Compositions and methods of making the same

Abstract

This application describes a method for preparing compounds derived from triglycerides or condensation polymers such as polyesters and / or polyamides. This method may include subjecting a substance containing triglycerides or condensation polymers to mechanical processing in the presence of a nucleophile.

Description

[0001] Cross-references to related applications

[0002] This application is a divisional application of Chinese Patent Application No. 202180073971.7. This application claims the benefit of U.S. Patent Application No. 63 / 108,168, filed October 30, 2020, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present invention discloses compounds and compositions derived from compounds such as condensates or triglycerides and combinations thereof, methods for preparing said compounds and compositions, and the use of said compounds and compositions in recycling and agricultural coating formulations. Background Technology

[0004] Common agricultural products are readily degraded and decomposed (i.e., spoiled) upon exposure to the environment. Such agricultural products can include, for example, eggs, fruits, vegetables, produce, seeds, nuts, flowers, and / or whole plants (including their processed and semi-processed forms). Non-agricultural products (e.g., vitamins, confectionery, etc.) are also readily degraded upon exposure to the surrounding environment. Degradation of agricultural products can occur through abiotic means due to evaporative moisture loss from the outer surface of the product to the atmosphere and / or oxidation by oxygen diffusing from the environment into the product and / or mechanical damage to the surface and / or photoinduced degradation (i.e., photodegradation). Furthermore, biological stressors such as bacteria, fungi, viruses, and / or pests can also infect and decompose agricultural products.

[0005] Conventional methods for preventing degradation of agricultural products, maintaining their quality, and extending their shelf life include refrigeration and / or special packaging. Refrigeration requires capital-intensive equipment, constant energy consumption, and can damage or degrade the product if not carefully controlled. It must be actively managed, and its benefits are lost if the temperature-controlled supply chain is disrupted. Special packaging may also require expensive equipment, consume packaging materials, increase transportation costs, and requires active management. While refrigeration and special packaging can provide benefits, the handling and transportation of agricultural products can cause surface abrasion or scratches, which are aesthetically unpleasant for consumers and provide entry points for bacteria and fungi. Furthermore, the costs associated with these methods can increase the overall cost of agricultural products. Invention Overview

[0006] The disclosure of this invention describes methods for converting polyester or polyamide-containing compounds into component monomers, oligomers, or both; methods for producing cutin-derived monomers, oligomers, or both from plant materials; and methods for producing component monomers, oligomers, or both from triglycerides in plant material seeds, beans, nuts, kernels, or pulp. These methods typically involve mechanochemical processes that decompose or depolymerize polymeric raw materials to generate component monomers and oligomers.

[0007] Although the disclosed inventive concept includes the inventive concept defined in the appended claims, it should be understood that the inventive concept may also be defined according to the following embodiments.

[0008] In addition to the embodiments described in the appended claims and the above-described embodiments, the embodiments numbered below are also innovative.

[0009] Implementation Scheme 1 is a method for depolymerizing a compound containing polyester or polyamide into constituent oligomers and / or monomers, the method comprising:

[0010] The compound containing polyester or polyamide is contacted with a nucleophile to form a first mixture;

[0011] The first mixture is mechanically processed to decompose at least a portion of the polyester- or polyamide-containing compound, thereby producing a second mixture comprising oligomers and / or monomers of the polyester- or polyamide-containing compound; and

[0012] At least a portion of the oligomers and / or monomers are separated from the second mixture.

[0013] Implementation scheme 2 is the method of implementation scheme 1, wherein the compound containing polyester or polyamide includes one or more of condensation polymers and triglycerides.

[0014] Implementation scheme 3 is the method of implementation scheme 2, wherein the condensation polymer is selected from keratin, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, poly(2-hydroxybutyrate), poly(caprolactone), poly(lactic acid), polyhydroxyalkanoate, polyglycolic acid, polyethylene glycol adipate, polybutylene succinate, nylon, aromatic polyamide and polyphthalamide.

[0015] Implementation scheme 4 is the method of implementation scheme 3, wherein the condensation polymer is keratin.

[0016] Implementation scheme 5 is the method of implementation scheme 2, wherein the polyester-containing compound is a triglyceride.

[0017] Implementation scheme 6 is a method of any one of implementation schemes 1-5, wherein the nucleophile is selected from hydroxides, alkoxides, carbonates, metal hydrides and their precursors.

[0018] Implementation scheme 7 is the method of implementation scheme 6, wherein the nucleophile is a hydroxide selected from potassium hydroxide, sodium hydroxide, barium hydroxide, cesium hydroxide and calcium hydroxide.

[0019] Implementation scheme 8 is a method of any one of implementation schemes 1-7, wherein the selected amount of the nucleophile is a catalytic amount, a stoichiometric amount, or a superstoichiometric amount.

[0020] Implementation method 9 is a method according to any one of implementation methods 1-8, wherein the first mixture is mechanically processed for about 1 minute to about 24 hours.

[0021] Implementation scheme 10 is a method of any one of implementation schemes 1-9, wherein the machining includes grinding the first mixture.

[0022] Implementation scheme 11 is the method of implementation scheme 10, wherein grinding the first mixture includes milling the first mixture.

[0023] Implementation scheme 12 is the method of implementation scheme 11, wherein the grinding is a planetary ball mill, and the first mixture is ground at a rotational frequency of about 1 rpm to about 1000 rpm.

[0024] Implementation scheme 13 is a method of any one of implementation schemes 1-9, wherein the machining includes stirring the first mixture.

[0025] Implementation scheme 14 is the method of any one of implementation schemes 1-13, wherein the machining reduces the particle size of at least a portion of the second mixture to an average particle size of less than about 1000 micrometers.

[0026] Embodiment 15 is a method according to any one of embodiments 1-14, wherein separating at least a portion of the component monomers from the second mixture includes subjecting the second mixture to at least one of acidification, distillation, filtration, and centrifugation.

[0027] Implementation scheme 16 is the method of implementation scheme 15, wherein separating at least a portion of the component monomers includes treating a second mixture with acid.

[0028] Implementation scheme 17 is the method of implementation scheme 16, wherein the acid is an inorganic acid.

[0029] Implementation scheme 18 is the method of implementation scheme 16 or implementation scheme 17, wherein the acid is selected from hydrochloric acid, phosphoric acid and sulfuric acid.

[0030] Implementation scheme 19 is a method of any one of implementation schemes 16-18, wherein the second mixture is treated with acid to form a solution with a pH less than or equal to 5.

[0031] Implementation scheme 20 is the method of any one of implementation schemes 16-19, wherein the second mixture is treated with acid for about 5 minutes to about 24 hours.

[0032] Implementation scheme 21 is the method of any one of implementation schemes 1-20, wherein the component monomer comprises at least one compound of formula I as described herein.

[0033] Implementation scheme 22 is the method of any one of implementation schemes 1-20, wherein the component monomer comprises at least one compound of formula II as described herein.

[0034] Implementation scheme 23 is the method of any one of implementation schemes 1-20, wherein the component monomer comprises at least one compound of formula III as described herein.

[0035] Implementation scheme 24 is a method for producing keratin-derived monomers, oligomers, or both from plant material, the method comprising:

[0036] Keratin is obtained from the keratin-containing parts of plant materials;

[0037] Contact the keratin with the nucleophile to form a first mixture; and

[0038] The first mixture is subjected to mechanical processing to decompose at least a portion of the keratin, thereby producing a second mixture containing keratin-derived monomers, oligomers, or both.

[0039] Implementation scheme 25 is the method of implementation scheme 24, wherein the nucleophile is selected from hydroxides, alkoxides, carbonates, metal hydrides and their precursors.

[0040] Implementation scheme 26 is the method of implementation scheme 25, wherein the nucleophile is a hydroxide selected from potassium hydroxide, sodium hydroxide, barium hydroxide, cesium hydroxide and calcium hydroxide.

[0041] Implementation scheme 27 is a method of any one of implementation schemes 24-26, wherein the keratin is contacted with a catalytic, stoichiometric, or superstoichiometric amount of a nucleophilic reagent.

[0042] Implementation scheme 28 is the method of any one of implementation schemes 24-27, wherein the first mixture is subjected to mechanical processing for about 1 minute to about 24 hours.

[0043] Implementation scheme 29 is the method of any one of implementation schemes 24-28, wherein the machining includes grinding the first mixture.

[0044] Implementation scheme 30 is the method of implementation scheme 29, wherein grinding the first mixture includes milling the mixture.

[0045] Implementation scheme 31 is the method of implementation scheme 30, wherein the grinding is a planetary ball mill, and the first mixture is ground at a rotational frequency of about 1 rpm to about 1000 rpm.

[0046] Implementation scheme 32 is the method of any one of implementation schemes 24-31, wherein the second mixture comprises at least one keratin-derived salt of formula IV as described herein.

[0047] Implementation scheme 33 is the method of any one of implementation schemes 24-31, wherein the second mixture comprises at least one keratin-derived salt of formula V as described herein.

[0048] Implementation scheme 34 is the method of any one of implementation schemes 24-31, wherein the second mixture comprises at least one keratin-derived salt of formula VI as described herein.

[0049] Embodiment 35 is a method of any one of Embodiments 24-34, further comprising separating keratin-derived monomers from the second mixture, wherein separating keratin-derived monomers includes one or more of acidification, distillation, filtration and centrifugation.

[0050] Implementation scheme 36 is the method of implementation scheme 35, wherein the second mixture is acidified.

[0051] Implementation scheme 37 is the method of implementation scheme 36, wherein the second mixture is acidified with an inorganic acid.

[0052] Implementation scheme 38 is the method of implementation scheme 37, wherein the inorganic acid is selected from hydrochloric acid, phosphoric acid and sulfuric acid.

[0053] Implementation scheme 39 is the method of any one of implementation schemes 37-38, wherein the second mixture is acidified to a pH less than or equal to 5.

[0054] Implementation scheme 40 is a method of any one of implementation schemes 35-39, wherein the keratin-derived monomer comprises at least one compound of formula I as described herein.

[0055] Implementation scheme 41 is a method of any one of implementation schemes 35-39, wherein the keratin-derived monomer comprises at least one compound of formula II as described herein.

[0056] Implementation scheme 42 is a method of any one of implementation schemes 35-39, wherein the keratin-derived monomer comprises at least one compound of formula III as described herein.

[0057] Embodiment 43 is a method for producing component monomers from at least a portion of triglycerides from plant material seeds, beans, nuts, kernels, or pulp materials, the method comprising:

[0058] Seeds, beans, nuts, kernels or pulp material that are at least partially separated from other parts of plant matter;

[0059] Oils may be extracted from seeds, beans, nuts, kernels or pulp materials;

[0060] The separated seeds, beans, nuts, kernels, or pulp material, or optionally the oils extracted from them, are contacted with a nucleophilic reagent to form a first mixture; and

[0061] The first mixture is subjected to mechanical processing to produce a second mixture containing component monomers derived from triglycerides.

[0062] Implementation scheme 44 is the method of implementation scheme 43, wherein the nucleophile is selected from hydroxides, alkoxides, carbonates, metal hydrides and their precursors.

[0063] Implementation scheme 45 is the method of implementation scheme 44, wherein the nucleophile is a hydroxide selected from potassium hydroxide, sodium hydroxide, barium hydroxide, cesium hydroxide and calcium hydroxide.

[0064] Implementation scheme 46 is a method of any one of implementation schemes 43-45, wherein the isolated seed, bean, nut, kernel or pulp material or optionally the oil extracted therefrom is contacted with a catalytic amount, stoichiometric amount or superstoichiometric amount of a nucleophilic reagent.

[0065] Implementation scheme 47 is the method of any one of implementation schemes 43-46, wherein the first mixture is subjected to mechanical processing for about 1 minute to about 24 hours.

[0066] Implementation scheme 48 is the method of any one of implementation schemes 43-47, wherein machining includes grinding the first mixture.

[0067] Implementation scheme 49 is the method of implementation scheme 48, wherein grinding the first mixture includes milling the mixture.

[0068] Implementation scheme 50 is the method of implementation scheme 49, wherein the grinding is a planetary ball mill, and the first mixture is ground at a rotational frequency of about 1 rpm to about 1000 rpm.

[0069] Embodiment 51 is the method of any one of embodiments 43-50, wherein the second mixture comprises at least one carboxylate or neutral compound of formula I as described herein.

[0070] Embodiment 52 is the method of any one of embodiments 43-50, wherein the second mixture comprises at least one carboxylate or neutral compound of formula II as described herein.

[0071] Embodiment 53 is a method according to any one of embodiments 43-50, wherein the second mixture comprises at least one carboxylate or neutral compound of formula III as described herein.

[0072] Implementation scheme 54 is the method of any one of implementation schemes 43-53, which further includes separating at least a portion of the monomers from the second mixture by one or more of acidification, distillation, filtration and centrifugation.

[0073] Implementation scheme 55 is the method described in implementation scheme 54, wherein the second mixture is acidified.

[0074] Implementation scheme 56 is the method of implementation scheme 55, wherein the second mixture is acidified with an inorganic acid.

[0075] Implementation scheme 57 is the method of implementation scheme 56, wherein the organic acid is selected from hydrochloric acid, phosphoric acid and sulfuric acid.

[0076] Implementation scheme 58 is the method of any one of implementation schemes 54-57, wherein the second mixture is acidified to a pH less than or equal to 5.

[0077] Implementation scheme 59 is the method of any one of implementation schemes 54-58, wherein the monomer comprises at least one compound of formula I as described herein.

[0078] Implementation scheme 60 is the method of any one of implementation schemes 54-58, wherein the monomer comprises at least one compound of formula II as described herein.

[0079] Implementation scheme 61 is the method of any one of implementation schemes 54-58, wherein the monomer comprises at least one compound of formula III as described herein.

[0080] This application also relates to the following implementation schemes:

[0081] 1. A method for depolymerizing a polyester or polyamide-containing compound into constituent oligomers and / or monomers, the method comprising:

[0082] The compound containing polyester or polyamide is contacted with a nucleophile to form a first mixture;

[0083] The first mixture is mechanically processed to decompose at least a portion of the polyester- or polyamide-containing compound, thereby producing a second mixture comprising oligomers and / or monomers of the polyester- or polyamide-containing compound; and

[0084] At least a portion of the oligomers and / or monomers are separated from the second mixture.

[0085] 2. The method according to embodiment 1, wherein the polyester or polyamide-containing compound comprises one or more of a condensation polymer and a triglyceride.

[0086] 3. The method according to embodiment 2, wherein the condensation polymer is selected from keratin, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, poly(2-hydroxybutyrate), poly(caprolactone), poly(lactic acid), polyhydroxyalkanoate, polyglycolic acid, polyethylene glycol adipate, polybutylene succinate, nylon, aromatic polyamide and polyphthalamide.

[0087] 4. The method according to embodiment 3, wherein the condensation polymer is keratin.

[0088] 5. The method according to embodiment 2, wherein the polyester-containing compound is a triglyceride.

[0089] 6. The method according to any one of embodiments 1-5, wherein the nucleophile is selected from hydroxides, alkoxides, carbonates, metal hydrides and their precursors.

