EP0143248B1 - Verfahren zur Umsetzung von Fluorwasserstoff mit Fettsäureestern - Google Patents

Verfahren zur Umsetzung von Fluorwasserstoff mit Fettsäureestern Download PDF

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Publication number
EP0143248B1
EP0143248B1 EP84111334A EP84111334A EP0143248B1 EP 0143248 B1 EP0143248 B1 EP 0143248B1 EP 84111334 A EP84111334 A EP 84111334A EP 84111334 A EP84111334 A EP 84111334A EP 0143248 B1 EP0143248 B1 EP 0143248B1
Authority
EP
European Patent Office
Prior art keywords
wax
process according
fatty acid
reaction
hydrogen fluoride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84111334A
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German (de)
English (en)
French (fr)
Other versions
EP0143248A1 (de
Inventor
Heinz-Rudi Dr. Rer. Nat./Dipl.-Chem. Feist
Hans Dr. Rer. Nat./Dipl.-Chem. Buchwald
Boleslaus Raschkowski
Werner Dr. Rer. Nat./Dipl.-Chem. Rudolph
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kali Chemie AG
Original Assignee
Kali Chemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19833335870 external-priority patent/DE3335870A1/de
Priority claimed from DE19843426438 external-priority patent/DE3426438A1/de
Application filed by Kali Chemie AG filed Critical Kali Chemie AG
Publication of EP0143248A1 publication Critical patent/EP0143248A1/de
Application granted granted Critical
Publication of EP0143248B1 publication Critical patent/EP0143248B1/de
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
    • C10M105/54—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen containing carbon, hydrogen, halogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom

Definitions

  • the present invention relates to a process for reacting hydrogen fluoride with fatty acid esters, the reaction products prepared by this process and their use.
  • DE-PS 551 787 discloses a process for reacting fatty acid glycerides of plant and animal origin with hydrogen fluoride. Triglycerides are directly reacted with hydrogen fluoride at temperatures below 100 ° C. Polymers are obtained as reaction products, products with different degrees of polymerization being obtained depending on the reaction time.
  • the object of the invention is to transfer the known reaction with hydrogen fluoride to other classes of substances.
  • Another object of the invention is to provide new, technically valuable products that can be obtained by such implementation.
  • the process according to the invention is based on the generic process and is characterized in that a wax with a melting point T s ⁇ 60 ° C, preferably T s ⁇ 40 ° C, is used as the fatty acid ester.
  • wax is understood to mean a fatty acid ester composed of a preferably unsaturated fatty acid with a preferably unsaturated monoalcohol or a mixture of such fatty acid esters.
  • a preferred variant provides that a mixture of esters of long-chain carboxylic acids and monoalcohols with a total of 34 to 50 carbon atoms is used as the fatty acid ester.
  • fatty acid esters which have an iodine number of less than 95, preferably 30 to 95, in particular 75 to 95. Mixtures of such fatty acid esters are commercially available as synthetic products or as products of vegetable or animal origin. According to the invention, products of a synthetic or vegetable type are preferably used as starting materials.
  • the reaction is carried out in particular at temperatures from 0 to 80.degree. Although it is also possible to work at atmospheric pressure, it is preferred to work at elevated pressure, e.g. at 1.1 to 10 bar.
  • a type of reaction product is obtained under relatively mild process conditions.
  • pressure and temperature are preferably worked in the lower part of the specified range, e.g. at 1.1 to 5 bar and / or at 0 to 30 ° C. It is crucial that a molar ratio of hydrogen fluoride to wax of 0.1: 1 to 2: 1, in particular 0.4: 1 to 1.8: 1, is maintained in this variant.
  • adducts are fluorine-containing, waxy masses which apparently result from the addition of hydrogen fluoride to the fatty acid esters and whose fluorine content can be varied within a wide range depending on the reaction conditions.
  • very mild conditions i.e. With short reaction times and / or low temperature and / or a low supply of hydrogen fluoride, adducts with a low fluorine content or relatively high iodine numbers and a low melting point are obtained.
  • adducts with a low fluorine content or relatively high iodine numbers and a low melting point are obtained.
  • in not so mild conditions i.e.
  • the fluorine content of the adducts is in the range from 0.1 to 4.3% by weight.
  • adducts with all iodine numbers between the iodine number of the liquid wax used and down to practically 0 can be produced.
  • the melting point of the adduct can also be varied, so it is possible to provide increasingly inert and higher-melting waxes that supplement the range of conventional waxes and that e.g. can be used as release agent components, lubricants or as additives for lubricant mixtures, in particular as components for cooling lubricants.
  • reaction product is obtained when working under more drastic process conditions.
  • pressure and / or temperature in the upper range e.g. worked at 3 to 10 bar and / or 20 to 80 ° C. It is crucial in this variant that a molar ratio of hydrogen fluoride to wax of 2: 1 to 15: 1, preferably 4: 1 to 10: 1 is maintained.
  • sesquimers are oily products which (compared to the starting wax) have a molecular weight of 1.1 to 1.9 times, in particular 1.2 to 1.6 times, and an unreacted wax content of less than 1% by weight. contain.
  • the molecular weight of the sesquimer is to be understood as the average molecular weight.
  • the sesquimers are therefore not mixtures of monomers and polymers such as di-, tri- or oligomers with a corresponding average molecular weight.
  • the reaction mechanism and the constitution of the sesquimers have not yet been fully elucidated; however, it can be considered certain that this implementation is not - as e.g. in the process of DE-PS 551 787 - is a polymerization.
  • the sesquimers contain very little, if any, bound fluorine. As a rule, the fluorine content is below 0.1% by weight.
  • the sesquimers Compared to the starting wax, the sesquimers have a significantly reduced iodine number, which in the case of a preferably obtained sesquimer is in the range from 1 to 20, preferably 5 to 20. Further characteristic data and spectroscopic data for preferred sesquimers are given in the examples.
  • the sesquimers and the adducts are technically valuable products.
  • a preferred use is in lubricants. Due to good frictional wear values and high thermal stability, the sesquimers in particular, as such or as additives in high-quality lubricants, e.g. for engines, gearboxes, chillers, where appropriate, on the use of other additives such as EP additives can be dispensed with.
  • the sesquimers can also be used as hydraulic fluids and, due to their thermal stability and their high flash point, in particular as heat transfer fluids.
  • Sesquimers in particular are suitable for use in cooling lubricants for the cutting, separating or abrasive treatment of various materials, preferably metals.
  • Cooling lubricants based on chlorofluorocarbon are particularly preferred.
  • such a cooling lubricant consists of 0.5 to 25% by weight, preferably 0.5 to 5% by weight, of sesquimer and / or adduct and 99.5 to 75% by weight, preferably 99.5 up to 95 wt .-% of a chlorofluorocarbon with 1 or 2 carbon atoms and a boiling point of more than 20 ° C.
  • Trichloromonofluoromethane 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,2,2-tetrachlorodifluoroethane, tetrachloromonofluoroethane and / or trichlorodifluoroethane are particularly suitable.
  • Another variant provides for replacing up to 35% by weight, preferably up to 15% by weight, of the HFC in those cases in which the cooling lubricant evaporates too quickly by a solvent which regulates evaporation and is toxicologically safe.
  • a solvent which regulates evaporation and is toxicologically safe for example, low aliphatic ketones with 3 to 4 carbon atoms are suitable. Evaporation regulating solvents normally have a higher boiling point than the HFC used. Ethanol, n- and / or i-propanol are particularly preferred.
  • Another variant envisages adding solubilizers for the sesquimer or adduct to the cooling lubricant.
  • solubilizers known, toxicologically harmless solvents with solvent-soluble properties come into question, which can replace up to 10% by weight of the HFC.
  • a preferred solution provides for the use of aliphatic hydrocarbons as sesquimer or adduct solubilizers, which can also be used as evaporation regulators, preferably in a concentration of up to 15% by weight of the HFC.
  • aliphatic hydrocarbons or gasoline fractions e.g. Gasoline with a boiling range of 40 - 80 ° C.
  • concentration corresponding to the azeotropic composition is optimally used.
  • An addition of n-heptane has proven to be particularly useful.
  • sesquimer or adduct solubilizer to be selected from the group of long-chain aliphatic alcohols which contain 16 to 24 carbon atoms and preferably contain one or more carbon double bonds.
  • a further embodiment of the invention provides for the cooling lubricant to be additionally added with up to 1% by weight of the HFC per se known corrosion inhibitors.
  • corrosion inhibitors for metals such as Magnesium, aluminum, titanium, brass, bronze, steel are commercially available. They are mostly based on compositions containing organic compounds with hetero atoms such as sulfur or, in particular, nitrogen.
  • benzothiazoles e.g. Mercaptobenzothiazole, benzimidazoles, e.g. 2-phenylbenzimidazole, triazoles, e.g. Benzotriazoles, tolyltriazoles, oxazolines, e.g. Alkyl and / or hydroxyalkyl substituted oxazolines, amides, amines, e.g. tertiary amines.
  • one embodiment of the invention provides for up to 10% by weight of the HFC to be replaced by solubilizers for the inhibitors.
  • solubilizers for the inhibitor and for the sesquimer or adduct solubilizers.
  • Preferred solubilizers both for the inhibitor and for the sesquimer or adduct are low aliphatic alcohols with 1 to 5 carbon atoms.
  • ethanol, n- and / or i-propanol are mentioned, which, as already mentioned, can advantageously also be used at the same time as evaporation regulators.
  • an additive belongs to several additional types, its maximum concentration is not to be calculated additively, but is based on the highest individual concentration.
  • the specified cooling lubricant can be used to process metals in all known ways. For example, can be applied as a liquid or as an aerosol. It can also be applied externally, i.e. can be brought to the tool from the outside, as well as internally, i.e. through suitable feeds provided in the tool itself. The internal application is e.g. when drilling deep holes or grinding inside.
  • the cooling lubricant can also be used generally for the machining, cutting or abrasive treatment of hard materials.
  • the improvement occurs particularly clearly when the cooling lubricant contains a corrosion inhibitor, preferably based on oxazoline.
  • the process according to the invention for converting hydrogen fluoride can be carried out in both variants, preferably in the presence of inert solvents.
  • the process for the preparation of the adducts is not very critical and can be carried out in solvents as diverse as e.g. in chlorinated hydrocarbons such as carbon tetrachloride, methylene chloride, in chlorofluorocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,2,2-tetrachlorodifluoroethane, in aromatic solvents such as benzene and in substituted aromatic solvents such as toluene or Xylene can be performed. But it is also possible to work without solvents.
  • chlorinated hydrocarbons such as carbon tetrachloride, methylene chloride
  • chlorofluorocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,2,2-tetrachlorodifluoroethane
  • aromatic solvents such as benzene and in substituted aromatic solvents such as toluene or Xylene
  • the processing of the reaction products is not critical in both process variants.
  • the adducts can be filtered off and washed after neutralization and optionally after concentration. Adducts with high iodine numbers and sesquimers are expediently isolated by removing the solvent. Other cleaning stages known per se, e.g. Distillation, chromatography or refining can be connected.
  • the sesquimers can be used in the production of pharmaceutical and / or cosmetic preparations.
  • the corresponding use of the waxes used below for the production of the sesquimers and melting below 60 ° C. (hereinafter referred to as monomers) is known per se.
  • monomers melting below 60 ° C.
  • the sesquimers are distinguished from the monomers by an improved galenical processability.
  • the emulsifiability is improved, that is, less emulsifier is required to achieve the same emulsion quality, as a result of which undesirable side effects caused by the emulsifier are avoided or largely weakened.
  • a phase separation could not be effected in the centrifugation test of the emulsified product.
  • the use of the sesquimers according to the invention is recommended in the production of cosmetic preparations such as ointments, creams, emulsions, oils, suspensions, lotions, powders. It is also recommended for the manufacture of pharmaceutical preparations, as a carrier or for coating medical preparations, and as an additive in fermentation processes. It has been possible to substitute previously used matrix lubricants such as stearic acid, paraffin, glycerin, jojoba and other waxy substances. Granules, powders and tablets can also be hydrophobized with the sesquimers. The use of sesquimers is therefore recommended for the production of various types of galenical preparations, e.g. Tablets, dragees, capsules, powders, granules, suspensions, emulsions, oils, syrups.
  • galenical preparations e.g. Tablets, dragees, capsules, powders, granules, suspensions, emulsions, oils, syrups.
  • sesquimers in the preparation of topically administrable preparations is particularly preferred. Not only do the advantageous technological properties of the sesquimers mentioned come into play in these, but there are also preparations with a rapid permeation rate. Furthermore, it was found that the sesquimers for an improved inhibition of a too rapid proliferation of the basal cell layer located in the corium into the epidermis and thus develop a particularly main care and healing effect.
  • the invention therefore also relates to pharmaceutical and / or cosmetic preparations, in particular preparations which can be applied topically and which contain sesquimers.
  • composition of sesquimers and / or adducts-containing cooling lubricants is shown in the following examples, which have proven themselves in the processing of metals.
  • R 11 trichloromonofluoromethane
  • R 112 1,1,2,2-tetrachlorodifluoroethane
  • R 113 1,1,2-trichloro-1,2,2-trifluoroethane
  • R 121 tetrachloromonofluoroethane
  • R 122 trichlorodifluoroethane.
  • the waxes used and the corrosion inhibitors are commercially available products.
  • the triazole-based agent is based on a benzotriazole
  • the oxazoline-based agent is based on an alkyl- and hydroxyalkyl-substituted oxazoline.
  • Molar masses given are average molar masses.
  • Example 2 further sesquimers were obtained; Product properties and deviating reaction conditions are given in Table 2.
  • the molar mass M was determined osmometrically in the Knauer vapor pressure osmometer.
  • Table 3 shows compositions according to the invention which can be used as cooling lubricants.
  • compositions for pharmaceutical and / or cosmetic use are mixed with one another in the proportions indicated and form compositions for pharmaceutical and / or cosmetic use.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Emergency Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)
  • Fats And Perfumes (AREA)
  • Saccharide Compounds (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Control Of El Displays (AREA)
EP84111334A 1983-10-03 1984-09-22 Verfahren zur Umsetzung von Fluorwasserstoff mit Fettsäureestern Expired EP0143248B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3335870 1983-10-03
DE19833335870 DE3335870A1 (de) 1983-10-03 1983-10-03 Verfahren zur umsetzung von fluorwasserstoff mit fettsaeureestern
DE19843426438 DE3426438A1 (de) 1984-07-18 1984-07-18 Verwendung von sesquimeren
DE3426438 1984-07-18

Publications (2)

Publication Number Publication Date
EP0143248A1 EP0143248A1 (de) 1985-06-05
EP0143248B1 true EP0143248B1 (de) 1986-09-03

Family

ID=25814548

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84111334A Expired EP0143248B1 (de) 1983-10-03 1984-09-22 Verfahren zur Umsetzung von Fluorwasserstoff mit Fettsäureestern

Country Status (10)

Country Link
US (2) US4659493A (ja)
EP (1) EP0143248B1 (ja)
JP (1) JPH064564B2 (ja)
AT (1) ATE21923T1 (ja)
AU (1) AU567586B2 (ja)
DE (1) DE3460625D1 (ja)
DK (1) DK165841C (ja)
ES (1) ES8601092A1 (ja)
FI (1) FI78314C (ja)
IL (1) IL73124A (ja)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61117746A (ja) * 1984-11-13 1986-06-05 Hitachi Ltd 光デイスク基板
US5019919A (en) * 1986-04-09 1991-05-28 Canon Kabushiki Kaisha Apparatus for recording and reproducing divided signals of an angle modulated signal
DE3905125A1 (de) * 1989-02-20 1990-08-23 Kali Chemie Ag Zusammensetzungen mit dichlormonofluorethanen
DE4210700A1 (de) * 1992-04-01 1993-10-07 Solvay Fluor & Derivate Zusammensetzungen mit 1-Chlor-2,2,2-trifluorethyldifluormethylether
DE4321288A1 (de) * 1993-06-26 1995-01-05 Solvay Fluor & Derivate Zusammensetzungen mit chlorfreien, gegebenenfalls wasserstoffhaltigen Fluorkohlenwasserstoffen
ATE419844T1 (de) * 2000-02-10 2009-01-15 Kao Corp Verwendung von sesquiterpenalkohol zur regulierung des autonomen nervensystems
JP4974136B2 (ja) * 2006-03-31 2012-07-11 株式会社興人 バイオディーゼル燃料の加水分解抑制剤及び該抑制剤を含有したバイオディーゼル燃料

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1944941A (en) * 1932-06-11 1934-01-30 Continental Oil Co Lubricating oil
US2109357A (en) * 1934-01-22 1938-02-22 Ellen M Henriksen Lubricating oil
GB452579A (en) * 1934-02-24 1936-08-25 Ig Farbenindustrie Ag Manufacture of fluorinated organic compounds
GB453830A (en) * 1935-03-12 1936-09-14 Ig Farbenindustrie Ag Manufacture of fluorinated organic compounds
US2262773A (en) * 1937-03-19 1941-11-18 Lubri Zol Dev Corp Lubrication
US2300403A (en) * 1940-09-25 1942-11-03 Continental Oil Co Addition agent for lubricating oils
US2621159A (en) * 1949-11-05 1952-12-09 Shell Dev Metal working lubricant
US2670361A (en) * 1951-11-09 1954-02-23 Croston Clarence Bradford Polymerization process using hydrogen fluoride
US2926139A (en) * 1952-11-08 1960-02-23 Bayer Ag Lubricants for refrigerating systems
US2837547A (en) * 1955-12-30 1958-06-03 Pennsalt Chemicals Corp Polymerization of unsaturated triglycerides
GB1376669A (en) * 1966-06-01 1974-12-11 Amchem Prod Lubricant compositions for application to metal surfaces and processes for applying such compositions to metal surfaces
US4036769A (en) * 1971-04-05 1977-07-19 Werner G. Smith, Inc. Sperm oil substitute from blend of alcohol-carboxylic acid esters with liquid fat
US4401436A (en) * 1981-12-21 1983-08-30 Atlantic Richfield Company Process for cooling particulate coal
NL189307C (nl) * 1982-12-02 1993-03-01 Kali Chemie Ag Werkwijze voor het verspanend, scheidend of slijpend bewerken van metalen onder toepassing van een koelsmeermiddel en koelsmeermiddel.

Also Published As

Publication number Publication date
ATE21923T1 (de) 1986-09-15
ES536428A0 (es) 1985-10-16
JPS6127946A (ja) 1986-02-07
FI843851L (fi) 1985-04-04
JPH064564B2 (ja) 1994-01-19
DE3460625D1 (en) 1986-10-09
FI78314C (fi) 1989-07-10
US4659493A (en) 1987-04-21
IL73124A (en) 1988-01-31
IL73124A0 (en) 1984-12-31
DK471784D0 (da) 1984-10-02
FI78314B (fi) 1989-03-31
DK471784A (da) 1985-04-04
EP0143248A1 (de) 1985-06-05
FI843851A0 (fi) 1984-10-01
AU3380984A (en) 1985-04-18
US4746463A (en) 1988-05-24
DK165841B (da) 1993-01-25
AU567586B2 (en) 1987-11-26
ES8601092A1 (es) 1985-10-16
DK165841C (da) 1993-06-21

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