# Patent

## Title
Curable fluoroelastomer composition

## Abstract

Compositions comprising fluoroelastomers having copolymerized units of a cyano-containing cure site monomer are cured (i.e. crosslinked) with a fluoropolymer having pendant sulfonyl azide groups. The latter fluoropolymer comprises copolymerized units of a fluoroalkanesulfonyl azide of formula CF2═CF—(O)p—Rf—(CH2)n—SO2N3, wherein p=0 or 1; n=0-4; and Rf is a C1-C16 perfluoroalkyl or perfluoroalkoxy group. The crosslinks are tetrazole rings formed by the reaction of the pendant sulfonyl azide groups on the fluoropolymer with pendant cyano groups on the fluoroelastomer.

## Background
FIELD OF THE INVENTION
This invention relates to curable fluoroelastomer compositions wherein the fluoroelastomer has cyano group cure sites and the curative is a fluoropolymer having pendant sulfonyl azide groups.
BACKGROUND OF THE INVENTION
Fluoroelastomers have achieved outstanding commercial success and are used in a wide variety of applications in which severe environments are encountered, in particular those end uses where exposure to high temperatures and aggressive chemicals occurs. For example, these polymers are often used in seals for aircraft engines, in oil-well drilling devices, and in sealing elements for industrial equipment that operates at high temperatures.
The outstanding properties of fluoroelastomers are largely attributable to the stability and inertness of the copolymerized fluorinated monomer units that make up the major portion of the polymer backbones in these compositions. Such monomers include vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene and perfluoro(alkyl vinyl) ethers. In order to develop elastomeric properties fully, fluoroelastomers are typically crosslinked, i.e. vulcanized. To this end, a small percentage of cure site monomer is copolymerized with the fluorinated monomer units. Cure site monomers containing at least one cyano group, for example perfluoro-8-cyano-5-methyl-3,6-dioxa-1-octene, are especially preferred. Such compositions are described in U.S. Pat. Nos. 4,281,092; 4,394,489; 5,789,489; 5,789,509 and in WO 2011084404.
U.S. Pat. No. 8,288,005 B2 discloses perfluoroelastomers having cyano cure sites that are cured with certain aliphatic mono-, di- and poly-azides. However, these azides may be difficult to synthesize and can be challenging to purify via distillation. The azides tend to have poor stability (both thermal and explosive). Also the azides are usually liquids at room temperature which can make it difficult to compound with fluoroelastomers.
U.S. Pat. No. 8,288,482 B2 discloses perfluoroelastomers having cyano cure sites that are cured with certain diazides. These diazides may suffer from many of the deficiencies mentioned above.
Fluoropolymers having pendant sulfonyl azide groups are disclosed in U.S. Pat. No. 6,365,693 B1. These fluoropolymers generally have good chemical stability, so they are relatively easy to handle.
SUMMARY OF THE INVENTION
Surprisingly, it has been discovered that fluoropolymers having pendant sulfonyl azide groups may be employed as curatives for fluoroelastomers having pendant cyano groups even though the curatives provides steric hindrance to the crosslinking reaction. The curable compositions exhibit good curing characteristics (e.g. cure rate and cure level) and result in cured fluoroelastomer compositions having good physical properties.
The present invention is directed to a curable fluoroelastomer composition which comprises a fluoroelastomer having cyano group cure sites and a fluoropolymer having pendant sulfonyl azide groups. More specifically, the present invention is directed to a curable composition comprising:

    
    
        A) a fluoroelastomer comprising copolymerized units of a cyano group-containing cure site monomer; and
        B) at least one fluoropolymer comprising copolymerized units of a fluoroalkanesulfonyl azide of formula CF2═CF—(O)p—Rf—(CH2)n—SO2N3, wherein p=0 or 1; n=0-4; and Rf is a C1-C16 perfluoroalkyl or perfluoroalkoxy group.
    
    


Another aspect of the present invention is a cured article made from the above composition.


DETAILED DESCRIPTION OF THE INVENTION
The fluoroelastomer that may be employed in the composition of the invention may be partially fluorinated or perfluorinated. Fluoroelastomers preferably contain between 25 and 70 weight percent, based on the total weight of the fluoroelastomer, of copolymerized units of a first monomer which may be vinylidene fluoride (VF2) or tetrafluoroethylene (TFE). The remaining units in the fluoroelastomers are comprised of one or more additional copolymerized monomers, different from said first monomer, selected from the group consisting of fluoromonomers, hydrocarbon olefins and mixtures thereof. Fluoromonomers include fluorine-containing olefins and fluorine-containing vinyl ethers.
Fluorine-containing olefins which may be employed to make fluoroelastomers include, but are not limited to vinylidene fluoride (VF2), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), 1,2,3,3,3-pentafluoropropene (1-HPFP), 1,1,3,3,3-pentafluoropropene (2-HPFP), chlorotrifluoroethylene (CTFE) and vinyl fluoride.
Fluorine-containing vinyl ethers that may be employed to make fluoroelastomers include, but are not limited to perfluoro(alkyl vinyl) ethers. Perfluoro(alkyl vinyl) ethers (PAVE) suitable for use as monomers include those of the formula

