CN101831145A - Aqueous epoxy resin and preparation method thereof - Google Patents
Aqueous epoxy resin and preparation method thereof Download PDFInfo
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- CN101831145A CN101831145A CN200910310409A CN200910310409A CN101831145A CN 101831145 A CN101831145 A CN 101831145A CN 200910310409 A CN200910310409 A CN 200910310409A CN 200910310409 A CN200910310409 A CN 200910310409A CN 101831145 A CN101831145 A CN 101831145A
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Abstract
The invention discloses an aqueous epoxy resin and a preparation method thereof. The aqueous epoxy resin comprises a DGEBA-type epoxy resin, water soluble radical initiator, a phase transfer catalyst and a water soluble hardener. The DGEBA-type epoxy resin is modified by the water soluble radical initiator so as to be able to disperse in water to form emulsion; and the phase transfer catalyst and the water soluble hardener are added, so that the emulsion, when coated on a rubber sheet, wood or metal surface, can be dried at room temperature by air and hardened into a thin film which is insoluble in water.
Description
Technical field
The present invention relates to a kind of preparation method of Resins, epoxy, relate to a kind of aqueous epoxy resins and preparation method thereof particularly.
Background technology
Resins, epoxy has high strength, water-repellancy, and also easy to use, therefore be widely used in fields such as matrix material, caking agent, coating, material of construction.The processing but the Resins, epoxy of high viscosity must add solvent or thinner, solvent or thinner are harmful material, may disengage in the course of processing, harm constructor or user's is healthy, and each industry begins to pay attention to solvent-free and aqueous epoxy resins in recent years.Solvent-free epoxy resin often must add reactive thinner reducing its viscosity, but some reactive thinner has volatility, and it has the same with solvent even more serious hazardness.Therefore, in order to solve the problem of solvent and other organic volatile, be that the Resins, epoxy of solvent is developed with water.
The technology of preparing of aqueous epoxy resins mainly contains and adds emulsifying agent method, phase reversion method and chemic modified method at present,
Summary of the invention
The present invention relates to a kind of aqueous epoxy resins and preparation method thereof, its stiffening system and phase-transfer catalysis system thereof.
Technical scheme provided by the invention is as follows:
The present invention relates to a kind of aqueous epoxy resins, it is characterized in that, comprise following component by mass ratio:
General purpose grade or special with 100 parts of grade bis phenol A Resins, epoxy
1～30 part of water-soluble radical initiator
1～50 part of water-soluble stiffening agent
0.1～5 part of phase-transfer catalyst
0～20 part of monomer
100～200 parts in water
In a preferred embodiment of the present invention, described general purpose grade or spy are E51 with grade bis phenol A Resins, epoxy, E20, E44, E41, Epon828, BE188, CYD128 and other relevant Resins, epoxy.More preferably, wherein, general purpose grade
Or the spy is the product B E188 of Changchun, Taiwan chemical industry group with grade bis phenol A Resins, epoxy.
