Functionalized poly(aryl ether sulfones) copolymers

Patent metadata

Field	Value
Publication number	US-12157797-B2
Application number	US-202017437457-A
Country	US
Kind code	B2
Filing date	Mar 12, 2020
Priority date	Mar 18, 2019
Publication date	Dec 3, 2024
Grant date	Dec 3, 2024

Abstract

The invention relates to a side-chain functionalized copolymer (P1) and to the process for preparing the side-chain functionalized copolymer (P1). The present invention also relates to the use of the copolymer (P1) in the preparation of a membrane, a composite material or a coating.

First claim

The invention claimed is:

1. A copolymer (P1) comprising:
recurring units (R P1 ) of formula (M):

recurring units (R* P1 ) of formula (N):

wherein
each R 1 is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;
each i is independently selected from 0 to 4;
T is selected from the group consisting of a bond, —CH 2 —; —O—; —SO 2 —; —S—; —C(O)—; —C(CH 3 ) 2 —; —C(CF 3 ) 2 —; —C(═CCl 2 )—; —C(CH 3 )(CH 2 CH 2 COOH)—; —N═N—; —R a C═CR b —, where each R a and R b , independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; —(CH 2 ) m — and —(CF 2 ) m — with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof;
G N is selected from the group consisting of at least one of the following formulas formulae:

each k is independently selected from 0 to 4;
each j is independently selected from 3 to 7;
each R 2 is independently selected from the group consisting of:
(CH 2 ) u —COOH, with u being selected from 1 to 5,
(CH 2 ) k —OH, with k being selected from 1 to 5,
(CH 2 ) p —NR a R b , with p being selected from 1 to 5, and R a and R b being independently a C1-C6 alkyl or H, with the proviso that R a and R b are not both CH 3 ,
(CH 2 )q-SO 3 Na, with q being selected from 1 to 5,
(CH 2 )a-COCH 3 , with a being selected from 0 to 10
(CH 2 )r-Si(OCH 3 ) 3 , with r being selected from 1 to 5,
(CH 2 )s-(CF 2 )t-CF 3 , with s being selected from 1 to 5 and t being selected from 1 to 10,
CO—R c , with R c being a C1-C6 alkyl or H,
(CH 2 )v-CH 3 , with v being selected from 5 to 30, and
(CH 2 )w-Ar, with w being selected from 1 to 10 and Ar comprising one or two aromatic or heteroaromatic rings.

2. The copolymer (P1) of claim 1 , wherein T in recurring units (R P1 ) is selected from the group consisting of a bond, —SO 2 — and —C(CH 3 ) 2 —.

3. The copolymer (P1) of claim 1 , wherein i is zero for each R 1 of recurring units (R P1 ) and recurring units (R* P1 ).

4. The copolymer (P1) of claim 1 , wherein k is 0 and j is 3 in recurring units (R* P1 ).

5. The copolymer (P1) of claim 1 , wherein the molar ratio of recurring units (R P1 )/recurring units (R* P1 ) varies between 0.01/100 and 100/0.01.

6. The copolymer (P1) of claim 1 , wherein recurring units (R P1 ) are according to formula (M1):

7. The copolymer (P1) of claim 1 , wherein R 2 in formulae (G N1 ), (G N2 ), (G N3 ), (G N4 ), (G N5 ) or (G N6 ) is independently selected from the group consisting of:
CH 2 —COOH,
(CH 2 ) 2 —OH,
(CH 2 ) 2 —NH 2 ,
(CH 2 ) 3 —SO 3 Na,
(CH 2 ) 3 —Si(OCH 3 ) 3 ,
(CH 2 ) 2 —(CF 2 ) 7 —CF 3 ,
C═O—H,
(CH 2 ) 9 —CH 3 ,
CH 2 -Ph, with Ph being benzene.

8. The copolymer (P1) of claim 1 , comprising collectively at least 50 mol. % of recurring units (R P1 ) and (R* P1 ), based on the total number of moles in the copolymer (P1).

9. A process for preparing copolymer (P1) comprising reacting in a solvent a copolymer (P0) comprising:
recurring units (R P0 ) of formula (M):

recurring units (R* P0 ) of formula (P):

wherein
each R 1 is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;
each i is independently selected from 0 to 4;
T is selected from the group consisting of a bond, —CH 2 —; —O—; —SO 2 —; —S—; —C(O)—; —C(CH 3 ) 2 —; —C(CF 3 ) 2 —; —C(═CCl 2 )—; —C(CH 3 )(CH 2 CH 2 COOH)—; —N═N—; —R a C═CR b —, where each R a and R b , independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; —(CH 2 ) m — and —(CF 2 ) m — with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof,
G P is selected from the group consisting of at least one of the following formulae:

each k is independently selected from 0 to 4, with a compound of formula (I): R 2 —SH

wherein R 2 is selected from the group consisting of:
(CH 2 )u-COOH, with u being selected from 1 to 5,
(CH 2 )k-OH, with k being selected from 1 to 5,
(CH 2 )p-NR a R b , with p being selected from 1 to 5, and R a and R b being independently a C1-C6 alkyl or H, with the proviso that R a and R b cannot be are not both CH 3 ,
(CH 2 )q-SO 3 Na, with q being selected from 1 to 5,
(CH 2 )a-COCH 3 , with a being selected from 0 to 10
(CH 2 )r-Si(OCH 3 ) 3 , with r being selected from 1 to 5,
(CH 2 )s-(CF 2 )t-CF 3 , with s being selected from 1 to 5 and t being selected from 1 to 10,
CO—R c , with R c being a C1-C6 alkyl or H,
(CH 2 )v-CH 3 , with v being selected from 5 to 30, and
(CH 2 )w-Ar, with w being selected from 1 to 10 and Ar comprising one or two aromatic or heteroaromatic rings,

wherein the molar ratio of compound (I)/polymer (P0) varies between 0.01/100 and 100/0.01, at a temperature ranging from 10° C. and 300° C.

10. The process of claim 9 , being carried out in a solvent selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, N,N-dimethylformamide (DMF), N,N dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene, anisole, chloroform, dichloromethane (DCM) and sulfolane.

11. The process of claim 9 , being carried out in the presence of:
at least one free radical initiator, and/or
at least one catalyst.

12. The process of claim 9 , being carried out in the presence of a base.

13. The process of claim 9 , being carried out by exposing the reaction mixture to UV light at a wavelength ranging from 300 nm to 600 nm.

14. The process of claim 9 , wherein the functionalized PAES copolymer (P0) comprises collectively at least 50 mol. % of recurring units (R P0 ) and (R* P0 ), based on the total number of moles in the copolymer (P0).

15. The process of claim 9 , wherein the functionalized PAES copolymer (P0) is prepared by condensation of at least one aromatic dihydroxy monomer (a1), with at least one aromatic sulfone monomer (a2) comprising at least two halogen substituents at at least one allyl-substituted aromatic dihydroxy monomer (a3).

Assignees

• Solvay Specialty Polymers Usa

Inventors

• Nair Kamlesh
• Thomas David B

Classifications

• C08J2381/06

  Polysulfones; Polyethersulfones · CPC title

• C08J5/18

  Manufacture of films or sheets · CPC title

• C08G75/23 Primary

  Polyethersulfones · CPC title

• C08G65/4087

  characterised by the catalyst used · CPC title

• C08G65/40

  from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group · CPC title