DE739299C - Process for the preparation of aryl ether esters of polyhydric alcohols - Google Patents

Description

Process for the preparation of aryl ether esters of polyhydric alcohols The products of the present process are obtained by partially @ Polyhydric alcohols etherified with phenols or phenol derivatives in whole or in part esterified with various types of fatty acids. The esterification is useful here made by heating the components.

As a phenolic component of the ethers with polyhydric alcohols, the various phenols or phenol derivatives, such as phenol itself, cresols or cresol mixtures, Resorcinol or naphthols or aminophenols, halogenated phenols and the like come, in which case it is expedient to also choose those substituents which reduce the surface tension have a beneficial effect in water. The most varied of alcohol components are used polyhydric alcohols or their derivatives with the exception of sugar and cellulose. Those formed during the esterification of such phenolic ether alcohols with fatty acids Products are very easy to emulsify and, in particular, also show a very high level of emulsification Detergency when appropriately emulsified. Particularly noteworthy is their effect on esterified or etherified celluloses (Artificial silk), for which such products are excellent as washing, Softening, sizing, rinsing and matting agents are suitable.

There are several in the phenolic ether alcohol used Containing hydroxyl groups, these can also only partially be esterified, with you get products that have special properties. You own in particular an increased emulsifying power. If one makes the phenolic ether alcohols from halohydrins here, the halogen can only be partially converted and is then obtained during the esterification halogenated compounds.

But you can also use the halogen not required for phenol ether formation utilize by reaction with fatty acid salts for the production of the esters, whereby so the heat esterification can possibly come to an end. In the same way can can also be done by replacing hydroxyl groups in a known manner Ethers of polyhydric alcohols using halogen are a prerequisite for create a phenol ether or ester formation by reacting with fatty acid salts.

The fatty acids come from oils, fats and waxes (also montan wax) produced high molecular weight carboxylic acids or their derivatives or corresponding Acids, such as naphthenic acid, or mixtures of these products in question. But you can also partially still low molecular weight fatty acids or any other organic Use acids or their derivatives and thereby the properties of the products change in various ways.

The various products obtained by the present process can be used alone or in a mixture with other substances when treating textiles with neutral, acidic or alkaline liquids (for carbonizing, milling, Sizing, dyeing, cupping, melting, finishing, washing, cleaning, emulsifying etc.), also in the leather, paper and metal industries, in the manufacture of Color pastes, pharmaceutical and cosmetic products.

It has already been proposed to use monophenyl ether of ethanediol-i, 2 or propanediol-i, 3 with monobasic acids for the production of fragrances to esterify. This method is relatively low molecular weight to the use Acids such as B. propionic acid or benzoic acid, bound, resulting in products, which are not suitable for textile purposes of this type. The one at hand Process, however, have underlying products on the basis of fatty acids does not have any odor that is in any way suitable for fragrance purposes, are against it for textile purposes, of excellent suitability.

Suggestions have also been made for O-alkylated products to use. In contrast, the arylated products obtained by the present process offer Process materials have significant technical advantages.

The process is explained in more detail in the following examples, without so that, however, the possible reactions should be presented in an exhaustive manner. Example i The diphenyl ether of glycerol (24 parts per cent) is esterified with the corresponding one Amount of olein (27o parts) by heating at about 240 ° for several hours.

