WO2003097566A1 - Procede de production de dialkyldicetenes - Google Patents

Procede de production de dialkyldicetenes Download PDF

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Publication number
WO2003097566A1
WO2003097566A1 PCT/EP2003/005054 EP0305054W WO03097566A1 WO 2003097566 A1 WO2003097566 A1 WO 2003097566A1 EP 0305054 W EP0305054 W EP 0305054W WO 03097566 A1 WO03097566 A1 WO 03097566A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
fatty acid
tertiary amine
acid chlorides
mixture
Prior art date
Application number
PCT/EP2003/005054
Other languages
German (de)
English (en)
Inventor
Horst Rieckert
Holger Keller
Gerhard Mayer
Original Assignee
Schill + Seilacher Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Schill + Seilacher Aktiengesellschaft filed Critical Schill + Seilacher Aktiengesellschaft
Priority to AU2003240244A priority Critical patent/AU2003240244A1/en
Publication of WO2003097566A1 publication Critical patent/WO2003097566A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/88—Ketenes; Dimeric ketenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/87—Preparation of ketenes or dimeric ketenes
    • C07C45/89—Preparation of ketenes or dimeric ketenes from carboxylic acids, their anhydrides, esters or halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
    • C07D305/12—Beta-lactones

Definitions

  • Dialkyldiketenes (alkyl ketene dimers) are mainly used as paper auxiliaries (sizing and waterproofing agents) for the production of high-quality papers with a glossy surface.
  • alkyl residues of these diketenes preferably originate from higher fatty acids which are prepared in a manner known per se by splitting off hydrogen chloride from the corresponding fatty acid chlorides with the aid of tertiary amines.
  • the known methods belong in essentially two groups, namely a first group in which fatty acid chlorides and tertiary amines are reacted in the presence of an inert organic solvent, and a second group in which the process is carried out without solvents.
  • EP-A-0 624 579 and US-A-2,369,919, methods of the second group are known from EP-A-0 550 107 and 0 612 739 and WO 94/19306.
  • the hydrochloride of the tertiary amine used ie mostly triethylammonium chloride, since triethylamine is the most frequently used tertiary amine because of its ready availability, precipitates in crystalline form.
  • the salt is either filtered off from the organic phase (US-A-2,369,919 and EP-A-0 624 579), or it is mixed with a dilute aqueous solution of a carboxylic acid (DE-A-23 35 488) or a neutral salt (DE- A-23 27 988) washed out.
  • reaction mixture is mixed with dilute hydrochloric acid after the reaction between fatty acid chloride and tertiary amine (cf. EP-A-0 550 107 and 0 612 739) in order to achieve this Wash out the ammonium salt formed and to be able to separate the organic phase containing the dialkyldiketene.
  • a further variant of the solvent-free process is known from WO94 / 19306, in which the reaction mixture after the reaction of the fatty acid chloride with the tertiary amine has ended with a previously formed mixture of ketene dimer and amine hydrochloride as initiator or nucleating agent for newly formed hydrochloride of the tertiary amine and is therefore used as a viscosity control agent for the reaction mixture.
  • the invention is therefore based on the object of providing a process for the preparation of dialkyldiketenes by solvent-free reaction of long-chain fatty acid chlorides with a tertiary amine, in which a hydrochloride of the tertiary amine is formed in crystalline form, which is washed out after the reaction has ended Improve that the dimerization is controlled in one direction, namely towards the lactone structure, that when the ammonium salts are washed out there is an optimal phase separation between the organic and aqueous phases and that the diketene can be separated in high purity and high yield without the environment to charge.
  • This object is achieved according to the invention in a process of the type mentioned in that the reaction of the starting materials (fatty acid chlorides and tertiary amine) is carried out in the presence of a catalyst for the dimerization of monomeric alkyl ketene.
  • Heterocyclic tertiary amines with three to nine carbon atoms and two heteroatoms in the ring system, of which at least one is a nitrogen atom, have proven to be particularly suitable.
  • Particularly preferred catalysts from the aforementioned group are N-methylimidazole, N-methylmorpholine and DABCO.
  • Another excellent catalyst for the reaction of long-chain fatty acid chlorides with tertiary amines to dialkyldiketenes is the group of 4-di-C 1 -C 4 -alkylaminopyridines and preferably 4-dimethylamino-pyridine.
  • the catalyst is used in an amount of 0.1 to 3.0% by weight, based on the mixture of the starting materials, particularly preferably in an amount of 0.5 to 1.0% by weight.
  • a long-chain fatty acid chloride is a fatty acid chloride with 8 to 32 carbon atoms or a mixture of fatty acid chlorides with 8 to 32 carbon atoms.
  • the most important compounds in this group are the chlorides of lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, palmitoleic acid and oleic acid.
  • Acid chlorides of the naturally occurring fatty acid mixtures, in particular from coconut fat, are economically and technically the most important starting materials for the process according to the invention. These mixtures contain palmitoyl chloride and stearoyl chloride or consist of these two fatty acid chlorides.
  • At least one amine of the formula R 1 , R 2 , R 3 N which is liquid under the reaction conditions is used, in which R 1 , R 2 and R 3 , independently of one another, are an alkyl or alkenyl , Aralkyl or cycloalkyl group, each with a maximum of ten carbon atoms, or R 1 and R 2 together mean an alkylene chain with up to six carbon atoms.
  • the most important tertiary amines in this group are triethylamine, diethylmethylamine, dimethylcyclohexylamine, di-isopropylethylamine, tripropylamine and mixtures thereof. Triethylamine is particularly preferred because of its easy availability, its low price and its chemical reactivity.
  • the amine hydrochloride formed in the reaction of the fatty acid chlorides with the tertiary amine is washed out with water, which is added to the reaction mixture after the reaction has ended.
  • the reaction mixture is preferably mixed with an acidified aqueous phase, particularly preferably with dilute hydrochloric acid, in order to wash out the hydrochloride formed and to achieve an optimal phase separation between the organic and aqueous phases.
  • the reaction of the starting materials is preferably carried out in the presence of a catalyst which is selected from the group consisting of N-C 1 -C 4 -alkylimidazole, 1,4-diazabicyclo (2.2.2) octane ( DABCO), l, 8-diazabicyclo (5.4.0) undec-7-en (DBU), 1,5-diazabicyclo (4.3.0) non-5-ene and 4-di-C 1 -C 4 -alkylaminopyridine existing group ,
  • a catalyst which is selected from the group consisting of N-C 1 -C 4 -alkylimidazole, 1,4-diazabicyclo (2.2.2) octane ( DABCO), l, 8-diazabicyclo (5.4.0) undec-7-en (DBU), 1,5-diazabicyclo (4.3.0) non-5-ene and 4-di-C 1 -C 4 -alkylaminopyridine existing
  • N-methylmorpholine as a tertiary amine for the reaction with fatty acid chlorides and DABCO as a catalyst has proven particularly useful, the catalyst only in an amount of 0.1 to 3.0% by weight, preferably 0.5 to 1.0 wt .-%, based on the mixture of starting materials, is used.
  • the separated organic phase was washed twice with 30 ml of water.
  • the product obtained was dried at 60 ° C. under reduced pressure (water jet pump), after which 65.5 g of product, corresponding to 97.7% of theory, were obtained.
  • the diketene content was determined to be 92.4% by the morpholine method.
  • the melting range of the diketenes was 48-53 ° C.
  • the IR spectrum showed the characteristic carbonyl bands at 1850 and 1720 cm '1 .
  • Active dialkyldiketenen content was 80%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production de dialkyldicétènes par réaction sans solvant de chlorures d'acides gras à chaîne longue avec des amines tertiaires. Selon l'invention, pour améliorer le taux de rendement et le degré de pureté des produits finaux, la réaction des substances de départ a lieu en présence d'un catalyseur favorisant la dimérisation d'alkylcétènes monomères. Le 1,4-diazabicyclo(2.2.2)octane (DABCO) constitue un catalyseur préféré.
PCT/EP2003/005054 2002-05-17 2003-05-14 Procede de production de dialkyldicetenes WO2003097566A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003240244A AU2003240244A1 (en) 2002-05-17 2003-05-14 Method for the production of dialkyl diketenes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2002122624 DE10222624A1 (de) 2002-05-17 2002-05-17 Verfahren zur Herstellung von Dialkyldiketenen
DE10222624.5 2002-05-17

Publications (1)

Publication Number Publication Date
WO2003097566A1 true WO2003097566A1 (fr) 2003-11-27

Family

ID=29285642

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/005054 WO2003097566A1 (fr) 2002-05-17 2003-05-14 Procede de production de dialkyldicetenes

Country Status (3)

Country Link
AU (1) AU2003240244A1 (fr)
DE (1) DE10222624A1 (fr)
WO (1) WO2003097566A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007079444A2 (fr) * 2006-01-03 2007-07-12 Hercules Incorporated Preparation de dimeres d’alkyle cetene

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3434212A1 (de) * 1984-09-18 1986-03-20 Schill & Seilacher GmbH & Co, 7030 Böblingen Verfahren zur herstellung von ketendimeren und deren verwendung
EP0550107A1 (fr) * 1991-12-30 1993-07-07 Akzo Nobel N.V. Cétènes dimères à longue chaîne
EP0612739A1 (fr) * 1993-02-22 1994-08-31 Eka Nobel Ab Procédé de production de cétènes dimères

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2927118C2 (de) * 1979-07-05 1981-10-15 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Fettalkyldiketenen
FI104714B (fi) * 1998-12-04 2000-03-31 Neste Oyj Menetelmä alkyyliketeenidimeerien valmistamiseksi

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3434212A1 (de) * 1984-09-18 1986-03-20 Schill & Seilacher GmbH & Co, 7030 Böblingen Verfahren zur herstellung von ketendimeren und deren verwendung
EP0550107A1 (fr) * 1991-12-30 1993-07-07 Akzo Nobel N.V. Cétènes dimères à longue chaîne
EP0612739A1 (fr) * 1993-02-22 1994-08-31 Eka Nobel Ab Procédé de production de cétènes dimères

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007079444A2 (fr) * 2006-01-03 2007-07-12 Hercules Incorporated Preparation de dimeres d’alkyle cetene
WO2007079444A3 (fr) * 2006-01-03 2007-08-30 Hercules Inc Preparation de dimeres d’alkyle cetene
AU2007203808B2 (en) * 2006-01-03 2011-07-07 Hercules Incorporated Preparation of alkyl ketene dimers

Also Published As

Publication number Publication date
DE10222624A1 (de) 2003-11-27
AU2003240244A1 (en) 2003-12-02

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