Compositions and methods of preparation thereof
Described herein are methods of preparing compounds derived from triglycerides or condensation polymers such as polyesters and/or polyamides. The methods may include subjecting triglyceride or condensation polymer containing matter to mechanical processing in the presence of a nucleophile.
1. A method for depolymerizing polyester-containing compounds into constituent oligomer and/or monomers, the method comprising:
contacting a polyester-containing compound with a nucleophile to form a first mixture, wherein the polyester-containing compound is a triglyceride, and the nucleophile is a hydroxide selected from potassium hydroxide, sodium hydroxide, barium hydroxide, cesium hydroxide, and calcium hydroxide;
mechanically processing the first mixture to decompose at least a portion of the polyester-containing compound to yield a second mixture comprising the constituent oligomer and/or monomers of the polyester-containing compound; and
isolating at least a portion of the constituent oligomer and/or monomers from the second mixture.
2. The method of claim 1 , wherein the mechanical processing comprises grinding the first mixture.
3. The method of claim 2 , wherein grinding the first mixture comprises ball milling.
4. The method of claim 2 , wherein grinding the first mixture comprises planetary ball milling, and the first mixture is milled at a spinning frequency of about 1 rpm to about 1000 rpm.
5. The method of claim 1 , wherein the mechanical processing comprises agitating the first mixture.
6. The method of claim 1 , wherein the mechanical processing reduces the particle size of at least a portion of the second mixture to a mean particle size of less than about 1000 microns.
7. The method of claim 1 , wherein isolating at least a portion of the constituent monomers from the second mixture comprises treating the second mixture with an acid.
8. The method of claim 7 , wherein the acid is an inorganic acid.
9. The method of claim 7 , wherein the acid is selected from hydrochloric acid, phosphoric acid, and sulfuric acid.
10. The method of claim 7 , wherein treating the second mixture with an acid forms a solution having a pH less than or equal to 5.
11. The method of claim 1 , wherein the constituent monomers comprise at least one compound of Formula I:
wherein:
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently —H, —OR 13 , —NR 13 R 14 , —SR 13 , halogen, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, —C 2 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR 13 , —NR 13 R 14 , —SR 13 , or halogen;
R 13 and R 14 are each independently —H, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, or —C 2 -C 6 alkynyl,
R 12 is —OH, —H, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, —C 2 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR 13 , —NR 13 R 14 , —SR 13 , halogen, —COOH, or —COOR 11 ;
m, n, and o are each independently an integer in the range of 0 to 30; and
the sum of m, n, and o is 0 to 30.
12. The method of claim 1 , wherein the constituent monomers comprise at least one compound of Formula II:
wherein:
R 1 , R 2 , R 4 , and R 5 are each independently —H, —OR 11 , —NR 11 R 12 , —SR 11 , halogen, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, —C 2 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, aryl, or 5- to 10-membered ring heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with —OR 11 , —NR 11 R 12 , —SR 11 , or halogen;
R 11 and R 12 are each independently —H, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, or —C 2 -C 6 alkynyl;
the symbol represents an optionally single or cis or trans double bond;
R 3 is —OH and R 3′ is selected from —H, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, —C 2 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, and aryl when between R 3 and R 3′ is a single bond, and R 3 and R 3′ are absent when between R 3 and R 3′ represents a double bond;
R 6 is —OH and R 6′ is selected from —H, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, —C 2 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, and —C 6 -C 10 aryl when between R 6 and R 6′ is a single bond, and R 6 and R 6′ are absent when between R 6 and R 6′ represents a double bond;
n is an integer in the range of 0 to 11;
m is an integer in the range of 0 to 25; and
the sum of m and n is 0 to 25.
13. The method of claim 1 , wherein the constituent monomers comprise at least one compound of Formula III:
wherein:
R 1 , R 2 , R 5 , R 6 , R 9 , R 10 , R 11 , R 12 , and R 13 are each independently, at each occurrence, —H, —OR 14 —NR 14 R 15 , —SR 14 , halogen, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, —C 2 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, aryl, or heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with one or more —OR 14 , —NR 14 R 15 , —SR 14 , or halogen;
R 3 , R 4 , R 7 , and R 8 are each independently, at each occurrence, —H, —OR 14 , —NR 14 R 15 , —SR 14 , halogen, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, —C 2 -C 6 alkenyl, —C 2 -C 6 alkynyl, —C 3 -C 7 cycloalkyl, aryl, or heteroaryl wherein each alkyl, alkynyl, cycloalkyl, aryl, or heteroaryl is optionally substituted with one or more —OR 14 , —NR 14 R 15 , —SR 14 , or halogen, wherein:
R 3 and R 4 can combine with the carbon atoms to which they are attached to form a C 3 -C 6 cycloalkyl, a C 4 -C 6 cycloalkenyl, or 3- to 6-membered ring heterocycle, and/or
R 7 and R 8 can combine with the carbon atoms to which they are attached to form a C 3 -C 6 cycloalkyl, a C 4 -C 6 cycloalkenyl, or 3- to 6-membered ring heterocycle;
R 14 and R 15 are each independently, at each occurrence, —H, —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, or —C 2 -C 6 alkynyl;
the symbol represents a single bond or a cis or trans double bond;
the symbol represents a cis or trans double bond;
n is 0, 1, 2, 3, 4, 5, 6, 7, or 8;
m is 0, 1, 2, or 3;
q is 0, 1, 2, 3, 4, or 5; and
r is 0, 1, 2, 3, 4, 5, 6, 7, or 8.