KR100191760B1 - Fluoroelastomer composition with improved bonding properties - Google Patents

Abstract

The present invention provides a fluoroelastomer comprising (A) a vinylidene fluoride, tetra fluoroethylene and a hybridized polymerized repeat unit derived from a copolymerizable hydrocarbon olefin, (B) a polyhydroxy compound, (C) an organo A curable elastomer composition comprising an onium compound and a (D) fluoroaliphatic sulfonyl compound bonding promoter, wherein the amount of the fluoroaliphatic sulfonyl compound in the elastic composition comprises an aminosilane compound after curing. Bonding strength of the elastic composition to the inorganic surface coated with the said initial composition comprising the aminosilane compound and the elastic composition comprising the components (A), (B), (C) without the fluoro aliphatic sulfonyl compound It is sufficient to be larger than can be obtained by the coated inorganic surface.

Description

Fluoroelastomers with improved bonding properties, products thereof and methods of making the products

The present invention relates to a fluoroelastomer composition comprising an elastomer and a curing agent of tetrafluoroethylene, vinylidene fluoride, and at least one hydrocarbon olefin. The present invention further relates to a method of curing a shaped or manufactured article of such a fluoroelastomer composition and to the resulting shaped or manufactured, cured article. On the other hand, it is related with the fluoroelastomer composition which further contains a fluoro aliphatic sulfonamide compound as a hardening | curing agent.

Silane compounds have been used to enhance bonding between polymeric substrates and inorganic materials such as metals, fiberglass and organics or substrates (eg, 23-012 B-85, published by Dow Corning, Midland, Mich.). See the documentation for Dow Corning Silane Binder). In some cases, a composition comprising a silane compound is hydrolyzed in the form of silanol, which can react with an inorganic substance, for example by reacting with a hydroxyl group present on the inorganic surface. In general, silane compounds also have organic functional groups that react with the polymeric material to enhance the bonding between the inorganic material and the polymer. Compositions comprising silane compounds have been used successfully as several fluoroelastomers and as bonding promoters. An example is Guide Y-IFE5150-2 (73.05) RI, Dynamer ^™ Binder Metal Binder-5150, published by 3M in 1983. However, Applicants have found that, using only silane compounds, copolymers comprising tetrafluoroethylene, vinylidene fluoride and one or more hydrocarbon olefins can be bonded to the inorganic substrate to exhibit good bonding and bonding strength between the inorganic substrate and the fluoroelastomer. Found none.

It is an object of the present invention to provide a fluoro elastomer having improved bonding properties, an article comprising the same and a method of making the article.

In one aspect, the present invention provides a curable elastomer composition comprising the following components:

(A) a fluoroelastomer gum comprising interpolymerized repeat units derived from vinylidene fluoride, tetra fluoroethylene and copolymerizable hydrocarbon olefins (eg propylene),

(B) a polyhydroxy compound,

(C) organo-onium compounds, and

(D) Fluoroaliphatic sulfonyl compound conjugation promoters (e.g., fluoro aliphatic sulfonamides and fluoro aliphatic disulfones).

The amount of fluoroaliphatic sulfonyl compound in the elastic composition is

The bonding strength of the elastic composition to the inorganic (eg, metal) surface coated with the initial composition comprising an aminosilane compound after curing is such that the components (A), (B) and (C) are free of fluoroaliphatic sulfonyl compounds. It is sufficient to be larger than what can be obtained by the inorganic surface coated with the initial composition comprising the elastic composition comprising the aminosilane compound and the aminosilane compound.

On the other hand, the present invention provides a composite comprising a substrate having (1) an elastic composition in a cured state and (2) an inorganic surface coated with an initial composition comprising an aminosilane compound to which the cured elastic composition is bonded.

On the other hand, the present invention provides a composition comprising (E) an amino silane compound and (F) a fluoroaliphatic sulfonyl compound adhesion promoter as a binding composition applied to an inorganic surface, wherein the components (E) and (F) Is present in the binding composition in relative proportions and concentrations such that the desired bond between the cured elastic composition comprising the components (A) (B) and (C) described above and the substrate having the inorganic surface is exhibited.

On the other hand, the present invention provides a composite comprising (1) a cured elastic composition comprising the components (A), (B), (C) and (2) a substrate having an inorganic surface coated with the bonding composition. do.

On the other hand, the present invention provides a method for producing a composite comprising the following steps.

(1) fluoroelastomer gum (A), polyhydroxy compound (B), organo-onium (C), fluoroaliphatic sulfonyl compound adhesion promoter (D) and acid acceptor (e.g. Providing a mixture comprising calcium hydroxide);

(2) preparing an initial composition comprising an aminosilane compound;

(3) adding the initial composition to the inorganic surface of the substrate;

(4) placing the coated substrate in a mold;

(5) filling the mold with the mixture prepared in step (1);

(6) curing the mixture; And

(7) separating the produced cast product from the mold.

On the other hand, the present invention provides a method comprising the following steps:

(i) providing a mixture comprising a fluoroelastomer gum (A), a polyhydroxy compound (B), an organo-onium compound (C), and an acid acceptor;

(ii) preparing a binding composition comprising an amino silane compound and a fluoroaliphatic sulfonyl compound adhesion promoter;

(iii) adding the binding composition to the inorganic surface of the substrate;

(iv) placing the coated substrate in a mold;

(v) filling the mold with the mixture prepared in step (i);

(vi) curing the mixture; And

(vii) separating the produced cast product from the mold.

Preferred elastic compositions may further comprise one or more diorganosulfur oxide compounds as co-curing agants.

The invention also provides a shaped or manufactured, cured product made according to one of the methods described above.

Fluoroelastomers useful in the present invention are fluorine-containing polymers comprising vinylidene fluoride, tetrafluoroethylene and interpolymerized repeat units derived from one or more, preferably one or two copolymerizable hydrocarbon olefin monomers. . Such fluoroelastomers are known.

One class of such fluoroelastomers is that they are saturated (ie essentially free of ethylene or acetylenic unsaturation) and consist essentially of units derived from vinylidene fluoride, tetrafluoroethylene and one or more copolymerizable hydrocarbon olefin monomers. .

The hydrocarbon olefin monomer may be represented by the formula R'R'C = CR'R ', wherein the R' groups may be the same or different and may be selected from the group consisting of hydrogen and aliphatic radicals such as alkenyl and alkyl radicals. When R 'is alkenyl or alkyl, it may be in straight or branched form and has 1 to 4 carbon atoms.

