Composition for thiol-ene-based polymerization and liquid crystalline network-containing objects formed therefrom using additive manufacturing

Patent metadata

Field	Value
Publication number	US-11708458-B2
Application number	US-202017076693-A
Country	US
Kind code	B2
Filing date	Oct 21, 2020
Priority date	Aug 21, 2020
Publication date	Jul 25, 2023
Grant date	Jul 25, 2023

Abstract

Disclosed herein are embodiments of a composition that can be used to make liquid crystalline networks using thiol-ene-based polymerization. In particular embodiments, the liquid crystalline networks can be formed by using the composition embodiments in additive manufacturing methods. The composition comprises a monomer, chain extender compound, and a crosslinker compound and each of these components can be selected so as to influence the thermomechanical and shape memory properties of the liquid crystalline networks and/or objects formed therewith.

First claim

We claim:

1. A liquid crystalline network, comprising:
(i) a monomer having a structure according to Formula I

wherein
each Ar group is an aromatic ring system;
each X independently is a linker group;
each Y independently comprises a heteroatom;
each of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 independently is selected from hydrogen, deuterium, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group;
n is an integer selected from 0 to 5; and
m is an integer selected from 0 to 50;

(ii) a chain extender compound having a structure according to Formula II
HS-A-SH   Formula II

wherein
A comprises an aliphatic group, a heteroaliphatic group, an aromatic group, or an organic functional group; and

(iii) a crosslinker compound having a structure according to Formula III

wherein
each X independently is O, S, or NR″, wherein R″ is hydrogen, aliphatic, or heteroaliphatic;
each q independently is an integer selected from 1 to 100;
r is an integer selected from 2, 3, or 4;
each t independently is an integer selected from 0 to 5; and
u is an integer selected from 0, 1, or 2; and

wherein the monomer is directly covalently coupled to the chain extender compound, the crosslinker compound, or both the chain extender compound and the crosslinker compound.

2. The liquid crystalline network of claim 1 , wherein each Ar group of the monomer is an aryl group or a heteroaryl group; each X independently is azo or ester; each Y independently is O, S, or NH; each of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is hydrogen; and m is an integer selected from 0 to 5.

3. The liquid crystalline network of claim 1 , wherein the monomer has a structure according to one of formulas IA, IB, IC, ID, IE, or IF

wherein each R 7 independently is selected from aliphatic, aromatic, or an organic functional group; and each p independently is an integer selected from 0 to 4.

4. The liquid crystalline network of claim 1 , wherein the monomer has a structure according to one of formulas IA′, IB′, IC′, ID′, IE′, or IF′

5. The liquid crystalline network of claim 1 , wherein the monomer has a structure according to one of formulas IA″, IB″, IC″, ID″, IE″, or IF″

6. The liquid crystalline network of claim 1 , wherein the monomer is selected from

7. The liquid crystalline network of claim 1 , wherein the A group of Formula II is —(CR′ 2 ) q , wherein each R′ independently is hydrogen or aliphatic and q is an integer selected from 1 to 100; —CH 2 CH 2 (OCH 2 CH 2 ) q —, wherein q is an integer selected from 1 to 100; —(CH 2 ) q C(O)O(CH 2 ) q OC(O)(CH 2 ) q —, wherein q is an integer selected from 1 to 100; —(CH 2 ) q C(O)N(H)(CH 2 ) q N(H)C(O)(CH 2 ) q —, wherein q is an integer selected from 1 to 100; or —(CH 2 ) q O-Ph-C(O)O-Ph-OC(O)-Ph-O(CH 2 ) q —, wherein q is an integer selected from 1 to 100.

8. The liquid crystalline network of claim 1 , wherein the chain extender compound is selected from 2,2′-(ethane-1,2-diylbis(oxy))bis(ethane-1-thiol), hexane-1,6-dithiol, butane-1,4-diylbis(2-mercaptoacetate), octane-1,8-dithiol, hexadecane-1,16-dithiol, 2,2′-oxybis(ethane-1-thiol), or 1,4-phenylene bis(4-((6-mercaptohexyl)oxy)benzoate).

9. The liquid crystalline network of claim 1 , wherein X of Formula III is oxygen; r of Formula III is 4; u of Formula III is 0; t is 1; and each q independently is 1 or 2.

10. The liquid crystalline network of claim 1 , wherein X of Formula III is oxygen; r of Formula III is 3; u of Formula III is 1; t is 1; and each q independently is 1 or 2.

11. The liquid crystalline network of claim 1 , wherein the crosslinker is selected from

12. The liquid crystalline network of claim 1 , wherein the liquid crystalline network exhibits a glass transition temperature ranging from −50° C. to 50° C., as measured using differential scanning calorimetry.

13. The liquid crystalline network of claim 1 , wherein the liquid crystalline network comprises a liquid crystalline phase and the liquid crystalline phase exhibits a thermal stability ranging from 40° C. to 180° C., as measured using differential scanning calorimetry.

14. The liquid crystalline network of claim 1 , wherein the liquid crystalline network exhibits a degree of liquid crystallinity ranging from 0 J/g to 40 J/g, as measured using differential scanning calorimetry.

15. A composition, comprising:
(i) a monomer having a structure according to Formula I

wherein
each Ar group is an aromatic ring system;
each X independently is a linker group;
each Y independently comprises a heteroatom;
each of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 independently is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group;
n is an integer selected from 0 to 5; and
m is an integer selected from 0 to 50;

(ii) a chain extender compound having a structure according to Formula II
HS-A-SH   Formula II

wherein
A comprises an aliphatic group, a heteroaliphatic group, an aromatic group, or an organic functional group; and

(iii) a crosslinker compound having a structure according to Formula III

wherein
each X independently is O, S, or NR″, wherein R″ is hydrogen, aliphatic, or heteroaliphatic;
q is an integer selected from 1 to 100;
r is an integer selected from 2, 3, or 4;
t is an integer selected from 0 to 5; and
u is an integer selected from 0, 1, or 2.

16. The composition of claim 15 , further comprising an initiator compound.

17. The composition of claim 15 , wherein the monomer, the chain extender compound, and the crosslinker compound are present in a ratio ranging from 3:1:1 (monomer:chain extender compound:crosslinker compound) to 8:6:1 (monomer:chain extender compound:crosslinker compound).

18. The composition of claim 15 , wherein the crosslinker is present at a mole fraction ranging from 5% to 35%.

19. A method, comprising:
adding the composition of claim 15 , or components thereof, into an additive manufacturing device;
depositing the composition using the additive manufacturing device to provide a deposited composition; and
polymerizing the deposited composition to provide a liquid crystalline network by exposing it to an energy source.

20. The method of claim 19 , further comprising exposing the deposited composition, the liquid crystalline network, or both to an external field selected from a magnetic field, and electric field, or a combination thereof.

Assignees

• Rios Orlando
• Carter William G
• Kessler Michael R
• Li Yuzhan
• Goswami Monojoy
• Ut Battelle Llc

Inventors

• Rios Orlando
• Carter William G
• Kessler Michael R
• Li Yuzhan
• Goswami Monojoy

Classifications

• C08G75/045 Primary

  from mercapto compounds and unsaturated compounds · CPC title

• B29C64/106

  using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material · CPC title

• B29C64/336

  of two or more materials · CPC title

• B33Y10/00 Primary

  Processes of additive manufacturing · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title