CN102504282A - Preparation method of waterborne epoxy resin emulsion - Google Patents
Preparation method of waterborne epoxy resin emulsion Download PDFInfo
- Publication number
- CN102504282A CN102504282A CN2011102991236A CN201110299123A CN102504282A CN 102504282 A CN102504282 A CN 102504282A CN 2011102991236 A CN2011102991236 A CN 2011102991236A CN 201110299123 A CN201110299123 A CN 201110299123A CN 102504282 A CN102504282 A CN 102504282A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- preparation
- emulsifying agent
- toluene
- glycol monomethyl
- 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.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to a preparation method of a waterborne epoxy resin emulsion. The preparation method comprises the following steps: mixing bisphenol A epoxy resin, polyethylene glycol monomethyl ether and toluene, stirring, and performing azeotropic dehydration to get a mixed liquid; dissolving a catalyst in the toluene, then raising the temperature of the mixed liquid under magnetic stirring, reacting under the protection of nitrogen, and removing a solvent by reduced pressure evaporation when the retention rate of epoxy in the bisphenol A epoxy resin is reduced to 50%, thus getting a reactive non-ionic epoxy emulsifying agent; and dropwise adding distilled water while intensely stirring the liquid-state epoxy resin, a cosolvent and the reactive non-ionic epoxy emulsifying agent, thus getting the waterborne epoxy resin emulsion. The preparation method disclosed by the invention has the beneficial effects that the epoxy resin emulsion emulsified by the non-ionic waterborne epoxy resin emulsifying agent is good in stability, has no toxicity and zero content of organic volatile matters, is safe and environmentally-friendly, and can be used for maintaining the excellent chemical-resistant performance of the epoxy resin and simultaneously increasing the flexibility of a paint film.
Description
Technical field
The present invention relates to the water-borne coatings field, the concrete preparation method who relates to a kind of aqueous epoxy resin emulsion.
Background technology
Epoxy resin is a kind of thermosetting resin, has characteristics such as excellent electric insulating, chemicalstability, cementability, processibility, is widely used in fields such as building, mechanical, electric, space flight and aviation.But traditional epoxy resin can only be dissolved in organic solvent, must dilute with organic solvent in the use, and the epoxy coating of preparation in use must work the mischief to operative employee's human and environment like this.In recent years, environment protection receives people's attention day by day, and many countries have issued the rules of control volatile organic compounds (VOC) in succession, and operative norm is strict further.Develop and contain the research focus that the environment-friendly type coating that does not even contain organic volatile matter has become coating industry less.
Aqueous epoxy resins is meant that it is the stable dispersion system that is mixed with in the disperse phase medium of external phase that epoxy resin is dispersed in water with particulate or drop form.Compare with traditional epoxy resin, aqueous epoxy resins has been avoided the environmental pollution and the wasting of resources that with an organic solvent cause, can under room temperature and wet environment, solidify, and construction and processing property are greatly improved.Technology according to preparation is different, can the epoxy resin water-based be divided three kinds of methods: mechanical process, phase reversion method, self-emulsification.Self-emulsification is that epoxy resin is carried out chemical modification; Make it in water, to have from disperseing the emulsive ability, this method need not add emulsifying agent, good emulsion stability; The mechanical property of paint film, outward appearance are all better; But complicated process of preparation, and the modified resin chemicalstability is bad, is prone to take place rotten.Mechanical process and phase reversion method all need add emulsifying agent, but traditional emulsifying agent is a tensio-active agent, and itself does not participate in the curing reaction of resin, and this emulsifying agent is easily separated out and influenced the outward appearance and the antiseptic property of paint film at coating surface behind resin solidification.Reactive emulsifier is participated in the curing reaction of resin, becomes a part of solidifying back corsslinking molecular structure, thereby less to the influence of paint film.The good reactive emulsifier of exploitation emulsifying property is the developing direction of epoxy resin emulsifying agent.
