CN105175687A - Preparation method of zero-VOC (volatile organic compound) high-toughness water-based epoxy resin curing agent - Google Patents
Preparation method of zero-VOC (volatile organic compound) high-toughness water-based epoxy resin curing agent Download PDFInfo
- Publication number
- CN105175687A CN105175687A CN201510671130.2A CN201510671130A CN105175687A CN 105175687 A CN105175687 A CN 105175687A CN 201510671130 A CN201510671130 A CN 201510671130A CN 105175687 A CN105175687 A CN 105175687A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- curing agent
- resin curing
- preparation
- glycidyl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 40
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000012855 volatile organic compound Substances 0.000 title abstract 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 20
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229920000768 polyamine Polymers 0.000 claims abstract description 11
- 229960000583 acetic acid Drugs 0.000 claims abstract description 10
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000004593 Epoxy Substances 0.000 claims description 22
- 229910003460 diamond Inorganic materials 0.000 claims description 13
- 239000010432 diamond Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- 229960001124 trientine Drugs 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- -1 ketone diamines Chemical class 0.000 claims description 5
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 4
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims 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 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- NPKKFQUHBHQTSH-UHFFFAOYSA-N 2-(decoxymethyl)oxirane Chemical compound CCCCCCCCCCOCC1CO1 NPKKFQUHBHQTSH-UHFFFAOYSA-N 0.000 claims description 3
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 claims description 3
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical group C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 3
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 3
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims description 2
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000003141 primary amines Chemical group 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- LYWVNPSVLAFTFX-UHFFFAOYSA-N 4-methylbenzenesulfonate;morpholin-4-ium Chemical compound C1COCCN1.CC1=CC=C(S(O)(=O)=O)C=C1 LYWVNPSVLAFTFX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006334 epoxy coating Polymers 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
- 150000002576 ketones Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The invention discloses a preparation method of a zero-VOC (volatile organic compound) high-toughness water-based epoxy resin curing agent. Polyamine is heated to 50 to 70 DEG C; double-end epoxy group glycidyl ether or a mixture of the double-end dpoxy group glycidyl ether and epoxy resin is dripped under a stirring condition; the dripping is completed within 1 to 2h; the materials are continuously stirred and are subjected to temperature preservation for reaction for 3 to 4h; reduced pressure distillation is carried out to obtain an intermediate a; end epoxy group glycidyl ether is dripped into the a at 50 to 70 DEG C; the heat preservation is carried out for 2 to 3h to obtain an intermediate b; glacial acetic acid is added into the b for neutralization; then, deionized water is added for dispersion; aqueous epoxy resin curing agents are obtained. Any organic solvents are not added in the process of preparing the water-based epoxy resin curing agent, and the finial product is the zero-VOC high-toughness water-based epoxy resin curing agent. The room-temperature curing toughness water-based epoxy resin curing agent synthesized by a two-step chain expansion method has the advantages that the preparation process is simple, the reaction condition is mild, and the like. The viscosity is smaller than that of the intermediate prepared from the pure epoxy resin; the toughness is higher than that of the intermediate prepared from the pure epoxy resin.
Description
Technical field
The invention belongs to technical field of coatings, be specifically related to a kind of aqueous epoxy resin curing agent.
Background technology
Traditional solvent based coating contains a large amount of volatilizable organic compound (VOC), all can cause serious harm to mankind itself and environment, and environment-friendly type coating replaces solvent based coating to become inevitable.And water-borne coatings has the features such as economy, environmental protection and safety, meet current demand for development, its exploitation and popularization will become focus.
Epoxy resin is the thermosetting polymer synthetic materials that a class has the performances such as bonds well, electric insulation, corrosion-resistant, high strength, applies increasingly extensive.Aqueous epoxy coating is made up of aqueous epoxy resins dispersion, aqueous epoxy curing agent and color stuffing.Traditional unmodified aqueous epoxy curing agent mainly polyamine, exists that response speed is fast, wayward, toxicity is large, CO in the easily strict and air of ratio requirement
2with shortcomings such as water reactions, therefore need to carry out modification to it.Prepare disclosed in patent CN101613460B in the method for nonionic waterborne epoxy curing agent, use can a certain amount of organic solvent, and preparation process complicated difficult is to control, and easy gel in preparation process, above shortcoming makes it be restricted when practical application.The polyether monoamine and for example adopted in the prior art polyether monoamine solidifying agent that especially molecular weight is higher, although its flexibility had, but curing speed slowly when temperature is lower, the tolerance performance for strong corrosive medium (strong acid, highly basic etc.) etc. can not meet the demands.
Summary of the invention
The object of the invention is the preparation method providing a kind of Diamond Search high-flexibility aqueous epoxy resin curing agent, and it is not containing solvent and do not add any auxiliary agent in preparation process, overcome can existing solidifying agent preparation process complexity, be difficult to control, the problem such as flexible difference.
For achieving the above object, adopt technical scheme as follows:
A preparation method for Diamond Search high-flexibility aqueous epoxy resin curing agent, comprises the following steps:
1) preparation of intermediate: polyamine is warming up to 50-70 DEG C, the mixture of both-end epoxy group(ing) glycidyl ether or itself and epoxy resin is dripped under agitation condition, add in 1-2h, continue to stir insulation reaction 3-4h, underpressure distillation removes excessive polyamine and obtains intermediate a;
2) primary amine groups is closed: at 50-70 DEG C, be added dropwise to epoxy terminated glycidyl ether to above-mentioned intermediate a, and insulation 2-3h obtains intermediate b;
3) in and salify: add in glacial acetic acid and salify in intermediate b, then add deionized water dispersion, obtain Diamond Search high-flexibility aqueous epoxy resin curing agent.
By such scheme, raw materials is as follows according to the mass fraction:
Polyamine 30-100 part; Mixture 25-52 part of both-end epoxy group(ing) glycidyl ether or itself and epoxy resin; Epoxy terminated glycidyl ether 23-78 part; Glacial acetic acid 10-20 part; Deionized water 60-118 part.
By such scheme, described polyamine amine is diethylenetriamine, one in your ketone of triethylene tetramine, tetraethylene pentamine, different fluorine diamines or mix arbitrarily.
By such scheme, described both-end base glycidyl ether is the one in 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidylether, butanediol diglycidyl ether, neopentylglycol diglycidyl ether, cylohexanediol diglycidyl ether, resorcinol diglycidyl ether.
By such scheme, described epoxy resin is bisphenol A type epoxy resin E-44, E-51 or the mixture of the two.
By such scheme, described epoxy terminated glycidyl ether is benzyl glycidyl ether, butylglycidyl ether, octyl glycidyl ether, decyl glycidyl ether, carbon lauryl diglycidyl ether.
By such scheme, the solid of described aqueous epoxy curing agent contains for 50-70wt%, and amine value is 90-300mgKOH/g.
Compared with prior art, the present invention has the following advantages:
(1) aqueous epoxy curing agent that prepared by the present invention does not add any organic solvent during the course, and the finished product are the environmentally friendly solidifying agent of Diamond Search high-flexibility.
(2) the present invention utilizes 1,6-hexanediol diglycidyl ether to replace or part replaces epoxy resin E-44, better compared with the snappiness of its film of solidifying agent right prepared by pure epoxy resin E-44.
(3) the present invention adopts a kind of self-vulcanizing toughness aqueous epoxy curing agent synthesized by two step chain extension methods, has the advantages such as preparation technology is simple, reaction conditions is gentle.
Embodiment
Following examples explain technical scheme of the present invention further, but not as limiting the scope of the invention.
Embodiment 1:
Under the protection of drying nitrogen, triethylene tetramine is put into reflux condensing tube is housed, temperature takes into account in the four-hole bottle of agitator; Heating in water bath, when temperature rises to 70 DEG C, uniform speed slow drips the E-44 epoxy resin and 1 of preheating, the mixture of 6-hexanediol diglycidyl ether, be incubated 4 hours after dropwising in 1 hour, excessive triethylene tetramine is sloughed in underpressure distillation, slowly end-capping reagent butylglycidyl ether is dripped in 1 hour, be incubated 3 hours, to add in Glacial acetic acid and after add water-dispersion, discharging obtains aqueous epoxy curing agent a.
Wherein the consumption (quality/g) of various raw material used is:
Embodiment 2
The present embodiment shows that the epoxy resin of different ratios and 1,6-hexanediol diglycidyl ether amine prepare epoxy hardener, and concrete steps are:
Under the protection of drying nitrogen, diethylenetriamine is put into reflux condensing tube is housed, temperature takes into account in the four-hole bottle of agitator; Heating in water bath, when temperature rises to 60 DEG C, uniform speed slow drips the E-44 epoxy resin of preheating and the mixture of ethylene glycol diglycidylether, 3 hours are incubated after dropwising in 2 hours, unreacted diethylenetriamine is sloughed in underpressure distillation, in 1 hour, slowly drip end-capping reagent benzyl glycidyl ether, be incubated 2 hours, add in Glacial acetic acid with after add water-dispersion discharging and obtain aqueous epoxy curing agent b.
Wherein the consumption (quality/g) of various raw material used is:
Embodiment 3
The present embodiment shows that the different polyamine of use prepares ring water-based oxygen solidifying agent, and its concrete steps are:
Under the protection of drying nitrogen, your ketone diamines of different fluorine is put into reflux condensing tube is housed, temperature takes into account in the four-hole bottle of agitator; Heating in water bath, when temperature rises to 60 DEG C, uniform speed slow drips the E-44 epoxy resin of preheating and the mixture of neopentylglycol diglycidyl ether, 3.5 hours are incubated after dropwising in 1.5 hours, unreacted different fluorine that ketone diamines is sloughed in underpressure distillation, in 1 hour, slowly drip end-capping reagent octyl glycidyl ether, be incubated 2.5 hours, add in Glacial acetic acid with after add water-dispersion discharging and obtain aqueous epoxy curing agent c.
Wherein the consumption (quality/g) of various raw material used is:
Embodiment 4
The present embodiment shows that the epoxy resin of the different trade mark prepares aqueous epoxy curing agent, and concrete steps are:
Under the protection of drying nitrogen, triethylene tetramine is put into reflux condensing tube is housed, temperature takes into account in the four-hole bottle of agitator; Heating in water bath, when temperature rises to 60 DEG C, uniform speed slow drips the E-51 epoxy resin of preheating and the mixture of cylohexanediol diglycidyl ether, 3 hours are incubated after dropwising in 1 hour, unreacted triethylene tetramine is sloughed in underpressure distillation, in 1 hour, slowly drip end-capping reagent butylglycidyl ether, be incubated 2 hours, add in Glacial acetic acid with after add water-dispersion discharging and obtain aqueous epoxy curing agent d.
Wherein the consumption (quality/g) of various raw material used is:
Embodiment 5
The present embodiment shows that different end-capping reagent prepares epoxy hardener, and concrete steps are:
Under the protection of drying nitrogen, tetraethylene pentamine is put into reflux condensing tube is housed, temperature takes into account in the four-hole bottle of agitator; Heating in water bath, when temperature rises to 70 DEG C, uniform speed slow drips 1,6-hexanediol diglycidyl ether, be incubated 3 hours after dropwising in 2 hours, unreacted tetraethylene pentamine is sloughed in underpressure distillation, in 1 hour, slowly drip end-capping reagent decyl glycidyl ether, be incubated 3 hours, to add in Glacial acetic acid and after add water-dispersion discharging and obtain aqueous epoxy curing agent e.
