CN111234178A - Self-emulsifying water-based epoxy resin curing agent and preparation method thereof - Google Patents
Self-emulsifying water-based epoxy resin curing agent and preparation method thereof Download PDFInfo
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- CN111234178A CN111234178A CN202010242408.5A CN202010242408A CN111234178A CN 111234178 A CN111234178 A CN 111234178A CN 202010242408 A CN202010242408 A CN 202010242408A CN 111234178 A CN111234178 A CN 111234178A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 101
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 101
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 239000011261 inert gas Substances 0.000 claims abstract description 17
- 229920013822 aminosilicone Polymers 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 14
- -1 aminomethylsiloxane Chemical class 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims 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 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 238000009413 insulation Methods 0.000 abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 24
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 21
- 239000004593 Epoxy Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000005028 tinplate Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920006334 epoxy coating Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
-
- 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
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1472—Fatty acids
-
- 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
-
- 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
-
- 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
- C09D5/08—Anti-corrosive paints
-
- 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
Abstract
The invention discloses a self-emulsifying water-based epoxy resin curing agent, which comprises the following components: 1-10 parts of amino silicone oil, 20-30 parts of epoxy resin, 0.01-5 parts of reaction auxiliary agent, 120-250 parts of solvent and 1-10 parts of end-capping agent. Also discloses a preparation method of the curing agent, which comprises the following steps: firstly, dissolving amino silicone oil in a solvent, adding a reaction auxiliary agent, uniformly stirring, dropwise adding a mixed solution of epoxy resin and the solvent at a constant speed under the condition of 60-80 ℃ and an inert gas atmosphere, and continuing to react after dropwise adding is finished; continuously dropwise adding a mixed solution of an end-capping reagent and a solvent at a constant speed to perform end-capping reaction; and finally, adding a regulator, and distilling under reduced pressure to obtain the product. The self-emulsifying water-based epoxy resin curing agent has self-emulsifying and defoaming performances, can have excellent curing performance on different water-based epoxy resins, and can ensure that the cured epoxy resin film has good performances such as heat resistance, weather resistance, electric insulation, chemical resistance, hydrophobicity and the like.
Description
Technical Field
The invention relates to the technical field of epoxy resin curing, in particular to a self-emulsifying water-based epoxy resin curing agent and a preparation method thereof.
Background
The epoxy resin coating has excellent performance and is widely applied in the coating industry. However, the solvent-based epoxy coating contains an organic solvent which brings harm to ecological environment and human beings, so that the pollution-free green environment-friendly water-based epoxy coating is a later trend. In recent years, the research on aqueous epoxy resins has been increasing, and most of the aqueous epoxy resins introduce hydrophilic groups into the main structure of the resin, which causes epoxy group loss, resulting in poor curing effect of the epoxy resin. Therefore, it is of great significance to realize the water-based epoxy resin by synthesizing the self-emulsifying water-based epoxy curing agent.
Most of the traditional waterborne epoxy curing agents are organic amine modified epoxy ionic epoxy curing agents, and the curing performance is unstable. Therefore, the nonionic silicon-containing self-emulsifying aqueous epoxy curing agent is the direction of the future.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a self-emulsifying water-based epoxy resin curing agent which has self-emulsifying and defoaming performances, can have excellent curing performance for different water-based epoxy resins, and can enable the cured epoxy resin film to have good performances such as heat resistance, weather resistance, electric insulation, chemical resistance, water repellency and the like.
The invention also aims to provide a preparation method of the self-emulsifying water-based epoxy resin curing agent, which is simple and feasible and is suitable for large-scale industrial production.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme.
The first technical scheme is as follows:
a self-emulsifying water-based epoxy resin curing agent comprises the following raw material components: 1-10 parts of amino silicone oil, 20-30 parts of epoxy resin, 0.01-5 parts of reaction auxiliary agent, 120-250 parts of solvent and 1-10 parts of end-capping agent.
The first technical scheme of the invention has the characteristics and further improvement that:
preferably, the amino silicone oil comprises at least one of aminomethyl silicone, polydimethyl siloxane, and bisaminopolydimethyl siloxane.
Preferably, the epoxy resin includes at least one of a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, a glycidyl amine epoxy resin, a linear aliphatic epoxy resin, and an alicyclic epoxy resin.
Preferably, the glycidyl ether type epoxy resin includes bisphenol a type epoxy resin, tetrabromobisphenol a type epoxy resin, hydrogenated bisphenol a type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.
Preferably, the reaction auxiliary agent comprises one or two of hexadecyl trimethyl ammonium chloride, ethylenediamine, dicyandiamide, triethylamine and ethanolamine.
