CN111909363A - Polyester resin for high-temperature-resistant and solvent-resistant matte powder coating and preparation method thereof - Google Patents

Polyester resin for high-temperature-resistant and solvent-resistant matte powder coating and preparation method thereof Download PDF

Info

Publication number
CN111909363A
CN111909363A CN202010863518.3A CN202010863518A CN111909363A CN 111909363 A CN111909363 A CN 111909363A CN 202010863518 A CN202010863518 A CN 202010863518A CN 111909363 A CN111909363 A CN 111909363A
Authority
CN
China
Prior art keywords
reaction
catalyst
succinic anhydride
heating
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010863518.3A
Other languages
Chinese (zh)
Other versions
CN111909363B (en
Inventor
汪云端
梁优莲
刘春容
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huangshan Jiaheng Technology Co ltd
Original Assignee
Huangshan Jiaheng Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huangshan Jiaheng Technology Co ltd filed Critical Huangshan Jiaheng Technology Co ltd
Priority to CN202010863518.3A priority Critical patent/CN111909363B/en
Publication of CN111909363A publication Critical patent/CN111909363A/en
Application granted granted Critical
Publication of CN111909363B publication Critical patent/CN111909363B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66Polyesters containing oxygen in the form of ether groups
    • C08G63/668Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672Dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03Powdery paints

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention belongs to the technical field of polyester resin production, and particularly relates to a high-temperature-resistant and solvent-resistant polyester resin for matte powder coating. The polyester resin comprises the following main raw materials in parts by mole: 10-15 parts of p-xylylene dimethyl ether; 15-24 parts of phenol; 5-8 parts of succinic anhydride; 20-30 parts of pyridine; 1, 6-dihydroxyhexane 8-15; 9-18 parts of hexahydrophthalic anhydride; 3, 7-dimethyl-1, 7-octanediol 6-12; 5-9 parts of isophthalic acid. The invention has the beneficial effects that a specific method is adopted, such as that the p-xylylene dimethyl ether and phenol are reacted under the catalytic action of anhydrous aluminum trichloride to obtain micromolecule polyphenol ether resin, then succinic anhydride is added to carry out phenol esterification reaction to obtain the micromolecule polyphenol ether resin grafted with carboxyl, and then the micromolecule polyphenol ether resin is polymerized with 1, 6-dihydroxyhexane, hexahydrophthalic anhydride, 3, 7-dimethyl-1, 7-octanediol and isophthalic acid, so that the obtained product has excellent high temperature resistance and solvent resistance.

