CN102190800B - Preparation method of nonionic waterborne epoxy curing agent - Google Patents
Preparation method of nonionic waterborne epoxy curing agent Download PDFInfo
- Publication number
- CN102190800B CN102190800B CN 201010142715 CN201010142715A CN102190800B CN 102190800 B CN102190800 B CN 102190800B CN 201010142715 CN201010142715 CN 201010142715 CN 201010142715 A CN201010142715 A CN 201010142715A CN 102190800 B CN102190800 B CN 102190800B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- reaction
- epoxy
- temperature
- under
- 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.)
- Active
Links
Landscapes
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a preparation method of a nonionic waterborne epoxy curing agent, which comprises the following steps: (1) heating and dissolving epoxy resin and polyether polyol, evenly mixing, dropwisely adding catalyst at 50-130 DEG C to carry out polymerization reaction, and after the reaction finishes, dissolving the product in the epoxy resin and solvent to prepare a mixed solution; (2) while stirring, dropwisely adding a monoepoxy compound into basic amine, and reacting at 10-100 DEG C; (3) dropwisely adding the mixed solution in the step (1) into the reaction product in the step (2) at 30-120 DEG C, and enabling the reaction at 10-90 DEG C; and after the reaction finishes, diluting by adding water until the solid content reaches 30-80%, thereby obtaining the nonionic waterborne epoxy curing agent. The method has the advantages of simple technique and mild reaction conditions; the adopted cosolvent has the advantages of low toxicity or no toxicity, and low VOC (volatile organic compound) content; and the substance cured by the product has the advantages of favorable compatibility with epoxy resin and high toughness of the paint film.
Description
Technical field
The present invention relates to a kind of preparation method of non-ion aqueous epoxy hardener.
Background technology
Aqueous epoxy coating development in recent years is very fast, and it is one type of eco-friendly macromolecular material, has plurality of advantages such as organic solvent content is low, smell is little, chemical-resistant, insulativity, has been widely used and application prospect.Solidifying agent is one of key factor that influences the bi-component epoxy coating property, is the key component of decision product Technology and characteristic.Common aliphatics amine self-vulcanizing agent stimulates bigger to human body, be prone to again generate salt or absorb the moisture whiting with the carbon dioxide in air reaction.The aqueous epoxy curing agent of the self-vulcanizing that use on the historical facts or anecdotes border adopts their modified product mostly; Comprise amidated polyamines, polymeric amide and epoxy-polyamines affixture; Because water tolerance of filming and chemical-resistant after the amides solidifying agent solidifies are relatively poor, using more at present is epoxy-polyamines affixture.
Along with the development of aqueous epoxy coating, the research of waterborne curing agent also begins development, but its correlative study is also fewer.Common in the market aqueous epoxy curing agent has ionic waterborne curing agent and non-ion aqueous solidifying agent etc.; The ionic solidifying agent is because adopt in the organic acid and salify; Its organic acid exists; Be used in to be prone on the metal produce and dodge rust, because of organic acid exists, when using, be prone to unstable phenomenon simultaneously with some alkaline color stuffings.
The waterborne curing agent that the US6277928 patented technology relates to is in the preparation process, and amine is excessive, and reaction need be deviate from unnecessary amine after accomplishing, and energy consumption is high; And add noxious solvents such as toluene in the reaction process, reaction need remove this part solvent after accomplishing on the one hand, requires the expenditure of energy not environmental protection of production process on the other hand.
CN 101007863 discloses a kind of preparation method of non-ion aqueous epoxy hardener, but its preparation technology is in chain extending reaction, and amine is a large amount of excessive; And add a large amount of solvents in the reaction process, and reaction need remove unnecessary amine and solvent after accomplishing, and the boiling point of amine is high on the one hand; Remove unnecessary amine and need very high temperature; Energy consumption is high, and in subtractive process, amine and solvent can not be separated fully on the other hand; Further adding high amounts of solvents in the chain extending reaction, reaction need be carried out the underpressure distillation desolventizing after accomplishing.Whole technology more complicated, energy consumption is high.