Document " Shanghai coating " [2006,44 (11): 19-22] at Potassium Persulphate catalysis, 180 ℃ of following reaction with same mole synthetic emulsifiers, adds epoxy resin with a certain amount of emulsifying agent with Macrogol 4000 and epoxy resin E-44; Drip zero(ppm) water, violent stirring can be processed water-based emulsion; But this method temperature of reaction is too high; Energy consumption is bigger, and stirring velocity is high, and is higher to equipment requirements.Chinese patent CN1415680A utilizes epoxy resin and polyether Glycols synthetic end group under Louis acid catalysis to be respectively the reactive emulsifier of epoxy group(ing) and hydroxyl; The used for epoxy resin cosolvent is dissolved; Add a certain amount of this reactive emulsifier again; Adopt impeller, get aqueous epoxy resin emulsion with the phase reversion legal system.But the reactive emulsifier that these two kinds of methods make belongs to the Polymerizable Emulsifier in multilist face active site; When dispersion and emulsion epoxy resin, can only form horizontal absorption; And can not form traditional micella emulsion particle, and particle size of emulsion is bigger, and the mechanical property of paint film is influenced.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of aqueous epoxy resin emulsion, prepared emulsifying agent to be used for emulsion epoxy resin to above-mentioned prior art, good stability; Can accomplish to join existing usefulness at present; Convenient in application, and method is simple, implements easily.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of preparation method of aqueous epoxy resin emulsion is characterized in that including following steps:
1) by the shared mass percent of each raw material be: bisphenol A epoxide resin 7%～24%, poly glycol monomethyl ether 30%～50% and toluene 30%～55%, choose bisphenol A epoxide resin, poly glycol monomethyl ether and toluene, subsequent use;
Under nitrogen protection, bisphenol A epoxide resin, poly glycol monomethyl ether and toluene are mixed, heat up under the magnetic agitation, be 130～150 ℃ of following azeotropic dehydrations 2.5～3 hours in temperature, get mixing liquid;
2) by the shared mass percent of each raw material be: mixing liquid 90%～94.95%, toluene 5%～9.95% and catalyzer 0.03%～0.06%, choose mixing liquid, toluene and the catalyzer of step 1) gained, subsequent use;
Catalyzer is dissolved in the toluene, and then joins in the mixing liquid of step 1) gained, heat up under the magnetic agitation; Be strict controlled in 85～95 ℃ of reactions down of temperature under the nitrogen protection; The oxirane value of regular sampling analysis system between the reaction period calculates bisphenol A epoxide resin epoxy retention rate, when the retention rate of bisphenol A epoxide resin epoxy drops to 50%; Remove solvent under reduced pressure, obtain reactive non-ionic type epoxy emulsifying agent;
3) by the shared mass percent of each raw material be: liquid-state epoxy resin 18%～22%, reactive non-ionic type epoxy emulsifying agent 8%～10%, zero(ppm) water 64%～70% and cosolvent 4%～5%; Choose liquid-state epoxy resin, step 2) reactive non-ionic type epoxy emulsifying agent, zero(ppm) water and the cosolvent of gained, subsequent use;
With liquid-state epoxy resin, cosolvent, the powerful stirring of reactive non-ionic type epoxy emulsifying agent down, drip zero(ppm) water, process the aqueous epoxy resin emulsion that solid content is 20wt%～40wt%.
Press such scheme, the relative molecular mass of described poly glycol monomethyl ether is between 1200～2000.
Press such scheme, step 2) described catalyzer is any one in boron trifluoride complex, triphenyl phosphorus and the aluminum chloride.
Press such scheme, step 2) described bisphenol A epoxide resin is any one in E-44 type epoxy resin, E-54 type epoxy resin and the E-51 type epoxy resin.
Press such scheme, the described cosolvent of step 3) is any one in propylene glycol monomethyl ether, Ucar 35 butyl ether and the 1-Methoxy-2-propyl acetate.
Press such scheme, the described liquid epoxies of step 3) is E-44 type epoxy resin or E-51 type epoxy resin.
Ultimate principle of the present invention is: addition reaction can take place in epoxide group and hydroxyl under high temperature and catalyzer condition.Through this reaction hydrophilic non-ionic segments and lipophilic epoxy resin segment have been linked and to have generated a macromole.In the non-ion aqueous epoxy resin emulsifying agent molecule of the present invention, both contain hydrophilic non-ionic segments, contained the oleophilicity group again, can participate in the emulsion reaction of epoxy resin.Come emulsion epoxy resin with this emulsifying agent, good stability can accomplish to join existing usefulness at present, and convenient in application, and contain epoxide group in this emulsifying agent molecule is used in the solidification process in emulsion and to be participated in curing reaction, so paint film appearance and mechanical property are better.This method is simple, implements to have a extensive future easily, and economic benefit is considerable, and actual application value is big.The aqueous epoxy resin emulsion that this method obtains has good stability, and is nontoxic, and it is zero that organic volatile divides content (VOC); Process aqueous epoxy coating, have the characteristics of snappiness, water-tolerant.
