Plant extract compositions for forming protective coatings

Patent metadata

Field	Value
Publication number	US-9957215-B2
Application number	US-201715680541-A
Country	US
Kind code	B2
Filing date	Aug 18, 2017
Priority date	Dec 10, 2015
Publication date	May 1, 2018
Grant date	May 1, 2018

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.

First claim

The invention claimed is:

1. A method of preparing cutin-derived monomers, oligomers, or combinations thereof from cutin-containing plant matter, comprising:
obtaining cutin from the cutin-containing plant matter;
adding the cutin 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 and second pressure, the second temperature being higher than the first temperature and the second pressure being higher than one atmosphere, to form a second mixture comprising the cutin-derived monomers, oligomers, or combinations thereof.

2. The method of claim 1 , further comprising separating the solvent from the cutin-derived monomers, oligomers, or combinations thereof in the second mixture to isolate the cutin-derived monomers, oligomers, or combinations thereof.

3. The method of claim 2 , further comprising dissolving the isolated cutin-derived monomers, oligomers, or combinations thereof in a second solvent.

4. The method of claim 1 , wherein at least a portion of the cutin-derived monomers, oligomers, or combinations thereof in the second mixture are unsaturated.

5. The method of claim 4 , further comprising hydrogenating the unsaturated cutin-derived monomers, oligomers, or combinations thereof.

6. The method of claim 1 , wherein a rate of depolymerization of the cutin in the solvent is at least 100 times greater at the second temperature and the second pressure than at the first temperature at one atmosphere.

7. The method of claim 1 , wherein the second temperature is at least 393 K.

8. The method of claim 7 , wherein the second pressure is greater than 5 atm.

9. The method of claim 8 , wherein the first mixture is held at the second temperature and second pressure for at least about two hours.

10. The method of claim 7 , wherein the second pressure is sufficiently high to maintain at least a portion of the solvent in a liquid phase at the second temperature.

11. The method of claim 1 , wherein the solvent is selected from the group consisting of water, glycerol, methanol, ethanol, liquid CO 2 , and supercritical CO 2 .

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

13. The method of claim 1 , wherein the process of forming the second mixture results in the production of both saturated and unsaturated fatty acids.

14. The method of claim 13 , wherein a concentration of saturated fatty acids is higher than a concentration of unsaturated fatty acids in the second mixture.

15. The method of claim 1 , wherein the process of forming the second mixture results in the production of both saturated and unsaturated fatty acid esters.

16. The method of claim 15 , wherein a concentration of saturated fatty acid esters is higher than a concentration of unsaturated fatty acid esters in the second mixture.

17. The method of claim 1 , wherein a depolymerization reaction at the second temperature results in the cutin-derived monomers, oligomers, or combinations thereof in the second mixture being uncharged.

18. A method of preparing cutin-derived monomers, oligomers, or combinations thereof from cutin-containing plant matter, comprising:
obtaining cutin from the cutin-containing plant matter;
adding the cutin 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 and second pressure, the second temperature being higher than the first temperature and the second pressure being higher than one atmosphere, to form a second mixture comprising a first group of compounds of Formula I:

wherein:
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently —H, —OR 13 , —NR 13 R 14 , —SR 13 , halogen, —C 1 -C 6 alkyl, —C 1 -C 6 alkenyl, —C 1 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR 13 , —NR 13 R 14 , —SR 13 , or halogen;
R 13 and R 14 are each independently —H, —C 1 -C 6 alkyl, —C 1 -C 6 alkenyl, or —C 1 -C 6 alkynyl;
R 11 is —H, -glyceryl, —C 1 -C 6 alkyl, —C 1 -C 6 alkenyl, —C 1 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR 13 , —NR 13 R 14 , —SR 13 , or halogen;
R 12 is —OH, —H, —C 1 -C 6 alkyl, —C 1 -C 6 alkenyl, —C 1 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR 13 , —NR 13 R 14 , —SR 13 , halogen, —COOH, or —COOR 11 ; and
m, n, and o are each independently an integer in the range of 0 to 30, and 0≤m+n+o≤30.

19. The method of claim 18 , wherein forming the second mixture further comprises producing compounds of Formula II:

wherein:
R 1 , R 2 , R 4 and R 5 are each independently —H, —OR 11 , —NR 11 R 12 , —SR 11 , halogen, —C 1 -C 6 alkyl, —C 1 -C 6 alkenyl, —C 1 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR 11 , —NR 11 R 12 , —SR 11 , or halogen;
R 11 and R 12 are each independently —H, —C 1 -C 6 alkyl, —C 1 -C 6 alkenyl, or —C 1 -C 6 alkynyl;
the symbol represents an optionally single or cis or trans double bond;
R 3 is —OH and R 3′ is selected from the group consisting of —H, —C 1 -C 6 alkyl, —C 1 -C 6 alkenyl, —C 1 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, and aryl when between R 3 and R 3′ is a single bond, and R 3 and R 3′ are absent when between R 3 and R 3′ represents a double bond;
R 6 is —OH and R 6′ is selected from the group consisting of —H, —C 1 -C 6 alkyl, —C 1 -C 6 alkenyl, —C 1 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, and —C 6 -C 10 aryl when between R 6 and R 6′ is a single bond, and R 6 and R 6′ are absent when between R 6 and R 6′ represents a double bond;
n is an integer in the range of 0 to 11;
m is an integer in the range of 0 to 25; and
0≤m+n≤25.

20. The method of claim 19 , wherein a concentration of the compounds of Formula I is greater than a concentration of the compounds of Formula II in the second mixture.

21. The method of claim 19 , wherein a concentration of the compounds of Formula II is greater than a concentration of the compounds of Formula I in the second mixture.

22. The method of claim 21 , further comprising modifying the compounds of Formula II to form a second group of compounds of Formula I.

23. The method of claim 18 , wherein forming the second mixture further comprises producing compounds of Formula III:

wherein:
R 1 , R 2 , R 5 , R 6 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently, at each occurrence, —H, —OR 14 , —NR 14 R 15 , —SR 14 , halogen, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, —C 2 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, aryl, or heteroaryl, wherein each a

Assignees

• Apeel Tech Inc

Inventors

• Perez Louis
• Mol Camille
• Bakus Ii Ronald C
• Rogers James
• Rodriguez Gabriel

Classifications

• C07C69/58

  Esters of straight chain acids with eighteen carbon atoms in the acid moiety · CPC title

• C07C51/00 Primary

  Preparation of carboxylic acids or their salts, halides or anhydrides (of acids by hydrolysis of oils, fats or waxes C11C) · CPC title

• C07C57/03

  Monocarboxylic acids · CPC title

• C09D167/00

  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 title

• C07C69/587

  Monocarboxylic acid esters having at least two carbon-to-carbon double bonds · CPC title