EP0233193A1 - 2-benzylalcanol-1-polyglycolether et leur procede de fabrication - Google Patents

2-benzylalcanol-1-polyglycolether et leur procede de fabrication

Info

Publication number
EP0233193A1
EP0233193A1 EP86903353A EP86903353A EP0233193A1 EP 0233193 A1 EP0233193 A1 EP 0233193A1 EP 86903353 A EP86903353 A EP 86903353A EP 86903353 A EP86903353 A EP 86903353A EP 0233193 A1 EP0233193 A1 EP 0233193A1
Authority
EP
European Patent Office
Prior art keywords
formula
benzyl alcohol
compounds
mol
atoms
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Withdrawn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
EP86903353A
Other languages
German (de)
English (en)
Inventor
Horst-Jürgen KRAUSE
Andreas Syldatk
Eric Sung
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0233193A1 publication Critical patent/EP0233193A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
    • C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents

Definitions

  • the invention relates to the new class of compounds of 2-benzylalkanol-1-polyglycol ethers and a process for their preparation and their use as surface-active compounds.
  • 2-Benzylalkonole- (1) have long been known. They were obtained from P. ASTAGLI, “Comptes Rendus", 20 * 1 (1937), pages 1656-1658 by mixed aldol condensation of aldehydes with benzyl alcohol and subsequent hydrogenation.
  • C. WEIZMANN "Che istry and Industry", 1937, pages 587-591 and EF PRATT, "Journal of the American Chemical Society", 7_6 (1954), pages 52-56 describe the preparation of 2-benzylalkanols from benzyl alcohol and alcohols with a maximum of 7 carbon atoms by means of the CUERBET reaction. The production of corresponding CUERBET alcohols from alkanols with more than 6 carbon atoms in this way has not yet been described.
  • the invention accordingly relates to 2-benzylalkanol-1-polyglycol ethers of the general formula I
  • R is an alkyl radical with 6-23 C atoms
  • R is an alkylene radical with 2-6 C atoms
  • n are integers from 1 to 100.
  • R preferably represents an alkyl radical with 8-18 C atoms.
  • R preferably represents an ethylene group or propylene
  • R - O stands for an ethylene glycol ether group (EO) and / or a propylene glycol ether group (PO).
  • EO ethylene glycol ether group
  • PO propylene glycol ether group
  • n is preferably 2-50 and in particular 3-30.
  • the connections are made in a first Step by heating a mixture of alkanol and benzyl alcohol to temperatures of 150 to 280 C in the presence of an alkali metal alkali metal compound (mixed GUERBET reaction).
  • an alkali metal alkali metal compound mixed GUERBET reaction.
  • the benzyl alcohol is expediently used in excess. This excess can be up to 10 times molar, preferably it is 2 times to 3 times molar.
  • Suitable alkaline catalysts are the hydroxides, carbonates, borates, silicates and phosphates of potassium or sodium, as well as those alkali metal compounds which react with the water of reaction formed to form the hydroxides, e.g. B. Alcoholates, oxides, amides and hydrides. Potassium hydroxide is preferably used in proportions of 0.1 to 0.25 mol%, based on the alkanol used.
  • the yield can be increased significantly if hydrogenation or dehydrogenation catalysts are also present in finely divided form.
  • hydrogenation or dehydrogenation catalysts are also present in finely divided form.
  • metals of the subgroups I and VI I I of the periodic system of the elements such as Cu, Fe, Ni, Co, Pt and Pd and mixed catalysts, and also salts of Fe, Zn, Co, Mn and Cr. Cn, Ni and platinum metals and their alloys have proven to be particularly suitable.
  • the addition of these dehydrogenation catalysts can be 0.1 to 5% by weight, preferably 0.2 to 2% by weight, based on the reaction mixture.
  • the GUERBET reaction takes place at temperatures between 150 to 280 ° C, preferably between 180 to 250 ° C.
  • temperatures above the boiling point of the alcohols octanol 194 °, decanol 229 °, benzyl alcohol 205 °
  • the water formed in the reaction is expediently removed from the reaction mixture, for example by distillation, the alcohol serving as entrainer.
  • the distilled azeotrope is dewatered before being returned to the reaction mixture, water-removing agents being expediently added because of the small difference in density between benzyl alcohol and water.
  • Suitable dehydrating agents are e.g. B. crystal water-binding salts and concentrated solutions of these salts solutions of these salts, such as sodium sulfate.
  • the reaction material generally contains, in addition to unreacted starting material, in particular excess benzyl alcohol, also aliphatic GUERBET alcohols which are formed by self-condensation of the alkanols with one another.
  • the 2-benzylalkanols (1) are isolated from this mixture by fractional distillation. In the cases in which the aliphatic GUERBET alcohols present do not interfere and their alkoxylates can be used in the form, it is sufficient if the excess benzyl alcohol and other by-products are separated off.
  • the main by-product is alkali metal salts of acids, in particular potassium benzoate, which is formed by dehydrogenation of the benzyl alcohol.
  • alkali metal salts of acids in particular potassium benzoate, which is formed by dehydrogenation of the benzyl alcohol.
  • 2-benzylalkanol (1) formed is reacted in a manner known per se with alkylene oxides to give the corresponding polyglycol ethers.
  • alkylene oxides Ethylene oxide and propylene oxide, butylene oxide and mixtures thereof in question.
  • the alkylene oxides can also be used in different orders, i. H . the 2-benzylalkanols are first reacted with ethylene oxide and then with propylene oxide or optionally butylene oxide. The reverse order is also possible and also leads to usable products.
  • alkylene oxide mixtures a statistical distribution of the glycol ether groups results.
  • the alkoxylation takes place at temperatures from 60 to 240 ° C., preferably 80 to 200 ° C. in the presence of acidic or alkaline catalysts, it being advantageous to work in a pressure vessel.
  • Acidic catalysts are, for example, LEWIS acids, such as boron trifluoride or aluminum chloride.
  • Alkaline catalysts such as the alcoholates, hydroxides, oxides, carbonates, amides and hydrides of alkali or alkaline earth metals, are preferred. Their amount is generally 0.1 to 0.8, preferably 0.2 to 0.6, mol per mol of benzylalkanol used.
  • the alkylene oxide is introduced into the reaction gas in gaseous form with vigorous stirring. After the reaction has ended, the catalyst can be inactivated by neutralization and the salt formed can be separated off mechanically.
  • the 2-benzylalkanol-1 polyglycol ethers according to the invention are water-soluble or oil-soluble surface-active substances which can be used as wetting, dispersing and emulsifying agents or as nonionic detergent active substances (surfactants).
  • 2-Benzylalkanols with a chain length of 8 to 20 carbon atoms and 3 to 20 EO groups are particularly suitable for use in detergents and cleaning agents.
  • Corresponding compounds with 5 to 30 EO groups, which additionally have 2 to 30 terminal PO groups, are distinguished by very little foaming. The means are regarding their Cleaning power superior to many known nonionic agents, in particular to the polyglycol ethers derived from fatty alcohols or oxo alcohols.
  • the product obtained was fractionally distilled through a fractionation column.
  • the 2-benzyldodecanol- (1) boiling at a pressure of 0.95 mb (millibar) at 178 ° C. was isolated.
  • the yield was 632 g (74% of theory).
  • the residue and a proportion of 3% by weight in the distillate consisted of 2-decyltetradecanol- (1).
  • the distillate obtained at 116 ° C./0.109 mb (0.08 Torr) in an amount of 1044 g consisted of 85% by weight of 2-benzyl-octanol (1) and 15% by weight. from 2-hexyldecanol- (1). Because of the very close together! Due to the boiling points of the two alcohols, no further fractionation was carried out.
  • n-octanol and n-decanol with a molecular weight (MW) of 141.1 was used as the starting material.
  • 1128.8 g (8 mol) of this mixture together with 1729.6 g (16 mol) of benzyl alcohol, 90.3 g of potassium hydroxide and 28.6 g of nickel catalyst were boiled over the course of 6 hours (195 to 178 ° C) heated and the water separated from the distillate.
  • the work-up was carried out as described under D).
  • Butyl diglycol-water mixture (according to DIN 53917, 6.2) determined T Trrüübbuunnggssppuunnkktt bbeettrrääggtt 6688 ,, 55 C. The average degree of ethoxylation is 8.5.
  • 2-benzyltetra-decanol-13 EO was produced with an OH of 67.8 (theoretically 63.0) and a cloud point of 72.degree.
  • the foaming test was carried out according to the “perforated disc impact method” according to DIN 53902 (sheet 2) in water of 16 dH (160 mg CaO per liter) at 30 ° C. Mixtures of 1 part by weight of the respective surfactant and 3 g of sodium sulfate were used in increasing concentration. The foam height (in mm) is shown in Table 4. Table 4
  • the foaming rate is in the range between the two comparison substances, i. H. it is comparatively small and does not lead to malfunctions when used.
  • the surfactants according to the invention are distinguished, in particular in the higher concentration range, by good to superior washing properties.
  • the washing drum was filled with 4.2 g of test fabric and 4.2 g of clean filler fabric (cotton) and 10 steel balls.
  • the washing time was 15 minutes each. It was then rinsed 3 times with tap water (16 ° dH).
  • the evaluation was carried out photometrically.
  • the Results are summarized in Table 6. They are significantly improved compared to the comparison product, particularly in the 60 wash range.
  • the compounds prepared according to Examples 1 to 26 meet the requirements of the RVO of the Detergent Act. After 19 days, the BiAS decrease was 99%.