The invention has the beneficial effects as follows: have satisfactory stability property with non-ion aqueous epoxy resin emulsifying agent emulsive epoxy resin latex; Nontoxic; Organic volatile branch (VOC) content is zero; Safety and environmental protection, the good chemical resistance while that has kept epoxy resin is because the introducing of non-ionic segments has increased the snappiness of paint film.The present invention solves the shortcoming of present aqueous epoxy resins stability with the preparation of ionize modification technology not high and cured coating film snappiness and poor water resistance.
Non-ion aqueous epoxy resin latex of the present invention is added aqueous epoxy curing agent be prepared into aqueous epoxy coating, the main performance of aqueous epoxy coating is following:
1. stable:
⑴ centrifugal stability: 2500r/min, 30min is not stratified, breakdown of emulsion not;
⑵ storage stability: 2 months not stratified, breakdowns of emulsion not;
⑶ median size:＜0.5 μ m;
2. sticking power: I level, GB/T 1725-89 " paint film adhesion assay method ";
3. snappiness: >=5 grades, GB/T 1748-89 " paint film flexibility assay method ";
4. water tolerance: 25 ℃, 36h, non-foaming, do not come off GB1733-79 (88) " paint film water tolerance assay method ";
5. alkali resistance: 10%NaOH, 8h, non-foaming, do not come off.
Embodiment
For a better understanding of the present invention, the present invention is done further detailed description, but the scope that the present invention requires to protect is not limited to the scope implementing to represent below in conjunction with embodiment.
Embodiment 1
A kind of preparation method of reactive epoxy resin latex, it comprises the steps:
1) the poly glycol monomethyl ether epoxy resin emulsifying agent is synthetic
In the four-hole boiling flask that has water trap, reflux condensing tube, add 20g E-44 type epoxy resin, 54g poly glycol monomethyl ether (relative molecular mass 1200), 57.85g toluene, heat up under the magnetic agitation; In temperature is 130～150 ℃ of following azeotropic dehydrations 3 hours; Obtain mixing liquid, be cooled to 85 ℃, the solution that then the 56.25mg boron trifluoride complex is dissolved in 8.66g toluene adds in the above-mentioned 131.85g mixing liquid; Nitrogen protection is reaction down; Every epoxy retention rate at a distance from 0.5h sampling analysis system when the epoxy retention rate reaches 50%, adds water destruct catalyzer stopped reaction between the reaction period; Underpressure distillation desolventize the water white transparency thick liquid, be the poly glycol monomethyl ether epoxy resin emulsifying agent;
2) preparation of aqueous epoxy resin emulsion
Add 30g E-44 type epoxy resin in the 250mL beaker; 7.5g propylene glycol monomethyl ether stirs, and the epoxy resin viscosity is reduced; The back adds 12g poly glycol monomethyl ether epoxy resin emulsifying agent; System is warming up to 60 ℃, drips 90.5g zero(ppm) water under the high-speed stirring, processes the aqueous epoxy resin emulsion that solid content is 30wt%.
The aqueous epoxy resin emulsion of present embodiment is added aqueous epoxy curing agent, promptly be mixed with aqueous epoxy coating.Aqueous epoxy coating is stable as follows:
1. stable
⑴ centrifugal stability: 2000r/min, 30min is not stratified, breakdown of emulsion not;
⑵ storage stability: 2 months not stratified, breakdowns of emulsion not;
⑶ median size:＜0.5 μ m;
2. sticking power: I level, GB/T 1725-89 " paint film adhesion assay method ";
3. snappiness: >=5 grades, GB/T 1748-89 " paint film flexibility assay method ";
4. water tolerance: 25 ℃, 36h, non-foaming, do not come off GB1733-79 (88) " paint film water tolerance assay method ";
5. alkali resistance: 10%NaOH, 8h, non-foaming, do not come off.
Embodiment 2
A kind of preparation method of reactive epoxy resin latex, it comprises the steps:
1) the poly glycol monomethyl ether epoxy resin emulsifying agent is synthetic
In the four-hole boiling flask that has water trap, reflux condensing tube, add 20g E-51 type epoxy resin, 64g poly glycol monomethyl ether (relative molecular mass 1200), 47.63g toluene.Heating up under the magnetic agitation, is 130～150 ℃ of following azeotropic dehydrations three hours in temperature, obtains mixing liquid, is cooled to 85 ℃, and the solution that the 56.25mg triphenyl phosphorus is dissolved in 8.66g toluene adds in the above-mentioned mixing liquid, and nitrogen protection is reaction down.Every epoxy retention rate at a distance from 0.5h sampling analysis system when the epoxy retention rate reaches 50%, adds water destruct catalyzer stopped reaction between the reaction period, underpressure distillation desolventize the water white transparency thick liquid, be the poly glycol monomethyl ether epoxy resin emulsifying agent;
2) preparation of aqueous epoxy resin emulsion
Add 30g E-51 type epoxy resin in the 250mL beaker; 4.5g propylene glycol monomethyl ether stirs, and the epoxy resin viscosity is reduced; The back adds 14g poly glycol monomethyl ether epoxy resin emulsifying agent; System is warming up to 60 ℃, drips 98.2g zero(ppm) water under the high-speed stirring, processes the aqueous epoxy resin emulsion that solid content is 30wt%.
