CN102250321B - Quick-drying room temperature curing waterborne epoxy resin curing agent and preparation method thereof - Google Patents
Quick-drying room temperature curing waterborne epoxy resin curing agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of chemical paints and particularly discloses a quick-drying room temperature curing waterborne epoxy resin curing agent and a preparation method thereof. The method comprises the following steps: mixing liquid epoxy resins, polyether containing epoxy groups on both ends or the mixture of polyether containing epoxy groups on one end and polyether containing epoxy groups on both ends with a bisphenol compound to react at 150-200 DEG C under the action of a catalyst and generate an intermediate, then using the intermediate and amine to react, performing reduced pressure distillation to remove excess amine and the solvent, cooling the obtained resins to 60-90 DEG C, and dropwise adding deionized water to obtain the amber or light yellow quick-drying room temperature curing waterborne epoxy resin curing agent. The waterborne epoxy resin curing agent has simple production process flow, the surface drying time for curing the epoxy resin emulsion is shorter, and the working life is longer; and the epoxy resin film cured by using the curing agent has excellent performance. The waterborne epoxy resin curing agent is suitable for waterborne paints, waterborne adhesives and the like; and for example, the curing agent can be used as a flooring paint, an industrial protective paint and a furniture adhesive.
Description
Technical field
The present invention relates to the chemistry painting industry technical field, be specifically related to a kind of quick-dry type cold curing watersoluble solidifying agent of epoxy resin and preparation method thereof.
Background technology
Traditional epoxypaint has that sticking power height, wear resistance are good, chemicals-resistant and solvent borne is excellent, the hardness advantages of higher, in industry, has obtained using widely.Along with people's is urgent day by day and strict to requirement on environmental protection, and low VOC (volatile organic matter) water-base resin system of exploitation and relevant coating products thereof have become new research direction.Advantages such as aqueous epoxide resin paint has better performances, pollution-free, service tool is prone to clean and relative cost is lower are the kinds of water-borne coatings focus development; And in the research and development of aqueous epoxide resin paint, the Water-borne modification of solidifying agent and modification occupy very big proportion.
Chinese invention patent (publication number CN 101434687A) discloses a kind of preparation method of room temperature epoxy hardener; This method is: under 50～70 ℃ of temperature condition; Drip GBL in fat polyamine or aromatic polyamine; Carry out addition reaction with aliphatic polyamine or aromatic polyamine, used aliphatic polyamine or aromatic polyamine and the GBL mol ratio that is dripped are 1～2: 1.Said aliphatic polyamine can be quadrol, hexanediamine, diethylenetriamine, triethylene tetramine or TEPA, aromatic polyamine be between benzene two methanediamines.Increase ester bond flexible and that extend working time though in the solidifying agent molecule, introduced; Improved the consistency of solidifying agent and epoxy resin; But this solidifying agent belongs to solvent type, is used with epoxy resin to add a large amount of organic solvents, does not meet environmental requirement.
Chinese invention patent (publication number CN 101402720A) discloses a kind of preparation method of cold curing watersoluble solidifying agent of epoxy resin, and concrete steps are: (1) earlier with mono-epoxy compounds to the diethylenetriamine end-blocking; (2) drip bis-epoxy and carry out addition; (3) add in the acetic acid and salify; (4) add curing catalyst, obtain lurid waterborne curing agent.This solidifying agent is because the introducing curing catalyst has than short surface drying time, and still through having increased its wetting ability with salify in the acetic acid, the organic acid existence can make the metal body be easy to generation sudden strain of a muscle rust phenomenon; In addition, because organic acid adds, when using jointly, can produce certain influence to the stability of coating with some alkaline color stuffings.
Chinese invention patent (publication number CN 101007863A) discloses a kind of preparation method of non-ionic room temperature-cured aqueous epoxy resin curing agent; This method is at first carried out chain extending reaction with the organic solution of polyether glycol diglycidylether or polyethers epoxy resin or the mixture of the two and aromatic polyamine or aliphatic polyamine, adds epoxy resin solution then and carries out further chain extending reaction and make the non-ionic room temperature-cured aqueous epoxy resin curing agent.But synthesized solidified dose of the feed way that should invention drips through two steps is removed unreacted amine and organic solvent through underpressure distillation in two steps, and complex operation has also increased cost; And the solidifying agent surface drying time of method preparation is longer thus.
Summary of the invention
To not enough described in the prior art; Leading-in end epoxy group(ing) polyethers hydrophilic segment when the present invention adopts liquid-state epoxy resin and bisphenol compound reaction chain extension; And then with polyamine reaction; Steam at last and desolventize and the technological line of unnecessary amine, invented a kind of quick-dry type cold curing watersoluble solidifying agent of epoxy resin and preparation method thereof.This method does not need organic acid to be neutralized into salt technology; Preparation technology is simple; Since epoxy resin through the bisphenol compound chain extension again with polyamine reaction, so solidifying agent has quick-drying characteristics, this solidifying agent also has the good emulsifying performance to liquid epoxies in addition.
The present invention realizes through following technical scheme:
The invention provides a kind of quick-dry type cold curing watersoluble solidifying agent of epoxy resin, this curing agent component and constituent mass degree are following:
Form mass parts (wt.%)
Aminated compounds 8%～22%,
Epoxy resin 2.5%～28%,
Bisphenol compound 1.5%～12%,
Catalyzer 0.03%～0.6%,
End epoxy group(ing) polyether compound 9.5%～38%,
Deionized water 30%～55%;
Said aminated compounds is one or more combination of your ketone diamines of quadrol, diethylenetriamine, triethylene tetramine, TEPA, polyether diamine, trimethylammonium hexanediamine, different fluorine, mphenylenediamine, m-xylene diamine.
Said epoxy resin is bisphenol-A liquid epoxy resin;
The flat molecular weight of said end epoxy group(ing) polyether compound is 200～10000;
Said bisphenol compound be various skeletons such as dihydroxyphenyl propane, Bisphenol F bis-phenol one or more.
Said bisphenol-A liquid epoxy resin is a kind of of EPON828, EPON1001, E-51, E-44.
Said catalyzer is one or more in triphenylphosphine, benzyl diamines, the TBuA.
A kind of in the mixture that said end epoxy group(ing) polyether compound is polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, polyethyleneglycol diglycidylether and single epoxy group(ing) polyethers or the mixture of polypropylene glycol diglycidyl ether and single epoxy group(ing) polyethers.
The present invention also provides a kind of preparation method of quick-dry type room temperature-cured aqueous epoxy curing agent, is specially following steps:
(1) intermediate product is synthetic: the liquid epoxies, bisphenol compound and the end epoxy group(ing) polyether compound that add said ratio are in reaction unit; Be warming up to 80 ℃～100 ℃ catalyzer that add said ratio; Be warming up to 150 ℃～200 ℃ then, constant temperature continues reaction 3h～4h, after reaction is accomplished; Add organic solvent, mix;
(2) said intermediate product further reacts chain extension with aminated compounds: under 60 ℃～90 ℃ conditions; The product of step (1) is added drop-wise in 1h in the device that contains the excess amine compounds; Dropwise back constant temperature and continue reaction 2h～4h, the organic solvent of removing unreacted amine after the reaction and not participating in reacting;
(3) preparation of solidifying agent: under 60 ℃～90 ℃ conditions, the deionized water of said ratio is added drop-wise in the described reaction unit of step (2), waits to dropwise the back and stir 20min～30min, promptly obtain a kind of quick-dry type cold curing watersoluble solidifying agent of epoxy resin.
The method of removing unreacted amine and organic solvent in the said step (2) is underpressure distillation.
Said organic solvent is a kind of of propylene glycol monomethyl ether, propylene-glycol ethyl ether, Ucar 35 butyl ether, butyl glycol ether, phenylcarbinol, and the consumption of organic solvent is the 0.5%-6% of raw material total mass.
Compared with prior art, the present invention has the following advantages:
(1) the present invention is at first with mixture and bisphenol compound hybrid reaction under catalyzer of liquid epoxies, both-end epoxy group(ing) polyethers or both-end epoxy group(ing) polyethers and single-ended epoxy group(ing) polyethers; Synthetic intermediate product; In the process that intermediate product generates; Introduce the polyethers hydrophilic segment again in the time of epoxy resin molecule segment chain extension, improved the consistency of solidifying agent and epoxy resin, improved the wetting ability of solidifying agent again.In addition; Introduce bisphenol compound and not only play chain extension and crane span structure effect, and further increased the molecular weight of solidifying agent, introduce phenyl ring a large amount of on the bisphenol compound simultaneously; Promptly shorten solidifying agent and made the surface drying time of time spent, also improved the hardness of filming after solidifying.