Description

Polyester resin for high-temperature-resistant and solvent-resistant matte powder coating and preparation method thereof
Technical Field
The invention belongs to the technical field of polyester resin production, and particularly relates to a high-temperature-resistant and solvent-resistant polyester resin for matte powder coating.
Background
In the common polyester resin powder coating, polyester resin is mostly formed by polymerizing common dibasic acid and dihydric alcohol, the high temperature resistance of raw materials per se is poor, the crosslinking density of a cured coating is low, the high temperature resistance and the solvent resistance are poor, and if a matte coating with excellent decoration (the gloss is 15-30%) is to be obtained, a flatting agent is additionally used, so that the problems of poor flatting stability and complex preparation are caused, and the high temperature resistant, solvent resistant and matte coating can be simultaneously obtained without the existing polyester resin product.
For example, the powder coating disclosed in CN110964180A can obtain 5-7% of low gloss and excellent dulling performance under the condition of adding a dulling agent. "in this document, it is necessary to add a matting agent to obtain a low gloss of 5 to 7%.
Therefore, the polyester resin for matte powder coating, which has high temperature resistance and excellent solvent resistance, and the preparation method thereof need to be developed in order to overcome the defects.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polyester resin for matte powder coating, which has high temperature resistance and excellent solvent resistance;
the invention also provides a preparation method of the polyester resin;
the polyester resin for the matte powder coating and the preparation method thereof have the advantages that dimethyl terephthalate and phenol are reacted under the catalytic action of anhydrous aluminum trichloride to obtain micromolecule polyphenol ether resin, then succinic anhydride is added to carry out phenol esterification reaction to obtain the micromolecule polyphenol ether resin grafted with carboxyl, and the micromolecule polyphenol ether resin is polymerized with 1, 6-dihydroxyhexane, hexahydrophthalic anhydride, 3, 7-dimethyl-1, 7-octanediol and isophthalic acid to obtain the polyester resin.
The finally obtained polyester resin molecular chain segment contains the polyphenol ether resin with excellent high temperature resistance and solvent resistance, the curing and film forming process is carried out by adopting a double curing agent mode, the surface gloss of the finally coated film is lower due to the difference of curing speeds, the gloss is basically 15-25%, the high temperature resistance of the coated film can reach 250 ℃/12h and 320 ℃/2h without obvious change on the basis that the basic mechanical property can be met, and the conventional solvent resistance is also excellent.
The invention provides a high-temperature-resistant and solvent-resistant polyester resin for matte powder coating, which comprises the following main raw materials in parts by mole:
10-15 parts of p-xylylene dimethyl ether; 15-24 parts of phenol; 5-8 parts of succinic anhydride; 20-30 parts of pyridine; 1, 6-dihydroxyhexane 8-15; 9-18 parts of hexahydrophthalic anhydride; 3, 7-dimethyl-1, 7-octanediol 6-12; 5-9 parts of isophthalic acid;
the catalyst also comprises other auxiliary agents, wherein the auxiliary agents comprise a first catalyst, a second catalyst, a third catalyst and an antioxidant;
a first catalyst: anhydrous aluminum trichloride, the amount of which is 0.8-1.5% of the mass of the p-xylylene dimethyl ether;
a second catalyst: 4-dimethylamino pyridine, the amount of which is 2-4% of the mass of the succinic anhydride;
a third catalyst: monobutyl tin oxide, the amount is 0.1-0.2% of the total mass of the raw materials;
the antioxidant is preferably 1010, namely tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the dosage of the antioxidant is 0.3-0.5 percent of the total mass of the raw materials.
The preparation method of the polyester resin provided by the invention comprises the following steps:
A. adding p-xylylene dimethyl ether, phenol and a first catalyst into a reaction kettle I, heating for polymerization reaction, continuing heating after no obvious methanol is distilled out of the system, starting a vacuum system at the same time, and removing unreacted micromolecule raw materials under reduced pressure to obtain polyphenol ether resin;
