Aziridinated triglycerides and polymers formed therefrom

Patent metadata

Field	Value
Publication number	US-2016289218-A1
Application number	US-201615085345-A
Country	US
Kind code	A1
Filing date	Mar 30, 2016
Priority date	Apr 6, 2015
Publication date	Oct 6, 2016
Grant date	—

Abstract

Various embodiments disclosed relate to aziridinated triglycerides and polymers formed therefrom. In various embodiments, the present invention provides an aziridinated triglyceride having the structure described herein. In various embodiments, the present invention provides a method of making the aziridinated triglyceride, a method of crosslinking the aziridinated triglyceride to form a polymer, the polymer formed from the aziridinated triglyceride, a triglyceride with at least one pendent unsaturated group that can be used to form the aziridinated triglyceride, and a method of making the triglyceride having at least one pendent unsaturated group.

First claim

What is claimed is:

1 . An aziridinated triglyceride having the structure:

wherein
R 1 , R 2 , and R 3 are each independently a substituted or unsubstituted (C 1 -C 50 )hydrocarbyl optionally interrupted or terminated by at least one -AZ— group having the structure:

at each occurrence, L 1 is independently a substituted or unsubstituted (C 2 -C 50 )hydrocarbyl interrupted or terminated with 0, 1, 2, or 3 groups independently chosen from —O—, —S—, and substituted or unsubstituted —NH—,
at each occurrence, R 4 , R 5 , R 6 , and R 7 are independently chosen from —H and substituted or unsubstituted (C 1 -C 10 )hydrocarbyl interrupted or terminated with 0, 1, 2, or 3 groups independently chosen from —O—, —S—, and substituted or unsubstituted —NH—, and
the aziridinated triglyceride comprises at least one of the -AZ— groups.

2 . The aziridinated triglyceride of claim 1 , wherein -AZ— has the structure:

3 . The aziridinated triglyceride of claim 1 having the structure:

4 . A method of crosslinking the aziridinated triglyceride of claim 1 , the method comprising:
contacting the aziridinated triglyceride with a crosslinker, to form a crosslinked triglyceride.

5 . The method of claim 4 , wherein the crosslinker is a polycarboxylic acid.

6 . The method of claim 5 , wherein the polycarboxylic acid is at least one of a HOC(O)—R a —C(O)OH wherein R a is a substituted or unsubstituted (C 1 -C 50 )hydrocarbylene interrupted or terminated by 0, 1, 2, or 3 groups independently chosen from —O—, —S—, substituted or unsubstituted —NH—, and —(O—(C 2 -C 3 )alkylene) n - wherein n is about 1 to about 10,000 and wherein the (C 2 -C 3 )alkylene is substituted or unsubstituted, oxalic acid, maleic acid, succinic acid, methylsuccinic acid, malonic acid, adipic acid, glutaric acid, fumaric acid, dihydroxyfumaric acid, malic acid, mesaconic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-, 1,3-, or 1,4-cyclohexane dicarboxylic acid, 1,2,3-cyclohexane tricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, 1,3,5-cyclohexane tricarboxylic acid, 1,2- or 1,3-cyclopentane dicarboxylic acid, citric acid, tartaric acid, dihydroxyterephthalic acid, 1,2,3-, 1,2,4-, or 1,2,5-benzene tricarboxylic acid, tricarballylic acid, 1,2,4,5-benzene tetracarboxylic acid, norbornene tetracarboxylic acid, 3,3′,4,4′-benzophenone tetracarboxylic acid, 1,2,3,4,5,6-benzene hexacarboxylic acid, aspartic acid, polyacrylic acid, and glutamic acid.

7 . The method of claim 5 , wherein the polycarboxylic acid has the structure:

wherein
fused rings A and B are each independently chosen from substituted or unsubstituted (C 5 -C 10 )cycloalkyl and (C 2 -C 10 )heterocyclyl,
m and n are each independently 1-8, and
at each occurrence R′ is independently chosen from substituted or unsubstituted (C 2 -C 10 )hydrocarbylene.

8 . The method of claim 7 , wherein the polycarboxylic acid has the structure:

9 . The method of claim 7 , wherein the polycarboxylic acid is chosen from

10 . The method of claim 5 , wherein the polycarboxylic acid is succinic acid, citric acid, an isosorbide-based diacid, or a combination thereof.

11 . A polymer formed from reaction of the aziridinated triglyceride of claim 1 and a polycarboxylic acid.

12 . A method of making the aziridinated triglyceride of claim 1 , the method comprising:
combining an epoxidized triglyceride with a substituted or unsubstituted (C 3 -C 50 )carboxylic acid including at least one aliphatic unsaturated carbon-carbon bond, and treating the (C 3 -C 50 )carboxylic acid-treated product with an aziridine having the structure:

to give the aziridinated triglyceride of claim 1 .

13 . A polymer having the structure:

wherein
R 1 , R 2 , and R 3 are each independently a substituted or unsubstituted (C 1 -C 50 )hydrocarbyl optionally interrupted or terminated by the A end of at least one -AZP— group having the structure:

at each occurrence, L 1 is independently a substituted or unsubstituted (C 2 -C 50 )hydrocarbyl interrupted or terminated with 0, 1, 2, or 3 groups independently chosen from —O—, —S—, and substituted or unsubstituted —NH—,
at each occurrence, R 4 , R 5 , R 6 , and R 7 are independently chosen from —H and substituted or unsubstituted (C 1 -C 10 )hydrocarbyl interrupted or terminated with 0, 1, 2, or 3 groups independently chosen from —O—, —S—, and substituted or unsubstituted —NH—,
R b is a substituted or unsubstituted (C 1 -C 50 )hydrocarbyl having a valence of z+1, wherein R b is interrupted or terminated by 0, 1, 2, or 3 groups independently chosen from —O—, —S—, substituted or unsubstituted —NH—, and —(O—(C 2 -C 3 )alkylene) n - wherein n is about 1 to about 10,000 and wherein the (C 2 -C 3 )alkylene is substituted or unsubstituted,
z is about 1 to about 1,000,
the triglyceride I comprises at least one of the -AZP— groups, and
each B end of the -AZP— group is independently interrupting or terminating R 1 , R 2 , or R 3 of the same or different triglyceride I, wherein at least one B end of at least one -AZP-group in the triglyceride I interrupts or terminates R 1 , R 2 , or R 3 of a different triglyceride I.

14 . The polymer of claim 13 , wherein the polymer has about 2 to about 100,000,000 triglycerides of structure I.

15 . The polymer of claim 13 , wherein at least one of R 1 , R 2 , and R 3 is interrupted or terminated with at least one of the -AZP— groups.

16 . The polymer of claim 13 , wherein -AZP— has the structure:

17 . The polymer of claim 13 , wherein triglyceride I has the structure:

18 . A triglyceride having the structure:

Assignees

• Univ Iowa State Res Found Inc

Inventors

• Chen Ruqi
• Chen Jason Shih-Hao
• Zhang Chaoqun
• Kessler Michael Richard

Classifications

• C08G63/6852

  derived from hydroxy carboxylic acids · CPC title

• C07D405/12 Primary

  linked by a chain containing hetero atoms as chain links · CPC title

• C08G73/02

  Polyamines · CPC title

• C08G63/685

  containing nitrogen · CPC title

• C08G63/78

  Preparation processes · CPC title