CN113831505B - 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
- Publication number
- CN113831505B CN113831505B CN202111287827.1A CN202111287827A CN113831505B CN 113831505 B CN113831505 B CN 113831505B CN 202111287827 A CN202111287827 A CN 202111287827A CN 113831505 B CN113831505 B CN 113831505B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- reaction
- gloss
- curing epoxy
- curing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 49
- 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
- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000006735 epoxidation reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 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
- 229910052740 iodine Inorganic materials 0.000 claims description 11
- 239000011630 iodine Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 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
- 238000000034 method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000000576 coating method Methods 0.000 abstract description 43
- 239000011248 coating agent Substances 0.000 abstract description 39
- 239000000843 powder Substances 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 15
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004645 polyester resin Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 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
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011812 mixed powder Substances 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000001038 titanium pigment 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
-
- 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
-
- 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
-
- 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
Abstract
The invention belongs to the technical field of powder coating, and particularly relates to high-gloss self-curing epoxy resin, and a preparation method and application thereof. The high-gloss self-curing epoxy resin is prepared by reacting bisphenol F, allyl glycidyl ether, E-51, isophthalic acid, maleic anhydride, pentaerythritol tetraglycidyl ether, adipic acid and dimethylbenzene and oxidizing with hydrogen peroxide. The acid value of the epoxy resin material is 33-40mgKOH/g, the epoxy equivalent is 1400-1500g/mol, the epoxy resin material itself has epoxy and carboxyl groups, and the softening point of the resin is low; and the carboxyl and the epoxy are very uniformly dispersed in the molecular structure, so that the product has uniform curing rate, high leveling grade and excellent luster.
Description
Technical Field
The invention belongs to the technical field of powder coating, and particularly relates to high-gloss self-curing epoxy resin, and a preparation method and application thereof.
Background
The powder paint is 100% solid powder without organic solvent, and is one kind of environment protecting paint with special coating film formed through heating and with no solvent or water as dispersing medium and air as dispersing medium. The powder coating has the advantages of no VOC, environmental protection, energy saving, high construction efficiency, wide application range and the like, and gradually replaces organic solvent type coating with the advantages of economy, environmental protection, high efficiency, excellent performance and the like, becomes an important development direction in the coating industry, and keeps a faster growth speed all the time.
With the development of the powder coating market, powder coatings have become the most commonly used product for metal surface coating. Epoxy polyester powder coatings are most widely used due to their excellent combination of properties. However, most of the powder coatings at present are prepared by adopting polyester and epoxy resin, and the powder coatings are required to be fully mixed and melted uniformly to obtain coating products with better performance, such as high-gloss surfaces, excellent curing impact performance and the like. However, because a single screw extruder is used by some manufacturers, the melt mixing effect is seriously insufficient, and the prepared powder coating is often poor in batch stability due to insufficient miscibility of the two, for example, the problems of low gloss, poor curing impact property and the like of the product are caused. Even if a twin-screw extruder with good miscibility is adopted, the problem of insufficient compatibility between the polyester resin and the epoxy resin produced in each batch is caused, so that a coating film with high gloss and high leveling is difficult to obtain.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide the high-gloss self-curing epoxy resin, wherein the epoxy resin can be self-cured to form a film without using polyester resin or other curing agents when in use, and the coating film has high gloss and high leveling grade;
the second technical problem to be solved by the 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 disclosed by the invention comprises the following components in parts by mole:
specifically, the preparation raw material also comprises a ring-opening polymerization catalyst, and the dosage of the ring-opening polymerization catalyst accounts for 0.5-0.8wt% of the bisphenol F.
Specifically, the ring-opening polymerization catalyst includes triphenylphosphine.
Specifically, the preparation raw material also comprises an epoxidation catalyst, and the dosage of the epoxidation catalyst accounts for 0.2-0.5wt% 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) Mixing bisphenol F, allyl glycidyl ether, E-51, dimethylbenzene and a ring-opening polymerization catalyst uniformly according to the formula amount, 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 lower than 1%, adding the maleic anhydride and pentaerythritol tetraglycidyl ether with 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 formula amount of isophthalic acid to continue to carry out end-capping reaction at 110-115 ℃;
(4) When the acid value of the detected reaction system reaches 33-40mgKOH/g, cooling to 50-55 ℃, adding the hydrogen peroxide and the epoxidation catalyst in 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 matter is less than 0.8%, discharging at high temperature, cooling, crushing and granulating.
