CN101659781A - Epoxy resin micro-particle, dispersion liquid and method for preparing same - Google Patents
Epoxy resin micro-particle, dispersion liquid and method for preparing same Download PDFInfo
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- CN101659781A CN101659781A CN200810124620A CN200810124620A CN101659781A CN 101659781 A CN101659781 A CN 101659781A CN 200810124620 A CN200810124620 A CN 200810124620A CN 200810124620 A CN200810124620 A CN 200810124620A CN 101659781 A CN101659781 A CN 101659781A
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Abstract
The invention discloses an epoxy resin micro-particle. The micro-particle is prepared by curing epoxy resin under the function of a curing agent, and has an average grain size of between 50 and 400nm.The invention also discloses a dispersion liquid for the epoxy resin micro-particle consisting of the epoxy resin micro-particle, a surfactant, the curing agent and water. The invention also discloses a method for preparing the dispersion liquid for the epoxy resin micro-particle. The method uses polyethenoxy ether and a derivative thereof as the surfactant for the epoxy resin; since the surfactant has a more appropriate HLB value (a hydrophobicity-hydrophilicity balance value), through the interaction between the surfactant and the epoxy resin micro-particle, the prepared aqueous dispersionliquid has long-term dispersion stability and can be widely applied in the fields such as coatings, adhesives and fine chemical additives. The epoxy resin micro-particle prepared by the method has small granularity and narrow particle size distribution.
Description
Technical field
The invention belongs to technical field of macromolecules, be specifically related to a kind of epoxy resin micro-particle and preparation method thereof with long-term stably dispersing characteristic.
Background technology
Resins, epoxy has excellent performance, as advantages such as sticking power height, hardness height, wear resistance are good, used widely in industrial acquisition, but Resins, epoxy often needs to use solvent when using, and this understands cause severe contamination to environment.Enhancing along with people's environmental protection consciousness; epoxy particle water dispersion liquid with long-term stably dispersing characteristic more and more is subjected to the attention of this field researcher; become popular research direction in recent years, obtained widespread use in a plurality of fields such as coating, tackiness agent, fine chemistry industry auxiliary agent.
At present, the method for preparing the epoxy resin micro-particle aqueous dispersions both at home and abroad mainly contains two kinds, promptly direct outer emulsion process and chemical modification reemulsification method.Directly outer emulsion process refers to Resins, epoxy under the situation of adding tensio-active agent, is prepared from by direct emulsification or phase reversion method.Chemical modification reemulsification method refers to Resins, epoxy earlier through the chemical reaction modification, introduces hydrophilic radical, and then is prepared from by emulsification or phase reversion method.Tensio-active agent is divided into ionogenic surfactant and nonionic surface active agent again.Nonionogenic tenside is a kind of compound that is not dissociated into the amphiphilic structure of ionic condition in water.Nonionogenic tenside has non-ionizing characteristics in water just, determine it superior than ionogenic surfactant in some aspects, as in water He in the organic solvent solvability preferably being arranged all, stability is high in solution, is not subject to the influence of strong electrolyte inorganic salt and acid, alkali.In addition, because it has multiple performances such as dispersion, emulsification, foam, wetting, increase-volume, therefore in a lot of fields, important use is being arranged all.Patent CN101117390A has reported a kind of method of aqueous epoxy emulsion, and this dispersion emulsion is by Resins, epoxy and tensio-active agent reaction, prepares by phase inversion technique.The epoxy resin micro-particle median size that this patent obtains is bigger than normal.Patent CN1911920A has reported 2-aminoethyl sulfonic acid modified aqueous epoxy resin and preparation method thereof and by the aqueous epoxy emulsion of this aqueous epoxy resins preparation, it is thinner that the aqueous epoxy emulsion of this invention preparation has a particle, stability of emulsion is higher, but its Resins, epoxy size-grade distribution is very wide.
Summary of the invention
The purpose of this invention is to provide a kind of have long-term stably dispersing characteristic, average particle diameter is the epoxy resin micro-particle of 50-400nm.
Another object of the present invention provides a kind of dispersion liquid of above-mentioned epoxy resin micro-particle.
A further object of the invention provides the preparation method of above-mentioned Resins, epoxy dispersion liquid.
Purpose of the present invention can reach by following measure:
A kind of epoxy resin micro-particle, this micropartical is solidified under the effect of solidifying agent and is formed by ring Resins, epoxy, and its median size is 50-400nm.
A kind of dispersion liquid of epoxy resin micro-particle, this dispersion liquid is made up of above-mentioned epoxy resin micro-particle, tensio-active agent, solidifying agent and water.Wherein the quality of tensio-active agent is the 10-50wt% of epoxy resin micro-particle, and solidifying agent is the 5-20wt% of epoxy resin micro-particle, and water is the 100-300wt% of epoxy resin micro-particle; Be preferably: tensio-active agent 10-30wt%, solidifying agent are 6-15wt%, water 150-200wt%.
A kind of preparation method of dispersion liquid of epoxy resin micro-particle, comprise the steps: earlier Resins, epoxy and tensio-active agent to be mixed, heat up and stir and make it reaction, adjust stirring velocity then, after adding the deionized water reaction, generate epoxy resin latex, add solidifying agent again and stir, be cured reaction and promptly obtain the epoxy resin micro-particle dispersion liquid.
Solidifying agent of the present invention is selected from one or more in piperazine, hydrazine, adipic dihydrazide, diethylenetriamine, triethylene tetramine, two (the amino ring of 4-ethyls), diamino-diphenyl maple or the diaminodiphenyl-methane.
Tensio-active agent of the present invention is meant the Soxylat A 25-7 or derivatives thereof, preferably has following structure:
Wherein, R is C
1-20Alkyl, n is the integer of 5-50.With respect to the total content of epoxy resin micro-particle, the content of tensio-active agent is between 10%-50%.
In the preparation method, the temperature of reaction in each step is 35-50 ℃; Stirring velocity was 300～350rpm when Resins, epoxy and tensio-active agent mixed, and before the adding deionized water stirring velocity was adjusted into 400～700rpm, and the stirring velocity during curing reaction is 300～350rpm.
A kind of concrete preparation method comprises the steps: in reaction vessel to add Resins, epoxy and tensio-active agent, stirs after being warmed up to 40 ℃, and stirring velocity is 320rpm, react after 20 minutes, adjusts stirring velocity to 400～700rpm, the adding deionized water.React after 10～20 minutes, add deionized water again, react after 10～20 minutes, add deionized water for the third time; React after 10～20 minutes, the aqueous solution that adds solidifying agent (as piperazine, hydrazine, adipic dihydrazide, diethylenetriamine, triethylene tetramine, two (the amino ring of 4-ethyls), diamino-diphenyl maple or diaminodiphenyl-methane etc.), under 40 ℃, 300～350rpm stirs and solidifies the aqueous dispersions that promptly obtains epoxy resin micro-particle.Wherein each component is counted by weight: Resins, epoxy: 100 parts; Tensio-active agent 10-50 part; Each amount of deionized water that adds: 10～50 parts; Aqueous solution of curing agent: 80～150 parts.Preferable range: tensio-active agent 10-30 part; Each amount of deionized water that adds: 20-30 part; Aqueous solution of curing agent 100-120 part.
The present invention adopts Soxylat A 25-7 and derivative thereof the tensio-active agent as Resins, epoxy, because it has more suitably HLB value (hydrophilic hydrophobic balance value), by and epoxy resin micro-particle between interaction, make the aqueous dispersions that obtains have long-term stably dispersing characteristic, can obtain widespread use in fields such as coating, tackiness agent, fine chemistry industry auxiliary agents.Little and the narrow diameter distribution of epoxy resin micro-particle granularity of gained of the present invention, big thereby particle has specific surface area, high adsorption capacity, strong with the reactive behavior of other materials, advantage such as contact area is big.
Description of drawings
The stereoscan photograph of the epoxy resin micro-particle that Fig. 1 obtains for the embodiment of the invention 3.
The epoxy resin micro-particle that Fig. 2 obtains for the embodiment of the invention 3 is preserved the size distribution figure after half a year.
Testing tool be Microtrac S3500 Particle Size Analyzer (NIKKISOCompany, Japan).
The stereoscan photograph of the epoxy resin micro-particle that Fig. 3 obtains for the embodiment of the invention 2.
The epoxy resin micro-particle that Fig. 4 obtains for the embodiment of the invention 2 is preserved the size distribution figure after half a year.
The same Fig. 2 of testing tool.
Embodiment
The present invention is further described in detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
100 weight part Resins, epoxy and 10 weight part polyoxyethylene ether surface active agents are joined in the reaction vessel, and 40 ℃ of stirrings, stirring velocity is 320rpm.React after 20 minutes, adjust stirring velocity, add 20 parts by weight of deionized water to 600rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 40 ℃, 320rpm stirs to solidify and promptly obtained the epoxy micro-dispersed liquid in 24 hours, and the median size of its particle is 350nm.
100 weight part Resins, epoxy and 10 weight part polyoxyethylene ether surface active agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, adjust stirring velocity, add 20 parts by weight of deionized water to 700rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 40 ℃, 320rpm stirs to solidify and promptly obtained the epoxy micro-dispersed liquid in 24 hours, and the median size of its particle is 300nm.After the epoxy micro-dispersed liquid that obtains preserved half a year, detect its size distribution, the result as shown in Figure 4, as can be seen from the figure, still have the characteristic of the little and narrow diameter distribution of granularity through this particle of preservation of half a year, this aqueous dispersions has long dispersion stability.
100 weight part Resins, epoxy and 16 weight part polyoxyethylene ether surface active agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, adjust stirring velocity, add 20 parts by weight of deionized water to 500rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 40 ℃, 320rpm stirs to solidify and promptly obtained the epoxy micro-dispersed liquid in 24 hours, and the median size of its particle is 200nm.After the epoxy micro-dispersed liquid that obtains preserved half a year, detect its size distribution, the result as shown in Figure 2, as can be seen from the figure, still have the characteristic of the little and narrow diameter distribution of granularity through this particle of preservation of half a year, this aqueous dispersions has long dispersion stability.
100 weight part Resins, epoxy and 16 weight part polyoxyethylene ether surface active agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, adjust stirring velocity, add 20 parts by weight of deionized water to 550rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 40 ℃, 320rpm stirs to solidify and promptly obtained the epoxy micro-dispersed liquid in 24 hours, and the median size of its particle is 190nm.
100 weight part Resins, epoxy and 25 weight part polyoxyethylene ether surface active agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, adjust stirring velocity, add 20 parts by weight of deionized water to 400rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 40 ℃, 320rpm stirs to solidify and promptly obtained the epoxy micro-dispersed liquid in 24 hours, and the median size of its particle is 230nm.
Embodiment 6
100 weight part Resins, epoxy and 25 weight part polyoxyethylene ether surface active agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, adjust stirring velocity, add 20 parts by weight of deionized water to 450rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 40 ℃, 320rpm stirs to solidify and promptly obtained the epoxy micro-dispersed liquid in 24 hours, and the median size of its particle is 210nm.
100 weight part Resins, epoxy and 40 weight part polyoxyethylene ether surface active agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, adjust stirring velocity, add 20 parts by weight of deionized water to 550rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 14 weight part piperazines and 111.6 parts by weight of deionized water.Under 40 ℃, 320rpm stirs to solidify and promptly obtained the epoxy micro-dispersed liquid in 24 hours, and the median size of its particle is 190nm.
100 weight part Resins, epoxy and 40 weight part polyoxyethylene ether surface active agents are joined in the reaction vessel, at 40 ℃ of stirrings, stirring velocity 320rpm.React after 20 minutes, adjust stirring velocity, add 20 parts by weight of deionized water to 550rpm.React after 10 minutes, add 20 parts by weight of deionized water again; React after 10 minutes, add 20 parts by weight of deionized water for the third time; React after 10 minutes, add the aqueous solution of curing agent that constitutes by 6 weight part hydrazines and 120 parts by weight of deionized water.Under 40 ℃, 320rpm stirs to solidify and promptly obtained the epoxy micro-dispersed liquid in 24 hours, and the median size of its particle is 200nm.
Claims (9)
1, a kind of epoxy resin micro-particle is characterized in that, this micropartical is solidified under the effect of solidifying agent by Resins, epoxy and forms, and its median size is 50-400nm.
2, epoxy resin micro-particle according to claim 1, it is characterized in that described solidifying agent is selected from one or more in piperazine, hydrazine, adipic dihydrazide, diethylenetriamine, triethylene tetramine, two (the amino ring of 4-ethyls), diamino-diphenyl maple or the diaminodiphenyl-methane.
3, a kind of dispersion liquid of epoxy resin micro-particle is characterized in that, this dispersion liquid is made up of the described epoxy resin micro-particle of claim 1, tensio-active agent, solidifying agent and water.
4, the dispersion liquid of epoxy resin micro-particle according to claim 3 is characterized in that, described tensio-active agent is meant the Soxylat A 25-7 or derivatives thereof.
5, the dispersion liquid of epoxy resin micro-particle according to claim 4 is characterized in that, described tensio-active agent has following structure:
Wherein, R is C
1-20Alkyl, n is the integer of 5-50.
6, dispersion liquid according to claim 3, it is characterized in that described solidifying agent is one or more in piperazine, hydrazine, adipic dihydrazide, diethylenetriamine, triethylene tetramine, two (the amino ring of 4-ethyls), diamino-diphenyl maple, the diaminodiphenyl-methane.
7, a kind of preparation method of dispersion liquid of epoxy resin micro-particle, it is characterized in that, comprise the steps: earlier Resins, epoxy and tensio-active agent to be mixed, heat up and stir and make it reaction, adjust stirring velocity then, after the reaction of adding deionized water, generate epoxy resin latex, add solidifying agent again and stir, be cured reaction and promptly obtain the epoxy resin micro-particle dispersion liquid.
8, the preparation method of the dispersion liquid of epoxy resin micro-particle according to claim 7 is characterized in that, temperature of reaction is 35-50 ℃.
9, the preparation method of the dispersion liquid of epoxy resin micro-particle according to claim 7, it is characterized in that, stirring velocity was 300～350rpm when Resins, epoxy and tensio-active agent mixed, before adding deionized water stirring velocity is adjusted into 400～700rpm, the stirring velocity during curing reaction is 300～350rpm.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810124620A CN101659781A (en) | 2008-08-27 | 2008-08-27 | Epoxy resin micro-particle, dispersion liquid and method for preparing same |
| JP2008305565A JP5375053B2 (en) | 2008-08-27 | 2008-11-28 | Epoxy resin cured fine particles, dispersion thereof, and production method |
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| CN200810124620A CN101659781A (en) | 2008-08-27 | 2008-08-27 | Epoxy resin micro-particle, dispersion liquid and method for preparing same |
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| CN101659781A true CN101659781A (en) | 2010-03-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734922B (en) * | 2018-12-27 | 2021-09-17 | 常熟耐素生物材料科技有限公司 | Nonionic reactive epoxy resin emulsifier and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59170114A (en) * | 1983-03-18 | 1984-09-26 | Toray Ind Inc | Epoxy fine particles and their preparation |
| JPS62106921A (en) * | 1985-11-05 | 1987-05-18 | Toray Ind Inc | Production of fine spherical particle of heat-resistant epoxy resin |
| US5242958A (en) * | 1991-07-12 | 1993-09-07 | Ppg Industries, Inc. | Chemical treating composition for glass fibers having emulsified epoxy with good stability and the treated glass fibers |
| DE4225999A1 (en) * | 1992-08-06 | 1994-02-10 | Hoechst Ag | Crosslinked polymer microparticles based on epoxy resin, their production and their use |
| US5506284A (en) * | 1993-02-26 | 1996-04-09 | Basf Corporation | Electrodeposition coating composition comprising crosslinked microparticles |
| JPH0867756A (en) * | 1994-08-30 | 1996-03-12 | Dainippon Ink & Chem Inc | Production of epoxy resin ionomer microparticle and its resin composition |
| JPH10200265A (en) * | 1997-01-06 | 1998-07-31 | Ibiden Co Ltd | Multilayer printed wiring board |
| US6525115B2 (en) * | 2000-12-05 | 2003-02-25 | Eastman Kodak Company | Method of making an aqueous dispersion of particles comprising an epoxy material for use in coatings |
| JP2007031603A (en) * | 2005-07-28 | 2007-02-08 | Sanyo Chem Ind Ltd | Method for producing resin particle |
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- 2008-08-27 CN CN200810124620A patent/CN101659781A/en active Pending
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109734922B (en) * | 2018-12-27 | 2021-09-17 | 常熟耐素生物材料科技有限公司 | Nonionic reactive epoxy resin emulsifier and preparation method thereof |
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| JP5375053B2 (en) | 2013-12-25 |
| JP2010053329A (en) | 2010-03-11 |
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Open date: 20100303 |