CN101074311A - Production of micron-solid epoxy-resin microsphere containing surface active group - Google Patents
Production of micron-solid epoxy-resin microsphere containing surface active group Download PDFInfo
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- CN101074311A CN101074311A CN 200710020939 CN200710020939A CN101074311A CN 101074311 A CN101074311 A CN 101074311A CN 200710020939 CN200710020939 CN 200710020939 CN 200710020939 A CN200710020939 A CN 200710020939A CN 101074311 A CN101074311 A CN 101074311A
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Abstract
Production of micron-solid epoxy-resin micro-pill containing activated group on surface is carried out by mixing Arabic gum with emulsifier accessory and deionized water proportionally, preparing into aqueous-phase system, mixing epoxy resin with activated diluting agent and liquefied imidazole curing agent, preparing into oil-phase system, agitating, pouring oil-phase system into aqueous-phase system, mixing, emulsifying, reacting at 80-85 degree, cooling, filtering and drying to obtain final product containing -OH group. It's simple, cheap, efficient and controllable. It has homogeneous grain size distribution and can be used for chromatographic separation, eigen toughening and biological medicine.
Description
Technical field
The present invention relates to the preparation method that a kind of surface contains the micron order atresia epoxide resin microballoon of active group, belong to synthetic chemistry material field.
Background technology
Micrograde polymer microsphere is a kind of new function material of excellent property, the surface effects that it had, volume effect, magnetic effect and biocompatibility, make it to have demonstrated great application prospect in fields such as solid phase organic synthesis, medical science and biological chemistry, biomedicine, analytical chemistry, colloid science and chromatographic separation, the synthetic and surface modification of micrograde polymer microsphere is one of new focus of present filed of functional research.
Micron order atresia epoxide resin microballoon is a kind of polymer microballoon paid close attention to that causes people in recent years, and it has outstanding chemical stability, good mechanical intensity, the broad pH value scope of application and is difficult for characteristics such as generation irreversible adsorption.For satisfying different application requiring, people expect that synthetic surface contains the micron order atresia epoxide resin microballoon of active group, so that realize surface modifications and/or give new functional by these active groups.
The traditional method of preparation micrograde polymer microsphere has dispersion copolymerization method, seeding polymerization method and emulsion polymerization, and if be used for the preparation of polycondensate microballoons such as Resins, epoxy, then there is the loaded down with trivial details shortcoming that gets of technology in the preparation of the general only suitable addition polymer microballoon of preceding two kinds of methods.The letex polymerization rule exist to reactant have relatively high expectations (as low water solubility, low viscosity), problem such as the emulsifying agent consumption is big.A kind of method that adopts phase inversion technique preparation surface to have the micron order epoxide resin microballoon of active group is disclosed in the Chinese invention patent " a kind of epoxy resin solidified microsphere water-base body and preparation method thereof " (CN 1139614C), with Resins, epoxy and emulsifying agent by weight 10-99.9: 0.1-90 stirs, add solidifying agent down at 10-50 ℃, under agitation add water, be cured reaction 1-10 hour at 50-99 ℃, obtaining product, is the porous microballoon but this kind surface has the microballoon of active group.Disclose a kind of employing in the Chinese invention patent " a kind of preparation method of alkyd resin based microballoon " (CN 1255457C) lacquer resin has been formed the resol alcoholic solution with being dissolved in after hexamethylenetetramine mixes in methyl alcohol and/or the ethanol; Tensio-active agent and water are made into the aqueous solution that contains tensio-active agent; The resol alcoholic solution is joined in the aqueous solution that contains tensio-active agent, be heated to 110～130 ℃ of following constant temperature 30～180min at agitation condition at the uniform velocity, obtain alkyd resin based microballoon, though this preparation method is simple, but, prepared alkyd resin based microspherulite diameter wider distribution, and the surface is not with active group, and its range of application has been subjected to certain restriction.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, provide a kind of technology is simple, easy to control, cost is low and synthetic yield is high preparation surface to contain the method for the micron order atresia epoxide resin microballoon of active group.
For achieving the above object, the technical solution used in the present invention is: a kind of surface contains the preparation method of the micron order atresia epoxide resin microballoon of active group, and step is as follows:
1, by weight, 3.75～10 parts of Sudan Gum-arabics, 0～10 part of assistant for emulsifying agent and 700～1000 parts of deionized waters are mixed, be mixed with aqueous phase system;
2, under the agitation condition, by weight, 100 parts of Resins, epoxy, 80～100 portions of reactive thinners and 8～20 parts of liquid imidazole curing agents are mixed, make the oil phase system;
3, under the agitation condition, the oil phase system is poured in the aqueous phase system, mixed back emulsification 10～30min in two-phase, slowly be warming up to 80～85 ℃ again, the reaction times is 2～5h;
4, behind the naturally cooling,, obtain the micron order atresia epoxide resin microballoon that the surface contains active group with product filtration, drying.
The content of liquid imidazoles is 8～15 parts in the described oil phase system of step 2, and the described reaction times of step 3 is 2～3.5h, obtain the surface to contain simultaneously-OH and
The micron order atresia epoxide resin microballoon of group.The content that preferred scheme is liquid imidazoles is 8～10 parts.
The content of liquid imidazoles is that 15～20 parts, described reaction times of step 3 are 3.5～5h in the described oil phase system of step 2, solidification treatment 1～3h under 100-150 ℃ temperature condition again obtains the surface to contain-the micron order atresia epoxide resin microballoon of OH group.
Described Resins, epoxy is a kind of or arbitrary combination in the Resins, epoxy of any kind.
Described reactive thinner is any one or the arbitrary combination in the epoxide resin reactive diluent.
Described assistant for emulsifying agent is a kind of or arbitrary combination in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyoxyethylene nonylphenol ether, the polyoxyethylene glycol.
Compared with prior art, the beneficial effect that has of the present invention is:
1, owing to the adding of epoxide resin reactive diluent, effectively reduce the viscosity of Resins, epoxy, be easy to emulsification, therefore, the micron order epoxide resin microballoon that makes is the atresia microballoon, its size distribution is monodispersity; Simultaneously, the adding of epoxide resin reactive diluent has improved the toughness of original Resins, epoxy, and prepared epoxide resin microballoon has good toughness.
2, technical solution of the present invention can be by the ratio and/or the change aftertreatment technology of regulating ring epoxy resins and solidifying agent, and the number of functional groups and the kind of coming gate ring epoxy resins microsphere surface have simple to operate, easy row, cost is low, productive rate is high characteristics.
Description of drawings
Fig. 1 is the infrared spectrogram of the epoxide resin microballoon that makes of embodiment 1;
The Electronic Speculum figure of the epoxide resin microballoon that Fig. 2 embodiment 1 makes;
The infrared spectrogram of the epoxide resin microballoon that Fig. 3 embodiment 5 makes.
Embodiment
The invention will be further elaborated below in conjunction with drawings and Examples.
Embodiment 1:
A kind of surface contains-preparation method of the epoxide resin microballoon of OH group: and in three mouthfuls of reaction flasks of 250ml, add 0.8g Sudan Gum-arabic, 0.4g Sodium dodecylbenzene sulfonate and 80ml deionized water, stir it is fully dissolved.Under agitation condition, liquid imidazoles JH-0512 mixes with 10g bisphenol A type epoxy resin E51,10g epoxy propane butyl ether and 1.6g modification, obtains the oil phase system.Then the oil phase system is joined in the there-necked flask, behind the stirring and emulsifying 20min, slowly be warming up between 80-85 ℃ isothermal reaction 4h.After reaction finishes, stop heating, make it naturally cool to room temperature.With product filtration, drying, obtain head product.Head product in 150 ℃ of following after fixing 1h, is promptly got epoxide resin microballoon, synthetic yield 95%.
Referring to accompanying drawing 1, press the epoxide resin microballoon of present embodiment technical scheme preparation, its infrared spectra (IR) spectrogram is at 915cm
-1Locate no peak, show
Group reacts completely through 150 ℃ of after fixing; And the IR spectrum is at 3300cm
-1About have absorption peak to occur, show that prepared epoxide resin microballoon has-the OH group.
Referring to accompanying drawing 2, press the epoxide resin microballoon of present embodiment technical scheme preparation, can be observed microballoon under Electronic Speculum is the atresia microballoon, and size distribution is even, is single dispersed, and median size is 79 μ m.
Embodiment 2
A kind of surface contains-preparation method of OH group epoxide resin microballoon: and in three mouthfuls of reaction flasks of 250ml, add 1g Sudan Gum-arabic and 100ml deionized water, stir it is fully dissolved.Under agitation condition, 5g bisphenol A type epoxy resin E51,5g alicyclic type epoxy resin TDE-85,10g epoxy propane butyl ether and 1.6g 2-ethyl-4-methylimidazole are mixed, obtain the oil phase system.Then the oil phase system is joined in the there-necked flask, behind the stirring and emulsifying 30min, slowly be warming up between 80-85 ℃ isothermal reaction 5h.After reaction finishes, stop heating, make it naturally cool to room temperature.With product filtration, drying, obtain head product, head product in 100 ℃ of following after fixing 3h, is promptly got epoxide resin microballoon.Its IR spectrogram is at 3300cm
-1About have absorption peak to occur, show that prepared epoxide resin microballoon has-the OH group.Can be observed microballoon under the Electronic Speculum is the atresia microballoon, and size distribution is even, is single dispersed, and median size is 80 μ m.Synthetic yield 95%.
Embodiment 3
A kind of surface contains-preparation method of OH group epoxide resin microballoon: and in three mouthfuls of reaction flasks of 250ml, add 0.375g Sudan Gum-arabic, 0.8g Sodium dodecylbenzene sulfonate, 0.2g polyoxyethylene glycol and 70ml deionized water, stir it is fully dissolved.Under agitation condition, 10g bisphenol A type epoxy resin E51,8g difunctionality epoxide resin reactive diluent 6690 and 2g 2-ethyl-4-methylimidazole are mixed, obtain the oil phase system.Then the oil phase system is joined in the there-necked flask, behind the stirring and emulsifying 10min, slowly be warming up between 80-85 ℃ isothermal reaction 3.5h.After reaction finishes, stop heating, make it naturally cool to room temperature.With product filtration, drying, obtain head product, head product in 120 ℃ of following after fixing 2h, is promptly got epoxide resin microballoon.Its IR spectrogram is at 3300cm
-1About have absorption peak to occur, show that prepared epoxide resin microballoon has-the OH group.Can be observed microballoon under the Electronic Speculum is the atresia microballoon, and size distribution is even, is single dispersed, and median size is 82 μ m.Synthetic yield 95%.
Embodiment 4
A kind of surface contains-preparation method of OH group epoxide resin microballoon: and in three mouthfuls of reaction flasks of 250ml, add 0.9g Sudan Gum-arabic, 0.8g Sodium dodecylbenzene sulfonate, 0.2g sodium lauryl sulphate and 80ml deionized water, stir it is fully dissolved.Under agitation condition, 10g bisphenol A type epoxy resin E51,8g propylene oxide benzylic ether and 1.5g modified imidazole LMY-2404 are mixed, obtain the oil phase system.Then the oil phase system is joined in the there-necked flask, behind the stirring and emulsifying 10min, slowly be warming up between 80-85 ℃ isothermal reaction 3.5h.After reaction finishes, stop heating, make it naturally cool to room temperature.With product filtration, drying, obtain head product, head product in 100 ℃ of following after fixing 2h, is promptly got epoxide resin microballoon.Its IR spectrogram is at 3300cm
-1About have absorption peak to occur, show that prepared epoxide resin microballoon has-the OH group.Can be observed microballoon under the Electronic Speculum is the atresia microballoon, and size distribution is even, is single dispersed, and median size is 83 μ m.Synthetic yield 95%.
Embodiment 5
A kind of surface contains-OH and
The preparation method of group epoxide resin microballoon: add 0.7g Sudan Gum-arabic, 0.4g Sodium dodecylbenzene sulfonate and 80ml deionized water in three mouthfuls of reaction flasks of 250ml, stirring is fully dissolved it.Under agitation condition, 10g bisphenol A type epoxy resin E51,9g epoxy propane butyl ether and 0.8g 2-ethyl-4-methylimidazole are mixed, obtain the oil phase system.Then the oil phase system is joined in the there-necked flask, behind the stirring and emulsifying 20min, slowly be warming up between 80-85 ℃ isothermal reaction 3h.After reaction finishes, stop heating, make it naturally cool to room temperature.With product filtration, drying, promptly obtain epoxide resin microballoon.
Referring to accompanying drawing 3, press the epoxide resin microballoon of present embodiment technical scheme preparation owing to do not carry out the after fixing process, the IR spectrogram of its product respectively 3300,915cm
-1About have absorption peak to occur, show prepared epoxide resin microballoon have-OH and
Group.Can be observed microballoon under the opticmicroscope is the atresia microballoon, and size distribution is even, is single dispersed, and median size is 78 μ m.Synthetic yield 96%.
Embodiment 6
The surface contains-OH and
The preparation method of group epoxide resin microballoon: add 0.7g Sudan Gum-arabic and 100ml deionized water in three mouthfuls of reaction flasks of 250ml, stirring is fully dissolved it.Under agitation condition, liquid imidazoles JH-0512 mixes with 10g bisphenol A type epoxy resin E51,3g difunctionality epoxide resin reactive diluent 6690,5g epoxy propane butyl ether and 1g modification, obtains the oil phase system.Then the oil phase system is joined in the there-necked flask, behind the stirring and emulsifying 30min, slowly be warming up between 80-85 ℃ isothermal reaction 2h.After reaction finishes, stop heating, make it naturally cool to room temperature.With product filtration, drying, promptly obtain epoxide resin microballoon.Its IR spectrogram respectively 3300,915cm
-1About have absorption peak to occur, show prepared epoxide resin microballoon have-OH and
Group.Can be observed microballoon under the Electronic Speculum is the atresia microballoon, and size distribution is even, is single dispersed, and median size is 78 μ m.Synthetic yield 96%.
Embodiment 7
A kind of surface contains-OH and
The preparation method of group epoxide resin microballoon: add 0.375g Sudan Gum-arabic, 0.8g Sodium dodecylbenzene sulfonate, 0.2g sodium lauryl sulphate and 70ml deionized water in three mouthfuls of reaction flasks of 250ml, stirring is fully dissolved it.Under agitation condition, 7g bisphenol A type epoxy resin E51,3g bisphenol A type epoxy resin E44,8g cresylglycidylether and 1g modified imidazole LMY-2404 are mixed, obtain the oil phase system.Then the oil phase system is joined in the there-necked flask, behind the stirring and emulsifying 10min, slowly be warming up between 80-85 ℃ isothermal reaction 3.5h.After reaction finishes, stop heating, make it naturally cool to room temperature.With product filtration, drying, promptly obtain epoxide resin microballoon.Its IR spectrogram respectively 3300,915cm
-1About have absorption peak to occur, show prepared epoxide resin microballoon have-OH and
Group.Can be observed microballoon under the Electronic Speculum is the atresia microballoon, and size distribution is even, is single dispersed, and median size is 79 μ m.Synthetic yield 96%.
Embodiment 8
A kind of surface contains-OH and
The preparation method of group epoxide resin microballoon: add 0.5g Sudan Gum-arabic, 0.4g Sodium dodecylbenzene sulfonate, 0.2g sodium lauryl sulphate and 90ml deionized water in three mouthfuls of reaction flasks of 250ml, stirring is fully dissolved it.Under agitation condition, 7g alicyclic type epoxy resin TDE-85,3g bisphenol A type epoxy resin E44,10g cresylglycidylether and 0.8g 2-ethyl-4-methylimidazole are mixed, obtain the oil phase system.Then the oil phase system is joined in the there-necked flask, behind the stirring and emulsifying 20min, slowly be warming up between 80-85 ℃ isothermal reaction 3h.After reaction finishes, stop heating, make it naturally cool to room temperature.With product filtration, drying, promptly obtain epoxide resin microballoon.Its IR spectrogram respectively 3300,915cm
-1About have absorption peak to occur, show prepared epoxide resin microballoon have-OH and
Group.Can be observed microballoon under the opticmicroscope is the atresia microballoon, and size distribution is even, is single dispersed, and median size is 80 μ m.Synthetic yield 95%.
Claims (7)
1. a surface contains the preparation method of the micron order atresia epoxide resin microballoon of active group, it is characterized in that the step of this method is as follows:
1) by weight, 3.75～10 parts of Sudan Gum-arabics, 0～10 part of assistant for emulsifying agent and 700～1000 parts of deionized waters are mixed, be mixed with aqueous phase system;
2) under agitation condition, by weight, 100 parts of Resins, epoxy, 80～100 portions of reactive thinners and 8～20 parts of liquid imidazole curing agents are mixed, make the oil phase system;
3) under agitation condition, the oil phase system is poured in the aqueous phase system, mix back emulsification 10～30min in two-phase, slowly be warming up to 80～85 ℃ again, the reaction times is 2～5h;
4) treat naturally cooling after, with product filter, drying, obtain the micron order atresia epoxide resin microballoon that the surface contains active group.
2, a kind of surface according to claim 1 contains the preparation method of the micron order atresia epoxide resin microballoon of active group, it is characterized in that: the content of liquid imidazoles is 8-15 part in the described oil phase system of step 2; The described reaction times of step 3 is 2-3.5h, obtain the surface to contain simultaneously-OH and
The micron order atresia epoxide resin microballoon of group.
3, a kind of surface according to claim 2 contains the preparation method of the micron order atresia epoxide resin microballoon of active group, it is characterized in that: the content of liquid imidazoles is 8～10 parts in the described oil phase system of step 2.
4, a kind of surface according to claim 1 contains the preparation method of the micron order atresia epoxide resin microballoon of active group, it is characterized in that: the content of liquid imidazoles is that 15～20 parts, described reaction times of step 3 are 3.5～5h in the described oil phase system of step 2, solidification treatment 1～3h under 100-150 ℃ temperature condition again obtains the surface to contain-the micron order atresia epoxide resin microballoon of OH group.
5, a kind of surface according to claim 1 contains the preparation method of the micron order atresia epoxide resin microballoon of active group, it is characterized in that: described Resins, epoxy is a kind of or arbitrary combination in the Resins, epoxy of any kind.
6, a kind of surface according to claim 1 contains the preparation method of the micron order atresia epoxide resin microballoon of active group, it is characterized in that: described reactive thinner is any one or the arbitrary combination in the epoxide resin reactive diluent.
7, a kind of surface according to claim 1 contains the preparation method of the micron order atresia epoxide resin microballoon of active group, it is characterized in that: described assistant for emulsifying agent is a kind of or arbitrary combination in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyoxyethylene nonylphenol ether, the polyoxyethylene glycol.
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| CN104945855A (en) * | 2014-03-24 | 2015-09-30 | Tcl集团股份有限公司 | Quantum dot/epoxy resin microspheres and preparation method thereof as well as color conversion film |
| CN105199322A (en) * | 2015-10-10 | 2015-12-30 | 苏州大学 | Epoxy resin microsphere and preparation method thereof |
| CN105586018A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Drilling fluid containing epoxy resin microspheres |
| CN106519567A (en) * | 2016-10-17 | 2017-03-22 | 长安大学 | Method for preparing shape-memory epoxy resin particles |
| CN107880492A (en) * | 2017-12-21 | 2018-04-06 | 河南省科学院化学研究所有限公司 | A kind of self toughening epoxide resin microballoon material |
| CN108047653A (en) * | 2017-12-21 | 2018-05-18 | 河南省科学院化学研究所有限公司 | A kind of Toughening Modification of Epoxy micro-sphere material |
| CN108129605A (en) * | 2017-12-21 | 2018-06-08 | 河南省科学院化学研究所有限公司 | A kind of impact resistance epoxide resin microballoon material |
| CN114085358A (en) * | 2020-08-24 | 2022-02-25 | 万华化学集团股份有限公司 | Low-heat-release modified curing agent composition and preparation method thereof, epoxy resin composition and application |
| CN115109302A (en) * | 2022-07-25 | 2022-09-27 | 江苏永成汽车零部件股份有限公司 | Micro-foaming material for internal injection molding of automobile plastic part and preparation method thereof |
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- 2007-03-29 CN CNB2007100209394A patent/CN100528959C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104945855A (en) * | 2014-03-24 | 2015-09-30 | Tcl集团股份有限公司 | Quantum dot/epoxy resin microspheres and preparation method thereof as well as color conversion film |
| CN105586018A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Drilling fluid containing epoxy resin microspheres |
| CN105199322A (en) * | 2015-10-10 | 2015-12-30 | 苏州大学 | Epoxy resin microsphere and preparation method thereof |
| CN105199322B (en) * | 2015-10-10 | 2017-03-22 | 苏州大学 | Epoxy resin microsphere and preparation method thereof |
| CN106519567A (en) * | 2016-10-17 | 2017-03-22 | 长安大学 | Method for preparing shape-memory epoxy resin particles |
| CN107880492A (en) * | 2017-12-21 | 2018-04-06 | 河南省科学院化学研究所有限公司 | A kind of self toughening epoxide resin microballoon material |
| CN108047653A (en) * | 2017-12-21 | 2018-05-18 | 河南省科学院化学研究所有限公司 | A kind of Toughening Modification of Epoxy micro-sphere material |
| CN108129605A (en) * | 2017-12-21 | 2018-06-08 | 河南省科学院化学研究所有限公司 | A kind of impact resistance epoxide resin microballoon material |
| CN114085358A (en) * | 2020-08-24 | 2022-02-25 | 万华化学集团股份有限公司 | Low-heat-release modified curing agent composition and preparation method thereof, epoxy resin composition and application |
| CN114085358B (en) * | 2020-08-24 | 2023-05-26 | 万华化学集团股份有限公司 | Low-exothermic modified curing agent composition and preparation method thereof, epoxy resin composition and application |
| CN115109302A (en) * | 2022-07-25 | 2022-09-27 | 江苏永成汽车零部件股份有限公司 | Micro-foaming material for internal injection molding of automobile plastic part and preparation method thereof |
| CN115109302B (en) * | 2022-07-25 | 2024-04-09 | 江苏永成汽车零部件股份有限公司 | Micro-foaming material for injection molding of automobile plastic part and preparation method thereof |
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