CN116854925A - Emulsifier for preparing zero VOC aqueous epoxy emulsion, and preparation method and application thereof - Google Patents
Emulsifier for preparing zero VOC aqueous epoxy emulsion, and preparation method and application thereof Download PDFInfo
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- CN116854925A CN116854925A CN202310774138.6A CN202310774138A CN116854925A CN 116854925 A CN116854925 A CN 116854925A CN 202310774138 A CN202310774138 A CN 202310774138A CN 116854925 A CN116854925 A CN 116854925A
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- polyethylene glycol
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- epoxy emulsion
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- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 111
- 239000004593 Epoxy Substances 0.000 title claims abstract description 94
- 239000000839 emulsion Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 37
- 238000004945 emulsification Methods 0.000 title description 13
- 239000003822 epoxy resin Substances 0.000 claims description 59
- 229920000647 polyepoxide Polymers 0.000 claims description 59
- 239000002202 Polyethylene glycol Substances 0.000 claims description 49
- 229920001223 polyethylene glycol Polymers 0.000 claims description 49
- 229920001451 polypropylene glycol Polymers 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007788 liquid Substances 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
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 2
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 66
- 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 description 32
- 239000012855 volatile organic compound Substances 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 17
- 239000011521 glass Substances 0.000 description 17
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 229910004039 HBF4 Inorganic materials 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000006184 cosolvent Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- -1 sodium laureth-11 carboxylate Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004353 Polyethylene glycol 8000 Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 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
- 238000009435 building construction Methods 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006333 epoxy cement Polymers 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming 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
- 230000036541 health Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229940085678 polyethylene glycol 8000 Drugs 0.000 description 1
- 235000019446 polyethylene glycol 8000 Nutrition 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000003313 weakening effect Effects 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses an emulsifier for preparing a zero VOC aqueous epoxy emulsion, a preparation method and application thereof, wherein the emulsifier has a special space structure and super-strong emulsifying property, can be used for preparing the zero VOC aqueous epoxy emulsion so as to realize zero VOC emission of a coating, does not harm construction personnel or ecological environment, and is increasingly valued in China for ecological conservation and navigation.
Description
Technical Field
The invention belongs to the technical field of epoxy emulsion production, and particularly relates to an emulsifier for preparing zero-VOC (volatile organic compound) waterborne epoxy emulsion, a preparation method of the emulsifier and application of the emulsifier in preparing zero-VOC waterborne epoxy emulsion.
Background
Epoxy resins refer to a generic term for a class of polymers containing more than two epoxy groups in the molecule. Because of the chemical activity of epoxy groups, epoxy resin can be cured and crosslinked with various compounds through chemical reaction to generate a three-dimensional reticular cured structure, so that the epoxy resin is thermosetting resin, and meanwhile, the molecular chain of the epoxy resin contains a large number of functional groups such as ether bonds, epoxy groups, benzene rings, hydroxyl groups and the like, so that the epoxy resin has good heat resistance, cohesiveness, electrical insulation, mechanical property, corrosion resistance and the like, and is widely used in the fields of adhesives, anticorrosive coatings, electronic insulating materials, engineering plastic composite materials, building construction raw materials (such as anticorrosive floors, epoxy cement mortar and the like) and the like. However, epoxy resin is very insoluble in water, and can only be diluted by a large amount of organic solvents such as alcohols, ethers and ketones, especially the amount of organic solvents added into solid epoxy resin with large molecular weight is larger, so that the traditional solvent type epoxy coating contains a large amount of organic solvents (namely volatile organic compounds, VOC for short), and causes great harm to the environment and human health. In recent years, the environmental protection of China is increasingly emphasized, and the low-organic solvent or water-based epoxy paint without the organic solvent becomes one of the important research directions of future development of the application field of epoxy resin.
