Plant extract compositions for forming protective coatings

• US 11,028,030 B2
• Filed: 11/22/2019
• Issued: 06/08/2021
• Est. Priority Date: 12/10/2015
• Status: Active Grant

• Current Assignee: Apeel Technology, Inc.
• Original Assignee: Apeel Technology, Inc.
• Inventors: Bakus, II, Ronald C., Perez, Louis, Mol, Camille, Rogers, James, Rodriguez, Gabriel
• Primary Examiner(s): Cutliff, Yate' K
• Application Number:
  US16/692,807
• Publication Number:
  US 20200100514A1
• Time in Patent Office: 564 Days
• CPC Class Codes: A23B 7/16 Coating with a protective layer; Compositions or apparatus therefor A23B7/08 takes precedence
• CPC Class Codes: A23L 3/3454 in the form of liquids or solids
• CPC Class Codes: A23V 2002/00 Food compositions, function of food ingredients or processes for food or foodstuffs
• CPC Class Codes: B01D 11/0284 Multistage extraction
• CPC Class Codes: B01D 11/0288 Applications, solvents
• CPC Class Codes: C07C 29/132 by reduction of an oxygen containing functional group
• CPC Class Codes: C07C 29/17 by hydrogenation of carbon-to-carbon double or triple bonds
• CPC Class Codes: C07C 51/00 Preparation of carboxylic acids or their salts, halides or anhydrides of acids by hydrolysis of oils, fats or waxes C11C
• CPC Class Codes: C07C 51/09 from carboxylic acid esters or lactones
• CPC Class Codes: C07C 51/36 by hydrogenation of carbon-to-carbon unsaturated bonds
• CPC Class Codes: C07C 51/367 by introduction of functional groups containing oxygen only in singly bound form
• CPC Class Codes: C07C 51/377 by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups C07C51/36 - C07C51/373 take precedence
• CPC Class Codes: C07C 53/126 Acids containing more than four carbon atoms
• CPC Class Codes: C07C 57/03 Monocarboxylic acids
• CPC Class Codes: C07C 57/12 Straight chain carboxylic acids containing eighteen carbon atoms
• CPC Class Codes: C07C 59/01 Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
• CPC Class Codes: C07C 59/105 having five or more carbon atoms, e.g. aldonic acids
• CPC Class Codes: C07C 59/42 containing hydroxy or O-metal groups
• CPC Class Codes: C07C 63/00 Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07C 67/03 by reacting an ester group with a hydroxy group
• CPC Class Codes: C07C 67/08 : by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C07C 67/475 : by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
• CPC Class Codes: C07C 69/24 : esterified with monohydroxylic compounds
• CPC Class Codes: C07C 69/533 : Monocarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C07C 69/58 : Esters of straight chain acids with eighteen carbon atoms in the acid moiety
• CPC Class Codes: C07C 69/587 : Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
• CPC Class Codes: C07C 69/675 : of saturated hydroxy-carboxylic acids
• CPC Class Codes: C07C 69/732 : of unsaturated hydroxy carboxylic acids
• CPC Class Codes: C07D 303/38 : with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C08G 63/00 : Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule polyester-amides C08G69/44; polyester-imides C08G73/16
• CPC Class Codes: C08G 63/06 : derived from hydroxycarboxylic acids
• CPC Class Codes: C08J 11/14 : by treatment with steam or water
• CPC Class Codes: C08J 11/24 : containing hydroxyl groups
• CPC Class Codes: C08J 2391/06 : Waxes
• CPC Class Codes: C09D 167/00 : Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain based on polyester-amides C09D177/12; based on polyester-imides C09D179/08; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09D 167/04 : Polyesters derived from hydroxycarboxylic acids, e.g. lactones C09D167/06 takes precedence
• CPC Class Codes: C09D 5/00 : Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced electrically insulating plastics, resins or waxes H01B3/30; Filling pastes

Abstract

Described herein are methods of preparing cutin-derived monomers, oligomers, or combinations thereof from cutin-containing plant matter. The methods can include heating the cutin-derived plant matter in a solvent at elevated temperature and pressure. In some preferred embodiments, the methods can be carried out without the use of additional acidic or basic species.

Claims

1. A method of preparing a composition comprising monomers, oligomers, or combinations thereof derived from cutin-containing plant matter, the method comprising:

adding cutin-containing plant matter to a solvent to form a mixture, the solvent having a boiling point at a first temperature at a pressure of one atmosphere; and

heating the mixture to a second temperature, wherein the second temperature is higher than the first temperature, and to a second pressure, wherein the second pressure is higher than one atmosphere, thereby forming the composition comprising the monomers, oligomers, or combinations thereof,

wherein the solvent comprises a nucleophilic solvent, liquid CO₂, supercritical CO₂, or combinations thereof.

2. The method of claim 1, wherein the solvent comprises water.

3. The method of claim 2, wherein the monomers, oligomers, or combinations thereof comprise fatty acid monomers, oligomers, or combinations thereof.

4. The method of claim 3, further comprising chemically modifying at least some of the fatty acid monomers, oligomers, or combinations thereof.

5. The method of claim 4, wherein the chemically modifying of the fatty acid monomers, oligomers, or combinations thereof comprises esterifying the fatty acid monomers, oligomers, or combinations thereof.

6. The method of claim 2, wherein the second pressure is sufficiently high to maintain at least a portion of the water in a liquid phase at the second temperature.

7. The method of claim 6, wherein the second temperature is at least 393 K.

8. The method of claim 1, wherein the cutin-containing plant matter comprises a polymer.

9. The method of claim 8, wherein a depolymerization reaction of the polymer at the second temperature results in the monomers, oligomers, or combinations thereof being uncharged.

10. The method of claim 8, wherein a rate of depolymerization of the polymer in the solvent is at least 100 times greater at the second temperature and the second pressure than at the first temperature and first pressure.

11. The method of claim 1, wherein the monomers, oligomers, or combinations thereof comprise compounds of Formula I:

12. The method of claim 1, wherein the solvent comprises ethanol and the monomers, oligomers, or combinations thereof comprise ethyl esters.

13. The method of claim 1, wherein the solvent comprises methanol and the monomers, oligomers, or combinations thereof comprise methyl esters.

14. The method of claim 1, wherein the solvent comprises glycerol and the monomers, oligomers, or combinations thereof comprise glyceryl esters.

15. The method of claim 1, wherein the mixture is substantially free of added acid or base.

16. The method of claim 1, wherein the monomers, oligomers, or combinations thereof comprise esters, and the method further comprises chemically modifying at least some of the esters.

17. The method of claim 16, wherein the chemically modifying of the esters comprises transesterification.

18. The method of claim 1, wherein the second pressure is sufficiently high to maintain at least a portion of the solvent in a liquid phase at the second temperature.

28. The method of claim 1, wherein the solvent is water, glycerol, methanol, ethanol, liquid CO₂, supercritical CO₂, or a combination thereof.

19. A method of forming a composition, comprising:

adding cutin-containing plant matter to a first solvent to form a first mixture, the first solvent having a boiling point at a first temperature at a pressure of one atmosphere;

heating the first mixture to a second temperature, wherein the second temperature is higher than the first temperature, and to a second pressure, wherein the second pressure is higher than one atmosphere, to form a second mixture comprising monomers, oligomers, or combinations thereof derived from the cutin-containing plant matter;

separating the first solvent from the monomers, oligomers, or combinations thereof in the second mixture; and

adding the monomers, oligomers, or combinations thereof to a second solvent;

wherein the first solvent comprises a nucleophilic solvent, liquid CO₂, supercritical CO₂, or combinations thereof.

20. The method of claim 19, wherein the second solvent comprises water or ethanol.

21. The method of claim 19, wherein the first mixture is substantially free of added acid or base.

22. The method of claim 19, wherein the second pressure is sufficiently high to maintain at least a portion of the first solvent in a liquid phase at the second temperature.

23. The method of claim 19, wherein the cutin-containing plant matter comprises a polymer.

29. The method of claim 19, wherein the first solvent is water, glycerol, methanol, ethanol, liquid CO₂, supercritical CO₂, or a combination thereof.

24. A method of forming a composition, comprising:

adding cutin-containing plant matter to a solvent to form a first mixture, the solvent having a boiling point at a first temperature at a pressure of one atmosphere; and

heating the first mixture to a second temperature, wherein the second temperature is higher than the first temperature, and to a second pressure, wherein and the second pressure is higher than one atmosphere, to form a second mixture comprising monomers, oligomers, or combinations thereof derived from the cutin-containing plant matter;

wherein

at least a portion of the monomers or oligomers in the second mixture are unsaturated; and

wherein the solvent comprises a nucleophilic solvent, liquid CO₂, supercritical CO₂, or combinations thereof.

25. The method of claim 24, wherein the solvent comprises water, ethanol, methanol, or glycerol.

30. The method of claim 24, wherein the solvent is water, glycerol, methanol, ethanol, liquid CO₂, supercritical CO₂, or a combination thereof.

26. A method of forming a composition, comprising:

adding cutin-containing plant matter to water to form a first mixture; and

heating the first mixture from a first temperature and first pressure to a second temperature and second pressure, wherein the second temperature is higher than the boiling point of water at one atmosphere and the second pressure is higher than one atmosphere, to form a second mixture comprising a group of compounds of Formula II, esters thereof, or compounds of Formula III, wherein Formula II and Formula III are;

27. The method of claim 26, further comprising modifying the group of compounds of Formula II, esters thereof, or compounds of Formula III to form compounds of Formula I: