CN109824878B - Fuel gas baking-resistant polyester resin and preparation method and application thereof - Google Patents
Fuel gas baking-resistant polyester resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of powder coatings, in particular to a fuel gas baking-resistant polyester resin, and a preparation method and application thereof. The invention relates to a fuel gas baking resistant polyester resin, which is mainly prepared from the following raw materials: 1, 8-naphthalic anhydride, 2,3,5, 6-tetrafluoroterephthalic acid, neopentyl glycol, 1,3, 3-tetramethyl-1, 3-disiloxane diol, N '-4, 4' -diphenylmethane bismaleimide, trimethylolpropane, nitrilotriacetic acid monoesters, isophthalic acid. The polyester resin molecule of the invention has a bismaleimide chain segment with excellent high temperature resistance, and contains fluorine and silicon components with fuel gas baking resistance, and the polyester chain segment contains hindered phenol functional groups with strong high temperature oxidation resistance and excellent fuel gas baking resistance.
Description
Technical Field
The invention relates to the field of powder coatings, in particular to a fuel gas baking-resistant polyester resin, a preparation method of the polyester resin and application of the polyester resin.
Background
CN105199086A A preparation method of a fuel gas baking resistant polyester resin for powder coating, which is characterized in that the preparation method comprises the following steps:
a. an esterification procedure: adding terephthalic acid, dihydric alcohol, a branching agent and an esterification catalyst in a formula amount into a synthesis reaction vessel, sealing the vessel, heating to 170-180 ℃, then heating to 210-220 ℃ at a heating rate of 1-1.2 ℃/15min, finally heating to 245-248 ℃ at a heating rate of 2-3 ℃/15min, maintaining for 2h, sampling, wherein the sample is transparent and free of impurities, and the acid value is detected to be 9-12 mgKOH/g;
b. an acidification process: reducing the temperature of the kettle to 180-220 ℃, adding antioxidant triphenyl phosphite with the formula amount, adding isophthalic acid and aliphatic dibasic acid with the formula amount, then heating to 230-235 ℃, maintaining for 1.5h, sampling a sample to be transparent and free of impurities, and detecting that the acid value is 45-48 mgKOH/g;
c. a vacuum process: cooling to 220 ℃ and 225 ℃, vacuumizing for 2.5-3.5 h under the vacuum degree of-0.096-0.098 MPa, sampling and detecting that the acid value is 32-36 mgKOH/g and the viscosity is 5000-6000 mPa.s.
d. Adding an auxiliary agent: and (3) cooling the kettle to 180-200 ℃, adding the curing accelerator and the antioxidant 626 in the formula amount, maintaining for 20-30 min, vacuumizing for 10min, and stopping stirring and discharging.
The product still belongs to the traditional polyester resin, the used polybasic acid mainly comprises terephthalic acid, adipic acid, sebacic acid and the like, the polyol comprises neopentyl glycol and ethylene glycol, and the high-temperature resistance of the polyester resin is enhanced to a certain extent only in the formula and the use of an antioxidant, but the high-temperature resistance and the gas baking resistance of the raw materials are still poor, so that the gas high-temperature baking resistance of the final product is also poor, carbonization and yellowing are easy to occur, the surface color difference of a coating is large, and even the coating is damaged.
Therefore, it is necessary to improve the above-mentioned drawbacks, such as selecting or synthesizing suitable raw materials or adjusting the formula, so that the obtained product has better gas-resistant and high-temperature baking performance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a fuel gas baking resistant polyester resin and a preparation method of the polyester resin;
the application of the polyester resin in the fuel gas baking resistant powder coating is also provided;
the polyester resin is prepared by copolymerizing monomers with excellent high temperature resistance and baking resistance, and is specifically prepared by polymerizing 1, 8-naphthalic anhydride, 2,3,5, 6-tetrafluoroterephthalic acid, neopentyl glycol, 1,3, 3-tetramethyl-1, 3-disiloxane diol, trimethylolpropane, N '-4.4' -diphenylmethane bismaleimide, nitrilotriacetic acid monoester and isophthalic acid. The finally obtained polyester resin molecule has a bismaleimide chain segment with excellent high-temperature resistance, and contains fluorine and silicon components with resistance to gas baking; meanwhile, the nitrilotriacetic acid monoester with high hindered phenol content is used to participate in polyester reaction, and the polyester chain segment contains hindered phenol functional groups with strong high-temperature oxidation resistance, so that the high-temperature oxidation resistance polyester coating has small color difference in a high-temperature gas baking furnace and excellent fuel gas baking resistance, and can be finally used in powder coating of an isocyanuric acid triglycidyl ester curing system to obtain a coating with excellent fuel gas baking resistance.
