CN102295735B - Polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion and preparation method thereof - Google Patents
Polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion and a preparation method thereof. The emulsion has solid content of 40-50%, an average particle size of less than 500nm and a viscosity of 500-650(mPa*S). A chain segment in the self-emulsifying nanometer waterborne emulsion of the invention is introduced with a compound containing a nonionic hydrophilic chain segment, so that epoxy resin can have a self-emulsifying property, and the corrosion resistance and curing time of a coating can be improved by the polyurethane-urea based chain segment.A water dispersion system formed by the modified epoxy resin is then subjected to high pressure emulsification by a homogenizer and the particle size is dispersed to a nanoscale, and after a long time storage, physicochemical properties change little. Thus, the emulsion of the invention has good stability. The synthesis process of the method provided in the invention adds no organic solvent and has simple operation, thus being easy to realize.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion and preparation method.
Background technology
Particularly Water-borne modification epoxypaint and nanometer modified epoxy cold coating develop rapidly epoxypaint in recent years.Because Resins, epoxy has excellent physics and chemical property, as good sticking power, chemical proofing and solvent resistance excellence, hardness height, corrosion-resistant, good heat stability, so cause people's attention always.Common solvent type epoxypaint contains the organic volatile solvent, and these organic solvents entered in the atmosphere owing to solvent evaporates in production and the construction stage of coating, environment were polluted harm humans health.Compare with solvent based coating, aqueous epoxy coating has many advantages, low such as organic volatile content, smell is little, use is safe, even do not contain organic solvent, can wash by water etc., so be widely used as high-performance building coating, equipment priming paint, transportation means priming paint, vehicle paint base and industrial maintenance finish paint etc.
The Resins, epoxy Water-borne modification mainly contains mechanical process, phase reversion method and three kinds of methods of chemic modified method in the worldwide at present: the less stable of the epoxy emulsion of mechanical process and the preparation of phase reversion method is used poor effect with aqueous epoxy curing agent, filler and various auxiliary agent; Chemic modified method is that the size of dispersed phase particles can reach nano level in the aqueous epoxy resin emulsion of self-emulsification preparation, can form the stabilized aqueous epoxy resin latex.
Chemical modification Resins, epoxy can be introduced hydrophilic polar group on the one hand, and these hydrophilic radicals can help Resins, epoxy to disperse in water; Also can introduce group or the macromolecular chain of other senses on the other hand, in order to the physicals of improving Resins, epoxy or give its more good characteristic.For example utilize the research of polyurethane modified epoxy resin to emerge in an endless stream in the oiliness system, and also begin in water-based system, to use, can improve the fragility of epoxy, increase toughness, but simple polyurethane-modified set time is longer, is unfavorable for spraying application, therefore need improve.Can utilize the high reactivity of urea groups to solve the problem of set time, can also improve corrosive nature simultaneously.
Summary of the invention
The preparation method of the polyurethane-urea modified self-emulsifying nanometer epoxy emulsion that the present invention proposes uses chemic modified method, hydrophilic segment, polyurethane-urea segment are introduced Resins, epoxy, it is the polyurethane-urea modified aqueous epoxy resin, again in conjunction with processing means such as high speed dispersor, colloidal mill, clarifixators, it is even to obtain particle diameter, nano level, and the polyurea modified self-emulsifying nanometer waterborne epoxy emulsion of excellent property.
Technical scheme of the present invention is as follows:
Polyurethane-polyurea modified self-emulsifying nanometer waterborne epoxy emulsion of the present invention, emulsion solid content 40-50%, median size＜500nm, viscosity 500-650 (mPaS).
The preparation method of polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion of the present invention, step is as follows:
1) adding is preheating to 50～60 ℃ non-ionic hydrophilic chain segment compounds in Resins, epoxy, adds boron trifluoride diethyl etherate or triphenylphosphine catalyzer again, and reaction 4～6h obtains modified epoxy under 80～100 ℃; Catalyst levels is 1～3% of weight epoxy;
2) drip the polyisocyanates reaction in the modified epoxy of step 1) and obtain performed polymer, 50～70 ℃ of temperature of reaction, reaction times 1～2h; Isocyanate group and 1) step institute to add the amido ratio be 1: 1～3;
3) with step 2) performed polymer that obtains mixes 60～90 ℃ of temperature of reaction, time 1～3h with raw material epoxy resin (identical with step (1)); The addition of performed polymer is 10～20% of weight epoxy;
4) the polyurea modified Resins, epoxy with the step 3) preparation drips deionized water under high speed dispersion, descends suddenly until system viscosity, obtains epoxy resin latex;
5) with 4) preparation emulsion grind through colloidal mill, carry out high-pressure emulsification with clarifixator again, obtain stable polyurea modified self-emulsifying nanometer waterborne epoxy emulsion.
The non-ionic hydrophilic chain segment compounds that adopts in the described step 1) is cetomacrogol 1000 or 4000 and the mixture of Amino Terminated polyether(ATPE) D2000, mass ratio 10: 1;
Described step 2) polyisocyanates that adopts in is tolylene diisocyanate, MDI or hexamethylene diisocyanate.
The rate of dispersion of described step 3 high speed dispersion machine is 1000～4000r/min.
The colloidal mill milling time is 0.5～1.5h in the described step 4, and rotating speed is 2500～3500r/min; High pressure homogenizer emulsification pressure is 30～100MPa, and emulsification times is 0.5～1.5h.
The self-emulsifying nanometer waterborne emulsion that the present invention proposes makes Resins, epoxy have automatic emulsifying performance owing to introduced a kind of compound that contains the non-ionic hydrophilic segment in the segment, and polyurethane-urea base segment has improved corrosion resistance nature and the set time of filming.The aqueous dispersion that modified epoxy forms passes through the clarifixator high-pressure emulsification again, disperses particle diameter to reach nano level, the long-time storage, and physical and chemical performance does not have considerable change, has good stability.This kind method building-up process is not added any organic solvent, and simple to operate, is easy to realize.
Adopt the performance of gained aqueous epoxy emulsion of the present invention as follows:
Embodiment
Below by example the present invention is described in further detail:
Embodiment 1
1, modified epoxy is synthetic: add the 13.6g epoxy resin E-44 in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed earlier, be warmed up to 50 ℃, slowly drip the mixture of 23.1gD2000 and PEG1000, be warmed up to 80 ℃, reaction 4h gets modified epoxy.
2, performed polymer is synthetic: above-mentioned reaction system is cooled to 50 ℃, slowly drips 1.7gTDI, and reaction 1h obtains epoxy prepolymer.
3, get the above-mentioned epoxy resin prepolymer 4g that obtains and mix with 40g E-44, react 1h down at 60 ℃, from reaction vessel, take out.
4, with above-mentioned product under the 1000r/min high speed dispersion, drip 110g distilled water, obtain the polyurea modified epoxy resin latex.
5, with under the above-mentioned emulsion process vertical colloid mill 2500r/min condition, disperse 30min, use the nanometer clarifixator to carry out 30MPa high-pressure emulsification 30min then, obtain stable polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion.
Embodiment 2
1, modified epoxy is synthetic: add the 4.5g epoxy resin E-44 in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed earlier, be warmed up to 60 ℃, slowly drip the mixture of 23.1gD2000 and PEG4000, be warmed up to 100 ℃, reaction 6h gets modified epoxy.
2, performed polymer is synthetic: above-mentioned reaction system is cooled to 70 ℃, slowly drips 2.6g MDI, and reaction 2h obtains epoxy prepolymer.
3, get the above-mentioned epoxy resin prepolymer 4g that obtains and mix with 20g E-44, react 3h down at 90 ℃, from reaction vessel, take out.
4, with above-mentioned product under the 1000r/min high speed dispersion, drip 48g distilled water, obtain the polyurea modified epoxy resin latex.
5, with under the above-mentioned emulsion process vertical colloid mill 3500r/min condition, disperse 1.5h, use the nanometer clarifixator to carry out 100MPa high-pressure emulsification 1.5h then, obtain stable polyurea modified self-emulsifying nanometer waterborne epoxy emulsion.
Embodiment 3
1, modified epoxy is synthetic: add the 13.6g epoxy resin E-44 in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed earlier, be warmed up to 55 ℃, slowly drip the mixture of 23.1g D2000 and PEG4000, be warmed up to 90 ℃, reaction 5h gets modified epoxy.
2, performed polymer is synthetic: above-mentioned reaction system is cooled to 60 ℃, slowly drips 1.7g HDI, and reaction 1.5h obtains epoxy prepolymer.
3, get the above-mentioned epoxy resin prepolymer 4g that obtains and mix with 40g E-44, react 2h down at 70 ℃, from reaction vessel, take out.
4, with above-mentioned product under the 1000r/min high speed dispersion, drip 88g distilled water, obtain the polyurea modified epoxy resin latex.
5, with under the above-mentioned emulsion process vertical colloid mill 2500r/min condition, disperse 1h, use the nanometer clarifixator to carry out 50MPa high-pressure emulsification 1h then, obtain stable polyurea modified self-emulsifying nanometer waterborne epoxy emulsion.
Embodiment 4
1, modified epoxy is synthetic: add the 4.5g epoxy resin E-44 in the 250mI four-hole boiling flask of agitator, electric mantle, prolong and thermometer is housed earlier, be warmed up to 60 ℃, slowly drip the mixture of 23.1gD2000 and PEG1000, be warmed up to 95 ℃, reaction 4h gets modified epoxy.
2, performed polymer is synthetic: above-mentioned reaction system is cooled to 65 ℃, slowly drips 1.3g MDI, and reaction 1.5h obtains epoxy prepolymer.
3, get the above-mentioned epoxy resin prepolymer 4g that obtains and mix with 20g E-44, react 2h down at 80 ℃, from reaction vessel, take out.