The aqueous epoxy resin emulsion of present embodiment is added aqueous epoxy curing agent, promptly be mixed with aqueous epoxy coating.Aqueous epoxy coating is stable as follows:
1. stable
⑴ centrifugal stability: 2500r/min, 30min is not stratified, breakdown of emulsion not;
⑵ storage stability: 3 months not stratified, breakdowns of emulsion not;
⑶ median size:＜0.4 μ m;
2. sticking power: I level, GB/T 1725-89 " paint film adhesion assay method ";
3. snappiness: >=5 grades, GB/T 1748-89 " paint film flexibility assay method ";
4. water tolerance: 25 ℃, 48h, non-foaming, do not come off GB1733-79 (88) " paint film water tolerance assay method ";
5. alkali resistance: 10%NaOH, 8h, non-foaming, do not come off.
Embodiment 3
A kind of preparation method of reactive epoxy resin latex, it comprises the steps:
1) the poly glycol monomethyl ether epoxy resin emulsifying agent is synthetic
In the four-hole boiling flask that has water trap, reflux condensing tube, add 10g E-44 type epoxy resin, 45.3g poly glycol monomethyl ether (relative molecular mass about 2000) 61.14g toluene.Heating up under the magnetic agitation, is 130～150 ℃ of following azeotropic dehydrations three hours in temperature, obtains mixing liquid, is cooled to 90 ℃, and the solution that the 56.25mg boron trifluoride complex is dissolved in 8.66g toluene adds in the above-mentioned mixing liquid, and nitrogen protection is reaction down.Every epoxy retention rate at a distance from 0.5h sampling analysis system when the epoxy retention rate reaches 50% left and right sides, adds water destruct catalyzer stopped reaction between the reaction period, underpressure distillation desolventize white solid, be the poly glycol monomethyl ether epoxy resin emulsifying agent;
2) preparation of aqueous epoxy resin emulsion
Add 30g E-44 type epoxy resin in the 250mL beaker; 7.5g propylene glycol monomethyl ether stirs, and the epoxy resin viscosity is reduced; The back adds 14g poly glycol monomethyl ether epoxy resin emulsifying agent; System is warming up to 60 ℃, drips 95.2g zero(ppm) water under the high-speed stirring, processes the aqueous epoxy resin emulsion that solid content is 30wt%.
The aqueous epoxy resin emulsion of present embodiment is added aqueous epoxy curing agent, promptly be mixed with aqueous epoxy coating.Aqueous epoxy coating is stable as follows:
1. stable
⑴ centrifugal stability: 2000r/min, 30min is not stratified, breakdown of emulsion not;
⑵ storage stability: 2 months not stratified, breakdowns of emulsion not;
⑶ median size:＜0.5 μ m;
2. sticking power: I level, GB/T 1725-89 " paint film adhesion assay method ";
3. snappiness: >=5 grades, GB/T 1748-89 " paint film flexibility assay method ";
4. water tolerance: 25 ℃, 36h, non-foaming, do not come off GB1733-79 (88) " paint film water tolerance assay method ";
5. alkali resistance: 10%NaOH, 12h, non-foaming, do not come off.
Embodiment 4
A kind of preparation method of reactive epoxy resin latex, it comprises the steps:
1) the poly glycol monomethyl ether epoxy resin emulsifying agent is synthetic
In the four-hole boiling flask that has water trap, reflux condensing tube, add 20g E-20 type epoxy resin, 39g poly glycol monomethyl ether (relative molecular mass 2000) 56.72g toluene.Heating up under the magnetic agitation, is 140 ℃ of following azeotropic dehydrations three hours in temperature, obtains mixing liquid, is cooled to 95 ℃, and the solution that the 56.25g boron trifluoride complex is dissolved in 8.66g toluene adds in the above-mentioned mixing liquid, and nitrogen protection is reaction down.Every epoxy retention rate at a distance from 0.5h sampling analysis system when the epoxy retention rate reaches 50% left and right sides, adds water destruct catalyzer stopped reaction between the reaction period, underpressure distillation desolventize white solid, be the poly glycol monomethyl ether epoxy resin emulsifying agent;
2) preparation of aqueous epoxy resin emulsion
Add 30g E-44 type epoxy resin in the 250mL beaker; 7.5g propylene glycol monomethyl ether stirs, and the epoxy resin viscosity is reduced; The back adds 15g poly glycol monomethyl ether epoxy resin emulsifying agent; System is warming up to 60 ℃, drips 97.5g zero(ppm) water under the high-speed stirring, processes the aqueous epoxy resin emulsion that solid content is 30wt%.
