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WO2018000422A1 - 基于自由基界面聚合的微胶囊及其制备方法 - Google Patents

基于自由基界面聚合的微胶囊及其制备方法 Download PDF

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WO2018000422A1
WO2018000422A1 PCT/CN2016/088132 CN2016088132W WO2018000422A1 WO 2018000422 A1 WO2018000422 A1 WO 2018000422A1 CN 2016088132 W CN2016088132 W CN 2016088132W WO 2018000422 A1 WO2018000422 A1 WO 2018000422A1
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parts
microcapsules
interfacial polymerization
water
aqueous phase
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French (fr)
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鲁希华
王丽英
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Anhui Microdelivery Smart Microcapsule Sci & Tech Co Ltd
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Anhui Microdelivery Smart Microcapsule Sci & Tech Co Ltd
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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
    • 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
    • B01J13/16—Interfacial polymerisation
    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • 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

Definitions

  • the invention belongs to the technical field of microcapsule preparation, and relates to a microcapsule based on free radical interfacial polymerization and a preparation method thereof, in particular to a microcapsule based on radical polymerization of an initiator in an oil phase and a preparation method thereof.
  • microcapsule wall material largely determines the application range of the microcapsule, such as non-toxicity, biocompatibility, mechanical strength and thermal stability.
  • the commonly used wall materials are high molecular polymers, and the high molecular polymers are further divided into natural polymers, semi-synthetic polymers and synthetic polymers.
  • synthetic polymers are widely used as wall materials for microcapsules because of their outstanding functionality and good thermal stability. More synthetic polymers are used including polyurethanes, polyureas, polyesters and polyacryls.
  • microcapsules have been applied to various industries that are in direct contact with the human body, such as food, flavors and fragrances, textiles, cosmetics and medicine. These applications are more stringent in the non-toxic requirements of microcapsule wall materials. Therefore, it is of great significance to synthesize microcapsules of non-toxic wall materials by selecting non-toxic and environmentally-friendly synthetic monomers and avoiding the use of cross-linking agents during the synthesis.
  • the technical problem to be solved by the present invention is to provide a microcapsule based on radical interfacial polymerization and a preparation method thereof, in particular to provide a microcapsule based on radical interface polymerization of an initiator in an oil phase and a preparation method thereof.
  • the preparation method of the microcapsule based on radical interfacial polymerization of the invention is characterized in that the initiator is in the oil phase and the monomer is in the aqueous phase.
  • the aqueous phase contains more than one monomer; the oil phase contains more than one initiator.
  • the aqueous phase further contains an initiator.
  • the oil phase contains at least one monomer.
  • the preparation method as described above which is an oil-in-water method or a water-in-oil method.
  • the invention also provides a preparation method of microcapsules based on free radical interfacial polymerization, in parts by mass:
  • Core material 1 to 60 parts
  • Monomer 1 1 to 10 parts
  • Initiator 0.1 to 0.5 parts
  • R 2 is Or —H
  • R 3 is Or —H
  • R 4 is Or —H
  • the core material is a liquid oil phase that is insoluble in water
  • Emulsifier 1.5 to 4.5 parts
  • Monomer 2 1 to 10 parts
  • R 6 is Or —H
  • R 7 is Or —H
  • R 8 is Or —H
  • the preparation process comprises the following steps: preparing an oil phase and an aqueous phase respectively; adding an aqueous phase to the oil phase, and shearing to form an emulsion; introducing nitrogen into the emulsion, and reacting at 40 ° C to 90 ° C for 0.5 to 8 hours to obtain a radical-based interfacial polymerization.
  • Microcapsules are the following steps: preparing an oil phase and an aqueous phase respectively; adding an aqueous phase to the oil phase, and shearing to form an emulsion; introducing nitrogen into the emulsion, and reacting at 40 ° C to 90 ° C for 0.5 to 8 hours to obtain a radical-based interfacial polymerization.
  • the monomer one is specifically: ethylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and 1,6-hexanediol dimethacrylate. More than one;
  • the core material is one or more of an ultraviolet absorber, a flavor and fragrance, a phase change material and a medicine;
  • the ultraviolet absorber is octocrylene, benzophenone-3, octyl salicylate, bason 1789 or methoxy
  • the isooctyl cinnamate is peppermint oil, rose essence, lemon essence, lavender essence, green tea essence, water lotus essence or floral fragrance
  • the phase change material is paraffin, n-tetradecane, Zhengshi Pentaline, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-icosane, n-docosane, n-docosane, n-docosane or n-twenty-four An alkane;
  • the drug is a vitamin oil or an antitumor drug;
  • the initiator is azobisisobutyronitrile or diacyl peroxide; the mass ratio of the initiator to monomer one is 0.1: 3 ⁇ 10;
  • the emulsifier is sodium dodecyl sulfate, gum arabic or polyvinyl alcohol, wherein the degree of hydrolysis of the polyvinyl alcohol is 80-90%;
  • the monomer 2 is specifically a polyhydric alcohol acrylate
  • the shear rate of the shear is 6000 to 24000 rpm, and the shear time is 1 to 10 min.
  • the invention further provides a microcapsule based on free radical interfacial polymerization, the microcapsule based on free radical interfacial polymerization, the core material entrapment amount is 10% to 60%, and the embedding rate is 80% to 99%, micro The capsules are evenly dispersed in the water.
  • microcapsules provided by the present invention have a particle diameter of 0.5 to 100 ⁇ m and an average particle diameter of 1 to 80 ⁇ m.
  • the mechanism of the invention is:
  • Free radical interfacial polymerization forms a microcapsule technology, usually using a water-soluble initiator to initiate a cross-linking polymerization microcapsule of a monomer in an oil phase at an oil-in-water emulsion interface, since the monomer dissolved in the oil phase is less hydrophilic, Therefore, the formed microcapsule polymer wall material has poor water absorbability. Numerous biomedical microcapsules, cosmetic microcapsules, and personal care microcapsules require good hydrophilicity of the microcapsule wall material. The original free radical interfacial polymerization to form microcapsule technology cannot solve this problem, and the present invention is soluble in the solution.
  • the oil-soluble initiator in the oil phase initiates cross-linking polymerization of the hydrophilic monomer in the aqueous phase at the emulsion interface to form microcapsules, and the microcapsule wall material prepared by the new method has good hydrophilicity and will satisfy the market. New demand.
  • the monomer used in the present invention is itself non-toxic, so there is no problem of leaving unreacted toxic monomer residues after the reaction.
  • the wall material synthesized by the present invention is a non-toxic material, so that such a microcapsule can be suitably applied to a product related to a human body.
  • the emulsifiers used in the present invention are sodium dodecyl sulfate (SDS), gum arabic (GA) and polyvinyl alcohol (PVA), the former being an anionic surfactant having excellent penetration, washing and moistening. Wet, decontamination and emulsification, the middle is a natural polymer material, green and environmentally friendly, the latter is a non-toxic synthetic polymer emulsifier. These three types of emulsifiers are non-toxic and environmentally friendly, and do not introduce any toxic substances into the reaction system, making the invention system green.
  • microcapsules prepared by the invention have high embedding rate of the core material and the wall material is uniform in thickness, and the microcapsules have stable performance; the microcapsule preparation process of the invention is green and environmentally friendly, and the prepared microcapsules are applied to the human body. It is harmless and has broad application prospects in the fields of sunscreen, flavor and fragrance, biomedicine, daily cosmetics and microcapsules.
  • Figure 1 is a radical polymerization mechanism of Example 1
  • Example 2 is an optical micrograph of the microcapsules prepared in Example 1;
  • Example 3 is a particle size distribution diagram of the microcapsules prepared in Example 3.
  • Example 4 is a scanning electron micrograph of the microcapsules prepared in Example 4.
  • a method for preparing microcapsules based on free radical interfacial polymerization wherein 1 part of octocrylene, 0.1 part of diacyl peroxide, and 3 parts of ethylene glycol dimethacrylate are formulated into an oil phase, and then 1 a portion of polyethylene glycol diacrylate, 1.5 parts gum arabic, 90 parts water to make an aqueous phase; then the aqueous phase is added to the oil phase at a shear rate of 6000 rpm with a shear time of 1 min.
  • the test shows that the core material of the obtained radical-interfacial polymerization-based microcapsules has a core loading of 1%, an embedding rate of 80%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle diameter of 0.5 to 15 ⁇ m, and the average particle size The diameter is 3 ⁇ m, as shown in Figure 2.
  • a method for preparing microcapsules based on radical interfacial polymerization comprising 40 parts of benzophenone-3, 0.3 parts of diacyl peroxide, and 10 parts of 1,4-butane dimethacrylate Phase, then 5 parts of polypolyol acrylate, 4 parts of sodium dodecyl sulfonate, 75 parts of water are formulated into an aqueous phase; then the aqueous phase is added In the oil phase, an emulsion was formed under shearing at a shear rate of 9000 rpm and a shear time of 4 min; nitrogen was introduced into the emulsion and reacted at 80 ° C for 7 hours to obtain a microcapsule based on radical interfacial polymerization.
  • the test shows that the core material loading of the obtained microcapsules based on free radical interfacial polymerization is 30%, the embedding rate is 99%, and the microcapsules are uniformly dispersed in water; the particle size of the microcapsules is 0.1-7.5 ⁇ m, and the average The particle size was 3 ⁇ m as shown in FIG.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 30 parts of octyl salicylate, 0.2 parts of azobisisobutyronitrile, and 8 parts of 1,6-hexanediol dimethacrylate
  • the oil phase further 5 parts of polypolyol acrylate, 4 parts of polyvinyl alcohol, wherein the degree of hydrolysis of polyvinyl alcohol is 80%, 55 parts of water is formulated into an aqueous phase; then the aqueous phase is added to the oil phase
  • the emulsion was formed under shearing at a shear rate of 10,000 rpm and a shear time of 4 min; nitrogen was introduced into the emulsion and reacted at 80 ° C for 7 hours to obtain a microcapsule based on radical interfacial polymerization.
  • the test shows that the core material loading of the obtained microcapsules based on free radical interfacial polymerization is 29%, the embedding rate is 89%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle size of 20-80 ⁇ m, and the average particle size The diameter is 30 ⁇ m as shown in FIG.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 30 parts of Bassoon 1789, 0.25 parts of diacyl peroxide, 10 parts of 1,4-dioldiol dimethacrylate and dimethacrylic acid 1 a mixture of 6-hexanediol esters formulated into an oil phase in which the mass ratio of 1,4-glycol dimethacrylate to 1,6-hexanediol dimethacrylate is 2:1, and then 8 parts of polyhydric alcohol acrylate, 2 parts of polyvinyl alcohol, wherein polyvinyl alcohol has a degree of hydrolysis of 90%, 87 parts of water is formulated into an aqueous phase; then the aqueous phase is added to the oil phase at a shear rate An emulsion was formed under the shearing action of 20,000 rpm and a shear time of 8 min; nitrogen gas was introduced into the emulsion, and reacted at 85 ° C for 6.5 hours to
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 22%, an embedding rate of 85%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle diameter of 4 to 30 ⁇ m and an average particle size. The diameter is 15 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 30 parts of isooctyl methoxycinnamate, 0.1 parts of azobisisobutyronitrile, and 8 parts of 1,4-dimethacrylate Alcohol esters and dimethacrylic acid
  • the mixture of ethylene glycol esters is formulated into an oil phase in which the mass ratio of 1,4-glycol dimethacrylate to ethylene glycol dimethacrylate is 2:3, and then 1 part of poly-polyol acrylic acid Ester, 4.5 parts of polyvinyl alcohol, wherein the degree of hydrolysis of polyvinyl alcohol is 85%, 90 parts of water is formulated into an aqueous phase; then the aqueous phase is added to the oil phase at a shear rate of 18000 rpm, and the shear time is Under the shearing action of 8 min, an emulsion was formed; nitrogen gas was introduced into the emulsion, and reacted at 75 °
  • the test shows that the core material loading of the obtained microcapsules based on free radical interfacial polymerization is 22%, the embedding rate is 82%, and the microcapsules are uniformly dispersed in water; the particle size of the microcapsules is 0.5-20 ⁇ m, and the average particle size The diameter is 6 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 25 parts of peppermint oil, 0.12 parts of azobisisobutyronitrile, 6 parts of 1,4-dioldiol dimethacrylate, dimethyl
  • a mixture of 1,6-hexanediol acrylate and ethylene glycol dimethacrylate is formulated into an oil phase, wherein 1,4-glycol dimethacrylate, 1,6-hexanediol dimethacrylate
  • the mass ratio of ester to ethylene glycol dimethacrylate is 2:1:5, and then 8 parts of polypolyol acrylate and 4 parts of polyvinyl alcohol, wherein the degree of hydrolysis of polyvinyl alcohol is 84%, 85
  • the water is formulated into an aqueous phase; then the aqueous phase is added to the oil phase, and an emulsion is formed under shear at a shear rate of 20,000 rpm and a shear time
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 20%, an embedding rate of 86%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle diameter of 0.5 to 5 ⁇ m and an average particle size. The diameter is 2 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 45 parts of rose essence, 0.3 parts of diacyl peroxide, 9 parts of 1,4-dioldiol dimethacrylate, and dimethacrylic acid 1 a mixture of 6-hexanediol ester and ethylene glycol dimethacrylate formulated into an oil phase, wherein 1,4-glycol dimethacrylate, 1,6-hexanediol dimethacrylate, and The mass ratio of ethylene glycol dimethacrylate is 4:1:3, and then 4 parts of polypolyol acrylate and 2 parts of polyvinyl alcohol, wherein the degree of hydrolysis of polyvinyl alcohol is 83%, 60 parts.
  • the water is formulated into an aqueous phase; then the aqueous phase is added to the oil phase, and an emulsion is formed under shear at a shear rate of 10,000 rpm and a shear time of 8 min; nitrogen is introduced into the emulsion and reacted at 40 ° C for 4 hours.
  • Microcapsules based on free radical interfacial polymerization were obtained.
  • Tests show that the core material loading of the obtained microcapsules based on free radical interfacial polymerization is 37%, embedded The rate was 90%, and the microcapsules were uniformly dispersed in water; the microcapsules had a particle diameter of 4 to 40 ⁇ m and an average particle diameter of 20 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization which comprises a mixture of 40 parts of octocrylene, rose essence and n-tetradecane (the ratio of octocrylene, rose essence and n-tetradecane is 2:1) : 3), 0.12 parts of azobisisobutyronitrile, 5 parts of 1,4-butane dimethacrylate, formulated into an oil phase, and then 7 parts of polypolyol acrylate, 3 parts of twelve Sodium alkane sulfonate and 50 parts of water are formulated into an aqueous phase; then the aqueous phase is added to the oil phase to form an emulsion at a shear rate of 14000 rpm and a shear time of 5 min; Nitrogen gas was reacted at 50 ° C for 3 hours to obtain a microcapsule based on radical interfacial polymerization.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 38%, an embedding rate of 84%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle size of 50 to 100 ⁇ m and an average particle size. The diameter is 80 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 50 parts of a mixture of octyl salicylate, green tea essence and vitamin oil (the ratio of octyl salicylate, green tea essence and vitamin oil is 2:4:1) ), 0.1 part of azobisisobutyronitrile, 6 parts of 1,6-hexanediol dimethacrylate to prepare an oil phase, and then 5 parts of polypolyol acrylate, 3 parts of gum arabic, 87
  • the water is formulated into an aqueous phase; then the aqueous phase is added to the oil phase, and an emulsion is formed under shear at a shear rate of 18,000 rpm and a shear time of 5 min; nitrogen is introduced into the emulsion and reacted at 60 ° C.
  • microcapsules based on free radical interfacial polymerization were obtained.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 33%, an embedding rate of 88%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle diameter of 0.5 to 40 ⁇ m, and the average particle size The diameter is 20 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization which comprises a mixture of 40 parts of octocrylene, rose essence, vitamin oil and n-tetradecane (the ratio of octocrylene, rose essence and n-tetradecane is 1:1:3:2), 0.1 part of diacyl peroxide, 5 parts of ethylene glycol dimethacrylate formulated into an oil phase, and then 7 parts of polypolyol acrylate, 4 parts of dodecane Sodium sulfonate and 60 parts of water are formulated into an aqueous phase; After the aqueous phase was added to the oil phase, an emulsion was formed under shearing at a shear rate of 10,000 rpm and a shear time of 5 min; nitrogen was introduced into the emulsion and reacted at 50 ° C for 2 hours to obtain a radical-based interfacial polymerization. Microcapsules.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 34%, an embedding rate of 82%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle size of 50 to 100 ⁇ m and an average particle size. The diameter is 70 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 50 parts of a mixture of octyl salicylate, green tea essence, paraffin and vitamin oil (the ratio of octyl salicylate, green tea essence and vitamin oil is 2:1) : 4:3), 0.1 part of diacyl peroxide, 7 parts of ethylene glycol dimethacrylate formulated into an oil phase, and then 5 parts of polypolyol acrylate, 3 parts of gum arabic, 87 parts
  • the water is formulated into an aqueous phase; then the aqueous phase is added to the oil phase, and an emulsion is formed under shearing at a shear rate of 8000 rpm and a shear time of 5 min; nitrogen is introduced into the emulsion and reacted at 60 ° C for 5 hours.
  • Microcapsules based on free radical interfacial polymerization were obtained.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 32%, an embedding rate of 88%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle diameter of 0.5 to 40 ⁇ m, and the average particle size The diameter is 18 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 55 parts of lemon essence, 0.3 parts of azobisisovaleronitrile to form an oil phase, and further 5 parts of N-isopropyl acrylamide, 2 parts Polyvinyl alcohol having a degree of hydrolysis of 85%, 20 parts of water is formulated into an aqueous phase; then the aqueous phase is added to the oil phase, and an emulsion is formed under shearing at a shear rate of 10,000 rpm and a shearing time of 8 min; Nitrogen gas was introduced into the emulsion, and reacted at 70 ° C for 4 hours to obtain a microcapsule based on radical interfacial polymerization.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 60%, an embedding rate of 92%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle diameter of 5 to 40 ⁇ m and an average particle size. The diameter is 25 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 25 parts of lavender essence, 0.2 parts of dimethyl azobisisobutyrate, and 5 parts of N-methylol acrylamide 2 parts of hydrolysis 89% polyvinyl alcohol and 20 parts of water are formulated into an aqueous phase; then the aqueous phase is added to the oil phase to form an emulsion at a shear rate of 10,000 rpm and a shearing time of 8 min; The emulsion was purged with nitrogen and reacted at 70 ° C for 4 hours to obtain a microcapsule based on radical interfacial polymerization.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 48%, an embedding rate of 95%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle size of 5 to 50 ⁇ m, and the average particle size The diameter is 35 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization which comprises 35 parts of green tea essence, 0.1 part of azoisobutylcyanoformamide, and an oil phase, and then 5 parts of methacrylic acid, 2 parts of hydrolysis degree Formulating an aqueous phase with 80% polyvinyl alcohol and 20 parts of water; then adding the aqueous phase to the oil phase, forming an emulsion at a shear rate of 10,000 rpm and a shearing time of 6 min; Nitrogen gas was introduced and reacted at 70 ° C for 4 hours to obtain a microcapsule based on radical interfacial polymerization.
  • the test shows that the core material loading of the obtained microcapsules based on free radical interfacial polymerization is 56%, the embedding rate is 85%, and the microcapsules are uniformly dispersed in water; the particle size of the microcapsules is 0.5-20 ⁇ m, and the average particle size The diameter is 5 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 40 parts of water lotus essence, 0.1 parts of dimethyl azobisisobutyrate and azoisobutylcyanocarboxamide as an oil phase , wherein the mass ratio of dimethyl azobisisobutyrate and azoisobutylcyanocarboxamide is 4:6, and 4 parts of acrylamide, 4 parts of gum arabic, and 60 parts of water are prepared into an aqueous phase.
  • aqueous phase was added to the oil phase, and an emulsion was formed under shearing at a shear rate of 15000 rpm and a shear time of 4 min; nitrogen was introduced into the emulsion and reacted at 60 ° C for 5 hours to obtain a radical-based interface.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 37%, an embedding rate of 96%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle size of 20 to 70 ⁇ m and an average particle size. The diameter is 50 ⁇ m.
  • a method for preparing microcapsules based on radical interfacial polymerization wherein a mixture of 35 parts of floral essence, 0.2 parts of azobisisobutyronitrile and azoisobutyryl formamide is formulated into an oil phase, wherein azodi
  • the mass ratio of isobutyronitrile to azoisobutylcyanocarboxamide is 3:7, and then 9 parts of 2-acrylamido-2-methylpropanesulfonate Acid, 2.5 parts of sodium dodecyl sulfate, and 75 parts of water are formulated into an aqueous phase; then the aqueous phase is added to the oil phase at a shear rate of 15,000 rpm and a shear time of 7 min.
  • An emulsion was formed; nitrogen gas was introduced into the emulsion, and reacted at 65 ° C for 5 hours to obtain a microcapsule based on radical interfacial polymerization.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 29%, an embedding rate of 98%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle size of 1 to 30 ⁇ m and an average particle size. The diameter is 6 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 55 parts of paraffin, 0.15 parts of azobisisovaleronitrile to form an oil phase, and then 9 parts of acrylamide and 2-acrylamido-2- a mixture of methylpropanesulfonic acid (mass ratio of acrylamide to 2-acrylamido-2-methylpropanesulfonic acid of 6:4), 3.5 parts of sodium dodecylsulfonate, and 70 parts of water
  • the aqueous phase the aqueous phase is then added to the oil phase, and an emulsion is formed under shear at a shear rate of 18,000 rpm and a shear time of 5 min; nitrogen is introduced into the emulsion and reacted at 60 ° C for 6 hours to obtain a free basis.
  • Microcapsules polymerized at the base interface.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 40%, an embedding rate of 92%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle size of 2 to 50 ⁇ m and an average particle size. The diameter is 20 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 40 parts of n-tetradecane, 0.15 parts of azobisisoheptanenitrile as an oil phase, and then 9 parts of tert-butyl methacrylate and a mixture of methyl acrylate (a ratio of tert-butyl methacrylate to methyl methacrylate of 2:8), 4 parts of gum arabic, and 80 parts of water to form an aqueous phase; then adding the aqueous phase to the oil In the phase, an emulsion was formed under shearing at a shear rate of 11,000 rpm and a shear time of 10 min; nitrogen gas was introduced into the emulsion and reacted at 60 ° C for 7 hours to obtain a microcapsule based on radical interfacial polymerization.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 30%, an embedding rate of 80%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle diameter of 4 to 40 ⁇ m, and the average particle size The diameter is 30 ⁇ m.
  • a method for preparing microcapsules based on radical interfacial polymerization wherein 60 parts of n-pentadecane, 0.1 parts of a mixture of azobisisovaleronitrile and azoisobutyrylformamide are formulated into an oil phase, wherein The mass ratio of nitrogen diisovaleronitrile and azoisobutylcyanocarboxamide is 5:6, and further 7 parts of a mixture of N-methylol acrylamide and N-isopropylacrylamide (N-hydroxymethyl group) The mass ratio of acrylamide to N-isopropylacrylamide is 1:9), 3 parts of sodium dodecyl sulfate, 60 parts of water are formulated into an aqueous phase; then the aqueous phase is added to the oil phase at a shear rate of 24000 rpm and a shear time of 1 min. Under the action, an emulsion was formed; nitrogen was introduced into the emulsion, and the reaction was carried out at 90 °
  • the test shows that the prepared core material of the free radical interfacial polymerization-based microcapsules has a core loading of 46%, an embedding rate of 99%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle diameter of 1 to 15 ⁇ m, and the average particle size The diameter is 30 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 25 parts of n-hexadecane, 0.1 part of azobisisovaleronitrile to form an oil phase, and then 9 parts of N-methylol acrylamide, 3.5 parts of gum arabic, 80 parts of water, 0.1 parts of ammonium persulfate were formulated into an aqueous phase; then the aqueous phase was added to the oil phase at a shear rate of 10,000 rpm and a shear time of 5 min. An emulsion was formed; nitrogen gas was introduced into the emulsion, and reacted at 60 ° C for 1 hour to obtain a microcapsule based on radical interfacial polymerization.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 21%, an embedding rate of 88%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle diameter of 0.5 to 5 ⁇ m and an average particle size. The diameter is 1 ⁇ m.
  • a method for preparing microcapsules based on radical interfacial polymerization wherein 10 parts of n-heptadecane, 0.3 parts of di-tert-butyl peroxide are formulated into an oil phase, and then 1 part of styrene and 4.5 parts of gum arabic a mixture of 90 parts of water, 0.2 parts of ammonium persulfate and potassium persulfate (mass ratio of ammonium persulfate and potassium persulfate is 1:1); then the aqueous phase is added to the oil phase,
  • the shearing rate was 20,000 rpm, and the shearing time was 8 min under shearing to form an emulsion; nitrogen was introduced into the emulsion and reacted at 50 ° C for 3 hours to obtain a microcapsule based on radical interfacial polymerization.
  • the test shows that the prepared core material based on free radical interfacial polymerization has a core loading of 10%, an embedding rate of 85%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle size of 2 to 10 ⁇ m and an average particle size. The diameter is 4 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization wherein 20 parts of n-octadecane, 0.2 parts of a mixture of azobisisoheptanenitrile and t-butyl peroxide are formulated into an oil phase, wherein azodi
  • the mass ratio of heptonitrile to t-butyl peroxide is 1:1, and then 1 part of N-methylol acrylamide, 4 parts of sodium dodecyl sulfate, 70 parts of water, 0.3 parts of persulfuric acid
  • Ammonium is formulated into an aqueous phase; then the aqueous phase is added to the oil phase to form an emulsion at a shear rate of 21,000 rpm and a shear time of 8 min; Nitrogen gas was introduced and reacted at 50 ° C for 3 hours to obtain a microcapsule based on radical interfacial polymerization.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 21%, an embedding rate of 85%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle size of 5 to 40 ⁇ m, and the average particle size The diameter is 24 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization comprising 40 parts of n-nonadecane, 0.1 part of peroxyoctanoate, an oil phase, and 5 parts of a mixture of ethylene and styrene (ethylene and The mass ratio of styrene is 3:7), 3 parts of gum arabic, 70 parts of water, and 0.25 parts of ammonium persulfate are formulated into an aqueous phase; then the aqueous phase is added to the oil phase at a shear rate of 10,000 rpm. Under the shearing time of 7 min, an emulsion was formed; nitrogen gas was introduced into the emulsion, and reacted at 70 ° C for 4 hours to obtain a microcapsule based on radical interfacial polymerization.
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 34%, an embedding rate of 89%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle size of 30 to 80 ⁇ m, and the average particle size The diameter is 55 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization wherein 20 parts of n-icosane, 0.5 parts of a mixture of tert-butyl peroxybenzoate and benzoyl peroxide are formulated into an oil phase, wherein benzoyl peroxide
  • the mass ratio of tert-butyl formate to benzoyl peroxide is 8:2, and then 2 parts of a mixture of polyurethane and polyurea (mass ratio of polyurethane to polyurea is 4:6), 2 parts of dodecyl Sodium sulfonate, 90 parts of water, and 0.15 parts of potassium persulfate were formulated into an aqueous phase; then the aqueous phase was added to the oil phase to form an emulsion at a shear rate of 6000 rpm and a shear time of 3 min.
  • the reaction was carried out by introducing nitrogen gas into the emulsion and reacting at 40 ° C for
  • the test shows that the core material of the obtained microcapsules based on free radical interfacial polymerization has a core loading of 17%, an embedding rate of 84%, and the microcapsules are uniformly dispersed in water; the microcapsules have a particle size of 5 to 50 ⁇ m and an average particle size. The diameter is 35 ⁇ m.
  • a method for preparing microcapsules based on free radical interfacial polymerization wherein 2 parts of a mixture of polyglyceryl distearate, 0.4 parts of t-butyl peroxybenzoate and peroxyoctanoate are formulated into an oil phase, wherein The mass ratio of tert-butyl peroxybenzoate to peroxyoctanoate is 4:6, and then 7 parts of a mixture of diallyl phthalate and isobutylene (diallyl phthalate and isobutylene) Mass ratio is 3:7), 20 parts a water-soluble grape essence, 10 parts of water, a mixture of 0.5 parts of ammonium persulfate and sodium metabisulfite (a ratio of ammonium persulfate to sodium metabisulfite of 1:1) is formulated into an aqueous phase; then the aqueous phase is added to the oil phase In the shearing rate of 15000 rpm and a shearing time of 5 min, an
  • the test shows that the core material loading of the obtained microcapsules based on free radical interfacial polymerization is 51%, the embedding rate is 86%, the microcapsules are uniformly dispersed in water; the microcapsules have a particle size of 30-100 ⁇ m, and the average particle size The diameter is 50 ⁇ m.

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Abstract

提供一种基于自由基界面聚合的微胶囊及其制备方法。微胶囊制备时一种以上引发剂在油相，一种以上单体在水相。制备得到的微胶囊的壁材无毒，使得微胶囊能够应用在日化品、纺织品及医药领域。

Description

基于自由基界面聚合的微胶囊及其制备方法 技术领域
本发明属微胶囊制备技术领域，涉及基于自由基界面聚合的微胶囊及其制备方法，特别是涉及引发剂在油相的基于自由基界面聚合的微胶囊及其制备方法。
背景技术
微胶囊壁材的性质很大程度决定了微胶囊的应用范围，如无毒性、生物相容性、机械强度及热稳定性等。目前，普遍应用的壁材都为高分子聚合物，而高分子聚合物又分为天然高分子、半合成高分子和合成高分子。其中，合成高分子因具有突出的功能性及良好的热稳定性，而被广泛地用作微胶囊的壁材。应用较多的合成高聚物包括聚氨酯、聚脲、聚酯及聚丙烯酸类。其中，部分高聚物在合成过程中会留下未反应完的有毒单体残基，或者在合成过程中会使用有毒的交联剂，加之部分高聚物生物相容性差，这很大程度上限制了合成高聚物在制备微胶囊中的应用。随着科技的发展，微胶囊已经应用到各个与人体直接接触的行业，如食品、香精香料、纺织品、化妆品及医药等。这些应用对微胶囊壁材的无毒性要求更为严格。因此，通过选择无毒环保的合成单体且在合成过程中避免交联剂的使用合成出无毒壁材的微胶囊具有重要的意义。
有关壁材微胶囊的制备的报道很多，但关于选择无毒单体，且不用交联剂，便能制备出无毒环保的壁材的微胶囊还未见报道。
自由基界面聚合的现有技术中，都是采用引发剂在水相，单体在油相的制备方法，得到的微胶囊囊壁的亲水性不足，在众多的化妆品、日化品、纺织品、生物应用领域中，常常需要高亲水性。因此为了改变囊壁材料的亲水性，需要采用水溶性单体。
发明内容
本发明所要解决的技术问题是提供基于自由基界面聚合的微胶囊及其制备方法，特别是提供引发剂在油相的基于自由基界面聚合的微胶囊及其制备方法。
本发明的基于自由基界面聚合的微胶囊的制备方法，特点是引发剂在油相，单体在水相。
作为优选的技术方案：
如上所述的制备方法，所述水相中包含一种以上单体；所述油相中包含一种以上引发剂。
如上所述的制备方法，所述水相中还包含引发剂。
如上所述的制备方法，所述油相中含有至少一种单体。
如上所述的制备方法，所述制备方法为水包油法或者油包水法。
本发明还提供了一种基于自由基界面聚合的微胶囊的制备方法，按质量份数计：
(a)油相组分：
芯材：1～60份；
单体一：1～10份；
引发剂：0.1～0.5份；
单体一的结构通式为：
Figure PCTCN2016088132-appb-000001
其中R1为
Figure PCTCN2016088132-appb-000002
R2为
Figure PCTCN2016088132-appb-000003
或—H；
R3为
Figure PCTCN2016088132-appb-000004
或—H；
R4为
Figure PCTCN2016088132-appb-000005
或—H；
m1＝2,3,4…；m2＝1,2,3,4…；m3＝2,3,4…；m4＝1,2,3,4…；m5＝2,3,4…；m6＝1,2,3,4…；m7＝2,3,4…；m8＝1,2,3,4…
其中，芯材为不溶于水的液体油相；
(b)水相组分：
乳化剂：1.5～4.5份；
单体二：1～10份；
水：10～90份；
单体二的结构通式为：
Figure PCTCN2016088132-appb-000006
其中R5为
Figure PCTCN2016088132-appb-000007
R6为
Figure PCTCN2016088132-appb-000008
或—H；
R7为
Figure PCTCN2016088132-appb-000009
或—H；
R8为
Figure PCTCN2016088132-appb-000010
或—H；
n1＝2,3,4…；n2＝1,2,3,4…；n3＝2,3,4…；n4＝1,2,3,4…；n5＝2,3,4…；n6＝1,2,3,4…；n7＝2,3,4…；n8＝1,2,3,4…
制备过程为：分别配制油相和水相；将水相加入到油相中，剪切，形成乳液；向乳液通入氮气，40℃～90℃反应0.5～8小时，得到基于自由基界面聚合的微胶囊。
如上所述的制备方法，所述单体一具体为：二甲基丙烯酸乙二醇酯、二甲基丙烯酸1,4-丁二醇酯和二甲基丙烯酸1,6-己二醇酯中的一种以上；
所述芯材为紫外吸收剂、香精香料、相变材料和医药中的一种以上；所述紫外吸收剂为奥克立林、二苯酮-3、水杨酸辛酯、巴松1789或甲氧基肉桂酸异辛酯；所述香精香料为薄荷素油、玫瑰香精、柠檬香精、薰衣草香精、绿茶香精、水清莲花香精或花香香精；所述相变材料为石蜡、正十四烷、正十五烷、正十六烷、正十七烷、正十八烷、正十九烷、正二十烷、正二十一烷、正二十二烷、正二十三烷或正二十四烷；所述医药为维生素油或抗肿瘤药物；
所述引发剂为偶氮二异丁腈或过氧化二酰；所述引发剂与单体一的质量比为0.1:3～10；
所述乳化剂为十二烷基磺酸钠、阿拉伯树胶或聚乙烯醇，其中聚乙烯醇的水解度为80～90％；
所述单体二具体为聚多元醇丙烯酸酯；
所述剪切的剪切速率为6000～24000rpm，剪切时间为1～10min。
本发明又提供了一种基于自由基界面聚合的微胶囊，所述基于自由基界面聚合的微胶囊，芯材包载量为10％～60％，包埋率为80％～99％，微胶囊均匀分散于水中。
本发明提供的微胶囊，所述微胶囊的粒径为0.5～100μm，平均粒径为1～80μm。
本发明的机理为：
自由基界面聚合形成微胶囊技术，通常采用水溶性引发剂在水包油乳液界面上引发油相中的单体进行交联聚合微胶囊，由于溶于油相中的单体亲水性弱，因此，所形成的微胶囊高分子壁材吸水性差。众多的生物医用微胶囊、化妆品微胶囊、个人护理品微胶囊需要微胶囊壁材具有良好的亲水性，原有的自由基界面聚合形成微胶囊技术不能解决这一难题，本发明采用溶于油相中的油溶性引发剂，在乳液界面上引发水相中的亲水性单体进行交联聚合形成微胶囊，新方法所制备的微胶囊壁材具有良好的亲水性，将满足市场的新需求。
有益效果
(1)本发明采用的单体，本身无毒，故不存在反应后留下未反应完的有毒单体残基问题。
(2)本发明合成的壁材属于无毒材料，使得这类微胶囊能很好地应用于和人体相关的产品中。
(3)本发明使用的乳化剂为十二烷基磺酸钠(SDS)、阿拉伯树胶(GA)和聚乙烯醇(PVA)，前者为阴离子型表面活性剂，具有优异的渗透、洗涤、润湿、去污和乳化作用，中间为天然高分子材料，绿色环保，后者是无毒的合成高分子乳化剂。这三类乳化剂都是无毒环保，不会给反应体系引入任何有毒的物质，使得该发明体系绿色环保。
(4)本发明制备的微胶囊对芯材的包埋率为高且形成的壁材厚度均匀，微胶囊性能稳定；本发明的微胶囊制备过程都是绿色环保，制备出的微胶囊对人体无害，在防晒霜、香精香料、生物医药、日用化妆品及防治微胶囊等行业有广泛的应用前景。
附图说明
图1为实施例1自由基聚合机理；
图2为实施例1中制备得到的微胶囊的光学显微镜图；
图3为实施例3中制备得到的微胶囊的粒径分布图；
图4为实施例4中制备得到的微胶囊的扫描电子显微镜照片。
具体实施方式
下面结合具体实施方式，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
一种基于自由基界面聚合的微胶囊的制备方法，将1份的奥克立林、0.1份的过氧化二酰、3份的二甲基丙烯酸乙二醇酯配制成油相，再将1份的聚乙二醇二丙烯酸酯、1.5份的阿拉伯树胶、90份的水配制成水相；然后将水相加入到油相中，在剪切速率为6000rpm，剪切时间为1min的剪切作用下，形成乳液；向乳液通入氮气，在40℃反应0.5小时，得到基于自由基界面聚合的微胶囊，其反应机理如图1所示。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为1％，包埋率为80％，微胶囊均匀分散于水中；微胶囊的粒径为0.5～15μm，平均粒径为3μm，如图2所示。
实施例2
一种基于自由基界面聚合的微胶囊的制备方法，将40份的二苯酮-3、0.3份的过氧化二酰、10份的二甲基丙烯酸1,4-定二醇酯配制成油相，再将5份的聚多元醇丙烯酸酯、4份的十二烷基磺酸钠、75份的水配制成水相；然后将水相加入 到油相中，在剪切速率为9000rpm，剪切时间为4min的剪切作用下，形成乳液；向乳液通入氮气，在80℃反应7小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为30％，包埋率为99％，微胶囊均匀分散于水中；微胶囊的粒径为0.1～7.5μm，平均粒径为3μm，如图3所示。
实施例3
一种基于自由基界面聚合的微胶囊的制备方法，将30份的水杨酸辛酯、0.2份的偶氮二异丁腈、8份的二甲基丙烯酸1,6-己二醇酯配制成油相，再将5份的聚多元醇丙烯酸酯、4份的聚乙烯醇，其中聚乙烯醇的水解度为80％、55份的水配制成水相；然后将水相加入到油相中，在剪切速率为10000rpm，剪切时间为4min的剪切作用下，形成乳液；向乳液通入氮气，在80℃反应7小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为29％，包埋率为89％，微胶囊均匀分散于水中；微胶囊的粒径为20～80μm，平均粒径为30μm，如图4所示。
实施例4
一种基于自由基界面聚合的微胶囊的制备方法，将30份的巴松1789、0.25份的过氧化二酰、10份的二甲基丙烯酸1,4-定二醇酯和二甲基丙烯酸1,6-己二醇酯的混合物配制成油相，其中二甲基丙烯酸1,4-定二醇酯和二甲基丙烯酸1,6-己二醇酯的质量比为2:1，再将8份的聚多元醇丙烯酸酯、2份的聚乙烯醇，其中聚乙烯醇的水解度为90％、87份的水配制成水相；然后将水相加入到油相中，在剪切速率为20000rpm，剪切时间为8min的剪切作用下，形成乳液；向乳液通入氮气，在85℃反应6.5小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为22％，包埋率为85％，微胶囊均匀分散于水中；微胶囊的粒径为4～30μm，平均粒径为15μm。
实施例5
一种基于自由基界面聚合的微胶囊的制备方法，将30份的甲氧基肉桂酸异辛酯、0.1份的偶氮二异丁腈、8份的二甲基丙烯酸1,4-定二醇酯和二甲基丙烯酸 乙二醇酯的混合物配制成油相，其中二甲基丙烯酸1,4-定二醇酯和二甲基丙烯酸乙二醇酯的质量比为2:3，再将1份的聚多元醇丙烯酸酯、4.5份的聚乙烯醇，其中聚乙烯醇的水解度为85％、90份的水配制成水相；然后将水相加入到油相中，在剪切速率为18000rpm，剪切时间为8min的剪切作用下，形成乳液；向乳液通入氮气，在75℃反应6小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为22％，包埋率为82％，微胶囊均匀分散于水中；微胶囊的粒径为0.5～20μm，平均粒径为6μm。
实施例6
一种基于自由基界面聚合的微胶囊的制备方法，将25份的薄荷素油、0.12份的偶氮二异丁腈、6份的二甲基丙烯酸1,4-定二醇酯、二甲基丙烯酸1,6-己二醇酯和二甲基丙烯酸乙二醇酯的混合物配制成油相，其中二甲基丙烯酸1,4-定二醇酯、二甲基丙烯酸1,6-己二醇酯和二甲基丙烯酸乙二醇酯的质量比为2:1:5，再将8份的聚多元醇丙烯酸酯、4份的聚乙烯醇，其中聚乙烯醇的水解度为84％、85份的水配制成水相；然后将水相加入到油相中，在剪切速率为20000rpm，剪切时间为6min的剪切作用下，形成乳液；向乳液通入氮气，在70℃反应6小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为20％，包埋率为86％，微胶囊均匀分散于水中；微胶囊的粒径为0.5～5μm，平均粒径为2μm。
实施例7
一种基于自由基界面聚合的微胶囊的制备方法，将45份的玫瑰香精、0.3份的过氧化二酰、9份的二甲基丙烯酸1,4-定二醇酯、二甲基丙烯酸1,6-己二醇酯和二甲基丙烯酸乙二醇酯的混合物配制成油相，其中二甲基丙烯酸1,4-定二醇酯、二甲基丙烯酸1,6-己二醇酯和二甲基丙烯酸乙二醇酯的质量比为4:1:3，再将4份的聚多元醇丙烯酸酯、2份的聚乙烯醇，其中聚乙烯醇的水解度为83％、60份的水配制成水相；然后将水相加入到油相中，在剪切速率为10000rpm，剪切时间为8min的剪切作用下，形成乳液；向乳液通入氮气，在40℃反应4小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为37％，包埋 率为90％，微胶囊均匀分散于水中；微胶囊的粒径为4～40μm，平均粒径为20μm。
实施例8
一种基于自由基界面聚合的微胶囊的制备方法，将40份的奥克立林、玫瑰香精和正十四烷的混合物(奥克立林、玫瑰香精和正十四烷的质量比为2:1:3)、0.12份的偶氮二异丁腈、5份的二甲基丙烯酸1,4-定二醇酯配制成油相，再将7份的聚多元醇丙烯酸酯、3份的十二烷基磺酸钠、50份的水配制成水相；然后将水相加入到油相中，在剪切速率为14000rpm，剪切时间为5min的剪切作用下，形成乳液；向乳液通入氮气，在50℃反应3小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为38％，包埋率为84％，微胶囊均匀分散于水中；微胶囊的粒径为50～100μm，平均粒径为80μm。
实施例9
一种基于自由基界面聚合的微胶囊的制备方法，将50份的水杨酸辛酯、绿茶香精和维生素油的混合物(水杨酸辛酯、绿茶香精和维生素油的质量比为2:4:1)、0.1份的偶氮二异丁腈、6份的二甲基丙烯酸1,6-己二醇酯配制成油相，再将5份的聚多元醇丙烯酸酯、3份的阿拉伯树胶、87份的水配制成水相；然后将水相加入到油相中，在剪切速率为18000rpm，剪切时间为5min的剪切作用下，形成乳液；向乳液通入氮气，在60℃反应7小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为33％，包埋率为88％，微胶囊均匀分散于水中；微胶囊的粒径为0.5～40μm，平均粒径为20μm。
实施例10
一种基于自由基界面聚合的微胶囊的制备方法，将40份的奥克立林、玫瑰香精、维生素油和正十四烷的混合物(奥克立林、玫瑰香精和正十四烷的质量比为1:1:3:2)、0.1份的过氧化二酰、5份的二甲基丙烯酸乙二醇酯配制成油相，再将7份的聚多元醇丙烯酸酯、4份的十二烷基磺酸钠、60份的水配制成水相；然 后将水相加入到油相中，在剪切速率为10000rpm，剪切时间为5min的剪切作用下，形成乳液；向乳液通入氮气，在50℃反应2小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为34％，包埋率为82％，微胶囊均匀分散于水中；微胶囊的粒径为50～100μm，平均粒径为70μm。
实施例11
一种基于自由基界面聚合的微胶囊的制备方法，将50份的水杨酸辛酯、绿茶香精、石蜡和维生素油的混合物(水杨酸辛酯、绿茶香精和维生素油的质量比为2:1:4:3)、0.1份的过氧化二酰、7份的二甲基丙烯酸乙二醇酯配制成油相，再将5份的聚多元醇丙烯酸酯、3份的阿拉伯树胶、87份的水配制成水相；然后将水相加入到油相中，在剪切速率为8000rpm，剪切时间为5min的剪切作用下，形成乳液；向乳液通入氮气，在60℃反应5小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为32％，包埋率为88％，微胶囊均匀分散于水中；微胶囊的粒径为0.5～40μm，平均粒径为18μm。
实施例12
一种基于自由基界面聚合的微胶囊的制备方法，将55份的柠檬香精、0.3份的偶氮二异戊腈配制成油相，再将5份的N-异丙基丙烯酰胺、2份水解度为85％的聚乙烯醇、20份的水配制成水相；然后将水相加入到油相中，在剪切速率为10000rpm，剪切时间为8min的剪切作用下，形成乳液；向乳液通入氮气，在70℃反应4小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为60％，包埋率为92％，微胶囊均匀分散于水中；微胶囊的粒径为5～40μm，平均粒径为25μm。
实施例13
一种基于自由基界面聚合的微胶囊的制备方法，将25份的薰衣草香精、0.2份的偶氮二异丁酸二甲酯配制成油相，再将5份的N-羟甲基丙烯酰胺、2份水解 度为89％的聚乙烯醇、20份的水配制成水相；然后将水相加入到油相中，在剪切速率为10000rpm，剪切时间为8min的剪切作用下，形成乳液；向乳液通入氮气，在70℃反应4小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为48％，包埋率为95％，微胶囊均匀分散于水中；微胶囊的粒径为5～50μm，平均粒径为35μm。
实施例14
一种基于自由基界面聚合的微胶囊的制备方法，将35份的绿茶香精、0.1份的偶氮异丁氰基甲酰胺配制成油相，再将5份的甲基丙烯酸、2份水解度为80％的聚乙烯醇、20份的水配制成水相；然后将水相加入到油相中，在剪切速率为10000rpm，剪切时间为6min的剪切作用下，形成乳液；向乳液通入氮气，在70℃反应4小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为56％，包埋率为85％，微胶囊均匀分散于水中；微胶囊的粒径为0.5～20μm，平均粒径为5μm。
实施例15
一种基于自由基界面聚合的微胶囊的制备方法，将40份的水清莲花香精、0.1份的偶氮二异丁酸二甲酯和偶氮异丁氰基甲酰胺的混合物配制成油相，其中偶氮二异丁酸二甲酯和偶氮异丁氰基甲酰胺的质量比为4:6，再将4份的丙烯酰胺、4份的阿拉伯树胶、60份的水配制成水相；然后将水相加入到油相中，在剪切速率为15000rpm，剪切时间为4min的剪切作用下，形成乳液；向乳液通入氮气，在60℃反应5小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为37％，包埋率为96％，微胶囊均匀分散于水中；微胶囊的粒径为20～70μm，平均粒径为50μm。
实施例16
一种基于自由基界面聚合的微胶囊的制备方法，将35份的花香香精、0.2份的偶氮二异丁腈和偶氮异丁氰基甲酰胺的混合物配制成油相，其中偶氮二异丁腈和偶氮异丁氰基甲酰胺的质量比为3:7，再将9份的2-丙烯酰氨基-2-甲基丙磺 酸、2.5份的十二烷基磺酸钠、75份的水配制成水相；然后将水相加入到油相中，在剪切速率为15000rpm，剪切时间为7min的剪切作用下，形成乳液；向乳液通入氮气，在65℃反应5小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为29％，包埋率为98％，微胶囊均匀分散于水中；微胶囊的粒径为1～30μm，平均粒径为6μm。
实施例17
一种基于自由基界面聚合的微胶囊的制备方法，将55份的石蜡、0.15份的偶氮二异戊腈配制成油相，再将9份的丙烯酰胺和2-丙烯酰氨基-2-甲基丙磺酸的混合物(丙烯酰胺和2-丙烯酰氨基-2-甲基丙磺酸的质量比为6:4)、3.5份的十二烷基磺酸钠、70份的水配制成水相；然后将水相加入到油相中，在剪切速率为18000rpm，剪切时间为5min的剪切作用下，形成乳液；向乳液通入氮气，在60℃反应6小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为40％，包埋率为92％，微胶囊均匀分散于水中；微胶囊的粒径为2～50μm，平均粒径为20μm。
实施例18
一种基于自由基界面聚合的微胶囊的制备方法，将40份的正十四烷、0.15份的偶氮二异庚腈配制成油相，再将9份的甲基丙烯酸叔丁酯和甲基丙烯酸甲酯的混合物(甲基丙烯酸叔丁酯和甲基丙烯酸甲酯的质量比为2:8)、4份的阿拉伯树胶、80份的水配制成水相；然后将水相加入到油相中，在剪切速率为11000rpm，剪切时间为10min的剪切作用下，形成乳液；向乳液通入氮气，在60℃反应7小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为30％，包埋率为80％，微胶囊均匀分散于水中；微胶囊的粒径为4～40μm，平均粒径为30μm。
实施例19
一种基于自由基界面聚合的微胶囊的制备方法，将60份的正十五烷、0.1份的偶氮二异戊腈和偶氮异丁氰基甲酰胺的混合物配制成油相，其中偶氮二异戊腈和偶氮异丁氰基甲酰胺的质量比为5:6，再将7份的N-羟甲基丙烯酰胺和N-异丙基丙烯酰胺的混合物(N-羟甲基丙烯酰胺和N-异丙基丙烯酰胺的质量比为 1:9)、3份的十二烷基磺酸钠、60份的水配制成水相；然后将水相加入到油相中，在剪切速率为24000rpm，剪切时间为1min的剪切作用下，形成乳液；向乳液通入氮气，在90℃反应8小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为46％，包埋率为99％，微胶囊均匀分散于水中；微胶囊的粒径为1～15μm，平均粒径为30μm。
实施例20
一种基于自由基界面聚合的微胶囊的制备方法，将25份的正十六烷、0.1份的偶氮二异戊腈配制成油相，再将9份的N-羟甲基丙烯酰胺、3.5份的阿拉伯树胶、80份的水、0.1份的过硫酸铵配制成水相；然后将水相加入到油相中，在剪切速率为10000rpm，剪切时间为5min的剪切作用下，形成乳液；向乳液通入氮气，在60℃反应1小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为21％，包埋率为88％，微胶囊均匀分散于水中；微胶囊的粒径为0.5～5μm，平均粒径为1μm。
实施例21
一种基于自由基界面聚合的微胶囊的制备方法，将10份的正十七烷、0.3份的过氧化二叔丁基配制成油相，再将1份的苯乙烯、4.5份的阿拉伯树胶、90份的水、0.2份的过硫酸铵和过硫酸钾的混合物(过硫酸铵和过硫酸钾的质量比为1:1)配制成水相；然后将水相加入到油相中，在剪切速率为20000rpm，剪切时间为8min的剪切作用下，形成乳液；向乳液通入氮气，在50℃反应3小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为10％，包埋率为85％，微胶囊均匀分散于水中；微胶囊的粒径为2～10μm，平均粒径为4μm。
实施例22
一种基于自由基界面聚合的微胶囊的制备方法，将20份的正十八烷、0.2份的偶氮二异庚腈和过氧化叔丁基的混合物配制成油相，其中偶氮二异庚腈和过氧化叔丁基的质量比为1:1，再将1份的N-羟甲基丙烯酰胺、4份的十二烷基磺酸钠、70份的水、0.3份的过硫酸铵配制成水相；然后将水相加入到油相中，在剪切速率为21000rpm，剪切时间为8min的剪切作用下，形成乳液；向乳液通 入氮气，在50℃反应3小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为21％，包埋率为85％，微胶囊均匀分散于水中；微胶囊的粒径为5～40μm，平均粒径为24μm。
实施例23
一种基于自由基界面聚合的微胶囊的制备方法，将40份的正十九烷、0.1份的过氧化辛酸酯配制成油相，再将5份的乙烯和苯乙烯的混合物(乙烯和苯乙烯的质量比为3:7)、3份的阿拉伯树胶、70份的水、0.25份的过硫酸铵配制成水相；然后将水相加入到油相中，在剪切速率为10000rpm，剪切时间为7min的剪切作用下，形成乳液；向乳液通入氮气，在70℃反应4小时，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为34％，包埋率为89％，微胶囊均匀分散于水中；微胶囊的粒径为30～80μm，平均粒径为55μm。
实施例24
一种基于自由基界面聚合的微胶囊的制备方法，将20份的正二十烷、0.5份的过氧化苯甲酸叔丁酯和过氧化苯甲酰的混合物配制成油相，其中过氧化苯甲酸叔丁酯和过氧化苯甲酰的质量比为8:2，再将2份的聚氨酯和聚脲的混合物(聚氨酯和聚脲的质量比为4:6)、2份的十二烷基磺酸钠、90份的水、0.15份的过硫酸钾配制成水相；然后将水相加入到油相中，在剪切速率为6000rpm，剪切时间为3min的剪切作用下，形成乳液；向乳液通入氮气，在40℃反应5小时，采用水包油的方法，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为17％，包埋率为84％，微胶囊均匀分散于水中；微胶囊的粒径为5～50μm，平均粒径为35μm。
实施例25
一种基于自由基界面聚合的微胶囊的制备方法，将2份的双硬脂酸聚甘油酯、0.4份的过氧化苯甲酸叔丁酯和过氧化辛酸酯的混合物配制成油相，其中过氧化苯甲酸叔丁酯和过氧化辛酸酯的质量比为4:6，再将7份的邻苯二甲酸二烯丙酯和异丁烯的混合物(邻苯二甲酸二烯丙酯和异丁烯的质量比为3:7)、20份 的水溶性葡萄香精、10份的水、0.5份的过硫酸铵和焦亚硫酸钠的混合物(过硫酸铵和焦亚硫酸钠的质量比为1:1)配制成水相；然后将水相加入到油相中，在剪切速率为15000rpm，剪切时间为5min的剪切作用下，形成乳液；向乳液通入氮气，在50℃反应6小时，采用油包水的方法，得到基于自由基界面聚合的微胶囊。
测试表明，制得的基于自由基界面聚合的微胶囊的芯材包载量为51％，包埋率为86％，微胶囊均匀分散于水中；微胶囊的粒径为30～100μm，平均粒径为50μm。

Claims (9)

  1. 基于自由基界面聚合的微胶囊的制备方法，其特征是：引发剂在油相，单体在水相。
  2. 根据权利要求1所述的制备方法，其特征在于，所述水相中包含一种以上单体；所述油相中包含一种以上引发剂。
  3. 根据权利要求1或2所述的制备方法，其特征在于，所述水相中还包含引发剂。
  4. 根据权利要求1或2所述的制备方法，其特征在于，所述油相中含有至少一种单体。
  5. 根据权利要求1或2所述的制备方法，其特征在于，所述制备方法为水包油法或者油包水法。
  6. 一种基于自由基界面聚合的微胶囊的制备方法，其特征是，按质量份数计：
    (a)油相组分：
    芯材：1～60份；
    单体一：1～10份；
    引发剂：0.1～0.5份；
    单体一的结构通式为：
    Figure PCTCN2016088132-appb-100001
    其中R1为
    Figure PCTCN2016088132-appb-100002
    R2为
    Figure PCTCN2016088132-appb-100003
    或—H；
    R3为
    Figure PCTCN2016088132-appb-100004
    或—H；
    R4为
    Figure PCTCN2016088132-appb-100005
    或—H；
    m1＝2,3,4…；m2＝1,2,3,4…；m3＝2,3,4…；m4＝1,2,3,4…；m5＝2,3,4…；m6＝1,2,3,4…；m7＝2,3,4…；m8＝1,2,3,4…
    其中，芯材为不溶于水的液体油相；
    (b)水相组分：
    乳化剂：1.5～4.5份；
    单体二：1～10份；
    水：10～90份；
    单体二的结构通式为：
    Figure PCTCN2016088132-appb-100006
    其中R5为
    Figure PCTCN2016088132-appb-100007
    R6为
    Figure PCTCN2016088132-appb-100008
    或—H；
    R7为
    Figure PCTCN2016088132-appb-100009
    或—H；
    R8为
    Figure PCTCN2016088132-appb-100010
    或—H；
    n1＝2,3,4…；n2＝1,2,3,4…；n3＝2,3,4…；n4＝1,2,3,4…；n5＝2,3,4…；n6＝1,2,3,4…；n7＝2,3,4…；n8＝1,2,3,4…
    制备过程为：分别配制油相和水相；将水相加入到油相中，剪切，形成乳液；向乳液通入氮气，40℃～90℃反应0.5～8小时，得到基于自由基界面聚合的微胶囊。
  7. 根据权利要求6所述的制备方法，其特征在于，所述单体一具体为：二甲基丙烯酸乙二醇酯、二甲基丙烯酸1,4-丁二醇酯或二甲基丙烯酸1,6-己二醇酯中的一种以上；
    所述芯材为紫外吸收剂、香精香料、相变材料或医药中的一种以上；所 述紫外吸收剂为奥克立林、二苯酮-3、水杨酸辛酯、巴松1789或甲氧基肉桂酸异辛酯；所述香精香料为薄荷素油、玫瑰香精、柠檬香精、薰衣草香精、绿茶香精、水清莲花香精或花香香精；所述相变材料为石蜡、正十四烷、正十五烷、正十六烷、正十七烷、正十八烷、正十九烷、正二十烷、正二十一烷、正二十二烷、正二十三烷或正二十四烷；所述医药为维生素油或抗肿瘤药物；
    所述引发剂为偶氮二异丁腈或过氧化二酰；所述引发剂与单体一的质量比为0.1:3～10；
    所述乳化剂为十二烷基磺酸钠、阿拉伯树胶或聚乙烯醇，其中聚乙烯醇的水解度为80～90％；
    所述单体二具体为聚多元醇丙烯酸酯；
    所述剪切的剪切速率为6000～24000rpm，剪切时间为1～10min。
  8. 如权利要求6或7的方法制得的基于自由基界面聚合的微胶囊，其特征是：所述基于自由基界面聚合的微胶囊，芯材包载量为10％～60％，包埋率为80％～99％，微胶囊均匀分散于水中。
  9. 根据权利要求8所述的微胶囊，其特征在于，所述微胶囊的粒径为0.5～100μm，平均粒径为1～80μm。
PCT/CN2016/088132 2016-06-29 2016-07-01 基于自由基界面聚合的微胶囊及其制备方法 Ceased WO2018000422A1 (zh)

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