CN108097182A - A kind of ultra-fine environment protection thermal expanding microcapsules and preparation method thereof - Google Patents
A kind of ultra-fine environment protection thermal expanding microcapsules and preparation method thereof Download PDFInfo
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- CN108097182A CN108097182A CN201810011067.3A CN201810011067A CN108097182A CN 108097182 A CN108097182 A CN 108097182A CN 201810011067 A CN201810011067 A CN 201810011067A CN 108097182 A CN108097182 A CN 108097182A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
Abstract
The present invention discloses a kind of ultra-fine environment protection thermal expanding microcapsules, it is made of the suspended dispersed liquid of oil phase constituent and water phase composition object through microwave radiation emulsion polymerization, the grain size of the ultra-fine environment protection thermal expanding microcapsules is in submicron order, expansion ratio is high, it is environment-protecting and non-poisonous, it can be applied to the fields such as weaving, papermaking, ink, engineering plastics.The invention also discloses the preparation methods of ultra-fine environment protection thermal expanding microcapsules, and thermal expansion microcapsules are made based on microwave radiation free-radical emulsion polymerization technology, and easy to operate, preparation process is simple, production efficiency is high.
Description
Technical field
The present invention relates to a kind of thermal expansion microcapsules, and in particular to be a kind of ultra-fine environment protection thermal expanding microcapsules and its system
Preparation Method.
Background technology
Thermal expansivity microcapsules, be by gas barrier property good thermoplastic polymer shell package low boiling point physical blowing agent and
The microcapsules of formation are generally formed by the polymerisable monomer in water soluble disperse system and foaming agent through suspension polymerisation.
In resin expanded lightweight and the regulation and control of foam structure are realized all using traditional chemical blowing method substantially.
But chemical blowing method is used, the surface quality problems of expanded material can not be but resolved.Either chemical blowing system is also
It is overcritical physical blowing system, the formation of abscess all relies on the diffusion of gas, and relevant abscess merges, roughening and table
Face quality problems are also all derived from the gas diffusion being effectively controlled.And it is to solve surface matter to use the foaming of thermal expansion microcapsules
Most effective, the basic method of amount problem, the method not only can effectively control the diffusion of foaming agent gas, and processing is simple, adds
Work window width, it is easier to foam structure is controlled, it is of low cost.
Thermal expansion microcapsules do not have decomposition residual as foaming agent, do not have apparent gas diffusion, will not reduce hair
Foam material surface quality, while cost is not high, processing is simple, and high pressure and high pressure drop rate is not required.But currently available heat
Size generally reaches 40~250 μm to expanding microcapsules size all after 10~50 μm, microcapsules heating expansion, this size pair
It is too big for microporous polymer, therefore be only used for preparing general expanded material, it is impossible to be used in prepare microporous polymer material
Material.
The patent of invention of Publication No. CN102633936A《Heat-swellable thermoplastic microspheres》With acrylonitrile and (methyl) third
The average diameter for the thermal expansion microcapsules that alkene acrylic monomer is prepared using suspension polymerization is all higher than 30 μm.Publication No.
The patent of invention of CN105555851A《The manufacturing method of heat-expandable microsphere》The microballoon average diameter being prepared is more than 20 μm.
Foreign patent EP2529830, the grain size of the thermal expansion microcapsules formed by suspension polymerization technique are all higher than 20 μm.Foreign patent
Described in US8247465, the grain size of the thermal expansion microcapsules prepared by suspension polymerization is more than 20 μm.
It can be seen that in existing technology of preparing, the thermal expansion microcapsules that are prepared using the method for suspension polymerisation
Grain size cannot get the product of submicron order.
The content of the invention
It is an object of the invention to provide a kind of ultra-fine environment protection thermal expanding microcapsules, and grain size is in submicron order, expansion ratio
Height, it is environment-protecting and non-poisonous, it can be applied to the fields such as weaving, papermaking, ink, engineering plastics.
It is an object of the invention to provide a kind of preparation method of ultra-fine environment protection thermal expanding microcapsules, based on microwave radiation from
Thermal expansion microcapsules are made by emulsion polymerization technology, easy to operate, preparation process is simple, production efficiency is high.
In order to achieve the above objectives, solution of the invention is：
A kind of ultra-fine environment protection thermal expanding microcapsules, by the suspended dispersed liquid of oil phase constituent and water phase composition object through microwave spoke
It penetrates emulsion polymerization to be made, wherein the mass percent that the oil phase constituent accounts for the suspended dispersed liquid is 10%~40%；
The oil phase constituent includes each component of following parts by weight：Low boiling point alkane is 10~40 parts by weight；Acrylonitrile
Monomer is 0~20 parts by weight；(methyl) acrylic ester copolymerization monomer is 50~100 parts by weight；(methyl) acrylic acid and its salt
Class comonomer is 0~20 parts by weight；Styrene co-monomer is 0~100 parts by weight；Oil-soluble initiator is 0.1~1 weight
Part；Crosslinking agent is 0.1~1 parts by weight；
The water phase composition object includes each component of following parts by weight：Emulsifier is 0.1~5 parts by weight, suspending agent be 0~
10 parts by weight, polymerization inhibitor are 0.1~1 parts by weight, and inorganic salts are 10~60 parts by weight, and deionized water is 200~400 parts by weight.
The low boiling point alkane is the alkane that carbon number is 4~8, and the low boiling point alkane includes butane, iso-butane, penta
One or any combination in alkane, isopentane, neopentane, hexane, isohexane, heptane, isoheptane, octane, isooctane；
(methyl) the acrylic ester copolymerization monomer is (methyl) methyl acrylate, (methyl) ethyl acrylate, (first
Base) acrylic acid norbornyl ester, N, N- dimethacrylamide, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate,
(methyl) allyl acrylate, (methyl) glycidyl acrylate, one kind in (methyl) acrylic acid tetrahydrofurfuryl alcohol ester are appointed
Meaning combination；
(methyl) acrylic acid and its esters comonomer are methacrylic acid, acrylic acid, magnesinm methacrylate, methyl
One kind or any combination in zinc acrylate resin, Sodium methacrylate；
The oil-soluble initiator is the one or any combination in peroxide initiator or azo-initiator；
The crosslinking agent is in binary acrylic ester monomer, ternary acrylate class monomer, styrene monomer
One or any combination.
The peroxide initiator is dibenzoyl peroxide or dilauroyl peroxide, and the azo-initiator is
Azodiisobutyronitrile or azobisisoheptonitrile；
The binary acrylic ester monomer be two-(methyl) acrylate of diethyl (third) glycol, the ternary acrylic acid
Esters monomer is three second (third) glycol, two-(methyl) acrylate, polyethylene glycol two (methyl) acrylate, second (third) oxidation three
Hydroxymethyl-propane three-(methyl) acrylate, methacrylate glyceride or methacrylate bisphenol-A ester；
The styrene monomer is divinylbenzene or trivinylbenzene.
The emulsifier is polyoxyethylene nonyl phenolic ether, polyoxyethylene nonyl phenolic ether sodium sulphate, lauryl sodium sulfate, dodecane
Base benzene sulfonic acid sodium salt, tween-20, tween-40, tween-60, span-20, span-40, span-60, OP-10, vinyl sulphur
One or any combination in sour sodium, sodium p styrene sulfonate, Sodium Allyl Sulfonate；
The suspending agent is high molecular weight water soluble polymer polyvinylpyrrolidone, sodium carboxymethylcellulose, methylol are fine
One or any combination in the plain sodium of dimension, polyvinyl alcohol；
The polymerization inhibitor is any one in sodium nitrite, potassium nitrite, sodium hydrogensulfite, potassium ferrate.
