CN111607068A - Water-based epoxy curing agent and preparation method thereof - Google Patents
Water-based epoxy curing agent and preparation method thereof Download PDFInfo
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- CN111607068A CN111607068A CN202010488826.2A CN202010488826A CN111607068A CN 111607068 A CN111607068 A CN 111607068A CN 202010488826 A CN202010488826 A CN 202010488826A CN 111607068 A CN111607068 A CN 111607068A
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- curing agent
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- emulsifier
- epoxy resin
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 63
- 239000004593 Epoxy Substances 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 21
- 229920000768 polyamine Polymers 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 10
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 9
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960001124 trientine Drugs 0.000 claims abstract description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims abstract description 6
- JDXQSTLUHNAVMN-UHFFFAOYSA-M sodium propane-2-sulfonate prop-2-enamide Chemical compound [Na+].NC(=O)C=C.CC(C)S([O-])(=O)=O JDXQSTLUHNAVMN-UHFFFAOYSA-M 0.000 claims abstract description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000004848 polyfunctional curative Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- FJSPGHNSBJVXEH-UHFFFAOYSA-N C(C=C)(=O)NOS(=O)(=O)C(C)C.[Na] Chemical group C(C=C)(=O)NOS(=O)(=O)C(C)C.[Na] FJSPGHNSBJVXEH-UHFFFAOYSA-N 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 abstract description 42
- 229920000647 polyepoxide Polymers 0.000 abstract description 42
- 239000006184 cosolvent Substances 0.000 abstract description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 4
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 4
- 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 4
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- -1 amidoamine Polymers 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JUEDJIRGERJMGO-UHFFFAOYSA-N C(C)(C)[Na].C(C=C)(=O)N Chemical compound C(C)(C)[Na].C(C=C)(=O)N JUEDJIRGERJMGO-UHFFFAOYSA-N 0.000 description 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 229920006334 epoxy coating Polymers 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 description 1
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 description 1
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 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
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The water-based epoxy curing agent adopts a mixed emulsifier, and the emulsifier is provided with a hydrophilic group and a lipophilic group; the mixed emulsifier is subjected to synthetic reaction with a fatty amine curing agent, and water is added to prepare a water-based curing agent; the reactive emulsifier is a mixture of acrylamide sodium isopropyl sulfonate and polyacrylamide fatty alcohol-polyoxyethylene ether, and the weight ratio is as follows: 30-70-30; the aliphatic polyamine in the aliphatic amine curing agent comprises at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylene tetramine and diethylaminopropylamine. The curing agent has the following novel properties: can react with pure bisphenol A epoxy resin or flexible epoxy resin, does not need to be matched with aqueous epoxy resin for use, thus avoiding 1.5-5 percent of cosolvent contained in the aqueous epoxy, and achieving real green in production and application).
Description
Technical Field
The invention relates to a water-based epoxy curing agent, a preparation method and application thereof, and belongs to the technical field of epoxy resin.
Background
The solvent-free high polymer material is the development direction of the industry; the applicant has also obtained an authorised method for the synthesis and curing of CN2016111495774 solvent-free high Tg liquid phosphorous epoxy resin; the applicant is a mass-production producer of epoxy resins; due to excellent adhesive force, electrical insulation, thermal stability and mechanical property, the epoxy resin is widely applied in the industrial production fields of coatings, advanced composite materials, engineering plastics, electronic and electrical appliance materials and the like. The water-based epoxy curing agent is an important component of a water-based epoxy system, and the composition and the structure of the water-based epoxy curing agent play a decisive role in the physical and chemical properties of a coating film. The research on the epoxy curing agent is relatively active abroad, the variety of the curing agent is more, the confidentiality is strong, and the development of the novel epoxy curing agent is favorable for opening up new application of the epoxy resin. The aqueous epoxy curing agent is usually modified polyamine, such as amidoamine, polyamide adduct, epoxy-polyamine adduct, etc., wherein the epoxy-polyamine adduct is suitable for room temperature curing aqueous epoxy coating. The key to preparing the curing agent is to ensure that primary amine on polyamine is converted as completely as possible through ring-opening reaction of epoxy resin and polyamine, thereby reducing the reactivity of polyamine, prolonging the room-temperature shelf life of the polyamine and simultaneously improving the compatibility with epoxy resin components. Chinese patent CN109517141A discloses a cardanol modified waterborne epoxy curing agent and a preparation method thereof, which improve the thermal stability and mechanical property of an epoxy resin cured product. Chinese patent CN101333286B discloses a synthesis method of a cardanol aldehyde amine epoxy curing agent, wherein the cardanol aldehyde amine epoxy curing agent has a long alkyl-substituted chain with good hydrophobicity and flexibility, so that the curing agent has excellent water resistance and flexibility. Chinese patent CN101676316A discloses a method for preparing an oil-water epoxy resin curing agent for cashew nut shells, which comprises the steps of end-capping triethylene tetramine with a monoepoxide compound, and adding cardanol into the product to prepare a curing agent. The prior art emulsifies epoxy resin to prepare waterborne epoxy, which is a technical line, and then forms a reaction system with a common curing agent, while in the process of emulsifying epoxy, a plurality of cosolvents are added more or less, so that a real solvent-free environment-friendly system cannot be achieved. CN 110128630A shows urushiol diglycidyl ether in a waterborne epoxy curing agent. The solvent-free process cannot be carried out by the subsequent users as long as the solvent is added.