Preferably, the end-capping agent comprises at least one of glycidyl methacrylate, butyl glycidyl ether, phenyl glycidyl ether, and alkyl glycidyl ether.
Preferably, the solvent comprises at least one of propylene glycol ethyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, and ethylene glycol methyl ether.
The second technical scheme is as follows:
a preparation method of a self-emulsifying water-based epoxy resin curing agent comprises the following steps:
step 1, dissolving amino silicone oil in a solvent, adding a reaction auxiliary agent, stirring uniformly, dropwise adding a mixed solution of epoxy resin and the solvent at a constant speed under the condition of 60-80 ℃ and an inert gas atmosphere, and continuously reacting for 2-3 hours at the temperature of 70-85 ℃ after dropwise adding;
step 2, continuously dripping the mixed solution of the end-capping reagent and the solvent at a constant speed at the temperature of 75-85 ℃ and under the inert gas atmosphere, carrying out end-capping reaction for 0.5-1.5h, continuously reacting for 2-3h, and then cooling to 60-70 ℃;
and 3, adding a regulator, and distilling under reduced pressure to obtain the self-emulsifying water-based epoxy resin curing agent.
The second technical scheme of the invention is characterized by further improvement:
preferably, in step 1, the amino silicone oil is dissolved in a solvent, and the amount of the solvent is 50-100 parts.
Preferably, in step 1, the epoxy resin and the solvent are mixed, wherein the epoxy resin is used in an amount of 20-30 parts, and the solvent is used in an amount of 50-100 parts.
Preferably, in step 2, the amount of the end-capping reagent is 1-10 parts and the amount of the solvent is 20-50 parts.
Preferably, in step 3, the regulator is citric acid.
Further preferably, the citric acid is used in an amount of 0.1 to 10 parts.
Preferably, in step 3, the reduced pressure distillation conditions are as follows: the vacuum degree is 2-50kPa, and the temperature is 40-90 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the self-emulsifying waterborne epoxy resin curing agent provided by the invention introduces the amino silicone oil structure into the main chain of the curing agent molecule, reserves the active amino group while introducing the silicon-oxygen bond structure, has high curing activity, and is suitable for various waterborne epoxy resins.
The self-emulsifying water-based epoxy resin curing agent is liquid at room temperature, is colorless and transparent, and has self-emulsifying and defoaming properties; and because the amino silicone oil modified epoxy resin has the advantages of large molecular weight, high boiling point and difficult volatilization, no pollution is caused in the using process.
The epoxy resin coating film cured by the self-emulsifying water-based epoxy resin curing agent has good performances such as heat resistance, weather resistance, electric insulation, chemical resistance, water repellency and the like.
Detailed Description
Embodiments of the present invention will be described in detail with reference to the following examples, and it is apparent that the described examples are only a part of the examples of the present invention, and not all of the examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the self-emulsifying water-based epoxy resin curing agent comprises the following steps:
step 1, dissolving 1 part of aminomethyl siloxane in 50 parts of propylene glycol ethyl ether, adding 0.15 part of reaction auxiliary agent ethylenediamine, uniformly stirring, dropwise adding a mixed solution consisting of 20 parts of E-51 epoxy resin and 50 parts of propylene glycol ethyl ether at a constant speed under the condition of 60 ℃ and an inert gas atmosphere, and continuously reacting for 3 hours at 70 ℃ after dropwise adding is finished;
step 2, continuously dripping a mixed solution consisting of 1 part of end capping agent glycidyl methacrylate and 20 parts of propylene glycol ethyl ether at a constant speed at 75 ℃ in an inert gas atmosphere, carrying out end capping reaction for 0.5h, continuously reacting for 2h, and then cooling to 60 ℃;
step 3, adding 0.1 part of citric acid to adjust the stability of the emulsion, and carrying out reduced pressure distillation under the conditions of vacuum degree of 2kPa and temperature of 40 ℃ to remove the solvent and free impurities;
and finally, adding 80 parts of deionized water, stirring and dispersing to obtain the self-emulsifying water-based epoxy resin curing agent with the solid content of 40%.
Example 2
The preparation method of the self-emulsifying water-based epoxy resin curing agent comprises the following steps:
step 1, dissolving 5 parts of amino polydimethylsiloxane in 80 parts of propylene glycol ethyl ether, adding 0.15 part of reaction auxiliary agent triethylamine, uniformly stirring, dropwise adding a mixed solution consisting of 10 parts of E-44 epoxy resin, 10 parts of E-51 epoxy resin and 50 parts of propylene glycol ethyl ether at a constant speed under the condition of 70 ℃ and in an inert gas atmosphere, and continuously reacting for 3 hours at 70 ℃ after dropwise adding;
step 2, continuously dripping a mixed solution consisting of 2 parts of end capping agent butyl glycidyl ether and 20 parts of propylene glycol ethyl ether at a constant speed under the condition of 75 ℃ and the inert gas atmosphere, carrying out end capping reaction for 1 hour, continuously reacting for 2 hours, and then cooling to 65 ℃;
step 3, adding 1 part of citric acid to adjust the stability of the emulsion, and carrying out reduced pressure distillation under the conditions of vacuum degree of 10kPa and temperature of 50 ℃ to remove the solvent and free impurities;
and finally, adding 90 parts of deionized water, and stirring and dispersing to obtain the self-emulsifying water-based epoxy resin curing agent with the solid content of 35%.
Example 3
The preparation method of the self-emulsifying water-based epoxy resin curing agent comprises the following steps:
step 1, dissolving 5 parts of amino polydimethylsiloxane and 5 parts of bisamino polydimethylsiloxane in 100 parts of dipropylene glycol methyl ether, adding 0.1 part of triethylamine and 0.2 part of ethylenediamine, uniformly stirring, dropwise adding a mixed solution consisting of 20 parts of E-51 epoxy resin, 10 parts of E-20 epoxy resin, 50 parts of propylene glycol ethyl ether and 50 parts of propylene glycol butyl ether at a constant speed under the condition of 80 ℃ and in an inert gas atmosphere, and continuously reacting for 2 hours at 85 ℃ after dropwise adding;
step 2, continuously dripping a mixed solution consisting of 3 parts of end capping agent butyl glycidyl ether and 20 parts of propylene glycol ethyl ether at a constant speed under the condition of 85 ℃ and the atmosphere of inert gas, carrying out end capping reaction for 1 hour, continuously reacting for 2 hours, and then cooling to 65 ℃;
step 3, adding 1 part of citric acid to adjust the stability of the emulsion, and carrying out reduced pressure distillation under the conditions of vacuum degree of 10kPa and temperature of 50 ℃ to remove the solvent and free impurities;
and finally, adding 90 parts of deionized water, stirring and dispersing to obtain the self-emulsifying water-based epoxy resin curing agent with the solid content of 38%.
Example 4
The preparation method of the self-emulsifying water-based epoxy resin curing agent comprises the following steps:
step 1, dissolving 5 parts of aminomethyl siloxane in 50 parts of propylene glycol ethyl ether and 30 parts of dipropylene glycol methyl ether, adding 0.3 part of hexadecyl trimethyl ammonium chloride, uniformly stirring, dropwise adding a mixed solution consisting of 20 parts of E-44 epoxy resin and 50 parts of propylene glycol ethyl ether at a constant speed under the condition of 70 ℃ and an inert gas atmosphere, and continuously reacting for 2 hours at the condition of 80 ℃ after dropwise adding;
step 2, continuously dripping a mixed solution consisting of 2 parts of end capping agent phenyl glycidyl ether, 3 parts of methacrylic acid glycidyl ether and 20 parts of propylene glycol ethyl ether at a constant speed at the temperature of 80 ℃ and in an inert gas atmosphere, carrying out end capping reaction for 1.5h, continuously reacting for 3h, and then cooling to 70 ℃;
step 3, adding 4 parts of citric acid to adjust the stability of the emulsion, and distilling under reduced pressure at the vacuum degree of 50kPa and the temperature of 40 ℃ to remove the solvent and free impurities;
and finally, adding 80 parts of deionized water, and stirring and dispersing to obtain the self-emulsifying water-based epoxy resin curing agent with the solid content of 35%.
Example 5
The preparation method of the self-emulsifying water-based epoxy resin curing agent comprises the following steps:
step 1, dissolving 10 parts of aminomethyl siloxane in 100 parts of propylene glycol ether, adding 0.1 part of hexadecyl trimethyl ammonium chloride and 0.2 part of dicyandiamide, uniformly stirring, dropwise adding a mixed solution consisting of 30 parts of hydrogenated bisphenol A epoxy resin and 100 parts of propylene glycol ether at a constant speed under the condition of 70 ℃ and an inert gas atmosphere, and continuously reacting for 3 hours at 80 ℃ after dropwise adding is finished;
step 2, continuously dripping a mixed solution consisting of 2 parts of end capping agent phenyl glycidyl ether, 4 parts of alkyl glycidyl ether and 20 parts of propylene glycol ethyl ether at a constant speed at 85 ℃ in an inert gas atmosphere, carrying out end capping reaction for 1.5h, continuously reacting for 3h, and then cooling to 70 ℃;
step 3, adding 4 parts of citric acid to adjust the stability of the emulsion, and distilling under reduced pressure at the vacuum degree of 30kPa and the temperature of 50 ℃ to remove the solvent and free impurities;
and finally, adding 100 parts of deionized water, stirring and dispersing to obtain the self-emulsifying water-based epoxy resin curing agent with the solid content of 35%.