A kind of preparation method of ultra-fine environment protection thermal expanding microcapsules, includes the following steps：
(1) water phase is prepared：By the emulsifier of 0.1~5 parts by weight, the suspending agent of 0~10 parts by weight, 10~60 parts by weight
Inorganic salts, the polymerization inhibitor of 0.1~1 parts by weight are added in the deionized water of 200~400 parts by weight and disperse, and obtain water phase group
Into object；
(2) oil phase is prepared：By the low boiling point alkane of 10~40 parts by weight, the acrylonitrile monemer of 0~20 parts by weight, 50~
(methyl) the acrylic ester copolymerization monomer of 100 parts by weight, (methyl) acrylic acid of 0~20 parts by weight and its esters copolymerization are single
Body, the styrene of 0~100 parts by weight, the crosslinking agent of the oil-soluble initiator of 0.1~1 parts by weight and 0.1~1 parts by weight mix
Close uniform, acquisition oil phase constituent；
(3) dispersion liquid is prepared：The oil phase constituent is added in the water phase composition object, at room temperature with 10000r/min
The mixing speed of~20000r/min, by the mixed liquor of the oil phase constituent and the water phase composition object uniformly emulsification 10~
20min obtains uniform and stable O/W type dispersion liquids；
(4) polymerisation：The O/W types dispersion liquid is placed in microwave reactor, under nitrogen atmosphere, be heated to 60 DEG C~
90 DEG C, start emulsion polymerization under the mixing speed of 300r/min~800r/min, react 5h~10h, obtain micro- containing thermal expansion
The white suspension of capsule by the filtering of white suspension liquid, is dried to obtain thermal expansion microscapsule powder.
, it is necessary to be removed using post-processing approach in the thermal expansion microscapsule powder after the completion of step (4) polymerisation
Monomer residue.
The average grain diameter of the thermal expansion microscapsule powder is in 80~800nm.
After adopting the above technical scheme, a kind of ultra-fine environment protection thermal expanding microcapsules of the present invention, with acrylonitrile monemer and (first
Base) esters of acrylic acid be comonomer, using crosslinking agent as cyst wall, using low boiling point alkane as core, through microwave radiation emulsion polymerization
It forms, has the advantages that：
(1) present invention is that thermal expansion microcapsules are made based on microwave radiation free-radical emulsion polymerization technology, easy to operate, system
It is standby it is simple for process, production efficiency is high, compared to common polymerization, polymerization time shorten 5~15 it is small when；
(2) reacted using microwave radiation polymerization, there is high rate of polymerization height, monomer conversion, cleaning, energy saving, system is easy
The characteristics of control, environmentally protective, high benefit；
(3) particle diameter distribution of the thermal expansion microcapsules prepared by the method for microwave radiation free-radical emulsion polymerization is uniform,
Average grain diameter is in 80~800nm, the supermicrocellular polymer material produced after being foamed using the thermal expansion microcapsules, pore size
150~800nm scopes are distributed in, and with fine and close surface, is conducive to improve the surface quality of poromerics, adds product
Aesthetics, reduce the density of product, expanded the application range of thermal expansion microcapsules；
(4) the thermal expansion microcapsules level of residual monomers that method of the invention is prepared is low, have it is nontoxic, do not pollute, to system
Product do not dye, do not influence the advantages that curing and shaping speed, and normal pressure, pressure expansion can make uniform in foaming；
(5) the thermal expansion microcapsules being prepared using the method for the present invention have higher expansion ratio, grain after foaming
Footpath averagely increases 4~5 times.
Specific embodiment
In order to further explain the technical solution of the present invention, the present invention is explained in detail below by specific embodiment
It states.
First, the preparation of thermal expansion microcapsules
Embodiment 1
A kind of preparation method of ultra-fine environment protection thermal expanding microcapsules, includes the following steps：
(1) water phase is prepared：By the tween-20 of the 0.2 parts by weight and Span-60 of 0.5 parts by weight, the polyethylene of 5 parts by weight
Pyrrolidones, the sodium chloride of 60 parts by weight, the sodium nitrite of 0.2 parts by weight are added in the deionized water of 400 parts by weight and divide
It dissipates, obtains water phase composition object；
(2) oil phase is prepared：By 10 parts by weight isopentane, 30 parts by weight isooctane, 20 parts by weight propylene nitrile monomers, 80 weight
Part methyl methacrylate, 1 parts by weight dilauroyl peroxide, the trimethylol propane trimethyl methyl acrylate of 1 parts by weight
It is uniformly mixed, obtains oil phase constituent；
(3) dispersion liquid is prepared：Oil phase constituent is added in water phase composition object, at room temperature with the stirring speed of 15000r/min
Degree, uniformly emulsifies 15min by the mixed liquor of oil phase constituent and water phase composition object, obtains uniform and stable O/W type dispersion liquids；
(4) polymerisation：O/W type dispersion liquids are placed in microwave reactor, under nitrogen atmosphere, are heated to 75 DEG C,
Start emulsion polymerization under the mixing speed of 550r/min, react 7.5h, obtain the white suspension of the microcapsules containing thermal expansion, it will be white
The filtering of color suspension liquid, the thermal expansion microscapsule powder for being dried to obtain white.
