Polymer glass transition temperature manipulation via z/e hydrazone photoswitching

Patent metadata

Field	Value
Publication number	US-11987654-B2
Application number	US-202218085404-A
Country	US
Kind code	B2
Filing date	Dec 20, 2022
Priority date	Sep 13, 2019
Publication date	May 21, 2024
Grant date	May 21, 2024

Abstract

In an embodiment, the present disclosure pertains to a method of changing the glass transition temperature of a polymer. In some embodiments, the polymer includes at least one hydrazone-containing compound. In general, the methods of the present disclosure include one or more of the following steps of: (1) applying light to the polymer; and (2) thereby changing the glass transition temperature of the polymer. In another embodiment, the present disclosure pertains to a polymer having a light-adjustable glass transition temperature. In some embodiments, the polymer includes at least one hydrazone-containing compound.

First claim

What is claimed is:

1. A method of increasing the glass transition temperature (T g ) of a polymer,
wherein the polymer is covalently linked to at least one hydrazone-containing compound,
wherein the hydrazone-containing compound comprises:

or combinations thereof,
wherein at least one of Y and R 1 comprises the polymer,
wherein Y, R 1 and R 2 are each independently selected from the group consisting of H, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, ketone groups, amine groups, amide groups, carboxyl groups, carboxylic acid groups, ester groups, thiol groups, sulfoxide groups, alcohol groups, alkyne groups, azide groups, CH 2 CH 3 , C(CH 3 ), (CH 2 ) 5 CH 3 , (CH 2 ) 7 CH 3 , (CH 2 ) 9 CH 3 , (CH 2 ) 11 CH 3 , (CH 2 ) 1-20 CH 3 , t-butyl, n- hexyl, n-octyl, n-decyl, n-dodecyl and combinations thereof, and
wherein the method comprises:
applying light to the polymer,
wherein the light increases the glass transition temperature (T g ) of the polymer,
wherein the increase in T g occurs through photo-isomerization, and
wherein the hydrazone in the hydrazone-containing compound transitions from a Z state to an E state upon photoisomerization.

2. The method of claim 1 , wherein the polymer is selected from the group consisting of polyethylene, polypropylene, polystyrene, poly(vinyl chloride), polyisobutylene, poly(methyl acrylate), poly(methyl methacrylate), polytetrafluoroethylene, poly(acrylic acid), polyacrylamide, polyacrylonitrile, poly(hydroxyethyl methacrylate), poly(hydroxyethyl acrylate), and combinations thereof.

3. The method of claim 1 , wherein the hydrazone-containing compound is part of a side chain of the polymer.

4. The method of claim 1 , wherein Y comprises the polymer.

5. The method of claim 1 , wherein R 1 comprises the polymer.

6. The method of claim 1 , wherein Y and R 1 comprise the polymer.

7. The method of claim 1 , wherein Y and R 1 are each independently selected from the group consisting of:

wherein n is an integer of more than 1.

8. The method of claim 1 , wherein the hydrazone-containing compound is selected from the group consisting of:

and combinations thereof,
wherein n is an integer of more than 1.

9. The method of claim 1 , wherein the light is derived from a light source selected from the group consisting of an arc lamp system, short-wave ultraviolet lamps, incandescent lamps, gas-discharge lamps, ultraviolet light emitting diodes, ultraviolet lasers, tunable vacuum ultraviolet systems, natural light, and combinations thereof.

10. The method of claim 1 , wherein the increase in T g results in stiffening of the polymer.

11. A polymer comprising a light-adjustable glass transition temperature (T g ), wherein the polymer is covalently linked to at least one hydrazone-containing compound, wherein the hydrazone-containing compound comprises:

or combinations thereof,
wherein at least one of Y and R 1 comprises the polymer,
wherein Y, R 1 and R 2 are each independently selected from the group consisting of H, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, ketone groups, amine groups, amide groups, carboxyl groups, carboxylic acid groups, ester groups, thiol groups, sulfoxide groups, alcohol groups, alkyne groups, azide groups, CH 2 CH 3 , C(CH 3 ), (CH 2 ) 5 CH 3 , (CH 2 ) 7 CH 3 , (CH 2 ) 9 CH 3 , (CH 2 ) 1-20 CH 3 , (CH 2 ) 1-20 CH 3 , t-butyl, n- hexyl, n-octyl, n-decyl, and n-dodecyl and combinations thereof, and
wherein the hydrazone in the hydrazone-containing compound is operational to transition from a Z state to an E state upon photoisomerization.

12. The polymer of claim 11 , wherein the polymer is selected from the group consisting of polyethylene, polypropylene, polystyrene, poly(vinyl chloride), polyisobutylene, poly(methyl acrylate), poly(methyl methacrylate), polytetrafluoroethylene, poly(acrylic acid), polyacrylamide, polyacrylonitrile, poly(hydroxyethyl methacrylate), poly(hydroxyethyl acrylate), and combinations thereof.

13. The polymer of claim 11 , wherein the hydrazone-containing compound is part of a side chain of the polymer.

14. The polymer of claim 11 , wherein Y comprises the polymer.

15. The polymer of claim 11 , wherein R 1 comprises the polymer.

16. The polymer of claim 11 , wherein Y and R 1 comprise the polymer.

17. The polymer of claim 11 , wherein Y and R 1 are each independently selected from the group consisting of:

and combinations thereof, wherein n is an integer of more than 1.

18. The polymer of claim 11 , wherein the hydrazone-containing compound is selected from the group consisting of:

and combinations thereof,
wherein n is an integer of more than 1.

Assignees

• Dartmouth College

Inventors

• Abrahamian Ivan
• Yang Sirun
• Jeliazkov Laura L
• Harris Jared D

Classifications

• C08F20/36 Primary

  containing oxygen in addition to the carboxy oxygen {, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate} · CPC title

• C08F8/48

  Isomerisation; Cyclisation · CPC title

• C08F16/28

  Monomers containing nitrogen · CPC title

• C08F18/22

  Esters containing nitrogen · CPC title

• C08F20/34

  Esters containing nitrogen {, e.g. N,N-dimethylaminoethyl (meth)acrylate} · CPC title