CN108484894B - High-leveling polyester resin and preparation method and application thereof - Google Patents
High-leveling polyester resin and preparation method and application thereof Download PDFInfo
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- CN108484894B CN108484894B CN201810445015.7A CN201810445015A CN108484894B CN 108484894 B CN108484894 B CN 108484894B CN 201810445015 A CN201810445015 A CN 201810445015A CN 108484894 B CN108484894 B CN 108484894B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/698—Polyesters containing atoms other than carbon, hydrogen and oxygen containing boron
- C08G63/6984—Polyesters containing atoms other than carbon, hydrogen and oxygen containing boron derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6988—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
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- 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)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of powder coatings, and particularly relates to a high-leveling polyester resin, and further discloses a preparation method and application thereof in preparing HAA system powder coatings. The high-leveling polyester resin is formed by copolymerizing diethyl phenylethylmalonate, a citric acid monoester compound, diglycolic acid, thiodiglycol, octyloxy glycerol, neopentyl glycol and hexahydrophthalic anhydride. The high leveling polyester resin has soft chain segment, good fluidity in a molten state and lower high-temperature viscosity, and can be used for preparing HAA curing system powder coating.
Description
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to a high-leveling polyester resin, and further discloses a preparation method and application thereof in preparing HAA system powder coatings.
Background
The powder coating is 100% solid powder without organic solvent, which is different from oil-based coating and water-based coating, and the powder coating is a novel environment-friendly coating which does not use solvent or water as a dispersion medium but uses air as a dispersion medium, is uniformly coated on the surface of a workpiece and forms a coating film with special purpose after being heated. The powder coating has the advantages of no VOC, environmental protection, energy conservation, high construction efficiency, wide application range and the like, and gradually replaces organic solvent type coatings with the advantages of economy, environmental protection, high efficiency, excellent performance and the like, thereby becoming an important development direction in the coating industry and keeping a faster growth rate all the time. The polyester powder coating is widely applied to the coating field due to the characteristics of excellent durability, decoration, processing formability and the like.
The traditional polyester for powder coating is carboxyl polyester resin or hydroxyl polyester resin mostly, but the polyester of the system can not realize self-curing of the polyester system, and all the polyester needs to be cured by adding a corresponding curing agent. At present, the curing agent of outdoor pure polyester powder coating is mainly TGIC and HAA, but in recent years, TGIC is found to cause mutation and inheritance to human germ cells, and most countries of European union have banned the use of TGIC as the curing agent. Therefore, there is a great tendency to develop environmentally friendly HAA system powder coatings.
However, in the conventional HAA powder coating, the HAA curing agent has high functionality, high curing activity and high curing speed, which results in insufficient leveling property of the coating film surface of the powder coating, and it is difficult to obtain a high-leveling coating film, which also becomes a technical problem for limiting the development of the HAA system powder coating.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a high leveling polyester resin and further disclose a preparation method thereof;
the second technical problem solved by the invention is to provide the application of the high leveling polyester resin for preparing HAA type powder coating.
In order to solve the technical problems, the preparation raw materials of the high-leveling polyester resin comprise the following raw material components in mole percentage based on the total amount of the polyester resin:
preferably, the preparation raw materials of the high-leveling polyester resin comprise the following raw material components in mole percentage based on the total amount of the polyester resin:
the citric acid monoester compound is a compound obtained by esterifying hydroxyl in citric acid molecules with acrylic acid, and has the following structure:
the high-leveling polyester resin also comprises an esterification catalyst, wherein the molar amount of the esterification catalyst accounts for 0.1-0.3 mol% of the total molar amount of the raw material components.
The esterification catalyst comprises tin stearate.
The high-leveling polyester resin also comprises an antioxidant, wherein the molar amount of the antioxidant accounts for 0.2-0.4 mol% of the total molar amount of the raw material components.
The antioxidant comprises L K-1081.
The invention also discloses a method for preparing the high-leveling polyester resin, which comprises the following steps:
(1) mixing selected amounts of thiodiglycol, octyloxy glycerol and neopentyl glycol, and heating and melting at a temperature of less than 135 ℃;
(2) adding a selected amount of terephthalic acid, diglycolic acid, citric acid monoester compound and diethyl phenylethylmalonate into the mixed material, adding a selected amount of catalyst, gradually heating under the protection of nitrogen to react until no obvious distillate is evaporated out and the acid value of the reactant is less than 20 mgKOH/g;
(3) adding a selected amount of the antioxidant, maintaining the vacuum degree of 40-60mmHg for 3-8h, promoting the formation of polyester resin, and stopping the reaction when the acid value is reduced to below 12 mgKOH/g;
(4) cooling the materials to 200-210 ℃, adding a selected amount of hexahydrophthalic anhydride, slowly heating to 240 ℃ to react for 2-8h, stopping the reaction when the acid value of the reactant is 27-35mgKOH/g, discharging at high temperature, cooling, crushing and granulating to obtain the polyester resin.
