JP5057215B2 - Process for producing polyoxyalkylene-modified organopolysiloxane compound - Google Patents

Description

  The present invention relates to a method for producing a polyoxyalkylene-modified organopolysiloxane compound. More specifically, the present invention provides a method for producing an α-hydro-ω-alkenyloxy-polyoxyalkylene compound having a production efficiency higher than that of conventionally used etherified polyoxyalkylene compounds, and does not use additives and solvents. In the hydrosilylation reaction performed in (1), the present invention relates to a production method for obtaining a polyoxyalkylene-modified organopolysiloxane compound in which gelation does not occur by using a specific α-hydro-ω-alkenyloxy-polyoxyalkylene compound.

  A method for obtaining a polyoxyalkylene-modified organopolysiloxane compound by a hydrosilylation reaction between a polyoxyalkylene compound having a double bond at the terminal and a hydrogen organopolysiloxane compound is widely known. However, when the α-hydro-ω-alkenyloxy-polyoxyalkylene compound is hydrosilylated, an isomerization reaction occurs in which part of the terminal olefin group in the polyoxyalkylene compound undergoes internal rearrangement during the hydrosilylation reaction. The resulting propanal has been reported to form a cross-linked structure between the hydroxyl group in the polyoxyalkylene compound and propanal, may have a higher viscosity than expected, and may even become a gel (e.g. Patent Document 1). As means for preventing side reactions, a method using a solvent such as isopropyl alcohol or toluene, or using an additive such as a carboxylate under conditions where no solvent is used has been conventionally performed. As a specific example, a method using sodium propionate as a reaction accelerator (for example, Patent Document 2) has been proposed. However, removal of the solvent after the reaction is complicated in the method of adding the solvent, and the method of adding the additive lowers the purity of the modified silicone and is difficult to remove. It may not be preferable. So far, a method for obtaining an α-hydro-ω-alkenyloxy-polyoxyalkylene-modified organopolysiloxane compound using a hydrophilic α-hydro-ω-alkenyloxy-polyoxyalkylene compound without using an additive and a solvent is It was not found.

Examples of other means include a method in which a hydroxyl group is changed to another functional group and then hydrosilylation is performed. Specifically, a method of substituting an alkyl group or an alkenyl group by an etherification reaction and an acyl group by an esterification reaction. Is mentioned. However, the etherification reaction uses a large amount of a catalyst, and after the reaction, an excess catalyst and a salt generated by the reaction are washed with a large amount of water. In addition, this method cannot be used when it is desired to leave a terminal hydroxyl group for the purpose of use. In the esterification reaction, the polyether terminal can be regenerated to a hydroxyl group by alkali hydrolysis after the hydrosilylation reaction, but removal of by-products is very complicated, and there is a problem that the siloxane bond of the organopolysiloxane is decomposed.
JP-A-10-212349 JP-A-1-101333

Patent Document 3 describes a compound in which a polyoxyalkylene side group having secondary and tertiary hydroxy ends is bonded to polysiloxane. Patent Documents 4 and 5 describe production methods by polymerization of α-hydro-ω-alkenyloxy-polyoxyalkylene compounds.
Japanese Patent Publication No. 6-8362 JP 2003-292607 A JP 2004-277548 A

It is necessary to solve simultaneously the problem of yield reduction of the polyoxyalkylene compound and the problem of gelation during the hydrosilylation reaction. Further, for example, in cosmetic applications, compatibility is required in applications where the amount of water is large, such as hair lotion or lotion.
The present invention simultaneously solves the problem of yield reduction of polyoxyalkylene compounds and the problem of gelation during hydrosilylation reaction, and can be used well even in applications where the amount of water is large. It aims at providing the manufacturing method of.

  As a result of intensive studies to solve the above-mentioned problems, an α-hydro-ω-alkenyloxy-polyoxyalkylene compound having a specific structure is used, so that a gel can be formed during a hydrosilylation reaction performed without using an additive and a solvent. As a result, it was found that the production efficiency is improved by increasing the yield as compared with the polyoxyalkylene compound in which side reactions such as oxidization are suppressed and the terminal hydroxyl group is etherified or esterified. It came to be completed.

  That is, the present invention performs hydrosilylation using an α-hydro-ω-alkenyloxy-polyoxyalkylene compound represented by the formula (1) and a hydrogen organopolysiloxane compound represented by the formula (2). This is a method for producing a polyoxyalkylene-modified organopolysiloxane compound.

^{R 1 O- (EO) m- (} BO) nH (1)
(In the formula, R ¹ represents an alkenyl group having 3 to 5 carbon atoms having a double bond at the terminal, EO represents an oxyethylene group, and BO represents an oxybutylene group, and m = 7 to 50 and n = 1 to 2. .)

（式中、Ｒ^２はメチル基又はフェニル基、Ｒ^３は水素原子、メチル基又はフェニル基であり、ｘ＝１〜２００、ｙ＝１〜１００である。）

(In the formula, R ² is a methyl group or a phenyl group, R ³ is a hydrogen atom, a methyl group or a phenyl group, and x = 1 to 200 and y = 1 to 100.)

Preferably, the polyoxyalkylene compound represented by the formula (1) is produced by the steps shown in the following (A) and (B).
(A) An alkylene oxide addition reaction step in which ethylene oxide is added to alkenyl alcohol, followed by addition reaction of butylene oxide. An alkali catalyst is used as a catalyst for the alkylene oxide addition reaction, and alkenyl alcohol, ethylene oxide and butylene oxide are used. And (B) a step of setting the addition amount of the alkali catalyst to 0.02 to 0.5 parts by weight when the total charge of is 100 parts by weight and performing the alkylene oxide addition reaction in a temperature range of 90 to 130 ° C .; In the adsorption step of adding an adsorbent to the reaction product of the alkylene oxide addition reaction, when the total amount of alkenyl alcohol, ethylene oxide and butylene oxide is 100 parts by weight, the adsorbent is 0.2 to 2.0 parts by weight added That process.

  In addition, the present invention provides an α-hydro-ω-alkenyloxy-polyoxyalkylene compound represented by the formula (1) and a hydrogenorganopolysiloxane compound represented by the formula (2), catalyzed by chloroplatinic acid. And hydrosilylation reaction is performed.

  The method for producing a polyoxyalkylene-modified organopolysiloxane compound of the present invention can be suitably used because side reactions such as gelation are suppressed in a hydrosilylation reaction performed without using an additive and a solvent. Further, it is useful because the yield is increased and the production efficiency is improved as compared with a polyoxyalkylene compound in which the terminal hydroxyl group is etherified or esterified. Furthermore, since the polyoxyalkylene-modified organopolysiloxane compound of the present invention has surface active properties, it can be suitably used in applications such as cosmetic materials, textile oils, paint additives, foam stabilizers and the like. .

  The method for producing the polyoxyalkylene-modified organopolysiloxane compound of the present invention can be specifically produced by the method described below.

(1. Alkylene oxide addition reaction)
As the raw material alcohol, alkenyl alcohol in which a hydroxyl group is bonded to R ¹ in the formula (1) is used. In the formula (1), R ¹ is an alkenyl group having 3 to 5 carbon atoms having a double bond at the terminal, for example, an allyl group, 3-butenyl group, methallyl group, 2-methyl-3-butenyl group, 3 Examples include alkenyl groups such as -methyl-3-butenyl group, 1,1, -dimethyl-2-propenyl group, and 4-pentenyl group, with allyl group being preferred.

  Examples of the reaction catalyst include alkali metals such as metal sodium and metal potassium; alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide and cesium hydroxide; alkalis such as sodium methoxide and potassium t-butoxide. Examples of the metal alkoxide include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide, and cesium hydroxide, and alkali metal alkoxides such as sodium methoxide and potassium t-butoxide. The amount of catalyst added is 0.02 to 0.5 parts by weight, preferably 0.05 to 0.2 parts by weight, based on the total amount charged. When the addition amount of the catalyst is less than 0.02 parts by weight, the alkylene oxide addition reaction does not proceed, and when it exceeds 0.5 parts by weight, the alkenyl group easily undergoes internal transfer, which is not preferable.

  The alkylene oxide addition reaction temperature is 90 to 130 ° C., preferably 100 to 120 ° C., and alkylene oxide is continuously supplied under an inert gas atmosphere of nitrogen, helium, argon or the like under 0.6 MPa (gauge pressure). While doing. When the reaction temperature is less than 90 ° C, the reaction does not proceed. When the reaction temperature exceeds 130 ° C, the alkenyl group easily undergoes internal transfer, which is not preferable. An α-hydro-ω-alkenyloxy-polyoxyalkylene compound having a terminal hydroxyl group can be produced by addition reaction of butylene oxide with a block after addition reaction of ethylene oxide.

