# US 10,766,989 B2 · Fluoroelastomer composition

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,766,989 B2
- Document ID: US10766989B2
- Status: Granted
- Kind: B2
- Application number: 15/572,656
- Filed: 2016-05-03
- Published: 2018-05-24
- Granted: 2020-09-08
- Earliest claimed: 2015-05-08
- Assignees: Solvay Speciality Polymers Italy S.P.A.
- Applicants: Solvay Specialty Polymers Italy S.P.A.
- Inventors: Matteo Fantoni; Vito Tortelli; Cristiano Monzani; Stefano Bossolo; Marco Avataneo
- Web page: https://patentgrep.com/patent/US10766989B2

## CPC

- C08F 214/222: {with fluorinated vinyl ethers}
- C08F 214/225: {with non-fluorinated comonomers}
- C08F 214/262: {with fluorinated vinyl ethers}
- C08J 3/24: Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K)
- C08K 3/22: of metals
- C08K 5/0025: {Crosslinking or vulcanising agents; including accelerators}
- C08K 5/17: Amines; Quaternary ammonium compounds
- C08K 5/20: Carboxylic acid amides
- C08K 5/34: Heterocyclic compounds having nitrogen in the ring
- C08K 5/3432: Six-membered rings
- C08K 5/3462: Six-membered rings
- C08L 27/16: Homopolymers or copolymers or vinylidene fluoride
- C08F 2800/20: as weight or mass percentages
- C08J 2300/26: Elastomers
- C08J 2327/16: Homopolymers or copolymers of vinylidene fluoride
- C08K 2003/2206: {of calcium, strontium or barium}
- C08K 2003/2217: {of magnesium}
- C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The invention pertains to a fluoroelastomer composition [composition (C)] comprising: —at least one fluoroelastomer [fluoroelastomer (A)]; —at least one basic compound [base (B)]; —at least one pyridinium-type salt [salt (P)] having at least two groups in ortho or para position to the quaternized nitrogen bearing a reactive hydrogen atom.

## Claims

### Claim 1

A fluoroelastomer composition [composition (C)] comprising:
at least one vinylidene-fluoride based fluoroelastomer comprising recurring units derived from vinylidene fluoride (VDF) and from at least one additional (per)fluorinated monomer different from VDF [fluoroelastomer (A)];
at least one basic compound [base (B)];
at least one pyridinium salt [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 C1-C12 hydrocarbon group;
E is N or a group of formula C—RoH;
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 R1H, R2H, R3H, R4H, R5H, R6H, R7H, R8H, R9H, R10H, R11H, R12H, R13H, R14H, R15H, R16H, R17H, R18H, R19H, R20H, R21H, R22H, R23H, R24H, R25H, R26H, R27H, R28H, R29H, R30H, R31H, R32H, R33H, R34H, R35H, R36H and RoH, equal to or different from each other, is independently at each occurrence —H or a group of formula [group (alpha-H)]:
wherein Ra, and Rb, equal to or different from each other, are independently H or a hydrocarbon C1-C6 group;
Y, equal to or different from each other, is independently oxygen or a C1-C12 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 R1H, R2H, and RoH are groups (alpha-H);
(ii) when salt (P) is of formula (P-2) R3H and R4H are groups (alpha-H);
(iii) when salt (P) is of formula (P-3), at least two of R5H, R6H, R7H, and R8H are groups (alpha-H);
(iv) when salt (P) is of formula (P-4), at least two of R9H, R10H, R11H, R12H, and RoH are groups (alpha-H);
(v) when salt (P) is of formula (P-5), at least two of R13H, R14H, and RoH are groups (alpha-H);
(vi) when salt (P) is of formula (P-6), at least two of R15H, R16H, R17H, and RoH are groups (alpha-H);
(vii) when salt (P) is of formula (P-7), at least two of R18H, R19H, R20H, R21H, and RoH are groups (alpha-H);
(viii) when salt (P) is of formula (P-8), at least two of R22H, R23H, R24H, and RoH are groups (alpha-H);
(ix) when salt (P) is of formula (P-9), at least two of R25H, R26H, R27H, and R28H are groups (alpha-H);
(x) when salt (P) is of formula (P-10), at least two of R29H, R30H, R31H, R32H, and R28H are groups (alpha-H);
(xi) when salt (P) is of formula (P-11), at least two of R33H, R34H, and R28H are groups (alpha-H); and
(xii) when salt (P) is of formula (P-12), at least two of R35H, R36H and RoH are groups (alpha-H).

### Claim 2 (depends on 1)

The composition (C) of claim 1,
(1) wherein salts (P) of formula (P-1) comply with formulae (P-1-a) to (P-1-e):
wherein:
Ra and Rb have the meaning as defined in claim 1;
Y has the meaning as defined in claim 1;
each of Rp and Rq, equal to or different from each other, is H or a C1-C12 hydrocarbon group;
A and m have the meanings as defined in claim 1; and/or
(2) wherein salts (P) of formula (P-2) comply with formula (P-2-a):
wherein:
Ra and Rb have the meaning as defined in claim 1;
Y has the meaning as defined in claim 1;
each of Rp and Rq, equal to or different from each other, is H or a C1-C12 hydrocarbon group;
A and m have the meanings as defined in claim 1; and/or
(3) wherein salts (P) of formula (P-3) comply with formula (P-3-a):
wherein:
Ra and Rb have the meaning as defined in claim 1;
Y has the meaning as defined in claim 1;
A and m have the meanings as defined in claim 1; and/or
(4) wherein salts (P) of formula (P-4) comply with formula (P-4-a):
wherein:
Ra and Rb have the meaning as defined in claim 1;
w is an integer of 1 to 12;
A and m have the meanings as defined in claim 1; and/or
(5) wherein salts (P) of formula (P-5) comply with formula (P-5-a):
wherein:
Ra and Rb have the meaning as defined in claim 1;
Y has the meaning as defined in claim 1;
A and m have the meanings as defined in claim 1; and/or
(6) wherein salts (P) of formula (P-11) comply with formula (P-11-a):
wherein:
Ra and Rb have the meaning as defined in claim 1;
Y has the meaning as defined in claim 1;
A and m have the meanings as defined in claim 1; and/or
(7) wherein salts (P) of formula (P-12) comply with formula (P-12-a):
wherein:
Ra and Rb have the meaning as defined in claim 1;
Y has the meaning as defined in claim 1;
A and m have the meanings as defined in claim 1.

### Claim 3 (depends on 1)

The composition (C) of claim 1, wherein salt (P) is selected from the group consisting of salts (P) of formula (P-1), (P-2), (P-3), (P-4), (P-5), (P-11), and (P-12).

### Claim 4 (depends on 3)

The composition (C) of claim 3, wherein salt (P) is selected from salts of formulae (Ex-1) to (Ex-9):

### Claim 5 (depends on 1)

The composition (C) of claim 1, wherein composition (C) comprises salt (P) in an amount of at least 0.1 weight part per 100 weight parts of fluoroelastomer (A), and/or in an amount of at most 20 weight parts per 100 parts of fluoroelastomer (A).

### Claim 6 (depends on 1)

The composition (C) of claim 1, wherein base (B) comprises one or more than one organic base, one or more than one inorganic base or mixtures of organic and inorganic base(s).

### Claim 7 (depends on 1)

The composition (C) of claim 1, wherein base (B) is an inorganic base selected from the group consisting of:
i) divalent metal oxides;
ii) hydroxides of metals; and
(iii) metal salts of weak acids having a pKa higher than 3.