[0090] 7. The method according to embodiment 6, wherein the nucleophile is a hydroxide selected from potassium hydroxide, sodium hydroxide, barium hydroxide, cesium hydroxide and calcium hydroxide.

[0091] 8. The method according to any one of embodiments 1-7, wherein the selected amount of the nucleophile is a catalytic amount, a stoichiometric amount, or a superstoichiometric amount.

[0092] 9. The method according to any one of embodiments 1-8, wherein the first mixture is mechanically processed for about 1 minute to about 24 hours.

[0093] 10. The method according to any one of embodiments 1-9, wherein the machining includes grinding the first mixture.

[0094] 11. The method according to embodiment 10, wherein grinding the first mixture comprises milling the first mixture.

[0095] 12. The method according to embodiment 11, wherein the milling is a planetary ball milling and the first mixture is milled at a rotational frequency of about 1 rpm to about 1000 rpm.

[0096] 13. The method according to any one of embodiments 1-9, wherein the machining includes stirring the first mixture.

[0097] 14. The method according to any one of embodiments 1-13, wherein the machining reduces the particle size of at least a portion of the second mixture to an average particle size of less than about 1000 micrometers.

[0098] 15. The method according to any one of embodiments 1-14, wherein separating at least a portion of the component monomer from the second mixture comprises subjecting the second mixture to at least one of acidification, distillation, filtration, and centrifugation.

[0099] 16. The method according to embodiment 15, wherein separating at least a portion of the component monomer comprises treating the second mixture with acid.

[0100] 17. The method according to implementation scheme 16, wherein the acid is an inorganic acid.

[0101] 18. The method according to embodiment 16 or embodiment 17, wherein the acid is selected from hydrochloric acid, phosphoric acid and sulfuric acid.

[0102] 19. The method according to any one of embodiments 16-18, wherein the second mixture is treated with acid to form a solution with a pH less than or equal to 5.

[0103] 20. The method according to any one of embodiments 16-19, wherein the second mixture is treated with acid for about 5 minutes to about 24 hours.

[0104] 21. The method according to any one of embodiments 1-20, wherein the constituent monomer comprises at least one compound of formula I:

[0105] (Formula I)

[0106] in:

[0107] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 Each is independently -H, -OR 13 -NR 13 R 14 -SR 13 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 Or halogen substitution;

[0108] R 13 and R 14Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0109] R 12 It is -OH, -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl, or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl, or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 halogen, -COOH or -COOR 11 replace;

[0110] m, n, and o are each an independent integer in the range 0 to 30; and

[0111] The sum of m, n, and o is between 0 and 30.

[0112] 22. The method according to any one of embodiments 1-20, wherein the constituent monomer comprises at least one compound of formula II:

[0113] (Formula II)

[0114] in:

[0115] R 1 R 2 R 4 and R 5 Each is independently -H, -OR 11 -NR 11 R 12 -SR 11 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 11 -NR 11 R 12 -SR 11 Or halogen substitution;

[0116] R 11 and R 12 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0117] symbol Indicates either a single key or a cis or trans double key;

[0118] When R 3 and R 3 Between When it is a single bond, R 3 It is -OH and R 3 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 alkynyl, -C3-C7 cycloalkyl, and aryl; and when R 3 and R 3 Between When representing a double bond, R 3 and R 3 It does not exist;

[0119] When R 6 and R 6 Between When it is a single bond, R 6 It is -OH and R 6 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl and -C6-C 10 Aryl, and when R 6 and R 6 Between When representing a double bond, R 6 and R 6 It does not exist;

[0120] n is an integer in the range of 0 to 11;

[0121] m is an integer in the range of 0 to 25; and

[0122] The sum of m and n is between 0 and 25.

[0123] 23. The method according to any one of embodiments 1-20, wherein the constituent monomer comprises at least one compound of formula III:

[0124] (Formula III)

[0125] in:

[0126] R 1 R 2 R 5 R 6 R 9 R 10 R 11 R 12 and R 13 Each occurrence is independently -H or -OR. 14-NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution;

[0127] R 3 R 4 R 7 and R 8 Each occurrence is independently -H or -OR. 14 -NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution; in which

[0128] R 3 and R 4 Optionally, they can be combined with the carbon atoms to which they are attached to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings, and / or

[0129] R 7 and R 8 Optionally combined with the carbon atoms to which they are attached to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings;

[0130] R 14 and R 15 Each time it appears, it is independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0131] symbol Indicates a single bond or a cis or trans double bond;

[0132] symbol Indicates a cis or trans double bond;

[0133] n is 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0134] m is 0, 1, 2, or 3;

[0135] q is 0, 1, 2, 3, 4, or 5; and

[0136] r can be 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0137] 24. A method for producing keratin-derived monomers, oligomers, or both from plant material, the method comprising:

[0138] Keratin is obtained from the keratin-containing parts of plant materials;

[0139] Contact the keratin with the nucleophile to form a first mixture; and

[0140] The first mixture is subjected to mechanical processing to decompose at least a portion of the keratin, thereby producing a second mixture containing keratin-derived monomers, oligomers, or both.

[0141] 25. The method according to embodiment 24, wherein the nucleophile is selected from hydroxides, alkoxides, carbonates, metal hydrides and their precursors.

[0142] 26. The method according to embodiment 25, wherein the nucleophile is a hydroxide selected from potassium hydroxide, sodium hydroxide, barium hydroxide, cesium hydroxide and calcium hydroxide.

[0143] 27. The method according to any one of embodiments 24-26, wherein the keratin is contacted with a catalytic amount, a stoichiometric amount, or a superstoichiometric amount of a nucleophilic reagent.

[0144] 28. The method according to any one of embodiments 24-27, wherein the first mixture is subjected to mechanical processing for about 1 minute to about 24 hours.

[0145] 29. The method according to any one of embodiments 24-28, wherein the machining includes grinding the first mixture.

[0146] 30. The method according to embodiment 29, wherein grinding the first mixture comprises milling the mixture.

[0147] 31. The method according to embodiment 30, wherein the grinding is a planetary ball mill, and the first mixture is milled at a rotational frequency of about 1 rpm to about 1000 rpm.

[0148] 32. The method according to any one of embodiments 24-31, wherein the second mixture comprises at least one keratin-derived salt of formula IV:

[0149] (Formula IV)

[0150] in:

[0151] X p+ It is a cationic counterion with a charge state p, and p is 1, 2 or 3;

[0152] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 Each is independently -H, -OR 13 -NR 13 R 14 -SR 13 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 Or halogen substitution;

[0153] R 13 and R 14 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0154] R 12 It is -OH, -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl, or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl, or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 halogen, -COOH or -COOR 11 replace;

[0155] m, n, and o are each an independent integer in the range 0 to 30; and

[0156] The sum of m, n, and o is between 0 and 30.

[0157] 33. The method according to any one of embodiments 24-31, wherein the second mixture comprises at least one keratin-derived salt of formula V:

[0158] (Formula V)

[0159] in:

[0160] X p+ It is a cationic counterion with a charge state p, and p is 1, 2 or 3;

[0161] R 1 R 2 R 4 and R 5 Each is independently -H, -OR 11 -NR 11 R 12 -SR 11 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 11 -NR 11 R 12 -SR 11 Or halogen substitution;

[0162] R 11 and R 12 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0163] symbol Indicates either a single key or a cis or trans double key;

[0164] When R 3 and R 3 Between When it is a single bond, R 3 It is -OH and R 3 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 alkynyl, -C3-C7 cycloalkyl, and aryl; and when R 3 and R 3 Between When representing a double bond, R 3 and R 3 It does not exist;

[0165] When R 6 and R 6 Between When it is a single bond, R 6 It is -OH and R 6 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl and -C6-C 10 Aryl, and when R 6 and R 6 Between When representing a double bond, R 6 and R 6 It does not exist;

[0166] n is an integer in the range of 0 to 11;

[0167] m is an integer in the range of 0 to 25; and

[0168] The sum of m and n is between 0 and 25.

[0169] 34. The method according to any one of embodiments 24-31, wherein the second mixture comprises at least one keratin-derived salt of formula VI:

[0170] (Formula VI)

[0171] in:

[0172] X p+ It is a cationic counterion with a charge state p, and p is 1, 2 or 3;

[0173] R 1 R 2 R 5 R 6 R 9 R 10 R 11 R 12 and R 13 Each occurrence is independently -H or -OR. 14 -NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution;

[0174] R 3 R 4 R 7 and R 8 Each occurrence is independently -H or -OR.14 -NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution;

[0175] R 3 and R 4 Optionally, they can be combined with the carbon atoms to which they are attached to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings, and / or

[0176] R 7 and R 8 Optionally combined with the carbon atoms to which they are attached to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings;

[0177] R 14 and R 15 Each time it appears, it is independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0178] symbol Indicates a single bond or a cis or trans double bond;

[0179] symbol Indicates a cis or trans double bond;

[0180] n is 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0181] m is 0, 1, 2, or 3;

[0182] q is 0, 1, 2, 3, 4, or 5; and

[0183] r can be 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0184] 35. The method according to any one of embodiments 24-34 further comprises separating the keratin-derived monomer from the second mixture, wherein separating the keratin-derived monomer comprises one or more of acidification, distillation, filtration and centrifugation.

[0185] 36. The method according to embodiment 35, wherein the second mixture is acidified.

[0186] 37. The method according to embodiment 36, wherein the second mixture is acidified with an inorganic acid.

[0187] 38. The method according to embodiment 37, wherein the inorganic acid is selected from hydrochloric acid, phosphoric acid, and sulfuric acid.

[0188] 39. The method according to any one of embodiments 37-38, wherein the second mixture is acidified to a pH less than or equal to 5.

[0189] 40. The method according to any one of embodiments 35-39, wherein the keratin-derived monomer comprises at least one compound of formula I:

[0190] (Formula I)

[0191] in:

[0192] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 Each is independently -H, -OR 13 -NR 13 R 14 -SR 13 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 Or halogen substitution;

[0193] R 13 and R 14 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0194] R 12 It is -OH, -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl, or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl, or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13halogen, -COOH or -COOR 11 replace;

[0195] m, n, and o are each an independent integer in the range 0 to 30; and

[0196] The sum of m, n, and o is between 0 and 30.

[0197] 41. The method according to any one of embodiments 35-39, wherein the keratin-derived monomer comprises at least one compound of formula II:

[0198] (Formula II)

[0199] in:

[0200] R 1 R 2 R 4 and R 5 Each is independently -H, -OR 11 -NR 11 R 12 -SR 11 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 11 -NR 11 R 12 -SR 11 Or halogen substitution;

[0201] R 11 and R 12 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0202] symbol Indicates either a single key or a cis or trans double key;

[0203] When R 3 and R 3 Between When it is a single bond, R 3 It is -OH and R 3 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 alkynyl, -C3-C7 cycloalkyl, and aryl; and when R 3 and R 3 Between When representing a double bond, R 3 and R 3 It does not exist;

[0204] When R 6 and R 6 Between When it is a single bond, R 6 It is -OH and R 6 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl and -C6-C 10 Aryl, and when R 6 and R 6 Between When representing a double bond, R 6 and R 6 It does not exist;

[0205] n is an integer in the range of 0 to 11;

[0206] m is an integer in the range of 0 to 25; and

[0207] The sum of m and n is between 0 and 25.

[0208] 42. The method according to any one of embodiments 35-39, wherein the keratin-derived monomer comprises at least one compound of formula III:

[0209] (Formula III)

[0210] in:

[0211] R 1 R 2 R 5 R 6 R 9 R 10 R 11 R 12 and R 13 Each occurrence is independently -H or -OR. 14 -NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution;

[0212] R 3 R 4 R 7 and R 8 Each occurrence is independently -H or -OR. 14 -NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution; in which

[0213] R 3 and R 4 Optionally, they can be combined with the carbon atoms to which they are attached to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings, and / or

[0214] R 7 and R 8 Optionally combined with the carbon atoms to which they are attached to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings;

[0215] R 14 and R 15 Each time it appears, it is independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0216] symbol Indicates a single bond or a cis or trans double bond;

[0217] symbol Indicates a cis or trans double bond;

[0218] n is 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0219] m is 0, 1, 2, or 3;

[0220] q is 0, 1, 2, 3, 4, or 5; and

[0221] r can be 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0222] 43. A method for producing a component monomer from at least a portion of triglycerides from plant material such as seeds, beans, nuts, kernels, or pulp, comprising:

[0223] Obtain at least partially isolated seeds, beans, nuts, kernels, or pulp material from other parts of plant matter;

[0224] Oils may be extracted from seeds, beans, nuts, kernels or pulp materials;

[0225] The separated seeds, beans, nuts, kernels, or pulp material, or optionally the oils extracted from them, are contacted with a nucleophilic reagent to form a first mixture; and

[0226] The first mixture is subjected to mechanical processing to produce a second mixture containing component monomers derived from triglycerides.

[0227] 44. The method according to embodiment 43, wherein the nucleophile is selected from hydroxides, alkoxides, carbonates, metal hydrides and their precursors.

[0228] 45. The method according to embodiment 44, wherein the nucleophile is a hydroxide selected from potassium hydroxide, sodium hydroxide, barium hydroxide, cesium hydroxide and calcium hydroxide.

[0229] 46. ​​The method according to any one of embodiments 43-45, wherein the isolated seed, bean, nut, kernel or pulp material or optionally the oil extracted therefrom is contacted with a catalytic, stoichiometric or superstoichiometric amount of a nucleophilic reagent.

[0230] 47. The method according to any one of embodiments 43-46, wherein the first mixture is subjected to mechanical processing for about 1 minute to about 24 hours.

[0231] 48. The method according to any one of embodiments 43-47, wherein the machining includes grinding the first mixture.

[0232] 49. The method according to embodiment 48, wherein grinding the first mixture comprises milling the mixture.

[0233] 50. The method according to embodiment 49, wherein the grinding is a planetary ball mill, and the first mixture is milled at a rotational frequency of about 1 rpm to about 1000 rpm.

[0234] 51. The method according to any one of embodiments 43-50, wherein the second mixture comprises at least one carboxylate or neutral compound of formula I:

[0235] (Formula I)

[0236] in:

[0237] R 1 R 2 R 3 R 4R 5 R 6 R 7 R 8 R 9 and R 10 Each is independently -H, -OR 13 -NR 13 R 14 -SR 13 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 Or halogen substitution;

[0238] R 13 and R 14 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0239] R 12 It is -OH, -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl, or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl, or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 halogen, -COOH or -COOR 11 replace;

[0240] m, n, and o are each an independent integer in the range 0 to 30; and

[0241] The sum of m, n, and o is between 0 and 30.

[0242] 52. The method according to any one of embodiments 43-50, wherein the second mixture comprises at least one carboxylate or neutral compound of formula II:

[0243] (Formula II)

[0244] in:

[0245] R 1 R 2 R 4 and R 5 Each is independently -H, -OR 11 -NR 11 R12 -SR 11 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 11 -NR 11 R 12 -SR 11 Or halogen substitution;

[0246] R 11 and R 12 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0247] symbol Indicates either a single key or a cis or trans double key;

[0248] When R 3 and R 3 Between When it is a single bond, R 3 It is -OH and R 3 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 alkynyl, -C3-C7 cycloalkyl, and aryl; and when R 3 and R 3 Between When representing a double bond, R 3 and R 3 It does not exist;

[0249] When R 6 and R 6 Between When it is a single bond, R 6 It is -OH and R 6 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl and -C6-C 10 Aryl, and when R 6 and R 6 Between When representing a double bond, R 6 and R 6 It does not exist;

[0250] n is an integer in the range of 0 to 11;

[0251] m is an integer in the range of 0 to 25; and

[0252] The sum of m and n is between 0 and 25.

