CN103301790B - A kind of preparation method to the pressure-sensitive temperature resistant encapsulation microcapsules in outside - Google Patents
A kind of preparation method to the pressure-sensitive temperature resistant encapsulation microcapsules in outside Download PDFInfo
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- CN103301790B CN103301790B CN201310271307.0A CN201310271307A CN103301790B CN 103301790 B CN103301790 B CN 103301790B CN 201310271307 A CN201310271307 A CN 201310271307A CN 103301790 B CN103301790 B CN 103301790B
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Abstract
The invention discloses a kind of preparation method to the pressure-sensitive temperature resistant encapsulation microcapsules in outside, first microcapsule wall material is prepared, control temperature is between 20 DEG C-80 DEG C, the core curing agent of epoxy resin and 0.50-0.85 times of equivalent is prepared prepolymer, and prepolymer wall material is dissolved in certain solvent forms concentrated solution; Then core to be added in this solution and to be uniformly dispersed, obtaining mixture; Pour in insulating liquid by this mixture, hierarchy of control temperature is between 20 DEG C-80 DEG C, and 100rpm-500rpm stirs until effect microcapsule wall curing molding; Article shaped filtered, washing, drying, obtain the pressure-sensitive temperature resistant encapsulation microcapsules in outside.Present invention process, equipment are simple, neither introduce aqueous phase simultaneously, also not water-soluble by microcapsules core or oil-soluble restriction, and by the ratio between control loop epoxy resins and curing agent and system degree of functionality, the mechanical strength of microcapsules, sealing and heat resistance effectively can be controlled.
Description
Technical field
The present invention relates to a kind of microcapsules and preparation method thereof, is specifically a kind of heat-resisting microcapsules to outside pressure-sensitive sealing excellence and preparation method thereof.
Background technology
Heat cured epoxy resin composite material excellent performance, is widely used.But its solidification process is often limited by various environmental condition, usually there is the contradiction between working life and condensate performance, contradiction between condition of cure and condensate performance.Therefore, be developed many latent curing agents, solve the contradiction between working life and condensate performance to a certain extent.But, the contradiction between condition of cure and condensate performance is still very outstanding.Such as, but in a lot of building or civil engineering, epoxy resin often needs to construct at a higher temperature, what therefore adopt is all high-temperature curing agent system, but after construction terminates, environment temperature declines rapidly, final condensate performance is caused to decline or needs closed solidification for a long time.Therefore, we wish that during high temperature, high-temperature curing agent is had an effect by high-temperature curing agent and low temperature curing agent isolation; When the temperature decreases, low temperature curing agent starts reaction.
Microcapsule method is a kind of comparatively novel being isolated with environmental condition by material in capsule, and under certain external condition, microcapsules rupture discharges curing agent wherein or epoxy resin comes, and triggers the process control technology of the new round reaction of epoxy resin.
Microcapsules technology extensive use and insoluble drug release, material selfreparing and the various aspects such as clad material as phase-change heat-storage material.The preparation method of microcapsules, roughly has three kinds from principle: i.e. Physical, chemical method and physical-chemical process.Physics and physico-chemical process mainly realize microencapsulation by the physical change of microcapsule wall material, as condensation and spraying dry etc. after solvent evaporation method, solution extraction, fusing dispersion, the microcapsules prepared of physics and physical-chemical process often poor sealing, mechanical strength are uncontrollable, and thermal stability is often poor because being subject to the restriction of preparation process mesospore material phase transition temperature.Obviously, the key performance such as its heat resistance, mechanical strength and sealing can not meet much special needs.
