Method for cross-linking polymers

Patent metadata

Field	Value
Publication number	US-11059922-B2
Application number	US-201716345674-A
Country	US
Kind code	B2
Filing date	Oct 17, 2017
Priority date	Oct 28, 2016
Publication date	Jul 13, 2021
Grant date	Jul 13, 2021

Abstract

The invention relates to a method for manufacturing a cross-linked polymer comprising reacting at least one polymer having at least one —SO2X group, with X being F or Cl, a basic compound, and certain salts including a ring-quaternized pyridinium-type nitrogen, and possessing at least two groups in ortho or para position thereto comprising reactive hydrogen atoms; cross-linking has been proven to proceed effectively, delivering cross-linked polymers possessing improved chemical resistance and mechanical performances.

First claim

The invention claimed is:

1. A method for manufacturing a cross-linked polymer (XPL), said method comprising reacting:
at least one polymer (I) wherein polymer (I) is a polymer comprising at least one —SO 2 X group, with X being F or Cl;
at least one base (B), wherein base (B) is at least one basic compound;
at least one pyridinium salt (P) complying with any of formulae (P-1) to (P-12):

wherein:
each of J and J′, equal to or different from each other, is independently at each occurrence C—R* or N, wherein R* is H or a C 1 -C 12 hydrocarbon group;
E is N or a group of formula C—R o H;
Z is a divalent hydrocarbon group comprising from 1 to 12 carbon atoms;
W is a bond or is a bridging group selected from the group consisting of divalent hydrocarbon groups comprising from 1 to 12 carbon atoms and divalent fluorocarbon groups comprising from 1 to 12 carbon atoms;
the group sketched with symbol:

in formula (P-11) and (P-12) designates an aromatic mono- or poly-nuclear ring condensed to the pyridinium-type aromatic ring, which may comprise one or more additional nitrogen atoms, optionally quaternized nitrogen atoms, in the ring(s);
each of R 1 H , R 2 H , R 3 H , R 4 H , R 5 H , R 6 H , R 7 H , R 8 H , R 9 H , R 10 H , R 11 H , R 12 H , R 13 H , R 14 H , R 15 H , R 16 H , R 17 H , R 18 H , R 19 H , R 20 H , R 21 H , R 22 H , R 23 H , R 24 H , R 25 H , R 26 H , R 27 H , R 28 H , R 29 H , R 30 H , R 31 H , R 32 H , R 33 H , R 34 H , R 35 H , R 36 H , R o H , equal to or different from each other, is independently at each occurrence —H or group (alpha-H), wherein group (alpha-H) is a
group of formula:

wherein R a , and R b equal to or different from each other, are independently H or a hydrocarbon C 1 -C 6 group;
Y, equal to or different from each other, is independently oxygen or a C 1 -C 12 hydrocarbon group, optionally comprising one or more than one heteroatoms selected from N, O, S and halogens;
A (m-) is an anion having valency m; with the provisio that
(i) when salt (P) is of formula (P-1) at least two of R 1 x, R 2 H , and R o H are groups (alpha-H);
(ii) when salt (P) is of formula (P-2) R 3 H and R 4 H are groups (alpha-H);
(iii) when salt (P) is of formula (P-3), at least two of R 5 H , R 6 H , R 7 H , and R 8 H are groups (alpha-H);
(iv) when salt (P) is of formula (P-4), at least two of R 9 H , R 10 H , R 11 H , R 12 H , and R o H are groups (alpha-H);
(v) when salt (P) is of formula (P-5), at least two of R 13 H , R 14 H , and R o H are groups (alpha-H);
(vi) when salt (P) is of formula (P-6), at least two of R 15 H , R 16 H , R 17 H , and R o H are groups (alpha-H);
(vii) when salt (P) is of formula (P-7), at least two of R 18 H , R 19 H , R 20 H , R 21 H , and R o H are groups (alpha-H);
(viii) when salt (P) is of formula (P-8), at least two of R 22 H , R 23 H , R 24 H , and R o H are groups (alpha-H);
(ix) when salt (P) is of formula (P-9), at least two of R 25 H , R 26 H , R 27 H , and R 28 H are groups (alpha-H);
(x) when salt (P) is of formula (P-10), at least two of R 29 H , R 30 H , R 31 H , R 32 H , and R 28 H are groups (alpha-H);
(xi) when salt (P) is of formula (P-11), at least two of R 33 H , R 34 H , and R 28 H are groups (alpha-H);
(xii) when salt (P) is of formula (P-12), at least two of R 35 H , R 36 H and R o H are groups (alpha-H);
wherein reacting the at least one polymer (I), at least one base (B), and at least one pyridinium salt (P) reacts at the at least one —SO 2 X group and the at least one pyridinium salt, thereby resulting in formation of a bridging group.

2. The method of claim 1 , wherein the amount of said —SO 2 X groups in polymer (I) is at least 0.01 meq/g.

3. The method of claim 2 , wherein the amount of said —SO 2 X groups in polymer (I) is at least 0.1 meq/g.

4. The method of claim 1 , wherein polymer (I) is selected from the group consisting of polymers comprising recurring units derived from at least one monomer (A) wherein monomer (A) is at least one ethylenically unsaturated fluorinated monomer containing at least one —SO 2 X group, with X being F or Cl; and recurring units derived from at least one monomer (B) wherein monomer (B) is at least one ethylenically unsaturated fluorinated monomer free from —SO 2 X group.

5. The method of claim 4 , wherein monomer (A) is selected from the group consisting of:
sulfonyl halide fluoroolefins of formula: CF 2 ═CF(CF 2 ) p SO 2 X, with X being F or Cl, wherein p is an integer between 0 and 10;
sulfonyl halide fluorovinylethers of formula: CF 2 ═CF—O—(CF 2 ) m SO 2 X, with X being F or Cl, wherein m is an integer between 1 and 10;
sulfonyl fluoride fluoroalkoxyvinylethers of formula: CF 2 ═CF—(OCF 2 CF(R F1 )) w —O—CF 2 (CF(RF 2 )) y SO 2 X with X being F or Cl, wherein w is an integer between 0 and 2, R F1 and R F2 , equal or different from each other, are independently F, Cl or a C 1 -C 10 fluoroalkyl group, optionally substituted with one or more ether oxygens, and y is an integer between 0 and 6; and
sulfonyl halide aromatic fluoroolefins of formula CF 2 ═CF—Ar—SO 2 X with X being F or Cl, wherein Ar is a C 5 -C 15 aromatic or heteroaromatic group;
and/or wherein monomer (B) is selected from the group consisting of:
C 2 -C 8 perfluoroolefins;
C 2 -C 8 hydrogen-containing fluoroolefins;
C 2 -C 8 chloro- and/or bromo- and/or iodo-containing fluoroolefins;
fluoroalkylvinylethers of formula CF 2 ═CFOR f1 , wherein R f1 is a C 1 -C 6 fluoroalkyl;
fluoro-oxyalkylvinylethers of formula CF 2 ═CFOR O1 , wherein R O1 is a C 1 -C 12 fluoro-oxyalkyl having one or more ether groups;
fluoroalkyl-methoxy-vinylethers of formula CF 2 ═CFOCF 2 OR f2 in which R f2 is a C 1 -C 6 fluoroalkyl, or a C 1 -C 6 fluorooxyalkyl having one or more ether groups;
fluorodioxoles of formula:

wherein each of R f3 , R f4 , R f5 , R f6 , equal or different each other, is independently a fluorine atom or a C 1 -C 6 fluoro(halo)fluoroalkyl, optionally comprising one or more oxygen atom.

6. The method of claim 5 , wherein polymer (I) is selected from fluorinated polymers consisting essentially of:
(1) recurring units derived from tetrafluoroethylene (TFE), in an amount of 25 to 99.9% moles, with respect to total moles of polymer (I);
(2) recurring units derived from at least one —SO 2 X groups-containing monomer selected from the group consisting of:
(j) sulfonyl halide fluorovinylethers of formula: CF 2 ═CF—O—(CF 2 ) m SO 2 X, with X being F or Cl, wherein m is an integer between 1 and 10;
(jj) sulfonyl fluoride fluoroalkoxyvinylethers of formula: CF 2 ═CF—(OCF 2 CF(R F1 )) w —O—CF 2 (CF(RF 2 )) y SO 2 X with X being For Cl, wherein w is an integer between 0 and 2, R F1 and R F2 , equal or different from each other, are independently F, Cl or a C 1 -C 10 fluoroalkyl group, optionally substituted with one or more ether oxygens, y is an integer between 0 and 6; and
(jjj) mixtures thereof;
in an amoun

Assignees

• Solvay Specialty Polymers It

Inventors

• Bossolo Stefano
• Oldani Claudio
• Manzoni Claudia

Classifications

• C08K2003/222

  Magnesia, i.e. magnesium oxide · CPC title

• C08F214/262

  with fluorinated vinyl ethers · CPC title

• C08K3/22

  of metals · CPC title

• C08F2800/20

  as weight or mass percentages · CPC title

• C08F8/30 Primary

  Introducing nitrogen atoms or nitrogen-containing groups · CPC title