(2) the catalyzer triphenylphosphine that when the synthetic mesophase product, uses of the present invention, benzyl diamines, TBuA etc. itself are exactly the promotor of amine curing reaction; Because the surface drying time that solidifying agent is done the time spent has been shortened in their existence, makes solidifying agent of the present invention have quick-drying advantage.
(3) solidifying agent viscosity of the present invention is less, and viscosity has made things convenient for being used and follow-up construction of solidifying agent and epoxy resin at 2000～8000mPas.
(4) solidifying agent of the present invention has good emulsifying capacity to liquid epoxies.
(5) solidifying agent outward appearance of the present invention is the amber or light yellow of clear, has good storage stability, and normal temperature storage no layering in 6 months, sedimentation, viscosity do not have obvious variation yet.
(6) the present invention also has preparation technology's flow process characteristic of simple.
Description of drawings
Fig. 1 is the infrared spectrum of the molecular structure of quick-dry type cold curing watersoluble solidifying agent of epoxy resin.
Fig. 2 is the size distribution figure behind the quick-dry type cold curing watersoluble solidifying agent of epoxy resin emulsion epoxy resin E-51.
Embodiment
For a better understanding of the present invention, 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 scope that embodiment representes.
Carrying out raw material according to the mass percent that accounts for total material prepares:
In the reactor drum that backflow, heating and whipping appts are housed; Add epoxy resin E-51, dihydroxyphenyl propane and and polyethyleneglycol diglycidylether, be warming up to 95 ℃ and add triphenylphosphines, slowly be warming up to 160 ℃ then; Constant temperature continues reaction 4h; Make intermediate product, add an amount of propylene glycol monomethyl ether at last, mix.
Under 60～90 ℃ of conditions, described midbody product slowly is added drop-wise to dress contains in the device of excessive diethylenetriamine in about 1h, dropwise back constant temperature and continue reaction 3h, unreacted amine and propylene glycol monomethyl ether are removed in the back underpressure distillation that reacts completely.Be warming up under 60～90 ℃ of conditions, slowly drip deionized water, high-speed stirring 30min promptly obtains a kind of amber aqueous epoxy resin curing agent of clear, solid content 58%, amine value 270mgKOH/g, viscosity 2600mPas.
The infrared spectrum of the molecular structure of a kind of aqueous epoxy resin curing agent of this examples preparation, shown in accompanying drawing 1: in infrared spectrum, the characteristic peak 916cm of epoxy group(ing)
-1The basic disappearance is at 1466cm
-1, 1576cm
-1, 1604cm
-1Near the characteristic peak of phenyl ring skeletal vibration appears, show and contain a large amount of rigidity phenyl ring in this solidifying agent molecule; At 1107cm
-1Near ehter bond CH appears
2OCH
2The stretching vibration characteristic peak, show in this solidifying agent molecule and contain polyether segment; 3298cm
-1, 3340cm
-1Be the charateristic avsorption band of primary amine, show in this solidifying agent molecule and contain primary amine group.
A kind of aqueous epoxy resin curing agent of this examples preparation has good emulsifying capacity to liquid epoxies; Accompanying drawing 2 forms distribution of particle size of emulsion figure after being depicted as aqueous epoxy resin curing agent emulsion epoxy resin E-51 of the present invention; Can know that by figure median size is 271nm, explain that solidifying agent of the present invention has good emulsifying capacity to liquid epoxies.
The use of this solidifying agent:
First component: epoxy resin E-51 95g
Component B: this solidifying agent 100g
With the first component: component B=1: 1 (equivalence ratio), mix and stir, be applied on the test plate (panel) that polishing is good in advance, form transparent coating behind the moisture evaporation.The salient features of filming is as shown in table 1:
Table 1 embodiment 1 solidifying agent solidified aqueous epoxy resins film performance
Embodiment 2
Carrying out raw material according to the mass percent that accounts for total material prepares:
In the reactor drum that backflow, heating and whipping appts are housed; Add epoxy resin E-51, dihydroxyphenyl propane and and polyethyleneglycol diglycidylether, be warming up to 100 ℃ and add the benzyl diamines, slowly be warming up to 170 ℃ then; Constant temperature continues reaction 4h; Make intermediate product, add an amount of Ucar 35 butyl ether at last, mix.
