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WO2018000422A1 - Microcapsule basée sur une polymérisation interfaciale par radicaux libres et procédé de préparation correspondant - Google Patents

Microcapsule basée sur une polymérisation interfaciale par radicaux libres et procédé de préparation correspondant 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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Chinese (zh)
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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

L'invention concerne une microcapsule basée sur une polymérisation interfaciale par radicaux libres et un procédé de préparation correspondant. Pendant la préparation de la microcapsule, au moins un amorceur est dans une phase huileuse, et au moins un monomère est dans une phase aqueuse. Le matériau de paroi de la microcapsule préparée est exempt de toxicité, de sorte que la microcapsule peut être utilisée dans le domaine des produits chimiques, des textiles et des médicaments utilisés quotidiennement.
PCT/CN2016/088132 2016-06-29 2016-07-01 Microcapsule basée sur une polymérisation interfaciale par radicaux libres et procédé de préparation correspondant Ceased WO2018000422A1 (fr)

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CN115025004A (zh) * 2022-05-24 2022-09-09 上海应用技术大学 一种防晒微胶囊及其制备方法和应用
CN115124962A (zh) * 2022-07-01 2022-09-30 南通金丝楠膜材料有限公司 一种无溶剂散香胶水及其制备方法、复合膜及其制备方法
CN115253699A (zh) * 2022-07-18 2022-11-01 浙江工业大学 一种高渗透性反渗透膜的制备方法
US11510236B2 (en) 2018-10-04 2022-11-22 Asustek Computer Inc. Method and apparatus of requesting resource for sidelink retransmission in a wireless communication system
CN116020366A (zh) * 2022-11-14 2023-04-28 武汉中科先进材料科技有限公司 一种热固自成膜相变微胶囊及其制备方法

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CN108066163A (zh) * 2017-12-19 2018-05-25 东华大学 一种以聚乙二醇二丙烯酸酯为壁材的防晒微胶囊及其制备方法
CN108420739A (zh) * 2018-03-28 2018-08-21 东华大学 以聚乙二醇二丙烯酸酯为壁材的防晒微胶囊及其制备方法
CN108425248B (zh) * 2018-03-28 2021-04-02 浙江理工大学 一种纳米温控缓释芳香微胶囊的制备方法
CN110511316A (zh) * 2019-08-30 2019-11-29 东莞苏氏卫生用品有限公司 一种界面聚合的薄膜状高吸水性树脂的制备方法
CN115970604A (zh) * 2023-02-22 2023-04-18 南京芬之怡生物科技有限公司 一种香精聚（乙酸二氢月桂烯醇酯）微囊的制备方法

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CN101701146A (zh) * 2009-10-22 2010-05-05 天津工业大学 一种相变材料微胶囊及其制备方法
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Cited By (8)

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Publication number Priority date Publication date Assignee Title
US11510236B2 (en) 2018-10-04 2022-11-22 Asustek Computer Inc. Method and apparatus of requesting resource for sidelink retransmission in a wireless communication system
CN115025004A (zh) * 2022-05-24 2022-09-09 上海应用技术大学 一种防晒微胶囊及其制备方法和应用
CN115124962A (zh) * 2022-07-01 2022-09-30 南通金丝楠膜材料有限公司 一种无溶剂散香胶水及其制备方法、复合膜及其制备方法
CN115124962B (zh) * 2022-07-01 2023-11-03 南通金丝楠膜材料有限公司 一种无溶剂散香胶水及其制备方法、复合膜及其制备方法
CN115253699A (zh) * 2022-07-18 2022-11-01 浙江工业大学 一种高渗透性反渗透膜的制备方法
CN115253699B (zh) * 2022-07-18 2024-05-03 浙江工业大学 一种高渗透性反渗透膜的制备方法
CN116020366A (zh) * 2022-11-14 2023-04-28 武汉中科先进材料科技有限公司 一种热固自成膜相变微胶囊及其制备方法
CN116020366B (zh) * 2022-11-14 2023-09-05 武汉中科先进材料科技有限公司 一种热固自成膜相变微胶囊及其制备方法

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