DE1227024B - Process for the production of carboxylic acid glycol monoesters - Google Patents
Process for the production of carboxylic acid glycol monoestersInfo
- Publication number
- DE1227024B DE1227024B DEC28188A DEC0028188A DE1227024B DE 1227024 B DE1227024 B DE 1227024B DE C28188 A DEC28188 A DE C28188A DE C0028188 A DEC0028188 A DE C0028188A DE 1227024 B DE1227024 B DE 1227024B
- Authority
- DE
- Germany
- Prior art keywords
- carboxylic acid
- glycol monoesters
- carboxylic acids
- acid glycol
- production
- 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
- 238000000034 method Methods 0.000 title claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title description 2
- 238000004519 manufacturing process Methods 0.000 title description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- -1 1: 1 to 4.3: 1 Chemical class 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000007126 N-alkylation reaction Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 3
- REIDAMBAPLIATC-UHFFFAOYSA-M 4-methoxycarbonylbenzoate Chemical compound COC(=O)C1=CC=C(C([O-])=O)C=C1 REIDAMBAPLIATC-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012259 ether extract Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- RLFUKRQRKCFAER-UHFFFAOYSA-N C1(=CC=CC=C1)CC(=O)O.C(C(C)O)O Chemical compound C1(=CC=CC=C1)CC(=O)O.C(C(C)O)O RLFUKRQRKCFAER-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. α.:Int. α .:
C 07 cC 07 c
Deutsche Kl.: 12 ο - 27German class: 12 ο - 27
Nummer: 1227 024Number: 1227 024
Aktenzeichen: C 28188 IV b/12 οFile number: C 28188 IV b / 12 ο
Anmeldetag: 16. Oktober 1962 Filing date: October 16, 1962
Auslegetag: 20. Oktober 1966Opened on: October 20, 1966
Nach Patent 1154 479 werden Äthylenglykolmonoester gesättigter Carbonsäuren dadurch hergestellt, daß man gesättigte Mono- oder Polycarbonsäuren allein oder in Mischung untereinander mit gegebenenfalls überschüssigen Mengen an Äthylenoxyd bei einer Temperatur zwischen 25 und 2000C, vorzugsweise 80 und 16O0C, in Abwesenheit von Katalysatoren und in Gegenwart von wasserhaltigen Amiden gesättigter niedermolekularer aliphatischer Carbonsäuren oder deren N-Alkylierungsprodukte umsetzt, wobei das anzuwendende Gewichtsverhältnis von Wasser zu Amid 1:1 bis 4,3 :1 beträgt.After Patent 1154 479 Äthylenglykolmonoester saturated carboxylic acids are prepared by reacting saturated mono- or polycarboxylic acids, alone or in mixture with one another with any excess amounts of ethylene oxide at a temperature between 25 and 200 0 C, preferably 80 and 16O 0 C, in the absence of catalysts and in the presence of hydrous amides of saturated low molecular weight aliphatic carboxylic acids or their N-alkylation products, the weight ratio of water to amide to be used being 1: 1 to 4.3: 1.
: Nach diesem Verfahren wurden in Zeiträumen von weniger als einer Stunde Umsätze und Ausbeuten bis über 90% der Theorie erhalten, während die Ausbeute nach bekannten Verfahren zwischen 35,4 und 67,8 % der Theorie bei 11- bis 20stündiger Reaktionsdauer liegt und zusätzlich besondere Nachteile auftreten. : Following this procedure, periods of less than one hour of conversions and yields of up to over 90% of theory are obtained, while the yield according to known processes between 35.4 and 67.8% of theory with a reaction time of 11 to 20 hours and there are also particular disadvantages.
■ ■. Als gesättigte Mono- oder Polycarbonsäuren komjpien beispielsweise die aliphatischen Carbonsäuren mit 1 bis 20 C-Atomen, Benzolcarbonsäuren und ihre Substitutionsprodukte, Phthalsäuren, Benzol-tri- und -tetracarbönsäuren oder Naphthalsäure in Frage. ί Die genannten Carbonsäuren können· nicht nur in reinster Form eingesetzt werden, sondern es ist auch möglich, technische Säuren zu verwenden.■ ■. Komjpien as saturated mono- or polycarboxylic acids for example the aliphatic carboxylic acids with 1 to 20 carbon atoms, benzenecarboxylic acids and their Substitution products, phthalic acids, benzene-tri- and -tetracarbonic acids or naphthalic acid in question. ί The carboxylic acids mentioned can · not only be used in purest form can be used, but it is too possible to use technical acids.
Als gesättigte niedermolekulare aliphatische Carbonsäureamide oder N-Substitutionsprodukte kommen beispielsweise Formamid, Dimethylformamid oder Dimethylacetamid in Frage.As saturated, low molecular weight aliphatic carboxamides or N-substitution products come for example formamide, dimethylformamide or dimethylacetamide in question.
Als Reaktionsgefäße sind Niederdruckautoklaven oder Kessel geeignet, die ein Arbeiten bei Drücken von 0 bis 15 atü gestatten. Die Gefäße sollen zweckmäßig mit Einfüllstutzen, Gasein- und -ableitungsrohr und einer Rührvorrichtung versehen sein. Das Material des Gefäßes hängt von der korrodierenden Eigenschaft der Carbonsäuren ab und sollte zweckmäßig ein hochwertiger Stahl sein.Low-pressure autoclaves or boilers that operate at pressures are suitable as reaction vessels Allow from 0 to 15 atm. The vessels should expediently have a filler neck, gas inlet and outlet pipe and a stirring device. The material of the vessel depends on the corrosive Property of the carboxylic acids and should be a high quality steel.
Es wurde nun gefunden, daß man Propylenglykolmonoester in weiterer Ausbildung des Verfahrens nach Patent 1154 479 herstellen kann, wenn man an Stelle von Äthylenoxyd Propylenoxyd einsetzt.It has now been found that propylene glycol monoesters can be used in a further development of the process according to patent 1154 479 can be produced if propylene oxide is used instead of ethylene oxide.
Die nach dem erfindungsgemäßen Verfahren herstellbaren Produkte stellen meist ohne besondere Reinigung wertvolle Zwischenprodukte für die Weichmacher-, Harz- und Lackherstellung dar. Die Ester von mehrbasischen Carbonsäuren, wie ζ. Β. von Terephthalsäure, sind leicht zu reinigen und dann ohne Katalysator durch Erhitzen auf 200 bis 3000C polykondensierbar. Sie liefern hochmolekulare Kunststoffe. The products that can be prepared by the process according to the invention are usually valuable intermediate products for the manufacture of plasticizers, resins and paints without special purification. The esters of polybasic carboxylic acids, such as ζ. Β. of terephthalic acid, are easy to clean, and then polycondensable without a catalyst by heating at 200 to 300 0 C. They deliver high molecular weight plastics.
Verfahren zur Herstellung von Carbonsäureglykolmonoestern Process for the preparation of carboxylic acid glycol monoesters
Zusatz zum Patent: 1154 479Addendum to the patent: 1154 479
Anmelder:Applicant:
Chemische Werke Witten ·
Gesellschaft mit beschränkter Haftung,
Witten/Ruhr, Arthur-Imhausen-Str. 92 aChemical Works Witten
Company with limited liability,
Witten / Ruhr, Arthur-Imhausen-Str. 92 a
Als Erfinder benannt:
Dipl.-Chem. Ewald Katzschmann,
Dortmund-Kruckel.Named as inventor:
Dipl.-Chem. Ewald Katzschmann,
Dortmund-Kruckel.
B eis.piel 1 ..... . .Example 1 ..... . .
90 gTerephthaisäuremonomethylester, 200 g Wasser, 150 g Dimethylformamid, 55 g Propylenoxyd wurden in einem V4A-Schüttelautoklav innerhalb von 30 Minuten auf 1300C erhitzt, 15 Minuten bei dieser Temperatur belassen und unter weiterem Schütteln abkühlen gelassen. Das Reaktionsprodukt war eine klare Lösung mit schwach saurer Reaktion. Es wurde kalt unter Rühren mit 10%iger Kalilauge neutralisiert, bei 900C über Kohle filtriert und zur Kristallisation stehengelassen. Es wurden 96 g Terephthalsäuremonomethylmonopropylenglykolmonoester erhalten mit einer Säurezahl = 1,1 und einer Verseifungszahl = 473 (berechnet: 471), der Schmelzpunkt betrug 79° C.90 g of monomethyl terephthalate, 200 g of water, 150 g of dimethylformamide, 55 g of propylene oxide were heated to 130 ° C. within 30 minutes in a V4A shaking autoclave, left at this temperature for 15 minutes and allowed to cool with continued shaking. The reaction product was a clear solution with a weakly acidic reaction. It was neutralized cold with stirring with 10% strength potassium hydroxide solution, filtered through charcoal at 90 ° C. and allowed to stand to crystallize. 96 g of terephthalic acid monomethyl monopropylene glycol monoester were obtained with an acid number = 1.1 and a saponification number = 473 (calculated: 471), the melting point was 79 ° C.
Die Ausbeute zur Theorie betrug 80,8 °/o> berechnet auf eingesetzten Terephthalsäuremonomethylester.The theoretical yield was 80.8% calculated on monomethyl terephthalate used.
B e i s ρ i e 1 2B e i s ρ i e 1 2
78 g p-Chlorbenzoesäure, 325 g Wasser, 75 g Dimethylformamid, 50 g Propylenoxyd wurden in einem V4A-Schüttelautoklav innerhalb einer Stunde auf 12O0C erhitzt und unter weiterem Schütteln abkühlen gelassen. Das Reaktionsprodukt war bei 6O0C eine klare Lösung mit einer Säurezahl = 6. Bei Zimmertemperatur wurde unter gutem Umrühren gegen Phenolphthalein mit 10°/0iger Kalilauge neutralisiert, heiß über Kohle filtriert und bei Zimmertemperatur ausgeäthert, da keine kristalline Abscheidung erfolgte. Als Ätherextrakt wurden 84 g einer klaren hochviskosen Flüssigkeit erhalten, die beim Stehen langsam in den78 g of p-chlorobenzoic acid, 325 g water, 75 g of dimethylformamide, 50 g of propylene oxide were heated in a V4A shaken within one hour to 12O 0 C and allowed to cool with continued shaking. The reaction product was sixth at 6O 0 C a clear solution with an acid value = At room temperature / 0 potassium hydroxide was neutralized, stirring well to phenolphthalein with 10 °, hot filtered through charcoal, and extracted with ether at room temperature, since no crystal deposition was carried out. 84 g of a clear, highly viscous liquid were obtained as the ether extract, which slowly poured into the when standing
I 227I 227
kristallinen Zustand überging. Die Ausbeute zur Theorie betrug 78,4%, die Säurezahl: = 0,8 und die Verseifungszahl = 264 (berechnet: 262). Der Ester läßt sich gut aus Ligroin Umkristallisieren. Sein Schmelzpunkt betrug 73,60C.crystalline state passed. The theoretical yield was 78.4%, the acid number = 0.8 and the saponification number = 264 (calculated: 262). The ester can easily be recrystallized from ligroin. Its melting point was 73.6 0 C.
B ei spi el 3 -Example 3 -
136 g Phenylessigsäure, 250 g Wasser, 50 g Formamid wurden in einem geschlossenen, mit Rückflußkühler, Rührer, Thermometer und Scheidetrichter versehenen zylindrischen Gefäß auf 65 0C erhitzt. Das Rohr des Scheidetrichters war so angeordnet, daß es fast auf den Boden des Gefäßes reichte.-Innerhalb von 10 Stunden wurden 200 g Propylenoxyd langsam zugetropft. 105g Propylenoxyd wurden über den kleinen Rückflußkühler in einer; damit- verbundenen mit Kohlensäureschnee gekühlten FaUe zurückgewonnen. Diese abdestillierte Menge kann ohne weiteres zurückgeführt werden.· ■■■■-■ -.-136 g of phenylacetic acid, 250 g water, 50 g of formamide were heated in a closed, with reflux condenser, stirrer, thermometer and a separating funnel cylindrical vessel provided at 65 0 C. The tube of the separating funnel was arranged so that it almost reached the bottom of the vessel. 200 g of propylene oxide were slowly added dropwise over a period of 10 hours. 105g propylene oxide were in a small reflux condenser in a; The associated faUe cooled with carbon dioxide snow was recovered. This distilled amount can easily be returned. · ■■■■ - ■ -.-
Der Abfall der Säurezahl wurde analytisch verfolgt:The drop in the acid number was followed analytically:
Nach " 0 Stunden 135After "0 hours 135
Nach 2 Stunden :-.=-..; 91After 2 hours: -. = - ..; 91
Nach 4 Stunden . 49After 4 hours . 49
Nach 8 Stunden ,. 17After 8 hours,. 17th
Nach 10 Stünden ..... : 7After 10 hours .....: 7
Nach 12 Stunden .. 3After 12 hours .. 3
Das Reaktionsprodukt trennte sich in zwei Schichten. Mechanisch konnten 260 g als ölige Unterschicht abgetrennt werden. 55 g wurden noch durch Ausäthern der wäßrigen Schicht erhalten. Die Gesamtmenge von 315 g Rohprodukt wurden zur Destillation eingesetzt:The reaction product separated into two layers. It was possible to remove 260 g mechanically as an oily sublayer. 55 g were still due to etherification the aqueous layer obtained. The total of 315 g of crude product were used for distillation used:
Vorlauf (Wasser, Propylenglykol, Formamid) bis 105°C/0,5mm 125gFlow (water, propylene glycol, formamide) up to 105 ° C / 0.5mm 125g
PhenylessigsäurepropylenglykolmonoesterPhenylacetic acid propylene glycol monoester
105 bis 107°C/0,5 mm 176g105 to 107 ° C / 0.5mm 176g
Destillationsrückstand 8 gDistillation residue 8 g
Als Kennzahlen für den Ester wurden gefunden:The following key figures for the ester were found:
Säurezahl 1,1Acid number 1.1
Verseifungszahl 289Saponification Number 289
(berechnet: 289)(calculated: 289)
Die Ausbeute zur Theorie an reinem Ester betrug 90,8 %.The theoretical yield of pure ester was 90.8%.
116 g Capronsäure (etwa 95%ig), 300 g Wasser, g Dimethylformamid, 85 g Propylenoxyd wurden in einem V4A-Schüttelautoklav innerhalb einer Stunde auf 125° C erhitzt und dann unter weiterem Schütteln auf 70^C abkühlen gelassen: Dasklare und einheitliche Reaktionsprodukt besaß eine Säurezahl von 5,6. Die Lösung wurde bei Zimmertemperatur mit 10%iger Kalilauge neutralisiert und anschließend ausgeäthert. Der Ätherextrakt wurde destilliert.116 g caproic acid (about 95%), 300 g water, g dimethylformamide, 85 g propylene oxide were heated in a V4A shaking autoclave to 125 ° C within one hour and then with further shaking left to cool to 70 ^ C: The clear and uniform The reaction product had an acid number of 5.6. The solution was at room temperature with 10% Potassium hydroxide neutralized and then etherified. The ether extract was distilled.
Als Hauptfraktion wurden bei 81 bis 83°C/0,9 mm g = 81,6% der Theorie Capronsäurepröpylenglykolmonoester mit einer Säurezahl = 0,7 und einer Verseifungszahl = 321 (berechnet: 322) erhalten.The main fraction at 81 to 83 ° C./0.9 mm was g = 81.6% of theory, caproic acid propylene glycol monoester with an acid number = 0.7 and a saponification number = 321 (calculated: 322).
Claims (1)
Priority Applications (18)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL123782D NL123782C (en) | 1961-04-11 | ||
| BE638154D BE638154A (en) | 1961-04-11 | ||
| NL130350D NL130350C (en) | 1961-04-11 | ||
| NL293407D NL293407A (en) | 1961-04-11 | ||
| NL277092D NL277092A (en) | 1961-04-11 | ||
| DEC23852A DE1154479B (en) | 1961-04-11 | 1961-04-11 | Process for the preparation of ethylene glycol monoesters of saturated carboxylic acids |
| DEC24564A DE1157623B (en) | 1961-04-11 | 1961-07-08 | Process for the preparation of ethylene glycol monoesters of saturated carboxylic acids |
| DEC25830A DE1150982B (en) | 1961-04-11 | 1961-12-23 | Process for the preparation of ethylene glycol monoesters of saturated carboxylic acids |
| CH172162A CH432491A (en) | 1961-04-11 | 1962-02-13 | Process for the production of ethylene glycol monoesters |
| GB1404462A GB956412A (en) | 1961-04-11 | 1962-04-11 | Improvements in or relating to carboxylic acid esters |
| DE19621443577 DE1443577A1 (en) | 1961-04-11 | 1962-10-04 | Process for the production of glycol monoesters |
| DEC28188A DE1227024B (en) | 1961-04-11 | 1962-10-16 | Process for the production of carboxylic acid glycol monoesters |
| DEC28198A DE1226579B (en) | 1961-04-11 | 1962-10-17 | Process for the preparation of carboxylic acid glycol monoesters |
| CH486963A CH468961A (en) | 1961-04-11 | 1963-04-18 | Process for the production of glycol monoesters |
| FR947135A FR84485E (en) | 1961-04-11 | 1963-09-11 | Process for the preparation of ethylene glycol monoesters |
| GB3676163A GB985368A (en) | 1961-04-11 | 1963-09-18 | Improvements in or relating to carboxylic acid esters |
| NL6601682A NL6601682A (en) | 1961-04-11 | 1966-02-10 | |
| NL6601674A NL6601674A (en) | 1961-04-11 | 1966-02-10 |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC23852A DE1154479B (en) | 1961-04-11 | 1961-04-11 | Process for the preparation of ethylene glycol monoesters of saturated carboxylic acids |
| DEC24564A DE1157623B (en) | 1961-04-11 | 1961-07-08 | Process for the preparation of ethylene glycol monoesters of saturated carboxylic acids |
| DEC25830A DE1150982B (en) | 1961-04-11 | 1961-12-23 | Process for the preparation of ethylene glycol monoesters of saturated carboxylic acids |
| DEC0028084 | 1962-10-04 | ||
| DEC28188A DE1227024B (en) | 1961-04-11 | 1962-10-16 | Process for the production of carboxylic acid glycol monoesters |
| DEC28198A DE1226579B (en) | 1961-04-11 | 1962-10-17 | Process for the preparation of carboxylic acid glycol monoesters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1227024B true DE1227024B (en) | 1966-10-20 |
Family
ID=27544785
Family Applications (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC23852A Pending DE1154479B (en) | 1961-04-11 | 1961-04-11 | Process for the preparation of ethylene glycol monoesters of saturated carboxylic acids |
| DEC24564A Pending DE1157623B (en) | 1961-04-11 | 1961-07-08 | Process for the preparation of ethylene glycol monoesters of saturated carboxylic acids |
| DEC25830A Pending DE1150982B (en) | 1961-04-11 | 1961-12-23 | Process for the preparation of ethylene glycol monoesters of saturated carboxylic acids |
| DE19621443577 Pending DE1443577A1 (en) | 1961-04-11 | 1962-10-04 | Process for the production of glycol monoesters |
| DEC28188A Pending DE1227024B (en) | 1961-04-11 | 1962-10-16 | Process for the production of carboxylic acid glycol monoesters |
| DEC28198A Pending DE1226579B (en) | 1961-04-11 | 1962-10-17 | Process for the preparation of carboxylic acid glycol monoesters |
Family Applications Before (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC23852A Pending DE1154479B (en) | 1961-04-11 | 1961-04-11 | Process for the preparation of ethylene glycol monoesters of saturated carboxylic acids |
| DEC24564A Pending DE1157623B (en) | 1961-04-11 | 1961-07-08 | Process for the preparation of ethylene glycol monoesters of saturated carboxylic acids |
| DEC25830A Pending DE1150982B (en) | 1961-04-11 | 1961-12-23 | Process for the preparation of ethylene glycol monoesters of saturated carboxylic acids |
| DE19621443577 Pending DE1443577A1 (en) | 1961-04-11 | 1962-10-04 | Process for the production of glycol monoesters |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC28198A Pending DE1226579B (en) | 1961-04-11 | 1962-10-17 | Process for the preparation of carboxylic acid glycol monoesters |
Country Status (6)
| Country | Link |
|---|---|
| BE (1) | BE638154A (en) |
| CH (1) | CH432491A (en) |
| DE (6) | DE1154479B (en) |
| FR (1) | FR84485E (en) |
| GB (2) | GB956412A (en) |
| NL (6) | NL6601682A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1248036B (en) | 1962-12-12 | 1967-08-24 | Basf Ag | Process for the preparation of alpha, beta-unsaturated carboxylic acid esters by esterifying the carboxylic acids with alkylene oxides |
| DE1248660B (en) * | 1965-05-29 | 1967-08-31 | Badische Anilin d. Soda Fabrik Aktiengesellschaft, Ludwigshafen/Rhem | Process for the preparation of glycol monoesters of carboxylic acids |
| US4722811A (en) * | 1984-10-15 | 1988-02-02 | Exxon Research & Engineering Co. | Process for preparing glycol monoesters |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL67041C (en) * | 1947-05-09 | 1950-07-15 | Ici Ltd | Preparation of terephthalic acid glycol esters |
| AT163642B (en) * | 1947-05-09 | 1949-07-25 | Ici Ltd | Process for the production of ethylene glycol esters of terephthalic acid |
| ES217092A2 (en) * | 1953-08-31 | 1955-09-16 | Ici Ltd | A PROCEDURE FOR MANUFACTURING POLYESTERS |
-
0
- NL NL293407D patent/NL293407A/xx unknown
- NL NL277092D patent/NL277092A/xx unknown
- NL NL130350D patent/NL130350C/xx active
- BE BE638154D patent/BE638154A/xx unknown
- NL NL123782D patent/NL123782C/xx active
-
1961
- 1961-04-11 DE DEC23852A patent/DE1154479B/en active Pending
- 1961-07-08 DE DEC24564A patent/DE1157623B/en active Pending
- 1961-12-23 DE DEC25830A patent/DE1150982B/en active Pending
-
1962
- 1962-02-13 CH CH172162A patent/CH432491A/en unknown
- 1962-04-11 GB GB1404462A patent/GB956412A/en not_active Expired
- 1962-10-04 DE DE19621443577 patent/DE1443577A1/en active Pending
- 1962-10-16 DE DEC28188A patent/DE1227024B/en active Pending
- 1962-10-17 DE DEC28198A patent/DE1226579B/en active Pending
-
1963
- 1963-09-11 FR FR947135A patent/FR84485E/en not_active Expired
- 1963-09-18 GB GB3676163A patent/GB985368A/en not_active Expired
-
1966
- 1966-02-10 NL NL6601682A patent/NL6601682A/xx unknown
- 1966-02-10 NL NL6601674A patent/NL6601674A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE1157623B (en) | 1963-11-21 |
| CH432491A (en) | 1967-03-31 |
| DE1443577A1 (en) | 1969-02-13 |
| FR84485E (en) | 1965-02-19 |
| NL6601674A (en) | 1966-05-25 |
| NL123782C (en) | |
| GB985368A (en) | 1965-03-10 |
| NL293407A (en) | |
| GB956412A (en) | 1964-04-29 |
| DE1154479B (en) | 1963-09-19 |
| NL6601682A (en) | 1966-05-25 |
| DE1226579B (en) | 1966-10-13 |
| NL277092A (en) | |
| NL130350C (en) | |
| DE1150982B (en) | 1963-07-04 |
| BE638154A (en) |
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