The aqueous epoxy resin emulsion of present embodiment is added aqueous epoxy curing agent, promptly be mixed with aqueous epoxy coating.Aqueous epoxy coating is stable as follows:
1. stable
⑴ centrifugal stability: 2000r/min, 20min is not stratified, breakdown of emulsion not;
⑵ storage stability: 2 months not stratified, breakdowns of emulsion not;
⑶ median size:＜0.6 μ m;
2. sticking power: I level, GB/T 1725-89 " paint film adhesion assay method ";
3. snappiness: >=4 grades, GB/T 1748-89 " paint film flexibility assay method ";
4. water tolerance: 25 ℃, 24h, non-foaming, do not come off GB1733-79 (88) " paint film water tolerance assay method ";
5. alkali resistance: 10%NaOH, 6h, non-foaming, do not come off.
Embodiment 5
A kind of preparation method of reactive epoxy resin latex, it comprises the steps:
1) the poly glycol monomethyl ether epoxy resin emulsifying agent is synthetic
In the four-hole boiling flask that has water trap, reflux condensing tube, add 10g E-51 type epoxy resin, 49.7g poly glycol monomethyl ether (relative molecular mass 2000) 70.15g toluene.Heating up under the magnetic agitation, is 130～150 ℃ of following azeotropic dehydrations three hours in temperature, obtains mixing liquid, is cooled to 85～95 ℃, and the solution that the 56.25mg boron trifluoride complex is dissolved in 8.66g toluene adds in the above-mentioned mixing liquid, and nitrogen protection is reaction down.Every epoxy retention rate at a distance from 0.5h sampling analysis system when the epoxy retention rate reaches 50% left and right sides, adds water destruct catalyzer stopped reaction between the reaction period, underpressure distillation desolventize white solid, be the poly glycol monomethyl ether epoxy resin emulsifying agent;
2) preparation of aqueous epoxy resin emulsion
Add 30g E-51 type epoxy resin in the 250mL beaker; 4.5g propylene glycol monomethyl ether stirs, and the epoxy resin viscosity is reduced; The back adds 15g poly glycol monomethyl ether epoxy resin emulsifying agent; System is warming up to 60 ℃, drips 100.5g zero(ppm) water under the high-speed stirring, processes the aqueous epoxy resin emulsion that solid content is 30wt%.
The aqueous epoxy resin emulsion of present embodiment is added aqueous epoxy curing agent, promptly be mixed with aqueous epoxy coating.Aqueous epoxy coating is stable as follows:
1. stable
⑴ centrifugal stability: 2000r/min, 30min is not stratified, breakdown of emulsion not;
⑵ storage stability: 2 months not stratified, breakdowns of emulsion not;
⑶ median size:＜0.5 μ m;
2. sticking power: I level, GB/T 1725-89 " paint film adhesion assay method ";
3. snappiness: >=5 grades, GB/T 1748-89 " paint film flexibility assay method ";
4. water tolerance: 25 ℃, 36h, non-foaming, do not come off GB1733-79 (88) " paint film water tolerance assay method ";
5. alkali resistance: 10%NaOH, 8h, non-foaming, do not come off.
Embodiment 6
A kind of preparation method of reactive epoxy resin latex, it comprises the steps:
1) the poly glycol monomethyl ether epoxy resin emulsifying agent is synthetic
In the four-hole boiling flask that has water trap, reflux condensing tube, add 20g E-44 type epoxy resin, 54g poly glycol monomethyl ether (relative molecular mass 1500) 57.84g toluene.Heating up under the magnetic agitation, is 130～150 ℃ of following azeotropic dehydrations three hours in temperature, obtains mixing liquid, is cooled to 85～95 ℃, 80mg catalyzer (aluminum chloride) is dissolved in 8.66g toluene adds in the above-mentioned mixing liquid.Every epoxy retention rate at a distance from 0.5h sampling analysis system when the epoxy retention rate reaches 50% left and right sides, adds water destruct catalyzer stopped reaction between the reaction period, underpressure distillation desolventize the water white transparency thick liquid, be the poly glycol monomethyl ether epoxy resin emulsifying agent.