### Claim 8 (depends on 1)

The composition (C) of claim 1, wherein base (B) is an organic base selected from the group consisting of:
(j) non-aromatic amines or amides complying with general formula (B1m) or (B1d):
Rbm—[C(O)]t—NRH2 (B1m)
RH2N—[C(O)]t′—Rdm—[C(O)]t″—NRH2 (B1d)
wherein:
each of t, t′ and t″, equal to or different from each other and at each occurrence is zero or 1;
each of RH is independently H or a C1-C12 hydrocarbon group;
Rbm is a monovalent hydrocarbon non-aromatic group having 1 to 30 carbon atoms;
Rbm is a divalent hydrocarbon non-aromatic group having 1 to 30 carbon atoms; and
(jj) cycloaliphatic secondary or tertiary amines complying with general formula (B2m) or (B2d):
wherein:
Cy represents a divalent aliphatic group comprising at least 4 carbon atoms, optionally comprising one or more than one ethylenically unsaturated double bond, and optionally comprising one or more catenary nitrogen atoms, forming a cycle with the nitrogen atom which is connected thereto;
Cy′ represent a trivalent aliphatic group comprising at least 5 carbon atoms, optionally comprising one or more than one ethylenically unsaturated double bond, and optionally comprising one or more catenary nitrogen atoms, forming a cycle with the nitrogen atom which is connected thereto;
(jjj) aromatic amines or amides complying with general formula (B3):
Arb-{[C(O)]t—NRH2}w (B3)
wherein:
t, equal to or different from each other and at each occurrence, is zero or 1;
w is an integer of 1 to 4;
each of RH is independently H or a C1-C12 hydrocarbon group;
Arb is a mono- or poly-nuclear aromatic group, optionally comprising one or more than one catenary heteroatoms selected from the group consisting of S and O;
(jv) heteroaromatic amines comprising at least one nitrogen atom comprised in a heteroaromatic cycle;
(v) guanidine derivatives of formula (B4) or (B5):
wherein:
each of R1, R2, R3, R4, R5, R6, R7, and R8, equal to or different from each other, is independently H or a C1-C12 hydrocarbon group and corresponding salts of said guanidines (B4) and (B5);
(vj) metal alkoxylates.

### Claim 9 (depends on 6)

The composition (C) of claim 6, wherein composition (C) comprises at least one organic base and at least one inorganic base.

### Claim 10 (depends on 1)

The composition (C) of claim 1, said composition additionally comprising one or more than one organic solvents [solvent (S)] selected from those wherein salt (P) has a solubility at room temperature exceeding 1 g/l.

### Claim 11 (depends on 1)

The composition (C) of claim 1, wherein fluoroelastomer (A) comprises at least 15% moles of recurring units derived from VDF, with respect to all recurring units of the fluoroelastomer, and/or wherein the fluoroelastomer (A) comprises at most 85% moles of recurring units derived from VDF, with respect to all recurring units of the fluoroelastomer.

### Claim 12 (depends on 1)

The composition (C) of claim 1, wherein said at least one additional (per)fluorinated monomer different from VDF is selected from the group consisting of:
(a) C2-C8 perfluoroolefins;
(b) hydrogen-containing C2-C8 olefins different from VDF;
(c) C2-C8 chloro and/or bromo and/or iodo-fluoroolefins;
(d) (per)fluoroalkylvinylethers (PAVE) of formula CF2═CFORf, wherein Rf is a C1-C6 (per)fluoroalkyl group;
(e) (per)fluoro-oxy-alkylvinylethers of formula CF2═CFOX, wherein X is a C1-C12 ((per)fluoro)-oxyalkyl comprising catenary oxygen atoms;
(f) (per)fluorodioxoles having formula:
wherein each of Rf3, Rf4, Rf5, Rf6, equal or different each other, is independently a fluorine atom, a C1-C6 fluoro- or per(halo)fluoroalkyl, optionally comprising one or more oxygen atom,
(g) (per)fluoro-methoxy-vinylethers (MOVE, hereinafter) having formula:
CFX2═CX2OCF2OR″f
wherein R″f is selected from C1-C6 (per)fluoroalkyls, linear or branched; C5-C6 cyclic (per)fluoroalkyls; and C2-C6 (per)fluorooxyalkyls, linear or branched, comprising from 1 to 3 catenary oxygen atoms, and X2 is F or H.