Summary of the invention
The objective of the invention is to the deficiency to prior art, a kind of preparation method of non-ion aqueous epoxy hardener is provided, this method technology is fairly simple; Reaction conditions is relatively gentleer; Raw materials used amine is inexcessive, the solubility promoter low toxicity of employing or nontoxic, and VOC (volatile organic compounds) content is low; The cured article and the epoxy resin compatibility property of products therefrom are good, the paint film good toughness.
The preparation method of a kind of non-ion aqueous epoxy hardener provided by the invention comprises the steps:
(1) epoxy resin and polyethers alcohols material heating fusion are mixed, under 50 ℃～130 ℃ temperature, drip catalyzer, carry out polyreaction, wherein: the mol ratio of epoxy resin and polyethers alcohols material is 0.5: 1～5: 1; Catalyst consumption is 0.1%～1% of epoxy resin and a polyethers alcohols material gross weight sum.Reaction is made into mixing solutions with resultant and epoxy resin, dissolution with solvents after accomplishing, and solvent load is 1～80% of a mixing solutions gross weight.
(2) under agitation condition, drip mono-epoxy compounds in single polyamines, under 10 ℃～100 ℃ temperature, react, wherein: the mol ratio of single polyamines and mono-epoxy compounds is 1: 0.05～1: 3.
(3) under the temperature of 30～120 ℃ of temperature, the mixing solutions of step (1) is added drop-wise in the reaction product of step (2), under 10 ℃～90 ℃ temperature, it is reacted; The mol ratio of epoxy group(ing) and single polyamines is 0.1: 1～4: 1 in the hierarchy of control, and the polyether segment that the polyethers alcohols material provides accounts for 10～50% of total solids part, and total solids part is single polyamines, mono-epoxy compounds, epoxy resin and polyethers alcohols material sum; Reaction adds entry after accomplishing, and it is diluted to solid content is 30～80%, promptly obtains non-ion aqueous epoxy hardener.
Said epoxy resin is that epoxy equivalent (weight) is 150～1000 bisphenol A type epoxy resin, bisphenol f type epoxy resin.
Said polyethers alcohols material is one or more the compsn in polyethylene glycol type, W 166 type, the polyether-type.
Said catalyzer is lewis acid catalyst or Louis's bases catalyzer, and lewis acid catalyst is Potassium Persulfate, BFEE, tin tetrachloride, Zinc Chloride Anhydrous etc.; Lewis-base catalyst is ammonia, amine, water, carbon monoxide, CH
3OH or CH
3COCH
3Deng.
Said solvent is gylcol ether and propylene glycol kind solvent.
Said mono-epoxy compounds comprises: methyl glycidyl ether, propyl glycidyl ether, butylglycidyl ether, ethylene glycol diglycidylether, hexanediol diglycidyl ether, phenyl glycidyl ether etc.
Said single polyamines is one or more the mixture in aromatic amine, aliphatic amide, the aliphatic cyclic amine; Said aromatic amine has mphenylenediamine, a benzene two methanediamines, diaminodiphenyl-methane etc.; Said aliphatic cyclic amine has alkane diamines in the Meng, isophorone diamine, N-aminoethyl piperazine etc.; Said aliphatic amide has quadrol, tn, tetramethylenediamine, pentamethylene diamine, hexanediamine, diethylenetriamine, triethylene tetramine, TEPA, diethylaminopropylamine etc.
With respect to prior art, the present invention has following advantage:
(1) the present invention carries out the end capping of part or all of primary amine hydrogen through adopting earlier mono-epoxy compounds to single polyamines class, can prevent that too much primary amine hydrogen from absorbing airborne moisture and paint film is turned white, and improved water resistance; Also can improve the consistency of solidifying agent and epoxy resin; And the working life of prolongation epoxy resin.