The polyester resin is mainly prepared from the following raw materials:
1, 8-naphthalic anhydride, 2,3,5, 6-tetrafluoroterephthalic acid, neopentyl glycol, 1,3, 3-tetramethyl-1, 3-disiloxane diol, N '-4, 4' -diphenylmethane bismaleimide, trimethylolpropane, nitrilotriacetic acid monoesters, isophthalic acid.
The mol percentage of each main raw material is as follows:
7-16 mol% of 1, 8-naphthalic anhydride; 8-20 mol% of 2,3,5, 6-tetrafluoroterephthalic acid;
neopentyl glycol 12-30 mol%; 10-20 mol% of 1,1,3, 3-tetramethyl-1, 3-disiloxane diol;
6-13 mol% of N, N '-4, 4' -diphenylmethane bismaleimide;
3-8 mol% of trimethylolpropane; 6-15 mol% of nitrilotriacetic acid monoester;
5-13 mol% of isophthalic acid.
In the preparation process of the polyester resin, a catalyst of 2-zinc ethylhexoate is also adopted, and the dosage of the catalyst is 0.2-0.5 percent of the total molar weight of the main raw materials.
In the preparation process of the polyester resin, a high-temperature-resistant antioxidant is also adopted, and the dosage of the high-temperature-resistant antioxidant is 0.8-1.5 percent of the total molar weight of the main raw materials; preferably, the antioxidant is diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ].
In the raw materials, the molecular structural formula of the nitrilotriacetic acid monoester is as follows:
the preparation principle of the nitrilotriacetic acid monoester is as follows: the reaction is that 1 carboxyl in nitrilotriacetic acid molecule and phenolic hydroxyl of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are esterified in a molar ratio of 1:1 to obtain nitrilotriacetic acid monoester.
The specific preparation method comprises the following steps: nitrilotriacetic acid and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are added into a toluene solvent according to the molar ratio of 1:1, 0.5 percent of p-toluenesulfonic acid is added as a catalyst, esterification reaction is carried out for 3-7h with water at the temperature of 110-125 ℃, and then the toluene solvent is removed through reduced pressure distillation to obtain nitrilotriacetic acid monoester.
The preparation method of the polyester resin comprises the following steps:
(1) adding neopentyl glycol, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst, namely 2-ethylhexoic acid zinc into a reactor, gradually heating, preserving heat and carrying out esterification reaction;
(2) when the acid value of the esterification reactant in the step (1) is reduced to below 120mgKOH/g, adding 1, 8-naphthalic anhydride and 1,1,3, 3-tetramethyl-1, 3-disiloxane diol into the mixture obtained by the esterification reaction, slowly heating under the protection of nitrogen, reacting until no obvious distillate is evaporated out, and when the acid value of the reactant is less than 100mgKOH/g, adding N, N '-4, 4' -diphenylmethane bismaleimide and nitrilotriacetic acid monoester, and gradually heating and preserving heat for reaction;
(3) adding antioxidant diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] and trimethylolpropane, reacting under heat preservation, reacting under vacuum to promote the formation of macromolecular polyester resin, and stopping vacuum pumping when the acid value is reduced to below 15 mgKOH/g;
(4) cooling, adding isophthalic acid for end-capping reaction, slowly heating to carry out esterification reaction again on the polyester resin, stopping the reaction when the acid value of a reactant is 28-35mgKOH/g, cooling, discharging at high temperature, cooling the polyester resin, crushing and granulating to obtain the polyester resin for the fuel gas baking-resistant powder coating.
