EP1497405B1 - Zusammensetzung enthaltend eine mischung aus mono- und polylactylalkyllactaten - Google Patents

Zusammensetzung enthaltend eine mischung aus mono- und polylactylalkyllactaten Download PDF

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Publication number
EP1497405B1
EP1497405B1 EP03725293A EP03725293A EP1497405B1 EP 1497405 B1 EP1497405 B1 EP 1497405B1 EP 03725293 A EP03725293 A EP 03725293A EP 03725293 A EP03725293 A EP 03725293A EP 1497405 B1 EP1497405 B1 EP 1497405B1
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EP
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Prior art keywords
composition
alkyl
weight
mixture
parts
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EP03725293A
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English (en)
French (fr)
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EP1497405A1 (de
Inventor
Rémy Teissier
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Arkema France SA
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Arkema France SA
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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 oligomeric composition of lactic acid esters comprising a mixture of alkyl mono- and polylactyllactates of formula: CH 3 CH (OH) [C (O) OCH (CH 3 )] n-1 CO 2 R (I) in which 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 invention particularly relates to a composition of ethyl mono- and polylactyllactates.
  • This composition can be used alone or in combination with other solvents, especially as cleaning and degreasing agents in the machine and in a non-aqueous medium for solid surfaces such as metal parts, ceramics, glass, plastics having have been soiled with oils or greases and / or their temporary protection. They can also be used for defluxing printed circuits. This defluxing operation consisting in eliminating the welding flux.
  • the cleaning agents and / or degreasing must have other characteristics such as in particular having a high flash point, low toxicity, be odorless and not release into the atmosphere volatile organic compounds ( VOCs).
  • composition of the present invention generally meets the criteria mentioned above.
  • composition of the present invention can also be used to obtain cyclic-cyclic lactides - which are precursors of choice for obtaining polylactides used as biomaterials.
  • HV Claborn (US 2,371,281) describes a process for obtaining alkyl lactyllactate by reacting lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) with an alcohol R 1 OH according to the reaction :
  • the main fraction (78 g) identified as ethyl lactyllactate is a slightly viscous, colorless and odorless liquid which distills at 110 ° C - 113 ° C at 7.5 mmHg.
  • CE Rehberg and MB Dixon (Journal of Amber Chem., 74, page 1609, 1952) which give the physical properties of several alkyl lactyllactates (methyl, ethyl n-propyl, n-butyl, n-hexyl, n -octyl) mention that these compounds can be obtained according to the method of HV Claborn previously mentioned (U5 2,371,281) or that these compounds are by-products in the preparation of simple alkyl lactates in the laboratory stage, the conversion to alkyl lactyllactate being usually of the order of 5% to 20% depends on the alcohol / lactic acid ratio used during the esterification of said lactic acid.
  • alkyl lactyllactates can be obtained by transesterification of alkyl lactate in the presence of H 2 SO 4 .
  • US 6,191,087 discloses a degreasing composition containing a lactic acid ester.
  • the subject of the present invention is therefore a composition
  • a composition comprising a mixture of alkyl mono- and polylactylactates of formula: CH 3 CH (OH) [C (O) OCH (CH 3 )] n-1 CO 2 R (I) in which 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, ethyl, propyl, isopropyl or n-butyl radical.
  • the alkyl radical is an ethyl radical.
  • composition according to the invention may furthermore 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), especially in the range of 0, 1 to 1 part by weight per 100 parts by weight of the mixture L 2 A + L 3 A + L 4 A.
  • It may also comprise oligomers of higher molecular masses, that is to say alkyl polylactylates in which n> 4 in particular, from 0.1 to 4 parts 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 achieved by removing water formed by azeotropic distillation.
  • the concentration of commercial lactic acid solutions can be achieved by simple evaporation in one or more steps, at a temperature ranging from 100 ° C to 170 ° C, at atmospheric pressure or under reduced pressure and until a composition is obtained.
  • the LAT corresponds to the mass of lactic acid monomer 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 done on a cation exchange column of the type "SHODEX SH 1011" in using N / 100 sulfuric acid as eluent. This technique makes it possible to determine the mass of lactic acid monomer contained in the tested sample and by simple calculation, the LAT.
  • HPLC high performance liquid chromatography
  • the concentration reaction is monitored by measuring the weight of water removed and the amount of water in the concentrate determined by the Karl Fisher water test method.
  • esterification is carried out in the conventional manner in the presence of an acid catalyst chosen in particular from the group comprising sulfuric acid, phosphoric acid, para-toluenesulfonic acid, methanesulfonic acid and the resins acids such as, for example, Amberlyst A15.
  • an acid catalyst chosen in particular from the group comprising sulfuric acid, phosphoric acid, para-toluenesulfonic acid, methanesulfonic acid and the resins acids such as, for example, Amberlyst A15.
  • azeotropic distillation By way of illustration of azeotropic entrainers which can be used according to the present invention, mention may be made of cyclohexane or 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 bed of basic resin such as Amberlyst resin A21, which resin bed is washed with a solvent such as an alkyl lactact.
  • basic resin such as Amberlyst resin A21
  • 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 may also be obtained from an alkyl lactate of formula (II) by transesterification in the presence of a catalyst selected from alkyl orthotitanates such as ethyl orthotitanate, zirconium acetylacetonate, tributyltin, strong bases such as KOH, NaOH, quaternary ammonium hydroxides.
  • a catalyst selected from alkyl orthotitanates such as ethyl orthotitanate, 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 to remove the unconverted alkyl lactate.
  • composition of the present invention is a colorless, odorless liquid having a flash point above 100 ° C.
  • a commercial lactic acid composition having a total lactic acid content -LAT of 88.7 and a free water content of 13.3% was used.
  • the LAT corresponds to the mass of lactic acid monomer contained in 100 g of the lactic acid composition.
  • the LAT is determined as previously described.
  • lactic acid is concentrated to a desired LAT.
  • the commercial lactic acid composition 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 monitored by measuring the amount of water removed and the percentage of water in the concentrate determined by the Karl Fisher method.
  • the LAT is measured as previously described.
  • Condensates at the top of the column are partially returned to the distillation column, partly to a decanter.
  • the light phase of settling is recycled to the boiler, the heavy phase is eliminated.
  • the reflux ratio is plotted to distill the cyclohexane / ethanol / water ternary azeotrope (75.5% / 19.7% / 4.8%) boiling at 61.2 ° C. It will be ensured 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 ratio will be adjusted during the course of handling.
  • the reaction lasts about 3:30.
  • the end-of-reaction criterion is the following:% 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 No. A21 type which is rinsed with 10 g of ethyl lactate.
  • the products were identified by chromatography coupled to a mass spectrometer.
  • Example 2 Same as Example 1 but replace the sulfuric acid with 6 g of Amberlyst A15.
  • the reaction time is 4 hours.
  • the effectiveness of said mixture is determined to remove 90% of a stain distributed on a square mesh (8 meshes per cm) 5 ⁇ 5 cm from WEBER in the form of a cylinder with a diameter of 20 mm, the two edges of the generator being 0.5 mm apart.
  • the grid is then immersed in 50 ml of mixture to be evaluated with stirring (500 rpm). At the same time, a stopwatch is triggered.
  • the grid is raised to 1, 3, 5, 7'30, 10, 12'30, 15 min and is then weighed at time (t) without stopping the stopwatch (duration of this operation about 20 seconds).
  • the 90% efficiency time is 45 min.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (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)

Claims (9)

  1. Zusammensetzung, enthaltend ein Gemisch von Mono- und Polylactylmilchsäurealkylestern der Formel:

            CH3CH(OH)[C(O)OCH(CH3)]n-1CO2R     (I)

    worin R für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen steht und n eine ganze Zahl mit einem Wert von 2, 3 oder 4 ist.
  2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß es sich bei dem Alkylrest um einen Methyl-, Ethyl-, Isopropyl- oder n-Butylrest handelt.
  3. Zusammensetzung nach Anspruch 2, dadurch gekennzeichnet, daß es sich bei dem Alkylrest um einen Ethylrest handelt.
  4. Zusammensetzung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie
    - 35 bis 85 Gewichtsteile Lactylmilchsäurealkylester (n=2 in Formel (I)), im folgenden L2A;
    - 10 bis 60 Gewichtsteile Dilactylmilchsäurealkylester (n=3 in Formel (I)), im folgenden L3A; und
    - 1 bis 20 Gewichtsteile Trilactylmilchsäurealkylester (n=4 in Formel (I)), im folgenden L4A;
    enthält, wobei die Summe L2A + L3A + L4A sich auf 100 Gewichtsteile beläuft.
  5. Zusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie außerdem einen Milchsäurealkylester der Formel CH3CH(OH)CO2R (II), worin R die gleiche Bedeutung wie in Formel (I) besitzt, in einem Anteil von 0,1 bis 1 Gewichtsteil auf 100 Gewichtsteile des Gemischs L2A + L3A + L4A enthält.
  6. Zusammensetzung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß sie außerdem Polylactylmilchsäurealkylester (I), in denen n größer als 4 ist, in einem Anteil von 0,1 bis 4 Gewichtsteilen auf 100 Gewichtsteile des Gemischs L2A + L3A + L4A enthält.
  7. Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis 6 als Reinigungs- und/oder Entfettungsmittel für Metallteile.
  8. Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis 6, die außerdem auch noch mindestens ein Lösungsmittel enthält, als Reinigungs- und/oder Entfettungsmittel für Metallteile.
  9. Verwendung nach Anspruch 8, dadurch gekennzeichnet, daß es sich bei dem Lösungsmittel um Butoxypropionsäure-n-butylester handelt.
EP03725293A 2002-04-12 2003-03-17 Zusammensetzung enthaltend eine mischung aus mono- und polylactylalkyllactaten Expired - Lifetime EP1497405B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0204591A FR2838435B1 (fr) 2002-04-12 2002-04-12 Composition comprenant un melange de mono et polylactyllactates d'alkyle
FR0204591 2002-04-12
PCT/FR2003/000843 WO2003087284A1 (fr) 2002-04-12 2003-03-17 Composition comprenant un melange de mono- et polylactyllactate d' alkyle

Publications (2)

Publication Number Publication Date
EP1497405A1 EP1497405A1 (de) 2005-01-19
EP1497405B1 true EP1497405B1 (de) 2006-10-04

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ID=28459780

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EP03725293A Expired - Lifetime EP1497405B1 (de) 2002-04-12 2003-03-17 Zusammensetzung enthaltend eine mischung aus mono- und polylactylalkyllactaten

Country Status (9)

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US (1) US20050215453A1 (de)
EP (1) EP1497405B1 (de)
JP (1) JP2005522570A (de)
AT (1) ATE341609T1 (de)
AU (1) AU2003227839A1 (de)
DE (1) DE60308854T2 (de)
ES (1) ES2274230T3 (de)
FR (1) FR2838435B1 (de)
WO (1) WO2003087284A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2885536B1 (fr) 2005-05-12 2007-07-27 Roquette Freres Composition a base d'ethers de dianhydrohexitol pour le traitement d'une matiere autre que le corps humain
ES2395676T3 (es) * 2006-07-06 2013-02-14 Stepan Company Procedimientos de preparación de lactil lactatos de alquilo
WO2008006058A2 (en) * 2006-07-06 2008-01-10 Stepan Company Alkyl lactyllactate solvent compositions
EP2810640A1 (de) * 2013-06-03 2014-12-10 Basf Se Ester von Oligohydroxycarbonsäuren und deren Verwendung
EP3250547B1 (de) * 2015-01-29 2019-05-01 Council of Scientific and Industrial Research Neuartiges verfahren zur herstellung von hydroxylfunktionellen estern und polyestern daraus

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2371281A (en) * 1945-03-13 Lactyuactic esters and process of
US5124166A (en) * 1987-08-13 1992-06-23 Nabisco, Inc. Carboxy/carboxylate disubstituted esters as edible fat mimetics
EP0539398A1 (de) * 1990-07-16 1993-05-05 E.I. Du Pont De Nemours And Company Abbaubare schaummaterialien
US6452051B1 (en) * 1996-02-22 2002-09-17 Cargill, Inc. Process for the production of a condensation products of a carboxylic acid
US6664413B1 (en) * 1998-11-19 2003-12-16 A. E. Staley Manufacturing Co. Process for production of esters
US6191087B1 (en) * 1999-09-03 2001-02-20 Vertec Biosolvents, Llc Environmentally friendly solvent
US6284720B1 (en) * 1999-09-03 2001-09-04 Vertec Biosolvents, Llc Environmentally friendly ink cleaning preparation
FR2802923B1 (fr) * 1999-12-28 2002-03-08 Roquette Freres Procede de preparation d'une composition d'ester d'acide lactique et son utilisation en tant que solvant

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AU2003227839A1 (en) 2003-10-27
DE60308854D1 (de) 2006-11-16
US20050215453A1 (en) 2005-09-29
ES2274230T3 (es) 2007-05-16
FR2838435B1 (fr) 2004-06-18
ATE341609T1 (de) 2006-10-15
EP1497405A1 (de) 2005-01-19
FR2838435A1 (fr) 2003-10-17
WO2003087284A1 (fr) 2003-10-23
DE60308854T2 (de) 2007-08-30
JP2005522570A (ja) 2005-07-28

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