B. cooling, adding pyridine, mixing and dissolving, adding a second catalyst 4-dimethylamino pyridine and succinic anhydride to perform phenol esterification reaction, keeping the temperature for reaction, stopping the reaction when the succinic anhydride participating in the reaction reaches more than 96%, removing the pyridine solvent under reduced pressure to obtain the succinic anhydride grafted polyphenylether resin,
cooling to room temperature, and crushing into particles;
C. adding 1, 6-dihydroxyhexane, hexahydrophthalic anhydride and a third catalyst of tin monobutyloxide into a reaction kettle II, heating and preserving heat for esterification dehydration reaction, then adding half of the mass of the succinic anhydride grafted polyphenol ether resin obtained in the step B, heating again and preserving heat for reaction;
D. when the acid value of the polymer in the step C is reduced to 110mgKOH/g, adding 3, 7-dimethyl-1, 7-octanediol and the other half of the mass of the succinic anhydride grafted polyphenol ether resin obtained in the step B, gradually heating and keeping the temperature for reaction until no obvious distillate is evaporated, wherein the acid value of a reactant is less than 30 mgKOH/g;
E. then adding an antioxidant, starting a vacuum system, continuing the reaction, and stopping the vacuum system when the acid value is reduced to be below 10 mgKOH/g;
F. cooling, adding isophthalic acid for end-capping reaction, heating and preserving heat for reaction, stopping reaction when the acid value of the reactant is 15-20 mgKOH/g, discharging at high temperature while the reactant is hot, cooling, and crushing and granulating to obtain the final product polyester resin.
Preferably, the method of the present invention comprises the steps of:
A. adding the p-xylylene dimethyl ether, the phenol and the first catalyst anhydrous aluminum trichloride into a reaction kettle I according to the formula amount, heating to 135-plus 145 ℃ for full polymerization reaction for 4-6 h, continuing heating to 160-plus 170 ℃ after no obvious methanol is distilled from the system, simultaneously starting a vacuum system, keeping the vacuum degree between-0.095 Mpa and-0.098 Mpa, and removing unreacted micromolecular raw materials under reduced pressure to obtain the polyphenol ether resin;
B. then cooling to 100-;
C. adding 1, 6-dihydroxyhexane, hexahydrophthalic anhydride and a third catalyst, namely monobutyltin oxide, into a reaction kettle II according to the formula ratio, heating to 180 ℃, carrying out heat preservation esterification dehydration reaction for 1-2 h, then adding half of the mass of the succinic anhydride grafted polyphenylether resin obtained in the step B, gradually heating to 200 ℃ at the heating rate of 10 ℃/h, and carrying out heat preservation reaction for 2-4 h;
D. when the acid value of the polymer in the step C is reduced to 110mgKOH/g, adding 3, 7-dimethyl-1, 7-octanediol with the formula amount and the other half of the mass of the succinic anhydride grafted polyphenol ether resin obtained in the step B, gradually heating to 230 ℃ at the speed of 5-7 ℃/h, and carrying out heat preservation reaction for 2-5 h until no obvious distillate is evaporated, wherein the acid value of a reactant is less than 30 mgKOH/g;
E. adding an antioxidant 1010, starting a vacuum system, keeping the vacuum degree between-0.095 Mpa and-0.098 Mpa, continuously reacting for 1-3 h, and stopping the vacuum system when the acid value is reduced to below 10 mgKOH/g;
F. when the temperature is reduced to 200 ℃, adding the isophthalic acid with the formula amount for end-capping reaction, heating to 230 ℃ at the speed of 6-8 ℃/h, continuing to perform heat preservation reaction for 2-4 h, stopping the reaction when the acid value of the reactant is 15-20 mgKOH/g, discharging at high temperature while the reactant is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the final product of the polyester resin.
The product obtained by the preparation method of the invention has the appearance of colorless transparent particles; the acid value is 15-20 mgKOH/g, and the softening point is 100-110 ℃.
