MXPA97003251A - Curable compositions of fluoroelastome - Google Patents

Abstract

The present invention relates to the use of additives of the mono- and / or di-hydroxypolyfluoroether classes comprising the fluoropolyoxy-alkylene repeat units selected from the following: (C3F6O)); (CFXO) wherein X = F , CF3; (CH2CF2CF2O); (CF2 (CF2) zCF2O) where z is an integer equal to 1 or 2; (C2F4O), in the curable compositions of fluoroelastomers to improve the coefficient of friction without decreasing adhesion with binding agents to reinforcements metal

Description

nOMPORTCTONFR FLUOROUS CURRENTS OF THE FLOWERS Description of the industrial invention in the name of: AUSIMONT Spfi., Of Italian nationality, with main office in Milano, Buonapar + e, 31. The present invention relates to additives to improve the coefficient of friction of curable compositions of fluoroelas mers without decrease in adhesion, with binding agents for ine + al reinforcements. Elastomers cured with copolymers based on vinylidene fluoride, in which the vinylidene fluoride is copolymerized with one or more monomers containing an unsaturation with ethylene and at least one fluorine atom, are well known and are widely used in a variety of fields of application where exceptional chemical resistance is required to lubricating solvents, fuels, acids and similar products. ftr + cured lenses obtained from these elastomeric polymers find their most convenient use as seals (packaging) in general, both in static conditions such as dynamics, in the aeronautical, naval, mechanical, chemical, and missile and engine fields, and in the test of protection of several supports, such as protective clothing for contact with aggressive chemical agents. The curable compositions of fluoroelastomers based on vinylidene fluoride can be cured in ionic and / or radical form. In ionic curing, the essential components are the following: (0) A copolymer of vinyl fluoride with at least one other fluorine-containing rnonomer, having an ethylenic unsaturation; (B) a curing catalyst selected in particular from the following: quaternary ammonium salt, quaternary phosphonium salt, derivative of fos foranarnin; (Or one or more basic acceptors, such as, for example, r gO and Ca (0H) a; (D) a polyhydroxylated crosslinking agent Examples of these compositions are described in patents GB 1,356,344 US 3,8876,654 , US 4,259,463 Other usable materials are those that are intertwined by radical healing, in this case, the fluoroelastorian must contain radical healing sites that derive from the introduction, in the chain, of rnonomers subject to radical attack, for example, bromine-containing compounds such as operfluoroolefins, for example, n-fluoroethylene brighteners, or bromoperfluoroalkyl-vinylesters, for example, brornoperfluoroethylvinyl ether. Preferably, the terminal chain groups contain iodine atoms which are derived from saturated organic compounds such as, for example, example, Rf'I or Rf'Is "wherein Rf 'is a hydrochlorocarbon, chlorofluorocarbon or hydrocarbon radical having from 1 to 12 carbon atoms, preferably of 4 6 carbon atoms. The formulations are entangled with the addition of radical initiators, generally of the peroxide type, such as alkyl peroxides and the addition of crosslinking agents, such as, for example, tpalyl isocyanurate (TRIO, triallyl cyanurate (TOO, and phosphate). Tnalyls are also added acceptors of such acids such as, for example, zinc oxide or bromide oxide.In both types of curing, inert fillers, such as silicate, flax and carbon black are also present. Processing aids which are intended to improve the processability of the product are also present The technical problem to be solved by the present invention is to have curated fluoroelast compositions available which combine the rheological properties , of processing capacity and the characteristics of chemical and thermal resistance of the known fluoroelastorneros, as well as a lower efficient friction, both static and dynamic, which is maintained over time, also maintaining the ability to adhere to metal surfaces pretreated with bonding agents. In the measurement of the coefficient of friction, there are generally three main phases: - I start, -II slip, -III static. An improved coefficient of friction has been sought for a long time by users, since it entails, for example, a longer duration of the manufactured product and the application of less energy in the operation phase. The use of processing aids to improve the characteristics of extrusion of the mixtures and to reduce the phenomena of adhesion to the molds and / or the screwing of the mold thereof, is well known. For example, vegetable waxes, low molecular weight polyurethane stearates, polyesters, chlorosilicon oils, etc. may be mentioned. It should be noted that the number of coadjuvants used in luoroelastó eros in the technique, is very high. However, no indication or teaching in any patent or publication of the technique is given to solve the problem of having t1? Oroelastóeros available with a lower coefficient of friction that persists with time, combined with the adhesion properties specified above. The tests carried out by the applicant have shown that with the adjuvants described above it is not possible to obtain a reduction in the coefficient of friction that persists with time. Surprisingly, the applicant has now found that by using the additives of the present invention, it is possible to achieve a reduction in the coefficient of friction that persists with time, in combination with an optimum balance of the other properties defined above. An object of the present invention is therefore the use of additives of the mono- and / or di-hydroxypol groups, ifluoroethers, which comprise the repeating units of fl io-polyoxyalkylene selected from: (C3FtoO); (CFXO) where X = F, CF; (CHaCFaCFaO); (CFa (CF5,) ^ CFO?) Where z is an integer equal to 1 or 2 >; (CzF.O). The group of rnonohydroxypolifl? Oroethers preferably comprises fluoropolyethers having an average molecular weight of 500 to 5,000, preferably 600,000, wherein the repetitive units distributed statistically along the chain are selected from the following: 1) (CaFtoO), (CFXO); 2) (CaF ^ O) 3) (CHaCFaCFaO). Preferably, the group of dihydroxypolyfluoroethers comprises fluoropolyethers having an average molecular weight of from 800 to 10,000, preferably from 1,000 to 5,000, preferably from 2,000 to 4,000 where the repetitive units statistically distributed along the chain are selected from of the following: 4) (CsF ^ 0), ÍCFaO); 5) (CsF ^ O), (CaF * 0), (CFXO); 6) (CHa-CFa-CFa-O), said units being joined to each other within the tl? Roropolioxialq? Ylene chain as follows: - (O-CFa-CFa.CHa) p -0-R'r "R- <CHa-CFa-CFa-0) ß-wherein R 'r is a fluoroalkylene group having from 1 to 6 carbon atoms, p and q are integers, in order to give the molecular weight as defined above. (CF (CFa) CFaO) said units being joined to each other within the fl ooropolyoxyalkylene chain as follows: - (O-CFa-CG (CFa)) .- 0- R * -0- (CF (CFB) -CFa-0) to-where Rr is a group of fl? Oroalq? Ileno which has the meaning of R'f, yayb are integers, in order to give the molecular weight as defined above. The above group can also be used mixed together The rnononohydroxy poly fluoroethers of group 1) are in particular from those included in the following general formula: CFB0- (CaF? 0) m, (CFXO) -n, -CFX- ZH with Z = -C (DE) - 0 - where D and E are the same or different in and yes they are selected from H, CHa and CF: », C is a carbon atom, X = F or CFa; m 'and n' are positive integers of odo that the proportion m '/ n' varies from 5 to 40 and rn 'and n' are such that they give the molecular weight indicated above.

These compounds are obtained by the process described in USP Patent 3,513,203 or USP 3, 84 ?, 978, wherein the terminal group COF is transformed into OH group in accordance with USP Patents 3,810,874, USP 5,143,589. The onohydroxypolifluoroethers of class 2) are in particular selected from those found in the following general formula: CaF 0 (CaFtí0) r. -CF (CF 3) -7. - H where r 'is integer and as such gives the molecular weight indicated above, Z has the indicated meaning. These products are described in US Pat. No. 3,242,218, wherein the COF group is transformed so as to have the OH terminal group, as described in USP Patents 3,847,978, and USP 3,810,874. The inonohydroxypolyfluoroethers of class 3) are in particular selected from those which are found in the following general formula: F (CHaCFaCF _0) m - - CHaCFa - ZH where s' is integer to give the molecular weight - indicated above, Z has the indicated meaning. These products are described in published European Patent Application No. 148,482, wherein the COF group is transformed so as to have the OH terminal group, as described in USP Patents 3,847,978, and USP 3,810,874. The fl ooropolyoxyalkylene diols belonging to class 4) in particular are selected from those found in the following general formula: HZ-CFaOICaF * 0) m (CF ^ O) r, CF »-ZH where Z has the meaning described above, m and n are integers to give the molecular weight indicated above and rn / n is between 0.5 and 1.5 with the oxyfluoroalkylene units statistically distributed over the chain. The preparation of these compounds can be carried out, for example, in accordance with the methods described in the U.S. Patent. 3,810,874. The (liles containing fluorine belonging to class 5) in particular are selected from the compounds with the following general formula: HZ-CFaO- (C3F? 0) - (CaF 0) m (CFXO) * - CFa-ZH where X is -F or -CFa, the indices r, s, t are integers to give the molecular weight indicated above and Z has the previously specified meaning. Said compounds can be obtained by photooxidation of mixtures of CgFe, and C »F ,,, as described in the U.S. Patent. 3,665,041 and subsequent transformation of terminals -COF into groups q? E containing the -OH terminal, carried out with known methods described in USP Patents 3,8-47,978 and USP 3,810,874. The fluorine-containing diols belonging to class 6) are selected in particular from the compounds q? E have the general formula: Z - CF aCr - OCFaCFaCHa J í »- OR ', -0- (CHaCFaCFaO) ßCHaC to -ZH where Z and R'? they have the indicated meaning, described in the published application of European Patent EP 148, 482, in which the terminal groups -COF can be transformed, in each case having terminal groups -OH as described in USP 3,847,978 and USP 3,810,874; p and q are integers, which give the molecular weight indicated above. Fluorine-containing diols q? E belong to class 7) are selected in particular from the compounds having the general formula: R-CF (CF ,,) - < OCFaCF (CFa)) or-OR * 0- (CF (CF3) CFaO) to-CF (CF3) -R where fl is a group comprising the -OH terminal group, eg, CHaOH, R is a group fluoroalkylene as defined above, and a and b are integers, so as to indicate the molecular weight mentioned above. Said compounds are described in the published application of European Patent EP 151,877. The fluoelastomers β-sizable in accordance with the present invention, as already stated, are copolymers of vinylidene fluoride having at least one other unsaturated monomer, wholly or partially fluorinated. Examples of hexafluoropropene, tet rafluoroethylene, chlorotrifluoroethylene, 1-hydropenta luoropropene, 2-hydropentane-oropropene and perfluoroalkyl-vinyl ethers, wherein alkyl has a number of C atoms of 1 to 3. In particular, there can be mentioned copolymers of vimlidene fluoride with hexafluoropropene, whether or not containing 1 or no 11. Instead of hexafluoropropene, chlorotrifluoroethylene, l-hydropentafluoropropene, 2-hydropentafl? Oropropene and perfl? Oroalkylvinyl ethers can be used. Mixtures of the cornonomers indicated above can also be used. The amount of perfluoroalkyl vinyl ether and / or perfluoropropene is generally between 0.5 and 30% by moles of the total copolymer; TFE ranges from 0 to 60% by moles, VdF generally varies between 10-80% by moles. Other fluorine-containing rnonomers can also be used as co-terminators provided they contain a double bond of ethylene type and at least one fluorine atom. Said fluoroelastornenals can be prepared as described in the literature (Kirk-Othner, Encyclopaedia of Chem. Technology vol.8, p.500 and sequential, 1979), preferably by operation in aqueous emulsion and optionally in the presence of water transfer agents. chain such as those described in US Patent 4,000,356. In particular, elastomers are preferred wherein the vinylidene fluoride is comprised between 40% and 85% by moles, perfl? Oropropene between 15% and 30% by moles and tet rafl uo or is filled between 0 and 30% by moles. In ionic curing, the preferred catalysts of the aforementioned classes are as follows: -between quaternary ammonium salts: rnethyl-tnoctylarylonium chloride, pyridium bromide, benzyl-octyl-tononium chloride; rabutiiamomo tea chloride. -between the quaternary salts of phosphine: benzylphenylphosphonium chloride, benzyltrifenphosphonium tetrafluoroborate, methylpoctylphosphonium acetate, carbethoxyrnethylphenylphosphonium bromide; tetrafethyl phosphine chloride. -among the phosphoramine or phospho- rine salts: 1-chloro, 1-benzyl, 1,1-d? feml, N (d? et? l) - phosphoranamma and 1-tet fluo robo while, 1-benz ? l, N, N ', N "(hexarnetii) phosphorantpamine, 1-bromo, l-benzyl, l-phenyl, N, N' (tetraet? i) phosphorandia ma. The basic reagents necessary for curing are inorganic compounds such as, for example, ZnO, MgO, PbO, CaO or an oxide and hydroxide mixture of these metals or salts of weak acids, as described in the U.S. Pat. 3,876,654. In radical curing, in accordance with the present invention, small amounts of the accelerators and basic reagents indicated above are also used for single cure. The curing agent in ionic curing is a polyhydroxy compound known as a curing agent for fluoroellers. They can be mentioned: hydroquinone, resorcin, 2,2'-b? S (ph? Drox? Phen? 1) -hexa luoropropane or bisfenoi RF, 2, 2 '-b? S (p.hydroxyphenyl) -propane or bisphenol? . Examples of these compounds are registered in the Patent of E.U.A. 3,876, 654. In general, for 100 parts by weight of an elastomeric copolymer of vimlidene fluoride (R) with one or more fluorine-containing monomers, as indicated above, the following are used: - l 40 parts by weight of the acceptor of inorganic acids, which consist of one or more basic bivalent metal oxides, as indicated above, optionally in the form of cationic complexes or chelates, optionally in the presence of 0 to 10 parts by weight of one or more basic compounds , selected from the group that purchased calcium, strontium and barium hydrates, the metallic salts of weak acids such as calcium, strontium, barium, sodium and potassium carbonates, benzoates and phosphates, optionally in the form of complexes with the normal chelators or cation complex complexers of a type well known to the person skilled in the art; - from 0.5 to 4 parts by weight, preferably 1 and 2, additives of mono and / or dihydroxypolyfluoroether of the invention; - from 0.2 to 4 parts of a healing accelerator selected from here Llos of the classes described above; - from 0.3 to 6 parts of curing agent in both single and peroxide curing. Said interlacing agents are indicated above; for radical type healing of 0.5 to 10 parts of the initiator-radical. Curable compositions of the type indicated above are cured by a process consisting in first heating said compositions under pressure, at temperatures of 130 ° C to 230 ° C, preferably 160 ° C to 200 ° C, for a time of 0.5 to 60 minutes and preferably 1 to 20 minutes; successively, the articles thus obtained are then cured in an oven, at atmospheric pressure, at temperatures of 130 ° C to 315 ° C, preferably from 200 ° C to 275 ° C, during the time between 5 and 48 and preferably between 10 and 24 hours. The Applicant, unexpectedly, has discovered that the additives of the invention during the curing process, although they give a chemical reaction with the epca elasto chain (see extraction tests with the appropriate solvent of the examples), are unexpectedly present in an amount sufficient to modify the surface properties of the cured rubber and thus decrease the coefficient of static and dynamic friction. As already mentioned, this reduced coefficient of friction, apart from being combined with the good rubber processing properties, is also combined with the surprising fact that the adhesion to metallic reinforcements treated with bonding agents does not undergo reduction. any. In addition, this result is quite surprising, since the conventional processing aids used to improve the processing of fluoroelastomers, should be used in low and low amounts, generally only up to 1 phr, to avoid unwanted effects on adhesion. The curable compositions according to the present invention, in addition to the substances indicated above and the additive of the invention, contain inert fillers such as, for example, black, white and colored fillers. The present invention does not consider the use of known plasticizers and lubricants, such as stearates, aphosphates, polyethers, polyesters, polyethylene, sulfones, sulfuricides, and other known additives, which would lead to the inconveniences indicated. The components of the curable compositions according to the present invention, can be easily incorporated, both separately and pre-blended, into the vinylidene fluoride elastomeric copolymer. In this way, good cure rates at normal processing temperatures can be achieved without any danger of singeing (precuration) in the preliminary work phases, before the actual healing operation. Some examples are recorded for purposes of illustrating and not limiting the scope of the present invention.