, it is necessary to remove the monomer in thermal expansion microscapsule powder using post-processing approach after the completion of step (4) polymerisation
Residual.
Embodiment 2~10
Except changing in oil phase constituent in addition to the species and dosage of each component, other conditions are same as Example 1, specific to join
It is shown in Table 1.
Comparative example 1
It is with the difference in embodiment 1：O/W type dispersion liquids are placed in autoclave, under nitrogen atmosphere 0.5MPa,
75 DEG C are heated to, starts emulsion polymerization under the mixing speed of 550r/min, 25h is reacted, obtains the white of the microcapsules containing thermal expansion
Color suspension by the filtering of white suspension liquid, is dried to obtain white thermal expansion microscapsule powder.
Comparative example 2
It is with the difference of embodiment 3：O/W type dispersion liquids are placed in autoclave, under nitrogen atmosphere 0.5MPa, are added
Heat starts emulsion polymerization to 75 DEG C under the mixing speed of 550r/min, reacts 25h, obtains the white of the microcapsules containing thermal expansion
Suspension by the filtering of white suspension liquid, is dried to obtain white thermal expansion microscapsule powder.
Comparative example 3
It is with the difference of embodiment 10：O/W type dispersion liquids are placed in autoclave, under nitrogen atmosphere 0.5MPa,
75 DEG C are heated to, starts emulsion polymerization under the mixing speed of 550r/min, 25h is reacted, obtains the white of the microcapsules containing thermal expansion
Color suspension by the filtering of white suspension liquid, is dried to obtain white thermal expansion microscapsule powder.
The species and dosage of 1 oil phase constituent of table
Note：MAA in table：Methacrylic acid；MMA：Methyl methacrylate；MA：Methyl acrylate；St：Styrene；
TMPTMA：Trimethylol propane trimethyl methyl acrylate；EGDMA：Ethylene glycol dimethacrylate；DVB：Divinyl
Benzene；PEG(200)DMA：Polyethylene glycol (200) dimethylacrylate；LPO：Dilauroyl peroxide；BPO：Diphenyl peroxide
Formyl；AIBN：Azodiisobutyronitrile；ABVN：Azobisisoheptonitrile；IB：Iso-butane；IP：Isopentane；IH：Isohexane；IO：It is different
Octane.
2nd, the evaluation of thermal expansion microcapsules
1st, particle diameter distribution
The particle diameter distribution of thermal expansion microcapsules is that the LS909 laser particle size analyzers measurement produced by Europe Mec AS is flat
Equal particle diameter distribution (D50).
2nd, foam characteristics are analyzed
The Q400 static state thermomechanical analyzers produced using TA instruments companies measure foaming start temperature
(Tstart), maximum displacement (Dmax) and maximum blowing temperature (Tmax).Specifically, sample 0.5mg is put into diameter 6.4mm,
In the aluminum cup of deep 4mm, in the state of the power of 0.06N applied from above, under the heating rate of 5 DEG C/min, added by 30 DEG C
To 300 DEG C, powder is carried out heat by measuring probe vertical displacement.
Using hot air, make thermal expansion uniform microcapsule after by heat foamable, the LS909 produced by Europe Mec AS
Particle diameter distribution D after laser particle size analyzer measurement foamingHeat, particle diameter distribution D before being heatedpre, expansion ratio=Dheat/Dpre。
3rd, level of residual monomers is analyzed
Post processing：After polymerisation, treat that temperature is down to 30 DEG C, under nitrogen atmosphere, add in tert-butyl hydroperoxide,
After 10min is stirred at room temperature, sodium hydrogensulfite is added in, boosts to 0.6MPa, then be warming up to 60 DEG C, reacted 7h, after reaction, treat
Temperature is down to 30 DEG C, and blowing centrifuges, dry, then removes the monomer residue in thermal expansion microscapsule powder.
