Polymer particles and encapsulated compositions using organoborane amine complexes

• US 7,649,068 B2
• Filed: 01/11/2006
• Issued: 01/19/2010
• Est. Priority Date: 02/16/2005
• Status: Active Grant

• Current Assignee: Dow Silicones Corporation (Dow, Inc.)
• Original Assignee: Dow, Inc.
• Inventors: Ahn, Dongchan
• Primary Examiner(s): Gulakowski; Randy
• Assistant Examiner(s): Loewe; Robert
• Application Number:
  US11/794,418
• Publication Number:
  US 20080085983A1
• Time in Patent Office: 1,469 Days
• Field of Search: 528/5, 528/7
• US Class Current: 528/5
• CPC Class Codes: B01J 13/14 Polymerisation; cross-linking
• CPC Class Codes: C08F 220/1802 C2-(meth)acrylate, e.g. ethyl (meth)acrylate
• CPC Class Codes: C08F 220/1803 C3-(meth)acrylate, e.g. (iso)propyl (meth)acrylate
• CPC Class Codes: C08F 220/1818 C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate

Abstract

A polymerized product is obtained from a mixture containing (i) a free radical polymerizable monomer, oligomer or polymer; (ii) an organoborane amine complex, (iii) a poor or non-solvent for the polymerized product of (i); and (iv) an amine reactive compound. The mixture may include (v) an active ingredient to be encapsulated by the polymerized product, and (vi) an optional component(s). Polymer particles are obtained by (A) forming a composition containing components (i)-(iv); (B) agitating components (i)-(iv) in the presence of oxygen to initiate polymerization, at a rate and for a time sufficient to provide a uniform dispersion and reaction of the components; (C) allowing the reaction to proceed to completion at room temperature; and (D) recovering the polymer particles by removing component (iii). The composition may include (v) the active ingredient to be encapsulated by the polymer particles.

Claims

1. A composition comprising a mixture or a polymerized product of a mixture comprising (i) a free radical polymerizable monomer, oligomer or polymer;

(ii) an organoborane amine complex, (iii) a poor or non-solvent for the polymerized product of (i); and

(iv) an amine reactive compound, wherein the organoborane amine complex (ii) is a complex formed between an organoborane and an amine compound, the organoborane having the formula BR″

₃ where R″

is a linear, branched, aliphatic, or aromatic hydrocarbon group containing 1-20 carbon atoms; and

wherein the amine compound is an organic amine compound or a silicon containing amine compound; and

the organoborane amine complex is attached to solid particles.

2. A composition according to claim 1 wherein the composition further comprises (v) an active ingredient that is encapsulated by the polymerized product.

3. A composition according to claim 2 wherein the active ingredient (v) is selected from the group consisting of vitamins, inks, conductive particles, magnetic particles, dielectric particles, drugs, solvents, fertilizers, herbicides, pesticides, cure catalysts, adhesion promoters, crosslinking agents free of free radical polymerizable groups, monomers and reactants for compositions curable by mechanisms other than free radical polymerization, solid particles, conductive solid particles, pigments, dyes, flavors, cosmetic agents, healthcare agents, fragrances, and water.

4. A composition according to claim 1 wherein the free radical polymerizable monomer, oligomer, or polymer (i) is an organic compound (a);

a mixture of mono-functional or multi-functional organic compounds (b);

an organosilicon monomer, oligomer, or polymer (c);

a mixture of mono-functional or multi-functional organosilanes (d);

a mixture of mono-functional or multi-functional organopolysiloxanes (e);

or a mixture of (a)-(e);

in which (a)-(e) are unsaturated and capable of undergoing free radical polymerization.

5. A composition according to claim 1 wherein the poor or non-solvent (iii) is selected from the group consisting of water, polar organic solvents, non-polar organic solvents, organosilanes, linear organosiloxane fluids, cyclic organosiloxane fluids, organosiloxane oligomers, organosiloxane resins, organosiloxane polymers, ionic liquids, and supercritical fluids.

6. A composition according to claim 1 wherein the amine reactive compound (iv) is a compound having amine reactive groups, and is selected from the group consisting of mineral acids, Lewis acids, carboxylic acids, carboxylic acid derivatives, carboxylic acid metal salts, isocyanates, aldehydes, epoxides, acid chlorides, and sulphonyl chlorides.

7. A composition according to claim 1, where components (ii) and (iv) are physically or chemically isolated until just prior to a time when it is desirable to initiate polymerization.

8. A composition comprising a mixture or a polymerized product of a mixture comprising (i) a free radical polymerizable monomer, oligomer or polymer;

(ii) an organoborane amine complex, (iii) a poor or non-solvent for the polymerized product of (i); and

(iv) an amine reactive compound;

wherein the amine reactive compound (iv) is a compound having amine reactive groups, and is selected from the group consisting of mineral acids, Lewis acids, carboxylic acids, carboxylic acid derivatives, carboxylic acid metal salts, isocyanates, aldehydes, epoxides, acid chlorides, and sulphonyl chlorides; and

wherein the amine reactive groups are borne by an organosilane, an organopolysiloxane, an organotitanate, or an organozirconate.

9. A composition according to claim 8 wherein the composition further comprises (v) an active ingredient that is encapsulated by the polymerized product.

10. A composition according to claim 9 wherein the active ingredient (v) is selected from the group consisting of vitamins, inks, conductive particles, magnetic particles, dielectric particles, drugs, solvents, fertilizers, herbicides, pesticides, cure catalysts, adhesion promoters, crosslinking agents free of free radical polymerizable groups, monomers and reactants for compositions curable by mechanisms other than free radical polymerization, solid particles, conductive solid particles, pigments, dyes, flavors, cosmetic agents, healthcare agents, fragrances, and water.

11. A composition according to claim 8 wherein the free radical polymerizable monomer, oligomer, or polymer (i) is an organic compound (a);

a mixture of mono-functional or multi-functional organic compounds (b);

an organosilicon monomer, oligomer, or polymer (c);

a mixture of mono-functional or multi-functional organosilanes (d);

a mixture of mono-functional or multi-functional organopolysiloxanes (e);

or a mixture of (a)-(e);

in which (a)-(e) are unsaturated and capable of undergoing free radical polymerization.

12. A composition according to claim 8 wherein the poor or non-solvent (iii) is selected from the group consisting of water, polar organic solvents, non-polar organic solvents, organosilanes, linear organosiloxane fluids, cyclic organosiloxane fluids, organosiloxane oligomers, organosiloxane resins, organosiloxane polymers, ionic liquids, and supercritical fluids.

13. A composition according to claim 8 wherein the amine reactive compound (iv) is attached to solid particles.

14. A composition according to claim 8, where components (ii) and (iv) are physically or chemically isolated until just prior to a time when it is desirable to initiate polymerization.

15. A composition comprising a mixture or a polymerized product of a mixture comprising (i) a free radical polymerizable monomer, oligomer or polymer;

(ii) an organoborane amine complex, (iii) a poor or non-solvent for the polymerized product of (i); and

(iv) an amine reactive compound;

wherein the amine reactive compound (iv) is a compound having amine reactive groups, and is selected from the group consisting of mineral acids, Lewis acids, carboxylic acids, carboxylic acid derivatives, carboxylic acid metal salts, isocyanates, aldehydes, epoxides, acid chlorides, and sulphonyl chlorides; and

wherein the amine reactive compound (iv) is attached to solid particles.

16. A composition comprising a mixture or a polymerized product of a mixture comprising (i) a free radical polymerizable monomer, oligomer or polymer;

(ii) an organoborane amine complex, (iii) a poor or non-solvent for the polymerized product of (i); and

(iv) an amine reactive compound;

wherein the amine reactive compound (iv) is a photoacid generator.

17. A composition according to claim 16 wherein the composition further comprises (v) an active ingredient that is encapsulated by the polymerized product.

18. A composition according to claim 17 wherein the active ingredient (v) is selected from the group consisting of vitamins, dyes, inks, conductive particles, magnetic particles, dielectric particles, drugs, solvents, fertilizers, herbicides, pesticides, cure catalysts, adhesion promoters, crosslinking agents free of free radical polymerizable groups, monomers and reactants for compositions curable by mechanisms other than free radical polymerization, solid particles, conductive solid particles, pigments, dyes, flavors, cosmetic agents, healthcare agents, fragrances, and water.

19. A composition according to claim 16 wherein the free radical polymerizable monomer, oligomer, or polymer (i) is an organic compound (a);

a mixture of mono-functional or multi-functional organic compounds (b);

an organosilicon monomer, oligomer, or polymer (c);

a mixture of mono-functional or multi-functional organosilanes (d);

a mixture of mono-functional or multi-functional organopolysiloxanes (e);

or a mixture of (a)-(e);

in which (a)-(e) are unsaturated and capable of undergoing free radical polymerization.

20. A composition according to claim 16 wherein the organoborane amine complex (ii) is a complex formed between an organoborane and an amine compound, the organoborane having the formula BR″

₃ where R″

is a linear, branched, aliphatic, or aromatic hydrocarbon group containing 1-20 carbon atoms; and

wherein the amine compound is an organic amine compound or a silicon containing amine compound.

21. A composition according to claim 16 wherein the poor or non-solvent (iii) is selected from the group consisting of water, polar organic solvents, non-polar organic solvents, organosilanes, linear organosiloxane fluids, cyclic organosiloxane fluids, organosiloxane oligomers, organosiloxane resins, organosiloxane polymers, ionic liquids, and supercritical fluids.

22. A composition according to claim 16 wherein the photoacid generator (iv) is attached to solid particles.

23. A composition according to claim 16, where components (ii) and (iv) are physically or chemically isolated until just prior to a time when it is desirable to initiate polymerization.

24. A method of making polymer particles comprising (A) forming a composition containing (i) a free radical polymerizable monomer, oligomer or polymer;

(ii) an organoborane amine complex, (iii) a poor or non-solvent for the polymerized product of (i); and

(iv) an amine reactive compound, wherein the amine reactive compound (iv) is a compound having amine reactive groups, and is selected from the group consisting of mineral acids, Lewis acids, carboxylic acids, carboxylic acid derivatives, carboxylic acid metal salts, isocyanates, aldehydes, epoxides, acid chlorides, and sulphonyl chlorides; and

wherein the amine reactive groups are borne by an organosilane, an organopolysiloxane, an organotitanate, or an organozirconate;

(B) agitating components (i)-(iv) of the composition in the presence of oxygen to initiate polymerization, at a rate and for a time sufficient to provide a uniform dispersion and reaction of the components;

(C) allowing the reaction to proceed to completion at room temperature; and

(D) recovering the polymer particles by removing the poor or non-solvent from the composition.

25. A method according to claim 24 wherein the composition includes (v) an active ingredient that is encapsulated by the polymer particles.

26. A method according to claim 25 wherein the active ingredient (v) is selected from the group consisting of vitamins, inks, conductive particles, magnetic particles, dielectric particles, drugs, solvents, fertilizers, herbicides, pesticides, cure catalysts, adhesion promoters, crosslinking agents free of free radical polymerizable groups, monomers and reactants for compositions curable by mechanisms other than free radical polymerization, solid particles, conductive solid particles, pigments, dyes, flavors, cosmetic agents, healthcare agents, fragrances, and water.

27. A method according to claim 24 wherein the free radical polymerizable monomer, oligomer, or polymer (i) is an organic compound (a);

a mixture of mono-functional or multi-functional organic compounds (b);

an organosilicon monomer, oligomer, or polymer (c);

a mixture of mono-functional or multi-functional organosilanes (d);

a mixture of mono-functional or multi-functional organopolysiloxanes (e);

or a mixture of (a)-(e);

in which (a)-(e) are unsaturated and capable of undergoing free radical polymerization.

28. A method according to claim 24 wherein the organoborane amine complex (ii) is a complex formed between an organoborane and an amine compound, the organoborane having the formula BR″

₃ where R″

is a linear, branched, aliphatic, or aromatic hydrocarbon group containing 1-20 carbon atoms; and

wherein the amine compound is an organic amine compound or a silicon containing amine compound.

29. A method according to claim 28 wherein the organoborane amine complex is attached to solid particles.

30. A method according to claim 24 wherein the poor or non-solvent (iii) is selected from the group consisting of water, polar organic solvents, non-polar organic solvents, organosilanes, linear organosiloxane fluids, cyclic organosiloxane fluids, organosiloxane oligomers, organosiloxane resins, organosiloxane polymers, ionic liquids, and supercritical fluids.

31. A method according to claim 30 wherein the poor or non-solvent (iii) is acetone, hexane, cyclohexane, heptane, hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, or a mixture thereof.

32. A method according to claim 24 wherein the amine reactive compound (iv) is attached to solid particles.

33. A method according to claim 24 wherein the amine reactive compound (iv) is a compound capable of generating amine reactive groups when exposed to ultraviolet radiation.

34. A method according to claim 24, further comprising physically or chemically isolating components (ii) and (iv) prior to step (A).

35. A method of making polymer particles comprising (A) forming a composition containing (i) a free radical polymerizable monomer, oligomer or polymer;

(ii) an organoborane amine complex, (iii) a poor or non-solvent for the polymerized product of (i); and

(iv) an amine reactive compound, wherein the organoborane amine complex (ii) is a complex formed between an organoborane and an amine compound, the organoborane having the formula BR″

₃ where R″

is a linear, branched, aliphatic, or aromatic hydrocarbon group containing 1-20 carbon atoms; and

wherein the amine compound is an organic amine compound or a silicon containing amine compound, and the organoborane amine complex is attached to solid particles;

(B) agitating components (i)-(iv) of the composition in the presence of oxygen to initiate polymerization, at a rate and for a time sufficient to provide a uniform dispersion and reaction of the components;

(C) allowing the reaction to proceed to completion at room temperature; and

(D) recovering the polymer particles by removing the poor or non-solvent from the composition.

36. A method according to claim 35 wherein the composition further comprises (v) an active ingredient that is encapsulated by the polymerized product.

37. A method of making polymer particles comprising (A) forming a composition containing (i) a free radical polymerizable monomer, oligomer or polymer;

(ii) an organoborane amine complex, (iii) a poor or non-solvent for the polymerized product of (i); and

(iv) an amine reactive compound;

wherein the amine reactive compound (iv) is a compound having amine reactive groups, and is selected from the group consisting of mineral acids, Lewis acids, carboxylic acids, carboxylic acid derivatives, carboxylic acid metal salts, isocyanates, aldehydes, epoxides, acid chlorides, and sulphonyl chlorides; and

wherein the amine reactive compound (iv) is attached to solid particles;

(B) agitating components (i)-(iv) of the composition in the presence of oxygen to initiate polymerization, at a rate and for a time sufficient to provide a uniform dispersion and reaction of the components;

(C) allowing the reaction to proceed to completion at room temperature; and

(D) recovering the polymer particles by removing the poor or non-solvent from the composition.

38. A method according to claim 37 wherein the composition further comprises (v) an active ingredient that is encapsulated by the polymerized product.

39. A method of making polymer particles comprising (A) forming a composition containing (i) a free radical polymerizable monomer, oligomer or polymer;

(ii) an organoborane amine complex, (iii) a poor or non-solvent for the polymerized product of (i); and

(iv) an amine reactive compound;

wherein the amine reactive compound (iv) is a photoacid generator (B) agitating components (i)-(iv) of the composition in the presence of oxygen to initiate polymerization, at a rate and for a time sufficient to provide a uniform dispersion and reaction of the components;

(C) allowing the reaction to proceed to completion at room temperature; and

(D) recovering the polymer particles by removing the poor or non-solvent from the composition.

40. A method according to claim 39 wherein the composition further comprises (v) an active ingredient that is encapsulated by the polymerized product.