CF2═CFO(Rf′—O)n(Rf′′—O)mRf  (I)

where Rf′ and Rf′′ are different linear or branched perfluoroalkylene groups of 2-6 carbon atoms, m and n are independently 0-10, and Rf is a perfluoroalkyl group of 1-6 carbon atoms.

A preferred class of perfluoro(alkyl vinyl) ethers includes compositions of the formula

CF2═CFO(CF2CFXO)nRf  (II)

where X is F or CF3, n is 0-5, and Rf is a perfluoroalkyl group of 1-6 carbon atoms.

A most preferred class of perfluoro(alkyl vinyl) ethers includes those ethers wherein n is 0 or 1 and Rf contains 1-3 carbon atoms. Examples of such perfluorinated ethers include perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE) and perfluoro(propyl vinyl ether) (PPVE). Other useful monomers include those of the formula

CF2═CFO[(CF2)mCF2CFZO]nRf  (III)

where Rf is a perfluoroalkyl group having 1-6 carbon atoms,

m=0 or 1, n=0-5, and Z=F or CF3. Preferred members of this class are those in which Rf is C3F7, m=0, and n=1.

Additional perfluoro(alkyl vinyl) ether monomers include compounds of the formula

CF2═CFO[(CF2CF{CF3}O)n(CF2CF2CF2O)m(CF2)p]CxF2x+1  (IV)

where m and n independently =0-10, p=0-3, and x=1-5. Preferred members of this class include compounds where n=0-1, m=0-1, and x=1.

Other examples of useful perfluoro(alkyl vinyl ethers) include

CF2═CFOCF2CF(CF3)O(CF2O)mCnF2n+1  (V)

where n=1-5, m=1-3, and where, preferably, n=1.

If copolymerized units of PAVE are present in fluoroelastomers employed in the invention, the PAVE content generally ranges from 25 to 75 weight percent, based on the total weight of the fluoroelastomer. If perfluoro(methyl vinyl ether) is used, then the fluoroelastomer preferably contains between 30 and 65 wt. % copolymerized PMVE units.
Hydrocarbon olefins useful in the fluoroelastomers employed in the invention include, but are not limited to ethylene and propylene. If copolymerized units of a hydrocarbon olefin are present in the fluoroelastomers, hydrocarbon olefin content is generally 4 to 30 weight percent.
The fluoroelastomer further contains copolymerized units of at least one cure site monomer, generally in amounts of from 0.1-5 mole percent. The range is preferably between 0.3-1.5 mole percent. Although more than one type of cure site monomer may be present, most commonly one cure site monomer is used and it contains at least one cyano substituent group. Suitable cure site monomers include cyano-containing fluorinated olefins and cyano-containing fluorinated vinyl ethers. Useful cyano-containing cure site monomers include those of the formulas shown below.

CF2═CF—O(CF2)n—CN  (VI)

where n=2-12, preferably 2-6;

CF2═CF—O[CF2—CFCF3—O]n—CF2—CFCF3—CN  (VII)

where n=0-4, preferably 0-2;

CF2═CF—[OCF2CFCF3]x—O—(CF2)n—CN  (VIII)

where x=1-2, and n=1-4; and

CF2═CF—O—(CF2)n—O—CF(CF3)CN  (IX)

where n=2-4.
Those of formula (VIII) are preferred. Especially preferred cure site monomers are perfluorinated polyethers having a cyano group and a trifluorovinyl ether group. A most preferred cure site monomer is

CF2═CFOCF2CF(CF3)OCF2CF2CN  (X)

i.e. perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene) or 8-CNVE.