Example 6
The preparation method of the self-emulsifying water-based epoxy resin curing agent comprises the following steps:
step 1, dissolving 6 parts of aminomethyl siloxane in 80 parts of ethylene glycol monomethyl ether, adding 0.01 part of ethanolamine, uniformly stirring, dropwise adding a mixed solution consisting of 30 parts of E-20 epoxy resin and 50 parts of ethylene glycol monomethyl ether at a constant speed under the condition of 60 ℃ and an inert gas atmosphere, and continuously reacting for 2 hours at 75 ℃ after dropwise adding;
step 2, continuously dripping a mixed solution consisting of 1 part of end capping agent phenyl glycidyl ether and 50 parts of ethylene glycol methyl ether at a constant speed under the condition of 75 ℃ and the inert gas atmosphere, carrying out end capping reaction for 0.5h, continuously reacting for 2h, and then cooling to 60 ℃;
step 3, adding 0.1 part of citric acid to adjust the stability of the emulsion, and carrying out reduced pressure distillation under the conditions of vacuum degree of 20kPa and temperature of 60 ℃ to remove the solvent and free impurities;
and finally, adding 80 parts of deionized water, stirring and dispersing to obtain the self-emulsifying water-based epoxy resin curing agent with the solid content of 45%.
Taking the self-emulsifying waterborne epoxy resin curing agent prepared in the above example 1, curing different waterborne epoxy resins, and the specific examples are as follows:
example 7
30 parts of waterborne epoxy curing agent, NPED-20100 parts of waterborne epoxy resin and 3 parts of accelerant imidazole, uniformly coating the mixture on a treated 150mmxl00mm tinplate template after stirring, putting the surface-dried film into an oven, and drying for lh at 80 ℃ and curing for lh at 150 ℃.
The film forming properties are shown in Table 1:
TABLE 1
| Hardness of pencil | 2H |
| Adhesion force | 1 |
| Contact angle | 105° |
| Colour(s) | Colorless and colorless |
| Flatness of | Is smooth and smooth |
| Light transmittance | Is transparent |
Example 8
30 parts of waterborne epoxy curing agent, NPEW-290W 60100 parts of waterborne epoxy resin and 3 parts of accelerant imidazole, wherein the waterborne epoxy curing agent, the NPEW-290W 60100 parts of waterborne epoxy resin and the accelerant imidazole are uniformly coated on a treated 150mmxl00mm tinplate template after being stirred, and the film which reaches surface drying is placed into an oven to be dried for lh at the temperature of 80 ℃ and is cured for lh at the temperature of 150 ℃.
The film forming properties are shown in Table 2:
TABLE 2
| Hardness of pencil | 4H |
| Adhesion force | 2 |
| Contact angle | 90° |
| Colour(s) | Colorless and colorless |
| Flatness of | Is smooth and smooth |
| Light transmittance | Is transparent |
Example 9
30 parts of water-based epoxy curing agent, 3903-2100 parts of water-based epoxy resin PZ and 3 parts of accelerant imidazole, uniformly coating the mixture on a treated 150mmxl00mm tinplate template after stirring, putting the surface-dried film into an oven, and drying for lh at the temperature of 80 ℃ and curing for lh at the temperature of 150 ℃.
The film forming properties are shown in Table 3:
TABLE 3
| Hardness of pencil | 6H |
| Adhesion force | 0 |
| Contact angle | 120° |
| Colour(s) | Colorless and colorless |
| Flatness of | Is smooth and smooth |
| Light transmittance | Is transparent |
Example 10
30 parts of water-based epoxy curing agent, 3907-1100 parts of water-based epoxy resin PZ and 3 parts of accelerant imidazole, uniformly coating the mixture on a treated 150mmxl00mm tinplate template after stirring, putting the surface-dried film into an oven, and drying for lh at the temperature of 80 ℃ and curing for lh at the temperature of 150 ℃.
The film forming properties are shown in Table 4:
TABLE 4
Example 11
30 parts of waterborne epoxy curing agent, 3 parts of waterborne epoxy resin NPED-510100 parts of accelerant imidazole, uniformly coating the mixture on a treated 150mmxl00mm tin plate after stirring, putting the film which reaches surface drying into an oven, drying for lh at 80 ℃, and curing for lh at 150 ℃.