[0253] 53. The method according to any one of embodiments 43-50, wherein the second mixture comprises at least one carboxylate or neutral compound of formula III:

[0254] (Formula III)

[0255] in:

[0256] R 1 R 2 R 5 R 6 R 9 R 10 R 11 R 12 and R 13 Each occurrence is independently -H or -OR. 14 -NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution;

[0257] R 3 R 4 R 7 and R 8 Each occurrence is independently -H or -OR. 14 -NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution; in which

[0258] R 3 and R 4Optionally, they can be combined with the carbon atoms to which they are attached to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings, and / or

[0259] R 7 and R 8 Optionally combined with the carbon atoms to which they are attached to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings;

[0260] R 14 and R 15 Each time it appears, it is independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0261] symbol Indicates a single bond or a cis or trans double bond;

[0262] symbol Indicates a cis or trans double bond;

[0263] n is 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0264] m is 0, 1, 2, or 3;

[0265] q is 0, 1, 2, 3, 4, or 5; and

[0266] r can be 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0267] 54. The method according to any one of embodiments 43-53 further includes separating at least a portion of the monomer from the second mixture by one or more of acidification, distillation, filtration and centrifugation.

[0268] 55. The method according to embodiment 54, wherein the second mixture is acidified.

[0269] 56. The method according to embodiment 55, wherein the second mixture is acidified with an inorganic acid.

[0270] 57. The method according to embodiment 56, wherein the organic acid is selected from hydrochloric acid, phosphoric acid and sulfuric acid.

[0271] 58. The method according to any one of embodiments 54-57, wherein the second mixture is acidified to a pH less than or equal to 5.

[0272] 59. The method according to any one of embodiments 54-58, wherein the monomer comprises at least one compound of formula I:

[0273] (Formula I)

[0274] in:

[0275] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 Each is independently -H, -OR 13 -NR 13 R 14 -SR 13 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 Or halogen substitution;

[0276] R 13 and R 14 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0277] R 12 It is -OH, -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl, or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl, or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 halogen, -COOH or -COOR 11 replace;

[0278] m, n, and o are each an independent integer in the range 0 to 30; and

[0279] The sum of m, n, and o is between 0 and 30.

[0280] 60. The method according to any one of embodiments 54-58, wherein the monomer comprises at least one compound of formula II:

[0281] (Formula II)

[0282] in:

[0283] R 1 R 2 R4 and R 5 Each is independently -H, -OR 11 -NR 11 R 12 -SR 11 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 11 -NR 11 R 12 -SR 11 Or halogen substitution;

[0284] R 11 and R 12 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0285] symbol Indicates either a single key or a cis or trans double key;

[0286] When R 3 and R 3 Between When it is a single bond, R 3 It is -OH and R 3 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 alkynyl, -C3-C7 cycloalkyl, and aryl; and when R 3 and R 3 Between When representing a double bond, R 3 and R 3 It does not exist;

[0287] When R 6 and R 6 Between When it is a single bond, R 6 It is -OH and R 6 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl and -C6-C 10 Aryl, and when R 6 and R 6 Between When representing a double bond, R 6 and R 6 It does not exist;

[0288] n is an integer in the range of 0 to 11;

[0289] m is an integer in the range of 0 to 25; and

[0290] The sum of m and n is between 0 and 25.

[0291] 61. The method according to any one of embodiments 54-58, wherein the monomer comprises at least one compound of formula III:

[0292] (Formula III)

[0293] in:

[0294] R 1 R 2 R 5 R 6 R 9 R 10 R 11 R 12 and R 13 Each occurrence is independently -H or -OR. 14 -NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution;

[0295] R 3 R 4 R 7 and R 8 Each occurrence is independently -H or -OR. 14 -NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution; in which

[0296] R3 and R 4 Optionally, they can be combined with the carbon atoms to which they are attached to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings, and / or

[0297] R 7 and R 8 Optionally combined with the carbon atoms to which they are attached to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings;

[0298] R 14 and R 15 Each time it appears, it is independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0299] symbol Indicates a single bond or a cis or trans double bond;

[0300] symbol Indicates a cis or trans double bond;

[0301] n is 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0302] m is 0, 1, 2, or 3;

[0303] q is 0, 1, 2, 3, 4, or 5; and

[0304] r can be 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0305] Mechanochemical reduction of the degree of polymerization provides an effective option for reducing the degree of polymerization of condensation polymers and also offers advantages in large-scale production, at least in part due to reduced solvent burden and increased chemical reaction rate. The decomposition products are more soluble than the corresponding polymers, thus making them more suitable for downstream applications. Chemical recycling (e.g., depolymerizing polymers into constituent monomers and using those monomers as starting materials to reconstruct the polymer) can be advantageously used to produce food-safe plastics from waste plastics without the compromised mechanical properties typically associated with plastics prepared using physical recycling. Furthermore, chemical recycling allows for the removal of organisms or other compounds or contaminants present in the polymer prior to depolymerization. Attached Figure Description

[0306] Figure 1 The graph shows the yield of keratin depolymerization in a ball mill as a function of time, compared to conventional alkaline hydrolysis in methanol.

[0307] Figure 2 This is a graph showing the yield of keratin depolymerization in a ball mill as a function of alkali, compared to alkaline hydrolysis in methanol.

[0308] Figure 3 This is a graph showing the yield of keratin depolymerization in a ball mill as a function of counterions, compared to alkaline hydrolysis in methanol.

[0309] Figure 4 This is a graph showing the yield of keratin depolymerization in a ball mill as a function of rotational frequency, compared to alkaline hydrolysis in methanol.

[0310] Figures 5A-5H The chemical structures of 10,16-dihydroxyhexadecanoic acid, 10,18-dihydroxyoctadecanoic acid, 9,16-dihydroxyhexadecanoic acid, 9,18-dihydroxyoctadecanoic acid, 9,10,16-trihydroxyhexadecanoic acid, 9,10,18-trihydroxyoctadecanoic acid, 9,10-epoxy-16-hydroxyhexadecanoic acid, and 9,10-epoxy-18-hydroxyhexadecanoic acid are shown respectively.

[0311] Figure 6A-6I The chemical structures of byproducts arising from the decomposition of 10,16-dihydroxyhexadecanoic acid monomers and / or oligomers are shown.

[0312] Figures 7A-7C The chemical structure of the molecule formed by the unsaturated indirect byproducts of keratin depolymerization is shown.

[0313] Figure 8 The reaction scheme for the base-catalyzed mechanochemical depolymerization of keratin in a ball mill to produce DHPA as the major product is shown. Detailed description

[0314] The disclosure of this invention describes the mechanochemical processing of raw materials such as condensation polymers (e.g., polyesters, polyamides, keratin, etc.), triglycerides, organic networks, and compounds having hydrolyzable bonds to produce compositions comprising decomposition or depolymerization products, said decomposition or depolymerization products including monomers, oligomers, or both. Mechanochemical processing involves contacting the raw materials with a nucleophile to produce a mixture, and subjecting the mixture to mechanical processes, such as grinding (e.g., milling) or agitation (e.g., sonic stirring), to produce the decomposition or depolymerization products. The depolymerization products (e.g., carboxylic acids or salts thereof) are suitable for a variety of applications, including coatings on substrates such as plant matter, agricultural products, and agricultural products.

[0315] The subject matter of the invention will now be described more fully with reference to the accompanying drawings and embodiments, in which representative embodiments are shown. However, the subject matter of the invention may be embodied in various forms and should not be construed as limited to the embodiments set forth herein. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter pertains. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety.

[0316] definition

[0317] In the claims, articles such as “a,” “an,” and “the” may indicate one or more members unless otherwise indicated or obvious from the context. A claim or description comprising one or more members of a group is satisfied if one, more than one, or all members of that group are present, used in, or otherwise associated with a given product or method, unless otherwise indicated or obvious from the context. An aspect of the invention includes embodiments in which exactly one member of that group is present, used in, or otherwise associated with a given product or process. An aspect of the invention also includes embodiments in which more than one or all members of that group are present, used in, or otherwise associated with a given product or process.

[0318] Furthermore, aspects of the invention include all variations, combinations, and permutations in which one or more limitations, elements, clauses, and descriptive terms from one or more of the enumerated claims are incorporated into another claim. For example, any claim dependent on another claim may be modified to include one or more limitations found in any other claim dependent on the same basic claim. Where elements are presented as a list, such as in Markush group format, each subgroup of elements is also disclosed, and any element may be removed from the group. It should be understood that, generally, where an aspect of the invention is referred to as comprising a particular element and / or feature, certain aspects of the invention consist of or substantially consist of such elements and / or features. For simplicity, these embodiments are not specifically described orally herein. It should also be noted that the terms “comprising” and “containing” are intended to be open-ended and allow for the inclusion of additional elements or steps. Where a range is given, endpoints are included. Furthermore, unless otherwise stated or apparent from the context and understanding of one of ordinary skill in the art, values ​​expressed as ranges may represent any specific value or subrange within the range, up to one-tenth of the lower limit of the range, in different embodiments of the invention, unless the context expressly specifies otherwise.

[0319] "Approximately" should be understood as indicating a specific value. 10%.

[0320] Unless otherwise stated, the term "alkyl," either on its own or as part of another substituent, refers to a straight-chain or branched or cyclic hydrocarbon group, or a combination thereof, which may be fully saturated or mono- or polyunsaturated, and may include groups having a specified number of carbon atoms (i.e., C1-C1). 10A saturated alkyl group refers to a divalent or polyvalent group (1-10 carbons). Examples of saturated alkyl groups include, but are not limited to, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, cyclohexyl, (cyclohexyl)methyl, cyclopropylmethyl, and homologues and isomers of, for example, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc. Unsaturated alkyl groups are alkyl groups having one or more double or triple bonds. Examples of unsaturated alkyl groups include, but are not limited to, vinyl, 2-propenyl, crotonyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and higher homologues and isomers. Unless otherwise stated, the term "alkyl" also means those derivatives that include alkyl groups, such as "heteroalkyl". Alkyl groups limited to hydrocarbon groups are called "homoalkyl". Unless otherwise stated, the alkyl group is optionally substituted independently in each case, i.e., unsubstituted (“unsubstituted alkyl”) or substituted by one or more substituents, such as 1 to 5 substituents, 1 to 3 substituents, or 1 substituent (“substituted alkyl”). In some embodiments, the alkyl group is an unsubstituted C1-C… 10 Alkyl group (e.g., -CH3). In some embodiments, the alkyl group is a substituted C1-C. 10 Alkyl. Common alkyl abbreviations include Me(-CH3), Et(-CH2CH3), iPr(-CH(CH3)2), nPr(-CH2CH2CH3), n-Bu(-CH2CH2CH2CH3) or i-Bu(-CH2CH(CH3)2).

[0321] "Alkenyl" refers to a straight-chain or branched hydrocarbon group having 2-20 carbon atoms, one or more carbon-carbon double bonds (e.g., 1, 2, 3, or 4 carbon-carbon double bonds), and optionally one or more carbon-carbon triple bonds (e.g., 1, 2, 3, or 4 carbon-carbon triple bonds). 20 Alkenyl group (“alkenyl”). In some embodiments, the alkenyl group does not contain any triple bonds. In some embodiments, the alkenyl group has 2 to 10 carbon atoms (“C2-C”). 10 (Alkenyl group). In some embodiments, the alkenyl group has 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, 2 to 3, or 2 carbon atoms. One or more carbon-carbon double bonds may be internal (e.g., in 2-butenyl) or terminal (e.g., in 1-butenyl). C 2-4Examples of alkenyl groups include vinyl (C2), 1-propenyl (C3), 2-propenyl (C3), 1-butenyl (C4), 2-butenyl (C4), butadienyl (C4), etc. Examples of C2-C6 alkenyl groups include the aforementioned C2-C4 alkenyl groups as well as pentenyl (C5), pentadienyl (C5), hexenyl (C6), etc. Other examples of alkenyl groups include heptenyl (C7), octenyl (C8), octetrinyl (C8), etc. Unless otherwise stated, the alkenyl group may optionally be independently substituted in each case, i.e., unsubstituted (“unsubstituted alkenyl”) or substituted by one or more substituents, such as 1 to 5 substituents, 1 to 3 substituents, or 1 substituent (“substituted alkenyl”). In some embodiments, the alkenyl group is an unsubstituted C2-C6 alkenyl group. 10 Alkenyl group. In some embodiments, the alkenyl group is a substituted C2-C group. 10 Alkenyl group.

[0322] "Alkyne" refers to a straight-chain or branched hydrocarbon group having 2 to 20 carbon atoms, one or more carbon-carbon triple bonds (e.g., 1, 2, 3, or 4 carbon-carbon triple bonds), and optionally one or more carbon-carbon double bonds (e.g., 1, 2, 3, or 4 carbon-carbon double bonds). 20 The alkynyl group (“alkynyl”) is present in some embodiments. In some embodiments, the alkynyl group has 2 to 10 carbon atoms (“C2-C”). 10 The alkynyl group (“C2 alkynyl”) has 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, 2 to 3, or 2 carbon atoms in some embodiments. One or more carbon-carbon triple bonds may be internal (as in 2-butynyl) or terminal (as in 1-butynyl). Examples of C2-C4 alkynyl groups include, but are not limited to, ethynyl (C2), 1-propynyl (C3), 2-propynyl (C3), 1-butynyl (C4), 2-butynyl (C4), etc. Examples of -C6 alkenyl groups include the aforementioned C2-C4 alkynyl groups, as well as pentynyl (C5), hexynyl (C6), etc. Other examples of alkynyl groups include heptynyl (C7), octyynyl (C8), etc. Unless otherwise stated, the alkynyl group may optionally be independently substituted in each case, i.e., unsubstituted (“unsubstituted alkynyl”) or substituted by one or more substituents, such as 1 to 5 substituents, 1 to 3 substituents, or 1 substituent (“substituted alkynyl”). In some embodiments, the alkynyl group is an unsubstituted C2-C4 alkenyl group. 10 Alkynyl group. In some embodiments, the alkynyl group is a substituted C2-C group. 10 Alkyne group.

[0323] Unless otherwise stated, the term "aryl" refers to a polyunsaturated aromatic hydrocarbon substituent, which can be a monocyclic or fused together or covalently linked polycyclic ring (preferably 1-3 rings). In some embodiments, the aryl group has 6 to 10 carbon atoms (i.e., "C6-C"). 10 The term "heteroaryl" refers to an aryl group (or ring) containing one to four heteroatoms selected from N, O, and S, wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom is optionally quaternized. The heteroaryl group can be linked to the rest of the molecule via a heteroatom. Non-limiting examples of aryl and heteroaryl groups include phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrole, 2-pyrrole, 3-pyrrole, 3-pyrazolyl, 2-imidazolyl, 4-imidazolyl, pyrazinyl, 2-oxazolyl, 4-oxazolyl, ... 2-Phenylacetyl-4-oxazolyl, 5-oxazolyl, 3-isooxazolyl, 4-isooxazolyl, 5-isooxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furanyl, 3-furanyl, 2-thienyl, 3-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-benzothiazolyl, purinel, 2-benzimidazolyl, 5-indolyl, 1-isoquinolinyl, 5-isoquinolinyl, 2-quinoxalinyl, 5-quinoxalinyl, 3-quinolinyl, and 6-quinolinyl.

[0324] The term "cycloalkyl" includes saturated cyclic, bicyclic, tricyclic, or polycyclic hydrocarbon groups (i.e., C3-C12) having 3-12 carbons. 12 (Cycloalkyl group). In some embodiments, the cycloalkyl group is a cycloalkyl group having 3 to 7 carbon atoms (i.e., C3-C7 cycloalkyl). Any ring atom can be substituted (e.g., substituted by one or more substituents).

[0325] The term "polymer" refers to a molecule with a high relative molecular mass whose structure essentially contains repeating units derived from molecules with a low relative molecular mass.

[0326] Unless otherwise stated, the term "monomer" refers to a molecule that can be polymerized, thereby contributing a constituent unit to the substantial structure of the polymer.

[0327] The term "oligomer" refers to molecules of medium relative molecular mass whose structure essentially contains a small number of units derived from molecules of lower relative molecular mass.

[0328] The term "condensation polymer" refers to a polymer composed of monomers of at least one type having not less than two condensable functional groups, said monomers being linked by the bonding of these functional groups. If the monomers are bifunctional, the condensation product is a linear polymer, and if at least one of the monomers is trifunctional or tetrafunctional, the resulting polymer is a crosslinked polymer. Examples of condensation polymers include polyesters, polyamides, and polycarbonates.

[0329] The terms "depolymerizing" and "depolymerization" each refer to a method of reducing the degree of polymerization of a polymer to produce a lower molecular weight compound (e.g., a monomer, oligomer, or both). In some embodiments, depolymerization is partial depolymerization, which includes degrading the polymer into component monomers and oligomers. In some embodiments, depolymerization is complete depolymerization, which includes completely degrading the polymer into component monomers.

[0330] The term "decompose" (or "decomposing" or "decomposition") refers to the process of transforming a compound (e.g., through a mechanochemical process) into constituent units (e.g., constituent monomers). Decomposition can include depolymerization processes (e.g., the depolymerization of keratin). Decomposition products include constituent monomers, oligomers, or both.

[0331] The term "component monomer" refers to a compound derived from the decomposition of a compound (e.g., undergoing a mechanochemical process). For the purposes of this disclosure, a component monomer can be a charged chemical substance (e.g., a fatty acid carboxylate) or a neutral chemical substance obtained by treating a charged chemical substance (e.g., a fatty acid obtained by acidification of a fatty acid carboxylate). A component monomer is a monomer of a polymer compound derived from a triglyceride.

[0332] "Polyester-containing compounds" refers to compounds that contain more than one ester group as part of their chemical composition. Polyester-containing compounds can be condensation polymers having repeating units linked by esters (e.g., condensation polymers such as polyesters) or compounds in which ester groups are chemically linked to the compound but do not form repeating structures (e.g., triglycerides).

[0333] "Polyamide-containing compounds" refer to compounds that contain more than one amide group as part of their chemical composition. Polyamide-containing compounds can be condensation polymers having repeating units linked by amides.

[0334] "Essentially decomposed" means that 70% to 100% of a compound has decomposed into its constituent units (e.g., constituent monomers).

[0335] "Basically depolymerized" means that 70%-100% of the polymers have depolymerized into monomers, oligomers, or both.

[0336] Compounds, compositions and their preparation methods

[0337] The disclosure of this invention describes compounds and compositions derived from sources such as plant materials, and methods for their preparation. The compositions can be formed by the decomposition (e.g., depolymerization) of polymers (e.g., condensates comprising keratin or other polyesters or triglycerides) and include hydroxy fatty acids and hydroxy fatty esters (and their oligomers and mixtures thereof) found in keratin layers or other polymer networks. The resulting compositions can then be applied to other plant or agricultural products to form a protective coating on the product, or to enhance or modify existing coatings (naturally occurring or deposited coatings) on the outer surface of the product. The applied coating can, for example, protect the product from biological stressors such as bacteria, fungi, viruses, or pests. The applied coating can be used to increase the shelf life of agricultural products without refrigeration, control the ripening rate of agricultural products, or both. In the case of plant materials, the method of forming the composition can result in a composition substantially free of compounds from other plant sources (e.g., proteins, polysaccharides, phenols, lignin, aromatic acids, terpenoids, flavonoids, carotenoids, alkaloids, alcohols, alkanes, and aldehydes), thereby improving the effectiveness of the protective coating formed by the composition.

[0338] Methods for recycling compounds such as condensation polymers (including compounds containing polyesters or polyamides) are also described. Chemical recycling may include depolymerizing the polymer to its component monomers and using those monomers as starting materials to reconstitute the polymer. This type of recycling can be used to produce food-safe plastics from waste plastics that do not have the impaired mechanical properties typically associated with plastics made using physical recycling. Additionally, chemical recycling allows for the removal of organisms or other compounds or contaminants present in the polymer prior to depolymerization. Methods of chemical recycling include contacting the material containing the condensation polymer with a nucleophilic agent (e.g., a strong base) to produce a mixture, and mechanically processing the mixture to depolymerize the condensation polymer into a composition containing component monomers, oligomers, or both. Mechanical depolymerization allows for rapid, efficient, and scalable depolymerization.

[0339] Some embodiments include contacting a polyester-containing compound with a nucleophile to form a first mixture and subjecting the first mixture to mechanical processing, thereby decomposing at least a portion of the polyester-containing compound in the first mixture to produce a second mixture comprising decomposition products of the polyester-containing compound, converting the polyester into decomposition products (component monomers, oligomers, or both). At least a portion of the decomposition products can be separated from the second mixture. The polyester-containing compound may include triglycerides and condensation polymers (e.g., polyesters). Triglycerides are commercially available or extracted from seeds, beans, nuts, kernels, or pulp material of plant matter.

[0340] The conversion of polyamides into decomposition products is also described. These methods involve contacting a polyamide-containing compound with a nucleophile to produce a first mixture, and subjecting the first mixture to mechanical processing to decompose at least a portion of the polyamide-containing compound to produce a second mixture containing decomposition products of the polyamide-containing compound. At least a portion of the decomposition products can be separated from the second mixture.

[0341] Starting Composition

[0342] Triglycerides

[0343] Polyester-containing compounds can be triglycerides. Triglycerides are commercially available or extracted from seeds, beans, nuts, kernels, or pulp of plant material. Triglyceride-containing oils can be extracted from plant material. For example, triglycerides can be extracted by mechanically extruding plant material (e.g., hydraulic extrusion, screw extrusion), using organic solvents (e.g., hexane, heptane, ethyl acetate, ethanol, methanol, diethyl ether, toluene), using supercritical solvents (e.g., CO2, propane), by distillation (steam, water, solvent), by maceration, or by aroma extraction. Triglycerides can be extracted from seeds, including rapeseed, grape seeds, citrus seeds, apple seeds, sunflower seeds, cottonseed, mango seeds, safflower seeds, and pumpkin seeds. As another example, triglycerides can be extracted from legumes such as soybeans, cocoa, castor beans, and coffee beans. Optionally, triglycerides can be extracted from nuts such as peanuts, shea butter, and tree nuts, or from kernels such as cherry kernels, nut kernels, palm kernels, and avocado kernels. In some cases, triglycerides are extracted from fruit pulp materials such as coconut, olive, palm, corn, or wood pulp.

[0344] In some embodiments, the triglyceride comprises the reaction product of glycerol and three fatty acids. In some embodiments, each fatty acid is independently saturated or unsaturated and has a carbon chain length of at least 7 carbon atoms (e.g., 7 to 21 or 16 to 18 carbon atoms). In some embodiments, the triglyceride comprises the reaction product of glycerol with a compound of formula I appearing three times, the reaction product of glycerol with a compound of formula II appearing three times, or the reaction product of glycerol with a compound of formula III appearing three times. In some embodiments, the triglyceride comprises the reaction product of glycerol with three compounds independently selected from formulas I, II, and III.

[0345] In some embodiments, triglycerides include the reaction product of glycerol with a compound of formula I appearing once and a compound of formula II appearing twice, the reaction product of glycerol with a compound of formula II appearing once and a compound of formula I appearing twice, the reaction product of glycerol with a compound of formula I appearing once and a compound of formula III appearing twice, the reaction product of glycerol with a compound of formula III appearing once and a compound of formula I appearing twice, the reaction product of glycerol with a compound of formula III appearing once and a compound of formula II appearing twice, or the reaction product of glycerol with a compound of formula I appearing once, a compound of formula II appearing once and a compound of formula III appearing once.

[0346] condensate

[0347] Condensation polymers that can be subjected to the disclosed methods include polyesters (e.g., natural or synthetic polyesters) and polyamides (e.g., natural or synthetic polyamides).

[0348] Examples of polyester and polyamide

[0349] Exemplary polyesters and polyamides that can be processed by the disclosed methods include keratin, polyethylene terephthalate, poly(2-hydroxybutyrate), poly(caprolactone), poly(lactic acid), polyhydroxyalkanoates, nylon, aromatic polyamides, and polyphthalamides. Other dimers, trimers, and oligomer analogs of compounds containing polyesters and polyamides can also be processed by the disclosed methods.

[0350] Keratin

[0351] In some embodiments, the cutin is derived from the plant peel. The embodiments include separating (or at least partially separating) the cutin-containing portion of the plant material from the non-cutin-containing portion, and obtaining the cutin from the cutin-containing portion. In an example where the cutin-containing portion is the pericarp, the pericarp is separated from the fruit body, and / or the cutin is separated from the pericarp.

[0352] To form a keratin-derived composition (e.g., a keratin-derived plant extract composition), the keratin-containing portion of the plant material can be separated from the keratin-free portion (e.g., at least partially separated). Separation can be achieved individually or in combination of various methods.

[0353] Keratin is derived from plant matter. Plant matter typically includes portions containing keratin and / or having a high keratin density (e.g., pericarp, leaves, buds, etc.) and other portions that do not contain keratin or have a low keratin density (e.g., pulp, seeds, etc.). Keratin-containing portions can be used to produce compositions comprising keratin-derived monomers and / or oligomers, and may also contain other components such as proteins, polysaccharides, phenols, lignin, aromatic acids, terpenes, flavonoids, carotenoids, alkaloids, alcohols, alkanes, and aldehydes. Compared to higher-density keratin-containing portions, low-keratin-density or keratin-free portions may lack decomposition products or otherwise contain a lower ratio of monomer and / or oligomer units to other components.

[0354] Keratin is a polymer of hydroxy fatty acids. Typical monomers constituting keratin polymers include, for example, 16-hydroxyhexadecanoic acid, 9,16-dihydroxyhexadecanoic acid, 10,16-dihydroxyhexadecanoic acid, 18-hydroxyoctadecanoic acid, 18-hydroxy-(9Z)-octadecenoic acid, 9,10-epoxy-18-hydroxyoctadecanoic acid, 9,10,18-trihydroxyoctadecanoic acid, or combinations thereof. The exact products directly produced by mechanochemical decomposition depend, at least in part, on the specific plant source of the keratin and the conditions used for mechanochemical decomposition. For example, keratin from tomatoes tends to have a high proportion of C. 16 Fatty acids (e.g., fatty acids with a carbon chain length of 16), for example Figure 5A , 5C And those from 5E, while the keratin from cranberries tends to have a high proportion of C. 18 Fatty acids, for example Figure 5B , 5D And those on 5F.

[0355] Keratin-derived monomers include palmitic acid-derived monomers such as 16-hydroxyhexadecanoic acid, 7,16-dihydroxyhexadecanoic acid, 8,16-dihydroxyhexadecanoic acid, 9,16-dihydroxyhexadecanoic acid, and 10,16-dihydroxyhexadecanoic acid; palmitoleic acid-derived monomers such as (Z)-16-hydroxyhexadecenoic acid, 9,10-epoxy-16-hydroxyhexadecanoic acid, and 9,10,16-trihydroxyhexadecanoic acid; and stearic acid-derived monomers such as 18-hydroxyoctadecanoic acid, 9,18-dihydroxyoctadecanoic acid, and 10,18-dihydroxydexadecanoic acid. Octadecanic acid; oleic acid-derived monomers such as (Z)-18-hydroxyoctadecanoic acid, 9,10-epoxy-18-hydroxyoctadecanoic acid, 9,10,18-trihydroxyoctadecanoic acid and (Z)-octadecanoic acid; and linoleic acid-derived monomers such as (9Z,12Z)-18-hydroxyoctadecanoic acid, (Z)-9,10-epoxy-18-hydroxyoctadecanoic acid, (Z)-9,10,18-trihydroxyoctadecanoic acid and (6Z,9Z)-octadecanoic acid-6,9-dienoic acid.

[0356] Other compounds

[0357] In some embodiments, the compound used to perform the disclosed methods comprises a single ester group. The compound may be a dimer, trimer, oligomer, or fragment thereof. For example, the compound may have one of the following structures:

[0358] ;

[0359] or

[0360] .

[0361] Nucleophilic reagent treatment

[0362] The disclosed method involves contacting a compound, such as a polyester- or polyamide-containing compound, with a nucleophile. In some cases, the nucleophile includes hydroxides, metal hydrides, and their precursors (e.g., carbonates). In other cases, the nucleophile is selected from hydroxide bases, alkoxide bases, carbonate bases, and hydride bases. Polymers, such as polyester-containing compounds, can be treated with the nucleophile for a certain period of time (e.g., from about 1 minute to about 24 hours).

[0363] Dosage range of nucleophilic reagents

[0364] The nucleophile can be present in a catalytic amount (e.g., less than 1 equivalent (w / w) of nucleophile relative to a polyester- or polyamide-containing compound), a stoichiometric amount (e.g., about 1 equivalent (w / w) of nucleophile relative to a polyester- or polyamide-containing compound), or a superstoichiometric amount (e.g., greater than 1 equivalent (w / w) of nucleophile relative to a polyester- or polyamide-containing compound). In some embodiments, the loading of the nucleophile is 0.0001 to 0.001, 0.001 to 0.01, 0.01 to 1, 0.03 to 10, 1 to 3.0, 3 to 10, 10 to 20, 10 to 30, 10 to 100, or 0.5 to 5 equivalents (w / w). The loading of the nucleophile is generally sufficient to substantially decompose the polyester- or polyamide-containing compound.

[0365] The amount of nucleophile used depends at least in part on the extent to which the polyester or polyamide compound decomposes into its decomposition products. An amount of nucleophile sufficient to partially or completely decompose the compound into its constituent monomers (e.g., triglycerides decompose into their constituent monomers) can be used.

[0366] Hydroxides and processing options

[0367] In some cases, the nucleophile is a hydroxide (e.g., a Group I or II metal hydroxide, such as lithium hydroxide, potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium hydroxide, cesium hydroxide, or calcium hydroxide). In other cases, the nucleophile is a precursor or compound that produces a hydroxide in a suitable reaction medium (e.g., ammonia in water). The nucleophile, temperature, reaction time, and / or rotation frequency can be adjusted so that the condensate or triglyceride is substantially decomposed by the nucleophile (e.g., depolymerized or hydrolyzed) into a variety of condensate or triglyceride-derived decomposition products (e.g., keratin-derived monomers or oligomers, monoacylglycerols, fatty acid salts, terephthalic acid, etc.). The concentration of metal hydroxide, the presence or absence of solvent, the pH of the solution, and / or the thermodynamic sink can promote the preservation of depolymerized condensates or decomposed triglyceride components (i.e., monomeric and / or oligomeric forms such as keratin monomers, monoacylglycerols, fatty acid salts, terephthalic acid, lactams, etc.), thereby reducing or preventing the oligomerization or repolymerization of released components (e.g., monomers and / or oligomers).

[0368] Depolymerization may include saponifying compounds containing polyesters or polyamides. Depolymerization may occur in the presence of a solvent. In some cases, the solvent is water, an alcohol (e.g., methanol or ethanol), or a mixture thereof. In some cases, the amount of solvent used is insufficient to dissolve the components of the mixture in which it is added (e.g., the solvent produces a slurry). In other embodiments, depolymerization occurs in a solvent-free environment.

[0369] In some implementations, decomposition includes the direct halogenation of condensation polymers (e.g., chlorination, bromination, or iodination) (e.g., keratin is converted into halogenated monomers, oligomers, or combinations thereof).

[0370] In some implementations, decomposition includes the direct reduction of condensation polymers (e.g., reduction of esters or carbonyl groups to alcohol-containing monomers, oligomers, or combinations thereof).

[0371] Processing time (nucleophile reagent)

[0372] Mixtures containing the compounds described herein (e.g., polyester-containing compounds) are typically subjected to nucleophilic treatment for durations ranging from 1 minute to 24 hours (e.g., at least 5, 10, 30, or 60 minutes). In some embodiments, the treatment duration is 1 hour to 5 hours, 1 hour to 10 hours, 1 hour to 24 hours, or 1 hour to 48 hours. The treatment duration can be adjusted to produce different concentrations of oligomers and monomers in the resulting composition. For example, a longer treatment time will result in a greater degree of depolymerization, producing a higher concentration of monomers than oligomers in the resulting composition. The treatment duration may be sufficient to substantially decompose the compound into component monomers.

[0373] Mechanochemical methods

[0374] Mechanochemical methods can be used to at least partially break down keratin or keratin-containing pericarps to produce a mixture comprising a variety of keratin-derived monomers, oligomers, or combinations thereof. Mechanochemical methods result in the initial separation of most or substantially all of the resulting monomers and / or oligomers (e.g., at least 95%) of the mixture as charged substances (e.g., base addition salts such as carboxylates). Further separation of the resulting monomers and / or oligomers from the mixture may require additional processes (e.g., acidification).

[0375] In some implementations, the charged substance is a salt of a compound of formula I:

[0376] (Formula I)

[0377] in:

[0378] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 Each is independently -H, -OR 13 -NR 13 R 14 -SR 13Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 Or halogen substitution;

[0379] R 13 and R 14 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0380] R 12 It is -OH, -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl, or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl, or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 halogen, -COOH or -COOR 11 replace;

[0381] m, n, and o are each an independent integer in the range 0 to 30; and

[0382] The sum of m, n, and o is between 0 and 30.

[0383] In some implementations, the charged substance is a compound of formula IV:

[0384] (Formula IV)

[0385] in:

[0386] X p+ It is a cationic counterion with a charge state p, and p is 1, 2 or 3;

[0387] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 Each is independently -H, -OR 13 -NR 13 R 14 -SR 13Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 Or halogen substitution;

[0388] R 13 and R 14 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0389] R 12 It is -OH, -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl, or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl, or heteroaryl is optionally prefixed with -OR 13 -NR 13 R 14 -SR 13 halogen, -COOH or -COOR 11 replace;

[0390] m, n, and o are each an independent integer in the range 0 to 30; and

[0391] The sum of m, n, and o is between 0 and 30.

[0392] In some implementations, X is a lithium, sodium, potassium, calcium, barium, magnesium, or cesium ion.

[0393] In some implementations, the charged substance is a salt of compound of formula II:

[0394] (Formula II)

[0395] in:

[0396] R 1 R 2 R 4 and R 5 Each is independently -H, -OR 11 -NR 11 R 12 -SR 11 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 11 -NR 11R 12 -SR 11 Or halogen substitution; R 11 and R 12 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0397] symbol Indicates either a single key or a cis or trans double key;

[0398] When R 3 and R 3 Between When it is a single bond, R 3 It is -OH and R 3 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 alkynyl, -C3-C7 cycloalkyl, and aryl; and when R 3 and R 3 Between When representing a double bond, R 3 and R 3 It does not exist;

[0399] When R 6 and R 6 Between When it is a single bond, R 6 It is -OH and R 6 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl and -C6-C 10 Aryl, and when R 6 and R 6 Between When representing a double bond, R 6 and R 6 It does not exist;

[0400] n is an integer in the range of 0 to 11;

[0401] m is an integer in the range of 0 to 25; and

[0402] The sum of m and n is between 0 and 25.

[0403] In some implementations, the charged substance is a compound of formula V:

[0404] (Formula V)

[0405] in:

[0406] X p+ It is a cationic counterion with a charge state p, and p is 1, 2 or 3;

[0407] R 1 R 2 R 4 and R 5 Each is independently -H, -OR 11 -NR 11 R 12 -SR 11 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or 5- to 10-membered heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl is optionally prefixed with -OR 11 -NR 11 R 12 -SR 11 Or halogen substitution;

[0408] R 11 and R 12 Each can be independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0409] symbol Indicates either a single key or a cis or trans double key;

[0410] When R 3 and R 3 Between When it is a single bond, R 3 It is -OH and R 3 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 alkynyl, -C3-C7 cycloalkyl, and aryl; and when R 3 and R 3 Between When representing a double bond, R 3 and R 3 It does not exist;

[0411] When R 6 and R 6 Between When it is a single bond, R 6 It is -OH and R 6 Selected from -H, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl and -C6-C10 Aryl, and when R 6 and R 6 Between When representing a double bond, R 6 and R 6 It does not exist;

[0412] n is an integer in the range of 0 to 11;

[0413] m is an integer in the range of 0 to 25; and

[0414] The sum of m and n is between 0 and 25.

[0415] In some implementations, X is a lithium, sodium, potassium, calcium, barium, magnesium, or cesium ion.

[0416] In some implementations, the charged substance is a salt of a compound of formula III:

[0417] (Formula III)

[0418] in:

[0419] R 1 R 2 R 5 R 6 R 9 R 10 R 11 R 12 and R 13 Each occurrence is independently -H or -OR. 14 -NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution;

[0420] R 3 R 4 R 7 and R 8 Each occurrence is independently -H or -OR. 14 -NR 14 R 15、 -SR 14Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution;

[0421] R 14 and R 15 Each time it appears, it is independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0422] symbol Indicates a single bond or a cis or trans double bond;

[0423] symbol Indicates a cis or trans double bond;

[0424] n is 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0425] m is 0, 1, 2, or 3; q is 0, 1, 2, 3, 4, or 5; and

[0426] r can be 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0427] In some implementation schemes, R 3 and R 4 The carbon atoms attached to them combine to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings. In some embodiments, R 7 and R 8 They combine with the carbon atoms they are attached to to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings.

[0428] In some implementations, the charged substance is a compound of formula VI:

[0429] (Formula VI)

[0430] in:

[0431] X p+ It is a cationic counterion with a charge state p, and p is 1, 2 or 3;

[0432] R 1 R 2 R 5 R 6 R 9 R 10 R 11 R12 and R 13 Each occurrence is independently -H or -OR. 14 -NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, alkenyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution;

[0433] R 3 R 4 R 7 and R 8 Each occurrence is independently -H or -OR. 14 -NR 14 R 15 -SR 14 Halogen, -C1-C6 alkyl, -C2-C6 alkenyl, -C2-C6 ynyl, -C3-C7 cycloalkyl, aryl or heteroaryl, wherein each alkyl, ynyl, cycloalkyl, aryl or heteroaryl group is optionally surrounded by one or more -OR 14 -NR 14 R 15 -SR 14 Or halogen substitution;

[0434] R 14 and R 15 Each time it appears, it is independently -H, -C1-C6 alkyl, -C2-C6 alkenyl, or -C2-C6 ynyl;

[0435] symbol Indicates a single bond or a cis or trans double bond;

[0436] symbol Indicates a cis or trans double bond;

[0437] n is 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0438] m is 0, 1, 2, or 3;

[0439] q is 0, 1, 2, 3, 4, or 5; and

[0440] r can be 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0441] In some implementation schemes, R 3 and R 4The carbon atoms attached to them combine to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings. In some embodiments, R 7 and R 8 They combine with the carbon atoms they are attached to to form C3-C6 cycloalkyl, C4-C6 cycloalkenyl, or 3- to 6-membered heterocyclic rings.

[0442] In some implementations, X is a lithium, sodium, potassium, calcium, barium, magnesium, or cesium ion.

[0443] The properties of charged substances depend on the starting materials used in the methods described herein (e.g., polyethylene terephthalate, poly(2-hydroxybutyrate), poly(caprolactone), poly(lactic acid), polyhydroxyalkanoates, nylon, aromatic polyamides, polyphthalamides). For example, when the methods disclosed in this invention are used for the depolymerization of polyethylene terephthalate, the resulting charged substances will correspond to, for example, salts of bis(2-hydroxyethyl) terephthalate, mono(2-hydroxyethyl) terephthalate, terephthalic acid, ethylene glycol, and their oligomers.

[0444] Mechanical processes (including mechanical phenomena such as friction, grinding, sound waves, and potential energy) can be used to impart chemical changes to compounds (e.g., compounds containing polyesters or polyamides as described herein) at the molecular level in mixtures. Machining can include grinding techniques, such as ball milling techniques, including planetary ball milling and grinding ball milling, as well as other grinding and agitation processes.

[0445] Grinding process

[0446] Grinding processes can include milling techniques. Examples of suitable milling techniques include ball milling, jet milling, roller milling, rotor milling, vibratory milling, hammer milling, impact milling, and media agitation milling (e.g., grinding). In some embodiments, the ball milling technique is a planetary ball mill. In one example, a planetary ball mill rotates two ceramic-lined chambers containing grinding media and reactants at a high rotational frequency. As the chambers rotate, the media impact the reactants and the sides of the chambers. The energy from these impacts, as well as the heat generated by friction, creates a high-energy environment capable of inducing chemical changes.

[0447] In some embodiments, the first mixture is converted into the second mixture, for example, by decomposition (e.g., depolymerization or hydrolysis), at an increased rate relative to the unstirred sample. In some embodiments, the conversion occurs at a rate at least two or three times that of the un-milled sample. For example, milling (e.g., grinding) can be carried out at a rotational frequency sufficient to substantially depolymerize the condensate. In some embodiments, the conversion rate with mechanical processing is greater than the conversion rate without mechanical processing. Milling can be carried out at a rotational frequency sufficient to hydrolyze the compounds described herein (e.g., the polyester-containing compounds described herein). Decomposition can occur at a rate faster than solvent-based chemical depolymerization methods (e.g., at least 2, 3, 5, 7, or 10 times faster than decomposition using solvent-based chemical depolymerization methods).

[0448] Parameters of the grinding process

[0449] Mixtures containing the compounds described herein (e.g., compounds containing polyesters or polyamides) can be subjected to a milling process for a sufficient time to substantially break down the compounds into decomposition products. In some embodiments, the time is less than 24 hours and greater than 1 minute. In some embodiments, the time is greater than 5, 10, 30, or 60 minutes. In some embodiments, the time is 1 to 5, 1 to 10, 1 to 24, or 1 to 48 hours. In some embodiments, the time is 0.5 to 24, 5 to 20, 8 to 18, 10 to 15, or 11 to 13 hours.

[0450] The grinding process described herein can be performed at rotational frequencies of 1-1000, 250-1000, 500-1000, 500-800, or 600-750 rpm. Grinding can also be performed at rotational frequencies of at least 1, 250, 500, 550, 600, or 650 rpm.

[0451] Stirring process

[0452] Mechanical methods may include stirring. Stirring processes include sonic stirring (including ultrasonic stirring) and grinding.

[0453] In some embodiments, the first mixture is converted into a second mixture by decomposition (e.g., depolymerization or hydrolysis) at a rate increasing relative to the unstirred sample. In some cases, the conversion occurs at a rate at least two or three times that of the unstirred sample. For example, stirring can be carried out at a rotational frequency sufficient to substantially depolymerize the condensate. The conversion rate can be greater in the presence of mechanical processing than in the absence of mechanical processing. In some embodiments, stirring can be carried out at a rotational frequency sufficient to hydrolyze compounds containing polyesters or polyamides. In some embodiments, decomposition occurs at a faster rate than solvent-based chemical depolymerization methods.

[0454] Parameters of the stirring process

[0455] A mixture containing a polyester-containing compound may be subjected to a stirring process for a sufficient time to allow the compound to substantially decompose into its constituent monomers. In some embodiments, the time is greater than 1 minute and less than 24 hours. In some embodiments, the time is greater than 5, 10, 30, or 60 minutes. In some embodiments, the time is 1 to 5, 1 to 10, 1 to 24, or 1 to 48 hours. In some embodiments, the time is 0.5 to 24, 5 to 20, 8 to 18, 10 to 15, or 11 to 13 hours.

[0456] In some implementations, the mixing process can be carried out at a rotational frequency of 1-1000, 250-1000, 500-1000, 500-800, or 600-750 rpm. Grinding and milling can also be carried out at a rotational frequency of at least 1, 250, 500, 550, 600, or 650 rpm.

[0457] Performance after machining

[0458] In some embodiments, the conversion (by mass) of the condensation polymer (e.g., polyamides such as nylon, polyesters such as keratin, or polyethylene terephthalate) or triglycerides to their respective depolymerization products (both as direct products and as byproducts of decomposition) is greater in the presence of mechanical processing than in the absence of mechanical processing. In some embodiments, the method further includes the hydrolysis of the condensation polymer. In some embodiments, the conversion can be at least 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%. Furthermore, at least 50%, 60%, 70%, 80%, 90%, or 95% of the resulting monomers, oligomers, esters, and / or salt decomposition products can be direct decomposition products (e.g., monomers, oligomers formed therefrom, or, in some embodiments, terephthalic acid and / or its oligomers). Significant decomposition (e.g., depolymerization) of compounds (e.g., polyester-containing compounds) can be achieved without the addition of heat energy. Mechanical processing can also result in particle size reduction. Mechanical forces applied to the mixture (e.g., by grinding, stirring, or milling, such as planetary milling or pulverizing) can produce particles with an average size less than about 1000, 500, 250, 100, 75, 50, 40, 30, 20, 10, 5, 2, or 1 micrometer. The average particle size can be from 0.1 micrometer to 1 micrometer, 1 micrometer to 50 micrometers, 1 micrometer to 100 micrometers, 1 micrometer to 200 micrometers, 1 micrometer to 250 micrometers, 1 micrometer to 300 micrometers, 1 micrometer to 350 micrometers, 1 micrometer to 400 micrometers, 1 micrometer to 500 micrometers, 1 micrometer to 600 micrometers, 1 micrometer to 700 micrometers, 1 micrometer to 800 micrometers, 1 micrometer to 900 micrometers, or 1 micrometer to 1000 micrometers. The resulting particles can be small enough to dissolve efficiently in water or other solvents at at least twice the rate of larger particles, thus allowing for rapid mixing of the solution formed from the decomposition products.

[0459] Monomer separation (including acidification)

[0460] Decomposition products can be separated from mechanically processed mixtures. Separation methods include acidification, distillation, filtration, melt filtration, precipitation, and centrifugation.

[0461] Examples of acids

[0462] Acidification may include adding an acid to a mixture. The acid may be inorganic or organic. In some embodiments, the acid is a strong acid, including inorganic acids such as hydrochloric acid, sulfuric acid, or phosphoric acid. Examples of suitable acids include 1-hydroxy-2-naphthylcarboxylic acid, 2,2-dichloroacetic acid, 2-hydroxyethanesulfonic acid, 2-oxoglutaric acid, 4-acetaminobenzoic acid, 4-aminosalicylic acid, acetic acid, adipic acid, ascorbic acid (L), aspartic acid (L), benzenesulfonic acid, benzoic acid, camphor-10-sulfonic acid (+), caprylic acid (decanoic acid), caprylic acid (caprylic acid), cinnamic acid, citric acid, cyclohexanesulfonic acid, dodecyl sulfate, ethane-1,2-disulfonic acid, formic acid, fumaric acid, galactopyric acid, gentian acid, glucoheptanoic acid (D), gluconic acid (D). ), glucuronic acid (D), glutamic acid, glutamate, glycerophosphate, glycolic acid, hippuric acid, hydrobromic acid, hydrochloric acid, isobutyric acid, lactic acid (DL), lactobionic acid, maleic acid, malic acid (-L), malonic acid, mandelic acid (DL), methanesulfonic acid, naphthalene-1,5-disulfonic acid, naphthalene-2-sulfonic acid, nicotinic acid, nitric acid, oxalic acid, palmitic acid, dihydroxynaphthalic acid, phosphoric acid, propionic acid, pyroglutamic acid (-L), salicylic acid, sebacic acid, sorbic acid, succinic acid, aminosulfonic acid, sulfuric acid, tartaric acid (+L), thioacetic acid, trifluoroacetic acid, thiocyanate, and toluenesulfonic acid (p).

[0463] pH range provided by acidification

[0464] Acidification can produce solutions with a pH of 5 or lower, 3 or lower, or 1 or lower. The pH of the solution can be, for example, 0 to 4.5, 2 to 4, or 2.5 to 3.5. In some cases, the solution has a pH suitable for completely neutralizing any carboxylate.

[0465] Processing time (acidification)

[0466] Mixtures containing the compounds described herein (e.g., the polyester- or polyamide-containing compounds described herein) may be acidified for a period of time, for example, greater than 1 minute and less than 24 hours (e.g., about 5 minutes to 24 hours). In some embodiments, the time is greater than 5, 10, 30, or 60 minutes. In some embodiments, the time is 1 to 5, 1 to 10, 1 to 24, or 1 to 48 hours. In some embodiments, the time is 0.5 to 24, 5 to 20, 8 to 18, 10 to 15, or 11 to 13 hours.

[0467] Additional steps in this method

[0468] Pretreatment options for starting compositions

[0469] The compounds described herein (e.g., polyester- or polyamide-containing compounds described herein) may first undergo pretreatment conditions before being treated with nucleophiles and / or mechanical energy. As described above, in order to form a keratin-derived composition suitable for coating applications, the keratin-containing portion of the plant material is first separated (or at least partially separated) from the non-keratin-containing portion. This can be achieved by a variety of methods, alone or in combination with each other. For example, the plant material may be subjected to thermal and / or mechanical and / or enzymatic and / or chemical treatments to at least partially separate the keratin-containing portion from the non-keratin-containing portion. Alternatively, the plant material may be subjected to elevated temperatures and / or pressures (e.g., as in pressure cooking) in an aqueous medium to partially separate the keratin-containing portion from the non-keratin-containing portion. Alternatively, the plant material may be subjected to lower temperatures (e.g., as in freezing) to partially separate the keratin-containing portion from the non-keratin-containing portion. The plant material may also be subjected to ultrasonic treatment in an aqueous medium to partially separate the keratin-containing portion from the non-keratin-containing portion. Optionally, the cutin-containing portion can be heated in a mixture of ammonium oxalate and oxalic acid to aid in the separation of the cutin-containing portion from the non-cutin-containing portion (e.g., the remainder of the cutin layer and unwanted plant material). Optionally, this separation can be enzymatically achieved (or aided) using enzymes capable of hydrolyzing ester bonds and / or alternatively, enzymes capable of breaking down polysaccharides containing the non-cutin-containing portion of the plant. The cutin-containing portion can optionally be refluxed in at least one organic solvent (e.g., chloroform and / or methanol) to remove residual wax and / or any remaining soluble components from the cutin. Alternatively, the removal of residual wax and remaining soluble components can be achieved using liquid or supercritical CO2.

[0470] Additional steps after machining

[0471] Decomposition products from machining can be chemically modified to provide derivatives with properties tailored to specific applications. For example, the oxygen and water barrier properties of the subsequently formed coating can be controlled by chemically modifying the decomposition products, and this modification may require the decomposition products to be protonated or neutralized first. Furthermore, the chemical modification of the decomposition products can be tailored to alter the solubility of the extract composition, thereby allowing for expanded options for coating deposition. In some cases, a mixture containing decomposition products of free fatty acids and / or free fatty esters is dissolved in another solvent to form a solution, thereby producing a composition suitable for coating applications (e.g., agricultural coating applications). Optionally, the free fatty acid and / or free fatty ester decomposition products of the mixture are activated or modified (e.g., dehydroxylated, dehydrated, hydrogenated, or glycerolized) prior to forming the composition. For example, free fatty acids and / or free fatty acid ester decomposition products can be modified to form a mixture of 1-monoacylglycerol esters and / or 2-monoacylglycerol esters, and the modified decomposition product mixture (e.g., 1-monoacylglycerol esters and / or 2-monoacylglycerol esters) is dissolved in a solvent to form a solution, thereby producing a composition. In some embodiments, isolated keratin-derived monomers are dehydroxylated to form free fatty acids or esters without any hydroxylation. One method of achieving this involves activating the hydroxyl groups with different reagents or by a hydrothermal method, followed by elimination, and then hydrogenation of the resulting unsaturation. These steps can be performed independently or simultaneously during the process. These hydroxyl-free fatty acids or esters can then be modified, for example, to form a mixture of 1-monoacylglycerol esters and / or 2-monoacylglycerol esters, and the modified decomposition product mixture (e.g., 1-monoacylglycerol esters and / or 2-monoacylglycerol esters) includes a mixture that can be dissolved in a solvent to form a solution, thereby producing a composition.

[0472] At least a portion of the decomposition products separated from the mixture can be esterified with glycerol molecules. In some embodiments, the decomposition products are dehydrated. For example, direct depolymerization products (e.g., in glycerol molecules) can be formed after a mechanochemical depolymerization process by esterification (e.g., Fischer esterification or enzymatic esterification). Figure 5A and 5B Esters (e.g., glycerides) containing 100 or 101 of the form. In some cases, esterification produces dimers, trimers, oligomers, or fragments thereof. In one example, the esterified compound is a dimer having the following structure:

[0473] .

[0474] Keratin depolymerization products can be purified, for example, by selective filtration, distillation, and / or crystallization, to form an extract composition suitable for coating applications, which is a direct decomposition product, such as... Figures 5A-5HThe composition is essentially pure of the monomers (and / or oligomers formed therefrom) or the esterified or glycerolized compounds formed therefrom.

[0475] In some implementations, a certain percentage (e.g., greater than 20%, 40%, 60%, 70%, 80%, or 90%) of the direct depolymerization products (e.g. Figures 5A-5H The monomers 100, 101, 102, 103, 104, 105, 106 and / or 107 and / or compounds of formula I) decompose into other monomer / oligomer byproducts (e.g., respectively). Figure 6A-6I The unsaturated byproducts 200, 201, 202, 203, 204, 205, 206, 207, and / or 208) are typically not generated by the depolymerization of keratin or keratin-containing components. Specifically, Figure 6A-6I The unsaturated byproducts 200, 201, 202, 203, 204, 205, 206, 207 and / or 208, as well as the compounds of formulas II and III, can be isolated and further processed, for example by hydrogenation with a catalyst (e.g., Ni, Pd or Pt) to form other saturated molecules, such as... Figures 7A-7C Those shown, among which Figure 7A It is 9,10,16-trihydroxyhexadecanoic acid (400). Figure 7B It is 16-hydroxyhexadecanoic acid (401), and Figure 7C It is palmitic acid (402). In some cases, palmitic acid is formed from non-palm sources. This is important, at least because the production of palm oil from oil palm has significant environmental impacts, including deforestation and habitat loss, as well as sociological impacts, as indigenous peoples are often relocated to make way for large plantations in developing countries.

[0476] The final product produced by the method

[0477] The method disclosed in this invention can produce carboxylic acids, carboxylates, carboxylic esters, alcohols, and / or amines as component monomers. The characteristics of the monomers will depend on the raw materials containing polyesters or polyamides, such as keratin, polyethylene terephthalate, poly(2-hydroxybutyrate), poly(caprolactone), poly(lactic acid), and polyhydroxyalkanoates, as well as the characteristics of polyamides such as nylon, aromatic polyamides, and polyphthalamides. The final products correspond to suitable monomers and oligomers characterizing the polyesters and polyamides. For example, for the depolymerization of polyethylene terephthalate, the resulting compounds may include, for example, bis(2-hydroxyethyl) terephthalate, mono(2-hydroxyethyl) terephthalate, terephthalic acid, ethylene glycol, and their oligomers. As another example, for the depolymerization of keratin, the resulting monomers may include hydroxy fatty acids, hydroxy fatty acid salts, and hydroxy fatty acid esters. For example, such as... Figure 8As shown, the base-catalyzed mechanochemical depolymerization of keratin in a ball mill can produce 10,16-dihydroxyhexadecanoic acid as the major product. Additionally, oligomers, for example,

[0478] or

[0479] It can be separated from the depolymerization of keratin.

[0480] In some embodiments, the method disclosed in this invention can be used to decompose triglycerides to produce, for example, glycerides of fatty acids. The glycerides may comprise the reaction product of glycerol and two fatty acids (i.e., 1,2-diglyceride and 1,3-diglyceride). In some embodiments, the glycerides comprise the reaction product of glycerol and one fatty acid (i.e., 1-monoglyceride and 2-monoglyceride). The fatty acids may be saturated or unsaturated. In some embodiments, the fatty acids have a carbon chain length of 7 or more carbon atoms (e.g., 7 to 22 or 16 to 18 carbon atoms). In some embodiments, the fatty acids are compounds of Formula I, Formula II, and / or Formula III.

[0481] Component monomers of Formula I, Formula II and Formula III

[0482] The methods described herein can produce component monomers of end products such as compounds (e.g., polyester-containing compounds). In some embodiments, the component monomers comprise at least one compound of formula I, at least one compound of formula II, at least one compound of formula III, or any combination thereof.

[0483] In some embodiments, the component monomers of Formula I comprise one or more of the following:

[0484] ;

[0485] ;

[0486] ;

[0487] ;

[0488] ;

[0489] ;

[0490] ;

[0491] ;

[0492] ;

[0493] ;

[0494] ;

[0495] ;

[0496] ; ; ; ; ; ; ;or .

[0497] In some embodiments, the monomers of Formula III include one or more of the following:

[0498] ; ; ; ; ; ; ;and

[0499] .

[0500] Conversion rate

[0501] The constituent monomers of Formula I can be prepared from compounds processed by the methods described herein (e.g., polyester-containing compounds described herein) with a conversion of greater than 50%. In some embodiments, the conversion is about 55%, 60%, 65%, 70%, 75%, or 80%. In some embodiments, the conversion is about 80% to about 100%.

[0502] The constituent monomers of Formula II can be prepared from compounds (e.g., polyester-containing compounds) processed by the methods described herein with a conversion of greater than 50%. In some embodiments, the conversion is about 55%, 60%, 65%, 70%, 75%, or 80%. In some embodiments, the conversion is about 80% to 100%.

[0503] The constituent monomers of Formula III can be prepared from compounds (e.g., polyester-containing compounds) processed by the methods described herein with a conversion of greater than 50%. In some embodiments, the conversion is about 55%, 60%, 65%, 70%, 75%, or 80%. In some embodiments, the conversion is about 80% to 100%.

[0504] Saturated products (e.g., Figures 5A-5H Compounds 100, 101, 102, 103, 104, 105, 106, and 107, and / or compounds of formula I) crosslink within the keratin layer, thereby directly separating into monomers, oligomers, or both via depolymerization, while unsaturated products (e.g., Figures 6A-6H Products 200, 201, 202, 203, 204, 205, 206, 207 and 208, and / or products of formulas II and III) are byproducts formed from the decomposition of the direct products.

[0505] Unsaturated products (e.g.) Figures 6A-6H Products of Formula II (200, 201, 202, 203, 204, 205, 206, 207, and 208, and / or products of Formula III) are indirect products formed by further subjecting keratin-derived monomers, oligomers, or combinations thereof to acidic or hydrothermal conditions. In other embodiments, unsaturated products (e.g., Figures 6A-6H Products 200, 201, 202, 203, 204, 205, 206, 207, and 208 (products of Formula II and / or Formula III) are present in the keratin layer and thus become components of the extract composition when the composition is formed by mechanochemical depolymerization and / or separation methods. When keratin depolymerization is performed using conventional depolymerization methods (e.g., under alkaline conditions), the formation of these unsaturated products can be suppressed or inhibited. Therefore, the method according to the disclosure of this invention can be used to obtain unsaturated products more directly compared to other solvent-based methods.

[0506] The direct products of keratin depolymerization (e.g., Figures 5A-5F Compounds of formula 100, 101, 102, 103, 104 and / or 105 and / or formula I) rather than indirect unsaturated byproducts (e.g., Figure 6A-6I Products of Formula II and / or Formula III (e.g., 200, 201, 202, 203, 204, 205, 206, 207, and 208) may be present in the second mixture resulting from the decomposition (e.g., elimination) of the direct product. For example, when monomeric and / or oligomer products are separated from this second mixture and subsequently used to form a protective coating, when the second mixture contains a majority of saturated depolymerization products (e.g., 200, 201, 202, 203, 204, 205, 206, 207, and 208) Figures 5A-5F(100, 101, 102, 103, 104 and / or 105) simultaneously have the lowest possible concentration of unsaturated indirect byproducts (e.g. Figure 6A-6I When using products of formulas 200, 201, 202, 203, 204, 205, 206, 207, and 208 and / or products of formula II), the coating can have desired qualities (e.g., higher crosslinking density, lower permeability to water and / or oxygen). In some embodiments, indirect unsaturated byproducts (e.g., Figures 6A-6H Products of Formula II and / or Formula III (200, 201, 202, 203, 204, 205, 206, 207, and 208) are present in the resulting mixture in amounts of less than 30%, 25%, 20%, 15%, 10%, or 5%. In some embodiments, unsaturated products are converted into saturated products.

[0507] Protective coating

[0508] The resulting compounds (e.g., polyester-containing compounds described herein, such as monomeric components of polyester-containing compounds extracted from plants) can be used to produce compositions (e.g., plant extract compositions) for applying protective coatings, such as those used in food packaging. These can then be separately derived from... Figures 5A-5F The composition for forming a protective coating is formed from molecules 100, 101, 102, 103, 104, and 105, and any one of 400, 401, and 402 in 7A-7C, as well as any other direct decomposition products (e.g., compounds of formula I). ​​The coating may be formed primarily of one of these types of molecules or a combination of these molecules. In other embodiments, the compounds produced by the methods described herein may be subsequently esterified (e.g., glycerolized to form 1-monoacylglycerol esters and / or 2-monoacylglycerol esters). The composition to be used for the coating may be formed from ester or glycerolized molecules, and the coating may be formed from the ester or glycerolized molecules in the composition. The ester or glycerolized molecules may be further combined with one or more fatty acid salts to form a composition used as a protective coating. One or more fatty acid salts may be obtained as depolymerization / decomposition products of polyester-containing compounds, or by saponification of esters and / or fatty acids produced by the methods disclosed in this invention. Figure 7A Or molecule 400 or molecule 401 of 7B, or by Figures 5A-5F Molecules 100, 101, 102, 103, 104, and 105, and Figures 5A-5C Combinations of 400, 401, and 402, or compositions formed from esters or glycerylated molecules thereof, can form coatings that allow for further control over the properties of both the extract composition and the coating. For example, Figures 7A-7CThe solubility of molecules 400, 401, and 402 (and the esters, glycerides, or salts formed therefrom) in various solvents differs from that in other molecules. Figures 5A-5F The solubility of molecules 100, 101, 102, 103, 104, and 105 (and the esters, glycerylated molecules, or salts formed therefrom). Therefore, it can be used with direct products and / or byproducts containing only large amounts of keratin depolymerization (e.g., Figures 5A-5F Compared to compositions of molecules 100, 101, 102, 103, 104, and 105, or esters, glycerylated molecules, or salts formed therefrom, a wider range of solvents are available for use with [the following]. Figures 7A-7C Molecules 400, 401, and 402 (or esters, glycerylated molecules, or salts formed therefrom), or derived from Figures 5A-5F Molecules 100, 101, 102, 103, 104, and 105, and Figures 7A-7C Compositions are formed by combinations of 400, 401, and 402 (or esters, glycerylated molecules, or salts formed therefrom). Alternatively, they can be used alone or in combination. Figure 7A and 7B Molecules 400, 401, and / or 402 (and / or their esters, glycerylated molecules, or salts), or with Figures 5A-5F Combinations of molecules 100, 101, 102, 103, 104, and / or 105, and / or combinations thereof, can further tailor the properties of the coating formed from the composition for a specific application. For example, the crosslinking density of the resulting protective film can be determined based on the composition. Figures 5A-5F Molecules 100, 101, 102, 103, 104, and 105, and Figures 7A-7C The composition varies by mass percentage of each of 400, 401, or 402 (and / or esters, glycerolized molecules, or salts thereof), allowing for the customization of membrane properties such as density and permeability for the specific application in which the membrane is used. Furthermore, these molecules can be chemically modified to tailor their properties, such as solubility, stability, and film-forming properties.

[0509] Molecules / compounds obtained directly from decomposition (e.g., Figures 5A-5F Compounds 100, 101, 102, 103, 104, or 105) or molecules / compounds indirectly obtained through subsequent processing steps (e.g., Figures 7A-7CCompounds 400, 401, or 402 are glycerolized to form 1-monoacylglycerol esters and / or 2-monoacylglycerol ester monomers, oligomers formed therefrom, or combinations thereof. In this case, the composition from which a protective coating subsequently forms (e.g., a plant extract composition) comprises 1-monoacylglycerol esters and / or 2-monoacylglycerol esters optionally dissolved in a solvent. The difference between 1-monoacylglycerol esters and 2-monoacylglycerol esters is the linking point of the glycerol ester groups. Protective coatings formed on substrates such as agricultural products (e.g., fruits, vegetables, eggs, etc.) from formulations comprising one or more 1-monoacylglycerol esters and optionally one or more 2-monoacylglycerol esters (or optionally different additives, such as fatty acids, fatty acid salts, or fatty acid esters, instead of 2-monoacylglycerol esters) can exhibit excellent performance in preventing moisture loss and oxidation of agricultural products without altering the physical appearance of the substrate.

[0510] Compositions obtained by the methods described herein can form protective coatings. The following are exemplary embodiments of preparing a protective coating from a composition comprising a compound prepared by the methods described herein (e.g., a component monomer of a polyester-containing compound, such as a polyester-containing compound derived from plant matter, or a component monomer of a polyester-containing compound such as keratin or triglycerides). First, a solid mixture of the component monomer, oligomer, or both is dissolved in a solvent (e.g., water, ethanol, or a combination thereof) to form a composition. The concentration of the solid mixture in the solvent can be, for example, from 0.1 to 100 mg / mL. Next, the solution comprising the component monomer, oligomer, or both is applied to the surface of a substrate to be coated, for example by spraying the substrate, by immersing the substrate in the solution, or by transferring it from a brush bed. After the solution is applied to the substrate, the substrate is allowed to dry or actively dried until all solvent evaporates, thereby allowing a coating consisting of monomer and / or oligomer units to form on the substrate surface.

[0511] Coatings formed from monomers, oligomers, or both produced by the methods described herein can prevent moisture loss and protect agricultural products from threats such as bacteria, fungi, and viruses. Coatings can also protect, for example, plants and food from physical damage (e.g., bruising), water loss, oxidation, and light damage. Therefore, compositions, solutions, and coatings can be used to assist in the extended storage of agricultural products without spoilage. Compositions and coatings formed from monomers and oligomers can also be edible (i.e., the coating can be non-toxic). Methods for forming the coating can be completely organic (e.g., compliant with 7 CFR 205, EEC 834 / 2007, and / or other applicable regulations). The coating can be tasteless, colorless, and / or odorless. The coating can be made from the same chemical raw materials naturally present in the cuticle layer of plants (e.g., hydroxy and / or dihydroxypalmitic acid, and / or hydroxyoleic acid and stearic acid) or from the same chemical raw materials extracted from the seeds, beans, nuts, kernels, or pulp of plant material (e.g., triglycerides, diglycerides, and monoglycerides), and therefore can be organic and all-natural.

[0512] A composition is formed from keratin-derived monomers and / or oligomers and / or esters extracted from the keratin of a first plant species (e.g., using a previously described mechanochemical decomposition method), and then the composition is placed on plant material of the same plant species, such that the extracted monomers and / or oligomers and / or esters form a protective coating on the plant material of the first plant species. This coating can, for example, enhance the keratin layer naturally present on the plant material. In other embodiments, a composition is formed from keratin-derived monomers and / or oligomers and / or esters extracted from the keratin of a first plant species (e.g., using a mechanochemical decomposition method), and then the composition is placed on plant material of a second plant species different from (although in some cases may be the same as) the first plant species, such that the extracted monomers and / or oligomers and / or esters form a protective coating on the plant material of the second plant species. For example, a composition can be formed from monomers and / or oligomers and / or esters extracted from keratin obtained from tomato or cranberry skins, and then applied to strawberries, bananas, finger oranges, lemons, or other plant species from which the keratin is obtained to form a protective coating. In other embodiments, a composition is formed from monomers and / or oligomers and / or esters derived from triglycerides extracted from seeds, beans, nuts, grains, or pulp material of a first plant species (e.g., using the mechanochemical decomposition method described herein), and then the composition is placed on plant material of the same or different types of a second plant species, such that the extracted monomers and / or oligomers and / or esters form a protective coating on the plant material. The protective coating formed from the monomers and / or oligomers and / or esters in this composition can provide a form of protection against biotic and abiotic stressors that the natural keratin layer of the second plant species cannot inherently provide. For example, a protective coating deposited on a substrate can provide better protection against moisture loss and oxidation than the natural keratin layer inherently provides. In some embodiments, the composition can be formulated to inhibit fungal growth or provide protection against fungal growth, against which the natural cuticle layer provides little or no protection. Prior to applying the composition to the plant material to form a coating, the cuticle-derived monomers and / or oligomers can be glycerolized to form monoacylglycerol esters. This can, for example, increase the reactivity of the monomers and / or oligomers and allow them to crosslink after application to the plant material.

[0513] The saturated products of the decomposition reaction, for example, separately Figure 5A and Figure 5B Free fatty acid compounds 100 and 101 in the solution can react with unsaturated products (or byproducts) of the decomposition reaction (e.g., Figure 6A-6IThe separation or at least partial separation of unsaturated fatty acid compounds in the reaction product can be used for purification. Separation or partial separation of different types of reaction products can be used for purification, such as saturated products (e.g., compounds in which hydroxyl groups have not been eliminated). In other words, extraction of crude products from mechanochemical decomposition reactions can be used to purify or enrich a given percentage of the product, depending on the solvent used.

[0514] Fiber-based materials

[0515] Compounds produced by the methods disclosed in this invention (e.g., polyester-containing compounds described herein, such as monomers of polyester-containing compounds extracted from plants) can be used to modify the properties of fibrous materials, such as textiles, paper products, packaging materials, polymer materials, etc. The compounds produced by the methods disclosed in this invention are associated with one or more fibers in the fibrous material. The association of one or more fibers of the fibrous material with one or more compounds allows for the modification of the properties of the resulting fibrous material, such as hydrophobicity, hydrophilicity, lipophobicity, lipophilicity, complete hydrophobicity, and air impermeability. The fibers can be, for example, cellulose, acrylic, Kevlar, modified acrylic, Nomex, nylon, polyester, polyethylene, polypropylene, polycarbonate, polyamide, spandex, rayon, Manila, acetate, aloe vera, bamboo, baba, kapok, coconut fiber, corn, flax, hemp, jute, kenaf, lyocell, modal, pineapple hemp, raffia fiber, ramie, rayon, sisal, seaweed fiber, lampel fiber, lyocell fiber, soybean protein, pineapple, alpaca, Angora wool, Azrun fiber, bisso, camel hair, cashmere wool, chigo, lamb wool, llamas, mohair wool, Arctic musk ox hair, rabbit fiber, silk, alpaca fiber, wool, and yak fiber. In some embodiments, the fibers are nylon, polyester, polyethylene, polypropylene, polycarbonate, polyamide, or cellulose fibers.

[0516] In the manufacturing process of fiber-based materials, one or more compounds produced by the methods disclosed in this invention can be combined with one or more fibers (e.g., during the pulping stage of paper and / or packaging materials or other fiber-based materials manufacturing, or, for example, the collection of individual fibers before weaving them into textiles) to coat the fibers with one or more compounds. In other embodiments, prefabricated fiber-based materials (e.g., paper, packaging materials, textiles, or other fiber-based materials) can be coated with compounds to coat the fiber-based material with one or more compounds. Known methods can be used to combine fibers and prefabricated fiber-based materials with one or more compounds. For example, one or more fibers can be combined with one or more compounds and a solvent. The solvent can then be removed from the fibers to form a coating containing one or more compounds on the surface of one or more fibers. As another example, one or more compounds can be added to a solvent to form an emulsion or solution. Subsequently, the emulsion or solution can be applied to the surface of the prefabricated fiber-based material, for example, by spraying, brushing, dipping, electro-spraying, or pouring the emulsion or solution onto the surface of the fiber-based material. Subsequently, the solvent can be removed to form a coating containing one or more compounds on the surface of the fiber-based material.

[0517] Compounds obtained using the methods disclosed in this invention can be suitable for polymerization. In some embodiments, the compound is... β-hydroxy fatty acids can be polymerized to form polyesters. -Hydroxy fatty acids can be polymerized with one or more other monomers (e.g., polyhydroxy alcohols, carboxylic acids, dicarboxylic acids, oxodicarboxylic acids, polyamines, diamides, adipic acid chlorides, and / or diisocyanates) to form polymers. The one or more other monomers can be compounds obtained using the methods disclosed in this invention. In some embodiments, the one or more other monomers are other synthetic or commercially available monomers.

[0518] Polymerization of compounds formed by mechanochemical methods can be accomplished using known methods. In some embodiments, polymerization is induced by heating one or more compounds and optionally one or more synthetic or commercially available monomers to an elevated temperature in the absence of a solvent. In some embodiments, polymerization is induced by heating one or more compounds and optionally one or more synthetic or commercially available monomers to an elevated temperature in the presence of a solvent. Suitable solvents include water, alcohols, ethers, amines, hydrocarbons, or any combination thereof. Polymerization can be carried out with or without a polymerization catalyst.

[0519] In some embodiments, the compound is polymerized in the presence of one or more fibers of the fibrous-based material to modulate the properties of the resulting fibrous-based material. One or more compounds may be combined with one or more fibers (e.g., during the pulping stage of paper and / or packaging materials or other fibrous-based material manufacturing, or before the fibers are woven into textiles, such as in the collection of individual fibers), and subsequently polymerized to form a fibrous-based material in which the fibers are intercalated with the polymer. In other embodiments, a pre-formed fibrous-based material (e.g., paper, packaging materials, textiles, or other fibrous-based materials) may be coated with a compound, followed by heating to induce polymerization of the compound, resulting in a polymer-coated fibrous-based material.

[0520] Example

[0521] The following examples describe condensation polymer-derived compositions and methods for obtaining them. In each of the examples below, unless otherwise stated, all reagents and solvents were commercially available and ready for use without further purification. Unless otherwise stated, all reactions were carried out under a nitrogen atmosphere using commercially available solvents. The reactions were monitored by thin-layer chromatography (TLC) using UV light as the visualization agent, an acidic mixture of anisaldehyde, cerium ammonium molybdate, or an alkaline aqueous solution of potassium permanganate (KMnO4), and heat as the developing agent. The TLC was performed on 0.25 mm E. Merck silica gel plates (60 Å, F-254). NMR spectra were recorded on a Bruker Avance 500 MHz and / or Varian V NMRS 600 MHz instrument, using residual undeuterated solvents as an internal reference (e.g., CHCl3 @ 7.26 ppm). 1 Calibration was performed using ¹H NMR. IR spectroscopy was performed on a ShimadzuIRspirit equipped with a QATR-S accessory. Unless otherwise specified, ball milling was performed in a 50 ml yttrium-stabilized zirconia jar using yttrium-stabilized zirconia media (sometimes referred to as YSZ, ZrO2, zirconia, or "ceramic") in a Retsch PM 200 planetary ball mill.

[0522] Abbreviations used:

[0523]

[0524] Example 1: Method for preparing tomato pomace before depolymerization

[0525] Tomato pomace obtained from commercial tomato processing facilities is ground in a cutting mill and then sieved to obtain different particle size distributions (e.g., >500). m, 250-500 m, 125-250 m, etc.). This corresponds to 250-500. The fractions of m were sequentially extracted overnight in a Soxhlet extractor with CHCl3, and then overnight in a Soxhlet extractor with methanol to remove surface wax and other soluble components, and then dried under vacuum (<1 Torr). The washed pomace was freeze-dried overnight (<0.02 Torr) to remove water, and then stored in a desiccator before use.

[0526] Example 2: Screening of catalysts for the mechanochemical depolymerization of tomato pomace

[0527] The general procedure for the mechanochemical depolymerization of tomato keratin using different catalysts in a ball mill is as follows: Add 1g of dried tomato peel (250-500mg / L) to the milling jar. The mixture was prepared by adding 1 oz (1 equivalent w / w) of zirconia media and grinding it in a planetary ball mill (1 h, 650 rpm). A catalyst was added, and in some cases water was added, and the resulting mixture was ground in a planetary ball mill for the reaction times shown in Table 1. After the reaction was complete, the mixture was diluted in H2O (100 mL), filtered, and the filtrate was collected. If an alkali was used, the filtrate was further treated with 3 M HCl until a solution with pH 3 was obtained. The resulting aqueous solution was extracted with EtOAc (150 mL), and the separated EtOAc phase was dried and passed through a diatomaceous earth (DEM) solution. 1 H NMR analysis.

[0528] Table 1. Effect of catalyst on depolymerization of tomato cutin

[0529]

[0530] The results indicate that acid catalysts promote alcohol elimination / oligopolymerization, which yields unsaturated compounds. The results also show that hydroxide bases are more selective for depolymerization.

[0531] Example 3: Sodium hydroxide-catalyzed ball milling depolymerization of tomato pomace

[0532] The depolymerization of tomato pomace by NaOH-catalyzed ball milling was carried out as follows: Tomato pomace (1 g, 1 equivalent w / w), NaOH (0.5 g, 0.5 equivalent w / w), and 40 g of zirconium oxide media were added to a milling jar. The resulting mixture was ground in a planetary ball mill (650 rpm, 1 h). After 1 hour, the ball mill was stopped, and water was used ( Rinse the tank with 150 mL of water and acidify with 3M HCl aqueous solution until pH 3 is obtained. Extract the aqueous phase with EtOAc (150 mL), collect the EtOAc phase and dry it, then... 1 1H NMR and GPC analysis yielded DHPA (0.3847 g, 38%).

[0533] Example 4: Reaction Time

[0534] The reaction time was varied to determine the effect of time on the degree of depolymerization and recovery. All experiments were conducted in a planetary ball mill at 650 rpm using 1 g dried tomato pomace, 40 g zirconium oxide media, and 3 g NaOH. Reaction times of 0.5 h, 1 h, 3 h, 6 h, and 12 h were evaluated. The results compared to conventional alkaline hydrolysis are summarized in Table 2 and plotted in [the table / plot]. Figure 1 Generally, longer reaction times lead to higher depolymerization rates. In summary, GPC analysis indicates that a reaction time of 12 hours results in the optimal monomer contribution and recovery.

[0535] Table 2. Effect of reaction time on depolymerization degree

[0536]

[0537] Example 5. Alkali strength

[0538] The stoichiometry and properties of the alkali were varied to determine the effect of alkali strength on the degree of depolymerization and recovery. All experiments were performed in a planetary ball mill at 650 rpm for 1 hour using 1 g of dried tomato peel and 40 g of zirconium oxide media. Experiments were conducted with NaOH loadings of 3 g (75 mmol), 1 g (25 mmol), 0.3 g (7.5 mmol), and 0.03 g (0.75 mmol) or Na₂CO₃ loadings of 8 g (75 mmol) and 0.8 g (7.5 mmol). The results are summarized in Table 3 and plotted on [the graph / plot]. Figure 2 Generally, reducing the base strength in the reaction decreases the contribution of monomers to the product. Optimal results were observed for reactions using the strong base NaOH at loadings of 3 g, 1 g, and 0.3 g. Reducing the NaOH loading to 0.03 g (Table 3, entry 4) resulted in a significant decrease in monomer contribution and low overall recovery. Na₂CO₃ was ineffective.

[0539] Table 3. Effect of alkali strength on the depolymerization of tomato cutin

[0540]

[0541] Example 6. Counterions

[0542] The effects of counterions in the alkali and the size of the cation on depolymerization degree and recovery were determined by varying the nucleophilicity and cation size. All experiments were performed in a planetary ball mill at 650 rpm for 1 hour using 1 g of dried tomato peel and 40 g of zirconium oxide media. Experiments were conducted with alkali metal hydroxides below 75 mmol: LiOH. H2O, NaOH, KOH or CsOH H2O. The results are summarized in Table 4 and plotted on [the graph]. Figure 3The results showed that NaOH was the most successful catalyst for the depolymerization of keratin, as evidenced by the yield and monomer contribution of the product (Table 4, entry 2). Experiments using KOH and CsOH resulted in yields comparable to those using NaOH; however, GPC analysis of the product showed a lower monomer contribution, indicating that KOH and CsOH were less effective than NaOH in the complete decomposition of the polymer.

[0543] Table 4. Effects of counterions on the depolymerization of tomato cutin

[0544]

[0545] Example 7. Rotational frequency in the depolymerization of tomato cutin

[0546] The effect of ball mill rotation frequency on the depolymerization of tomato cutin was evaluated. All experiments were conducted for 1 hour in a Retsch PM 200 planetary ball mill using 1 g of dried tomato peel, 40 g of zirconia media, and 3 g of NaOH. Rotation frequencies were studied at 100 rpm intervals, starting from 150 rpm and ending at 650 rpm. The results are summarized in Table 5 and plotted on [the graph / plotting table]. Figure 4 The results showed that 650 rpm was the only effective rotational frequency for completely breaking down keratin into its monomers by GPC analysis, with yields similar to those achieved using conventional chemistry.

[0547] Table 5. Effect of rotation frequency on the depolymerization of tomato cutin

[0548]

[0549] 650 rpm was found to be the optimal rotational frequency for the Retsch PM 200 planetary ball mill. However, depending on the impact energy associated with the grinding process in the ball mill, ball mills with different constructions may not require a high rotational frequency, or may require an even higher rotational frequency.

[0550] Example 8. Effect of water as an additive on the depolymerization of tomato cutin

[0551] The role of water as an additive in the hydroxide-promoted depolymerization of tomato keratin was evaluated. All experiments were run in a planetary ball mill at 650 rpm for 1 hour, using 1 g of dried tomato peel, 40 g of zirconium oxide medium, and 3 g of NaOH, with or without water (1 mL). The results are summarized in Table 6. Runs without H2O resulted in the best yields and monomer contributions in the products (by GPC). Adding water to the reaction slightly reduced the yields, but significantly decreased the monomer contribution in the products of the water-added experiments. Wet assays still broke down keratin into dimers, but GPC chromatograms showed significant oligomer peaks and very small monomer peaks.

[0552] Table 6. Effect of water as an additive on the depolymerization of tomato cutin. Depolymerization of polyethylene terephthalate.

[0553]

[0554] Example 9. Depolymerization of polyethylene terephthalate

[0555] The mechanochemical depolymerization of polyethylene terephthalate (PET) in a ball mill was performed as follows: PET was shredded with dry ice in a fragrance mill, and the shredded PET (1 g, 1 equivalent w / w) was transferred to a grinding jar. Then, NaOH (3 g, 3 equivalent w / w) and 40 g of zirconium oxide media were added to the grinding jar, and the resulting mixture was ground in a planetary ball mill (1 h, 650 rpm).

[0556] Post-treatment 1: After the reaction was complete, the ground mixture was diluted with H2O (150 mL) and filtered. The filtrate was collected and 3M HCl was added. 30 mL) until a solution with pH 3 is obtained. Extract the resulting aqueous solution with EtOAc (150 mL). Dry the separated EtOAc solution to obtain terephthalic acid monomer (3.81% mass yield) and pass through... 1 H NMR analysis.

[0557] Post-treatment 2: After the reaction was complete, the ground mixture was diluted with H2O (100 mL) and filtered. The filtrate was collected and 3M HCl was added until a solution with pH 3 was obtained. The resulting aqueous solution was then treated with EtOAc (2... Extract (150 mL), filter, and dry the separated EtOAc solution and filter cake to obtain terephthalic acid monomer (6.58% mass yield).

[0558] Example 10. Triglyceride cleavage

[0559] Hydrogenated grape seed oil (1.00 g, 1.1 mmol) was added to a zirconia grinding jar, followed by zirconia beads (40 g). Then, reagent-grade powdered NaOH (0.136 g, 3.4 mmol) was added to the jar, which was then capped and milled at 650 rpm for 60 minutes in a Retsch PM 200 planetary ball mill. A small sample was removed from the jar and characterized by IR spectroscopy to confirm the presence of sodium stearate.

[0560] Hydrogenated grape seed oil (5.0 g, 5.5 mmol) was added to a 50 mL zirconia grinding jar containing 40 g of grinding media, and NaOH (0.68 g, 17 mmol) was added. The ball mill was then set to 650 rpm for 1 hour. The reaction mixture was passed through a 2 mm sieve to remove the grinding media and obtain 5.2 g of hydrogenated grape seed oil fatty acid salt.

[0561] Example 11. Cleavage of fatty acid esters

[0562] Ethyl palmitate (1.00 g, 3.5 mmol) was added to a zirconia grinding jar, followed by zirconia beads (40 g). Then, reagent-grade powdered NaOH (0.148 g, 3.7 mmol) was added to the jar, which was then capped and milled at 650 rpm for 120 minutes in a Retsch PM 200 planetary ball mill. A small sample was removed from the jar and characterized by IR spectroscopy to confirm the presence of sodium palmitate.

[0563] Methyl stearate (1.00 g, 3.4 mmol) was added to a zirconia grinding jar, followed by zirconia beads (40 g). Then, reagent-grade powdered NaOH (0.144 g, 3.6 mmol) was added to the jar, which was then capped and ground in a Retsch PM 200 planetary ball mill at 650 rpm for 30 minutes. A small sample was removed from the jar and characterized by IR spectroscopy to confirm the presence of sodium stearate.

[0564] Example 12. Neutralization of stearic acid

[0565] Stearic acid (1.00 g, 3.5 mmol) was added to a zirconia grinding jar, followed by zirconia beads (40 g). Then, reagent-grade powdered NaOH (0.148 g, 3.7 mmol) was added to the jar, which was then capped and ground at 650 rpm for 30 minutes in a Retsch PM 200 planetary ball mill. A small sample was removed from the jar and characterized by IR spectroscopy to confirm the presence of sodium stearate.

[0566] Stearic acid (1.00 g, 3.5 mmol) was added to a zirconia grinding jar, followed by zirconia beads (40 g). Reagent-grade powdered Na₂CO₃ (0.148 g, 3.7 mmol) and 0.1 mL of water were then added to the jar, which was capped and ground at 650 rpm for 1 hour in a Retsch PM 200 planetary ball mill. The solid was extracted with ethyl acetate to remove any unreacted stearic acid. Analysis of ethyl acetate showed <1 mg of extractable residual stearic acid. The presence of sodium stearate was confirmed by characterizing a small sample of the ethyl acetate-insoluble solid by IR spectroscopy.

[0567] Stearic acid (1.0 g, 3.5 mmol), powdered NaOH (1.05 equivalents), and zirconia grinding beads (40 g, 3 mm) were added to a 50 mL zirconia grinding jar. The mixture was ground in a Retsch CM 200 planetary ball mill at 650 rpm for 1 hour. The resulting mixture was extracted with hot methanol (50 mL). The solids were removed by filtration through diatomaceous earth, and the filtrate was concentrated under reduced pressure to give 925 mg of sodium stearate.

[0568] Example 13. Using ultrasonic energy to depolymerize keratin

[0569] Add 31g of tomato skin (250-500g) The mixture (particle size m) was mixed with 12.2 g of KOH in 300 mL of MeOH and sonicated for 1 hour (applied power 200 W). After 1 hour, the solid was filtered off, and methanol was evaporated. The crude material was dissolved in 500 mL of ethyl acetate and washed three times with 250 mL of water. The ethyl acetate was evaporated to dryness to give 32% of the initial mass recovered in the form of crude depolymerized DHPA.

[0570] Example 14. Direct acquisition of fatty acid salts from seeds and other biomass

[0571] Grinded, dried grape seeds (5 g), powdered NaOH (140 mg), and ZrO2 grinding beads (40 g, 3 mm) were added to a 50 mL ZrO2 grinding jar. The mixture was ground in a Retsch CM 200 planetary ball mill at 650 rpm for 1 hour. The resulting mixture was extracted with hot methanol (50 mL). The solids were removed by diatomaceous earth filtration, and the filtrate was concentrated under reduced pressure to obtain a crude mixture of 230 mg of fatty acid salts derived from grape seeds.

[0572] Add 5 g of dried, used coffee grounds, 140 mg of powdered NaOH, and 40 g, 3 mm ZrO2 grinding beads to a 50 mL ZrO2 grinding jar. Grind the mixture in a Retsch CM 200 planetary ball mill at 650 rpm for 1 hour. Extract the resulting mixture with hot methanol (50 mL). Remove the solids by filtration through diatomaceous earth, and concentrate the filtrate under reduced pressure to obtain a crude mixture of 150 mg of fatty acid salts.

Claims

1. A method for depolymerizing a polyester or polyamide-containing compound into constituent oligomers and / or monomers, the method comprising: The compound containing polyester or polyamide is contacted with a nucleophile to form a first mixture; The first mixture is mechanically processed to decompose at least a portion of the polyester- or polyamide-containing compound, thereby producing a second mixture comprising oligomers and / or monomers of the polyester- or polyamide-containing compound; and At least a portion of the oligomers and / or monomers are separated from the second mixture.

2. The method of claim 1, wherein the polyester or polyamide-containing compound comprises one or more of a condensation polymer and a triglyceride.

3. The method according to claim 2, wherein the condensation polymer is selected from keratin, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, poly(2-hydroxybutyrate), poly(caprolactone), poly(lactic acid), polyhydroxyalkanoate, polyglycolic acid, polyethylene glycol adipate, polybutylene succinate, nylon, aromatic polyamide, and polyphthalamide.

4. The method of claim 3, wherein the condensation polymer is keratin.

5. The method according to claim 2, wherein the polyester-containing compound is a triglyceride.

6. The method according to any one of claims 1-5, wherein the nucleophile is selected from hydroxides, alkoxides, carbonates, metal hydrides and their precursors.

7. The method according to claim 6, wherein the nucleophile is a hydroxide selected from potassium hydroxide, sodium hydroxide, barium hydroxide, cesium hydroxide and calcium hydroxide.

8. The method according to any one of claims 1-7, wherein the selected amount of the nucleophile is a catalytic amount, a stoichiometric amount, or a superstoichiometric amount.

9. The method according to any one of claims 1-8, wherein the first mixture is mechanically processed for about 1 minute to about 24 hours.

10. The method according to any one of claims 1-9, wherein the machining includes grinding the first mixture.

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