Fluoroelastomers that may be employed in the invention have a number average molecular weight (Mn) in the range of 10,000 to 250,000.
A first aspect of this invention is a curable composition comprising A) a fluoroelastomer comprising copolymerized units of a cyano group-containing cure site monomer; and B) a certain fluoropolymer having pendant sulfonyl azide groups. The latter fluoropolymers are described in U.S. Pat. No. 6,365,693 B1.
The pendant sulfonyl azide groups result from the incorporation into the fluoropolymer of copolymerized units of a fluoroalkanesulfonyl azide having the formula CF2═CF—(O)p—Rf—(CH2)n—SO2N3, wherein p=0 or 1; n=0—4; and Rf is a C1—C16 perfluoroalkyl or perfluoroalkoxy group. Preferably, p=1; n=0; and Rf is selected from the group consisting of —CF2CF(CF3)OCF2CF2—and —(CF2)m—, wherein m=2-4. Specifically, these fluoroalkanesulfonyl azides include, but are not limited to, CF2═CFOCF2CF(CF3)OCF2CF2—SO2N3 (8-SAVE); CF2═CFOCF2CF2—SO2N3; CF2═CFOCF2CF2CF2—SO2N3; and CF2═CFOCF2CF2CF2CF2—SO2N3.
Fluoropolymers having sulfonyl azide pendant groups comprise copolymerized i) units derived from the fluoroalkanesulfonyl azide defined above and ii) units derived from at least one other fluorinated monomer. By “other fluorinated monomer” is meant a copolymerizable fluoromonomer other than a fluoroalkanesulfonyl azide. In addition, copolymers may optionally contain units derived from one or more fluorine-free monomers.
Preferably, units derived from the fluoroalkanesulfonyl azide are present in minor amounts in the fluoropolymers having sulfonyl azide pendant groups. Typically, fluoropolymers contain 0.02-10 mole percent (based on the total monomer units in the polymer) of units derived from the fluoroalkanesulfonyl azide, preferably 0.1-5 mole percent and most preferably 0.3-3 mole percent.
Fluorinated monomers suitable for forming copolymers with the fluoroalkanesulfonyl azide include, but are not limited to: tetrafluoroethylene (TFE); chlorotrifluoroethylene (CTFE); trifluoroethylene; vinylidene fluoride (VF2); vinyl fluoride (VF); hexfluoropropylene (HFP); 1- or 2-hydropentafluoropropylene; 3,3,3-trifluoropropylene; hexafluoroisobutylene; perfluoro(alkyl vinyl ethers) (PAVE) having alkyl groups containing 1-5 carbon atoms (preferably 1-3 carbon atoms); perfluoro(alkoxy vinyl ethers) having alkoxy groups containing 1-5 carbon atoms; perfluoro-(2,2-dimethyl-1,3-dioxole) (PDD) and perfluoro-(2-methylene-4-methyl-1,3-dioxolane) (PMD). Also included in this group of fluorinated monomers are perfluoro(alkyl vinyl ethers) which contain functional groups such as acid fluorides or esters. Examples of these ethers include CF2═CFOCF2CF(CF3)OCF2CF2SO2F (PSEPVE) and CF2═CFOCF2CF(CF3)OCF2CF2COOCH3 (EVE). Preferably, at least one of the fluorinated monomers is selected from the group consisting of TFE, CTFE and VF2.
Fluorine free monomers that can be used in the fluoropolymers having pendant sulfonyl azide groups include: ethylene, propylene, n-butylene, iso-butylene, vinyl acetate (VAc), and vinyl ethers such as methyl vinyl ether.
The fluoropolymers having pendant sulfonyl azide groups may be glassy, thermoplastic or elastomeric. They may be amorphous or partially crystalline, melt-fabricable or non-melt-fabricable. One skilled in the art will readily recognize that such polymer properties are controlled by the type of monomers used in the copolymer and their relative levels.
Typical elastomeric fluoropolymers having pendant sulfonyl azide groups comprise, in addition to minor amounts of units derived from the fluoroalkanesulfonyl azide, units derived from a combination of monomers selected from the group consisting of a) VF2 and HFP; b) VF2, HFP and TFE; c) VF2, PAVE and TFE; d) TFE and PAVE; e) TFE and propylene; f) TFE, VF2 and propylene; and g) TFE, PAVE and ethylene.
Typical thermoplastic fluoropolymers having pendant sulfonyl azide groups comprise, in addition to units derived from the fluoroalkanesulfonyl azide, units derived from either TFE or CTFE and up to 10 mole percent of one or more additional monomers such as HFP, PDD, PMD and ethylene.
Fluoropolymers having pendant sufonyl azide groups typically have a number average molecular weight (Mn) in the range of 10,000 to 250,000.
These fluoropolymers having pendant sulfonyl azide groups crosslink the fluoroelastomer copolymer by reacting with pendant cyano groups on the fluoroelastomer polymer chains to form tetrazole rings. The resulting crosslinks are stable to high temperatures.
In order to be useful as a curative for fluoroelastomers having cyano cure sites, the level of fluoropolymer having pendant sulfonyl azide groups should be about 30 to 250 parts per 100 parts of the fluoroelastomer having cyano cure sites, preferably about 50 to 150 parts fluoropolymer having pendant sulfonyl azide groups per 100 parts of the fluoroelastomer having cyano cure sites. As used herein, “parts” refers to parts by weight, unless otherwise indicated.
Optionally, the curable compositions of the invention may further comprise 0.1 to 3 parts of a metal halide, e.g. ZnCl2 or CuBr, per 100 parts fluoroelastomer. The metal halide catalyzes the crosslinking reaction to form tetrazole rings.
Additives, such as carbon black, fluoropolymer micropowders, stabilizers, plasticizers, lubricants, fillers, and processing aids typically utilized in fluoroelastomer compounding can be incorporated into the compositions of the present invention, provided they have adequate stability for the intended service conditions.
The curable compositions of the invention may be prepared by mixing the fluoroelastomer having pendant cyano groups, fluoropolymer having pendant sulfonyl azide groups and other components using standard rubber compounding procedures. For example, the components may be mixed on a two roll rubber mill, in an internal mixer (e.g. a Banbury® internal mixer), or in an extruder. The curable compositions may then be crosslinked (i.e. cured) by application of heat and/or pressure. When compression molding is utilized, a press cure cycle is generally followed by a post cure cycle during which the press cured composition is heated at elevated temperatures in excess of 200° C. for several hours.
The curable compositions of the present invention are useful in production of gaskets, tubing, and seals. Such cured articles are generally produced by molding a compounded formulation of the curable composition with various additives under pressure, curing the part, and then subjecting it to a post cure cycle.
Other fluoropolymers containing cyano cure sites, such as fluoroplastics may be substituted for fluoroelastomers in the compositions of the invention.
Also the curable compositions of the invention may optionally contain (in addition to the fluoropolymer having pendant sulfonyl azide groups) more than one type of curative commonly employed in the crosslinking of fluoroelastomers, e.g. organic peroxide, diamino bisphenol AF, urea, an organotin compound such as tetraphenyltin, etc.
The invention is now illustrated by certain embodiments wherein all parts are by weight unless otherwise specified.
EXAMPLES
Test Methods
Cure Characteristics
Cure characteristics were measured using a Monsanto MDR 2000 instrument under the following conditions:

