CN110591444A - Coating curing agent and preparation method thereof - Google Patents
Coating curing agent and preparation method thereof Download PDFInfo
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- CN110591444A CN110591444A CN201910879654.9A CN201910879654A CN110591444A CN 110591444 A CN110591444 A CN 110591444A CN 201910879654 A CN201910879654 A CN 201910879654A CN 110591444 A CN110591444 A CN 110591444A
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- curing agent
- pyromellitate
- coating curing
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- pyromellitic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
-
- 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
-
- 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
- C09D5/033—Powdery paints characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a coating curing agent, which comprises tetraglycidyl pyromellitate and triglycidyl pyromellitate, wherein the tetraglycidyl pyromellitate accounts for 40-99% of the total weight, and discloses a preparation method of the coating curing agent, which comprises the following preparation steps: (1) mixing pyromellitic acid with a solvent and alkali, adding chloropropene, controlling the reaction temperature at 55-85 ℃, and reacting to obtain pyromellitic acid tetrallyl ester serving as a product A; (2) and adding the product A, a surfactant and hydrogen peroxide into a catalyst aqueous solution, controlling the reaction temperature at 50-80 ℃, and reacting to obtain the coating curing agent containing the tetraglycidyl pyromellitate and the triglycidyl pyromellitate.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a coating curing agent and a preparation method thereof.
Background
Powder coatings are environmentally friendly coatings and have developed rapidly in recent years. Among the curing agents used in the polyester powder coating, Triglycidyl isocyanurate (1,3, 5-Triglycidyl isocyanurate, TGIC for short) and hydroxyalkylamide (N, N' -Tetrakis (2-hydroxyethenyl) amide, HAA for short) are used in the largest amount.
TGIC was developed earlier and is highly functional, but it is irritating to the skin and eyes, and in 1991 it was found to be carcinogenic and mutagenic and therefore banned in many countries. HAA has no irritation and carcinogenicity, and is used for replacing TGIC to become the most used curing agent for weather-resistant powder coating. However, HAA has certain characteristics which are not as good as TGIC, so that the application range is limited. Therefore, HAA cannot completely replace TGIC in other regions except Europe, which is well known for environmental protection.
The inventor searches and tests for many years and finds that the pyromellitic acid glycidyl ester has the same curing agent function as TGIC but is nontoxic, and is superior to HAA in the properties of coating film gloss, corrosion resistance, gloss retention, solvent resistance, high temperature resistance and the like, and is obviously a better choice than TGIC and HAA.
At present, the method for preparing the pyromellitic acid tetraglycidyl ester is mainly obtained by reacting pyromellitic acid with epoxy chloropropane. However, this method uses a large amount of Epichlorohydrin (ECH) and has the following disadvantages:
1. the raw material epichlorohydrin has irritation, toxicity and carcinogenicity;
2. the residual chloride ions in the product affect the electrical property of the product, have great limitation on the application of electronic materials, and can be used only by purifying and removing the chloride ions at a high cost;
3. the overall yield is low (about 60%).
Therefore, there is a need to develop a safe, environment-friendly and high-yield production method, and the product has wide industrial applicability.
The CN107418287A discloses a method for manufacturing a coating curing agent and application thereof in coating, and particularly discloses that trimesic acid is taken as a raw material, and a composition of triglycidyl trimesate and diglycidyl trimesate is prepared to be used as a novel curing agent which can replace TGIC.
Disclosure of Invention
The invention aims to: the coating curing agent and the preparation method thereof have the advantages of high curing agent yield, few and harmless byproducts, environmental protection, low raw material cost and excellent application test performance.
The technical scheme adopted by the invention is as follows:
in order to achieve the above object, the present invention provides a paint curing agent comprising tetraglycidyl pyromellitate and triglycidyl pyromellitate.
Preferably, the pyromellitic acid tetraglycidyl ester accounts for 40-99% of the total weight.
