CN110922854A - Preparation method of nonionic waterborne epoxy resin emulsion and curing agent thereof - Google Patents
Preparation method of nonionic waterborne epoxy resin emulsion and curing agent thereof Download PDFInfo
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- CN110922854A CN110922854A CN201911114444.7A CN201911114444A CN110922854A CN 110922854 A CN110922854 A CN 110922854A CN 201911114444 A CN201911114444 A CN 201911114444A CN 110922854 A CN110922854 A CN 110922854A
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- epoxy resin
- nonionic
- addition reaction
- catalyst
- resin emulsion
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 134
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 134
- 239000000839 emulsion Substances 0.000 title claims abstract description 61
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000007259 addition reaction Methods 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 28
- -1 polyoxyethylene Polymers 0.000 claims abstract description 26
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 15
- 239000006184 cosolvent Substances 0.000 claims abstract description 14
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- 229920000768 polyamine Polymers 0.000 claims abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 239000012745 toughening agent Substances 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims description 49
- 239000002253 acid Substances 0.000 claims description 26
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 16
- 208000037516 chromosome inversion disease Diseases 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 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 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000000539 dimer Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 6
- HJOVHMDZYOCNQW-UHFFFAOYSA-N Isophorone Natural products CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-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
- 238000001816 cooling Methods 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 claims description 3
- NJXBVBPTDHBAID-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 NJXBVBPTDHBAID-UHFFFAOYSA-M 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- CHNLPLHJUPMEOI-UHFFFAOYSA-N oxolane;trifluoroborane Chemical compound FB(F)F.C1CCOC1 CHNLPLHJUPMEOI-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000004848 polyfunctional curative Substances 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 17
- 239000003513 alkali Substances 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000003995 emulsifying agent Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 125000003700 epoxy group Chemical group 0.000 description 9
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000005187 foaming Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 230000002087 whitening effect Effects 0.000 description 6
- 235000012424 soybean oil Nutrition 0.000 description 5
- 239000003549 soybean oil Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 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 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000011850 water-based material Substances 0.000 description 1
Classifications
-
- 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
- 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
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a non-ionic waterborne epoxy resin emulsion and a preparation method of a curing agent thereof. The preparation of the nonionic aqueous epoxy resin emulsion comprises the following steps: mixing macromolecular polyoxyethylene and epoxy resin A, adding a catalyst, heating, dropwise adding polyether amine, and stirring to obtain a nonionic emulsifier; uniformly mixing the epoxy resin B, the chain extender and the toughening agent, and carrying out addition reaction to obtain a product of the addition reaction; mixing the nonionic emulsifier, the product of the addition reaction, the cosolvent and water, and heating to obtain the nonionic waterborne epoxy resin emulsion. Preparation of a curing agent comprising: mixing epoxy resin and macromolecular polyethylene glycol uniformly, adding a catalyst, carrying out addition reaction, adding water, and stirring to obtain an adduct; the curing agent is obtained by adding the adduct dropwise to a mixture of the polyamine and the cosolvent and adding water. The emulsion was mixed with a curing agent to obtain a paint film. The paint film has the comprehensive properties of good adhesive force, water resistance, alkali resistance, high toughness and the like.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a non-ionic epoxy resin emulsion and a preparation method of a curing agent thereof.
Background
Bisphenol a type epoxy resins impart special functions due to their special structure: the epoxy groups with strong reaction capability at two ends of the molecule and a plurality of secondary hydroxyl groups regularly and far from each other on the molecular chain, so that the epoxy resin has good reactivity and the cured resin has strong cohesive force and adhesive force. Ether bonds and hydroxyl groups in the molecule are polar groups, which contributes to the improvement of wettability and adhesion. The ether and C-C bonds provide flexibility to the macromolecule. The benzene ring imparts heat resistance and rigidity to the polymer. Isopropyl groups also impart some rigidity to the macromolecule. The bond energy of the-C-O-bond is high, thereby improving alkali resistance. Therefore, the epoxy resin is easily and widely applied to the field of coatings, and the VOC content of the traditional solvent-based coatings is too high, so that the environmental impact is great. Thus, waterborne coatings have emerged, with waterborne epoxy coatings being the focus of research.
