CN112375210A - Phenol curing agent for high-temperature-resistant and high-hardness epoxy resin powder coating and preparation method thereof - Google Patents
Phenol curing agent for high-temperature-resistant and high-hardness epoxy resin powder coating and preparation method thereof Download PDFInfo
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- CN112375210A CN112375210A CN202011218167.7A CN202011218167A CN112375210A CN 112375210 A CN112375210 A CN 112375210A CN 202011218167 A CN202011218167 A CN 202011218167A CN 112375210 A CN112375210 A CN 112375210A
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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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- 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
- C09D5/18—Fireproof paints including high temperature resistant 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)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Abstract
Discloses a preparation method of a phenol curing agent for high-temperature-resistant and high-hardness epoxy resin powder coating, which comprises the following raw materials in parts by mole: 4-8 parts of p-cresol, 5-9 parts of formaldehyde, 2-4 parts of 2, 6-dimethylphenol, 10-17 parts of resorcinol diglycidyl ether, 4-9 parts of 1, 6-hexanediol diglycidyl ether, 7-13 parts of hydrogenated bisphenol A, 3-6 parts of resorcinol, a catalyst and a pH regulator. The phenolic curing agent is obtained by adopting low molecular weight phenolic aldehyde to carry out chain extension and end capping, has high functionality, all molecular structures are linked by ether bonds, and the curing activity of the end group is high, so that a coating finally cured with the E-12 epoxy resin at a low temperature of 160 ℃ has high crosslinking density, high hardness, strong adhesive force, long-term high temperature resistance and excellent gasoline resistance.
Description
Technical Field
The invention belongs to the field of powder coating, and relates to a preparation method of a phenolic curing agent for epoxy resin powder coating and the phenolic curing agent prepared by the method.
Background
With the development of the powder coating market, it has become one of the most common products for metal surface coating. The phenol curing agent is used as a special powder coating curing agent in the field of pipeline corrosion prevention, and is developed rapidly in the powder coating market in recent years.
The common phenolic curing agent is generally obtained by chain extension of linear liquid epoxy resin E-51 and bisphenol A, and the product has low molecular branching degree, low crosslinking density with a coating film formed by curing the E-12 epoxy resin and poor corrosion resistance.
Chinese patent ZL201611039784.4 adopts E-51 epoxy resin and dihydrazide compound to modify, and then obtains phenolic curing agent with bisphenol A end capping mode, although can improve the functionality of the product, but also brings some defects, such as poor heat resistance of dihydrazide structure substance, easy yellowing at high temperature and damage, and simultaneously, because the molecular weight is too large, the number average molecular weight reaches about 6000, and the chain segment is softer, the end group activity is low, it can not be used in the field with high requirements for high temperature resistance and hardness.
Chinese patent ZL201710962292.0 adopts added amino silane to improve the high temperature resistance of the product, but the hardness and the high temperature resistance of the product cannot achieve satisfactory results.
When high-temperature equipment (such as an oven, a drying room and the like) for chemical experiments and production is used at present, a coating film is easy to damage due to being touched, and the coating film is often damaged due to the fact that solvents such as gasoline and the like are remained in a product and are contacted with the coating film in the drying process; the common powder coating (including the phenolic curing agent system powder coating) has the problem that the high-temperature performance, the hardness and the gasoline resistance can not meet the requirements at the same time for a long time.
Therefore, a new phenol curing agent for epoxy resin powder coating with high temperature resistance and high hardness is needed to solve the above technical problems.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a high-temperature-resistant and high-hardness phenolic curing agent for an epoxy resin powder coating, which comprises the following raw materials in parts by mole:
the molar amount of the catalyst is 0.05-0.1% of that of the p-cresol; and
a pH regulator.
Wherein the catalyst is triphenylphosphine.
Wherein the pH regulator comprises a concentrated ammonia water solution with the mass concentration of 25%.
Wherein the formaldehyde is a formaldehyde water solution with the formaldehyde mass content of 35%.
