CN108097182B - Superfine environment-friendly thermal expansion microcapsule and preparation method thereof - Google Patents
Superfine environment-friendly thermal expansion microcapsule and preparation method thereof Download PDFInfo
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- 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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- 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
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- 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
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- 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
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Abstract
The invention discloses a superfine environment-friendly thermal expansion microcapsule, which is prepared by a microwave radiation emulsion polymerization method of a suspension dispersion liquid of an oil phase composition and a water phase composition, has the particle size of submicron level, high foaming multiplying power, environmental protection and no toxicity, and can be applied to the fields of textile, papermaking, printing ink, engineering plastics and the like. The invention also discloses a preparation method of the superfine environment-friendly thermal expansion microcapsule, which is prepared by the microwave radiation free radical emulsion polymerization technology, and has the advantages of simple operation, simple preparation process and high production efficiency.
Description
Technical Field
The invention relates to a thermal expansion microcapsule, in particular to a superfine environment-friendly thermal expansion microcapsule and a preparation method thereof.
Background
The thermally expandable microcapsule is a microcapsule in which a low-boiling physical blowing agent is encapsulated by a thermoplastic polymer shell having good gas barrier properties, and is generally obtained by suspension polymerization of a polymerizable monomer and a blowing agent in a water-soluble dispersion system.
The traditional chemical foaming method is basically adopted in resin foaming, so that the light weight and the regulation and control of the cell structure are realized. However, the problem of surface quality of the foaming material cannot be solved by adopting a chemical foaming method. Whether it is a chemical foaming system or a supercritical physical foaming system, the formation of cells depends on the diffusion of gas, and the associated cell consolidation, coarsening and surface quality problems are also due to the effectively controlled diffusion of gas. The most effective and fundamental method for solving the surface quality problem is to adopt the thermal expansion microcapsule for foaming, the method not only can effectively control the diffusion of foaming agent gas, but also has simple processing, wide processing window, easier control of the cell structure and low cost.
The thermal expansion microcapsule as a foaming agent has no decomposition residue, no obvious gas diffusion, no reduction of the surface quality of the foaming material, low cost, simple processing and no need of high pressure and high pressure reduction rate. However, the size of the currently available thermal expansion microcapsules is 10-50 μm, the size of the microcapsules after heating expansion can reach 40-250 μm, and the size is too large for a microporous polymer, so that the microcapsules can only be used for preparing a common foaming material and cannot be used for preparing a microporous polymer material.
The average diameter of the thermal expansion microcapsules prepared by the invention patent CN102633936A through suspension polymerization of acrylonitrile and (methyl) acrylic monomers is more than 30 μm. The microspheres obtained in patent publication CN105555851A entitled "method for producing thermally expandable microspheres" had an average diameter of greater than 20 μm. The particle size of the heat expandable microcapsules formed by the suspension polymerization technique of foreign patent EP2529830 is greater than 20 μm. In foreign patent US8247465 it is described that the particle size of the heat expandable microcapsules prepared by suspension polymerization is greater than 20 μm.
Therefore, in the existing preparation technology, the particle size of the thermal expansion microcapsule prepared by the suspension polymerization method can not obtain a product in a submicron level.
Disclosure of Invention
The invention aims to provide a superfine environment-friendly thermal expansion microcapsule which has submicron particle size, high foaming ratio, environmental protection and no toxicity and can be applied to the fields of textile, papermaking, printing ink, engineering plastics and the like.
The invention aims to provide a preparation method of superfine environment-friendly thermal expansion microcapsules, which is prepared by microwave radiation free radical emulsion polymerization technology, and has the advantages of simple operation, simple preparation process and high production efficiency.