The first is a study of the preparation of aqueous epoxy emulsions. According to Chinese patent CN102666634A, polyethylene glycol 4000 and low molecular weight liquid epoxy resin are adopted to carry out ring-opening reaction on hydroxyl and epoxy groups under the catalysis condition of boron trifluoride diethyl etherate to prepare a multi-block resin emulsifier with high epoxy equivalent, then a certain amount of liquid epoxy resin, a chain extender and a catalyst are added, and water is added for emulsification to obtain emulsion with small particle size and stability until the epoxy equivalent of a system reacts to a certain value. However, the synthesis reaction of the emulsifier is difficult to control. Chinese patent CN106987194A adopts end polyether amine to react with E51 to generate an emulsifier with oleophilic one end and hydrophilic one end, and then directly emulsifies solid epoxy resin E20 to form emulsion with good stability and small particle size. However, this reaction requires a large amount of emulsifier, so that the water resistance and acid resistance at the later stage are poor.
The molecular structure of the bisphenol A epoxy resin has the obvious defects of low toughness, high hardness of a formed paint film caused by too high rigidity, and great internal stress, and finally the adhesive force, water resistance, acid resistance, alkali resistance and the like of the paint film are reduced. Therefore, the toughening modification of the epoxy resin is very important. The toughening of the epoxy resin is realized by adding and mixing flexible resin or inoculating flexible molecules for toughening. According to Chinese patent CN102666634A, epoxidized soybean oil is adopted for toughening, liquid epoxy resin and the epoxidized soybean oil react with a chain extender to generate the epoxy resin with toughness, so that the epoxy resin is grafted into the epoxidized soybean oil with long carbon chains, and the emulsified emulsion has toughness. However, as the epoxy groups in the epoxy soybean oil structure are too many and the activity is higher than that of the epoxy groups on the bisphenol A epoxy resin, the epoxy soybean oil finally reacts with the bisphenol A to form the epoxy resin with high functionality, and the improvement of the toughening effect is limited.
In the two-component waterborne epoxy resin, the waterborne epoxy resin emulsion and the waterborne epoxy resin curing agent play an important role in the performance of the waterborne epoxy resin coating, and the waterborne epoxy resin emulsion does not have good mechanical strength, water resistance, acid resistance and alkali resistance after self-film formation. And a proper amount of curing agent is required to be added into the waterborne epoxy resin, so that the epoxy groups are subjected to a crosslinking reaction to form a network structure, and the waterborne epoxy resin has excellent comprehensive performance. The epoxy curing agents are widely used, and amine curing agents are most widely used because they can easily react with epoxy resins at normal temperature. Because the compatibility of the small molecular amine and the epoxy resin is poor, and the small molecular amine is easy to volatilize, has toxicity, short reaction active period and the like. The water-based epoxy curing agent on the market is also mainly ionic, and is prepared by the addition reaction of liquid epoxy resin and amine and finally neutralization of acid radical ions to form salt. The ionic curing agent can react with the later-stage ionic filler, and flash rust is easy to occur, so that the method has certain limitation in the field of water-based materials.
Disclosure of Invention
Aiming at the problems of synthesis of the emulsifier, toughening of epoxy resin and flash rust of epoxy amine addition product, the invention provides a nonionic aqueous epoxy emulsion, epoxy resin toughening modification and a preparation method and application of a curing agent thereof. Macromolecular polyethylene glycol is reacted with liquid epoxy resin, chain extension is carried out by using end polyether amine to increase the molecular weight of the liquid epoxy resin, an amphiphilic macromolecular emulsifier is obtained, epoxy emulsion is prepared by a phase inversion method, the hydrophilic dosage is small, the emulsion is stable, and the emulsifier contains epoxy groups and can carry out crosslinking reaction with a curing agent. The doped polypropylene glycol diglycidyl ether is mixed with bisphenol A epoxy resin, and the liquid epoxy resin is subjected to chain extension by using bisphenol A or dimer acid, so that a soft long chain segment is introduced, and the toughness of the epoxy resin is greatly improved. The liquid epoxy resin and the macromolecular polyethylene glycol 1000 react according to a certain proportion to generate a mixture with good water solubility, and excessive isophorone amine is mixed with the mixture to react to obtain the non-ionic waterborne epoxy curing agent. The waterborne epoxy emulsion and the curing agent are mixed according to a reasonable proportion, and a paint film with good comprehensive performance can be obtained.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a preparation method of nonionic water-based epoxy resin emulsion, which comprises the following steps:
(1) mixing macromolecular polyoxyethylene and epoxy resin A, heating to 80-100 ℃, adding a catalyst under a stirring state, heating, cooling to 60-80 ℃, dropwise adding terminal polyether amine under a constant temperature state, and stirring for reaction to obtain a non-ionic emulsifier;
(2) under the condition of constant temperature, uniformly mixing the epoxy resin B, the chain extender and the toughening agent, then adding a catalyst, and carrying out addition reaction to obtain a product of the addition reaction;
(3) mixing the nonionic emulsifier in the step (1), the product of the addition reaction in the step (2), a cosolvent and water, and then heating for phase inversion treatment to obtain the nonionic waterborne epoxy resin emulsion.
