CN103537238B - Preparation method of residual emulsifying agent-free flame-retardant phase-change material capsule - Google Patents
Preparation method of residual emulsifying agent-free flame-retardant phase-change material capsule Download PDFInfo
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Abstract
The invention discloses a preparation method of a residual emulsifying agent-free flame-retardant phase-change material capsule. The preparation method comprises the following steps of: heating a core material to be higher than a phase-change temperature point to melt, and mixing the core material with an initiator and a wall material precursor to get a dispersed phase; adding a polymerizable emulsifying agent into deionized water to obtain a continuous phase; mixing the dispersed phase with the continuous phase, and performing high-speed shearing emulsification; carrying out polymerization reaction on the mixed liquid, and adding the polymerizable emulsifying agent halfway; cooling, centrifugally separating, washing, and drying under vacuum condition to obtain the residual emulsifying agent-free flame-retardant phase-change material capsule. The preparation method of the residual emulsifying agent-free flame-retardant phase-change material capsule has the advantages that the flame-retardant polymer is copolymerized from the wall material through free radical polymerization, the preparation method is simple, the conditions are mild, the prepared phase-change material capsule is flame-retardant and free of residual emulsifying agent, environmental pollution caused by the emulsifying agent is eliminated, phase-change temperature is adjustable, and the preparation method is green and environment-friendly, and is suitable for industrial large-scale production.
Description
Technical field
The present invention relates to a kind of intelligent temperature control material, particularly a kind of preparation method with the phase-change material capsule of flame-retardant nature.
Background technology
Phase-change material refer to a kind of can self undergoes phase transition according to the change of ambient temperature, release simultaneously or absorb heat and own temperature is constant or change little material.Be latent heat storage material again.Phase-change material can be divided into solid-solid phase transition material, solid-liquid phase change material, solid-gas phase-change material and liquid-gas phase-change material four kinds by the mode of phase transformation.Exist owing to being attended by gas during the phase transformation of latter two phase-change material, Volume Changes is large, although therefore they have very large enthalpy of phase change, practical application is little.Solid-solid phase transition material because kind is few, easy aging, the factor such as easy firing, the capacity of heat transmission are poor, enthalpy is low, practical application product is also considerably less.Comparatively speaking, solid-liquid phase change material enthalpy is large, kind is many, moderate, the most extensive in actual applications.But solid-liquid phase change material is Shortcomings also, expand when phase transformation or shrink, can leak time liquid, high to containers demand.
Phase-change material capsule utilizes microencapsulation technology to be undertaken coated by phase-change material, obtains the composite with nucleocapsid structure.Phase-change material capsule efficiently solve solid-liquid phase change material very easily melt-flow, infiltration migration, be separated, the problem such as burn into pyroconductivity is low, and remain the essential advantage of solid-liquid phase change material intelligent temperature control.Therefore phase-change material capsule is also widely used in the field such as building energy conservation, weaving dress ornament, functional thermal fluid, solar energy, Aero-Space, medical treatment, electronic device.Meanwhile, phase-change material capsule is also the focus of research both at home and abroad, and the phase-change material capsule of various shell material is successfully synthesized.
A kind of microcapsule coated phase-change material and preparation method thereof (country origin: China, publication number: 1513938, publication date: 2004-7-21) disclose with melamine and formaldehyde for presoma, adopt situ aggregation method prepare with aliphatic hydrocarbon compound and ester type compound be core, the melamine resin phase-change material micro-capsule that is shell material.Phase-change material micro-capsule core content prepared by the method is high, compactness good, but limits by technique, inevitable residual carcinogen formaldehyde in product.
A kind of preparation method of phase-change energy-storage nano capsule powder and application (country origin: China thereof, publication number: 101480596, publication date: 2009-7-15) to disclose a kind of be filmogen using alkanes as phase-change material, styrene, with lauryl sodium sulfate and non-ionic surface active agent APES (OP-10) for emulsifying agent, fine emulsion polymerization is adopted to prepare the method for phase-change material Na capsule.But the anti-flammability of not mentioned phase-change material capsule, and the restriction by polymerization technique in prepared product unavoidably carries residual emulsifying agents, and cannot remove completely, affect the follow-up use of phase-change material capsule, when such as phase-change material capsule and coating being mixed to get phase change energy storage paint, the emulsifying agent that phase-change material capsule remains often causes the negatively influencings such as bubble.
A kind of preparations and applicatio method (country origin: China, publication number: 103212351A, publication date: 2013-7-24) of high heat conductive flame-retarding phase-change microcapsule discloses a kind of preparations and applicatio method of high heat conductive flame-retarding phase-change microcapsule.Its preparation method takes in core, add fire retardant chlorinated paraffin wax and high heat conductive flame-retarding material, then be presoma with vinyl monomer, obtains the phase-change material capsule with fire-retardant and high heat conduction after polymerization.Although this preparation method can obtain the phase-change material capsule with anti-flammability, but, in order to ensure that phase-change material micro-capsule shell material has certain intensity, adding of fire retardant result in the reduction of phase-change material core content, thus under square one, prepared phase-change material micro-capsule phase transformation enthalpy is on the low side.
A kind of interfacial polymerization Manufacturing approach and use (country origin: China of functional Na capsule slurries, publication number: 102172502A, publication date: 2011-9-7) although expect making phase-change material capsule have fire resistance, but this invention adopts interfacial polymerization, reaction speed is fast, wayward, and also not mentioned removal product residual emulsifying agents problem.
Summary of the invention
Goal of the invention: for the problems referred to above, the object of this invention is to provide a kind of simple to operate, size is controlled, can suitability for industrialized production, there is the preparation method of phase-change material capsule of fire resistance, product noresidue emulsifying agent, the easy purifying of product.
Technical scheme: the preparation method of the fire-retardant phase-change material capsule of a kind of noresidue emulsifying agent, comprises the following steps:
(1) phase-change material core being heated to more than phase transformation temperature points keeps 1h to make it thoroughly melt, then mixes with initator and wall material presoma, stirs and obtains decentralized photo;
Wherein, core and wall material presoma weigh proportioning in mass ratio at 3: 7 ~ 8: 2, core phase transformation temperature points according to core material at-26 DEG C ~ 70 DEG C, initator is 0.5% ~ 5% of wall material presoma, wall material presoma comprises flame-retardant monomer and reaction monomers, flame-retardant monomer is 10% ~ 50% of decentralized photo, and reaction monomers is 20% ~ 60% of decentralized photo; Above percentage is mass percent;
(2) polymerizable emulsifier is joined in deionized water, stir 1h with 1000rpm and obtain continuous phase; Wherein, polymerizable emulsifier is 1.5% ~ 10% of decentralized photo, and above percentage is mass percent;
(3) by decentralized photo and continuous phase 1: 4 ~ 1: 10 mixing in mass ratio, carry out high speed shear emulsification with 1000rpm ~ 20000rpm, the time is 20min, obtains mixed liquor;
(4) mixed liquor is warmed up to 60 DEG C ~ 80 DEG C and carries out polymerisation 5 ~ 24h, and then be warmed up to 90 DEG C of continuation reaction 3h; Wherein, when the polymerisations of 60 DEG C ~ 80 DEG C proceed to 3h, add described polymerizable emulsifier, additional amount is 0.1% ~ 2% of decentralized photo, and above percentage is mass percent;
(5) after system cools naturally, centrifugation product, and wash more than 3 times respectively with deionized water and ethanol, obtain the fire-retardant phase-change material capsule of noresidue emulsifying agent after vacuum drying.
Described core is one or more following combination according to phase transformation temperature points: n-undecane, n-tridecane, n-tetradecane, n-pentadecane, hexadecane, n-heptadecane, n-octadecane, NSC 77136, n-eicosane, Heneicosane, n-tricosane, n-tetracosane, pentacosane, n-hexacosane, heptacosane, positive octacosane, positive nonacosane, positive hentriacontane; The positive butyl ester of stearic acid, dodecylic acid; Technical grade product, comprises 5# phase-change wax, 15# phase-change wax, 20# phase-change wax, 25# phase-change wax, 30# phase-change wax, 40# phase-change wax, 70# phase-change wax.
Described polymerizable emulsifier is one or more following combination: sodium p styrene sulfonate, octadecyldimethyl vinyl phenyl ammonium chloride, ALS, alpha-olefin sodium sulfonate.Be preferably sodium p styrene sulfonate.
