CN102516511B - Polyester resin for high-performance aqueous coating and preparation method thereof - Google Patents
Polyester resin for high-performance aqueous coating and preparation method thereof Download PDFInfo
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- CN102516511B CN102516511B CN201110358498.5A CN201110358498A CN102516511B CN 102516511 B CN102516511 B CN 102516511B CN 201110358498 A CN201110358498 A CN 201110358498A CN 102516511 B CN102516511 B CN 102516511B
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Abstract
The invention discloses polyester resin for a high-performance aqueous coating. The polyester resin is prepared by mainly carrying out melt polycondensation reaction on the following raw materials in percentage by weight: 25-70% of polylol, 1-20% of branching agent, 20-35% of aromatic polybasic acid, 5-20% of fat polybasic acid, 3-15% of acidolysis agent and 0.005-0.15% of esterification catalyst. The invention further discloses a preparation method of the polyester resin. The polyester resin provided by the invention is low in viscosity and good in storage stability, the adopted process is simple and feasible, and the polyester resin is used in a polyester resin/aqueous amino resin curing system; and the prepared aqueous coating has the advantages of excellent water-fast resistance, high glaze and excellent mechanical properties.
Description
Technical field
The present invention relates to vibrin that a kind of coating uses and preparation method thereof, relate in particular to vibrin that a kind of high-performance aqueous coating uses and preparation method thereof.
Technical background
Along with restriction and the people enhancing to environmental consciousness of various countries' rules to VOC, environment-friendly type coating is more and more subject to the attention in market.And water-borne coatings is as the environmentally friendly coating of one, do not need special preparation of construction, applied widely, obtain a wide range of applications.Waterborne polyester coating is the representative water-borne coatings of a class, and excellent combination property is widely used in protection and the decoration on metal and woodenware surface, has that gloss is high, a feature such as strong adhesion, fullness ratio are high, excellent impact resistance.But because general polyester is compared with facile hydrolysis, causes the application of waterborne polyester to be subject to certain restriction, but design the vibrin of available water-tolerant by optimization of C/C composites.
The reported for work method of polyvalent alcohol and polyprotonic acid synthetic water-borne coatings vibrin under the condition of organotin catalysts of lot of documents, but be mainly used in coil coating, and synthetic acid number is between 65-75mg KOH/g, and solid content is lower, generally, below 50%, seldom refer to water tolerance and the storage stability of coating.Separately have, patent 200710045920 adopts pyromellitic acid acid anhydride to replace the method for trimellitic acid 1,2-anhydride to synthesize the lower water-base resin of viscosity, but in the monomer adopting, acid includes phthalic acid, because the water tolerance of phthalic acid itself is poor, thereby cause synthetic vibrin water tolerance to be affected.At present, waterborne polyester coating on the market usually can run into the not good situation of poor water resistance and stability in storage in the process using.
Summary of the invention
One of object of the present invention is to provide the vibrin that a kind of high-performance aqueous coating is used, this vibrin viscosity is low, storage stability good, what adopt is simple for process, for vibrin/water-compatible amino resin curing system, and the water-borne coatings of preparation has excellent water resistance, high gloss and excellent mechanical property.
Two of object of the present invention is to provide the preparation method of the vibrin that above-mentioned high-performance aqueous coating uses.
First object of the present invention is achieved through the following technical solutions: the vibrin that a kind of high-performance aqueous coating is used is mainly to be obtained through melt polycondensation reaction by the raw material of following weight percent content:
Polyvalent alcohol: 25 ~ 70%, branching agent: 1 ~ 20%, aromatic polycarboxylic acid: 20%～35%, fatty polyprotonic acid: 5%～20%, acidolysis agent: 3%～15%, esterifying catalyst: 0.005%～0.15%.
Polyvalent alcohol of the present invention comprises neopentyl glycol, 2-ethyl-2-butyl-1, ammediol, ethylene glycol, 2-methyl isophthalic acid, ammediol, 1, ammediol, hexylene glycol and 1, one or more mixtures in 4-cyclohexanedimethanol etc., preferably neopentyl glycol and 2-ethyl-2-butyl-1,3-PD.
