JP3617830B2 - Production method of phosphate ester - Google Patents

Description

【００３６】
［色の測定］
試料をエタノールで１０倍に希釈した後、（株）島津製作所製 分光光度計ＵＶ−１６００を使用し、波長４２０ｎｍの吸光度を測定した。測定値を１０００倍した値を「色」とした。なお、この値が低いものほど、「色に優れている」と判断される。
【００３７】
［臭い評価］
試料を有効成分２７％（リン酸モノエステル＋リン酸ジエステルでありリン酸エステル基準）になる様に４８％水酸化カリウム水溶液で中和した。
１１０ｍＬ容ガラス製広口規格ビンに、このリン酸エステル塩を５０ｍＬサンプリングし、一人の熟練したパネラーが直接ビン口の臭いを嗅ぎ、臭いの強さを０［無臭］〜６［強］の７段階で評価した。
【００３８】
【表１】

【００３９】
表１の結果より、実施例１〜４で得られたリン酸エステルは、いずれも、比較例１、２で得られたものに比べ、色に優れ、かつ臭いの少ないものであることがわかる。
【００４０】
【発明の効果】
本発明によれば、容易に、かつ簡易な設備で、リン酸化反応と同時に臭気を少なくでき、かつ色の良好なリン酸エステルを得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a phosphate ester. More specifically, for example, the present invention relates to a method for producing a phosphate ester that can be suitably used as a body cleanser, an emulsifier and the like.
[0002]
[Prior art]
Phosphoric acid ester salts of organic hydroxy compounds are used in the fields of detergents, emulsifiers, fiber treatment agents, rust inhibitors, and medical products. In particular, alkali metal salts such as sodium and potassium phosphate monoesters having a long-chain alkyl group and alkanolamine salts such as triethanolamine are water-soluble and have excellent foaming and detergency, and are toxic and irritating to the skin. Therefore, it is useful for products that are used directly on the human body, such as shampoos and facial cleansers. When a phosphate ester salt is blended with such a product used directly on the human body, it is important as a quality that the smell based on the phosphate ester salt is weak.
[0003]
In general, phosphate esters are produced by reacting an organic hydroxy compound with a phosphorylating agent such as phosphorus pentoxide, polyphosphoric acid, or phosphorus oxychloride.
[0004]
However, in this phosphate ester, unreacted organic hydroxy compound, a compound derived from the organic hydroxy compound, and a by-product generated during the phosphorylation reaction are present as impurities. Since these impurities may adversely affect the hue as a coloring component and may adversely affect the odor as a odorous component, a decolorization step and a complicated purification step are required to remove the impurities after the phosphorylation reaction. It is said.
[0005]
In general, phosphate ester is a compound that is easily decomposed by thermal history. As a purification method that suppresses heat history as much as possible, a method of recrystallizing a phosphate ester using a solvent, a phosphate ester with a basic compound is extracted as a phosphate ester salt into an aqueous layer, and impurities are extracted into an organic layer A method has been proposed (Japanese Patent Publication No. 03-027558).
[0006]
On the other hand, as a purification method that does not use a solvent, there has been proposed a method in which a liquid film of phosphate ester is formed using a rotating thin film evaporator, a wet wall tower, etc., and brought into contact with an inert gas (JP-A-57). -35595). However, in the method according to Japanese Patent Laid-Open No. 57-35595, coloring of the phosphate ester after purification cannot be avoided.
[0007]
These methods require a purification operation after the phosphorylation reaction, require heavy equipment, and are economically disadvantageous. Therefore, it is desired to develop an industrial production method of a phosphoric acid ester which is easy and simple and has few coloring components, reduces odorous components, and has little odor.
[0008]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a phosphoric acid ester having a good color and easily having less odor.
[0009]
[Means for Solving the Problems]
The present invention relates to a method for producing a phosphate ester, wherein an inert gas is introduced and the reaction is carried out under a reduced pressure of 70 kPa or less when a phosphate ester is produced by reacting an organic hydroxy compound with a phosphorylating agent. About.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
As described above, the present invention is characterized in that an inert gas is introduced to react when an organic hydroxy compound and a phosphorylating agent are reacted to produce a phosphate ester.
[0011]
The phosphoric acid ester usually contains an unreacted organic hydroxy compound or a compound derived from the organic hydroxy compound as an odorous component, and a by-product generated during the phosphorylation reaction. On the other hand, by using the production method of the present invention, by performing a phosphorylation reaction while introducing an inert gas, only a odorous component is selectively reduced, and a phosphoric acid ester having a good odor is produced. There is an advantage that you can.
[0012]
Further, by using the production method of the present invention, it is possible to suppress an increase in coloring components due to oxidation of the phosphate ester, so that an excellent effect that the color of the obtained phosphate ester is extremely good is exhibited. .
[0013]
Examples of the organic hydroxy compound used in the present invention include compounds represented by the general formula (I).
RO (AO) _n H (I)
(In the formula, R represents a linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms, preferably 8 to 18 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and n A's are the same. And n represents the average number of moles of alkylene oxide added, and is 0 to 20, preferably 0 to 10.)
[0014]
Examples of the organic hydroxy compound include undecyl alcohol and its addition mole number 3 ethylene oxide adduct, dodecyl alcohol and its addition mole number 2 ethylene oxide adduct, and the like.
[0015]
Examples of the phosphorylating agent used for phosphorylating the organic hydroxy compound include phosphorus pentoxide, polyphosphoric acid, phosphorus oxychloride, and the like, and these can be used alone or in admixture of two or more. What is necessary is just to adjust the quantity of a phosphorylating agent according to the composition of the target phosphate ester. Among these, phosphorus pentoxide and polyphosphoric acid are preferable because there is no by-product such as hydrochloric acid gas and it is difficult to apply a load on equipment.
[0016]
The phosphorylating agent may be dissolved in water. In particular, when phosphorus pentoxide and polyphosphoric acid are used as a phosphorylating agent, it usually has a negative impact on the viewpoint of reducing by-product of orthophosphoric acid, which adversely affects the stability of products such as cleaning agents, and cleaning properties. From the viewpoint of reducing the by-product of the phosphoric acid diester, phosphorus pentoxide (value obtained by converting the orthophosphoric acid to 138% by weight, in the case of polyphosphoric acid, the value obtained by dividing the polyphosphoric acid concentration by 138 is the phosphorus pentoxide equivalent weight ratio. The amount of water is preferably 0.5 to 1.5 mol and the amount of the organic hydroxy compound is preferably 1 to 3 mol with respect to 1 mol.
[0017]
The “inert gas” of the present invention means a gas that does not adversely affect the quality and yield of the phosphate ester. Examples of the inert gas include nitrogen gas, argon gas, helium gas, carbon dioxide gas, nitrogen gas and carbon dioxide gas are preferable, and nitrogen gas is more preferable.
[0018]
The introduction method of the inert gas cannot be generally limited depending on the form of the phosphorylation reaction. For example, in the case of a batch system, a method of introducing an inert gas into the gas phase part or the liquid can be mentioned. Especially, the method of introduce | transducing in a liquid from a viewpoint of reducing an odorous component more efficiently is preferable. Furthermore, odorous components can be more efficiently reduced by using a gas disperser or the like.
[0019]
The introduction amount of the inert gas is reduced to 1 kg of the total amount of the organic hydroxy compound and the phosphorylating agent from the viewpoint of suppressing waste of the inert gas, reducing the load on the vacuum equipment, and avoiding the necessity of high vacuum. Preferably, it is 0.0001 to 0.5 m ³ / (hr · kg), more preferably 0.0001 to 0.1 m ³ / (hr · kg), and still more preferably 0.0001 to 0.05 m ³ / (hr.・ Kg). In the present invention, “inert gas introduction amount (m ³ / (hr · kg))” is a flow rate in a standard state (temperature 0 ° C., pressure 101.3 kPa).
[0020]
The introduction start of the inert gas is not particularly limited as long as it is introduced when the inert gas reacts, but from the viewpoint of suppressing coloring due to air contamination, for example, when using phosphorus pentoxide as a phosphorylating agent, It is preferably carried out before the addition of phosphorus pentoxide, that is, after the completion of the preparation of the organic hydroxy compound. Further, the introduction may be performed continuously or may be performed in a plurality of times, but from the viewpoint of suppressing coloring due to oxidation of the phosphate ester and from the viewpoint of continuously removing odorous components. It is preferable.
[0021]
In addition, as the reaction temperature, from the viewpoint of preventing the reaction time from becoming long and deteriorating in productivity, reducing the introduction amount of inert gas, and avoiding the necessity of high vacuum, the produced phosphate ester From the viewpoint of avoiding the thermal decomposition of the mixture and preventing the increase of odorous components and the deterioration of the color due to this, it is preferably 50 to 130 ° C, more preferably 70 to 110 ° C. Since the reaction time varies depending on the reaction temperature, it cannot be generally described, but from the viewpoint of reducing the amount of the remaining organic hydroxy compound, it is preferably about 5 to 20 hours, more preferably about 8 to 15 hours.
[0022]
The reaction pressure is not particularly limited, but the viewpoint of reducing the amount of inert gas introduced and avoiding the need for a high reaction temperature (avoids thermal decomposition of phosphate ester, thereby increasing odorous components) And a reduced pressure of 70 kPa or less, more preferably 20 kPa or less, and even more preferably 10 kPa or less.
[0023]
In addition, when the phosphorylating agent used in the present invention contains water as described above, the reaction pressure is adjusted in the reaction system from the viewpoint of preventing deviation of the charged molar ratio due to water evaporation. It is preferable to carry out after water is not present. For example, when the reaction temperature is 90 ° C., after the preparation is completed, the liquid temperature reaches the target reaction temperature of 90 ° C., and then the reaction pressure is adjusted to prevent deviation of the preparation molar ratio due to water evaporation. . Further, when water vapor is used as the inert gas, the water vapor and the phosphorylating agent react during the phosphorylation reaction, so that the charged molar ratio is shifted and the effect of preventing coloring is reduced, which is not preferable. The water concentration in the reaction system can be measured using a general water concentration measuring device, for example, using a Karl Fischer coulometric titrator (manufactured by Hiranuma Sangyo Co., Ltd .: AQUACOUNTER AQ-7). it can.
[0024]
In addition, in the obtained phosphate ester, a pyrophosphate compound derived from a phosphorylating agent is present, and from the viewpoint of suppressing an increase in odorous components due to this pyrophosphate compound, ion exchange water is further added. Thus, it is desirable to perform the hydrolysis at 50 to 100 ° C, preferably 70 to 90 ° C.
[0025]
Examples of the phosphoric acid ester obtained by such a method include phosphoric acid monoester and phosphoric acid diester. Such phosphoric acid esters have excellent qualities such as excellent color and low odor even without complicated post-treatment, so that detergents, emulsifiers, fiber treatment agents, rust inhibitors, medical products It can be suitably used in such fields.
[0026]
【Example】
Examples 1 and 4 are used as reference examples.
Example 1
548 g (1.84 mol) of ethoxylate of higher alcohol having 11 carbon atoms, 20% branching rate, 3 average EO addition mole number 3 (trade name Neodol 1-3, manufactured by Shell, molecular weight 298.6), 85% phosphorus It was mixed with 43 g of acid (equivalent to 0.19 mol of phosphorus pentoxide, 0.92 mol of water). Next, nitrogen gas was introduced into the gas phase portion at 1,300 mL / min (0.11 m ³ / (hr · kg): standard state), and 109 g (0.76 mol) of phosphorus pentoxide was added at a temperature of 40 to 70 ° C. Slowly added. After the temperature was raised to 90 ° C., water disappeared from the reaction system, and the reaction was carried out at a pressure of 101.3 kPa for 8 hours. Thereafter, 14.0 g of ion-exchanged water was added and hydrolyzed at 90 ° C. for 3 hours.
[0027]
Example 2
548 g (1.84 mol) of ethoxylate of higher alcohol having 11 carbon atoms, 20% branching rate, 3 average EO addition mole number 3 (trade name Neodol 1-3, manufactured by Shell, molecular weight 298.6), 85% phosphorus It was mixed with 43 g of acid (equivalent to 0.19 mol of phosphorus pentoxide, 0.92 mol of water). Next, nitrogen gas is introduced into the liquid at 140 mL / min (0.012 m ³ / (hr · kg): standard state), and 109 g (0.76 mol) of phosphorus pentoxide is gradually added at a temperature of 40 to 70 ° C. did. After the temperature was raised to 90 ° C., when no water was present in the reaction system, the pressure was reduced to 2.67 kPa and the reaction was allowed to proceed for 8 hours. Thereafter, 14.0 g of ion-exchanged water was added under normal pressure and hydrolyzed at 90 ° C. for 3 hours.
[0028]
Example 3
The phosphorylation reaction was carried out in the same manner as in Example 1 except that the pressure during phosphorylation was 50 kPa.
[0029]
Example 4
The phosphorylation reaction was carried out in the same manner as in Example 1 except that the amount of nitrogen gas to be introduced was 3000 mL / min (0.26 m ³ / (hr · kg): standard state).
[0030]
Comparative Example 1
After mixing ethoxylate of higher alcohol and 85% phosphoric acid, phosphorylation reaction was carried out in the same manner as in Example 1 except that nitrogen gas was not introduced.
[0031]
Comparative Example 2
A phosphorylation reaction was performed in the same manner as in Example 3 except that nitrogen gas was not introduced.
[0032]
[Measurement of phosphoric acid monoester, phosphoric diester, orthophosphoric acid content]
1 g of the sample was accurately weighed and dissolved by adding 100 mL of ethanol and 50 mL of water. Potentiometric titration was performed using 1 / 2N KOH, and the first equivalent point (AV1) and the second equivalent point (AV2) were measured.
[0033]
Next, 1 g of the sample was accurately weighed, and about 20 mL of 2N CaCl ₂ was added to the sample dissolved by adding 100 mL of ethanol and 50 mL of water, and potentiometric titration was performed using 1/2 N KOH to obtain a third equivalent point (AV3). Was measured. The amounts of phosphoric acid monoester, phosphoric diester and orthophosphoric acid were calculated from the formulas (1) to (3).
Orthophosphoric acid amount (% by weight)
= (AV3-AV2) × 98/56108 (1)
Phosphoric acid diester (wt%)
= (2. AV1-AV2) x phosphoric acid diester molecular weight / 56108 (2)
Phosphoric acid monoester (wt%)
= (2. AV2-AV1-AV3) x phosphoric acid monoester molecular weight / 56108 (3)
[0034]
[Measurement of petroleum ether soluble matter]
A sample was accurately weighed in an amount of 5 g, and 100 mL each of petroleum ether, ethanol, and triethanolamine 15% by volume aqueous solution was added to separate the layers in a 500 mL separatory funnel (A). This lower layer was placed in another 500 mL separating funnel, and 100 mL of petroleum ether was added to separate the layers (B). This lower layer was separated in the same manner as (B) (C). Each upper layer of (A), (B), (C) was mixed and washed twice with 50% ethanol by volume aqueous solution, and then petroleum ether was evaporated in a 60 ° C. hot water bath, and the extracted petroleum ether soluble Got the minute. The amount of petroleum ether-soluble component was calculated from the formula (1). The petroleum ether-soluble component is an unreacted organic hydroxy compound or a compound derived from an organic hydroxy compound, and contains an odorous component.
[0035]
[Expression 1]

[0036]
[Measurement of color]
After diluting the sample 10 times with ethanol, absorbance at a wavelength of 420 nm was measured using a spectrophotometer UV-1600 manufactured by Shimadzu Corporation. A value obtained by multiplying the measured value by 1000 was defined as “color”. Note that the lower this value is, the better the color.
[0037]
[Odor evaluation]
The sample was neutralized with a 48% aqueous potassium hydroxide solution so that the active ingredient was 27% (phosphate monoester + phosphate diester, phosphate ester standard).
Sampling 50 mL of this phosphate ester salt in a 110 mL glass wide-mouth standard bottle, and one skilled panelist sniffs the bottle mouth odor directly, and the odor intensity is 7 levels from 0 [no odor] to 6 [strong] It was evaluated with.
[0038]
[Table 1]

[0039]
From the results in Table 1, it can be seen that the phosphoric acid esters obtained in Examples 1 to 4 are both excellent in color and less odor than those obtained in Comparative Examples 1 and 2. .
[0040]
【The invention's effect】
According to the present invention, it is possible to easily obtain a phosphoric acid ester that can reduce the odor simultaneously with the phosphorylation reaction and has a good color with simple equipment.

Claims (4)

A method for producing a phosphate ester, comprising reacting an organic hydroxy compound and a phosphorylating agent to produce a phosphate ester, and introducing an inert gas under a reduced pressure of 70 kPa or less . ^{0.0001~0.5m 3 / (hr · kg)} ( standard condition) The process according to claim 1 Symbol placement introducing the total charged amount 1kg of an organic hydroxy compound with the phosphorylating agent with an inert gas. The process according to claim 1 or 2 , wherein the inert gas is nitrogen gas. The process according to any one of claims 1 to 3, wherein the reaction temperature is 70 to 110 ° C.