Under 60～90 ℃ of conditions, described midbody product slowly is added drop-wise in the device that excessive quadrol is housed in about 1h, dropwise back constant temperature and continue reaction 3h, unreacted amine and Ucar 35 butyl ether are removed in the back underpressure distillation that reacts completely.Be warming up under 60～90 ℃ of conditions, slowly drip deionized water, high-speed stirring 30min promptly obtains a kind of light yellow aqueous epoxy resin curing agent of clear, solid content 60%, amine value 200mgKOH/g, viscosity 5000mPas.
The use of this solidifying agent:
First component: epoxy resin E-51 95g
Component B: this solidifying agent 136g
With the first component: component B=1: 1 (equivalence ratio), mix and stir, be applied on the test plate (panel) that polishing is good in advance, form transparent coating behind the moisture evaporation.The salient features of filming is as shown in table 2:
Table 2 embodiment 2 solidifying agent solidified aqueous epoxy resins film performances
Embodiment 3
Carrying out raw material according to the mass percent that accounts for total material prepares:
In the reactor drum that backflow, heating and whipping appts are housed; Add epoxy resin E-51, dihydroxyphenyl propane and and polypropylene glycol diglycidyl ether, be warming up to 90 ℃ and add triphenylphosphines, slowly be warming up to 160 ℃ then; Constant temperature continues reaction 4h; Make intermediate product, add an amount of propylene glycol monomethyl ether at last, mix.
Under 60～90 ℃ of conditions, described midbody product slowly is added drop-wise in the device that excessive m-xylene diamine is housed in about 1h, dropwise back constant temperature and continue reaction 3h, unreacted amine and propylene glycol monomethyl ether are removed in the back underpressure distillation that reacts completely.Be warming up under 60～90 ℃ of conditions, slowly drip deionized water, high-speed stirring 30min promptly obtains a kind of amber aqueous epoxy resin curing agent of clear, solid content 50%, amine value 210mgKOH/g, viscosity 2900mPas.
The use of this solidifying agent:
First component: epoxy resin E-51 95g
Component B: this solidifying agent 129g
With the first component: component B=1: 1 (equivalence ratio), mix and stir, be applied on the test plate (panel) that polishing is good in advance, form transparent coating behind the moisture evaporation.The salient features of filming is as shown in table 3:
Table 3 embodiment 3 solidifying agent solidified aqueous epoxy resins film performances
Embodiment 4
Carrying out raw material according to the mass percent that accounts for total material prepares:
In the reactor drum that backflow, heating and whipping appts are housed; Add epoxy resin E-51, Bisphenol F and and polypropylene glycol diglycidyl ether, be warming up to 90 ℃ and add triphenylphosphines, slowly be warming up to 170 ℃ then; Constant temperature continues reaction 4h; Make intermediate product, add an amount of propylene-glycol ethyl ether at last, mix.
Under 60～90 ℃ of conditions, described midbody product slowly is added drop-wise in the device that excessive trimethylammonium hexanediamine is housed in about 1h, dropwise back constant temperature and continue reaction 3h, unreacted amine and propylene-glycol ethyl ether are removed in the back underpressure distillation that reacts completely.Be warming up under 60～90 ℃ of conditions, slowly drip deionized water, high-speed stirring 30min promptly obtains a kind of amber aqueous epoxy resin curing agent of clear, solid content 52%, amine value 230mgKOH/g, viscosity 2500mPas.
The use of this solidifying agent:
First component: epoxy resin E-51 95g
Component B: this solidifying agent 118g
With the first component: component B=1: 1 (equivalence ratio), mix and stir, be applied on the test plate (panel) that polishing is good in advance, form transparent coating behind the moisture evaporation.The salient features of filming is as shown in table 4:
Table 4 embodiment 4 solidifying agent solidified aqueous epoxy resins film performances
Carrying out raw material according to the mass percent that accounts for total material prepares:
In the reactor drum that backflow, heating and whipping appts are housed; Add epoxy resin E-51, dihydroxyphenyl propane and and polyethyleneglycol diglycidylether, be warming up to 80 ℃ and add triphenylphosphines, slowly be warming up to 160 ℃ then; Constant temperature continues reaction 3h; Make intermediate product, add an amount of propylene glycol monomethyl ether at last, mix.