At present, the preparation method of the water-based epoxy emulsion mainly comprises an external emulsification method and an internal emulsification method, wherein the external emulsification method is to forcedly emulsify epoxy resin by the action of an external emulsifier and high shearing force to obtain the water-based epoxy emulsion, and the epoxy emulsion prepared by the method has large particle size and poor stability and water resistance. The internal emulsification method is to prepare the epoxy emulsion by preparing a reactive emulsifier through the reaction of active groups on the epoxy resin and hydrophilic chain segments, the reactive emulsifier has strong affinity with the epoxy resin body, and the formed emulsion particles are stable and have better performance and stability. However, the internal emulsification method has higher structural requirements on the reactive emulsifier, and if the structure of the prepared reactive emulsifier is unsuitable or the synthesis process is poorly controlled, the prepared emulsifier has poor efficacy, so that the final aqueous epoxy emulsion product contains a large amount of emulsifier, and finally the hydrophilization degree of a paint film prepared from the epoxy emulsion is high, and the performance is affected. In addition, most of the two emulsification methods currently require the addition of a small amount of cosolvent to improve the production efficiency and product stability.
CN106349906a discloses an aqueous epoxy emulsion and a preparation method thereof, which comprises forming a self-emulsifying epoxy resin, then adding a first solvent and a first catalyst into the self-emulsifying epoxy resin to obtain a first solution, dripping polyisocyanate into the first solution to generate a first reaction product, finally adding a second solvent into the first reaction product from which the first solvent is removed to obtain a second solution, and preparing the aqueous epoxy emulsion with preset viscosity by a phase inversion emulsification method.
CN107522873a discloses a zero VOC aqueous epoxy emulsion and a method for preparing the same, the zero VOC aqueous epoxy emulsion is composed of bisphenol a type epoxy resin, an epoxy diluent, an epoxy emulsifier, bisphenol a, a first catalyst and a water dispersion medium, wherein the epoxy emulsifier is made of bisphenol a type epoxy resin, hydrophilic dihydric alcohol and a second catalyst. Although no organic solvent is used in the preparation process of the aqueous epoxy emulsion, the amount of the emulsifier is larger, and the particle size of the product is larger.
In summary, developing a zero VOC aqueous epoxy emulsion with simple preparation process and stable performance becomes an important research direction in the application field of epoxy resin.
Disclosure of Invention
The invention overcomes the problems in the prior art, develops an emulsifier for preparing the zero VOC aqueous epoxy emulsion based on the requirements of the prior aqueous epoxy emulsion, has special space structure and super-strong emulsifying property, and can be used for preparing the zero VOC aqueous epoxy emulsion so as to realize zero VOC emission of the coating.
According to a first aspect of the invention, there is provided an emulsifier for preparing a zero VOC aqueous epoxy emulsion, which is prepared from the following components in parts by weight:
in the invention, polyethylene glycol provides a hydrophilic chain segment, polypropylene glycol provides a flexible hydrophobic chain segment, oxygen atoms in epoxy groups of epoxy resin and hydrogen atoms of hydroxyl groups in polypropylene glycol and polyethylene glycol react with each other in a nucleophilic way under the action of a catalyst to open an epoxy ring, an open carbon atom center is formed, then, oxygen atoms in hydroxyl groups and oxygen atoms on the carbon atom center form a new chemical bond to generate alcohol compounds, and the generated products have a plurality of branched structures, so that stable epoxy emulsion can be prepared without adding cosolvent. The surfactant in the emulsifier can quickly reduce the interfacial tension in the subsequent preparation of the epoxy emulsion, so that the epoxy emulsion is prepared in a shorter time, and the production efficiency is improved.
Preferably, in the above-mentioned emulsifier, the number average molecular weight of the polyethylene glycol is 1000 to 10000, more preferably 2000 to 6000, and if the molecular weight of the polyethylene glycol is too high, the viscosity of the whole emulsifier system will be too high, which results in more energy consumption during the preparation process and the subsequent use process, while if the molecular weight of the polyethylene glycol is too low, the emulsification efficiency of the emulsifier is affected, and more emulsifier is required during the subsequent preparation process of the epoxy emulsion.
Preferably, in the emulsifier, the weight part of the polyethylene glycol is 30-40 parts.