Specifically, in the step (4), the method further comprises the step of preparing the hydrogen peroxide into an aqueous hydrogen peroxide solution with the mass concentration of 20-40 wt%.
Specifically, in the step (6), the vacuum degree of the vacuum procedure is controlled to be-0.098 to-0.099 Mpa.
The invention also discloses application of the high-gloss self-curing epoxy resin in preparing 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 is prepared by reacting bisphenol F, allyl glycidyl ether, E-51, isophthalic acid, maleic anhydride, pentaerythritol tetraglycidyl ether, adipic acid and dimethylbenzene, oxidizing with hydrogen peroxide when the acid value is 33-40mgKOH/g, and stopping the reaction when the iodine value is less than 2g/100g and the epoxy equivalent is 1400-1500 g/mol. The acid value of the epoxy resin material is 33-40mgKOH/g, the epoxy equivalent is 1400-1500g/mol, the epoxy resin material itself has epoxy and carboxyl groups, and the softening point of the resin is low (97-106 ℃); and the carboxyl and the epoxy are very uniformly dispersed in the molecular structure, so that the product has uniform curing rate, high leveling grade and excellent luster.
The high-gloss self-curing epoxy resin can directly form powder coating with filler, auxiliary agent and the like without using polyester resin, can realize self-curing film formation without using other curing agents, has high film gloss and high leveling grade, can meet the application requirements of the powder coating with other conventional properties such as impact, adhesive force and the like, and effectively solves the problem that the conventional polyester/epoxy resin mixed powder coating has unsatisfactory glossiness and leveling property.
Detailed Description
Example 1
The high-gloss self-curing epoxy resin of the embodiment comprises the following raw materials in parts by mole:
sodium tungstate: benzyltrimethylammonium chloride=1: 0.2, accounting for 0.2 weight percent of the bisphenol F.
The preparation method of the high-gloss self-curing epoxy resin comprises the following steps:
(1) Adding bisphenol F, allyl glycidyl ether, E-51, dimethylbenzene and a ring-opening polymerization catalyst in a formula amount into a reaction kettle, 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 a liquid spectrum, when the amount of free bisphenol F in the system is lower than 1%, adding the maleic anhydride and pentaerythritol tetraglycidyl ether with the formula amount into a reaction kettle at the moment, and heating to 110 ℃ for chain extension reaction;
(3) Detecting the change of the acid value of the system, and when the acid value of the reaction system is lower than 2mgKOH/g, indicating that the basic reaction of the maleic anhydride is finished, adding the formula amount of isophthalic acid at the moment, and continuously carrying out end-capping reaction at 110 ℃;
(4) When the acid value of the reaction system reaches 33-40mgKOH/g, cooling to 50 ℃, then adding a formula amount of hydrogen peroxide aqueous solution with the mass concentration of 20% prepared by hydrogen peroxide 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 reaction temperature to room temperature, standing for layering, removing the water phase, and collecting the organic phase for later use;
(6) Starting a vacuum system, 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%, removing the vacuum system, discharging at high temperature while the material is hot, cooling the resin by using a steel belt with condensed water, and crushing and granulating to obtain the required high-gloss self-curing epoxy resin.
The test shows that the epoxy resin prepared in the embodiment is light yellow transparent particles, the acid value is 35mgKOH/g, the epoxy equivalent is 1420g/mol, and the softening point is 99 ℃.
Example 2
The high-gloss self-curing epoxy resin of the embodiment comprises the following raw materials in parts by mole:
sodium tungstate: benzyltrimethylammonium chloride=1: 0.4, accounting for 0.5 weight percent of the bisphenol F.
The preparation method of the high-gloss self-curing epoxy resin comprises the following steps:
(1) Adding bisphenol F, allyl glycidyl ether, E-51, dimethylbenzene and a ring-opening polymerization catalyst in a formula amount into a reaction kettle, 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 a liquid spectrum, when the amount of free bisphenol F in the system is lower than 1%, adding the maleic anhydride and pentaerythritol tetraglycidyl ether with the formula amount into a reaction kettle at the moment, and heating to 115 ℃ for chain extension reaction;
(3) Detecting the change of the acid value of the system, and when the acid value of the reaction system is lower than 2mgKOH/g, indicating that the basic reaction of the maleic anhydride is finished, adding the formula amount of isophthalic acid at the moment, and continuously carrying out end-capping reaction at 115 ℃;
(4) When the acid value of the reaction system reaches 33-40mgKOH/g, cooling to 55 ℃, then adding 40% hydrogen peroxide aqueous solution prepared by the formula amount of hydrogen peroxide 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 reaction temperature to room temperature, standing for layering, removing the water phase, and collecting the organic phase for later use;
(6) Starting a vacuum system, 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%, removing the vacuum system, discharging at high temperature while the material is hot, cooling the resin by using a steel belt with condensed water, and crushing and granulating to obtain the required high-gloss self-curing epoxy resin.
The test shows that the epoxy resin prepared in the embodiment is light yellow transparent particles, the acid value is 38mgKOH/g, the epoxy equivalent is 1492g/mol, and the softening point is 104 ℃.
Example 3
The high-gloss self-curing epoxy resin of the embodiment comprises the following raw materials in parts by mole:
sodium tungstate: benzyltrimethylammonium chloride=1: 0.3, accounting for 0.4 weight percent of the bisphenol F.
The preparation method of the high-gloss self-curing epoxy resin comprises the following steps:
(1) Adding bisphenol F, allyl glycidyl ether, E-51, dimethylbenzene and a ring-opening polymerization catalyst in a formula amount into a reaction kettle, 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 a liquid spectrum, when the amount of free bisphenol F in the system is lower than 1%, adding the maleic anhydride and pentaerythritol tetraglycidyl ether with the formula amount into a reaction kettle at the moment, and heating to 112 ℃ for chain extension reaction;
(3) Detecting the change of the acid value of the system, and when the acid value of the reaction system is lower than 2mgKOH/g, indicating that the basic reaction of the maleic anhydride is finished, adding the formula amount of isophthalic acid at the moment, and continuously carrying out end-capping reaction at 112 ℃;
(4) When the acid value of the reaction system reaches 33-40mgKOH/g, cooling to 52 ℃, then adding 30% hydrogen peroxide aqueous solution prepared by the formula amount of hydrogen peroxide 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 reaction temperature to room temperature, standing for layering, removing the water phase, and collecting the organic phase for later use;
(6) Starting a vacuum system, 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%, removing the vacuum system, discharging at high temperature while the material is hot, cooling the resin by using a steel belt with condensed water, and crushing and granulating to obtain the required high-gloss self-curing epoxy resin.
The test shows that the epoxy resin prepared in the embodiment is light yellow transparent particles, the acid value is 34mgKOH/g, the epoxy equivalent is 1455g/mol, and the softening point is 101 ℃.
Example 4
The high-gloss self-curing epoxy resin of the embodiment comprises the following raw materials in parts by mole:
sodium tungstate: benzyltrimethylammonium chloride=1: 0.3, accounting for 0.3 weight percent of the bisphenol F.
The preparation method of the high-gloss self-curing epoxy resin comprises the following steps:
(1) Adding bisphenol F, allyl glycidyl ether, E-51, dimethylbenzene and a ring-opening polymerization catalyst in a formula amount into a reaction kettle, 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 a liquid spectrum, when the amount of free bisphenol F in the system is lower than 1%, adding the maleic anhydride and pentaerythritol tetraglycidyl ether with the formula amount into a reaction kettle at the moment, and heating to 112 ℃ for chain extension reaction;
(3) Detecting the change of the acid value of the system, and when the acid value of the reaction system is lower than 2mgKOH/g, indicating that the basic reaction of the maleic anhydride is finished, adding the formula amount of isophthalic acid at the moment, and continuously carrying out end-capping reaction at 112 ℃;
(4) When the acid value of the reaction system reaches 33-40mgKOH/g, cooling to 52 ℃, then adding 30% hydrogen peroxide aqueous solution prepared by the formula amount of hydrogen peroxide 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 reaction temperature to room temperature, standing for layering, removing the water phase, and collecting the organic phase for later use;
(6) Starting a vacuum system, 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%, removing the vacuum system, discharging at high temperature while the material is hot, cooling the resin by using a steel belt with condensed water, and crushing and granulating to obtain the required high-gloss self-curing epoxy resin.
