Bromosulphonated fluorinated cross-linkabke elastomers based on vinylidene fluoride having low t9 and processes for their preparation

• US 20030181615A1
• Filed: 03/06/2003
• Published: 09/25/2003
• Est. Priority Date: 06/13/2000
• Status: Abandoned Application

• Current Assignee: Hydro-Quebec (Province of Québec)
• Original Assignee: Hydro-Quebec (Province of Québec)
• Inventors: armand, Michel, Manseri, Abdellatif, Boucher, Mario, Ameduri, Bruno Michel
• Application Number:
  US10/296,833
• Publication Number:
  US 20030181615A1
• Time in Patent Office: Days
• US Class Current: 526/227
• CPC Class Codes: C07C 17/04 to unsaturated halogenated hydrocarbons
• CPC Class Codes: C07C 17/23 by dehalogenation
• CPC Class Codes: C07C 17/275 of hydrocarbons and halogenated hydrocarbons
• CPC Class Codes: C07C 19/14 and bromine
• CPC Class Codes: C07C 21/18 containing fluorine
• CPC Class Codes: C08F 214/182 Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28

Abstract

Compounds corresponding to formula (I)

F₂C═CFX(CY₂)_nBr  (I)

in which:

X represents an atom of oxygen or no atom;

Y represents an atom of hydrogen or of fluorine; and

n is a whole natural number ranging from 0 to 10 inclusive,

excluding bromotrifluoroethylene, 3-bromo-perfluoropropene, 4-bromo-1,1,2,-trifluorobutene, 4-bromo-perfluorobutene-1 and perfluoro(2-bromo-ethylvinyl ester), and their use in the synthesis of fluorinated copolymers then in the synthesis of homosulphonated fluorinated elastomers, exhibiting a low glass transition temperature.

Claims

1. Compound corresponding to formula I:

F₂C═

CFX(CY₂)_nBr 

 

(I)

in which;

X represents an atom of oxygen or no atom;

Y represents an atom of hydrogen or of fluorine; and

n is a whole natural number varying between 0 and 10 inclusive,

excluding bromotrifluoroethylene, 3-bromo-perfluoropropene, 4-bromo-1,1,2,-trifluorobutene, 4-bromo-perfluorobutene-1 and perfluoro(2-bromo-ethylvinyl ester).

2. Compound according to claim 1, corresponding to formula II:

F₂C═

CF(CH₂)_nBr 

 

(II)

in which;

n is a natural number varying between 0 and 10 inclusive.

3. Process for preparing a fluorinated copolymer by radical copolymerisation, said process comprising the reaction of a compound corresponding to formula I:

F₂C═

CFX(CY₂)_nBr 

 

(I)

in which;

X represents an atom of oxygen or no atom;

Y represents an atom of hydrogen or of fluorine; and

n is a whole natural number varying between 0 and 10 inclusive,

with a compound corresponding to formula III₁;

F₂C═

CFOR_F1 

 

(III₁)

in which R_F1 is;

a linear or branched group of formula C_nF_{2n 1} (n denoting a whole natural number ranging from 1 to

     10);

or

with a compound corresponding to formula III₂;

F₂C═

CFOR_F2—

G 

 

(III₂)

in which R_F2 is;

a linear or branched group of formula C_nF_2n (n denoting a whole natural number ranging from 1 to

     10); and

in which G represents;

a functional group SO₂F, CO₂R (R is the group C_pH_{2p 1}, in which p is a whole natural number ranging from 0 to

     5) or a functional group P(O)(OR′

) in which R′

is independently an atom of hydrogen or a C₁-C₅ alkyl group.