Preferably, among the above emulsifiers, the polypropylene glycol has a number average molecular weight of 1000 to 10000, more preferably 2000 to 6000, and most preferably 2500 to 4000, and if the molecular weight of the polypropylene glycol is too high, the viscosity of the whole emulsifier system is too high, resulting in more energy consumption during the preparation and subsequent use, while if the molecular weight of the polypropylene glycol is too low, the emulsification efficiency of the emulsifier is affected, and more emulsifier is required during the subsequent preparation of the epoxy emulsion.
Preferably, in the emulsifier, the weight part of the polypropylene glycol is 15-20 parts.
Preferably, in the above-mentioned emulsifier, the weight ratio of the polyethylene glycol to the polypropylene glycol is (1.5-2.5): 1, and in the present invention, the reasonable ratio of the polyethylene glycol to the polypropylene glycol can adjust the two-stage structure of the polyethylene glycol and the polypropylene glycol involved in the emulsifier, so that the particle size of the epoxy emulsion is smaller, if the amount of the polyethylene glycol is too large, the viscosity of the prepared emulsifier is too high, and if the amount of the polypropylene glycol is too large, the film forming strength of the epoxy emulsion prepared by the emulsifier is reduced, which is unfavorable for application.
Preferably, in the above emulsifier, the catalyst includes, but is not limited to, one or more of triphenylphosphine, tribenzyl methyl ammonium chloride and fluoroboric acid.
Preferably, in the above emulsifier, the first epoxy resin includes, but is not limited to, one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenolic epoxy resin.
Preferably, in the above-mentioned emulsifier, the weight ratio of the first epoxy resin to the polyethylene glycol is 1 (2-6), and if the epoxy resin is too much or too little, the hydrophilic-lipophilic value of the emulsifier is not suitable, and further the emulsification efficiency is lowered, and if the amount of the first epoxy resin is too much, the emulsion particle size becomes large, and if the amount of the polyethylene glycol is too much, the system viscosity is too high.
Preferably, in the above-mentioned emulsifier, the surfactant includes, but is not limited to, one or more of sodium dodecyl benzene sulfonate, sodium laureth-11 carboxylate, sodium laurylsulfate and the like, and the surfactant can quickly reduce interfacial tension when preparing the epoxy emulsion, shorten the time for preparing the epoxy emulsion, and is beneficial to improving the production efficiency.
Preferably, in the above-mentioned emulsifier, the weight ratio of the surfactant to the first epoxy resin is 1 (1-2), and if the amount of the surfactant is too large, the hydrophilicity of a coating film formed when the epoxy emulsion prepared from the emulsifier is carried out is high, which results in low water resistance and salt spray resistance, and if too small, the emulsifier cannot quickly reduce the surface tension, cannot quickly form the epoxy emulsion, which further prolongs the production period, and reduces the production efficiency.
Preferably, in the above-mentioned emulsifier, the water is deionized water to avoid introducing unnecessary impurities, thereby deteriorating the stability of the emulsifier.
The first epoxy resin in the emulsifier has a plurality of polyethylene glycol and polypropylene glycol branched structures, so that the space structure of the emulsifier can have super-strong emulsifying capacity, stable epoxy emulsion can be prepared finally without adding a cosolvent, and the added surfactant can quickly reduce interfacial tension, so that the preparation of the zero-VOC epoxy emulsion can be realized.
According to a second aspect of the present invention, there is provided a preparation method for preparing the above-mentioned emulsifier, comprising the steps of:
(S1) uniformly mixing polyethylene glycol and polypropylene glycol with an organic solvent, heating to 90-120 ℃, and then maintaining at the temperature for 30-120min to enable the mixed system to be in a liquid form;
(S2) adding a catalyst into the system obtained in the step (S1) and uniformly mixing;
(S3) adding a first epoxy resin into the system obtained in the step (S2), and reacting at the temperature of 90-120 ℃ under the condition of stirring until the epoxy equivalent in the reaction system is more than 5000 g/equivalent;
(S4) removing the organic solvent and adding a surfactant;
and (S5) adding water into the system obtained in the step (S4), and uniformly stirring to obtain the emulsifier.
