Plant extract compositions for forming protective coatings
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.
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 CO 2 , supercritical CO 2 , 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:
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.
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.
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 CO 2 , supercritical CO 2 , 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.
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 CO 2 , supercritical CO 2 , or combinations thereof.
25. The method of claim 24 , wherein the solvent comprises water, ethanol, methanol, or glycerol.
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:
wherein for Formula II:
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;
the symbol ══ represents a 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;
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;
wherein for Formula III:
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 alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with one or more —OR 14 , —NR 14 R 15 , —SR 14 , or halogen;
R 3 , R 4 , R 7 , and R 8 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 alkenyl, —C 2 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, aryl, or heteroaryl wherein each alkyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with one or more —OR 14 , —NR 14 R 15 , —SR 14 , or halogen; or
R 3 and R 4 can combine with the carbon atoms to which they are attached to form a C 3 -C 6 cycloalkyl, a C 4 -C 6 cycloalkenyl, or 3- to 6-membered ring heterocycle; and/or
R 7 and R 8 can combine with the carbon atoms to which they are attached to form a C 3 -C 6 cycloalkyl, a C 4 -C 6 cycloalkenyl, or 3- to 6-membered ring heterocycle;
R 14 and R 15 are each independently, at each occurrence, —H, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, or —C 2 -C 6 alkynyl;
the symbol represents a single bond or a cis or trans double bond;
the symbol ══ represents a cis or trans double bond;
n is 0, 1, 2, 3, 4, 5, 6, 7 or 8;
m is 0, 1, 2 or 3;
q is 0, 1, 2, 3, 4 or 5;
r is 0, 1, 2, 3, 4, 5, 6, 7 or 8; and
R is selected from —H, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, —C 2 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, aryl, 1-glyceryl, 2-glyceryl, or heteroaryl.
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:
wherein for Formula I:
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.
28. The method of claim 1 , wherein the solvent is water, glycerol, methanol, ethanol, liquid CO 2 , supercritical CO 2 , or a combination thereof.
29. The method of claim 19 , wherein the first solvent is water, glycerol, methanol, ethanol, liquid CO 2 , supercritical CO 2 , or a combination thereof.
30. The method of claim 24 , wherein the solvent is water, glycerol, methanol, ethanol, liquid CO 2 , supercritical CO 2 , or a combination thereof.