JPS6237039B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing sorbitan-modified silicone compounds.

Organopolysiloxane, especially dimethylpolysiloxane, has various properties such as excellent heat resistance and weather resistance, and low surface tension, but on the other hand, it is difficult to dissolve in polar solvents such as water or alcohol. Because of this property, there is a problem in that its usage is restricted.

Therefore, in order to solve such problems, attempts have been made to introduce various hydrophilic groups into the dimethylpolysiloxane, and these hydrophilic groups include (1) anionic groups such as sulfate groups or sulfonate groups; (2) cationic hydrophilic groups such as quaternary ammonium salts, (3) zwitterionic hydrophilic groups of (1) and (2) above, or (4) polyoxyalkylene groups (especially polyethylene glycol residues). ) and other nonionic hydrophilic groups are known.

Generally known HLB of oxyethylene group
The number of bases is 0.33, whereas that of alcoholic hydroxyl groups is 1.9, and alcoholic hydroxyl groups have strong hydrophilicity.

Therefore, it is naturally predicted that sorbitan-modified silicone, which simultaneously has a dimethylsiloxane moiety as a hydrophobic group and a polyhydric alcohol (sorbitan group) moiety as a hydrophilic group in the same molecule, has a function as a surfactant. However, it is currently completely unknown.

The reasons for this are not clear, but the polyhydric alcohols of sorbitans have a high viscosity, and there are no suitable solvents other than alcohol-based solvents, and there is no good way to introduce them into silicones as modified groups, and how to handle them. This is presumed to be due to the fact that it is not easy.

On the other hand, silicone surfactants having a polyhydric alcoholic hydroxyl group as a hydrophilic group are hardly known at present, and only a few silicone surfactants are known.
Publication No. 19941 describes the application of silicone compounds containing alcoholic hydroxyl groups obtained by reacting (dehydrogenation reaction) methylhydrodiene polysiloxane with aliphatic polyhydric alcohol or polyoxyalkylene alcohol to cosmetics. It has only been done.

The above reaction involves dehydrogenating methylhydrodiene polysiloxane and polyhydric alcohol,
This method is based on adding a hydrophilic group to siloxane, but such a reaction has the disadvantage that the gelation reaction progresses significantly, making it impossible to easily obtain the desired product.

In addition, in the above method, alcohol-based solvents cannot be used as reaction solvents,
Therefore, aromatic or ether-based alcohols such as toluene must be used, but polyhydric alcohols such as sorbitan do not dissolve in toluene, so dehydrogenation cannot actually be used.

Furthermore, polyhydric alcohol-modified silicones synthesized by dehydrogenation reactions generally have Si--O--C type bonds, which are hydrolyzable and therefore cannot be said to be sufficiently stable bonds.

The present invention aims to provide a new method for producing sorbitan-modified silicone, which is a new compound, which is an organohydrodiene polysiloxane having at least one hydrogen atom directly bonded to a silicon atom in one molecule. and expression (wherein, X is a hydrocarbon group having an aliphatic unsaturated bond having 6 or less carbon atoms or a hydrocarbon group containing an oxygen atom) is reacted with the sorbitan derivative in the presence of an addition reaction catalyst. do, expression [Here, R ¹ to ^{R 8} are hydrogen atoms, methyl groups, and formula (Y is a hydrocarbon group having 6 or less carbon atoms or a hydrocarbon group containing oxygen), and at least one of R ¹ to R ⁸ is represented by the above formula (ii). The present invention relates to a method for producing a sorbitan-modified silicone compound represented by a group represented by the following formula, where n is a positive integer.

That is, in the method of the present invention, the risk of gelation progressing due to the crosslinking reaction is extremely small, and the reaction can be carried out using Pt etc. as an addition reaction catalyst without using a dehydrogenation catalyst (alkali). For this purpose, an alcoholic solvent such as isopropyl alcohol can be used as a reaction solvent, and since sorbitan has good compatibility with alcohols, it is possible to carry out the reaction in a homogeneous system, which is extremely preferable.