The preparation method of the phenolic curing agent for the epoxy resin powder coating comprises the following steps:
A. adding p-cresol, formaldehyde and 2, 6-dimethylphenol in a formula ratio into a reaction kettle, stirring, heating to 85-90 ℃, adding a pH regulator to regulate the pH value of a system to 8-10, and controlling the reaction temperature to be 85-90 ℃ to react for 4-8 h;
B. monitoring the viscosity of the reaction system, stopping the reaction when the viscosity of the reaction mixture reaches 3000-3500 mpa.s (25 ℃), starting a vacuum system, keeping the vacuum degree at-0.096 to-0.098 Mpa, and carrying out reduced pressure distillation at 90-95 ℃ for 1-3h to remove water, ammonia gas, unreacted formaldehyde and other small molecular substances;
C. after no obvious material is evaporated, closing the vacuum system, adding resorcinol diglycidyl ether, 1, 6-hexanediol diglycidyl ether and a catalyst according to the formula amount, and continuously heating to the temperature of 115 ℃ and 125 ℃ to carry out chain extension reaction for 2-5 h;
D. when the epoxy equivalent of the reaction system reaches 500-550g/mol, heating to 135-140 ℃, and adding the bisphenol A with the formula amount for end-capping reaction for 1-3 h;
E. when the epoxy equivalent of the resin is more than 2000g/mol and the hydroxyl equivalent is 500g/mol with 450-plus-one, stopping the reaction, washing with hot water, then removing the water phase by layers, performing reduced pressure dehydration at 140 ℃ with 130-plus-one, discharging at high temperature while the resin is hot, cooling the resin, and then crushing and granulating.
In the step E, the hot water washing is carried out for 1 time or more by adding hot water with the temperature of 90-95 ℃, and the washing water amount of each time is 40-60% of the total mass of the phenolic curing agent product.
Wherein, in the step E, the decompression dehydration pressure is between-0.096 MP and-0.1 MPa, and preferably between-0.098 MPa.
The invention also provides a phenolic curing agent prepared by the preparation method of the phenolic curing agent for the epoxy resin powder coating.
Wherein the obtained phenolic curing agent has a hydroxyl equivalent of 450-500g/mol and a softening point of 83-90 ℃.
Wherein the obtained phenolic curing agent is colorless or light yellow transparent particles in appearance.
The invention also provides an epoxy resin powder coating prepared by adopting the phenolic curing agent.
The beneficial technical effects of the invention are embodied in the following aspects:
the invention mainly uses p-cresol, formaldehyde, 2, 6-dimethylphenol, resorcinol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, hydrogenated bisphenol A, resorcinol and the like as raw materials to carry out reaction to obtain a phenolic curing agent product with the hydroxyl equivalent of 450-500 g/mol. The phenol curing agent is obtained by chain extension and end capping on the basis of special phenolic resin, has high functionality and good high-temperature resistance, molecular structures are linked by ether bonds, high-temperature resistance and gasoline resistance, high hardness and impact resistance, high hydroxyl end activity of hydrogenated bisphenol A and resorcinol for end capping, and finally high crosslinking density, strong adhesive force, high hardness, long-time high-temperature resistance and good gasoline resistance of a coating film after being cured at low temperature (160 ℃/20min) with E-12 epoxy resin.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A phenolic curing agent for epoxy resin powder coatings was prepared according to the following raw material formulation of the examples, according to the following method, comprising:
A. adding p-cresol, formaldehyde and 2, 6-dimethylphenol in a formula ratio into a reaction kettle, stirring, heating to 85-90 ℃, adding a pH regulator to regulate the pH value of a system to 8-10, and controlling the reaction temperature to be 85-90 ℃ to react for 4-8 h;
B. monitoring the viscosity of the reaction system, stopping the reaction when the viscosity of the reaction mixture reaches 3000-3500 mpa.s (25 ℃), starting a vacuum system, keeping the vacuum degree at-0.096 to-0.098 Mpa, and carrying out reduced pressure distillation at 90-95 ℃ for 1-3h to remove water, ammonia gas, unreacted formaldehyde and other small molecular substances;
C. after no obvious material is evaporated, closing the vacuum system, adding resorcinol diglycidyl ether, 1, 6-hexanediol diglycidyl ether and a catalyst according to the formula amount, and continuously heating to the temperature of 115 ℃ and 125 ℃ to carry out chain extension reaction for 2-5 h;
D. when the epoxy equivalent of the reaction system reaches 300-360g/mol, the temperature is raised to 135-140 ℃, and the bisphenol A with the formula amount is added for end-capping reaction for 1-3 h;
E. when the epoxy equivalent of the resin is more than 2000g/mol and the hydroxyl equivalent is 500g/mol with 450-plus-one, stopping the reaction, washing with hot water, then removing the water phase by layers, performing reduced pressure dehydration at 140 ℃ with 130-plus-one, discharging at high temperature while the resin is hot, cooling the resin, and then crushing and granulating.