In the process of preparing the emulsifier, firstly, the polyethylene glycol and the polypropylene glycol are completely dissolved at a certain temperature by using an organic solvent, and because the polyethylene glycol is solid, the temperature of a system is firstly required to be raised to promote the dissolution of the polyethylene glycol, then a catalyst and a first epoxy resin are added, under the action of the catalyst, the epoxy functional group of the first epoxy resin is ring-opened and reacts with the hydroxyl groups of the polyethylene glycol and the polypropylene glycol until the epoxy equivalent in a reaction system is more than 5000g/eq, so that the epoxy resin reacts with the polyethylene glycol and the polypropylene glycol as much as possible, and the polyethylene glycol and the polypropylene glycol are connected to the first epoxy resin as much as possible, so that the product is ensured to have a plurality of polyethylene glycol and polypropylene glycol branched structures, and the emulsifier has super-strong emulsifying capacity, and can prepare stable epoxy emulsion under the condition of no need of adding a cosolvent. In addition, the surfactant is added into the emulsifier to realize the purpose of rapid emulsification, so that the production period is shortened, the production efficiency is improved, and the emulsifier is in a liquid form, is convenient to take and saves a great amount of labor.
Preferably, in the above preparation method, the weight ratio of the sum of the masses of the polyethylene glycol and the polypropylene glycol to the organic solvent is 1: (25-40), more preferably 1:30, so that the polyethylene glycol and polypropylene glycol have suitable viscosities, and if the amount of the organic solvent is too small, the viscosity of the system is too large, which is disadvantageous in terms of improvement of production efficiency, and if the amount of the organic solvent is too large, more time and cost are required for removing the organic solvent at a later stage.
In the above preparation method, the manner of removing the organic solvent in the step (S4) may be any manner as long as the organic solvent can be removed, such as baking, precipitation, filtration, air drying, etc., but it is preferable that the operation is simple by distillation under reduced pressure and no other substances are introduced.
In the above preparation method, the organic solvent added in the step (S1) includes, but is not limited to, glycol ethers such as ethylene glycol diethyl ether and ethylene glycol butyl ether; propylene glycol ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and esters thereof; and the like. The specific kind of the organic solvent in the present invention is not strictly limited as long as it satisfies low toxicity and low boiling point.
According to a third aspect of the present invention there is also provided the use of an emulsifier as described above for the preparation of a zero VOC aqueous epoxy emulsion, more specifically the use of the emulsifier to prepare a zero VOC aqueous epoxy emulsion.
More preferably, the zero-VOC aqueous epoxy emulsion comprises the following components in parts by weight:
40-60 parts of a second epoxy resin;
2-5 parts of the emulsifier;
40-60 parts of water.
The emulsifier adopted by the aqueous epoxy emulsion is an emulsifier with a plurality of branch structures, no cosolvent is added in the preparation of the epoxy emulsion, the particle size of the prepared epoxy emulsion is smaller, meanwhile, the emulsifier is lower in dosage due to the ultra-strong emulsifying capacity, the mass of the emulsifier accounts for 1.6-5.9% of the mass of the whole epoxy emulsion, and the emulsifier is obviously lower than the amount of the emulsifier required in the preparation of the existing epoxy emulsion. Most importantly, the aqueous epoxy emulsion does not contain volatile organic compounds, so that the emission of the volatile organic compounds does not exist in the use process, no harm is caused to constructors or ecological environment, and the aqueous epoxy emulsion is an increasingly important ecological protection for China.
In the present invention, the second epoxy resin is a solid epoxy resin, but the kind thereof is not strictly limited, such as E20 bisphenol a type epoxy resin, and the like.
Preferably, the water is deionized water to avoid introducing unnecessary impurities that would render the epoxy emulsion system unstable.
In the invention, the preparation process of the zero VOC aqueous epoxy emulsion is as follows: firstly, melting a second epoxy resin into a liquid state at 130-190 ℃, then, reducing the temperature of a system to 80-110 ℃, adding the emulsifier, stirring uniformly, adding water under high-speed stirring (generally, the stirring rotating speed is more than 2000 RPM), and finally, cooling to room temperature to obtain the zero VOC aqueous epoxy emulsion.
The preparation process of the zero VOC aqueous epoxy emulsion is simple, the existing production equipment is not required to be improved, the cost is saved, and meanwhile, the aqueous epoxy emulsion does not contain volatile organic compounds, is friendly to the environment and human beings both in the production process and in the actual use process, and has wide application prospect.
Compared with the prior art, the emulsifier provided by the invention is an emulsifier with a plurality of branch structures, no cosolvent is added in the preparation of the epoxy emulsion, the particle size of the prepared epoxy emulsion is smaller, and meanwhile, the amount of the emulsifier is lower due to the super-strong emulsifying capacity of the emulsifier, so that the emulsifier is obviously lower than the amount of the emulsifier required in the preparation of the existing epoxy emulsion. Most importantly, the aqueous epoxy emulsion does not contain volatile organic compounds, so that the emission of the volatile organic compounds does not exist in the use process, no harm is caused to constructors or ecological environment, and the aqueous epoxy emulsion is increasingly important ecological conservation and navigation in China. In addition, the prepared coating film of the epoxy emulsion has high strength and excellent water resistance and salt spray resistance.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Preparation example preparation of emulsifier
Preparation example 1
(S1) into a 1L glass reaction vessel were charged 300g of polyethylene glycol 6000, 200g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 52g of the E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and the reaction was carried out by stirring at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 50g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier which is denoted as A1.
Preparation example 2
(S1) into a 1L glass reaction vessel were charged 400g of polyethylene glycol 6000, 200g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 82g of an E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 50g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier which is denoted as A2.
Preparation example 3
(S1) into a 1L glass reaction vessel were charged 400g of polyethylene glycol 6000, 160g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 92g of an E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2) and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 50g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier, which is denoted as A3.
Preparation example 4
(S1) into a 1L glass reaction vessel were charged 300g of polyethylene glycol 6000, 200g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 52g of the E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 52g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier which is denoted as A4.
Preparation example 5
(S1) into a 1L glass reaction vessel were charged 400g of polyethylene glycol 6000, 200g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 52g of the E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 26g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier, which is denoted as A5.
Preparation example 6
(S1) into a 1L glass reaction vessel were charged 300g of polyethylene glycol 6000, 200g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 94g of an E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 50g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier, which is denoted as A6.
Preparation example 7
(S1) into a 1L glass reaction vessel were charged 300g of polyethylene glycol 8000, 200g of polypropylene glycol 5000 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 52g of the E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 50g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier, which is denoted as A7.
Preparation example 8
(S1) into a 1L glass reaction vessel were charged 300g of polyethylene glycol 2000, 200g of polypropylene glycol 1500 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 52g of the E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 50g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier, which is denoted as A8.
Comparative example emulsifier preparation
Comparative example 1
(S1) 600g of polyethylene glycol 6000 and 20g of propylene glycol methyl ether were added to a 1L glass reaction vessel, and then the mixed system was warmed to 100℃and maintained at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 52g of the E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 50g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier which is denoted as B1.
Comparative example 2
(S1) 600g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether were charged into a 1L glass reactor, and then the mixed system was warmed to 100℃and maintained at that temperature for 1 hour to dissolve polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 52g of the E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 50g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier which is denoted as B2.
Comparative example 3
(S1) 200g of polyethylene glycol 6000, 400g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether were charged into a 1L glass reactor, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) adding 2g of HBF4 aqueous solution with the mass fraction of 0.3wt% into the system obtained in the step (S1) and uniformly mixing.
(S3) 52g of the E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 50g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier which is denoted as B3.
Comparative example 4
(S1) into a 1L glass reaction vessel were added 1000g of polyethylene glycol 6000, 100g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 52g of the E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 50g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier which is denoted as B4.
Comparative example 5
(S1) into a 1L glass reaction vessel were charged 400g of polyethylene glycol 6000, 200g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 52g of the E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 5g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier which is denoted as B5.