4. Process for preparing a fluorinated copolymer according to claim 3, by reaction:

of a compound corresponding to formula II′

;

F₂C═

CFBr 

 

(II′

)

with the compound of formula III₁ or III₂ as defined in claim 3,

so as to obtain a statistical copolymer corresponding to formula IV;

in which;

R_F represents the groups R_F1 and R_F2 defined in claim 3, the group G being absent when R_F represents R_F1, and

in which;

n, m and p represent independently whole natural numbers such that the ratio n/m ranges from 1 to 25 and such that p ranges from 10 to 300, preferably the ratio n/m ranges from 2 to 23 and p ranges from 15 to 200, more preferably still the ratio n/m ranges from 6 to 19 and p ranges from 20 to 100.

5. Process for preparing a fluorinated copolymer according to claim 3, by reaction of a compound corresponding to formula II″

;

F₂C═

CF(CH₂)₂Br 

 

(II″

)

with a compound of structure III₁ or III₂ as defined in claim 3 so as to obtain a statistical copolymer corresponding to formula V;

in which;

R_F represents the groups R_F1 and R_F2 defined in claim 3, the group G being absent when R_F represents R_F1; and

in which;

q, r and s represent independently whole natural numbers such that the ratio q/r ranges from 1 to 20 and s ranges from 10 to 300, preferably the ratio q/r ranges from 2 to 15 and s ranges from 15 to 200, more preferably still the ratio q/r ranges from 2 to 10 and s ranges from 20 to 100.

6. Copolymerisation process, comprising the reaction:

of a compound corresponding to formula II′

;

F₂C═

CFBr 

 

(II′

)

with a compound corresponding to formula III₁;

F₂C═

CFOR_F1 

 

(III₁)

in which R_F1 is;

a linear or branched group of formula C_nF_{2n 1} (n being a whole natural number ranging from 1 to

     10);

or

with a compound corresponding to formula III₂;

F₂C═

CFOR_F2—

G 

 

(III₂)

in which R_F2 is;

a linear or branched group of formula C_nF_2n (with n being a natural number ranging from 1 to

     10); and

in which G represents;

a functional group SO₂F, CO₂R with R being the group C_pH_{2p 1}, in which p represents a whole natural number ranging from 0 to 5, or being a functional group P(O)(OR′

) in which R′

is independently an atom of hydrogen or a C₁-C₅ alkyl group; and

with;

a compound corresponding to formula VI;

FCX═

CYZ 

 

(VI)

in which;

X, Y and Z represent independently atoms of hydrogen, fluorine, chlorine or groups of formula C_nF_{2n 1} (n equalling 1, 2 or

     3), but X, Y and Z cannot simultaneously represent an atom of fluorine,

so as to obtain a statistical copolymer corresponding to formula VII;

in which;

R_F represents the groups R_F1 or R_F2 defined previously in claim 3, the group G being absent when R_F represents R_F1; and

in which;

a, b, c and d represent independently whole natural numbers such that the ratio b/a ranges from 0.1 to 15, such that the ratio b/c ranges from 1 to 20 and such that d ranges from 10 to 200, preferably the ratio b/a ranges from 1 to 10, the ratio b/c ranges from 1 to 15 and d ranges from 15 to 150, and more preferably still the ratio b/a ranges from 2 to 6, the ratio b/c ranges from 2 to 9 and d ranges from 25 to 100.

7. Copolymerisation process comprising the reaction:

of a compound corresponding to formula II″

;

F₂C═

CF(CH₂)₂Br 

 

(II″

)

with a compound corresponding to formula III₁;

F₂C═

CFOR_F1 

 

(III₁)

in which R_F1 denotes;

a linear or branched group of formula C_nF_{2n 1} (with n being a whole natural number ranging from 1 to

     10);

or

with a compound corresponding to formula III₂;

F₂C═

CFOR_F2—

G 

 

(III₂)

in which R_F2 denotes;

a linear or branched group of formula C_nF_2n (n being a whole natural number ranging from 1 to

     10); and

in which G represents;

a functional group SO₂F, CO₂R with R being the group C_pH_{2p 1}, in which p represents a whole natural number ranging from 0 to 5 or being a functional group P(O)(OR′