In order to achieve the above purpose, the solution of the invention is:
a superfine environment-friendly thermal expansion microcapsule is prepared by a microwave radiation emulsion polymerization method of a suspension dispersion liquid of an oil phase composition and a water phase composition, wherein the oil phase composition accounts for 10-40% of the suspension dispersion liquid by mass percent;
the oil phase composition comprises the following components in parts by weight: 10-40 parts by weight of low-boiling-point alkane; 0-20 parts by weight of acrylonitrile monomer; 50-100 parts by weight of (meth) acrylate comonomer; 0-20 parts by weight of (meth) acrylic acid and its salt comonomer; 0-100 parts by weight of styrene comonomer; 0.1-1 part by weight of an oil-soluble initiator; 0.1-1 part by weight of a crosslinking agent;
the water phase composition comprises the following components in parts by weight: 0.1-5 parts of emulsifier, 0-10 parts of suspending agent, 0.1-1 part of polymerization inhibitor, 10-60 parts of inorganic salt and 200-400 parts of deionized water.
The low-boiling-point alkane is an alkane with 4-8 carbon atoms, and the low-boiling-point alkane comprises one or any combination of butane, isobutane, pentane, isopentane, neopentane, hexane, isohexane, heptane, isoheptane, octane and isooctane;
the (methyl) acrylate comonomer is one or any combination of methyl (methyl) acrylate, ethyl (methyl) acrylate, norbornyl (methyl) acrylate, N-dimethylacrylamide, hydroxyethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate, allyl (methyl) acrylate, glycidyl (methyl) acrylate and tetrahydrofurfuryl (methyl) acrylate;
the (methyl) acrylic acid and the (methyl) acrylic acid salt comonomer are one or any combination of methacrylic acid, acrylic acid, magnesium methacrylate, zinc methacrylate and sodium methacrylate;
the oil-soluble initiator is one or any combination of a peroxy initiator or an azo initiator;
the cross-linking agent is selected from one or any combination of binary acrylate monomers, ternary acrylate monomers and styrene monomers.
The peroxy initiator is dibenzoyl peroxide or dilauroyl peroxide, and the azo initiator is azobisisobutyronitrile or azobisisoheptonitrile;
the binary acrylate monomer is diethylene glycol di- (methyl) acrylate, and the ternary acrylate monomer is triethylene glycol di- (methyl) acrylate, polyethylene glycol di (methyl) acrylate, ethylene (propylene) oxide trimethylolpropane tri- (methyl) acrylate, glycerol dimethacrylate or bisphenol A dimethacrylate;
the styrene monomer is divinylbenzene or trivinylbenzene.
The emulsifier is one or any combination of polyoxyethylene nonylphenol ether, polyoxyethylene nonylphenol ether sodium sulfate, sodium dodecyl benzene sulfonate, tween-20, tween-40, tween-60, span-20, span-40, span-60, OP-10, sodium vinyl sulfonate, sodium p-styrene sulfonate and sodium allyl sulfonate;
the suspending agent is one or any combination of water-soluble high molecular polymer polyvinylpyrrolidone, sodium carboxymethylcellulose and polyvinyl alcohol;
the polymerization inhibitor is any one of sodium nitrite, potassium nitrite, sodium bisulfite and potassium ferrate.
A preparation method of an ultrafine environment-friendly thermal expansion microcapsule comprises the following steps:
(1) preparing an aqueous phase: adding 0.1-5 parts by weight of emulsifier, 0-10 parts by weight of suspending agent, 10-60 parts by weight of inorganic salt and 0.1-1 part by weight of polymerization inhibitor into 200-400 parts by weight of deionized water and dispersing to obtain a water-phase composition;
(2) preparing an oil phase: uniformly mixing 10-40 parts by weight of low-boiling-point alkane, 0-20 parts by weight of acrylonitrile monomer, 50-100 parts by weight of (methyl) acrylate comonomer, 0-20 parts by weight of (methyl) acrylic acid and salt comonomer thereof, 0-100 parts by weight of styrene, 0.1-1 part by weight of oil-soluble initiator and 0.1-1 part by weight of cross-linking agent to obtain an oil phase composition;
(3) preparing a dispersion liquid: adding the oil phase composition into the water phase composition, and uniformly emulsifying the mixed solution of the oil phase composition and the water phase composition at room temperature at a stirring speed of 10000 r/min-20000 r/min for 10-20 min to obtain a uniform and stable O/W type dispersion liquid;
(4) polymerization reaction: and (2) placing the O/W type dispersion liquid in a microwave reactor, heating to 60-90 ℃ under the nitrogen atmosphere, starting emulsion polymerization at the stirring speed of 300-800 r/min, reacting for 5-10 h to obtain white suspension containing the thermal expansion microcapsules, and filtering and drying the white suspension to obtain thermal expansion microcapsule powder.
