EP0088895B1 - Synthetische flüssige Wachsester - Google Patents

Synthetische flüssige Wachsester Download PDF

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Publication number
EP0088895B1
EP0088895B1 EP83101381A EP83101381A EP0088895B1 EP 0088895 B1 EP0088895 B1 EP 0088895B1 EP 83101381 A EP83101381 A EP 83101381A EP 83101381 A EP83101381 A EP 83101381A EP 0088895 B1 EP0088895 B1 EP 0088895B1
Authority
EP
European Patent Office
Prior art keywords
unsaturated
fatty acids
fatty alcohols
fatty
alcohols
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.)
Expired
Application number
EP83101381A
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German (de)
English (en)
French (fr)
Other versions
EP0088895A3 (en
EP0088895A2 (de
Inventor
Hans Leo Dr. Hülsmannn
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.)
Huels Troisdorf AG
Original Assignee
Huels Troisdorf AG
Dynamit Nobel AG
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.)
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Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6158005&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0088895(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Huels Troisdorf AG, Dynamit Nobel AG filed Critical Huels Troisdorf AG
Priority to AT83101381T priority Critical patent/ATE25663T1/de
Publication of EP0088895A2 publication Critical patent/EP0088895A2/de
Publication of EP0088895A3 publication Critical patent/EP0088895A3/de
Application granted granted Critical
Publication of EP0088895B1 publication Critical patent/EP0088895B1/de
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom

Definitions

  • the invention relates to synthetic liquid wax esters of the jojoba oil type based on long-chain alkenols and alkenoic acids, which are free of glycerol and / or glycerol derivatives.
  • Jojoba oil is obtained from the fruits of various desert plants from the family of jojoba, which u. a. are native to California and Mexico.
  • Jojoba oil is not a fatty oil in the traditional sense, i.e. not an ester of glycerin with fatty acids, but the chemical structure of a liquid wax from esters of monounsaturated straight-chain alcohols and acids with chain length maxima at 20 to 22 carbon atoms.
  • jojoba oil The properties of jojoba oil are unusual and very different from those of fatty oils; despite the unsaturated bond in both ester components, the oil does not become rancid; the decomposition point is about 300 ° C; the oil can be kept unchanged for many years; the tolerance on the skin and when administered internally is very good, and the oil is not digestible.
  • the task was to produce a substitute for natural jojoba oil from raw materials which are readily available in sufficient quantities and which has the demanding property profile of the natural product.
  • the liquid wax esters contain in the component of the unsaturated alcohols, apart from impurities that are present at random, monounsaturated straight-chain primary alcohols, which are produced industrially by high-pressure hydrogenation of unsaturated fatty acids.
  • a content of octadecen-1-oi should always be present, although the content of the other primary alcohols and the position of the double bond can vary depending on the starting materials used in the hydrogenation.
  • Contents of the C14, C16 and C20 alcohols (tetradecen-1-ol, hexadecen-l-ol and eicosen-1-ol) are also preferably present, very preferably the C14 alcohols in amounts of 2 to 15% and the C16 alcohols in amounts of 2 to 40%.
  • the component of the unsaturated carboxylic acids can only consist of straight-chain monocarboxylic acids of component a 1 or additionally from the acids of components a 2 and / or a 3 .
  • the monounsaturated C22 ⁇ acid (docosenoic acid) should always be present, whereby isomers with the position of the double bond occur at different points, among which the 13-cis-docosenoic acid (13c-C22: 1), ie the eruic acid, is more important Is part of.
  • the monounsaturated C20 fatty acids 9-cis-eicosenoic acid (9c-C20: 1) and in the unsaturated C18 fatty acids 9-cis-octadecenoic acid (9c-C18 1) is the most common component.
  • component a As well as components a 2 and a 3, are used in particular to adjust and vary important properties such as the iodine number, the viscosity or the cloud points.
  • 9cis, 12cis-octadecadienoic acid (9c, 12c-C18: 2) can be used as di-unsaturated C18 fatty acid and as triple unsaturated acid 9cis, 12cis, 15cis-octadecatrienoic acid (9c, 12c, 15c-C18: 3), but their isomers also serve with a different position of the double bonds.
  • impurities especially saturated alcohols and saturated carboxylic acids, in amounts of up to about 3% by weight are often unavoidable, but are harmless.
  • Component a 2 can be present in amounts of 0 to 25% of C21 dicarboxylic acids, which are formed by addition of Diels-Alder from acrylic acid to the conjugated double bond, in particular linoleic acid.
  • the main components of the addition products are the 6-carboxy-4-hexyl-2-cyclohexenoctanoic acid-1 of the formula and the 5-carboxy-4-hexyl-2-cyclohexene-octenoic acid-1 of the formula (BF Ward et al: J. Am. Oil Chem. Soc. Vol 52, no. 7 (1975) p. 219-224).
  • component a 3 the so-called «dimeric fatty acids •, namely those according to e.g.
  • BEH Pryde Fatty Acids, Copyright 1979 by the American Oil Chemists Society may contain condensation products of fatty acids resulting from alkaline catalytic treatment of certain fatty acids.
  • the main components are acyclic, monocyclic and bicyclic acids of the types in addition to which other components, including small portions of trimerization products and unchanged and isomerized fatty acids are contained.
  • the synthetic liquid wax esters are preferably neutral esters with a low acid number in the range from 0 to 5 and a low hydroxyl number in the range from 0 to 10.
  • esters with contents of carboxyl or hydroxyl groups can also be prepared by slight deviation from the equivalence of the carboxyl groups and the hydroxyl groups in components a) and b).
  • the synthetic liquid wax esters are prepared by esterifying mixtures of acids of component a) with mixtures of components b) according to a procedure known per se.
  • Components a) and b) can be used in equivalent amounts, based on the content of carboxyl and hydroxyl groups, or initially have an excess of one component in order to accelerate the esterification.
  • Non-esterified starting materials can according to the The reaction is distilled off or removed by refining with acids or bases, or remains in the product as acetyl derivatives through the reaction mentioned with acetic anhydride.
  • esterification catalysts preferably zinc salts, such as zinc acetate, or organic titanium acid derivatives, such as tetrabutyl titanate, are used as catalysts in amounts of 0.05 to 2% by weight, based on the weight of the starting materials.
  • the reaction is carried out at temperatures in the range from 120 to 200 ° C., preferably at 140 to 160 ° C., with the exclusion of oxygen, preferably in a nitrogen atmosphere.
  • An entrainer for example xylene, can be added to accelerate the removal of the water of reaction. After the calculated amount of water has been separated off, any entrainer added and non-esterified starting materials, insofar as neutral esters are produced, are removed and refined, deodorized, bleached and dried in the customary manner.
  • the synthetic wax esters surprisingly agree with the demanding property profile, which is unique among the esters occurring in nature, despite their differing chemical composition to the extent that they can be mixed up with matched product batches, and surpass the natural product in essential and characteristic properties. Advantages result in particular from the high iodine number, low peroxide number, low viscosity and low cloud points. It should be particularly emphasized that the products according to the invention do not become rancid, are very well tolerated by the skin and have skin-care properties, and are so non-toxic with LD50 values of over 20 g / kg that they are part of diet food - since they are difficult to digest and of low nutritional value - can serve.
  • the molecular structure is unusually stable with a temperature resistance above 300 ° C, high resistance to oxygen even at high temperatures due to very low peroxide numbers and high resistance to enzymatic attack in the presence of water or hydrolases.
  • the wax esters do not contain any hydrocarbons, steroids, sterols, free alcohols or acids or other accompanying substances which could be harmful from a physiological and toxicological point of view, for example as allergens or eczematogens.
  • the products can be completely adjusted to the characteristic properties of natural jojoba oil, or even on particularly high-quality lots, on the other hand, these property values can be varied so that the properties are more adaptable than the natural product for selected applications.
  • the natural product is surpassed especially with regard to the iodine number, a low peroxide number, low viscosity and the cloud points which are up to 10 ° C lower.
  • the wax esters according to the invention also show advantages of the cloud points which are up to 10 ° C lower.
  • the products according to the invention can therefore replace natural jojoba oil in all preparations and also natural sperm oil, which has the advantage of being free from lipids.
  • the liquid wax esters can be, for example, basic or auxiliary substances in cosmetic formulations, such as creams, lotions, skin and hair oils, shampoos, sunscreens, lipsticks, deodorants and soaps, for dietetic preparations and also vehicles in pharmaceutical preparations. They can be processed together with the vegetable, animal and synthetic oils, fats and waxes, for example to very stable W / O or O / W emulsions. They have an excellent lubrication behavior and are therefore to be used as such or as components of alloyed lubricant systems. They can also be chemically modified in a variety of ways and converted into valuable follow-up products for technical applications, for example in machining, pressing or rolling processing. Waxes of semi-solid to solid consistency can be produced by hydrogenation, by adding sulfur high pressure lubricants, by epoxidation, chlorination or isomerization, intermediate products of various types can be produced.
  • antioxidants such as 2 (3) tert-butyl-4-hydroxyanisole or toluene TBHA or BHT can be redeemed in amounts of 0 to 1% by weight.
  • Products stabilized in this way are practically unchanged after 200 hours of gassing with air in a very fine stream at 90 ° C in the peroxide number, color and sensory properties.
  • Another object of the invention is the use of the products as substitutes for jojoba oil.
  • the acid mixtures are composed as follows (data in% by weight), the acids having a cis configuration and predominantly at the position indicated in the description: (See table on page 5 f.)
  • the alcohol mixtures are composed as follows (% by weight)
  • the crude ester is extracted with water, deacidified using a bicarbonate or soda solution, if necessary acetylated with an amount of acetic anhydride equivalent to the hydroxyl number of the crude ester, washed neutral with water, bleached using activated carbon and / or bleaching earth, deodorized and dried.
  • the yields of ester are approximately quantitative, based on the component used in the deficit.
  • S1 / A1 and the following compositions each mean neutral esters from the components mentioned.
  • the viscosities are in mm 2 / sec. measured. (See table on page 6 f.)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Fats And Perfumes (AREA)
  • Lubricants (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
EP83101381A 1982-03-12 1983-02-14 Synthetische flüssige Wachsester Expired EP0088895B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83101381T ATE25663T1 (de) 1982-03-12 1983-02-14 Synthetische fluessige wachsester.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3208930 1982-03-12
DE3208930A DE3208930C1 (de) 1982-03-12 1982-03-12 Synthetische fluessige Wachsester

Publications (3)

Publication Number Publication Date
EP0088895A2 EP0088895A2 (de) 1983-09-21
EP0088895A3 EP0088895A3 (en) 1985-03-27
EP0088895B1 true EP0088895B1 (de) 1987-03-04

Family

ID=6158005

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83101381A Expired EP0088895B1 (de) 1982-03-12 1983-02-14 Synthetische flüssige Wachsester

Country Status (10)

Country Link
US (1) US4510093A (es)
EP (1) EP0088895B1 (es)
JP (1) JPS58167543A (es)
AT (1) ATE25663T1 (es)
AU (1) AU561896B2 (es)
BR (1) BR8301219A (es)
CA (1) CA1215072A (es)
DE (2) DE3208930C1 (es)
DK (1) DK118183A (es)
ES (1) ES520491A0 (es)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3788661T2 (de) * 1986-02-20 1994-05-19 Procter & Gamble Kalorienarme Fettprodukte mit verbessertem Geschmack.
WO1990015127A1 (en) * 1989-06-09 1990-12-13 Ag-Seed Pty Limited Artificial jojoba oil
US5227503A (en) * 1990-02-13 1993-07-13 Chesebrough Pond's Usa Co., Division Of Conopco, Inc. Cosmetic composition
GB9003201D0 (en) * 1990-02-13 1990-04-11 Unilever Plc Cosmetic composition
DE4228594A1 (de) * 1992-08-27 1994-03-03 Maeurer & Wirtz Gmbh & Co Kg Mittel zum Reinigen und Konditionieren der Haare, der Haut sowie von Textilien und harten Oberflächen
US5959130A (en) * 1996-07-02 1999-09-28 Finetex, Inc. Castor based benzoate esters
AUPO368896A0 (en) * 1996-11-19 1996-12-12 Beku Environmental Products Ltd A lubricant composition
US6280746B1 (en) 1997-10-17 2001-08-28 International Flora Technologies Ltd. Dry emollient compositions
USRE38141E1 (en) * 1997-10-17 2003-06-10 International Flora Technologies Ltd. Dry emollient compositions
CA2249508A1 (en) * 1997-10-24 1999-04-24 Unilever Plc Wax ester compositions
US6582748B1 (en) * 1999-05-18 2003-06-24 Cargill Incorporated Fat compositions containing waxes
US8741822B2 (en) * 2011-02-13 2014-06-03 Trent University Esters for use as a base stock and in lubricant applications
US10364354B2 (en) * 2017-05-15 2019-07-30 International Flora Technologies, Ltd. Wax ester compositions and methods of manufacture

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1944887A (en) * 1931-07-03 1934-01-30 Du Pont Esters and method of preparing same
US3226406A (en) * 1963-01-03 1965-12-28 Thomas K Miwa Wax ester substitute for jojoba oil from the seed of limnanthes douglash
US4152278A (en) * 1978-05-19 1979-05-01 The United States Of America As Represented By The Secretary Of Agriculture Wax esters of vegetable oil fatty acids useful as lubricants
DE2851104A1 (de) * 1978-11-25 1980-06-12 Henkel Kgaa Backtrennoel-komponente
FR2498075B2 (fr) * 1980-01-25 1985-07-12 Oreal Solution stable a l'oxydation d'un acide gras essentiel ou d'un melange de ces acides et compositions cosmetiques la contenant
JPS5745199A (en) * 1980-09-01 1982-03-13 Nisshin Oil Mills Ltd:The Esterification product and cosmetic or external use preparation containing the same
FR2509322A1 (fr) * 1981-07-10 1983-01-14 Cirta Ct Int Rech Tech Appliqu Huile, sa preparation et son utilisation
DE3220973A1 (de) * 1981-09-24 1983-03-31 Scher Chemicals, Inc., 07012 Clifton, N J. Erucasaeureester

Also Published As

Publication number Publication date
CA1215072A (en) 1986-12-09
DK118183D0 (da) 1983-03-11
DK118183A (da) 1983-09-13
BR8301219A (pt) 1983-11-22
ES8404308A1 (es) 1984-04-16
AU1127583A (en) 1983-09-15
ES520491A0 (es) 1984-04-16
DE3208930C1 (de) 1983-10-13
EP0088895A3 (en) 1985-03-27
DE3369970D1 (en) 1987-04-09
JPS58167543A (ja) 1983-10-03
ATE25663T1 (de) 1987-03-15
EP0088895A2 (de) 1983-09-21
US4510093A (en) 1985-04-09
AU561896B2 (en) 1987-05-21

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