MXPA06000763A - A functional fluid and the use thereof - Google Patents

Abstract

The present invention concerns a functional fluid comprising A) 1 to 99%by weight based on the total weight of the functional fluid of alkyl(meth)acrylate polymers obtainable by polymerizing a mixture of olefinically unsaturated monomers, which consists of a) 1-100 wt%based on the total weight of the ethylenically unsaturated monomers of one or more ethylenically unsaturated ester compounds of formula (I) where R is hydrogen or methyl, R1 means a linear or branched alkyl residue with 1-6 carbon atoms, R2 and R3 independently represent hydrogen or a group of the formula -COOR', where R'means hydrogen or a alkyl group with 1-6 carbon atoms, b) 0-99 wt%based on the total weight of the ethylenically unsaturated monomers of one or more ethylenically unsaturated ester compounds of formula (II) where R is hydrogen or methyl, R4 means a linear or branched alkyl residue with 7-40 carbon atoms, R5 and R6 independently are hydrogen or a group of the formula -COOR", where R"means hydrogen or an alkyl group with 7-40 carbon atoms, c) 0-50 wt%based on the total weight of the ethylenically unsaturated monomers comonomers, and B) 1 to 99%by weight based on the total weight of the functional fluid of an oxygen containing compound selected from to group of organophosphorus compounds, carboxylic acid esters and/or polyether polyols.

Description

A FUNCTIONAL FLUID AND THE USE OF THE SAME The present invention is directed to a functional fluid and the use thereof. Functional fire-resistant fluids are well known in the art. These fluids can be used as hydraulic fluids. The current leak-resistant hydraulic market is dominated by four major classes of fluids: HFA: Fluids with high water content, > 80% water HFB: Water Emulsions in Oil < 50% water HFC: Water / glycol fluids HFD: Anhydrous fluids HFD-R: Phosphate ester fluids HFD-U: All others, including polyol esters, vegetable esters, fluorocarbons, silicate esters, silanes, and certain fluids PAO A wide range of cost and performance options can be found within this fluid class. The low cost fire resistant fluid option is the water / glycol systems, however, they are limited to low pressure applications and invite corrosion and high maintenance. The operating temperature window is limited to -20 to 60 ° C. The vegetable oil and polyol ester systems are anhydrous systems available with the lowest price. Vegetable oil or vegetable derived fluids offer excellent biodegradation, however, these systems offer (relatively) weak resistance to fire and poor oxidant stability, and often unacceptable low temperature performance. The operating temperature windows are in the range of -10 to 100 ° C. Fully saturated synthetic polyol ester fluids offer good oxidation stability and a wide operating window at temperature (-40 to 120 ° C), however they provide a low resistance to fire (Factory Mutual Group 2 classifications by FMRC 6930) . Many of the polyol ester and vegetable oil fluids employ the use of high molecular weight polymers for anti-fog control, and these additives are subject to shear degradation. Triaryl phosphates offer a high level of fire resistance and applicability, but their benefits are offset by high cost, seal compatibility problems and generation of phenolic waste at the time of decomposition. The use of fatty acid esters and phosphate esters with or without the use of polymeric additives is typical for industrial hydraulic fire resistant fluid technology. It is commonly known that the use of polymer additives with a low molecular weight prove to be inefficient to improve fire resistance properties until Hara, Shigeo, et al., Idemitsu Kosan Co., Ltd., (Japanese Patent Application No. 269480/1999, Idemitsu Kosan, Co., Ltd.) demonstrated a Efficient improvement to fire-resistant property through the use of a combination of high and low molecular weights in a polymer combination system. The inventors claim that the use of low molecular weight polymers alone is not effective. The German Patent DE 1979-2948020, Mobil Oil Corp., describes that hydraulic fluids can be formulated from oleic acid esters of a polyol (especially pentaerythritol, trimethylol propane or neopentyl glycol). The claims indicate synergies between antioxidants and defoaming additives that lead to a prolonged life of the fluid. There are no claims about the use of polymer components. It is unlikely that these compositions can meet the requirements of the fire resistance tests of Factor Mutual, and performance at low temperatures will be bad. Taking into consideration the above technology, it is an object of this invention to provide new functional fluids which have a higher resistance to fire and which do not invite corrosion. Additionally, it is an object of the present invention to provide functional fire-resistant fluids having better properties at low temperature. In addition, it is assumed that the new fluids are producible in a simple way and with a favorable cost. Even moreIt is an object of the present invention to provide fluids that are biodegradable and environmentally friendly. Additionally, it is an object of the present invention to provide new functional fluids that are applicable over a wide temperature range. In addition, the fluid must be correct for high pressure applications. These and other tasks not explicitly mentioned, which, however, can easily be delivered or developed from the introductory part, are solved through the functional fluids of the present invention. The expedient modifications of the fluids according to the invention are described in the claims. A functional fluid comprising: A) 1 to 99% by weight based on a total functional fluid weight of alkyl (meth) acrylate polymers obtained by polymerizing a mixture of olefinically unsaturated monomers, consisting of a) 1-100% weight based on the total weight of the ethylenically unsaturated monomers of one or more of the ester compounds ethylenically unsaturated of the formula (I) where R is hydrogen or methyl R1 means a linear or branched alkyl residue with 1-6 carbon atoms, R2 and R3 independently represent hydrogen or a group of the formula -COOR ', where R' signifies hydrogen or an alkyl group with 1-6 carbon atoms, b) 0-99% by weight based on the total weight of ethylenically unsaturated monomers of one or more ethylenically unsaturated ester compounds of the formula (II) where R is hydrogen or methyl, R4 is a linear or branched alkyl residue with 7-40 carbon atoms, R5 and Rs independently are hydrogen or a group of the formula -COOR ", where R" signifies hydrogen or an alkyl group with 7-40 carbon atoms. c) 0-50% by weight based on the total weight of the ethylenically unsaturated monomer comonomers, and B) 1 to 99% by weight based on the total weight of the functional fluid of an oxygen containing a compound selected from the group of organophosphorus compounds, carboxylic acid esters and / or polyether polyols. They provide a high resistance to fire that can be applied over a wide temperature range. At the same time a number of other advantages can be achieved through the functional fluids according to the invention. Among these are: The functional fluid of the present invention has combustion / flammability characteristics. The functional fluid of the present invention has an improved cost / performance ratio. The functional fluid of the present invention is biodegradable and environmentally acceptable. The functional fluid of the present invention shows improved performance at low temperature. The functional fluid of the present invention can be produced on a cost-favorable basis. The functional fluid of the present invention exhibits good resistance to oxidation and is chemically stable. The viscosity of the functional fluid of the present invention can be adjusted over a wide range. In addition, the fluids of the present invention are correct for pressure applications. The fluids functionalities of the present invention show low degradation to the cut. The fluid of the present invention comprises 1 a 99% by weight, especially 2 to 50% by weight, and preferably from 5 to 30% by weight, based on the total weight of the functional fluid, of one or more functional (meth) acrylate polymers. The composition from which the alkyl (meth) acrylate polymers are obtained, contain in particular (meth) acrylates, maleates and fumarates having different alcohol residues. The term (meth) acrylates includes methacrylates and acrylates as well as mixtures of the two. These monomers are known to a large extent. The alkyl residue may be linear, cyclic or branched. The blends for obtaining alkyl (meth) acrylate polymers contain from 1 to 100% by weight, preferably from 1 to 90% by weight, especially from 10 to 80% by weight, more preferably from 15 to 70% by weight based on the total weight of the monomer mixture of one or more ethylenically unsaturated ester compounds of the formula (I) where R is hydrogen or methyl, R1 means a linear or branched alkyl residue with 1-6, especially 1 to 5 and preferably 1 to 3 carbon atoms, R2 and R3 are independently hydrogen or a group of the formula -COOR ', where R 'means hydrogen or an alkyl group with 1-6 carbon atoms. Examples of components (a) are, inter alia, (meth) acrylates, fumarates and maleates, which are derived from saturated alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, n-methyl (meth) acrylate and propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate; cycloalkyl (meth) acrylates, such as cyclopentyl (meth) acrylate. In addition, the monomer compositions for producing polyalkyl (meth) acrylates useful in the present invention contain from 0-99, preferably from 10-99% by weight, especially 20-90% by weight and more preferably from 30 to 85% by weight based on the total weight of the monomer mixture of one or more ethylenically unsaturated compounds of the formula (II) where R is hydrogen or methyl, R4 means a linear or branched alkyl residue with 7-40, especially 10 to 30 and preferably 12 to 24 carbon atoms, R5 and R6 are independently hydrogen or a group of the formula -COOR " , where R "means hydrogen or an alkyl group with 7 to 40, especially 10 to 30 and preferably 12 to 24 carbon atoms. Among these are (meth) acrylates, fumarates and maleates which are derived from saturated alcohols such as 2-ethylhexyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylate. of 3-isopropylheptyl, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate , tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, (meth) pentadecyl acrylate, 2-methylhexadecyl (meth) acrylate, heptadecyl (meth) acrylate, -isopropylheptadecyl (meth) acrylate, 4-tert-butyloctadecyl (meth) acrylate, 5-ethyl-octadecyl (meth) acrylate, 3-isopropyloctadecyl (meth) acrylate, octadecyl (meth) acrylate, (meth) acrylate, nonadecyl, eicosyl (meth) acrylate, cetileicosyl (meth) acrylate, stearylcosyl (meth) acrylate, docosyl (meth) acrylate, and / or eicosyltetratriacontyl (meth) acrylate; cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, (methyl) bornyl acrylate, 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth) acrylate; and the corresponding fumarates and maleates. The ester compounds with a long-chain alcohol residue, especially component (b), which can be obtained, for example, by reacting the corresponding (meth) acrylates, fumarates, maleates and / or acids with long-chain fatty alcohols, where in general, a mixture of esters such as (meth) acrylates with different long chain alcohol residues results. These fatty alcohols include, among others, Oxo Alcohol® 7911, Oxo Alcohol® 7900, Oxo Alcohol® 1100, Alfol® 610, Alfol® 810, Lial® 125 and types of Nafol® (Sasol Olefins &Surfactants GMBH); Alphanol® 79 (ICI); Epal® 610 and Epal® 810 (Ethl Corporation); Linevol® 70, Linevol® 911 and Neodol® 25E (Shell AG); Deity®-, Hidrenol®- and types of Lorol® (Cogins); Acrpol® 35 and Exxal® 10 (Exxon Chemicals GMBH); Balcol 2465 (Kao Chemicals). Of the ethylenically unsaturated ester compounds, the (meth) acrylates are particularly preferred over the maleates and fumarates, ie R2, R3, R5, R6 of the formulas (I) and (II) represent hydrogen in particular in the preferred embodiments. The component (c) comprises in particular ethylenically unsaturated monomers which can be copolymerized with ethylenically unsaturated ester compounds of the formula (I) and / or (II). The comonomers corresponding to the following formula are especially suitable for polymerization according to the invention: where R1 * and R2 * independently are selected from the group consisting of hydrogen, halogens, CN, linear or branched alkyl groups with 1-20, preferably 1-6 and especially preferably 1-4 carbon atoms, which can be substituted with 1 a (2n + l) halogen atoms, where n is the number of carbon atoms of the alkyl group (for example CF3), aminoalkyl, α-unsaturated (meth) acrylates, and aminoalkyl (meth) acrylamides such as methacrylamide N- (3-dimethylaminopropyl), 3-diethylaminopentyl (meth) acrylate, 3-dibutylaminohexadecyl (meth) acrylate; nitriles of (meth) acrylic acid and other nitrogen-containing (meth) acrylates such as N- (-metacryloyloxyethyl) diisobutyl ketimine, N- (methacryloyloxyethyl) dihexadecylkethimine, (meth) acryloylamidoacetonitrile, 2-methacryloyloxyethyl ethyl cyanamide, cyanomethyl (meth) acrylate; aryl (meth) acrylates such as benzyl (meth) acrylate or phenyl (meth) acrylate, where the acrylic residue in each case can be unsubstituted or replaced up to four times; (met) carbonyl-containing crilates such as 2-carboxyethyl (meth) acrylate, carboxymethyl (meth) acrylate, oxasolidinylethyl (meth) acrylate, N-methylacryloyloxy) formamide, acetonyl (meth) acrylate, N-methacryloylmorpholine, N- methacryloyl-2-pyrrolidone, N- (2-methylacryloxyoxyethyl) -2-pyrrolidinone, N- (3-methacryloyloxypropyl) 2-pyrrolidone, N- (2-methylacryloyloxypetadecyl (2-pyrrolidone, N- (3-methacryloyloxyheptadecyl-2-pyrrolidone (meth) acrylates of ether alcohols such as tetrahydrofurfuryl (meth) acrylates, vinyloxyethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, 1-butoxypropyl (meth) acrylate, 1-methyl- (meth) acrylate 2-vinyloxy) ethyl, cyclohexyloxymethyl (meth) acrylate, methoxymethoxyethyl (meth) acrylate, benzyloxymethyl (meth) acrylate, furfuryl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-ethoxyethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ) ethoxylated acrylates, Allyloxymethyl (meth) acrylate, 1-ethoxybutyl (meth) acrylate, methoxymethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate; (meth) acrylates of halogenated alcohols such as 2,3-dibromopropyl (meth) acrylate, 4-bromophenyl (meth) acrylate, 1,3-dichloro-2-propyl (meth) acrylate, 2- (meth) acrylate bromoethyl, 2-iodoethyl (meth) acrylate, chloromethyl methyl (meth) acrylate, oxirane (meth) acrylate such as 2,3-epoxybutyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (met) 10,11 epoxyundecyl acrylate, 2,3-epoxycyclohexyl (meth) acrylate, oxirane (meth) acrylates such as 10-11-epoxyhexadecyl (meth) acrylate, glycidyl (meth) acrylate; (meth) acrylates containing phosphorus, boron and / or silicon such as 2- (dimethylphosphate) propyl (meth) acrylate, 2- (ethylphosphite) propyl (meth) acrylate, 2-dimethylphosphinomethyl (meth) acrylate, (Met) dimethyl phenethonoethyl acrylate, diethylmethacryloyl phosphonate, dipropylmethacryloyl phosphate, 2- (dibutylphosphono) ethyl (meth) acrylate, 2,3-butylene-methacryloylethyl borate, methyldiethoxymethacryloyloxysilane, diethylphosphate ethyl (meth) acrylate; (met) acrylates containing sulfur as (meth) ethylsulfinylethyl acrylate, 4-thiocyanatobutyl (meth) acrylate, ethylsulfonylethyl (meth) acrylate, thiocyanatomethyl (meth) acrylate, methylsulfinylmethyl (meth) acrylate, bis) methacryloyloxyethyl sulfide); heterocyclic (meth) acrylates such as 2- (i-imidazolyl) ethyl (meth) acrylate, 2- (4-mofolinyl) ethyl (meth) acrylate, and 1- (2-methaloyloxy-ethyl) -2 pyrrolidone; vinyl halides, such as, for example, vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride; vinyl esters such as vinyl acetate; vinyl monomers containing aromatic groups such as styrene, styrenes substituted with an alkyl substituent on the side chain, such as α-methylstyrene and α-ethylstyrene, styrenes substituted with an alkyl substituent on the ring such as vinyl-toluene and p-methylstyrene, halogenated styrenes as monochlorostyrenes, dichlorostyrenes, tribrominesters and tetrabromostyrenes; Heterocyclic vinyl compounds such as 2-vinylpyridene, 3-vinylpyridene, 2-methyl-, 5-vinylpyridene, 3-ethyl-4-vinylpyridene, 2,3-dimethyl-5-vinylpyridene, vinylpiperidene, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 2-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, vinylxalano, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles, and hydrogenated vinylthiazoles, vinyl oxazoles and hydrogenated vinyl oxazoles; vinyl and isoprenyl ethers; maleic acid derivatives such as maleic anhydride, methylmalic anhydride, maleinimide, methyl maleimide; fumaric acid and fumaric acid derivatives, such as, for example, mono- and diesters of fumaric acid. Monomers having dispersion functionality can also be used as comonomers.

These monomers are well known in the art and usually contain heteroatoms such as oxygen and / or nitrogen. For example, the aforementioned Hydroxyalkyl (meth) acrylates, aminoalkyl (meth) acrylates, aminoalkyl (meth) acrylamides, ether (meth) acrylates, heterocyclic (meth) acrylates, and heterocyclic vinyl compounds are considered as dispersion comonomers. Preferred mixtures essentially contain methyl methacrylate, lauryl methacrylate, and / or stearyl methacrylate. The components can be used individually or as mixtures. The molecular weight of the (alkyl methacrylate) polymers is not critical.

Alkyl (meth) acrylate polymers have a molecular weight in the range of 300 to 1, 000,000 g / mol, preferably in the range of 500 to 500,000 g / mol and especially preferred in the range of 800 to 300,000 g / mol, without any intentional limitation for this. These values refer to the average molecular weight of the polydispersed polymers. According to a special aspect of the present invention, the alkyl (meth) acrylate polymers have a low molecular weight. These polymers have a very good performance at low temperature. According to that special aspect of the present invention, the alkyl (meth) acrylate polymers, preferably have a molecular weight in the range of 300 to 50,000 g / mol, especially 500 to 30,000 g / mol and more preferably 1,000 to 10,000 g / mol. Without intending any limitation by this, the alkyl (meth) acrylate polymers exhibit a polydispersity, given by the ratio of the average molecular weight to the number average molecular weight Mw / Mn in the range of 1 to 15, preferably from 1.1 to 10. , especially preferred from 1.2 to 5. The monomer mixtures described above can be polyewned by any known method. The conventional radical initiators can be used to perform a classical radical polymerization. These initiators are well known in technology. Examples of these radical initiators are azo initiators, such as 2, 2 '-azodiisobutyronitrile (AISN), 2,2'-azobis (2-methylbutyronitrile) and 1,1-azobiscyclohexane carbonitrile; peroxide compounds, for example, methyl ethyl ketone peroxide, acetyl acetone peroxide, dilauryl peroxide, tert-butyl per-2 haxanoate. ethyl, ketone peroxide, ketone isobutyl methyl peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl perbenzoate, peroxybutyl isopropyl carbonate, 2,5-bis (2-ethylhexanoyl-peroxy) -2, 5- dimethyl hexane, tert-butyl peroxy 2-ethyl haxanoate, tert-butyl peroxy-3, 5, 5, -trimethyl hexanoate, dicumary peroxide, 1,1-bis (tert-butyl peroxy) 3,4-cyclohexane, 5-trimethyl, eumeno hydroperoxide and tert-butyl hydroperoxide. the low molecular weight poly (meth) acrylates can be obtained using chain transfer agents. This technology is ubiquitously known and practiced in the polymer industry and is described in Odian Principles of Polymerization, 1991. Examples of chain transfer agents are sulfur-containing compounds such as thiols, for example n- and t- dodecanothiol, 2-mercaptoethanol and mercapto carboxylic acid esters, for example, methyl-e-mercaptopropinate. Chain transfer agents preferred contain up to 20, especially up to 15 and more preferably up to 12 carbon atoms. In addition, the chain transfer agents can contain at least 1, especially at least 2 oxygen atoms. In addition, poly (meth) acrylates with low molecular weight can be obtained through the use of transition metal complexes, such as slow spin cobalt complexes. These technologies are well known and for example described in patent USSR 940,487-A and by Heuts, et al., Macromolecules 1999, p. 2511-2519 and 30 '7-3912. In addition, novel polymerization techniques such as ATRP (Radical Atomic Transfer Polymerization) and / or RAFT (Reversible Addition Fragmentation Chain Transfer) can be applied to obtain useful poly (meth) acrylates. These methods are well known. The ARRP reaction method is described, for example, by JS Wang, et al., J. Am., Chem., Soc., Vol 117 pages 5614-5615 (1995) and by Matyjaszewski, Macromolecules, Vol. 28 pages 7901 -7910 (1995). Moreover, patent applications WO 96/30421, WO 97/47661, WO 97/18247, WO 98/40415 and W? / 9910397 disclose variations of the ARTP discussed above, of which reference is made expressly for purposes of disclosure. The RAFT method is presented extensively in WO 98/01478, for example, whose reference is made expressly for purposes of the revelation. The polymerization can be carried out with a normal pressure, a reduced pressure or a high pressure. The polymerization temperature is also not critical. However, in general it lies in the range of -20-200 ° C, preferably from 0 - 130 ° C and especially preferably from 60-120 ° C, without any intention of limitation for this. The polymerization can be carried out with or without solvents. The term solvent must be understood broadly here. The fluid of the present invention comprises from 1 to 99%, preferably by weight, especially from 50 to 89% by weight and preferably from 70 to 95% by weight based on the total weight of one or more oxygen-containing fluid compounds selected from carboxylic acid esters, polyether polyols and phosphate esters. The esters and ethers according to component B) are different from polyalkyl (meth) acrylates according to component a). The oxygen-containing compound according to component B) usually has a high fire point and a low viscosity at 40 ° C. According to a particular aspect of the present invention, the oxygen-containing compound has a fire point according to ASTM D 92 of at least 250 ° C, preferably at least minus 280 ° C and more preferably at least 300 ° C. The kinematic viscosity at 40 ° C per ASTM D 445 of the oxygen-containing compound is preferably useful as component B) is 40 mm 2 / s or less, especially 35 mm 2 / s or less and more preferably more than 30 mm 2 / s less . Compounds useful as component B are well known in the art. Examples are organophosphoric compounds, carboxylic acid esters and polyether polyols. The functional fluid of the present invention may comprise organophosphorus compounds. The first class of compounds suitable for use are phosphoric ester fluids such as alkyl aryl phosphate ester, trialkyl phosphates such as tributyl phosphate or tri-2-ethylhexyl phosphate; triaryl phosphates such as mixed isopropylphenyl phosphates, mixed t-butylphenyl phosphates, trixylenyl phosphate or tricresylphosphate. Additional classes of organophosphorus compounds are phosphonates and phosphinates, which may contain alkyl and / or aryl substituents. Dialkyl phosphonates such as di-2-ethylhexylphosphonate; Alkyl phosphinates such as di-2-ethylhexylphosphinate are possible. As the alkyl group herein, straight or branched chain alkyls are preferred consisting of 1 to 10 carbon atoms. As the aryl group herein, aryls consisting of from 6 to 10 carbon atoms which can be substituted by alkyls are preferred. Usually the functional fluids contain organophosphorus compounds from 0 to 60% by weight, preferably from 5 to 50% by weight. As reaction products of carboxylic acid esters of alcohols such as polyhydric alcohol, monohydric alcohol and the like, and fatty acids such as monocarboxylic acid, polycarboxylic acid and the like can be used. These carboxylic acid esters can, of course, be a partial ester. The carboxylic acid esters may have a carboxylic ester group having the formula R-COO-R, where R is independently a group comprising 1 to 40 carbon atoms. Preferred ester compounds comprise at least two ester groups. These compounds can be based on polycarboxylic acids having at least two acid groups and / or polyols having at least two hydroxyl groups. The polycarboxylic acid residue usually has 2 to 40, preferably 4 to 24, especially 4 to 12 carbon atoms. The esters of useful polycarboxylic acids are, for example, esters of atypical, azelaic, sebacic, phthalate and / or dodecanoic acids. He The alcohol component of the polycarboxylic acid compound preferably comprises from 1 to 20, especially from 2 to 10, carbon atoms. Examples of useful alcohols are methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and octanol. In addition, the oxoalcohols that can be used are diethylene glycol, triethylene glycol, tetraethylene glycol, and decamethylene glycol. Especially preferred compounds are polycarboxylic acid esters with alcohols comprising a hydroxyl group. Examples of these three compounds are described in Ullmanns Encyclopaedia der Technischen Chemie, third edition, volume 15, pages 287-292, Urban & Schwarzenber (1964)). Useful polyols for obtaining ester compounds comprise at least two groups of esters usually containing from 2 to 40, preferably from 4 to 22, carbon atoms. Examples are neopentyl glycol, diethylene glycol, dipropylene glycol propionate 2, 2-dimethyl-3-hydroxypropyl-2 ', 2' -dimethyl-3 '-hydroxy, glycerol, trimethylolethane, propane trimetanol, trimetilolnonano, ditrimethylolpropane, petaerythritol, sorbitol, mannitol and dipentaerythritol. The carboxylic acid component of the polyester may contain 1 to 40, preferably 2 to 24, carbon atoms. The examples are linear or branched saturated fatty acids such as formic acid, acetic acid, propionic acid, octanoic acid, capric acid, enantic acid, caprylic acid, pelargonic acid, capric acid, undecanic acid, lauric acid, tridecanic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, acid archaic, behenic acid, isomiristic acid, isoplamitic acid, isostearic acid, 2, 2-dimethylbutanoic acid, dimethylpentanoic acid, 2,3-dimethyloctanoic acid, 2-ethyl-l-2,3, 3-trimethylbutanoic acid, 2,2-acid, 3,4-tetramethylpentanoic, 2,5,5-trimethyl-2-t-butylhexanoic acid, 2,3,3-trimethyl-2-ethylbutanoic acid, 2,3-dimethyl-2-isopropylbutanoic acid, 2-ethylhexanoic acid , 3, 5, 5, -trimetilhexanóico acid; linear or branched unsaturated fatty acid such as linoleic acid, linolenic acid, 9-octadecene acid, undeceneic acid, elaidic acid, catholic acid, erucic acid, bradydic acid commercial grades of oleic acid from a variety of animal fat or vegetable oil sources. Fatty acid mixtures can be used as tallow oil fatty acids. Especially useful compounds comprising at least two ester groups are, e.g., neopentyl glycol talate, glycol dioleate neopentyl, propylene glycol talate, propylene glycol dioleate, diethylene glycol talate and diethylene glycol diolate. Many of these compounds are commercially available from Inolex Chemical Co. , under the trademark of Lexolube 2G-214, of Cognis Corp., under the trademark of ProEco 2965, of Uniqema Corp., under the trademark Priolub 1430 and Priolub 1446 and of Georgia Pacific under the trademarks of Xtolub 1301 and Xtolube 1320. In addition, the ethers are useful as oxygen-containing compounds according to component B) of the inventive fluid. Preferably, polyether polyols are used as component B). These compounds are well known. Examples of polyalkylene glycols such as, for example, polyethylene glycols, polypropylene glycols and polybutylene glycols. The polyalkylene glycols can be based on mixtures of alkylene oxides. These compounds preferably comprise from 1 to 40 units of alkylene oxide, more preferably from 5 to 30 units of alkylene oxide. Polybutylene glycols are preferred compounds for anhydrous fluids. The polyether polyols may comprise additional groups, such as, for example, alkylene or amylene groups comprising from 1 to 40, especially from 2 to 22. carbon atoms. Especially useful polyether polyols are the butylene oxide monobutyl ether. Although the functional fluid of the present invention may contain phenol-based compounds, alkyl hydrocarbons are preferred. According to a special aspect of the present invention, the functional fluid contains 25% by weight or less, preferably 15% by weight or less of phenolic compounds based on the total fluid. The phenolic compounds contain an aromatic residue having at least one hydroxyl group. The functional fluids of the present invention may contain a lower amount of halogens. These halogens can be part of the alkyl (meth) acrylate according to component A) or of the oxygen containing a compound according to component B). Preferably the fluids according to the present invention comprise 0.5% by weight or less, especially 1.0% by weight or less halogens such as chloride or bromide based on the total fluid. More preferably the fluids of the present invention do not comprise any essential amount of halogens. . Preferably, the functional fluids of the present invention are anhydrous fluids. According to a Special aspect of the present invention, the functional fluid contains 5% by weight or less, presently 2% by weight or less water based on the total fluid. The carboxylic acid esters or the polyether polyols can be used as single compounds or as a mixture of two or more. Preferably, the weight ratio of the alkyl (meth) acrylate polymers with the oxygen-containing compounds is in the range of 10: 1 to 1:20, especially 5: 1 to 1:15 and more preferably 2: 1. at 1:10. The functional fluid of the present invention may further comprise additives well known in the art such as viscosity index testers, anti-oxidants, anti-wear agents, corrosion inhibitors, detergents, dispersants, EP additives, defoamers, friction reduction agents, depressants, point of runoff, dyes, odorants and / or demulsifiers. These additives are used in conventional amounts. Usually the functional fluids contain from 0 to 10% by weight of additives. The functional fluid of the present invention provides fire resistance and is considered "less hazardous" than standard mineral oil functional fluids. Fire resistance can be evaluated by the Factory Mutual FMRC 6930 standard. The fluids of preference according to the present invention achieve a Group 1 classification. According to the needs of the consumer, the viscosity of the functional fluid of the present invention can be adapted to a wide range. ISO VG 32, 46, 68, 100 fluid degrees can be achieved, for example: Preferably the kinematic viscosity of 40 ° C according to ASTM D 445 is in the range of 15 mm2 / s to 150 mm2 / s, preferably 28 mm2 / s to 110 mm2 / s. The functional fluid of the present invention has a high viscosity index. Preferably the viscosity index according to ASTM D 2270 is at least 150, especially at least 180, and more preferably from at least 200. The functional fluid of the present invention has a good performance at low temperature. The low temperature performance can be evaluated through the Brookfield viscometer according to ASTM D 2983. The functional fluid of the present invention can be used for high pressure applications. The preferred embodiments can be used at pressures between 0 to 700 bars, and specifically between 70 and 400 bars. In addition, the functional fluids of the present invention have a low pour point, which can be determined, for example, in accordance with ASTM D 97. Fluids preferably have a pour point of -30 ° C or less, especially -40 ° C or less and more preferably -45 ° C or less. The functional fluid of the present invention can be used over a wide range of temperatures. For example, the fluid can be used in a window from -40 ° C to 120 ° C. In addition, the preferred functional fluids of the present invention have a high flash point in accordance with ASTM D 92 of at least 280 ° C, preferably 300 ° C and more preferably 320 ° C. The functional fluid has a biodegradability high in accordance with CEC L-33-A94 or OECD 30IB. The fluids of preference show a degradation greater than 60%, or conversion to C02. The fire-resistant functional fluids of the present invention are useful, for example in industrial hydraulic, automotive, mining, power generation, marine and military hydraulic applications. Typical operations require the use of fire-resistant fluids in stationary operations including metal smelters, metal processing, coal mining, food processing plants. Mobile equipment applications include construction, forestry, delivery vehicles and municipal fleets (garbage collection, snow removal, etc.). Maritime applications include cranes in springs. The fire-resistant functional fluids of the present invention are useful in hydraulic power generation equipment as electrohydraulic turbine control systems. Typical operations requiring the use of fire-resistant fluids include aircraft hydraulics, catapult launch systems, ship lifts, tanks and ground transportation equipment. In addition, the fire-resistant functional fluids of the present invention are useful as liquids transformers or tempering oils. The invention is illustrated in greater detail below through the examples and comparison examples, without intending to limit the invention of these examples. Preparation Example 1 200 g 9-octadeceneic acid ester with 2, 2-dimethyl-1,3-propanediol solvent (®Lexolube 2G-214 commercially available from Inolex Chemical Co.), 15Og LMA (LMA: lauryl methacrylate, mixture of long-chain methacrylates obtained from the reaction of methyl methacrylate with ®Loro (Henkel KGaA)), 183g of methylmethacrylate, lOg of 1-dodecanethiol (Aldrich 98 +%) and 0.66g of 2, 2'-azobis [2-methylbutyronitrile ] (Vazo 67 commercially available with DuPont) was mixed in a three-liter flask, with inert gas purged, four-necked and round bottom. Then the reaction mixture was heated to 95 ° C with stirring under the purge of inert gas. Thereafter, a composition containing 300 g of AML, 367 g of methyl methacrylate, 20 g of 1-dodecanethiol and 1.33 g of 2,2'-azobis [2-methylbutyronitrile] was added over a period of 90 minutes. After finishing the addition, 1.5g of 2,2'-azobis [2-methylbutyronitrile] dissolved in 2,6-dimethyl-4-heptanone, mixed with 400g of 9-octadecenic acid ester with 2: 2 solvent were mixed. -dimethyl-l, 3-propanediol added at constant rate for 90 minutes. At the end of the feed, the mixture was stirred for another 20 minutes at 95 ° C. The solids of the final product are 50% (theoretical, based on the monomer feed) with Mw / Mn of 8.89 x 103 / 7.41 x 103 (as characterized by a standardized poly (methyl) methacrylate GPC). Example 2 A polymer with low molecular weight synthesized from 100% BMA / butyl methacrylate) without solvent dilution. The polymer solids of the final product without > 99% with an average molecular weight of (Mw) of 2.3 x 103. Examples 3 to 10 and Controls of 1 to 3 The compositions according to Table 1 are mixed using the polymers obtained in the Preparation of Example 1 and / or the Example 2, Triaryl Phosphate Esters available from Great Lakes Chemical Corp. (Durad 300), Neopentyl Glycol Dioleate available from Inolex Chemical Co. (Lexolube 2G-214). Neopentyl Glycol Talate available with Georgia Pacific (Xtolube 1301), Diethylene Glycol Talate available with Georgia Pacific (Xtolube 1320), Propylene Glycol Diolate available from Uniquema (Priolube 1430). The quantity of the components of da in% per weight based on the total fluid. The compositions were evaluated according to the classification system for fire resistant fluids provided by Factory Mutual. This system is based on the determination of the chemical heat release rate of the combustion fluid from an atomized aerosol, as well as the critical heat of the ignition flux (maximum heat flux in or below which there is no ignition) - as is described by the Factory Mutual Approval Standard for Flammability Classification of Industrial Fluids - 6390. This data is calculated in what is called a Flame Flame Parameter (SFP) -a measurement of the degree of flammability of a fluid in a highly atomized condition when pressurized, passed in the following formula: SFP = 11.02 x 102 x Qoh / (üfqcrmf) where: Qch is the chemical heat release rate determined in kW qcr is the critical heat flux for ignition in kW / m2 cif is the density of the fluid in kg / m3 mf is the flow rate of the mass of fluid during the release of chemical heat in g / s -Divisor used to "normalize" the SFP for comparison in e the devices that have different dynamics of flow. Therefore, all SFP classifications are normalized to a unit of flow measurement. These classifications are staggered as follows: The SFP classification and the SFP value of the mixtures are presented in Table 1. The fire point was determined in accordance with ASTM D 92. The pour point was measured in accordance with ASTM D 97. The kinematic viscosity was measured using the ASTM D 445 standard. Additional evaluation methods and their results are described in Table 1. Table 1 Example Example Reference Reference Reference Component 3 4 1 2 3 Example 1 20.3% 20.3% PAMA Glycol Dioleate of 79.7% 59.7% 100% Neopentyl Phosphate Ester of 20% 100% Tiarilo Mineral Oil 100% Viscosity Grade ISO VG 46 VG 46 VG 46 VG 22 VG 46 3448 Viscosity @ 46.96 50.6 46 24.8 46 40 ° C, mm2 / s Viscosity @ 10.10 9.81 6.72 6.02 100 ° C, mm2 / s index 210 185 100 205 Viscosity Easily Biodegradable Yes NO NO Yes NO through CEC L-33-A94 Drain Point, -54 -27 -20 ° C Point 320 320 252 320 350 Fire, ° C Value FMRC 6930 SFP 3 3 11 5 3 Classification FMRC 6930 Group 1 Group 1 Group 3 Group 1 Group 1 Cut stability, PSSI by ASTM < 1 < 1 0 0 0 D 5621 Table 1 (continued) Table 1 (continued)

Claims (22)

1. CLAIMS 1. A functional fluid comprising A) from 1 to 99% by weight based on the total functional fluid weight of the alkyl (meth) acrylate polymers obtained through polymerizing a mixture of olefinically unsaturated monomers, consisting of ) 1-100% by weight based on the total weight of the ethylenically unsaturated monomers of one or more ethylenically unsaturated ester compounds of the formula (I)

   where R is hydrogen or methyl R1 means a linear or branched alkyl residue with 1-6 carbon atoms, R2 and R3 independently represent hydrogen or a group of the formula -COOR ', where R' signifies hydrogen or an alkyl group with 1-6 carbon atoms, b) 0-99% by weight based on the total weight of ethylenically unsaturated monomers of one or more ethylenically unsaturated ester compounds of the formula (II)

   where R is hydrogen or methyl, R4 is a linear or branched alkyl residue with 7-40 carbon atoms, R5 and R6 independently are hydrogen or a group of the formula -COOR ", where R" signifies hydrogen or an alkyl group with 7-40 carbon atoms. c) 0-50% by weight based on the total weight of the ethylenically unsaturated monomer comonomers, YB) 99% by weight based on the total functional fluid weight of an oxygen containing a compound selected from the group of carboxylic acid esters polyether polyols and / or organophosphorus compounds.
2. 2. The functional fluid according to claim 1, wherein the oxygen-containing compound has a fire point according to ASTM D92 of at least 250 ° C.
3. 3. The functional fluid according to Claims 1 or 2, wherein the oxygen-containing compound has a kinematic viscosity at 40 ° C according to ASTM D 445 of 35 mm2 / s or less.
4. 4. The functional fluid according to one of
5. The preceding claims, wherein the oxygen-containing compound is a diester of carboxylic acids containing from 4 to 12 carbon atoms.
6. 6. The functional fluid according to Claim 5, wherein the diester is an ester of atypical, azelaic, sebacic, phthalate and / or dodecaic acids.
7. 7. The functional fluid according to one of the preceding claims wherein the oxygen-containing compound is an ester of a polyol.
8. 8. The functional fluid according to the

   Claim 7, wherein the polyol contains from 4 to 22 carbon atoms.
9. 9. The functional fluid according to claim 8, wherein the ester is a neopentyl glycol ester, diethylene glycol, dipropylene glycol, trimetanol propane, or pentaerythritol.
10. 10. The functional fluid according to one of the preceding claims, wherein the oxygen-containing compound is a polyalkylene glycol.
11. 11. The functional fluid according to the

    Claim 10, wherein the polyether polyol is based on a butylene oxide.
12. 12. The functional fluid according to one of the preceding claims wherein the alkyl (meth) acrylate polymers have a molecular weight in the range

    from 300 g / mol to 50 000 g / mol.
13. 13. The functional fluid according to one of the preceding claims wherein the alkyl (meth) acrylate polymers are obtained through a mixture comprising 15-70% by weight of one or more of the ethylenically unsaturated ester compounds of the formula (I)

    where R is hydrogen or methyl R1 means a linear or branched alkyl residue with 1-6 carbon atoms, R2 and R3 independently represent hydrogen or a group of the formula -COOR ', where R' signifies hydrogen or an alkyl group with 1-6 carbon atoms.
14. 14. The functional fluid according to one of the preceding claims wherein the alkyl (meth) acrylate polymers are obtained through a mixture comprising 30-85% by weight of one or more ethylenically unsaturated ester compounds of the formula ( II)

    where R is hydrogen or methyl, R4 is a linear or branched alkyl residue with 7-40 carbon atoms,

    R5 and R6 independently are hydrogen or a group of the formula -COOR ", where R" signifies hydrogen or an alkyl group with 7-40 carbon atoms.
15. 15. The functional fluid according to one of the preceding claims, wherein the alkyl (meth) acrylate polymers are obtained through a mixture comprising dispersing monomers.
16. 16. The functional fluid according to one of the preceding claims, wherein the alkyl (meth) acrylate polymers are obtained through a mixture comprising vinyl monomers containing aromatic groups.
17. 17. The functional fluid according to one of the preceding claims, wherein the weight ratio of the alkyl (meth) acrylate polymers with the oxygen-containing compounds are in the range of 2: 1 to 1:10.
18. 18. A hydraulic oil comprising the functional fluid according to one of the preceding claims.
19. 19. The hydraulic oil according to Claim 18, wherein the hydraulic oil comprises at least 20% by weight of the functional fluid according to one of Claims 1 to 17.
20. 20. The use of a functional fluid according to one of the preceding Claims to improve the fire resistance of hydraulic fluids, transformer oils and tempering oils.
21. 21. The use according to Claim 20, wherein the hydraulic fluid is an anhydrous fluid.
22. 22. A method for manufacturing the functional fluid according to one of Claims 1 to

    19, where the olefinically unsaturated monomer mixture is polymerized in a fluid of an oxygen-containing compound according to component B).

    SUMMARY OF THE INVENTION

    work

    Functional fluid of alkyl (meth) acrylate polymers obtained by polymerizing a mixture of olefinically unsaturated monomers, consisting of a) 1-100% by weight based on the total weight of the ethylenically unsaturated monomers of one or more of the ester compounds ethylenically unsaturated of the formula (I)

    where R is hydrogen or methyl R1 means a linear or branched alkyl residue with 1-6 carbon atoms, R2 and R3 independently represent hydrogen or a group of the formula -COOR ', where R' signifies hydrogen or an alkyl group with 1-6 carbon atoms, b) 0-99% by weight based on the total weight of ethylenically unsaturated monomers of one or more ethylenically unsaturated ester compounds of the formula (II)

    where R is hydrogen or methyl, R4 is a linear or branched alkyl residue with 7-40 carbon atoms,

    R5 and R6 independently are hydrogen or a group of the formula -COOR ", where R" signifies hydrogen or an alkyl group with 7-40 carbon atoms. c) 0-50% by weight based on the total weight of the ethylenically unsaturated monomer comonomers, YB) 99% by weight based on the total functional fluid weight of an oxygen containing a compound selected from the group of organophosphorus compounds, esters of carboxylic acid and / or polyether polyols.