(2) the present invention carries out further addition reaction with epoxy resin to the end-blocking product, thereby in the solidifying agent molecular structure, introduces the epoxy resin molecule segment, further improves the consistency of solidifying agent and epoxy resin.
(3) the present invention carries out further addition reaction with the intermediate materials with hydrophilicity to the end-blocking product, in the solidifying agent molecular structure, introduces the flexible polyether segment of possess hydrophilic property, increases the wetting ability of solidifying agent and the snappiness of paint film.
(4) the prepared aqueous epoxy curing agent of the present invention has the function of self-emulsifying epoxy resin.
(5) the prepared aqueous epoxy curing agent VOC of the present invention content is low, and product does not fire.
(6) preparing method's technology of the present invention is fairly simple, and the solubility promoter add-on seldom removes or do not remove after reaction is accomplished, because add-on is few, removes also and is easy to, and energy consumption is low, and synthesis condition is relatively gentleer.
Embodiment
In order to understand the present invention better, below in conjunction with embodiment the present invention is done detailed description further, but the scope that the present invention requires to protect is not limited to the represented scope of embodiment.
Embodiment 1
200g Macrogol 2000 and 69gCYD-128 are put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, TM, whisking appliance, and the heating fusion is 100 ℃ of temperature; Under-0.095MPa the vacuum condition, underpressure distillation 1 hour, holding temperature; The mixing solutions of 0.65g BFEE and 7g ethylene glycol ethyl ether progressively increases under normal pressure; Dropwised in 70 minutes, and kept reaction 3 hours, obtain light solid matter.Get this material of 19g and 35g CYD-128 and under 70 ℃ temperature, be dissolved in the 2g ethylene glycol ethyl ether and process mixing solutions, keep temperature for use.
The 31g triethylene tetramine is put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, TM, whisking appliance, and normal temperature drips the 13g butylglycidyl ether down in reaction flask, dropwises in 20 minutes, and insulation reaction is 3 hours under the condition of 50 ℃ of temperature.Be cooled to 40 ℃, drip above-mentioned mixing solutions so far in the material of four-hole reaction flask, added in 60 minutes; Temperature maintenance is 65～75 ℃ of insulation reaction, and reaction removes solubility promoter after accomplishing; Drip the 98g pure water, added in 30 minutes, obtain the aqueous epoxy curing agent of solid content 50%, VOC＜1g/L.
It is composite that this waterborne curing agent and aqueous epoxy resins are pressed epoxy equivalent (weight) and amine hydrogen equivalent 1: 1, and its pencil hardness is 3H, and sticking power is 1 grade, and shock resistance is 60cmKg, and in 10% sodium chloride aqueous solution, the above paint film of 200h is excellent, and not having comes off does not have and bubble.
Embodiment 2
200g Macrogol 2000 and 69gCYD-128 are put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, TM, whisking appliance, and the heating fusion is 100 ℃ of temperature; Under-0.095MPa the vacuum condition, underpressure distillation 1 hour, holding temperature; The mixing solutions of 0.65g BFEE and 7g ethylene glycol ethyl ether progressively increases under normal pressure; Dropwised in 70 minutes, and kept reaction 3 hours, obtain light solid matter.Get this material of 35g and 40g E-44 and under 60 ℃ temperature, be dissolved in the 3g propylene glycol monomethyl ether and process mixing solutions, keep temperature for use.
The 22g mphenylenediamine is put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, TM, whisking appliance, and normal temperature drips the 16g phenyl glycidyl ether down in reaction flask, dropwises in 30 minutes, and insulation reaction is 2 hours under the condition of 60 ℃ of temperature.Drip above-mentioned mixing solutions in the material of this four-hole reaction flask, added in 75 minutes, temperature maintenance is 50～70 ℃ of insulation reaction; After reaction is accomplished, improve stirring velocity, drip the 110g pure water; Added in 30 minutes, and obtained the aqueous epoxy curing agent of solid content 50%, VOC13g/L.