Wherein the consumption (quality/g) of various raw material used is:
With the index of above-mentioned aqueous epoxy curing agent a, b, c, d and e and with water-based ring resin emulsion (as 3520 of Shell Co. Ltd, the EP384W/53WAMP of profound new company, the AEH-20 of the Dow Chemical Company) solidify after film performance list in respectively in table 1.
Table 1
Claims (7)
1. the preparation method of Diamond Search high-flexibility aqueous epoxy resin curing agent, is characterized in that comprising the following steps:
1) preparation of intermediate: polyamine is warming up to 50-70 DEG C, the mixture of both-end epoxy group(ing) glycidyl ether or itself and epoxy resin is dripped under agitation condition, add in 1-2h, continue to stir insulation reaction 3-4h, underpressure distillation removes excessive polyamine and obtains intermediate a;
2) primary amine groups is closed: at 50-70 DEG C, be added dropwise to epoxy terminated glycidyl ether to above-mentioned intermediate a, and insulation 2-3h obtains intermediate b;
3) in and salify: add in glacial acetic acid and salify in intermediate b, then add deionized water dispersion, obtain Diamond Search high-flexibility aqueous epoxy resin curing agent.
2. the preparation method of Diamond Search high-flexibility aqueous epoxy resin curing agent as claimed in claim 1, is characterized in that raw materials is as follows according to the mass fraction:
Polyamine 30-100 part; Mixture 25-52 part of both-end epoxy group(ing) glycidyl ether or itself and epoxy resin; Epoxy terminated glycidyl ether 23-78 part; Glacial acetic acid 10-20 part; Deionized water 60-118 part.
3. the preparation method of Diamond Search high-flexibility aqueous epoxy resin curing agent as claimed in claim 1, is characterized in that described polyamine amine is diethylenetriamine, one in your ketone diamines of triethylene tetramine, tetraethylene pentamine, different fluorine or mix arbitrarily.
4. the preparation method of Diamond Search high-flexibility aqueous epoxy resin curing agent as claimed in claim 1, it is characterized in that described both-end base glycidyl ether is the one in 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidylether, butanediol diglycidyl ether, neopentylglycol diglycidyl ether, cylohexanediol diglycidyl ether, resorcinol diglycidyl ether.
5. the preparation method of Diamond Search high-flexibility aqueous epoxy resin curing agent as claimed in claim 1, is characterized in that described epoxy resin is bisphenol A type epoxy resin E-44, E-51 or the mixture of the two.
6. the preparation method of Diamond Search high-flexibility aqueous epoxy resin curing agent as claimed in claim 1, is characterized in that described epoxy terminated glycidyl ether is benzyl glycidyl ether, butylglycidyl ether, octyl glycidyl ether, decyl glycidyl ether, carbon lauryl diglycidyl ether.
7. the preparation method of Diamond Search high-flexibility aqueous epoxy resin curing agent as claimed in claim 1, it is characterized in that the solid containing being 50-70wt% of described aqueous epoxy curing agent, amine value is 90-300mgKOH/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510671130.2A CN105175687B (en) | 2015-10-15 | 2015-10-15 | The preparation method of Diamond Search high-flexibility aqueous epoxy resin curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510671130.2A CN105175687B (en) | 2015-10-15 | 2015-10-15 | The preparation method of Diamond Search high-flexibility aqueous epoxy resin curing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105175687A true CN105175687A (en) | 2015-12-23 |
| CN105175687B CN105175687B (en) | 2017-07-11 |
Family
ID=54898175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510671130.2A Active CN105175687B (en) | 2015-10-15 | 2015-10-15 | The preparation method of Diamond Search high-flexibility aqueous epoxy resin curing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105175687B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336500A (en) * | 2016-08-31 | 2017-01-18 | 重庆南方漆业有限公司 | Waterborne epoxy curing agent and preparation method thereof |
| CN107286324A (en) * | 2017-06-07 | 2017-10-24 | 常州兆威不锈钢有限公司 | A kind of preparation method of modified aqueous epoxy resin curing agent |
| CN109096874A (en) * | 2018-07-13 | 2018-12-28 | 安徽康瑞高科新材料技术工程有限公司 | A kind of aqueous glass paint and preparation method thereof |
| CN111234178A (en) * | 2020-03-31 | 2020-06-05 | 陕西立高涂料有限公司 | Self-emulsifying water-based epoxy resin curing agent and preparation method thereof |
| CN112500553A (en) * | 2020-12-03 | 2021-03-16 | 武汉市科达云石护理材料有限公司 | Waterborne epoxy back-mesh adhesive curing agent, preparation method and back-mesh adhesive |
| CN112745482A (en) * | 2020-12-28 | 2021-05-04 | 上海瀚岱化学有限公司 | Water-based epoxy resin curing agent and preparation method thereof |
| CN113583538A (en) * | 2021-07-15 | 2021-11-02 | 海洋化工研究院有限公司 | Solvent-free nontoxic anticorrosive paint for marine culture cabin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649041A (en) * | 2009-09-04 | 2010-02-17 | 武汉工程大学 | Method for preparing self-emulsifying aqueous epoxy resin curing agent |
| CN103554438A (en) * | 2013-10-12 | 2014-02-05 | 瑞奇化工（松滋）有限公司 | Preparation method of modified epoxy hardener for reducing bleaching |
| CN103554439A (en) * | 2013-10-12 | 2014-02-05 | 瑞奇化工（松滋）有限公司 | Low-odor epoxy curing agent and preparation method thereof |
| CN103788343A (en) * | 2014-01-26 | 2014-05-14 | 浙江环达漆业集团有限公司 | VOC (Volatile Organic Compounds)-free water-based epoxy curing agent |
-
2015
- 2015-10-15 CN CN201510671130.2A patent/CN105175687B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649041A (en) * | 2009-09-04 | 2010-02-17 | 武汉工程大学 | Method for preparing self-emulsifying aqueous epoxy resin curing agent |
| CN103554438A (en) * | 2013-10-12 | 2014-02-05 | 瑞奇化工（松滋）有限公司 | Preparation method of modified epoxy hardener for reducing bleaching |
| CN103554439A (en) * | 2013-10-12 | 2014-02-05 | 瑞奇化工（松滋）有限公司 | Low-odor epoxy curing agent and preparation method thereof |
| CN103788343A (en) * | 2014-01-26 | 2014-05-14 | 浙江环达漆业集团有限公司 | VOC (Volatile Organic Compounds)-free water-based epoxy curing agent |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336500A (en) * | 2016-08-31 | 2017-01-18 | 重庆南方漆业有限公司 | Waterborne epoxy curing agent and preparation method thereof |
| CN107286324A (en) * | 2017-06-07 | 2017-10-24 | 常州兆威不锈钢有限公司 | A kind of preparation method of modified aqueous epoxy resin curing agent |
| CN109096874A (en) * | 2018-07-13 | 2018-12-28 | 安徽康瑞高科新材料技术工程有限公司 | A kind of aqueous glass paint and preparation method thereof |
| CN111234178A (en) * | 2020-03-31 | 2020-06-05 | 陕西立高涂料有限公司 | Self-emulsifying water-based epoxy resin curing agent and preparation method thereof |
| CN112500553A (en) * | 2020-12-03 | 2021-03-16 | 武汉市科达云石护理材料有限公司 | Waterborne epoxy back-mesh adhesive curing agent, preparation method and back-mesh adhesive |
| CN112500553B (en) * | 2020-12-03 | 2023-06-02 | 武汉市科达云石护理材料有限公司 | Waterborne epoxy back-screen adhesive curing agent, preparation method thereof and back-screen adhesive |
| CN112745482A (en) * | 2020-12-28 | 2021-05-04 | 上海瀚岱化学有限公司 | Water-based epoxy resin curing agent and preparation method thereof |
| CN113583538A (en) * | 2021-07-15 | 2021-11-02 | 海洋化工研究院有限公司 | Solvent-free nontoxic anticorrosive paint for marine culture cabin |