As an embodiment of the invention: neopentyl glycol: 20～40%, 2-ethyl-2-butyl-1,3-PD: 5 ~ 30%, branching agent: 2 ~ 20%, aromatic polycarboxylic acid: 25%～35%, fatty polyprotonic acid: 5%～20%, acidolysis agent: 3%～15%, esterifying catalyst: 0.005%～0.15%.
Described branching agent comprises TriMethylolPropane(TMP), the mixture of one or more in trimethylolethane and tetramethylolmethane etc., wherein preferred TriMethylolPropane(TMP).
Described aromatic polycarboxylic acid comprises one or both the mixture wherein such as terephthalic acid and m-phthalic acid, preferably m-phthalic acid.
Described fatty polyprotonic acid comprises one or more the mixture wherein such as hexanodioic acid, sebacic acid and 1,4 cyclohexanedicarboxylic acid, preferably hexanodioic acid or 1,4 cyclohexanedicarboxylic acid.
Described acidolysis agent comprises m-phthalic acid, hexanodioic acid, 1, the mixture of one or more in 4-cyclohexane cyclohexanedimethanodibasic, trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydride, fumaric acid anhydride and maleic anhydride etc., the preferably mixture of one or more in trimellitic acid 1,2-anhydride, m-phthalic acid and 1,4 cyclohexanedicarboxylic acid.
Described esterifying catalyst is organic tin compound, comprises Mono-n-butyltin, Dibutyltin oxide.
Second object of the present invention realizes by following technical measures: the preparation method of the vibrin that a kind of high-performance aqueous coating is used, comprises the following steps:
(1) measure polyvalent alcohol and polyprotonic acid and branching agent by proportioning and be placed in reactor, add esterifying catalyst to carry out esterification condensation reaction at 160 ℃～240 ℃, to acid number 2 ~ 5 mgKOH/g;
(2) add acidolysis agent to carry out end-blocking and depolymerization, synthetic take terminal hydroxy group as vibrin main, that end carboxyl is used as auxiliary high-performance aqueous coating.
As an embodiment of the invention: the preparation method of the vibrin that described high-performance aqueous coating is used, its concrete steps are:
(1) in reactor, add polyvalent alcohol and the branching agent of proportional quantity, be heated to material melting; Then add successively the aromatic polycarboxylic acid of proportional quantity, fatty polyprotonic acid and esterifying catalyst, logical nitrogen continues temperature reaction, starts to generate and distillate to 180 ℃ of esterification water, is then warming up to gradually 240 ℃, after coreaction is discharged to 95% esterification water for 5～10 hours, acid number reaches 2～5mgKOH/g
(2) be cooled to 185 ℃, add acidolysis agent, reaction 0.5～1h, acid number reaches 15～60mgKOH/g, is cooled to 80 ℃, and stopped reaction obtains synthetic take terminal hydroxy group as vibrin main, that end carboxyl is used as auxiliary high-performance aqueous coating.
Vibrin of the present invention can also adopt one-step preppn process preparation, after mixing by polyvalent alcohol, aromatic polycarboxylic acid, fatty polyprotonic acid, branching agent, acidolysis agent and esterifying catalyst, carrying out esterification condensation reaction, is also to obtain the vibrin that high-performance aqueous coating of the present invention is used.
Vibrin hydroxyl value prepared by the inventive method is 100～150mgKOH/g, acid number 15～60mgKOH/g, and melt viscosity is 50～150mPa.s, number-average molecular weight is 1000～3000.The synthetic vibrin of the inventive method has suitable second-order transition temperature, softening temperature, feature that storage stability is good, solidifies the coating of making have excellent water boiling resistance effect, fabulous flow leveling, mechanical property with aminoresin.