AXLE? PLOS In the examples recorded in Tables 1 to 4, the following products were labeled: Fluoroelastomer 1Q = copolymer CHa = CFa / C3F? in molar ratio of 4/1 having a specific weight of 1.8 to 25 ° C, known co o TECN0FL0NR FOR 420 by AUSINONT; Nooney (1 «-10) at 121 ° C equal to 22 (RSTH D 1646). Formulation composition: Polymer: 100 parts Bisphenol AF: 2.1 phr Accelerator-: 1 chloro-L, l diphenol-1 benzyl, N-diethylphosphine forane: 0.4 phr Fl uo st omero 20 - copol imero CHa = CFa / CnF6 in molar ratio of 4/1, specific gravity of 1.8 at 25 ° C; Mooney (1 + 10) at 121 ° C equal to 34 (ASTM D 1646). Composition of the formulation: Polymer: 100 parts Bisphenol RF: 2.1 phr Accelerator: 1 chloro-1,1 d? Feml-1 benc? L-N, N diethyl phosphorane ina: 0.42 phr Ib FluoroDOii.tether 1 of the formula: CF30 (C, 3F60) rn, (CFaO) l CFaCHaOH with an average molecular eo (of hydroxyl title) of 700. FluoroDolieter 2 of the general formula: HO-CHaCFaO (CFaCFaO) m (CFw0) "CFaCHaOH with m / n - 1 and molecular weight of 2,000 Fluoropolyt r 3 of the general formula equal to fl oor polyester 2 and with a molecular weight of 4,000. MT neuro: thermal black smoke medium Trernin 283 600 EST: Ulalasto i ta treated with epoxysilanes. SKRUKTOL US 280: silicone oil supported on inorganic vehicle (25%). The results of the tests are recorded in Tables 1, 2 and 4.

CHARACTERIZATION OF LQS FLUQROELASTQ? ERQS CURADOS Determination of the coefficient of friction. The procedure adopted is the following: - The rubber sheets after the molding and after the subsequent cure, were hung in a container to avoid any contamination on the surface. - The sheets were conditioned at 23 ° C and 50% RH (relative humidity) for at least 48 hours. - The sheets were placed in a rigid horizontal plane of the dynamometer and adhered by means of double adhesive tape. - The device containing the two steel spheres having a diameter of 12.7 nm, was put on the test plate after having carefully cleaned the two spheres with acetone and after having dried them to perfection. The test was carried out at the sliding speed of 100 m / mm applying in the spheres three different load levels (2.11 N, 4.07 N and 7. 01 N) each time taking into account the different areas of the sheet. For each sample, two sheets were examined. The test cycle consisted of sliding the spheres for a stretch of approximately 60 minutes and then interrupting the machine by continuing with the friction force record. In this way, the friction force curves against time were obtained, from which the following friction force values were obtained: - I start - II slip - III static The coefficient of friction (fc) for each phase is determined by the well-known equation: 10 f.c. = F / LJ where F = friction force U = weight applied to the spheres. The variation of the coefficient of friction depending on the curing time at 200 ° C, for example 1, 11 and 2, 12, is recorded in table 4. The extraction tests of the fluoroethers 1, 2, 3 of examples 5, 9, 11, 12, from the rubber cured with 1, 1, 2 t chlorine, 2, 2 t rx f l uoroethane in an azeotropic mixture with acetone, carried out in the SOXTEC Extraction Unit SYSTEM 1045, are shown in Table 3. The F3- "NMR analysis of the extracts showed the presence of polymers having a low molecular weight atpb to the starting elastomer and only 2 to 3% of the extract resulted to be fluoroeter.

TABLE 1 (1) ASTM D 412 (2) ASTM D 2240 (3) ASTM D 1414 (4) ASTM D 395 C U A D R O 1 Continuation (1) ASTM D 412 (3) ASTM D 1414 (2) ASTM O 2240 (4) ASTM D 395 TABLE 2 COEFFICIENT OF FRICTION OF SPHERES OF STEEL IN HULE T = 23 ° C V = 100 mm / rpin. rü * N = LOAD APPLIED IN NEWTON FIGURE 3 Examples Extract 0.10% 9 0.0045% 11 0.060% 12 0.0055% TABLE 4 VARIATION OF THE FRICTION COEFFICIENT IN TIME AT 200 ° C * N = LOAD APPLIED IN NEWTON

Claims (14)

NOVELTY PE THE INVENTION CLAIMS

1. - Use of additives of the classes of rnono and / or di-hydroxypol -fluoroethers comprising the repeating units of fl uoropolyoxy-alkylene selected from the following: (C3FtIO); (CFXO) where X = F, CFa; (CHaCFaCrsjO); (CF -, (CFa) * CFaO) where z is an integer equal to 1 or 2; (CS-FAO), in curable compositions of fluoroelast eros to improve the coefficient of friction without decreasing adhesion with binding agents to metal reinforcements.

2. Use of additives of the mono- and / or di-hydroxypol-fluoroether classes according to claim 1, further characterized by the class of mono hydroxyfluoropolyethers comprising 500 to 5,000, wherein the units do not repeat statistically distributed over the chain are selected from the following: 1) (CaF ^ O) (CFXO); 2) (CaFtó0); 3) (CHaCF ^ CF ^ O); The class of dihydroxypolyfluoroethers comprises fluoropolyethers having a molecular weight of from 800 to 10,000, wherein the repeating units statistically distributed on the chain are selected from the following: 4) (C2F ^ 0), (CF20); 5) (CaF ^ O), (CaF ^ O), (CFXO); 6) (CHa-CFa-CFa-O), said units being joined together within the fluoropolyoxyalkylene chain as follows: - (O-CF ^ -CF ».CHa ^ -O-R'- r-0 - (CH.-CFz-CFa-0) e, -, where R '»is a fluoroalkyl group, p and q are integers, 7) (CF (CF

3) CFs.O), said units being joined together within of the fluoropolyoxyalkylene chain as follows: - (0-CF2.-CF (CF ^) ^ -OR * -0- (CF (CFa) -CFs »-0) t> -, where R is a fluoroalkylene group, a and b are integers 3.- Use of additives of the mono and / or di-hydroxypol classes Lfluoroethers according to claim 2, further characterized in that the tle class rnono hydroxypolyfluoroethers has a molecular weight composed of 600 to 3,000, the class of di-hydroxypol io? Uoroethers has a molecular weight of 2,000 to 4,000

4. Use of additives of the rnonono and / or di-hydroxypolifluoroether classes according to claims 2 and 3, further characterized in that rnonohydroxy pol i fluoro-ether is class 1) are chosen from those that are in the following general formula: CF30 ~ (CaF __. 0) m- (CFX0) n- -CFX-ZH with Z = - CADE) - O - , where D and E are equal to or different from one another and are selected from H, CH and CF3, C is a carbon atom, X = F or CF3; rn 'and n' are positive integers of odo that the ratio of m '/ n' varies from 5 to 40 and m 'and n' are such to give the molecular weight indicated above; the onohydroxypolyfluoroethers of class 2) are chosen from those which are found in the following general formula: Ca ^ OICaF ^ O) and -CF (CFa) -ZH, where r 'is an integer and as such the indicated molecular weight 2 (5 before, Z has the indicated meaning; the monohydroxy poly-fluoroethe is of Ciase 3) are chosen from those found in the following general formula: FfCHaCFaCFaO), '' -CH.aCF3.-ZH, where s' is an integer and horn such gives the molecular weight indicated above, Z has the indicated meaning; the fluoropolyoxyalkylene diols are selected from: those of class 4) are chosen from the ones found in the following general formula: HZ-CF! 20 (Ci2F.0) m (CF: 20) l-, CF¡:? - ZH, where Z has the meaning described above, rn and n are integers to give the molecular weight indicated above and m / n is between 0.5 and 1.5 with the oxy-fluoroalkylene units statistically distributed on the chain; those of class 5) are chosen from the compounds represented by the following general formula: HZ-CFaO-ZH, where X is -F or -CFa, the indices r, syt are integers to give the indicated molecular weight before and X has the previously specified meaning; those of class 6) are chosen from the compounds having the general formula: HZ-CFaCHa (OCF2CF2CH: 2) ts-OR / .r-0- where Z and R J have the indicated meaning; those of class 7) are chosen from the compounds having the general formula: A-CF (0Fa) - (0CF2CF (CFa)) ß-0R ^ 0- (CFtCF ^ CFaO) * -.- CF (CFa ) -fi, where fi is a group comprising the final group -OH, R * is a q-ylene fluoroal group, a and b are integers to indicate the molecular weight mentioned above.

5. - Use of additives of the mono and / or dihydroxypolyfluoroether classes according to claims 2 and 3, further characterized in that the fluoroelastorneros are capable of giving unsaturations subject to nucleophilic attack.

6. Use of additives of the mono- and / or di-hydroxypol-fluoride classes according to claims 2 and 3, further characterized in that the fluoroelastoners are based on copolymers of violidene fluoride.

7. Use of additives of the mono and / or di-hydroxypoly fluoroethers classes according to claim 6, further characterized in that the fluoroelast eros are ionically and / or radically cured.

8. Use of additives of the rnonono and / or di-hydroxypolyanoleter classes according to claims 5 to 7, further characterized in that the f "luoroe1 astomeros are copolymers of vimlidene fluoride with at least one other ononero, or partially flowered, comprising an ethylene unsaturation 9.- Use of additives of the mono and / or di-hydroxypoly luoroetere classes according to claim 8, further characterized in that the comonomers are exafluoro-μropane, tetrafluoroethylene, chlorot pfluoroethylene, 1-hydro-pentafluoropropene, 2-hydroquinone luoropropene, perfluoroalkyl-vi-ethers, where alkyl has a number of carbon atoms of 1 to 3. 10.- Use of additives of mono classes and / or dihydroxypolifluoroethers according to claim 9, further characterized in that the fluoroelast esters are copolymers of vimli fluoride with hexafluoropropene, which contains or not etrafluoroethylene. The mono- and / or di-hydroxypolifluoroether classes according to claims 9 and 10, further characterized in that the amount of perfluoroalkylvinyl ether and / or perfluoropropene is from 0.5 to 30 mol% in the total copolymer, TFE varies from 0 to 60% in moles, VdF generally ranges from 10 to 80% in moles. 12.- Use of additives of the mono and / or di-hydroxypolyfluoroether classes according to claim 11, further characterized in that the vinylidene fluoride is composed of 40% to 85% by moles, perfluoropropene of 15% to 30% by weight. moles, and tetrafluoroethylene from 0 to 30% by moles. 13.- Use of additives of the classes of nono and / or di-hydroxypolifluoroethers according to claims 12, further characterized by the amount of mono and / or or di-hydroxy ol i fluoroeter ranges from 0.5 to 4 parts by weight per 100 parts by weight of fluoroelastornero. 14. Use of additives of the classes of rnonus and / or di-hydroxy olifluoroethers according to claim 13, further characterized in that the amount of mono and / or di-hydroxypolifluoroether varies between 1 and 2.