The invention also provides a preparation method of the coating curing agent, which comprises the following preparation steps:
(1) mixing pyromellitic acid with a solvent and alkali, adding chloropropene, controlling the reaction temperature at 55-85 ℃, and reacting to obtain pyromellitic acid tetrallyl ester serving as a product A; the reaction formula is as follows:
(2) adding the product A, a surfactant and hydrogen peroxide into a catalyst aqueous solution, controlling the reaction temperature at 50-80 ℃, and reacting to obtain a coating curing agent containing tetraglycidyl pyromellitate (C) and triglycidyl pyromellitate (D); the reaction formula is as follows:
preferably, in the step (1), the molar ratio of the base to the pyromellitic acid is 3.0-8.0, and the molar ratio of the chloropropene to the pyromellitic acid is 3-6.
Preferably, the base in the step (1) is any one of triethylamine, sodium hydroxide, potassium hydroxide, sodium formate and potassium benzoate, and triethylamine is most preferably used.
Preferably, the solvent in the step (1) is dichloroethane, N-dimethylformamide, petroleum ether or toluene.
Preferably, in the step (2), the weight ratio of the surfactant to the tetraallyl pyromellitate is 0.01-0.1, the weight ratio of the catalyst to the tetraallyl pyromellitate is 0.05-0.15, and the molar ratio of the hydrogen peroxide to the tetraallyl pyromellitate is 4.5-6.0.
Preferably, the reaction time of the step (2) is 12-24 hours.
Preferably, the catalyst in the step (2) is sodium tungstate.
Preferably, the surfactant in step (2) is tetrabutylammonium bromide, phenyltrimethylammonium chloride or methyltrioctylammonium chloride.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. in the preparation process of the curing agent, epoxy chloropropane with carcinogenicity is not used as a raw material, hydrogen peroxide is used as an oxygen source, a small amount of harmless water is generated by reaction, and the preparation method is easy to treat, and is a very green, safe and environment-friendly curing agent preparation process.
2. The curing agent has high preparation yield (more than or equal to 90 percent), the product contains tetraglycidyl ester and triglycidyl ester, both of which can react with polyester resin, and when the triglycidyl ester reaches 20 percent, the highest conversion rate (97 percent) and the highest yield (92 percent) can be obtained by the reaction.
3. The coating application test of the curing agent prepared by the invention shows that all performances are equivalent to TGIC coating, and the curing agent can replace TGIC to be used as a new green environment-friendly curing agent, and has strong industrial applicability and popularization.
4. The curing agent prepared by the invention does not contain chloride ions and can be applied to electronic materials.
5. The curing agent prepared by the invention has lower raw material cost, has better advantages compared with other curing agents in application tests under the condition of less application addition amount, and can replace a triglycidyl trimesate mixture to be used as the curing agent.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a coating curing agent comprises the following preparation steps:
(1) weighing pyromellitic acid in a four-mouth bottle, mechanically stirring the bottle, a condensing tube and a thermometer, adding toluene and triethylamine (the molar ratio of triethylamine to pyromellitic acid is 4), heating to 60 ℃, slowly adding chloropropene (the molar ratio of chloropropene to pyromellitic acid is 4.2), controlling the temperature to about 65 ℃, stirring for 5 hours, sampling and detecting, completing the reaction when the content of an initial substance is less than 1%, cooling to 50 ℃, and washing with 2-3 times of water. After layering, combining organic layers to obtain the tetrallyl pyromellitate (product A, the purity is more than 98.0 wt%);
(2) taking a catalyst (sodium tungstate) aqueous solution, adjusting the pH value to 3.0, adding a tetra-alkenyl pyromellitic acid solution, tetrabutylammonium bromide and hydrogen peroxide, wherein the weight ratio of the tetrabutylammonium bromide to the product A is 0.05, the weight ratio of the catalyst to the product A is 0.02, and the molar ratio of the hydrogen peroxide to the product A is 5.0, reacting for 22 hours at 60 ℃, sampling and detecting, and adding a solvent after the reaction is determined to be finished. Collecting an organic layer after layering, cooling, crystallizing, and carrying out suction filtration to obtain a white solid product, and obtain the coating curing agent containing tetraglycidyl pyromellitate (B, 90 wt%) and diglycidyl pyromellitate (C, 10 wt%).