The invention has the beneficial effects that the adopted specific method comprises the steps of firstly using dimethyl terephthalate and phenol to react under the catalytic action of anhydrous aluminum trichloride to obtain micromolecule polyphenol ether resin, then adding succinic anhydride to carry out phenol esterification reaction to obtain micromolecule polyphenol ether resin grafted with carboxyl, and then carrying out polymerization with 1, 6-dihydroxyhexane, hexahydrophthalic anhydride, 3, 7-dimethyl-1, 7-octanediol and isophthalic acid, so that the obtained product has excellent high temperature resistance and solvent resistance.
Detailed Description
The present invention will now be further described with reference to specific embodiments in order to enable those skilled in the art to better understand the present invention.
The polyester resin for the matte powder coating, which has high temperature resistance and excellent solvent resistance, comprises the following main raw materials in parts by mole:
10-15 parts of p-xylylene dimethyl ether
Phenol 15-24
Succinic anhydride 5-8
Pyridine 20-30
1, 6-dihydroxyhexane 8-15
Hexahydrophthalic anhydride 9-18
3, 7-dimethyl-1, 7-octanediol 6-12
Isophthalic acid 5-9
The catalyst for synthesizing the polyphenol ether resin is anhydrous aluminum trichloride, and the using amount of the catalyst is 0.8-1.5 percent of the total mass of the raw material of the p-xylylene dimethyl ether; (hereinafter referred to as a first catalyst);
the phenol esterification catalyst is 4-dimethylamino pyridine (DMAP), and the using amount of the phenol esterification catalyst is 2-4% of the mass of the succinic anhydride; (hereinafter referred to as a second catalyst);
the chain extension esterification catalyst is monobutyl tin oxide, and the using amount of the chain extension esterification catalyst is 0.1-0.2% of the total mass of the raw materials; (hereinafter referred to as a third catalyst);
the antioxidant is 1010, namely tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the using amount of the antioxidant is 0.3-0.5 percent of the total mass of the raw materials.
Example 1
The proportions of the raw materials in example 1 are shown in table 1; the polyester resin in example 1 was prepared as follows:
A. adding the p-xylylene dimethyl ether, the phenol and the first catalyst anhydrous aluminum trichloride into a reaction kettle I according to the formula amount, heating to 135-plus 145 ℃ for full polymerization reaction for 4-6 h, continuing heating to 160-plus 170 ℃ after no obvious methanol is distilled from the system, simultaneously starting a vacuum system, keeping the vacuum degree between-0.095 Mpa and-0.098 Mpa, and removing unreacted micromolecular raw materials under reduced pressure to obtain the polyphenol ether resin;
B. then cooling to 100-;
C. adding 1, 6-dihydroxyhexane, hexahydrophthalic anhydride and a third catalyst, namely monobutyltin oxide, into a reaction kettle II according to the formula ratio, heating to 180 ℃, carrying out heat preservation esterification dehydration reaction for 1-2 h, then adding half of the mass of the succinic anhydride grafted polyphenylether resin obtained in the step B, gradually heating to 200 ℃ at the heating rate of 10 ℃/h, and carrying out heat preservation reaction for 2-4 h;
D. when the acid value of the polymer in the step C is reduced to 110mgKOH/g, adding 3, 7-dimethyl-1, 7-octanediol with the formula amount and the other half of the mass of the succinic anhydride grafted polyphenol ether resin obtained in the step B, gradually heating to 230 ℃ at the speed of 5-7 ℃/h, and carrying out heat preservation reaction for 2-5 h until no obvious distillate is evaporated, wherein the acid value of a reactant is less than 30 mgKOH/g;
E. adding an antioxidant 1010, starting a vacuum system, keeping the vacuum degree between-0.095 Mpa and-0.098 Mpa, continuously reacting for 1-3 h, and stopping the vacuum system when the acid value is reduced to below 10 mgKOH/g;
F. when the temperature is reduced to 200 ℃, adding the isophthalic acid with the formula amount for end-capping reaction, heating to 230 ℃ at the speed of 6-8 ℃/h, continuing to perform heat preservation reaction for 2-4 h, stopping the reaction when the acid value of the reactant is 15-20 mgKOH/g, discharging at high temperature while the reactant is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the final product of the polyester resin. (in other embodiments, on the basis of embodiment 1, the parameters of the reaction conditions are selected within the above range, for example, the reaction is performed under the condition of heat preservation for 2-4 hours, and the reaction is performed for 3 hours or 3.5 hours according to actual conditions, and then, for example, the temperature is decreased to 110 ℃ and actually decreased to 102 ℃, 108 ℃ or 105 ℃, so as to satisfy the reaction conditions in the interval defined in embodiment 1).