With the step that vibrin of the present invention is prepared weather resistant water-thinned coating be by synthetic vibrin by add in solubility promoter and diethanolamine, deionized water and after make water dispersed resin, then after weighing up in proportion with aminoresin, filler, pigment and other auxiliary agents, mix rear grinding and make water-borne coatings.The water tolerance of the synthetic vibrin of the present invention is good, is mainly used in the curing water-based stoving paint of aminoresin, and solid content reaches more than 70%, and acid number is that 15 ~ 30mg KOH/g hydroxyl value is 100 ~ 130mg KOH/g, and the coating after solidifying has good water tolerance and mechanical property.
concrete embodiment
The present invention will be described to enumerate a part of specific embodiment below, the example that table 1 is vibrin, and A～F is the comparison example of different monomers and process combination.The neopentyl glycol of the listed proportional quantity of table 1,2-ethyl-2-butyl-1,3-PD, ethylene glycol and TriMethylolPropane(TMP) are added in reactor, be heated to material melting, then add successively m-phthalic acid, terephthalic acid, hexanodioic acid, 1, 4-cyclohexane cyclohexanedimethanodibasic and Dibutyltin oxide, logical nitrogen continues temperature reaction, 180 ℃ of left and right esterification water start to generate and distillate, then be warming up to gradually 240 ℃, after coreaction is discharged to 95% esterification water for 5～10 hours, acid number reaches 2～5mgKOH/g, be cooled to 185 ℃, after adding acidolysis agent reaction 0.5 ~ 1h, detect acid number and viscosity, when acid number reaches 15 ~ 60mgKOH/g, hydroxyl value can be cooled to 80 ℃ after reaching 100～150mgKOH/g, stopped reaction obtains the vibrin that high-performance aqueous coating is used, the acid number of this vibrin: 15～60mgKOH/g, hydroxyl value 100～150mgKOH/g, 200 ℃ of melt viscosities (ICI bores plate viscometer): 50～150mPas, number-average molecular weight is 1000～3000.
In the vibrin of gained, add solubility promoter butyl glycol ether, strengthen stir speed (S.S.) and dissolve 10min, be cooled to 60 ℃ of left and right and add again neutralizing agent diethanolamine, deionized water, after rear stirring 30min, can obtain water-base resin.
Acidolysis agent adopts trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydride or m-phthalic acid.
The component of table 1 vibrin and performance
After vibrin A-F synthetic the present invention is weighed up in the ratio in table 2 with aminoresin, flow agent, titanium dioxide, barium sulfate, st-yrax, pigment etc. respectively, mix, after grinding, make water-borne coatings.Be sprayed on the metal sheet of surface treatment (phosphatization), solidify through 150 ℃/20～30min, 24h is soaked in the beaker the inside that then ready-made model is put into deionized water, then carries out various performance tests, and the performance test results is as shown in table 2.
The composition of table 2 water-borne coatings and coating performance
From table 1～table 2, the synthetic vibrin second-order transition temperature of the inventive method is suitable, melt viscosity is suitable, and the coating gloss of making has excellent water tolerance, satisfactory mechanical property.
The present invention can summarize with other the specific form without prejudice to spirit of the present invention or principal character.Above-mentioned embodiment of the present invention all can only be thought explanation of the present invention rather than restriction, as be not limited to the two step method preparation method of vibrin of the present invention, adopt one-step preppn process, after mixing by polyvalent alcohol, aromatic polycarboxylic acid, fatty polyprotonic acid, branching agent, acidolysis agent and esterifying catalyst, carrying out esterification condensation reaction, is also to obtain the vibrin that high-performance aqueous coating of the present invention is used.Therefore every foundation essence technology of the present invention is done above embodiment any trickle modification, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
Claims (7)
1. the vibrin that high-performance aqueous coating is used, it is characterized in that, hydroxyl value is 100～150mgKOH/g, acid number 15～60mgKOH/g, melt viscosity is 50～150mPa.s, number-average molecular weight is 1000～3000, is mainly to be obtained through melt polycondensation reaction by the raw material of following weight percent content:
Polyvalent alcohol: 25 ~ 70%, branching agent: 1 ~ 20%, aromatic polycarboxylic acid: 20%～35%, fatty polyprotonic acid: 5%～20%, acidolysis agent: 3%～15%, esterifying catalyst is 0.005%～0.15%;
Described polyvalent alcohol is neopentyl glycol and 2-ethyl-2-butyl-1,3-PD.
