Fluoroelastomer composition

Patent metadata

Field	Value
Publication number	US-10358551-B2
Application number	US-201113810918-A
Country	US
Kind code	B2
Filing date	Jul 14, 2011
Priority date	Jul 20, 2010
Publication date	Jul 23, 2019
Grant date	Jul 23, 2019

Abstract

A (per)fluoroelastomer composition having improved plasma resistance comprising at least one (per)fluoroelastomer [fluoroelastomer (A)] and from 0.1 to 50 weight parts per 100 parts by weight of said fluoroelastomer (A) of alkaline-earth metal carbonate particles [particles (P)]. Each particle comprises a core consisting essentially of at least one alkaline-earth metal carbonate and a shell consisting essentially of at least one Group IV transition metal compound.

First claim

The invention claimed is:

1. A (per)fluoroelastomer composition comprising:
at least one (per)fluoroelastomer [fluoroelastomer (A)]; and
from 0.1 to 50 weight parts, per 100 parts by weight of said fluoroelastomer (A) of alkaline-earth metal carbonate particles [particles (P)], each said particle comprising:

(a) a core consisting essentially of at least one alkaline-earth metal carbonate; and
(b) a shell consisting essentially of at least one Group IV transition metal compound.

2. The (per)fluoroelastomer composition of claim 1 , wherein said fluoroelastomer (A) comprises recurring units derived from at least one (per)fluorinated monomer selected from the group consisting of:
C 2 -C 8 fluoro- and/or perfluoroolefins;
C 2 -C 8 hydrogenated monofluoroolefins;
(per)fluoroalkylethylenes complying with formula CH 2 ═CH—R f0 , wherein R f0 is a C 1 -C 6 (per)fluoroalkyl or a C 1 -C 6 (per)fluorooxyalkyl having one or more ether groups;
chloro- and/or bromo- and/or iodo-C 2 -C 6 fluoroolefins;
fluoroalkylvinylethers complying with formula CF 2 ═CFOR f1 wherein R f1 is a C 1 -C 6 fluoro- or perfluoroalkyl;
hydrofluoroalkylvinylethers complying with formula CH 2 ═CFOR f1 wherein R f1 is a C 1 -C 6 fluoro- or perfluoroalkyl;
fluoro-oxyalkylvinylethers complying with formula CF 2 ═CFOX 0 , wherein X 0 is a C 1 -C 12 oxyalkyl, or a C 1 -C 12 (per)fluorooxyalkyl having one or more ether groups;
fluoroalkyl-methoxy-vinylethers complying with formula CF 2 ═CFOCF 2 OR f2 wherein R f2 is a C 1 -C 6 fluoro- or perfluoroalkyl or a C 1 -C 6 (per)fluorooxyalkyl having one or more ether groups;
functional fluoro-alkylvinylethers complying with formula CF 2 ═CFOY 0 , wherein Y 0 is a C 1 -C 12 alkyl or (per)fluoroalkyl, or a C 1 -C 12 oxyalkyl or a C 1 -C 12 (per)fluorooxyalkyl, said Y 0 group comprising a carboxylic or sulfonic acid group, in its acid, acid halide or salt form;
fluorodioxoles, of formula:

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

3. The (per)fluoroelastomer composition of claim 1 , wherein (per)fluoroelastomer (A) is selected from the group consisting of:
(1) VDF-based copolymers, in which VDF is copolymerized with at least one comonomer selected from the group consisting of:
(a) C 2 -C 8 perfluoroolefins;
(b) hydrogen-containing C 2 -C 8 olefins;
(c) C 2 -C 8 chloro and/or bromo and/or iodo-fluoroolefins;
(d) (per)fluoroalkylvinylethers (PAVE) of formula CF 2 ═CFOR f , wherein R f is a C 1 -C 6 (per)fluoroalkyl group;
(e) (per)fluoro-oxy-alkylvinylethers of formula CF 2 ═CFOX, wherein X is a C 1 -C 12 ((per)fluoro)-oxyalkyl comprising catenary oxygen atoms;
(f) (per)fluorodioxoles having formula:

wherein R f3 , R f4 , R f5 , R f6 , equal or different from each other, are independently selected from the group consisting of fluorine atoms and C 1 -C 6 (per)fluoroalkyl groups, optionally comprising one or more than one oxygen atom;
(g) (per)fluoro-methoxy-vinylethers (MOVE, hereinafter) having formula:
CFX 2 ═CX 2 OCF 2 OR″ f

