Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
  • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
  • C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
  • C11D7/5004—Organic solvents
  • C11D7/5022—Organic solvents containing oxygen

Definitions

• the present invention relates to an oligo-eric composition of lactic acid esters comprising a mixture of alkyl mono- and polylactyllactates of formula:
• the invention relates more particularly to a composition of ethyl mono- and polylactyllactates.
• This composition can be used alone or in combination with other solvents, in particular, as agents for cleaning and degreasing in a machine and in a non-aqueous medium of solid surfaces such as metal parts, ceramics, glass, plastics having been soiled with oils or greases from machining and / or their temporary protection. They can also be used for defluxing printed circuits. This defluxing operation consisting in eliminating the flux of solder.
• the cleaning and / or degreasing agents must have other characteristics such as in particular having a high flash point, a low toxicity, being odorless and not releasing volatile organic compounds into the atmosphere ( VOCs).
• composition of the present invention broadly meets the criteria mentioned above.
• composition of the present invention can also be used for obtaining lactides - cyclic dimers - which are the precursors of choice for obtaining polylactides used as biomaterials.
• HV Claborn (US 2,371,281) describes a process for obtaining alkyl lactyllactate by reacting the lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) with an alcohol l- ⁇ OH according to the reaction: * R'OH * ⁇ CH 3 - CH (OH) C (0) OCH (CH 3 ) C0 2 P. (1)
• the main fraction (78 g) identified as ethyl lactyllactate is a slightly viscous, colorless and odorless liquid which distills at 110 ° C - 113 ° C under 7.5 mmHg.
• alkyl lactyllactate usually being of the order of 5% to 20% depends on the alcohol / lactic acid ratio used during the esterification of said lactic acid.
• the subject of the present invention is therefore a composition comprising a mixture of alkyl mono- and polylactyllactates of formula: 0
• R represents an alkyl radical having a number of carbon atoms ranging from 1 to 4 and n is an integer equal to 2, 3 or 4.
• the alkyl radical is a methyl, propyl, isopropyl or n-butyl methyl radical.
• the alkyl radical is an ethyl radical.
• composition according to the invention may also contain an alkyl lactate of formula CH 3 CH (OH) CO 2 R (II) in which R has the same meaning as in formula (I), in particular at 0, 1 to 1 part by weight per 100 parts by weight of the mixture L 2 A + L 3 A + L 4 A.
• composition of the present invention can be obtained by total conversion esterification of a previously concentrated commercial lactic acid solution, said total conversion being obtained by eliminating the water formed by distillation. azeotropic.
• the concentration of commercial lactic acid solutions can be carried out by simple evaporation in one or more stages, at a temperature ranging from 100 ° C. to 170 ° C., at atmospheric pressure or under reduced pressure, until a composition is obtained.
• lactic acid with a desired total lactic acid (LAT) content The LAT corresponds to the mass of monomeric lactic acid contained in 100 g of the lactic acid composition.
• This mass is determined after saponification at a determined weight (0.1 to 0.3 g) of the oligomeric composition. After neutralization of the reaction mixture, it is analyzed by the high performance liquid chromatography (HPLC) technique with refractometric detection. This analysis can be carried out on a cation exchange column of the "SHODEX SH 1011" type in using N / 100 sulfuric acid as eluent. This technique makes it possible to determine the mass of monomeric lactic acid contained in the sample tested and by simple calculation, the LAT.
• HPLC high performance liquid chromatography
• the concentration reaction is followed by measuring the weight of water removed and the amount of water in the concentrate determined by the Karl Fisher water assay method.
• the esterification is carried out conventionally in the presence of an acid catalyst chosen in particular from the group comprising sulfuric acid, phosphoric acid, para-toluene sulfonic acid, methane sulfonic acid as well as the resins acids such as for example Amberlyst A15.
• an acid catalyst chosen in particular from the group comprising sulfuric acid, phosphoric acid, para-toluene sulfonic acid, methane sulfonic acid as well as the resins acids such as for example Amberlyst A15.
• the water is removed by azeotropic distillation.
• azeotropic trainers which can be used according to the present invention, mention will be made of cyclohexane and toluene.
• cyclohexane will be used.
• the total conversion esterification of the concentrated lactic acid solution is carried out at temperatures between 70 ° C and 100 ° C at atmospheric pressure and with an alcohol / lactic acid molar ratio ranging from 1.3 to 2.
• reaction medium is subjected to a basic treatment in order to neutralize the acid catalyst.
• this treatment is carried out on a basic resin bed such as on Amberlyst A21 resin, which resin bed is washed with a solvent such as an alkyl lactact.
• the products of the composition according to the invention were identified by gas chromatography (GC) coupled to a mass spectrometer.
• GC gas chromatography
• composition of the invention can also be obtained from an alkyl lactate of formula (II) by transesterification in the presence of a catalyst chosen from alkyl orthotitanates such as ethyl orthotitanate, l zirconium acetylacetonate, tributyltin, strong bases such as KOH, NaOH, quaternary ammonium hydroxides.
• a catalyst chosen from alkyl orthotitanates such as ethyl orthotitanate, l zirconium acetylacetonate, tributyltin, strong bases such as KOH, NaOH, quaternary ammonium hydroxides.
• reaction medium is treated in a known manner in order to eliminate the catalyst used.
• the reaction medium is then concentrated under reduced pressure so as to remove the unconverted alkyl lactate.
• composition of the present invention is a colorless, odorless liquid with a flash point above 100 ° C.
• a commercial lactic acid composition is used having a total lactic acid content -LAT- of 88.7 and a free water content of 13.3%.
• the LAT corresponds to the mass of monomeric lactic acid contained in 100 g of the lactic acid composition.
• the LAT is determined as described above.
• lactic acid is concentrated until a desired LAT is obtained.
• the commercial composition of lactic acid to be concentrated is introduced into a rotary evaporator and then the water is removed under 100 mbar at a temperature ranging from 60 ° C to 130 ° C.
• the reaction is followed by measuring the amount of water removed and the percentage of water in the concentrate determined by the Karl Fisher method.
• Example 1 In a 250 ml reactor, equipped with a thermostatically controlled heating system, with a temperature measurement, and connected to an adiabatic distillation column of 10 theoretical plates connected to a variable reflux column head, the following is introduced :
• the condensates at the top of the column are partly returned to the distillation column, partly to a decanter.
• the light decantation phase is recycled to the boiler, the heavy phase is eliminated.
• the reflux rate is brought so as to distill the ternary azeotrope cyclohexane / ethanol / water (75.5% / 19.7% / 4.8%) whose boiling point is 61.2 ° C. Care should be taken throughout the reaction not to exceed this temperature at the top of the column by more than 0.3 to 0.4 ° C. For this, the reflux rate will be adjusted during the course of handling. 123 g of aqueous phase are eliminated at 18% water. To compensate for the loss of ethanol in the heavy phase, during the reaction, 80 g of ethanol are gradually introduced into the boiler using a pump.
• the reaction is monitored by dosing on successive samples from the boiler: - dosing of water by the Karl Fischer method,
• the reaction lasts approximately 3:30.
• the end-of-reaction criterion is as follows:% H + (expressed as lactic acid) ⁇ 0.5%.
• the medium is cooled and the reaction mixture is treated with 10 g of a strong basic resin of the Amberlyst type No. A21 which is rinsed with 10 g of ethyl lactate.
• the oligomeric ethyl lactate composition is determined by CP ⁇ . - Chromatograph: HP 5890
• the mixture is brought to reflux under atmospheric pressure and the liberated ethanol is gradually distilled, ie 17.3 g in 3 hours.
• the wire mesh is cleaned with methylene chloride with the precautions associated with methylene chloride.
• the grid is rinsed with the solvent to be evaluated, then is weighed and finally dried.
• a brush distribute about 2 g of dirt (weighed precisely) consisting, by weight, of:
• the grid is then immersed in 50 ml of mixture to be evaluated with stirring (500 rpm). At the same time, a stopwatch is started.
• the grid is raised to 1, 3, 5, 7 '30, 10, 12' 30, 15 min then is weighed at time (t) without stopping the stopwatch (duration of this manipulation approximately 20 seconds).
• the 90% efficiency time is 45 min.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Materials Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Emergency Medicine (AREA)
• Life Sciences & Earth Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Detergent Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Cleaning By Liquid Or Steam (AREA)

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  • 2002-04-12 FR FR0204591A patent/FR2838435B1/fr not_active Expired - Fee Related
• 2003
  • 2003-03-17 AU AU2003227839A patent/AU2003227839A1/en not_active Abandoned
  • 2003-03-17 WO PCT/FR2003/000843 patent/WO2003087284A1/fr active IP Right Grant
  • 2003-03-17 US US10/510,929 patent/US20050215453A1/en not_active Abandoned
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