Further, the molecular weight of the macromolecular polyoxyethylene in the step (1) is 2000-10000; the structural general formula of the macromolecular polyoxyethylene is
Wherein n is more than or equal to 44 and less than or equal to 228;
further, the molar ratio of the epoxy resin A to the macromolecular polyoxyethylene is 1.5-2.5: 1;
preferably, the polyoxyethylene macromolecule in step (1) is polyethylene glycol, and the molecular weight thereof is 4000.
Preferably, the molar ratio of the epoxy resin A to the macromolecular polyoxyethylene in the step (1) is 2: 1.
further, the epoxy resin A is one of epoxy resin E51 and epoxy resin E44;
preferably, the epoxy resin a in the step (1) is E44.
Further, the stirring speed under the stirring state is 50r/min-300 r/min;
preferably, the stirring rate of step (1) is 200 r/min.
Further, the catalyst in the step (1) is one of boron trifluoride diethyl etherate complex, tetrafluoroboric acid aqueous solution and boron trifluoride tetrahydrofuran complex; the mass percentage concentration of the tetrafluoroboric acid aqueous solution is 30-50 wt%;
preferably, the mass percentage of the aqueous tetrafluoroborate solution in the step (1) is 40%.
Further, the mass of the catalyst in the step (1) is 0.3-0.9 wt% of the mass of the epoxy resin A;
preferably, the mass of the catalyst in the step (1) is 0.5-0.6% of the mass of the epoxy resin A.
Further, the temperature of the heating treatment in the step (1) is 120-.
Further, the molecular weight of the terminal polyetheramine in the step (1) is 600-2000;
preferably, the molecular weight of the terminal polyetheramine of step (1) is 600.
Preferably, the mole ratio of the terminal polyetheramine of step (1) is 2: 1.
Further, the end polyether amine in the step (1) is one of L207, L100 and MZ 600; the stirring speed of the stirring reaction is 50r/min-300r/min, and the stirring reaction time is 3-4 h; the molar ratio of the macromolecular polyoxyethylene to the end polyether amine is 1-3: 1.
Preferably, the stirring speed of the stirring reaction in the step (1) is 200 r/min.
Preferably, step (1) is stirred for a reaction time of 3.5 h.
Further, the structural general formula of the amino-terminated polyether amine is as follows:
wherein x is more than or equal to 19 and less than or equal to 58, and y is more than or equal to 3 and less than or equal to 10.
Further, the temperature of the step (2) under the constant temperature condition is 120-160 ℃; the chain extender is one of dihydric alcohol, dibasic acid and diamine; the molecular weight of the chain extender is 100-500, and the structural general formula of the chain extender is
OH-R-OH、
Or NH2-R-NH2；
Wherein R is
；3≤n≤11。
preferably, the chain extender in the step (2) is more than one of bisphenol A and small-molecule dimer acid.
Preferably, the temperature of the constant temperature condition of step (2) is 130 ℃.
Further, the toughening agent in the step (2) is long-carbon-chain dimer acid or polyoxyethylene ether-chain diglycidyl ether (PPGDGE); the structural formula of the toughening agent is
Wherein n is more than or equal to 3 and less than or equal to 20.
Further, the epoxy equivalent of the epoxy resin B in the step (2) is 150-300; the epoxy resin B is bisphenol A type or bisphenol F type epoxy resin; the epoxy resin B is one of epoxy resin E51 and epoxy resin E44; the molar ratio of the epoxy resin B to the chain extender is 1.7-1.9: 1; the molar ratio of the epoxy resin B to the toughening agent is 5-23: 1; the temperature of the addition reaction is 120-160 ℃, and the time of the addition reaction is 3-6 h; the catalyst is one of triphenylphosphine, ethyltriphenylphosphonium bromide and ethyltriphenylphosphonium chloride; the mass of the catalyst is 0.05-0.4% of that of the epoxy resin B.
Preferably, the epoxy equivalent of the epoxy resin B in the step (2) is 150-250.
Preferably, the addition reaction temperature in step (2) is 140 ℃.
Further, the catalyst in the step (2) is one of triphenylphosphine, ethyltriphenylphosphonium bromide and ethyltriphenylphosphonium chloride. The mass of the catalyst is 0.05-0.4% of that of the epoxy resin B.
Preferably, the catalyst in step (2) is triphenylphosphine.
Preferably, the mass of the catalyst in the step (2) is 0.1-0.2% of the mass of the epoxy resin B.