Measure the monomer residue in treated thermal expansion microscapsule powder：The GC2014C gas produced using Shimadzu Corporation
Chromatography, chromatographic condition：40 DEG C, constant temperature 1min of initial temperature is warming up to 100 DEG C, constant temperature 2min with 5 DEG C/min, then with 6 DEG C/min
200 DEG C are warming up to, constant temperature 5min.250 DEG C of detector temperature；225 DEG C of injector temperature.Oil phase head space temperature：80℃；Water mutually pushes up
Air temperature degree：60 DEG C, equilibration time：20min.
Evaluation result is shown in Table 2, the results showed that：The thermal expansion prepared by the method for microwave radiation free-radical emulsion polymerization is micro-
The particle diameter distribution of capsule is uniform, and for average grain diameter in 80~800nm, the level of residual monomers of thermal expansion microcapsules is low, has nontoxic, no
It pollutes, product is not dyed, not influencing the advantages that curing and shaping speed, normal pressure, pressure expansion can make uniform in foaming, utilize
The thermal expansion microcapsules that the method for the present invention is prepared have higher expansion ratio, and grain size averagely increases 4~5 after foaming
Times.
The evaluation result of 2 thermal expansion microcapsules of table
Note：ND：It does not detect
The product form and style of above-described embodiment and the non-limiting present invention, the ordinary skill people of any technical field
The appropriate variation or modification that member does it all should be regarded as not departing from the patent category of the present invention.
Claims (7)
1. a kind of ultra-fine environment protection thermal expanding microcapsules, it is characterised in that：By the suspended dispersed of oil phase constituent and water phase composition object
Liquid is made through microwave radiation emulsion polymerization, wherein the mass percent that the oil phase constituent accounts for the suspended dispersed liquid is
10%~40%；
The oil phase constituent includes each component of following parts by weight：Low boiling point alkane is 10~40 parts by weight；Acrylonitrile monemer
For 0~20 parts by weight；(methyl) acrylic ester copolymerization monomer is 50~100 parts by weight；(methyl) acrylic acid and its esters are total to
Polycondensation monomer is 0~20 parts by weight；Styrene co-monomer is 0~100 parts by weight；Oil-soluble initiator is 0.1~1 parts by weight；
Crosslinking agent is 0.1~1 parts by weight；
The water phase composition object includes each component of following parts by weight：Emulsifier is 0.1~5 parts by weight, suspending agent is 0~10 weight
Amount part, polymerization inhibitor are 0.1~1 parts by weight, and inorganic salts are 10~60 parts by weight, and deionized water is 200~400 parts by weight.
2. a kind of ultra-fine environment protection thermal expanding microcapsules according to claim 1, it is characterised in that：The low boiling point alkane is
Carbon number is 4~8 alkane, and the low boiling point alkane includes butane, iso-butane, pentane, isopentane, neopentane, hexane, different
One or any combination in hexane, heptane, isoheptane, octane, isooctane；
(methyl) the acrylic ester copolymerization monomer is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) third
Olefin(e) acid norbornyl ester, N, N- dimethacrylamide, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl)
One kind or any combination in allyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid tetrahydrofurfuryl alcohol ester；
(methyl) acrylic acid and its esters comonomer are methacrylic acid, acrylic acid, magnesinm methacrylate, metering system
One kind or any combination in sour zinc, Sodium methacrylate；
The oil-soluble initiator is the one or any combination in peroxide initiator or azo-initiator；
The crosslinking agent is one in binary acrylic ester monomer, ternary acrylate class monomer, styrene monomer
Kind or any combination.
