CN104874339A - Preparation method of double-layered wall material phase-variable micro capsule - Google Patents
Preparation method of double-layered wall material phase-variable micro capsule Download PDFInfo
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Abstract
The invention discloses a preparation method of a double-layered wall material phase-variable micro capsule and in particular relates to a dense double-layered structure which is formed by connecting inner and outer two layers of wall materials by adopting an interface polymerization under the action of a cross-linking agent, wherein the inner and outer layers of the wall materials are prepared by adopting an in-situ polymerization. The preparation method comprises the step of forming the stable double-layered structure under the action of the cross-linking agent with urea formaldehyde as the outer layer wall material and an alkene polymer as the inner layer wall material, wherein the cross-linking agent is an organic micromolecule containing double bonds and hydroxymethyl radical groups. The method is suitable for an organic core material; on the basis that the particle size is uniform and the embedding rate is high, the double-layered wall material phase-variable micro capsule also has the advantages of the hydrophilic performance and not-easily-agglomeration performance of a urea formaldehyde resin micro capsule, is hydrophobic with polymethyl methacrylate and is low in permeability.
Description
Technical field
That the present invention relates to is a kind of preparation method of double wall material microcapsules, it is specifically core with organic material, take Lauxite as outer wall material, vinyl polymer is inner layer wall material, situ aggregation method is adopted to be polymerized in aqueous phase and oil phase respectively, simultaneously under the effect of crosslinking agent, adopt interfacial polymerization that the grafting of two layers of walls material is formed stable double-decker;
Background technology
Microcapsules technology is technology microparticle material (solid, liquids and gases) the coated formation of dispersiveness by filmogen in recent years with the miniature vessel of nucleocapsid structure; there is state, quality, volume and the performance that can change material; protection sensitive composition; strengthen stability; control Release of core material; reduce or cover disagreeable taste, reduction volatility; the functions such as isolation component, are widely used in food, medicine, weaving, coating, agricultural, cosmetics industry etc.
Traditional microcapsule wall material polymerization is most widely used is situ aggregation method or interfacial polymerization.Situ aggregation method (in situ polymerization) is the outside or inside making reaction monomers or solubility performed polymer and initator all be present in core material dispersant liquid drop, the polymerizate generated moves to drop surface, such core material surface can form one deck polymeric membrane, and the film of generation can be coated on the surface of core drop.Interfacial polymerization (Interfacial polymerization) is by core emulsification or is dispersed in one and has in the continuous phase of wall material monomer, and monomer is at core surfaces through polymerisation film forming, and core is wrapped to form microcapsules the most at last.These two kinds of methods are applicable to single kind wall material material mostly, as Lauxite, and olefin polymer series (comprising polystyrene, polyacrylate series and copolymer thereof), polyureas etc.
Phase-change microcapsule wall material determines the range of application of phase-change microcapsule, and while selecting a kind of applicable wall material material, some defects of this material also must be avoided.Phase-change microcapsule wall material as the most frequently used at present has polymethyl methacrylate to be acrylic polymer and the Lauxite of representative.This bi-material mechanical property, calorifics and chemically stable excellent, cost is lower, is the ideal material of the phase-change microcapsule marketization.But bi-material respectively has its pluses and minuses: acrylic polymer wall material is water-fast, and weather resistance is splendid, but not oil resistant, not wear-resisting, as applying filler in such as foam, fabric, or deposit at organic solvent and easily break in case, cause the leakage of core, dispersiveness simultaneously in preparation process is bad, extends finishing time; Lauxite oil resistant; wear-resisting; with low cost; phase-change microcapsule good dispersion can be made as wall material; and due to surface hydrophilic group existence and shorten phase-change microcapsule finished product suction filtration technical process, but simple Lauxite wall material density is inadequate, and has hygroscopicity; weaken the protection to core, cause the leakage of core.If bi-material is combined under certain reaction condition formation double wall material to be coated on core surfaces, then can form complementation to a certain extent, expand the scope of application of microcapsules.
CN102653671A discloses microcapsules of capsule core and capsule wall material and preparation method thereof, and described capsule core is paraffin, and described capsule wall material is made up of olefin polymer single kind wall material, and described preparation method is situ aggregation method.
CN103468222A discloses microcapsules of capsule core and capsule wall material and preparation method thereof, and described capsule core is lauryl alcohol, and described capsule wall material is made up of olefin polymers such as methyl methacrylates, and described preparation method is situ aggregation method.
CN102056656A discloses microcapsules of capsule core and capsule wall material and preparation method thereof, and described capsule core is essence, and described capsule wall material is made up of the single wall material of polyureas, and described preparation method is interfacial polymerization.
CN104011193A discloses microcapsules of capsule core and capsule wall material and preparation method thereof, and described capsule core is perfumery oil, and described capsule wall material is made up of the single wall material of polyureas, and described preparation method is interfacial polymerization.
Summary of the invention
The present invention relates to a kind of preparation method of double wall material microcapsules, it is characterized in that comprising core, outer wall material and inner layer wall material, described core adopts organic phase change material, described outer wall material adopts Lauxite to make, described inner layer wall material adopts vinyl polymer to make, and connects between ectonexine wall material with crosslinking agent;
Technical scheme of the present invention
A kind of preparation method of double wall material microcapsules, it is specifically core with organic material, take Lauxite as outer wall material, vinyl polymer is inner layer wall material, adopt situ aggregation method to be polymerized in aqueous phase and oil phase respectively, under the effect of crosslinking agent, adopt interfacial polymerization that the grafting of two layers of walls material is formed stable double-decker simultaneously;
Described crosslinking agent is the organic molecule with double bond and methylol two kinds of groups, comprises one or more in N hydroxymethyl acrylamide, hydroxy-ethyl acrylate, hydroxypropyl acrylate;
Described vinyl polymer comprise in polymethyl methacrylate, EMA, polybutyl methacrylate, polystyrene one or more;
Described core is organic material, comprises one or more in n-dodecanol, atoleine, n-tetradecane, hexadecane, n-octadecane, solid paraffin;
The preparation method of described a kind of double wall material phase-change microcapsule, specifically comprises the steps:
(1), urea resin prepolymer is prepared
The formalin of 37%, urea, melamine and water are mixed in beaker, with triethanolamine, the pH value of mixed solution is adjusted to 8 ~ 9, then under the condition of 70-80 DEG C, 400rpm rotating speed, react 1h, obtain urea resin prepolymer;
Above-mentioned course of reaction used 37% formalin, urea, melamine and water amount, calculate in mass ratio, i.e. the formalin of 37%: urea: melamine: water is 1: 0.38-0.48: 0.03-0.08: 1.5-3.5;
(2), emulsion is prepared
Vinyl monomer, organic phase change material, crosslinking agent, deionized water, emulsifying agent is miscible according to sequencing, the emulsion of disperseing is obtained with the emulsification of high speed dispersion homogenizer.
The amount of above-mentioned organic phase change material, vinyl monomer, emulsifying agent and deionized water, calculates in mass ratio, i.e. organic phase change material: emulsifying agent: deionized water is 1: 0.13-0.25: 0.06-0.08: 4;
Above-mentioned emulsifying agent is one in TritonX-100, OP-10, neopelex, lauryl sodium sulfate or two or more composition;
(3), the preparation of double-deck phase-change microcapsule
The urea resin prepolymer dropwise that step (1) is obtained adds in the emulsion in step (2), regulate mixed solution pH value to 2.0-2.5, under 60-70 DEG C, 400-600rpm speed conditions, react 1h, then heat up continuation reaction 3h under 80-90 DEG C of condition.
After having reacted, with triethanolamine, solution ph is adjusted to 8-9, then carry out vacuum filtration, filter cake spends deionized water 3-4 time, can obtain white powder microcapsules, drying 24 hours at 40 DEG C.
In described double-deck phase-change microcapsule wall material, the amount of Lauxite and vinyl polymer calculates in mass ratio, i.e. Lauxite: vinyl polymer is 1: 0.3-3.
In sum, the preparation method of a kind of double wall material microcapsules of the present invention, be namely core with organic material, take Lauxite as outer wall material, vinyl polymer is inner layer wall material, and wherein both mass ratioes are 1: 0.3-3.Being connected with having the crosslinking agent of double bond with methylol Liang Zhong functional group between two-layer, forming stable double-decker.
Beneficial effect of the present invention
The preparation method of bilayered microcapsule of the present invention, provides a kind of preparation method of novel double-layer wall material phase-change microcapsule, realizes hydrophobic vinyl polymer and hydrophilic Lauxite two kinds of wall materials unite two into one by suitable crosslinking agent.In this patent, Lauxite is the thermosetting resin by urea and oxymethylene polymerization, with low cost, calorifics and stable mechanical property, phase-change microcapsule good dispersion can be made as wall material, and due to surface hydrophilic group existence and shorten phase-change microcapsule finished product suction filtration technical process, this is outbalance in actual production process.But because its surface exists hydrophilic group, the hygroscopicity of urea-formaldehyde resin microcapsule is strong, weakens the protection to core, causes the leakage of core.Polymethyl methacrylate, EMA, polybutyl methacrylate, polystyrene medium vinyl polymer hydrophobicity is strong, there is not the situation causing core to be revealed because of moisture absorption, but this kind of material is not wear-resisting, not oil resistant, as applying filler in such as foam, fabric, or deposit at organic solvent and easily break in case, cause the leakage of core.And be used alone polymethyl methacrylate, EMA, polybutyl methacrylate, the medium vinyl polymer of polystyrene are poor as the microcapsules dispersiveness of wall material, and because its strong-hydrophobicity can cause in later stage suction filtration process consumption a large amount of time.Therefore, if bi-material is combined under certain reaction condition formation double wall material to be coated on core surfaces, then can form complementation to a certain extent, expand the scope of application of microcapsules.Meanwhile, the hydrophily group of Lauxite can improve the solubility of wall material in water and reactivity, finally reaches the effect of the clad ratio improving core.
Detailed description of the invention
Embodiment 1
A preparation method for double wall material phase-change microcapsule, specifically comprises the steps:
(1), urea resin prepolymer is prepared
The formalin of 37%, urea, melamine and water are mixed in beaker, with triethanolamine, the pH value of mixed solution is adjusted to 8 ~ 9, then under the condition of 70-80 DEG C, 400rpm rotating speed, react 1h, obtain urea resin prepolymer;
Above-mentioned course of reaction used 37% formalin, urea, melamine and water amount, calculate in mass ratio, i.e. the formalin of 37%: urea: melamine: water is 1: 0.38-0.48: 0.03-0.08: 1.5-3.5;
(2), emulsion is prepared
Methyl methacrylate monomer, n-dodecanol, hydroxy-ethyl acrylate, deionized water, emulsifying agent is miscible according to sequencing, the emulsion of disperseing is obtained with the emulsification of high speed dispersion homogenizer.
The above-mentioned amount having n-dodecanol, methyl methacrylate monomer, emulsifying agent and deionized water, calculates, i.e. organic phase change material: emulsifying agent in mass ratio: deionized water is 1: 0.16: 0.06-0.08: 4;
Above-mentioned emulsifying agent is one in TritonX-100, OP-10, neopelex, lauryl sodium sulfate or two or more composition;
(3), the preparation of double-deck phase-change microcapsule
The urea resin prepolymer dropwise that step (1) is obtained adds in the emulsion in step (2), regulate mixed solution pH value to 2.0-2.5, under 60-70 DEG C, 400-600rpm speed conditions, react 1h, then heat up continuation reaction 3h under 80-90 DEG C of condition.
After having reacted, with triethanolamine, solution ph is adjusted to 8-9, then carry out vacuum filtration, filter cake spends deionized water 3-4 time, can obtain white powder microcapsules, drying 24 hours at 40 DEG C.
In described double-deck phase-change microcapsule wall material, the amount of Lauxite and polymethyl methacrylate calculates in mass ratio, i.e. Lauxite: polymethyl methacrylate is 1: 1.
The double wall material phase-change microcapsule Stability Analysis of Structures of above-mentioned gained is fine and close, and Waterproofing/oilproofing performance is improved, and can be widely used in multiple environment, comprises microcapsules fluid, coating, weaving, building energy field; Finishing time greatly shortens compared with the single wall material of polymethyl methacrylate, saves the batch production time, enhances productivity; Its latent heat of phase change is 178KJ/Kg, belongs to high energy storage phase-change microcapsule.
Embodiment 2
A preparation method for double wall material phase-change microcapsule, specifically comprises the steps:
(1), urea resin prepolymer is prepared
The formalin of 37%, urea, melamine and water are mixed in beaker, with triethanolamine, the pH value of mixed solution is adjusted to 8 ~ 9, then under the condition of 70-80 DEG C, 400rpm rotating speed, react 1h, obtain urea resin prepolymer;
Above-mentioned course of reaction used 37% formalin, urea, melamine and water amount, calculate in mass ratio, i.e. the formalin of 37%: urea: melamine: water is 1: 0.38-0.48: 0.03-0.08: 1.5-3.5;
(2), emulsion is prepared
Styrene monomer, n-octadecane, N hydroxymethyl acrylamide, deionized water, emulsifying agent is miscible according to sequencing, the emulsion of disperseing is obtained with the emulsification of high speed dispersion homogenizer.
The above-mentioned amount having n-tetradecane, styrene monomer, emulsifying agent and deionized water, calculates, i.e. organic phase change material: emulsifying agent in mass ratio: deionized water is 1: 0.375: 0.06-0.08: 4;
Above-mentioned emulsifying agent is one in TritonX-100, OP-10, neopelex, lauryl sodium sulfate or two or more composition;
(3), the preparation of double-deck phase-change microcapsule
The urea resin prepolymer dropwise that step (1) is obtained adds in the emulsion in step (2), regulate mixed solution pH value to 2.0-2.5, under 60-70 DEG C, 400-600rpm speed conditions, react 1h, then heat up continuation reaction 3h under 80-90 DEG C of condition.
After having reacted, with triethanolamine, solution ph is adjusted to 8-9, then carry out vacuum filtration, filter cake spends deionized water 3-4 time, can obtain white powder microcapsules, drying 24 hours at 40 DEG C.
In described double-deck phase-change microcapsule wall material, the amount of Lauxite and polystyrene calculates in mass ratio, i.e. Lauxite: polystyrene is 1: 3.
The double wall material phase-change microcapsule Stability Analysis of Structures of above-mentioned gained is fine and close, and Waterproofing/oilproofing performance is improved, and can be widely used in multiple environment, comprises microcapsules fluid, coating, weaving, building energy field; Finishing time greatly shortens compared with the single wall material of polystyrene, saves the batch production time, enhances productivity; Be mixed with polystyrene in wall material material, the compatibility of phase-change microcapsule and polystyrene foam can be improved, so be suitable for retardant polystyrene insulation foam material.
Embodiment 3
A preparation method for double wall material phase-change microcapsule, specifically comprises the steps:
(1), urea resin prepolymer is prepared
The formalin of 37%, urea, melamine and water are mixed in beaker, with triethanolamine, the pH value of mixed solution is adjusted to 8 ~ 9, then under the condition of 70-80 DEG C, 400rpm rotating speed, react 1h, obtain urea resin prepolymer;
Above-mentioned course of reaction used 37% formalin, urea, melamine and water amount, calculate in mass ratio, i.e. the formalin of 37%: urea: melamine: water is 1: 0.38-0.48: 0.03-0.08: 1.5-3.5;
(2), emulsion is prepared
EMA monomer, n-tetradecane, hydroxypropyl acrylate, deionized water, emulsifying agent is miscible according to sequencing, the emulsion of disperseing is obtained with the emulsification of high speed dispersion homogenizer.
The above-mentioned amount having n-octadecane, EMA monomer, emulsifying agent and deionized water, calculates, i.e. organic phase change material: emulsifying agent in mass ratio: deionized water is 1: 0.125: 0.06-0.08: 4;
Above-mentioned emulsifying agent is one in TritonX-100, OP-10, neopelex, lauryl sodium sulfate or two or more composition;
(3), the preparation of double-deck phase-change microcapsule
The urea resin prepolymer dropwise that step (1) is obtained adds in the emulsion in step (2), regulate mixed solution pH value to 2.0-2.5, under 60-70 DEG C, 400-600rpm speed conditions, react 1h, then heat up continuation reaction 3h under 80-90 DEG C of condition.
After having reacted, with triethanolamine, solution ph is adjusted to 8-9, then carry out vacuum filtration, filter cake spends deionized water 3-4 time, can obtain white powder microcapsules, drying 24 hours at 40 DEG C.
In described double-deck phase-change microcapsule wall material, the amount of Lauxite and polyethyl methacrylate calculates in mass ratio, i.e. Lauxite: polyethyl methacrylate is 1: 0.3.
The double wall material phase-change microcapsule Stability Analysis of Structures of above-mentioned gained is fine and close, and Waterproofing/oilproofing performance is improved, and can be widely used in multiple environment, comprises microcapsules fluid, coating, weaving, building energy field; Finishing time greatly shortens compared with the single wall material of polyethyl methacrylate, saves the batch production time, enhances productivity; Its latent heat of phase change is 165KJ/Kg, belongs to high energy storage phase-change microcapsule.
Claims (5)
1. the preparation method of double wall material microcapsules, it is characterized in that comprising core, outer wall material and inner layer wall material, described core adopts organic phase change material, described outer wall material adopts Lauxite to make, described inner layer wall material adopts vinyl polymer to make, and connects between ectonexine wall material with crosslinking agent.
2. the preparation method of a kind of double wall material microcapsules according to claim 1, it is characterized in that described crosslinking agent is the organic molecule with double bond and methylol two kinds of groups, comprise one or more in N hydroxymethyl acrylamide, hydroxy-ethyl acrylate, hydroxypropyl acrylate.
3. the preparation method of a kind of double wall material microcapsules according to claim 1 and 2, it is characterized in that described vinyl polymer comprises in polymethyl methacrylate, EMA, polybutyl methacrylate, polystyrene one or more.
4. the preparation method of a kind of double wall material microcapsules according to claim 1 and 2, it is characterized in that described core is organic material, comprise one or more in n-dodecanol, atoleine, n-tetradecane, hexadecane, n-octadecane, solid paraffin.
5. the preparation method of a kind of double wall material microcapsules according to claim 1 and 2, is characterized in that specifically comprising the steps:
(1), urea resin prepolymer is prepared
(2), emulsion is prepared
With high speed dispersion homogenizer by miscible according to sequencing to vinyl monomer, organic phase change material, crosslinking agent, deionized water, emulsifying agent, and be dispersed into emulsion;
The amount of described organic phase change material, vinyl monomer, emulsifying agent and deionized water, calculates in mass ratio, i.e. organic phase change material: emulsifying agent: deionized water is 1: 0.13-0.25: 0.06-0.08: 4;
Described emulsifying agent is one in TritonX-100, OP-10, neopelex, lauryl sodium sulfate or two or more composition;
(3), the preparation of double-deck phase-change microcapsule
The urea resin prepolymer dropwise that step (1) is obtained adds in the emulsion in step (2), regulate mixed solution pH value to 2.0-2.5, under 60-70 DEG C, 400-600rpm speed conditions, react 1h, under being then warming up to 80-90 DEG C of condition, continue reaction 3h;
After having reacted, solution ph is adjusted to 8-9, then carry out vacuum filtration, filter cake spends deionized water 3-4 time, can obtain white powder microcapsules, and drying obtains product in 24 hours;
In described double-deck phase-change microcapsule wall material, the amount of Lauxite and vinyl polymer calculates in mass ratio, i.e. Lauxite: vinyl polymer is 1: 0.3-3.
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| CN105647423A (en) * | 2016-03-21 | 2016-06-08 | 广东恒大新材料科技有限公司 | Two-layer amine type accelerator microcapsule and preparation method thereof |
| CN105854745A (en) * | 2016-04-15 | 2016-08-17 | 广州秘理普植物技术开发有限公司 | Method for preparing microcapsules through polymer precoating |
| CN107970868A (en) * | 2017-11-30 | 2018-05-01 | 青岛理工大学 | Externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule and preparation method thereof |
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| CN105647423A (en) * | 2016-03-21 | 2016-06-08 | 广东恒大新材料科技有限公司 | Two-layer amine type accelerator microcapsule and preparation method thereof |
| CN105854745A (en) * | 2016-04-15 | 2016-08-17 | 广州秘理普植物技术开发有限公司 | Method for preparing microcapsules through polymer precoating |
| CN105854745B (en) * | 2016-04-15 | 2018-07-24 | 广州秘理普植物技术开发有限公司 | A method of microcapsules are prepared by polymer pre-coated |
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| CN108949112A (en) * | 2018-09-17 | 2018-12-07 | 佛山市森昂生物科技有限公司 | A kind of preparation method of low-temperature phase-change micro-capsule |
| CN110171173B (en) * | 2019-05-05 | 2021-12-21 | 江阴芗菲纺织科技有限公司 | All-season functional fabric and preparation method thereof |
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| CN112852402A (en) * | 2020-12-22 | 2021-05-28 | 厦门安踏体育用品有限公司 | Durable thermochromic material, preparation method thereof and application thereof in textiles |
| CN112852402B (en) * | 2020-12-22 | 2023-06-23 | 厦门安踏体育用品有限公司 | Durable thermochromic material, preparation method thereof and application thereof in textiles |
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| CN113913160B (en) * | 2021-11-09 | 2023-08-15 | 青岛尼希米生物科技有限公司 | Double-layer capsule wall energy storage temperature adjustment microcapsule, polyacrylonitrile fiber and preparation method thereof |
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| CN114703670A (en) * | 2022-04-22 | 2022-07-05 | 上海水星家用纺织品股份有限公司 | Preparation method of natural aromatic antibacterial multifunctional composite material |
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