The film formation properties are shown in Table 5:
TABLE 5
| Hardness of pencil | 3H |
| Adhesion force | 2 |
| Contact angle | 95° |
| Colour(s) | Colorless and colorless |
| Flatness of | Is smooth and smooth |
| Light transmittance | Is transparent |
Comparative example
0 part of waterborne epoxy curing agent, 0 part of waterborne epoxy resin NPED-20100 part of waterborne epoxy resin and 3 parts of accelerant imidazole, uniformly coating the mixture on a treated 150mmxl00mm tinplate template after stirring, putting the surface-dried film into an oven for baking lh at the temperature of 80 ℃, and curing lh at the temperature of 150 ℃.
The film forming properties are shown in Table 6:
TABLE 6
As is clear from the above examples 7 to 11 and comparative examples, the self-emulsifying aqueous epoxy resin curing agent prepared in example 1 is suitable for various aqueous epoxy resins, has high curing activity, and has good heat resistance, weather resistance, electrical insulation, chemical resistance, water repellency and the like when formed into a film.
The self-emulsifying aqueous epoxy hardener prepared in examples 2 to 6 has the same performance as the self-emulsifying aqueous epoxy hardener prepared in example 1, and can be applied to various epoxy resins.
The self-emulsifying water-based epoxy resin curing agent has self-emulsifying performance and can be diluted by water to prepare emulsion. Due to the introduction of silicon, the whole system has no foam, the curing agent has defoaming performance, and the heat resistance is improved.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The self-emulsifying water-based epoxy resin curing agent is characterized by comprising the following raw material components: 1-10 parts of amino silicone oil, 20-30 parts of epoxy resin, 0.01-5 parts of reaction auxiliary agent, 120-250 parts of solvent and 1-10 parts of end-capping agent.
2. The self-emulsifying aqueous epoxy resin curing agent according to claim 1, wherein the aminosilicone oil comprises at least one of aminomethylsiloxane, aminopolydimethylsiloxane, and bisaminopolydimethylsiloxane.
3. The self-emulsifying aqueous epoxy resin curing agent according to claim 1, wherein the epoxy resin comprises at least one of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, linear aliphatic epoxy resin, and alicyclic epoxy resin.
4. The self-emulsifying aqueous epoxy resin curing agent according to claim 3, wherein the glycidyl ether type epoxy resin comprises bisphenol A type epoxy resin, tetrabromobisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.
5. The self-emulsifying aqueous epoxy resin curing agent according to claim 1, wherein the reaction auxiliary agent comprises one or two of cetyltrimethylammonium chloride, ethylenediamine, dicyandiamide, triethylamine and ethanolamine.
6. The self-emulsifying aqueous epoxy resin curing agent according to claim 1, wherein the blocking agent comprises at least one of glycidyl methacrylate, butyl glycidyl ether, phenyl glycidyl ether, and alkyl glycidyl ether.
7. The self-emulsifying aqueous epoxy resin curing agent according to claim 1, wherein the solvent comprises at least one of propylene glycol ethyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, and ethylene glycol methyl ether.
8. A preparation method of a self-emulsifying water-based epoxy resin curing agent is characterized by comprising the following steps:
step 1, dissolving amino silicone oil in a solvent, adding a reaction auxiliary agent, stirring uniformly, dropwise adding a mixed solution of epoxy resin and the solvent at a constant speed under the condition of 60-80 ℃ and an inert gas atmosphere, and continuously reacting for 2-3 hours at the temperature of 70-85 ℃ after dropwise adding;
step 2, continuously dripping the mixed solution of the end-capping reagent and the solvent at a constant speed at the temperature of 75-85 ℃ and under the inert gas atmosphere, carrying out end-capping reaction for 0.5-1.5h, continuously reacting for 2-3h, and then cooling to 60-70 ℃;
and 3, adding a regulator, and distilling under reduced pressure to obtain the self-emulsifying water-based epoxy resin curing agent.
9. The method for preparing a self-emulsifying aqueous epoxy resin curing agent according to claim 8, wherein the mixed solution of the epoxy resin and the solvent is prepared in step 1, wherein the amount of the epoxy resin is 20 to 30 parts and the amount of the solvent is 50 to 100 parts.
10. The method for preparing a self-emulsifying aqueous epoxy resin curing agent according to claim 8, wherein in step 2, the amount of the blocking agent is 1 to 10 parts and the amount of the solvent is 20 to 50 parts.
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