Lignin biomaterial as agricultural drug carrier

Patent metadata

Field	Value
Publication number	US-11311010-B2
Application number	US-202016844135-A
Country	US
Kind code	B2
Filing date	Apr 9, 2020
Priority date	Feb 5, 2016
Publication date	Apr 26, 2022
Grant date	Apr 26, 2022

Abstract

The present invention provides lignin nanoparticles containing a hydrophobic active agent and a process for the production of the lignin nanoparticles. The process involves the following steps: (i) dissolving modified lignin and a hydrophobic active agent in an organic solvent having low solubility in water; (ii) combining the solution with water and a surfactant to form a pre-emulsion; (iii) forming an emulsion from the pre-emulsion; and (iv) crosslinking the modified lignin to form the lignin nanoparticles, in which the modified lignin is lignin which is chemically modified to contain at least two functional groups suitable for polymerization and/or crosslinking.

First claim

The invention claimed is:

1. A process for the production of lignin nanoparticles comprising a hydrophobic active agent,
the process comprising the following steps:
(i) dissolving modified lignin and a hydrophobic active agent in an organic solvent having low solubility in water to form a solution;
(ii) combining the solution with water and a surfactant to form a pre-emulsion;
(iii) forming an emulsion from the pre-emulsion; and
(iv) crosslinking the modified lignin to form lignin nanoparticles comprising the hydrophobic active agent,
wherein the modified lignin is lignin which is chemically modified to comprise at least two functional groups suitable for polymerization and/or crosslinking, and
wherein the nanoparticles are solid particles that are not hollow, and wherein the crosslinked lignin and the hydrophobic active agent are homogeneously distributed throughout the particle.

2. The process of claim 1 , further comprising after the crosslinking step (iv) a step (v):
(v) evaporating the organic solvent.

3. The process of claim 2 , further comprising after the step (v) a step (vi):
(vi) separating the lignin nanoparticles from the aqueous phase.

4. The process of claim 3 , further comprising after the separating step (vi) a step (vii):
(vii) removing remaining water and organic solvent to achieve a powder of lignin nanoparticles comprising the hydrophobic active agent.

5. The process of claim 1 , wherein the modified lignin is a lignin which is chemically modified to comprise at least two functional groups per modified lignin molecule which are suitable for polymerization and/or crosslinking.

6. The process of claim 5 , wherein the functional groups are selected from terminal double bonds, epoxy groups, alkynyl groups, aldehyde groups, keto groups, or silane groups.

7. The process of claim 6 , wherein the functional groups are (meth)acrylate groups.

8. The process of claim 5 , wherein at least 50% of the hydroxyl groups present in the lignin before the modification are modified.

9. The process of claim 1 , wherein the organic solvent having low solubility in water is selected from hydrocarbon solvents, halogenated hydrocarbons, alcohols, or organic compounds having a nitro group.

10. The process of claim 1 , wherein the hydrophobic active agent is a pesticide.

11. The process of claim 1 , wherein the organic solvent having low solubility in water employed in step (i) comprises an osmotic pressure agent.

12. The process of claim 11 , wherein in step (iii) a miniemulsion is formed.

13. The process of claim 1 , wherein the surfactant employed in step (ii) is selected from an anionic surfactant, a cationic surfactant, a nonionic surfactant, or a combination thereof.

14. The process of claim 1 , wherein the emulsion is formed in step (iii) by ultrasonication and/or high-pressure homogenization.

15. The process of claim 1 , wherein the modified lignin is lignin having terminal double bonds and the crosslinking in step (iv) is achieved by:
(1) adding an amine compound having at least two amino groups and/or a thiol compound having at least two thiol groups to the emulsion obtained in step (iii) and conducting a Michael addition;
(2) conducting radical polymerization; or
(3) adding a diene to the emulsion obtained in step (iii) and conducting olefin metathesis.

16. The process of claim 15 , wherein modified lignin is (meth)acrylated lignin which is obtained by one of the following methods:
(a) reacting OH-groups of lignin with (meth)acrylic anhydride;
(b) reacting OH-groups of lignin with (meth)acryloyl chloride; or
(c) reacting OH-groups of lignin with epichlorohydrin and reacting the reaction product with (meth)acrylic acid.

17. The process of claim 1 , wherein the modified lignin is a lignin modified with epoxy groups and the crosslinking in step (iv) is achieved by:
adding an amine compound having at least two amino groups to the emulsion obtained in step (iii).

18. The process of claim 1 , wherein the modified lignin is an alkynated lignin and the crosslinking in step (iv) is achieved by:
(1) adding a compound having at least two azide groups to the emulsion obtained in step (iii) and conducting azide-alkyne-cycloaddition; or
(2) conducting alkyne metathesis.

19. The process of claim 1 , wherein the modified lignin is a lignin modified with aldehyde or keto groups and the crosslinking in step (iv) is achieved by:
adding an amine compound having at least two amino groups to the emulsion obtained in step (iii).

20. The process of claim 1 , wherein the modified lignin is a lignin modified with silane groups and the crosslinking in step (iv) is achieved by:
conducting hydrosilylation.

Assignees

• Max Planck Gesellschaft
• Inst Fuer Biotechnologie Und Wirkstoff Forschung Ggmbh

Inventors

• Wurm Frederik
• Landfester Katharina
• Yiamsawas Doungporn
• Thines Eckhard
• Fischer Jochen

Classifications

• C08L33/10

  Homopolymers or copolymers of methacrylic acid esters · CPC title

• B82Y40/00

  Manufacture or treatment of nanostructures · CPC title

• A01N25/10

  Macromolecular compounds · CPC title

• A01N47/24

  containing the groups [IMAGE cpc-sch-A01N-0944.gif], [IMAGE cpc-sch-A01N-0945.gif] or[IMAGE cpc-sch-A01N-0946.gif]; Thio analogues thereof · CPC title

• A01N25/04 Primary

  Dispersions, {emulsions, suspoemulsions, suspension concentrates} or gels (foams A01N25/16) · CPC title