JP3596765B2 - Method for producing phosphate ester - Google Patents

Description

【００４６】
表１に示された結果から、各実施例によれば、臭いが低減され、かつ色相が良好なリン酸エステルを大きな処理速度で得ることができることがわかる。
【００４７】
一方、比較例１及び４では、回分式又は攪拌膜型蒸発機が用いられているため、処理速度が小さいことがわかる。また、比較例２では、接触温度が高いため、臭い評価及び色相評価に著しく劣ることがわかる。比較例３では、接触温度が低いため、臭い評価が殆ど改善されないことがわかる。
【００４８】
【発明の効果】
本発明の製造法によれば、同程度の大きさの回分式又は攪拌膜型蒸発機を用いた場合と対比して、有臭成分量をより高い除去処理速度で低減し、臭い評価及び色相評価に優れたリン酸エステルを容易に得ることができる。
【００４９】
また、本発明の製造法によれば、処理速度が同一である場合、従来の回転薄膜式蒸発機よりも小型の充填塔を用いて効率よく臭いが低減され、色相が良好なリン酸エステルを容易に製造することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a phosphate ester. More specifically, the present invention relates to a method for producing a phosphoric ester useful as, for example, a shampoo, a face wash, a solid detergent and the like.
[0002]
[Prior art]
Phosphate esters are used in the fields of detergents, emulsifiers, fiber treatment agents, rust inhibitors, medical products and the like. Among the phosphate esters, particularly, alkali metal salts such as sodium and potassium and alkanolamine salts such as triethanolamine of monoalkyl phosphate esters having a long-chain alkyl group are water-soluble and have excellent foaming power and detergency, Moreover, since it has low toxicity and skin irritation, it is useful for products used directly on the human body, such as shampoos and facial cleansers. When a phosphate ester is blended into such a product that is directly used for the human body, it is important as quality that the odor based on the phosphate ester is weak.
[0003]
Usually, phosphate esters are produced by reacting an organic hydroxy compound with a phosphorylating agent such as phosphorus pentoxide, polyphosphoric acid, phosphorus oxychloride, and the like.
[0004]
However, unreacted organic hydroxy compounds, compounds derived from the organic hydroxy compounds, and by-products generated during the phosphorylation reaction are present as impurities in the phosphate ester. Since these impurities may adversely affect the odor as odorous components, a complicated process for removing the odorous components after the phosphorylation reaction is required.
[0005]
In general, phosphate ester is a compound that is liable to be decomposed due to heat history. Therefore, in order to minimize the heat history, as a deodorization method for removing odorous components, phosphate ester is re-used using a solvent. A method of crystallizing and a method of extracting a phosphate ester with a basic compound from a phosphate ester salt into an aqueous layer and extracting an odorous component into an organic layer have been proposed (Japanese Patent Publication No. 03-027558). .
[0006]
However, the method of recrystallizing a phosphate ester has a disadvantage that a large amount of a solvent is required for the phosphate ester, so that loss of the phosphate ester to the solvent cannot be avoided. In addition, the method of extracting a phosphate ester requires a large amount of a solvent, which is inferior in productivity, and requires equipment for recovering the solvent, thereby increasing the cost. There is.
[0007]
On the other hand, as a deodorizing method that does not use a solvent, there is a method in which a liquid film of a phosphate ester is formed using a stirred film evaporator, a wet wall tower, or the like, and the liquid film of the phosphate ester is brought into contact with an inert gas. It has been proposed (JP-A-57-35595).
[0008]
However, in these apparatuses, since the liquid film and the deodorizing gas come into contact only with the wall surface of the apparatus, there is a disadvantage that the speed of the removal process of the odorous component is low and the apparatus is large. In addition, since the clearance between the inner peripheral surface of the cylindrical main body and the outer peripheral surface of the scraper is very small (approximately 0.1 mm), the main body and the scraper must have precision in order to maintain this clearance. Since perfect round processing is required, there is a disadvantage that the cost is increased as a result.
[0009]
Therefore, there is a demand for the development of an economically advantageous industrial method for producing phosphate esters that can easily reduce the amount of remaining odorous components while maintaining the yield of phosphate esters.
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide a method capable of easily and quickly reducing the amount of odorous components and producing a phosphoric acid ester having good hue.
[0011]
[Means for Solving the Problems]
The present invention relates to a method for producing a phosphate ester having a reduced amount of odorous components, wherein a phosphate ester at 100 to 160 ° C. and an inert gas are brought into contact in a packed tower.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
Representative examples of the phosphoric acid ester include a phosphoric acid ester of an organic hydroxy compound.
[0013]
The organic hydroxy compound is an organic compound having a hydroxyl group. Examples of the organic hydroxy compound include straight-chain or branched-chain saturated or unsaturated alcohols, and alkylene oxide adducts thereof (alkylene oxide having 2 to 4 carbon atoms). More than one species can be used in combination. Among these, alcohols having 6 to 30 carbon atoms and polyoxyalkylene alkyl ethers obtained by adding alkylene oxides having 2 to 4 carbon atoms to the alcohols at an average addition mole number of 1 to 10 mol are preferable, and those having 8 to 14 carbon atoms are preferable. Alcohols and polyoxyalkylene alkyl ethers obtained by adding alkylene oxides having 2 to 4 carbon atoms to the alcohols at an average addition mole number of 2 to 4 mol are more preferred.
[0014]
The phosphoric esterification of the organic hydroxy compound can be obtained by esterifying the organic hydroxy compound with a phosphorylating agent.
[0015]
Examples of the phosphorylating agent include phosphorus pentoxide, polyphosphoric acid, phosphorus oxychloride and the like, and these can be used alone or in combination of two or more. The amount of the phosphorylating agent may be adjusted according to the desired composition of the phosphoric ester. Among these, phosphorus pentoxide and polyphosphoric acid are preferred because they do not produce by-products such as hydrochloric acid gas and are hardly loaded with equipment.
[0016]
When phosphorus pentoxide and polyphosphoric acid are used as a phosphorylating agent, the viewpoint of reducing by-products of orthophosphoric acid which adversely affects the stability and the like of products such as detergents using a phosphoric acid ester as a raw material, and from the viewpoint of reducing by-product adversely affects phosphodiester washability, phosphorus pentoxide (value was defined as 138% by weight orthophosphoric acid terms, the value obtained by dividing the polyphosphoric acid concentration in 138 the case of polyphosphoric acid P ₂ and O ₅ equivalent weight. hereinafter the same) relative to 1 mole, the amount of water is 0.5 to 1.5 moles, the amount of the organic hydroxy compound is preferably 1 to 3 mol.
[0017]
Phosphate esters usually contain unreacted organic hydroxy compounds, compounds derived from organic hydroxy compounds, and by-products generated during the phosphorylation reaction, as odorous components.
[0018]
The phosphoric acid ester in which the amount of the odorous component is reduced can be produced by bringing the phosphoric acid ester at 100 to 160 ° C into contact with an inert gas in a packed tower.
[0019]
A packed tower refers to a tower in which a filler is packed. Since the packed tower has a larger gas-liquid contact area per unit volume than the stirred film evaporator, the multi-stage tower and the wet wall tower, the processing speed for reducing the amount of odorous components can be increased, Since the apparatus itself can be reduced in size and does not have a drive unit such as a stirred film evaporator, it is excellent in terms of energy efficiency and maintenance.
[0020]
The packing material used for the packing tower is made of metal such as stainless steel, titanium, Hastelloy, ceramic, or the like. The packing material preferably has a porosity of 90 to 99% in order to reduce the pressure loss in the column.
[0021]
The types of the filler are roughly classified into two types. One of them is regular packing such as Sulzer packing (trade name) and Sulzer Lab packing (trade name) manufactured by Sulzer, and Monz packing (trade name) manufactured by Montz. The other is Raschig ring or Berlassador. And the like. These fillers may be used alone or in combination. Among these fillers, an ordered packing is preferred because it is easy to handle, has a small pressure loss, and hardly generates drift due to a filling method.
[0022]
The supply rate of the phosphate ester supplied to the packed tower is equal to the processing rate of the phosphate ester discharged from the packed tower after the treatment. The processing speed of the packed tower is compared with the processing speed of the conventional batch-type evaporator and the stirring-film-type evaporator in terms of the processing speed per volume of the contact portion of those devices. The volume of the contact portion means the volume of the packed portion in which the packing material is filled in the packed tower, and the volume of the inside of the cylinder having the scraping surface as a side surface in the case of the stirred film evaporator.
[0023]
When the phosphate ester and the inert gas are brought into contact with each other, the flow direction of the phosphate ester and the inert gas may be any of a horizontal flow and a vertical flow. Among these flow directions, a vertical flow is preferred from the viewpoint of improving the deodorizing efficiency. The flow direction of the inert gas with respect to the flow direction of the phosphate ester includes alternating current and cocurrent. Among these flow directions, countercurrent is preferable from the viewpoint of improving the deodorizing efficiency.
[0024]
From these facts, it is more preferable that the flowing directions of the phosphate ester and the inert gas are countercurrent in the vertical direction. Also, utilizing the free fall of the phosphate ester in the packed tower due to gravity, from the viewpoint of eliminating the need for power, the phosphate ester is supplied from the top of the packed tower, and the inert gas is supplied from the bottom of the packed tower. More preferably, it is provided.