) in which R′

is independently an atom of hydrogen or a C₁-C₅ alkyl group; and

with a compound corresponding to formula VI;

FCX═

CYZ 

 

(VI)

in which;

X, Y and Z represent independently atoms of hydrogen, fluorine, chlorine or groups of formula C_nF_{2n 1} (n equalling 1, 2 or

     3), but X, Y and Z cannot simultaneously represent a fluorine atom,

so as to obtain a statistical copolymer corresponding to formula VIII;

in which;

R₄ represents the groups R_F1 and R_F2 defined previously in claim 3, the group G being absent when R_F represents R_F1; and

in which;

e, f, g and h independently represent whole natural numbers such that the ratio f/e ranges from 1 to 10, such that the ratio f/g ranges from 1 to 10 and such that h ranges from 10 to 250, preferably the ratio f/e ranges from 1 to 5, the ratio f/g ranges from 2 to 8 and h ranges from 15 to 200, more preferably still the ratio f/e ranges from 1 to 3, the ratio f/g ranges from 3 to 7 and h ranges from 20 to 150.

8. Copolymerisation process according to claim 6 or 7, characterised in that the reaction is carried out in batch.

9. Copolymerisation process according to any one of claims 6 to 8, characterised in that the reaction is conducted in emulsion, microemulsion, suspension or solution.

10. Copolymerisation process according to any one of claims 6 to 9, characterised in that the reaction is initiated in the presence of at least one organic radical initiator chosen preferably from the group constituted by peroxides, peresters, percarbonates, alkyl peroxypivalates and diazoic compounds.

11. Copolymerisation process according to any one of claims 6 to 10, characterised in that the reaction is carried out in the presence of:

at least one peroxide chosen preferably from the group constituted of t-butyl peroxide, t-butyl hydroperoxide and t-butyl peroxypivalate and t-amyl peroxypivalate, and/or

at least one perester which is preferably benzoyl peroxide, and/or

at least one percarbonate, which is preferably t-butyl cyclohexyl peroxydicarbonate.

12. Copolymerisation process according to claim 11, characterised in that the concentration of peroxide and/or of perester and/or of percarbonate in the reaction medium is such that the initial molar ratio between the initiator and the monomers ([initiator]_o/[monomers]_o) lies between 0.1 and 2%, and preferably between 0.5 and 1%, the initiator being the compound with the formula tBuO—

OtBu or tBuO—

OC(O)tBu and the monomers being the compounds of formula I, II, III₁, III₂, II′

, II″ and

VI, the expression [initiator]_o expresses the initial molar concentration of initiator and the expression [monomers]_o expresses the total initial concentration of monomers.

13. Copolymerisation process according to any one of claims 6, 7, 8, 9, 11 and 12, characterised in that the reaction is conducted:

in the presence of t-butyl peroxypivalate and at a reaction temperature of between 70 and 80°

C., preferably at a temperature of about 75°

C.;

or

in the presence of t-butyl peroxide and at a reaction temperature of between 135 and 145°

C., preferably at a temperature of about 140°

C.

14. Copolymerisation process according to any one of claims 6 to 9 and 11 to 13, characterised in that the reaction is carried out in the presence of at least one organic solvent.

15. Copolymerisation process according to claim 14, characterised in that the organic solvent is chosen from the group constituted by perfluoro-n-hexane, acetonitrile or mixtures of perfluoro-n-hexane and acetonitrile.

16. Copolymerisation process according to claim 14 or 15, characterised in that the content of solvent in the reaction medium is preferably such that the initial ratio by weight between the solvent and the monomers lies between 0.5 and 1.5, and preferably between 0.6 and 1.2.

17. Copolymerisation process according to any one of claims 6, 7, 8, 9, 11, 12 and 15, characterised in that the reaction is conducted with an initial molar ratio between the initiator and the. monomers ([initiator]_o/[monomers]_o) that lies between 0.1 and 2%, and preferably between 0.5 and 1%;

the initiator being the compound with the formula tBuO—

OtBu or tBuO—

OC(O)tBu and the monomers being the compounds of formula I, II, III₁, III₂, II′

, II″ and

VI, the expression [initiator]_o expressing the initial molar concentration of initiator and the expression [monomers]_o expressing the total initial concentration of monomers.