The epoxy resin prepared in this example was tested as pale yellow transparent particles, acid value 39mgKOH/g, epoxy equivalent 1478g/mol, and softening point 102 ℃.
Experimental example
The epoxy resins prepared in the examples 1 to 4 of the invention are respectively taken, and the preparation of the powder coating of the epoxy resin system is carried out according to the following components:
preparing a powder paint coating: according to the formula of the powder coating, the materials are evenly mixed, and are subjected to high-temperature melt extrusion (the temperature of a screw is controlled at 130-140 ℃) by a single screw extruder, tabletting and crushing, and then the tablets are crushed and sieved to prepare the powder coating (160-180 meshes). The powder coating is sprayed on the tinplate base material after surface treatment by adopting an electrostatic spray gun, and is solidified at 150 ℃/15min to obtain the coating layer with the film thickness of 80-90 mu m.
Comparative example 1
As comparative example 1, a conventional commercially available 50/50 type mixed powder coating was used. The formula of the powder coating is as follows: 300g of E-12 epoxy resin, 300g of 50/50 polyester resin, 180g of barium sulfate, 180g of titanium pigment, 10g of flatting agent and 8g of brightening agent. The preparation method of the powder coating is the same as that of the previous examples 1-4, and the curing conditions are as follows: 150 ℃/15min.
Comparative example 2
The powder coating protocol described in this comparative example is identical to that described in comparative example 1 above, except that the curing conditions are 180 ℃/15min.
Comparative example 3
The powder coating scheme of this comparative example is identical to that of comparative example 1 described above, except that the powder coating is prepared by extrusion melting using a twin screw extruder with high miscibility and curing conditions of 180 ℃/15min.
Coating index detection is carried out according to GB/T21776-2008 'powder coating and detection Standard guidelines for coating thereof'; the leveling grade is according to JB-T3998-1999 coating leveling scratch determination method.
The coating properties obtained for the powder coating systems of examples 1-4 and comparative examples 1-3 described above are shown in Table 1 below.
TABLE 1 film coating Properties
As can be seen from the technical effects of examples 1-4 and comparative examples 1-3 in Table 1, the epoxy resin according to the present invention can realize self-curing film formation without using a polyester resin raw material and without the presence of a curing agent under the condition of low-temperature curing (150 ℃ C./15 min) by the mutual cooperation and synergistic effect between the raw material components. The coating film formed by the epoxy resin has smooth and fine appearance, high gloss reaching more than 95%, and 8-level leveling grade, and shows excellent comprehensive performance.
While comparative examples 1 to 3 are all coating films obtained by curing common E-12 epoxy resin and mixed 50/50 polyester resin, the scheme in comparative example 1 is poor in coating performance due to insufficient curing due to the fact that 150 ℃/15min is adopted for curing; in the scheme of comparative example 2, although the full curing can be realized by adopting normal high-temperature curing conditions (180 ℃/15 min), the appearance and luster of the coating are general; comparative example 3, except for adopting normal high temperature curing conditions (180 ℃/15 min), adopts a double screw extruder with better miscibility effect for extrusion to prepare powder coating, and the appearance, leveling, gloss and the like are slightly improved compared with comparative example 2, but still worse than the product of the invention.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (6)
1. The preparation method of the high-gloss self-curing epoxy resin is characterized in that the preparation raw materials comprise the following components in molar quantity:
the preparation raw materials also comprise a ring-opening polymerization catalyst and an epoxidation catalyst, wherein the dosage of the ring-opening polymerization catalyst accounts for 0.5-0.8wt% of the bisphenol F; the dosage of the epoxidation catalyst accounts for 0.2 to 0.5 weight percent of the bisphenol F;
the preparation method comprises the following steps:
(1) Mixing bisphenol F, allyl glycidyl ether, E-51, dimethylbenzene and a ring-opening polymerization catalyst uniformly according to the formula amount, 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 lower than 1%, adding the maleic anhydride and pentaerythritol tetraglycidyl ether with 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 formula amount of isophthalic acid to continue to carry out end-capping reaction at 110-115 ℃;
(4) When the acid value of the detected reaction system reaches 33-40mgKOH/g, cooling to 50-55 ℃, adding the hydrogen peroxide and the epoxidation catalyst in 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 matter is less than 0.8%, discharging at high temperature, cooling, crushing and granulating.
2. The method for preparing a high-gloss self-curing epoxy resin according to claim 1, wherein the ring-opening polymerization catalyst is triphenylphosphine.
3. The method for preparing a high-gloss self-curing epoxy resin according to claim 1, wherein the epoxidation catalyst is a mixture of sodium tungstate and benzyl trimethyl ammonium chloride.
4. The method for preparing the high-gloss self-curing epoxy resin according to claim 3, wherein the mass ratio of sodium tungstate to benzyl trimethyl ammonium chloride is 1:0.2-0.4.
5. The method for producing a high-gloss self-curing epoxy resin according to claim 1, further comprising the step of preparing the hydrogen peroxide into an aqueous hydrogen peroxide solution having a mass concentration of 20 to 40% by weight in the step (4).
6. The method for producing a high-gloss self-curing epoxy resin according to claim 1, wherein in said step (6), the vacuum degree of said vacuum program is controlled to be-0.098 to-0.099 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111287827.1A CN113831505B (en) | 2021-11-02 | 2021-11-02 | High-gloss self-curing epoxy resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111287827.1A CN113831505B (en) | 2021-11-02 | 2021-11-02 | High-gloss self-curing epoxy resin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113831505A CN113831505A (en) | 2021-12-24 |
| CN113831505B true CN113831505B (en) | 2024-02-06 |
Family
ID=78966889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111287827.1A Active CN113831505B (en) | 2021-11-02 | 2021-11-02 | High-gloss self-curing epoxy resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113831505B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB896711A (en) * | 1958-09-08 | 1962-05-16 | Hudson Foam Plastics Corp | Process for reducing the acid number of polyesters |
| US6114489A (en) * | 1997-03-27 | 2000-09-05 | Herberts Gmbh | Reactive hyperbranched polymers for powder coatings |
| JP2013112649A (en) * | 2011-11-29 | 2013-06-10 | Showa Denko Kk | Method for producing multivalent glycidyl compound |
| CN104312235A (en) * | 2014-10-14 | 2015-01-28 | 苏州洛特兰新材料科技有限公司 | Anti-corrosion acrylic acid epoxy resin powder paint for ceramic |
| WO2015080059A1 (en) * | 2013-11-26 | 2015-06-04 | 昭和電工株式会社 | Liquid epoxy resin composition |
| JP2017132798A (en) * | 2017-04-10 | 2017-08-03 | 協立化学産業株式会社 | Peroxide and thermosetting resin composition |
| CN108329766A (en) * | 2018-01-31 | 2018-07-27 | 江苏佳铝实业股份有限公司 | Surface layer is from exfoliated special antifouling powdery paints of building aluminum alloy pattern plate and preparation method thereof |
| CN112321799A (en) * | 2020-11-04 | 2021-02-05 | 黄山新佳精细材料有限公司 | Epoxy resin for high-hardness and low-temperature curing type powder coating and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2002226010A1 (en) * | 2000-12-14 | 2002-06-24 | Dow Global Technologies Inc. | Epoxy resins and process for making the same |
-
2021
- 2021-11-02 CN CN202111287827.1A patent/CN113831505B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB896711A (en) * | 1958-09-08 | 1962-05-16 | Hudson Foam Plastics Corp | Process for reducing the acid number of polyesters |
| US6114489A (en) * | 1997-03-27 | 2000-09-05 | Herberts Gmbh | Reactive hyperbranched polymers for powder coatings |
| JP2013112649A (en) * | 2011-11-29 | 2013-06-10 | Showa Denko Kk | Method for producing multivalent glycidyl compound |
| WO2015080059A1 (en) * | 2013-11-26 | 2015-06-04 | 昭和電工株式会社 | Liquid epoxy resin composition |
| CN104312235A (en) * | 2014-10-14 | 2015-01-28 | 苏州洛特兰新材料科技有限公司 | Anti-corrosion acrylic acid epoxy resin powder paint for ceramic |