After the polymerization reaction in the step (4) is completed, a post-treatment method is adopted to remove the monomer residues in the thermal expansion microcapsule powder.
The average particle size of the thermal expansion microcapsule powder is 80-800 nm.
After the technical scheme is adopted, the ultrafine environment-friendly thermal expansion microcapsule is prepared by polymerizing a microwave radiation emulsion by taking an acrylonitrile monomer and (methyl) acrylate as comonomers, a cross-linking agent as a capsule wall and low-boiling-point alkane as a core material, and has the following beneficial effects:
(1) the invention is based on microwave radiation free radical emulsion polymerization technology to prepare thermal expansion microcapsules, has simple and convenient operation, simple preparation process and high production efficiency, and shortens the polymerization time by 5 to 15 hours compared with the common polymerization reaction;
(2) the microwave radiation polymerization reaction is adopted, so that the method has the characteristics of high polymerization rate, high monomer conversion rate, cleanness, energy conservation, easy system control, environmental protection and high benefit;
(3) the heat expansion microcapsule prepared by the microwave radiation free radical emulsion polymerization method has uniform particle size distribution, the average particle size is 80-800 nm, the micropore size of the ultramicropore polymer material produced by adopting the heat expansion microcapsule after foaming is distributed in the range of 150-800 nm, and the ultramicropore polymer material has a compact surface, is beneficial to improving the surface quality of the micropore material, increases the aesthetic property of the product, reduces the density of the product, and expands the application range of the heat expansion microcapsule;
(4) the thermal expansion microcapsule prepared by the method has low monomer residue, has the advantages of no toxicity, no pollution, no dyeing to products, no influence on curing and forming speed and the like, and can foam uniformly under normal pressure and pressurization;
(5) the thermal expansion microcapsule prepared by the method has higher foaming ratio, and the average particle size after foaming is increased by 4-5 times.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Preparation of thermal expansion microcapsule
Example 1
A preparation method of an ultrafine environment-friendly thermal expansion microcapsule comprises the following steps:
(1) preparing an aqueous phase: adding 0.2 part by weight of tween-20, 0.5 part by weight of Span-60, 5 parts by weight of polyvinylpyrrolidone, 60 parts by weight of sodium chloride and 0.2 part by weight of sodium nitrite into 400 parts by weight of deionized water and dispersing to obtain an aqueous phase composition;
(2) preparing an oil phase: uniformly mixing 10 parts by weight of isopentane, 30 parts by weight of isooctane, 20 parts by weight of acrylonitrile monomer, 80 parts by weight of methyl methacrylate, 1 part by weight of dilauroyl peroxide and 1 part by weight of trimethylolpropane trimethacrylate to obtain an oil phase composition;
(3) preparing a dispersion liquid: adding the oil phase composition into the water phase composition, and uniformly emulsifying the mixed solution of the oil phase composition and the water phase composition at room temperature at a stirring speed of 15000r/min for 15min to obtain uniform and stable O/W type dispersion;
(4) polymerization reaction: placing the O/W type dispersion liquid in a microwave reactor, heating to 75 ℃ under the nitrogen atmosphere, starting emulsion polymerization at the stirring speed of 550r/min, reacting for 7.5h to obtain white suspension liquid containing the thermal expansion microcapsules, and filtering and drying the white suspension liquid to obtain white thermal expansion microcapsule powder.