[0025]
The value of the ratio of the flow rate of the inert gas to the flow rate of the phosphate ester [the flow rate of the inert gas (m ³ / h) / the flow rate of the phosphate ester (kg / h)] is such that a high vacuum is required. From the viewpoint of avoiding, and the viewpoint of reducing the amount of the inert gas used and the recovery process, 0.1 to 3 is preferable, and 0.2 to 1.5 is more preferable. The “flow rate of the inert gas (m ³ / h)” referred to in the present specification is a value in a standard state, that is, when the temperature is 0 ° C. and the pressure is 101.3 kPa.
[0026]
As used herein, the term "inert gas" refers to a gas that does not adversely affect the quality of the phosphate ester or the yield of the phosphate ester having a reduced amount of odorous components. Examples of the inert gas include water vapor, nitrogen gas, air, carbon dioxide gas and the like. Among them, steam which has a small thermal energy load on the condenser due to easy condensation and a small load on the exhaust system is preferable.
[0027]
The temperature of the phosphoric acid ester when the phosphoric acid ester is brought into contact with the inert gas is reduced from the viewpoint that the amount of the inert gas is reduced so that a high vacuum is not required, and the thermal decomposition of the phosphoric acid ester is avoided, thereby causing odor. From the viewpoint of avoiding an increase in the amount of components and deterioration of hue, the temperature is 100 to 160 ° C, preferably 120 to 140 ° C.
[0028]
The contact time between the phosphate ester and the inert gas varies depending on the contact conditions between the phosphate ester and the inert gas, and cannot be unconditionally determined. Usually, from the viewpoint of suppressing the thermal decomposition of the phosphate ester and preventing the amount of the inert gas for reducing the residual odorous component from increasing, the contact time between the phosphate ester and the inert gas is 1 to 1. It takes about 30 minutes.
[0029]
The pressure at which the phosphate ester is brought into contact with the inert gas is preferably 20 kPa or less, more preferably 14 kPa or less, and even more preferably 7 kPa or less, in consideration of the heat history, the amount of the inert gas, and the size of the apparatus.
[0030]
Thus, by bringing the phosphate ester into contact with the inert gas, a phosphate ester having a reduced amount of odorous components can be produced.
[0031]
【Example】
Example 1
(Step A)
287.5 g (0.95 mol) of undecyl alcohol (manufactured by Shell Co., trade name: Neodol 1-3) to which 3 mol of ethylene oxide has been added, and 22.2 g of an 85% phosphoric acid aqueous solution (phosphorus pentoxide 0. 096 mol and 0.474 mol of water), 54.3 g (0.377 mol) of phosphorus pentoxide was gradually added while maintaining the temperature at 40 to 50 ° C, and then the temperature was raised to 80 ° C. For 12 hours. Thereafter, 18.2 g of ion-exchanged water was added, and the mixture was hydrolyzed at 80 ° C. for 3 hours to obtain a phosphate ester.
[0032]
(Step B)
Next, while continuously raising the temperature of the phosphate ester to 130 ° C., the packed tower was controlled at 30 g / min at a pressure of 4 kPa [inner diameter 50 mm, height 22 cm, filler: Sumitomo Heavy Industries, Ltd. And trade name: Sulzer Lab Packing], and steam is countercurrently contacted at 90 ° C. and 15 g / min from the bottom of the column to reduce the amount of odorous components from the bottom of the column after a contact time of 3 minutes. A phosphoric acid ester was obtained.
[0033]
Example 2
(Step A)
Instead of the undecyl alcohol and the 85% phosphoric acid aqueous solution used in Step A of Example 1, 262.5 g (1.411 mol) of dodecyl alcohol, 24.1 g of 85% phosphoric acid (0.105 mol of phosphorus pentoxide) , Water, 0.514 mol) and phosphorous pentoxide (77.4 g, 0.545 mol), and phosphorylation was carried out in the same manner as in step A of Example 1 except that ion-exchanged water was not added. Thus, a phosphoric ester was obtained.
[0034]
(Step B)
Packing tower [inner diameter 50 mm, height 55 cm, packing material: Sumitomo Heavy Industries, Ltd.] at 30 g / min while controlling the pressure at 4 kPa while continuously raising the temperature of the phosphate ester obtained in step A to 130 ° C. Co., Ltd., trade name: Sulzer Lab Packing], and steam is brought into countercurrent contact at 90 ° C. and 10 g / min from the bottom of the tower, and after 8 minutes of contact time, the amount of odorous components is reduced from the bottom of the tower. A reduced phosphate ester was obtained.
[0035]
Example 3
Except that in step B of Example 1, an irregular filler (outer diameter: 6 mm, mesh size: 100 mesh (Tyler mesh), manufactured by Sankyo Special Wire Mesh Chemical Co., Ltd., trade name: McMahon Packing) was used as the filler. In the same manner as in Example 1, a deodorized product was obtained.
[0036]
Example 4
The phosphate ester obtained in Step A of Example 1 was mixed with steam at a temperature of 100 ° C., a pressure of 1 kPa, a contact time of 8 minutes and a steam flow rate of 21 g / min in the packed tower used in Step B of Example 2. By countercurrent contact, a phosphate ester with a reduced amount of odorous components was obtained from the bottom of the tower.
[0037]
Example 5
In Step B of Example 1, a phosphate ester having a reduced amount of odorous components was obtained in the same manner as in Example 1 except that the pressure of the packed tower was changed to 20 kPa.
[0038]
Comparative Example 1
200 g of the phosphate ester (odor evaluation 6) obtained in the step A of Example 1 was charged into a 500 mL batch type evaporator (four-necked flask) equipped with a blowing tube, and 100 g at a pressure of 2.7 kPa. The temperature was raised to ° C. Thereafter, steam was blown into the batch type evaporator at 90 ° C. at a flow rate of 100 g / h for 3 hours to obtain a phosphate ester having a reduced amount of odorous components.
[0039]
Comparative Example 2
In step B of Example 1, a phosphorus having a reduced amount of odorous components was used in the same manner as in Example 1 except that the contact temperature between the phosphoric ester and steam in the packed tower was changed from 130 ° C to 170 ° C. An acid ester was obtained.
[0040]
Comparative Example 3
In step B of Example 1, a phosphorus having a reduced amount of odorous components was used in the same manner as in Example 1 except that the contact temperature between the phosphoric ester and steam in the packed tower was changed from 130 ° C to 90 ° C. An acid ester was obtained.
[0041]
Comparative Example 4
In Step B of Example 1, phosphorus was used in place of the packed tower using a stirred film evaporator (manufactured by Shinko Pantech Co., Ltd., model number: 2-03, heat transfer area: 0.03 m ² , glass). Example 1 except that the supply rate of the acid ester was 3 g / min, the supply rate of the steam was 1.5 g / min, the contact time was 1 minute, the pressure was 4 kPa, and the rotation speed of the scraper was 400 r / min. Similarly, a phosphoric acid ester having a reduced amount of odorous components was obtained.
[0042]
Next, the phosphoric acid ester obtained in step A of each example and each comparative example (the phosphoric acid ester before the treatment) and the phosphoric acid ester obtained in the step B in which the amount of the odorous component was reduced (the phosphoric acid ester after the treatment) (Phosphate ester) was evaluated for odor and hue according to the following methods. Table 1 shows the results.
[0043]
[Odor evaluation]
50 mL of phosphate ester before or after treatment is placed in a glass wide-mouthed bottle having a capacity of 110 mL, and one expert panelist smells the smell of the bottle directly. The evaluation is sensuously determined according to the intensity of the odor in seven levels from 0 to 6 (0 is odorless and 6 is the strongest odor).
[0044]
(Hue evaluation)
The phosphate ester before or after the treatment is diluted to 10% by weight with ethanol, put into a quartz glass cell, and absorbance at a wavelength of 420 nm is measured with an absorbance meter (trade name: UV-1600, manufactured by Shimadzu Corporation). Is measured, and the value is multiplied by 1000.
[0045]
[Table 1]

[0046]
From the results shown in Table 1, it can be seen that according to each example, a phosphoric acid ester with reduced odor and good hue can be obtained at a high processing speed.
[0047]
On the other hand, in Comparative Examples 1 and 4, it can be seen that the processing speed is low because a batch type or stirred film type evaporator is used. In Comparative Example 2, the contact temperature was high, so that the odor evaluation and the hue evaluation were significantly poor. In Comparative Example 3, it can be seen that the odor evaluation is hardly improved because the contact temperature is low.
[0048]
【The invention's effect】
According to the production method of the present invention, the amount of odorous components is reduced at a higher removal treatment rate, compared with the case of using a batch type or stirred film type evaporator of the same size, and the odor evaluation and hue are reduced. It is possible to easily obtain a phosphate ester excellent in evaluation.
[0049]
Further, according to the production method of the present invention, when the processing speed is the same, the odor is efficiently reduced by using a smaller packed tower than the conventional rotary thin film evaporator, and a phosphoric acid ester having a good hue can be obtained. It can be easily manufactured.

Claims (4)

A method for producing a phosphate ester having a reduced amount of odorous components, wherein a phosphate ester at 100 to 160 ° C. is contacted with an inert gas in a packed tower. The method according to claim 1, wherein the phosphate ester and the inert gas are brought into contact under a reduced pressure of 20 kPa or less. The ratio of the flow rate of the inert gas to the flow rate of the phosphate ester (the flow rate of the inert gas (m ³ / h) / the flow rate of the phosphate ester (kg / h)) is 0.1 to 3. 3. The production method according to 1 or 2. 4. The method according to claim 1, wherein the inert gas is water vapor.