It is composite that this waterborne curing agent and aqueous epoxy resins are pressed epoxy equivalent (weight) and amine hydrogen equivalent 1: 1, and its pencil hardness is 2H, and sticking power is 1 grade, and shock resistance is 70cmKg, and in 10% sodium chloride aqueous solution, the above paint film of 200h is excellent, and not having comes off does not have and bubble.
Embodiment 3
200g Macrogol 4000 and 26gE-44 are put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, TM, whisking appliance, and the heating fusion is 100 ℃ of temperature; Under-0.095MPa the vacuum condition, underpressure distillation 1 hour, holding temperature; The mixing solutions of 0.45g BFEE and 8.5g butyl glycol ether progressively increases under normal pressure; Dropwised in 50 minutes, and kept reaction 3 hours, obtain light solid intermediate material.This material of 40g and 32g CYD-1283g are dissolved in the mixing solutions of butyl glycol ether under 65 ℃ temperature, keep temperature for use.
With 15g1, the 3-tn is put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, TM, whisking appliance, and normal temperature drips 20g CYDPG660 down in reaction flask, dropwises in 30 minutes, and insulation reaction is 3 hours under the condition of 65 ℃ of temperature.Be cooled to 50 ℃, drip above-mentioned mixing solutions in the material of this four-hole reaction flask, added in 100 minutes; Temperature maintenance after reaction is accomplished, improves stirring velocity 70～80 ℃ of insulation reaction; Drip the 104g pure water, added in 30 minutes, obtain the aqueous epoxy curing agent of solid content 50%, VOC14g/L.
It is composite that this waterborne curing agent and standardized liquid bisphenol A epoxide resin are pressed epoxy equivalent (weight) and amine hydrogen equivalent 1: 1, and its pencil hardness is 3H, and sticking power is 1 grade; Shock resistance is 70cmKg; In 10% sodium chloride aqueous solution, the above paint film of 200h is excellent, and not having comes off does not have foaming.
Embodiment 4
200g Macrogol 2000 and 69gCYD-128 are put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, TM, whisking appliance, and the heating fusion is 100 ℃ of temperature; Under-0.095MPa the vacuum condition, underpressure distillation 1 hour, holding temperature; The mixing solutions of 0.65g BFEE and 7g ethylene glycol ethyl ether progressively increases under normal pressure; Dropwised in 70 minutes, and kept reaction 3 hours, obtain light solid matter.Get this material of 41.8g and 31.2g CYD-128 and under 55 ℃ temperature, be dissolved in the 4g propylene glycol monomethyl ether and process mixing solutions, keep temperature for use.
The 33g isophorone diamine is put in the four-hole reaction flask that 500ml is equipped with reflux condensing tube, TM, whisking appliance; Normal temperature drips the 12g phenyl glycidyl ether down in reaction flask; Dropwised in 30 minutes, insulation reaction is 2 hours under the condition of 55～65 ℃ of temperature.Drip above-mentioned mixing solutions in the material of this four-hole reaction flask, added in 90 minutes, temperature maintenance after reaction is accomplished, adds the 114g pure water 50～90 ℃ of insulation reaction, obtains the aqueous epoxy curing agent of solid content 50%, VOC17g/L.
It is composite that this waterborne curing agent and standardized liquid bisphenol A epoxide resin are pressed epoxy equivalent (weight) and amine oxygen equivalent 1: 1, and its pencil hardness is 3H, and sticking power is 1 grade; Shock resistance is 70cmKg; In 10% sodium chloride aqueous solution, the above paint film of 200h is excellent, and not having comes off does not have foaming.
Claims (7)
1. the preparation method of a non-ion aqueous epoxy hardener is characterized in that: comprise the steps:
(1) epoxy resin and polyethers alcohols material heating fusion are mixed, under 50 ℃～130 ℃ temperature, drip catalyzer, carry out polyreaction, wherein: the mol ratio of epoxy resin and polyethers alcohols material is 0.5: 1～5: 1; Catalyst consumption is 0.1%～1% of epoxy resin and a polyethers alcohols material gross weight sum; Reaction is made into mixing solutions with resultant and epoxy resin, dissolution with solvents after accomplishing, and solvent load is 1～80% of a mixing solutions gross weight;
(2) under agitation condition, drip mono-epoxy compounds in single polyamines, under 10 ℃～100 ℃ temperature, react, wherein: the mol ratio of single polyamines and mono-epoxy compounds is 1: 0.05～1: 3;
(3) under 30～120 ℃ temperature, the mixing solutions of step (1) is added drop-wise in the reaction product of step (2), under 10 ℃～90 ℃ temperature, it is reacted; The mol ratio of epoxy group(ing) and single polyamines is 0.1: 1～4: 1 in the hierarchy of control, and the polyether segment that the polyethers alcohols material provides accounts for 10～50% of total solids part, and total solids part is single polyamines, mono-epoxy compounds, epoxy resin and polyethers alcohols material sum; Reaction adds entry after accomplishing, and it is diluted to solid content is 30～80%, promptly obtains non-ion aqueous epoxy hardener.
2. method according to claim 1 is characterized in that: said epoxy resin is that epoxy equivalent (weight) is 150～1000 bisphenol A type epoxy resin, bisphenol f type epoxy resin.
3. method according to claim 1 is characterized in that: said polyethers alcohols material is one or more the compsn in polyethylene glycol type, the W 166 type.
4. method according to claim 1 is characterized in that: said solvent is gylcol ether and propylene glycol kind solvent.
5. method according to claim 1 is characterized in that: said catalyzer is lewis acid catalyst or Louis's bases catalyzer, and lewis acid catalyst is Potassium Persulfate or BFEE or tin tetrachloride or Zinc Chloride Anhydrous; Lewis-base catalyst is ammonia or amine or water or carbon monoxide or CH
3OH or CH
3COCH
3
6. method according to claim 1 is characterized in that: said mono-epoxy compounds comprises: methyl glycidyl ether, propyl glycidyl ether, butylglycidyl ether, ethylene glycol diglycidylether, hexanediol diglycidyl ether, phenyl glycidyl ether.
7. method according to claim 1 is characterized in that: said single polyamines is one or more the mixture in aromatic amine, aliphatic amide, the aliphatic cyclic amine; Said aromatic amine has mphenylenediamine, a benzene two methanediamines, diaminodiphenyl-methane; Said aliphatic cyclic amine has alkane diamines in the Meng, isophorone diamine, N-aminoethyl piperazine; Said aliphatic amide has quadrol, tn, tetramethylenediamine, pentamethylene diamine, hexanediamine, diethylenetriamine, triethylene tetramine, TEPA, diethylaminopropylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010142715 CN102190800B (en) | 2010-03-06 | 2010-03-06 | Preparation method of nonionic waterborne epoxy curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010142715 CN102190800B (en) | 2010-03-06 | 2010-03-06 | Preparation method of nonionic waterborne epoxy curing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102190800A CN102190800A (en) | 2011-09-21 |
| CN102190800B true CN102190800B (en) | 2012-12-12 |
Family
ID=44599737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010142715 Active CN102190800B (en) | 2010-03-06 | 2010-03-06 | Preparation method of nonionic waterborne epoxy curing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102190800B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492149B (en) * | 2011-11-24 | 2013-03-20 | 中国海洋石油总公司 | Preparation method of nonionic aqueous epoxy resin curing agent |
