CN113831505A - High-gloss self-curing epoxy resin and preparation method and application thereof - Google Patents
High-gloss self-curing epoxy resin and preparation method and application thereof Download PDFInfo
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- CN113831505A CN113831505A CN202111287827.1A CN202111287827A CN113831505A CN 113831505 A CN113831505 A CN 113831505A CN 202111287827 A CN202111287827 A CN 202111287827A CN 113831505 A CN113831505 A CN 113831505A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 54
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000576 coating method Methods 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000004593 Epoxy Substances 0.000 claims abstract description 18
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims abstract description 8
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 E-51 Chemical compound 0.000 claims abstract description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008096 xylene Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000011248 coating agent Substances 0.000 claims description 43
- 238000006735 epoxidation reaction Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002685 polymerization catalyst Substances 0.000 claims description 12
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 11
- 239000011630 iodine Substances 0.000 claims description 11
- 229910052740 iodine Inorganic materials 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 8
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003700 epoxy group Chemical group 0.000 abstract description 4
- 239000002932 luster Substances 0.000 abstract description 3
- 235000011037 adipic acid Nutrition 0.000 abstract description 2
- 239000001361 adipic acid Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 15
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004645 polyester resin Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/145—Compounds containing one epoxy group
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of powder coatings, and particularly relates to a high-gloss self-curing epoxy resin, and a preparation method and application thereof. The high-gloss self-curing epoxy resin provided by the invention is prepared by reacting bisphenol F, allyl glycidyl ether, E-51, isophthalic acid, maleic anhydride, pentaerythritol tetraglycidyl ether, adipic acid and xylene, and oxidizing with hydrogen peroxide to obtain the self-curing epoxy resin with carboxyl and epoxy groups. The epoxy resin material has the acid value of 33-40mgKOH/g, the epoxy equivalent of 1400-1500g/mol, the epoxy resin material has epoxy and carboxyl groups, and the softening point of the resin is lower; and because the carboxyl and the epoxy are uniformly dispersed in the molecular structure, the product has uniform curing rate, high leveling grade and excellent luster.
Description
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to a high-gloss self-curing epoxy resin, and a preparation method and application thereof.
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.
With the development of the powder coating market, powder coatings have become the most common product for metal surface coating. Epoxy polyester powder coatings are most widely used due to their excellent combination of properties. However, most of the current powder coatings are prepared by using polyester and epoxy resin, so that coating products with good performance, such as high-gloss surface and excellent curing impact property, can be obtained only by fully mixing and melting uniformly when preparing the powder coatings. However, since some manufacturers use a single screw extruder, the melt mixing effect is seriously insufficient, and the compatibility between the two is insufficient, so that the batch stability of the prepared powder coating is poor, such as the problems of low gloss and poor curing impact property of the product. Even if a double-screw extruder with good mixing effect is adopted, the polyester resin and the epoxy resin produced in each batch have the problem of insufficient compatibility, so that a coating film with high gloss and high leveling property is difficult to obtain.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a high-gloss self-curing epoxy resin, which can be self-cured to form a film without additionally using polyester resin or other curing agents when in use, and the film has high gloss and high leveling grade;
the second technical problem to be solved by the present invention is to provide a preparation method and application of the high gloss self-curing epoxy resin.
In order to solve the technical problems, the high-gloss self-curing epoxy resin provided by the invention comprises the following components in molar weight:
specifically, the preparation raw materials further comprise a ring-opening polymerization catalyst, and the dosage of the ring-opening polymerization catalyst accounts for 0.5-0.8 wt% of the mass of the bisphenol F.
Specifically, the ring-opening polymerization catalyst comprises triphenylphosphine.
Specifically, the preparation raw material also comprises an epoxidation catalyst, and the dosage of the epoxidation catalyst accounts for 0.2-0.5 wt% of the mass of the bisphenol F.
Specifically, the epoxidation catalyst comprises a mixture of sodium tungstate and benzyltrimethylammonium chloride.
Preferably, the mass ratio of the sodium tungstate to the benzyltrimethylammonium chloride is 1: 0.2-0.4.
