Biomimetic synthetic rubber and methods for controlling its physical properties through backbone double bond stereochemistry by monomer selection and end group modification

Patent metadata

Field	Value
Publication number	US-10968303-B2
Application number	US-201615756256-A
Country	US
Kind code	B2
Filing date	Aug 29, 2016
Priority date	Aug 28, 2015
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

Abstract

In various embodiments, the present invention provides a strong, synthetic elastomer materials (and related methods for making same) with mechanical properties that are controlled by the stereochemically-defined double bonds within their backbone, yet have physical properties that are derived from monomer selection and defined, modifiable, chain end groups. The use of the organocatalyzed, stereospecific addition of thiols to activated alkynes, affords isolated high molar mass materials (>100 kDa) via step-growth polymerization with high levels of cis- or trans-double bond content. Furthermore, in various aspects of the present invention, it has been found that changing the monomer composition and chain end groups provides additional control over the materials' physical properties to provide more efficient compounding with polar additives. Using this approach to elastomer synthesis, further end group modification and toughening through various vulcanization strategies are also possible.

First claim

What is claimed is:

1. A thiol-yne elastomer composition comprising the residue of a multi-functional alkyne monomer and the residue of a multi-functional thiol monomer, said thiol-yne elastomer composition having a cis-trans double bond ratio of from 99:1 to about 1:99 having a glass transition temperature (T g ) of from about −50° C. or more to about 10° C. or less.

2. The thiol-yne elastomer composition of claim 1 further comprising one or more functional end groups.

3. The thiol-yne elastomer composition of claim 2 wherein said one or more functional end groups are selected from the group consisting of alkyne, alkene, hydroxyl, carboxylic acid, fluoro, trifluoro, perfluoro, and combinations thereof.

4. The thiol-yne elastomer of claim 1 wherein said multi-functional alkyne comprises an alkyne ester, an activated alkyne amide, or a dialkyne with a ketone.

5. The thiol-yne elastomer composition of claim 1 wherein said multi-functional alkyne is a dialkyne having the formula:

where R 1 , and R 3 are each an H, alkyl or aryl group; R 2 is an alkyl, alkylene, ethoxy, or arylene group; and X 1 and X 2 are an O, NH, or S group.

6. The thiol-yne elastomer of claim 1 wherein said multi-functional alkyne is a dialkyne having the formula:

where R 1 , and R 3 are each an H, alkyl or aryl group; R 2 is an alkyl, alkylene, ethoxy, or arylene group; and X 1 and X 2 are an O, NH, or S group.

7. The thiol-yne elastomer of claim 1 wherein said multi-functional thiol monomer comprises a linear dithiol, a branched trithiol, a branched tetrathiol, or a combination thereof.

8. A thiol-yne elastomer composition comprising the residue of a multi-functional alkyne monomer and the residue of a multi-functional thiol monomer, said thiol-yne elastomer composition having a cis-trans double bond ratio of from 99:1 to about 1:99 having an elastic modulus (E) of from about 1.0 MPa to about 90 MPa.

9. The thiol-yne elastomer of claim 8 wherein said multi-functional alkyne comprises an alkyne ester, an activated alkyne amide, or a dialkyne with a ketone.

10. The thiol-yne elastomer of claim 8 wherein said multi-functional alkyne is a dialkyne having the formula:

where R 1 , and R 3 are each an H, alkyl or aryl group; R 2 is an alkyl, alkylene, ethoxy, or arylene group; and X 1 and X 2 are an O, NH, or S group.

11. The thiol-yne elastomer of claim 8 wherein said multi-functional thiol monomer comprises a linear dithiol, a branched trithiol, a branched tetrathiol, or a combination thereof.

12. A thiol-yne elastomer composition comprising the residue of a multi-functional alkyne monomer and the residue of a multi-functional thiol monomer, said thiol-yne elastomer composition having a cis-trans double bond ratio of from 99:1 to about 1:99 having an elongation at break (ε break ) of from 50% or more to 3000% or less.

13. The thiol-yne elastomer of claim 12 wherein said multi-functional alkyne comprises an alkyne ester, an activated alkyne amide, or a dialkyne with a ketone.

14. The thiol-yne elastomer of claim 12 wherein said multi-functional alkyne is a dialkyne having the formula:

where R 1 , and R 3 are each an H, alkyl or aryl group; R 2 is an alkyl, alkylene, ethoxy, or arylene group; and X 1 and X 2 are an O, NH, or S group.

15. The thiol-yne elastomer of claim 12 wherein said multi-functional thiol monomer comprises a linear dithiol, a branched trithiol, a branched tetrathiol, or a combination thereof.

16. A thiol-yne elastomer composition comprising the residue of a multi-functional alkyne monomer and the residue of a multi-functional thiol monomer, said thiol-yne elastomer composition having a cis-trans double bond ratio of from 99:1 to about 1:99 and a glass transition temperature (T g ) of from about −50° C. or more to about 10° C. or less wherein said multi-functional alkyne is a dialkyne having the formula:

where R 1 and R 2 are H, alkyl or aryl groups.

17. The thiol-yne elastomer composition of claim 16 wherein said multi-functional thiol monomer comprises a branched trithiol, a branched tetrathiol, or a combination thereof.

18. The thiol-yne elastomer of claim 16 wherein said multi-functional thiol monomer has the formula:

where R is an alkylene or arlyene group and X 1 and X 2 are SH groups.

19. The thiol-yne elastomer of claim 16 having a weight average molecular mass (M W ) of from about 1,000 Da or more to about 1,000,000 Da or less.

20. A method of making the thiol-yne elastomer composition of claim 1 comprising:
A. combining a multi-functional alkyne monomer and a multi-functional thiol monomer, with a suitable reaction solvent or solvent combination in a suitable vessel at a temperature of from about −20° C. to about 40° C.;
B. adding a suitable base catalyst, allowing the temperature to rise to about ambient temperature, and stirring for from about 0.05 hours to about 10 hours;
C. diluting the mixture of step B with additional reaction solvent or solvent combination and adding a radical inhibitor compound to prevent undesired radical reactions; and
D. precipitating the mixture of step C into a suitable polar solvent to produce a thiol-yne elastomer composition.

21. The method of claim 20 wherein said multi-functional alkyne is a dialkyne monomer having the formula:

where R 1 , and R 3 are H, alkyl or aryl groups; R 2 is alkyl, alkylene, ethoxy, or aryl group; and X 1 and X 2 is an O, NH, or S group.

22. The method of claim 20 wherein said reaction solvent or solvent combination comprises a mixture of solvents having different polarities.

23. The method of claim 20 wherein said reaction solvent or solvent combination comprises a solvent selected from the group consisting of chloroform (CHCl 3 ), N,N-dimethylformamide (DMF), dioxane, methylene chloride (CH 2 Cl 2 ), N-methylpyrolidone (NMP), and combinations thereof.

24. The method of claim 20 wherein said base catalyst is selected from the group consisting of 1,8-diazabicycloundecene (DSU), triazabicyclodecene (TBD), triethylamine (Et 3 N), tetramethyl guanidine (TMG), benzotriazole, dimethylphenylphosphine (DMPP), and combinations thereof.

25. The method of claim 20 wherein said radical inhibitor is 2,6-di-tert-butyl-4-methylphenol (BHT).

26. The method of claim 20 wherein the molar ratio of the multi-functional alkyne monomer to the multi-functional thiol monomer is approximately 1:1.

27. The method of claim 20 further comprising controlling the cis-trans double bond ratio of the resulting thiol-yne elastomer composition by using triethylamine as said base catalyst and varying the polarity of said suitable solvent or solvent combination, w

Assignees

• Becker Matthew L
• Dove Andrew P
• Truong Vinh X
• Bell Craig A
• Barker Ian A
• Yu Jiayi
• Univ Akron

Inventors

• Becker Matthew L
• Dove Andrew P
• Truong Vinh X
• Bell Craig A
• Barker Ian A
• Yu Jiayi

Classifications

• C08F2/46

  Polymerisation initiated by wave energy or particle radiation · CPC title

• C08F2500/04

  Broad molecular weight distribution, i.e. Mw/Mn > 6 · CPC title

• C08F238/00 Primary

  Copolymers of compounds having one or more carbon-to-carbon triple bonds · CPC title

• C08F2500/21

  Rubbery or elastomeric properties · CPC title

• C08F2500/01

  High molecular weight, e.g. >800,000 Da. · CPC title