After the polymerization reaction in the step (4) is completed, a post-treatment method is needed to remove the monomer residues in the thermal expansion microcapsule powder.
Examples 2 to 10
The conditions were the same as in example 1 except that the kinds and amounts of the components in the oil phase composition were changed, and see table 1 for details.
Comparative example 1
The difference from example 1 is that: placing the O/W type dispersion liquid in a high-pressure reaction kettle, heating to 75 ℃ under the nitrogen atmosphere of 0.5MPa, starting emulsion polymerization at the stirring speed of 550r/min, reacting for 25h to obtain white suspension containing the thermal expansion microcapsules, and filtering and drying the white suspension to obtain white thermal expansion microcapsule powder.
Comparative example 2
The difference from example 3 is that: placing the O/W type dispersion liquid in a high-pressure reaction kettle, heating to 75 ℃ under the nitrogen atmosphere of 0.5MPa, starting emulsion polymerization at the stirring speed of 550r/min, reacting for 25h to obtain white suspension containing the thermal expansion microcapsules, and filtering and drying the white suspension to obtain white thermal expansion microcapsule powder.
Comparative example 3
The difference from example 10 is that: placing the O/W type dispersion liquid in a high-pressure reaction kettle, heating to 75 ℃ under the nitrogen atmosphere of 0.5MPa, starting emulsion polymerization at the stirring speed of 550r/min, reacting for 25h to obtain white suspension containing the thermal expansion microcapsules, and filtering and drying the white suspension to obtain white thermal expansion microcapsule powder.
TABLE 1 type and amount of oil phase composition
Note: MAA in the table: methacrylic acid; MMA: methyl methacrylate; MA: methyl acrylate; st: styrene; TMPTMA: trimethylolpropane trimethacrylate; EGDMA: ethylene glycol dimethacrylate; DVB (digital video broadcasting): divinylbenzene; PEG (200) DMA: polyethylene glycol (200) dimethacrylate; LPO: dilauroyl peroxide; BPO: dibenzoyl peroxide; AIBN: azobisisobutyronitrile; ABVN: azobisisoheptonitrile; IB: isobutane; IP: isopentane; IH: isohexane; IO: isooctane.
Second, evaluation of thermally expandable microcapsules
1. Particle size distribution
The particle size distribution of the heat-expandable microcapsules was measured by an LS909 laser particle size analyzer manufactured by Oumec corporation to measure the average particle size distribution (D50).
2. Analysis of foaming Properties
The foaming initiation temperature (T) was measured using a Q400 static thermomechanical analyzer manufactured by TA instrumentsstart) Maximum displacement (D)max) And maximum foaming temperature (T)max). Specifically, 0.5mg of the sample was placed in an aluminum crucible having a diameter of 6.4mm and a depth of 4mm, and the sample was heated from 30 ℃ to 300 ℃ at a temperature increase rate of 5 ℃/min under a condition that a force of 0.06N was applied from the upper surface, and the powder was moved vertically by a measuring probe.
After the heat-expandable microcapsules were heated uniformly by heating with hot air and foamed, the particle size distribution D after foaming was measured by an LS909 laser particle size analyzer manufactured by Oumec corporationHeatParticle size distribution before heating DpreExpansion ratio of Dheat/Dpre。
3. Analysis of residual amount of monomer
And (3) post-treatment: after the polymerization reaction is finished, when the temperature is reduced to 30 ℃, under the nitrogen atmosphere, adding tert-butyl hydroperoxide, stirring at room temperature for 10min, adding sodium bisulfite, increasing the pressure to 0.6MPa, then heating to 60 ℃, reacting for 7h, when the temperature is reduced to 30 ℃ after the reaction is finished, discharging, centrifuging, drying, and removing the monomer residues in the thermal expansion microcapsule powder.
Measurement of monomer residue in the heat-expandable microcapsule powder after treatment: using a GC2014C gas chromatograph manufactured by shimadzu corporation, chromatographic conditions: the initial temperature is 40 ℃, the temperature is kept for 1min, the temperature is increased to 100 ℃ at the speed of 5 ℃/min, the temperature is kept for 2min, the temperature is increased to 200 ℃ at the speed of 6 ℃/min, and the temperature is kept for 5 min. The temperature of the detector is 250 ℃; injector temperature 225 ℃. Oil phase headspace temperature: 80 ℃; water phase headspace temperature: 60 ℃, equilibration time: and 20 min.
The evaluation results are shown in Table 2, and the results show that: the thermal expansion microcapsules prepared by the microwave radiation free radical emulsion polymerization method have uniform particle size distribution, the average particle size is 80-800 nm, the monomer residue of the thermal expansion microcapsules is low, the thermal expansion microcapsules have the advantages of no toxicity, no pollution, no dyeing to products, no influence on curing and forming speed and the like, the foaming can be uniform under normal pressure and pressurization, the thermal expansion microcapsules prepared by the method have higher foaming multiplying power, and the average particle size after foaming is increased by 4-5 times.
Table 2 evaluation results of thermally expandable microcapsules
Note: ND: not detected out
The above embodiments are not intended to limit the form and style of the present invention, and any suitable changes or modifications made by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (4)
1. An ultrafine environment-friendly thermal expansion microcapsule is characterized in that: the microwave radiation emulsion is prepared from a suspension dispersion liquid of an oil phase composition and a water phase composition by a microwave radiation emulsion polymerization method, wherein the oil phase composition accounts for 10-40% of the suspension dispersion liquid by mass percent;
the oil phase composition comprises the following components in parts by weight: 10-40 parts by weight of low-boiling-point alkane; 0-20 parts by weight of acrylonitrile monomer; 50-100 parts by weight of (meth) acrylate comonomer; 0-20 parts by weight of (meth) acrylic acid and its salt comonomer; 0-100 parts by weight of styrene comonomer; 0.1-1 part by weight of an oil-soluble initiator; 0.1-1 part by weight of a crosslinking agent;
the water phase composition comprises the following components in parts by weight: 0.1-5 parts by weight of emulsifier, 0-10 parts by weight of suspending agent, 0.1-1 part by weight of polymerization inhibitor, 10-60 parts by weight of inorganic salt and 200-400 parts by weight of deionized water;
the low-boiling-point alkane is an alkane with 4-8 carbon atoms, and the low-boiling-point alkane comprises one or any combination of butane, isobutane, pentane, isopentane, neopentane, hexane, isohexane, heptane, isoheptane, octane and isooctane;
the (methyl) acrylate comonomer is one or any combination of methyl (methyl) acrylate, ethyl (methyl) acrylate, norbornyl (methyl) acrylate, N-dimethylacrylamide, hydroxyethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate, allyl (methyl) acrylate, glycidyl (methyl) acrylate and tetrahydrofurfuryl (methyl) acrylate;
the (methyl) acrylic acid and the (methyl) acrylic acid salt comonomer are one or any combination of methacrylic acid, acrylic acid, magnesium methacrylate, zinc methacrylate and sodium methacrylate;
the oil-soluble initiator is one or any combination of a peroxy initiator or an azo initiator; the cross-linking agent is selected from one or any combination of binary acrylate monomers, ternary acrylate monomers and styrene monomers;
the styrene monomer is divinylbenzene or trivinylbenzene;
the preparation method of the superfine environment-friendly thermal expansion microcapsule comprises the following steps:
(1) preparing an aqueous phase: adding 0.1-5 parts by weight of emulsifier, 0-10 parts by weight of suspending agent, 10-60 parts by weight of inorganic salt and 0.1-1 part by weight of polymerization inhibitor into 200-400 parts by weight of deionized water and dispersing to obtain a water-phase composition;
(2) preparing an oil phase: uniformly mixing 10-40 parts by weight of low-boiling-point alkane, 0-20 parts by weight of acrylonitrile monomer, 50-100 parts by weight of (methyl) acrylate comonomer, 0-20 parts by weight of (methyl) acrylic acid and salt comonomer thereof, 0-100 parts by weight of styrene, 0.1-1 part by weight of oil-soluble initiator and 0.1-1 part by weight of cross-linking agent to obtain an oil phase composition;
(3) preparing a dispersion liquid: adding the oil phase composition into the water phase composition, and uniformly emulsifying the mixed solution of the oil phase composition and the water phase composition at room temperature at a stirring speed of 10000 r/min-20000 r/min for 10-20 min to obtain a uniform and stable O/W type dispersion liquid;
(4) polymerization reaction: placing the O/W type dispersion liquid in a microwave reactor, heating to 60-90 ℃ under the nitrogen atmosphere, starting emulsion polymerization at the stirring speed of 300-800 r/min, reacting for 5-10 h to obtain a white suspension containing the thermal expansion microcapsules, filtering and drying the white suspension to obtain thermal expansion microcapsule powder, wherein the average particle size of the thermal expansion microcapsule powder is 80-800 nm.
2. The environment-friendly ultrafine thermal expansion microcapsule according to claim 1, wherein: the peroxy initiator is dibenzoyl peroxide or dilauroyl peroxide, and the azo initiator is azobisisobutyronitrile or azobisisoheptonitrile; the binary acrylate monomer is diethylene glycol di- (methyl) acrylate, and the ternary acrylate monomer is triethylene glycol di- (methyl) acrylate, polyethylene glycol di (methyl) acrylate, ethylene (propylene) oxide trimethylolpropane tri- (methyl) acrylate, glyceryl dimethacrylate or bisphenol A dimethacrylate.
3. The environment-friendly ultrafine thermal expansion microcapsule according to claim 1, wherein: the emulsifier is one or any combination of polyoxyethylene nonylphenol ether, polyoxyethylene nonylphenol ether sodium sulfate, sodium dodecyl benzene sulfonate, tween-20, tween-40, tween-60, span-20, span-40, span-60, OP-10, sodium vinyl sulfonate, sodium p-styrene sulfonate and sodium allyl sulfonate;
the suspending agent is one or any combination of water-soluble high molecular polymer polyvinylpyrrolidone, sodium carboxymethylcellulose and polyvinyl alcohol;
the polymerization inhibitor is any one of sodium nitrite, potassium nitrite, sodium bisulfite and potassium ferrate.
4. The environment-friendly ultrafine thermal expansion microcapsule according to claim 1, wherein: after the polymerization reaction in the step (4) is completed, a post-treatment method is adopted to remove the monomer residues in the thermal expansion microcapsule powder.
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| CN109970466A (en) * | 2019-03-29 | 2019-07-05 | 东莞市泰赛特汽车用品科技有限公司 | A kind of environmental protection brick face antilubricant and preparation method thereof |
| 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 |
| BR112022018378A2 (en) * | 2020-04-03 | 2022-11-08 | Nouryon Chemicals Int Bv | THERMOPLASTIC POLYMERIC MICROSPHERES, PROCESS FOR PREPARING THERMOPLASTIC POLYMERIC MICROSPHERES, METHOD FOR THE PRODUCTION OF EXPANDED THERMOPLASTIC POLYMERIC MICROSPHERES AND USE OF THERMOPLASTIC POLYMERIC MICROSPHERES |
| JP2023519741A (en) * | 2020-04-03 | 2023-05-12 | ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップ | Thermally expandable microspheres prepared from bio-based monomers |
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