Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine

1. A process for preparation of a homopolymer having the structure of formula (I):

wherein

is a repeating group of the polymer;

X is NH or O;

R is independently selected from the group consisting of H and C 1-20 alkyl;

R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of H, —C 3-1002 alkyl, —C 1-20 alkyl-OH, and

wherein each —C 3-1002 alkyl and —C 1-20 alkyl-OH, can be optionally substituted 1-4 times with a substituent independently selected at each occurrence thereof from the group consisting of H, —OH, —SO 3 R 5 , —P(O)(OR 5 ) 2 , —N(R 5 ) 2 , —N(R 5 ) 3 + Hal − , and

with the proviso that at least one of R 1 , R 2 , R 3 , or R 4 is not hydrogen;

A and I are independently selected from the group consisting of *-,

H, —Si(R 6 ) 3 , C 1-20 alkyl,

B, C, D, E, F, G, and H are independently selected from the group consisting of a bond, C, O, Si, N, or U;

R 5 is independently selected at each occurrence thereof from the group consisting of H, C 1-6 alkyl, and halogen;

R 6 is optional, and if present, is independently selected at each occurrence thereof from the group consisting of *-, H, OH, halogen, C 1-6 alkyl, —CN, and phenyl, wherein each phenyl and C 1-6 alkyl can be optionally substituted 1-4 times with a substituent independently selected at each occurrence thereof from the group consisting of H, —OH, halogen, —CN, —N(R 7 ) 2 , —C(O)R 7 , and —C(O)—X—CH 2 —(CH 2 ) s —XR 7 ;

R 7 is independently selected at each occurrence thereof from the group consisting of H, C 1-6 alkyl, and

U is optional and, if present, is —(S) p —;

*- is a point of attachment to formula (I) or R 1 , R 2 , R 3 , or R 4 ;

is a terminal group of the polymer;

a is 1-1,000,000;

b is 1-1,000,000;

c is 1-1,000,000;

d is 1-1,000,000;

e is 1-1,000,000;

m is 0 to 1,000,000;

n is 0 to 10;

p is 1 to 8;

s is 1 to 50;

z is 45.8 to 10,000,000;

or a salt thereof,

said process comprising:

providing a first intermediate polymeric compound comprising a repeating group having the structure of formula (II):

wherein each is independently a single or a double bond with no adjacent double bonds, and

wherein at least one is a double bond; and

forming the homopolymer having the structure of formula (I) from the first intermediate polymeric compound comprising a repeating group having the structure of formula (II).

2. The process according to claim 1 further comprising:

providing a second intermediate compound of formula (III):

wherein each is independently a single or a double bond with no adjacent double bonds, and

wherein at least one is a double bond; and

forming the first intermediate polymeric compound from the second intermediate compound.

3. The process according to claim 2 , wherein the second intermediate compound of formula (III) is provided as a blend of hexenedioic acid (HDA)/adipic acid.

4. The process according to claim 2 further comprising:

providing muconic acid and

forming the second intermediate compound from the muconic acid.

5. The process according to claim 4 , wherein said forming is carried out by electrocatalytic hydrogenation of the muconic acid.

6. The process according to claim 4 further comprising:

providing glucose and

forming muconic acid from the glucose.

7. The process according to claim 6 , wherein said forming is carried out by fermenting the glucose.

8. The process according to claim 1 , wherein R 1 , R 2 , R 3 , or R 4 is

and k is 1 to 1,000,000.

9. The process according to claim 1 , wherein R 1 , R 2 , R 3 , or R 4 is

and m is 1 to 999,999.

10. The process according to claim 1 , wherein R 1 , R 2 , R 3 , or R 4 is

and m is 1 to 1,000,000.

11. The process according to claim 1 , wherein the repeating group of the polymer has the structure of formula (Ia):

s is 1-50, and k is 1 to 1,000,000.

12. The process according to claim 1 , wherein the repeating group of the polymer has the structure of formula (Ie):

and s is 1-50.

13. The process according to claim 1 , wherein the repeating group of the polymer has the structure of formula (If):

s is 1-50, and t is 2-1000.

14. The process according to claim 1 , wherein the repeating group of the polymer has the structure of formula (Ig):

s is 1-50, and m is 2-1000.

15. The process according to claim 1 , wherein the repeating group of the polymer has the structure of formula (Ih):

s is 1-50, and m is 2-1000.

16. A process for preparation of a polymer comprising a repeating group having the structure of formula (I′):

wherein

X is NH or O;

R is independently selected from the group consisting of H and C 1-20 alkyl;

R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of H, —C 3-1002 alkyl, —C 1-20 alkyl-OH, and

wherein each —C 3-1002 alkyl and —C 1-20 alkyl-OH, can be optionally substituted 1-4 times with a substituent independently selected at each occurrence thereof from the group consisting of H, —OH, —SO 3 R 5 , —P(O)(OR 5 ) 2 , —N(R 5 ) 2 , —N(R 5 ) 3 + Hal − , and

with the proviso that at least one of R 1 , R 2 , R 3 , or R 4 is not hydrogen;

A and I are independently selected from the group consisting of *-,

H, —Si(R 6 ) 3 , C 1-20 alkyl

B, C, D, E, F, G, and H are independently selected from the group consisting of a bond, C, O, Si, N, or U;

R 5 is independently selected at each occurrence thereof from the group consisting of H, C 1-6 alkyl, and halogen;

R 6 is optional, and if present, is independently selected at each occurrence thereof from the group consisting of *-, H, OH, halogen, C 1-6 alkyl, —CN, and phenyl, wherein each phenyl and C 1-6 alkyl can be optionally substituted 1-4 times with a substituent independently selected at each occurrence thereof from the group consisting of H, —OH, halogen, —CN, —N(R 7 ) 2 , —C(O)R 7 , and —C(O)—X—CH 2 —(CH 2 ) s —XR 7 ;

R 7 is independently selected at each occurrence thereof from the group consisting of H, C 1-6 alkyl, and

U is optional and, if present, is —(S) p —;

*- is a point of attachment to formula (I) or R 1 , R 2 , R 3 , or R 4 ;

is a terminal group of the polymer;

a is 1-1,000,000;

b is 1-1,000,000;

c is 1-1,000,000;

d is 1-1,000,000;

e is 1-1,000,000;

m is 0 to 1,000,000;

n is 0 to 10;

p is 1 to 8;

s is 1 to 50;

or a salt thereof,

said process comprising:

providing muconic acid;

forming, from the muconic acid, a second intermediate compound of formula (III):

wherein each is independently a single or a double bond with no adjacent double bonds, and

wherein at least one is a double bond;

forming, from the second intermediate compound, a first intermediate polymeric compound comprising a repeating group having the structure of formula (II):

and

forming the polymer comprising a repeating group having the structure of formula (I′) from the first intermediate polymeric compound comprising a repeating group having the structure of formula (II).

17. The process according to claim 16 , wherein the polymer has 2-10,000,000 repeating groups with the structure of formula (I′).

18. The process according to claim 16 , wherein the second intermediate compound of formula (III) is provided as a blend of hexenedioic acid (HDA)/adipic acid.

19. The process according to claim 16 , wherein said forming the second intermediate compound of formula (III) is carried out by electrocatalytic hydrogenation of the muconic acid.

20. The process according to claim 16 further comprising:

providing glucose and

forming muconic acid from the glucose.

21. The process according to claim 20 , wherein said forming is carried out by fermenting the glucose.

22. The process according to claim 16 , wherein R 1 , R 2 , R 3 , or R 4 is

and k is 1 to 1,000,000.

23. The process according to claim 16 , wherein R 1 , R 2 , R 3 , or R 4 is

and m is 1 to 999,999.

24. The process according to claim 16 , wherein R 1 , R 2 , R 3 , or R 4 is

and m is 1 to 1,000,000.

25. The process according to claim 16 , wherein the repeating group has the structure of formula (I′a):

s is 1-50, and k is 1 to 1,000,000.

26. The process according to claim 16 , wherein the repeating group has the structure of formula (I′e):

and s is 1-50.

27. The process according to claim 16 , wherein the repeating group has the structure of formula (I′f):

s is 1-50, and t is 2-1000.

28. The process according to claim 16 , wherein the repeating group has the structure of formula (I′g):

s is 1-50, and m is 2-1000.

29. The process according to claim 16 , wherein the repeating group has the structure of formula (I′h):

s is 1-50, and m is 2-1000.

30. A process for preparation of a polymer comprising a repeating group having the structure of formula (I′e), (I′f), (I′g), or (I′h):

or a salt thereof

wherein

U is optional and, if present, is —(S) p —;

p is 1 to 8;

s is 1-50;

t is 2-1000; and

m is 2-1000,

said process comprising:

providing a first intermediate polymeric compound comprising a repeating group having the structure of formula (II):

wherein each is independently a single or a double bond with no adjacent double bonds, and

wherein at least one is a double bond;

X is NH;

R is independently selected from the group consisting of H and C 1-20 alkyl; and

forming the polymer comprising a repeating group having the structure of formula (I′e), (I′f), (I′g), or (I′h) from the first intermediate polymeric compound comprising a repeating group having the structure of formula (II).