Example 1
A preparation method of a high-temperature-resistant and high-hardness phenolic curing agent for epoxy resin powder coating comprises the following raw materials in parts by mole:
the catalyst is triphenylphosphine, and the molar amount of the catalyst is 0.1 percent of the molar amount of the p-cresol; and
a pH regulator.
The phenolic curing agent obtained had a hydroxyl equivalent weight of 471g/mol, a softening point of 84 DEG C
Example 2
A preparation method of a high-temperature-resistant and high-hardness phenolic curing agent for epoxy resin powder coating comprises the following raw materials in parts by mole:
the catalyst is triphenylphosphine, and the molar amount of the triphenylphosphine is 0.05 percent of the molar amount of the p-cresol.
The phenolic curing agent obtained had a hydroxyl equivalent weight of 458g/mol and a softening point of 90 ℃.
Example 3
A preparation method of a high-temperature-resistant and high-hardness phenolic curing agent for epoxy resin powder coating comprises the following raw materials in parts by mole:
the catalyst is triphenylphosphine, and the molar amount of the triphenylphosphine is 0.08 percent of the molar amount of the p-cresol.
The phenolic curing agent obtained had a hydroxyl equivalent weight of 493g/mol and a softening point of 86 ℃.
Example 4
A preparation method of a high-temperature-resistant and high-hardness phenolic curing agent for epoxy resin powder coating comprises the following raw materials in parts by mole:
the catalyst is triphenylphosphine, and the molar amount of the triphenylphosphine is 0.06 percent of the molar amount of the p-cresol.
The phenolic curing agent obtained had a hydroxyl equivalent weight of 485g/mol and a softening point of 88 ℃.
The phenolic curing agents of the above examples 1-4 were extruded at low temperature (screw temperature controlled at 110 ℃ C.) by a twin-screw extruder, tabletted, crushed, and then the tabletted materials were pulverized and sieved to prepare a powder coating (160-180 mesh) according to the following formulation of epoxy resin powder coating. The powder coating is sprayed on the galvanized iron substrate after surface treatment by adopting an electrostatic spray gun, and is solidified at 160 ℃/20min to obtain a coating layer with the film thickness of 80-90 mu m.
The epoxy resin powder coating comprises the following components in parts by weight:
the E-12 epoxy resin is purchased from Hengyuan New materials, Inc. of Anhui province, and has an epoxy equivalent of 825 g/mol.
Comparative example 1
The product of example 1 in ZL201611039784.4 was used as comparative example 1 in place of the phenolic curing agent of the present invention. The coating formula is ZL201611039784.4, and the curing conditions are as follows: 200 ℃/15min, and the coating thickness is 80-90 μm.
Comparative example 2
The phenolic hardener product of this invention was replaced with the product of example 1 in ZL201710962292.0 as comparative example 4. The coating formula is ZL201710962292.0, and the curing conditions are as follows: 200 ℃/15min, and the coating thickness is 80-90 μm.
The epoxy resin powder coating coatings prepared in examples 1 to 4 and comparative examples 1 to 2 described above were subjected to performance tests. The test criteria are as follows:
the detection of the coating index is carried out according to GB/T21776 2008 'Standard guide for powder coating and coating detection';
the hardness test is carried out according to GB/T6739-;
the high temperature resistance test is carried out according to the method of GB/T1735-2009 determination of heat resistance of colored paint and varnish, the temperature is 240 ℃, and the time is 48 hours;
the gasoline resistance test is carried out according to the method A (gasoline immersion method) in standard GB/T1734-1993 'paint film gasoline resistance determination method', and 120 solvent oil is selected as a medium. The results of the performance tests are shown in table 1.
TABLE 1 test results of coating properties of epoxy resin powder coatings of examples and comparative examples
As can be seen from the comparison between examples 1-4 and comparative examples 1-2 in Table 1, the phenolic curing agent obtained by the invention and the E-12 epoxy resin cured at low temperature (160 ℃/20min) have smooth appearance, excellent gloss and impact resistance, especially high hardness (up to 2H or above), superior gasoline resistance and high temperature resistance, and hardly change at high temperature of 240 ℃/48H. .
The phenolic curing agent adopted in the comparative example 1 is prepared from a dihydrazide compound, and the molecular weight design is large, so that the product has poor high-temperature resistance, insufficient hardness and moderate gasoline resistance.
Compared with the prior art, the phenolic curing agent adopted in the comparative example 2 has the advantages that the amino silane coupling agent is introduced into the molecular structure of the phenolic curing agent, although the high-temperature resistance can be improved a little, the branching degree of the phenolic curing agent is low, the high-temperature yellowing of the coating film is still easily caused by the existence of amino groups, the high-temperature resistance (240 ℃/48h) of the final coating film is still poor, and the hardness and the gasoline resistance are obviously poor.
In addition, the test results also show that the powder coating formulas of the corresponding phenolic curing agents adopted in the comparative examples 1 and 2 can realize full curing at 200 ℃/15min, and if the curing conditions are changed from high-temperature curing conditions (200 ℃/15min) to low-temperature curing conditions (160 ℃/20min) used in the invention, the powder coating can not realize full curing, so that the conventional properties such as impact resistance (50cm) and forward and backward impact can not pass smoothly, and the appearance and the gloss of the coating film are poor, therefore, the phenolic curing agents in the comparative examples 1 and 2 can not be used in a low-temperature curing system.
Claims (10)
1. A preparation method of a high-temperature-resistant and high-hardness phenolic curing agent for epoxy resin powder coating comprises the following raw materials in parts by mole:
the molar amount of the catalyst is 0.05-0.1% of that of the p-cresol; and
a pH regulator.
2. The method for producing a phenolic curing agent according to claim 1, wherein the catalyst is triphenylphosphine.
3. The method for producing a phenolic curing agent according to claim 1, wherein the pH adjuster comprises a concentrated aqueous ammonia solution having a mass concentration of 25%.
4. The method for producing a phenolic curing agent according to claim 1, wherein the formaldehyde is an aqueous formaldehyde solution having a formaldehyde concentration of 35% by mass.
5. A process for the preparation of the phenolic curing agent of claims 1-4 comprising the steps of:
A. adding p-cresol, formaldehyde and 2, 6-dimethylphenol in a formula ratio into a reaction kettle, stirring, heating to 85-90 ℃, adding a pH regulator to regulate the pH value of a system to 8-10, and controlling the reaction temperature to be 85-90 ℃ to react for 4-8 h;
B. monitoring the viscosity of the reaction system, stopping the reaction when the viscosity of the reaction mixture reaches 3000-3500 mpa.s (25 ℃), starting a vacuum system, keeping the vacuum degree at-0.096 to-0.098 Mpa, and carrying out reduced pressure distillation at 90-95 ℃ for 1-3h to remove water, ammonia gas and unreacted small molecular substances;
C. after no obvious material is evaporated, closing the vacuum system, adding resorcinol diglycidyl ether, 1, 6-hexanediol diglycidyl ether and a catalyst according to the formula amount, and continuously heating to the temperature of 115 ℃ and 125 ℃ to carry out chain extension reaction for 2-5 h;
D. when the epoxy equivalent of the reaction system reaches 500-550g/mol, heating to 135-140 ℃, and adding hydrogenated bisphenol A and resorcinol according to the formula amount to carry out end-capping reaction for 1-3 h;
E. when the epoxy equivalent of the resin is more than 2000g/mol and the hydroxyl equivalent is 500g/mol with 450-plus-one, stopping the reaction, washing with hot water, then removing the water phase by layers, performing reduced pressure dehydration at 140 ℃ with 130-plus-one, discharging at high temperature while the resin is hot, cooling the resin, and then crushing and granulating.
6. The method for preparing phenolic curing agent according to claim 5, wherein in the step E, the hot water washing is carried out for 1 or more times by adding hot water with the temperature of 90-95 ℃, and the washing water amount in each time is 40% -60% of the total mass of the phenolic curing agent product; the pressure of the reduced pressure dehydration is between-0.096 MP and-0.1 MPa.
