Environmentally biodegradable microcapsules
Disclosed is a modified biopolymer having the formula A-XY wherein: (a) A is a starting material selected from the group consisting of a polysaccharide, a protein and a cellulose; (b) X is a first moiety bearing a functionality co-reactive with A; (c) Y is a second moiety covalently bound to X, capable of undergoing free radical polymerization and bearing at least two ethylenically unsaturated functional groups; (d) the starting material A and the first moiety X are linked covalently through linkages selected from the group consisting of an ester, an amide, a urethane, a urea, a sulfonate ester, a phosphate ester and an ether; and (e) a degree of substitution of the starting material A with the first moiety X is less than 0.5 but more than 0.1. Compositions including the modified biopolymer and methods for making them are also disclosed.
1. A modified biopolymer having the formula A-XY wherein:
A is a starting material of a polysaccharide selected from the group consisting of tapioca starch, potato starch, corn starch, rice starch, wheat starch, carboxymethyl starch, carboxymethyl chitosan, chitosan oligosaccharide, and octenyl succinic anhydride modified starch;
X is a first moiety bearing a functionality co-reactive with the starting material A, wherein the first moiety X is selected from the group consisting of t-butyl acetoacetate, t-butyl cyanoacetate, and a Michael adduct of alkyl acetoacetate or alkyl cyanoacetate with ethylenically unsaturated monomer bearing an anhydride functionality, an epoxy functionality, an isocyanate functionality or an oxazoline functionality;
Y is a second moiety covalently bound to the first moiety X, capable of undergoing free radical polymerization and having an acrylate, methacrylate, styrenic, vinyl ester or vinyl ether bearing at least three ethylenically unsaturated groups;
the starting material A and the first moiety X are linked covalently through linkages selected from the group consisting of an ester, an amide, a urethane, a urea, a sulfonate ester, a phosphate ester and an ether; and
a degree of substitution of the starting material A with the first moiety X is less than 0.5 but more than 0.1, and
wherein the modified biopolymer has an Environmental Biodegradability greater than 30% within 28 days according to OECD 301.
2. The modified biopolymer of claim 1 , wherein the starting material A is adjusted to a lower molecular weight before incorporation into the modified biopolymer.
3. A composition comprising controlled release particles, wherein each of the controlled release particles comprises:
at least one hydrophobic active ingredient; and
a reaction product of a free radical polymerization of the modified biopolymer of claim 1 and at least one ethylenically unsaturated monomer.
4. The composition of claim 3 , further comprising at least one member selected from the group consisting of a free radical initiator, a cationic deposition aid, an isocyanate, an epoxy, an organofunctional silane, an epoxide curing agent, a plasticizer and an inorganic solid particle.
5. The composition of claim 3 , wherein the at least one hydrophobic active ingredient is a member selected from the group consisting of a flavorant, a fragrance, a chromogen, a dye, an essential oil, a sweetener, an oil, a pigment, an active pharmaceutical ingredient, a moldicide, a herbicide, a fertilizer, a phase change material, an adhesive, a vitamin oil, a vegetable oil, a triglyceride and a hydrocarbon.
6. The composition of claim 3 , wherein the controlled release particles have a diameter from 0.1 microns to less than 200 microns.
7. The composition of claim 3 , which is a powdered food product, a fluid food product, a powdered nutritional supplement, a fluid nutritional supplement, a fluid fabric enhancer, a solid fabric enhancer, a fluid shampoo, a solid shampoo, a hair conditioner, a body wash, a solid antiperspirant, a fluid antiperspirant, a solid deodorant, a fluid deodorant, a fluid detergent, a solid detergent, a fluid hard surface cleaner, a solid hard surface cleaner, a fluid fabric refresher spray, a diaper, an air freshening product, a nutraceutical supplement, a controlled release fertilizer, a controlled release insecticide, a controlled release dye or a unit dose detergent comprising a detergent and the controlled release particles in a water soluble film.
8. The composition of claim 3 , wherein the composition comprises two different controlled release particles which are friction-triggered release microcapsules which release the at least one hydrophobic active ingredient at different rates due to a difference in shell material friability or core material viscosity.
9. A method of preparing a composition comprising controlled release particles, said method comprising the sequential steps of:
(a) preparing an oil phase, wherein the oil phase comprises:
(i) at least one hydrophobic active ingredient, and at least one ethylenically unsaturated monomer or free radical initiator; or
(ii) at least one hydrophobic active ingredient, at least one ethylenically unsaturated monomer and free radical initiator and optionally one or more compounds selected from the group consisting of: an isocyanate, an epoxy, an organofunctional silane, an epoxide curing agent, a plasticizer and an inorganic solid particle;
(b) preparing an aqueous phase comprising the modified biopolymer according to claim 1 , and optionally an emulsifier, buffer, ionic strength modifier or water soluble free radical initiator;
(c) combining the oil phase and the aqueous phase to emulsify the at least one hydrophobic active ingredient to provide an aqueous suspension of the at least one hydrophobic active ingredient;
(d) heating the aqueous suspension; and
(e) adding structuring agents to the aqueous suspension to provide the controlled release particles homogeneously suspended in an aqueous dispersion.
10. The method of claim 9 , wherein the free radical initiator is a member selected from the group consisting of azo initiators and alkyl peroxides.
11. The method of claim 9 , wherein at least one suspension agent is included in the composition to suspend the controlled release particles, wherein the at least one suspension agent is at least one member selected from the group consisting of a rheology modifier, a structurant and a thickener.
12. The method of claim 11 , wherein the at least one suspension agent has a high shear viscosity at, 20 sec −1 shear rate and at 21° C., of from 1 to 7000 cps and a low shear viscosity, at 0.5 sec −1 shear rate at 21° C., of greater than 1000 cps.
13. The method of claim 11 , wherein a finished capsule slurry is a fluid having a high shear viscosity, at 20 sec −1 and at 21° C., of from 50 to 3000 cps and a low shear viscosity, at 0.5 sec −1 shear rate at 21° C., of greater than 1000 cps.
14. The method of claim 11 , wherein the at least one suspension agent is a member selected from the group consisting of polyacrylates, polymethacrylates, polycarboxylates, pectin, alginate, gum arabic, gelatin, carrageenan, gellan gum, xanthan gum, guar gum, hydroxyl-containing fatty acids, hydroxyl-containing fatty esters, hydroxyl-containing fatty waxes, castor oil, castor oil derivatives, hydrogenated castor oil derivatives, hydrogenated castor wax, perfume oil, and mixtures thereof.
15. A composition comprising the controlled release particles prepared by the method of claim 9 , each of the controlled release particles comprises: at least one hydrophobic active ingredient; and a reaction product of a free radical polymerization of the modified biopolymer of claim 1 and at least one ethylenically unsaturated monomer.