WO1992000944A1 - Ethers insatures - Google Patents

Ethers insatures Download PDF

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Publication number
WO1992000944A1
WO1992000944A1 PCT/EP1991/001191 EP9101191W WO9200944A1 WO 1992000944 A1 WO1992000944 A1 WO 1992000944A1 EP 9101191 W EP9101191 W EP 9101191W WO 9200944 A1 WO9200944 A1 WO 9200944A1
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WO
WIPO (PCT)
Prior art keywords
telomerization
unsaturated ethers
palladium
self
glycerol
Prior art date
Application number
PCT/EP1991/001191
Other languages
German (de)
English (en)
Inventor
Reinhard Bunte
Bert Gruber
James Tucker
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1992000944A1 publication Critical patent/WO1992000944A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
    • C07C43/1785—Unsaturated ethers containing hydroxy or O-metal groups having more than one ether bound
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers

Definitions

  • the invention relates to unsaturated ethers, obtainable by joint telomerization of conjugated dienes
  • Unsaturated ethers which have at least one aliphatic hydrocarbon residue with more than 6 carbon atoms, are interesting intermediates for the production of anionic surfactants [DE-A-37 25030] and polyurethane foams [Fat, Sei., Techno!., 89 , 147 (1987)].
  • Unsaturated ethers of the type mentioned are usually prepared from unsaturated fatty alcohols, which are reacted with alkyl halides under the conditions of Wi11iamson 1, see ether synthesis.
  • unsaturated alcohols are only technically available in the range from 16 to 22 carbon atoms, which severely limits the scope of application of this synthesis process.
  • Another possibility is to epoxidize some of the double bonds contained in olefins or unsaturated esters and then to react the oxirane compounds formed with nucleophiles.
  • the object of the invention was therefore to provide unsaturated ethers, the preparation of which does not suffer from the disadvantages described.
  • the invention relates to unsaturated ethers obtainable by jointly telomerizing conjugated dienes with polyhydroxy compounds selected from the group consisting of
  • Unsaturated ethers with particularly favorable application properties are obtained if the diene component is butadiene-1,3, isoprene or piperylene and the self-condensation products of glycerol used as a further starting material contain an average of 2 to 50, in particular 2 to 10, glycerol units.
  • the telomerization proceeds particularly quickly and with high selectivity when the palladium salt is palladium bis-acetyl acetonate and the phosphine derivatives are trialkyl or triarylphosphines.
  • conjugated dienes are to be understood as meaning conjugated linear or cyclic dienes having 4 to 10 carbon atoms, which may optionally be substituted by chlorine, a C 1 -C 4 -alkyl radical, a cycloalkyl radical or a phenyl group.
  • the starting materials for the preparation of the unsaturated ethers according to the invention are, in particular, those conjugated dienes which arise during naphtha pyrolysis and which are therefore also available on an industrial scale. These are therefore primarily isoprene, piperylene and particularly preferably 1,3-butadiene. Of course, other conjugated dienes, such as. B.
  • Self-condensation products of glycerol which are known compounds and can be prepared by the relevant methods of preparative organic chemistry, are suitable as further starting components for the preparation of the unsaturated ethers according to the invention. Processes for their preparation are based, for example, on glycerol which is reacted with chlorohydrins at 50 to 120 ° C., if appropriate at high pH values [US 2,520,670, EP-A-0333984].
  • the conjugated dienes can also be used together with compounds in the telomerization. are set which are obtained by ring opening of olefin epoxides with water or alcohols and which follow the formula (I),
  • R * and R 2 independently of one another represent alkyl radicals having 1 to 16 carbon atoms
  • R 2 additionally also represents hydrogen
  • R3 represents hydrogen or an alkyl group having 1 to 8 carbon atoms, the. Sum of the carbon atoms in R 1 and R 2 is 4 to 16.
  • the ring opening products can be derived from linear or branched olefin epoxides with alpha or internal epoxy function, which in total have 6 to 18, preferably 8 to 12 carbon atoms. Typical examples are the epoxides of octene-1, octene-2, octene-4, decen-1, decen-2, decen-5, dodecen-1, dodecen-2 or dodecen-6.
  • the ring opening can have been carried out with water or short-chain aliphatic alcohols having 1 to 8 carbon atoms.
  • Typical examples are ethanol, propanol-1, propanol-2, butanol-1, pentanol-1, capro alcohol, caprylic alcohol or 2-ethyl-hexanol. Ring opening products obtained with water or methanol are preferred.
  • the ring opening of epoxies with water or alcohols is e.g. B. in Fat, Sei.Techno1., 89, 147 (1987).
  • the invention further relates to a process for the preparation of unsaturated ethers, characterized in that conjugated dienes with polyhydroxy compounds selected from the group consisting of a) self-condensation products of glycerol or b) ring opening products of olefin epoxides with water or alcohols
  • telomerization of conjugated dienes are e.g. B. known from German patent DE-B-18 07 491.
  • the process is carried out in the presence of palladium compounds.
  • salts of palladium such as. B. Bis (allyl) palladium [Pd (C3H5) 3], bis (cyclooctadiene) palladium [Pd (C0D) 2 palladium chloride (PdCl2), palladium acetate [Pd (0Ac) 2], allyl palladium chloride [Pd (C3H5) Cl] and in particular Palladium-bis-acetylacetonate [Pd (acac) 2] has been proven.
  • Phosphine derivatives in particular trialkyl- or triarylphosphines such as, for. B. trimethylphosphine, o-, m-, p-toluylphosphine, l, 2-bis (diphenylphosphino) ethane, l, 2-bis (di-p-toluylphosphino) ethane or in particular triphenylphosphine.
  • Mixtures of alkyl, aryl and aryl / alkylphosphines can also be used as co-catalysts.
  • telomerization it is possible to use the catalyst and cocatalyst together in the form of tetrakis (triphenylphosphine) palladiu [Pd (PPh3) 4] in the telomerization.
  • the number of hydroxyl groups is used as the basis for calculating the molar ratio of diene to self-condensation product or ring opening product.
  • the telomerization is preferably carried out with a molar ratio of 1: 1 to 5: 1, preferably 1: 1 to 2: 1, based on the hydroxyl number.
  • the conjugated dienes are reacted with the self-condensation products or ring opening products even in the presence of extremely small amounts of catalyst.
  • the telomerization is advantageously carried out with a molar ratio of diene to palladium compound of 5,000: 1 to 150,000: 1.
  • An operating ratio of 10,000: 1 to 75,000: 1, in particular from 15,000: 1 to 25,000: 1, has proven to be optimal.
  • the selectivity of the telomerization is also significantly influenced by the molar ratio of catalyst and cocatalyst.
  • the reaction is advantageously carried out with a molar ratio of palladium compound to phosphine derivative of 1: 1 to 1: 5.
  • a catalyst system has proven optimal in which 2 moles of triphenylphosphine account for one mole of palladium acetylacetonate.
  • the telomerization is carried out at elevated temperatures of 40 to 100 ° C. An optimal reaction rate is obtained at 60 to 80 ° C.
  • the reaction time is a function of the temperature; at higher temperatures, the same degrees of conversion are achieved in shorter times and vice versa. Overall, satisfactory yields of unsaturated ethers are achieved within 1 to 24, preferably 5 to 10 hours.
  • the telomerization can be carried out in the absence of solvents. In a preferred embodiment of the invention, however, the reaction takes place in the presence of an organic solvent, the use of isopropyl alcohol, 1,2-propanediol or 1,3-propanediol being particularly preferred.
  • Telomerization leads to a complex product mix.
  • butadiene-1.3 z. B. preferably cis / trans 1-substituted 2,7-octadienyl ether and 3-substituted 1, 7-0ctadienyl ether are formed.
  • 16 isomers can be formed solely by the fact that the dimerization can take place in four different ways (head-head, head-tail, tail-head, tail-tail linkage).
  • the number of products is increased by the fact that both the self-condensation products and the ring opening products are polyhydroxy compounds and thus mono- and / or polyethers of different degrees of substitution can be formed.
  • the unsaturated ethers have defoaming and washing-strengthening properties and can be used in liquid or powdered surface-active agents, such as, for example, washing, rinsing or cleaning agents.
  • Their application concentration can be 1 to 10% by weight, based on the surfactant content of the products.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On produit des éthers insaturés par télomérisation en commun de diènes conjugués avec des composés polyhydroxyles sélectionnés dans le groupe formé (a) des produits naturels de condensation de la glycérine ou (b) des produits de clivage d'époxydes d'oléfine cycliques avec de l'eau ou des alcools, en présence de composés de palladium et de dérivés de phosphine. Ces éthers sont utiles dans la production d'agents tensio-actifs.
PCT/EP1991/001191 1990-07-05 1991-06-26 Ethers insatures WO1992000944A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4021511A DE4021511A1 (de) 1990-07-05 1990-07-05 Ungesaettigte ether
DEP4021511.3 1990-07-05

Publications (1)

Publication Number Publication Date
WO1992000944A1 true WO1992000944A1 (fr) 1992-01-23

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ID=6409761

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/001191 WO1992000944A1 (fr) 1990-07-05 1991-06-26 Ethers insatures

Country Status (2)

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DE (1) DE4021511A1 (fr)
WO (1) WO1992000944A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5470128A (en) * 1992-11-02 1995-11-28 Sebel Furniture Limited Article of furniture

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005016152A1 (de) * 2005-04-07 2006-10-12 Basf Ag Herstellung von (Co)Tensiden durch Umsetzung von Polyolen mit Olefinen

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science, Band 30, Nr. 8, Teil 2, 20. Februar 1982, Plenum Publishing Corp., U.M. Dzhemilev et al.: "Telomerization of cyclic and linear glycols with butadiene, catalyzed by phosphine complexes of palladium", Seiten 1506-1510, siehe Seiten 1507-1509 *
Chemical Abstracts, Band 93, Nr. 19, 10. November 1980, (Columbus, Ohio, US), U.M. Dzhemilev et al.: "Telomerization of polyhydric alcohols with butadiene catalyzed by low-valence palladium complexes", siehe Seite 602, Zusammenfassung 185682k, & Zh. Org. Khim. 1980, 16(6), 1157-61 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5470128A (en) * 1992-11-02 1995-11-28 Sebel Furniture Limited Article of furniture

Also Published As

Publication number Publication date
DE4021511A1 (de) 1992-01-09

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