The preparation method of the polyester resin comprises the following steps:
(1) adding neopentyl glycol, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst, namely 2-ethylhexoic acid zinc into a reactor, gradually heating to 155-190 ℃, and preserving heat for 3-6 hours to perform esterification reaction;
(2) when the acid value of the esterification reactant in the step (1) is reduced to below 120mgKOH/g, adding 1, 8-naphthalic anhydride and 1,1,3, 3-tetramethyl-1, 3-disiloxane diol into a mixture obtained by the esterification reaction, slowly heating to 220 ℃ under the protection of nitrogen, controlling the heating time to be completed within 2h, adding N, N '-4, 4' -diphenylmethane bismaleimide and nitrilotriacetic acid monoester when the reaction product is not evaporated till no obvious distillate is evaporated out and the acid value of the reactant is less than 100mgKOH/g, gradually heating to 240 ℃, and carrying out heat preservation reaction for 4-6h, wherein the heating speed is controlled to be 4 ℃/h, and the reaction temperature is less than or equal to 245 ℃;
(3) adding antioxidant diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] and trimethylolpropane, reacting at 240 ℃ for 1-2h, keeping the vacuum degree of 50-70mmHg for 3-7h to promote the formation of macromolecular polyester resin, and stopping vacuum pulling when the acid value is reduced to below 15 mgKOH/g;
(4) cooling to 200 ℃, adding isophthalic acid for end-capping reaction, slowly heating to 235 ℃ for carrying out esterification reaction on the polyester resin for 4-6h, stopping the reaction when the acid value of a reactant is 28-35mgKOH/g, cooling to 210 ℃, 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 polyester resin for the fuel gas baking-resistant powder coating;
the dosage of each raw material is as follows:
the main raw materials are as follows:
catalyst 2-zinc ethylhexoate, the dosage of which is 0.2-0.5 percent of the total molar weight of the main raw materials;
antioxidant diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] in 0.8-1.5 wt% of the total molar amount of the main material.
The polyester resin prepared by the preparation method of the polyester resin is characterized in that the acid value of the polyester resin is 28-36mgKOH/g, the viscosity: 3500 ℃ and 6000 mPa.s/200 ℃.
The application of the polyester resin prepared by the preparation method of the polyester resin in the fuel gas baking resistant powder coating, in particular to the application of the polyester resin in the powder coating of the triglycidyl isocyanurate curing system, is also within the protection scope of the invention.
The traditional polyester resin matched with a triglycidyl isocyanurate curing agent (TGIC for short) system uses terephthalic acid and adipic acid as polyatomic acid, and neopentyl glycol and diethylene glycol as polyatomic alcohol, so that the product has poor fuel gas high-temperature baking resistance, is easy to carbonize and yellow, and causes large color difference on the surface of a coating, even the coating is damaged.
The scheme provided by the invention is as follows: raw materials such as nitrilotriacetic acid monoester prepared by a specific method are reacted with other raw materials to obtain a special fuel gas baking resistant polyester resin matched with an isocyanuric acid triglycidyl ester curing system, and the obtained polyester resin has bismaleimide chain segments with excellent high temperature resistance in molecules and contains fluorine and silicon components with fuel gas baking resistance; meanwhile, nitrilotriacetic acid monoester with high hindered phenol content is used to participate in polyester reaction, and a polyester chain segment contains hindered phenol functional groups with strong high-temperature oxidation resistance, so that the high-temperature gas curing coating has small color difference in a high-temperature gas baking furnace and excellent fuel gas baking resistance, and can be finally used in powder coating of triglycidyl isocyanurate (TGIC) curing system to obtain a coating with excellent fuel gas baking resistance.
The invention has the beneficial effects that because the invention adopts a specific raw material formula, particularly, the nitrilotriacetic acid monoester with higher hindered phenol content prepared by a specific method participates in the polyester reaction, and the polyester chain segment contains hindered phenol functional groups with strong high-temperature oxidation resistance, the obtained polyester resin has small color difference in a high-temperature gas baking furnace and excellent gas baking resistance; and the molecule of the polyester resin has a bismaleimide chain segment with excellent high-temperature resistance, and contains fluorine and silicon components with fuel gas baking resistance, so that the fuel gas baking resistance of the product polyester resin is enhanced.
Detailed Description
In order to better describe the invention, it will now be illustrated in further detail by the following examples.