Disclosure of Invention
The invention aims to provide a water-based epoxy curing agent and a preparation method thereof; in particular to a solvent-free waterborne epoxy curing agent: can react with pure bisphenol A epoxy resin or other epoxy resin, does not need to be matched with aqueous epoxy resin for use, and avoids 1.5-5 percent of cosolvent contained in the aqueous epoxy.
The technical scheme of the invention is that the waterborne epoxy curing agent adopts a mixed emulsifier, and the emulsifier is provided with a hydrophilic group and a lipophilic group; the mixed emulsifier is then reacted with fatty amine curing agent and compounded with water to compound water-thinned curing agent. The reactive emulsifier is a mixture of acrylamide sodium isopropyl sulfonate and polyacrylamide fatty alcohol-polyoxyethylene ether, and the weight ratio is as follows: 30-70-30; the aliphatic polyamine in the aliphatic amine curing agent comprises at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylene tetramine and diethylaminopropylamine. 1000PPM of polymerization inhibitor (various phenols) may be added.
The mixed emulsifier adopts acrylamide sodium isopropyl sulfonate and polyacrylamide fatty alcohol polyoxyethylene ether; stirring and mixing at 80 +/-15 ℃;
the second step of the preparation of the curing agent comprises the following steps: mixing type emulsifier: aliphatic polyamine is synthesized at about 60 +/-15 ℃ with the weight ratio of 1: 1.5-2.5, and water is added to prepare aqueous solution. The aliphatic polyamine is at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and diethylaminopropylamine.
The application of the invention is as follows: reaction system: pure epoxy resin: forming a solvent-free water-based reaction system by using a solvent-free curing agent which is 1: 1-1.5;
the water-based epoxy curing agent prepared by the invention has excellent water solubility, is mainly applied to modification of various water-based resins and can be prepared into water-based epoxy emulsion with the average particle size of less than or equal to 0.5um and the average particle size of less than or equal to 1.0um, is stable at normal temperature, is baked and cured at low, medium and high temperatures, and can be used as baking coatings, hydrophilic coatings, adhesives and the like.
The reactive emulsifier adopts acrylamide isopropyl sodium sulfonate and polyacrylamide fatty alcohol-polyoxyethylene ether in a weight ratio of: 30-70 to 70-30.
The water-based epoxy system is a dispersed phase structure and consists of water-based epoxy resin, a water-based epoxy curing agent, water and other multiple phases, the film forming mechanism of the water-based epoxy system is different from the film forming mechanism of a common polymer emulsion coating such as acrylic emulsion and can be condensed into a film, the film forming mechanism is not completely the same as the film forming mechanism of a solvent-based epoxy coating, in the solvent-based epoxy system, the epoxy resin and the curing agent are dissolved in an organic solvent in a molecular form, the formed system is homogeneous, the curing reaction is carried out among molecules, so the curing reaction is relatively complete, and the formed cured product is homogeneous. The aqueous epoxy is a multiphase system, the epoxy resin and the curing agent are dispersed in the water phase in a disperse phase, and the cross-linking and curing process is an interpenetration and internal diffusion cross-linking reaction process among particles in the process of water evaporation, so the curing degree of the aqueous epoxy depends on the following four factors: a) compatibility: the better the compatibility of the waterborne epoxy resin and the waterborne epoxy curing agent is, the better the compatibility is, the more the mutual internal diffusion of the curing agent particles and the epoxy resin particles is facilitated, and the proceeding of the curing reaction is facilitated; b) particle size: when the particle size is smaller, the waterborne epoxy resin and the waterborne epoxy curing agent disperse phase particles can fully interpenetrate to the inner core so as to achieve more complete curing degree; c) hydrophilic lipophilic balance value: the hydrophilic-lipophilic balance values of the waterborne epoxy resin and the waterborne epoxy curing agent are close to each other, the components reach a consistent coexistence state in the water phase, and if the difference is large, the components with strong hydrophilicity gradually gather in the water phase, so that the resin phase and the curing agent are separated; d) degree of dispersion uniformity: under the condition of multi-phase separation, the resin phase and the curing agent phase can be more uniformly distributed in the water phase only through a certain mechanical stirring action; the epoxy resin is very important to be uniformly stirred and mixed in application, and the curing process is easy to control and the reaction is complete.
