EP0888295A1 - Synthese d'agents de nettoyage anioniques - Google Patents

Synthese d'agents de nettoyage anioniques

Info

Publication number
EP0888295A1
EP0888295A1 EP97901911A EP97901911A EP0888295A1 EP 0888295 A1 EP0888295 A1 EP 0888295A1 EP 97901911 A EP97901911 A EP 97901911A EP 97901911 A EP97901911 A EP 97901911A EP 0888295 A1 EP0888295 A1 EP 0888295A1
Authority
EP
European Patent Office
Prior art keywords
diol
cyclic anhydride
reduction step
substituted cyclic
anhydride
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Withdrawn
Application number
EP97901911A
Other languages
German (de)
English (en)
Other versions
EP0888295A4 (fr
Inventor
Steven Wayne Heinzman
Robert Edward Shumate
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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 Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0888295A1 publication Critical patent/EP0888295A1/fr
Publication of EP0888295A4 publication Critical patent/EP0888295A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols

Definitions

  • the present invention relates to an improved method for the synthesis of disulfated cleaning agents, for use in detergent compositions.
  • dianionic surfactants that is surfactants having two anionically charged groups, as detergent components has been previously described.
  • Disulfated surfactants in particular 1 ,4 disulfated surfactants and alkoxylated forms thereof, are specific examples of such dianionic surfactants.
  • Disulfated surfactants have not to date found common use in the detergent industry because of the difficulty associated in deriving a commercially viable route for their bulk preparation.
  • Commercial viability is, in general terms, dictated by the need to employ inexpensive, readily available starting materials capable of translation into 'end product' via a synthetic route which is energy efficient, employs inexpensive, readily available reagents and provides high yields.
  • Known syntheses of disulfated surfactants in general, use an alkyl or aikenyl succinic anhydride as the principal starting material. This is initially subjected to a reduction step from which a diol is obtained. Subsequently the diol is subjected to a sulfation step to give the disulfated product. Optionally, an alkoxylation step may be introduced prior to the sulfation step such that alkoxylated disulfate cleaning agents are obtained.
  • US-A-3,634,269 describes phosphate-free detergent compositions containing 2-alkyl or alkenyl-1 ,4-butanediol disulfates. Described therein, is their preparation by the reduction of aikenyl succinic anhydrides with lithium aluminium hydride to produce either aikenyl or alkyl diols which are then sulfated. Additionally, US-A-3,959,334 and US-A-4,000,081 describe 2-hydrocarbyl- 1 ,4-butanediol disulfates said to be suitable as lime soap dispersants. Again, the method for synthesizing these disulfates involves the reduction of aikenyl succinic anhydrides with lithium aluminium hydride to produce either aikenyl or alkyl diols which are then sulfated.
  • US-A-3, 832,408 and US-A-3,860,625 describe phosphate-free detergent compositions containing 2-alkyl or alkenyl-1 ,4-butanediol ethoxylate disulfates. Their preparation by the reduction of aikenyl succinic anhydrides with lithium aluminium hydride to produce either aikenyl or alkyl diols which are then ethoxylated prior to sulfation is described.
  • a problem associated with the known synthetic routes to 1 ,4 disulfated surfactants is that the reduction step involves the use of pyrophoric and expensive lithium aluminum hydride (L1AIH4) to reduce the anhydride to the 1 ,4-diol.
  • L1AIH4 lithium aluminum hydride
  • Safe handling of pyrophoric materials requires special process equipment which further adds to processing complexity and cost. Additionally, aluminium salts which are formed in the process require special care in their disposal.
  • a method of synthesis of a disulfated cleaning agent from a substituted cyclic anhydride having one or more carbon chain substituents comprising in total at least 5 carbon atoms comprising the following steps:
  • said reduction step comprises hydrogenation under pressure in the presence of a transition metal-containing hydrogenation catalyst.
  • the cyclic anhydride starting material has a ring structure and comprises an acid anhydride linkage.
  • Cyclic anhydrides are generally formed by a ring forming condensation reaction of a single organic compound having a first carboxylic acid (-COOH) functional group and a second -COY functional group separated from the carboxylic acid functional group by at least two carbon atoms, wherein Y is usually an -OH, or halogen functionality.
  • a specific example of an organic compound which may be condensed to form a cyclic anhydride is maleic acid which on self-condensation provides maleic anhydride.
  • Maleic anhydride is readily available commercially.