Example 1
Preparing the following main raw materials:
1, 8-naphthalic anhydride, 2,3,5, 6-tetrafluoroterephthalic acid, neopentyl glycol, 1,3, 3-tetramethyl-1, 3-disiloxane diol, N '-4, 4' -diphenylmethane bismaleimide, trimethylolpropane, nitrilotriacetic acid monoesters, isophthalic acid;
the preparation method of the fuel gas baking resistant polyester resin comprises the following steps:
(1) adding 24 mol% of neopentyl glycol, 15 mol% of 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst of 2-ethylzinc caproate into a reactor, gradually heating to about 180 ℃, and keeping the temperature for about 4 hours to perform esterification reaction; the catalyst 2-zinc ethylhexanoate accounts for 0.2 percent of the total molar weight of the main raw materials;
(2) when the acid value of the esterification reactant is reduced to be below 120mgKOH/g, adding 14mol percent of 1, 8-naphthalic anhydride and 15mol percent of 1,1,3, 3-tetramethyl-1, 3-disiloxane diol into the mixed material, slowly heating to 220 ℃ under the protection of nitrogen, controlling the heating time to be completed within 2 hours, reacting until no obvious distillate is evaporated, and when the acid value of the reactant is less than 100mgKOH/g, adding 10mol percent of N, N '-4, 4' -diphenylmethane bismaleimide and 10mol percent of nitrilotriacetic acid monoester, gradually heating to 240 ℃ for carrying out heat preservation reaction for about 5 hours, controlling the heating speed to be 4 ℃/h, and controlling the reaction temperature to be 240 ℃ (injection, not more than 245 ℃);
(3) adding an antioxidant TH-245 (namely diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ]) and 5 mol% trimethylolpropane, reacting for about 2 hours at 240 ℃, then reacting for about 6 hours under the vacuum degree of about 60mmHg, promoting the formation of macromolecular polyester resin, and stopping vacuum pulling when the acid value is reduced to below 15 mgKOH/g; the dosage of the antioxidant TH-245 is 0.9 percent of the mole percentage of the main material;
(4) when the temperature is reduced to 200 ℃, 7 mol% of isophthalic acid is added for end-capping reaction, the temperature is slowly raised to 235 ℃ for carrying out esterification reaction again for 5 hours, the reaction is stopped when the acid value of the reactant is about 32mgKOH/g, the temperature is reduced to about 210 ℃, the polyester resin is discharged at high temperature while the polyester resin is hot, a steel belt with condensed water is used for cooling the polyester resin, and then the polyester resin is crushed and granulated to obtain the polyester resin.
Acid value of the prepared polyester resin: 29mgKOH/g, viscosity 4520 mPas/200 ℃.
The methods of examples 2-6 are the same as example 1, except that the raw material ratio is different from that of example 1, and specifically the following steps are included:
TABLE 1 proportioning tables of raw materials, acid values and viscosity indexes of products in examples 2 to 6
Comparative example 1: the procedure is as in example 1 except that no 1, 8-naphthalic anhydride is added. And adjusting the dosage of other main raw materials to ensure that the total mole percentage is 100 percent; the following proportions are the same;
the acid value of the prepared polyester resin is 28mgKOH/g, and the viscosity is 3630 mPa.s/200 ℃.
Comparative example 2: the procedure of example 1 was repeated, except that 2,3,5, 6-tetrafluoroterephthalic acid was not added.
The step (1) is as follows: adding 24 mol% of neopentyl glycol and a catalyst into a reactor, gradually heating to 180 ℃, and preserving heat for 4 hours;
the prepared polyester resin has an acid value of 35mgKOH/g and a viscosity of 4280mPa & s/200 ℃.
Comparative example 3: otherwise the same as in example 1 except that neopentyl glycol was not added.
The step (1) is as follows: adding 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst into a reactor, gradually heating to 180 ℃, and preserving heat for 4 hours;
the prepared polyester resin has an acid value of 39mgKOH/g and a viscosity of 6510mPa · s/200 ℃.
Comparative example 4: the procedure of example 1 was repeated, except that 1,1,3, 3-tetramethyl-1, 3-disiloxane diol was not added.
The acid value of the prepared polyester resin is 37mgKOH/g, and the viscosity is 6270 mPa.s/200 ℃.
Comparative example 5: the procedure is as in example 1, except that N, N '-4.4' -diphenylmethane bismaleimide is not added.
The acid value of the prepared polyester resin is 32mgKOH/g, and the viscosity is 4920 mPa.s/200 ℃.
Comparative example 6: the procedure was as in example 1 except that trimethylolpropane was not added.
The prepared polyester resin has an acid value of 35mgKOH/g and a viscosity of 4150mPa · s/200 ℃.
Comparative example 7: the procedure is as in example 1, except that no monoacetate is added.
The acid value of the prepared polyester resin is 31mgKOH/g, and the viscosity is 4320 mPa.s/200 ℃.
Comparative example 8: the procedure was as in example 1 except that isophthalic acid was not added.
The prepared polyester resin has an acid value of 24mgKOH/g and a viscosity of 3650mPa & s/200 ℃.
Comparative example 9: polyester resin for a commercially available common triglycidyl isocyanurate system, acid value: 32mgKOH/g, viscosity 5140 mPas/200 ℃.