The invention also discloses a method for preparing the high-gloss self-curing epoxy resin, which comprises the following steps:
(1) uniformly mixing the bisphenol F, allyl glycidyl ether, E-51, xylene and a ring-opening polymerization catalyst according to the formula ratio, and heating to 90-95 ℃ for heat preservation reaction;
(2) when the amount of free bisphenol F in the reaction system to be detected is less than 1%, adding the maleic anhydride and the pentaerythritol tetraglycidyl ether according to the formula amount, and heating to 110-115 ℃ for chain extension reaction;
(3) when the acid value of the reaction system to be detected is lower than 2mgKOH/g, adding the isophthalic acid with the formula amount to continue the end-capping reaction at the temperature of 110-115 ℃;
(4) when the acid value of the reaction system to be detected reaches 33-40mgKOH/g, cooling to 50-55 ℃, adding the hydrogen peroxide and the epoxidation catalyst according to the formula amount, and carrying out low-temperature epoxidation reaction at 50-55 ℃;
(5) stopping the reaction when the iodine value of the reaction system to be detected is less than 2g/100g and the epoxy equivalent reaches 1400-1500g/mol, and collecting an organic phase for later use;
(6) starting a vacuum program, gradually heating to 110-115 ℃ to remove residual water and solvent, removing the vacuum system when the volatile component to be detected is less than 0.8%, discharging at high temperature while the vacuum system is hot, cooling, crushing and granulating to obtain the product.
Specifically, the step (4) further comprises the step of preparing the hydrogen peroxide into an aqueous hydrogen peroxide solution with a mass concentration of 20-40 wt%.
Specifically, in the step (6), the vacuum degree of the vacuum program is controlled to be-0.098 to-0.099 Mpa.
The invention also discloses application of the high-gloss self-curing epoxy resin in preparation of powder coating.
The invention also discloses a powder coating prepared from the high-gloss self-curing epoxy resin.
The high-gloss self-curing epoxy resin provided by the invention is prepared by reacting bisphenol F, allyl glycidyl ether, E-51, isophthalic acid, maleic anhydride, pentaerythritol tetraglycidyl ether, adipic acid and xylene, oxidizing with hydrogen peroxide when the acid value is 33-40mgKOH/g, and stopping reaction when the iodine value is less than 2g/100g and the epoxy equivalent is 1400-1500g/mol, thus obtaining the self-curing epoxy resin with carboxyl and epoxy groups. The epoxy resin material has an acid value of 33-40mgKOH/g, an epoxy equivalent of 1400-1500g/mol, and the epoxy resin material has epoxy and carboxyl groups, and the softening point of the resin is lower (97-106 ℃); and because the carboxyl and the epoxy are uniformly dispersed in the molecular structure, the product has uniform curing rate, high leveling grade and excellent luster.
The high-gloss self-curing epoxy resin can be directly combined with fillers, auxiliaries and the like to form a powder coating without additionally using polyester resin, can also be self-cured to form a film without additionally using other curing agents, has high gloss and high leveling grade of the film, can meet the application requirements of the powder coating on other conventional performances such as impact and adhesive force, and effectively solves the problems of unsatisfactory gloss and leveling performance of the conventional polyester/epoxy resin mixed powder coating.
Detailed Description
Example 1
The high gloss self-curing epoxy resin of the embodiment is prepared from the following raw materials in molar weight:
sodium tungstate: benzyl trimethyl ammonium chloride ═ 1: 0.2, accounting for 0.2 wt% of the mass of the bisphenol F.
The preparation method of the high-gloss self-curing epoxy resin comprises the following steps:
(1) adding the bisphenol F, allyl glycidyl ether, E-51, xylene and a ring-opening polymerization catalyst into a reaction kettle according to the formula ratio, starting stirring, gradually heating to 90 ℃, and then carrying out heat preservation reaction;
(2) detecting the amount of free bisphenol F in the system by using a liquid spectrum, adding the maleic anhydride and pentaerythritol tetraglycidyl ether in the formula amount into a reaction kettle when the amount of free bisphenol F in the system is lower than 1%, and heating to 110 ℃ for chain extension reaction;
(3) detecting the acid value change of the system, when the acid value of the reaction system is lower than 2mgKOH/g, indicating that the maleic anhydride basically finishes reacting, adding the isophthalic acid with the formula amount, and continuing to perform end capping reaction at 110 ℃;
(4) when the acid value of a reaction system reaches 33-40mgKOH/g, cooling to 50 ℃, adding a hydrogen peroxide aqueous solution with the mass concentration of 20% and prepared by the hydrogen peroxide according to the formula amount and the epoxidation catalyst, and carrying out low-temperature epoxidation reaction at 50 ℃;
(5) detecting the iodine value of the reaction system, stopping the reaction when the iodine value is less than 2g/100g and the epoxy equivalent is 1400-1500g/mol, naturally reducing the temperature to room temperature, standing for layering, removing the water phase, and collecting the organic phase for later use;
(6) starting a vacuum system, and gradually heating to 110 ℃ under negative pressure (keeping-0.098 to-0.099 Mpa) to remove residual water and solvent; and when the volatile matter is less than 0.8 percent, removing the vacuum system, discharging at high temperature while the vacuum system is hot, cooling the resin by using a steel belt with condensed water, and then crushing and granulating to obtain the required high-gloss self-curing epoxy resin.