The invention also discloses the application of the polyester resin in preparing powder coating.
The powder coating is HAA system polyester powder coating.
The high leveling polyester resin is formed by copolymerizing diethyl phenylethylmalonate, a citric acid monoester compound, diglycolic acid, thiodiglycol, octyloxy glycerol, neopentyl glycol and hexahydrophthalic anhydride, and the finally obtained polyester resin has an acid value of 27-35mgKOH/g and a softening point of 100-115 ℃. The high leveling resin has soft chain segment, good fluidity in a molten state and lower high-temperature viscosity, and can be used for preparing HAA curing system powder coating; meanwhile, the polyester resin is terminated by hexahydrophthalic anhydride with low carboxyl activity, so that the carboxyl activity of a polyester resin final product is low, the gelling time is long, and the enough leveling time is ensured; and because the citric acid monoester compound and the octoxyglycerol are used in the molecular structure, the polyester molecular structure contains functional groups such as acrylate groups, octyl ester groups and the like which have lubricating and leveling functions, and the polyester molecular structure is used for preparing powder coating of an HAA system, can obtain a coating film with high leveling grade, and has excellent product performance.
Detailed Description
Example 1
The high leveling polyester resin described in this embodiment is prepared from the following raw material components in mol percentage, based on the total amount of the polyester resin:
the citric acid monoester compound is a compound obtained by esterifying hydroxyl in citric acid molecules with acrylic acid, and has the following structure: the compound is obtained by esterifying hydroxyl in a citric acid molecule and acrylic acid, and has the following structure:
taking citric acid and acrylic acid according to a molar ratio of 1: 3 is dissolved in a toluene solvent, concentrated sulfuric acid which accounts for 0.5 to 1.5 weight percent of the total molar amount of the raw materials is added as a catalyst, the temperature is controlled at 108-115 ℃ to carry out esterification reaction with water for 2 to 6 hours, and then the toluene solvent and the excessive acrylic acid are removed through reduced pressure distillation to obtain the citric acid monoester compound with the structure.
The preparation method of the high leveling polyester resin described in this embodiment includes the following steps:
(1) adding selected amounts of thiodiglycol, octyloxy glycerol and neopentyl glycol into a mixer, and controlling the temperature to be lower than 135 ℃ for heating and melting;
(2) adding a selected amount of terephthalic acid, diglycolic acid, citric acid monoester compound and diethyl phenylethylmalonate into the mixed material, adding a selected amount of catalyst, gradually heating under the protection of nitrogen to react until no obvious distillate is evaporated out and the acid value of the reactant is less than 20 mgKOH/g; and controlling the reaction temperature in the whole process not to exceed 245 ℃;
(3) adding a selected amount of the antioxidant, maintaining the vacuum degree of 40-60mmHg for 3-8h, promoting the formation of polyester resin, and stopping the reaction when the acid value is reduced to below 12 mgKOH/g;
(4) cooling the materials to 200-210 ℃, adding a selected amount of hexahydrophthalic anhydride, slowly heating to 240 ℃ to react for 2-8h, stopping the reaction when the acid value of the reactant is 27-35mgKOH/g, discharging at high temperature, cooling, crushing and granulating to obtain the polyester resin.
The polyester resin prepared in this example was tested to have an acid value of 32mgKOH/g and a softening point of 108 ℃.
Example 2
The high-leveling polyester resin is prepared from the following raw material components in percentage by mole:
the structure and preparation method of citric acid monoester compound described in this example are the same as example 1.
The preparation method of the high leveling polyester resin described in this example is the same as that of example 1.
The polyester resin prepared in this example was tested to have an acid value of 30mgKOH/g and a softening point of 102 ℃.
Example 3
The high-leveling polyester resin is prepared from the following raw material components in percentage by mole:
the structure and preparation method of citric acid monoester compound described in this example are the same as example 1.
The preparation method of the high leveling polyester resin described in this example is the same as that of example 1.