Representative examples of olefin monomers are ethylene, propylene, and butenes (eg, isobutylene, butene-1, and butene-2 and butadiene). The molar ratio of the monomers used to make the fluoropolymer is chosen to achieve the desired properties for the cured polymer (eg, chemical resistance, high temperature stability, low temperature flexibility, and resistance to fluids such as fuels, coolants, lubricants, etc.). The choice will be within the skill of the art on the basis of known relationships between the relative amounts of specific monomers and the physical properties of the copolymers Generally, copolymers of the type are from about 2 to 90 mole percent vinylidene fluoride, 5 to 65 Mole percent tetrafluoroethylene and 5 to 45 mole percent hydrocarbon olefins, preferably they are about 2 to 65 mole percent vinylidene fluoride, 20 to 60 mole percent tetrafluoro ethylene, and 10 to 50 mole percent hydrocarbon olefin, preferably the hydrocarbon olefin is propylene.

Many fluoroelastomers or gums useful in the present invention are known in the art and can be prepared according to the methods described in the prior art. For example, Japanese Patent Digestion 60 [1985] -19324 and Japanese Patent Digestion 60 [1985] -19325 describe many fluoroelastomers useful in the present invention and methods for producing such fluoroelastomers.

In general, aminosilane compounds useful in the present invention are di- or tri-alkoxy (eg, methoxy and ethoxy) or acetoxy silanes having one or two organo groups directly bonded to silicon atoms. At least one of the organo groups should have a primary amino moiety. In use, the silane compound is hydrolyzed to silanol (e.g., by accidental water addition or water addition), i.e. hydrolyzed to the alkoxy and / or acetoxy addition hydroxylation portion of the silane compound. This hydroxyl portion reacts with the inorganic surface and reacts with the hydroxyl portion of other silanol molecules (via condensation reaction) to produce polysiloxane molecules that are linked or bonded to the inorganic surface.

The class of aminosilane compounds useful in the present invention have the following general formula:

Wherein a is 2 or 3, preferably 3, b is 1 or 2 preferably 1 and a + b is 4; R'O is a monovalent organic, hydrolyzable group such as an alkoxy group having 1 to 8, preferably 1 to 4 carbon atoms, such as a methoxy, ethoxy or acetoxy group;

R ² is a monovalent organic radical selected from the group consisting of alkyl, alkenyl, arylradicals and combinations thereof such as arylalkyl and arylalkenyl radicals; At least one such R ² group has a primary amino moiety. R ² may be straight and branched and may be cyclic if large enough. R ² may contain chains (ie, back-bone heteroatoms) such as sulfur, oxygen and nitrogen, and may be substituted with such heteroatoms. In general, R ² is 1 to 20 carbon atoms Will preferably have from 1 to 12 carbon atoms Some R ² groups can be represented by the following general formula:

C is 1 to 5, preferably 1 to 3; The R ³ and R ⁴ moieties are divalent organic moieties that can each be independently selected from the group consisting of alkylene, alkenylene, arylene moieties, and combinations thereof.

R ³ and R ⁴ generally have 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Examples of R ³ and R ⁴ moieties are propylene, ethylene, butylene, oxydiethylene or phenylene moieties and the like.

Representative amino silane compounds useful in the present invention include:

The aminosilane compounds useful in the present invention are described in Technical Bulletin Pigments No. published by Degussa Corp., Ridgefield Park, N. J. 75 pp5-6 can be prepared by the same method as described.

Many aminosilane compounds useful in the present invention are commercially available, such as Dow Corning ^™ A-1100, Z-6020, Z-6026 and Z-6032 silanes from Dow Corning. These products are available in selection guides of 23-181E-85 Dow Corning Organosilene Chemicals and A0695, A0696, A0698, A0699, A0700, A0710, A0720, A0724, A0725, A0728, A-733, A0742 in Petrarch Systems, Bristol, PA , A0750, A0800 and A0808. These products are described in Silicone Compound Registration and Review PP105 and 106, published by Petrarch Systems in 1987.

An initial composition comprising an aminosilane compound is a solution, dispersion or mixture of aminosilane compound, alcohol and water. Initial compositions comprising mixtures of one or more aminosilane compounds may also be used in the present invention. The alcohol is selected according to the solubility of the given aminosilane compound in that alcohol, but methanol and ethanol are generally useful as the solvent of the present invention. Preferably, it is readily evaporated at room temperature to facilitate the formation of a dry coating of the initial composition on the inorganic surface of the substrate. One method of preparing the initial composition is to dissolve or disperse an amount of the aminosilane compound in a mixture comprising a portion of the total amount of alcohol and the entire amount of water constituting the initial composition. The resulting mixture is then diluted with additional alcohol to get the final concentration of the desired amino silane. Typically, one part of this mixture is diluted with an additional 3-10 parts by weight of alcohol. Prior to addition to the substrate, the initial composition should be left at room temperature for 15 seconds to 48 hours (depending on the aminosilane compound) so that the aminosilane compound is hydrolyzed in silanol form. The amount of water in the initial composition should be sufficient to allow the majority of the hydrolyzable groups of the aminosilane compound to be hydrolyzed to hydroxy groups, and preferably must be sufficient to allow all of the hydrolyzable groups of the aminosilane compound to be hydrolyzed. Excess water in the initial composition should be avoided because it will interfere with the bond between the substrate and the elastomer. Typically, the alcohol comprises about 85 to 96.4 weight percent of the initial composition and the water comprises about 0.05 to 5, preferably 0.1 to 1.0 weight percent of the initial composition, and the aminosilane compound comprises about 0.1 to 10.0 of the initial composition. Weight percent, preferably 0.1 to 5 weight percent. Generally, if the fluoroaliphatic sulfonyl compound is compounded with a fluoroelastomer gum, the initial composition need not include any fluoroaliphatic sulfonyl compound. Optionally, the initial composition may also include other silane compounds that copolymerize with the aminosilane compound but do not react with the fluoroaliphatic sulfonyl compound or fluoroelastomers such as vinyl triethoxysilane. Those skilled in the art will appreciate that copolymerizable silanes can be added to the initial composition to enhance the strength, such as the adhesive strength of the dried initial composition coating.