3. a kind of ultra-fine environment protection thermal expanding microcapsules according to claim 2, it is characterised in that：The peroxide initiator
For dibenzoyl peroxide, either the dilauroyl peroxide azo-initiator is that azodiisobutyronitrile or azo two are different
Heptonitrile；The binary acrylic ester monomer be two-(methyl) acrylate of diethyl (third) glycol, the ternary acrylate class
Monomer is three second (third) glycol, two-(methyl) acrylate, polyethylene glycol two (methyl) acrylate, second (third) aoxidize three hydroxyl first
Base propane three-(methyl) acrylate, methacrylate glyceride or methacrylate bisphenol-A ester；The styrene
Class monomer is divinylbenzene or trivinylbenzene.
4. a kind of ultra-fine environment protection thermal expanding microcapsules according to claim 1, it is characterised in that：The emulsifier is polyoxy
Ethylene nonyl phenolic ether, polyoxyethylene nonyl phenolic ether sodium sulphate, lauryl sodium sulfate, neopelex, tween-20,
Tween-40, tween-60, span-20, span-40, span-60, OP-10, sodium vinyl sulfonate, sodium p styrene sulfonate,
One or any combination in Sodium Allyl Sulfonate；
The suspending agent is high molecular weight water soluble polymer polyvinylpyrrolidone, sodium carboxymethylcellulose, hydroxymethyl cellulose
One or any combination in sodium, polyvinyl alcohol；
The polymerization inhibitor is any one in sodium nitrite, potassium nitrite, sodium hydrogensulfite, potassium ferrate.
5. prepare a kind of preparation of ultra-fine environment protection thermal expanding microcapsules as described in any one of Claims 1 to 4 claim
Method, it is characterised in that：Include the following steps：
(1) water phase is prepared：By the emulsifier of 0.1~5 parts by weight, the suspending agent of 0~10 parts by weight, 10~60 parts by weight it is inorganic
Salt, the polymerization inhibitor of 0.1~1 parts by weight are added in the deionized water of 200~400 parts by weight and disperse, and obtain water phase composition object；
(2) oil phase is prepared：By the low boiling point alkane of 10~40 parts by weight, the acrylonitrile monemer of 0~20 parts by weight, 50~100 weights
Measure (methyl) the acrylic ester copolymerization monomer of part, (methyl) acrylic acid of 0~20 parts by weight and its esters comonomer, 0~
The crosslinking agent of the styrene of 100 parts by weight, the oil-soluble initiator of 0.1~1 parts by weight and 0.1~1 parts by weight is uniformly mixed,
Obtain oil phase constituent；
(3) dispersion liquid is prepared：The oil phase constituent is added in the water phase composition object, at room temperature with 10000r/min~
The mixing speed of 20000r/min, by the mixed liquor of the oil phase constituent and the water phase composition object uniformly emulsification 10~
20min obtains uniform and stable O/W type dispersion liquids；
(4) polymerisation：The O/W types dispersion liquid is placed in microwave reactor, under nitrogen atmosphere, is heated to 60 DEG C~90
DEG C, start emulsion polymerization under the mixing speed of 300r/min~800r/min, react 5h~10h, obtain micro- glue containing thermal expansion
The white suspension of capsule by the filtering of white suspension liquid, is dried to obtain thermal expansion microscapsule powder.
6. a kind of preparation method of ultra-fine environment protection thermal expanding microcapsules according to claim 5, it is characterised in that：Step
(4), it is necessary to remove the monomer residue in the thermal expansion microscapsule powder using post-processing approach after the completion of polymerisation.
7. a kind of preparation method of ultra-fine environment protection thermal expanding microcapsules according to claim 5, it is characterised in that：The heat
The average grain diameter of expanding microcapsules powder is in 80~800nm.
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| CN110721644A (en) * | 2019-10-22 | 2020-01-24 | 北京理工大学 | Radiation preparation method of vinyl polymer microcapsule |
| CN111073027A (en) * | 2019-12-30 | 2020-04-28 | 贵州师范大学 | High-temperature-resistant thermal expansion type foaming microcapsule and preparation method thereof |
| WO2021198487A1 (en) * | 2020-04-03 | 2021-10-07 | Nouryon Chemicals International B.V. | Thermally expandable microspheres prepared from bio-based monomers |
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| WO2021198487A1 (en) * | 2020-04-03 | 2021-10-07 | Nouryon Chemicals International B.V. | Thermally expandable microspheres prepared from bio-based monomers |
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