The polyester resin prepared in this example was tested to have an acid value of 28mgKOH/g and a softening point of 113 ℃.
Example 4
The high-leveling polyester resin is prepared from the following raw material components in percentage by mole:
the structure and preparation method of citric acid monoester compound described in this example are the same as example 1.
The preparation method of the high leveling polyester resin described in this example is the same as that of example 1.
The polyester resin prepared in this example was found to have an acid value of 34mgKOH/g and a softening point of 105 ℃.
Comparative example 1
The composition of the raw material of the polyester resin of this comparative example was the same as that of example 1 except that no terephthalic acid was contained.
The polyester resin prepared in the comparative example was tested to have an acid value of 27mgKOH/g and a softening point of 94 ℃.
Comparative example 2
The composition of the polyester resin of this comparative example was the same as that of example 1 except that diglycolic acid was not contained.
Through detection, the acid value of the low-temperature curing polyester resin prepared by the comparative example is 29mgKOH/g, and the softening point is 119 ℃.
Comparative example 3
The composition of the raw materials of the polyester resin of this comparative example was the same as that of example 1 except that diethyl phenylethyl malonate was not contained.
The polyester resin prepared in the comparative example has an acid value of 30mgKOH/g and a softening point of 93 ℃ through detection.
Comparative example 4
The composition of the raw material of the polyester resin according to this comparative example was the same as that of example 1 except that the citric acid monoester compound was not contained.
The polyester resin prepared in the comparative example has an acid value of 28mgKOH/g and a softening point of 91 ℃ through detection.
Comparative example 5
The composition of the raw material of the polyester resin according to this comparative example was the same as that of example 1 except that thiodiglycol was not contained.
Through detection, the acid value of the low-temperature curing polyester resin prepared by the comparative example is 39mgKOH/g, and the softening point is 95 ℃.
Comparative example 6
The composition of the raw material of the polyester resin according to this comparative example was the same as that of example 1 except that octyloxy glycerin was not contained.
Through detection, the acid value of the low-temperature curing polyester resin prepared by the comparative example is 37mgKOH/g, and the softening point is 96 ℃.
Comparative example 7
The composition of the raw material of the polyester resin according to this comparative example was the same as that of example 1 except that neopentyl glycol was not contained.
Through detection, the acid value of the low-temperature curing polyester resin prepared by the comparative example is 35mgKOH/g, and the softening point is 89 ℃.
Comparative example 8
The composition of the raw materials of the polyester resin of this comparative example was the same as that of example 1 except that hexahydrophthalic anhydride was not contained.
Through detection, the acid value of the low-temperature curing polyester resin prepared by the comparative example is 20mgKOH/g, and the softening point is 92 ℃.
Examples of the experiments
The high leveling polyester resins prepared in the embodiments 1 to 4 of the invention are respectively taken to prepare HAA type polyester powder coating according to the following components:
and the polyester resin (acid value 32mgKOH/g, softening point 120 ℃ C.) conventionally used in HAA powder coating system in the prior art was used in place of the high leveling polyester resin described in the present invention as comparative example 9.
The polyester resins obtained in examples 1 to 4 and comparative examples 1 to 9 were mixed uniformly according to the HAA system powder coating, extruded by a twin-screw extruder, tabletted, and crushed, and then the flakes were pulverized and sieved to prepare a powder coating. And spraying the powder coating on the galvanized iron substrate after surface treatment by using an electrostatic spray gun, and curing at 180 ℃/15min to obtain the corresponding coating coatings.
The detection of the coating index is based on GB/T21776 2008 'Standard guide for powder coating and coating detection'; the leveling rating was determined according to JB-T3998-1999 "paint leveling scratch test", and the various test data are reported in Table 1 below.
TABLE 1 powder coating Property test data
As can be seen from the comparison of the data in the table 1, the high leveling resin has soft chain segment, good fluidity in a molten state and lower high-temperature viscosity, and can be used for preparing HAA curing system powder coating; meanwhile, the polyester resin is terminated by hexahydrophthalic anhydride with low carboxyl activity, so that the carboxyl activity of a polyester resin final product is low, the gelling time is long, and the enough leveling time is ensured; and because the citric acid monoester compound and the octoxyglycerol are used in the molecular structure, the polyester molecular structure contains functional groups such as acrylate groups, octyl ester groups and the like which have lubricating and leveling functions, and the polyester molecular structure is used for preparing powder coating of an HAA system and can obtain a coating film with high leveling grade.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The high-leveling polyester resin is characterized in that the preparation raw materials comprise the following raw material components in mole percentage based on the total amount of the polyester resin:
2. the high leveling polyester resin according to claim 1, wherein the preparation raw materials comprise the following raw material components in mole percentage based on the total amount of the polyester resin:
3. the high leveling polyester resin according to claim 1 or 2, wherein the citric acid monoester compound is a compound obtained by esterifying hydroxyl in a citric acid molecule with acrylic acid, and has a structure as shown in the following:
4. the high leveling polyester resin of claim 1, further comprising an esterification catalyst in a molar amount of 0.1 to 0.3 mol% based on the total molar amount of the raw material components.