EXAMPLE 2 By prolonged heating of 1 mole of the resorcinol dioxäthyläthers, CO H, 1 (O # CH. # CH, # OH) "which can easily be obtained by reacting resorcinol with ethylene chlorohydrin in an alkaline medium, with 1 mole of oleic acid, expediently The esterification is brought about in an indifferent atmosphere. Instead of resorcinol, other polyhydric phenols or partially etherified products, such as guaiacol, and in place of oleic acid, other acids mentioned in the description can also be used. Example 3 Glycerin, In which one hydroxyl group is etherified with the butyl radical and a second with the cresyl radical, it is esterified by heating with an equimolecular amount of oleic acid. Instead of butyl-o-cresylglycerol, other mixed ethers can be used. The oleic acid can be mixed with other ethers Example 4 344 parts of the di-ß-naplithol ether of glycerol are heated with 270 parts of oleic acid to about 250 ° for about 6 hours, expediently in a K carbon dioxide atmosphere, with an almost complete esterification being achieved. The acid number is about 7. You can also clean it by heating with twice the amount of fuel; when it cools down, a fairly pure product is deposited. EXAMPLE 5 266 parts of the mono-p-phenolsulfonic acid ether of glycerol dichlorohydrin, which can be obtained by reacting 1 mole of glycerol dichlorohydrin with 1 mole of p-phenolsulfonic acid in alkaline solution, are dissolved in the form of the potassium salt in fuel, whereupon 32o parts of potassium ricinoleate are obtained is added and refluxed until the esterification is complete. A clear water-soluble product is obtained which is expediently freed from the precipitated salt by filtration and from the solvent by evaporation. This product shows good water solubility, high resistance and remarkable foaming and cleaning properties. EXAMPLE 6 The procedure is as in Example 5, but the equivalent amount of β-naphthol-6-sulfonic acid ether is used in place of the p-phenol sulfonic acid ether. Instead of fuel, other suitable solvents, such as ethylene glycol monomethyl ether, can also be used, and the reaction time can also be shortened by heating with pressure. Other fatty acids can be used in place of ricinoleic acid. The product obtained is a thick paste which is readily water-soluble and stable. Example 7 160 parts of di-p-chloro-m-cresylglycerol are heated with 130 parts of olein to temperatures of about 220 ° for a prolonged period. Unbound fractions can be removed by reprecipitation with fuel. EXAMPLE 8 170 parts of the monophenyl ether of glycerol monochlorohydrin are reacted in an alcoholic solution with 300 parts of ricinoleic acid and 56 parts of potassium hydroxide by prolonged heating. The ether and ester formation can also be brought about in one reaction by starting from glycerol dichlorohydrin and mixing the molecular amounts of phenol, ricinoleic acid and the corresponding amount of potassium hydroxide. After the esterification has taken place, the precipitated salt is filtered off and evaporated. This is followed by heating with an excess of acetic anhydride, the alcoholic groups being blocked. The excess anhydride and acetic acid are removed by distillation. EXAMPLE 9 122 parts of the diphenyl ether of glycerol are heated with 175 parts of technical grade chlorodioxystearic acid for a few hours to 160 ° to 50 °, with rapid esterification. EXAMPLE IO 131 parts of the dixylenol ether of glycerol are heated to 200 ° with 100 parts of coconut oil fatty acid until esterification is complete. Example ii I86 parts of the phenol ether of glycerol monochlorohydrin, Cr, -H.5-0-CH ', -CH-OH-CH, -Cl, are mixed with 300 parts of castor oil fatty acid and 56 parts of potassium hydroxide, in fuel solution until complete esterification on Heated to reflux. After filtering off, the reaction product is evaporated. Example 12 136 parts of the dicresyl ether of glycerol are esterified with 1q.o parts of stearic acid by heating at about 250 ° for several hours. EXAMPLE 13 140 parts of di-o-cresylglycerol ether are heated to about 130 ° with 100 parts of coconut oil fatty acid while passing through hydrogen chloride until complete esterification has taken place. The product obtained can advantageously be used in the form of an emulsion with soap or other known emulsifiers, e.g. B. for finishing acetate silk.

Claims (1)

PATENT CLAIM: Process for the production of aryl ether esters of polyvalent Alcohols, characterized in that one is partly with phenols or their substitution products or mixtures thereof, etherified polyhydric alcohols or their derivatives with Except for sugar and cellulose, wholly or partially with from oils, fats or Fatty acids obtained from waxes or their derivatives or corresponding acids or Mixtures of these products, possibly with the addition of other organic acids, esterified.