Has the advantages that: the curing agent in the prior art forms a reaction system, and more or less cosolvent is added in the process of emulsifying epoxy, so that a real solvent-free environment-friendly system cannot be achieved. The invention can be used as a curing agent of all epoxy emulsification systems, has no solvent addition, has excellent water solubility, is mainly applied to modification of various water-based resins, has the average particle size of less than or equal to 0.5um and the average particle size of less than or equal to 1.0um, and is stable at normal temperature, and is baked and cured at low, medium and high temperatures. The curing agent has the following novel properties: the epoxy resin can react with pure bisphenol A epoxy resin or flexible epoxy resin, and does not need to be matched with waterborne epoxy resin for use, so that 1.5-5% of cosolvent (completely solvent-free can achieve real green in the production process) contained in waterborne epoxy is avoided, and a real solvent-free waterborne epoxy curing system is realized. And the brittleness of the water-based epoxy curing agent is overcome, and the using effect is good.
The waterborne epoxy curing agent and the preparation method thereof provided by the invention have the advantages that the method is simple to operate, and the raw material source is wide; the waterborne epoxy curing agent prepared by the method can improve the toughness and mechanical property of the epoxy resin material. And can obtain a water-based epoxy curing agent for curing epoxy resin at low temperature (less than 70 ℃). The weight ratio of the epoxy resin composition to the epoxy resin A component (such as bisphenol A, which is also used in other steps) is 1: 1-1.5. Pure epoxy can react, and the formed reaction system is absolutely solvent-free and environment-friendly. The packaging material (the invention is especially used for packaging glue of high-temperature batteries) adopts resin with high epoxy value (>0.40), such as E20(601) and E44 (6101).
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The epoxy resin raw materials in the examples of the present application were purchased commercially unless otherwise specified. The formula and the application are as follows:
emulsifier: aliphatic polyamine is synthesized at about 60 +/-15 ℃ in a ratio of 1: 1.2-1.3, and then water is added to prepare an aqueous solution.
The reactive emulsifier adopts acrylamide isopropyl sodium sulfonate and polyacrylamide fatty alcohol-polyoxyethylene ether in a weight ratio of: 30-70-30;
curing agent of the invention (solid content without water): the epoxy resin is 100: 100-150.
According to another aspect of the present application, there is also provided a method for preparing a water-based epoxy curing agent, comprising at least the following steps:
in the preparation method of the waterborne epoxy curing agent provided by the application, the waterborne epoxy curing agent is the waterborne epoxy curing agent.
The mixed emulsifier adopts acrylamide sodium isopropyl sulfonate and polyacrylamide fatty alcohol-polyoxyethylene ether in a weight ratio of 3: 7; stirring and mixing the mixture for 30 minutes at the temperature of 80 ℃ to obtain 100; the second step of the preparation of the curing agent comprises the following steps: mixing type emulsifier: aliphatic polyamine 100:120 weight portions, synthesizing at 60 ℃, stirring for 20 minutes, and adding 20 portions of water to prepare aqueous solution. The aliphatic polyamine is at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and diethylaminopropylamine. 1000PPM of hydroquinone polymerization inhibitor can be added.
Acrylamide sodium isopropyl sulfonate and polyacrylamide fatty alcohol polyoxyethylene ether, 5:5 weight parts.
Curing agent of the invention (solid content without water): the epoxy resin can be hydantoin epoxy resin or bisphenol A (S) epoxy resin 100: 100; when the epoxy resin is used for packaging materials (particularly for packaging glue of a high-temperature battery), the epoxy resin with a high epoxy value (>0.40) is adopted, such as E20(601) and E44 (6101). The amines are used in amounts of MG/Hn, where M is the molecular weight of the amine, Hn is the number of active hydrogens, and G is the epoxy number (equivalents of epoxy per 100G of epoxy resin) does not vary from 10 to 20%, which, if cured with excess amine, can embrittle the resin. If the amount is too small, the curing is incomplete.