2. the vibrin that high-performance aqueous coating according to claim 1 is used, is characterized in that, described vibrin is mainly to be obtained through melt polycondensation reaction by the raw material of following weight percent content:
Neopentyl glycol: 20～40%, 2-ethyl-2-butyl-1,3-PD: 5 ~ 30%, branching agent: 2 ~ 20%, aromatic polycarboxylic acid: 25%～35%, fatty polyprotonic acid: 5%～20%, acidolysis agent: 3%～15%, esterifying catalyst is 0.005%～0.15%.
3. the vibrin of using according to the high-performance aqueous coating described in the arbitrary claim of claim 1 or 2, is characterized in that, described branching agent comprises TriMethylolPropane(TMP), the mixture of one or more in trimethylolethane and tetramethylolmethane.
4. the vibrin that high-performance aqueous coating according to claim 3 is used, is characterized in that, described aromatic polycarboxylic acid comprises terephthalic acid and m-phthalic acid one or both mixture wherein.
5. the vibrin of wanting the high-performance aqueous coating described in 4 to use according to right, is characterized in that, described fatty polyprotonic acid comprises hexanodioic acid, sebacic acid and 1,4 cyclohexanedicarboxylic acid one or more mixture wherein; Described acidolysis agent comprises one or more the mixture in m-phthalic acid, hexanodioic acid, 1,4 cyclohexanedicarboxylic acid, trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydride, fumaric acid anhydride and maleic anhydride; Described esterifying catalyst is organic tin compound.
6. a preparation method for the vibrin that the high-performance aqueous coating described in claim 1 to 5 any one is used, is characterized in that, comprises the following steps:
(1) measure polyvalent alcohol and polyprotonic acid and branching agent by proportioning and be placed in reactor, add esterifying catalyst to carry out esterification condensation reaction at 160 ℃～240 ℃, to acid number 2 ~ 5 mgKOH/g;
(2) add acidolysis agent to carry out end-blocking and depolymerization, synthetic take terminal hydroxy group as vibrin main, that end carboxyl is used as auxiliary high-performance aqueous coating.
7. the preparation method of the vibrin that high-performance aqueous coating according to claim 6 is used, is characterized in that, comprises the following steps:
(1) in reactor, add polyvalent alcohol and the branching agent of proportional quantity, be heated to material melting; Then add successively the aromatic polycarboxylic acid of proportional quantity, fatty polyprotonic acid and esterifying catalyst, logical nitrogen continues temperature reaction, starts to generate and distillate to 180 ℃ of esterification water, is then warming up to gradually 240 ℃, after coreaction is discharged to 95% esterification water for 5～10 hours, acid number reaches 2～5mgKOH/g;
(2) be cooled to 185 ℃, add acidolysis agent, reaction 0.5～1h, acid number reaches 15～60mgKOH/g, is cooled to 80 ℃, and stopped reaction obtains synthetic take terminal hydroxy group as vibrin main, that end carboxyl is used as auxiliary high-performance aqueous coating.
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| KR20140024503A (en) * | 2012-08-17 | 2014-03-03 | 삼성정밀화학 주식회사 | Method of preparation for biodegradable aliphatic-aromatic co-polyester resin with improved hydrolysis resistance |
| RU2645341C2 (en) * | 2013-06-21 | 2018-02-21 | Ппг Индастриз Огайо, Инк. | Container coating compositions |
| CN103613746A (en) * | 2013-12-04 | 2014-03-05 | 衡阳山泰化工有限公司 | Pure polyester resin for high weather-resistant outdoor powder coating and preparation method thereof |
| CN105694012A (en) * | 2014-11-27 | 2016-06-22 | 合众（佛山）化工有限公司 | Preparation method of high-performance waterborne polyester resin |
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| CN112341610A (en) * | 2020-10-11 | 2021-02-09 | 芜湖市森沐知识产权科技服务有限公司 | Mixed polyester resin and synthetic method thereof |
| CN113105612B (en) * | 2021-02-26 | 2023-05-16 | 广东顺德纪明新材料有限公司 | Polyester resin for wet-on-wet process and preparation method and application thereof |
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