JPH0236585B2 - EETERUKARUBONSANENNOSEIHO - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing highly pure and high quality ether carboxylic acid salts from ether alcohols and monohalogen lower carboxylic acids.

Ether carboxylates produced from ether alcohol and monohalogenated lower carboxylic acids or their salts are useful surfactants that have the advantages of nonionic surfactants and soaps, respectively.
An industrially advantageous method for producing ether carboxylic acid salts of high purity and high quality has not yet been found. Conventionally, the following methods are known as methods for manufacturing the same.

(1) A method in which an alkali monohalogenated acetic acid salt is supplied to an alkali metal alcoholate and reacted with the alkali metal alcoholate. (US Patent No. 2183853) (2) A method of supplying monohalogenated acetic acid or its alkali salt into a mixture of alcohol and solid caustic alkali and causing the reaction. (U.S. Patent No. 2623900
(British Patent No. 793113) (3) A method in which a solid caustic alkali is supplied into a mixture of an alcohol and a monohalogenated acetic acid alkali salt to cause a reaction. (Japanese Unexamined Patent Publication No. 137924/1983) (4) A method in which an aqueous caustic alkali solution is gradually fed under reduced pressure into a mixture of an alcohol and an alkali monohalogenated acetic acid salt to cause a reaction. (Tokuko Showa 54-4932
In general, when producing ether carboxylates from ether alcohols and monohalogenated lower carboxylic acids or their salts, monohalogenated lower carboxylic acids or their salts are hydrated in the presence of caustic alkali or in the coexistence of caustic alkali and water. There are problems such as decomposition and formation of hydroxy lower carboxylic acid salts, and coloring of reaction products due to the presence of caustic alkali. However, it cannot be said that any of the above methods sufficiently overcomes these points. In other words, method (1) involves the reaction of a viscous or pasty alkali metal alcoholate with a powder of monohalogenated acetic acid alkali salt, and because the reaction rate is slow, it must be carried out at a high temperature of 100°C or higher, or it must be carried out in large excess. of ether alcohol or solvent. Furthermore, coloration occurs due to the inclusion of a small amount of air during alcoholation and carboxymethyl etherification, and the reaction must be carried out in two steps: an alcoholation step and a carboxymethyl etherification step. According to method (2), an excess of caustic alkali is always present in the reaction solution, which tends to cause coloring and also tends to cause decomposition of the monohalogenated acetic acid alkali salt. In cases of (2) and (3), solid caustic alkali is used, but if commercially available pellet or flake caustic alkali is used, the surface area of the caustic alkali cannot be increased and the reaction rate is slow. In addition, decomposition of the monohalogenated acetic acid alkali salt is likely to occur. In order to speed up the reaction rate and increase the degree of carboxymethyl etherification of the ether alcohol using this method, the caustic alkali must be ground, which is not industrially safe, or the monohalogenated acetic acid alkali salt and the caustic alkali must be used in excess. need to use. In addition, in all cases (1) to (3), workability is poor because solids of caustic alkali and/or monohalogenated acetic acid alkali salts are handled, and vigorous stirring is required to advance the reaction.
Moreover, since intense heat is generated during the reaction, the caustic alkali or monohalogenated acetic acid alkali salt must be gradually fed, but since it is a solid, special equipment is required to feed it continuously. Among the conventional methods (1) to (4), method (4) is industrially the most advantageous method. That is, a liquid aqueous caustic alkali solution can be used without using a solid caustic alkali, which is problematic in operation, and continuous supply is also easy. In addition, the intense heat generated during carboxymethyl etherification is easily removed by the latent heat of vaporization of water since dehydration is carried out in a reduced pressure system. However, this method uses a powdered monohalogenated alkali acetic acid salt, and the commercially available powdered monohalogenated alkali acetic acid salt has a large particle size and a small surface area, so the reaction rate is slow.
Moreover, hydrolysis of the monohalogenated acetic acid alkali salt is likely to occur. To speed up the reaction and increase the degree of carboxymethyl etherification of the ether alcohol, it is necessary to use vigorous stirring and excess monohalogenated acetic acid alkali salt and caustic alkali.

Therefore, the present inventors have developed an industrially advantageous method using substantially equimolar moles of raw materials from ether alcohol and monohalogenated lower carboxylic acids or their alkali salts, which are industrially advantageous, that is, have good workability. The present invention was achieved as a result of intensive research to obtain a high quality ether carboxylate with almost no coloration.

That is, the present invention relates to the general formula RO(AO) _o H [wherein R is an alkyl group or alkenyl group having an average of 8 to 24 carbon atoms, or an alkylphenyl group having an alkyl group having 6 to 16 carbon atoms, and A is an alkylene group having 2 to 4 carbon atoms or a mixed group thereof. Moreover, n is an integer of 1 to 20 on average. ] The present invention relates to a method for producing an ether carboxylate salt, which comprises supplying an aqueous caustic alkali solution under heating and reduced pressure into a mixture containing an ether alcohol represented by the formula and a monohalogen lower carboxylic acid to cause the reaction.

Ether alcohols used in the method of the present invention include, for example, octanol, decanol, dodecanol, coconut oil, palm oil, beef tallow,
Selected from the group consisting of higher alcohols derived from natural animal and vegetable oils such as whale oil, synthetic higher alcohols synthesized by the oxo method, Ziegler method, paraffin oxidation method, etc., and alkylphenols such as octylphenol, nonylphenol, and decylphenol. Addition of a desired number of moles of one or more alkylene oxides selected from the group of ethylene oxide, propylene oxide, butylene oxide, etc. to the alcohol in any proportion in blocks or randomly by a known method. I will give you what I have earned. Examples of synthetic higher alcohols that can be used as raw materials for ether alcohol include the following.

Namely, it is a random secondary alcohol obtained by liquid-phase oxidation of linear paraffin, and is sold under the trade name "Softanol" by Nippon Shokubai Chemical Co., Ltd., or by Union Carbide Corporation. "Tajitor",
"Dovanol" is a primary alcohol produced by the oxo process and containing approximately 20% alpha branched substances and sold by Shell Chemicals Limited and Shell Oil Corporation, respectively.
and "Neodol", "Acropol", manufactured by Uzingmann et c., an oxo alcohol containing about 25% alpha methyl branched material and about 10% ethyl branched material, 45-55% alkyl "Simperonics", sold by Imperial Chemicals Industries Limited, containing branched components (mostly methyl branches), a primary grade containing about 60% branched components, manufactured from olefins by Liquishimica Preferred are the oxo alcohol "Ryallus", the Ziegler primary alcohol derived from ethylene and manufactured by Conoco Condia, "Alfur", and the "Lutensols" sold by BASF. Can be used for

In addition, examples of monohalogen lower carboxylic acids used in the present invention include monochloroacetic acid, monobromoacetic acid, monochloropropionic acid,
Examples include monochlorobutyric acid and monobromopropionic acid, which can be used in solid form or as an aqueous solution. Examples of the caustic alkali aqueous solution include aqueous solutions of alkali metal hydroxides such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution, and the concentration thereof is preferably 20 to 50% by weight.

To produce an ether carboxylic acid salt by the method of the present invention, first, predetermined amounts of raw materials, ether alcohol and monohalogen lower carboxylic acid or an aqueous solution thereof, are charged into a reaction tank and mixed and dissolved. Once dissolved, the mixture containing the ether alcohol and monohalogen lower carboxylic acid is usually in a homogeneous liquid state at room temperature. Then 40~100℃
Preferably maintained in the temperature range of 50-70℃, 200mm
The water vapor pressure is maintained at a pressure of Hg or less, preferably 50 mmHg or less, and a caustic alkali aqueous solution is supplied for reaction.
As mentioned above, when producing an ether carboxylate from an ether alcohol and a monohalogen lower carboxylic acid, hydrolysis of the monohalogen lower carboxylate tends to result in the formation of a hydroxyl lower carboxylate, but this side reaction occurs only when the temperature increases. The higher the temperature and the larger the amount of water in the reaction system, the more likely it is to occur. 50~ to suppress side reactions and allow the reaction to proceed in a short time
A temperature range of 70°C is desirable, and in order to reduce the amount of water in the reaction system, it is desirable to carry out the reaction under a water vapor pressure of 50 mmHg or less. The supply time of the caustic aqueous solution is not particularly limited, but it depends on the rate of water removal from the system, that is, the water vapor pressure within the system. For example, if the water vapor pressure is 20 mmHg or less, 1
~2 hours is preferred, and in the case of approximately 50 mmHg, 4 to 6 hours is preferred. Further, the raw material molar ratio of ether alcohol and monohalogen lower carboxylic acid is not particularly limited, but may be substantially equimolar, and preferably 0.9 to 1.1. The amount of caustic alkali used may be substantially twice the molar amount of the monohalogen lower carboxylic acid used. Further, the method of supplying the caustic alkali is not particularly limited, but it can be supplied to the surface of the reaction liquid or into the reaction liquid, and may be supplied continuously or intermittently.

In the method of the present invention, additives to the mixture or reaction solution containing the raw materials ether alcohol and monohalogen lower carboxylic acid are not normally required, but additives such as water, benzene, xylene, paraffin, ether, dioxane, etc. , an organic solvent such as dimethylformamide, or an inorganic salt. Although not normally required, the reaction may be carried out while supplying an inert gas such as nitrogen, carbon dioxide, helium, or argon into the reaction system. For example, depending on the depth of the reaction solution, the water vapor pressure at the deepest part of the reaction solution may be In cases where the pressure is high or the total pressure in the system is high, the water vapor pressure can be lowered by supplying these inert gases.

The first feature of the method of the present invention is that the raw materials, ether alcohol and monohalogen lower carboxylic acid, uniformly dissolve in each other, so the reaction proceeds while feeding caustic alkali into this uniform mixture under heating and reduced pressure. The point is that the monohalogen lower carboxylic acid alkali salt produced as an intermediate raw material becomes ultrafine particles. Therefore, the dispersion is much better than when a commercially available alkali monohalogen lower carboxylic acid salt powder with a large particle size is directly used as in the conventional method, and the monohalogen lower carboxylic acid alkali salt dispersed as a solid The surface area of the reaction mixture increases dramatically, and therefore, it becomes possible to react almost quantitatively without requiring strong stirring and with almost no side reactions.

The second feature of the method of the present invention is that all liquid raw materials that are easy to handle can be used. That is, ether alcohol is usually liquid at 50° C. or lower, and monohalogen lower carboxylic acid is usually solid at room temperature, but its aqueous solution is liquid at room temperature even at a high concentration of about 80% by weight or more. For example, monochloroacetic acid is actually commercially available as an industrial raw material in an aqueous solution of approximately 80% by weight, and when this aqueous solution is used, mixtures containing ether alcohol, monohalogen lower carboxylic acid, and water are usually turned into a homogeneous liquid at room temperature. It is.

Another feature of the method of the present invention is that the supplied caustic alkali is quickly consumed, and the dilution water of the caustic alkali and the water produced by the reaction are quickly removed from the system. Therefore, the intense heat generated by the reaction is absorbed by the latent heat of vaporization of water, and since almost no caustic alkali remains in the reaction solution, side reactions and coloring of the reaction solution hardly occur.

From the above points, the method of the present invention is industrially advantageous; in other words, the reaction can proceed in one step in a short time without the need for strong stirring, resulting in high yield and high quality. The ether carboxylate is obtained.

Examples are described below to further specifically explain the present invention, but these are not intended to limit the method of the present invention.

Example 1 Higher secondary alcohol 3 mole ethoxylate [trade name Softanol-30 (trade name)] prepared by adding an average of 3 moles of ethylene oxide to a random secondary alcohol having 12 to 14 carbon atoms and removing unreacted alcohol to 0.5% by weight or less. Average molecular weight: 333 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) 333 g (1 mole) and 99.2 g (1.05 mole) of monochloroacetic acid were placed in a reactor and uniformly dissolved. To this mixture, 175 g (2.1 mol) of a 48% aqueous solution of caustic soda was added dropwise over 2 hours while stirring. During this time, the temperature was maintained at 60°C and the pressure was 20 mmHg, and the water contained in the caustic soda aqueous solution and the water produced by the reaction were simultaneously condensed in a cooling trap and removed from the system. Thereafter, the mixture was further aged for 1 hour under the same conditions to obtain a white slurry-like viscous liquid. A predetermined amount of this reaction product was collected, and using liquid phase chromatography, it was passed through an anion-cation amphoteric ion exchange resin to separate and quantify only the nonionic substance, that is, the raw material ether alcohol. The degree of methyl etherification was 96.2 mol%.

Comparative Example 1 333 g (1 mole) of the same higher secondary alcohol 3 mole ethoxylate used in Example 1 and sodium monochloroacetate (95% purity product)
A 129 g (1.05 mol) mixture was kept at 60° C. with vigorous stirring, and powdered caustic soda (pulverized flake caustic soda) was gradually added to the mixture over a period of 4 hours to cause a reaction. After the addition was completed, the mixture was further aged for 1 hour under the same conditions, and the degree of carboxymethyl etherification was measured in the same manner as in Example 1.
It was 80.5 mol%.

Comparative Example 2 333 g (1 mole) of the same higher secondary alcohol 3 mole ethoxylate used in Example 1 and sodium monochloroacetate (95% purity product)
129 g (1.05 mol) of the mixture under vigorous stirring 48%
87.5 g (1.05 mol) of a caustic soda aqueous solution was added dropwise over a period of 2 hours. During this time, the water contained in the caustic soda aqueous solution and the water produced by the reaction were condensed in a cooling trap, and the pressure was maintained at 60°C and 20 mmHg. After dropping the caustic soda aqueous solution, the temperature was further aged for 1 hour under the same conditions. The degree of carboxymethyl etherification was measured in the same manner as in Example 1 and found to be 86.5 mol%.

Example 2 In Example 1, the number of carbon atoms as raw material alcohol
12-14 higher secondary alcohol 7 mole ethoxylate [Product name Softanol 70 (average molecular weight 509)
The same method as in Example 1 was used except that 509 g (1 mol) of Nippon Shokubai Kagaku Kogyo Co., Ltd. was used, and the degree of carboxymethyl etherification was measured as 96.3.
It was mol%.

Example 3 In Example 1, the number of carbon atoms as raw material alcohol
Average 7 mole ethylene oxide adduct of primary oxo alcohols of 12 and 13 (average molecular weight 502) 502
The process was carried out in the same manner as in Example 1 except that g (1 mol) was used, and the degree of carboxymethyl etherification was measured and found to be 95.1 mol%.

Example 4 The same method as in Example 1 was repeated except that 527 g (1 mol) of an average 7 mol ethylene oxide adduct of nonylphenol (average molecular weight 527) was used as the raw alcohol. The degree of carboxymethyl etherification was 96.3 mol%.

Example 5 In Example 1, 129 g (1.05 g) of 80% monochloroacetic acid aqueous solution was used as monohalogen lower carboxylic acid.
The same procedure as in Example 1 was carried out except that mol) was used, and the degree of carboxymethyl etherification was measured and found to be 96.0 mol%.

Claims (1)

[Claims] 1 General formula RO(AO) _o H [wherein R is an alkyl group or alkenyl group having an average of 8 to 24 carbon atoms, or an alkylphenyl group having an alkyl group having 6 to 16 carbon atoms; and A is an alkylene group having 2 to 4 carbon atoms or a mixed group thereof. Moreover, n is an integer of 1 to 20 on average. ] into a mixture containing an ether alcohol and a monohalogen lower carboxylic acid,
A method for producing an ether carboxylate salt, which comprises supplying an aqueous caustic alkali solution under heating and reduced pressure to cause a reaction. 2. The method according to claim 1, wherein the reaction is carried out at a temperature of 40 to 100°C. 3. The method according to claim 1 or 2, wherein the reaction is carried out under a water vapor pressure of 200 mmHg or less.