Polymerizable emulsifier is embedded on capsule wall by the mode of covalent bond is permanent, avoid occurring that the conventional emulsifiers such as lauryl sodium sulfate, neopelex, softex kw come off from capsule surface desorb and affect resistance to water, the chemical resistance of follow-up glued membrane, coated to core of wall material can be promoted, increase the compactness of wall material, in removal product, emulsifying agent is residual, the easy purifying of product; Simultaneously, conventional emulsifier only plays emulsification in polymerization, after being polymerized, containing a large amount of emulsifying agent in mother liquor, not only be difficult to reclaim, and be difficult to degraded, to environment, and while polymerizable emulsifier plays emulsification in polymerization, participate in free-radical polymerized, after being polymerized, only containing minute quantity emulsifying agent in mother liquor, environment is polluted hardly.
Described initator is one or more following combination: azodiisobutyronitrile, ABVN, dibenzoyl peroxide.Be preferably azodiisobutyronitrile.
Described flame-retardant monomer is one or more following combination: containing halogen class vinyl monomer, comprises dichlorostyrene, 1,2-dichloroethene, the bromo-1-propylene of 3-, isoprenyl bromide, 2-bromstyrol; Phosphorous vinyl monomer, comprises vinyl phosphonic diethyl phthalate, two trimethylsilyl vinyl phosphate, vinyl phosphoric acid; The phosphorous functional acrylic monomer PAM100 of suitability for industrialized production.Be preferably phosphorous vinyl monomer, good environmental protection.
Described reaction monomers is two or more following combination: the just own ester of styrene, methyl methacrylate, n-butyl acrylate, methacrylic acid, n-butyl acrylate, acrylic acid, isobutyl acrylate, tert-butyl acrylate, isopropyl methacrylate, acrylic acid.Be preferably styrene and methacrylic acid.
The inventive method, by controlling the mass ratio of core and wall material presoma, obtains the phase-change material capsule of different core content, obtains different phase transformation enthalpies simultaneously; By controlling the ratio of flame-retardant monomer and reaction monomers, obtain the phase-change material capsule that fire resistance is different; By controlling polymerizable emulsifier and emulsification pretreatment speed, the size of regulation and control phase-change material capsule; By controlling the phase transition temperature of core, control the temperature of final phase-change material capsule.
The fire-retardant phase-change material capsule of noresidue emulsifying agent obtained by the present invention, belongs to composite material of core-shell structure.Core is the alkanes material of different phase transition temperature, fatty acid ester material, technical grade phase-change wax or their mixture mainly, and wall material is the organic high molecular polymer containing flame-retardant polymer.Particle is spherical, and particle diameter is 200nm ~ 50 μm, phase transformation enthalpy at 50J/g ~ 190J/g, size tunable.
Beneficial effect: compared with prior art, advantage of the present invention is from wall material copolymerization flame-retardant polymer by radical polymerization, preparation method is simple, mild condition, obtained phase-change material capsule has fire resistance, not containing residual emulsifying agents, eliminate emulsifying agent to the pollution of environment, phase transition temperature is adjustable, environmental protection, is applicable to industrialization large-scale production.
Detailed description of the invention
Below in conjunction with specific embodiment, illustrate the present invention further, these embodiments should be understood only be not used in for illustration of the present invention and limit the scope of the invention, after having read the present invention, the amendment of those skilled in the art to the various equivalent form of value of the present invention has all fallen within the application's claims limited range.
Embodiment 1: take 60g n-octadecane and be heated to 40 DEG C of constant temperature and keep 1h to make it thoroughly melt, stir obtain uniform decentralized photo with 0.4g azodiisobutyronitrile, 10g vinyl phosphonic diethyl phthalate, 25g styrene, 5g methacrylic acid.Take 2g sodium p styrene sulfonate, join in 400g deionized water, stir 1h with 1000rpm and obtain uniform continuous phase.Above-mentioned decentralized photo and continuous phase mixing, under 10000rpm rotating speed, high speed shear emulsification 20min, obtains mixed liquor.Mixed liquor is warmed up to 70 DEG C and carries out polymerisation, after 3h, add 1g sodium p styrene sulfonate, continue reaction 5h, and then reaction system is warmed up to 90 DEG C of reaction 3h.Treat after having reacted that system cools naturally, centrifugation goes out product, washs more than 3 times respectively with deionized water and ethanol, and dry under vacuo, and obtaining particle diameter is 1 μm ~ 5 μm fire-retardant phase-change material capsules, phase transformation enthalpy 135J/g.
Embodiment 2: take 50g n-eicosane and be heated to 50 DEG C of constant temperature and keep 1h to make it thoroughly melt, stir with 0.8g ABVN, 20g dichlorostyrene, 25g methyl methacrylate, 5g acrylic acid and obtain uniform decentralized photo.Take 10g sodium p styrene sulfonate, join in 1000g deionized water, stir 1h with 1000rpm and obtain uniform continuous phase.Above-mentioned decentralized photo and continuous phase mixing, under 20000rpm rotating speed, high speed shear emulsification 20min, obtains mixed liquor.Mixed liquor is warmed up to 70 DEG C and carries out polymerisation, after 3h, add 2g sodium p styrene sulfonate, continue reaction 3h, and then reaction system is warmed up to 90 DEG C of reaction 3h.Treat after having reacted that system cools naturally, centrifugation goes out product, washs more than 3 times respectively with deionized water and ethanol, and dry under vacuo, and obtaining particle diameter is 200nm ~ 1 μm fire-retardant phase-change material capsule, phase transformation enthalpy 135J/g.
Embodiment 3: take NSC 77136, the positive butyl ester of stearic acid altogether 70g be heated to 40 DEG C of constant temperature and keep 1h to make it thoroughly melt, stir with 0.3g ABVN, 5g vinyl phosphonate, 25g styrene, 1g methacrylic acid and obtain uniform decentralized photo.Take 3g ALS, join in 400g deionized water, stir 1h with 1000rpm and obtain uniform continuous phase.Above-mentioned decentralized photo and continuous phase mixing, under 1000rpm rotating speed, high speed shear emulsification 20min, obtains mixed liquor.Mixed liquor is warmed up to 70 DEG C and carries out polymerisation, after 3h, add 0.2g ALS, continue reaction 9h, and then reaction system is warmed up to 90 DEG C of reaction 3h.Treat after having reacted that system cools naturally, centrifugation goes out product, washs more than 3 times respectively with deionized water and ethanol, and dry under vacuo, and obtaining particle diameter is 10 μm ~ 50 μm fire-retardant phase-change material capsules, phase transformation enthalpy 135J/g.
Embodiment 4: take the positive hentriacontane of 50g and be heated to 80 DEG C of constant temperature and keep 1h to make it thoroughly melt, stir with 0.5g dibenzoyl peroxide, 15g, 35g methyl methacrylate, 1g isobutyl acrylate and obtain uniform decentralized photo.Take 1g ALS, join in 500g deionized water, stir 1h with 1000rpm and obtain uniform continuous phase.Above-mentioned decentralized photo and continuous phase mixing, under 6000rpm rotating speed, high speed shear emulsification 20min, obtains mixed liquor.Mixed liquor is warmed up to 75 DEG C and carries out polymerisation, after 3h, add 1g ALS, continue reaction 21h, and then reaction system is warmed up to 90 DEG C of reaction 3h.Treat after having reacted that system cools naturally, centrifugation goes out product, washs more than 3 times respectively with deionized water and ethanol, and dry under vacuo, and obtaining particle diameter is 4 μm ~ 20 μm fire-retardant phase-change material capsules, phase transformation enthalpy 110J/g.
Embodiment 5: take 50g n-octadecane and be heated to 50 DEG C of constant temperature and keep 1h to make it thoroughly melt, stir with 0.5g dibenzoyl peroxide, 20g dichlorostyrene, 30g styrene, 2g acrylic acid and obtain uniform decentralized photo.Take 2g octadecyldimethyl vinyl phenyl ammonium chloride, join in 500g deionized water, stir 1h with 1000rpm and obtain uniform continuous phase.Above-mentioned decentralized photo and continuous phase mixing, under 10000rpm rotating speed, high speed shear emulsification 20min, obtains mixed liquor.Mixed liquor is warmed up to 75 DEG C and carries out polymerisation, after 3h, add 0.5g octadecyldimethyl vinyl phenyl ammonium chloride, continue reaction 21h, and then reaction system is warmed up to 90 DEG C of reaction 3h.Treat after having reacted that system cools naturally, centrifugation goes out product, washs more than 3 times respectively with deionized water and ethanol, and dry under vacuo, and obtaining particle diameter is 1 μm ~ 10 μm fire-retardant phase-change material capsules, phase transformation enthalpy 120J/g.