After preparation, the initial composition is applied to the inorganic surface (prepared by the method described above) using all conventional methods of applying a coating to the substrate, such as impregnation, spraying, painting or curtain coating methods. After application, excess initial composition is removed from the inorganic surface of the substrate and the coating is dried at room temperature (eg for about 10 to 30 minutes) or the coated substrate is dried at a temperature of 50 to 60 ° C. or higher, for example at 120 ° C., about 15 Heat for minutes. The heat is thought not only to help dry the initial coating but also to form the polysiloxane mesh structure bonded to the substrate surface. The dried initial film thickness is generally 1.25 to 7.5 μm (0.05 to 0.3 mil) thickness.

The fluoroaliphatic sulfonyl compounds used in the present invention are contact promoters having an amphoteric acid, ie at least one -SO ₂ NH- or -SO ₂ CH- moiety. The fluoroaliphatic sulfonyl compound used with the aminosilane compound increases the adhesion between the cured elastic composition and the inorganic surface. The fluoroaliphatic sulfonyl compound is used between the cured fluoroelastomer and the inorganic surface, regardless of whether the compound is incorporated into the fluoroelastomer composition or applied to the inorganic surface in the form of a binder further comprising an aminosilane compound. To improve adhesion. In general, the fluoro aliphatic sulfonyl compound is selected from the group consisting of fluoro aliphatic sulfonamides and fluoro aliphatic disulfones.

Some of the class of fluoroaliphatic sulfonyl compounds useful in the present invention have the following general formula;

In this case, X is selected from the group consisting of -NHR ⁶ and -CHR ⁷ SO ₂ R _f . R ⁵ and R ⁶ are hydrogen or monovalent organic radicals, eg. It is selected from the group consisting of alkyl, aryl or combinations thereof, having 1 to 15, preferably 1 to 4 carbon atoms. R ⁵ and R ⁶ may be linear, branched and, if sufficiently large, cyclic or a combination thereof, and may be substituted by one or more non-interfering moieties such as chlorine and the like. R ⁷ is H, Br, Cl, I, alkyl having 1 to 20, preferably 1 to 4 carbon atoms, alkenyl having 3 to 4 carbon atoms (eg phenyl, pyridyl, naphthyl, thienyl , Benzthienyl), or alkaryl (up to 10 carbon atoms); If desired, alkyl, aryl and alkaryl may be substituted by, for example, one or more halogen, high fluorinated alksulfonyl, carboxyl, alkoxycarbonyl, nitro, alkoxy or acyloxy.

The carbon atom of R _f or R _f ′ bonded directly to a sulfur atom of —SO ₂ —part is at least one strong electronegative group or electron withdrawing group, preferably at least one fluorine atom or at least one high fluorinated alkyl It must be substituted by a radical. For example, this carbon atom can be represented as follows. -CF _2- , -CF (CF ₃ ), -C (CF ₃ ) ₂ , -CF (C ₂ F ₅ ), CFC 1-, -CFH-, and (CF =) CF-.

R _f is a stable, inert, nonpolar, oleophobic and hydrophobic monovalent fluoroaliphatic radical. R _f can be straight chain, branched and, if sufficiently large, cyclic or a combination thereof, eg an alkylcycloaliphatic radical. Generally R _f has 1 to 20 carbon atoms, preferably 4 to 20 and most preferably 4 to 12 carbon atoms. Preferred compounds are those in which the R _f group is fully or substantially completely fluorinated, for example R _f is perfluoroalkyl, ie C _n F _{2n + 1} (n is 4 to 20) or perfluorocyclo alkyl, ie C _n F _2n-1 (n is 5 seismic 20) or a combination of perfluoroalkyl and perfluorocycloalkyl, eg It is

R _f ′ is a divalent fluoro aliphatic radical that is stable and inert, nonpolar, oleophobic, hydrophobic. It may be straight chain, branched chain and, if sufficiently large, cyclic or a combination thereof, such as alkylcycloaliphatic diradicals. Generally R _f ′ has 1 to 20, preferably 4 to 20, most preferably 4 to 12 carbon atoms. Preferred compounds are those in which the R _f 'group is fully or substantially completely fluorinated, for example R _f ' is perfluoroalkyl, ie C _n F _2n (n is 4 to 20) or perfluorocyclo alkyl, ie C _n F _2n-2 (n is 5 to 20) or a combination of perfluoroalkyl and perfluorocycloalkyl.

In any one of R _f or R _f ′, the backbone chain or carbon atom comprises divalent oxygen, hexavalent sulfur, and / or trivalent nitrogen heteroatoms, each of which only binds to a carbon atom, which hetero atom They provide a stable bond between the fluorocarbon moieties of R _f or R _f ′ and do not interfere with the inert properties of the radicals. Preferably, when such hetero atoms are present, the backbone chain does not contain more than one hetero atom for two carbon atoms. Sometimes carbon bonded hydrogen or chlorine atoms may be present; However, when present, they are preferably not present for more than one for two carbon atoms in each chain. R _f preferably has 5 or 6 ring member atoms when R _f ′ is or comprises a ring structure, one or two of which are heteroatoms, ie oxygen and / or It may be nitrogen. In general the R _f and R _f 'radicals may comprise from 40 to 78 weight percent, preferably from 50 to 78 weight percent of fluorine. Examples of R _f radicals include fluorinated alkyls such as C ₆ F _13- , C ₈ F _17- , and alkoxy alkyls such as C ₃ F ₇ OCF ₂ -and the like. Examples of R _f ′ are fluorinated alkylenes such as —C ₄ F ₈ — and —C ₆ F ₁₂ —. If R _f and R _f ′ are designated as special radicals, such as C ₈ F _17- , it should be understood that these radicals represent the average structure of the mixture, eg C ₆ F ₁₃ -to C ₁₀ F ₂₁ -and such mixtures also It may include a side chain structure.

Fluoroaliphatic compounds useful in the present invention are prepared by reacting ammonia or primary amines with perfluoroalkane sulfonyl fluorides (eg, sulfonyl fluorides obtained by electrochemical fluorination of alkyl or alkylene sulfonyl halides). Can be. Many of the fluoro aliphatic sulfonamides useful in the present invention are known compounds (see, eg, US Pat. No. 2,732,398 (Brice et al.)).

Fluoroaliphatic disulfones useful in the present invention can be prepared by conventional methods (e.g., U.S. Patent Nos. 3,776,960 (Coshar et al.), 4,053,519 (Coshar), 4,054,596 (Coshar), No. 4,069,233 (Koshar), 3,984,357 (Koshar) and 3,794,687 (Koshhar)).

Representative fluoroaliphatic sulfonamides, and fluoroaliphatic disulfone compounds useful in the present invention include:

Other exemplary fluoroaliphatic disulfone compounds are described in column 7, lines 10-17 of US Pat. No. 4,115,295 (Robin et al.), Which is incorporated herein by reference.

Fluoroaliphatic sulfonyl compounds may be used alone or one or more such compounds may be used in the present invention.

The binding composition may be prepared by the same process as preparing the initial composition, except that the fluoroaliphatic sulfonyl compound is dissolved or dispersed in alcohol and water together with the aminosilane compound. The choice of alcohol is determined by the solubility of the preferred aminosilane and fluoroaliphatic sulfonyl compounds, although methanol or ethanol are generally useful for the preparation of the binding composition. Typically, the binding composition is 0.1 to 10 weight percent, preferably 0.1 to 5 weight percent of the aminosilane compound, 0.5 to 5 weight percent, preferably 0.5 to 2 weight percent of the fluoroaliphatic sulfonyl compound, 0.5 to 5 weight percent, preferably 0.1 to 1.0 weight percent water and 80 to 99 weight percent alcohol. Like the initial composition, the aminosilane compound in the resulting mixture must be hydrolyzed and then applied to the substrate depending on how the initial composition is applied. Like the initial coating, the bond composition coating may be air dried and also heated at 50 to 60 ° C. or higher, such as 120 ° C. for about 15 minutes.

The polyhydroxy compound mixed with the copolymer can act as a crosslinking agent for the copolymer. Such crosslinkers are known and described in the prior art. Examples include US Pat. Nos. 4,259,463 (such as mosquitoes), 3,876,654 (Patisons) and 4,233,421 (worms), and such crosslinking agents include aromatic polyhydroxy compounds and aliphatic polyhydroxy compounds and derivatives of these compounds. do. Mixtures of polyhydroxy compounds can also be used in the present invention.

Representative aromatic polyhydroxy compounds include:

Di-, tri- and tetrahydroxy-benzene, naphthalene, and anthracene, and bisphenol of the formula:

Wherein A is a divalent aliphatic, cyclo aliphatic, or aromatic radical having 1 to 13 carbon atoms or a thio, oxy, carbonyl, sulfinyl or sulfonyl radical; A is optionally substituted with one or more chlorine or fluorine atoms; X is 0 or 1; n is 1 or 2; The aromatic ring of the polyhydroxy compound may optionally contain at least one chlorine, fluorine, or bromine or carboxy or alkyl or acyl (eg, -COR ⁸ , where R ⁸ is C ₁ to C ₈ organic radical alkyl, aryl or cycloalkyl Group). Wherein the —OH group may be attached at any position of each ring (other than the carbon atom A is attached to the ring, ie, first). Aromatic polyhydroxy compounds include 4,4'-thiodiphenol, isopropylidene-bis (4-hydroxybenzene) (i.e. bisphenol A), hexa fluoroisopropylidene-bis (4-hydroxybenzene) ( Ie bisphenol AF), which is described in US Pat. No. 4,233,421 (worm).

Representative aliphatic polyhydroxy compounds include those described in fluoroaliphaticdiols such as 1,1,6,6-tetrahydrooctafluorohexanediol and US Pat. No. 4,356,599 (Holcombe et al.) And the references cited therein. Include. Polyhydroxy derivatives of representative polyhydroxy compounds that can be used as crosslinking agents are described in US Pat. No. 4,446,270 (Guensner et al.) And described, for example, 2- (4-allyloxyphenyl) -2- (4-hydride). Oxyphenyl) propane.

Preferred polyhydroxy compounds are aromatic polyhydroxy compounds of formula (IV) such as bisphenol A and bisphenol AF. Mixtures of two or more polyhydroxy compounds can be used in the present invention. When one polyhydroxy compound is replaced with another polyhydroxy compound in a given composition, one skilled in the art will be able to select a curing temperature and time that provides an appropriate cure rate for the specific application.

The organo-onium compound mixed with the copolymer can act as a curing accelerator. Organo onium compounds are conjugate acids of Lewis bases (eg phosphines, amines, ethers or sulfides) and can be prepared by reacting the Lewis bases with a suitable alkylating agent (eg alkyl halides or acyl halides). This reaction results in the expansion of the valence of the electron donor atom of the Lewis base and the positive charge of the organo-onium compound. Many organo-onium compounds useful in the present invention include at least one heteroatom, ie non-carbon atoms such as N, P, S, 0 bonded to an organic or inorganic moiety.

Organo-onium compounds useful in the present invention have been published in the art. Examples include U.S. Patent Nos. 3,655,727 (Patel et al.), 3,712,877 (Patel et al.), 3,857,807 (Kometani), 3,686,143 (Bowmann), 3,933,732 (Schugel), 3,876,654 (Patson), 4,233,421 (worms), and 4,259,463 (mosquitoes, etc.), European Patent Applications 018229A2 and 0120462A 1; Also West A. C. and Holcomb, A. rat fluorinated elastomers, Kirt-Othmer; See Chemical Technology Dictionary, Vol. 8, Third Edition, John Wiley Sons, pp. 500-515 (1979). Mixtures of organo-onium compounds are also useful in the present invention.

The organo-onium compound is a quaternary organo selected from the group consisting of ammonium, arsonium, phosphonium, styvonium, amino-phosphonium, phosphoran (e.g. triaryl phosphoran), and iminium compounds No-onium compounds and sulfonium compounds.

One class of quaternary organo-onium compounds are organic compounds that are ionically linked to anions, wherein at least one nitrogen, phosphorus, arsenic or antimony atom is covalently bonded to four organic moieties. Some of these quaternary organo-onium compounds broadly include relative positive and relative negative ions. Heteroatoms such as phosphorus, arsenic, intimones or nitrogen atoms generally contain the central atom of the zwitterion. Such compounds are generally known as ammonium, phosphonium, arsonium, stybornium salts or compounds and preferably have the following general formula:

Wherein Q is selected from the group consisting of nitrogen, phosphorus, arsenic and antimony; X is an organic or inorganic anion (eg, halides, sulfates, acetates, phosphates, phosphonates, hydroxides, alkoxides, phenoxides, bisphenoxides, etc.); n is equal to the valence of the anion x; R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are selected from radical groups consisting of alkyl, aryl, alkenyl or combinations thereof. R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may be substituted with chlorine, fluorine, bromine, cyano, -OR ¹³ and -COOR ¹³ parts, wherein R ¹³ is C ₁ to C ₂₀ alkyl, aryl, aralkyl, and It is selected from the group consisting of alkenyl. Any pair of R groups is linked to each other and to a Q atom to form a heterocyclic ring. However, in compositions wherein the copolymer is derived from vinylidene fluoride tetrafluoroethylene and propylene monomers, the polyhydroxy compound is bisphenol AF, Q is phosphorus, X is a chlorine anion, n is 1 and R ⁹ , R ¹⁰ , Three of R ¹¹ and R ¹² are phenyl moieties and the remaining R groups cannot be benzyl moieties. A preferred class of quaternary organo-onium compounds have formula (VI) and at least one of groups R ⁹ , R ¹⁰ , R ¹¹ or R ¹² is alkyl or alkenyl.

In another class of quaternary organo-onium compounds, the nitrogen, phosphorus, arsenic or antimony atoms are selected from the ring structures such as 8-benzyl-1,8-diazobicyclo [5,4,0] -7-undecnium chloride. It may be a hetero atom.

Another class of quaternary organo-onium compounds useful in the present invention are amino-phosphonium compounds, some of which have been disclosed in the art. See, eg, US Pat. No. 4,259,433 (mosquitoes, etc.). Another class of quaternary organo-onium compounds useful in the present invention are phosphoran compounds such as triarylphosphoran compounds. Some of the triarylphosphoran compounds are known and the techniques are described. See, for example, US Pat. No. 3,572,787 (D Bruner). Some of the triarylphosphorane compounds useful in the present invention have the following general formula.

Wherein Ar is aryl, for example selected from phenyl, substituted phenyl such as methoxyphenyl, chloropetyl, toryl and other known aryl groups such as naphthyl. R ¹⁴ and R ¹⁵ is (1) (a) In the case of R ¹⁴ hydrogen, methyl, ekil, propyl, and carbalkoxy alkoxy (C ₁ to C ₆ alkyl) and (b) in the case of R ¹⁵ carbalkoxy alkoxy (C ₁ to C ₆ alkyl) is selected from the group consisting of each group individually selected from cyano and -CONH ₂ and (2) a single group together with the carbon atom to which the single group is bonded to form a cyclic group selected below. .

Another class of quaternary organo-onium compounds useful in the present invention are iminium compounds. Some of the iminium compounds useful in the present invention are organic compounds having the following general formula.

Wherein R ¹⁶ is a monovalent organic radical that terminates with a non-carbon atom such as P, S, O or N and this organic radical is covalently bonded to the nitrogen atom via the non-carbon atom, and C is the valence of the anion X, e.g. 1 or 2 and X are organic or inorganic anions, such as halides, hydroxy, sulfates, thiosulfates, nitrates, formates, acetates, cyanates, thiocyanates, tetraphenylborates, 2-merchatobenzothiazolates, phosphates , Phosphonate, alkoxide, phenoxide, bisphenoxide or perchlorate ion. The positive charge of the cation can be transferred to the N atom, but can also be uniformly distributed between the two nitrogens and the other hetero atom to which it is bonded.

Other classes of iminium compounds useful in the present invention are disclosed in the prior art and include, for example, European patent applications 182299A 2 and 120462A 1.

Representative quaternary organo-onium compounds include phenyltrimethyl ammonium chloride, tetrapentylammonium chloride, tetrapropylammonium bromide, tetrahexylammonium chloride, tetraheptylammonium bromide, tetramethylphosphonium chloride, tetramethylammonium chloride, tetrabutylforce Phosphorus chloride, tributylbenzyl phosphonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tributylallylphosphonium chloride, tetraphenylphosphonium chloride, tetraphenylarsonium chloride, tetraphenylstibonium chloride, 8-benzyl- 1,8-diazobicyclo [5.4.0] 7-undecenium chloride, benzyltris (dimethylamino) phosphonium chloride, tributyl (2-methoxy) propyl phosphonium chloride, dibutyldiphenyl phosphonium chloride and Vis ( Jildi is phenyl phosphine) already contains nium chloride.

Sulfonium compounds useful in the present invention are shown in the prior art. See, eg, US Pat. No. 4,233,421 (worm). Sulfonium compounds are sulfur-containing organic compounds in which at least one sulfur atom is covalently bonded to three organic moieties having from 1 to 20 carbon atoms by carbon-sulfur covalent bonds. The organic moieties can be the same or different. Sulfonium compounds are generally ionically linked with anions. Sulfonium compounds may have one or more relative positive sulfur atoms, eg, (C ₆ H ₅ ) ₂ S ⁺ (CH ₂ ) ₄ S ⁺ (C ₆ H ₅ ) ₂ ] 2Cl ⁻ , two of the carbon-sulfur covalent bonds The dog may be between the carbon atoms of the divalent organic moiety, ie the sulfur atom may be a hetero atom in the ring structure.

A preferred class of sulfonium compounds are salts having the general formula

Wherein R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different when at least one of these groups is aromatic. The R group can be selected from the group consisting of aromatic radicals having 4 to 20 carbon atoms (eg substituted and unsubstituted phenyl, thiethyl and furanyl), and alkyl radicals having 1 to 20 carbon atoms. Alkyl radicals include substituted alkyl radicals (eg substituted with halides, hydroxy, alkoxy, aryl moieties). Z is oxygen;

sulfur; S = 0; C = 0; It is selected from the group consisting of.

In which R ²⁰ represents an aryl or acyl moiety (acetyl, benzoyl, etc.), a carbon-carbon bond and It is selected from the group consisting of. Wherein R ²¹ and R ²² are selected from the group consisting of hydrogen, alkyl radicals having 1 to 4 carbon atoms and alkenyl radicals having 2 to 4 carbon atoms.

n is 0 or 1, x is an inorganic or organic anion, and a is the valence of x. Examples of suitable representative x anions are halides such as chlorine and bromine, sulphate, bisulfate, nitrate, hydroxide, piclorate, trifluoromethane sulfonate, acetate, benzene sulfonate, tetrafluoroborate, hexa Chlorophosphate, hexafluorophosphate, hexachlorostanate, hexanefluoroalsenate, hexafluoroantimonate, phenoxide and bisphenoxide.

An additional component in this composition is the acid acceptor. Acid acceptors can be inorganic or organic compounds. Organic acid acceptors include sodium stearate, and magnesium oxalate. However, acid acceptors are generally inorganic bases and include magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphite, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate and the like. do. Preferred acid acceptors are magnesium oxide and calcium hydroxide. The acid acceptors can be used singly or in combination and are preferably used in an amount of 2 to 25 parts by weight per 100 parts by weight of the polymer.

Preferred elastomer compositions include one or more diorgano sulfoxide compounds. The diorgano compound may function to enhance the curing rate of the composition when combined with other components in the composition. The diorgano compounds are also shown in the prior art, for example, US Pat. No. 4,287,320 (Colb). The compound, briefly described, comprises at least one sulfur atom, one or two oxygen atoms bonded only to each sulfur atom, and, in addition, two neutral organic radicals which are bonded directly to the sulfur atoms by a single CS bond. R ²³ ) ₂ SO _x (x is 1 or 2 and each R ²³ is an organic radical). Each organic radical, R ²³ , may be the same or different and each radical may contain 1 to 20 or more carbon atoms, but preferably 1 to 8 carbon atoms and the total number linked to each sulfur atom is preferably about 30 carbon atoms or less. Both R ²³ groups may be a single alkylene group which together with the sulfur atom form a heterocyclic ring.

The carbon skeletal chain of the R ²³ group can be straight, branched or cyclic and can be aliphatic or aromatic and can include chain heteroatoms such as oxygen in addition to carbon. The chain may or may not be substituted with, for example, halides, alkoxy, -SOR, -SO ₂ R, carboalkoxy, oxo, hydroxyl, nitro, cyano, alkyl, aryl. Such compounds include diorgano sulfoxides, (R ²³ ) ₂ SO, and diorganosulfones, (R ²³ ) ₂ SO _2, and include, for example, Basic Principles of Organic Chemistry, Robert and Caserio, WA Benjamin Company, New York, New York, 1954, in particular pp 756-760, and Organic Syntheses Volume 1 pp 718-725, Volume 2 pp 1709-1715, Reinhold Press, New York, New York 1957. Representative diorgano sulfoxides include dimethyl sulfone, tetramethylene sulfone and bis (4-chlorophenyl) sulfone. Diorgano sulfur oxides to be added are described in US Pat. No. 4,287,320 (Colb).

Fillers are often added to the polymers described above to alter the properties of the cured elastomer. When a filler is used, it is added in the cured state up to about 100 parts by weight per 100 parts by weight of rubber, preferably between about 15 and 50 parts by weight per 100 parts by weight of rubber. Examples of fillers that can be used are reinforced thermal grade carbon black or non-black pigments having relatively low reinforcing properties such as clays, barite.

Organo-onium compounds, poly hydroxy compounds and fluoro aliphatic sulfonyl compounds can be introduced into the curable copolymer in finely pulverized solid form by pulverizing the compound into copolymer gumstock. After mixing, the gum stock can be stored for a long time, typically at room temperature, for example for two years or more. Prior to curing, the acid acceptor is ground into gumstock comprising organo-onium, polyhydroxy and fluoro aliphatic sulfonyl compounds, after which the storage period of the stock is further limited. Of course, all components of the curing system can be mixed before incorporation into the elastomer without departing from the scope of the present invention. Another method of incorporating the components of the present invention into the curable copolymer is to prepare a complex of a metal salt of a polyhydroxy compound (e.g., sodium, calcium, etc.) and an organo-onium compound, and the complex is fluoroaliphatic sulfonyl Adding to the non-vulcanized cured copolymer with the compound and, if desired, other additional polyhydroxy compounds. However, another method of incorporating the components of the present invention into the curable copolymers is to prepare metal salt complexes of metal salts of polyhydroxy compounds and fluoroaliphatic sulfonyl compounds together with organo-onium compounds, Addition to coalescing. The complexes are generally combined with a polyhydroxy compound and a fluoro aliphatic sulfonyl compound in a suitable solvent (e.g. methanol) in an equimolar amount of sodium methoxide in the reaction mixture to form a monosodium salt and a fluoro of the polyhydroxy compound. It is prepared by forming a monosodium salt of an aliphatic sulfonyl compound. The resulting salt then reacts with the same molar amount of the organo-onium compound to form a complex of a polyhydroxy compound and an organo-onium compound and a complex of a fluoro aliphatic sulfonyl compound and an organo-onium compound .

Polyhydroxy and organo-onium compounds are present in the composition in relative amounts that, when mixed with an acid acceptor, give the composition the desired state of cure. Representative proportions of the components of the curing system are shown in Table 1. All amounts described are given in abbreviations phr as parts per 100 parts by weight of rubber or mmhr as abbreviations per 100 parts of rubber, and rubber refers to elastomeric copolymers or gums unless otherwise indicated. This ratio is in the general range and the specific amounts for each specific curing time and temperature will be apparent to those skilled in the art.

When compounded with a gum, the amount of fluoro aliphatic sulfonyl compound is sufficient to bind with the aminosilane compound, resulting in greater adhesion between the cured elastomer and the substrate surface than without the fluoro aliphatic sulfonyl compound. shall. Generally, fluoro aliphatic sulfonyl compounds are used at levels of 0.1 to 10 phr, preferably 0.2 to 1 phr.

Useful elastomers are obtained within the blending ranges described above, and elastomeric products of particularly desirable properties can be obtained by varying the relative amounts of components within certain ranges. Preferably, the composition comprises 2.3 to 3.0 mmhr organo-onium compound and 2.0 to 6.0 mmhr polyhydroxy compound. Preferred compositions also comprise a diorgano sulfoxide compound, most preferably tetramethylene sulfone and / or dimethyl sulfone in a concentration of 0.01 to 5 phr.

In some cases, it may be desirable to add other conventional adjuvants or ingredients, such as retarders, process aids, reinforcing agents, plasticizers, and fillers, to gumstock.

According to the present invention, a fluoroaliphatic sulfonyl compound (when combined with a fluoroelastomer gum), an acid acceptor, an organo-onium compound, a polyhydroxy compound, a diorgano sulfur oxide compound, and optionally other A preferred amount of conventional adjuvant or ingredient is added to the uncured copolymer (ie gumstock) and mixed or compounded sufficiently using one of the conventional rubber mixers such as a Banbury mixer, roll mill, or other conventional mixer. Let's do it.

For good results, the temperature of the mixture in the mill should not be raised above about 120 ° C. During mixing it is necessary to distribute the components and adjuvants uniformly throughout the curable polymer. Typically the curing process extrudes or presses the compounded mixture around an inorganic substrate, such as a metal injector, in a mold (eg, cavity or transfer mold) and then oven cures. Pressurization (press hardening) of the combined mixture is carried out between about 95 ° C. and about 230 ° C., preferably between about 150 ° C. and 205 ° C. for 1 minute to about 15 hours, generally 5 minutes to 30 minutes. A pressure between about 700 KPa and about 20,600 KPa, preferably between about 3,400 KPa and about 6,800 KPa is applied to the compounded mixture in the mold. Initially the mold is coated with a release agent, for example silicone oil, and then preheated. The cast cured product is then post-cured (oven cured) at about 150 ° C. and about 315 ° C., typically about 232 ° C., for about 20 to 50 hours or more, depending on the cross-sectional thickness of the specimen. If desired, for example, when the cross section is thick, the post curing temperature is gradually increased from the lower limit to the desired maximum temperature. The maximum temperature used is preferably about 232 ° C. and maintained at this value for at least about 4 hours.

The inorganic substrate surface was coated with Davis, D. second. And Cosmara, Jay. Practical approach to fluoroelastomer binding to metals of L., published in the Air Rubber Group Adhesion Symposium, Houston, Texas, May 30, 1985 and in Chemlok ^TM 607 brochure DSIO-6005J, published by Rodman, 1981 It should be prepared using the same conventional method. For example, the nonmetallic surface should be thoroughly cleaned using a suitable solvent. For example, the glass can be cleaned using an alkaline bath. The manufacture of a metal base material depends on the kind of metal to a certain extent. However, if rough processing of the substrate surface is required, the substrate is first degreased with a suitable solvent such as trichloroethylene or Stoddard solvent and then sand blasted (eg using 40 to 60 mesh alumina grit) and then the sand blasted surface is Degrease again.

The main utility of the cured, highly fluorinated elastomers of the present invention is in applications as shaft seals in automobiles, gaskets, and the like, which contain fluids under pressure at elevated temperatures, for example used in aircraft hydraulic systems or in chemical processes. It can be used as a part.

The following examples are provided to aid the understanding of the present invention and do not limit the scope of the present invention.

EXAMPLE

32.4 mol% vinylidene fluoride, 42.1 mol% tetrafluoroethylene and 25.5 mol% propylene were used in all of the following examples.

[Examples 1-6 and C1-C5]

Compounded curable gumstocks containing various fluoro aliphatic sulfone amides were prepared. The components of the combined gumstock are shown in Table 2. All amounts are expressed in parts by weight, millimoles per 100 parts by weight of rubber (mmhr) or parts by weight (phr) per 100 parts by weight of rubber.

Bisphenol AF and tributyl (2-methoxy) propyl phosphonium chloride were combined together before mixing into the gum. The complex was prepared by reacting sodium methoxide 2.3 mmoles with bisphenol AF 3.7 mmoles in methanol to form the mono sodium salt of bisphenol AF. This mono sodium salt was then reacted with tributyl (2-methoxy) propyl phosphonium chloride. Sodium chloride formed and precipitated from the solution while the bisphenol-phosphonium complex remained in solution. Bisphenol-phosphonium complexes, unreacted bisphenol AF, and the other components described above were combined under two rolls using standard methods.

The curing fluidity of the samples was uncured and compounded using Monsanto Oscillating Disc Rheometer (ODR) Model 100S and by the method of ASTM D2084-82 (using microdie, no preheating, oscillator frequency 100cpm and 3 ° arc). Was measured by measuring. All samples showed good curing.

An initial composition comprising 3-aminopropyltriethoxy silane was prepared by first dissolving 5 weight percent of 3-aminopropyltriethoxy silane in a solution comprising 0.5 weight percent water and 94.5 weight percent methanol. The silane was hydrolyzed for nearly 4 hours. A portion of this solution was then diluted with 3 parts by weight of methanol to form the initial composition. Immediately sand blasted, twice washed with trichloroethylene and air dried carbon strips were immersed in a composition comprising hydrolyzed 3-aminopropyl triethoxy and then air dried. The strip was then heated to about 50 [deg.] C. for about 30-45 minutes, cooled at room temperature and then the combined elastic gum was added to the sample and pressure cured at 177 [deg.] C., 2500 kPa for 10 minutes.

The sample was pressure cured, the cured cured product was cooled to room temperature, and the adhesion to the metal strip of the cured elastomer was measured. Adhesion defects between the cured elastomeric composition and the metal strip, i.e. poor bonding or non-bonding, have been characterized by the use of forceps to peel off the cured product from the metal strip by hand or the cured product falling off the metal strip by weight. Agglomeration defects, ie, good bonds between the cured elastomeric composition and the metal strip, were so strongly bonded to the metal strip that the rubber was damaged instead of falling off the metal strip by forceps. Cohesion defects in the elastomer exhibit excellent bonds between the cured elastomer composition and the metal strip. The fluoro aliphatic sulfone amides used in this example, their binding performance, and their defect forms are shown in Table 3.

In Examples C1 and C2, the elastomeric composition included hydrocarbon sulfone amides and no fluoro aliphatic sulfone amides of the present invention. This cured product showed adhesive defects showing only poor and non-bonding with the metal strip. Thus, these data show that the sulfone amides useful for promoting adhesion between the cured elastomer and the metal should be fluoro aliphatic. Example C3 It is shown that a sulfur atom of -SO ₂ -parts should be directly bonded to a strong electron-reactive moiety, for example, -CF ₂ -parts to obtain good bonds. Example C4 shows that the nitrogen atom of fluoroaliphatic sulfonamide must be bonded to at least one hydrogen atom in order to obtain a good bond between the cured elastomeric composition and the metal strip.

Example 7 and C6

This example illustrates the concentration of fluoro aliphatic sulfone amides effective to obtain good binding. A combined gumstock (A) comprising C ₈ F ₁₇ SO ₂ NHCH ₃ (1 mmhr) as fluoro aliphatic sulfone amide was prepared according to the process of Examples 1-6. A similar compounded gumstock (B) was also prepared according to the ingredients in Table 2 but this did not include any fluoro aliphatic sulfonamides. Various amounts of (A) and (B) were then combined to obtain final gumstock (C) with different fluoroaliphatic sulfonamide concentrations. The resulting specimens were pressure cured on a carbon steel strip coated with the initial composition described in Examples 1-6 according to the process described in Examples 1-6. The adhesion between the resulting cured product and the metal strip was measured according to the method described in Examples 1-6. The weight ratio of compounded gumstock used, (A) / (B), final concentration of fluoroaliphatic sulfonamide of gumstock (C), and binding properties for the metal strip of the cured product are summarized in Table 4.

This data shows that the lower limit of fluoroaliphatic sulfonamide is 0.25 mmhr.

This example shows the preparation and use of the binding composition. Initially, the binding composition was prepared by preparing a solution of 5 weight percent 3-aminopropyltriethoxy silane, 0.5 weight percent water and 94.5 weight percent methanol. 0.3 g (0.58 mmoles) of C ₈ F ₁₇ SO ₂ NHCH ₃ was dissolved in 5 g of this solution. The resulting solution was then diluted with three times the weight of methanol. This solution was added to the surface of the metal strip prepared according to the process of Examples 1-6. The strip was air dried, heated to about 50 ° C. for about 30-45 minutes and cooled to room temperature.

A fluoroelastomer composition similar to that described in Table 2 was prepared according to the process described in Examples 1-6, except that no fluoro aliphatic compound was included. The combined elastomer composition was then pressure cured at 177 ° C., 2500 kPa for 10 minutes on the coated metal strip. After curing, the cured product was cooled to room temperature and the adhesion between the metal strip and the cured elastomer composition was measured according to the method described in Examples 1-6. The cured product exhibited cohesive bonds, ie formed very good bonds between the metal strip and the cured product. Indeed, the bond was as strong as the bond formed between the metal strip of Example 2 and the cured product.

[Examples 9 and C7]

This example illustrates the use of various amino silane compounds. The metal strip was coated with an initial composition prepared by dissolving 5 weight percent of the amino silane compound in 94.5 weight percent of methanol and 0.5 weight percent of water. The resulting solution was hydrolyzed at room temperature for 4 hours and diluted with 3 parts by weight of methanol. The cleaned metal strip was then immersed in the resulting solution and dried according to the method described in Examples 1-6. A combined gum having the composition of Table 2 was prepared according to the method described in Examples 1-6, except that 0.5 phr of C ₈ F ₁₇ SO ₂ NH ₂ was included as fluoroaliphatic sulfonamide. The compound gum was then pressure cured for 15 minutes at 177 ° C. 2500 kPa against the metal strip. After cooling the cured product to room temperature, the bonding force between the cured elastomeric composition and the metal strip was measured according to the method described in Examples 1-6. The aminosilane compounds used and the binding properties observed are summarized in Table 5.

This data shows that the aminosilane compound must have at least one primary amino moiety to obtain good binding.

Example 10 and C8

This example shows the use of a fluoro aliphatic disulfone compound as the fluoro aliphatic sulfone compound. Fluoroaliphatic disulfone, (C ₆ F ₁₃ SO ₂ ), in place of the fluoroaliphatic sulfonamide compound used in Example 1-6 for preparing the elastomer composition according to the components and methods described in Examples 1-6. ₂ CH _{2 1} mmhr was used.

An initial composition comprising 3-aminopropyl triethoxy silane and a metal strip were prepared according to the method described in Examples 1-6, and the metal strip was coated according to the method described in Examples 1-6. Then, according to the method described in Examples 1-6, a sample of the compounded elastomer composition was pressure-cured with respect to the coated metal strip, the cured product was cooled to room temperature, and then the adhesion between the cured elastomer composition and the metal strip was performed. It measured according to the method described in Example 1-6. Cohesion defects in the elastomer composition indicate that the presence of the fluoroaliphatic disulfone compound was efficient at forming good bonds between the cured elastomer composition and the metal strip.

Various modifications and variations will be possible to those skilled in the art within the scope and spirit of the present invention.

Applicant's invention relates to curable fluoroelastomers comprising hybrid polymerized repeat units derived from vinylidene fluoride, tetrafluoroethylene and hydrocarbon olefins (e.g., propylene), shaft seals, valve stem seals, Improves bonding or bonding between inorganic substrates such as metal cores, supports or implants used in various cast seals such as gaskets.

Claims (7)

(a) about 0.1 to 10% by weight aminosilane compound and (b) about 0.5 to 5% by weight fluoroaliphatic sulfonyl compound, which is useful for improving adhesion between the substrate and the curable fluoroelastomer composition after curing. Binding composition. The binding composition of claim 1, wherein the binding composition further comprises about 80-99 wt% alcohol and about 0.5-5 wt% water. The fluoroelastomer gum according to claim 1 or 2, wherein the curable fluoroelastomer composition comprises (a) a hybridized polymerized repeating unit of vinylidene fluoride, tetrafluoroethylene and a copolymerizable hydrocarbon olefin, (b ) A binding composition comprising a polyhydroxy compound and (c) an organo-onium compound. An article comprising an adhesive cured fluoroelastomer composition portion with a substrate treated with the bonding composition of claim 1 prior to curing the adhesive fluoroelastomer composition. 5. The fluoroelastomer gum of claim 4, wherein the cured fluoroelastomer composition portion comprises a hybridized polymerized repeat unit of (a) vinylidene fluoride, tetrafluoroethylene and copolymerizable hydrocarbon olefins, (b) poly An article prepared by curing a curable fluoroelastomer composition comprising a hydroxy compound and (c) an organo-onium compound. (a) providing a curable fluoroelastomer composition, (b) applying the binding composition of claim 1 to at least one side of the substrate, (c) placing the coated substrate in a mold, ( d) filling a mold with the curable fluoroelastomer composition and (e) curing the fluoroelastomer composition. 7. The fluoroelastomer gum according to claim 6, wherein said curable fluoroelastomer composition comprises a hybridized repeating unit of (a) vinylidene fluoride, tetrafluoroethylene and copolymerizable hydrocarbon olefins, and (b) polyhydroxy Compound and (c) an organo-onium compound.