wherein R″ f is selected from the group consisting of C 1 -C 6 (per)fluoroalkyls, linear or branched; C 5 -C 6 cyclic (per)fluoroalkyls; and C 2 -C 6 (per)fluorooxyalkyls, linear or branched, comprising from 1 to 3 catenary oxygen atoms, and X 2 ═F, H; and
(h) C 2 -C 8 non-fluorinated olefins (OI); and
(2) TFE-based copolymers, wherein TFE 15 copolymerized with at least one comonomer selected from the group consisting of classes (c), (d), (e), (g), (h) as above detailed and:
(i) perfluorovinyl ethers containing cyanide groups.

4. The (per)fluoroelastomer composition of claim 1 , wherein the fluoroelastomer (A) comprises recurring units derived from a bis-olefin [bis-olefin (OF)] having general formula:

wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 , equal or different from each other, are H or C 1 -C 5 alkyl; Z is a linear or branched C 1 -C 18 alkylene or cycloalkylene radical, optionally containing oxygen atoms and optionally at least partially fluorinated, or a (per)fluoropolyoxyalkylene radical.

5. The (per)fluoroelastomer composition of claim 4 , wherein said bis-olefin (OF) is selected from the group consisting of those complying with formulae (OF-1), (OF-2) and (OF-3):
(OF-1)

wherein j is an integer between 2 and 10 and R1, R2, R3, R4, equal or different from each other, are H, F or C 1-5 alkyl or (per)fluoroalkyl group;

wherein each of A, equal or different from each other and at each occurrence, is independently selected from the group consisting of F, Cl, and H; each of B, equal or different from each other and at each occurrence, is independently selected from the group consisting of F, Cl, H and OR B , wherein R B is a branched or straight chain alkyl radical which can be partially, substantially or completely fluorinated or chlorinated; E is a divalent group having 2 to 10 linkages;

wherein E, A and B have the same meaning as above defined; R5, R6, R7, equal or different from each other, are H, F or C 1-5 alkyl or (per)fluoroalkyl group.

6. The (per)fluoroelastomer composition of claim 5 , wherein j is an integer between 4 and 8.

7. The (per)fluoroelastomer composition of claim 5 , wherein E is a —(CF 2 ) m — group and m is an integer from 3 to 5.

8. The (per)fluoroelastomer composition of claim 4 , wherein Z is at least partially fluorinated.

9. The (per)fluoroelastomer composition of claim 1 , wherein the particles (P) comprise a core consisting essentially of at least one carbonate selected from the group consisting of magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, and mixtures thereof.

10. The (per)fluoroelastomer composition of claim 9 , wherein the particles (P) comprise a core consisting essentially of barium carbonate.

11. The (per)fluoroelastomer composition of claim 1 , wherein the particles (P) comprise a shell consisting of at least one compound selected from the group consisting of titanium compounds, zirconium compounds, hafnium compounds and mixtures thereof.

12. The (per)fluoroelastomer composition of claim 11 , wherein the particles (P) comprise a shell consisting essentially of at least one titanium compound.

13. The (per)fluoroelastomer composition of claim 1 , wherein the Group IV transition metal compound of the shell is a titanium compound, and wherein said shell comprises TiO 2 , in amorphous and/or crystalline form.

14. The (per)fluoroelastomer composition of claim 13 , wherein shell comprises TiO 2 in at least partially crystalline form.

15. A method for fabricating shaped articles, comprising moulding, calendering, or extruding the (per)fluoroelastomer composition of claim 1 .

16. The method according to claim 15 , further co

Assignees

• Fantoni Matteo
• Apostolo Marco
• Comino Giovanni
• Solvay Specialty Polymers It

Inventors

• Fantoni Matteo
• Apostolo Marco
• Comino Giovanni

Classifications

• C08L29/10 Primary

  Homopolymers or copolymers of unsaturated ethers (C08L35/08 takes precedence) · CPC title

• C08K9/02 Primary

  Ingredients treated with inorganic substances · CPC title

• C08L27/12 Primary

  containing fluorine atoms · CPC title

• C08K7/00

  Use of ingredients characterised by shape · CPC title

• C08K3/26

  Carbonates; Bicarbonates · CPC title