for the 60% of PEN mass；Mixed type binary acid two Methyl esters solvent accounts for the 40% of PEN mass, and curing accelerator accounts for the 0.8% of PEN mass, and impurity is removed by filtration and obtains polyester tree Rouge.

Example 2

The pure poly- type thermosetting powder coating preparation method of polyester resin of a kind of open air high glass transition temperature, using recycling Polyethylene naphthalate PEN waste material, PEN waste material melting temperature are 170~235 DEG C, need to be ground into the broken of 5mm~10mm partial size After material with polyalcohol, polyacid, epoxy resin, catalyst Mono-n-butyltin, heat stabilizer 1010 carry out ester exchange reaction and Esterification, polyalcohol be ethylene glycol, diethylene glycol (DEG), triethylene glycol, neopentyl glycol, 2- methyl-1,3-propanediol, 1,3-PD, Propylene glycol, butanediol, special pentanediol and trimethylolpropane it is one or more, polyacid is M-phthalic acid, essence to benzene two Formic acid, stearic acid, ethanedioic acid, maleic acid and adipic acid it is one or more, polyalcohol additional amount accounts for the 150% of PEN mass；It is single Butyl tin oxide accounts for the 0.3% of PEN mass；Epoxy resin accounts for the 45% of PEN mass；Polyacid accounts for the 200% of PEN mass；Heat Stabilizer 1010 accounts for the 0.3% of PEN mass, and transesterification and esterification reaction temperature are 180 DEG C~250 DEG C；Transesterification and esterification are anti- Answer termination condition are as follows: sampling analysis acid value is 10 ± 5mgKOH/g, and viscosity is 3 ± 2cSt, and viscosimeter test temperature is 200 ± 5 DEG C, after ester exchange reaction and esterification, M-phthalic acid is added, and the reaction was continued, and M-phthalic acid accounts for PEN mass 40%, continuation reaction temperature is 245 ± 5 DEG C after M-phthalic acid is added, and reacts termination condition are as follows: acid value is 50 ± 5mgKOH/ G, viscosity is 5 ± 2cSt, and viscosimeter test temperature is 200 ± 5 DEG C, carries out depressurization condensation reaction after reaction, depressurizes polycondensation Reaction condition are as follows: reacting kettle inner pressure control is in 0.09Mpa~0.095Mpa, and 230~250 DEG C of temperature；The decompression polycondensation React termination condition are as follows: sampling analysis viscosity reaches 40 ± 10cSt, and viscosimeter temperature is 200 ± 5 DEG C, and acid value reaches 35 ± 10mgKOH/g, hydroxyl value reach < 5mgKOH/g, and depressurization condensation reaction adds dimethylbenzene to carry out reflux dewatering after terminating into material, It is dilute to acid value 10mgKOH/g hereinafter, addition polyacrylic resin and mixed type dibasic acid dimethyl ester solvent are diluted after cooling Discharging adds curing accelerator after releasing to suitable viscosity, and polyacrylic resin accounts for the 40% of PEN mass；Mixed type binary acid two Methyl esters solvent accounts for the 80% of PEN mass, and curing accelerator accounts for the 0.8% of PEN mass, and impurity is removed by filtration and obtains polyester tree Rouge.

Example 3

The pure poly- type thermosetting powder coating preparation method of polyester resin of a kind of open air high glass transition temperature, using recycling Polyethylene naphthalate PEN waste material, PEN waste material melting temperature are 170~235 DEG C, need to be ground into the broken of 5mm~10mm partial size After material with polyalcohol, polyacid, epoxy resin, catalyst Mono-n-butyltin, heat stabilizer 1010 carry out ester exchange reaction and Esterification, polyalcohol be ethylene glycol, diethylene glycol (DEG), triethylene glycol, neopentyl glycol, 2- methyl-1,3-propanediol, 1,3-PD, Propylene glycol, butanediol, special pentanediol and trimethylolpropane it is one or more, polyacid is M-phthalic acid, essence to benzene two Formic acid, stearic acid, ethanedioic acid, maleic acid and adipic acid it is one or more, polyalcohol additional amount accounts for the 300% of PEN mass；It is single Butyl tin oxide accounts for the 1.5% of PEN mass；Polyacid accounts for the 550% of PEN mass；Epoxy resin accounts for the 120% of PEN mass； Heat stabilizer 1010 accounts for the 1.5% of PEN mass, and transesterification and esterification reaction temperature are 180 DEG C~250 DEG C；Transesterification and esterification React termination condition are as follows: sampling analysis acid value be 10 ± 5mgKOH/g, viscosity be 3 ± 2cSt, viscosimeter test temperature be 200 ± 5 DEG C, after ester exchange reaction and esterification, M-phthalic acid is added, and the reaction was continued, and M-phthalic acid accounts for PEN mass 120%, continuation reaction temperature is 245 ± 5 DEG C after M-phthalic acid is added, and reacts termination condition are as follows: acid value is 50 ± 5mgKOH/ G, viscosity is 5 ± 2cSt, and viscosimeter test temperature is 200 ± 5 DEG C, carries out depressurization condensation reaction after reaction, depressurizes polycondensation Reaction condition are as follows: reacting kettle inner pressure control is in 0.09Mpa~0.095Mpa, and 230~250 DEG C of temperature；The decompression polycondensation React termination condition are as follows: sampling analysis viscosity reaches 40 ± 10cSt, and viscosimeter temperature is 200 ± 5 DEG C, and acid value reaches 35 ± 10mgKOH/g, hydroxyl value reach < 5mgKOH/g, and depressurization condensation reaction adds dimethylbenzene to carry out reflux dewatering after terminating into material, It is dilute to acid value 10mgKOH/g hereinafter, addition polyacrylic resin and mixed type dibasic acid dimethyl ester solvent are diluted after cooling Discharging adds curing accelerator after releasing to suitable viscosity, and polyacrylic resin accounts for the 60% of PEN mass；Mixed type binary acid two Methyl esters solvent accounts for the 60% of PEN mass, and curing accelerator accounts for the 3% of PEN mass, and impurity is removed by filtration and obtains polyester tree Rouge.