CN112375210B - 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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- 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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- 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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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 ZL 20161103978.4 adopts E-51 epoxy resin and dihydrazide compound for modification, and then obtains phenol curing agent with bisphenol A end capping mode, although the functionality of the product can be improved, some defects are brought, such as poor heat resistance of dihydrazide structure substance, easy yellowing at high temperature and damage, and simultaneously, as the molecular weight is too large, the number average molecular weight reaches about 6000, the chain segment is soft, the end group activity is low, and the phenol curing agent can not be used in the fields with high requirements on high temperature resistance and hardness.
The Chinese patent ZL201710962292.0 adopts the 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 powder coating of a phenolic curing agent system) 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 according to the 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 hours;
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 a vacuum system, adding resorcinol diglycidyl ether, 1, 6-hexanediol diglycidyl ether and a catalyst according to the formula amount, and continuously heating to 115-125 ℃ to carry out chain extension reaction for 2-5 hours;
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 1-3h;
E. stopping reaction when the epoxy equivalent of the resin is more than 2000g/mol and the hydroxyl equivalent is 450-500g/mol, washing with hot water, then removing the water phase by layers, decompressing and dehydrating at 130-140 ℃, discharging at high temperature when 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 or more times by adding hot water at 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-0.096 MP to-0.1 MPa, and is preferably-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 weight 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 of which are linked by ether bonds, high temperature resistance and gasoline resistance, high hardness and impact resistance, high hydroxyl-terminated 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 with E-12 epoxy resin at low temperature (160 ℃/20 min).
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 4-8h;
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 a vacuum system, adding resorcinol diglycidyl ether, 1, 6-hexanediol diglycidyl ether and a catalyst according to the formula amount, and continuously heating to 115-125 ℃ to carry out chain extension reaction for 2-5 hours;
D. when the epoxy equivalent of the reaction system reaches 300-360g/mol, heating to 135-140 ℃, and adding the bisphenol A with the formula amount for end capping reaction for 1-3h;
E. stopping reaction when the epoxy equivalent of the resin is more than 2000g/mol and the hydroxyl equivalent is 450-500g/mol, washing with hot water, then removing the water phase by layers, decompressing and dehydrating at 130-140 ℃, discharging at high temperature when 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 using amount of the triphenylphosphine is 0.06 percent of the molar using 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 examples 1 to 4 were extruded at a low temperature (screw temperature controlled at 100 to 110 ℃) by a twin-screw extruder according to the following formulation of epoxy resin powder coating, and then tabletted and crushed, and the tablets were pulverized and sieved to prepare powder coating (160 to 180 mesh). 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 825g/mol.
Comparative example 1
The product of example 1 of ZL 20161103978.4 was used as comparative example 1 in place of the phenolic curing agent of the present invention. The coating formula is ZL 20161103978.4, 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 the invention was replaced by the product of example 1 of 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 mu m.
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 coating index detection is carried out according to GB/T21776-2008 'Standard guidelines for powder coating and coating detection';
the hardness test is carried out according to GB/T6739-2006 paint film hardness determination by a color paint and varnish pencil method, the pencil hardness parameter is 5B-4B-3B-2B-B-HB-F-H-2H-3H-4H-5H, and the hardness grade gradually increases from left to right;
the high temperature resistance test is carried out according to the method of standard 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 the standard GB/T1734-1993 test for gasoline resistance of paint films, 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 ℃/20 min) 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 ℃/48 h) 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 formulations 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 the high-temperature curing conditions (200 ℃/15 min) to the low-temperature curing conditions (160 ℃/20 min) used in the invention, the powder coating formulations cannot realize full curing, so that the conventional properties such as impact resistance (50 cm) and forward and backward impact cannot pass smoothly, the appearance and the gloss of the coating film are poor, and the phenolic curing agents in the comparative examples 1 and 2 cannot be used in a low-temperature curing system.
Claims (5)
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:
catalyst, its content is 0.05-0.1% of the mol content of p-cresol; and
a pH adjusting agent;
the catalyst is triphenylphosphine;
the pH regulator comprises a concentrated ammonia water solution with the mass concentration of 25%;
the formaldehyde is a formaldehyde water solution with the formaldehyde mass concentration of 35%;
the preparation method of the phenolic curing agent comprises the following steps:
A. adding p-cresol, formaldehyde and 2, 6-dimethylphenol according to the 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 hours;
B. monitoring the viscosity of the reaction system, stopping the reaction when the viscosity of the reaction mixture reaches 3000-3500 mpa.s at 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 a vacuum system, adding resorcinol diglycidyl ether, 1, 6-hexanediol diglycidyl ether and a catalyst according to the formula amount, and continuously heating to 115-125 ℃ to carry out chain extension reaction for 2-5 hours;
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 1-3h;
E. stopping the reaction when the epoxy equivalent of the resin is more than 2000g/mol and the hydroxyl equivalent is 450-500g/mol, washing with hot water, then removing the water phase by layers, decompressing and dehydrating at 130-140 ℃, discharging at high temperature when the resin is hot, cooling the resin, and then crushing and granulating;
wherein the phenolic curing agent prepared has a hydroxyl equivalent weight of 450-500 g/mol.
2. The method for preparing phenolic curing agent according to claim 1, 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.
3. The phenolic curing agent prepared by the method for preparing a phenolic curing agent for epoxy resin powder coating according to claim 1 or 2, the phenolic curing agent having a hydroxyl equivalent weight of 450 to 500 g/mol.
4. The phenolic curing agent of claim 3, which has a softening point of 83 to 90 ℃.
5. An epoxy resin powder coating prepared by using the phenolic curing agent of claim 3 or 4.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0616995A (en) * | 1993-04-19 | 1994-01-25 | Dainippon Ink & Chem Inc | Formation of cured coating film |
Family Cites Families (9)
| 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 |
| EP0343219B1 (en) * | 1987-11-30 | 1993-03-03 | ISOVOLTAÖsterreichische IsolierstoffwerkeAktiengesellschaft | 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 |
| US7919567B2 (en) * | 2006-06-07 | 2011-04-05 | Dow Global Technologies Llc | Oligomeric halogenated chain extenders for preparing epoxy resins |
| TWI324164B (en) * | 2006-06-21 | 2010-05-01 | Chang Chun Plastics Co Ltd | Novel phenolic resin, its preparation and its use |
| CN105778717A (en) * | 2016-04-01 | 2016-07-20 | 厦门大学 | Fluorine-silicone containing epoxy resin radiation-resistant coating and preparation method thereof |
| CN106589319B (en) * | 2016-11-22 | 2018-10-12 | 天津翔盛新材料有限公司 | A kind of super flexible linear phenols curing agent of the special four-functional group of double antiseptic powder coating and synthetic method and application |
| CN107629194B (en) * | 2017-10-16 | 2020-05-19 | 六安捷通达新材料有限公司 | Heat-resistant phenol curing agent for epoxy powder coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0616995A (en) * | 1993-04-19 | 1994-01-25 | Dainippon Ink & Chem Inc | Formation of cured coating film |
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