CN102408550A - Carboxyl-terminated polyester resin for super weather-proof powder coating and preparation method thereof - Google Patents
Carboxyl-terminated polyester resin for super weather-proof powder coating and preparation method thereof Download PDFInfo
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- CN102408550A CN102408550A CN2011103600333A CN201110360033A CN102408550A CN 102408550 A CN102408550 A CN 102408550A CN 2011103600333 A CN2011103600333 A CN 2011103600333A CN 201110360033 A CN201110360033 A CN 201110360033A CN 102408550 A CN102408550 A CN 102408550A
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Abstract
The invention discloses carboxyl-terminated polyester resin for super weather-proof powder coating. The carboxyl-terminated polyester resin is prepared by the condensation polymerization of the following raw materials in percentage by weight: 23-50% of polyhydric alcohol, 40-65% of aromatic polybasic acid, 0-10% of fatty polybasic acid, 0-2% of branching agent, 10-20% of acidolysis agent and 0.01-0.15% of esterification catalyst. The invention also discloses a preparation method of the polyester resin. The super weather-proof polyester resin disclosed by the invention has proper glass-transition temperature and storage stability; and the prepared powder coating has excellent mechanical performance and weather resistance; and the polyester resin is particularly applicable to the powder coating of the polyester/TGI (triglycidyl isocyanurate) solidifying system.
Description
Technical field
The present invention relates to a kind of ultra weather-resistant powder paint with terminal carboxyl polyester resin and preparation method thereof.
Technical background
In recent years, powder coating substitutes organic solvent type coating just gradually with advantages such as its economy, environmental protection, efficient and performance brilliances, becomes the important development direction in the coating industry, is keeping rate of growth faster always.Be mainly used in fields such as household electrical appliance, garden art metal furniture, hardware component, automobile component, outdoor hurdle frame.Development along with building material industry; The weathering resistance powder coating more and more receives the favor in market; And the outside durabitity that adopts general weatherable polyether resins also is difficult to satisfy this demand, and this makes industry be more prone to the weathering resistance that super-weatherable polyether powder coating satisfies the open air.
Generally speaking; From the consideration to mechanical property and cost, the weather resistant vibrin adopts terephthalic acid and m-phthalic acid copolycondensation to make more, and conventional super-weatherable polyether resin adopts m-phthalic acid to make more; Cause the mechanical property of resin relatively poor like this, influenced the use of resin.At present patent documentation 200910184341 has been reported the preparation method of ultra weather-resistant powder paint, but is mostly through selecting for use weather resistant vibrin and fluorocarbon resin blend to obtain super-weathering resistance, and is not the weather resistance that improves vibrin; Patent documentation 201010191395 has been reported the preparation of ultra weather-resistant powder paint; Wherein mentioned the preparation of super-weatherable polyether resin generally; But be confined to adopt the conventional weather resistant polyester of conventional NSC 6366 and m-phthalic acid preparation, and the mechanical property of not mentioned coating also.
Summary of the invention
One of the object of the invention provides a kind of ultra weather-resistant powder paint and uses terminal carboxyl polyester resin; This super-weatherable polyether resin has suitable second-order transition temperature and storage stability; The powder coating of preparation has excellent mechanical property and weathering resistance, especially is fit to be used in polyester/TGI curing system powder coating.
Two of the object of the invention provides the preparation method of above-mentioned vibrin.
First purpose of the present invention realizes through following technical measures: a kind of ultra weather-resistant powder paint is used terminal carboxyl polyester resin, mainly is synthetic by following raw materials by weight percent polycondensation:
Polyvalent alcohol: 23%～50%, aromatic polycarboxylic acid: 40%～65%, fatty polyprotonic acid: 0%～10%, branching agent: 0%～2%, the acidolysis agent: 10%～20%, esterifying catalyst: 0.01%～0.15%.
Polyvalent alcohol of the present invention adopts NSC 6366,2,2-ethyl-2-butyl-1, one or more mixtures in ammediol, 1,4 cyclohexane dimethanol, pinakon and the hydroxypivalic acid NSC 6366 monoesters etc.
The mixing of one or more in branching agent employing TriMethylolPropane(TMP) of the present invention, trimethylolethane, ditrimethylolpropane and the tetramethylolmethane etc., wherein, preferred TriMethylolPropane(TMP).
M-phthalic acid is adopted in aromatic polycarboxylic acid of the present invention.
The mixture of one or more in fatty polyprotonic acid employing hexanodioic acid of the present invention, sebacic acid, nonane diacid, 1,4 cyclohexanedicarboxylic acid, Hydrogenated Bisphenol A 99 and the HHPA etc.
Acidolysis agent of the present invention comprises one or more mixtures in m-phthalic acid, hexanodioic acid, sebacic acid, 1,4 cyclohexanedicarboxylic acid, HHPA and the trimellitic acid 1,2-anhydride etc., preferred m-phthalic acid and 1,4 cyclohexanedicarboxylic acid.
Esterifying catalyst of the present invention is organic tin compound or Titanium series catalyst, comprises Mono-n-butyltin, Dibutyltin oxide, tetrabutyl titanate etc.
Second purpose of the present invention realizes through following technical scheme: a kind of ultra weather-resistant powder paint may further comprise the steps with the preparation method of terminal carboxyl polyester resin:
(1) measures polyvalent alcohol and polyprotonic acid and branching agent by proportioning and place reaction kettle, add esterifying catalyst and under 180 ℃～240 ℃, carry out the esterification condensation reaction;
(2) add the acidolysis agent and carry out end-blocking and depolymerization, the vacuum polycondensation becomes ultra weather-resistant powder paint to use terminal carboxyl polyester resin then.
As an embodiment of the invention: described ultra weather-resistant powder paint is with the preparation method of terminal carboxyl polyester resin, and its concrete steps are:
(1) in reaction kettle, add the polyvalent alcohol and the branching agent of proportional quantity, heat temperature raising is to material melting; Add the aromatic polycarboxylic acid of proportional quantity, fatty polyprotonic acid and esterifying catalyst then successively; Logical nitrogen continues temperature reaction; Begin to generate and distillate to 180 ℃ of esterification water; Be warming up to 240 ℃ then gradually, acid number reached 6～25mgKOH/g to coreaction to 95% esterification water discharge in 5～10 hours;
(2) add acidolysis agent reaction 0.5～3h, acid number reaches 33～45mgKOH/g, vacuumizes polycondensation 1～5h, and acid number reaches 28～36mgKOH/g, and promptly stopped reaction obtains ultra weather-resistant powder paint and uses terminal carboxyl polyester resin.
Vibrin of the present invention can also adopt the one-step preppn process preparation; Be about to carry out the esterification condensation reaction after polyvalent alcohol, aromatic polycarboxylic acid, fatty polyprotonic acid, branching agent, acidolysis agent and esterifying catalyst mix, also can obtain ultra weather-resistant powder paint of the present invention and use terminal carboxyl polyester resin.
The vibrin acid number of the inventive method preparation is 28～36mgKOH/g, and hydroxyl value is less than 10mgKOH/g, and second-order transition temperature is 55～75 ℃, and melt viscosity is 2000～8500mPa.s, and number-average molecular weight is 2000～8000.Characteristics such as the inventive method synthetic vibrin has suitable second-order transition temperature, storage stability is good and synthetic technology of resins is simple are solidified the powder coating of processing with TGIC and are had excellent mechanical property and weather-proof effect.
The preparation process that is applicable to powder coating according to the invention is for weigh up the back mixing with TGIC, color stuffing and other auxiliary agents respectively with the synthetic vibrin in proportion, melt extrudes, cool off fragmentation, crushing screening is processed powder coating.Color stuffing comprises white titanium pigment, permanent white, lime carbonate etc., and other auxiliary agents comprise st-yrax, flow agent etc.
The practical implementation instance
The present invention will be described to enumerate a part of specific embodiment below, and A～F is embodiments of the invention in the table 1, and G is the Comparative Examples that contains solid terephthalic acid.Wherein, the polyvalent alcohol among embodiment A～F adopts NSC 6366,2-ethyl-2-butyl-1, the mixture of one or more in ammediol and the 1,4 cyclohexane dimethanol.M-phthalic acid is adopted in aromatic polycarboxylic acid, and terephthalic acid is adopted in the aromatic polycarboxylic acid among the Comparative Examples G.The mixture of one or both in fat polyprotonic acid employing 1,4 cyclohexanedicarboxylic acid and the hexanodioic acid.Branching agent adopts TriMethylolPropane(TMP).Esterifying catalyst adopts dibutyl tin oxide.M-phthalic acid or 1,4 cyclohexanedicarboxylic acid are adopted in the acidolysis agent.
The preparation method: in 50 liters of reaction kettles, the polyvalent alcohol of the listed proportional quantity of adding table 1 and branching agent heat temperature raising are to material melting; Add aromatic polycarboxylic acid, fatty polyprotonic acid and esterifying catalyst then successively; Logical nitrogen continues temperature reaction, and 180 ℃ of left and right sides esterification water begin to generate and distillate, and are warming up to 240 ℃ then gradually; Acid number reached 6～25mgKOH/g to coreaction to 95% esterification water discharge in 5～10 hours; Add the acidolysis agent then, reaction 0.5～3h when being reacted to acid number 33～45mgKOH/g, vacuumizes the about 1～5h of polycondensation, and acid number reaches and gets final product stopped reaction after 28～36mgKOH/g reaches requirement.
Acid number: 28～36mgKOH/g; Second-order transition temperature: 55～75 ℃; Softening temperature: 95～115 ℃; 200 ℃ of melt viscosities (ICI bores plate viscometer): 2000～8000mPas, number-average molecular weight is 2000～8000.
The component of table 1 vibrin and performance
Can embody through the performance of the powder coating that is made into the performance of the inventive method synthetic vibrin.With synthetic vibrin A of the present invention, C, E, H respectively with TGIC,, flow agent (PV88), white titanium pigment, permanent white, st-yrax, brightening agent (701) etc. weigh up the back mixing in the ratio in the table 2; With the screw extrusion press fusion extrude respectively, compressing tablet, fragmentation, then the sheet stock crushing screening is processed powder coating.Powder coating adopts electrostatic gun to be sprayed on the metal sheet of surface treatment (phosphatization), solidifies through 200 ℃/10～20min, carries out various performance tests then, and The performance test results is as shown in table 2.
The composition of table 2 powder coating and coating performance
Can know by table 1,2; Can see the weather-proof resin of the weather-proof resin guarantor of excess of export light rate by the aging resistance of comparative resin far above routine; And adopting the inventive method synthetic super-weatherable polyether resin weather resistance mechanical property to match in excellence or beauty with the weather-proof resin of routine, weather resistance is far above common weather-proof resin.It is to adopt conventional inorganic raw material and auxiliary agent that the present invention does powder making sheet test, and the weather-proof data of table 2 only supply to contrast reference, have better performance as in practical application, selecting higher powder auxiliary of quality and mineral filler for use.The super-weatherable polyether resin of synthetic used for powder coating of the present invention has suitable second-order transition temperature and storage stability, and the powder coating of preparation has excellent mechanical property and weathering resistance.
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; Be about to carry out the esterification condensation reaction after polyvalent alcohol, aromatic polycarboxylic acid, fatty polyprotonic acid, branching agent, acidolysis agent and esterifying catalyst mix, also can obtain ultra weather-resistant powder paint of the present invention and use terminal carboxyl polyester resin.Therefore every foundation essence technology of the present invention all belongs in the scope of technical scheme of the present invention any trickle modification, equivalent variations and modification that above embodiment did.
Claims (9)
1. a ultra weather-resistant powder paint is used terminal carboxyl polyester resin, it is characterized in that, mainly is synthetic by following raw materials by weight percent polycondensation:
Polyvalent alcohol: 23%～50%, aromatic polycarboxylic acid: 40%～65%, fatty polyprotonic acid: 0%～10%, branching agent: 0%～2%, the acidolysis agent: 10%～20%, esterifying catalyst: 0.01%～0.15%.
2. ultra weather-resistant powder paint according to claim 1 is used terminal carboxyl polyester resin; It is characterized in that; Described polyvalent alcohol adopts NSC 6366,2,2-ethyl-2-butyl-1; One or more mixtures in ammediol, 1,4 cyclohexane dimethanol, pinakon and the hydroxypivalic acid NSC 6366 monoesters.
3. ultra weather-resistant powder paint according to claim 1 is used terminal carboxyl polyester resin, it is characterized in that, described branching agent adopts TriMethylolPropane(TMP), the mixing of one or more in trimethylolethane, ditrimethylolpropane and the tetramethylolmethane.
4. ultra weather-resistant powder paint according to claim 1 is used terminal carboxyl polyester resin, it is characterized in that, m-phthalic acid is adopted in described aromatic polycarboxylic acid.
5. ultra weather-resistant powder paint according to claim 1 is used terminal carboxyl polyester resin; It is characterized in that; The mixture of one or more in described fatty polyprotonic acid employing hexanodioic acid, sebacic acid, nonane diacid, 1,4 cyclohexanedicarboxylic acid, Hydrogenated Bisphenol A 99 and the HHPA.
6. ultra weather-resistant powder paint according to claim 1 is used terminal carboxyl polyester resin; It is characterized in that; Described acidolysis agent comprises one or more mixtures in m-phthalic acid, hexanodioic acid, sebacic acid, 1,4 cyclohexanedicarboxylic acid, HHPA and the trimellitic acid 1,2-anhydride.
7. ultra weather-resistant powder paint according to claim 1 is used terminal carboxyl polyester resin, it is characterized in that, described esterifying catalyst is organic tin compound or Titanium series catalyst.
8. the described ultra weather-resistant powder paint of arbitrary claim is characterized in that with the preparation method of terminal carboxyl polyester resin in the claim 1～7, may further comprise the steps:
(1) measures polyvalent alcohol and polyprotonic acid and branching agent by proportioning and place reaction kettle, add esterifying catalyst and under 180 ℃～240 ℃, carry out the esterification condensation reaction;
(2) add the acidolysis agent and carry out end-blocking and depolymerization, the vacuum polycondensation becomes ultra weather-resistant powder paint to use terminal carboxyl polyester resin then.
9. ultra weather-resistant powder paint according to claim 8 is characterized in that with the preparation method of terminal carboxyl polyester resin, may further comprise the steps:
(1) in reaction kettle, add the polyvalent alcohol and the branching agent of proportional quantity, heat temperature raising is to material melting; Add the aromatic polycarboxylic acid of proportional quantity, fatty polyprotonic acid and esterifying catalyst then successively; Logical nitrogen continues temperature reaction; Begin to generate and distillate to 180 ℃ of esterification water; Be warming up to 240 ℃ then gradually, acid number reached 6～25mgKOH/g to coreaction to 95% esterification water discharge in 5～10 hours;
(2) add acidolysis agent reaction 0.5～3h, acid number reaches 33～45mgKOH/g, vacuumizes polycondensation 1～5h, and acid number reaches 28～36mgKOH/g, and promptly stopped reaction obtains ultra weather-resistant powder paint and uses terminal carboxyl polyester resin.
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