Example 2
A preparation method of a coating curing agent comprises the following preparation steps:
(1) weighing pyromellitic acid in a four-mouth bottle, mechanically stirring the bottle, a condensing tube and a thermometer, adding toluene and triethylamine (the molar ratio of triethylamine to pyromellitic acid is 7), heating to 70 ℃, slowly adding chloropropene (the molar ratio of chloropropene to pyromellitic acid is 6), controlling the temperature to about 80 ℃, stirring for 5 hours, sampling and detecting, completing the reaction when the content of an initial substance is less than 1%, cooling to 50 ℃, and washing with 2-3 times of water. After layering, combining organic layers to obtain the tetrallyl pyromellitate (product A, the purity is more than 98.0 wt%);
(2) taking a catalyst (sodium tungstate) aqueous solution, adjusting the pH value to 3.0, adding a tetra-alkenyl pyromellitic acid solution, tetrabutylammonium bromide and hydrogen peroxide, wherein the weight ratio of the tetrabutylammonium bromide to the product A is 0.1, the weight ratio of the catalyst to the product A is 0.05, and the molar ratio of the hydrogen peroxide to the product A is 6.0, reacting for 18 hours at 80 ℃, sampling and detecting, and adding a solvent after the reaction is determined to be finished. And collecting an organic layer after layering, cooling, crystallizing, and performing suction filtration to obtain a white solid product, thus obtaining the coating curing agent containing the tetraglycidyl pyromellitate (B, 92 wt%) and the diglycidyl pyromellitate (C, 8 wt%).
Example 3
A preparation method of a coating curing agent comprises the following preparation steps:
(1) weighing pyromellitic acid in a four-mouth bottle, mechanically stirring the bottle, a condensing tube and a thermometer, adding toluene and triethylamine (the molar ratio of triethylamine to pyromellitic acid is 5), heating to 60 ℃, slowly adding chloropropene (the molar ratio of chloropropene to pyromellitic acid is 4.5), controlling the temperature to about 70 ℃, stirring for 5 hours, sampling and detecting, completing the reaction when the content of an initial substance is less than 1%, cooling to 50 ℃, and washing with 2-3 times of water. After layering, combining organic layers to obtain the tetrallyl pyromellitate (product A, the purity is more than 98.0 wt%);
(2) taking a catalyst (sodium tungstate) aqueous solution, adjusting the pH value to 3.0, adding a tetra-alkenyl pyromellitic acid solution, tetrabutylammonium bromide and hydrogen peroxide, wherein the weight ratio of the tetrabutylammonium bromide to the product A is 0.05, the weight ratio of the catalyst to the product A is 0.1, and the molar ratio of the hydrogen peroxide to the product A is 4.5, reacting for 13 hours at 70 ℃, sampling and detecting, and adding a solvent after the reaction is determined to be finished. After layering, collecting an organic layer, cooling, crystallizing, and carrying out suction filtration to obtain a white solid product, and obtain the coating curing agent containing the tetraglycidyl pyromellitate (B, 85 wt%) and the diglycidyl pyromellitate (C, 15 wt%).
Performance and application testing
Mixing HAA, TGIC, a triglycidyl trimesate mixture and a tetraglycidyl pyromellitate mixture curing agent prepared by the method of the invention with polyester powder and an auxiliary agent respectively (the proportion of the curing agent is controlled to be 2-8 wt% of the whole), so as to obtain a polyester powder coating, wherein the formula is shown in Table 1:
TABLE 1 polyester powder coating formulations
The polyester powder coating formulations obtained above were tested for performance and compared, and the results are shown in table 2:
TABLE 2 comparative data of coating film properties of three polyester powder coatings
Preferably, the color difference is compared with the standard of 200 ℃ and 10min, and the smaller color difference is better.
The experimental data can prove that the curing agent produced by the method has good curing effect, the used amount of the curing agent is minimum, the curing agent accords with the test standard and specification of a common coating curing agent, can replace HAA and TGIC to be used as a new green environment-friendly curing agent, has strong industrial utilization and popularization, has lower cost of raw materials, has better advantages compared with other curing agents in application test under the condition of less application addition amount, and can replace a triglycidyl trimesate mixture curing agent.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; these modifications and substitutions do not cause the essence of the corresponding technical solution to depart from the scope of the technical solution of the embodiments of the present invention, and are intended to be covered by the claims and the specification of the present invention.
