Fluoroelastomer composition

Patent metadata

Field	Value
Publication number	US-10513593-B2
Application number	US-201515523023-A
Country	US
Kind code	B2
Filing date	Oct 29, 2015
Priority date	Oct 31, 2014
Publication date	Dec 24, 2019
Grant date	Dec 24, 2019

Abstract

The invention pertains to a fluoroelastomer composition comprising:
at least one fluoroelastomer [perfluoroelastomer (A)], said fluoroelastomer (A) comprising iodine and/or bromine atoms and having a backbone comprising: recurring units derived from tetrafluoroethylene (TFE); recurring units derived from at least one perfluorinated monomer selected from the group consisting of: perfluoroalkylvinylethers complying with formula CF 2 ═CFOR f1 in which Rn is a C 1 -C 6 perfluoroalkyl (monomers of this type being referred to, herein after, as PAVE), e.g. —CF 3 , —C 2 F 5 , —C 3 F 7 ; perfluoro-oxyalkylvinylethers complying with formula CF 2 ═CFOX 0 , in which X 0 can be (i) a C 1 -C 12 perfluorooxyalkyl having one or more ether groups, e.g. —C 2 F 5 —O—CF 3 ; or (ii) a group of formula —CF 2 OR f2 in which R f2 is a C 1 -C 6 perfluoroalkyl, e.g. —CF 3 , —C 2 F 5 , —C 3 F 7 (monomers of this type being referred to, herein after, as MOVE); recurring units derived from vinylidene fluoride (VDF) in an amount of up to 30% by moles, with respect to the total moles of recurring units; and optionally, recurring units derived from at least one perfluorinated C 3 -C 8 alpha-olefin, in an amount of up to 5% moles; optionally, recurring units derived from at least one fluorine-free alpha-olefin, in an amount of up to 10% moles; from 0.5 to 5 weight parts, per 100 parts by weight of said fluoroelastomer (A), of at least one polyunsaturated compound; from 0.1 to 3 weight parts, per 100 parts by weight of said fluoroelastomer (A), of at least one organic peroxide; from 0.1 to 3 weight parts, per 100 parts by weight of said fluoroelastomer (A), of at least one organic base [base (B)] selected from the group consisting of: (i) non-aromatic primary amines or amides complying with general formula (B1m) or (Bid):

R bm —[C(O)] t —NH 2   (B1m)

H 2 N—[C(O)] t′ —R dm —[C(O)] t″ —NH 2   (B1d)

wherein:
each of t, t′ and t″, equal to or different from each other and at each occurrence is zero or 1; R bm is a monovalent hydrocarbon non-aromatic group having 12 to 30 carbon atoms; R bm is a divalent hydrocarbon non-aromatic group having 6 to 30 carbon atoms; and (ii) 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.

First claim

The invention claimed is:

1. A fluoroelastomer composition comprising:
at least one fluoroelastomer (A), said fluoroelastomer (A) comprising iodine and/or bromine atoms and having a backbone comprising:
recurring units derived from tetrafluoroethylene (TFE);
recurring units derived from at least one perfluorinated monomer selected from the group consisting of:
PAVE monomers, wherein PAVE monomers are perfluoroalkylvinylethers complying with formula CF 2 ═CFOR f1 in which R f1 is a C 1 -C 6 perfluoroalkyl;
MOVE monomers, wherein MOVE monomers are perfluoro-oxyalkylvinylethers complying with formula CF 2 ═CFOX 0 , in which X 0 is (i) a C 1 -C 12 perfluorooxyalkyl having one or more ether groups; or (ii) a group of formula —CF 2 OR f2 in which R f2 is a C 1 -C 6 perfluoroalkyl;

recurring units derived from vinylidene fluoride (VDF) in an amount of up to 30% by moles, with respect to the total moles of recurring units; and
optionally, recurring units derived from at least one perfluorinated C 3 -C 8 alpha-olefin, in an amount of up to 5% moles;
optionally, recurring units derived from at least one fluorine-free alpha-olefin, in an amount of up to 10% moles;

from 0.5 to 5 weight parts, per 100 parts by weight of said fluoroelastomer (A), of at least one polyunsaturated compound;
from 0.1 to 3 weight parts, per 100 parts by weight of said fluoroelastomer (A), of at least one organic peroxide;
from 0.1 to 3 weight parts, per 100 parts by weight of said fluoroelastomer (A), of at least one organic base (B) selected from the group consisting of:
(i) non-aromatic primary amines or amides complying with general formula (B1m) or (B1d):
R bm —[C(O)] t —NH 2   (B1m)

H 2 N—[C(O)] t′ —R dm —[C(O)] t″ —NH 2   (B1d)

wherein:
each of t, t′ and t″, equal to or different from each other and at each occurrence is zero or 1;
R bm is a monovalent hydrocarbon non-aromatic group having 12 to 30 carbon atoms;
R bm is a divalent hydrocarbon non-aromatic group having 6 to 30 carbon atoms; and

(ii) 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; and
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.

