DE1086689B - Process for the transesterification of dialkyl benzene dicarboxylates with glycols - Google Patents
Process for the transesterification of dialkyl benzene dicarboxylates with glycolsInfo
- Publication number
- DE1086689B DE1086689B DED30702A DED0030702A DE1086689B DE 1086689 B DE1086689 B DE 1086689B DE D30702 A DED30702 A DE D30702A DE D0030702 A DED0030702 A DE D0030702A DE 1086689 B DE1086689 B DE 1086689B
- Authority
- DE
- Germany
- Prior art keywords
- transesterification
- salts
- acid
- glycols
- dialkyl benzene
- 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.)
- Pending
Links
- 238000005809 transesterification reaction Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 7
- 150000002334 glycols Chemical class 0.000 title description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 title description 2
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 claims description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229940091181 aconitic acid Drugs 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 235000013985 cinnamic acid Nutrition 0.000 claims description 2
- 229930016911 cinnamic acid Natural products 0.000 claims description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 150000007519 polyprotic acids Polymers 0.000 claims description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- UGJBHEZMOKVTIM-UHFFFAOYSA-N N-formylglycine Chemical compound OC(=O)CNC=O UGJBHEZMOKVTIM-UHFFFAOYSA-N 0.000 claims 1
- 150000001661 cadmium Chemical class 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 6
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- RSECMQCYQHGSFP-UHFFFAOYSA-N methanol;terephthalic acid Chemical compound OC.OC(=O)C1=CC=C(C(O)=O)C=C1 RSECMQCYQHGSFP-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds 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
- 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
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J2231/49—Esterification or transesterification
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
Verfahren zur Umesterung - . von Benzoldicarbonsäuredialkylestern mit Glykolen Ein bekanntes und vielfach angewandtes Verfahren zur Gewinnung von neutralen Glykolestern aromatischer Dicarbonsäuren ist die Umesterung der entsprechenden Dialkylester, besonders des Dimethylesters, mit Glykolen in Gegenwart bestimmter Katalysatoren, die die Umesterung zum Teil erheblich beschleunigen. Diese Umesterungsreaktion hat besondere Bedeutung erlangt für die Herstellung der Ausgangsprodukte zur Gewinnung von hochmolekularen Polyestern. Als wirksame Katalysatoren ist unter anderem eine Anzahl von Metallen, Metalloxyden, für sich oder in Kombination, und vor allem eine Vielzahl von Metallsalzen bekanntgeworden. Unter den Metallsalzen werden vornehmlich solche mit organischem Anion empfohlen und unter anderem auch als besondere Gruppe Salze von solchen Säuren, deren Dissoziationskonstante unterhalb eines bestimmten Wertes liegt.Process for transesterification -. of dialkyl benzene dicarboxylates with glycols A well-known and widely used process for the production of neutral glycol esters of aromatic dicarboxylic acids is the transesterification of the corresponding Dialkyl esters, especially the dimethyl ester, with glycols in the presence of certain Catalysts, which in some cases considerably accelerate the transesterification. This transesterification reaction has acquired particular importance for the manufacture of the raw materials for extraction of high molecular weight polyesters. Effective catalysts include one Number of metals, metal oxides, alone or in combination, and above all one A large number of metal salts have become known. Among the metal salts are mainly those with organic anions are recommended and, among other things, as a special group Salts of such acids whose dissociation constant is below a certain Worth.
Es wurde nun überraschenderweise gefunden, daü unter den Metallsalzen organischer Säuren eine Gruppe bezüglich ihrer Fähigkeit, die genannte Umesterung zu beschleunigen, besonders hervortritt. Es handelt sich hierbei um die Salze der Metalle der II. Gruppe des Periodensystems der Elemente, besonders des Zinks und Cadmiums, mit solchen organischen Säuren, deren Molekül ungesättigten Charakter in Form einer Doppelbindung hat. Es ist hierbei gleichgültig, ob es sich um ein- oder mehrbasische Säuren handelt.It has now surprisingly been found that among the metal salts Organic acids a group with regard to their ability, the so-called transesterification to accelerate, especially emerges. These are the salts of Metals of group II of the periodic table of the elements, especially zinc and Cadmium, with such organic acids, whose molecule is unsaturated in character in the form of a double bond. It does not matter whether it is a or polybasic acids.
Die Anwendung des Katalysators geschieht in bekannter Weise so, daB man 0,02 bis 0,2°/o, vornehmlich 0,0,5 bis 0,1'°/o, berechnet auf die Menge des oder der eingesetzten Benzoldicarbonsäureester, zu dem Alkylester-Glykol-Gemisch gibt und dann die Umesterung in bekannter Weise unter Rühren bei Temperaturen zwischen 170 und 200' C durchführt, wobei der ursprünglich in Estergruppierung vorhanden gewesene Alkylalkohod, in den meisten Fällen der Methylalkohol, abdestilliert.The catalyst is used in a known manner in such a way that 0.02 to 0.2%, especially 0.0.5 to 0.1%, calculated on the amount of the benzenedicarboxylic acid ester (s) used, is added to the There are alkyl ester-glycol mixture and then the transesterification is carried out in a known manner with stirring at temperatures between 170 and 200 ° C, the alkyl alcohol originally present in ester grouping, in most cases the methyl alcohol, being distilled off.
Die besonders gute katalytische Wirksamkeit der angeführten Verbindungsklasse zeigt sich in einer sehr schnell verlaufenden vollständigen Umesterung im Vergleich zu anderen als Katalysatoren brauchbaren Salzen. Die im folgenden beschriebenen Versuche wurden unter mengenmäßig und apparativ völlig gleichartigen Bedingungen durchgeführt, so daB die angeführten Zeitwerte vergleichbar sind.The particularly good catalytic effectiveness of the listed class of compounds is shown in a very rapid complete transesterification in comparison to other salts which can be used as catalysts. The ones described below Experiments were carried out under conditions of the same type in terms of quantity and equipment carried out so that the quoted fair values are comparable.
Beispiel 100 g Terephthalsäuredimethylester werden mit 110 g Äthylenglykol
gemischt und :das Gemisch unter Zusatz von 0,05 bis 0,2g Katalysator in einem 500
cm3 fassenden Dreihalskolben, der mit einem mechanischen Rührer, einem absteigenden
Kühler und einer Kapillare zum Durchleiten von trockenem Stickstoff versehen ist,
im Ölbad erwärmt. Die Badtemperatur wird so geregelt, daß nach Einsetzen der Umesterung,
was zwischen 170 und 1851 C geschieht, das Abdestidlleren des frei werdenden
Methanols möglichst mit konstanter Geschwindigkeit vor sich geht. Die Temperatur
übersteigt lin keinem Falle 200'C (im Bad gemessen). Als Umesterungszeit
wird,die Dauer des Abdestilllierens von Methanol gemessen, beginnend
Die entsprechend der vorstehenden Versuchsbeschreibung erhaltenen Ergebnisse sind in der vorstehenden Tabelle zusammengefaßt.Those obtained according to the above description of the experiment Results are summarized in the table above.
Die unter Nr.6 und 7 aufgeführten Beispiele der Verwendung von Zinksalzen mit Anionen, die keine Doppelbindung enthalten, sind zum Vergleich aufgeführt.The examples of the use of zinc salts listed under Nos. 6 and 7 with anions that do not contain a double bond are listed for comparison.
Claims (4)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL251667D NL251667A (en) | 1959-05-20 | ||
| DED30702A DE1086689B (en) | 1959-05-20 | 1959-05-20 | Process for the transesterification of dialkyl benzene dicarboxylates with glycols |
| CH476960A CH378303A (en) | 1959-05-20 | 1960-04-26 | Process for the catalytic transesterification of benzene dicarboxylic acid alkyl esters with glycols |
| GB17004/60A GB922467A (en) | 1959-05-20 | 1960-05-13 | Improvements in or relating to the catalytic transesterification of aromatic dicarboxylic acid dialkyl esters with glycols |
| BE590976A BE590976A (en) | 1959-05-20 | 1960-05-18 | Process for the catalytic transesterification of alkyl esters of benzene dicarboxylic acids. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED30702A DE1086689B (en) | 1959-05-20 | 1959-05-20 | Process for the transesterification of dialkyl benzene dicarboxylates with glycols |
| FR826880A FR1256829A (en) | 1960-05-11 | 1960-05-11 | Catalytic trans-esterification process, using glycols, of alkyl esters of benzenedicarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1086689B true DE1086689B (en) | 1960-08-11 |
Family
ID=25970950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED30702A Pending DE1086689B (en) | 1959-05-20 | 1959-05-20 | Process for the transesterification of dialkyl benzene dicarboxylates with glycols |
Country Status (4)
| Country | Link |
|---|---|
| CH (1) | CH378303A (en) |
| DE (1) | DE1086689B (en) |
| GB (1) | GB922467A (en) |
| NL (1) | NL251667A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1244797B (en) | 1962-07-06 | 1967-07-20 | Witten Gmbh Chem Werke | Process for the preparation of phenyl esters of carbocyclic, aromatic, optionally ring-substituted mono- and polycarboxylic acids |
-
0
- NL NL251667D patent/NL251667A/xx unknown
-
1959
- 1959-05-20 DE DED30702A patent/DE1086689B/en active Pending
-
1960
- 1960-04-26 CH CH476960A patent/CH378303A/en unknown
- 1960-05-13 GB GB17004/60A patent/GB922467A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1244797B (en) | 1962-07-06 | 1967-07-20 | Witten Gmbh Chem Werke | Process for the preparation of phenyl esters of carbocyclic, aromatic, optionally ring-substituted mono- and polycarboxylic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| NL251667A (en) | 1900-01-01 |
| GB922467A (en) | 1963-04-03 |
| CH378303A (en) | 1964-06-15 |
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