Claims (10)
1. The paint curing agent is characterized by comprising tetraglycidyl pyromellitate and triglycidyl pyromellitate.
2. The coating curing agent according to claim 1, wherein the tetraglycidyl pyromellitate accounts for 40 to 99% of the total weight.
3. A method for preparing the coating curing agent according to claim 1 or 2, comprising the following steps:
(1) mixing pyromellitic acid with a solvent and alkali, adding chloropropene, controlling the reaction temperature at 55-85 ℃, and reacting to obtain pyromellitic acid tetrallyl ester serving as a product A; the reaction formula is as follows:
(2) adding the product A, a surfactant and hydrogen peroxide into a catalyst aqueous solution, controlling the reaction temperature to be 50-80 ℃, and reacting to obtain a coating curing agent containing tetraglycidyl pyromellitate and triglycidyl pyromellitate; the reaction formula is as follows:
4. the method for preparing a coating curing agent according to claim 3, wherein the molar ratio of the base to the pyromellitic acid in the step (1) is 3.0 to 8.0, and the molar ratio of the chloropropene to the pyromellitic acid is 3 to 6.
5. The method for preparing a coating curing agent according to claim 3, wherein the base in the step (1) is any one of triethylamine, sodium hydroxide, potassium hydroxide, sodium formate and potassium benzoate.
6. The method for preparing a coating curing agent according to claim 3, wherein the solvent in the step (1) is dichloroethane, N-dimethylformamide, petroleum ether or toluene.
7. The preparation method of the coating curing agent according to claim 3, wherein in the step (2), the weight ratio of the surfactant to the tetraallyl pyromellitate is 0.01-0.1, the weight ratio of the catalyst to the tetraallyl pyromellitate is 0.05-0.15, and the molar ratio of the hydrogen peroxide to the tetraallyl pyromellitate is 4.5-6.0.
8. The method for preparing the coating curing agent according to claim 3, wherein the reaction time of the step (2) is 12-24 hours.
9. The method for preparing a coating curing agent according to claim 3, wherein the catalyst in the step (2) is sodium tungstate.
10. The method for preparing a coating curing agent according to claim 3, wherein the surfactant in the step (2) is tetrabutylammonium bromide, phenyltrimethylammonium chloride or methyltrioctylammonium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910879654.9A CN110591444A (en) | 2019-09-18 | 2019-09-18 | Coating curing agent and preparation method thereof |
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| CN201910879654.9A CN110591444A (en) | 2019-09-18 | 2019-09-18 | Coating curing agent and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070925A (en) * | 1991-10-03 | 1993-04-14 | 希巴-盖吉股份公司 | Molecular weight is less than the solids composition of 1500 multi-shrinking glyceryl compound |
| CN107418287A (en) * | 2016-05-23 | 2017-12-01 | 上海药合生化科技有限公司 | Manufacture the method for coating curing agent and its application in coating |
| CN109161006A (en) * | 2018-09-17 | 2019-01-08 | 河北汉兴树脂材料科技有限公司 | The preparation method of the indoor polyester resin for powder coating of Pyromellitic Acid sealing end |
| CN109852127A (en) * | 2019-02-18 | 2019-06-07 | 安徽泰达新材料股份有限公司 | A kind of polyester type powder paint composite curing agent and the preparation method and application thereof |
-
2019
- 2019-09-18 CN CN201910879654.9A patent/CN110591444A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070925A (en) * | 1991-10-03 | 1993-04-14 | 希巴-盖吉股份公司 | Molecular weight is less than the solids composition of 1500 multi-shrinking glyceryl compound |
| CN107418287A (en) * | 2016-05-23 | 2017-12-01 | 上海药合生化科技有限公司 | Manufacture the method for coating curing agent and its application in coating |
| CN109161006A (en) * | 2018-09-17 | 2019-01-08 | 河北汉兴树脂材料科技有限公司 | The preparation method of the indoor polyester resin for powder coating of Pyromellitic Acid sealing end |
| CN109852127A (en) * | 2019-02-18 | 2019-06-07 | 安徽泰达新材料股份有限公司 | A kind of polyester type powder paint composite curing agent and the preparation method and application thereof |
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Application publication date: 20191220 |