2) preparation of aqueous epoxy resin emulsion
Add 30g E-44 type epoxy resin in the 250mL beaker; 7.5g propylene glycol monomethyl ether stirs, and the epoxy resin viscosity is reduced; The back adds 15g poly glycol monomethyl ether epoxy resin emulsifying agent; System is warming up to 60 ℃, drips 97.5g zero(ppm) water under the high-speed stirring, processes the aqueous epoxy resin emulsion that solid content is 30 wt%.
The aqueous epoxy resin emulsion of present embodiment is added aqueous epoxy curing agent, promptly be mixed with aqueous epoxy coating.Aqueous epoxy coating is stable as follows:
1. stable
⑴ centrifugal stability: 2000r/min, 30min is not stratified, breakdown of emulsion not;
⑵ storage stability: 2 months not stratified, breakdowns of emulsion not;
⑶ median size:＜0.5 μ m;
2. sticking power: I level, GB/T 1725-89 " paint film adhesion assay method ";
3. snappiness: >=5 grades, GB/T 1748-89 " paint film flexibility assay method ";
4. water tolerance: 25 ℃, 36h, non-foaming, do not come off GB1733-79 (88) " paint film water tolerance assay method ";
5. alkali resistance: 10%NaOH, 8h, non-foaming, do not come off.
Claims (6)
1. the preparation method of an aqueous epoxy resin emulsion is characterized in that including following steps:
1) by the shared mass percent of each raw material be: bisphenol A epoxide resin 7%～24%, poly glycol monomethyl ether 30%～50% and toluene 30%～55%, choose bisphenol A epoxide resin, poly glycol monomethyl ether and toluene, subsequent use;
Under nitrogen protection, bisphenol A epoxide resin, poly glycol monomethyl ether and toluene are mixed, heat up under the magnetic agitation, be 130～150 ℃ of following azeotropic dehydrations 2.5～3 hours in temperature, get mixing liquid;
2) by the shared mass percent of each raw material be: mixing liquid 90%～94.95%, toluene 5%～9.95% and catalyzer 0.03%～0.06%, choose mixing liquid, toluene and the catalyzer of step 1) gained, subsequent use;
Catalyzer is dissolved in the toluene, and then joins in the mixing liquid of step 1) gained, heat up under the magnetic agitation; Be strict controlled in 85～95 ℃ of reactions down of temperature under the nitrogen protection; The oxirane value of regular sampling analysis system between the reaction period calculates bisphenol A epoxide resin epoxy retention rate, when the retention rate of bisphenol A epoxide resin epoxy drops to 50%; Remove solvent under reduced pressure, obtain reactive non-ionic type epoxy emulsifying agent;
3) by the shared mass percent of each raw material be: liquid-state epoxy resin 18%～22%, reactive non-ionic type epoxy emulsifying agent 8%～10%, zero(ppm) water 64%～70% and cosolvent 4%～5%; Choose liquid-state epoxy resin, step 2) reactive non-ionic type epoxy emulsifying agent, zero(ppm) water and the cosolvent of gained, subsequent use;
With liquid-state epoxy resin, cosolvent, the powerful stirring of reactive non-ionic type epoxy emulsifying agent down, drip zero(ppm) water, process the aqueous epoxy resin emulsion that solid content is 20wt%～40wt%.
2. by the preparation method of the described aqueous epoxy resin emulsion of claim 1, the relative molecular mass that it is characterized in that described poly glycol monomethyl ether is between 1200～2000.
3. by the preparation method of claim 1 or 2 described aqueous epoxy resin emulsions, it is characterized in that step 2) described catalyzer is any one in boron trifluoride complex, triphenyl phosphorus and the aluminum chloride.
4. by the preparation method of claim 1 or 2 described aqueous epoxy resin emulsions, it is characterized in that step 2) described bisphenol A epoxide resin is any one in E-44 type epoxy resin, E-54 type epoxy resin and the E-51 type epoxy resin.
5. by the preparation method of claim 1 or 2 described aqueous epoxy resin emulsions, it is characterized in that the described cosolvent of step 3) is any one in propylene glycol monomethyl ether, Ucar 35 butyl ether and the 1-Methoxy-2-propyl acetate.