5. The high leveling polyester resin of claim 4 wherein the esterification catalyst comprises tin stearate.
6. The high leveling polyester resin of claim 1, further comprising an antioxidant in a molar amount of 0.2 to 0.4 mol% based on the total molar amount of the raw material components.
7. The high leveling polyester resin of claim 6, wherein the antioxidant comprises L K-1081.
8. A method for preparing a high leveling polyester resin according to any one of claims 1 to 7 comprising the steps of:
(1) mixing selected amounts of thiodiglycol, octyloxy glycerol and neopentyl glycol, and heating and melting at a temperature of less than 135 ℃;
(2) adding a selected amount of terephthalic acid, diglycolic acid, citric acid monoester compound and diethyl phenylethylmalonate into the mixed material, adding a selected amount of catalyst, gradually heating under the protection of nitrogen to react until no obvious distillate is evaporated out and the acid value of the reactant is less than 20 mgKOH/g;
(3) adding a selected amount of the antioxidant, maintaining the vacuum degree of 40-60mmHg for 3-8h, promoting the formation of polyester resin, and stopping the reaction when the acid value is reduced to below 12 mgKOH/g;
(4) cooling the materials to 200-210 ℃, adding a selected amount of hexahydrophthalic anhydride, slowly heating to 240 ℃ to react for 2-8h, stopping the reaction when the acid value of the reactant is 27-35mgKOH/g, discharging at high temperature, cooling, crushing and granulating to obtain the polyester resin.
9. Use of the polyester resin according to any one of claims 1 to 7 for the preparation of powder coatings.
10. Use according to claim 9, characterized in that the powder coating is a HAA system polyester powder coating.
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| CN109206599B (en) * | 2018-09-07 | 2020-12-18 | 安徽恒隆新材料有限公司 | Polyester resin for high-leveling powder coating and preparation method and application thereof |
| CN109762539A (en) * | 2019-02-15 | 2019-05-17 | 北京启顺京腾科技有限责任公司 | A kind of New drilling fluid oil lubricant and its synthetic method |
| CN110183617B (en) * | 2019-07-01 | 2021-09-07 | 黄山正杰新材料有限公司 | A transparent powder with excellent wear resistance is prepared from (A) 50: 50 polyester resin and preparation method and application thereof |
| CN116082611A (en) * | 2022-12-19 | 2023-05-09 | 江苏达美瑞新材料有限公司 | Polyester resin containing alkyl ether main chain, powder coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51117728A (en) * | 1975-04-10 | 1976-10-16 | Nippon Ester Co Ltd | Polyester resin composition for powder coating |
| EP0918810A1 (en) * | 1996-08-12 | 1999-06-02 | McWHORTER TECHNOLOGIES, Inc. | Low temperature cure carboxyl terminated polyesters |
| CN1318094A (en) * | 1998-09-18 | 2001-10-17 | 麦克霍登技术股份有限公司 | Powder coatings based on branched oligoesters and triazole blocked polyisocyanates |
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| CN107177033B (en) * | 2017-07-14 | 2019-01-04 | 黄山市徽州康佳化工有限责任公司 | A kind of powdery paints Self-leveling polyester resin, preparation method and the powder paint compositions containing it |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51117728A (en) * | 1975-04-10 | 1976-10-16 | Nippon Ester Co Ltd | Polyester resin composition for powder coating |
| EP0918810A1 (en) * | 1996-08-12 | 1999-06-02 | McWHORTER TECHNOLOGIES, Inc. | Low temperature cure carboxyl terminated polyesters |
| CN1318094A (en) * | 1998-09-18 | 2001-10-17 | 麦克霍登技术股份有限公司 | Powder coatings based on branched oligoesters and triazole blocked polyisocyanates |
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