4, with above-mentioned product under the 1000r/min high speed dispersion, drip 60g distilled water, obtain the polyurea modified epoxy resin latex.
5, with under the above-mentioned emulsion process vertical colloid mill 3000r/min condition, disperse 1h, use the nanometer clarifixator to carry out 70MPa high-pressure emulsification 1h then, obtain stable polyurea modified self-emulsifying nanometer waterborne epoxy emulsion.
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 the art 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 (4)
1. the preparation method of polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion is characterized in that the polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion, emulsion solid content 40-50%, median size＜500nm, viscosity 500-650mPaS; The preparation method, step is as follows:
1) adding is preheating to 50～60 ℃ non-ionic hydrophilic chain segment compounds in Resins, epoxy, adds boron trifluoride diethyl etherate or triphenylphosphine catalyzer again, and reaction 4～6h obtains modified epoxy under 80～100 ℃; Catalyst levels is 1～3% of weight epoxy;
2) drip the polyisocyanates reaction in the modified epoxy of step 1) and obtain performed polymer, 50～70 ℃ of temperature of reaction, reaction times 1～2h; Isocyanate group and 1) step institute to add the amido ratio be 1:1～3;
3) with step 2) performed polymer and the raw material epoxy resin that obtain mix 60～90 ℃ of temperature of reaction, time 1～3h; The addition of performed polymer is 10～20% of weight epoxy;
4) the polyurethane-urea modified epoxy with the step 3) preparation drips deionized water under high speed dispersion, descends suddenly until system viscosity, obtains epoxy resin latex;
5) emulsion of step 4) preparation is ground through colloidal mill, carry out high-pressure emulsification with clarifixator again, obtain stable polyurethane-urea modified self-emulsifying nanometer waterborne epoxy emulsion;
The non-ionic hydrophilic chain segment compounds is the mixture of a kind of of cetomacrogol 1000 and Macrogol 4000 and Amino Terminated polyether(ATPE) D2000, mass ratio 10:1.
2. the method for claim 1 is characterized in that described step 2) in the polyisocyanates that adopts be tolylene diisocyanate, '-diphenylmethane diisocyanate or hexamethylene diisocyanate.
3. the method for claim 1, the rate of dispersion that it is characterized in that described step 3) high speed dispersion machine is 1000～4000r/min.
4. the method for claim 1 is characterized in that the colloidal mill milling time is 0.5～1.5h in the described step 4), and rotating speed is 2500～3500r/min; High pressure homogenizer emulsification pressure is 30～100MPa, and emulsification times is 0.5～1.5h.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003715A (en) * | 2007-01-05 | 2007-07-25 | 华南理工大学 | Method for preparing modified aqueous adhesion agent of polyurethane |
| CN101402739A (en) * | 2008-11-14 | 2009-04-08 | 天津大学 | Production process for water-soluble epoxy resin emulsions |
| CN101717484A (en) * | 2009-11-20 | 2010-06-02 | 天津大学 | Method for preparing polyurethane-modified self-emulsifying nanometer waterborne epoxy emulsion |
| CN101798484A (en) * | 2010-03-05 | 2010-08-11 | 四川大学 | Dendritic organic-inorganic hybrid water-borne nano polyurethane-epoxy anticorrosive coating and preparation method thereof |
| CN101824133A (en) * | 2010-04-28 | 2010-09-08 | 天津大学 | Preparation method for waterborne polyurethane modified epoxy resin curing agent |
| CN101880508A (en) * | 2010-06-24 | 2010-11-10 | 同济大学 | Preparation method of high abrasion water-borne wood coating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6797789B2 (en) * | 2001-10-19 | 2004-09-28 | Visuron Technologies, Inc. | Phenolic/polyurea coating co-polymer compositions and process |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003715A (en) * | 2007-01-05 | 2007-07-25 | 华南理工大学 | Method for preparing modified aqueous adhesion agent of polyurethane |
| CN101402739A (en) * | 2008-11-14 | 2009-04-08 | 天津大学 | Production process for water-soluble epoxy resin emulsions |
| CN101717484A (en) * | 2009-11-20 | 2010-06-02 | 天津大学 | Method for preparing polyurethane-modified self-emulsifying nanometer waterborne epoxy emulsion |
| CN101798484A (en) * | 2010-03-05 | 2010-08-11 | 四川大学 | Dendritic organic-inorganic hybrid water-borne nano polyurethane-epoxy anticorrosive coating and preparation method thereof |
| CN101824133A (en) * | 2010-04-28 | 2010-09-08 | 天津大学 | Preparation method for waterborne polyurethane modified epoxy resin curing agent |
| CN101880508A (en) * | 2010-06-24 | 2010-11-10 | 同济大学 | Preparation method of high abrasion water-borne wood coating |
Non-Patent Citations (1)
| Title |
|---|
| 张郃,吴跃焕.环氧-聚氨酯乳液合成涂料的研究.《山西化工》.2006,第26卷(第3期), * |
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