Landscapes

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

Abstract

Produits d'alcoxylation de 2-benzylalcanol de formule (I) où R1 représente des radicaux alkyle contenant de 6 à 22 atomes de C, R2 représente un radical alcène contenant de 2 à 6 atomes de C, et n des nombres entiers de 1 à 100. Des composés préférés sont les éthoxylates et proposcylates de 2-benzylalcanols avec n compris entre 2 et 50. Leur fabrication s'effectue par chauffage de mélanges d'une mole d'un alcool de formule R1-CH2-CH2OH avec 1 et 10 moles, de préférence entre 1 et 3 moles d'alcool benzylique en présence de composés de métaux alcalins et éventuellement de catalyseurs d'hydrogénation à des températures comprises entre 180o et 250oC (réaction de Guerbet ), séparation de l'alcool benzylique en excès et alcoxylation de l'alcool de Guerbet obtenu. Les composés s'utilisent avantageusement comme agents mouillants, dispersants, émulsifiants et détersifs.
EP86903353A 1985-06-05 1986-05-28 2-benzylalcanol-1-polyglycolether et leur procede de fabrication Withdrawn EP0233193A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3520185 1985-06-05
DE19853520185 DE3520185A1 (de) 1985-06-05 1985-06-05 2-benzylalkanol-1-polyglykolether sowie verfahren zu ihrer herstellung

Publications (1)

Publication Number Publication Date
EP0233193A1 true EP0233193A1 (fr) 1987-08-26

Family

ID=6272523

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86903353A Withdrawn EP0233193A1 (fr) 1985-06-05 1986-05-28 2-benzylalcanol-1-polyglycolether et leur procede de fabrication

Country Status (4)

Country Link
US (1) US4648984A (fr)
EP (1) EP0233193A1 (fr)
DE (1) DE3520185A1 (fr)
WO (1) WO1986007352A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3530405A1 (de) * 1985-08-26 1987-02-26 Henkel Kgaa Verwendung von 2-alkylalkanol-1-polyglykolethern
US4952315A (en) * 1987-05-05 1990-08-28 Nabil Saab Method, system and emulsifier substance for treatment of materials containing harmful substances
US4894173A (en) * 1988-06-08 1990-01-16 The Standard Oil Company Divalent ion tolerant aromatic sulfonates
US4836283A (en) * 1988-06-08 1989-06-06 The Standard Oil Company Divalent ion tolerant aromatic sulfonates
DE3830019A1 (de) * 1988-09-03 1990-03-15 Basf Ag Verfahren zur herstellung von 3-aryl-isobutylalkoholen
US5232628A (en) * 1989-09-27 1993-08-03 Ciba-Geigy Corporation Polyadducts of alkylene oxide and styrene oxide with aryl alkanols
DE4416303A1 (de) * 1994-05-09 1995-11-16 Bayer Ag Schaumarmes Netzmittel und seine Verwendung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2620360A (en) * 1952-12-02 Manufacture of glycol ethers
FR1302430A (fr) * 1960-05-10 1962-08-31 Exxon Research Engineering Co Produits d'addition de l'oxyde d'éthylène et d'alcools supérieurs et leurs sulfates
US4517128A (en) * 1982-08-31 1985-05-14 Mobil Oil Corporation Two-tailed surfactants having one aromatic containing tail and their use in chemical waterflooding

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8607352A1 *

Also Published As

Publication number Publication date
US4648984A (en) 1987-03-10
DE3520185A1 (de) 1986-12-11
WO1986007352A1 (fr) 1986-12-18

Similar Documents

Publication Publication Date Title
EP1501775B9 (fr) Melanges d'alkoxylate et lessives les contenant
WO2010070088A1 (fr) Mélange de tensioactifs contenant des composants ramifiés à chaîne courte et des composants ramifiés à chaîne longue
DE69730682T2 (de) Zusammensetzungen von höheren Sekundäralkoholalkoxylaten, Verfahren zu ihrer Herstellung und diese enthaltende Waschmittel und Emulgatoren
EP0231890A2 (fr) Méthode pour la purification d'alkylglycosides, les produits ainsi obtenus et leur utilisation
DE2643699B2 (de) Granulierte oder pulvrige Reinigungsmittelmischung
EP0233193A1 (fr) 2-benzylalcanol-1-polyglycolether et leur procede de fabrication
DE3018135A1 (de) Verfahren zur herstellung von polyglykolethermischformalen und neue polyglykolethermischformale
DE4439086C2 (de) Verfahren zur Herstellung von endgruppenverschlossenen nichtionischen Tensiden
EP0224523B1 (fr) Esters partiels de 2-benzylalcanols-(1) et de 2-benzylalcanol-1-polyglycol-ethers ainsi que leur procede de fabrication
WO1990005127A1 (fr) Melanges d'alcools gras et leurs ethoxylates a comportement a froid ameliore
DE19500842C2 (de) Verfahren zur Herstellung von endgruppenverschlossenen nichtionischen Tensiden
DE1519545B2 (de) Oberflächenaktive Verbindung
DE19738108A1 (de) Kältestabile Fettalkoholalkoxylate
EP0036550B2 (fr) Utilisation d'alcools gras oxyalkylés comprenant un groupe propylène terminal, comme tensides pauvres en mousse, résistant aux acides et aux alcalis
DE69830486T2 (de) Aluminiumverbindungen und deren verwendung
DE4127231A1 (de) Neue alkyletherglycoside
DE3416289C2 (fr)
EP0615521B1 (fr) Alkyl- et/ou alkenyloligoglucoside-isethionates
DE4014736A1 (de) Verfahren zur herstellung von guerbetalkoholen
DE3923562A1 (de) Verfahren zur herstellung von alkylenoxid- und dioxan-1,4-armen nicht-ionogenen tensiden mittels alkalimetallalkoholat als katalysator
EP0433309A1 (fr) Utilisation d'acetylacetonates metalliques comme catalyseurs pour l'ethoxylation ou la propoxylation
DE3243691A1 (de) Textil-bearbeitungsoele
EP0577637A1 (fr) Procede ameliore de preparation de composes tensio-actifs non ioniques.
DE2853064A1 (de) Verfahren zur herstellung von oxalkylierungsprodukten
DE4333101A1 (de) Verfahren zur Herstellung nichtionischer Tensidgemische

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE

17P Request for examination filed

Effective date: 19870302

17Q First examination report despatched

Effective date: 19880415

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19900605

R18W Application withdrawn (corrected)

Effective date: 19900605

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KRAUSE, HORST-JUERGEN

Inventor name: SUNG, ERIC

Inventor name: SYLDATK, ANDREAS