Surface-modified hydrogels and hydrogel microparticles

• US 9,574,109 B2
• Filed: 02/17/2011
• Issued: 02/21/2017
• Est. Priority Date: 02/18/2010
• Status: Active Grant

• Current Assignee: Dow Silicones Corporation (Dow, Inc.)
• Original Assignee: Dow, Inc.
• Inventors: Ahn, Dongchan, Thompson, James
• Primary Examiner(s): Barham, Bethany
• Assistant Examiner(s): Anthopolos, Peter
• Application Number:
  US13/579,011
• Publication Number:
  US 20120309623A1
• Time in Patent Office: 2,196 Days
• US Class Current: 1/1
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08J 2300/14 Water soluble or water swellable polymers, e.g. aqueous gels
• CPC Class Codes: C08J 2443/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: C08J 3/126 Polymer particles coated by polymer, e.g. core shell structures
• CPC Class Codes: C08K 5/55 Boron-containing compounds C08K5/0091 takes precedence
• CPC Class Codes: C08L 33/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• CPC Class Codes: C08L 43/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 133/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• CPC Class Codes: C09D 143/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: C09D 183/06 containing silicon bound to oxygen-containing groups C09D183/12 takes precedence

Abstract

Provided in various embodiments are surface-modified hydrogels and hydrogel microparticles, methods for their preparation, and uses thereof for delivery of personal care and healthcare active ingredients, and agricultural active ingredients. In some embodiments, such hydrogels and hydrogel microparticles comprise surface coatings that are resistant to solvent washing and can act as barriers for the migration of water and/or water-compatible alcohols and actives soluble therein.

Claims

1. A method for the preparation of surface-modified hydrogels and hydrogel microparticles, comprising:

treating in the presence of oxygen a hydrogel comprising Component (A), at least one water-compatible organic polymer, alcohol-compatible organic polymer, or any combination thereof, wherein Component (A) is selected from polyacrylic acid, poly(meth)acrylic acid, salts of polyacrylic acid, salts of polymethacryliccr lic anhydride, polyacrylic anhydride, and any combination thereof, with

Component (B), at least one free-radical polymerizable organopolysiloxane that is immiscible with water, water-compatible alcohols, or combinations thereof, and that is selected from acrylate and methacrylate-functional polydimethylsiloxanes and acrylate and methacrylate-functional silanes,

at least one suitable water-immiscible solvent for Component (B) selected from hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane, and

Component (C), at least one organoborane free radical initiator;

wherein

the hydrogel is fully-or partially-swollen with an absorbable solvent selected from water, alcohols, and any combination thereof, prior to the treating with each of the Component (B), the at least one suitable solvent for Component (B), and the Component (C),

the hydrogel is at least one of a non-flowable monolith, a sheared or pulverized monolith, and microparticles, and

the treating forms at least one modified surface on the hydrogel or hydrogel microparticles.

2. The method according to claim 1, wherein Component (C) is selected from triethylborane-propanediamine, triethylborane-butylimidazole, triethylboranemethoxypropylamine, tri-n-butyl borane-methoxypropylamine, and triethylborane-aminosilane, triethylborane-aminosiloxane complexes, and any combination thereof.

3. The method according to claim 1, wherein the absorbable solvent is selected from water, methanol, ethanol, isopropyl alcohol, and any combination thereof.

4. The method according to claim 1, wherein the hydrogel is treated in the presence of Component (E), at least one organonitrogen-reactive compound.

5. The method according to claim 4, wherein Component (E) is selected from acids, anhydrides, isocyanates, epoxides, aldehydes, and any combination thereof.

6. The method according to claim 1, wherein the hydrogel comprises or is treated with Component (F), at least one active ingredient selected from personal care, healthcare, and agricultural active ingredients.

7. The method according to claim 6, wherein the active ingredient is selected from Vitamin C, green tea extract, lidocaine, nicotine, niacinnamide, salicylic acid, ketoprofen, ketoconazole, and urea.

8. The method according to claim 6, wherein the active ingredient is selected from urea, ammonium nitrate, potassium nitrate, sodium nitrate, potassium phosphate, and ammonium phosphate.

9. The method according to claim 1, wherein the hydrogel is treated in the presence of Component (G), at least one surfactant.

10. The method according to claim 9, wherein the surfactant is selected from sorbitan monooleate, polyglycol-modified trimethsilylated silicate, polyglycol-modified siloxanes, polyglycol-modified silicas, ethoxylated quaternary ammonium salt solutions, cetyltrimethylammonium chloride solutions, and any combination thereof.

11. Surface-modified hydrogels prepared by the method of claim 1.

12. Surface-modified hydrogel microparticles prepared by the method of claim 1.

13. Surface-modified hydrogels prepared by the method of claim 6.

14. Surface-modified hydrogel microparticles prepared by the method of claim 6.

15. The method according to claim 1, wherein Component (B) is selected from acryloxyalkyl-alkoxysilanes, methacryloxyalkyl-alkoxysilanes, acrylate-terminated polydimethylsiloxane, tetramethyl, dimethacryloxypropyl-disiloxane, 3-methacryloypropyltrimethoxysilane, methacryloxypropyldimethylsiloxy-terminated polydimethylsiloxane, methacryloxymethylsiloxy-terminated polydimethylsiloxanes, acryloxypropyldimethylsiloxy-terminated polydimethylsiloxanes, acryloxymethyldimethylsiloxy-terminated polydimethylsiloxanes, polydimethylsiloxanepolymethyl-methacryloxypropylsiloxane copolymers, polydimethylsiloxane-polymethylacryloxypropylsiloxane copolymers, and any combination thereof.

16. The method of claim 1, wherein the hydrogel is substantially free of external treatment with the absorbable solvent during the treating with each of the Component (B), the at least one suitable solvent for Component (B), and the Component (C).

17. A method for the preparation of surface-modified hydrogels and hydrogel microparticles, comprising:

treating in the presence of oxygen a hydrogel comprising Component (A), at least one water-compatible organic polymer, alcohol-compatible organic polymer, or any combination thereof, wherein Component (A) is polyacrylic acid, with

Component (B), at least one free-radical polymerizable organopolysiloxane that is immiscible with water, water-compatible alcohols, or combinations thereof, and that is a methacryloxypropyldimethylsiloxy-terminated polydimethylsiloxane,

at least one suitable water-immiscible solvent for Component (B) that is hexamethyldisiloxane, and

Component (C), at least one organoborane free radical initiator;

wherein

the hydrogel is fully-or partially-swollen with an absorbable solvent that is water prior to the treating with each of the Component (B), the at least one suitable solvent for Component (B), and the Component (C),

the hydrogel is at least one of a non-flowable monolith, a sheared or pulverized monolith, and microparticles, and

the treating forms at least one modified surface on the hydrogel or hydrogel microparticles.

18. The method of claim 17, wherein the hydrogel is substantially free of external treatment with the absorbable solvent during the treating with each of the Component (B), the at least one suitable solvent for Component (B), and the Component (C).