Comparative example 6
(S1) into a 1L glass reaction vessel were charged 400g of polyethylene glycol 6000, 200g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) 2g of an aqueous HBF4 solution with a mass fraction of 0.3wt% was added to the system obtained in the step (S1) and mixed uniformly.
(S3) 52g of the E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 100g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier which is denoted as B6.
Comparative example 7
(S1) into a 1L glass reaction vessel were charged 400g of polyethylene glycol 6000, 200g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) adding 2g of HBF4 aqueous solution with the mass fraction of 0.3wt% into the system obtained in the step (S1) and uniformly mixing,
(S3) 26g of an E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃at which the epoxy equivalent was less than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 50g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier which is denoted as B7.
Comparative example 8
(S1) into a 1L glass reaction vessel were charged 100g of polyethylene glycol 6000, 200g of polypropylene glycol 3000 and 20g of propylene glycol methyl ether, and then the mixed system was warmed to 100℃and kept at that temperature for 1 hour to dissolve the polyethylene glycol.
(S2) adding 2g of HBF4 aqueous solution with the mass fraction of 0.3wt% into the system obtained in the step (S1) and uniformly mixing,
(S3) 130g of the E51 bisphenol A type epoxy resin was added to the system obtained in the step (S2), and stirred and reacted at a constant temperature of 100℃until the epoxy equivalent was more than 5000 g/equivalent.
(S4) heating the system reacted in the step (S3) to 150 ℃, then distilling under reduced pressure to remove propylene glycol methyl ether, then reducing the temperature of the system to 80 ℃, and then adding 50g of sodium dodecyl benzene sulfonate and stirring uniformly.
(S5) adding 450g of deionized water into the system obtained in the step (S4), and uniformly stirring to obtain an emulsifier which is denoted as B8.
Preparation of application example emulsion
Application example 1
Step one: 450g of E20 solid bisphenol A epoxy resin and 20g of emulsifier A1 are added into A1L glass reaction kettle, then the system is heated to the temperature of 95 ℃ and stirred until the E20 solid epoxy resin is completely dissolved so that the system is transparent;
step two: 400g of deionized water was added with stirring at a high speed of 2000rpm to form a phase inversion, and finally a milky aqueous epoxy emulsion, designated C1, was obtained.
Application examples 2 to 8
The procedure of application examples 2-8 was the same as that of application example 1, except that the emulsifiers used in the steps were A2, A3, A4, A5, A6, A7 and A8, respectively, and the obtained products were designated as C2, C3, C4, C5, C6, C7 and C8, respectively.
Comparative application examples 1 to 7
Comparative application examples 2 to 8 the procedure of application example 1 was the same except that the emulsifiers used in the steps were B1, B2, B3, B4, B5, B6, B7 and B8, respectively, and the obtained products were designated as D1, D2, D3, D4, D5, D6 and D7, respectively.
Test examples
The following performance tests were conducted on the products C1 to C8 and D1 to D7 obtained in application examples 1 to 8 and comparative application examples 1 to 7, respectively, and the test procedures were as follows, and the test results are shown in Table 1 below.
Solid content: the solid content was calculated by taking 5g of a sample, placing the sample in an oven, baking at 150C for 1 hour, and testing the mass of the remaining components according to the test method prescribed in astm d 1259.
Viscosity: the test was performed according to the test method specified in astm d2196, specifically using an Shanghai fine day RVDV-1 viscometer at 25 ℃ and using a number 5 spindle at a rotational speed of 10 RPM.
Particle size: the particle size of the sample was measured using an European and American laser particle sizer, and the particle size was a number average particle size in μm.
Water resistance the test was carried out according to the paint film water resistance test method specified in GB/T1733, and the time of foaming of a 50 μm paint film under the condition of warm water was specifically tested in days.
Salt spray resistance: the test is carried out according to the test method of the neutral salt spray resistance specified in GB/T1771, and the specific test is carried out on the time of a 50 mu m paint film under the neutral salt spray condition, wherein the unit is hours.
Storage stability: the sample was placed in an oven at 50c for one month and then the bottom precipitate was observed.
TABLE 1 Performance test results
From the results of Table 1 above, it is understood that the emulsifier prepared in comparative example 1, if only polyethylene glycol is used as the emulsifier, is poor in the effect of weakening the hydrogen bond on the polyether by polypropylene glycol methyl group, so that the viscosity of the whole system is high, and the water-salt mist resistance of the paint film prepared from the epoxy emulsion is remarkably lowered due to the strong hydrophilicity of polyethylene glycol. However, if polypropylene glycol alone, i.e., the emulsifier prepared in comparative example 2, the efficacy of the emulsifier prepared is insufficient to obtain a stable aqueous epoxy emulsion due to insufficient hydrophilicity. The presence of polyethylene glycol may help to better emulsify the epoxy resin, but in the case of insufficient amount, i.e., the emulsifier prepared in comparative example 3, the particle size of the obtained epoxy emulsion is large and the stability is poor, but in the case of too much polyethylene glycol and too little polypropylene glycol, i.e., the emulsifier prepared in comparative example 4, the particle size of the obtained epoxy emulsion is not small enough and the performance is lowered in various respects. In addition, if the amount of the surfactant used is too small, i.e., the emulsifier prepared in comparative example 5, the particle size of the obtained epoxy emulsion is large, whereas if the amount of the surfactant used is excessive, i.e., the emulsifier prepared in comparative example 6, an epoxy resin emulsion having a smaller particle size can be obtained, but excessive hydrophilicity causes deterioration in water resistance and salt spray properties. Meanwhile, if the amount of the first epoxy resin is insufficient, the emulsifier is made to be hydrophilic, the performance of the obtained epoxy emulsion is lowered, and if the amount of the first epoxy resin is excessive, the emulsifier is made to be hydrophobic excessively, and the performance of the obtained epoxy emulsion is also not ideal. In conclusion, the components of the emulsifier need to be strictly prepared to show super-strong emulsifying capacity, and the prepared epoxy emulsion has excellent performance.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (10)
1. The emulsifier for preparing the zero VOC aqueous epoxy emulsion is characterized by comprising the following components in parts by weight:
2. an emulsifier according to claim 1, wherein the polyethylene glycol has a number average molecular weight of 1000-10000, more preferably 2000-6000.
3. The emulsifier according to claim 1, wherein the polyethylene glycol is present in an amount of 30-40 parts by weight.
4. An emulsifier according to claim 1, wherein the polypropylene glycol has a number average molecular weight of 1000-10000, more preferably 2000-6000, most preferably 1500-4000.
5. The emulsifier of claim 1 wherein the polypropylene glycol is present in an amount of 15 to 20 parts by weight.
6. The emulsifier of claim 1 wherein the weight ratio of polyethylene glycol to polypropylene glycol is (1.5-2.5): 1.
7. The emulsifier of claim 1 wherein the catalyst includes, but is not limited to, one or more of triphenylphosphine, tribenzyl methyl ammonium chloride, fluoroboric acid.
8. An emulsifier according to any one of claims 1 to 7, comprising the steps of:
(S1) uniformly mixing polyethylene glycol and polypropylene glycol with an organic solvent, heating to 90-120 ℃, and then maintaining at the temperature for 30-120min to enable the mixed system to be in a liquid form;
(S2) adding a catalyst into the system obtained in the step (S1) and uniformly mixing;
(S3) adding a first epoxy resin into the system obtained in the step (S2), and reacting at the temperature of 90-120 ℃ under the condition of stirring until the epoxy equivalent in the reaction system is more than 5000 g/equivalent;
(S4) removing the organic solvent and adding a surfactant;
and (S5) adding water into the system obtained in the step (S4), and uniformly stirring to obtain the emulsifier.
9. The method of claim 8, wherein the weight ratio of the sum of the mass of polyethylene glycol and polypropylene glycol to the organic solvent is (25-40): 1.
10. use of an emulsifier according to any one of claims 1 to 7, wherein the use is to prepare a zero VOC aqueous epoxy emulsion with the emulsifier.
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