### Claim 13 (depends on 1)

The composition of claim 1, wherein fluoroelastomer (A) is selected from the group consisting of fluoroelastomers having the following monomer compositions (in mol %):
(i) vinylidene fluoride (VDF) 35-85%, hexafluoropropene (HFP) 10-45%, tetrafluoroethylene (TFE) 0-30%, perfluoroalkyl vinyl ethers (PAVE) 0-15%, bis-olefin (OF) 0-5%;
(ii) vinylidene fluoride (VDF) 50-80%, perfluoroalkyl vinyl ethers (PAVE) 5-50%, tetrafluoroethylene (TFE) 0-20%, bis-olefin (OF) 0-5%;
(iii) vinylidene fluoride (VDF) 20-30%, C2-C8 non-fluorinated olefins (01) 10-30%, hexafluoropropene (HFP) and/or perfluoroalkyl vinyl ethers (PAVE) 18-27%, tetrafluoroethylene (TFE) 10-30%, bis-olefin (OF) 0-5%;
(vii) tetrafluoroethylene (TFE) 33-75%, perfluoroalkyl vinyl ethers (PAVE) 15-45%, vinylidene fluoride (VDF) 5-30%, hexafluoropropene HFP 0-30%, bis-olefin (OF) 0-5%; and
(viii) vinylidene fluoride (VDF) 35-85%, fluorovinyl ethers (MOVE) 5-40%, perfluoroalkyl vinyl ethers (PAVE) 0-30%, tetrafluoroethylene (TFE) 0-40%, hexafluoropropene (HFP) 0-30%, bis-olefin (OF) 0-5%.

### Claim 14 (depends on 1)

A method for fabricating a shaped article[s], the method comprising moulding, calendering, or extruding the composition (C) of claim 1, into the shaped article and optionally subjecting the composition (C) to vulcanization.

### Claim 15 (depends on 1)

A cured article comprising the composition (C) of claim 1.

### Claim 16 (depends on 2)

The composition (C) of claim 2,
(1) wherein salts (P) of formula (P-1) are those complying with formulae (P-1-a) to (P-1-e) and wherein Ra and Rb are each H and Y is methyl; and/or
(2) wherein salts (P) of formula (P-2) are those complying with formula (P-2-a) and wherein Ra and Rb are each H and Y is methyl; and/or
(3) wherein salts (P) of formula (P-3) are those complying with formula (P-3-a) and wherein Ra and Rb are H and Y is methyl; and/or
(4) wherein salts (P) of formula (P-4) are those complying with formula (P-4-a) and wherein Ra and Rb are H and w is 3; and/or
(5) wherein salts (P) of formula (P-5) are those complying with formula (P-5-a) and wherein Ra and Rb are H and Y is methyl; and/or
(6) wherein salts (P) of formula (P-11) are those complying with formula (P-11-a) and wherein Ra and Rb are H and Y is methyl; and/or
(7) wherein salts (P) of formula (P-12) are those complying with formula (P-12-a) and wherein Ra and Rb are H and Y is methyl.

### Claim 17 (depends on 5)

The composition (C) of claim 5, wherein composition (C) comprises salt (P) in an amount of at least 1 weight part per 100 weight parts of fluoroelastomer (A) and in an amount of at most 10 weight parts per 100 parts of fluoroelastomer (A).

### Claim 18 (depends on 7)

The composition (C) of claim 7, wherein base (B) is an inorganic base selected from the group consisting of:
i) alkali-earth metal oxides and oxides of Zn, Mg, Pb, or Ca;
ii) hydroxides of alkali and alkali-earth metals; and
(iii) Na, K, Ca, Sr, and Ba salts of carbonates, benzoates, oxalates and phosphites.

### Claim 19 (depends on 10)

The composition (C) of claim 10, wherein solvent (S) is selected from the group consisting of:
polar aprotic organic solvents selected from the group consisting of sulfolane and 4,4′-dichlorodiphenylsulfone; and
ionic liquids selected from the group consisting of methylpyrrolidinium bis(trifluoromethansulonylimide) of formula PY1,4-Tf2N and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonylimide) of formula BMIm-Tf2N:

### Claim 20 (depends on 11)

The composition (C) of claim 11, wherein fluoroelastomer (A) comprises at least 35% moles of recurring units derived from VDF, with respect to all recurring units of the fluoroelastomer, and wherein the fluoroelastomer (A) comprises at most 78% moles of recurring units derived from VDF, with respect to all recurring units of the fluoroelastomer.