The epoxy resin prepared in this example was tested as light yellow transparent particles with an acid number of 35mgKOH/g, an epoxy equivalent weight of 1420g/mol, and a softening point of 99 ℃.
Example 2
The high gloss self-curing epoxy resin of the embodiment is prepared from the following raw materials in molar weight:
sodium tungstate: benzyl trimethyl ammonium chloride ═ 1: 0.4, accounting for 0.5 wt% of the mass of the bisphenol F.
The preparation method of the high-gloss self-curing epoxy resin comprises the following steps:
(1) adding the bisphenol F, allyl glycidyl ether, E-51, xylene and a ring-opening polymerization catalyst into a reaction kettle according to the formula ratio, starting stirring, gradually heating to 95 ℃, and then carrying out heat preservation reaction;
(2) detecting the amount of free bisphenol F in the system by using a liquid spectrum, adding the maleic anhydride and pentaerythritol tetraglycidyl ether in the formula amount into a reaction kettle when the amount of free bisphenol F in the system is lower than 1%, and heating to 115 ℃ for chain extension reaction;
(3) detecting the acid value change of the system, when the acid value of the reaction system is lower than 2mgKOH/g, indicating that the maleic anhydride basically finishes reacting, adding the isophthalic acid with the formula amount, and continuing to perform end capping reaction at 115 ℃;
(4) when the acid value of a reaction system reaches 33-40mgKOH/g, cooling to 55 ℃, adding a hydrogen peroxide aqueous solution with the mass concentration of 40% and prepared by the hydrogen peroxide according to the formula amount and the epoxidation catalyst, and carrying out low-temperature epoxidation reaction at 55 ℃;
(5) detecting the iodine value of the reaction system, stopping the reaction when the iodine value is less than 2g/100g and the epoxy equivalent is 1400-1500g/mol, naturally reducing the temperature to room temperature, standing for layering, removing the water phase, and collecting the organic phase for later use;
(6) starting a vacuum system, and gradually heating to 114 ℃ under negative pressure (keeping-0.098 to-0.099 Mpa) to remove residual water and solvent; and when the volatile matter is less than 0.8 percent, removing the vacuum system, discharging at high temperature while the vacuum system is hot, cooling the resin by using a steel belt with condensed water, and then crushing and granulating to obtain the required high-gloss self-curing epoxy resin.
The epoxy resin prepared in this example was tested as light yellow transparent particles with an acid number of 38mgKOH/g, an epoxy equivalent weight of 1492g/mol and a softening point of 104 ℃.
Example 3
The high gloss self-curing epoxy resin of the embodiment is prepared from the following raw materials in molar weight:
sodium tungstate: benzyl trimethyl ammonium chloride ═ 1: 0.3, accounting for 0.4 wt% of the mass of the bisphenol F.
The preparation method of the high-gloss self-curing epoxy resin comprises the following steps:
(1) adding the bisphenol F, allyl glycidyl ether, E-51, xylene and a ring-opening polymerization catalyst into a reaction kettle according to the formula ratio, starting stirring, gradually heating to 92 ℃, and then carrying out heat preservation reaction;
(2) detecting the amount of free bisphenol F in the system by using a liquid spectrum, adding the maleic anhydride and pentaerythritol tetraglycidyl ether in the formula amount into a reaction kettle when the amount of free bisphenol F in the system is lower than 1%, and heating to 112 ℃ for chain extension reaction;
(3) detecting the acid value change of the system, when the acid value of the reaction system is lower than 2mgKOH/g, indicating that the maleic anhydride basically finishes reacting, adding the isophthalic acid with the formula amount, and continuing to perform end capping reaction at 112 ℃;
(4) when the acid value of a reaction system reaches 33-40mgKOH/g, cooling to 52 ℃, adding a hydrogen peroxide aqueous solution with the mass concentration of 30% and prepared by the hydrogen peroxide according to the formula amount and the epoxidation catalyst, and carrying out low-temperature epoxidation reaction at 52 ℃;
(5) detecting the iodine value of the reaction system, stopping the reaction when the iodine value is less than 2g/100g and the epoxy equivalent is 1400-1500g/mol, naturally reducing the temperature to room temperature, standing for layering, removing the water phase, and collecting the organic phase for later use;
(6) starting a vacuum system, and gradually heating to 112 ℃ under negative pressure (keeping-0.098 to-0.099 Mpa) to remove residual water and solvent; and when the volatile matter is less than 0.8 percent, removing the vacuum system, discharging at high temperature while the vacuum system is hot, cooling the resin by using a steel belt with condensed water, and then crushing and granulating to obtain the required high-gloss self-curing epoxy resin.