18. Copolymerisation process according to claims 6, 7, 8, 9, 11, 12. 15 and 16, characterised in that the reagent with formula III₂ is perfluoro(4-methyl-3,6-dioxaoct-7-ene) sulphonyl fluoride (PFSO₂F) and that the compound of formula VI is vinylidene fluoride.

19. Fluorinated polymer, preferably fluorinated copolymer, capable of being obtained according to any one of claims 3 to 5.

20. Bromofunctional fluorinated copolymer capable of being obtained according to any one of claims 3 to 18.

21. Bromofunctional fluorinated copolymer according to claim 20, containing:

from 7 to 24% of bromotrifluoroethylene;

from 20 to 30% of perfluoro(4-methyl-3,6-dioxaoct-7-ene) sulphonyl fluoride, and

from 56 to 73% of vinylidene fluoride.

22. Bromofunctional fluorinated copolymer according to claim 20, containing:

from 2 to 15% of 1,1,2-trifluoro-4-bromobutene;

from 20 to 30% of perfluoro(4-methyl-3,6-dioxaoct-7-ene) sulphonyl fluoride; and

from 65 to 78% of vinylidene fluoride.

23. Bromofunctional fluorinated copolymers according to claim 20, characterised in that they possess the following chemical functions or fluorinated groups:

—

SO₂F;

—

OCF₂CF(CF₃)OCF₂CF₂SO₂F;

tBuO—

CF2—

CH₂—

;

—

CH₂CF₂—

CH₂CF₂—

CH₂—

CF₂—

;

—

CH₂CF₂—

CH₂CF₂—

CF₂—

CH₂—

;

tBuO—

CH₂CF₂—

CH₂CF₂—

;

—

CH₂CF₂—

(CF—

CFBr)_n—

;

—

CF₂CF(OR_FSO₂F)—

CH₂CF₂—

CF₂CF(OR_FSO₂F)—

;

—

CH₂CF₂—

CF₂CF(OR_FSO₂F)—

;

—

OCF₂CF(CF₃)OCF₂CF₂SO₂F;

—

CH₂CF₂—

CH₂CF₂—

CF₂CH₂—

;

—

CH₂CF₂—

CF₂CH₂—

CH₂CF₂—

;

—

CF₂CFBrCH₂CF₂;

—

CH₂CF₂—

CF₂CF(OR_FSO₂F)—

CH₂CF₂—

;

—

CH₂CF₂—

CF₂CF(OR_FSO₂F)—

CH₂CF₂—

;

—

(CF₂CFBr)_n—

;

—

CH₂CF₂—

CF₂CF(OR_FSO₂F)—

CF₂CH₂—

; and

—

OCF₂CF(CF₃)OC₂F₄SO₂F;

associated respectively with the following chemical shifts, expressed in ppm, in RMN of ¹⁹F;

45;

−

77 to −

80;

−

83;

−

91;

−

95;

−

102;

−

103 to 105;

−

108;

−

110;

−

112;

−

113;

−

116;

−

118;

−

122;

−

125;

−

126;

−

127; and

−

144.

24. Bromofunctional fluorinated copolymers according to claim 20, characterised in that they possess the following chemical functions or fluorinated groups:

—

SO₂F;

—

OCF₂CF(CF₃)OCF₂CF₂SO₂F;

tBuO—

CF2—

CH₂—

;

—

CH₂CF₂—

CH₂CF₂—

CH₂CF₂—

;

—

CF₂CF(R_F)—

CH₂CF₂—

CH₂CF₂—

;

—

CF₂CF (R_F)—

CH₂ CF₂(CH₂CF₂—

CF₂CF₂—

;