Furthermore, the sorbitan-modified silicone compound finally obtained is stable against hydrolysis.
It is a C bond, and has excellent surfactant effects such as the ability to lower surface tension without the risk of quality deterioration due to changes over time.

Furthermore, both the organohydrodiene polysiloxane and the sorbitan derivative used as starting materials in the present invention are non-toxic and highly safe substances, so the sorbitan-modified silicone obtained may come into direct contact with the human body. It can be used safely in certain fields.

Furthermore, the sorbitan-modified silicone compound also has the properties inherent to general silicone compounds, such as heat resistance, weather resistance, and low surface tension, and is used in fields that require these properties, such as toiletries, cosmetics, and antifogging. It can be widely applied as a surfactant in various industrial fields, including antifogging agents, antistatic agents, paint additives, adhesives, foam stabilizers, textile oils, and plastic additives.

The method of the present invention will be explained in detail below.

First, the organohydrodiene polysiloxane used as the starting material in the method of the present invention is as follows:
There are no particular restrictions on viscosity, degree of polymerization, molecular structure, etc., and various conventionally known compounds can be used, except that the molecule must have at least one Si-H bond. Examples of this include the compounds shown below.

(In the above formulas (iii) and (iv), (R' is a methyl group or a hydrogen atom, p, q, and r are positive integers).

Further, the sorbitan derivative used together with the organohydrodiene polysiloxane in the method of the present invention has at least one aliphatic unsaturated bond in its molecule, including, for example, etc. can be given.

The sorbitan derivative represented by the above formula (v) is
For example, sorbitan and allyl glycidyl ether in the presence of an alkali catalyst, and the sorbitan derivative represented by formula (vi) can be synthesized by treating sorbitan with an alkali and then reacting it with allyl bromide. I can do it.

Furthermore, addition reaction catalysts used when carrying out the method of the present invention include chloroplatinic acid, alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972),
Complex of chloroplatinic acid and olefin (U.S. Pat. No. 3159601, U.S. Pat. No. 3159662 or U.S. Pat.
3775452), solid platinum supported on a carrier such as platinum black, alumina, or silica, and a rhodium-olefin complex.

In the method of the present invention, the above-mentioned organohydrodiene polysiloxane and a sorbitan derivative are simply reacted (addition reaction) in the presence of an addition reaction catalyst, and the ratio of the two used is determined by the Si-H bond in the siloxane. Ratio to aliphatic unsaturated bonds in sorbitan derivatives (〓Si-H/-C=C- or -
C≡C-, etc.) is preferably in the range of 0.1 to 1.5, preferably 0.6 to 1.0.

In carrying out the method of the present invention, the use of a reaction solvent is not essential, but it may be used if necessary, and the reaction solvent is one that does not inhibit the addition reaction between siloxane and sorbitan derivative. Various types of alcohol can be used, and specific examples include isopropyl alcohol.

The addition reaction rate in the above addition reaction can be easily confirmed by the amount of hydrogen gas generated from the reaction system or by an infrared absorption spectrum.

When the desired addition reaction rate is reached by carrying out the reaction as described above, the desired sorbitan-modified silicone compound can be obtained by distilling off the reaction solvent by a conventional method, if necessary.

In addition, in the above reaction, 〓Si-H and -
In order to prevent or suppress the dehydrogenation reaction with OH, an ethanol solution of potassium acetate etc.
Preferably, a PH regulator is used.

The above formula finally obtained by the method of the present invention
The sorbitan-modified silicone compound represented by (i) can have various polymerization degrees and molecular structures depending on the organohydrodiene polysiloxane and the sorbitan derivative used as starting materials.

Examples of the sorbitan-modified silicone compound represented by formula (i) include those shown below.

However, Me in each of the above formulas is a methyl group, and A is the following group.

In the method of the present invention, the above two reactions,
That is, the reaction of introducing an organic group containing an aliphatic unsaturated bond into sorbitan (synthesis of a sorbitan derivative) and the addition reaction of the sorbitan derivative with an organohydrodiene polysiloxane may be performed in the same system.