| JP2017132798A (en) * | 2017-04-10 | 2017-08-03 | 協立化学産業株式会社 | Peroxide and thermosetting resin composition |
| CN108329766A (en) * | 2018-01-31 | 2018-07-27 | 江苏佳铝实业股份有限公司 | Surface layer is from exfoliated special antifouling powdery paints of building aluminum alloy pattern plate and preparation method thereof |
| CN112321799A (en) * | 2020-11-04 | 2021-02-05 | 黄山新佳精细材料有限公司 | Epoxy resin for high-hardness and low-temperature curing type powder coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113831505A (en) | 2021-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109180922B (en) | Low-temperature curing type polyester resin and preparation method and application thereof | |
| CN110964416B (en) | Weather-resistant wear-resistant polyester resin, powder coating and preparation method thereof | |
| CN109207030B (en) | Polyester resin for high-gloss powder coating and preparation method and application thereof | |
| CN112321799B (en) | Epoxy resin for high-hardness and low-temperature curing type powder coating and preparation method thereof | |
| CN109880072B (en) | Self-catalyzed fast-curing pure polyester resin and preparation method and application thereof | |
| JP2003012763A (en) | Epoxy resin, epoxy resin composition including the same, and cured product of the composition | |
| CN110437711B (en) | Epoxy resin for low-temperature curing type B68 extinction powder and preparation method and application thereof | |
| CN114573820B (en) | Polyester resin for weather-resistant paint | |
| CN110982319A (en) | Outdoor pure polyester/TGIC powder coating system extremely-low gloss delustering agent and preparation method thereof | |
| CN113831505B (en) | High-gloss self-curing epoxy resin and preparation method and application thereof | |
| CN108503814B (en) | Epoxidized polyester resin and preparation method and application thereof | |
| CN112521591B (en) | Polyester resin with lasting high temperature resistance and excellent hardness for powder coating and preparation method thereof | |
| CN111944137B (en) | Epoxidized polyester resin for weather-resistant high-impact-resistance powder coating and preparation method thereof | |
| CN113372544A (en) | Polyester resin with excellent low-temperature impact resistance for powder coating and preparation method thereof | |
| CN112552497A (en) | High-hydroxyl-value polyester resin for extinction type powder coating and preparation method and application thereof | |
| CN112048057A (en) | Epoxy resin, application and high-leveling ultralow-temperature curing type pure powder coating | |
| CN109181483B (en) | Extinction curing agent for epoxy resin powder coating and preparation method and application thereof | |
| CN111748082A (en) | Special high-performance carboxyl-terminated polyester resin for powder coating and synthesis method thereof | |
| CN114181384B (en) | Polyester resin for low-cost, pinhole-resistant and high-hardness HAA system and preparation method thereof | |
| CN109111783B (en) | Curing agent for pure polyester powder coating system and preparation method thereof | |
| CN111440296B (en) | Water-boiling-resistant outdoor polyester resin and preparation method thereof | |
| CN111607075B (en) | High-pressure-resistant poached and acidic-salt-fog-resistant polyester resin for powder and preparation method thereof | |
| CN109503823B (en) | Low-temperature curing type polyester resin and preparation method and application thereof | |
| CN113501934A (en) | Epoxy resin for self-leveling low-temperature curing powder coating and preparation method thereof | |
| CN115197397B (en) | Epoxy resin for low-light powder coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |