# US 11,028,030 B2 · Plant extract compositions for forming protective coatings

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- Number: US 11,028,030 B2
- Document ID: US11028030B2
- Status: Granted
- Kind: B2
- Application number: 16/692,807
- Filed: 2019-11-22
- Published: 2020-04-02
- Granted: 2021-06-08
- Earliest claimed: 2015-12-10
- Assignees: Apeel Technology, Inc.
- Applicants: Apeel Technology, Inc.
- Inventors: Ronald C. Bakus, II; Louis Perez; Camille Mol; James Rogers; Gabriel Rodriguez
- Web page: https://patentgrep.com/patent/US11028030B2

## CPC

- C07C 29/132: by reduction of an oxygen containing functional group
- B01D 11/0288: {Applications, solvents}
- C07C 29/17: by hydrogenation of carbon-to-carbon double or triple bonds
- C07C 51/00: Preparation of carboxylic acids or their salts, halides or anhydrides (of acids by hydrolysis of oils, fats or waxes C11C)
- C07C 51/09: from carboxylic acid esters or lactones
- C07C 51/36: by hydrogenation of carbon-to-carbon unsaturated bonds
- C07C 51/367: by introduction of functional groups containing oxygen only in singly bound form
- C07C 51/377: by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)}
- C07C 63/00: Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C 67/03: by reacting an ester group with a hydroxy group
- C07C 67/08: by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
- C07C 67/475: by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of [IMAGE cpc-sch-C07C-0963.gif] groups between different molecules
- 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
- C08G 63/06: derived from hydroxycarboxylic acids
- C08J 11/14: by treatment with steam or water
- C08J 11/24: containing hydroxyl groups
- A23B 2/725: in the form of liquids or solids
- A23B 7/16: Coating with a protective layer; Compositions or apparatus therefor (A23B7/08 takes precedence)
- A23V 2002/00: Food compositions, function of food ingredients or processes for food or foodstuffs
- B01D 11/0284: {Multistage extraction}
- 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)
- C08J 2391/06: Waxes
- 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
- 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
- C09D 167/04: Polyesters derived from hydroxycarboxylic acids, e.g. lactones (C09D167/06 takes precedence)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- A23B: PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
- A23V: INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## 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

### Claim 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.

### Claim 2 (depends on 1)

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

### Claim 3 (depends on 2)

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

### Claim 4 (depends on 3)

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

### Claim 5 (depends on 4)

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.

### Claim 6 (depends on 2)

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.

### Claim 7 (depends on 6)

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

### Claim 8 (depends on 1)

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

### Claim 9 (depends on 8)

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.

### Claim 10 (depends on 8)

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.

### Claim 11 (depends on 1)

The method of claim 1, wherein the monomers, oligomers, or combinations thereof comprise compounds of Formula I:
wherein:
R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are each independently —H, —OR13, —NR13R14, —SR13, halogen, —C1-C6 alkyl, —C1-C6 alkenyl, —C1-C6 alkynyl, —C3-C7 cycloalkyl,
aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR13, —NR13R14, —SR13, or halogen;
R13 and R14 are each independently —H, —C1-C6 alkyl, —C1-C6 alkenyl, or —C1-C6 alkynyl;
R11 is —H, -glyceryl, —C1-C6 alkyl, —C1-C6 alkenyl, —C1-C6 alkynyl, —C3-C7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR13, —NR13R14, —SR13, or halogen;
R12 is —OH, —H, —C1-C6 alkyl, —C1-C6 alkenyl, —C1-C6 alkynyl, —C3-C7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR13, —NR13R14, —SR13, halogen, —COOH, or —COOR11; and
m, n, and o are each independently an integer in the range of 0 to 30, and 0<m+n+o<30.

### Claim 12 (depends on 1)

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

### Claim 13 (depends on 1)

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

### Claim 14 (depends on 1)

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

### Claim 15 (depends on 1)

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

### Claim 16 (depends on 1)

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.

### Claim 17 (depends on 16)

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

### Claim 18 (depends on 1)

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.

### Claim 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.

### Claim 20 (depends on 19)

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

### Claim 21 (depends on 19)

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

### Claim 22 (depends on 19)

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.

### Claim 23 (depends on 19)

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

### Claim 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.

### Claim 25 (depends on 24)

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

### Claim 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:
R1, R2, R4 and R5 are each independently —H, —OR11, —NR11R12, —SR11, halogen, —C1-C6 alkyl, —C1-C6 alkenyl, —C1-C6 alkynyl, —C3-C7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR11, —NR11R12, —SR11, or halogen;
R11 and R12 are each independently —H, —C1-C6 alkyl, —C1-C6 alkenyl, or —C1-C6 alkynyl;
the symbol represents an optionally single or cis or trans double bond;
the symbol ══ represents a cis or trans double bond;
R3 is —OH and R3′ is selected from the group consisting of —H, —C1-C6 alkyl, —C1-C6 alkenyl, —C1-C6 alkynyl, —C3-C7 cycloalkyl, and aryl when between R3 and R3′ is a single bond, and R3 and R3′ are absent when between R3 and R3′ 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:
R1, R2, R5, R6, R9, R10, R11, R12, and R13 are each independently, at each occurrence, —H, —OR14, —NR14R15, —SR14, halogen, —C1-C6 alkyl, —C2-C6 alkenyl, —C2-C6 alkynyl, —C3-C7 cycloalkyl, aryl, or heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with one or more —OR14, —NR14R15, —SR14, or halogen;
R3, R4, R7, and R8 are each independently, at each occurrence, —H, —OR14, —NR14R15, —SR14, halogen, —C1-C6 alkyl, —C2-C6 alkenyl, —C2-C6 alkenyl, —C2-C6 alkynyl, —C3-C7 cycloalkyl, aryl, or heteroaryl wherein each alkyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with one or more —OR14, —NR14R15, —SR14, or halogen; or
R3 and R4 can combine with the carbon atoms to which they are attached to form a C3-C6 cycloalkyl, a C4-C6 cycloalkenyl, or 3- to 6-membered ring heterocycle; and/or
R7 and R8 can combine with the carbon atoms to which they are attached to form a C3-C6 cycloalkyl, a C4-C6 cycloalkenyl, or 3- to 6-membered ring heterocycle;
R14 and R15 are each independently, at each occurrence, —H, —C1-C6 alkyl, —C2-C6 alkenyl, or —C2-C6 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, —C1-C6 alkyl, —C2-C6 alkenyl, —C2-C6 alkynyl, —C3-C7 cycloalkyl, aryl, 1-glyceryl, 2-glyceryl, or heteroaryl.

### Claim 27 (depends on 26)

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:
R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are each independently —H, —OR13, —NR13R14, —SR13, halogen, —C1-C6 alkyl, —C1-C6 alkenyl, —C1-C6 alkynyl, —C3-C7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR13, —NR13R14, —SR13, or halogen;
R13 and R14 are each independently —H, —C1-C6 alkyl, —C1-C6 alkenyl, or —C1-C6 alkynyl;
R11 is —H, -glyceryl, —C1-C6 alkyl, —C1-C6 alkenyl, —C1-C6 alkynyl, —C3-C7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR13, —NR13R14, —SR13, or halogen;
R12 is —OH, —H, —C1-C6 alkyl, —C1-C6 alkenyl, —C1-C6 alkynyl, —C3-C7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR13, —NR13R14, —SR13, halogen, —COOH, or —COOR11; and
m, n, and o are each independently an integer in the range of 0 to 30, and 0≤m+n+o≤30.

### Claim 28 (depends on 1)

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

### Claim 29 (depends on 19)

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

### Claim 30 (depends on 24)

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