Heat resistance, the better mechanical properties such as melamine resin, Lauxite and epoxy resin, therefore with them for microcapsule wall material, be good selection.Amine curing agent is one of the most frequently used curing agent of epoxy resin, and often solidification temperature is lower.But the amine curing agent of epoxy resin, has amphipathic and high activity, and microencapsulation difficulty is very large.Mostly people were to utilize physical method to carry out microencapsulation in the past, and therefore the sealing of wall material is poor, mechanical strength is low and production equipment is complicated.US Patent No. 3791980 adopts orifice to drip coagulating bath method, utilizes the coated ethylenediamine of thermoplastic.Chinese patent CN200710029990.1 gives a kind of method adopting melamine resin or the coated polythiol of Lauxite to prepare multi-thiol micro-capsule.But melamine resin prepolymer itself is water miscible, can be coated oil-soluble but can not coated water miscible low viscosity amine curing agent.Epoxy prepolymer itself is water-fast, classical interfacial polymerization or situ aggregation method generally believe, it can only be coated water miscible and can not coated oil-soluble low viscosity amine curing agent, meanwhile, exactly because the reaction of also oil-water interfaces, it is inner that the moisture in amine curing agent has also been covered by microcapsules, if it is improper therefore to control at drying stage, to destroy the sealing of microcapsules, if water can not be removed clean, so water is again the polymerization inhibitor of epoxy resin cure.
Summary of the invention
The object of this invention is to provide a kind of preparation method to the pressure-sensitive temperature resistant encapsulation microcapsules in outside, this preparation method's technique, equipment are simple, neither introduce aqueous phase, also not water-soluble by microcapsules core or oil-soluble restriction, and by the ratio between control loop epoxy resins and curing agent and system degree of functionality, effectively can control the mechanical strength of microcapsules, sealing and heat resistance, natural compatible between the microcapsules obtained and epoxy resin, be easy to be scattered in epoxy resin.
The object of the invention is to be achieved through the following technical solutions:
To a preparation method for the pressure-sensitive temperature resistant encapsulation microcapsules in outside, it is characterized in that the method step is as follows:
1) first prepare microcapsule wall material, the core curing agent of epoxy resin and 0.50-0.85 times of equivalent, between 20 DEG C-80 DEG C, is prepared prepolymer by control temperature, and is dissolved in certain solvent by prepolymer wall material and forms concentrated solution; Described wall material is the cured resin generated after epoxy resin and amine curing agent react;
2) then core to be added in this solution and to be uniformly dispersed, obtaining mixture; Pour in insulating liquid by this mixture, hierarchy of control temperature is between 20 DEG C-80 DEG C, and 100rpm-500rpm stirs until effect microcapsule wall curing molding; Core is the amine curing agent of epoxy resin; The core of microcapsules and the mass ratio of wall material are between 1:5-5:1;
3) article shaped filtered, washing, drying, obtain the pressure-sensitive temperature resistant encapsulation microcapsules in outside.
In the present invention, described microcapsules core, can can form the needs of three-dimensional network at a lower temperature with epoxy resin rapid solidification for meeting core, low temperature curing agent, toughess at room temperature and intermediate temperature setting agent or their mixture can be selected as the core in microcapsules, and these materials mainly comprise polymercaptan, aliphatic polyamine, aromatic polyamine, polyamide, tertiary amine, boron trifluoride complex and imidazoles, tertiary ammonium salt and aliphatic cyclic amine etc.; The curing agent of these epoxy resin, as the general knowledge in the industry of epoxy resin, can with reference to " curing agent " (Hu Yuming, Wu Liangyi etc., Chemical Industry Press, 2004) or " epoxy hardener and additive " (Hu Yuming, Chemical Industry Press, 2011) etc.Both can be certain compound, also can be the mixture of several compound.When being preferably 25 DEG C, viscosity is within 1-25,000mPa.s, and boiling point is low temperature and toughess at room temperature between 100-300 DEG C, as low-molecular-weight polymercaptan, aliphatic polyamine, aromatic polyamine, tertiary amine, imidazoles, low molecular polyamides etc.When more optimizedly selecting 25 DEG C, viscosity is within 1-3000mPa.s, and the toughess at room temperature of boiling point between 110-250 DEG C, as aliphatic polyamine, aromatic polyamine and tertiary amine etc.
Described microcapsule wall material is the prepolymer of epoxy resin and selected curing agent.Selected epoxy resin is advisable with liquid-state epoxy resin, and preferred bisphenol A type epoxy resin, as E-51, E-44 etc. or its mixture, also can add diluent.During as microcapsule wall material, selected curing agent and various curing agent used as microcapsules core and composition thereof can identical also can be different.But, by control loop epoxy resins and the proportioning of curing agent and reaction temperature must be added, form the prepolymer of epoxy resin and not gel, when ensureing that this prepolymer uses as wall material after reacting further, there is gratifying sealing simultaneously.
The solvent of described dissolving prepolymer can be acetone, carbon tetrachloride and if toluene, dimethylbenzene, benzylalcohol, repefral, diethyl phthalate, dibutyl phthalate, ethylene acetate, ethylene carbonate etc. are containing the lowering viscousity compound of phenyl ring or mixture etc.
Described insulating liquid can be the various silicone oil of 25 DEG C of viscosity at 20mPa.s-10,000mPa.s, as methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methylethyl silicone oil, methyl phenyl silicone oil etc.
The present invention is insulating liquid method, first microcapsule wall material is prepared, the prepolymer of epoxy resin and amine curing agent, then prepolymer wall material is dissolved in certain solvent and is formed dense " solution ", capsule heartwood material is added in this solution, for controlling the self aggregation of core, adopting dripping method to introduce, controlling rate of addition, from container face and evenly dripping or the stirring of dropping limit, limit; Also can prevent self aggregation by adding interleaving agent, the generation that declines gradually of the dissolubility of microcapsules in " solution " is separated.Filter, drying obtains final microcapsule product.Key finds suitable solvent, and the prepolymer of energy dissolved epoxy, but can not dissolve the core curing agent of microcapsules.The liquid-liquid interface utilizing deliquescent difference to produce and the controlled epoxy resin cure reaction occurred on the surface, prepare epoxy curing agent microcapsules.The principle signal of the method corresponding process as shown in Figure 1.In Fig. 1,11 are microcapsules, 12 in solidification are interleaving agents, 13 is prepolymers.
Present invention process, equipment are simple, neither introduce aqueous phase, also not water-soluble by microcapsules core or oil-soluble restriction, and by the ratio between control loop epoxy resins and curing agent and system degree of functionality, the mechanical strength of microcapsules, sealing and heat resistance effectively can be controlled.Meanwhile, natural compatible between this microcapsules and epoxy resin, be easy to be scattered in epoxy resin.These microcapsules can be used for self-repair material as a kind of " micro-container ", latency adhesive or other any fields needing Co ntrolled release or isolate core.
Accompanying drawing explanation
Fig. 1 is insulating liquid method microcapsules preparation principle schematic diagram.
Specific embodiment
Below by specific embodiment, the present invention is further described, but embodiment is not all limitation of the present invention.
embodiment 1
To a preparation method for the pressure-sensitive temperature resistant encapsulation microcapsules in outside, be insulating liquid method, the method step is as follows:
50g epoxy resin E-51 and 3.5g2E4MZ-CN imidazoles, 30 DEG C of pre-polymerization 15min, this is dissolved in 200ml toluene, add 8g capsule heartwood material low molecular polyamides Versamid V-140, again mixture is added in 300ml dimethicone (25 DEG C of viscosity 300mPa.s) and keep 30 DEG C to stir, after effect microcapsule wall curing molding with 300rpm.Filter, washing, drying obtain final microcapsule product.
embodiment 2
35g epoxy resin E-44,15g cresyl glycidyl ether CGE and 2.5g m-xylene diamine modifier G-328,60 DEG C of pre-polymerization 6min, then this prepolymer core is dissolved in 200ml carbon tetrachloride, again mixture is added maintenance 60 DEG C in 300ml dimethicone (25 DEG C of viscosity 500mPa.s) to stir with 200rpm, filter after effect microcapsule wall curing molding, washing, dry microcapsules.
Claims (7)
1., to a preparation method for the pressure-sensitive temperature resistant encapsulation microcapsules in outside, it is characterized in that the method step is as follows:
1) first prepare microcapsule wall material, the microcapsules core curing agent of epoxy resin and 0.50-0.85 times of equivalent, between 20 DEG C-80 DEG C, is prepared microcapsule wall material by control temperature, and is dissolved in certain solvent by microcapsule wall material and forms concentrated solution; Described microcapsule wall material is the cured resin generated after epoxy resin and amine curing agent react; The solvent of described dissolving microcapsule wall material is toluene, dimethylbenzene, benzylalcohol, repefral, diethyl phthalate, dibutyl phthalate class contain phenyl ring lowering viscousity compound or mixture; Described microcapsules core curing agent is low temperature curing agent, toughess at room temperature and intermediate temperature setting agent or their mixture, comprise 25 DEG C of viscositys within 1mPa.s to 25000mPa.s, boiling point one or more mixtures between 100 DEG C-300 DEG C in aliphatic polyamine, aromatic polyamine, polyamide, tertiary amine, tertiary ammonium salt, aliphatic cyclic amine; The amine curing agent used in described microcapsule wall material is low viscous low temperature curing agent, toughess at room temperature and intermediate temperature setting agent or their mixture, mainly comprise 25 DEG C of viscositys within 1mPa.s to 25000mPa.s, boiling point one or more mixtures between 100 DEG C-300 DEG C in aliphatic polyamine, aromatic polyamine, polyamide, tertiary amine, tertiary ammonium salt, aliphatic cyclic amine;
2) then microcapsules core to be added in this solution and to be uniformly dispersed, obtaining mixture; Pour in insulating liquid by this mixture, hierarchy of control temperature is between 20 DEG C-80 DEG C, and 100rpm-500rpm stirs until effect microcapsule wall curing molding; Microcapsules core is the amine curing agent of epoxy resin; The mass ratio of microcapsules core and microcapsule wall material is between 1:5-5:1;
3) article shaped filtered, washing, drying, obtain the pressure-sensitive temperature resistant encapsulation microcapsules in outside.
2. the preparation method to the pressure-sensitive temperature resistant encapsulation microcapsules in outside according to claim 1, is characterized in that: described epoxy resin is liquid-state epoxy resin.
3. the preparation method to the pressure-sensitive temperature resistant encapsulation microcapsules in outside according to claim 2, is characterized in that: described epoxy resin is bisphenol A type epoxy resin.
4. the preparation method to the pressure-sensitive temperature resistant encapsulation microcapsules in outside according to claim 3, is characterized in that: described epoxy resin is E-51, E-44 or its mixture.
5. the preparation method to the pressure-sensitive temperature resistant encapsulation microcapsules in outside according to claim 4, is characterized in that: the epoxide resin reactive diluent of viscosity between 1mPa.s to 200mPa.s during interpolation 25 DEG C in the epoxy.
6. the preparation method to the pressure-sensitive temperature resistant encapsulation microcapsules in outside according to claim 1, is characterized in that: described insulating liquid, is the silicone oil of 25 DEG C of viscosity at 20mPa.s to 10000mPa.s.
7. the preparation method to the pressure-sensitive temperature resistant encapsulation microcapsules in outside according to claim 6, is characterized in that: described silicone oil is one or more in methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methylethyl silicone oil, methyl phenyl silicone oil.
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| CN106345378B (en) * | 2015-07-14 | 2019-06-21 | 深圳市百安百科技有限公司 | A kind of preparation method of pre- catalysis polymercaptan microcapsules |
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| CN101224403B (en) * | 2007-10-26 | 2011-06-29 | 清华大学 | Method for preparing microcapsule |
| CN102504743B (en) * | 2011-11-07 | 2013-11-06 | 深圳市鑫东邦科技有限公司 | Single-component underfill capable of being stored at room temperature and preparation method thereof |
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