The methods of examples 2 to 4 are the same as example 1, and the molar ratios of the raw materials are shown in Table 1:
TABLE 1 amounts of raw materials used for the products of examples 1-4
Example 1 Example 2 Example 3 Example 4
P-xylylene dimethyl ether 10 14 12 15
Phenol and its preparation 15 22 20 24
Succinic anhydride 5 7 6 8
Pyridine compound 20 23 25 30
1, 6-dihydroxyhexane 8 11 12 15
Hexahydrophthalic anhydride 9 12 14 18
3, 7-dimethyl-1, 7-octanediol 6 10 9 12
Isophthalic acid 5 6 7 9
First catalyst (%) 0.8 1.2 1.0 1.5
Second catalyst (%) 2 3.5 3 4
Third catalyst (%) 0.1 0.18 0.15 0.2
Antioxidant agent 0.3 0.45 0.4 0.5
(note: in Table 1, the amount of anhydrous aluminum trichloride as the first catalyst is the percentage of the total mass of the raw material p-xylylene dimethyl ether, the amount of 4-dimethylaminopyridine as the second catalyst is the percentage of the mass of succinic anhydride, the amount of monobutyltin oxide as the third catalyst is the percentage of the total mass of the raw material, and the antioxidant is the percentage of the total mass of the main raw material, wherein the main raw material refers to other raw materials except auxiliary materials).
The acid values and softening points of the products of examples 1-4 are shown in Table 2 below:
TABLE 2 acid number and softening point of the products of examples 1 to 4
Example 1 Example 2 Example 3 Example 4
Acid value (mgKOH/g) 16 18 17 20
Softening Point (. degree. C.) 109 106 104 101
Example 5
In this embodiment, a dual curing system is used to cure the products of embodiments 1 to 4, and the formula of the powder coating comprises the following components in parts by weight:
Figure BDA0002648960780000081
preparing a coating layer: and (3) uniformly mixing the materials according to the formula of the curing system powder coating, extruding, tabletting and crushing by using a double-screw extruder, and then crushing and sieving the tablets to prepare the powder coating. The powder coating is sprayed on the galvanized iron substrate after surface treatment by an electrostatic spray gun, the film thickness is about 80 mu m, and the powder coating is fully cured at 200 ℃/20min to obtain the coating.
Comparative example 1: polyester resin for commercial common TGIC system, acid value: 35mgKOH/g, softening point 108 ℃, model SJ4C, purchased from New Material Ltd of Shenjian, Anhui. The TGIC powder coating formula matched with the polyester resin in the industry is adopted for coating preparation of the powder coating, the film thickness is about 80 mu m, and the curing conditions are as follows: 200 ℃/10 min.
The detection of the coating index is based on GB/T21776 2008 'Standard guide for powder coating and coating detection'; the high temperature resistance is carried out according to GB/T1735-2009 determination of heat resistance of colored paint and varnish; the performance of the conventional solvent resistance is realized by adopting a dropping method, 5 drops of the test solvent are respectively dropped on the surface of the coating film at room temperature, and the condition that the surface of the coating film is discolored or bubbled is observed after 6 hours (if the solvent is volatilized, the solvent is timely added at the original dropping position).
TABLE 3 Performance testing of examples and comparative examples
Figure BDA0002648960780000091
As can be seen from the data in Table 3, after the products in examples 1-4 are applied, the film appearance is flat and the front and back sides pass through; the gloss (60 DEG angle) is only 16.5-22.4; in the high-temperature performance test, the high-temperature resistance time at 250 ℃ is as long as 20 hours, and the appearance is not changed even after 20 hours pass; no significant change after 2 hours at 320 ℃; the performance of methanol, acetone and toluene resistance is good.
The powder coating film prepared from the similar commercial polyester resin product in the comparative example 1 has unsatisfactory high temperature resistance and solvent resistance, and shows obvious yellowing at high temperature and a phenomenon of light loss or bubbling in a solvent.