| CN113583538B (en) * | 2021-07-15 | 2022-07-26 | 海洋化工研究院有限公司 | Solvent-free nontoxic anticorrosive paint for marine culture cabin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105175687B (en) | 2017-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105175687A (en) | Preparation method of zero-VOC (volatile organic compound) high-toughness water-based epoxy resin curing agent | |
| CN106987194B (en) | Nonionic waterborne epoxy resin emulsion, nonionic waterborne epoxy curing agent, preparation methods of nonionic waterborne epoxy resin emulsion and nonionic waterborne epoxy curing agent and waterborne epoxy resin varnish | |
| CN110066383B (en) | Ionic waterborne epoxy curing agent and preparation method and application thereof | |
| CN101555386B (en) | Epoxy organosilicone ultraviolet curing coating modified by (methyl) acrylic acid and preparation method thereof | |
| CN102250321B (en) | Quick-drying room temperature curing waterborne epoxy resin curing agent and preparation method thereof | |
| CN109294407B (en) | Water-based anticorrosive paint and preparation method thereof | |
| CN109824869A (en) | A kind of epoxy curing agent and preparation method thereof | |
| CN115819039B (en) | High-strength environment-friendly artistic micro-cement and preparation method thereof | |
| CN103694637B (en) | A kind of High-tenacity vacuum slow epoxy resin for wind power blade and preparation method thereof | |
| CN113980248A (en) | Water-based epoxy curing agent and preparation method and application thereof | |
| CN110511356A (en) | A kind of silicon oil modified aqueous epoxy curing agent of epoxy and phenyl and preparation method thereof | |
| CN106554482B (en) | A kind of preparation method of the star-like aqueous epoxy curing agent of high-performance | |
| CN105330822A (en) | Water-borne epoxy resin curing agent | |
| CN108373533B (en) | Preparation method of self-emulsifying water-based epoxy curing agent | |
| CN114133872B (en) | Rubber asphalt waterproof paint and preparation method thereof | |
| CN114591492B (en) | Water-based epoxy curing agent and preparation method and application thereof | |
| CN103044657B (en) | Nano-modified epoxy resin and preparation method thereof | |
| CN114573793A (en) | Preparation method of waterborne epoxy curing agent based on addition of cardanol glycidyl ether | |
| CN110669206A (en) | Water-soluble cardanol waterborne epoxy resin curing agent and preparation method and application thereof | |
| CN107236097A (en) | A kind of anticorrosive paint water-base resin and preparation method thereof | |
| CN112898516B (en) | Phenolic aldehyde modified amine and preparation method thereof | |
| CN112175169A (en) | Heat-resistant water-based epoxy resin and preparation method thereof | |
| CN111378321A (en) | Online water-based ink suitable for two-dimensional code spraying and preparation method thereof | |
| CN110128630A (en) | A kind of aqueous epoxy curing agent and preparation method thereof | |
| CN104610239A (en) | Preparation method for composite terminated waterborne epoxy resin curing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200417 Address after: 515500 south side of the middle section of Hua'an Road, Jiedong Economic Development Zone, Jieyang City, Guangdong Province (block 16) Patentee after: GUANGDONG TIANYIN INDUSTRIAL CO.,LTD. Address before: 430074, No. 693 Xiong Chu street, Hongshan District, Hubei, Wuhan Patentee before: WUHAN INSTITUTE OF TECHNOLOGY |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of zero VOC high flexibility and toughness waterborne epoxy resin curing agent Effective date of registration: 20231113 Granted publication date: 20170711 Pledgee: Jiedong County Branch of China Postal Savings Bank Co.,Ltd. Pledgor: GUANGDONG TIANYIN INDUSTRIAL CO.,LTD. Registration number: Y2023980065232 |