7. The phenolic curing agent prepared by the method for preparing a phenolic curing agent for epoxy resin powder coating according to any one of claims 1 to 6.
8. The phenolic curing agent of claim 7 having a hydroxyl equivalent weight of 450 and 500 g/mol.
9. The phenolic curing agent of claim 7 or 8, which has a softening point of 83 to 90 ℃.
10. An epoxy resin powder coating prepared using the phenolic curing agent of any one of claims 7 to 9.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4552814A (en) * | 1984-05-21 | 1985-11-12 | The Dow Chemical Company | Advanced epoxy resins having improved impact resistance when cured |
| US4767832A (en) * | 1987-05-29 | 1988-08-30 | Shell Oil Company | Phenolic curing agents for epoxy resins |
| EP0343219A1 (en) * | 1987-11-30 | 1989-11-29 | Isovolta | Use of a solid phenol formaldehyde condensation product as a hardener in epoxy resin mixtures and process for making a powder paint from said mixtures. |
| US5264503A (en) * | 1990-01-29 | 1993-11-23 | Shell Oil Company | Phenol-terminated epoxy resin with functional elastomer |
| JPH0616995A (en) * | 1993-04-19 | 1994-01-25 | Dainippon Ink & Chem Inc | Formation of cured coating film |
| US20070287811A1 (en) * | 2006-06-07 | 2007-12-13 | Joseph Gan | Oligomeric halogenated chain extenders for preparing epoxy resins |
| US20070299163A1 (en) * | 2006-06-21 | 2007-12-27 | Chang Chun Plastics Co., Ltd. | Novel phenolic resin, its preparation and use thereof |
| CN106589319A (en) * | 2016-11-22 | 2017-04-26 | 天津翔盛新材料有限公司 | Four-functional-group super-flexible linear phenolic curing agent dedicated for heavy-duty anticorrosive powder coating, and synthetic method and application thereof |
| WO2017166913A1 (en) * | 2016-04-01 | 2017-10-05 | 厦门大学 | Radiation-resistant fluorine-silicon containing epoxy-resin coating and preparation method thereof |
| CN107629194A (en) * | 2017-10-16 | 2018-01-26 | 六安捷通达新材料有限公司 | A kind of epoxide powder coating heat resistance phenols curing agent and preparation method thereof |
-
2020
- 2020-11-04 CN CN202011218167.7A patent/CN112375210B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4552814A (en) * | 1984-05-21 | 1985-11-12 | The Dow Chemical Company | Advanced epoxy resins having improved impact resistance when cured |
| US4767832A (en) * | 1987-05-29 | 1988-08-30 | Shell Oil Company | Phenolic curing agents for epoxy resins |
| EP0343219A1 (en) * | 1987-11-30 | 1989-11-29 | Isovolta | Use of a solid phenol formaldehyde condensation product as a hardener in epoxy resin mixtures and process for making a powder paint from said mixtures. |
| US5264503A (en) * | 1990-01-29 | 1993-11-23 | Shell Oil Company | Phenol-terminated epoxy resin with functional elastomer |
| JPH0616995A (en) * | 1993-04-19 | 1994-01-25 | Dainippon Ink & Chem Inc | Formation of cured coating film |
| US20070287811A1 (en) * | 2006-06-07 | 2007-12-13 | Joseph Gan | Oligomeric halogenated chain extenders for preparing epoxy resins |
| US20070299163A1 (en) * | 2006-06-21 | 2007-12-27 | Chang Chun Plastics Co., Ltd. | Novel phenolic resin, its preparation and use thereof |
| WO2017166913A1 (en) * | 2016-04-01 | 2017-10-05 | 厦门大学 | Radiation-resistant fluorine-silicon containing epoxy-resin coating and preparation method thereof |
| CN106589319A (en) * | 2016-11-22 | 2017-04-26 | 天津翔盛新材料有限公司 | Four-functional-group super-flexible linear phenolic curing agent dedicated for heavy-duty anticorrosive powder coating, and synthetic method and application thereof |
| CN107629194A (en) * | 2017-10-16 | 2018-01-26 | 六安捷通达新材料有限公司 | A kind of epoxide powder coating heat resistance phenols curing agent and preparation method thereof |
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