Further, the cosolvent in the step (3) is more than one of propylene glycol methyl ether, propylene glycol butyl ether, ethylene glycol propyl ether and ethylene glycol butyl ether; the mass ratio of the nonionic emulsifier to the addition reaction product is 6-9: 39-44; the mass ratio of the product of the addition reaction to the cosolvent is 39-44: 8-13; the mass ratio of the nonionic emulsifier to the water is 6-9: 38-42; the temperature of the phase inversion treatment is 75-80 ℃, and the time of the phase inversion treatment is 2-3 h.
Preferably, the time for the phase inversion treatment is 2.5 h.
The invention provides a nonionic water-based epoxy resin emulsion prepared by the preparation method.
The invention also provides a method for preparing the nonionic epoxy curing agent matched with the nonionic waterborne epoxy resin emulsion, which comprises the following steps:
A. under the condition of constant temperature (60-80 ℃), uniformly mixing epoxy resin and macromolecular polyethylene glycol, adding a catalyst, heating to carry out addition reaction, cooling to 60-80 ℃, adding water, and uniformly stirring to obtain an adduct (the adduct has water solubility);
B. and (3) under the constant temperature condition (60-80 ℃), dropwise adding the adduct in the step A into a mixture of polyamine and cosolvent, carrying out heat preservation treatment, and then adding water to obtain the nonionic epoxy curing agent.
Further, the temperature of the constant temperature condition in the step A is 60-80 ℃;
preferably, the temperature of the constant temperature condition in step a is 80 ℃.
Further, the epoxy resin in the step A is epoxy resin E51; the molecular weight of the macromolecular polyethylene glycol in the step A is 1000; the molar ratio of the epoxy resin to the macromolecular polyethylene glycol in the step A is 3-5:1, and the addition reaction time in the step A is 3-5 h;
further, the temperature of the addition reaction in the step A is 100-120 ℃;
preferably, the reaction temperature in step A is 100 ℃;
further, the solid content of the adduct in the step A is 80-100%; the catalyst in the step A is a tetrafluoroboric acid aqueous solution, and the mass percentage concentration of the tetrafluoroboric acid aqueous solution is 40 wt%; the mass of the catalyst in the step A is 0.3-0.9 wt% of that of the epoxy resin;
further, the temperature of the constant temperature condition in the step B is 60-80 ℃;
preferably, the temperature of the constant temperature condition in the step B is 80 ℃.
Further, the polyamine in the step B is one of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, isophorone amine and polyether amine; the molar ratio of the polyamine in the step B to the epoxy resin in the step A is 1.59-1.91: 1; the cosolvent in the step B is more than one of propylene glycol methyl ether, propylene glycol butyl ether, ethylene glycol propyl ether and ethylene glycol butyl ether; the molar ratio of the polyamine to the cosolvent in the step B is 1.7-2.2: 1; the mass ratio of the polyamine to the water in the step B is 1.29-1.66: 1; and the time of the heat preservation treatment in the step B is 2-3 h.
The nonionic waterborne epoxy curing agent is prepared by the preparation method.
The nonionic aqueous epoxy resin emulsion is matched with a nonionic epoxy curing agent for use, and the aqueous epoxy resin varnish can be prepared. The molar ratio of the epoxy group in the nonionic aqueous epoxy resin emulsion to the amine hydrogen in the nonionic epoxy curing agent is 1: 1. The non-ionic water-based epoxy resin emulsion and the non-ionic epoxy curing agent are uniformly mixed to obtain the water-based epoxy resin varnish. The paint film of the water-based epoxy resin varnish has the comprehensive properties of good water resistance, alkali resistance, acid resistance, high hardness, toughness and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method of the nonionic waterborne epoxy resin emulsion provided by the invention is simple, and can form a high molecular emulsifier under a relatively mild condition; the emulsifier molecule contains epoxy group, can participate in curing reaction, and can prepare stable emulsion with small particle size and less emulsifier dosage;
(2) the preparation method of the nonionic waterborne epoxy resin emulsion provided by the invention can be used for toughening and modifying epoxy resin, a linear long carbon chain extender or linear aliphatic glycidyl ether is introduced, and the addition of a soft chain segment can increase the toughness of a cured paint film;
(3) according to the preparation method of the nonionic epoxy curing agent provided by the invention, macromolecule polyethylene glycol and epoxy resin are used as the nonionic hydrophilic agent, so that the water solubility of the whole amine adduct is increased, molecules of the curing agent can be easily diffused into emulsion colloidal particles, the selectivity of the filling agent in the later period is expanded, and the problem of flash rust of a paint film is reduced.