Embodiment 6: take 40g n-heptadecane and be heated to 45 DEG C of constant temperature and keep 1h to make it thoroughly melt, stir with 2.4g azodiisobutyronitrile, 30g1,2-dichloroethylene, 30g methyl methacrylate, 1g methacrylic acid and obtain uniform decentralized photo.Take 4g sodium p styrene sulfonate, join in 800g deionized water, stir 1h with 1000rpm and obtain uniform continuous phase.Above-mentioned decentralized photo and continuous phase mixing, under 15000rpm rotating speed, high speed shear emulsification 20min, obtains mixed liquor.Mixed liquor is warmed up to 72 DEG C and carries out polymerisation, after 3h, add 1g sodium p styrene sulfonate, continue reaction 9h, and then reaction system is warmed up to 90 DEG C of reaction 3h.Treat after having reacted that system cools naturally, centrifugation goes out product, washs more than 3 times respectively with deionized water and ethanol, and dry under vacuo, and obtaining particle diameter is 500nm ~ 5 μm fire-retardant phase-change material capsules, phase transformation enthalpy 90J/g.
Embodiment 7: the 25# phase-change wax taking 55g is heated to 45 DEG C of constant temperature and keeps 1h to make it thoroughly melt, stirs obtain uniform decentralized photo with the 2-bromstyrol of 0.9g azodiisobutyronitrile, 15g, 30g styrene, 1g methacrylic acid.Take 8g sodium p styrene sulfonate, join in 800g deionized water, stir 1h with 1000rpm and obtain uniform continuous phase.Above-mentioned decentralized photo and continuous phase mixing, under 18000rpm rotating speed, high speed shear emulsification 20min, obtains mixed liquor.Mixed liquor is warmed up to 68 DEG C and carries out polymerisation, after 3h, add 1.5g sodium p styrene sulfonate, continue reaction 18h, and then reaction system is warmed up to 90 DEG C of reaction 3h.Treat after having reacted that system cools naturally, centrifugation goes out product, washs more than 3 times respectively with deionized water and ethanol, and dry under vacuo, and obtaining particle diameter is 400nm ~ 2 μm fire-retardant phase-change material capsules, phase transformation enthalpy 115J/g.
Claims (10)
1. a preparation method for the fire-retardant phase-change material capsule of noresidue emulsifying agent, is characterized in that comprising the following steps:
(1) phase-change material core being heated to more than phase transformation temperature points keeps 1h to make it thoroughly melt, then mixes with initator and wall material presoma, stirs and obtains decentralized photo;
Wherein, core and wall material presoma weigh proportioning in mass ratio at 3: 7 ~ 8: 2, core phase transformation temperature points according to core material at-26 DEG C ~ 70 DEG C, initator is 0.5% ~ 5% of wall material presoma, wall material presoma comprises flame-retardant monomer and reaction monomers, flame-retardant monomer is 10% ~ 50% of decentralized photo, and reaction monomers is 20% ~ 60% of decentralized photo; Above percentage is mass percent;
(2) polymerizable emulsifier is joined in deionized water, stir 1h with 1000rpm and obtain continuous phase; Wherein, polymerizable emulsifier is 1.5% ~ 10% of decentralized photo, and above percentage is mass percent;
(3) by decentralized photo and continuous phase 1: 4 ~ 1: 10 mixing in mass ratio, carry out high speed shear emulsification with 1000rpm ~ 20000rpm, the time is 20min, obtains mixed liquor;
(4) mixed liquor is warmed up to 60 DEG C ~ 80 DEG C and carries out polymerisation 5 ~ 24h, and then be warmed up to 90 DEG C of continuation reaction 3h; Wherein, when the polymerisations of 60 DEG C ~ 80 DEG C proceed to 3h, add described polymerizable emulsifier, additional amount is 0.1% ~ 2% of decentralized photo, and above percentage is mass percent;
(5) after system cools naturally, centrifugation product, and wash more than 3 times respectively with deionized water and ethanol, obtain the fire-retardant phase-change material capsule of noresidue emulsifying agent after vacuum drying.
2. the preparation method of the fire-retardant phase-change material capsule of a kind of noresidue emulsifying agent according to claim 1, is characterized in that: described core is one or more following combination according to phase transformation temperature points: n-undecane, n-tridecane, n-tetradecane, n-pentadecane, hexadecane, n-heptadecane, n-octadecane, NSC 77136, n-eicosane, Heneicosane, n-tricosane, n-tetracosane, pentacosane, n-hexacosane, heptacosane, positive octacosane, positive nonacosane, positive hentriacontane; The positive butyl ester of stearic acid, dodecylic acid; 5# phase-change wax, 15# phase-change wax, 20# phase-change wax, 25# phase-change wax, 30# phase-change wax, 40# phase-change wax, 70# phase-change wax.
3. the preparation method of the fire-retardant phase-change material capsule of a kind of noresidue emulsifying agent according to claim 1, is characterized in that: described polymerizable emulsifier is one or more following combination: sodium p styrene sulfonate, octadecyldimethyl vinyl phenyl ammonium chloride, ALS, alpha-olefin sodium sulfonate.
4. the preparation method of the fire-retardant phase-change material capsule of a kind of noresidue emulsifying agent according to claim 1, is characterized in that: described initator is one or more following combination: azodiisobutyronitrile, ABVN, dibenzoyl peroxide.
5. the preparation method of the fire-retardant phase-change material capsule of a kind of noresidue emulsifying agent according to claim 1, it is characterized in that: described flame-retardant monomer is one or more following combination: the bromo-1-propylene of dichlorostyrene, 1,2-dichloroethene, 3-, isoprenyl bromide, 2-bromstyrol; Vinyl phosphonic diethyl phthalate, two trimethylsilyl vinyl phosphate, vinyl phosphoric acid; The phosphorous functional acrylic monomer PAM100 of suitability for industrialized production.
6. the preparation method of the fire-retardant phase-change material capsule of a kind of noresidue emulsifying agent according to claim 1, is characterized in that: described reaction monomers is two or more following combination: the just own ester of styrene, methyl methacrylate, n-butyl acrylate, methacrylic acid, n-butyl acrylate, acrylic acid, isobutyl acrylate, tert-butyl acrylate, isopropyl methacrylate, acrylic acid.
7. the preparation method of the fire-retardant phase-change material capsule of a kind of noresidue emulsifying agent according to claim 3, is characterized in that: described polymerizable emulsifier is sodium p styrene sulfonate.
8. the preparation method of the fire-retardant phase-change material capsule of a kind of noresidue emulsifying agent according to claim 4, is characterized in that: described initator is azodiisobutyronitrile.
9. the preparation method of the fire-retardant phase-change material capsule of a kind of noresidue emulsifying agent according to claim 5, is characterized in that: described flame-retardant monomer is phosphorous vinyl monomer.
10. the preparation method of the fire-retardant phase-change material capsule of a kind of noresidue emulsifying agent according to claim 6, is characterized in that: described reaction monomers is styrene and methacrylic acid.
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| CN105112020A (en) * | 2015-06-11 | 2015-12-02 | 宁波绿凯节能科技有限公司 | Flame-retardant microcapsule phase-change material |
| CN106750543B (en) * | 2016-12-21 | 2018-10-19 | 普信氟硅新材料（衢州）有限公司 | A kind of preparation method of nano inorganic compound flame retardant |
| CN108003840B (en) * | 2017-11-29 | 2020-12-11 | 广东聚航新材料研究院有限公司 | Preparation method of phase-change material emulsion |
| CN110229287A (en) * | 2019-07-12 | 2019-09-13 | 江苏恒峰线缆有限公司 | A kind of high-performance refractory SEBS graft polymers and preparation method thereof |
| CN111672436B (en) * | 2020-05-21 | 2021-08-17 | 中国科学院化学研究所 | Flame-retardant phase-change microcapsule and preparation method and application thereof |
| CN111821926B (en) * | 2020-07-22 | 2022-08-09 | 襄阳三沃航天薄膜材料有限公司 | Preparation method of melamine phase change microcapsule with low formaldehyde content |
| CN112075419A (en) * | 2020-09-15 | 2020-12-15 | 江苏艾津作物科技集团有限公司 | Pesticide microcapsule suspending agent without residual emulsifier and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101822962A (en) * | 2010-04-28 | 2010-09-08 | 清华大学深圳研究生院 | Preparation method of phase-change energy-storing capsule adopting non-isocyanate polyurethane as capsule walls |
| CN102174142A (en) * | 2011-01-24 | 2011-09-07 | 天津工业大学 | Free radical emulsion polymerization manufacturing method and application of functional nanocapsule slurry |
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| CN101822962A (en) * | 2010-04-28 | 2010-09-08 | 清华大学深圳研究生院 | Preparation method of phase-change energy-storing capsule adopting non-isocyanate polyurethane as capsule walls |
| CN102174142A (en) * | 2011-01-24 | 2011-09-07 | 天津工业大学 | Free radical emulsion polymerization manufacturing method and application of functional nanocapsule slurry |
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