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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- 239000004593 Epoxy Substances 0.000 title claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 39
- 239000000839 emulsion Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 239000003973 paint Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 3
- 238000007792 addition Methods 0.000 claims description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 5
- 229920000768 polyamine Polymers 0.000 abstract description 5
- 150000003384 small molecules Chemical class 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 3
- 229920006334 epoxy coating Polymers 0.000 description 2
- 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 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- -1 polyoxyethylene Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
本发明水性聚脲改性环氧乳液固化剂制备方法及应用。在水性聚脲改性环氧树脂固化剂由于链段中引入了一种含非离子型亲水链段的化合物，改善了固化物膜的脆性，与环氧乳液的相容性增强，提高了环氧乳液的韧性，同时使固化剂具有水溶性。而聚脲链段引入环氧树脂使其固化后所得漆膜具有优越的耐水性、耐溶剂性、柔韧性，以及更高的强度，从而具备了聚脲的优良特性，克服了环氧树脂本身的缺点。此方法合成的固化剂，解决了第一代与第二代固化剂存在的问题，去除了小分子活性剂与小分子多胺，改善了固化剂与乳液的相容性，从而提高了涂膜的机械性能与耐水性能。The preparation method and application of the water-based polyurea modified epoxy emulsion curing agent of the present invention. In the water-based polyurea modified epoxy resin curing agent, a compound containing a non-ionic hydrophilic segment is introduced into the segment, which improves the brittleness of the cured product film, enhances the compatibility with the epoxy emulsion, and improves the Toughness of the epoxy emulsion, while making the curing agent water-soluble. The polyurea segment is introduced into the epoxy resin to make the cured paint film have superior water resistance, solvent resistance, flexibility, and higher strength, thus possessing the excellent characteristics of polyurea and overcoming the epoxy resin itself. Shortcomings. The curing agent synthesized by this method solves the problems of the first-generation and second-generation curing agents, removes small-molecule active agents and small-molecule polyamines, and improves the compatibility between the curing agent and the emulsion, thereby improving the coating film. Excellent mechanical properties and water resistance.
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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| 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 |
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| 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 |
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Cited By (15)
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| CN109485848A (en) * | 2018-09-20 | 2019-03-19 | 中北大学 | A kind of aqueous polyureas of non-isocyanate and preparation method thereof |
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