Under 60～90 ℃ of conditions; In about 1h, slowly be added drop-wise to described midbody product in the device that excessive diethylenetriamine and m-xylene diamine are housed; Dropwise back constant temperature and continue reaction 4h, unreacted amine and propylene glycol monomethyl ether are removed in the back underpressure distillation that reacts completely.Be warming up under 60～90 ℃ of conditions, slowly drip deionized water, high-speed stirring 20min promptly obtains a kind of amber aqueous epoxy resin curing agent of clear, solid content 52%, amine value 230mgKOH/g, viscosity 2500mPas.
The use of this solidifying agent:
First component: epoxy resin E-51 95g
Component B: this solidifying agent 156g
With the first component: component B=1: 1 (equivalence ratio), mix and stir, be applied on the test plate (panel) that polishing is good in advance, form transparent coating behind the moisture evaporation.The salient features of filming is as shown in table 5:
Table 5 embodiment 5 solidifying agent solidified aqueous epoxy resins film performances
Embodiment 6
Carrying out raw material according to the mass percent that accounts for total material prepares:
In the reactor drum that backflow, heating and whipping appts are housed; Add epoxy resin E-51, dihydroxyphenyl propane, polyethyleneglycol diglycidylether and single epoxy group(ing) polyethers, be warming up to 95 ℃ and add triphenylphosphine, slowly be warming up to 160 ℃ then; Constant temperature continues reaction 4h; Make intermediate product, add an amount of phenylcarbinol at last, mix.
Under 60～90 ℃ of conditions, described midbody product slowly is added drop-wise in the device that excessive triethylene tetramine is housed in about 1h, dropwise back constant temperature and continue reaction 3h, unreacted amine and phenylcarbinol are removed in the back underpressure distillation that reacts completely.Be warming up under 60～90 ℃ of conditions, slowly drip deionized water, high-speed stirring 30min promptly obtains a kind of lurid aqueous epoxy resin curing agent of clear, solid content 53%, amine value 220mgKOH/g, viscosity 2000mPas.
The use of this solidifying agent:
First component: epoxy resin E-51 95g
Component B: this solidifying agent 128g
With the first component: component B=1: 1 (equivalence ratio), mix and stir, be applied on the test plate (panel) that polishing is good in advance, form transparent coating behind the moisture evaporation.The salient features of filming is as shown in table 6:
Table 6 embodiment 6 solidifying agent solidified aqueous epoxy resins film performances
Claims (6)
1. a quick-dry type cold curing watersoluble solidifying agent of epoxy resin is characterized in that, is made up of the component of following quality percentage composition:
Aminated compounds 8% ~ 22%,
Epoxy resin 2.5% ~ 28%,
Bisphenol compound 1.5% ~ 12%,
Catalyzer 0.03% ~ 0.6%,
End epoxy group(ing) polyether compound 9.5% ~ 38%,
Deionized water 30% ~ 55%;
Said aminated compounds is diethylenetriamine, triethylene tetramine, TEPA, quadrol, polyether diamine, trimethylammonium one or more of your ketone diamines of diamines, different fluorine, mphenylenediamine, m-xylene diamine;
Said epoxy resin is bisphenol-A liquid epoxy resin;
The molecular-weight average of said end epoxy group(ing) polyether compound is 200 ~ 10000, and said end epoxy group(ing) polyether compound is polyethyleneglycol diglycidylether or polypropylene glycol diglycidyl ether;
Said bisphenol compound is a dihydroxyphenyl propane.
2. according to the said quick-dry type cold curing watersoluble solidifying agent of epoxy resin of claim 1, it is characterized in that said bisphenol-A liquid epoxy resin is a kind of among EPON828, E-51 or the E-44.
3. according to the said quick-dry type cold curing watersoluble solidifying agent of epoxy resin of claim 1, it is characterized in that said catalyzer is one or more in triphenylphosphine, benzyl diamines, the TBuA.
4. the preparation method of the described a kind of quick-dry type cold curing watersoluble solidifying agent of epoxy resin of one of claim 1 ~ 3 is characterized in that, concrete steps are:
(1) intermediate product is synthetic: the liquid epoxies, bisphenol compound and the end epoxy group(ing) polyether compound that add said ratio are in reaction unit; Be warming up to 80 ℃ ~ 100 ℃ catalyzer that add said ratio; Be warming up to 150 ℃ ~ 200 ℃ then, constant temperature continues reaction 3h ~ 4h, after reaction is accomplished; Add organic solvent, mix;
(2) said intermediate product further reacts chain extension with aminated compounds: under 60 ℃ ~ 90 ℃ conditions; The product of step (1) is added drop-wise in 1h in the device that contains the excess amine compounds; Dropwise back constant temperature and continue reaction 2h ~ 4h, the organic solvent of removing unreacted amine after the reaction and not participating in reacting;
(3) preparation of solidifying agent: under 60 ℃ ~ 90 ℃ conditions; The deionized water of said ratio is added drop-wise in the described reaction unit of step (2); Wait to dropwise the back and stir 20 min ~ 30min, promptly obtain a kind of quick-dry type cold curing watersoluble solidifying agent of epoxy resin.
5. the preparation method of a kind of quick-dry type cold curing watersoluble solidifying agent of epoxy resin according to claim 4 is characterized in that, the method for removing unreacted amine and organic solvent described in the step (2) is underpressure distillation.
6. the preparation method of a kind of quick-dry type cold curing watersoluble solidifying agent of epoxy resin according to claim 4; It is characterized in that; Said organic solvent is a kind of in propylene glycol monomethyl ether, propylene-glycol ethyl ether, Ucar 35 butyl ether, butyl glycol ether, the phenylcarbinol, and the consumption of organic solvent is the 0.5%-6% of raw material total mass.
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| CN102516502B (en) * | 2011-12-07 | 2013-07-03 | 湖南大学 | Preparation method of novel Mannich water-based epoxy curing agent |
| KR102375219B1 (en) | 2014-07-17 | 2022-03-17 | 다우 글로벌 테크놀로지스 엘엘씨 | Epoxy systems employing triethylaminetetraamine and tin catalysts |
| 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 |
| CN105367755B (en) * | 2015-12-01 | 2017-10-27 | 江苏丰彩新型建材有限公司 | A kind of epoxy hardener, antiseptic varnish and preparation method thereof |
| CN106047087A (en) * | 2016-08-22 | 2016-10-26 | 湖南太子化工涂料有限公司 | Room temperature self-drying two-component epoxy heavy anti-corrosion prime coat and preparation method thereof |
| CN106957409B (en) * | 2017-04-07 | 2020-04-10 | 哈尔滨工业大学（威海） | Water-based epoxy resin curing agent |
| CN106977698A (en) * | 2017-05-02 | 2017-07-25 | 惠州市惠阳区嘉泰涂料有限公司 | A kind of water-dispersion type epoxy hardener |
| CN108997713B (en) * | 2018-06-28 | 2020-12-11 | 广州均实复合材料科技有限公司 | Pressure-resistant water-permeable porous material and preparation method thereof |
| CN112375208A (en) * | 2020-11-27 | 2021-02-19 | 芜湖春风新材料有限公司 | High-throwing-power toughened cathode electrophoresis resin and preparation method thereof, and electrophoresis emulsion and preparation method thereof |
| CN113278133A (en) * | 2021-05-18 | 2021-08-20 | 黄山锦峰实业有限公司 | Phenol curing agent, and synthesis method and application thereof |
| CN113662338B (en) * | 2021-08-13 | 2023-09-08 | 广东顺德周大福珠宝制造有限公司 | Hollowed-out jewelry and surface treatment method thereof |
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| US4246148A (en) * | 1979-08-27 | 1981-01-20 | Celanese Corporation | Two component aqueous coating composition based on an epoxy-polyamine adduct and a polyepoxide |
| US6277928B1 (en) * | 1998-03-03 | 2001-08-21 | Charles J. Stark | Epoxy-functional amidoamine reacted with excess polyamine and monoepoxy as epoxy curative |
| CN100547010C (en) * | 2007-01-12 | 2009-10-07 | 华南理工大学 | A kind of preparation method of non-ionic room temperature-cured aqueous epoxy curing agent |
| CN101402720B (en) * | 2008-11-14 | 2010-11-17 | 天津大学 | Process for producing room temperature curing watersoluble solidifying agent of epoxy resin |
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