CN105175654A - Hexagonal boron nitride micro-constrained acrylate latex nanocomposite - Google Patents
Hexagonal boron nitride micro-constrained acrylate latex nanocomposite Download PDFInfo
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- CN105175654A CN105175654A CN201510632631.XA CN201510632631A CN105175654A CN 105175654 A CN105175654 A CN 105175654A CN 201510632631 A CN201510632631 A CN 201510632631A CN 105175654 A CN105175654 A CN 105175654A
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Abstract
The invention belongs to the technical field of nanocomposites and relates to a hexagonal boron nitride micro-constrained acrylate latex nanocomposite and a preparation method thereof. Firstly, hexagonal boron nitride is subjected to surface modification, a reactive type emulsifier is dissolved in water, a monomer I, a crosslinking agent, a buffering agent and the modified hexagonal boron nitride are sequentially added for ultrasonic dispersion pre-emulsification, a pre-emulsified solution I is prepared, then the pre-emulsified solution I and an initiator are mixed to react to prepare a polymer emulsion I, a pre-emulsified solution II is prepared from a monomer II with the method for preparing the pre-emulsified solution I, the polymer emulsion I, the pre-emulsified solution II and the initiator are mixed, and hexagonal boron nitride-acrylate composite latex is finally obtained. The hexagonal boron nitride is successfully introduced into acrylate latex particles and the hexagonal boron nitride-acrylate latex nanocomposite is formed. The electric insulativity, the thermal conductivity, the chemical corrosion resistance, the thermal stability and the damping property of the composite are much higher than those of acrylate latex.
Description
Technical field
The invention belongs to nano composite material technical field, relate to a kind of hexagonal boron nitride micro-constraint acrylate latex nano composite material and preparation method thereof.
Background technology
Acrylic elastomer is because of the high polarity of its molecular structure and complete saturability, there is superior resistance to mineral oil and pyro-oxidation resistance, there is excellent ozone resistants, resistance to air loss, resistance to rich characteristic in the wrong simultaneously, irreplaceable effect is played in the hard-core technology such as Aeronautics and Astronautics, weapons field, irreplaceable critical material in national defence sophisticated industry, often for the manufacture of the rubber oil sea used under high temperature, pad, sebific duct and tackiness agent.
Along with the development of China's aerospace and national defense and military cause, requirement for material is more and more higher also more and more harsher, particularly can heat oxygen aging resistance and to have the demand of excellent high temperature mechanical property and dynamic property of material under high temperature material growing for some, acrylic elastomer does not become the preferred material of heat oxygen aging resistance because main chain does not contain double bond, but existing acrylic elastomer mechanical property at high temperature and dynamic properties performance poor, limit the application of acrylic elastomer in hot environment, further lifting acrylic elastomer material mechanical property at high temperature and dynamic properties are necessary.
Summary of the invention
The object of the invention is: for the deficiency of acrylic elastomer wide temperature range dynamic properties at room temperature ~ 120 DEG C, especially damping is on the low side, proposes a kind of hexagonal boron nitride micro-constraint acrylate latex nano composite material and preparation method thereof.
Technical scheme of the present invention is: the hexagonal boron nitride after modification adds acrylate adhesive Ruzhong to and forms hexagonal boron nitride-acrylate latex nano composite material, it is characterized in that: described hexagonal boron nitride-acrylate latex nano composite material material of main part is methyl methacrylate (MMA), butyl acrylate (BA), ethyl propenoate (EA).First with alcohol solution, silane coupling agent is diluted, then mix with hexagonal boron nitride, obtained the hexagonal boron nitride of finishing by the method for heating in water bath, mechanical stirring, suction filtration and drying.Emulsifying agent is water-soluble, adds monomer, linking agent, buffer reagent and the hexagonal boron nitride after modifying successively, carries out ultrasonic disperse pre-emulsification, obtain pre-emulsion I and pre-emulsion II.Again pre-emulsion I and initiator are carried out being obtained by reacting polymer emulsion I.Last polymer emulsion I, pre-emulsion II and initiator hybrid reaction obtain hexagonal boron nitride-acrylate compound latex.
The concrete grammar preparing hexagonal boron nitride-acrylate latex nano composite material is,
(1) hexagonal boron nitride finishing.With alcohol solution (ethanol: water=3:1), dialkylene triethoxyl silane is diluted, injecting is equipped with in the there-necked flask of hexagonal boron nitride, heating in water bath, heat while mechanical stirring, suction filtration is started after 2h, put into the dry 4h of vacuum drying oven again, obtain the hexagonal boron nitride of finishing;
(2) preparation of pre-emulsion I.ELEMINOLJS-2 is water-soluble, add methyl methacrylate MMA, butyl acrylate BA successively, to divinylbenzene, sodium bicarbonate and the hexagonal boron nitride after modifying, hyperacoustic method is adopted to carry out ultrasonic disperse pre-emulsification, ultrasonic disperse 30min, normal temperature high speed pre-emulsification 1h obtains pre-emulsion I;
(3) preparation of polymer emulsion I.Being equipped with electric mixer, reflux condensing tube, temperature take into account in the four-hole boiling flask of constant pressure funnel stir while add 1/4 pre-emulsion I, be warming up to 75 DEG C, then instill 1/4 ammonium persulphate until in flask emulsion become blue, insulation 5min, be warming up to 80 DEG C again, drip pre-emulsion I and ammonium persulphate respectively, insulation reaction 60min, then be cooled to 60 DEG C and obtain polymer emulsion I;
(4) preparation of pre-emulsion II.According to the preparation method of pre-emulsion I, ELEMINOLJS-2 is water-soluble, add ethyl propenoate EA successively, to divinylbenzene, sodium bicarbonate and the hexagonal boron nitride after modifying, ultrasonic wave is adopted to carry out ultrasonic disperse pre-emulsification, ultrasonic disperse 30min, normal temperature high speed pre-emulsification 1h prepares pre-emulsion II;
(5) preparation of hexagonal boron nitride-acrylate compound latex.Add 1/4 pre-emulsion II being equipped with in polymer emulsion I reaction flask, be warming up to 75 DEG C, then the ammonium persulphate of 1/4 is instilled, 80 DEG C are warming up to after insulation 5min, drip pre-emulsion II and ammonium persulphate respectively again, about 60min drips off, insulation reaction 120min, obtains hexagonal boron nitride-acrylate compound latex.
Advantage of the present invention is: the present invention, by doing finishing to hexagonal boron nitride, adds in acrylate monomer and prepares pre-emulsion, and recycling pre-emulsion prepares polymer emulsion, and last end-blocking obtains hexagonal boron nitride-acrylate compound latex.This matrix material is retaining acrylate latex primary characteristic as the basis of electrical insulating property, thermal conductivity and chemical resistance there being further optimization, the resistance toheat of this matrix material, dynamic properties, particularly damping capacity obtain comparatively significantly promoting.
Hexagonal boron nitride is laminated structure, hexagonal boron nitride after modification can enter inside the nucleocapsid structure of emulsion particle, when the macromolecular chain of acrylate latex is subject to external force and moves, laminated structure hexagonal boron nitride can hinder macromolecular chain to move, Microscopic can play effect of contraction to polymer molecule chain movement at hexagonal boron nitride, be called micro-effect of contraction, macro manifestations is obviously promoting the dynamic properties, particularly damping capacity of acrylate latex within the scope of the temperature range of broadness due to micro-effect of contraction.
Hexagonal boron nitride is carried out modification by the present invention, and modified hexagonal boron nitride major part can enter in the nucleocapsid structure of latex particle, combines with acrylic ester polymer particle, forms homogeneous system with acrylic ester emulsion.Dynamic properties test shows to compare acrylate latex in the temperature range of room temperature ~ 120 DEG C, and the dissipation factor of boron nitride-acrylate compound latex is larger.Because hexagonal boron nitride is laminated structure, hexagonal boron nitride after modification can enter in acrylate latex particle, retrain each other with acrylate latex particle and form micro-restraining structure, when matrix material is subject to external force, acrylate latex macromolecular chain can produce relative movement, hexagonal boron nitride can hinder the motion of macromolecular chain thus produce micro-effect of contraction, and this micro-effect of contraction can improve the dissipation factor of acrylate latex thus improve damping.
