Nova Patents
EP4257638A2

Production method for fluoropolymer, surfactant for polymerization, and use of surfactant

Abstract

The invention aims to provide a novel method for producing a fluoropolymer. The method for producing a fluoropolymer of the invention includes polymerizing a fluoromonomer in an aqueous medium in the presence of a surfactant to provide a fluoropolymer. The surfactant includes at least one selected from the group consisting of a surfactant represented by R1a-CO-R2 a-CO-R3 a-Aa and a surfactant represented by R1b-CO-(CR2b2)n-(OR3b)p-(CR4b2)q-L-Ab.

EP4257638A2, drawing sheet 1
Sheet 1 of 115

Term

11.5 yearsto projected expiry

Projected expiry 30 March 2038, counted from filing; an application has no term until it is granted.

  1. Priority
  2. Filed
  3. Published
  4. Today
  5. Projected expiry

21 claims: 12 independent, 9 dependent

  1. 1
    A surfactant suitable for polymerization, comprising at least one of the compounds of the formulae (a) and (b):R 1a -C(=O)-R 2a -C(=O)-R 3a -A a (a) wherein R 1a is linear or branched C ≥1 -alkyl or C ≥3 -cycloalkyl, each optionally substituted by OH or a monovalent organic group which contains an ester bond and optionally contains a carbonyl group when containing ≥ 2 carbon atoms and optionally contains a monovalent or divalent heterocycle or optionally forms a ring when containing ≥ 3 carbon atoms;R 2a is a single bond or a divalent linking group;R 3a is a single bond or a divalent linking group;R 1a -R 3a contain ≥ 5 carbon atoms in total;and any two of R 1a -R 3a optionally bind to each other to form a ring;and A a is -COOX a or -SO 3 X a , wherein X a is H, a metal atom, NR 4a 4 wherein R 4a each independently is H or an organic group, or imidazolium, pyridinium or phosphonium each optionally substituted;R 1b -C(=O)-(CR 2b 2 ) n -(OR 3b ) p -(CR 4b 2 ) q -L-A b (b) wherein R 1b is -optionally substituted linear or branched C ≥1 -alkyl or optionally substituted C ≥3 -cycloalkyl, and optionally contains a monovalent or divalent heterocycle or optionally forms a ring when containing ≥ 3 carbon atoms;R 2b each individually is H or a substituent;n is an integer of ≥ 1;R 3b is optionally substituted C 1-10 -alkylene;q is an integer of ≥ 0;R 4b each individually is H or a substituent;p is an integer of ≥ 0;and any two of R 1b - R 4b optionally bind to each other to form a ring;and L is a single bond, -CO 2 -B-*, -OCO-B-*, -CONR 6b -B-*,-NR 6b CO-B-*, or -CO- other than the carbonyl groups in -CO 2 -B-, -OCO-B-, -CONR 6b -B-, and -NR 6b CO-B-, where B is a single bond or optionally substituted C1-10-alkylene, R 6b is H or optionally substituted C1-4-alkyl, and * indicates the bond to -A b ;and A b is -SO 3 X b or -COOX b , wherein X b is H, a metal atom, NR 5b 4 wherein R 4a each independently is H or an organic group, or imidazolium, pyridinium or phosphonium each optionally substituted.
  2. 4
    The surfactant of any of claims 1-3, wherein X a is NH 4 .
  3. 5
    The surfactant of any of claims 1-4, wherein ( n + p + q ) ≥ 6.
  4. 6
    The surfactant of any of claims 1-5, wherein R 1b is methyl.
  5. 7
    The surfactant of any of claims 1-6, wherein X b is a metal atom or NR 5b 4 .
  6. 8
    The surfactant of any of claims 1-7, which has a 1 H-NMR spectrum in which all peak intensities observed in a chemical shift range of 2.0-5.0 ppm give an integral of ≥ 10%.
  7. 9
    A method for producing a fluoropolymer comprising polymerizing a fluoromonomer in an aqueous medium in the presence of at least one surfactant as defined in any of claims 1-8.
  8. 10
    Use of the surfactant of any of claims 1-8 for production of a fluoropolymer by polymerizing a fluoromonomer in an aqueous medium,
  9. 11
    A composition comprising a fluoropolymer, and at least one surfactant of any of claims 1-8.
  10. 12
    A composition comprising a fluoropolymer and being substantially free from a compound of formula (3):H-(CF 2 ) 8 -SO 3 ) q M 2      (3) , wherein M 2 is H, a metal atom, NR 5 4 wherein R 5 each independently is H or an organic group, or imidazolium, pyridinium or phosphonium each optionally substituted;and q is 1 or 2;preferably having a content of the compound of formula (3), relative to the fluoropolymer, of ≤ 1,000 ppb;and more preferably of≤ 25 ppb.
  11. 17
    The composition of any of claims 13-16, wherein the fluoropolymer is obtained by polymerization using a hydrocarbon-based surfactant.
  12. 18
    The composition of any of claims 13,14 and 17, which is in the form of powder.
  13. 21
    A composition comprising a fluoropolymer and being substantially free from a compound of formula (3):H-(CF 2 ) 8 -SO 3 ) q M 2 (3), wherein M 2 is H, a metal atom, NR 5 4 wherein R 5 each independently is H or an organic group, or imidazolium, pyridinium or phosphonium each optionally substituted;and q is 1 or 2;the composition further comprising (i) a compound of formula (4) and/or a compound of formula (4'), preferably a compound of formula (4) :         (H-(CF 2 ) 7 -COO) p M 1      (4)         (H-(CF 2 ) 8 -COO) p M 1      (4') ;or (ii) a compound of formula (5) and/or a compound of formula (5'), preferably a compound of formula (5) :         (H-(CF 2 ) 13 -COO) p M 1      (5)         (H-(CF 2 ) 14 -COO) p M 1      (5') ;wherein M 1 is H, a metal atom, NR 5 4 wherein R 5 each independently is H or an organic group, or imidazolium, pyridinium or phosphonium each optionally substituted;and p is 1 or 2;and wherein the amount of the compound (4), (4'), (5) and (5'), if present, each independently is ≤ 1,000 ppb, and preferably ≤ 100 ppb, relative to the fluoropolymer;preferably having a content of the compound of formula (3), relative to the fluoropolymer, of ≤ 1,000 ppb;and more preferably of ≤ 25 ppb.
Independent claims13