TABLE 2 proportioning (mol%) of each raw material in example 1 and comparative examples 1 to 9
TABLE 3 acid number and viscosity ratio table for the products of example 1 and comparative examples 1 to 9
As can be seen from Table 3 above, the acid value and viscosity of the product of example 1 are different from those of comparative examples 1 to 9, and the acid value and viscosity of the product of the present invention are maintained in a preferable range.
Example 7
The application of the product in the fuel gas baking resistant powder coating is as follows:
triglycidyl isocyanurate (TGIC) system powder coating formulations, the formulations are generally as follows in parts by weight:
preparing a coating layer: mixing the materials uniformly according to triglycidyl isocyanurate (TGIC) system powder coating, extruding by a double-screw extruder, tabletting, crushing, and crushing the tablets and sieving to prepare the powder coating. The powder coating is sprayed on the galvanized iron substrate after surface treatment by adopting an electrostatic spray gun, and is baked and cured at 200 ℃/10min in a gas furnace to obtain the coating layer.
The detection of the coating index is based on GB/T21776 2008 'Standard guide for powder coating and coating detection';
the method for testing the gas-resistant baking performance comprises the following steps: the paint formulations of the examples and the comparative examples are respectively cured by an electric heating baking furnace and a gas baking furnace (200 ℃/10min) according to the paint formulations, wherein a spray plate which is electrically heated and baked for 200 ℃/10min is used as a standard plate, and a color difference value/dE between the baking and curing of the spray plate and the standard plate is measured by a color difference meter, wherein the larger the color difference value/dE is, the poorer the baking resistance to gas is, and conversely, the better the baking resistance to gas is.
TABLE 4 comparison of product characteristics of examples 1-6 and comparative examples 1-9
As can be seen from the comparison, compared with comparative examples 1-9, the product of the invention has the advantages of flat film appearance, good surface, high impact property and gloss, and can meet the use requirements of customers; most importantly, the product of the invention has almost no change in the gas baking resistance (color difference/dE) (≦ 0.3). This shows that the selected raw materials with excellent baking performance against fuel gas of the present invention, such as 1, 8-naphthalic anhydride, 2,3,5, 6-tetrafluoroterephthalic acid, 1,3, 3-tetramethyl-1, 3-disiloxane diol, N '-4, 4' -diphenylmethane bismaleimide, nitrilotriacetic acid monoester, etc. participate in the polyester reaction, and the polyester chain segment contains hindered phenol functional groups with strong baking performance against fuel gas, fluorine, silicon, etc. components, so that the obtained polyester resin has small color difference in a high temperature fuel gas baking furnace and excellent baking performance against fuel gas; and the obtained polyester resin product has bismaleimide chain segments with excellent high-temperature resistance in molecules, and the fuel gas baking resistance of the polyester resin product is enhanced.
Therefore, in the invention, the performance of the product can be changed by reducing the raw materials in any one link or adjusting the amount of the reaction link. The raw materials of the invention are taken as a whole, have no defects, and jointly play a role in esterification and copolymerization reaction, so that the obtained product has a bismaleimide chain segment with excellent high-temperature resistance, has fluorine and silicon components with fuel gas baking resistance and also contains hindered phenol functional groups with strong high-temperature oxidation resistance, can have small color difference in high-temperature fuel gas baking and excellent fuel gas baking resistance, and can play excellent fuel gas baking resistance when being applied to powder coating.
Claims (9)
1. The fuel gas baking-resistant polyester resin is characterized by being prepared from the following raw materials in percentage by mole:
7-16 mol% of 1, 8-naphthalic anhydride; 8-20 mol% of 2,3,5, 6-tetrafluoroterephthalic acid;
neopentyl glycol 12-30 mol%; 10-20 mol% of 1,1,3, 3-tetramethyl-1, 3-disiloxane diol;
6-13 mol% of N, N '-4, 4' -diphenylmethane bismaleimide;
3-8 mol% of trimethylolpropane; 6-15 mol% of nitrilotriacetic acid monoester;
5-13 mol% of isophthalic acid;
the molecular structural formula of the nitrilotriacetic acid monoester is as follows:
the preparation method of the nitrilotriacetic acid monoester comprises the following steps: nitrilotriacetic acid and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are added into a toluene solvent according to the molar ratio of 1:1, 0.5 percent of p-toluenesulfonic acid is added as a catalyst, esterification reaction is carried out for 3-7h with water at the temperature of 110-125 ℃, and then the toluene solvent is removed through reduced pressure distillation to obtain nitrilotriacetic acid monoester.
2. The fuel gas baking resistant polyester resin of claim 1, wherein the polyester resin is prepared by using zinc 2-ethylhexanoate as a catalyst in an amount of 0.2-0.5% based on the total molar amount of the main raw materials.
3. The gas-baking resistant polyester resin as claimed in claim 1, wherein the polyester resin is prepared by using an antioxidant in an amount of 0.8 to 1.5% based on the total molar amount of the main raw materials.
4. The gas fire-resistant polyester resin according to claim 3, wherein the antioxidant is triethylene glycol bis [ β - (3-t-butyl-4-hydroxy-5-methylphenyl) propionate ].
5. The method for preparing the fuel baking resistant polyester resin as claimed in claim 1, comprising the steps of:
(1) adding neopentyl glycol, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst, namely 2-ethylhexoic acid zinc into a reactor, gradually heating, preserving heat and carrying out esterification reaction;
(2) when the acid value of the esterification reactant in the step (1) is reduced to below 120mgKOH/g, adding 1, 8-naphthalic anhydride and 1,1,3, 3-tetramethyl-1, 3-disiloxane diol into the mixture obtained by the esterification reaction, slowly heating under the protection of nitrogen, reacting until no obvious distillate is evaporated out, and when the acid value of the reactant is less than 100mgKOH/g, adding N, N '-4, 4' -diphenylmethane bismaleimide and nitrilotriacetic acid monoester, and gradually heating and preserving heat for reaction;
(3) adding antioxidant diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] and trimethylolpropane, reacting under heat preservation, reacting under vacuum to promote the formation of macromolecular polyester resin, and stopping vacuum pumping when the acid value is reduced to below 15 mgKOH/g;
(4) cooling, adding isophthalic acid for end-capping reaction, slowly heating to carry out esterification reaction again on the polyester resin, stopping the reaction when the acid value of a reactant is 28-35mgKOH/g, cooling, discharging at high temperature, cooling the polyester resin, crushing and granulating to obtain the polyester resin for the fuel gas baking-resistant powder coating.
6. The method for preparing the fuel baking resistant polyester resin as claimed in claim 1, comprising the steps of:
(1) adding neopentyl glycol, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst, namely 2-ethylhexoic acid zinc into a reactor, gradually heating to 155-190 ℃, and preserving heat for 3-6 hours to perform esterification reaction;
(2) when the acid value of the esterification reactant in the step (1) is reduced to below 120mgKOH/g, adding 1, 8-naphthalic anhydride and 1,1,3, 3-tetramethyl-1, 3-disiloxane diol into a mixture obtained by the esterification reaction, slowly heating to 220 ℃ under the protection of nitrogen, controlling the heating time to be completed within 2h, adding N, N '-4, 4' -diphenylmethane bismaleimide and nitrilotriacetic acid monoester when the reaction product is not evaporated till no obvious distillate is evaporated out and the acid value of the reactant is less than 100mgKOH/g, gradually heating to 240 ℃, and carrying out heat preservation reaction for 4-6h, wherein the heating speed is controlled to be 4 ℃/h, and the reaction temperature is less than or equal to 245 ℃;
(3) adding antioxidant diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] and trimethylolpropane, reacting at 240 ℃ for 1-2h, keeping the vacuum degree of 50-70mmHg for 3-7h to promote the formation of macromolecular polyester resin, and stopping vacuum pulling when the acid value is reduced to below 15 mgKOH/g;
(4) cooling to 200 ℃, adding isophthalic acid for end-capping reaction, slowly heating to 235 ℃ for carrying out esterification reaction on the polyester resin for 4-6h, stopping the reaction when the acid value of a reactant is 28-35mgKOH/g, cooling to 210 ℃, 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 polyester resin for the fuel gas baking-resistant powder coating;
the dosage of each raw material is as follows:
the main raw materials are as follows:
catalyst 2-zinc ethylhexoate, the dosage of which is 0.2-0.5 percent of the total molar weight of the main raw materials;
antioxidant diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], the dosage of which is 0.8-1.5 percent of the total molar weight of the main raw materials.
7. The polyester resin obtained by the process for producing a fuel gas baking-resistant polyester resin according to claim 6, wherein the polyester resin has an acid value of 28 to 36mgKOH/g, a viscosity: 3500 ℃ and 6000 mPa.s/200 ℃.
8. Use of the polyester resin obtained by the method for producing a fuel baking resistant polyester resin according to claim 6 in a fuel baking resistant powder coating.
9. Use of the polyester resin obtained by the method for producing a gas-bake resistant polyester resin according to claim 6 in powder coating of triglycidyl isocyanurate curing system.
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