The number of moles of ethylene oxide added is m = 7-50 in the formula (1), preferably m = 7-20. When m is less than 7, the addition reaction of butylene oxide is subsequently performed, and thus the hydrophilicity as the polyoxyalkylene compound becomes insufficient, which is not preferable. Moreover, when m exceeds 50, since it becomes high viscosity and handling becomes complicated, it is not preferable. Moreover, the addition mole number of butylene oxide is n = 1-2 in Formula (1). When n is less than 1, the possibility of gelation in the hydrosilylation reaction increases. On the other hand, when n exceeds 2, the hydrophobicity becomes strong and the hydrophilicity as a polyoxyalkylene compound becomes insufficient, which is not preferable. Moreover, it is preferable that the secondary hydroxylation rate of the terminal hydroxyl group of the compound represented by Formula (1) is 90% or more. The secondary hydroxylation rate of the terminal hydroxyl group is measured by ¹ H-NMR analysis using a sample that has been esterified with trifluoroacetic anhydride.

(2. Purification of α-hydro-ω-alkenyloxy-polyoxyalkylene compound)
After the alkylene oxide addition reaction, purification can be performed by a known method. Neutralization can be performed by a known method using an acid such as sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid and the like. In the production method of the present invention, it is preferable to add 2 to 10 parts by weight of water and neutralize the pH in the range of 5.0 to 7.0.

  For the dehydration, a known method such as a method of dehydrating at normal pressure while blowing an inert gas or a method of dehydrating under a vacuum condition can be used, but a dehydration temperature of 60 to 130 ° C., preferably 70 to 120 ° C. 1 to 10 hours, preferably 2 to 8 hours while distilling an inert gas, to crystallize the salt, and after distilling the water, the system is evacuated and then the inert gas is blown for 30 minutes to More preferably, dehydration is performed for 5 hours, preferably 1 to 3 hours. Further, during dehydration, mixing may be performed using a stirring blade.

  After the dehydration process is completed, an adsorbent is added to perform an adsorption process. The adsorption treatment can be performed using a known method such as a method of treating at normal pressure while blowing an inert gas, a method of treating under pressure or vacuum conditions, etc., but a dehydration temperature of 60 to 110 ° C., preferably It is more preferable to perform the adsorption treatment for 20 minutes to 3 hours, preferably 30 minutes to 2 hours, while blowing an inert gas between 70 to 100 ° C. Moreover, you may carry out during an adsorption process, mixing using a stirring blade.

  Examples of the adsorbent include synthetic adsorbent, activated clay, synthetic zeolite, activated carbon, activated alumina, silica gel, and magnesia. Among them, synthetic adsorbent is preferable, and commercially available adsorbents include Kyoward 100, Kyoward 200, KYOWARD 300, KYODWARD 400, KYODWARD 500, KYODWARD 600, KYODWARD 700, KYOWARD 1000, KYOWARD 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.), TOMICS AD100, TOMICS AD200, TOMICS AD300, TOMICS AD400, TOMICS Examples include AD500, Tomix AD600, Tomix AD700, Tomix AD800 (manufactured by Iwata Pharmaceutical Co., Ltd.), and the like. The amount of adsorbent added is preferably in the range of 0.2 to 2.0 parts by weight, more preferably 0.3 to 1.0 parts by weight, based on the total amount charged. When the amount of adsorbent added is less than 0.2 parts by weight, the reaction may not be completed in the hydrosilylation reaction. On the other hand, if it exceeds 2.0 parts by weight, the adsorbability may not be improved and the filtration efficiency may be lowered. Moreover, this process can also process using several adsorption agent. After completion of the adsorption treatment step, filtration is performed, and the salt and adsorbent are separated by filtration to obtain the target α-hydro-ω-alkenyloxy-polyoxyalkylene compound. It is also possible to remove the catalyst only by an adsorption treatment process using an alkali adsorbent without neutralization. Moreover, you may repeat until an external appearance becomes transparent.

(3. Hydrosilylation reaction)
The raw material hydrogen organopolysiloxane used in the hydrosilylation reaction is represented by formula (2), wherein R ² is a methyl group or a phenyl group, R ³ is a hydrogen atom, a methyl group or a phenyl group, preferably a methyl group. Further, x = 1 to 200 and y = 1 to 100.

  Examples of the catalyst used for the reaction between the α-hydro-ω-alkenyloxy-polyoxyalkylene compound and the hydrogen organopolysiloxane include Group VIII transition metals such as nickel, ruthenium, rhodium, palladium, iridium, platinum, or compounds thereof. Although chloroplatinic acid is easily available and the alcohol solution is a homogeneous catalyst, it is easy to handle and is preferable.

  In addition, the charging method includes a method of charging an α-hydro-ω-alkenyloxy-polyoxyalkylene compound and hydrogen organopolysiloxane at once, a part of the α-hydro-ω-alkenyloxy-polyoxyalkylene compound, There are a method in which siloxane is charged in a lump and the remainder is continuously charged, a method in which hydrogen organopolysiloxane is charged in a lump and an α-hydro-ω-alkenyloxy-polyoxyalkylene compound is continuously charged. After completion of the reaction, the target polyoxyalkylene-modified organopolysiloxane compound can be obtained by removing the catalyst.

Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
Allyl alcohol 377.0 g (6.5 mol) and potassium hydroxide 1.43 g (0.025 mol) were charged into a 5 liter autoclave, the system was replaced with nitrogen, and the temperature was raised to 110 ° C. with stirring. Then, 2587 g (58.8 mol) of ethylene oxide was injected over 16 hours under conditions of 110 ° C. and 0.5 MPa (gauge pressure) or less, and the reaction was continued for another hour. Subsequently, 470.0 g (6.5 mol) of butylene oxide was injected over 3 hours under conditions of 110 ° C. and 0.5 MPa (gauge pressure) or less, and the reaction was continued for another 4 hours. Next, the temperature was lowered to 85 ° C., unreacted butylene oxide was removed in nitrogen bubbling at −0.097 MPa (gauge pressure) or less, neutralized with dilute phosphoric acid, and the pH was adjusted to 6.3.

Water was removed by nitrogen bubbling for 1 hour at 100 ° C., −0.097 MPa (gauge pressure) or less after the water stopped distilling while blowing nitrogen at 80 ° C. while blowing nitrogen. Subsequently, 13.7 g of KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and an adsorption treatment was carried out for 1 hour by nitrogen bubbling at −0.097 MPa (gauge pressure) or less. Next, 5 kinds A filter paper was set in the filter, and Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) was added as a filter aid on the filter paper, followed by filtration. Α-hydro-ω represented by the formula (3) -3159 g of allyloxy-polyoxyalkylene compounds were obtained. The physical properties of the obtained compound were a hydroxyl value of 106 KOH mg / g, a kinematic viscosity (25 ° C.) of 43.2 mm ² / s, an unsaturation of 1.79 meq / g, and a terminal hydroxyl group secondaryization rate of 90.8%. It was.

式（３）中のエチレンオキシドの平均付加モル数は９モル、ブチレンオキシドの平均付加モル数は１モルである。
続いて５００ミリリットル容四ツ口フラスコに撹拌装置、冷却管、窒素導入管を取り付け、式（４）で表されるハイドロジェンジメチルポリシロキサン１００ｇ（ＨＭＳ−０８２、アヅマックス（株）製）と、得られた式（３）で表されるα−ヒドロ−ω−アリルオキシ−ポリオキシアルキレン化合物７２．５ｇを加え、さらに触媒として塩化白金酸六水和物のイソプロピルアルコール溶液（１×１０^-3モル／リットル）を白金換算で１５ｐｐｍとなるように仕込み、窒素雰囲気下８０℃で撹拌を行い、途中サンプリングを行いＮ／１０水酸化カリウムのイソプロピルアルコール溶液を加えて水素ガスが発生しなくなるまで反応を継続し、式（５）で表されるポリオキシアルキレン変性オルガノポリシロキサン化合物を得た。１週間後合成物の流動性を確認したところ、ゲル化は生じず流動性を保持していた。

In Formula (3), the average added mole number of ethylene oxide is 9 moles, and the average added mole number of butylene oxide is 1 mole.
Subsequently, a stirrer, a cooling tube, and a nitrogen introduction tube were attached to a 500 ml four-necked flask, and 100 g of hydrogen dimethylpolysiloxane represented by formula (4) (HMS-082, manufactured by AMAX Co., Ltd.) was obtained. 72.5 g of the α-hydro-ω-allyloxy-polyoxyalkylene compound represented by the formula (3) was added, and a chloroplatinic acid hexahydrate solution in isopropyl alcohol (1 × 10 ⁻³ mol / Liter) was added to 15 ppm in terms of platinum, stirred at 80 ° C. in a nitrogen atmosphere, sampled halfway, and an isopropyl alcohol solution of N / 10 potassium hydroxide was added to continue the reaction until no hydrogen gas was generated. Thus, a polyoxyalkylene-modified organopolysiloxane compound represented by the formula (5) was obtained. When the fluidity of the composite was confirmed after one week, gelation did not occur and the fluidity was maintained.

  In formula (4), x = 75 and y = 6.5.

  In the formula (5), the average added mole number of ethylene oxide is 9 moles, the average added mole number of butylene oxide is 1 mole, x = 75, and y = 6.5.

(Example 2)
301.6 g (5.2 mol) of allyl alcohol and 3.64 g (0.067 mol) of sodium methylate were charged into a 5-liter autoclave, and the system was replaced with nitrogen. Then, 2781.2 g (63.2 mol) of ethylene oxide was injected over 18 hours under the conditions of 100 ° C. and 0.5 MPa (gauge pressure) or less, and the reaction was continued for another hour. Subsequently, 455.1 g (6.3 mol) of butylene oxide was injected over 3 hours under conditions of 110 ° C. and 0.5 MPa (gauge pressure) or less, and the reaction was continued for further 4 hours. Next, the temperature was lowered to 85 ° C., unreacted butylene oxide was removed in a nitrogen bubbling at −0.097 MPa (gauge pressure) or less, neutralized with dilute phosphoric acid, and the pH was adjusted to 6.0.

Water was removed by nitrogen bubbling for 1 hour at 100 ° C., −0.097 MPa (gauge pressure) or less after the water stopped distilling while blowing nitrogen at 80 ° C. while blowing nitrogen. Subsequently, 10.6 g of KYOWARD 300 and KYOWARD 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, respectively, and an adsorption treatment was carried out for 1 hour by nitrogen bubbling at −0.097 MPa or less. Next, 5 kinds A filter paper was set in the filter, and Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) was added as a filter aid on the filter paper, followed by filtration, α-hydro-ω represented by the formula (6) -3215 g of allyloxy-polyoxyalkylene compound was obtained. The physical properties of the obtained compound were a hydroxyl value of 83.9 KOH mg / g, a kinematic viscosity (100 ° C.) of 7.24 mm ² / s, an unsaturation of 1.46 meq / g, and a terminal hydroxyl group secondaryization rate of 92.7%. Met.

  In formula (6), the average addition mole number of ethylene oxide is 13 moles, and the average addition mole number of butylene oxide is 1.2 moles.

Subsequently, a stirrer, a cooling tube, and a nitrogen introduction tube were attached to a 500 ml four-necked flask, and 100 g of hydrogen dimethylpolysiloxane represented by formula (4) (HMS-082, manufactured by AMAX Co., Ltd.) was obtained. 88.8 g of the α-hydro-ω-allyloxy-polyoxyalkylene compound represented by the formula (6) was added, and a chloroplatinic acid hexahydrate isopropyl alcohol solution (1 × 10 ⁻³ mol / Liter) was added to 15 ppm in terms of platinum, stirred at 80 ° C. in a nitrogen atmosphere, sampled halfway, and an isopropyl alcohol solution of N / 10 potassium hydroxide was added to continue the reaction until no hydrogen gas was generated. Thus, a polyoxyalkylene-modified organopolysiloxane compound represented by the formula (7) was obtained. When the fluidity of the composite was confirmed after one week, gelation did not occur and the fluidity was maintained.

  In formula (7), the average number of moles of ethylene oxide added is 13 moles, the average number of moles of butylene oxide added is 1.2 moles, x = 75, and y = 6.5.

(Comparative Example 1)
446.6 g (7.7 mol) of allyl alcohol and 1.82 g (0.03 mol) of potassium hydroxide were charged into a 5-liter autoclave, and the system was purged with nitrogen. Then, 3064.6 g (69.7 mol) of ethylene oxide was injected over 16 hours under the conditions of 110 ° C. and 0.5 MPa (gauge pressure) or less, and the reaction was further continued for 1 hour. Next, the temperature was lowered to 85 ° C., unreacted ethylene oxide was removed in a nitrogen bubbling at −0.097 MPa (gauge pressure) or less, neutralized with dilute acetic acid, and the pH was adjusted to 6.6.

Water was removed by nitrogen bubbling for 1 hour at 100 ° C., −0.097 MPa (gauge pressure) or less after the water stopped distilling while blowing nitrogen at 80 ° C. while blowing nitrogen. Subsequently, 10.5 g of KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and adsorption treatment was carried out for 1 hour by nitrogen bubbling at −0.097 MPa (gauge pressure) or less. Next, 5 kinds A filter paper was set in the filter, and Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) was added as a filter aid on the filter paper, followed by filtration, α-hydro-ω represented by the formula (8) -3267 g of allyloxy-polyoxyalkylene compounds were obtained. The physical properties of the obtained compound were a hydroxyl value of 123 KOH mg / g, a kinematic viscosity (25 ° C.) of 38.5 mm ² / s, and an unsaturation degree of 2.13 meq / g.

式（８）中のエチレンオキシドの平均付加モル数は９モルである。

The average added mole number of ethylene oxide in the formula (8) is 9 moles.

Subsequently, a stirrer, a condenser tube, and a nitrogen introduction tube were attached to a 500 ml four-necked flask, and 100 g of hydrogen dimethylpolysiloxane represented by formula (4) (HMS-082, manufactured by AMAX Co., Ltd.) 60.9 g of an α-hydro-ω-allyloxy-polyoxyalkylene compound represented by (8) is added, and an isopropyl alcohol solution of chloroplatinic acid hexahydrate (1 × 10 ⁻³ mol / liter) is further added as a catalyst. Charged to 15 ppm in terms of platinum, stirred at 80 ° C. in a nitrogen atmosphere, sampled halfway, added N / 10 potassium hydroxide isopropyl alcohol solution, and continued the reaction until no hydrogen gas was generated. A polyoxyalkylene-modified organopolysiloxane compound represented by (9) was obtained. After a review, gelation occurs.

  The average added mole number of ethylene oxide of the formula (9) is 9 moles, x = 75, y = 6.5.

(Comparative Example 2)
A 500 ml four-necked flask was equipped with a stirrer, a cooling tube, and a nitrogen introduction tube, and 60 g of hydrogen dimethylpolysiloxane represented by formula (10) (HMS-301, manufactured by AMAX Co., Ltd.) and formula (8 138.0 g of the α-hydro-ω-allyloxy-polyoxyalkylene compound of Comparative Example 1 represented by the formula (1)) and an isopropyl alcohol solution of chloroplatinic acid hexahydrate (1 × 10 ⁻³ mol / liter) as a catalyst. ) Was added at 15 ppm in terms of platinum and stirred at 80 ° C. in a nitrogen atmosphere, but the reaction product caused a cross-linking reaction and became a resin, making stirring impossible, and the experiment was stopped.

式（１０）中、ｘ＝１８、ｙ＝８である。

In formula (10), x = 18 and y = 8.

(Comparative Example 3)
Allyl alcohol 638 g (11.0 mol) and sodium methylate 2.0 g (0.04 mol) were charged into a 5 liter autoclave and the system was replaced with nitrogen. Then, 2904 g (66.0 mol) of ethylene oxide was injected over 12 hours under conditions of 110 ° C. and 0.5 MPa (gauge pressure) or less, and the reaction was continued for another hour. Next, the temperature was lowered to 85 ° C., unreacted ethylene oxide was removed in a nitrogen bubbling at −0.097 MPa (gauge pressure) or less, neutralized with dilute acetic acid, and the pH was adjusted to 6.9.

Water was removed by nitrogen bubbling for 1 hour at 100 ° C., −0.097 MPa (gauge pressure) or less after the water stopped distilling while blowing nitrogen at 80 ° C. while blowing nitrogen. Subsequently, 10.5 g of KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and adsorption treatment was carried out for 1 hour by nitrogen bubbling at −0.097 MPa (gauge pressure) or less. Next, 5 types A filter paper was set in the filter, and Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) was added as a filter aid on the filter paper, followed by filtration, α-hydro-ω represented by the formula (11) -3371 g of an allyloxy-polyoxyalkylene compound was obtained. The physical properties of the obtained compound were a hydroxyl value of 175 KOH mg / g, a kinematic viscosity (25 ° C.) of 21.3 mm ² / s, and an unsaturation of 3.04 meq / g.

式（１１）中のエチレンオキシドの平均付加モル数は６モルである。

The average added mole number of ethylene oxide in the formula (11) is 6 moles.

Subsequently, a stirrer, a cooling tube, and a nitrogen introducing tube were attached to a 500 ml four-necked flask, and 60 g of hydrogen dimethylpolysiloxane represented by formula (10) (HMS-301, manufactured by AMAX Co., Ltd.) 96.7 g of the α-hydro-ω-allyloxy-polyoxyalkylene compound represented by (11) is added, and an isopropyl alcohol solution (1 × 10 ⁻³ mol / liter) of chloroplatinic acid hexahydrate is further added as a catalyst. The mixture was charged to 15 ppm in terms of platinum, and stirred at 80 ° C. in a nitrogen atmosphere. However, the reaction product caused a cross-linking reaction and became a resin, making stirring impossible, and the experiment was stopped.

(Comparative Example 4)
Allyl alcohol 319.0 g (5.5 mol) and potassium hydroxide 1.3 g (0.02 mol) were charged into a 5 liter autoclave, the system was replaced with nitrogen, and the temperature was raised to 110 ° C. with stirring. Then, 2189 g (49.8 mol) of ethylene oxide was injected over 16 hours under conditions of 110 ° C. and 0.5 MPa (gauge pressure) or less, and the reaction was continued for another hour. Next, the temperature was lowered to 85 ° C., and unreacted ethylene oxide was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling.

  After cooling to 50 ° C. or lower, 464.8 g (8.3 mol) of potassium hydroxide was charged, and after replacing the system with nitrogen, the pressure was reduced to −0.097 MPa (gauge pressure) or lower. After raising the temperature to 85 ° C., methyl chloride 306 0.8 g (6.1 mol) was added, and the temperature was further raised to 115 ° C. to conduct methyl etherification reaction for 2 hours. After completion, the temperature was lowered to 85 ° C., and unreacted methyl chloride was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling. Next, 1673 g of water was added, stirred for 10 minutes and allowed to stand for 1 hour to remove the separated aqueous layer, neutralized with dilute hydrochloric acid, and adjusted to pH 6.2.

Water was removed for 1 hour by nitrogen bubbling at 90 ° C., −0.097 MPa (gauge pressure) or less after the water stopped distilling while blowing nitrogen at 90 ° C. while blowing nitrogen. After cooling to 80 ° C., 8.4 g of KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and an adsorption treatment was performed by nitrogen bubbling for 1 hour under −0.097 MPa (gauge pressure). 5 types A filter paper is set in the filter, and Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) is added as a filter aid to the filter paper, followed by filtration. Α-Methyl-ω- shown in Formula (12) 2209 g of allyloxy-polyoxyalkylene compound was obtained. The physical properties of the obtained compound were a hydroxyl value of 3.9 KOH mg / g, a kinematic viscosity (25 ° C.) of 28.3 mm ² / s, and an unsaturation degree of 2.07 meq / g.

式（１２）中のエチレンオキシドの平均付加モル数は９モルである。

The average added mole number of ethylene oxide in the formula (12) is 9 moles.

  Explaining the above comparative example, in Comparative Examples 1 to 3, since the terminal hydroxyl group is not capped with butylene oxide, a gelled product is generated by a side reaction during the hydrosilylation reaction performed without using an additive and a solvent. Comparative Example 4 is a conventional method for producing a polyoxyalkylene compound in which a terminal hydroxyl group is etherified with a methyl group, and it has been revealed that the yield is reduced by about 30% as compared with Examples. Therefore, the method for producing a polyoxyalkylene-modified organopolysiloxane compound of the present invention can be suitably used because side reactions such as gelation are suppressed in a hydrosilylation reaction performed without using an additive and a solvent. Further, it is useful because the yield is increased and the production efficiency is improved as compared with a polyoxyalkylene compound in which the terminal hydroxyl group is etherified or esterified.

(Comparative Example 5)
Allyl alcohol 754.0 g (13.0 mol) and potassium hydroxide 3.08 g (0.055 mol) were charged into a 5 liter autoclave and the system was purged with nitrogen. Then, 1716 g (39.0 mol) of ethylene oxide was injected over 9 hours under the conditions of 100 ° C. and 0.5 MPa (gauge pressure) or less, and the reaction was continued for another hour. Subsequently, 936.0 g (13.0 mol) of butylene oxide was injected over 10 hours under conditions of 100 ° C. and 0.5 MPa (gauge pressure) or less, and the reaction was continued for another 4 hours. Next, the temperature was lowered to 85 ° C., unreacted butylene oxide was removed in nitrogen bubbling at −0.097 MPa (gauge pressure) or less, neutralized with dilute phosphoric acid, and the pH was adjusted to 5.6.

Water was removed by nitrogen bubbling for 1 hour at 100 ° C., −0.097 MPa (gauge pressure) or less after the water stopped distilling while blowing nitrogen at 80 ° C. while blowing nitrogen. Subsequently, 6.8 g of KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and an adsorption treatment was carried out for 1 hour by nitrogen bubbling at −0.097 MPa (gauge pressure) or less. Next, 5 types A filter paper was set in the filter, Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) was added as a filter aid on the filter paper, and filtration was performed. Α-hydro-ω represented by the formula (13) -3130 g of allyloxy-polyoxyalkylene compound was obtained. The physical properties of the obtained compound were a hydroxyl value of 209 KOH mg / g, a kinematic viscosity (25 ° C.) of 13.6 mm ² / s, an unsaturation degree of 3.74 meq / g, and a terminal hydroxyl group secondaryization rate of 90.2%. It was.

式（１３）中のエチレンオキシドの平均付加モル数は３モル、ブチレンオキシドの平均付加モル数は１モルである。

In Formula (13), the average addition mole number of ethylene oxide is 3 mol, and the average addition mole number of butylene oxide is 1 mol.

Subsequently, a stirrer, a cooling tube, and a nitrogen introduction tube were attached to a 500 ml four-necked flask, and 130 g of hydrogen dimethylpolysiloxane represented by the formula (4) (HMS-082, manufactured by AMAX Co., Ltd.) was obtained. Further, 45.1 g of an α-hydro-ω-allyloxy-polyoxyalkylene compound represented by the formula (13) was added, and a chloroplatinic acid hexahydrate isopropyl alcohol solution (1 × 10 ⁻³ mol / liter) was further used as a catalyst. ) To 15 ppm in terms of platinum, stirred at 80 ° C. in a nitrogen atmosphere, sampled halfway, added N / 10 potassium hydroxide isopropyl alcohol solution, and continued the reaction until hydrogen gas was not generated. The polyoxyalkylene modified organopolysiloxane compound represented by the formula (14) was obtained. When the fluidity of the composite was confirmed after one week, gelation did not occur and the fluidity was maintained.

式（１４）中、のエチレンオキシドの平均付加モル数は３モル、ブチレンオキシドの平均付加モル数は１モル、ｘ＝７５、ｙ＝６．５である。

In the formula (14), the average added mole number of ethylene oxide is 3 moles, the average added mole number of butylene oxide is 1 mole, x = 75, and y = 6.5.

Using the polyoxyalkylene-modified organopolysiloxane compounds obtained in Examples 1-2 and Comparative Example 5, hair lotions having the following compositions were prepared.
Polyoxyalkylene-modified organopolysiloxane compound 0.2% by weight
Glycerin 5.0% by weight
Dipropylene glycol 5.0% by weight
Polyethylene glycol 400 3.0% by weight
Ethanol 25.0% by weight
Stearyltrimethylammonium chloride 0.2% by weight
Methylparaben 0.1% by weight
Fragrance 0.1% by weight
Purified water balance

When the compatibility after blending was visually observed, Example 1 and Example 2 were good, but Comparative Example 5 was separated without being compatible. From this result, since Comparative Example 5 has a small number of added moles of polyoxyethylene and strong hydrophobicity as a polyoxyalkylene-modified organopolysiloxane compound, it is limited in use.

Claims (3)

A method for producing a polyoxyalkylene-modified organopolysiloxane compound, comprising hydrosilylating a polyoxyalkylene compound represented by formula (1) with an organopolysiloxane compound represented by formula (2).
^{R 1 O- (EO) m- (} BO) nH (1)
(In the formula, R ¹ represents an alkenyl group having 3 to 5 carbon atoms having a double bond at the terminal, EO represents an oxyethylene group, and BO represents an oxybutylene group, and m = 7 to 50 and n = 1 to 2. .)

(In the formula, R ² is a methyl group or a phenyl group, R ³ is a hydrogen atom, a methyl group or a phenyl group, and x = 1 to 200 and y = 1 to 100.) The method according to claim 1, wherein the polyoxyalkylene compound represented by the formula (1) is produced by the steps shown in the following (A) and (B).
(A) An alkylene oxide addition reaction step in which ethylene oxide is added to alkenyl alcohol, followed by addition reaction of butylene oxide. An alkali catalyst is used as a catalyst for the alkylene oxide addition reaction, and alkenyl alcohol, ethylene oxide and butylene oxide are used. And (B) a step of setting the addition amount of the alkali catalyst to 0.02 to 0.5 parts by weight when the total charge of is 100 parts by weight and performing the alkylene oxide addition reaction in a temperature range of 90 to 130 ° C .; In the adsorption step of adding an adsorbent to the reaction product of the alkylene oxide addition reaction, when the total amount of alkenyl alcohol, ethylene oxide and butylene oxide is 100 parts by weight, the adsorbent is 0.2 to 2.0 parts by weight added That process.   The method according to claim 1 or 2, wherein the hydrosilylation reaction is performed using chloroplatinic acid as a catalyst.