Controlled release microcapsules
View Patent ↗A method of forming microcapsules having improved physical properties and release control as well as the microcapsules formed by the process wherein the capsule wall is formed by the concurrent polymerization of monomers, oligomer and/or prepolymers on the inside of the capsule wall and different monomers, oligomers and/or prepolymers on the exterior of the capsule wall as it forms.
1. A method of making microcapsules whose shell wall comprises on one surface a first (meth)acrylate polymer and on its other surface a second (meth)acrylate polymer, said first (meth)acrylate polymer derived from an aqueous phase (meth)acrylate polymer wall forming composition (I) and said second (meth)acrylic polymer derived from an oil phase (meth)acrylate polymer wall forming composition (II), both the aqueous phase (meth)acrylate polymer wall forming composition (I) and the oil phase (meth)acrylate polymer wall forming composition (II) comprising wall forming materials, and an intermediate region comprising an interpenetrating network and/or copolymer of the two wall forming compositions, said method comprising:
(i) forming an oil-in-water or a water-in-oil emulsion of the two (meth)acrylate polymer wall forming compositions,
(ii) subjecting the emulsion to conditions for concurrently, at last in part, polymerizing the wall forming materials of each of the oil phase and aqueous phase, and
(iii) allowing the reaction to continue until the microcapsules of desired wall thickness are attained wherein said aqueous phase (meth)acrylate polymer wall forming composition (I) comprises one or more polyethylene glycol di(meth)acrylates, ethoxylated mono- or multi-functional (meth)acrylates, and/or (meth)acrylate monomers and/or oligomers.
2. The method of claim 1 wherein the oil phase (meth)acrylate polymer wall forming composition (II) comprises either (A) a combination of (a) at least one oil soluble or dispersible amine (meth)acrylate, (b) at least one oil soluble or dispersible acidic (meth)acrylate or at least one oil soluble or dispersible simple acid or both, and (c) at least one oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer, (B) a combination of (a) at least one oil soluble or dispersible acidic (meth)acrylate, (b) at least one oil soluble or dispersible simple base, and (c) at least one oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer, or (C) one or more oil soluble or dispersible mono-, di- or multi-functional (meth)acrylate monomers or oligomers.
3. The method of claim 2 wherein the method further comprises the step of oligomerizing and/or prepolymerizing some or all of the (meth)acrylate polymer wall forming components of the oil phase composition (II), the aqueous phase composition (I) or both (I) and (II) prior to forming the emulsion.
4. The method of claim 2 wherein the method further comprises the step of oligomerizing and/or prepolymerizing some or all of the (meth)acrylate polymer wall forming components of the oil phase composition (II), the aqueous phase composition (I) or both (I) and (II) subsequent to forming the emulsion but prior to initiating wall formation.
5. The method of claim 2 wherein the oil phase wall forming composition (II) comprises (A) (a) at least one oil soluble or dispersible amine (meth)acrylate, (b) at least one oil soluble or dispersible acidic (meth)acrylate, and (c) at least one oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer.
6. The method of claim 2 wherein the oil phase wall forming composition (II) comprises (A) (a) at least one oil soluble or dispersible amine (meth)acrylate, (b) at least one oil soluble or dispersible simple acid, and (c) at least one oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer.
7. The method of claim 2 wherein the oil phase wall forming composition (II) comprises (A) (a) at least one oil soluble or dispersible amine (meth)acrylate, (b) the combination of at least one oil soluble or dispersible acidic (meth)acrylate and at least one oil soluble or dispersible simple acid, and (c) at least one oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer.
8. The method of claim 2 wherein the oil phase wall forming composition (II) comprises (B) (a) at least one oil soluble or dispersible acidic (meth)acrylate, (b) at least one oil soluble or dispersible simple base, and (c) at least one oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer.
9. The method of claim 2 wherein the oil phase wall forming composition (II) comprises (C) one or more oil soluble or dispersible mono-, di- or multi-functional (meth)acrylate monomers or oligomers.
10. The method of claim 1 wherein the water phase composition (I) further comprises a polymeric emulsifier.
11. The method of claim 1 wherein the wall formation step (b) is itself a two-step reaction process where the first reaction step comprises subjecting the emulsion to such conditions as will form oligomers and/or prepolymers of the wall forming materials of the oil phase composition (II), the aqueous phase composition (I) or both (I) and (II) and the second reaction step comprises subjecting the emulsion to a second set of conditions which effectuates the formation of the shell wall.
12. The method of claim 1 wherein the wall formation step (b) is itself a three-step reaction process where the first step comprises subjecting the emulsion to such conditions as will form oligomers and/or prepolymers of the wall forming materials of the oil phase composition (II), the aqueous phase composition (I) or both (I) and (II), the second step comprises subjecting the emulsion to a second set of conditions which effectuates building of the shell wall and the third step comprises subjecting the emulsion to a third set of conditions, which may be merely an extension or continuation of the second set of conditions, to cross-link the polymer(s) of the shell wall.
13. The method of claim 12 wherein the third step effects the cross-linking of the second (meth)acrylate polymer.
14. The method of claim 1 wherein initiation of wall formation from the oil phase composition (II) and the aqueous phase composition (I) is concurrent.
15. The method of claim 1 wherein initiation of the wall formation from one of the oil phase composition (II) and the aqueous phase composition (I) is staggered relative to the other.
16. The method of claim 15 wherein initiation of the second to be initiated wall forming composition is initiated after the shell wall is partially formed from the first to be initiated wall forming material but before the shell wall is impermeable to the wall forming material of the second wall forming composition.
17. The method of claim 15 wherein initiation of the second to be initiated wall forming composition is initiated after a seed capsule Is formed of the first to be initiated wall forming material.
18. The method of claim 1 wherein the aqueous phase (meth)acrylate polymer wall forming composition (I) comprises oligomers and/or prepolymers of the stated monomers and/or oligomers.
19. The method of claim 1 wherein the oil phase (meth)acrylate polymer wall forming composition (II) comprises oligomers and/or prepolymers of the therein contained wall forming materials.
20. The method of claim 1 wherein both the aqueous phase (meth)acrylate polymer wall forming composition (II) and the oil phase (meth)acrylate polymer wall forming composition (II) comprises oligomers and/or prepolymers of the therein contained wall forming materials.
21. The method of claim 11 wherein only one of the oil phase composition (II) and the aqueous phase composition (I) is subjected to the oligomerization and/or prepolymerization step.
22. The method of claim 11 wherein both of the oil phase composition (II) and the aqueous phase composition (I) are subjected to the oligomerization and/or prepolymerization step.
23. The method of claim 12 wherein only one of the oil phase composition (II) and the aqueous phase composition (I) is subjected to the oligomerization and/or prepolymerization step.
24. The method of claim 12 wherein both of the oil phase composition (II) and the aqueous phase composition (I) are subjected to the oligomerization and/or prepolymerization step.