6. by the preparation method of claim 1 or 2 described aqueous epoxy resin emulsions, it is characterized in that the described liquid epoxies of step 3) is E-44 type epoxy resin or E-51 type epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110299123 CN102504282B (en) | 2011-09-28 | 2011-09-28 | Preparation method of waterborne epoxy resin emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110299123 CN102504282B (en) | 2011-09-28 | 2011-09-28 | Preparation method of waterborne epoxy resin emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102504282A true CN102504282A (en) | 2012-06-20 |
| CN102504282B CN102504282B (en) | 2013-11-06 |
Family
ID=46216420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110299123 Expired - Fee Related CN102504282B (en) | 2011-09-28 | 2011-09-28 | Preparation method of waterborne epoxy resin emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102504282B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554509A (en) * | 2013-10-28 | 2014-02-05 | 武汉工程大学 | Self-emulsifying nonionic waterborne epoxy resin emulsion and preparation method thereof |
| WO2015058678A1 (en) * | 2013-10-22 | 2015-04-30 | 北京金汇利应用化工制品有限公司 | Method for preparing self-emulsifiable, dual-component epoxy resin |
| CN105061753A (en) * | 2015-08-14 | 2015-11-18 | 深圳市三十一科技有限公司 | Preparation method of solar concentrating resin |
| CN105505132A (en) * | 2016-01-06 | 2016-04-20 | 南京信息工程大学 | Waterborne epoxy resin coating and preparation method thereof |
| CN107189084A (en) * | 2017-07-03 | 2017-09-22 | 安徽艾珀希德化工科技有限公司 | The aqueous epoxy emulsion prepared by the emulsifying agent of the functional group of bis-epoxy containing isocyanates |
| CN108485458A (en) * | 2018-02-06 | 2018-09-04 | 河北晨阳工贸集团有限公司 | A kind of aqueous dual-component epoxy orange-peel paint of bottom surface unification |
| CN108624267A (en) * | 2017-03-22 | 2018-10-09 | 上海固瑞泰复合材料科技有限公司 | A kind of preparation method of water-based mono-component high molecular weight epoxy adhesive |
| CN109503861A (en) * | 2018-11-05 | 2019-03-22 | 江南大学 | A kind of aqueous epoxy resin emulsion and preparation method thereof |
| CN112175169A (en) * | 2020-10-27 | 2021-01-05 | 衡阳拓创聚合新材料有限公司 | Heat-resistant water-based epoxy resin and preparation method thereof |
| CN113307984A (en) * | 2021-04-29 | 2021-08-27 | 广西桂林荣鑫新材料科技有限公司 | Preparation method of aqueous epoxy resin dispersion |
| CN113881018A (en) * | 2021-11-04 | 2022-01-04 | 埃夫科纳聚合物股份有限公司 | Nonionic epoxy emulsifier, preparation method thereof and water-based epoxy emulsion |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5459180A (en) * | 1993-03-29 | 1995-10-17 | Hoechst Ag | Polyol/epoxy adducts for use as emulsifier for liquid epoxy resins |
| CN1415680A (en) * | 2002-10-24 | 2003-05-07 | 同济大学 | Paint of aqueous epoxy resin and its preparation method |
| CN101497737A (en) * | 2008-02-02 | 2009-08-05 | 中国石油化工集团公司 | Preparation of aqueous epoxy resin |
-
2011
- 2011-09-28 CN CN 201110299123 patent/CN102504282B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5459180A (en) * | 1993-03-29 | 1995-10-17 | Hoechst Ag | Polyol/epoxy adducts for use as emulsifier for liquid epoxy resins |
| CN1415680A (en) * | 2002-10-24 | 2003-05-07 | 同济大学 | Paint of aqueous epoxy resin and its preparation method |
| CN101497737A (en) * | 2008-02-02 | 2009-08-05 | 中国石油化工集团公司 | Preparation of aqueous epoxy resin |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015058678A1 (en) * | 2013-10-22 | 2015-04-30 | 北京金汇利应用化工制品有限公司 | Method for preparing self-emulsifiable, dual-component epoxy resin |
| CN103554509A (en) * | 2013-10-28 | 2014-02-05 | 武汉工程大学 | Self-emulsifying nonionic waterborne epoxy resin emulsion and preparation method thereof |
| CN103554509B (en) * | 2013-10-28 | 2016-01-06 | 武汉工程大学 | A kind of self-emulsifiable non-ionic water-borne epoxy resin latex and preparation method thereof |
| CN105061753A (en) * | 2015-08-14 | 2015-11-18 | 深圳市三十一科技有限公司 | Preparation method of solar concentrating resin |
| CN105505132B (en) * | 2016-01-06 | 2018-05-11 | 南京信息工程大学 | A kind of aqueous epoxide resin paint and preparation method thereof |
| CN105505132A (en) * | 2016-01-06 | 2016-04-20 | 南京信息工程大学 | Waterborne epoxy resin coating and preparation method thereof |
| CN108624267A (en) * | 2017-03-22 | 2018-10-09 | 上海固瑞泰复合材料科技有限公司 | A kind of preparation method of water-based mono-component high molecular weight epoxy adhesive |
| CN107189084A (en) * | 2017-07-03 | 2017-09-22 | 安徽艾珀希德化工科技有限公司 | The aqueous epoxy emulsion prepared by the emulsifying agent of the functional group of bis-epoxy containing isocyanates |
| CN108485458A (en) * | 2018-02-06 | 2018-09-04 | 河北晨阳工贸集团有限公司 | A kind of aqueous dual-component epoxy orange-peel paint of bottom surface unification |
| CN109503861A (en) * | 2018-11-05 | 2019-03-22 | 江南大学 | A kind of aqueous epoxy resin emulsion and preparation method thereof |
| CN112175169A (en) * | 2020-10-27 | 2021-01-05 | 衡阳拓创聚合新材料有限公司 | Heat-resistant water-based epoxy resin and preparation method thereof |
| CN113307984A (en) * | 2021-04-29 | 2021-08-27 | 广西桂林荣鑫新材料科技有限公司 | Preparation method of aqueous epoxy resin dispersion |
| CN113881018A (en) * | 2021-11-04 | 2022-01-04 | 埃夫科纳聚合物股份有限公司 | Nonionic epoxy emulsifier, preparation method thereof and water-based epoxy emulsion |
| CN113881018B (en) * | 2021-11-04 | 2024-03-29 | 埃夫科纳聚合物股份有限公司 | Nonionic epoxy emulsifier, preparation method thereof and water-based epoxy emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102504282B (en) | 2013-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102504282B (en) | Preparation method of waterborne epoxy resin emulsion | |
| CN101463179B (en) | Aqueous self-emulsifying epoxy resin emulsion and preparation thereof | |
| CN101899196B (en) | Water-borne phenolic epoxy resin emulsion and preparation method thereof | |
| CN101117390B (en) | Method for preparing aqueous epoxy emulsion | |
| CN104389176B (en) | Emulsion type carbon fiber sizing agent containing graphene oxide and preparation method thereof | |
| CN101497737B (en) | Preparation of aqueous epoxy resin | |
| CN102702920B (en) | Aqueous polyaniline anti-corrosive paint and preparation method thereof | |
| CN102516594B (en) | Recovery method of thermosetting epoxy resin or composite material thereof | |
| CN101899163A (en) | Method for preparing self-emulsifiable non-ionic water-borne novolac epoxy resin emulsion | |
| CN1891772B (en) | Epoxy resin emulsion for water-based coating, and its preparing method | |
| CN101003664B (en) | Latex of epoxy resin of aqueous phenolic aldehyde, and preparation method | |
| CN103086472A (en) | High-temperature sewage treatment reverse demulsifier of ultra-heavy oil | |
| CN101037564A (en) | Self-emulsification crylic acid epoxy emulsification agent and its aqueous crylic acid epoxy resin latex | |
| CN101463180A (en) | Aqueous single-component external emulsion epoxy resin emulsion and preparation thereof | |
| CN101974162B (en) | Low-VOC (Volatile Organic Compound) self-emulsifying solid epoxy resin water-based emulsion and preparation method thereof | |
| CN104962176A (en) | Water-based epoxy resin paint and preparation method thereof | |
| CN101260183A (en) | Non-ionic self-emulsification solid epoxy resin and preparation method for emulsion thereof | |
| CN107325265A (en) | A kind of self-emulsifiable non-ionic water-borne epoxy hardener | |
| CN112142951B (en) | Bio-based latent waterborne epoxy resin and preparation method thereof | |
| CN107299531B (en) | A kind of carbon fiber heat-resistance type emulsion pasting agent and preparation method thereof | |
| CN101037530B (en) | Light-curved aqueous crylic acid epoxy resin latex and coating prepared thereby | |
| CN104910667B (en) | UV gloss oil for LED (light-emitting diode)-curing light sources and preparation method thereof | |
| CN102942683B (en) | Composite epoxy resin emulsifier and method for preparing same | |
| CN103450722A (en) | Method for preparing UV (Ultraviolet) oily adhesion primer acting on bamboo-wood base materials | |
| CN101402739A (en) | Production process for water-soluble epoxy resin emulsions |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20120620 Assignee: Wuhan Jinghe chemical (Qianjiang) Co., Ltd. Assignor: Wuhan Institute of Technology Contract record no.: 2015420000006 Denomination of invention: Preparation method for waterborne epoxy resin emulsion Granted publication date: 20131106 License type: Exclusive License Record date: 20150106 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131106 Termination date: 20160928 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |