Method for preparing organic-inorganic hybrid microcapsule

Patent metadata

Field	Value
Publication number	US-11951449-B2
Application number	US-201917257159-A
Country	US
Kind code	B2
Filing date	Jul 2, 2019
Priority date	Jul 3, 2018
Publication date	Apr 9, 2024
Grant date	Apr 9, 2024

Abstract

The present disclosure relates to a method for preparing a biodegradable and eco-friendly organic-inorganic hybrid microcapsule having few toxic substances with high versatility and economical efficiency by using a pickering emulsion method with a specific outer wall reinforcing material, a reactive material, and inorganic nanoparticles, and allowing polymerization of the outer wall reinforcing material and the reactive material to proceed at the interface. Specifically, the organic-inorganic hybrid microcapsule can stably support an active ingredient and then effectively express its activity by pressure, and exhibit a characteristic of gradually releasing the active ingredient at room temperature.

First claim

The invention claimed is:

1. A method for preparing an organic-inorganic hybrid microcapsule comprising the steps of:
a first step of preparing a first continuous-phase solution containing inorganic nanoparticles and a second continuous-phase solution containing a polymer precursor 1 for reinforcing an outer wall;
a second step of preparing a dispersed-phase solution containing a polymer precursor 2 which reacts with the polymer precursor 1 or containing an active ingredient and the polymer precursor 2; and
a third step of forming a picketing emulsion by adding the dispersed-phase solution to the first solution, and then forming an outer wall of the capsule through interfacial polymerization by adding the second solution,
wherein the outer wall of the capsule comprises i) at least one polymer selected from the group consisting of polyamide, polyurethane, polyurea, polyester and poly(β-amino ester), and ii) inorganic nanoparticles; and
the polymer precursor 1 for reinforcing the outer wall and the polymer precursor 2 each independently contain at least one precursor for forming a polymer selected from the group consisting of polyamide, polyurethane, polyurea, polyester, and poly(β-amino ester),
wherein the polymer precursor 2 is at least one selected from the group consisting of a compound containing two or more acid chloride structures represented by the Chemical Formula 3, and a compound containing two or more chloroformate structures represented by the following Chemical Formula 5:

(in Chemical Formula 3, each R 3 may independently comprise C1 to C50 alkylene, a C3 to C60 cyclic hydrocarbon group, or C1 to C50 alkylene and a C3 to C60 cyclic hydrocarbon group having or not having at least one acid chloride (-COCl) or at least one heteroatom)

(in Chemical Formula 5, each R 5 may independently comprise C1 to C50 alkylene, a C3 to C60 cyclic hydrocarbon group, or C1 to C50 alkylene and a C3 to C60 cyclic hydrocarbon group having or not having at least one chloroformate (-OCOCl) or at least one heteroatom).

2. The method for preparing an organic-inorganic hybrid microcapsule of claim 1 ,
wherein the polymer precursor 1 is at least one selected from the group consisting of a compound having two or more amine groups represented by the following Chemical Formula 1, a compound having two or more hydroxyl groups represented by the following Chemical Formula 2, and a natural polymer:

(in Chemical Formula 1, each R 1 may independently comprise C1 to C50 alkylene, a C3 to C60 cyclic hydrocarbon group, or C1 to C50 alkylene and a C3 to C60 cyclic hydrocarbon group having or not having at least one amine group or at least one heteroatom, and
n is an integer of 1 to 5000)

(in Chemical Formula 2, each R 2 may independently comprise C1 to C50 alkylene, a C3 to C60 cyclic hydrocarbon group, or C1 to C50 alkylene and a C3 to C60 cyclic hydrocarbon group having or not having at least one hydroxyl group or at least one heteroatom, and
m is an integer of 1 to 5000).

3. The method for preparing an organic-inorganic hybrid microcapsule of claim 2 ,
wherein the compound having two or more amine groups is at least one selected from the group consisting of m ethylenedi amine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris(2-aminoethyl)amine, polyethyleneimine, poly(propylene glycol) bis(2-aminopropyl ether), trimethylolpropane tris[poly(propylene glycol), amine terminated]ether, polyethylene glycol) bis(amine), o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,3-diaminotoluene, 2, 5-diaminotoluene, 3,3′diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-ethylenedianiline, 4,4′-diaminodiphenyl sulfide, 4,4′-oxydianiline, pararosaniline base, melamine and tetrakis(4-aminophenyl)methane).

4. The method for preparing an organic-inorganic hybrid microcapsule of claim 2 ,
wherein the natural polymer is at least one selected from the group consisting of gelatin, chitosan, polylysine, gum arabic, polysaccharides, pectin, and alginate.

5. The method for preparing a biodegradable organic-inorganic hybrid microcapsule of claim 1 ,
wherein the polymer precursor 2 is a compound containing two or more acrylate structures represented by the following Chemical Formula 6:

(in Chemical Formula 6, each R 3 may independently comprise C1 to C50 alkylene, a C3 to C60 cyclic hydrocarbon group, or C1 to C50 alkylene and a C3 to C60 cyclic hydrocarbon group having or not having at least one acrylate or at least one heteroatom).

6. The method for preparing an organic-inorganic hybrid microcapsule of claim 1 ,
wherein the inorganic nanoparticles are contained in an amount of 0001 to 30 wt % based on a total weight of the first continuous-phase solution.

7. The method for preparing an organic-inorganic hybrid microcapsule of claim 1 ,
wherein the polymer precursor 1 is contained in an amount of 0,001 to 20 wt % based on a total weight of the second continuous-phase solution.

8. The method for preparing an organic-inorganic hybrid microcapsule of claim 1 ,
wherein the polymer precursor 2 is contained in an amount of 0.001 to 30 wt % based on a total weight of the dispersed-phase solution.

9. The method for preparing an organic-inorganic hybrid microcapsule of claim 1 ,
wherein the dispersed-phase solution further comprises at least one solvent selected from the group consisting of pentane, hexane, cyclohexane, heptane, octane, isododecane, dodecane, ethyl ether, butyl ether, methyl-t-butyl ether, ethyl acetate, butyl acetate, ethyl butyrate, methyl ethyl ketone, benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethicone, and cyclomethicone.

10. The method for preparing an organic-inorganic hybrid microcapsule of claim 1 ,
wherein the inorganic nanoparticles are at least one selected from the group consisting of halloysite nanotuhes, laponite, kaolinite clay, colloidal silica, calcium hydroxide, magnesium hydroxide, magnesium oxide, alumina, aluminum hydroxide, aluminum phosphate, calcium pyrrolate, aluminum pyrrolate, and zinc pyrrolate.

11. The method for preparing an organic-inorganic hybrid microcapsule of claim 1 ,
wherein the active ingredient is at least one selected from the group consisting of fragrance, dye, catalyst, antioxidant, and drug.

12. An organic-inorganic hybrid microcapsule, comprising a dispersed phase which is a core, and a hybrid capsule outer wall formed at an interface of the dispersed phase and surrounding outside of the dispersed phase;
wherein the hybrid capsule outer wall is an inorganic nanoparticles-polymer resin composite containing i) at least one polymer selected from the group consisting of polyamides polyurethane, polyurea, polyester and poly(β-amino ester), and ii) inorganic nanoparticles,
wherein the polymer precursor 2 is at least one selected from the group consisting of a compound containing two or more acid chloride structures represented by the Chemical Formula 3, and a compound containing two or more chloroformate structures represented by

Assignees

• Lg Household & Health Care Ltd
• Lg Chemical Ltd

Inventors

• PARK Nojin
• Shim Woo Sun
• Yeom Junseok
• Kim Jee Seon
• Lee Sangryeo
• Kim Chanjoong
• KIM MinChae
• Kim Myeongho

Classifications

• B01J13/16 Primary

  Interfacial polymerisation · CPC title

• A61K9/5031

  obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, poly(lactide-co-glycolide) · CPC title

• B01J35/23

  in a colloidal state · CPC title

• C09B67/0097

  Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes · CPC title

• C09K15/02

  containing inorganic compounds · CPC title