DE10014922A1 - New neocarboxylic acids useful for producing compositions, especially lubricants and pressure transmission agents, comprise fatty acids and/or derivatives with acyloxylated double bond(s) - Google Patents

Abstract

New neocarboxylic acids for the production of compositions, especially lubricants and pressure transmission agents, are 3-propyloxy-2,2-dimethylpropionic acid, 3-butyloxy-2,2-dimethylpropionic acid, 3-isobutyloxy-2,2-dimethylpropionic acid, 3-(2-ethylbutyloxy)-2,2-dimethylpropionic acid, 3-benzyloxy-2,2-dimethylpropionic acid and 3-(2-methylphenyloxy)-2,2-dimethylpropionic acid. Independent claims are also included for: (1) Compositions, especially lubricants and pressure transmission agents, containing fatty acids and/or fatty acid derivatives, in which >= 1 double bond is acyloxylated. (2) The preparation of these compositions by acylating double bond(s) of fatty acid(s) and/or derivative(s) with carboxylic acids, anhydrides or halides.

Description

The present application relates to lubricants and pressure transmission means from esters of fatty acids, of fatty acid derivatives and their mixtures and a process for the production of these esters according to the invention by addition of carboxylic acids and / or Carboxylic anhydrides on the double bond and / or double bonds of Carboxylic acid halides on fatty acids, fatty acid derivatives and their mixtures and the Use of these esters according to the invention as environmentally friendly, biologically light degradable lubricants, lubricant components, lubricant additives, hydraulic oils, Pressure transmission media, gear oils and functional fluids.

State of the art

Lubricants based on vegetable and animal fats have been around since ancient times used to reduce friction and wear on equipment and vehicles. First in the last century they were used in the course of technical oil production and -processing replaced by mineral oil products that had better aging stability and in the course of their development a high level of quality through targeted additives reached.

Since in Germany alone around 520,000 t of lubricants are released into the environment through leaks in seals or hoses, during repair work, in oil spills or through evaporation and atomization, intensive work is being done on the development of environmentally compatible and biodegradable lubricants that meet the requirements of highly developed machine technology . By using renewable raw materials, directly or in the form of their conversion products, not only fossil raw materials can be saved, but also the CO ₂ balance can be balanced and set-aside to avoid agricultural overproduction can be avoided.

Limits of application of natural oils and the underlying fatty acids result their low stability against thermal oxidative stress and hydrolysis as well the limited cold flow behavior, d. H. Properties that can also be achieved with additives Chemicals such as sulfonates, phenol derivatives or amines can only be influenced gradually. Breeding measures for the enrichment of certain fatty acids in the triglycerides of Vegetable oils can improve the technical properties. Are more important however chemical transformations that take place both on the alcohol component and on the  Can attack acid component. For example, glycerin is used to increase Hydrolysis stability replaced by trimethylolpropane or pentaerythritol [Th. Mang Lubricants and pressure transmission media and their use as. Construction element in fluid power machines, script, IFAS, RWTH Aachen, 1997].

Point of attack for the oxidative aging of natural oils and theirs underlying fatty acids are the double bonds contained herein, with specific Double bonds with (Z) conformation easily from oxygen to form peroxidic Intermediates are attacked.

To increase the oxidation stability of natural oils or the ones on which they are based Fatty acids can be used in different ways. The most common method is the partial one Hydrogenation of the polyunsaturated acids. In the presence of suitable catalysts, e.g. B. Nickel, platinum or palladium, adds hydrogen to the unsaturated double bonds Fatty acids to form the saturated acids or increase the degree of saturation [J. Baltes, B. Cornils, Chem.-Ing.-Tech., 1975, 47, 522; H. Hsu, L. L. Diosady, W. F. Graydon, J. At the. Oil Chem. Soc., 1986, 63, 1551]. Catalytic fat hydrogenation is used in industrial Scale, e.g. B. for margarine production. If the stability of the oils against oxidation is thereby increased, but is a modification of the obtained Unreachable substances beyond the degree of hydrogenation. Also worsen tribological properties such as viscosity and pour point with higher saturation of the oils.

Further additions to the carbon chain of the fats can be done by the mechanism of En reaction Lewis acid catalyzed. Thus, in the presence of Alkyl aluminum halides with formaldehyde, acyl chlorides or carboxylic acid anhydrides Allyl alcohols or β, γ-unsaturated ketones [U. Biermann, J.O. Metzger, Fat Sci. Technol., 1994, 96, 425]. The en-reaction of unsaturated fatty acids goes along uncatalyzed Maleic anhydride [J. O. Metzger, U. Biermann, Fat Sci. Technol., 1994, 96, 425]. The substances obtained also have an oxidation-sensitive double bond, the is not fully protected by branched substituents. In addition, the use of corrosive Lewis acids are not desirable for ecological reasons. Also under The Diels-Alder reaction of the diunsaturated occurs when the double bond is retained Fatty acids. After double bond isomerization, linolenic acid, for example, can be used as Diene with the dienophiles maleic anhydride, fumaric acid or acrylic acid Formation of cyclic compounds react [G. S. R. Sastry, B. G. K. Murthy, J. S. Aggarwal, J. Am. Oil Chem. Soc., 1971, 48, 686].  

With the double bond saturated, the hydroformylation and the Hydrocarboxylation of fats in the presence of cobalt or carbonyl complexes Rhodium-Tripheüylphosphane complexes can be carried out [E. N. Frankel, S. Metlin, W. K. Rohwedder, I. Wender, J. Am. Oil Chem. Soc., 1969, 46, 133; E. N. Frankel, J. At the. Oil Chem. Soc., 1971, 48, 248). The formyl group obtained in the hydroformylation can be oxidized to the carboxy group or reduced to the hydroxy group [A. W. Schwab, E.N. Frankel, E.J. Dufek, J.C. Cowan, J. Am. Oil Chem. Soc., 1972, 49, 75]. In the Hydrocarboxylieiung carboxylic acids or their derivatives are obtained. Is examined here in primarily the reaction with methyl oleate, but also natural soybean oil was included in the reaction used. The Koch synthesis is related, that under catalysis with strong. Acids too leads branched carboxylic acids. Due to the primary formation of carbenium ions Scaffolding rearrangement takes place, so that primarily α-branched dicarboxylic acids are formed [J. Falbe, New Syntheses with Carbon Monoxide, Springer-Verlag, Berlin, 1980]. In addition to the Toxicity of carbonyl complexes and the high price of rhodium compounds here also the separation of the homogeneous catalysts from the product mixture Difficulty presents. The products obtained represent a substitute for petrochemically produced ones Substances represent an important source of raw materials for industrial organic chemistry [E. H. Piyde (ed.), Fatty Acids, Amer. Oil Chem. Soc., Champaign, Illinois, 1979].

Additions to the double bond of fats and oils can be electrophilic, nucleophilic and run radically. The radical addition of alkanes can thermally Temperatures above 400 ° C occur [J. Hartmanns, K. Klenke, J.O. Metzger, Chem. Ber., 1986, 119, 488] or initiated by electron transfer, for example the Addition of haloalkanes to various fatty acid methyl esters in the presence of copper [J. O. Metzger, R. Mahler, Angew. Chem., 1995, 107, 1012].

Nucleophilic addition requires activation of the double bond by oxidation of one adjacent OH group to the carbonyl group; subsequently can be base catalyzed Alcohols with ether formation, malonic acid esters and acyl anions with C-C linkage. be added. Highly functionalized fatty acids are obtained [R. Maletz, H. J. Schäfer, R. Quermann, Fett / Lipid, 1996, 11, 370].

Under acid catalysis, aromatic compounds can be substituted on the ring Double bond of fats and oils can be added [Y. Nakano, T.A. Foglia, J. Am. Oil Chem. Soc., 1984, 61, 569; W. C. Ault, A. Eisner, J. Am. Oil Chem. Soc., 1962, 39, 132]. If phenols are used, mixtures of phenyl ethers and  Hydroxyphenyl Compounds [A. Eisner, T. Perlstein, W.C. Ault, J. Am. Oil Chem. Soc., 1962, 290]. The acids are polysiloxanes or sulfonic acid groups Methanesulfonic acid [A. Eisner, T. Perlstein, W.C. Ault, J. Am. Oil Chem. Soc., 1963, 40, 594} used. Using methanesulfonic acid, the addition of Benzoic acid examined to form an ester function; however, this did not succeed at Use of long-chain olefins, but only with cyclohexene as an unsaturated component.

One of the most important additive reactions to the double bond is epoxidation is preferably carried out according to the in situ performic acid process. The oxirane groups react easily with nucleophilic compounds to form vicinally functionalized ones Derivatives [H. Baumann, M. Bühler, H. Fochem, F. Hirsinger, H. Zoebelein, J. Falbe, Angew. Chem., 1988, 100, 41]. Thus, when using alcohols, one obtains alcoholic alcohols when used of carboxylic acid hydroxy esters and when using water diols. The one with alcohol The alkoxy alcohols obtained are suitable for building up a wide range of oleochemicals Polyols which are suitable for the production of PUR foams and casting resins [B. Gruber, R. Höfer, H. Kluth, A. Meffert, Fat Sci. Technol., 1987, 89, 147].

Various other processes can be used to prepare vicinal diols. Mixtures of formic acid and H ₂ O ₂ or acetic acid with H ₂ O ₂ and sulfuric acid can be reacted with fatty acid esters. With hydrolysis of the product obtained, 1,2-glycols are formed [D. Swern, JT Scanian, TW Findley, US 2,492,201, Jun 7, 1946; D. Swern, JT, Scanlan, US 2,443,280, May 29, 1946]. Sulfonation with sulfuric acid leads to sulfuric acid esters, the hydrolysis of which also leads to diols [ET Roe, BB Schaeffer, JA Dixon, WC Ault, J. Am. Oil Chem. Soc., 1947, 24, 45]. Direct hydroxylation is carried out with 70% hydrogen peroxide using tungstic acid as a catalyst [TM Luong, H. Schriftmann, D. Swern, J. Am. Oil Chem. Soc., 1967, 44, 316] or with an H ₂ O ₂ / acetic acid mixture in the presence of ion exchange resins containing sulfonic acid groups [JG Wallace, WR Peterson, AF Chadwick, DO Barlow, J. Am. Oil Chem. Soc., 1958, 35, 205] possible.

These vicinal glycols can be reacted with acid halides or Carboxylic acid anhydrides can be further modified. So belong vicinal acetoxy-substituted. Compounds to the state of the art and are used as plasticizers, synthetic Lubricants and foam regulators used. In addition to the implementation of vicinal Diols, or epoxides with acetic anhydride or acetic acid chloride [G. Stoll, EP 0 341 548 A2, November 15, 1989, Henkel AG; Ind. Eng. Chem., 1954, 46, 2205; J. Chem. Soc. Perkin Trans., 1975,  231] these compounds can be modified by oxidative acetylation with acetates Metals in high oxidation states are obtained [G. Stoll, EP 0 341 548 A2, November 15, 1989, Henkel AG]. Above all, the two-stage process is disadvantageous because of the actual synthesis the preparation of the epoxides or glycols must precede. The application of On the one hand, metal acetates have their price, on the other hand, as in the case of lead (IV) acetate, their price Towards toxicity.

Monohydroxylated products can be obtained by hydroboration of methyl oleate [SP Fore, WG Bickford, J. Org. Chem., 1959, 24, 920]. However, due to the high price of the boron-containing reagents, this method is not suitable for preparations on a larger scale. The addition of formic or acetic acid and subsequent hydrolysis of the esters obtained [HB Knight, RE Koos, D. Swern, J. Am. Chem. Soc., 1953, 75, 6212; HB Knight, RE Koos, D. Swern, J. Am. Oil Chem. Soc., 1954, 31, 1]. So boiling anhydrous formic acid adds uncatalyzed to oleic acid with 80% conversion in 24 hours. If small amounts of perchloric acid are added, the reaction time is reduced to 5 minutes; 15 minutes with sulfuric acid or a BF ₃ acetic acid complex. Uncatalyzed, acetic acid only adds negligible amounts of oleic acid; Perchloric acid catalysis leads to 40% conversion in 15 minutes, with a triple excess of acetic acid, conversions of 60-70% are achieved after 70 hours [WO Munns, S. Kairys, DA Manion, J. Am. Oil Chem. Soc., 1963; 40, 22]. Sulfuric acid leads to poor sales. If the cheaper 90% solution is used instead of anhydrous formic acid, the addition only takes place in the presence of catalysts; best results are provided by sulfuric acid, which leads to 70% conversion after one hour. The aim of all the processes described is not the preparation of the formyloxy or acetoxy compounds, but rather their hydrolysis to monohydroxystearic acid, which is an important component for the production of lubricating greases and oils and plasticizers.

The acetoxylation to obtain the monoesters, which act as plasticizers for PVC from technical interest, was under catalysis with the acid. Amberlyst 15 ion exchanger examined [L. T. Black, R.E. Beal, J. Am. Oil Chem. Soc., 1967, 44, 310]. At a Mass ratio of methyl oleate / catalyst of two and a 50-fold molar Excess acetic acid yields 42% methyl acetoxystearate over 8 hours achieved. When using formic acid, no catalytic effect of Amberlyst 15 be determined. The addition of propionic acid and butyric acid was also investigated; these gave lower yields than acetic acid. There were no branched carboxylic acids used. However, there was no systematic study of the rheological  Properties of the adducts obtained. The regeneration of the catalyst will not described. The aim of these experiments was an alternative route for the production of Monohydroxystearic acid methyl ester, which is formed by saponification of the intermediates acetoxy- and methyl formyloxystearate can be obtained.

While higher molecular weight linear and branched carboxylic acids as additives for Increase in viscosity of cosmetic and pharmaceutical oils are used [C. J. Taletsky, S.L. Shawn, R.J. Nadolsky, FR 2 763 844, May 14, 1998, Baker Hughes Inc.] is here no reaction between carboxylic acid and the oils and fats used as a base he wishes.

An oligomerization of oleic acid with addition of the carboxyl group to the double bond can be catalyzed by strong acids [T. A. Isbell, R. Kleimann, B. A. Plattner, J. Am. Oil Chem. Soc., 1994, 71, 169]. The protonation of the Double bond suspected to form a carbenium ion. This is done by adding the OH group of another oleic acid molecule. The adduct stabilizes by splitting off a proton. By rearrangement of the primary carbenium ion the link position varies. By treating oleic acid with one equivalent Perchloric acid at 50 ° C, for example, a yield of 76% oligoestolide is obtained. Montmorillonite also catalyzes the reaction. By concentration of the acid and the The degree of polymerization can be controlled at the reaction temperature. The products can Used in lubricants, cosmetics and paints. In this process, however a variation of the added acids is not possible; leads to a co-oligomerization inevitably to a product mix. In addition, when using the heterogeneous Montmorillonite catalyst only achieved a yield of 10-30%. This is also the case Working in an expensive protective gas atmosphere is necessary.

The addition of carboxylic acids to alkenes under catalysis by Al ³⁺ -, Cr ³⁺ - or H ⁺ - ion exchanged montmorillonite was investigated on various alkenes and dienes. However, only non-functionalized alkenes up to a C number of 10 were used; in addition, acetic acid was primarily used; maximum yields of 20% were achieved with propionic acid and butyric acid [JA Ballantine, M. Davies, RM O'Neil, I. Patel, JH Purnell, M. Rayanakorn, KJ Williams, JM Thomas, J. Mol. Catal., 1984 , 26, 57].

None of the acylations of fatty acids or Fatty acid derivatives are used as lubricants and / or pressure transfer agents mentioned or become known.  

With the help of the described processes based on fatty acids, natural Fatty acid derivatives and their mixtures can be new materials for lubricants The critical properties of these natural raw materials such as low Aging resistance, oxidation resistance and hydrolysis stability, critical Improve cold properties without the good properties such as good lubricating effectiveness or negatively influence the low temperature dependence of the viscosity. Through the Flexibility of the reaction are certain properties such as viscosity, cold properties, Elastomer compatibility adjustable in a wide range.

Fabric protection

Novel lubricants and pressure transmission systems of the general formula VI based on fatty acid and fatty acid derivatives have been found.

with R ₁₄ = R ₁ = R ₃
and R ₁₅ = R ₂ = R ₄
and with R ₁₆ = H or R ₁₆ =
Alkyl residues with 1-10 C atoms, e.g. B.
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl
Aryl radicals with alkyl and other substituents on the aromatic ring, e.g. B.
Phenyl, methylphenyl, ethylphenyl, mesityl, cumyl, p-nitrophenyl, xylyl, hydroxyphenyl, naphthyl
Aralkyl radicals, e.g. B.
Benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, cumylmethyl, mesitylmethyl
Alkyloxy radicals with 1-10 carbon atoms and phosphorus or sulfur as further heteroatoms, e.g. B.
Methoxy, ethoxy, propyloxy, butyloxy, 2-ethylbutyloxy, 3-thiabutyloxy, 3-phosphabutyloxy
Aralkyloxy radicals with alkyl and heteroatom-containing substituents on the aromatic ring, e.g. B.
Benzyloxy, 1-phenylethyloxy, 2-methylphenylmethoxy, p-sulfobenzyloxy, p-nitrobenzyloxy
and with R ₁₇ = R ₁₈ = R ₁₆ except R ₁₆ = H
are used, where R ₁₆ , R ₁₇ and R _{18 may be the} same or different and in the case of R ₁₆ = HR ₁₇ and R _{18 may be the} same or different.

Procedural protection

For the preparation of compounds of the general formula VI, compounds of the general formula VII

be used
with R ₁₄ = R1 = R ₃
and R ₁₅ = R ₂ = R ₄

Such double bond components can be represented by oleic acid, linoleic acid, Linolenic acid, palmitoleic acid, eicosenoic acid and erucic acid and their mixtures Oleic acid methyl ester, linoleic acid methyl ester, linolenic acid methyl ester, palmitolein acid methyl ester.

Glycerol trioleate, glycerol trilinolate, Glycerol trilinoleate, trimethylolpropane trioleate, trimethylolpropane trilinolate, Trimethylolpropane trilinoleate, pentaerythritol tetraoleate, pentaerythritol tetralinolate and Pentaerythritol tetralinoleate and their mixtures and renewable raw materials such as rapeseed oil, Sunflower oil, palm oil, coconut oil or olive oil can be used.

To produce these new lubricants and pressure transfer agents, the double bonds of the fatty acids and fatty acid derivatives and their mixtures with unbranched carboxylic acids with formula IV should be esterified,

where R ₈ = H, C ₁ -C ₂₁ carbon atoms, preferably H, C ₁ -C ₄ carbon atoms.

To produce these new lubricants and pressure transmission media, the Double bonds of fatty acids, fatty acid derivatives and their, mixtures with aromatic Carboxylic acids such as benzoic and benzoyl acids are esterified, the Aromatic nucleus can also be substituted with alkyl groups and / or halogens such as F.

Other added carboxylic acids obey Formula VIII

with R ₁₆ = H or R ₁₆ =
Alkyl residues with 1-10 C atoms, e.g. B.
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl
Alkenyl residues with 1-10 C atoms, e.g. B.
Ethenyl, n-propenyl, isopropenyl, hexenyl, 3-methylpentenyl, 3-ethylbutenyl
Aryl radicals with alkyl and other substituents on the aromatic ring, e.g. B.
Phenyl, methylphenyl, ethylphenyl, mesityl, cumyl, p-nitrophenyl, xylyl, hydroXyphenyl, naphthyl
Aralkyl radicals, e.g. B.
Benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, cumylmethyl, mesitylmethyl
Alkyloxy radicals with 1-10 carbon atoms and phosphorus or sulfur as further heteroatoms, e.g. B.
Methoxy, ethoxy, propyloxy, butyloxy, 2-ethylbutyloxy, 3-thiabutyloxy, 3-phosphabutyloxy
Aralkyloxy radicals with alkyl and heteroatom-containing substituents on the aromatic ring, e.g. B.
Benzyloxy, 1-phenylethyloxy, 2-methylphenylmethoxy, p-sulfobenzyloxy, p-nitrobenzyloxy
and with R ₁₇ = R ₁₈ = R ₁₆ except R ₁₆ = H
are used, where R ₁₆ , R ₁₇ and R _{18 may be the} same or different and in the case of R ₁₆ = H = R ₁₇ and R _{18 may be the} same or different.

Neocarboxylic acids of the general formula V are particularly preferred

added, in which R ₉ , R ₁₀ , R ₁₂ and / or R _{13 are} identical or different and are hydrogen, straight-chain or branched alkyl, alkenyl or alkynyl radicals having up to 18 carbon atoms, cycloalkyl or cycloalkenyl radicals having 5 to 8 carbon atoms, Aryl, aralkyl or alkenylaryl radicals having 6 to 16 carbon atoms or heterocyclic radicals, where in each case the radicals R ₉ and R ₁₀ and / or R ₁₂ and R ₁₃ together with the carbon atom to which they are attached are a cycloalkane,, cycloalkene or can form a heterocycle having 5 to 7 ring members, R ₉ , R ₁₀ , R ₁₂ and R ₁₃ moreover can carry substituents, in particular those which are inert under the reaction conditions, and R _{11 represents} hydrogen or a straight-chain or branched alkyl radical.

Preference is given to carboxylic acids in which R ₉ , R ₁₀ , R ₁₂ and R _{13 are} identical or different and hydrogen, straight-chain or branched alkyl radicals having 1 to 12 and in particular 1 to 6 carbon atoms, alkenyl or alkynyl radicals having 2 to 12 and in particular 2 to 6 carbon atoms. Also preferred are compounds in which R ₁₉ , R ₂₀ , R ₂₂ and R _{23 are} cycloalkyl or cycloalkenyl radicals having 5 or 6 carbon atoms, aryl, alkylaryl, aralkyl or alkenylaryl radicals having 6 to 12 carbon atoms and heterocyclic Residues that contain one or more nitrogen and / or oxygen and / or sulfur atoms. Dioxanes in which R _{21 is} a straight-chain or branched alkyl radical having 1 to 12, in particular 1 to 8, preferably 1 to 4, carbon atoms are also preferred. R ₁₁ particularly preferably represents hydrogen.

Examples of alkyl, alkenyl or alkynyl radicals are the methyl, ethyl, n-propyl, Isopropyl, propenyl, isopropenyl, n-butyl, isobutyl, n-bututeriyl, i-butenyl, n-butinyl, Pentyl, pentenyl, pentinyl, hexyl, hexenyl, heptyl, heptenyl, octyl, octenyl, nonyl, Nonenyl, decyl, decenyl, dodecyl or dodecenyl radical.

Cycloalkyl radicals are exemplified by the cyclopentyl, cyclohexyl, cycloheptyl, Represent cyclopentenyl or cyclohexenyl radical.  

As aromatic residues such. B. the phenyl, benzyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 2-phenylbutyl, 3-phenylbutyl or 4-phenylbutyl radical into consideration.

Examples of heterocyclic radicals are furan dihydrofuran, tetrahydrofuran, Thiophene, dihydrothiophene, pyridine and thiopyran residue.

The alkyl, cycloalkyl aromatic and heterocyclic radicals can be substituted, in particular by residues which are inert under reaction conditions, such as halogen, alkoxy, Carboxy or carboxylate groups. However, it is also not excluded in individual cases that consciously select substituents that are changed in the course of the reaction, e.g. B. formyl groups, which are converted into formoxy radicals.

In this way, for example, branched in the α-position to the carboxyl group Carboxylic acids are used like

3-propyloxy-2,2-dimethylpropionic acid,

¹ H NMR 0.89 ppm tr 3H, 1.19 ppm 2 6H, 3.42 ppm s 2H, 3.40 ppm s 2H, 1.56 ppm m 2H
¹³ C NMR 10.66 CH ₃ , 23.06 CH ₂ , 77.54 and 73.69 O-CH ₂ , 43.83 quaternary C, 22.46 ppm 2 CH ₃ , 183.01 C = O
IR 1706 cm ^-1 C = O, 2976, 2935, 2879cm ^-1 ν _{s, as} CH ₂ , CH ₃ , broad shoulder at 2700- 2500 cm ^-1
MS m / z: 175 (M ⁺ .), 131, 115, 101, 102, 87, 83

3-butyloxy-2,2-dimethylpropionic acid

¹ H NMR 0.90 ppm tr 3H, 1.34 ppm m 2H, 1.53 ppm q 2H, 3.45 ppm tr 2H, 3.42 ppm s 2H; 1.19 ppm s 6H.
¹³ C-NMR 14.01 ppm CH ₃ , 19.69 ppm CH ₂ , 31.95 ppm CH ₂ , 77.65 ppm and 71.80 ppm O-CH ₂ , 43.87 ppm quaternary C, 22.44 ppm 2 CH ₃ , 183.72 C = O
IR 1706 cm ^-1 C = O, 2971, 2935, 2879 cm ^-1 ν _{s, as} CH ₂ , CH ₃ broad shoulder at 2700- 2500 cm ^-1
MS m / z: 189 (M ⁺ .), 131, 114, 102, 101, 87, 73

3-isobutyloxy-2,2-dimethylpropionic acid

¹ H NMR 0.88 ppm s 3H, 0.89 ppm s 3H, 1.84 ppm m 1H, 3.20 ppm d 2H, 3.41 ppm s 2H, 1.20 ppm s 6H
¹³ C-NMR 19.36 ppm 2 CH ₃ , 28.70 ppm CH, 78.83 and 77.75 ppm O-CH ₂ , 22.44 ppm two CH ₃ , 43.87 ppm quaternary C, 183.04 ppm C = O
IR 1706 cm ^-1 C = O, 2976, 2935, 2868 cm ^-1 ν _{s, as} CH ₂ , CH ₃ , broad shoulder at 2700- 2500 cm ^-1
MS m / z: 189 (M ⁺ .), 131, 115, 102, 101, 87, 73

3- (2-ethylbutyloxy) -2,2-dimethylpropionic acid

¹ H NMR 0.93 ppm tr 3H, 0.86 tr 3H, 1.59 ppm m 4H, 2.22 ppm m 1H, 3.33 ppm d 2H, 3.40 ppm s 2H, 1.19 ppm s 6H
¹³ C NMR 11.87 and 11.26 ppm CH ₃ , 23.86 and 25.16 ppm CH ₂ , 49.34 ppm CH, 77.92 and 74.36 ppm O-CH ₂ , 22.46 ppm 2 CH ₃ , 43.90 ppm quaternary C, 183.16 ppm C = O
IR 1706 cm ^-1 C = O, 2966, 2935, 2879 cm ^-1 ν _{s, as} CH ₂ , CH ₃ broad shoulder at 2700- 2500 cm ^-1
MS m / z: 217 (M ⁺ .), 185, 145, 133, 131, 115, 102, 101, 85, 73

3-benzyloxy-2,2-dimethylpropionic acid

¹ H NMR 7.20 ppm m 5H, 4.37 ppm s 2H, 3.35 ppm s 2H, 1.08 ppm s 6H
¹³ C NMR 125-130 ppm aromatic C, 77.13 and 73.28 ppm O-CH ₂ , 21.87 ppm 2 CH ₃ , 43.80 ppm quaternary C, 182.89 ppm C = O
IR 1701 cm ^-1 C = O, 3094, 3063, 3033 cm ^-1 ν _ar CH, 2984, 2909, 2878 cm ^-1 ν _{s, as} CH ₂ , CH ₃ , broad shoulder at 2700-2500cm ^-1
MS m / z: 222 (M ⁺ .), 191, 116, 107, 101, 91, 65

3- (2-methylphenyloxy) -2,2-dimethylpropionic acid

¹ H NMR 7.0-7.3 ppm m 4H, 2.28 ppm s 3H, 3.48 ppm s 2H, 3.44 ppm s 2H, 1.21 ppm s 6H
¹³ C NMR 125-130 ppm aromatic C, 77.31 and 72.28 ppm O-CH ₂ , 43.78 ppm quaternary C, 22.46 ppm CH ₃ -ar, 18.82 and 15.32 ppm CH ₃ , 182.79 ppm C = O
IR 1703 cm ^-1 C = O, 3073, 3027 cm ^-1 ν _ar CH, 2976, 2935, 2868 cm ^-1 ν _{s, as} CH ₂ , CH ₃ , broad shoulder at 2700-2500cm ^-1
MS m / z: 237 (M ⁺ .), 209, 193, 145, 131, 121, 115, 105

Fabric protection

New lubricants and pressure transfer media have been based on the acylation of the double bond or the double bonds of the general formula IX

found
with R ₁₄ = R ₁ = R ₃
R ₁₅ = R ₂ = R ₄
and with R ₉ = linear alkyl radicals with C ₂ -C ₁₆ carbon atoms, preferably C ₁ -C ₄ carbon atoms or aromatic radicals, the aromatic nucleus of which can be substituted with alkyl groups and / or halogens.

Procedural protection

For the preparation of compounds of the general formula X, double bond components of the general formula VII can be used.

Added carboxylic acids obey the formula X.

R ₂₄ = linear alkyl radicals with C ₂ -C ₁₆ carbon atoms, preferably C ₁ -C ₄ carbon atoms or aromatic radicals, the aromatic nucleus of which can be substituted with alkyl groups and / or halogens.

To produce these new lubricants and pressure transmission media, the Double bonds of natural fatty acids, natural fatty acid derivatives and their Mixtures instead of carboxylic acids with the corresponding carboxylic acid anhydrides and / or  Carboxylic acid halides are esterified. The fatty acids or Fatty acid derivatives can be of natural or synthetic origin.

The reactions are carried out in the presence of homogeneous and heterogeneous catalysts. It could be shown that good conversions and high selectivities in the addition reaction can be achieved by using homogeneous and heterogeneous acidic catalysts. Heterogeneous catalysts such as zeolites, solid phosphoric acid, phosphates of aluminum, boron, iron, strontium, cerium and zirconium, oxides such as Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , Fe ₂ O ₃ , ZrO ₂ are particularly advantageous. SnO ₂ and GeO ₂ and organic ion exchangers such as Amberlyst or Nafion, which are easy to separate from the products formed. Nafion silica composite materials in particular provide good results. It is advantageous here to dry the catalyst in vacuo for several hours at elevated temperature before use in the reaction. The heterogeneous catalysts mentioned can be regenerated and can be used repeatedly in the process. While formic acid can be added to the double bond of natural fatty acids and fatty acid derivatives even without a catalyst, no conversion is achieved when higher carboxylic acids are used in the absence of catalysts, and the reaction with carboxylic acids can also be autocatalytic in individual cases.

H ₂ SO ₄ , methylsulfonic acid, H ₃ PO ₄ and their derivatives, H ₃ BO ₃ , HNO ₃ , HCl, HF, HF * BF _3, AlCl ₃ , FeCl ₃ , SnCl ₂ , AlBr ₃ can be used as homogeneous acidic catalysts and FeBr ₃ are used.

In the above-mentioned manner, novel esters of natural fatty acids and fatty acid derivatives could be prepared according to equation 1 or equation 2.

The analysis was carried out via HPLC and GC. Evidence of the identity of the products obtained were obtained by mass spectrometry. The educated Addition products can be obtained in a purity by distillation or column chromatography isolated from 70-99% and characterized by NMR and IR spectroscopy.

For example, the ester (compound I) below has the following characteristic features:

¹ H-NMR 0.8 ppm tr 3H (methyl group chain end), 1.13 ppm s 9H (tert-butyl group), 1.19 ppm - 1.6 ppm several broad peaks (methylene groups of the chain), 2.12 ppm tr 2H (CH ₂ group in proximity to the methyl ester group), 3.59 ppm s 3H (O-CH ₃ = Gituppe), 4.78 ppm q 1H (ester-substituted CH group)
¹³ C-NMR 14.12 ppm (CH ₃ group chain end), 27.25 ppm (tert-butyl group), 7 peaks from 22.66-34.14 ppm (chain methyl groups), 38.84 ppm (( CH ₃ ) ₃ C), 51.44 ppm (O-CH ₃ group), 73.81 ppm (ester-substituted CH group), 174.35 ppm (-CH ₂ CO ₂ CH ₃ ), 178.27 ppm ( (CH ₃ ) ₃ C-CO ₂ -CH)
IR 1164 cm ^-1 ν _as COC, 1283 cm ^-1 ν _as COC, 1435 cm ^-1 δs CH ₂ / -CH ₂ -CO-C, 1462 cm ^-1 δas CH ₃ , 1480 cm δs CH ₂ , 1742, 1726 cm ^-1 C = O, 2950, 2926, 2856 cm ^-1 ν _{s, as} CH ₂ , CH ₃
MS m / z: 399 (M ⁺ .), 313, 297, 265, 247, 220, 111, 97, 95, 83, 69, 57, 55
Boiling point: 170-174 ° C / l.10 ^-1 mbar
Elemental analysis:
C (measured): 72.4% C (calculated): 72.3%
H (measured): 12.0 H (calculated): 11.6%

It is advantageous to use the carboxylic acid and / or carboxylic anhydride and / or Carboxylic acid halides in excess and to use as a solvent, whereby the Use of additional solvents is avoided.

The carboxylic acid is added to the double bonds of the oleochemical component. Due to the carbenium ion mechanism, to a small extent Double bond isomerization occur. Polymers can be by-products of the reaction arise and to a small extent transesterification products by cleaving the fatty acid esters and esterification of the excess carboxylic acid component.

The heterogeneous catalysts can be easily filtered off, washed and after the reaction be regenerated, whereby the initial activity can be restored.

Unreacted carboxylic acids or their derivatives can, like the oil component be separated from the product formed by distillation or chromatography. As well can the addition products formed by distillation or column chromatography in a purity of 70-99% isolated and characterized by NMR and IR spectroscopy become.

The addition of the carboxylic acid or its derivatives to the natural fatty acid and Natural fatty acid derivatives take place in the liquid phase at 0 to 400 ° C, especially at 25 to 250 ° C, especially at 70 to 180 ° C. The reaction is carried out at pressures from 1000 hPa to 10000 hPa, especially at 1000 to 5000 hPa, especially at 1000 to 2000 hPa carried out. There are loads of 0.001 mmol to 50 mol of educt per gram Catalyst used, especially from 0.01 mmol to 30 mol, in particular from 0.1 to 10 mol.  

The response time is between one minute and 12 days, especially 10 minutes up to 5 days, especially from one hour to 48 hours. The molar excess of Acid component in relation to the oil component is 0.3-300, especially 1.2-150, especially 10-80.

Higher branching of the added carboxylic acid or carboxylic acid derivatives is reduced their reactivity as expected. At the same time, however, the selectivity of the reaction significantly increased because of the lower acidity of polymerization and transesterification be promoted less strongly.

When scaling up the reaction, the good selectivities and conversions can be maintained longer reaction times are sometimes required.

The reaction can be carried out in a batch or continuous process become. For example, stirred tanks can be used as reactors in the discontinuous, depressurized process are used; stainless steel autoclaves can be used when working under pressure become. In a semi-continuous mode of operation, stirred tank cascades are used. In Continuous reaction control are preferred tubular reactors with a fixed catalyst bed used. Loop and trickle bed reactors can also be used.

To carry out the reaction, the native fatty acids or native fatty acid derivatives in the presence of the catalyst at room temperature with stirring added the acid component and the, flask into a heating bath of the desired Given reaction temperature. The reaction takes place with stirring and cooling using a Reflux condenser. For analysis, a defined one is set at different reaction times Sample amount taken and examined by HPLC or GC. After completion of the Reaction, the catalyst is filtered off, rinsed with an organic solvent and regenerated with hydrochloric or nitric acid. The reaction mixture is by HV distillation or fractionated column chromatography and remaining oil and acid components in the Response returned.

The oil component used can be modified by prior partial hydrogenation. For this purpose, the natural fatty acids or natural fatty acid derivatives can be increased Hydrogen pressure on various heterogeneous catalysts, e.g. B. nickel, platinum or Palladium on support materials, implemented in the liquid phase at temperatures around 150 ° C become. The remaining double bonds can be used as described above Carboxylic acids are added catalytically.  

The new lubricants and pressure transmission systems show a high oxidation and Resistant to hydrolysis, improved viscosity properties with a wide viscosity range, lower vapor pressure and optimized lubricating film formation as well as reduced frictional moments e.g. B. in the spindle bearing. They are easily biodegradable. The substances according to the invention or substance mixtures can also be used as functional fluids and lubricant additives Find use.

The invention is explained in more detail below on the basis of preferred exemplary embodiments.

Examples Catalyst A

Catalyst A = Nafion SAC 13, i.e. H. Nafion silica composite material with a Nafion 13% content

Nafion is a registered trademark of DuPont. It is a perfluorinated polymer which receives highly acidic acid functions through sulfonation. By co-precipitation of Nafion with silica gel, materials with changing Nafion content with a surface area of around 300-400 m ² .g ^-1 are obtained, which are referred to as Nafion composites.

Catalyst B

Catalyst B = Amberlyst 15 from Fluka with a surface area of 45 m ² / g and a porosity of 32%

Amberlyst is a trademark of Rohm and Haas Company. Macroreticular ion exchangers are produced by co-polymerizing styrene with 3-5% divinylbenzene for crosslinking. The acid function is formed by SO ₃ H groups.

Examples 1 and 2

190 g of methyl oleic acid are stirred with a magnetic stirrer at 600 g Formic acid reacted at 120 ° C. The mixture is stirred under reflux for 18 h. After the reaction a sample is taken and with a 60 m SE-54 column from Chrompack examined by gas chromatography.

The reaction proceeds according to equation (3):

The reaction mixture is fractionated in a high vacuum. Here formic acid passes over at 54 ° C / 150 torr, oleic acid methyl ester and other educt components at 133 ° C / l.10 ^-1 mbar and 9 (10) -formyloxystearic acid methyl ester at 160-174 ° C / l.10 ^-1 mbar. 105 g of product mixture containing 90% of 9 (10) -formyloxystearic acid methyl ester are obtained.

Characterization of the compound I = 9- (10) -formyloxystearic acid methyl ester ¹

H-NMR 0.83 ppm tr 3H (methyl group chain end), 1.19 ppm-1.6 ppm several broad peaks (methylene groups of the chain), 2.25 ppm tr 2H (CH ₂

Group adjacent to the methyl ester group), 3.61 ppm s 3H (O-CH ₃

Group), 4.7 ppm q ¹

H (ester-substituted CH group), 8.04 ppm s (formyloxy group)
¹³

C NMR 14.13 ppm (CH ₃

Group chain end), 7 peaks from 22.70-34.09 ppm (chain methylene groups), 51.44 ppm (O-CH ₃

Group), 74.53 ppm (ester-substituted CH group), 161.14 ppm (HCO ₂

CH), 174.31 ppm (-CH ₂

- CO ₂

-CH _3rd

)
IR 1183 cm ^-1

ν _as

COC (strong peak for formates), 1377 cm ^-1

δs CH ₃

, 1437 cm ^-1

δs CH ₂

/ -CH ₂

-CO-C, 1465 cm ^-1

δas CH ₃

, 1377 cm ^-1

δs CH ₂

, 1742, 1725 cm ^-1

C = 0.2928, 2856 cm ^-1

ν _{s, as}

CH ₂

, CH ₃

MS m / z: 343 (M ⁺

), 313, 297, 265, 264, 246, 235, 222, 208, 111, 109, 81, 67, 55
Boiling point: 160-174 ° C / l.10 ^-1

mbar
Elemental analysis:
C (measured): 70.4% C (calculated): 70.13%
H (measured): 11.38% H (calculated): 11.18%

Example 3 Formic acid with Amberlyst

Oleic acid methyl ester: 2.5 g
Formic acid: 19.55 g
Catalyst: 2.5 g
Temperature: 120 ° C

Example 4

Formic acid with Nafion / Silica Composite SAC 13 instead of Amberlyst

Example 5 Acetic acid with sulfuric acid

Oleic acid methyl ester: 2.5 g
Acetic acid: 25.5 g
Catalyst: 2.5 g
Temperature: 120 ° C

Example 6

Acetic acid with phosphoric acid on silica instead of sulfuric acid

Example 7

Acetic acid with Nafion / Silica Composite SAC 13 instead of sulfuric acid

Analysis of the methyl acetoxystenate Characterization of compound II: 9 (10) -acetoxystearic acid methyl ester ¹

H = NMR 0.81 ppm tr 3H (methyl group chain end), 1.19 ppm-1.6 ppm several broad peaks (chain methylene groups); 1.97 ppm s 3H (CH ₃

Group acetoxy group), 2.27 ppm tr 2H (CH ₂

Group in the vicinity of the methyl ester group), 3.60 ppm), 3.60 ppm s 3H (O-CH ₃

Group), 4.78 ppm q 1H (ester-substituted CH group),
¹³

C NMR 14.15 ppm (CH ₃

Group chain end), 21.34 ppm (CH ₃

Group acetoxy group), peaks of 22.73-3417 ppm (chain methylene groups), 74.53 ppm (ester-substituted CH group), 174.13 ppm (CH ₂

CO ₂

CH), 179.97 ppm (CH ₃

C-CO ₂

-CH)
IR 1164 cm ^-1

ν _as

COC, 1283 cm ^-1

ν _as

COC, 1361 cm ^-1

δs CH ₃

/ CH ₃

-CO ₂

-, 1435 cm ^-1

δs CH ₂

/ -CH ₂

-CO-C, 1462 cm ^-1

δas CH ₃

, 1481 cm ^-1

δs CH ₂

, 1745, 1726 cm ^-1

C = 0.2926, 2856 cm ^-1

ν _{s, as}

CH ₂

, CH ₃

MS m / z: 356 (M ⁺

.), 355, 313, 295, 281, 263, 245, 187, 155, 109, 95, 81, 67, 55
Boiling point: 170-182 ° C / 5.10 ^-2

mbar

Example 8

30 g of Nafion SAC 13 are dried under high vacuum at 100 ° C. for four hours, then placed in a 21-necked flask and mixed with 100 g of a fatty acid methyl ester mixture. Content of 66% oleic acid methyl ester added. While stirring with a magnetic stir bar, 570 g of pivalic acid are added and the flask is placed in an oil bath heated to 120 ° C. The mixture is stirred for 15 h with cooling by a reflux condenser. After the reaction is complete, a sample is taken and analyzed by gas chromatography using a 60 m SE-54 column from Chrompack. A conversion of oleic acid methyl ester of 45% with a selectivity to the addition product of 96% is detected. The reaction proceeds according to equation (4):

The catalyst is filtered off and residues of the reaction mixture are removed by washing with acetone. The acetone is distilled off at atmospheric pressure and the remainder is combined with the reaction mixture. If the catalyst is deactivated after such a reaction, it is regenerated by treatment with hydrochloric acid. The reaction mixture is fractionated in a high vacuum. Here pivalic acid passes over at 82 ° C / 25 clay, oleic acid methyl ester and other educt components at 133 ° C / l.10 ^-1 mbar and 9- (10) [2,2-dimethylpropionyloxy] stearic acid riethyl ester at 170-174 ° C / l .10 ^-1 mbar. 30 g of product mixture containing 70% methyl 9- (10) -dimethylpropionyloxystearirisate are obtained.

Characterization of the compound I = 9- (10) -dimethylpropionyloxystearic acid methyl ester ¹

H-NMR 0.8 ppm tr 3H (methyl group chain end), 1.13 ppm s 9H (tert-butyl group), 1.19 ppm-1.6 ppm several broad peaks (methylene groups of the chain), 2.12 ppm tr 2H (CH ₂

Group in the vicinity of the methyl ester group), 3.59 ppm s 3H (O-CH ₃

-Group); 4.78 ppm q 114 (ester-substituted CH group)
¹³

C NMR 14.12 ppm (CH ₃

= Chain end group), 27.25 ppm (tert-butyl group), 7 peaks from 22.66-34.14 ppm (chain methylene groups), 38.84 ppm ((CH ₃

) ₃

C), 51.44 ppm (O-CH ₃

Group), 73.81 ppm (ester-substituted CH group), 174.35 ppm (-CH ₂

CO ₂

CH ₃

), 178.27 ppm (((CH ₃

) ₃

C-CO ₂

-CH)
IR 1164 cm ^-1

ν _as

COC, 1283 cm ^-1

ν _as

COC 1435 cm ^-1

δs CH ₂

/ -CH ₂

-CO-C, 1462 cm ^-1

δas CH ₃

, 1480 cm ^-1

δs CH ₂

, 1742, 1726 cm ^-1

C = O, 2950, 2926, 2856 cm ^-1

ν _{s, as}

CH ₂

, CH ₃

MS mz: 399 (M ⁺

), 313, 297, 265, 247, 220, 111, 97, 95, 83, 69, 57, 55
Boiling point: 170-174 ° C / l.10 ^-1

mbar
Elemental analysis:
C (measured): 72.4% C (calculated): 72.3%
H (measured): 12.0 H (calculated): 11.6%

Examples 9 and 10

Examples 9 and 10 show a comparison of the catalysts Nafion SAC 13 (A) and Amberlyst 15 (B) in the addition of pivalic acid to the double bond of methyl oleic acid. The reaction parameters are: catalyst loading 4 mmol / g catalyst, molar excess pivalic acid in proportion to oleic acid methyl ester = 25, temperature 120 ° C., reaction time 8 h, batch reaction under normal pressure; Use of the catalysts without prior drying

Examples 11-13

Examples 11 to 13 show the effect of a higher degree of branching of the added carboxylic acid on conversion and selectivity. Are input materials. Oleic acid methyl ester, catalyst Nafion SAC 13, molar excess of carboxylic acid in relation to oleic acid methyl ester = 50 (pivalic acid = 25), temperature 120 ° C., reaction time 8 h, batch reaction under normal pressure; Use of the catalyst without prior drying

Examples 14 and 15

Examples 14 and 15 show the scale up of the addition of pivalic acid to the double bond of. Oleic acid methyl ester. The catalyst is Nafion SAC 13, the reaction parameters are: catalyst loading 4 mmol / g catalyst, molar excess pivalic acid in proportion to oleic acid methyl ester = 25, temperature 120 ° C., batch reaction under normal pressure; Use of the catalysts without prior drying.

Examples 16-20

Examples 16 to 20 show the behavior of the reaction system during pretreatment, reuse and regeneration of Nafion SAC 13 in the addition of pivalic acid to the double bond of methyl oleic acid, catalyst loading 4 mmol / g catalyst; molar excess of pivalic acid in relation to oleic acid methyl ester = 25, temperature 120 ° C., batch reaction under normal pressure. Response time 15 h

Example 21

In another experiment, 3-benzyloxy-2,2-dimethylpropionic acid was used as Acid component used.

3-benzyloxy-2,2-dimethylpropionic acid

¹ H NMR 7.20 ppm m 5H, 4.37 ppm s 2H, 3.35 ppm s 2H, 1.08 ppm s 6H
¹³ C-NMR 125-130 ppm aromatic C, 77.13 and 73.28 ppm O-CH ₂ , 21.87 ppm 2 CH ₃ , 43.80 ppm quaternary C, 182.89 ppm C = O
IR 1701 cm ^-1 C = O, 3094, 3063, 3033 cm ^-1 ν _ar CH, 2984, 2909, 2878 cm ^-1 ν _{s, as} CH ₂ , CH ₃ , broad shoulder at 2700-2500 cm ^-1
MS m / z: 222 (M ⁺ ), 191, 116, 107, 101, 91, 65

Nafion SAC 13 was used as a catalyst for the acylation of methyl oleic acid. The following reaction conditions were chosen: catalyst loading 4 mmol / g catalyst, molar excess pivalic acid in proportion to oleic acid methyl ester = 25, temperature 120 ° C., batch reaction under normal pressure. Response time 24 h

Example 22

Example 22 shows the properties of the esters methyl formyloxysteatate and methyl [2,2-dimethylpropionyloxy] stearate prepared according to examples 1 and 4 compared to the pure methyl oleic acid (basic raw material).

Further examples

As further branched carboxylic acids for addition, the double bonds are more natural Fatty acids and natural fatty acid derivatives come e.g. B. the following carboxylic acids with the assigned characteristics into consideration:

3-propyloxy-2,2-dimethylpropionic acid

¹ H NMR 0.89 ppm tr 3H, 1.19 ppm 2 6H, 3.42 ppm s 2H, 3.40 ppm s 2H, 1.56 ppm m 2H
¹³ C NMR 10.66 CH ₃ , 23.06 CH ₂ , 77.54 and 73.69 O-CH ₂ , 43.83 quaternary C, 22.46 ppm 2CH ₃ , 183.01 C = O
IR 1706 cm ^-1 C = O, 2976, 2935, 2879 cm ^-1 ν _{s, as} CH ₂ , CH ₃ , broad shoulder at 2700- 2500 cm ^-1
MS m / z: 1775 (M ⁺ .), 131, 115, 101, 102, 87, 83

3-butyloxy-2,2-dimethylpropionic acid

¹ H NMR 0.90 ppm tr 3H, 1.34 ppm m 2H, 1.53 ppm q 2H, 3.45 ppm tr 2H, 3.42 ppm s 2H, 1.19 ppm s 6H
¹³ C-NMR 14.01 ppm CH ₃ , 19.69 ppm CH ₂ , 31.95 ppm CH ₂ , 77.65 ppm and 71.80 ppm O-CH ₂ , 43.87 ppm quaternary C, 22.44 ppm 2 CH ₃ , 183.72 C = O
IR 1706 cm ^-1 C = O, 2971, 2935, 2879 cm ^-1 ν _{s, as} CH ₂ , CH ₃ broad shoulder at 2700- 2500 cm ^-1
MS m / z: 189 (M ⁺ .), 131, 114, 102, 101, 87, 73

3-isobutyloxy-2,2-dimethylpropionic acid

¹ H NMR 0.88 ppm s 3H, 0.89 ppm s 3H, 1.84 ppm m 1H, 3.20 ppm d 2H, 3.41 ppm s 2H, 1.20 ppm s 6H
¹³ C-NMR 19.36 ppm 2 CH ₃ , 28.70 ppm CH, 78.83 and 77.75 ppm O-CH ₂ , 22.44 ppm two CH ₃ , 43.87 ppm quaternary C, 183.04 ppm C = O
IR 1706 cm ^-1 C = O, 2976, 2935, 2868 cm ^-1 ν _{s, as} CH ₂ , CH ₃ , broad shoulder at 2700- 2500 cm ^-1
MS m / z: 189 (M ⁺ .), 131, 115, 102, 101, 87, 73

3- (2-ethylbutyloxy) -2,2-dimethylpropionic acid

¹ H NMR 0.93 ppm tr 3H, 0.86 tr 3H, 1.59 ppm m 4H, 2.22 ppm m 1H, 3.33 ppm d 2H, 3.40 ppm s 2H, 1.19 ppm s 6H
¹³ C NMR 11.87 and 11.26 ppm CH ₃ , 23.86 and 25.16 ppm CH ₂ , 49.34 ppm CH, 77.92 and 74.36 ppm O-CH ₂ , 22.46 ppm 2 CH ₃ , 43.90 ppm quaternary C, 183.16 ppm C = O
IR 1706 cm ^-1 C = O, 2966, 2935, 2879 cm ^-1 ν _{s, as} CH ₂ , CH ₃ broad shoulder at 2700- 2500 cm ^-1
MS m / z: 217 (M ⁺ .), 185, 145, 133, 131, 115, 102, 101, 85, 73

3- (2-methylphenyloxy) -2,2-dimethylpropionic acid

¹ H NMR 7.0-7.3 ppm m 4H, 2.28 ppm s 3H, 3.48 ppm s 2H, 3.44 ppm s 2H, 1.21 ppm s 6H
¹³ C NMR 125-130 ppm, aromatic C, 77.31 and 72.28 ppm O-CH ₂ , 43.78 ppm quaternary C, 22.46 ppm CH ₃ -ar, 18.82 and 15.32 ppm CH ₃ , 182.79 ppm C = O
IR 1703 cm ^-1 C = O, 3073, 3027 cm ^-1 ν _ar CH, 2976, 2935, 2868 cm ^-1 , ν _{s, as} CH ₂ CH ₃ , broad shoulder at 2700-2500 cm ^-1
MS m / z: 237 (M ⁺ .), 209, 193, 145, 131, 121, 115, 105

Claims (31)

1. New lubricants and pressure transmission media consisting of fatty acids and / or Fatty acid derivatives whose double bond or double bonds are acylated. 2. New lubricants and pressure transmission media consisting of fatty acids and / or Fatty acid derivatives, on the double bond or double bonds of carboxylic acid residues are added. 3. Process for the production of new lubricants and pressure transmission media Oleochemicals, characterized in that fatty acids and / or fatty acid derivatives with carboxylic acids and / or carboxylic anhydrides and / or carboxylic acid halides acylated at the positions of the double bond or double bonds by addition become. 4. Process for the production of new lubricants and pressure transmission media according to Claim 3, characterized in that the addition of carboxylic acids and / or, Cabonic anhydrides and / or carboxylic acid halides on the double bond or / and the double bonds are carried out catalytically. 5. Process for the production of new lubricants and pressure transmission media after Claim 4 characterized in that the addition of carboxylic acids also is done autocatalytically.   6. Process for the production of new lubricants and pressure transmission media according to Claims 3-4 characterized in that branched and / or unbranched aliphatic and / or aromatic carboxylic acids and / or cabonic anhydrides and / or carboxylic acid halides can be used. 7. Process for the production of new lubricants and pressure transmission means Claim 6, characterized in that formic acid, acetic acid, propionic acid, Butyric acid, pentanoic acid, hexanoic acid and their mixtures as unbranched aliphatic carboxylic acids are used. 8. Process for the production of new lubricants and pressure transmission media according to Claim 6, characterized in that benzoic acid and benzylic acid as aromatic Carboxylic acids are used. 9. Lubricants and pressure transmission means, characterized in that branched Carboxylic acid residues on the double bond or the double bonds of the fatty acids and / or the fatty acid derivatives are added. 10. Process for the production of lubricants and pressure transmission media, characterized in that branched carboxylic acids on the double bond or the double bonds of the fatty acids and / or the fatty acid derivatives are added. 11. Process for the production of lubricants and pressure transmission media according to Claim 9, characterized in that the addition of branched carboxylic acids to the double bond or the double bonds of the fatty acids and / or. the Fatty acid derivatives are carried out catalytically. 12. A process for the production of lubricants and pressure transmission means according to claim 3-11, characterized in that compounds of the general formula I as fatty acids
be used
with R ₁ = X-COOHY, where X = saturated and unsaturated alkyl radicals with 3-11 C atoms and the number of double bonds in this alkyl radical is 0-2. And where Y stands for H.
with R ₂ = saturated and unsaturated alkyl radicals with 3-10 C atoms and the number of double bonds in this alkyl radical is 0-2. 13. Process for the production of lubricants and pressure transmission media according to Claim 12, characterized in that oleic acid, linoleic acid, Linolenic acid, palmitoleic acid, eicosenoic acid and erucic acid and their mixtures and the esters of these acids can be used for the addition of carboxylic acids. 14. A process for the production of lubricants and pressure transmission means according to claims 3-11, characterized in that compounds of the general formula II as fatty acid derivatives
be used
with R ₃ = X-COOY where X = saturated and unsaturated alkyl radical with 3-11 C atoms and the number of double bonds is 0-2 and where Y stands for linear and branched alkyl groups with a C number of 1-12
with R ₄ = saturated and unsaturated alkyl radicals with 3-10 C atoms and the number of double bonds in this alkyl radical is 0-2. 15. Process for the production of lubricants and pressure transmission media according to Claim 14, characterized in that as fatty acid derivatives oleic acid methyl ester, Methyl linoleic acid, methyl linolenic acid, methyl palmitoleic acid and whose mixtures are used. 16. Process for the production of lubricants and pressure transmission media according to Claim 3, characterized in that as fatty acid derivatives glycerol trioleate, Glycerol trilinolate, glycerol trilinoleate, trimethylolpropane trioleate,  Trimethylolpropane trilinolate, trimethylolpropane trilinoleate, pentaerythritol tetraoleate, Pentaerythritol tetralinolate and pentaerythritol tetralinoleate and, their mixtures used become. 17. Process for the production of. Lubricants and pressure transmission media Claim 3, characterized in that renewable fatty acid derivatives Raw materials such as rapeseed oil, sunflower oil, palm oil, coconut oil or olive oil are used become. 18. A process for the production of lubricants and pressure transmission means according to claim 6, characterized in that compounds of the general formula III as carboxylic acids
with R ₅ = H or R ₅ =
Alkyl residues with 1-10 C atoms, e.g. B.
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl
Aryl radicals with alkyl and other substituents on the aromatic ring, e.g. B.
Phenyl, methylphenyl, ethylphenyl, mesityl, cumyl, p-nitrophenyl, xylyl, hydroxyphenyl, naphthyl
Aralkyl radicals, e.g. B.
Benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, cumylmethyl, mesitylmethyl
Alkyloxy radicals with 1-10 carbon atoms and phosphorus or sulfur as further heteroatoms, e.g. B.
Methoxy, ethoxy, propyloxy, butyloxy, 2-ethylbutyloxy, 3-thiabutyloxy, 3-phosphabutyloxy
Aralkyloxy radicals with alkyl and heteroatom-containing substituents on the aromatic ring, e.g. B.
Benzyloxy, 1-phenylethyloxy, 2-methylphenylmethoxy, p-sulfobenzyloxy, p-nitrobenzyloxy
and with R ₅ = R ₆ = R ₇ except R ₅ = H
are used, where R ₅ , R ₆ and R _{7 may be the} same or different and in the case of R ₅ = HR ₆ and R7 may be the same or different. 19. Process for the production of lubricants and pressure transmission media according to Claim 10, characterized in that as branched, carboxylic acids Isobutyric acid, 2,2-dimethylbutyric acid, 2-methylbutyric acid. 3-methylbutyric acid, Pivalic acid, 3-benzyloxypivalic acid, 3-ethyloxypivalic acid, 3- Butyloxypivalic acid, 3-isobutyloxypivalic acid, 3- (2-ethylbutyl) pivalic acid and 3- (2-Methylphenyl) methoxypivalic acid can be used. 20. Process for the production of lubricants and pressure transmission media according to Claims 3-4, characterized in that the addition of the carboxylic acids and / or Carboxylic acid halides and / or carboxylic acid anhydrides on the double bonds of Fatty acids and fatty acid derivatives on acidic homogeneous and heterogeneous catalysts he follows. 21. A process for the production of lubricants and pressure transmission media according to claim 20, characterized in that H ₂ SO ₄ , methylsulfonic acid, H ₃ PO ₄ and its derivatives, H ₃ BO ₃ , HNO ₃ , HCl, HF, HF are used as homogeneous acid catalysts. BF ₃ , AlCl ₃ , FeCl ₃ , SnCl ₂ , AlBr ₃ and FeBr ₃ can be used. 22. A process for the production of lubricants and pressure transfer agents according to claim 20, characterized in that the acidic heterogeneous catalysts are zeolites, organic, solid phosphoric acid, ion exchange resins, phosphates of aluminum, boron, iron, strontium, cerium and zirconium, oxides such as Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , Fe ₂ O ₃ , ZrO ₂ , SnO ₂ and GeO ₂ can be used. 23. Process for the production of lubricants and pressure transmission media according to Claim 20, characterized in that Nafion- as acidic heterogeneous catalysts Silica composite catalysts are used. 24. Process for the production of lubricants and pressure transmission media according to Claim 3, characterized in that a part of the double bonds of Fatty acids and / or fatty acid derivatives are hydrogenated and the remaining Double bonds carboxylic acids and / or carboxylic acid halides and / or Carboxylic anhydrides are added. 25. Process for the production of lubricants and pressure transmission media according to Claim 3, characterized in that the addition in the temperature range from 0 up to 400 ° C is carried out. 26. Process for the production of lubricants and pressure transmission media according to Claim 3, characterized in that at a catalyst loading of 0.01 mmol up to 30 mol fatty acid and fatty acid derivatives per gram of catalyst is worked. 27. Process for the production of lubricants and pressure transmission media according to Claim 3, characterized in that the reaction time from 1 min to 10 days is. 28. Process for the production of lubricants and pressure transmission media according to Claim 3, characterized in that the without the use of further solvents  Acid component as solvent in a molar excess of 1.2-150 is used. 29. Process for the production of lubricants and pressure transmission media according to Claims 1-3, characterized in that the invention Additive products in pure form or additive as lubricants and Functional fluids and hydraulic oils are used. 30. Process for the production of lubricants and pressure transmission media according to Claims 1-3, characterized in that the invention Additive products in pure form or additive as lubricants for tribological systems be used. 31. Process for the production of lubricants and pressure transmission media according to Claims 1-3, characterized in that the invention Addition products are used as lubricant additives.