Self-assembling polymers—III

Patent metadata

Field	Value
Publication number	US-9328206-B2
Application number	US-201414292722-A
Country	US
Kind code	B2
Filing date	May 30, 2014
Priority date	May 30, 2014
Publication date	May 3, 2016
Grant date	May 3, 2016

Abstract

Disclosed are self-assembling diblock copolymers of the formula (I):

wherein R 1 is —(CHR—CH 2 —O) p —R′, p=2-6, R is H or methyl, and R′ is H, C 1 -C 6 alkyl, or C 3 -C 11 cycloalkyl, R 2 is C 6 -C 20 aryl, one of R 3 and R 4 is C 6 -C 14 aryl or heteroaryl, and the other is C 1 -C 22 alkoxy, and n and m are independently 2 to about 2000, which find use in preparing self-assembled structures and porous membranes. Embodiments of the self-assembled structures contain the diblock copolymer in a cylindrical morphology. Also disclosed is a method of preparing such copolymers.

First claim

The invention claimed is:

1. A diblock copolymer of the formula (I):

wherein:
R 1 is a poly(alkyleneoxide) group of the formula, —(CHR—CH 2 —O) p —R′, wherein p=3-6, R is H or methyl, and R′ is H, a C 1 -C 6 alkyl group, or a C 3 -C 11 cycloalkyl group;
R 2 is a C 6 -C 20 aryl group, optionally substituted with a substituent selected from halo, alkoxy, alkylcarbonyl, alkoxycarbonyl, amido, and nitro;
one of R 3 and R 4 is a C 6 -C 14 aryl group or a heteroaryl group, optionally substituted with a substituent selected from hydroxy, halo, amino, and nitro, and the other of R 3 and R 4 is a C 1 -C 22 alkoxy group, optionally substituted with a substituent selected from carboxy, amino, mercapto, alkynyl, alkenyl, halo, azido, and heterocyclyl; and
n and m are independently 2 to about 2000.

2. The diblock copolymer of claim 1 , wherein R is H.

3. The diblock copolymer of claim 1 , wherein R′ is a C 1 -C 6 alkyl group.

4. The diblock copolymer of claim 1 , wherein R′ is methyl.

5. The diblock copolymer of claim 1 , wherein R 2 is a C 6 -C 10 aryl group, optionally substituted with a substituent selected from halo, alkoxy, alkylcarbonyl, alkoxycarbonyl, amido, and nitro.

6. The diblock copolymer of claim 1 , wherein R 2 is a phenyl group, optionally substituted with a substituent selected from halo, alkoxy, alkylcarbonyl, alkoxycarbonyl, amido, and nitro.

7. The diblock copolymer of claim 1 , wherein R 2 is phenyl.

8. The diblock copolymer of claim 1 , wherein R 3 is phenyl.

9. The diblock copolymer of claim 1 , wherein R 4 is a C 1 -C 6 alkoxy group.

10. The diblock copolymer of claim 1 , wherein n is about 30 to about 350 and m is about 150 to about 1775.

11. The diblock copolymer of claim 1 , wherein n is about 70 to about 200.

12. The diblock copolymer of claim 1 , wherein m is about 350 to about 1000.

13. The diblock copolymer of claim 1 , which has the following structure:

14. A method of preparing a diblock copolymer of claim 1 , comprising:
(i) polymerizing one of the two monomers of the formulas:

with a ring opening metathesis polymerization (ROMP) catalyst to obtain a ring-opened polymer having a living chain end;
(ii) polymerizing the other of the two monomers on the living end of the ring-opened polymer obtained in (i) to obtain a diblock copolymer having a living end; and
(iii) terminating the living end of the diblock copolymer obtained in (ii) with an optionally substituted alkyl vinyl ether.

15. The method of claim 14 , wherein the ROMP catalyst is of the formula:

16. A self-assembled structure comprising a diblock copolymer of claim 1 .

17. A porous membrane prepared from the self-assembled structure of claim 16 .

18. A diblock copolymer of the formula (I):

wherein:
R 1 is a poly(alkyleneoxide) group of the formula, —(CHR—CH 2 —O) p —R′, wherein p=2-6, R is H or methyl, and R′ is a C 1 -C 6 alkyl group or a C 3 -C 11 cycloalkyl group;
R 2 is a C 6 -C 20 aryl group, optionally substituted with a substituent selected from halo, alkoxy, alkylcarbonyl, alkoxycarbonyl, amido, and nitro;
one of R 3 and R 4 is a C 6 -C 14 aryl group or a heteroaryl group, optionally substituted with a substituent selected from hydroxy, halo, amino, and nitro, and the other of R 3 and R 4 is a C 1 -C 22 alkoxy group, optionally substituted with a substituent selected from carboxy, amino, mercapto, alkynyl, alkenyl, halo, azido, and heterocyclyl; and
n and m are independently 2 to about 2000.

19. A self-assembled structure comprising a diblock copolymer of claim 18 .

20. A method of preparing a diblock copolymer of claim 18 , comprising:
(i) polymerizing one of the two monomers of the formulas:

with a ring opening metathesis polymerization (ROMP) catalyst to obtain a ring-opened polymer having a living chain end;
(ii) polymerizing the other of the two monomers on the living end of the ring-opened polymer obtained in (i) to obtain a diblock copolymer having a living end; and
(iii) terminating the living end of the diblock copolymer obtained in (ii) with an optionally substituted alkyl vinyl ether.

Assignees

• Pall Corp

Inventors

• Aamer Khaled Abdel-Hakim Helmy

Classifications

• C08G61/12 Primary

  Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule · CPC title

• C08G2261/126

  block · CPC title

• C08G61/125

  with a five-membered ring containing one oxygen atom in the ring · CPC title

• C08G2261/1424

  containing ether groups, including alkoxy · CPC title

• C08F293/00

  Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule (on to polymers modified by introduction of unsaturated end groups C08F290/02) · CPC title