In addition, when carrying out two reactions in the same system in this way, in the first stage reaction, the sorbitan-modified silicone compound according to the present invention is a 1 molar adduct, a 2 molar adduct, a 2 molar adduct of an aliphatic unsaturated bond-containing organic group, Although it is obtained as a mixture of the 3-mole adduct, unreacted raw materials, and other components, it goes without saying that in the present invention, this mixture may be used as it is in the next step of addition reaction.

Next, examples of the present invention will be given.

Example 1 When 1 mole of a mixture consisting of 70.3 wt% sorbitan, 24.0 wt% sorbitate, and 5.7 wt% sorbide was reacted with 1 mole of allyl glycidyl ether in the presence of an alkali catalyst, a 1 mole adduct of allyl glycidyl ether ( (shown in the formula below) 43.1wt
%, 2 molar adduct 25.3wt%, 3 molar adduct 6.7wt
%, unreacted raw material 23.6wt% and other components
A mixture consisting of 1.3 wt% was obtained.

(Hereinafter, this product will be referred to as sorbitan derivative (i)) The general physical properties of this product were as follows.

Hydroxyl value 768 Degree of unsaturation (meq/g) 3.56 Viscosity (100°C, cS) 91.9 Moisture (%) 0.07 PH (Impro water 10:6) 5.6 In addition, IR spectrum and NMR spectrum analysis of the sorbitan derivative (i) were conducted. As a result, the results shown in FIGS. 1 and 2 were obtained. (Absorption of unsaturated groups is seen in the δ value of 5.5 to 6.5 ppm).

Example 2 A mixture containing the same sorbitan as the main component used in Example 1 was treated with an alkali and then reacted with allyl bromide, resulting in a 1 mol adduct of allyl bromide (shown by the following formula) at 42.5 wt%.
A mixture was obtained consisting of 21.5 wt% of the 2-mole adduct, 33.2 wt% of unreacted raw materials, and 2.8 wt% of other components.

(Hereinafter, this product will be referred to as sorbitan derivative (ii)) The general physical properties of this product were as follows.

Hydroxyl value 776 Unsaturation (meq/g) 4.15 Viscosity (100℃, cP) 83.2 Moisture (%) 0.07 PH (isoprowater 10:6) 5.9 Example 3 Sorbitan derivative (i) 100g, 62 g, 200 g of isopropyl alcohol, 0.5 g of a 10% ethanol solution of potassium acetate, and a solution of chloroplatinic acid in isopropyl alcohol (platinum concentration 2).
%, hereinafter abbreviated as Pt-IPA) 0.3g,
Pour into a four-necked flask with an internal volume of 1 and equipped with a stirring blade stirrer, a tube condenser, a thermometer, and a stopper, heat with a mantle heater, and boil at the reflux temperature of isopropyl alcohol (approximately 87°C).
The reaction was allowed to take place for a period of time. When the amount of residual Si-H was measured using a hydrogen gas generator, the amount of hydrogen gas generated was
It was 0.12ml/g. It was confirmed that the addition reaction was progressing at a reaction rate of 99.6%.

When isopropyl alcohol was stripped from the reaction solution under reduced pressure (100℃, 5mmHg for 1 hour),
155g of reaction product was obtained.

This substance was a very viscous syrup-like substance with a viscosity of over 100,000 cP at room temperature, but when the temperature was raised to about 100°C by heating, it changed to a substance with a relatively low viscosity (792 cP).

When we performed IR spectrum and NMR spectrum analysis on the starch syrup-like substance obtained above, we found that
The results shown in FIGS. 3 and 4 were obtained.

Comparing this Fig. 4 with Fig. 2, in Fig. 4 the absorption of unsaturated groups almost disappears, and in its place a new absorption of 〓Si-Me is observed at a δ value of 0.7 ppm. Also, in Figure 3, 850cm ^-1 and
A characteristic absorption of organopolysiloxane is seen at 1270 cm ^-1 .

From these results and the manufacturing method, the compound obtained in this example has the molecular formula It was identified as a sorbitan-modified silicone compound represented by

The 1% aqueous solution (white cloudy) of the sorbitan-modified silicone compound had a surface tension of 20.6 dyne/cm (72.8 dyne/cm in distilled water).

Example 4 100 g of sorbitan derivative (ii) obtained in Example 2, 72 g, 200 g of ethanol, 0.5 g of a 10% ethanol solution of potassium acetate, and 0.3 g of Pt-IPA were reacted under the same conditions as in Example 3. When the ethanol was stripped under reduced pressure, 168 g of a starch syrup-like reaction product was obtained. Ta.

This product has a viscosity of 358 cP at 100°C, and a 1% aqueous solution has a cloudy appearance, and the surface tension is
It was 21.2dyne/cm.

Example 5 250 g of sorbitan derivative (i) obtained in Example 1, 580 g, 2000 g of isopropyl alcohol, 3 g of a 10% ethanol solution of potassium acetate and Pt-
After reacting 0.4 g of IPA under the same conditions as in Example 3, isopropyl alcohol was stripped under reduced pressure to obtain a viscous liquid having a viscosity of 371 cP at 100°C.

This product was insoluble in water, but readily soluble in alcohols.

Example 6 100 g of sorbitan derivative (i) obtained in Example 1, 60 g, 300 g of isopropyl alcohol, 0.5 g of a 10% ethanol solution of potassium acetate and Pt-
When 0.5 g of IPA was reacted under the same conditions as in Example 3, an extremely viscous liquid with a viscosity of 48012 cP at 100°C was obtained.

In this way, as organohydrodiene polysiloxane The reason why the viscosity of the obtained product becomes extremely high when using sorbitan is presumed to be that the crosslinking reaction progresses because the sorbitan derivative contains 2-molar adducts, 3-molar adducts, etc. Ru.

Example 7 100 g of sorbitan derivative (i) obtained in Example 1, 61 g, 300 g of isopropyl alcohol, 0.5 g of a 10% ethanol solution of potassium acetate and Pt-
When 0.5g of IPA was reacted, the viscosity was 9405cP.
(100℃) liquid was obtained.

This product dissolved in water, self-emulsified, became cloudy, and had a surface tension of 21.2 dyne/cm.

Example 8 100 g of sorbitan derivative (ii) obtained in Example 2, 70 g, 300 g of isopropyl alcohol, 0.5 g of a 10% ethanol solution of potassium acetate and Pt-
When 0.5g of IPA was reacted in the same manner as in Example 3, a product with a viscosity of 20920cP (100℃) was obtained, and this product became cloudy when dissolved in water.
It showed a surface tension of 20.7dyne/cm.

Example 9 100 g of sorbitan derivative (i) obtained in Example 1, 25 g, 300 g of isopropyl alcohol, 0.5 g of a 10% ethanol solution of potassium acetate and Pt-
When 0.5 g of IPA was reacted in the same manner as in Example 3, a product with a viscosity of 56,200 cP (100°C) was obtained.

When a 1% aqueous solution was prepared using the reaction product obtained here, it became a completely transparent aqueous solution, the surface tension of this was 25.8 dyne/cm, and the Ross Miles values were 14.3 cm (initial) and 11.8 cm. (After 5 minutes)
It was hot.

[Brief explanation of the drawing]

Figures 1 and 2 are the IR spectrum and NMR analysis results of the sorbitan derivative obtained in Example 1, and Figures 3 and 4 are the IR spectrum and NMR analysis results of the sorbitan modified silicone obtained in Example 4. This is the analysis result.

Claims (1)

[Claims] 1 Organohydrodiene polysiloxane having at least one hydrogen atom directly bonding a silicon atom in one molecule and the formula (wherein, X is a hydrocarbon group having an aliphatic unsaturated bond having 6 or less carbon atoms or a hydrocarbon group containing an oxygen atom) is reacted with the sorbitan derivative in the presence of an addition reaction catalyst. do, expression [Here, R ¹ to ^{R 8} are hydrogen atoms, methyl groups, and formula (Y is a hydrocarbon group having 6 or less carbon atoms or a hydrocarbon group containing oxygen), and at least one of R ¹ to ^{R 8} is an atom or group selected from the above formula A method for producing a sorbitan-modified silicone compound represented by a group represented by the following formula, where n is a positive integer.