2. The fluoroelastomer composition according to claim 1 , wherein said non-aromatic primary amines or amides are selected from the group consisting of:
octadecylamine of formula CH 3 (CH 2 ) 17 —NH 2 ;
erucamide of formula H 2 N—C(O)—(CH 2 ) 11 —CH═CH—(CH 2 ) 7 CH 3 ;
oleamide of formula H 2 N—C(O)—(CH 2 ) 7 —CH═CH—(CH 2 ) 7 CH 3 ; and
hexamethylenediamine of formula H 2 N—(CH 2 ) 6 —NH 2 ;

and said cycloaliphatic secondary or tertiary amines are selected from the group consisting of:
1,8-diazabicycloundec-7-ene (DBU) of formula:

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

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 F, Cl, and H; each of B, equal or different from each other and at each occurrence, is independently selected from 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 carbon atom, optionally fluorinated, which may be inserted with ether 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.

4. The fluoroelastomer composition of claim 3 , wherein bis-olefin (OF) is a compound of formula (OF1), as above detailed.

5. The fluoroelastomer composition of claim 1 , wherein fluoroelastomer (A) comprises iodine and/or bromine atoms in an amount of 0.001 to 10% wt, with respect to the total weight of fluoroelastomer (A).

6. The fluoroelastomer composition of claim 5 wherein the amount of iodine and/or bromine in fluoroelastomer (A) is of at least 0.05% wt, with respect to the total weight of fluoroelastomer (A).

7. The fluoroelastomer composition of claim 3 , wherein fluoroelastomer (A) is selected from the group consisting of those having a backbone comprising:
recurring units derived from TFE in an amount of 30 to 70% moles;
recurring units derived from at least one perfluorinated monomer selected from the group consisting of:
PAVE monomers, wherein PAVE monomers are perfluoroalkylvinylethers complying with formula CF 2 ═CFOR f1 in which R f1 is a C 1 -C 6 perfluoroalkyl; and
MOVE monomers, wherein MOVE monomers are perfluoro-oxyalkylvinylethers complying with formula CF 2 ═CFOX 0 , in which X 0 is (i) a C 1 -C 12 perfluorooxyalkyl having one or more ether groups; or (ii) a group of formula —CF 2 OR f2 in which R f2 is a C 1 -C 6 perfluoroalkyl;

in an amount of 25 to 40% moles;
recurring units derived from VDF in an amount of 1 to 25% moles;
optionally, recurring units derived from ethylene (E) in an amount from 0 to 5% moles;
optionally, recurring units derived from hexafluoropropylene (HFP) in an amount from 0 to 5% moles;
optionally, recurring units derived from at least one bis-olefin (OF).

8. The fluoroelastomer composition of claim 1 , wherein said organic peroxide is selected from the group consisting of di-tert-butyl peroxide; 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; bis(1,1-diethylpropyl)peroxide; bis(1-ethyl-1-methylpropyl)peroxide; 1,1-diethylpropyl-1-ethyl-1-methylpropyl-peroxide; 2,5-dimethyl-2,5-bis(tert-amylperoxy)hexane; dicumyl peroxide; dibenzoyl peroxide; di-tert-butyl perbenzoate; and bis[1,3-dimethyl-3-(tert-butylperoxy)butyl] carbonate.

9. The fluoroelastomer composition of claim 1 , wherein fluoroelastomer (A) is selected from the group consisting of fluoroelastomers having the following monomer compositions (in mol %):
(i) tetrafluoroethylene (TFE) 40-65%, perfluoroalkyl vinyl ethers (PAVE) 20-50%, vinylidene fluoride (VDF): 10-25%; bis-olefin (OF): 0-5%; hexafluoropropylene (HFP): 0-5%; and
(ii) tetrafluoroethylene (TFE) 40-65%, perfluoroalkyl vinyl ethers (PAVE) 20-45%, vinylidene fluoride (VDF): 10-25%; ethylene (E): 1-5%; bis-olefin (OF) 0-5%; hexafluoropropylene (HFP): 0-5%.

10. A method for fabricating a shaped article, the method comprising moulding, calendering, or extruding the fluoroelastomer composition of claim 1 , such that a shaped article is fabricated.

Assignees

• Solvay Specialty Polymers It

Inventors

• Avataneo Marco
• Fantoni Matteo
• Cirillo Luca
• Bossolo Stefano

Classifications

• C08K5/0025 Primary

  Crosslinking or vulcanising agents; including accelerators · CPC title

• B29C43/003

  characterised by the choice of material · CPC title

• B29C35/00

  Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor (moulds with incorporated heating or cooling means B29C33/02 {; thermal after-treatment of shaped articles B29C71/02}; curing devices for plastics dental prostheses A61C13/14; before moulding B29B13/00) · CPC title

• B29C45/0001

  characterised by the choice of material · CPC title

• B29K2027/12

  containing fluorine · CPC title