The epoxy resin prepared in this example was tested as light yellow transparent particles having an acid value of 34mgKOH/g, an epoxy equivalent weight of 1455g/mol and a softening point of 101 ℃.
Example 4
The high gloss self-curing epoxy resin of the embodiment is prepared from the following raw materials in molar weight:
sodium tungstate: benzyl trimethyl ammonium chloride ═ 1: 0.3, accounting for 0.3 wt% of the bisphenol F.
The preparation method of the high-gloss self-curing epoxy resin comprises the following steps:
(1) adding the bisphenol F, allyl glycidyl ether, E-51, xylene and a ring-opening polymerization catalyst into a reaction kettle according to the formula ratio, starting stirring, gradually heating to 92 ℃, and then carrying out heat preservation reaction;
(2) detecting the amount of free bisphenol F in the system by using a liquid spectrum, adding the maleic anhydride and pentaerythritol tetraglycidyl ether in the formula amount into a reaction kettle when the amount of free bisphenol F in the system is lower than 1%, and heating to 112 ℃ for chain extension reaction;
(3) detecting the acid value change of the system, when the acid value of the reaction system is lower than 2mgKOH/g, indicating that the maleic anhydride basically finishes reacting, adding the isophthalic acid with the formula amount, and continuing to perform end capping reaction at 112 ℃;
(4) when the acid value of a reaction system reaches 33-40mgKOH/g, cooling to 52 ℃, adding a hydrogen peroxide aqueous solution with the mass concentration of 30% and prepared by the hydrogen peroxide according to the formula amount and the epoxidation catalyst, and carrying out low-temperature epoxidation reaction at 52 ℃;
(5) detecting the iodine value of the reaction system, stopping the reaction when the iodine value is less than 2g/100g and the epoxy equivalent is 1400-1500g/mol, naturally reducing the temperature to room temperature, standing for layering, removing the water phase, and collecting the organic phase for later use;
(6) starting a vacuum system, and gradually heating to 115 ℃ under negative pressure (keeping-0.098 to-0.099 Mpa) to remove residual water and solvent; and when the volatile matter is less than 0.8 percent, removing the vacuum system, discharging at high temperature while the vacuum system is hot, cooling the resin by using a steel belt with condensed water, and then crushing and granulating to obtain the required high-gloss self-curing epoxy resin.
The epoxy resin prepared in this example was tested as light yellow transparent particles having an acid value of 39mgKOH/g, an epoxy equivalent of 1478g/mol, and a softening point of 102 ℃.
Examples of the experiments
The epoxy resin prepared in the embodiments 1-4 of the invention is respectively taken and prepared into the epoxy resin system powder coating according to the following components, and the specific formula is as follows:
preparation of powder coating: the materials are uniformly mixed according to the formula of the powder coating, and are subjected to high-temperature melt extrusion (the temperature of a screw is controlled at 130-. The powder coating is sprayed on the galvanized iron substrate after surface treatment by adopting an electrostatic spray gun and is solidified at 150 ℃/15min to obtain a coating layer with the film thickness of 80-90 mu m.
Comparative example 1
A conventional commercially available 50/50 type hybrid powder coating was used as comparative example 1. The formula of the powder coating comprises: 300g of E-12 epoxy resin, 300g of 50/50 polyester resin, 180g of barium sulfate, 180g of titanium dioxide, 10g of a leveling agent and 8g of a brightener. The powder coating was prepared as in examples 1-4 above, with the curing conditions: 150 ℃/15 min.
Comparative example 2
The powder coating scheme of this comparative example differs from that of comparative example 1 above only in that the curing conditions are 180 deg.C/15 min.
Comparative example 3
The powder coating scheme of this comparative example differs from that of comparative example 1 described above only in that the powder coating is prepared by extrusion melting using a high miscibility twin screw extruder and curing conditions of 180 ℃/15 min.
The detection of the coating index is carried out according to GB/T21776 2008 'Standard guide for powder coating and coating detection'; the leveling rating is in accordance with JB-T3998-1999 paint leveling scratch test.