In a preferred embodiment of the present invention, described water-soluble radical initiator is one of following component or its combination: Sodium Persulfate, Potassium Persulphate, 4,4-azo two (4 cyanopentanoic acid), 4,4-azo two (4 cyanopentanoic acid sodium), 4,4-azo two (4-cyano group amylalcohol), methylethyl ketone peroxide, cyclohexanone peroxide, and other relevant initiator, water-soluble action of free radical initiator is that hydrophilic radical is introduced Resins, epoxy, it is water-soluble to make Resins, epoxy become.Can add non-aqueous initiator as 4,4-azo two (4-cyano group butane peroxy dicarbonate two-2-phenoxy group ester), peroxy dicarbonate two (4-tertiary butyl hexanaphthene), 2,5-two (the own vinegar peroxide of 2-ethyl)-2,5-dimethyl ethane, peroxidation benzene first vinegar, tert-butyl hydroperoxide-2-ethylhexanoate, 2-tertiary butyl azo-2-dicyanopropane, 2-tertiary butyl azo-dicyanobutane, 1,1-two (t-butyl peroxy) 3,3, the 5-trimethyl-cyclohexane, 1,1-two (t-butyl peroxy) hexanaphthene, 1-tertiary butyl azo-1-cyanocyclohexanoic alkane, O, the O-tertiary butyl-O-sec.-propyl list peroxycarbonates, butyl perbenzoate, ethyl-3,3-two (tert-butyl peroxide) butyric ester, dicumyl peroxide, peroxidation lauric acid, 2,5-dimethylhexane-2,5-diperoxy ethylhexoate, peroxide-2-ethyl hexanoic acid tert-butyl, peroxide acid tert-butyl, 3,3-two (t-butyl peroxy) ethyl butyrate, and other relevant initiator.Hydrophobicity and water-based initiator that non-aqueous initiator can increase behind the hardened material are shared, and regulate material and can be dispersed in emulsification in the water before sclerosis, have certain hydrophobicity after the sclerosis.
More preferably, aforesaid water-soluble radical initiator is 4,4-azo two (4-cyanopentanoic acid).
In a preferred embodiment of the present invention, described water-soluble stiffening agent is a trolamine, quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, polyvinylamine, phenolic aldehyde amine, 2,4,6-three (dimethylamino methyl) phenol, aqueous polyurethane, aqueous polyamide, poly-second wine amine, dicyanamide, boron trifluoride-amine complex is disliked boron heterocycle boron amide complex compound, the water-based polyureas, Jeffamine, hexanediamine, amine end-blocking water-based polyimide, ammoniacal liquor, diethylin is for propylamine, water-soluble aromatic amine, isophorone diamine, thiocarbamide, mercaptan amine, thiocarbamide-polyamine condenses, and other relevant stiffening agent.Water-soluble stiffening agent is the stiffening agent of aqueous epoxy resins, must have the water-based performance, with the Resins, epoxy commissure.
More preferably, aforesaid water-soluble stiffening agent is a diethylenetriamine, polyvinylamine, and mercaptan amine, poly-ethanamide is used alone or as a mixture.
In a preferred embodiment of the present invention, described phase-transfer catalyst is a crown ether, polyoxyethylene glycol, quaternary amine ， quaternary alkylphosphonium salt, sulfonium salt or arsenic salt, cave ether, bromination Shi six alkyl San Ding Ji Phosphonium, Tetrabutylammonium bromide, other related compound of methyl trioctylphosphine ammonium chloride.The epoxide functional groups that act as the catalysis oil phase of phase-transfer catalyst and the reaction of the stiffening agent of water.Because in the aqueous epoxy resin emulsion, epoxide functional groups is at oil phase, and the functional group of water-based stiffening agent is at water, carries out catalysis between the two-phase because of needing phase-transfer catalyst a bit.
More preferably, aforesaid phase-transfer catalyst is a polyoxyethylene glycol.
In a preferred embodiment of the present invention, described monomer is a vinylbenzene, vinyl cyanide, divinyl, butylene, vinylformic acid, methacrylic acid, methyl methacrylate, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, the different monooctyl ester of propylene, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, toxilic acid, maleic anhydride, and other relevant monomer.Monomeric acting as promotes the water-based initiator and grafts in the Resins, epoxy and reduce cost, and increases material filming.
Residence more, aforesaid monomer is a vinylbenzene, methyl methacrylate, vinylformic acid, vinyl mercaptan, the propenyl glycidyl ether, vinyl cyanide, divinyl is used alone or as a mixture.
Compare with the method for other Water-borne modification, advantage of the present invention is that making method is simple, can not produce waste water in the production process, the reacted by product of initiator is not had a volatility, and energy and epoxy reaction, because the initiator amount ratio is bigger, if adding small amounts of monomer (also can not add monomer) is arranged, all monomers all can react, and do not have the problem of monomer residue.Material of the present invention is a self-emulsifying drug delivery systems, need not additionally to add the incoming interface promoting agent.
Embodiment
Prescription of the present invention is
General purpose grade or special with 100 parts of grade bis phenol A Resins, epoxy
1～30 part of water-soluble radical initiator
1～50 part of water-soluble stiffening agent
0.1～5 part of phase-transfer catalyst
0～20 part of monomer
100～200 parts in water
Embodiment 1:
Form
100 parts of bisphenol A epoxide resin BE188 (Changchun, Taiwan chemical industry group)
4, two (the 4-cyanopentanoic acids) 30 parts of 4-azo
20 parts of water-soluble stiffening agent diethylenetriamine
150 parts in water
30 parts of ammoniacal liquor
10 parts of polyoxyethylene glycol
Bisphenol A epoxide resin BE188 and 4,4-azo two (4-cyanopentanoic acid) mixes, put into reaction ax, with 150 ℃, compressive reaction 1 hour adds entry and ammoniacal liquor, adds polyoxyethylene glycol again, cooperate the high sonic concussion to stir 1 hour with homogenizer (1000rpm), promptly get the aqueous epoxy resins A liquid of milk yellow; Diethylenetriamine is B liquid.A liquid and B liquid are mixed, cooperate high sonic concussion stirring 1 minute and become aqueous epoxy resins/water-based stiffening agent mixed solution with homogenizer (1000rpm), aqueous epoxy resins/water-based stiffening agent mixed solution is applied in the transparent PET film, left standstill after air-dry several days, aqueous epoxy resins hardens into a film.
Embodiment 2:
100 parts of bisphenol A epoxide resin BE188 (Changchun, Taiwan chemical industry group)
4, two (the 4-cyanopentanoic acids) 30 parts of 4-azo
20 parts of water-soluble stiffening agent diethylenetriamine
150 parts in water
10 parts of polyoxyethylene glycol
Bisphenol A epoxide resin BE188 and 4,4-azo two (4-cyanopentanoic acid) mixes, put into reaction ax, with 150 ℃, compressive reaction 1 hour adds entry, adds polyoxyethylene glycol again, cooperate the high sonic concussion to stir 1 hour with homogenizer (1000rpm), promptly get aqueous epoxy resins A liquid (not dissolving each other); Diethylenetriamine is B liquid.A liquid and B liquid are mixed, cooperate high sonic concussion stirring 1 minute and become aqueous epoxy resins/water-based stiffening agent mixed solution (emulsion) with homogenizer (1000rpm), aqueous epoxy resins/water-based stiffening agent mixed solution is applied in the transparent PET film, left standstill after air-dry several days, aqueous epoxy resins hardens into a film.
Embodiment 3:
100 parts of bisphenol A epoxide resin BE188 (Changchun, Taiwan chemical industry group)
4, two (the 4-cyanopentanoic acids) 30 parts of 4-azo
20 parts of water-soluble stiffening agent diethylenetriamine
150 parts in water
10 parts of polyoxyethylene glycol
3 parts of vinylbenzene
3 parts of methyl methacrylates
3 parts of propenyl glycidyl ethers
Bisphenol A epoxide resin BE188, vinylbenzene, methyl methacrylate, propenyl glycidyl ether and 4,4-azo two (4-cyanopentanoic acid) mixes, put into reaction ax, with 150 ℃, compressive reaction 1 hour, add entry, add polyoxyethylene glycol again, cooperate the high sonic concussion to stir 1 hour, promptly get aqueous epoxy resins A liquid (not dissolving each other) with homogenizer (1000rpm); Diethylenetriamine is B liquid.A liquid and B liquid are mixed, cooperate high sonic concussion stirring 1 minute and become aqueous epoxy resins/water-based stiffening agent mixed solution (emulsion) with homogenizer (1000rpm), aqueous epoxy resins/water-based stiffening agent mixed solution is applied in the transparent PET film, left standstill after air-dry several days, aqueous epoxy resins hardens into a film, and its film is more smooth than the film of embodiment 1.
Reference examples 1:
100 parts of bisphenol A epoxide resin BE188 (Changchun, Taiwan chemical industry group)
20 parts of water-soluble stiffening agent diethylenetriamine
150 parts in water
10 parts of polyoxyethylene glycol
Bisphenol A epoxide resin BE188 adds entry, adds polyoxyethylene glycol again, cooperates the high sonic concussion to stir 1 hour with homogenizer (1000rpm); Diethylenetriamine is B liquid.A liquid and B liquid are mixed, and cooperating the high sonic concussion to stir 1 minute Resins, epoxy with homogenizer (1000rpm) cannot mix with water.Resins, epoxy/water is put into plastic disk, and water is air-dry, and Resins, epoxy is still unhardened.
Reference examples 2
100 parts of bisphenol A epoxide resin BE188 (Changchun, Taiwan chemical industry group)
4, two (the 4-cyanopentanoic acids) 30 parts of 4-azo
20 parts of water-soluble stiffening agent diethylenetriamine
150 parts in water
Bisphenol A epoxide resin BE188 and 4,4-azo two (4-cyanopentanoic acid) mixes, and puts into reaction ax, with 150 ℃, compressive reaction 1 hour adds entry, cooperate the high sonic concussion to stir 1 hour with homogenizer (1000rpm), promptly get aqueous epoxy resins A liquid (not dissolving each other); Diethylenetriamine is B liquid.A liquid and B liquid are mixed, cooperate high sonic concussion stirring 1 minute and become aqueous epoxy resins/water-based stiffening agent mixed solution (emulsion) with homogenizer (1000rpm), aqueous epoxy resins/water-based stiffening agent mixed solution is applied in the transparent PET film, left standstill after air-dry several days, aqueous epoxy resins is still unhardened.It is put into 120 ℃ of baking ovens toast, epoxy cure becomes a film after one hour, and its film is similar to the film of embodiment 1.
Above-mentioned only is specific embodiments of the invention, but design concept of the present invention is not limited thereto, and allly utilizes this design that the present invention is carried out the change of unsubstantiality, all should belong to the behavior of invading protection domain of the present invention.
Claims (8)
1. an aqueous epoxy resins is characterized in that, comprises following component by mass ratio:
General purpose grade or special with 100 parts of grade bis phenol A Resins, epoxy
1～30 part of water-soluble radical initiator
1～50 part of water-soluble stiffening agent
0.1～5 part of phase-transfer catalyst
0～20 part of monomer
100～200 parts in water
2. a kind of aqueous epoxy resins as claimed in claim 1 is characterized in that: described general purpose grade or spy are E51 with grade bis phenol A Resins, epoxy, E20, E44, E41, Epon828, BE188, a kind of or its combination among the CYD128.
3. a kind of aqueous epoxy resins as claimed in claim 1 is characterized in that: described water-soluble radical initiator is one of following component or its combination: Sodium Persulfate, Potassium Persulphate, 4,4-azo two (4-cyanopentanoic acid), 4,4-azo two (4-cyanopentanoic acid sodium), 4,4-azo two (4-cyano group amylalcohol), methylethyl ketone peroxide, cyclohexanone peroxide
4. a kind of aqueous epoxy resins as claimed in claim 3, it is characterized in that: also can add a kind of or its combination in the following non-aqueous initiator: 4,4-azo two (4-cyano group butane peroxy dicarbonate two-2-phenoxy group ester), peroxy dicarbonate two (4-tertiary butyl hexanaphthene), 2,5-two (the own vinegar peroxide of 2-ethyl)-2,5-dimethyl ethane, peroxidation benzene first vinegar, tert-butyl hydroperoxide-2-ethylhexanoate, 2-tertiary butyl azo-2-dicyanopropane, 2-tertiary butyl azo-dicyanobutane, 1,1-two (t-butyl peroxy) 3,3,5-trimethyl-cyclohexane, 1,1-two (t-butyl peroxy) hexanaphthene, 1-tertiary butyl azo-1-cyanocyclohexanoic alkane, O, the O-tertiary butyl-O-sec.-propyl list peroxycarbonates, butyl perbenzoate, ethyl-3,3-two (tert-butyl peroxide) butyric ester, dicumyl peroxide, the peroxidation lauric acid, 2,5-dimethylhexane-2,5-diperoxy ethylhexoate, peroxide-2-ethyl hexanoic acid tert-butyl, peroxide acid tert-butyl, 3,3-two (t-butyl peroxy) ethyl butyrate.
5. a kind of aqueous epoxy resins as claimed in claim 1 is characterized in that: described water-soluble stiffening agent is a kind of or its combination in the following component: trolamine, quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, polyvinylamine, phenolic aldehyde amine, 2,4,6-three (dimethylamino methyl) phenol, aqueous polyurethane, aqueous polyamide, poly-second wine amine, dicyanamide, boron trifluoride-amine complex, dislike boron heterocycle boron amide complex compound, water-based polyureas, Jeffamine, hexanediamine, amine end-blocking water-based polyimide, ammoniacal liquor, diethylin is for propylamine, water-soluble aromatic amine, isophorone diamine, thiocarbamide, mercaptan amine, thiocarbamide polyamine condenses.
6. a kind of aqueous epoxy resins as claimed in claim 1 is characterized in that: described phase-transfer catalyst is a kind of or its combination in the following component: crown ether, polyoxyethylene glycol, quaternary amine quaternary alkylphosphonium salt, sulfonium salt or arsenic salt, cave ether, bromination Shi six alkyl San Ding Ji Phosphonium, Tetrabutylammonium bromide, methyl trioctylphosphine ammonium chloride.
7. a kind of aqueous epoxy resins as claimed in claim 1 is characterized in that: a kind of or its combination in the following component of described monomer: be vinylbenzene, vinyl cyanide, divinyl, butylene, vinylformic acid, methacrylic acid, methyl methacrylate, olefin(e) acid methyl esters, ethyl propenoate, propyl acrylate, butyl acrylate, the different monooctyl ester of propylene, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, toxilic acid, maleic anhydride.
8. preparation method of water-dilutable epoxide resin, it is characterized in that: with the general purpose grade in the claim 1 or special with grade bis phenol A Resins, epoxy, the mixing of water-soluble radical initiator, put into reaction ax, with 150 ℃ of compressive reactions 1 hour, add entry and ammoniacal liquor, add phase-transfer catalyst again, cooperate the high sonic concussion to stir 1 hour, promptly get the aqueous epoxy resins A liquid of milk yellow with homogenizer 1000rpm; Water-soluble stiffening agent is B liquid; A liquid and B liquid are mixed, cooperate high sonic concussion stirring 1 minute and become aqueous epoxy resins/water-based stiffening agent mixed solution with homogenizer 1000rpm.
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| CN2009103104092A CN101831145B (en) | 2009-11-25 | 2009-11-25 | Aqueous epoxy resin and preparation method thereof |
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| CN2009103104092A CN101831145B (en) | 2009-11-25 | 2009-11-25 | Aqueous epoxy resin and preparation method thereof |
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| CN101831145B CN101831145B (en) | 2012-03-21 |
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| CN103865460A (en) * | 2014-03-13 | 2014-06-18 | 漳州市奈特新型建材有限责任公司 | Resin composition as well as preparation method and application thereof |
| CN103865460B (en) * | 2014-03-13 | 2016-01-20 | 漳州市奈特新型建材有限责任公司 | Resin combination and its preparation method and application |
| CN105368269A (en) * | 2014-08-26 | 2016-03-02 | 中国石油天然气集团公司 | Low-temperature-cured liquid-state anticorrosive epoxy resin coating and preparation method thereof |
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