JP5172627B2 - Process for producing polyoxyalkylene adduct - Google Patents

Description

  The present invention relates to a polyoxyalkylene adduct and a method for producing a sulfate thereof.

  A polyoxyalkylene adduct such as polyoxyalkylene alkyl ether can be obtained by adding an alkylene oxide to an active hydrogen-containing compound in the presence of an alkali metal hydroxide catalyst or the like. In general, potassium hydroxide is used as the alkali metal hydroxide catalyst, and the reaction temperature is 60 to 200 ° C. and the maximum reaction pressure is 0 while continuously introducing alkylene oxide into a reaction vessel charged with an active hydrogen compound as a polymerization initiator. The reaction is carried out under the condition of 0.01 to 1.0 MPa until a predetermined molecular weight is obtained to obtain a crude polyoxyalkylene alkyl ether. Next, the catalyst in the crude polyoxyalkylene alkyl ether may be deactivated by adsorption filtration with an adsorbent, or neutralization with mineral acid, organic acid or the like.

  Acetic acid is used as a general neutralizing acid, but it is known to have an acetic acid odor. In addition, improvement in quality stability during long-term storage is also desired.

As a conventional technique, Patent Document 1 proposes a method for producing an alkylene oxide adduct having very little temporal change in the carbonyl value, acid value, pH, hue, and odor of the alkylene oxide adduct. This relates to a stabilized alkylene oxide adduct in which the quality of the alkylene oxide adduct obtained by reacting an alcohol with ethylene oxide and an alkylene oxide having 3 to 4 carbon atoms is very little changed with time.
JP-A 61-197536

  However, in Patent Document 1, a two-step reaction is performed, an addition reaction in the presence of an acid catalyst such as boron trifluoride, and an addition reaction in the presence of an alkali catalyst such as potassium hydroxide. In this case, it is necessary to use two types of catalysts, which is complicated. In addition, the use of an acid catalyst increases the carbonyl value in the product, and the product and the color when it is blended are not preferred.

  From such a background, a production method capable of obtaining a simple and high-quality polyoxyalkylene adduct has been desired.

The present invention relates to a method for producing a polyoxyalkylene adduct comprising the following steps (I) to (III).
Step (I): Step of adding propylene oxide to an alcohol represented by the following general formula (1) in the presence of an alkali catalyst to obtain a propylene oxide adduct represented by the following general formula (2) R- OH (1)
(In the formula, R represents a hydrocarbon group having 6 to 22 carbon atoms.)
R—O— (PO) _m —H (2)
(In the formula, R is the same as described above. PO represents a propyleneoxy group, and m represents an average addition mole number of more than 0 and 5 or less.)
Step (II): a reaction comprising the polyoxyalkylene adduct represented by the general formula (3) by adding ethylene oxide to the propylene oxide adduct obtained in step (I) in the presence of an alkali catalyst. Step of obtaining a product R—O— (PO) _m — (EO) _n —H (3)
(In the formula, R, PO, and m are the same as described above. EO represents an ethyleneoxy group, and n represents an average added mole number of 1 to 20)
Step (III): A step of neutralizing the alkali catalyst in the reaction product obtained in Step (II) with lactic acid.

The present invention also relates to a method for producing a sulfate comprising the following steps (I) to (IV).
Step (I): Propylene oxide is added to an alcohol represented by the following general formula (1) [hereinafter referred to as alcohol (1)] in the presence of an alkali catalyst, and represented by the following general formula (2). Step of obtaining propylene oxide adduct R—OH (1)
(In the formula, R represents a hydrocarbon group having 6 to 22 carbon atoms.)
R—O— (PO) _m —H (2)
(In the formula, R is the same as described above. PO represents a propyleneoxy group, and m represents an average addition mole number of more than 0 and 5 or less.)
Step (II): The propylene oxide adduct (hereinafter referred to as PO adduct) obtained in step (I) is added with ethylene oxide in the presence of an alkali catalyst, and is represented by the general formula (3). Step for obtaining a reaction product containing a polyoxyalkylene adduct R—O— (PO) _m — (EO) _n —H (3)
(In the formula, R, PO, and m are the same as described above. EO represents an ethyleneoxy group, and n represents an average added mole number of 1 to 20)
Step (III): A step of neutralizing the alkali catalyst in the reaction product obtained in Step (II) with lactic acid.
Step (IV): The polyoxyalkylene adduct in the reaction product after neutralization obtained in Step (III) is sulfated and then neutralized to obtain a compound represented by the following general formula (4). Step of obtaining R—O— (PO) _m — (EO) _n —SO ₃ M (4)
(In the formula, R, PO, EO, m, and n are the same as described above. M is a cation.)

  According to the production method of the present invention, a polyoxyalkylene adduct having a good quality such as a good hue during storage, no increase in carbonyl value during storage, and no odor problem can be obtained. The polyoxyalkylene adduct obtained by the production method of the present invention is useful as a raw material for various derivatives such as its sulfates.

<Process (I)>
In the step (I), the alcohol (1) represented by the general formula (1) is used. R in the general formula (1) is preferably an alkyl group, and is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. R has 6 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and more preferably 12 to 14 carbon atoms.

  In step (I), propylene oxide is added to alcohol (1) in the presence of an alkali catalyst. It is preferable that the usage-amount (ratio) of the alkali catalyst used by process (I) is more than 0 mol% and 5 mol% or less per mol of active hydrogen of alcohol (1). The molar ratio of the catalyst is more preferably 0.1 mol% or less and 3 mol% or less, and further preferably 0.3 mol% or less and 2 mol% or less.

  Although it does not specifically limit as an alkali catalyst used for the manufacturing method of this invention, For example, alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, etc. can be used. Potassium hydroxide is preferred.

  Sodium hydroxide or potassium hydroxide may be used in a dried state or used in the form of an aqueous solution, regardless of the form. As sodium hydroxide or potassium hydroxide, industrially available products can be used, and general industrial grade products can be used as they are.

  In the step (I), propylene oxide is used in an average of more than 0 mol and not more than 5 mol, preferably more than 0 mol and not more than 3 mol, more preferably more than 0 mol and not more than 1 mol per mol of active hydrogen of the alcohol (1). That is, m in the general formula (2) is more than 0 and 5 or less, preferably more than 0 mol and 3 mol or less, more preferably more than 0 mol and 1 mol or less, particularly preferably 0.2 mol or more and 0.8 mol or less. It is.

  In the addition reaction of propylene oxide in the step (I), the reaction temperature is preferably 100 to 200 ° C, more preferably 130 to 170 ° C, and more preferably 130 to 160 ° C. By performing the addition reaction of alcohol (1) and propylene oxide at this reaction temperature, the reaction rate is increased and the productivity is improved.

<Process (II)>
In step (II), EO is added to the PO adduct obtained in step (I) in the presence of an alkali catalyst, and the polyoxyalkylene adduct represented by general formula (3) is included. A reaction product is obtained.
R—O— (PO) _m — (EO) _n —H (3)

  As the alkali catalyst used in the step (II), those described in the step (I) can be used. In the present invention, the alkali catalyst used in step (I) can be used as the alkali catalyst in step (II), that is, as it is as the alkali catalyst in step (II). That is, the step (I) and the step (II) can be performed continuously without performing an operation such as removal of the alkali catalyst. Depending on the situation, for example, an alkali catalyst may be added separately in order to maintain the activity of the catalyst.

  In step (II), ethylene oxide is an average of 1 to 20 mol, preferably 1 to 10 mol, more preferably 1 to 5 mol, more preferably 1 to 3 mol, especially 1 mol, per mol of active hydrogen of alcohol (1). Preferably 1-2 mol is used.

  In the addition reaction of ethylene oxide in step (II), the reaction temperature is preferably 100 to 200 ° C, more preferably 130 to 170 ° C, and more preferably 130 to 160 ° C. By performing the addition reaction between the PO adduct and ethylene oxide at this reaction temperature, the reaction rate is increased and the productivity is improved.

  In general, so-called batch reactors are used for the production of industrial polyoxyalkylene adducts, and the step (I) and / or step (II) of the present invention is also used for such batch reactors. Can be implemented. For example, a high-efficiency stirring tank (such as Max Blend) equipped with a large special blade, a circulation reactor, or the like can be used.

  Step (I) and / or step (II) can be carried out without solvent or in the presence of a reaction solvent, but when a reaction solvent is used, a solvent having no active hydrogen (acetone, hexane, etc.) is preferred. It is.

  In the general formula (3), m is small, specifically, a polyoxyalkylene adduct having m of more than 0 and less than 1 is branched from linear alcohol like so-called synthetic alcohol even when linear alcohol is used as a raw material. Like a polyoxyalkylene adduct obtained from a mixture containing a chain alcohol, it has a low melting point, a low freezing point, and excellent low-temperature stability. On the other hand, various nonionic surfactants and anionic surfactants derived from alcohols derived from fats and oils, which are a kind of natural alcohol, have higher foaming properties and lower cmc than derivatives derived from synthetic alcohols. It is known to have characteristics such as high cloud point and high emulsifying power. The polyoxyalkylene adduct having m in the above-mentioned range in the general formula (3) maintains the characteristics of a surfactant produced from a so-called natural alcohol containing a large amount of linear alcohol, and has the characteristics of the synthetic system as described above. Therefore, it is effective for improving the physical properties of the polyoxyalkylene adduct.

<Process (III)>
Step (III) is a step of neutralizing the alkali catalyst in the reaction product containing the polyoxyalkylene adduct represented by the general formula (3) obtained in Step (II) with lactic acid. Lactic acid is preferably used in the same number of equivalents as the alkali catalyst. When the alkali catalyst is an alkali metal hydroxide, it is 0.9 to 1.1 moles, and more preferably equimolar to the charged moles of the catalyst. It is preferable to use it. Completion of neutralization can be confirmed when the pH of the 1 to 5% by mass aqueous solution of the reaction product becomes near neutral, for example, 5.0 to 8.0. The degree of neutralization can be 50 to 150%, and further 80 to 120%.

The present invention relates to a method for producing a sulfate of a polyoxyalkylene adduct having the following steps (IV) in the steps (I) to (III). In the method for producing a sulfate, preferred embodiments of steps (I) to (III) are the same as those described above.
Step (IV): The polyoxyalkylene adduct in the reaction product after neutralization obtained in Step (III) is sulfated and then neutralized to obtain a compound represented by the following general formula (4). Step of obtaining R—O— (PO) _m — (EO) _n —SO ₃ M (4)
(In the formula, R, PO, EO, m, and n are the same as described above. M is a cation.)

  M in the general formula (4) is preferably an alkali metal ion, and examples of the alkali metal include sodium, potassium, and lithium. Among these, sodium and potassium are preferable, and sodium is particularly preferable.

  Sulfation of the polyoxyalkylene adduct is performed by reacting the adduct with a sulfating agent. Examples of the sulfating agent include sulfur trioxide gas and chlorosulfonic acid. From the viewpoint of reducing the amount of chloride in the compound represented by the general formula (4), it is preferable to use sulfur trioxide gas.

  There is no restriction | limiting in particular in the method of sulfation, It can carry out by a conventional method. For example, it is diluted with an inert gas such as air or nitrogen using a thin film type continuous reaction apparatus, preferably a sulfur trioxide gas having a concentration of 1 to 30% by volume, more preferably 1 to 20% by volume. Sulfation of the adduct can be performed. When the concentration of sulfur trioxide is in the range of 1 to 30% by volume, the gas volume is not too large and excessive reaction can be suppressed.

  The amount of sulfur trioxide used is usually in the range of stoichiometric amount × (0.95 to 1.05), preferably in the range of stoichiometric amount × (0.97 to 1.01). If the amount of sulfur trioxide used is within the above range, the amount of unreacted substances can be reduced, and the production of colored components and odorous components (for example, lower aldehydes, lower ketones, cyclic ethers, etc.) as by-products can be suppressed. be able to.

  Although the apparatus which performs a sulfation reaction is not specifically limited, For example, a tank reactor, a thin film reactor, etc. can be used. As the thin film reactor, for example, a falling thin film reactor, a rising thin film reactor, a tubular gas-liquid mixed phase flow reactor, and the like can be used. The reaction time when using a thin film reactor is about 10 to 300 seconds.

  The sulfation temperature is preferably 15 to 70 ° C, more preferably 15 to 50 ° C. If it is 15 degreeC or more, the local excess reaction by fluid fall can be suppressed, and if it is 70 degrees C or less, decomposition | disassembly of a product can be suppressed.

  The sulfate obtained as described above is then neutralized to obtain a compound represented by the general formula (4). For the neutralization reaction, alkali metal hydroxide (eg, sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal oxide and hydroxide (eg, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, etc.), Alkali metal carbonates and bicarbonates, ammonia, mono-, di- and tri-alkanolamines having 2 to 4 carbon atoms in the alkyl chain, and primary, 2 to 4 carbon atoms in the alkyl chain And a tertiary or tertiary alkylamine. From the viewpoint of cost and availability, sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, and triethanolamine are preferable. Two or more kinds of the above alkalis may be combined. In addition, it is preferable that the addition amount of a neutralizing agent is normally added more than an equivalent with respect to a sulfate, and the amount by which the pH of the obtained neutralized product of sulfate is 5 to 13 is more preferable. The compound represented by the general formula (4) is preferably handled as an aqueous solution having a concentration of 10 to 70% by mass, and preferably neutralized using an aqueous solution of a neutralizing agent so as to obtain this concentration.

  The compound represented by the general formula (4) can be used as an anionic surfactant.

Example 1
11L autoclave equipped with stirrer, temperature controller and automatic introduction device 4790 g (24.6 mol) of coconut composition alcohol as a catalyst, 14.5 g of 48% potassium hydroxide aqueous solution as catalyst [activity of coconut composition dodecyl alcohol as potassium hydroxide After adding 0.005 mol (0.5 mol%) per hydrogen and replacing the inside of the mixed system with nitrogen, dehydration was performed at 110 ° C. for 0.5 hours under reduced pressure (1.3 kPa). . Next, the reaction was carried out while introducing 575 g of propylene oxide (0.4 mol per active hydrogen of the palm composition dodecyl alcohol) at 155 ° C. so that the pressure was 0.1 to 0.4 MPa. After introducing propylene oxide, the mixture was reacted at 155 ° C. for 1 hour. Subsequently, the reaction was carried out while introducing 1625 g of ethylene oxide (1.5 mol per active hydrogen of the palm composition dodecyl alcohol) at 155 ° C. so that the pressure was 0.1 to 0.4 MPa. After introducing ethylene oxide, the mixture was reacted at 155 ° C. for 1 hour. After completion of the ethylene oxide addition reaction, unreacted ethylene oxide was removed under reduced pressure.

  12.4 g of 90% by weight aqueous lactic acid solution (1.0 mol with respect to potassium hydroxide) was added to the reaction mixture, neutralized at 80 ° C. for 1 hour, and the average propylene oxide content of dodecyl alcohol was 0. .4 mol, ethylene oxide 1.5 mol adduct was obtained.

  The hue and carbonyl value of the adduct of propylene oxide average 0.4 mol and ethylene oxide average 1.5 mol of the obtained dodecyl alcohol were measured. The results are shown in Table 1. The hue was measured with APHA according to JIS K 0071-1, and the carbonyl value was measured with ASTM E411.

Comparative Example 1
With reference to Example 2 of JP-A-61-197536, an adduct of alcohol having an average of 0.4 mol of propylene oxide and an average of 1.5 mol of ethylene oxide was produced.

  A 6-liter autoclave equipped with a stirrer, temperature controller, and automatic introduction device was charged with 2667 g of coconut alcohol and 15.3 g of boron trifluoride ether complex as an acid catalyst, and the interior of the autoclave was sufficiently replaced with nitrogen and heated to 50 ° C. Propoxylation was performed by inserting 320 g of propylene oxide. The reaction solution was heated and washed with an aqueous solution of sodium hydroxide 4 times mol of boron trifluoride, and further washed twice with water to remove the catalyst. After dehydration under reduced pressure, an average propylene oxide 0.4 mol adduct of coconut alcohol was obtained.

  Next, 1916 g of this propylene oxide adduct and 1.3 g of potassium hydroxide were charged into an autoclave similar to that used in the propoxylation reaction, and the interior of the autoclave was sufficiently substituted with nitrogen, and then heated to 155 ° C. to react with 584 g ethylene oxide. . Subsequently, the mixture was neutralized with 2.4 g of a 90% by mass aqueous lactic acid solution to obtain an adduct having an average of 0.4 mol of propylene oxide and an average of 1.5 mol of ethylene oxide. The hue and carbonyl value of the resulting alkylene oxide adduct were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
In Example 1, an average of 0.4 mol of propylene oxide of dodecyl alcohol, ethylene oxide, except that neutralization was performed using 7.5 g of 99 mass% aqueous acetic acid instead of 12.4 g of 90 mass% lactic acid aqueous solution. A 1.5 molar adduct was obtained. The hue and carbonyl value of the resulting alkylene oxide adduct were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 2 (sulfur oxide)
The production of the sulfate having the steps (I) to (IV) was carried out using the adduct of Example 1 as a raw material for the step (IV). That is, a propylene oxide average of 0.4 mol and an ethylene oxide average of 1.5 mol adduct of dodecyl alcohol obtained in Example 1 by a thin film type sulfation reactor were sulfated with sulfur trioxide gas diluted with dry air, It neutralized with the sodium hydroxide solution containing ethanol so that it might become the aqueous solution whose density | concentration of the salt of a sulfate is 68-72 mass% and the density | concentration of water is 25-29 mass%. The hue of the resulting sulfate salt (Krett, pH 7, absorbance at 420 nm × 1000) was evaluated. The results are shown in Table 2.

Comparative Examples 3-4 (sulfur oxide)
In Example 2, the propylene oxide average of 0.4 mol of the dodecyl alcohol obtained in Example 1 and the average propylene oxide of the dodecyl alcohol obtained in Comparative Examples 2 to 3 instead of the adduct of ethylene oxide average 1.5 mol The same operation as in Example 2 was performed except that an adduct of .4 mol and an average of 1.5 mol of ethylene oxide was used. The hue (klet) of the obtained sulfate salt was evaluated in the same manner as in Example 2. The results are shown in Table 2.

Claims (4)

A method for producing a polyoxyalkylene adduct comprising the following steps (I) to (III).
Step (I): Step of adding propylene oxide to an alcohol represented by the following general formula (1) in the presence of an alkali catalyst to obtain a propylene oxide adduct represented by the following general formula (2) R- OH (1)
(In the formula, R represents an alkyl group having 12 to 14 carbon atoms.)
R—O— (PO) _m —H (2)
(In the formula, R is the same as described above. PO represents a propyleneoxy group, and m represents an average addition mole number of more than 0 and 1 or less.)
Step (II): a reaction comprising the polyoxyalkylene adduct represented by the general formula (3) by adding ethylene oxide to the propylene oxide adduct obtained in step (I) in the presence of an alkali catalyst. Step of obtaining a product R—O— (PO) _m — (EO) _n —H (3)
(Wherein, R, PO, m are as .EO said ethylene radical, n represents an average addition mole number of 21 to.)
Step (III): A step of neutralizing the alkali catalyst in the reaction product obtained in Step (II) with lactic acid.   The method for producing a polyoxyalkylene adduct according to claim 1, wherein the alkali catalyst used in step (I) is used as the alkali catalyst in step (II). A method for producing a sulfate comprising the following steps (I) to (IV).
Step (I): Step of adding propylene oxide to an alcohol represented by the following general formula (1) in the presence of an alkali catalyst to obtain a propylene oxide adduct represented by the following general formula (2) R- OH (1)
(In the formula, R represents an alkyl group having 12 to 14 carbon atoms.)
R—O— (PO) _m —H (2)
(In the formula, R is the same as described above. PO represents a propyleneoxy group, and m represents an average addition mole number of more than 0 and 1 or less.)
Step (II): a reaction comprising the polyoxyalkylene adduct represented by the general formula (3) by adding ethylene oxide to the propylene oxide adduct obtained in step (I) in the presence of an alkali catalyst. Step of obtaining a product R—O— (PO) _m — (EO) _n —H (3)
(Wherein, R, PO, m are as .EO said ethylene radical, n represents an average addition mole number of 21 to.)
Step (III): A step of neutralizing the alkali catalyst in the reaction product obtained in Step (II) with lactic acid.
Step (IV): The polyoxyalkylene adduct in the reaction product after neutralization obtained in Step (III) is sulfated and then neutralized to obtain a compound represented by the following general formula (4). Step of obtaining R—O— (PO) _m — (EO) _n —SO ₃ M (4)
(In the formula, R, PO, EO, m, and n are the same as described above. M is a cation.)   The method for producing a sulfate according to claim 3, wherein the alkali catalyst used in step (I) is used as the alkali catalyst in step (II).