JP5568043B2 - Process for producing polyoxyalkylene derivative and polyoxyalkylene derivative obtained by the process - Google Patents

Description

The present invention relates to a method for producing a polyoxyalkylene derivative and a polyoxyalkylene derivative obtained by the production method. Specifically, the present invention relates to a method for producing a polyoxyalkylene derivative containing a hydroxyl group and a carboxyl group, and a polyoxyalkylene derivative obtained by the production method.

The polyoxyalkylene derivative is usually obtained by converting an alkylene oxide into an alcohol in the presence of a base catalyst such as an alkali metal hydroxide or amine, or an acid catalyst comprising a mineral acid such as sulfuric acid, phosphoric acid or hydrochloric acid or a metal salt thereof. It is produced by addition reaction to the product.

  On the other hand, polyoxyalkylene derivatives containing both a hydroxyl group and a carboxyl group can add alkylene oxide in the presence of a catalyst such as an alkali metal hydroxide as described above. There is a problem that the yield of is reduced.

  As a method for introducing a carboxyl group into the α-terminal, a carboxy ester of hydroxycarboxylic acid is used as a raw material, and after addition of alkylene oxide, the ester is hydrolyzed to have a carboxyl group at the α-terminal and a hydroxyl group at the ω-terminal. There exists a manufacturing method of the compound which has this (patent document 1). Moreover, there is a method of adding an alkylene oxide using an alkyl ester of a carboxylic acid having a hydroxyl group as an initiator (Patent Document 2). In these methods, esterification of hydroxycarboxylic acid and ester hydrolysis after polymerization are required, and the operation becomes complicated.

  On the other hand, a method is also reported in which hydroxypivalic acid dissolved in tetrahydrofuran is dropped into a solution obtained by adding tetrahydrofuran to potassium naphthalene, and after metalation, ethylene oxide is addition-polymerized (Patent Document 3). However, this method has not been industrialized because an organic solvent is used and the purification operation after the reaction is complicated.

Japanese Patent Laid-Open No. 5-194777 JP 7-242588 A JP 2011-32349 A

The present invention has been made in view of the above circumstances, and its purpose is to produce an industrial hydroxyl group and carboxyl group-containing polyoxyalkylene derivative which is simple in operation and does not use an organic solvent, and the production thereof. The object is to provide a polyoxyalkylene derivative obtained by the method.

As a result of extensive research by the present inventors, by using hydroxycarboxylic acid as a starting material and addition polymerization of alkylene oxide using Lewis acid as a catalyst, hydroxyl groups and carboxyls can be easily operated without using an organic solvent. It has been found that a polyoxyalkylene derivative containing a group can be produced, and the present invention has been completed.
That is, this invention is a manufacturing method of the polyoxyalkylene derivative containing the hydroxyl group and carboxyl group which are represented by the following general formula (1), Comprising: In hydroxycarboxylic acid represented by the following general formula (2), The first gist is a method for producing a polyoxyalkylene derivative characterized by addition polymerization of alkylene oxide using a Lewis acid.

（式中、Ｒは炭素数１〜２０の直鎖または分岐のアルキレン基、及び／又はアリーレン基を示し、ＡＯは炭素数２〜４のオキシアルキレン基を示し、０＜ｎ≦１０、１＜ｍ≦１０である。）

(In the formula, R represents a linear or branched alkylene group having 1 to 20 carbon atoms and / or an arylene group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and 0 <n ≦ 10, 1 < m ≦ 10.)

（式中、Ｒは炭素数１〜２０の直鎖または分岐のアルキレン基、及び／又はアリーレン基、を示し、１＜ｍ≦１０である。）
本発明の製造方法は、前記ルイス酸が、アルミニウムアルコラート化合物、三フッ化ホウ素錯塩、及びホウフッ化水素酸塩から選択された１種又は２種以上である事が好ましい。
さらに、本発明は前記製造方法で得られるポリオキシアルキレン誘導体であって、下記計算式（１）で算出される数値が０．８〜１．０であるポリオキシアルキレン誘導体である事を第２の要旨とする。

(In the formula, R represents a linear or branched alkylene group having 1 to 20 carbon atoms and / or an arylene group, and 1 <m ≦ 10.)
In the production method of the present invention, the Lewis acid is preferably one or more selected from an aluminum alcoholate compound, a boron trifluoride complex salt, and a borofluoride salt.
Furthermore, the present invention relates to a polyoxyalkylene derivative obtained by the above production method, wherein the numerical value calculated by the following formula (1) is 0.8 to 1.0. The gist of

Next, the form for implementing this invention is demonstrated.
The production method of the present invention is characterized in that an alkylene oxide is addition-polymerized to a hydroxycarboxylic acid using a Lewis acid.
The hydroxycarboxylic acid used in the present invention is a compound represented by the following general formula ( 2 ).

（式中、Ｒは炭素数１〜２０の直鎖または分岐のアルキレン基、及び／又はアリーレン基、を示し、１≦ｍ≦１０である。）

(In the formula, R represents a linear or branched alkylene group having 1 to 20 carbon atoms and / or an arylene group, and 1 ≦ m ≦ 10.)

R in General formula ( 2 ) shows a C1-C20 linear or branched alkylene group and / or an arylene group. These substituents are not particularly limited, but alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, undecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, Linear alkylene groups such as heptadecylene, octadecylene, nonadecylene, or neopentylene, dimethylbutylene, methylhexylene, ethylhexylene, dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethyl Heptylene, ethylheptylene, methyloctylene, methylnonylene, methyldecylene, methyldodecylene, methylundecylene, methyltridecylene, methyl Rutetoradeshiren may indicate methylpentanoyl decylene, methylhexahydrophthalic decylene, Methylheptadecanoic decylene, methyl octadecylene, a branched alkylene group such as methyl Bruno pat cyclohexylene.
The arylene group may have a substituent such as a phenylene group or a methyl group, and examples thereof include methylphenylene and dimethylphenylene.

M in the general formula ( 2 ) is 1 or more and 10 or less. A compound in which m exceeds 10 is not suitable as a starting material of the present invention because it is difficult to obtain it as a general-purpose material on the market.
Specific examples of the hydroxycarboxylic acid used in the present invention include glycolic acid, lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 12-hydroxystearic acid, hydroxycarboxylic acids having an alkylene group or an arylene group. Examples thereof include ester condensate 12-hydroxystearic acid condensate and salicylic acid. Among these, although not particularly limited, 12-hydroxystearic acid condensate is preferable.

The Lewis acid used in the present invention is not particularly limited, but one or more selected from an aluminum alcoholate compound, a boron trifluoride complex salt, and a borohydrofluoride are preferable.
Examples of the aluminum alcoholate compound include aluminum ethylate, aluminum isopropylate, and aluminum secondary butyrate.
Examples of the boron trifluoride complex salt include boron trifluoride amine complex, boron trifluoride ethyl ether complex, boron trifluoride phenol complex, boron trifluoride acetic acid complex, boron trifluoride methyl alcohol complex, and the like. Examples of borohydrofluoric acid salts include hydrofluoric acid, stannous borofluoride, copper borofluoride, lead borofluoride, zinc borofluoride, ferrous borofluoride, antimony borofluoride, indium borofluoride, potassium borofluoride, and boron fluoride. Ammonium bromide, sodium borofluoride, magnesium borofluoride and the like can be mentioned.
Of the above compounds, boron trifluoride ethyl ether complex is particularly preferred.

The alkylene oxide used in the present invention may be any alkylene oxide that can react with a compound having active hydrogen to produce an alkoxylate, but has an oxirane ring such as ethylene oxide, propylene oxide, butylene oxide, and the like. Of these, ethylene oxide and propylene oxide are particularly preferable.

In the present invention, the number of added moles of alkylene oxide exceeds 0 and is 10 or less, preferably 3 or more and 10 or less, more preferably 5 or more and 10 or less. When the number of added moles is small, the function as a surfactant is not expressed, and when the number of added moles is large, a side reaction such as transesterification occurs.

The addition reaction of alkylene oxide in the present invention can be easily carried out in a pressure reactor such as an autoclave under ordinary operating procedures and reaction conditions. In that case, it is preferable that reaction temperature is 50-150 degreeC, More preferably, it is 60-120 degreeC. When the reaction temperature is 50 ° C. or lower, the progress of the alkylene oxide addition reaction is slowed. On the other hand, when the reaction temperature exceeds 150 ° C., the Lewis acid is deactivated and it is difficult to obtain a sufficient effect.

  In addition, although the usage-amount of a catalyst is not specifically limited, It is preferable that it is 0.01 to 5.0 weight% with respect to hydroxycarboxylic acid.

The polyoxyalkylene derivative obtained by the production method of the present invention is a compound represented by the following general formula (1).

（式中、Ｒは炭素数１〜２０の直鎖または分岐のアルキレン基、及び／又はアリーレン基を示し、ＡＯは炭素数２〜４のオキシアルキレン基を示し、０＜ｎ≦１０、１＜ｍ≦１０である。）
式中のＲは前述のヒドロキシカルボン酸を示す一般式（２）に定義したとおりである。ｎはアルキレンオキサイドの付加モル数を示し、前記の付加モル数に定義したとおりである。

(In the formula, R represents a linear or branched alkylene group having 1 to 20 carbon atoms and / or an arylene group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and 0 <n ≦ 10, 1 < m ≦ 10.)
R in the formula is as defined in the general formula (2) showing the hydroxycarboxylic acid. n represents the number of moles of alkylene oxide added, as defined in the above number of moles of addition.

The polyoxyalkylene derivative obtained by the production method of the present invention is characterized in that the numerical value calculated by the following formula (1) is 0.8 to 1.0.

The numerical value according to the above formula indicates the yield of the polyoxyalkylene derivative of the present invention, and side reactions such as transesterification occur with respect to the carboxyl group of the hydroxycarboxylic acid which is the starting material during the addition polymerization reaction of alkylene oxide. And the acid value of the resulting polyoxyalkylene derivative is lowered and the numerical value is lowered.
Although the said numerical value in this invention is 0.8-1.0, Preferably it is 0.9-1.0. When a by-product is generated by a side reaction such as a transesterification reaction, the numerical value is out of this range.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In Examples and Comparative Examples, parts and% are based on weight unless otherwise specified.
<Measurement of acid value>
The acid value was measured by the acid value test method described in JIS K 0070.
<Example 1>
In a stainless steel autoclave, 711 g (0.40 mol) of 12-hydroxystearic acid condensate (trade name PHF-33, manufactured by Ito Oil Co., Ltd., acid value: 31.7 mg KOH / g), boron trifluoride ethyl ether complex as a catalyst 1.14 g (0.008 mol) was charged, and the inside of the reactor was purged with nitrogen. After nitrogen substitution, the temperature was raised to 70 ° C., and 89 g (2.01 mol) of ethylene oxide (EO) was introduced while maintaining the internal pressure at 2.5 kg / cm 2 G or less. After completion of the introduction of EO, the mixture was kept at 70 ° C. for 1 hour and reacted until no pressure drop was observed. Thereafter, the volatile component was removed under reduced pressure at 70 ° C. for 15 minutes to obtain 792 g of an EO adduct of 12-hydroxystearic acid condensate. When the acid value of the obtained EO adduct was measured, it was 25.6 mgKOH / g, and the numerical value obtained from the calculation formula (1) was 0.91. As a result of NMR analysis, a peak derived from an ester in which ethylene oxide was added to carboxylic acid was not confirmed.
<Example 2>
In a stainless steel autoclave, 711 g (0.40 mol) of 12-hydroxystearic acid condensate (trade name PHF-33, manufactured by Ito Oil Co., Ltd., acid value: 31.7 mg KOH / g), zinc borofluoride [Zn (BF ₄ ) ₂ ] 1.92 g (0.008 mol) was charged, and the inside of the reactor was purged with nitrogen. After nitrogen substitution, the temperature was raised to 80 ° C., and 89 g (2.01 mol) of ethylene oxide (EO) was introduced while maintaining the internal pressure at 2.5 kg / cm 2 G or less. After the end of EO introduction, the reaction was held at 80 ° C. for 1 hour until the pressure drop was not observed. Thereafter, volatile components were removed under reduced pressure at 80 ° C. for 15 minutes to obtain 793 g of an EO adduct of 12-hydroxystearic acid condensate. When the acid value of the obtained EO adduct was measured, it was 25.5 mgKOH / g, and the value obtained from the calculation formula (1) was 0.90. As a result of NMR analysis, a peak derived from an ester in which ethylene oxide was added to carboxylic acid was not confirmed.
<Comparative Example 1>
In a stainless steel autoclave, 711 g (0.40 mol) of 12-hydroxystearic acid condensate (trade name PHF-33, manufactured by Ito Oil Co., Ltd., acid value: 31.7 mg KOH / g) and 0.80 g of potassium hydroxide as a catalyst 0.014 mol) was charged, and the inside of the reactor was purged with nitrogen. After nitrogen substitution, the temperature was raised to 120 ° C., and 89 g (2.01 mol) of ethylene oxide (EO) was introduced while maintaining the internal pressure at 2.5 Kg / cm 2 G or less. After completion of the introduction of EO, the mixture was kept at 120 ° C. for 1 hour and reacted until no pressure drop was observed. Thereafter, the volatile component was removed under reduced pressure at 100 ° C. for 15 minutes to obtain 793 g of an EO adduct of 12-hydroxystearic acid condensate. The acid value of the obtained EO adduct was 1.3 mg KOH / g, and the value obtained from the calculation formula (1) was 0.05. As a result of NMR analysis, a peak derived from an ester was confirmed, and it was confirmed that not only a hydroxyl group but also a compound in which ethylene oxide was added to a carboxylic acid or a compound in which a transesterification reaction proceeded was included.

According to the present invention, a polyoxyalkylene derivative having a carboxylic acid group can be produced only by an alkylene oxide addition reaction, and the polyoxyalkylene derivative thus obtained can be used for household detergents, industrial surfactants, and various surfactants. It can be used for a wide range of applications as an agent raw material.

Claims (3)

A method for producing a polyoxyalkylene derivative containing a hydroxyl group and a carboxyl group represented by the following general formula (1), wherein a Lewis acid is used as the hydroxycarboxylic acid represented by the following general formula (2) A method for producing a polyoxyalkylene derivative, which comprises addition polymerization of an oxide.

(In the formula, R represents a linear or branched alkylene group having 1 to 20 carbon atoms and / or an arylene group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and 0 <n ≦ 10, 1 < m ≦ 10.)

(In the formula, R represents a linear or branched alkylene group having 1 to 20 carbon atoms and / or an arylene group, and 1 <m ≦ 10.) 2. The production of a polyoxyalkylene derivative according to claim 1, wherein the Lewis acid is one or more selected from an aluminum alcoholate compound, a boron trifluoride complex salt, and a borohydrofluoride salt. Method. A polyoxyalkylene derivative obtained by the production method according to claim 1 or 2, wherein a numerical value calculated by the following formula (1) is 0.8 to 1.0.