The above examples 1-4 and comparative examples 1-3 are powder coating systems and the results of the coating properties are shown in table 1 below.
TABLE 1 coating film Properties
As can be seen from the technical effects of examples 1-4 and comparative examples 1-3 in Table 1, the epoxy resin of the present invention, through the mutual coordination and synergistic effect of the raw material components, can realize self-curing film formation without using polyester resin raw materials and curing agent under the condition of low temperature curing (150 ℃/15 min). The coating formed by the epoxy resin disclosed by the invention is smooth and fine in appearance, high in gloss and up to more than 95%, and excellent in comprehensive performance, and the leveling grades are all 8 grades.
The comparative examples 1 to 3 are all coating films formed by curing common E-12 epoxy resin and mixed 50/50 polyester resin, and the coating film in the comparative example 1 has poor performance because the coating film cannot be fully cured due to the curing at 150 ℃/15 min; the scheme of comparative example 2 can realize full curing by adopting normal high-temperature curing conditions (180 ℃/15min), but the appearance, the luster and the leveling property of the coating are general; comparative example 3 except that normal high-temperature curing conditions (180 ℃/15min) are adopted, the powder coating is prepared by extruding the powder coating by using a double-screw extruder with better mixing effect, and the appearance, leveling, gloss and the like are slightly improved compared with those of comparative example 2, but the powder coating is still inferior to the product of the invention.
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-gloss self-curing epoxy resin is characterized in that the preparation raw materials comprise the following components in molar weight:
2. the high gloss self-curing epoxy resin according to claim 1, wherein the raw material for preparation further comprises a ring-opening polymerization catalyst, and the amount of the ring-opening polymerization catalyst is 0.5 to 0.8 wt% of the bisphenol F.
3. The high gloss self-curing epoxy resin of claim 2, wherein said ring opening polymerization catalyst comprises triphenylphosphine.
4. The high gloss self-curing epoxy resin according to any one of claims 1-3, wherein the raw material for preparation further comprises an epoxidation catalyst, and the amount of the epoxidation catalyst is 0.2-0.5 wt% based on the mass of bisphenol F.
5. The high gloss self-curing epoxy resin of claim 4, wherein the epoxidation catalyst comprises a mixture of sodium tungstate and benzyltrimethylammonium chloride.
Preferably, the mass ratio of the sodium tungstate to the benzyltrimethylammonium chloride is 1: 0.2-0.4.
6. A process for preparing the high gloss self-curing epoxy resin according to any one of claims 1 to 5, comprising the steps of:
(1) uniformly mixing the bisphenol F, allyl glycidyl ether, E-51, xylene and a ring-opening polymerization catalyst according to the formula ratio, and heating to 90-95 ℃ for heat preservation reaction;
(2) when the amount of free bisphenol F in the reaction system to be detected is less than 1%, adding the maleic anhydride and the pentaerythritol tetraglycidyl ether according to the formula amount, and heating to 110-115 ℃ for chain extension reaction;
(3) when the acid value of the reaction system to be detected is lower than 2mgKOH/g, adding the isophthalic acid with the formula amount to continue the end-capping reaction at the temperature of 110-115 ℃;
(4) when the acid value of the reaction system to be detected reaches 33-40mgKOH/g, cooling to 50-55 ℃, adding the hydrogen peroxide and the epoxidation catalyst according to the formula amount, and carrying out low-temperature epoxidation reaction at 50-55 ℃;
(5) stopping the reaction when the iodine value of the reaction system to be detected is less than 2g/100g and the epoxy equivalent reaches 1400-1500g/mol, and collecting an organic phase for later use;
(6) starting a vacuum program, gradually heating to 110-115 ℃ to remove residual water and solvent, removing the vacuum system when the volatile component to be detected is less than 0.8%, discharging at high temperature while the vacuum system is hot, cooling, crushing and granulating to obtain the product.
7. The method for preparing a high gloss self-curing epoxy resin according to claim 6, further comprising the step of preparing the hydrogen peroxide into an aqueous hydrogen peroxide solution having a mass concentration of 20 to 40 wt% in the step (4).
8. The method for preparing a high gloss self-curing epoxy resin according to claim 6 or 7, wherein in the step (6), the vacuum degree of the vacuum process is controlled to be-0.098 to-0.099 Mpa.
9. Use of the high gloss self-curing epoxy resin according to any one of claims 1 to 5 for the preparation of powder coatings.
10. A powder coating prepared from the high gloss self-curing epoxy resin of any one of claims 1 to 5.
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