—

CH₂CF₂—

CH₂CF₂—

CF₂CH₂—

;

—

CF₂CF(OR_FSO₂F)—

CH₂CF₂—

CF₂CF(OR_FSO₂F)—

;

—

CH₂CF₂—

CH₂CF₂—

CF₂CF(R₄)—

;

—

OCF₂CF(CF₃)OCF₂CF₂SO₂F;

—

CH₂CF₂—

CH₂CF₂—

CF₂CH₂—

;

—

CH₂CF₂—

CF₂CH₂—

CH₂CF₂—

;

—

CH₂ CF₂—

CF₂CF(C₂H₄Br)—

CH₂CF₂—

;

—

CF₂CF(OR_F—

SO₂F)—

CF₂CF(C₂H₄Br)—

CH₂—

CF₂—

;

—

CH₂CF₂—

CF₂CF(OR_FSO₂F)—

CH₂CF₂—

;

—

CH₂CF₂—

CF₂CF(OR_FSO₂F)—

CH₂CF₂—

;

—

CH₂CF₂—

CF₂CF(OR_FSO₂F)—

CF₂CH₂—

;

—

OCF₂CF(CF₃)OC₂F₄SO₂F;

—

CH₂CF₂—

CF₂CF(C₂H₄Br)—

CH₂CF₂—

;

—

CH₂CF₂—

CF₂CF(C₂H₄Br)—

CF₂—

;

associated respectively with the following chemical shifts, expressed in ppm, in NMR of ¹⁹F;

45;

−

77 to −

80;

−

83;

−

91;

−

92;

−

93;

−

95;

−

108;

−

110;

−

112;

−

113;

−

116;

−

119;

−

120;

−

122;

−

125;

−

127;

−

144;

−

161 to −

165 and

−

178 to −

182.

25. Process for preparing a bromosulphonated fluorinated elastomer, characterised in that the polymers obtained in any one of claims 3 to 18 is subjected to a cross-linking stage carried out preferably in the presence of at least one peroxide (preferably in a concentration of between 1 and 5%) and/or in the presence of at least one triallylisocyanurate (preferably in a concentration of between 5 and 20%) followed by a hot post-cross-linking stage preferably carried out at a temperature of between 200 and 220°

C., limits included.

26. Bromosulphonated fluorinated elastomer capable of being obtained by the process of claim 25.

27. Bromosulphonated fluorinated elastomer, according to claim 25, characterised in that it exhibits very low glass transition temperatures (T_g), these glass transition temperatures, which are measured according to the standard ASTM E-1356-98, preferably lie between −

45 and −

18°

C., more preferably still between −

35 and −

21°

C.

28. Bromosulphonated fluorinated elastomer according to claim 25 or 26, characterised in that it exhibits an inherent viscosity measured according to the ASTM D-2857-95 method that lies between 0.8 and 1.8 mL/g.

29. Bromosulphonated fluorinated elastomer according to any one of claims 25 to 28, characterised in that it exhibits a thermal stability ATG of up to 325°

C. in air at 10°

C./min, at which temperature value weight loss of 5% is measured.

30. Use of one or more cross-linkable bromosulphonated fluorinated elastomers according to any one of claims 23 to 28, for:

the manufacture of membranes, polymeric electrolytes, ionomers, components of fuel cells supplied for example with hydrogen or methanol;

the making of sealing joints and O-rings, radiator hoses, pipes, pump housings, diaphragms, piston heads (for applications in the aeronautical, petroleum, automotive, mining, nuclear industries); and

for plastics processing (aid processing products).

31. Process for cross-linking the sulphonyl groups of a sulphonated polymer chosen from the family of the bromosulphonated fluorinated elastomers defined in any one of claims 25 to 29, during which process at least one fraction of the cross-linking bonds carries an ionic charge, said process including the bringing of said polymer into contact with a cross-linking agent permitting the reaction between two sulphonyl groups originating from adjacent polymer chains, in order to form said cross-linking bonds.