    
    
        Moving die frequency: 1.66 Hz
        Oscillation amplitude: ±0.5 degrees
        Temperature: 199° C., unless otherwise noted
        Sample size: Disks having diameter of 1.5 inches (38 mm)
        Duration of test: 30 minutes
    
    


The following cure parameters were recorded:

    
    
        MH: maximum torque level, in units of dN·m
        ML: minimum torque level, in units of dN·m
        Tc90: time to 90% of maximum torque, minutes
    
    


Test specimens were prepared from elastomer compounded with appropriate additives, as described in the formulations listed in the Examples below. Compounding was carried out on a rubber mill. The milled composition was formed into a sheet and a 10 g sample was die cut into a disk to form the test specimen.
Compression set of O-ring samples was determined in accordance with ASTM D395-89, 25% deflection for 70 hours at 200° C. Mean values are reported.
The following fluoroelastomer polymer was used in the Examples: A terpolymer containing 61.8 mole percent units of TFE, 37.4 mole percent units of PMVE and 0.8 mole percent units of 8-CNVE was prepared according to the general process described in U.S. Pat. No. 5,789,489.
The following fluoropolymer having pendant sufonyl azide groups was employed as the curative in the Examples:
A terpolymer containing 65.4 mole percent units of TFE, 33.3 mole percent units of PMVE and 1.35 mole percent units of 8-SAVE was prepared according to the general process described in U.S. Pat. No. 6,365,693 B1.
Examples 1-3
Curable compositions of the invention were compounded on a two-roll rubber mill in the proportions shown in Table I. Cure characteristics of the compounded compositions are also shown in Table I.
O-rings were made by press curing at 199° C., followed by a post cure under nitrogen at 305° C. for 42 hours. Compression set values of the o-rings are also shown in Table I.












TABLE I







 




Ex. 1
Ex. 2
Ex. 3





















Formulation






(phr)1






Fluoroelastomer
100
100
100



Carbon Black MT
30
30
30



N990






Curative
100
100
100



ZnCl2
0
1.0
0



CuBr
0
0
1.0



Cure






Characteristics






ML (dN · m)
2.74
2.75
3.61



MH (dN · m)
13.11
11.93
12.47



Tc90, minutes
0.90
0.90
0.82



Compression set






%
35.0
48.0
45.0







1Parts per hundred parts fluoroelastomer

## Claims

1. A curable composition comprising:
A) a fluoroelastomer comprising copolymerized units of a cyano group-containing cure site monomer; and
B) at least one fluoropolymer comprising copolymerized units of a fluoroalkanesulfonyl azide of formula CF2═CF—(O)p—Rf—(CH2)n—SO2N3, wherein p=0 or 1; n=0-4; and Rf is a C1-C16 perfluoroalkyl or perfluoroalkoxy group.

2. A cured article made from the composition of claim 1.