Hexagonal boron nitride is successfully introduced in acrylate latex grain and is formed hexagonal boron nitride-acrylate latex nano composite material by the present invention.The electrical insulating property of this matrix material, thermal conductivity, chemical resistance, thermostability and damping capacity all have than the performance of acrylate latex and significantly promote.
The present invention has the resistance toheat more excellent compared with conventional acrylic ester gum, dynamic properties, and cost is low, and preparation technology is simple, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is hexagonal boron nitride micro-constraint acrylate polymeric chain schematic diagram.
Embodiment
The specific embodiment of the present invention is,
(1) hexagonal boron nitride finishing.With alcohol solution (ethanol: water=3:1), silane coupling agent dialkylene triethoxyl silane is diluted, injecting is equipped with in the there-necked flask of hexagonal boron nitride, heating in water bath, heat while mechanical stirring, suction filtration is started after 2h, put into the dry 4h of vacuum drying oven again, obtain the hexagonal boron nitride of finishing;
(2) preparation of pre-emulsion I.By water-soluble for reactive emulsifier ELEMINOLJS-2, add monomers methyl methacrylate MMA, butyl acrylate BA, linking agent successively to divinylbenzene, buffer reagent sodium bicarbonate and the hexagonal boron nitride after modifying, hyperacoustic method is adopted to carry out ultrasonic disperse pre-emulsification, ultrasonic disperse 30min, normal temperature high speed pre-emulsification 1h obtains pre-emulsion I;
(3) preparation of polymer emulsion I.Being equipped with electric mixer, reflux condensing tube, temperature take into account in the four-hole boiling flask of constant pressure funnel stir while add 1/4 pre-emulsion I, be warming up to 75 DEG C, then instill 1/4 initiator ammonium persulfate until in flask emulsion become blue, insulation 5min, be warming up to 80 DEG C again, drip pre-emulsion I and initiator ammonium persulfate respectively, about 60min drips off, insulation reaction 60min, then be cooled to 60 DEG C and obtain polymer emulsion I;
(4) preparation of pre-emulsion II.According to the preparation method of pre-emulsion I, by water-soluble for reactive emulsifier ELEMINOLJS-2, add monomer propylene acetoacetic ester EA, linking agent successively to divinylbenzene, buffer reagent sodium bicarbonate and the hexagonal boron nitride after modifying, ultrasonic wave is adopted to carry out ultrasonic disperse pre-emulsification, ultrasonic disperse 30min, normal temperature high speed pre-emulsification 1h prepares pre-emulsion II;
(5) preparation of hexagonal boron nitride-acrylate compound latex.Add 1/4 pre-emulsion II being equipped with in polymer emulsion I reaction flask, be warming up to 75 DEG C, then 1/4 initiator ammonium persulfate is instilled, 80 DEG C are warming up to after insulation 5min, drip pre-emulsion II and initiator ammonium persulfate respectively again, about 60min drips off, insulation reaction 120min, obtains hexagonal boron nitride-acrylate compound latex.
Principle of work of the present invention is: hexagonal boron nitride is laminated structure, hexagonal boron nitride after modification can enter in the nucleocapsid structure of Acrylic emulsion particle, the macromolecular chain of acrylate latex and the hexagonal boron nitride after modifying produce and interact when exposed to external forces, hexagonal boron nitride limits the motion of acrylate latex macromolecular chain to a certain extent, micro-effect of contraction is created to acrylate latex macromolecular chain, this micro-effect of contraction can improve the second-order transition temperature of acrylate latex, improve the dynamic properties of acrylate latex, particularly damping capacity.
Claims (2)
1. hexagonal boron nitride micro-constraint acrylate latex nano composite material, it is characterized in that, described material of main part is methyl methacrylate, butyl acrylate and ethyl propenoate, separately add ELEMINOLJS-2 emulsifying agent, to divinylbenzene, ammonium persulphate, dialkylene triethoxyl silane and hexagonal boron nitride, hexagonal boron nitride is laminated structure.