The ammonia value is tested by adopting a test method of the total ammonia value of the JIS K7237-1995 epoxy resin amino hardener, the solid content is tested by adopting the GB/T2793-1995 adhesive non-volatile content, and the viscosity is tested by adopting a GB/T22314-. The viscosity (mPa. s, 25 ℃) can be controlled at 800-2000 ℃.
The curing agent has the following novel properties: the epoxy resin can react with pure bisphenol A epoxy resin or flexible epoxy resin, and does not need to be matched with waterborne epoxy resin for use, so that 1.5-5% of cosolvent contained in waterborne epoxy is avoided, and a real solvent-free waterborne epoxy curing system is realized.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (4)
1. The water-based epoxy curing agent is characterized in that a mixed emulsifier is adopted, and the emulsifier is provided with a hydrophilic group and a lipophilic group; the mixed emulsifier is subjected to synthetic reaction with a fatty amine curing agent, and water is added to prepare a water-based curing agent; the reactive emulsifier is a mixture of acrylamide sodium isopropyl sulfonate and polyacrylamide fatty alcohol-polyoxyethylene ether, and the weight ratio is as follows: 30-70-30; the aliphatic polyamine in the aliphatic amine curing agent comprises at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylene tetramine and diethylaminopropylamine.
2. The aqueous epoxy curing agent according to claim 1, wherein 1000PPM of a polymerization inhibitor is added.
3. The aqueous epoxy hardener as claimed in claim 1, wherein the reaction system used is: pure epoxy: and (3) forming a solvent-free water-based reaction system by using the solvent-free curing agent which is 1: 1-1.5.
4. The preparation method of the aqueous epoxy hardener as claimed in one of claims 1 to 3, wherein the mixed emulsifier is selected from sodium acrylamido isopropyl sulfonate and polyacrylamide fatty alcohol polyoxyethylene ether; stirring and mixing at 80 +/-15 ℃; the second step of the preparation of the curing agent comprises the following steps: mixing type emulsifier: aliphatic polyamine is synthesized at about 60 +/-15 ℃ in a weight ratio of 1: 1.5-2.5, and water is added to prepare an aqueous solution; the aliphatic polyamine is at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and diethylaminopropylamine.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010488826.2A CN111607068A (en) | 2020-06-02 | 2020-06-02 | Water-based epoxy curing agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010488826.2A CN111607068A (en) | 2020-06-02 | 2020-06-02 | Water-based epoxy curing agent and preparation method thereof |
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| CN111607068A true CN111607068A (en) | 2020-09-01 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702484A (en) * | 2012-05-31 | 2012-10-03 | 天津大学 | Epoxy modified water-based polyacrylamide curing agent and preparation method thereof |
| CN103012689A (en) * | 2013-01-06 | 2013-04-03 | 江苏金陵特种涂料有限公司 | Organic silicon acrylic acid modified waterborne epoxy emulsion and preparation method thereof |
| CN105732881A (en) * | 2016-05-16 | 2016-07-06 | 北京化工大学 | Waterborne epoxy/polyacrylate composite emulsion and preparation method thereof |
| CN106634388A (en) * | 2016-12-29 | 2017-05-10 | 海洋化工研究院有限公司 | Waterborne acrylic acid modified epoxy emulsion and high-performance waterborne epoxy anticorrosive coating |
-
2020
- 2020-06-02 CN CN202010488826.2A patent/CN111607068A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702484A (en) * | 2012-05-31 | 2012-10-03 | 天津大学 | Epoxy modified water-based polyacrylamide curing agent and preparation method thereof |
| CN103012689A (en) * | 2013-01-06 | 2013-04-03 | 江苏金陵特种涂料有限公司 | Organic silicon acrylic acid modified waterborne epoxy emulsion and preparation method thereof |
| CN105732881A (en) * | 2016-05-16 | 2016-07-06 | 北京化工大学 | Waterborne epoxy/polyacrylate composite emulsion and preparation method thereof |
| CN106634388A (en) * | 2016-12-29 | 2017-05-10 | 海洋化工研究院有限公司 | Waterborne acrylic acid modified epoxy emulsion and high-performance waterborne epoxy anticorrosive coating |
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Application publication date: 20200901 |