  • the ring structure of the cyclic anhydride starting material contains from 4 to 7 carbon atoms, preferably from 4 to 6 carbon atoms in the ring structure. Most preferably the cyclic anhydride starting material is based on succinic anhydride which has a 5-membered ring structure containing 4 carbon atoms in the ring.
  • the cyclic anhydride starting material is substituted by one or more carbon containing substituents, such that in total, these substitutents contain at least 5 carbon atoms, preferably from 5 to 25 carbon atoms, more preferably from 7 to 21 carbon atoms.
  • all of the carbon chain substituent(s) comprise either alkyl or aikenyl chains, which may be branched or unbranched. In one preferred aspect they are essentially unbranched. In another preferred aspect the chains are primarily monobranched, that is more than 50% by weight of the chains are monobranched.
  • the substituted cyclic anhydride has a single carbon chain substituent. In another preferred aspect the substituted cyclic anhydride has two carbon chain substituents each having different points of attachment to the ring structure.
  • Substituted alkenylsuccinic and alkylsuccinic anhydrides are suitable starting materials herein.
  • Preferred anhydrides of this type have the following structures:
  • R and R2 are either H or an alkyl group.
  • R2 is H.
  • Linear alkenylsuccinic anhydrides may be obtained in high yield from the single stage 'ene reaction' of maleic anhydride with an alpha-olefin.
  • Branched alkenylsuccinic anhydrides may be obtained from the single stage 'ene reaction' of maleic anhydride with an intemal olefin, such as those obtainable from the familiar SHOP (tradename of the Shell Corporation) olefin making process.
  • the substituted alkenylsuccinic or alkylsuccinic anhydride starting materials will be substantially pure and, in particular, dimeric impurities are preferably minimised.
  • the cyclic anhydride starting material contains less than 30% dimeric impurities, more preferably less than 10%, most preferably less than 5% or even less than 2.5 or 1 % by weight.
  • impurities can be minimised by conventional techniques within the limit of the skilled person, for example either by selection of appropriate reaction conditions in producing the cyclic anhydride starting material (such as low temperature) or by subsequent purification, for example by distillation.
  • Alkylsuccinic anhydride starting materials can be made by reducing alkenylsuccinic anhydrides. This reduction can be achieved under the conditions of the catalytic hydrogenation reduction step of the present invention.
  • the first step of the synthetic method of the invention is the reduction of the substituted cyclic anhydride to form a diol.
  • the reduction step comprises hydrogenation under pressure in the presence of a transition metal- containing hydrogenation catalyst.
  • the hydrogenation catalyst acts functionally to enhance the efficiency of the reductive hydrogenation process.
  • the catalyst is easy to regenerate.
  • the catalyst contains a transition metal selected from the group consisting of the group VIA (particularly Cr), VIIA (particularly Mn), VIII (particularly Fe, Co, Ni, Ru, Rh) and IB (particularly Cu) elements.
  • a transition metal selected from the group consisting of the group VIA (particularly Cr), VIIA (particularly Mn), VIII (particularly Fe, Co, Ni, Ru, Rh) and IB (particularly Cu) elements.
  • Catalysts containing mixtures of any of these transition metals are envisaged as are catalysts containing other metals including the alkali and alkaline earth metals.
  • Copper-containing catalysts particularly copper chromite (which is commercially available and relatively easy to regenerate) are most preferred.
  • the hydrogenation catalyst may advantageously be supported on an inert support material.
  • the support material generally comprises an oxide salt comprising a metal selected from the group consisting of aluminium, silicon and any mixtures thereof. Supports comprising aluminium oxide or silicon dioxide are especially preferred. Clay materials are also suitable supports.
  • the reductive hydrogenation step is carried out under pressure, and generally at elevated temperature. Usually a solvent is employed. This step can be carried out by a batch, continuous or vapor-phase process. A continuous process is preferred.
  • the pressure is typically from 1 x 10-5 to 1 x 10 7 Pa, more preferably from 1 x 10 6 to 5 x 1 ⁇ 6 Pa.
  • the temperature is generally from 150 to 350°C, more preferably from 200 to 300°C.
  • the time of reaction is generally from 30 minutes to 10 hours.
  • Suitable solvents include alcohols, particularly methanol, ethanol, propanol and butanol.
  • lactones are formed. These are however, convertible to diols by further catalytic hydrogenation. It may be advantageous to carry out the hydrogenation in two steps, preferably as part of a continuous step- wise process, such that a lactone is formed in the first step followed by a second step in which the lactone is reduced to the diol.
  • Conditions which favour lactone formation are high temperature ( ⁇ 300 °C) and low pressures ( ⁇ 1 x 10 5 Pa). Any water formed during the hydrogenation will primarily be in the vapour phase, so that the anhydride is unlikely to be converted to a carboxylic acid which can inhibit the catalyst.
  • the best conditions for diol formation from the lactone are lower temperatures (-220 °C) and high pressures ( ⁇ 1 x 10? Pa), both of which conditions minimize the production of furan by-product.
  • Furans can be formed by a ring closure reaction of the diol product. Generally any furan by-product should be present in an amount below 5% of the desired diol, preferably below 2%, most preferably below 1.5% or even below 1% by weight of the desired diol.
  • the tendency for such furans to form is greater at higher reaction temperatures and can be promoted by the transition-metal containing catalysts employed in the reduction step.
  • the formation of furans may therefore be minimzed by the use of lower reaction temperatures and by designing the process such that once formed the diol is removed from the catalytic environment.
  • the latter objective is met by the use of a continuous process whereby the reactants contact a high level of catalyst for a relatively short time and are then removed from the catalytic environment. By optimization of the time of contact with the catalyst the formation of the desired diol is maximized and that of the furan by-product minimized.
  • the diol may optionally be alkoxylated prior to the sulfation step, such that alkoxylated disulfate cleaning agents are obtained as the final product.
  • the sulfation step may be carried out using any of the sulfation steps known in the art, including for example those described in US-A-3,634,269, US-A- 3,959,334 and US-A-4,000,081.
  • the sulfation may be carried out in two stages where the first stage involves treatment of the diol with a sulfation agent, generally selected from the group consisting of chlorosulfonic acid, sulfur trioxide, adducts of sulfur trioxide with amines and any mixtures thereof.
  • the second stage involves neutralization, which is generally carried out using NaOH.
  • the reactor utilized was an electrically heated 500 ml (39 mm internal diameter x 432 mm internal length) Autoclave Engineers type 316 (tradename) stainless steel rocking autoclave fitted with an internal thermocouple and valving for periodic sampling of reaction mixtures.
  • the reactor was charged with 50 ml of alcohol solvent and 5 grams of copper chromite catalyst, as sold by Engelhardt under the tradename CU- 1885P, that had been washed several times with high purity water then several times with alcohol solvent.
  • the reactor and contents were then heated to 250°C at a hydrogen pressure of 2.4 x 10 6 Pa and held for 1 hour.
  • the reactor was then cooled and charged (without exposing the catalyst to air) with 20 grams of the cyclic anhydride starting material and an additional 50 ml of alcohol solvent.
  • the process was carried out under different conditions of pressure and temperature, and with varying reaction times. Details of the different reaction conditions and of the yields obtained are summarized in the table below:
  • the sulfation step was carried out, in each case, on the 1 ,4-alkyl diol product obtained from the reduction step. Chlorosulfonic acid was used which resulted in a high yield (typically > 90%) of the required C-14 alkyl 1 ,4 disulfate end-product as shown below:
  • R a heptyl group
  • Example Set I The method steps of Example Set I are followed to give the 1 ,4 alkyl diol. This is then treated with an excess of ethylene oxide to give the ethoxylated diol. The sulfation step of Example Set I is then repeated to give a C14 alkyl-1 ,4-ethoxylate disulfate end-product.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Cette invention concerne un procédé de synthèse d'un agent de nettoyage disulfaté, lequel est obtenu à partir d'un anhydride cyclique substitué, et plus particulièrement, à partir d'un anhydride succinique substitué qui possède un ou plusieurs substituants de chaîne de carbone, cette dernière contenant au moins 5 atomes de carbone. Ce procédé comprend les étapes suivantes: (i) réduire l'anhydride cyclique substitué de manière à obtenir un diol; (ii) éventuellement alcoxyler le diol de manière à obtenir un diol alcoxylé; et (iii) sulfater le diol de manière à obtenir un disulfate. L'étape de réduction consiste à effectuer une hydrogénation en présence d'un catalyseur d'hydrogénation contenant un métal de transition, ladite hydrogénation étant effectuée sous pression.
EP97901911A 1996-01-31 1997-01-06 Synthese d'agents de nettoyage anioniques Withdrawn EP0888295A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9601880 1996-01-31
GB9601880A GB2310206A (en) 1996-01-31 1996-01-31 Disulfated cleaning agent synthesis
PCT/US1997/000082 WO1997028119A1 (fr) 1996-01-31 1997-01-06 Synthese d'agents de nettoyage anioniques

Publications (2)

Publication Number Publication Date
EP0888295A1 true EP0888295A1 (fr) 1999-01-07
EP0888295A4 EP0888295A4 (fr) 2000-12-06

Family

ID=10787827

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97901911A Withdrawn EP0888295A4 (fr) 1996-01-31 1997-01-06 Synthese d'agents de nettoyage anioniques

Country Status (8)

Country Link
EP (1) EP0888295A4 (fr)
JP (1) JPH11503485A (fr)
CN (1) CN1214040A (fr)
AR (1) AR005605A1 (fr)
BR (1) BR9707225A (fr)
GB (1) GB2310206A (fr)
MX (1) MX9806220A (fr)
WO (1) WO1997028119A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0143634A2 (fr) * 1983-11-29 1985-06-05 DAVY McKEE (LONDON) LIMITED Procédépour la préparation de butane-1,4-diol
EP0373946A1 (fr) * 1988-12-14 1990-06-20 Tonen Corporation Procédé de préparation de butanediol-1,4

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634269A (en) * 1969-01-10 1972-01-11 Chevron Res Hydrocarbyl butanediol disulfate phosphate-free detergent compositions
US4000081A (en) * 1969-01-10 1976-12-28 Chevron Research Company Lime soap dispersant compounds
US3860625A (en) * 1969-02-10 1975-01-14 Chevron Res Ethoxylated hydrocarbyl butanediols and their disulfate derivatives as phosphate-free compositions
DE2605107C3 (de) * 1976-02-10 1983-12-29 Chemische Werke Hüls AG, 4370 Marl Verfahren zur Herstellung von Diolen durch katalytische Hydrierung der entsprechenden Dicarbonsäuren

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0143634A2 (fr) * 1983-11-29 1985-06-05 DAVY McKEE (LONDON) LIMITED Procédépour la préparation de butane-1,4-diol
EP0373946A1 (fr) * 1988-12-14 1990-06-20 Tonen Corporation Procédé de préparation de butanediol-1,4

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9728119A1 *

Also Published As

Publication number Publication date
MX9806220A (es) 1998-10-31
GB2310206A (en) 1997-08-20
GB9601880D0 (en) 1996-04-03
EP0888295A4 (fr) 2000-12-06
CN1214040A (zh) 1999-04-14
AR005605A1 (es) 1999-06-23
WO1997028119A1 (fr) 1997-08-07
BR9707225A (pt) 1999-07-20
JPH11503485A (ja) 1999-03-26

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