| CN103450448A (en) * | 2012-05-31 | 2013-12-18 | 中国石油化工股份有限公司 | Preparation method of compound aqueous curing agent |
| CN103910856B (en) * | 2013-01-08 | 2016-06-08 | 深圳市景江化工有限公司 | Nonionic waterborne epoxy curing agent and its preparation method |
| CN103145955A (en) * | 2013-02-04 | 2013-06-12 | 广东工业大学 | Non-ionic self-emulsifying epoxy resin curing agent and preparation method thereof |
| CN105295658B (en) * | 2015-11-30 | 2017-07-07 | 株洲时代新材料科技股份有限公司 | A kind of water-based insulating paint and preparation method thereof |
| CN105646844B (en) * | 2016-01-04 | 2018-11-27 | 江苏丰彩新型建材有限公司 | A kind of epoxy curing agent and preparation method thereof |
| CN105754073A (en) * | 2016-03-03 | 2016-07-13 | 哈尔滨理工大学 | Method for preparing and curing water-borne epoxy resin |
| CN105801869A (en) * | 2016-04-08 | 2016-07-27 | 苏州圣杰特种树脂有限公司 | Epoxy resin curing agent with good hydrophilic property |
| CN106317381B (en) * | 2016-08-29 | 2018-04-06 | 佛山市高明同德化工有限公司 | A kind of aqueous epoxy curing agent and preparation method thereof |
| CN106366854A (en) * | 2016-08-31 | 2017-02-01 | 中国科学院兰州化学物理研究所 | High-water-resistance self-emulsified double-component water-borne epoxy glass baking lacquer as well as preparation method and application thereof |
| CN107011502A (en) * | 2016-11-28 | 2017-08-04 | 佛山市尚好门窗有限责任公司 | A kind of aqueous epoxy curing agent and preparation method thereof |
| CN107760166A (en) * | 2017-11-22 | 2018-03-06 | 江门市水星涂料科技有限公司 | A kind of double-component aqueous epoxide terrace paint of high-performance and preparation method thereof |
| CN110563927A (en) * | 2019-10-10 | 2019-12-13 | 杭州崇成科技有限公司 | Water-based epoxy resin curing agent and preparation method thereof |
| CN112661936B (en) * | 2019-10-16 | 2023-10-13 | 中国石油化工股份有限公司 | Preparation method of water-based epoxy curing agent |
| CN112759743B (en) * | 2019-11-06 | 2022-04-19 | 万华化学集团股份有限公司 | Epoxy curing agent for zinc-rich primer and preparation method and application thereof |
| CN111826055A (en) * | 2020-07-22 | 2020-10-27 | 增城市惠顺化工有限公司 | Waterborne epoxy zinc-rich primer curing agent and preparation method thereof |
| CN111777922B (en) * | 2020-07-22 | 2021-12-10 | 广州惠顺新材料有限公司 | Anticorrosion and mildewproof waterborne epoxy curing agent and preparation method thereof |
| CN111892893A (en) * | 2020-08-20 | 2020-11-06 | 常州市建筑科学研究院集团股份有限公司 | Novel environment-friendly seam beautifying agent and preparation method thereof |
| CN114835881A (en) * | 2022-04-21 | 2022-08-02 | 江西百盛精细化学品有限公司 | Preparation method of water-based epoxy curing agent |
| CN115850664A (en) * | 2022-12-28 | 2023-03-28 | 浩力森涂料（上海）有限公司 | Preparation method and application of waterborne epoxy floor coating curing agent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527839A (en) * | 1994-12-13 | 1996-06-18 | Air Products And Chemicals, Inc. | Self-emulsifying epoxy curing agent based on the reaction product of epoxy resin and polyether polyol |
| US5539023A (en) * | 1993-02-08 | 1996-07-23 | Hoechst Aktiengesellschaft | Curing agents for aqueous epoxy resin dispersions |
| CN101007863A (en) * | 2007-01-12 | 2007-08-01 | 华南理工大学 | Preparation method of non-ionic room temperature-cured aqueous epoxy curing agent |
| CN101050300A (en) * | 2007-04-18 | 2007-10-10 | 广州秀珀化工有限公司 | Self-emulsifying type aqueous latex of epoxy hardener, and preparation method |
| CN101265321A (en) * | 2008-05-06 | 2008-09-17 | 中南民族大学 | Method for preparing branching type water-based epoxy curing agent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3375160B2 (en) * | 1992-12-15 | 2003-02-10 | 旭電化工業株式会社 | Aqueous epoxy resin curable composition |