(4) The nonionic waterborne epoxy resin emulsion provided by the invention is mixed with a matched nonionic epoxy curing agent to prepare a waterborne epoxy resin varnish; the paint film of the water-based epoxy resin varnish has the comprehensive properties of good water resistance, alkali resistance, acid resistance, high hardness, toughness and the like.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
A preparation method of nonionic water-based epoxy resin emulsion comprises the following steps:
(1) preparation of emulsifiers
300.5g of polyethylene glycol 4000(0.075mol) and 68.3g of epoxy resin E44(0.15mol) are mixed in a 500ml three-neck round-bottom flask provided with a stirrer and a thermometer, the temperature is raised to 100 ℃, then 0.34g of aqueous tetrafluoroborate solution (the mass percent concentration is 40 wt%) is added in a stirring state at the rotating speed of 200r/min, then the system is raised to 130 ℃ for heating treatment, and the heating treatment time is 3.5h, so that the epoxy equivalent of the system is 2524; taking 100g of the product after heating treatment, cooling to 80 ℃, dropwise adding 6.27g of amino-terminated polyetheramine MZ600(0.01mol, molecular weight 600) while keeping the temperature unchanged, and carrying out stirring reaction at 80 ℃, wherein the stirring speed of the stirring reaction is 200r/min, and the stirring reaction time is 3h to obtain a non-ionic emulsifier (waxy yellow solid);
(2) under the constant temperature condition of 140 ℃, 32.26g of epoxy resin E51, 7.34g of chain extender (selected from bisphenol A) and 4.4g of flexibilizer (dimer acid) (0.0078mol, molecular weight of 560.91g/mol) are added into a 250ml three-neck round-bottom flask provided with a stirrer and a thermometer and are uniformly mixed, then 0.044g of triphenylphosphine is added as a catalyst for addition reaction, the temperature of the addition reaction is 140 ℃, and the time of the addition reaction is 4.5h, so as to obtain a product of the addition reaction;
(3) mixing 6g of the nonionic emulsifier in the step (1), 44g of the product of the addition reaction in the step (2) and 8g of propylene glycol methyl ether, then adding 42g of deionized water in batches under the stirring state of 800r/min, and then heating for phase inversion treatment, wherein the temperature of the phase inversion treatment is 70 ℃, and the time of the phase inversion treatment is 2.5h, so as to obtain the nonionic waterborne epoxy resin emulsion. The nonionic aqueous epoxy resin emulsion obtained in example 1 was a milky-white stable epoxy resin emulsion having a solid content of 50%, a viscosity of 533mPas, and a particle diameter of 252.2 nm.
Example 2
Preparation of non-ionic water-based epoxy resin emulsion.
(1) Under the constant temperature condition of 140 ℃, adding 33.08g of epoxy resin E51, 8.72g of chain extender (bisphenol A) and 2.3g of flexibilizer (dimer acid) into a 250ml three-mouth round-bottom flask provided with a stirrer and a thermometer, uniformly mixing, adding 0.061g of triphenylphosphine serving as a catalyst, and carrying out addition reaction at the temperature of 140 ℃ for 3 hours to obtain a product of the addition reaction;
(2) 6g of the nonionic emulsifier in the step (1) of example 1, 44g of the product of the addition reaction in the step (2) and 8g of propylene glycol methyl ether are mixed, 42g of deionized water is added in batches under the stirring state at the rotating speed of 800r/min, and then the mixture is heated for phase inversion treatment, wherein the temperature of the phase inversion treatment is 70 ℃, and the time of the phase inversion treatment is 2.5 hours, so that the nonionic waterborne epoxy resin emulsion is obtained. The nonionic aqueous epoxy resin emulsion obtained in example 2 was a milky-white stable epoxy resin emulsion having a solid content of 50%, a viscosity of 139mPas and a particle diameter of 389.2 nm.
Example 3
Preparation of non-ionic water-based epoxy resin emulsion.
(1) Under the constant temperature condition of 140 ℃, adding 30.62g of epoxy resin E51, 4.58g of chain extender bisphenol A and 8.8g of toughening agent dimer acid into a 250ml three-neck round-bottom flask provided with a stirrer and a thermometer, uniformly mixing, adding 0.033g of triphenylphosphine serving as a catalyst, and carrying out addition reaction at 140 ℃ for 3 hours to obtain a product of the addition reaction;
(2) 6g of the nonionic emulsifier in the step (1) of example 1, 44g of the product of the addition reaction in the step (2) and 8g of propylene glycol methyl ether are mixed, 42g of deionized water is added in batches under the stirring state at the rotating speed of 800r/min, and then the mixture is heated for phase inversion treatment, wherein the temperature of the phase inversion treatment is 70 ℃, and the time of the phase inversion treatment is 2.5 hours, so that the nonionic waterborne epoxy resin emulsion is obtained. The nonionic aqueous epoxy resin emulsion obtained in example 3 was a milky-white stable epoxy resin emulsion having a solid content of 50% and a viscosity of 163mPas, and the particle diameter of the particles in the emulsion was 395.2 nm.
Example 4
A method for preparing a nonionic epoxy curing agent matched with the nonionic water-based epoxy resin emulsion comprises the following steps:
A. under the constant temperature condition of 80 ℃, 321.95g of epoxy resin E51 and 209.6g of polyethylene glycol 1000(0.2096mol, the weight is 1000) are uniformly mixed in a 500ml three-neck round-bottom flask provided with a stirrer and a thermometer, 2g of tetrafluoroborate aqueous solution (the concentration is 40 wt%) is added as a catalyst, then the system is heated to 100 ℃ for addition reaction, the time of the addition reaction is 4h, the epoxy equivalent of the system is 424, the temperature of the system is reduced to 80 ℃, then 28.08g of deionized water is added, and the mixture is uniformly stirred to obtain an adduct;
B. adding 36.62g of isophorone amine (0.215mol, molecular weight of 170.25) and 9.38g of propylene glycol methyl ether into a three-neck round-bottom flask at a constant temperature of 70 ℃, uniformly mixing to form a mixture, then dropwise adding 80g of the adduct in the step A into the mixture, carrying out heat preservation treatment for 4 hours, and then adding 24.16g of deionized water to obtain the nonionic epoxy curing agent. The nonionic epoxy curing agent prepared in example 4 had a solids content of 75% and a viscosity of 67500 mPs. The nonionic epoxy curing agent prepared in example 4 was a clear yellow liquid.
Example 5 preparation of epoxy curing agent
A method for preparing a nonionic epoxy curing agent matched with the nonionic water-based epoxy resin emulsion comprises the following steps:
A. under the constant temperature condition of 80 ℃, 267.66g of epoxy resin E51 and 232.34g of polyethylene glycol 1000(0.2323mol, the weight is 1000) are uniformly mixed in a 500ml three-neck round-bottom flask provided with a stirrer and a thermometer, 2.4g of tetrafluoroborate aqueous solution (the concentration is 40 wt%) is added as a catalyst, then the system is heated to 100 ℃ for addition reaction, the time of the addition reaction is 5h, the epoxy equivalent of the system is 542, the temperature of the system is reduced to 80 ℃, then 26.44g of deionized water is added, and the mixture is uniformly stirred to obtain an adduct;
B. 28.65g of isophorone amine (0.204mol, molecular weight of 170.25) and 8.71g of propylene glycol methyl ether are added into a three-neck round-bottom flask under the constant temperature condition of 70 ℃ and are uniformly mixed to form a mixture, then 80g of the adduct in the step A is dropwise added into the mixture, the mixture is subjected to heat preservation treatment for 4 hours, and then 22.17g of deionized water is added to obtain the nonionic epoxy curing agent. The nonionic epoxy curing agent prepared in example 5 had a solids content of 75% and a viscosity of 72200 mPas. The nonionic epoxy curing agent prepared in example 5 was a clear yellow liquid.
Example 6 (preparation of epoxy curing agent)
A method for preparing a nonionic epoxy curing agent matched with the nonionic water-based epoxy resin emulsion comprises the following steps:
A. under the constant temperature condition of 80 ℃, 328.77g of epoxy resin E51 and 171.23g of polyethylene glycol 1000(0.1712mol, the weight is 1000) are uniformly mixed in a 500ml three-neck round-bottom flask provided with a stirrer and a thermometer, 1.0g of tetrafluoroborate aqueous solution (the concentration is 40 wt%) is added as a catalyst, then the system is heated to 100 ℃ for addition reaction, the time of the addition reaction is 3h, the epoxy equivalent of the system is 368, the temperature of the system is reduced to 80 ℃, then 26.37g of deionized water is added, and the mixture is uniformly stirred to obtain an adduct;
B. 42.19g of isophorone amine (0.204mol, molecular weight of 170.25) and 9.84g of propylene glycol methyl ether are added into a three-neck round-bottom flask under the constant temperature condition of 70 ℃ and are uniformly mixed to form a mixture, then 80g of the adduct in the step A is added into the mixture dropwise, the mixture is subjected to heat preservation treatment for 4 hours, and then 25.56g of deionized water is added to obtain the nonionic epoxy curing agent. The nonionic epoxy curing agent prepared in example 6 had a solids content of 75% and a viscosity of 14000 mPas. The nonionic epoxy curing agent prepared in example 6 was a clear yellow liquid.
Effect verification
The nonionic epoxy curing agent obtained in example 4 was uniformly mixed with the nonionic aqueous epoxy resin emulsion obtained in example 1, the nonionic aqueous epoxy resin emulsion obtained in example 2, and the nonionic aqueous epoxy resin emulsion obtained in example 3, respectively, and the molar ratio of the epoxy group in the nonionic aqueous epoxy resin emulsion to the amine hydrogen in the nonionic epoxy curing agent was 1:1, thereby obtaining 3 parts of mixed solution. The 3 parts of the mixed solution were applied to the surface of a tinplate (specification of 120mm × 50mm) sanded with sand paper, respectively, and the mixed solution was uniformly distributed on the surface of the tinplate, to obtain 3 parts of a paint film. The thickness of 3 paint films is 40 um.
The test was carried out as follows:
surface drying time: according to the requirements of national standard GB/T1728-79, the surface drying time of various paint films is tested by a finger touch method;
hardness: the test is carried out according to the national standard GB/T6739-2006 'determination of paint film hardness by a colored paint and varnish pencil method'.
Adhesion force: the adhesion of the different paint films was rated by a manual cross-hatch method according to the requirements of the national standard GB/T9286-1998.
Water resistance: the test is carried out according to the requirements of the national standard GB/T1733-99.
Acid resistance: the test was carried out according to the requirements of the national standard GB 1763-79.
Alkali resistance: the test was carried out according to the requirements of the national standard GB 1763-79.
The properties of paint films obtained by mixing the nonionic aqueous epoxy resin emulsions obtained in examples 1, 2 and 3 with the nonionic epoxy curing agent obtained in example 4 are shown in Table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | |
| Time to surface dry | 30min | 30min | 30min |
| Hardness of | H | 3H | HB |
| Impact strength | ≥50cm | ≤50cm | ≤50cm |
| Adhesion force | Level 0 | Level 0 | Stage 2 |
| Water resistance | No foaming and no whitening after 30 days | No foaming and no whitening after 30 days | No foaming and no whitening after 30 days |
| Acid resistance (5% H)2SO4) | 5d does not foam or whiten | 3d does not foam or whiten | 4d no foaming and no blushing |
| Alkali resistance (5% NaOH) | No foaming and no whitening after 30 days | No foaming and no whitening after 30 days | Whitening after 10 days |
From the above test results, in the examples provided by the present invention, the paint film obtained by uniformly mixing the aqueous epoxy emulsion and the aqueous epoxy curing agent has good water resistance, acid resistance, alkali resistance, high hardness, and other comprehensive properties.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of nonionic water-based epoxy resin emulsion is characterized by comprising the following steps:
(1) mixing macromolecular polyoxyethylene and epoxy resin A, heating to 80-100 ℃, adding a catalyst under a stirring state, heating, cooling to 60-80 ℃, dropwise adding terminal polyether amine under a constant temperature state, and stirring for reaction to obtain a non-ionic emulsifier;
(2) under the condition of constant temperature, uniformly mixing the epoxy resin B, the chain extender and the toughening agent, then adding a catalyst, and carrying out addition reaction to obtain a product of the addition reaction;
(3) mixing the nonionic emulsifier in the step (1), the product of the addition reaction in the step (2), a cosolvent and water, and then heating for phase inversion treatment to obtain the nonionic waterborne epoxy resin emulsion.
2. The method for preparing the non-ionic aqueous epoxy resin emulsion according to claim 1, wherein the molecular weight of the polyoxyethylene in step (1) is 2000-10000; the structural general formula of the macromolecular polyoxyethylene is
Wherein n is more than or equal to 44 and less than or equal to 228;
the molar ratio of the epoxy resin A to the macromolecular polyoxyethylene is 1.5-2.5: 1; the epoxy resin A is one of epoxy resin E51 and epoxy resin E44; the stirring speed under the stirring state is 50r/min-300 r/min; the catalyst is one of boron trifluoride diethyl etherate complex, tetrafluoroboric acid aqueous solution and boron trifluoride tetrahydrofuran complex; the mass percentage concentration of the tetrafluoroboric acid aqueous solution is 30-50 wt%; the mass of the catalyst is 0.3-0.9 wt% of that of the epoxy resin A; the temperature of the heating treatment is 120-130 ℃, and the time of the heating treatment is 1-3 h.
3. The method for preparing the non-ionic aqueous epoxy resin emulsion as claimed in claim 1, wherein the molecular weight of the terminal polyetheramine in step (1) is 600-2000; the type of the end polyether amine is one of L207, L100 and MZ 600; the stirring speed of the stirring reaction is 50r/min-300r/min, and the stirring reaction time is 3-4 h; the molar ratio of the macromolecular polyoxyethylene to the end polyether amine is 1-3: 1.
4. The method for preparing the non-ionic aqueous epoxy resin emulsion according to claim 1, wherein the temperature of step (2) under the constant temperature condition is 120-160 ℃; the chain extender is one of dihydric alcohol, dibasic acid and diamine; the molecular weight of the chain extender is 100-500, and the structural general formula of the chain extender is
OH-R-OH、
Or NH2-R-NH2；
Wherein R is
5. The method for preparing the nonionic aqueous epoxy resin emulsion according to claim 1, wherein the toughening agent in the step (2) is a long-carbon-chain dimer acid or a polyoxyethylene ether-chain diglycidyl ether; the structural formula of the toughening agent is
Wherein n is more than or equal to 3 and less than or equal to 20.
6. The method for preparing the nonionic aqueous epoxy resin emulsion as claimed in claim 1, wherein the epoxy equivalent of the epoxy resin B in the step (2) is 150-300; the epoxy resin B is bisphenol A type or bisphenol F type epoxy resin; the epoxy resin B is one of epoxy resin E51 and epoxy resin E44; the molar ratio of the epoxy resin B to the chain extender is 1.7-1.9: 1; the molar ratio of the epoxy resin B to the toughening agent is 5-23: 1; the temperature of the addition reaction is 120-160 ℃, and the time of the addition reaction is 3-6 h; the catalyst is one of triphenylphosphine, ethyltriphenylphosphonium bromide and ethyltriphenylphosphonium chloride; the mass of the catalyst is 0.05-0.4% of that of the epoxy resin B.
7. The method for preparing the nonionic aqueous epoxy resin emulsion according to claim 1, wherein the cosolvent in the step (3) is one or more of propylene glycol methyl ether, propylene glycol butyl ether, ethylene glycol propyl ether and ethylene glycol butyl ether; the mass ratio of the nonionic emulsifier to the addition reaction product is 6-9: 39-44; the mass ratio of the product of the addition reaction to the cosolvent is 39-44: 8-13; the mass ratio of the nonionic emulsifier to the water is 6-9: 38-42; the temperature of the phase inversion treatment is 75-80 ℃, and the time of the phase inversion treatment is 2-3 h.
8. A nonionic aqueous epoxy resin emulsion obtained by the production method according to any one of claims 1 to 7.
9. A method for preparing a nonionic epoxy hardener for use with the nonionic aqueous epoxy resin emulsion of claim 8, comprising the steps of:
A. under the condition of constant temperature, epoxy resin and macromolecular polyethylene glycol are uniformly mixed, a catalyst is added, then the temperature is raised for addition reaction, then the temperature is reduced to 60-80 ℃, water is added, and the mixture is uniformly stirred to obtain an adduct;
B. and (3) under the constant temperature condition, dropwise adding the adduct in the step A into a mixture of polyamine and a cosolvent, carrying out heat preservation treatment, and then adding water to obtain the nonionic epoxy curing agent.
10. The method for preparing the nonionic epoxy curing agent according to claim 9, wherein the temperature of the constant temperature condition in the step A is 60 ℃ to 80 ℃; the epoxy resin in the step A is epoxy resin E51; the molecular weight of the macromolecular polyethylene glycol in the step A is 1000; the molar ratio of the epoxy resin to the macromolecular polyethylene glycol in the step A is 3-5:1, and the addition reaction time in the step A is 3-5 h; the temperature of the addition reaction in the step A is 100-120 ℃; the solid content of the adduct in the step A is 80-100%; the catalyst in the step A is a tetrafluoroboric acid aqueous solution, and the mass percentage concentration of the tetrafluoroboric acid aqueous solution is 40 wt%; the mass of the catalyst in the step A is 0.3-0.9% of that of the epoxy resin; the temperature of the constant temperature condition in the step B is 60-80 ℃; the polyamine in the step B is one of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, isophorone amine and polyether amine; the molar ratio of the polyamine in the step B to the epoxy resin in the step A is 1.59-1.91: 1; the cosolvent in the step B is more than one of propylene glycol methyl ether, propylene glycol butyl ether, ethylene glycol propyl ether and ethylene glycol butyl ether; the molar ratio of the polyamine to the cosolvent in the step B is 1.7-2.2: 1; the mass ratio of the polyamine to the water in the step B is 1.29-1.66: 1; and the time of the heat preservation treatment in the step B is 2-3 h.
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