Polyurea and poly(beta-amino ester) capsules with enhanced degradability

Patent metadata

Field	Value
Publication number	US-11945946-B2
Application number	US-202117473180-A
Country	US
Kind code	B2
Filing date	Sep 13, 2021
Priority date	Sep 14, 2020
Publication date	Apr 2, 2024
Grant date	Apr 2, 2024

Abstract

Microcapsules encapsulating oily core materials have a shell material of hybrid polyurea and poly(beta-amino esters) (PU/PBAE). The microcapsules may have a single shell of hybrid PU/PBAE, dual shells including hybrid PU/PBAE in an inner shell and PBAE in an outer shell crosslinked and deposited to the inner shell, or multiple shells including PU in an inner shell, hybrid PU/PBAE in a transitioning shell, and PBAE in an outer shell. Formation of the microcapsules includes polymerization between multifunctional amine and multifunctional acrylate to produce a water soluble PBAE; polymerization between polyisocyanate in oil phase and multifunctional amine in aqueous solution to produce PU microcapsule, polymerization between polyisocyanate and the amine moiety of PBAE prepolymer to produce hybrid PU/PBAE microcapsule wall; and polymerization between multifunctional acrylate and primary or secondary amine moiety of the PBAE prepolymer to form a PBAE outer shell.

First claim

The invention claimed is:

1. A polyurea and poly(beta-amino esters) (PU/PBAE) microcapsule, comprising: a core material; and
a shell comprising PU, hybrid PU/PBAE, and PBAE,
wherein the PBAE comprises a reaction product of a multifunctional amine and a multifunctional acrylate having an α,β-unsaturated carbonyl, wherein the multifunctional amine adds by aza-Michael addition to a β-carbon atom of the α,β-unsaturated carbonyl.

2. The PU/PBAE microcapsule of claim 1 , wherein the shell is derived from i) 5% to 90% of a preformed PBAE prepolymer, or polyamines, or a reaction product of a first multifunctional acrylate and a multifunctional amine, ii) 0.1% to 90% of a polyisocyanate, and iii) 0% to 90% of a second multifunctional acrylate, by weight of the shell.

3. The PU/PBAE microcapsule of claim 2 , wherein the preformed PBAE prepolymer is derived from the first multifunctional acrylate and the multifunctional amine, wherein a molar ratio of the first multifunctional acrylate to the multifunctional amine is in a range between 100/1-1/100.

4. The PU/PBAE microcapsule of claim 3 , wherein the molar ratio of the first multifunctional acrylate to the multifunctional amine is in a range between 10/1-1/10.

5. The PU/PBAE microcapsule of claim 3 , wherein the molar ratio of the first multifunctional acrylate to the multifunctional amine is in a range between 2/1-1/2.

6. The PU/PBAE microcapsule of claim 2 , wherein a molar ratio of the polyisocyanate to the multifunctional amine is 1/100-1/1.

7. The PU/PBAE microcapsule of claim 1 , wherein the shell has a single shell structure comprising hybrid PU/PBAE.

8. The PU/PBAE microcapsule of claim 1 , wherein the shell has a dual shell structure comprising an inner shell and an outer shell, a composition of the inner shell comprises hybrid PU/PBAE, a composition of the outer shell comprises PBAE, wherein the composition of the outer shell crosslinks or deposits to the composition of the inner shell.

9. The PU/PBAE microcapsule of claim 1 , wherein the shell has a multi-shell structure comprising an inner shell, a transitional shell and an outer shell, a composition of the inner shell comprises PU, a composition of the transitional shell comprises hybrid PU/PBAE, a composition of the outer shell comprises PBAE, and the composition of each shell crosslinks or deposits to the composition of an adjacent shell.

10. The PU/PBAE microcapsule of claim 1 , wherein a median particle size of the PU/PBAE microcapsule is 3-100 μm.

11. The PU/PBAE microcapsule of claim 1 , wherein a zeta potential of the PU/PBAE microcapsule is −100 mV-+200 mV at pH 3 and −200 mV-+100 mV at pH 10.

12. A method of producing the PU/PBAE microcapsule of claim 1 , comprising:
providing a first aqueous solution comprising an emulsifier and water;
providing a second aqueous solution comprising a multifunctional amine, a first multifunctional acrylate having an α,β-unsaturated carbonyl, and water, and mixing the second aqueous solution at a first temperature for a first period of time to form a PBAE prepolymer, wherein the PBAE prepolymer is a reaction product of the multifunctional amine and the first multifunctional acrylate having an α,β-unsaturated carbonyl, wherein the multifunctional amine adds by aza-Michael addition to a β-carbon atom of the α,β-unsaturated carbonyl;
adding the first aqueous solution into the second aqueous solution under mixing to obtain a mixture of the first aqueous solution and the second aqueous solution;
providing an oil phase comprising the core material and a polyisocyanate;
adding the oil phase into the mixture of the first aqueous solution and the second aqueous solution, applying high shear agitation until a target particle size is reached to obtain an emulsion at a second temperature;
providing a third aqueous solution comprising a second multifunctional acrylate, adding the third aqueous solution into the emulsion under mixing; and
increasing a temperature to a third temperature in a second period of time and holding the temperature at the third temperature for a third period of time under mixing.

13. The method of claim 12 , the multifunctional amine is diethylenetriamine, ethylenediamine, tetraethylenepentaamine, pentaethylenehexamine or polyethylenimine, the first and the second multifunctional acrylate is diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, poly(ethylene glycol) diacrylate, trifunctional trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate or a combination thereof independently, and the polyisocyanate is dicyclohexylmethane diisocyanate, hexamethylene diisocyanate uretdione, or xylyene diisocyanate based aliphatic polyisocyanate adduct prepolymer.

14. The method of claim 12 , wherein the first temperature is 25-70° C., the second temperature is 5-55° C., the third temperature is 50-95° C., the first period of time is 10-360 mins, the second period of time is 30-120 mins, and the third period of time is 2-24 hours.

15. A method of producing the PU/PBAE microcapsule of claim 1 , comprising:
providing a first aqueous solution comprising an emulsifier and water;
providing a second aqueous solution comprising a multifunctional amine and water;
adding the first aqueous solution into the second aqueous solution under mixing to obtain a mixture of the first aqueous solution and the second aqueous solution;
providing an oil phase comprising the core material and a polyisocyanate;
adding the oil phase into the mixture of the first aqueous solution and the second aqueous solution, applying high shear agitation at a first temperature until a target particle size is reached to obtain an emulsion;
providing a third aqueous solution comprising a multifunctional acrylate having an α,β-unsaturated carbonyl, adding the third aqueous solution into the emulsion under mixing, wherein the multifunctional amine reacts with the multifunctional acrylate having the α,β-unsaturated carbonyl to form PBAE, in which the multifunctional amine adds by aza-Michael addition to a β-carbon atom of the α,β-unsaturated carbonyl; and
increasing a temperature to a second temperature in a first period of time and holding the temperature at the second temperature for a second period of time under mixing.

16. The method of claim 15 , the multifunctional amine is diethylenetriamine, ethylenediamine, tetraethylenepentaamine, tentaethylenehexamine or olyethylenimine, the multifunctional acrylate is diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, poly(ethylene glycol) diacrylate, trifunctional trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, or a combination thereof, and the polyisocyanate is dicyclohexylmethane diisocyanate, hexamethylene diisocyanate uretdione, or a xylyene diisocyanate (XDI) based aliphatic polyisocyanate adduct prepolymer.

17. The method of claim 15 , wherein the first temperature is 5-55° C., the second temperature is 50-95° C., the first period of time is 30-120 mins, the second period of time is 2-24 hours.

18. A method of producing the PU/PBAE microcapsule of claim 1 , comprising:
providing a first aqueous solution comprising an emulsifier and water;
providing a second aqueous solution comprising a multifunctional amine, a multifunctional acrylate having an α,β-unsaturated carbonyl, and water, and mixing the second aqueous solution at a first temperature for a first period of time to form a PBAE prepolymer, wherein the PBAE prepolymer is a reaction product of the multifunctional

Assignees

• Encapsys Llc

Inventors

• Feng Linsheng

Classifications

• C08L75/02 Primary

  Polyureas · CPC title

• A01N25/28

  Microcapsules {or nanocapsules} · CPC title

• A01N43/40

  six-membered rings · CPC title

• A61K8/11

  Encapsulated compositions · CPC title

• A61K8/8129

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether · CPC title