-
2010
- 2010-03-06 CN CN 201010142715 patent/CN102190800B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5539023A (en) * | 1993-02-08 | 1996-07-23 | Hoechst Aktiengesellschaft | Curing agents for aqueous epoxy resin dispersions |
| US5527839A (en) * | 1994-12-13 | 1996-06-18 | Air Products And Chemicals, Inc. | Self-emulsifying epoxy curing agent based on the reaction product of epoxy resin and polyether polyol |
| CN101007863A (en) * | 2007-01-12 | 2007-08-01 | 华南理工大学 | Preparation method of non-ionic room temperature-cured aqueous epoxy curing agent |
| CN101050300A (en) * | 2007-04-18 | 2007-10-10 | 广州秀珀化工有限公司 | Self-emulsifying type aqueous latex of epoxy hardener, and preparation method |
| CN101265321A (en) * | 2008-05-06 | 2008-09-17 | 中南民族大学 | Method for preparing branching type water-based epoxy curing agent |
Non-Patent Citations (2)
| Title |
|---|
| 刘刚等.水性环氧固化剂分散体的制备及改性.《电镀与涂饰》.2009,第28卷(第10期),第49-54页. * |
| 祝宝英.非离子水性环氧低温固化剂的制备及固化研究.《涂料工业》.2009,第39卷(第12期),第51-54页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102190800A (en) | 2011-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102190800B (en) | Preparation method of nonionic waterborne epoxy curing agent | |
| CN102010572B (en) | Environment-friendly epoxy resin composition as well as preparation method and application thereof | |
| CN100569826C (en) | A kind of self-emulsifying type aqueous latex of epoxy hardener and preparation method thereof | |
| CN101134806A (en) | Method for preparing aqueous epoxy resin hardener | |
| CN103910856B (en) | Nonionic waterborne epoxy curing agent and its preparation method | |
| CN103450448A (en) | Preparation method of compound aqueous curing agent | |
| CN112135855B (en) | Modified phenolic amine curing agent for epoxy resin composition and application thereof | |
| CN102120865B (en) | Epoxy-phenolic aldehyde amine composition and preparation method and application thereof | |
| CN101265321A (en) | Method for preparing branching type water-based epoxy curing agent | |
| EP2912092A2 (en) | Ambient cure weatherable coatings | |
| CN112533887B (en) | Salts of diamino acetals and diamino ketals, their synthesis and their conversion to diamino acetals and diamino ketals | |
| US6274682B1 (en) | Epoxy resin system | |
| CN103435504B (en) | A kind of preparation method of degradable primary amine curing agent | |
| CN101775196A (en) | Preparation method of novel quinone amine curing agent and application to normal temperature epoxy curing system | |
| AU2022320855A1 (en) | Amine hardener with high content in renewable carbon | |
| WO2003020789A1 (en) | Low viscosity curing agents compositions in epoxy resin systems for low temperature cure applications | |
| CN105330822A (en) | Water-borne epoxy resin curing agent | |
| CN105949958A (en) | Waterborne epoxy modified polyamine curing agent and waterborne epoxy anti-corrosion primer coating | |
| WO2023072992A1 (en) | Mannich base with high content in renewable carbon | |
| CN105315436A (en) | Polyether type epoxy resin curing agent and preparation method thereof | |
| CN106433401A (en) | Waterbome epoxy resin primer with long-term high corrosion resistance for steel structure and preparation method of primer | |
| CN106497315A (en) | A kind of steel construction montmorillonite intercalation epoxy resin aqueous priming paint and preparation method thereof | |
| CN109554073A (en) | A kind of water-based epoxy zinc-rich primer of oil resistant efficient corrosion resisting | |
| CN106497314A (en) | A kind of steel construction excellent water-base epoxy priming paint of salt spray corrosion resistance and preparation method thereof | |
| CN108059711A (en) | A kind of new type resin curing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |