CN102276781A - Preparation method and application of waterborne polyurea modified epoxy emulsion curing agent - Google Patents
Preparation method and application of waterborne polyurea modified epoxy emulsion curing agent Download PDFInfo
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- CN102276781A CN102276781A CN 201110134842 CN201110134842A CN102276781A CN 102276781 A CN102276781 A CN 102276781A CN 201110134842 CN201110134842 CN 201110134842 CN 201110134842 A CN201110134842 A CN 201110134842A CN 102276781 A CN102276781 A CN 102276781A
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Abstract
The invention provides a preparation method and application of a waterborne polyurea modified epoxy emulsion curing agent. In the waterborne polyurea modified epoxy emulsion curing agent, a compound containing a non-ionic hydrophilic chain segment is introduced into a chain segment, so that the fragility of a condensate film is improved, the compatibility with the epoxy emulsion is reinforced, the toughness of the epoxy emulsion is improved, and the curing agent has water solubility. Epoxy resin is introduced into a polyurea chain segment, a paint film obtained after the polyurea is cured has excellent water resistance, solvent resistance and flexibility and higher strength, so that the paint film has excellent characteristics of the polyurea and overcomes the defect of the epoxy resin. According to the curing agent synthesized by the method, the problem of first and second generations of curing agents is solved, small molecular active agent and small molecular polyamine are removed, and the compatibility of the curing agent and the emulsion is improved, so that mechanical performance and water resistance of the paint film are increased.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to water-based polyurea modified epoxy emulsion solidifying agent preparation method and application.
Background technology
Water-borne coatings is a solvent with water, and filmogen is dispersed in the water, is called water-based paint or latex coating again.It because of have the source wide, be easy to purify, characteristics such as low cost, low viscosity, good coating adaptation and nontoxicity, non-stimulated, uninflammability, and become the main developing direction of " environmental friendliness coating ".
This wherein, aqueous epoxy coating has plurality of advantages, as low VOC, less smell, safe in utilization, can wash by water etc., and possess good physical and chemical performance, therefore used widely.But this coating is widely applied at home as yet, and major reason is that the solidifying agent with its compatibility still has limitation, so the exploitation of solidifying agent just becomes the key of promoting aqueous epoxy coating.
First-generation waterborne curing agent is with after Resins, epoxy and primary amine, the mixed reaction of secondary amine, be that nonionogenic tenside or polyvinyl alcohol are distributed in the water with reaction mixture and polyoxyethylene again, make the emulsion-type epoxy curing agent, but owing to contain a large amount of free tensio-active agents, with the aqueous epoxy resins film-forming, the consistency of they and Resins, epoxy is poor, work-ing life short, poor water resistance.
After this researched and developed again the 2nd generation aqueous epoxy curing agent, promptly adopt low relatively molecular mass liquid epoxy and diethylenetriamine or polyethylene polyamine reaction, generate and hold amino epoxy-amine affixture, again through end-blocking and salify technology synthesizing water-solubility epoxy hardener.This kind solidifying agent has influenced the use properties of paint film because the skewness of resin and solidifying agent causes paint film can not form effective successive reticulated structure.So after the 2nd generation water-base epoxy film forming, the mechanics that is difficult to reach the solvent-borne type epoxy is given birth to fundamental propertys such as energy, resistance to chemical attack.
This research has proposed to utilize the polyurea modified water-base epoxy to prepare the synthetic method of new epoxy hardener on the basis of s-generation aqueous epoxy curing agent.
Summary of the invention
The preparation method of the water-based polyurea modified epoxy curing agent that the present invention proposes is the utilization chemic modified method, hydrophilic segment, polyureas performed polymer are introduced Resins, epoxy, it is the polyurea modified aqueous epoxy resins, this development work, by the modification of polyureas to Resins, epoxy, the toughness reinforcing epoxypaint performance of having improved.With the polyamines addition, prepared the aqueous epoxy curing agent with automatic emulsifying performance again, with its coatings formulated high comprehensive performance, cost is lower.
Technical scheme of the present invention is as follows:
Water-based polyurea modified epoxy curing agent of the present invention is characterized in that: do not use to add tensio-active agent, strengthened water tolerance, and do not use the small molecules polyamines, improved the consistency with epoxy emulsion, thereby improved paint film property.
The preparation method of water-based polyurea modified epoxy curing agent of the present invention, step is as follows:
(1) chooses a kind of Amino Terminated polyether(ATPE), drip the polyisocyanates normal-temperature reaction and obtain polyureas, reaction times 5～30min; The amino mol ratio with isocyanate group of end is 1.5～2: 1;
(2) product drips hydrophilic chain extender and epoxy resin E-44 in (1), is warmed up to 60～80 ℃, continues reaction 2～4h and obtains performed polymer; Epoxy group(ing) in the Resins, epoxy is that 1: 1～1.5 hydrophilic chain extender additions are 5%～10% of Resins, epoxy quality with the amino ratio;
(3) choose diethylenetriamine, drip equimolar mono-epoxy compounds butylglycidyl ether, prepare the end-blocking product; Temperature of reaction is 60～80 ℃, and the reaction times is 1.5～2.5h;
(4) in the end-blocking product that prepare (3), drip the performed polymer that prepare (2), obtain adduct; The mass ratio of end-blocking product and performed polymer is 1～2: 1, and temperature of reaction is 60～90 ℃, and the reaction times is 1.5～2.5h;
(5) in (4) adduct, drip in the glacial acetic acid and salify, add entry then and prepare water-based polyurea modified epoxy curing agent; Wherein thin up to solid content is 40～60%, and temperature of reaction is 60～90 ℃, and the reaction times is 1.5～2.5h.
The Amino Terminated polyether(ATPE) that adopts in the described step (1) is a kind of among polyetheramine D2000 or the polyetheramine D5000.
Described polyisocyanates is a kind of in tolylene diisocyanate, MDI or the hexamethylene diisocyanate.
Hydrophilic chain extender in the described step (2) is a kind of in water-based glycine, the water-based diethanolamine.
The water-based polyurea modified epoxy curing agent that the present invention proposes is owing to introduced a kind of non-ionic hydrophilic segmental compound that contains in the segment, improved the fragility of cured article film, strengthen with the consistency of epoxy emulsion, improved the toughness of epoxy emulsion, it is water-soluble that solidifying agent is had.And polyureas segment introducing Resins, epoxy makes its curing back gained paint film have superior water tolerance, solvent resistance, snappiness, and higher intensity, thereby has possessed the good characteristic of polyureas, has overcome the shortcoming of Resins, epoxy itself.
The physical function parameter of gained aqueous epoxy resin curing agent:
Mix the film forming performance perameter in back with epoxy emulsion as follows:
This method synthetic solidifying agent has solved the problem that the first-generation and s-generation solidifying agent exist, and has removed small molecule active agent and small molecules polyamines, has improved the consistency of solidifying agent and emulsion, thereby has improved the mechanical property and the water resistance of filming.
Embodiment
Below by example the present invention is described in further detail:
Embodiment 1
1, polyureas is synthetic: add 30gD2000 earlier in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed, stirs and slowly drip 3.5gTDI, reaction 5min obtains polyureas.
2, performed polymer is synthetic: above-mentioned product is warmed up to 60 ℃, slowly drips 3.4g E-44, with 0.17g water-based diethanolamine, reaction 2h obtains performed polymer.
3, the end-blocking product is synthetic: add the 10.3g diethylenetriamine and be warmed up to 60 ℃ in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed, slowly drip 20g epoxy 501, reaction 1.5h obtains the end-blocking product.
4, adduct is synthetic: in above-mentioned end-blocking product, continue to drip the performed polymer of 30.3g, and 60 ℃ of temperature, reaction 1.5h obtains adduct.
5, water-based polyurea modified epoxy curing agent: drip 17.2g glacial acetic acid salify, and 60 ℃ of temperature controls, reacting 1.5 hours, thin up to solid content is 60% then, obtains water-based polyurea modified epoxy curing agent.
6, the preparation of bi-component aqueous epoxy resin paint film
First component: aqueous epoxy resin curing agent second component: aqueous epoxy resin emulsion
According to first component (active hydrogen number mol/g): the mixed of second component (epoxy base value mol/g)=1: 1, stir, be coated on the iron plate with brush.Treat to form transparent film after the moisture evaporation.
The paint film property of gained aqueous epoxy resin curing agent:
Embodiment 2
1, polyureas is synthetic: add 30g D2000 earlier in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed, stirs also slowly Dropwise 5 .2gMDI, reaction 30min obtains polyureas.
2, performed polymer is synthetic: above-mentioned product is warmed up to 80 ℃, slowly drips 2.3g E-44, with 0.11g water-based glycine, reaction 4h obtains performed polymer.
3, the end-blocking product is synthetic: add the 10.3g diethylenetriamine and be warmed up to 80 ℃ in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed, slowly drip 20g epoxy 501, reaction 2.5h obtains the end-blocking product.
4, adduct is synthetic: in above-mentioned end-blocking product, continue to drip the performed polymer of 15.1g, and 90 ℃ of temperature, reaction 2.5h obtains adduct.
5, water-based polyurea modified epoxy curing agent: drip 15.8g glacial acetic acid salify, and 90 ℃ of reactions of temperature control 2.5h, thin up to solid content is 40% then, obtains water-based polyurea modified epoxy curing agent.
6, the preparation of bi-component aqueous epoxy resin paint film
First component: aqueous epoxy resin curing agent second component: aqueous epoxy resin emulsion
According to first component (active hydrogen number mol/g): the mixed of second component (epoxy base value mol/g)=1: 1, stir, be coated on the iron plate with brush.Treat to form transparent film after the moisture evaporation.
The paint film property of gained aqueous epoxy resin curing agent:
Embodiment 3
1, polyureas is synthetic: add 30g D2000 earlier in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed, stirs and slowly drip 1.7gHDI, reaction 10min obtains polyureas.
2, performed polymer is synthetic: above-mentioned product is warmed up to 70 ℃, slowly drips 3.4g E-44, with 0.11g water-based diethanolamine, reaction 3h obtains performed polymer.
3, the end-blocking product is synthetic: add the 10.3g diethylenetriamine and be warmed up to 70 ℃ in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed, slowly drip 20g epoxy 501, reaction 2h obtains the end-blocking product.
4, adduct is synthetic: in above-mentioned end-blocking product, continue to drip the performed polymer of 20g, and 70 ℃ of temperature, reaction 2h obtains adduct.
5, water-based polyurea modified epoxy curing agent: drip 18.2g glacial acetic acid salify, and 70 ℃ of temperature controls, reacting 2 hours, thin up to solid content is 50% then, obtains water-based polyurea modified epoxy curing agent.
6, the preparation of bi-component aqueous epoxy resin paint film
First component: aqueous epoxy resin curing agent second component: aqueous epoxy resin emulsion
According to first component (active hydrogen number mol/g): the mixed of second component (epoxy base value mol/g)=1: 1, stir, be coated on the iron plate with brush.Treat to form transparent film after the moisture evaporation.
The paint film property of gained aqueous epoxy resin curing agent:
Embodiment 4
1, polyureas is synthetic: add 30gD2000 earlier in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed, stirs and slowly drip 2.6gMDI, reaction 15min obtains polyureas.
2, performed polymer is synthetic: above-mentioned product is warmed up to 75 ℃, slowly drips 3.4g E-44, with 0.22g water-based diethanolamine, reaction 3h obtains performed polymer.
3, the end-blocking product is synthetic: add the 10.3g diethylenetriamine and be warmed up to 75 ℃ in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed, slowly drip 20g epoxy 501, reaction 2h obtains the end-blocking product.
4, adduct is synthetic: in above-mentioned end-blocking product, continue to drip the performed polymer of 15.1g, and 80 ℃ of temperature, reaction 2h obtains adduct.
5, water-based polyurea modified epoxy curing agent: drip 17.5g glacial acetic acid salify, and 80 ℃ of temperature controls, reacting 2 hours, thin up to solid content is 60% then, obtains water-based polyurea modified epoxy curing agent.
6, the preparation of bi-component aqueous epoxy resin paint film
First component: aqueous epoxy resin curing agent second component: aqueous epoxy resin emulsion
According to first component (active hydrogen number mol/g): the mixed of second component (epoxy base value mol/g)=1: 1, stir, be coated on the iron plate with brush.Treat to form transparent film after the moisture evaporation.
The paint film property of gained aqueous epoxy resin curing agent:
The present invention is not limited to the technology described in the embodiment; its description is illustrative; and it is nonrestrictive; authority of the present invention is limited by claim; based on present technique field personnel according to the present invention can change, technology related to the present invention that method such as reorganization obtains, all within protection scope of the present invention.
Claims (5)
1. the preparation method of water-based polyurea modified epoxy curing agent is characterized in that step is as follows:
(1) chooses a kind of Amino Terminated polyether(ATPE), drip the polyisocyanates normal-temperature reaction and obtain polyureas, reaction times 5～30min; The amino mol ratio with isocyanate group of end is 1.5～2: 1;
(2) product drips hydrophilic chain extender and epoxy resin E-44 in (1), is warmed up to 60～80 ℃, continues reaction 2～4h and obtains performed polymer; Epoxy group(ing) in the Resins, epoxy is that 1: 1～1.5 hydrophilic chain extender additions are 5%～10% of Resins, epoxy quality with the amino ratio;
(3) choose diethylenetriamine, drip equimolar mono-epoxy compounds butylglycidyl ether, prepare the end-blocking product; Temperature of reaction is 60～80 ℃, and the reaction times is 1.5～2.5h;
(4) in the end-blocking product that prepare (3), drip the performed polymer that prepare (2), obtain adduct; The mass ratio of end-blocking product and performed polymer is 1～2: 1, and temperature of reaction is 60～90 ℃, and the reaction times is 1.5～2.5h;
(5) in (4) adduct, drip in the glacial acetic acid and salify, add entry then and prepare water-based polyurea modified epoxy curing agent; Wherein thin up to solid content is 40～60%, and temperature of reaction is 60～90 ℃, and the reaction times is 1.5～2.5h.
2. the method for claim 1 is characterized in that the Amino Terminated polyether(ATPE) that adopts in the described step (1) is a kind of among D2000 or the D5000.
3. the method for claim 1 is characterized in that described polyisocyanates is a kind of in tolylene diisocyanate, MDI or the hexamethylene diisocyanate.
4. the method for claim 1 is characterized in that hydrophilic chain extender in the described step (2) is a kind of in water-based glycine, the water-based diethanolamine.
5. the application of water-based polyurea modified epoxy curing agent is characterized in that being applied to the preparation of bi-component aqueous epoxy resin paint film, according to the first component: aqueous epoxy resin curing agent, second component: aqueous epoxy resin emulsion; With active hydrogen number mol/g in the first component: second component epoxy base value mol/g=1: 1 mixed, stir, be coated on the iron plate with brush; Treat to form transparent film after the moisture evaporation.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650322A (en) * | 2015-02-18 | 2015-05-27 | 中国科学院长春应用化学研究所 | Preparation method of carbon-dioxide-base polyurea high polymer material |
| CN104673053A (en) * | 2015-02-28 | 2015-06-03 | 江苏千龙新型材料有限公司 | Water-based corrosion-resistant epoxy coating and preparation method thereof |
| CN105968303A (en) * | 2016-03-22 | 2016-09-28 | 安徽大学 | Preparation method of water-based epoxy resin curing agent |
| CN106632971A (en) * | 2016-12-19 | 2017-05-10 | 钦州市高新技术产业服务中心 | Anticorrosive material for epoxy resin and preparation method of anticorrosive material |
| CN109266157A (en) * | 2018-09-17 | 2019-01-25 | 湘江涂料科技有限公司 | A kind of preparation method of aqueous polyurea modified epoxy ester resin |
| CN109485848A (en) * | 2018-09-20 | 2019-03-19 | 中北大学 | A kind of aqueous polyureas of non-isocyanate and preparation method thereof |
| CN110229310A (en) * | 2019-07-16 | 2019-09-13 | 上海骁鹏新材料科技有限公司 | Modified aqueous epoxy resin curing agent and preparation method thereof |
| CN115594825A (en) * | 2022-12-15 | 2023-01-13 | 中远关西涂料化工（天津）有限公司（Cn） | Preparation method of isocyanate modified waterborne epoxy curing agent |
| CN115678394A (en) * | 2022-11-21 | 2023-02-03 | 信和新材料（苏州）有限公司 | Functional marine long-acting antifouling paint |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650322A (en) * | 2015-02-18 | 2015-05-27 | 中国科学院长春应用化学研究所 | Preparation method of carbon-dioxide-base polyurea high polymer material |
| CN104673053A (en) * | 2015-02-28 | 2015-06-03 | 江苏千龙新型材料有限公司 | Water-based corrosion-resistant epoxy coating and preparation method thereof |
| CN104673053B (en) * | 2015-02-28 | 2017-01-25 | 江苏千龙新型材料有限公司 | Water-based corrosion-resistant epoxy coating and preparation method thereof |
| CN105968303A (en) * | 2016-03-22 | 2016-09-28 | 安徽大学 | Preparation method of water-based epoxy resin curing agent |
| CN106632971A (en) * | 2016-12-19 | 2017-05-10 | 钦州市高新技术产业服务中心 | Anticorrosive material for epoxy resin and preparation method of anticorrosive material |
| CN109266157A (en) * | 2018-09-17 | 2019-01-25 | 湘江涂料科技有限公司 | A kind of preparation method of aqueous polyurea modified epoxy ester resin |
| CN109485848A (en) * | 2018-09-20 | 2019-03-19 | 中北大学 | A kind of aqueous polyureas of non-isocyanate and preparation method thereof |
| CN110229310A (en) * | 2019-07-16 | 2019-09-13 | 上海骁鹏新材料科技有限公司 | Modified aqueous epoxy resin curing agent and preparation method thereof |
| CN110229310B (en) * | 2019-07-16 | 2020-07-07 | 上海骁鹏新材料科技有限公司 | Curing agent for modified waterborne epoxy resin and preparation method thereof |
| CN115678394A (en) * | 2022-11-21 | 2023-02-03 | 信和新材料（苏州）有限公司 | Functional marine long-acting antifouling paint |
| CN115678394B (en) * | 2022-11-21 | 2023-08-29 | 信和新材料（苏州）有限公司 | Functional marine long-acting antifouling paint |
| CN115594825A (en) * | 2022-12-15 | 2023-01-13 | 中远关西涂料化工（天津）有限公司（Cn） | Preparation method of isocyanate modified waterborne epoxy curing agent |
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