DE4407035A1 - Di:lactone(s) prodn. - Google Patents
Di:lactone(s) prodn.Info
- Publication number
- DE4407035A1 DE4407035A1 DE4407035A DE4407035A DE4407035A1 DE 4407035 A1 DE4407035 A1 DE 4407035A1 DE 4407035 A DE4407035 A DE 4407035A DE 4407035 A DE4407035 A DE 4407035A DE 4407035 A1 DE4407035 A1 DE 4407035A1
- Authority
- DE
- Germany
- Prior art keywords
- reaction
- alkyl
- alcohol
- formula
- lactic acid
- 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.)
- Withdrawn
Links
- 150000002596 lactones Chemical class 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 15
- 239000011541 reaction mixture Substances 0.000 claims description 7
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229930182843 D-Lactic acid Natural products 0.000 claims description 2
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- 229940022769 d- lactic acid Drugs 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- GXOHBWLPQHTYPF-ZETCQYMHSA-N pentyl (2s)-2-hydroxypropanoate Chemical compound CCCCCOC(=O)[C@H](C)O GXOHBWLPQHTYPF-ZETCQYMHSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von Dilactonen aus alpha-Hydroxycarbonsäureestern der allgemeinen Formel IThe present invention relates to a new method for Production of dilactones from alpha-hydroxycarboxylic acid esters general formula I.
in der R¹ für einen C₁-C₈-Alkylrest und R² und R³ unabhängig von einander für Wasserstoff oder einen C₁-C₆-Alkylrest stehen.in the R¹ for a C₁-C₈ alkyl radical and R² and R³ regardless of are hydrogen or a C₁-C₆ alkyl group.
Die WO 92/00292 lehrt ein kontinuierliches Verfahren zur Herstellung von Dilactonen aus alpha-Hydroxycarbonsäuren und deren Estern. Nach dieser Lehre werden die Ausgangsverbindungen verdampft, an einem Festbettkatalysator zum Dilacton cyclisiert und anschließend aus dem gasförmigen Reaktionsgemisch isoliert. Bei einer solchen Verfahrensweise ist mit einer Rückreaktion des Dilactons mit während der Reaktion freigesetztem Wasser bzw. Alkohol zu rechnen, da diese Komponenten erst bei der Aufarbei tung aus dem Reaktionsgemisch abgetrennt werden. Weiterhin kommt dieses Verfahren nur für verdampfbare Ausgangsverbindungen in Be tracht.WO 92/00292 teaches a continuous process for Production of dilactones from alpha-hydroxycarboxylic acids and their esters. According to this teaching, the starting connections evaporated, cyclized on a fixed bed catalyst to the dilactone and then isolated from the gaseous reaction mixture. In such a procedure, a back reaction of the Dilactons with water released during the reaction or Alcohol is to be expected, as these components are only processed tion are separated from the reaction mixture. Continues to come this method only for vaporizable starting compounds in Be dress.
Die kontinuierliche Herstellung von Dilactonen aus alpha-Hydroxy carbonsäuren in einem Reaktor unter Austragen des Verfahrens produktes sowie des bei der Cyclisierung gebildeten Wassers durch einen inerten Gasstrom beschreibt die US-A 5 043 458. Auch in diesem Verfahren kann die Rückreaktion von Dilacton mit Alkohol die Ausbeute senken, da diese Reaktionsprodukte gemeinsam im Reaktionsaustrag vorliegen, bevor sich eine Isolierung des Dilactons anschließt.The continuous production of dilactones from alpha-hydroxy carboxylic acids in a reactor with discharge of the process product as well as the water formed during the cyclization US Pat. No. 5,043,458 describes an inert gas stream This process can reverse react Dililone with alcohol lower the yield because these reaction products together in the Reaction discharge before isolation of the Dilactons joins.
Der vorliegenden Erfindung lag somit die Aufgabe zugrunde, ein Verfahren zur Herstellung von Dilactonen bereitzustellen, das die oben genannten Nachteile vermeidet.The present invention was therefore based on the object Provide process for the preparation of dilactones that the avoids the disadvantages mentioned above.
Demgemäß wurde das eingangs definierte Verfahren gefunden, das dadurch gekennzeichnet ist, daß man einen Ester der Formel I in flüssiger Phase in Gegenwart wirksamen Mengen eines Umesterungs katalysators umsetzt, wobei der während der Reaktion gebildete Alkohol R¹-OH andestilliert, und das Dilacton aus dem Reaktions gemisch isoliert.Accordingly, the process defined at the outset was found, the is characterized in that an ester of formula I in liquid phase in the presence of effective amounts of a transesterification converts catalyst, the formed during the reaction Alcohol R¹-OH distilled, and the dilactone from the reaction mixture isolated.
Die dem erfindungsgemäßen Verfahren zugrundeliegende Umsetzung läßt sich durch folgende Reaktionsgleichung veranschaulichen.The implementation on which the method according to the invention is based can be illustrated by the following reaction equation.
Als Ausgangsverbindungen der Formel I kommen C₁-C₈-Alkylester in Betracht, von denen C₄-C₈-Alkylester bevorzugt sind. Beispiele für solche Alkylreste sind Methyl, Ethyl, n-Propyl, n-Butyl, Amyl, Hexyl, Heptyl und Octyl, wobei die längerkettigen Alkylreste ver zweigt oder bevorzugt geradkettig sein können.C₁-C Formel alkyl esters come in as starting compounds of the formula I. Consider, of which C₄-C₈ alkyl esters are preferred. examples for such alkyl radicals are methyl, ethyl, n-propyl, n-butyl, amyl, Hexyl, heptyl and octyl, the longer chain alkyl residues ver branches or can preferably be straight-chain.
Die den Estern zugrundeliegenden Säuren tragen in alpha-Position Wasserstoff- oder C₁-C₆-Alkylreste. Bevorzugte Ester leiten sich von Glykolsäure oder Milchsäure ab, wobei die Milchsäure als D-, L- oder Gemisch von D- und L-Milchsäure vorliegen kann.The acids on which the esters are based are in the alpha position Hydrogen or C₁-C₆ alkyl radicals. Preferred esters are derived from glycolic acid or lactic acid, the lactic acid being D-, L or mixture of D and L lactic acid may be present.
Die Ausgangsverbindungen der Formel I sind beispielsweise in an sich bekannter Weise durch Veresterung der alpha-Hydroxycarbon säuren mit den entsprechenden Alkoholen erhältlich.The starting compounds of the formula I are, for example, in known way by esterification of the alpha-hydroxycarbon acids with the corresponding alcohols available.
Die Ester der Formel I werden zur Reaktion in einen Reaktor ge geben, der sich zweckmäßigerweise auf Reaktionstemperatur befin det. Diese Temperatur beträgt im allgemeinen 150 bis 300°C, vor zugsweise 200 bis 250°C. Die Reaktion wird in der Regel unter einem Druck von 1 bis 10 bar, vorzugsweise unter Normaldruck, durchgeführt.The esters of formula I are reacted in a reactor give, which is conveniently at the reaction temperature det. This temperature is generally 150 to 300 ° C, before preferably 200 to 250 ° C. The reaction is usually under a pressure of 1 to 10 bar, preferably under normal pressure, carried out.
Das flüssige Reaktionsgemisch enthält einen Umesterungs katalysator. Darunter sind Katalysatoren zu verstehen, die den Austausch der Alkoholkomponenten in Carbonsäureestern kataly sieren. Solche Katalysatoren sind z. B. in Ullmann′s Encyclopedia of Ind. Chem., 5. Auflage, VCH 1987, Band A3, S. 575, beschrie ben. Insbesondere kommen solche Verbindungen in Betracht, die die Strukturelemente CH₃OM, MOX, RCOOM und/oder MOM aufweisen, wobei M für die Metalle Mn, Zn, Sn, Sb, Pb, Ge, Co, Ni, Ca, Sr, Mg, Ca und Ba, X für Chlorid und Sulfat und R für einen C₁-C₁₀-Alkylrest steht. Vorzugsweise werden Katalysatoren verwendet, die im Re aktionsgemisch unlöslich sind, da in diesen Fällen eine einfache Abtrennung des Produktes vom Katalysator möglich ist. Sie sind beispielsweise durch Hydrolyse von Hydroxiden oder Carboxylaten der genannten Metalle oder durch Abspaltung der organischen Reste durch Erhitzen erhältlich, wobei sie MOM-Strukturen ausbilden, die die Katalysatoren unlöslich machen. Man kann die Katalysatoren in Substanz oder auf inerten Trägern wie Al₂O₃, SiO₂, ZrO₂ oder Metallen einsetzen.The liquid reaction mixture contains a transesterification catalyst. These are to be understood as catalysts that Replacement of the alcohol components in catalytic carboxylic esters sieren. Such catalysts are e.g. B. in Ullmann's Encyclopedia of Ind. Chem., 5th edition, VCH 1987, volume A3, p. 575, described ben. In particular, such compounds come into consideration that the Structural elements CH₃OM, MOX, RCOOM and / or MOM have, wherein M for the metals Mn, Zn, Sn, Sb, Pb, Ge, Co, Ni, Ca, Sr, Mg, Ca and Ba, X for chloride and sulfate and R for a C₁-C₁₀ alkyl radical stands. Catalysts are preferably used, which in Re action mixture are insoluble, because in these cases a simple Separation of the product from the catalyst is possible. you are for example by hydrolysis of hydroxides or carboxylates of the metals mentioned or by splitting off the organic radicals available by heating, forming MOM structures, that make the catalysts insoluble. You can do that Catalysts in bulk or on inert supports such as Al₂O₃, Use SiO₂, ZrO₂ or metals.
Besonders bevorzugt als Katalysatoren sind Titanylsulfat und Titanverbindungen, die durch Hydrolyse von 1 mol Titantetra alkoxid wie Titantetrabutoxid mit 1,1 bis 1,5 mol Wasser erhält lich sind, vorzugsweise in Gegenwart eines porösen inerten Trägers.Particularly preferred catalysts are titanyl sulfate and Titanium compounds by hydrolysis of 1 mol titanium tetra alkoxide such as titanium tetrabutoxide with 1.1 to 1.5 mol of water Lich, preferably in the presence of a porous inert Carrier.
Der Katalysator muß in wirksamen Mengen im Reaktionsgemisch vor handen sein. Bei Verwendung von Heterogenkatalysatoren sollte die Kontaktzeit zweckmäßigerweise 0,01 bis 10 Minuten, vorzugsweise 0,1 bis 1 Minute betragen.The catalyst must be present in the reaction mixture in effective amounts be there. When using heterogeneous catalysts, the Contact time expediently 0.01 to 10 minutes, preferably 0.1 to 1 minute.
Während der Reaktion wird der freiwerdende Alkohol abdestilliert. Dies geschieht vorteilhaft durch einen Auslaß über ein Druck halteventil. Gegebenenfalls mit dem Alkohol ausgeschleuster Ester der Formel I kann nach Abtrennung des Alkohols in die Reaktion zurückgeführt werden. Es hat sich für diese Abtrennung als vor teilhaft erwiesen, wenn der Reaktor nur zu maximal zwei Dritteln gefüllt ist.The alcohol liberated is distilled off during the reaction. This is advantageously done through an outlet via a pressure holding valve. If necessary, esters removed with the alcohol of the formula I can after separation of the alcohol in the reaction to be led back. It has turned out to be for this separation Proven partially if the reactor is only two thirds maximum is filled.
Das produkthaltige Reaktionsgemisch wird dem Reaktor flüssig ent nommen und bevorzugt destillativ auf das Produkt aufgearbeitet. Dabei abgetrennte oligomere Verbindungen, die sich aus den Ausgangsverbindungen gebildet haben, können wieder in den Reaktor zurückgeführt werden.The product-containing reaction mixture is ent liquid in the reactor taken and preferably worked up by distillation on the product. Separated oligomeric compounds resulting from the Output compounds have formed can be returned to the reactor to be led back.
Das erfindungsgemäße Verfahren weist den Vorteil auf, daß das er wünschte Verfahrensprodukt schnell von dem in der Reaktion frei gesetzten Alkohol getrennt wird, so daß die Rückreaktion stark verringert werden kann.The inventive method has the advantage that it desired process product quickly from that in the reaction put alcohol is separated, so that the back reaction strong can be reduced.
Die Verfahrensprodukte, insbesondere Dilactid, dienen als Ausgangsstoff für die Herstellung von Polymeren, die z. B. als resorbierbares chirurgisches Nahtmaterial Verwendung finden.The process products, especially dilactide, serve as Starting material for the production of polymers which, for. B. as resorbable surgical sutures are used.
Zu 500 g 3 bis 4 mm großen Al₂O₃-Pellets mit einer spezifischen Oberfläche von 3,5 m²/g in 2 l Ethylenglykoldimethylether wurden 170 g (0,5 mol) Titantetrabutylat gegeben. Unter starkem Rühren wurden innerhalb von 30 Minuten 10,8 g (0,6 mol) Wasser und 200 ml Ethylendiglykoldimethylether zugegeben. Nach 30 Minuten wurde der Feststoff dekantiert und unter Stickstoff getrocknet.To 500 g 3 to 4 mm large Al₂O₃ pellets with a specific Surface area of 3.5 m² / g in 2 l of ethylene glycol dimethyl ether 170 g (0.5 mol) of titanium tetrabutylate added. With vigorous stirring 10.8 g (0.6 mol) of water and 200 ml of ethylene diglycol dimethyl ether were added. After 30 minutes the solid was decanted and dried under nitrogen.
In ein senkrecht stehendes Stahlrohr mit 30 mm Innendurchmesser, das mit 110 g des oben beschriebenen Katalysators gefüllt ist, wurden 650 g/h L-Milchsäureamylester, der auf 230°C vorgeheizt war, gefördert, wobei der Füllgrad durch Abpumpen des Reaktions sumpfes konstant gehalten wurde. Die Reaktionstemperatur betrug 230°C. Über ein auf 2 bar eingestelltes Druckhalteventil wurde über Kopf abdestilliert (340 g/h, davon ca. 88 Gew.-% Amylalkohol und 12 Gew.-% Ausgangsmaterial).In a vertical steel tube with an inner diameter of 30 mm, which is filled with 110 g of the catalyst described above, were 650 g / h L-lactic acid amyl ester, which was preheated to 230 ° C was promoted, the degree of filling by pumping the reaction swamp was kept constant. The reaction temperature was 230 ° C. Via a pressure control valve set to 2 bar distilled off at the top (340 g / h, thereof approx. 88% by weight amyl alcohol and 12% by weight of starting material).
Der Flüssigaustrag (307 g/h) wurde destillativ aufgearbeitet und enthielt neben 76 Gew.-% L-Lactid ca. 4 Gew.-% Oligomere und 20 Gew.-% Ausgangsmaterial. Der Umsatz betrug 80%, die Selektivität 95%.The liquid discharge (307 g / h) was worked up by distillation and in addition to 76% by weight of L-lactide contained approx. 4% by weight of oligomers and 20% by weight of starting material. The turnover was 80% Selectivity 95%.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4407035A DE4407035A1 (en) | 1994-03-03 | 1994-03-03 | Di:lactone(s) prodn. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4407035A DE4407035A1 (en) | 1994-03-03 | 1994-03-03 | Di:lactone(s) prodn. |
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| Publication Number | Publication Date |
|---|---|
| DE4407035A1 true DE4407035A1 (en) | 1995-09-07 |
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ID=6511747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE4407035A Withdrawn DE4407035A1 (en) | 1994-03-03 | 1994-03-03 | Di:lactone(s) prodn. |
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| Country | Link |
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| DE (1) | DE4407035A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999043669A1 (en) * | 1998-02-24 | 1999-09-02 | Brussels Biotech | Method for producing dimeric cyclic esters |
| JP2010270102A (en) * | 2009-05-20 | 2010-12-02 | Korea Research Inst Of Chemical Technology | Catalyst for direct conversion of lactic acid ester to lactide and method for producing lactide by using the same |
| WO2018055170A1 (en) * | 2016-09-23 | 2018-03-29 | Katholieke Universiteit Leuven | Process for preparing cyclic esters from alpha-hydroxy esters and catalysts used therein |
-
1994
- 1994-03-03 DE DE4407035A patent/DE4407035A1/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999043669A1 (en) * | 1998-02-24 | 1999-09-02 | Brussels Biotech | Method for producing dimeric cyclic esters |
| BE1011759A3 (en) * | 1998-02-24 | 1999-12-07 | Brussels Biotech S A | Method for producing cyclic esters. |
| JP2010270102A (en) * | 2009-05-20 | 2010-12-02 | Korea Research Inst Of Chemical Technology | Catalyst for direct conversion of lactic acid ester to lactide and method for producing lactide by using the same |
| WO2018055170A1 (en) * | 2016-09-23 | 2018-03-29 | Katholieke Universiteit Leuven | Process for preparing cyclic esters from alpha-hydroxy esters and catalysts used therein |
| US10899730B2 (en) | 2016-09-23 | 2021-01-26 | Katholieke Universiteit Leuven | Process for preparing cyclic esters from alpha-hydroxy esters and catalysts used therein |
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