WO2006080583A1 - Procede de production d’un phosphate - Google Patents

Procede de production d’un phosphate Download PDF

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Publication number
WO2006080583A1
WO2006080583A1 PCT/JP2006/301935 JP2006301935W WO2006080583A1 WO 2006080583 A1 WO2006080583 A1 WO 2006080583A1 JP 2006301935 W JP2006301935 W JP 2006301935W WO 2006080583 A1 WO2006080583 A1 WO 2006080583A1
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WO
WIPO (PCT)
Prior art keywords
hydroxy compound
organic hydroxy
acid
mol
same manner
Prior art date
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PCT/JP2006/301935
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English (en)
Japanese (ja)
Inventor
Makoto Kohama
Akira Matsunaga
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Kao Corporation
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Publication date
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Publication of WO2006080583A1 publication Critical patent/WO2006080583A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids

Definitions

  • TECHNICAL FIELD The present invention relates to a method for producing a phosphate ester.
  • Prior Art Phosphoric esters of organic hydroxy compounds are used in the field of cleaning agents, emulsifiers, fiber treatment agents, antifungal agents, or medical products.
  • alkylene oxide adducts are used as organic hydroxy compounds, and acid-type phosphate esters are superior in foaming and detergency in weakly acidic regions, and have low toxicity and skin irritation. It is useful for products that are used directly on the human body, such as skin care products and facial cleansers, and is particularly useful for skin care products.
  • Such acid-type phosphate ester is produced, for example, by reacting an aliphatic monohydric alcohol and alkylene oxide in the presence of an alkali catalyst, neutralizing with acetic acid, and further phosphorylating.
  • the phosphoric acid ester produced by such a method has a bad smell and is not satisfactory.
  • Japanese Patent Laid-Open No. 2000-0 2 1 7 6 3 1 discloses that after an organic hydroxy compound and a phosphorylating agent are reacted, purification is performed to reduce unreacted organic hydroxy compound. So that the water content is within a specific range by adding water to the purified product.
  • a process for preparing a phosphate ester is disclosed.
  • the present invention provides a method for producing a phosphate ester comprising the following steps 1 and 2, or a method for producing a phosphate ester further comprising the following step 3.
  • Step 1 After reacting an aliphatic monohydric alcohol having 6 to 36 carbon atoms with an alkylene oxide having 2 to 4 carbon atoms in the presence of an alkali catalyst, a hydroxycarboxylic acid having 2 to 10 carbon atoms, A step of neutralizing with at least one acid selected from dicarboxylic acids and tricarboxylic acids to obtain an organic hydroxy compound.
  • Step 2 A step of reacting the organic hydroxy compound obtained in Step 1 with a phosphorylating agent.
  • Step 3 A step of purifying the reaction product obtained in Step 2.
  • DETAILED DESCRIPTION OF THE INVENTION Japanese Patent Application Laid-Open No. 2000-0 2 1 7 6 3 1 does not describe any method for improving odor by a method for producing an organic hydroxy compound used as a raw material.
  • the present invention relates to a production method in which an organic hydroxy compound constituting a phosphate ester is an alkylene oxide adduct, and the odor of an acid phosphate ester is improved. Produces high-quality phosphate esters with low odor.
  • the aliphatic monohydric alcohol used in Step 1 of the present invention is a saturated or unsaturated aliphatic monohydric alcohol having 6 to 36 carbon atoms, and a saturated or unsaturated aliphatic monohydric alcohol having 8 to 30 carbon atoms.
  • Preferred is a saturated or unsaturated aliphatic monovalent alkyl having 8 to 22 carbon atoms. More preferred is call.
  • Examples of the alkylene oxide having 2 to 4 carbon atoms used in Step 1 include ethylene oxide, propylene oxide, butylene oxide, etc., and alkylene oxide having 2 to 3 carbon atoms is preferable. More preferred is oxide or a mixture of ethylene oxide and propylene oxide.
  • the average number of moles of alkylene oxide added in the organic hydroxy compound is preferably from 0.1 to 100, more preferably from 0.1 to 50, and particularly preferably from 0.1 to 20.
  • the alkali catalyst used in Step 1 include alkali metal hydroxides and alkali metal alkoxides, potassium hydroxide and sodium hydroxide are preferred, and potassium hydroxide is particularly preferred.
  • the amount of the alkali catalyst added is preferably from 0.001 to 0.1 mol, more preferably from 0.005 to 0.05 mol, per 1 mol of the aliphatic monovalent alcohol.
  • the temperature at the time of reacting the aliphatic monohydric alcohol and the alkylene oxide is preferably from 50 to 180, more preferably from 60 to 120.
  • the reaction pressure is preferably under pressure, more preferably 0.1 to 0.5 MPa.
  • the acid used for neutralization is at least one selected from hydroxycarbonic acid, dicarboxylic acid and tricarboxylic acid having 2 to 10 carbon atoms, lactic acid, glyceric acid, malonic acid, glycolic acid, At least one selected from citrate and malic acid is preferable, and the amount dissolved in water is 50% by volume or more or
  • Step 2 of the present invention is a step of reacting the organic hydroxy compound obtained in Step 1 with a phosphorylating agent.
  • the phosphorylating agent used include orthophosphoric acid, phosphorus pentoxide (phosphoric anhydride), Examples thereof include phosphoric acid and phosphorus oxychloride, and orthophosphoric acid and phosphorus pentoxide (phosphoric anhydride) are preferable. These can be used alone or in combination of two or more.
  • the amount of the phosphorylating agent can be appropriately determined according to the target phosphate ester composition.
  • the reaction temperature at the time of reacting the organic hydroxy compound and the phosphorylating agent is preferably from 40 to 120, and more preferably from 60 to 100. After the phosphorylation reaction, it is preferable to reduce by-products and the like by hydrolysis.
  • step 3 is preferably included from the viewpoint of further improving the odor of the phosphate ester.
  • Step 3 is a step of purifying the reaction product obtained in Step 2.
  • the purification method is not particularly limited. For example, Japanese Patent Publication No. 3-2 7 5 5 8
  • a method by distillation such as steam distillation, and further inert For example, a method of blowing gas.
  • distillation under reduced pressure and blowing of inert gas are preferable, and steam distillation and blowing of inert gas are more preferable.
  • purification can be performed under milder conditions, which is preferable in improving the hue of the product.
  • the organic hydroxy compound constituting the phosphoric acid ester is an alkylene oxide adduct, and the odor of the phosphoric acid ester that is in the acid form can be improved and obtained by the method of the present invention.
  • Phosphate esters have excellent foaming and detergency in weakly acidic regions, and are low in toxicity and skin irritation, and do not deteriorate odors. Therefore, various washing bases, especially hands, face, and body wash It is extremely useful as a base.
  • Example 2 In Step 2 of Example 1, after raising the temperature to 80 and carrying out the reaction for 12 hours, the pressure was reduced to 4 kPa while maintaining the temperature at 80 ° C, and water vapor was supplied into the reactor at a rate of 12 g / hour. Steam distillation was performed under the same conditions for 10 hours. After cooling, 1213 g of phosphate ester containing 2.0% organic hydroxy compound and 0.8% water was obtained. Comparative Example 1 In Step 1 of Example 1, reaction was carried out in the same manner as in Example 1 except that 1. lg (0.018 mol) of acetic acid was used instead of lactic acid to neutralize the power hydroxide.
  • Comparative Example 2 In the same manner as in Comparative Example 1, an organic hydroxy compound was obtained, and after phosphorylation was performed in the same manner, steam distillation was performed in the same manner as in Example 2 to obtain an organic hydroxy compound content of 2.1% and a water content of 0.9%. 1212 g of phosphate ester containing Test Example 1 25 g of each phosphate ester obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was placed in a 50 mL screw tube, and sensory evaluation (odor evaluation) was performed at the bottle mouth by four functional panelists. The The sensory evaluation was carried out with the following 6 levels of 0-5, and the average value of 4 people. The results are shown in Table 1.
  • Example 4 In Step 2 of Example 3, the temperature was raised to 80, the reaction was carried out for 12 hours, and the pressure was reduced to 4 kPa while maintaining the temperature at 80, and steam was blown into the reactor at a rate of 10 g per hour. Steam distillation was performed for 10 hours under the same conditions. After cooling, 1014 g of phosphate ester containing 2. G% organic hydroxy compound and 0.9% water was obtained.
  • phosphorylation and subsequent hydrolysis treatment were carried out in the same manner as in Step 2 of Example 3. In this manner, 1021 g of a phosphoric acid este
  • Comparative Example 4-An organic hydroxy compound was obtained in the same manner as in Comparative Example 3, and phosphorylation was performed in the same manner, followed by steam distillation in the same manner as in Example 4 to obtain an organic hydroxy compound content of 2.1% and moisture. 1016 g of phosphate ester containing 0.9% was obtained. Comparative Example 5 In Step 1 of Example 3, the reaction was completed without neutralizing the power hydroxide hydroxide with lactic acid. The product after completion of the reaction was extracted from the lower drain of the reaction tank to obtain 5040 g of an organic hydroxy compound (ethylene oxide average 0.5 mol adduct, average molecular weight 215.8).
  • Example 6 In Example 5, the temperature was raised to 80 ° C and the reaction was carried out for 12 hours, then the pressure was reduced to 4 kPa at 80 ° C, and steam was blown into the reactor at a rate of 10 g per hour. Steam distillation was performed for 10 hours under the same conditions. After cooling, 1015 g of phosphoric acid: sterel containing 2.0% organic hydroxy compound content and 0.9% moisture was obtained.
  • Comparative Example 1 Using the same stored product as in Comparative Example 9, phosphorylation was performed in the same manner, and then steam distillation was performed in the same manner as in Example 6 to obtain an organic hydroxy compound content of 2.1% and a water content of 0.9%. 1014 g of phosphate ester containing Test Example 2 In the same manner as in Test Example 1, sensory evaluation of odor was performed on each phosphate ester obtained in Examples 3 to 6 and Comparative Examples 3 to 10. The results are shown in Table 2.
  • Example 7 The reaction was completed in the same manner as in Step 1 of Example 1 except that potassium hydroxide was neutralized with 2.9 g (0.018 mol) of 65% aqueous solution of dalliceric acid instead of lactic acid.
  • 919.lg (3.28 mol) 919.lg (3.28 mol)
  • the phosphorylation reaction and the subsequent hydrolysis treatment were carried out in the same manner as in Step 2 of Example 1. 1209 g of phosphoric acid ester containing 2.1% of organic hydroxy compound and 1.2% of water was obtained.
  • Example 8 An organic hydroxy compound was obtained in the same manner as in Example 7. After phosphorylation was carried out in the same manner, steam distillation was carried out in the same manner as in Example 2 to obtain an organic hydroxy compound content of 2.0% and a water content of 0. 1210 g of phosphate ester containing 9% was obtained.
  • Example 10 An organic hydroxy compound was obtained in the same manner as in Example 9. After phosphorylation was performed in the same manner, steam distillation was performed in the same manner as in Example 2 to obtain an organic hydroxy compound content of 2.2% and water content of 0%. 1209 g of phosphate ester containing 8% was obtained.
  • Test Example 3 The odor sensory evaluation of each phosphate ester obtained in Examples 7 to 10 was performed in the same manner as in Test Example 1. The results are shown in Table 3.
  • Example 1 1 Step 1> A 3 L autoclave (made by S US) was used as a reaction tank, and here, Neodol 23 (Neodol 23) 1794.8 g (9.30 mol) made by Ciel Chemicals Japan, flaky potassium hydroxide (made by Nippon Soda Co., Ltd.) 1.3 g (0.023 mol) was added, and the inside of the reaction tank was replaced with nitrogen. The temperature was raised to 110 while stirring in the tank, and the pressure was reduced to 13 Pa with a vacuum pump, followed by dehydration for 1 hour (distilled water: 1.2 g).
  • Neodol 23 Neodol 23
  • flaky potassium hydroxide made by Nippon Soda Co., Ltd.
  • Og (P 2 0 5 ⁇ nH 2 0 P 2 0 5 ; 1.72 mol, H 2 0; 2.58 mol) were added, stirred and mixed, and stirred for 1 hour while maintaining the temperature at 80 ° C.
  • 66.0 g (0.46 mol) of phosphorus pentoxide (effective component 99.0%) was gradually added while maintaining the temperature at 50 to 70, and then the temperature was raised to 80 and the reaction was carried out for 12 hours.
  • Example 1 2 In Step 2 of Example 1 1, after the temperature was raised to 80 ° C. and the reaction was performed for 12 hours, the pressure was reduced to 4 kPa while maintaining at 80, and steam was blown into the reactor at a rate of 12 g / hour, Steam distillation was performed for 10 hours under the same conditions. After cooling, 1204 g of phosphate ester containing 2.2% organic hydroxy compound and 0.9.% Moisture was obtained.
  • Example 1 3 Example 1 In Step 1 of Example 1, the reaction was carried out in the same manner except that 2.4 g of 50% malonic acid aqueous solution was used instead of darlicolic acid to neutralize the hydroxylated power, and the reaction finished product was placed at the bottom of the reaction vessel.
  • the obtained organic hydroxy compound (average molecular weight 215.8) 844. g, 1169.8% polyphosphoric acid 289.8 g and phosphorus pentoxide (active ingredient 99.0%) 65.7 g in the same manner as in Step 2 of Example 1 1.
  • Example 14 An organic hydroxy compound was obtained in the same manner as in Example 13 and after phosphorylation was carried out in the same manner, steam distillation was carried out in the same manner as in Example 12 to obtain an organic hydroxy compound content of 2.1% and a water content of 0.8. 1198 g of phosphoric acid ester containing% was obtained.
  • Example 1 5 Example 1 In Step 1 of 1 above, the reaction was performed in the same manner except that 3.0 g of 50% aqueous citrate solution was used in place of glycolic acid to neutralize the power hydroxide. Extracted from the bottom drain of the tank, organic hydroxy compounds (average of ethylene oxide)
  • Example 1 6 An organic hydroxy compound was obtained in the same manner as in Example 15 and phosphorylated in the same manner, followed by steam distillation in the same manner as in Example 12 to obtain an organic hydroxy compound content of 2.3% and a water content of 0.9%. As a result, 1202 g of phosphoric acid ester was obtained.
  • Example 1 8 An organic hydroxy compound was obtained in the same manner as in Example 17. After phosphorylating in the same manner, steam distillation was performed in the same manner as in Example 12 to obtain an organic hydroxy compound content of 2.2% and moisture of 0.8%. 1186 g of phosphate ester was obtained.
  • Example 1 9 Example 1 In Step 1 of 1, using 2.4 g of 90% aqueous lactic acid instead of glycolic acid.
  • Example 20 An organic hydroxy compound was obtained in the same manner as in Example 19 and phosphorylation was carried out in the same manner, followed by steam distillation in the same manner as in Example 12. The organic hydroxy compound content was 2.1% and the water content was 0.9. 1196 g of phosphoric acid ester containing% was obtained. Test Example 4 Example 1 Each of the phosphate esters obtained in 1 to 20 was subjected to a sensory evaluation of odor in the same manner as in Test Example 1. The results are shown in Table 4. Table 4
  • Example 2 1 Phosphate ester obtained by the same operation as in steps 1 and 2 of Example 1 (containing 2.1% of organic hydroxy compound and 1.3% of water, odor evaluation result similar to Test Example 1
  • Comparative Example 1 Phosphate ester obtained by the same procedure as in Steps 1 and 2 of Comparative Example 1 (containing 2.2% organic hydroxy compound and 1.2% moisture, odor evaluation result similar to Test Example 1 3 4) Using a Smith distiller, 600 g of water was supplied at a pressure of 2 kPa and a distillation temperature of 150, while supplying phosphate ester from the top of the column at 4 g / min and water from the bottom at 3 g / min. Steam distillation was performed. Organic hydroxy compound 0.3% and moisture 0.1% from drain 5 87 g of phosphate ester containing Test Example 5 In the same manner as in Test Example 1, the sensory evaluation results of odor were performed on the phosphate esters obtained in Example 21 and Comparative Examples 11 and 12.
  • each phosphate ester was precisely weighed and dissolved in ethanol and then made up to 100 ml, and the hue was measured with a spectrophotometer.
  • the hue is a value obtained by multiplying the absorption at a wavelength of 420 ⁇ by 100 and the results are shown in Table 5.

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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Abstract

L’invention concerne un procédé de production d’un phosphate qui comprend les étapes 1 et 2 suivantes. L’étape 1 consiste à faire réagir un alcool monohydrique aliphatique ayant de 6 à 36 atomes de carbone et un oxyde d'alkylène ayant de 2 à 4 atomes de carbone en présence d'un catalyseur alcalin, puis à neutraliser le produit avec au moins un acide choisi parmi les acides hydroxycarboxyliques, les acides dicarboxyliques et les acides tricarboxyliques ayant de 2 à 10 atomes de carbone, donnant de ce fait un composé organique de type hydroxy. L’étape 2 consiste à faire réagir le composé organique de type hydroxy obtenu dans l’étape 1 avec un agent de phosphorylation.
PCT/JP2006/301935 2005-01-31 2006-01-31 Procede de production d’un phosphate WO2006080583A1 (fr)

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JP2005-022644 2005-01-31
JP2005022644 2005-01-31

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CN103374029A (zh) * 2013-06-04 2013-10-30 宁波市联凯化学有限公司 一种脂肪醇磷酸聚氧乙烯酯钾盐的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56112931A (en) * 1980-02-12 1981-09-05 Sanyo Chem Ind Ltd Polyol composition
JPH0253417B2 (fr) * 1985-02-08 1990-11-16 Nippon Shokubai Kagaku Kogyo Kk
JPH0341045A (ja) * 1989-07-07 1991-02-21 Sanyo Chem Ind Ltd ビスフェノールａジオキシアルキレンエーテルの製造法および組成物
JP2002308811A (ja) * 1998-09-29 2002-10-23 Sanyo Chem Ind Ltd ノニオン性界面活性剤の製造方法
JP2004217631A (ja) * 2002-12-26 2004-08-05 Kao Corp リン酸エステルの製造法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56112931A (en) * 1980-02-12 1981-09-05 Sanyo Chem Ind Ltd Polyol composition
JPH0253417B2 (fr) * 1985-02-08 1990-11-16 Nippon Shokubai Kagaku Kogyo Kk
JPH0341045A (ja) * 1989-07-07 1991-02-21 Sanyo Chem Ind Ltd ビスフェノールａジオキシアルキレンエーテルの製造法および組成物
JP2002308811A (ja) * 1998-09-29 2002-10-23 Sanyo Chem Ind Ltd ノニオン性界面活性剤の製造方法
JP2004217631A (ja) * 2002-12-26 2004-08-05 Kao Corp リン酸エステルの製造法

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