Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine
The present invention relates to a polymer comprising a repeating group having the structure of formula (I) wherein R, R 1 , R 2 , R 3 , R 4 , X, and s are as described herein and salt thereof. Also disclosed is a process of synthesizing such polymers.
1. A polymer comprising a repeating group having the structure of formula (I):
wherein
X is NH;
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, —U—C 1-1002 alkyl, wherein each —U—C 1-1002 alkyl can be optionally substituted 1 time 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;
wherein R 1 , R 2 , R 3 , or R 4 is
A and I are independently selected from a point of attachment to formula (I) or R 1 , R 2 , R 3 , or R 4 or —Si(R 6 ) 3 ;
B, C, D, E, F, G, and H are independently selected from the group consisting of a bond, O, or Si;
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
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 1 to 999,999;
n is 0 to 10;
p is 1 to 8; and
s is 1 to 50;
or a salt thereof.
2. A polymer comprising a repeating group having the structure of formula (I):
wherein
X is NH;
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, —U—C 1-1002 alkyl, wherein each —U—C 1-1002 alkyl can be optionally substituted 1 time 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;
wherein R 1 , R 2 , R 3 , or R 4 is
A and I are independently selected from a point of attachment to formula (I) or R 1 , R 2 , R 3 , or R 4 or —Si(R 6 ) 3 ;
B, C, D, E, F, G, and H are independently selected from the group consisting of a bond, O, or Si;
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
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 1 to 999,999;
n is 0 to 10;
p is 1 to 8; and
s is 1 to 50;
or a salt thereof.
3. A polymer comprising a repeating group having the structure of formula (I):
wherein
X is NH;
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, —U—C 1-1002 alkyl, wherein each —U—C 1-1002 alkyl can be optionally substituted 1 time 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;
wherein R 1 , R 2 , R 3 , or R 4 is
A and I are independently selected from a point of attachment to formula (I) or R 1 , R 2 , R 3 , or R 4 or —Si(R 6 ) 3 ;
B, C, D, E, F, G, and H are independently selected from the group consisting of a bond, O, or Si;
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
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 2 to 1000;
n is 0 to 10;
p is 1 to 8; and
s is 1 to 50;
or a salt thereof.
4. A polymer comprising a repeating group having the structure of formula (Ig):
wherein
U is optional and, if present, is
is a terminal group of the polymer;
s is 1-50;
p is 1 to 8; and
m is 2-1000;
or a salt thereof.
5. A polymer comprising a repeating group having the structure of formula (Ig′):
wherein
U is optional and, if present, is
is a terminal group of the polymer;
s is 1-50;
p is 1 to 8; and
m is 2-1000;
or a salt thereof.