2. prepare a method for a kind of hexagonal boron nitride micro-constraint acrylate latex nano composite material described in claim 1, it is characterized in that:
(1) hexagonal boron nitride finishing, with ethanol: silane coupling agent dialkylene triethoxyl silane dilutes by the solution of water=3:1, injecting is equipped with in the there-necked flask of hexagonal boron nitride, heating in water bath, heat while mechanical stirring, start suction filtration after 2h, then it is dry to put into vacuum drying oven, obtains the hexagonal boron nitride of finishing;
(2) preparation of pre-emulsion I, by water-soluble for emulsifier EL EMINOLJS-2, add monomers methyl methacrylate, butyl acrylate, linking agent successively to divinylbenzene, buffer reagent sodium bicarbonate and the hexagonal boron nitride after modifying, hyperacoustic method is adopted to carry out ultrasonic disperse pre-emulsification, ultrasonic disperse 30min, normal temperature high speed pre-emulsification 1h obtains pre-emulsion I;
(3) preparation of polymer emulsion I, being equipped with electric mixer, reflux condensing tube, temperature take into account in the four-hole boiling flask of constant pressure funnel stir while add 1/4 pre-emulsion I, be warming up to 75 DEG C, then instill 1/4 initiator ammonium persulfate until in flask emulsion become blue, insulation 5min, then be warming up to 80 DEG C, drip pre-emulsion I and ammonium persulphate respectively, about 60min drips off, insulation reaction 60min, then is cooled to 60 DEG C and obtains polymer emulsion I;
(4) preparation of pre-emulsion II, according to the preparation method of pre-emulsion I, by water-soluble for emulsifier EL EMINOLJS-2, add monomer propylene acetoacetic ester, linking agent successively to divinylbenzene, buffer reagent sodium bicarbonate and the hexagonal boron nitride after modifying, ultrasonic wave is adopted to carry out ultrasonic disperse pre-emulsification, ultrasonic disperse 30min, normal temperature high speed pre-emulsification 1h prepares pre-emulsion II;
(5) pre-emulsion II adding 1/4 is being housed in polymer emulsion I reaction flask, be warming up to 75 DEG C, then the initiator ammonium persulfate of 1/4 is instilled, 80 DEG C are warming up to after insulation 5min, drip pre-emulsion II and ammonium persulphate respectively again, till dripping off, insulation reaction 120min, obtains hexagonal boron nitride-acrylate compound latex.
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| CN105860364A (en) * | 2016-05-25 | 2016-08-17 | 青海大学 | Surface treatment method for novel crystal whiskers applied to PVC |
| CN108276770A (en) * | 2018-01-05 | 2018-07-13 | 广东纳路纳米科技有限公司 | A kind of modified white graphite alkene/polyamide composite heat conducting material and preparation method thereof |
| CN110467706A (en) * | 2019-09-03 | 2019-11-19 | 武汉工程大学 | A kind of preparation method of hexagonal boron nitride modification acrylate core-shell emulsion |
| CN111484626A (en) * | 2020-04-24 | 2020-08-04 | 叶笃梁 | Modified boron nitride grafted waterborne acrylic resin insulating material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860364A (en) * | 2016-05-25 | 2016-08-17 | 青海大学 | Surface treatment method for novel crystal whiskers applied to PVC |
| CN108276770A (en) * | 2018-01-05 | 2018-07-13 | 广东纳路纳米科技有限公司 | A kind of modified white graphite alkene/polyamide composite heat conducting material and preparation method thereof |
| CN110467706A (en) * | 2019-09-03 | 2019-11-19 | 武汉工程大学 | A kind of preparation method of hexagonal boron nitride modification acrylate core-shell emulsion |
| CN111484626A (en) * | 2020-04-24 | 2020-08-04 | 叶笃梁 | Modified boron nitride grafted waterborne acrylic resin insulating material and preparation method thereof |
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