Claims (9)

1. The polyester resin for the high-temperature-resistant and solvent-resistant matte powder coating is characterized by comprising the following main raw materials in parts by mole:
10-15 parts of p-xylylene dimethyl ether; 15-24 parts of phenol; 5-8 parts of succinic anhydride; 20-30 parts of pyridine; 1, 6-dihydroxyhexane 8-15; 9-18 parts of hexahydrophthalic anhydride; 3, 7-dimethyl-1, 7-octanediol 6-12; 5-9 parts of isophthalic acid;
the catalyst also comprises other auxiliary agents, wherein the auxiliary agents comprise a first catalyst, a second catalyst, a third catalyst and an antioxidant;
a first catalyst: anhydrous aluminum trichloride, the amount of which is 0.8-1.5% of the mass of the p-xylylene dimethyl ether;
a second catalyst: 4-dimethylamino pyridine, the amount of which is 2-4% of the mass of the succinic anhydride;
a third catalyst: monobutyl tin oxide, the amount is 0.1-0.2% of the total mass of the raw materials;
the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the dosage is 0.3-0.5% of the total mass of the raw materials.
2. A method for preparing the polyester resin of claim 1, comprising the steps of:
A. adding p-xylylene dimethyl ether, phenol and a first catalyst into a reaction kettle I, heating for polymerization reaction, continuing heating after no obvious methanol is distilled out of the system, starting a vacuum system at the same time, and removing unreacted micromolecule raw materials under reduced pressure to obtain polyphenol ether resin;
B. cooling, adding pyridine, mixing and dissolving, then adding a second catalyst, namely 4-dimethylaminopyridine and succinic anhydride, to perform a phenol esterification reaction, performing a heat preservation reaction, stopping the reaction when the content of succinic anhydride participating in the reaction reaches more than 96%, removing the pyridine solvent under reduced pressure to obtain succinic anhydride grafted polyphenol ether resin, cooling to room temperature, and crushing into particles;
C. adding 1, 6-dihydroxyhexane, hexahydrophthalic anhydride and a third catalyst of tin monobutyloxide into a reaction kettle II, heating and preserving heat for esterification dehydration reaction, then adding half of the mass of the succinic anhydride grafted polyphenol ether resin obtained in the step B, heating again and preserving heat for reaction;
D. when the acid value of the polymer in the step C is reduced to 110mgKOH/g, adding 3, 7-dimethyl-1, 7-octanediol and the other half of the mass of the succinic anhydride grafted polyphenol ether resin obtained in the step B, gradually heating and keeping the temperature for reaction until no obvious distillate is evaporated, wherein the acid value of a reactant is less than 30 mgKOH/g;
E. then adding an antioxidant, starting a vacuum system, continuing the reaction, and stopping the vacuum system when the acid value is reduced to be below 10 mgKOH/g;
F. cooling, adding isophthalic acid for end-capping reaction, heating and preserving heat for reaction, stopping reaction when the acid value of the reactant is 15-20 mgKOH/g, discharging at high temperature while the reactant is hot, cooling, and crushing and granulating to obtain the final product polyester resin.
3. The method as claimed in claim 2, wherein A, the formula amount of p-xylylene dimethyl ether, phenol and the first catalyst anhydrous aluminum trichloride are added into the reaction vessel I, the temperature is raised to 135-145 ℃ for full polymerization reaction for 4-6 h, after no significant methanol is distilled out of the system, the temperature is continuously raised to 160-170 ℃, simultaneously, the vacuum system is started, the vacuum degree is maintained between-0.095 Mpa and-0.098 Mpa, and the unreacted small molecular raw materials are removed under reduced pressure to obtain the polyphenol ether resin.
4. The method as claimed in claim 2, wherein B is cooled to 100-110 ℃, pyridine with the formula amount is added for mixing and dissolving, then a second catalyst 4-Dimethylaminopyridine (DMAP) with the formula amount and succinic anhydride are added for phenol esterification reaction, the reaction is stopped when the succinic anhydride participating in the reaction reaches more than 96 percent, the pyridine solvent is removed under reduced pressure to obtain the succinic anhydride grafted polyphenylether resin, the resin is cooled to room temperature, and the resin is crushed into particles with 30-50 meshes.
5. The method of claim 2, wherein C, adding 1, 6-dihydroxyhexane, hexahydrophthalic anhydride and a third catalyst of monobutyltin oxide in formula amounts into a reaction kettle II, heating to 180 ℃ and carrying out an esterification dehydration reaction for 1-2 h, then adding half of the mass of the succinic anhydride grafted polyphenylene ether resin obtained in the step B, gradually heating to 200 ℃ at a heating rate of 10 ℃/h, and carrying out an incubation reaction for 2-4 h.
6. The method of claim 2, wherein D, when the acid value of the polymer in the step C is reduced to 110mgKOH/g, adding the formula amount of 3, 7-dimethyl-1, 7-octanediol and the other half of the mass of the succinic anhydride grafted polyphenylene ether resin obtained in the step B, gradually raising the temperature to 230 ℃ at the rate of 5-7 ℃/h, and keeping the temperature for reaction for 2-5 h until no significant distillate is distilled out, and the acid value of the reactant is less than 30 mgKOH/g.
7. The method of claim 2, wherein E, then adding antioxidant 1010, starting the vacuum system, keeping the vacuum degree between-0.095 MPa and-0.098 MPa, continuing the reaction for 1-3 h, and stopping the vacuum system when the acid value is reduced to below 10 mgKOH/g.
8. The method of claim 2, wherein F, when the temperature is reduced to 200 ℃, adding the isophthalic acid with the formula amount for end-capping reaction, raising the temperature to 230 ℃ at 6-8 ℃/h, continuing the heat preservation reaction for 2-4 h, stopping the reaction when the acid value of the reactant is 15-20 mgKOH/g, discharging at high temperature while the reaction is hot, cooling the polyester resin by a steel belt with condensed water, and then crushing and granulating to obtain the final product of the polyester resin.
9. The method of claim 2,
A. adding the p-xylylene dimethyl ether, the phenol and the first catalyst anhydrous aluminum trichloride into a reaction kettle I according to the formula amount, heating to 135-plus 145 ℃ for full polymerization reaction for 4-6 h, continuing heating to 160-plus 170 ℃ after no obvious methanol is distilled from the system, simultaneously starting a vacuum system, keeping the vacuum degree between-0.095 Mpa and-0.098 Mpa, and removing unreacted micromolecular raw materials under reduced pressure to obtain the polyphenol ether resin;
B. then cooling to 100-;
C. adding 1, 6-dihydroxyhexane, hexahydrophthalic anhydride and a third catalyst, namely monobutyltin oxide, into a reaction kettle II according to the formula ratio, heating to 180 ℃, carrying out heat preservation esterification dehydration reaction for 1-2 h, then adding half of the mass of the succinic anhydride grafted polyphenylether resin obtained in the step B, gradually heating to 200 ℃ at the heating rate of 10 ℃/h, and carrying out heat preservation reaction for 2-4 h;
D. when the acid value of the polymer in the step C is reduced to 110mgKOH/g, adding 3, 7-dimethyl-1, 7-octanediol with the formula amount and the other half of the mass of the succinic anhydride grafted polyphenol ether resin obtained in the step B, gradually heating to 230 ℃ at the speed of 5-7 ℃/h, and carrying out heat preservation reaction for 2-5 h until no obvious distillate is evaporated, wherein the acid value of a reactant is less than 30 mgKOH/g;
E. adding an antioxidant 1010, starting a vacuum system, keeping the vacuum degree between-0.095 Mpa and-0.098 Mpa, continuously reacting for 1-3 h, and stopping the vacuum system when the acid value is reduced to below 10 mgKOH/g;
F. when the temperature is reduced to 200 ℃, adding the isophthalic acid with the formula amount for end-capping reaction, heating to 230 ℃ at the speed of 6-8 ℃/h, continuing to perform heat preservation reaction for 2-4 h, stopping the reaction when the acid value of the reactant is 15-20 mgKOH/g, discharging at high temperature while the reactant is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the final product of the polyester resin.
CN202010863518.3A 2020-08-25 2020-08-25 Polyester resin for high-temperature-resistant and solvent-resistant matte powder coating and preparation method thereof Active CN111909363B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010863518.3A CN111909363B (en) 2020-08-25 2020-08-25 Polyester resin for high-temperature-resistant and solvent-resistant matte powder coating and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010863518.3A CN111909363B (en) 2020-08-25 2020-08-25 Polyester resin for high-temperature-resistant and solvent-resistant matte powder coating and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111909363A true CN111909363A (en) 2020-11-10
CN111909363B CN111909363B (en) 2022-08-19

Family

ID=73278694

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010863518.3A Active CN111909363B (en) 2020-08-25 2020-08-25 Polyester resin for high-temperature-resistant and solvent-resistant matte powder coating and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111909363B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR890010031A (en) * 1987-12-31 1989-08-05 정상영 Hydroxyl polyester resin manufacturing method and powder coating composition for powder coating
TW200848447A (en) * 2006-12-08 2008-12-16 Unichema Chemie Bv Unsaturated polymers
CN104130391A (en) * 2013-04-30 2014-11-05 财团法人工业技术研究院 Polyphenol ether oligomers and products containing the same
WO2015074622A1 (en) * 2013-11-25 2015-05-28 蒋云 Method for preparing polyester resin used for powder coating in continuous process
CN109054008A (en) * 2018-08-20 2018-12-21 黄山市徽州康佳化工有限责任公司 A kind of yellowing-resistant HAA system polyester resin for powder coating, preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR890010031A (en) * 1987-12-31 1989-08-05 정상영 Hydroxyl polyester resin manufacturing method and powder coating composition for powder coating
TW200848447A (en) * 2006-12-08 2008-12-16 Unichema Chemie Bv Unsaturated polymers
CN104130391A (en) * 2013-04-30 2014-11-05 财团法人工业技术研究院 Polyphenol ether oligomers and products containing the same
WO2015074622A1 (en) * 2013-11-25 2015-05-28 蒋云 Method for preparing polyester resin used for powder coating in continuous process
CN109054008A (en) * 2018-08-20 2018-12-21 黄山市徽州康佳化工有限责任公司 A kind of yellowing-resistant HAA system polyester resin for powder coating, preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
曹俊等: "高性能水性聚酯树脂的合成及应用研究", 《涂料技术与文摘》 *

Also Published As

Publication number Publication date
CN111909363B (en) 2022-08-19

Similar Documents

Publication Publication Date Title
CN109880494B (en) 50:50 polyester resin for indoor high-hardness and high-gloss powder and preparation method thereof
CN109180922B (en) Low-temperature curing type polyester resin and preparation method and application thereof
CN111647149B (en) Polyester resin with excellent wear resistance and chemical resistance for powder and preparation method thereof
CN111533892B (en) Polyester resin for high-weather-resistance low-temperature TGIC (triglycidyl isocyanurate) curing powder coating and preparation method thereof
CN113861398A (en) Polyester resin containing diphenyl ether structure, powder coating and preparation method thereof
CN109054008B (en) Polyester resin for anti-yellowing HAA system powder coating, preparation method and application
CN110408013A (en) A kind of polyester resin for powder coating and preparation method thereof
CN113372544B (en) Polyester resin with excellent low-temperature impact resistance for powder coating and preparation method thereof
CN112521591B (en) Polyester resin with lasting high temperature resistance and excellent hardness for powder coating and preparation method thereof
CN113549208B (en) Polyester resin for self-leveling powder coating and preparation method thereof
CN111909363B (en) Polyester resin for high-temperature-resistant and solvent-resistant matte powder coating and preparation method thereof
CN117264510A (en) Polyester resin for thick coating pinhole-resistant self-curing powder coating and preparation method thereof
CN114015023B (en) Low-cost polyester resin with excellent surface fineness and preparation method thereof
CN114149575B (en) High-leveling and durable high-temperature-resistant polyester resin and preparation method thereof
CN111607075B (en) High-pressure-resistant poached and acidic-salt-fog-resistant polyester resin for powder and preparation method thereof
CN114181384B (en) Polyester resin for low-cost, pinhole-resistant and high-hardness HAA system and preparation method thereof
CN109651093B (en) Preparation method of bis-hydroxyethyl bisphenol fluorene ether
CN109824878B (en) Fuel gas baking-resistant polyester resin and preparation method and application thereof
CN113045738A (en) Indoor polyester resin capable of reducing consumption of epoxy resin and preparation method thereof
SU1037845A3 (en) Process for producing thermohardening polymeric coatings
CN113999378B (en) Polyester resin for powder coating with low cost and excellent thermal transfer printing effect and preparation method thereof
CN110396182B (en) Polyester resin prepared from bio-based raw materials and preparation method and application thereof
CN113801307B (en) Easily-extinction polyester resin and preparation method and application thereof
CN115449064B (en) Artificial quartz stone unsaturated polyester resin and preparation method thereof
CN115505112B (en) Low-cost low-light type polyester resin for powder coating and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant