Functionalized poly(aryl ether sulfones) copolymers and polymer adducts obtained therefrom
The present invention relates to copolymers comprising moieties able to undergo a crosslinking reaction under certain stimuli, thereby forming polymer adducts having improved or additional properties, such as resistance to solvents, increased thermal performance and increased adhesion to surfaces.
1 . A polymer adduct obtained by crosslinking a copolymer (P1) comprising:
recurring units (R P1 ) of formula (M):
recurring units (R* P1 ) of formula (N):
wherein
G N is selected from the group consisting of at least one of the following formulas:
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;
R 2 is —(CH 2 )r-Si(OCH 3 ) 3 , with r being selected from 1 to 5;
R 3 is an alkyl group, an aryl group or an halogen group;
each k is independently selected from 0 to 4;
each j is independently selected from 3 to 7; and
T and Q are independently selected from the group consisting of a bond, —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.
2 . The polymer adduct of claim 1 , wherein T in the recurring units (R P1 ) is selected from the group consisting of a bond, —SO 2 — and —C(CH 3 ) 2 —.
3 . The polymer adduct of claim 1 , wherein Q in the formulas (G N1 ), (G N2 ) and/or (G N3 ) of the recurring units (R* P1 ) is selected from the group consisting of a bond, —SO 2 — and —C(CH 3 )= 2 —.
4 . The polymer adduct of claim 1 , wherein i is zero for each R 1 of the recurring units (R P1 ) and the recurring units (R* P1 ) of the copolymer (P1).
5 . The polymer adduct of claim 1 , wherein k is 0 and j is 3 in the recurring units (R* P1 ).
6 . The polymer adduct of claim 1 , wherein the molar ratio of the recurring units (R P1 )/recurring units (R* P1 ) varies between 0.01/100 and 100/0.01.
7 . The polymer adduct of claim 1 , wherein the recurring units (R P1 ) are according to formula (M1):
8 . The polymer adduct of claim 1 , wherein R 2 in the recurring units (R* P1 ) of the copolymer (P1) is —(CH 2 ) 3 —Si(OCH 3 ) 3 .
9 . The polymer adduct of claim 1 , comprising collectively at least 50 mol. % of the recurring units (R P1 ) and (R* P1 ), based on the total number of moles in the copolymer (P1).
10 . The polymer adduct of claim 1 , wherein crosslinking of the copolymer (P1) is obtained by at least one of the following:
heating at a temperature ranging from 60° C. to 250° C.,
exposing to acid/basic conditions, respectively to a pH <5 or a pH >9, and/or
exposing to humidity with a humidity percentage of a least 30%.
11 . A method for coating a surface, comprising:
a) applying to the surface a copolymer (P1), optionally in combination with one or more solvents and/or additives, and
b) heating the surface at a temperature ranging from 60° C. to 250° C., and/or exposing the surface to humidity with a humidity percentage of a least 30%, wherein the copolymer (P1) comprises:
recurring units (R P1 ) of formula (M):
recurring units (R* P1 ) of formula (N):
wherein
G N is selected from the group consisting of at least one of the following formulas:
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;
R 2 is —(CH 2 )r-Si(OCH 3 ) 3 , with r being selected from 1 to 5;
R 3 is an alkyl group, an aryl group or an halogen group;
each k is independently selected from 0 to 4;
each j is independently selected from 3 to 7; and
T and Q are independently selected from the group consisting of a bond, —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.
12 . A method for preparing the adduct of claim 1 , said adduct being used as a coating, as an additive in a composite material to improve binding between a filler and a polymeric matrix or as a self-crosslinkable resin to prepare composite products, said method comprising crosslinking the copolymer (P1).
13 . A method for improving compatibility between a resin and sized fibers, comprising using a polymer (P1) in a sizing formulation comprising the resin and the sized fibers and heating the sized fibers and/or exposing the sized fibers to humidity with a humidity percentage of a least 30%,
wherein the copolymer (P1) comprises:
recurring units (R P1 ) of formula (M):
recurring units (R* P1 ) of formula (N):
wherein
G N is selected from the group consisting of at least one of the following formulas:
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;
R 2 is —(CH 2 )r-Si(OCH 3 ) 3 , with r being selected from 1 to 5;
R 3 is an alkyl group, an aryl group or an halogen group;
each k is independently selected from 0 to 4;
each j is independently selected from 3 to 7; and
T and Q are independently selected from the group consisting of a bond, —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.
14 . The method of claim 13 , comprising reacting the copolymer (P1) with a sizing agent located at the surface of the sized fibers.
15 . The method for preparing the adduct of claim 12 , wherein the crosslinking of the copolymer (P1) is obtained by at least one of the following:
heating at a temperature ranging from 60° C. to 250° C.,
exposing to acid/basic conditions, respectively to a pH <5 or a pH >9, and/or
exposing to humidity with a humidity percentage of a least 30%.
16 . The polymer adduct of claim 1 , being used as a coating, as an additive in a composite material to improve binding between filler and a polymeric matrix, or as a self-crosslinkable resin to prepare composite products.
17 . The polymer adduct of claim 1 , wherein the molar ratio of the recurring units (R P1 )/recurring units (R* P1 ) varies between 1/1 and 12/1.