JPH10158401A - Production of fluroalkylated siloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the introduction of longer-chain fluoroalkyl groups in an arbitrary ratio into a polyorganosiloxane, the synthesis of a high-viscosity fluoroaklylated polyorganosiloxane, and esp. the synthesis of a heat-resistant branched liq. fluoroalkylated polyorganosiloxane. SOLUTION: In producing a fluoroalkylated siloxane, 100 pts.wt. fluoroalkylated silane represented by the formula: R<f> SiRa X3-a (wherein R<f> is fluoroalkyl; R is H or a 1-20C optionally substd. hydrocarbon group; X is a hydrolyzable group; and (a) is an integer of 0-3) and 5-5,000 pts.wt. polyorganosiloxane are equilibrated in the presence of 0.0001-0.1 pt.wt. phosphorus chloride nitride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a siloxane containing a fluoroalkyl group.

[0002]

2. Description of the Related Art Conventionally, polyorganosiloxane oils have excellent properties such as heat resistance, weather resistance, lubricating properties, and releasability. Therefore, hydraulic oils for various machines, lubricating oils, and additives for copying machine rolls. It is used in a wide range of fields such as surface coating agents, plastic film blocking inhibitors, additives to cosmetics, and fiber treatment agents. In addition,
A polyorganosiloxane oil having a fluoroalkyl group as a substituent is known as one having improved oil resistance, solvent resistance, etc., and this fluoroalkyl group-containing siloxane is also used in various fields.

[0003] As a method for producing such a fluoroalkyl group-containing siloxane, for example, a hexaorganodisiloxane is used as a terminal stopper, and a fluorosiloxane-containing cyclic siloxane is converted to a basic catalyst such as sodium silanolate or trifluoromethane. A method of ring-opening polymerization in the presence of an acidic catalyst such as sulfonic acid, or a method of polycondensing a fluoroalkylsilane having a hydroxyl group or a hydrolyzable chlorine atom is known (JP-A-3-95226).
No., JP-A-5-1150).

However, in the method using a fluoroalkyl group-containing cyclic siloxane, it is difficult to introduce a long-chain fluoroalkyl group from the viewpoint of synthesis of raw materials and the like. There was a problem that it was difficult to obtain polysiloxane. Further, in the method by polycondensation of fluoroalkylsilane, since the compatibility between the silane and an alkylsilane such as methylsilane or the like is low, it is difficult to carry out the copolymerization of these silanes favorably, and it is difficult to contain a desired fluoroalkyl group. However, there is a problem that it is difficult to synthesize a polysiloxane having a high viscosity.

[0005] In addition, as the liquid fluoroalkyl group-containing siloxane, a low viscosity linear siloxane is generally known, and it is expected that it has better heat resistance and does not easily gel at high temperatures. It is said that high-viscosity, branched-structure fluoroalkyl group-containing siloxanes are difficult to synthesize.

[0006]

As described above, in the conventional method for producing a siloxane containing a fluoroalkyl group, it is difficult to introduce a long-chain fluoroalkyl group or to obtain a polysiloxane having a branched structure. There is a problem that it is difficult, and it is difficult to synthesize a high-viscosity polysiloxane containing a desired fluoroalkyl group.

SUMMARY OF THE INVENTION The present invention has been made in order to solve such a problem, and a longer-chain fluoroalkyl group can be introduced at an optional ratio, and a high-viscosity fluoroalkyl group-containing polyorganosiloxane is provided. , A fluoroalkyl group-containing siloxane that can be synthesized relatively easily, and a fluoroalkyl group that enables the synthesis of a liquid fluoroalkyl-containing polyorganosiloxane having a branched structure with excellent heat resistance An object of the present invention is to provide a method for producing a contained siloxane.

[0008]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventors have equilibrated a fluoroalkyl group-containing silane with a polyorganosiloxane using a specific compound as a catalyst. As a result, it has been found that a fluoroalkyl group-containing siloxane can be favorably produced, and furthermore, a fluoroalkyl group-containing siloxane having excellent heat resistance can be obtained, and the present invention has been completed. .

That is, the process for producing a fluoroalkyl group-containing siloxane according to the present invention comprises, as described in claim 1, a process for producing a fluoroalkyl group-containing siloxane, wherein (A) the general formula: R ^f SiR _a Χ _{3- a} (where R ^f
Is a fluoroalkyl group, and R is a hydrogen atom or carbon number 1
-20 unsubstituted or substituted hydrocarbon group, X represents a hydrolyzable group, and a represents an integer of 0 to 3) 100 parts by weight of a fluoroalkyl group-containing silane represented by the following formula (B): 5 to 5000 parts by weight of (C) phosphorous oxynitride
It is characterized by equilibrating in the presence of 0.0001 to 0.1 parts by weight.

The process for producing a fluoroalkyl group-containing siloxane according to the present invention comprises, for example,

Embedded image Is characterized by producing a fluoroalkyl group-containing siloxane represented by the formula:

[0011]

Embodiments of the present invention will be described below.

In the process for producing a fluoroalkyl group-containing siloxane according to the present invention, (A) a general formula: R ^f SiR _a Χ _3-a (1) wherein R ^f is a fluoroalkyl group, and R is A hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms,
X represents a hydrolyzable group, a represents an integer of 0 to 3), and (B) a polyorganosiloxane as a starting material.

As the fluoroalkyl group-containing silane of the component (A), a hydrolyzable or non-hydrolyzable silane containing a fluoroalkyl group is used. In the above formula (1), R ^f is a fluoroalkyl group, for example, a general formula: — (CH ₂ ) _b (CF ₂ ) _c CF ₃ ... (2) or a general formula: — (CH ₂ ) _b CF ( CF ₃ ) ₂ (3) (where b represents an integer of 2 to 6, and c represents an integer of 3 to 15). Among these, the reaction proceeds favorably, and the obtained fluoroalkyl group-containing siloxane can be given particularly good water repellency and heat resistance, and the synthesis of the raw material silane is easy. ) In the formula, a fluoroalkyl group wherein b is 2-3 and c is 5-7 is preferred.

In the above formula (1), R is a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms. Examples of the unsubstituted monovalent hydrocarbon group include a methyl group, an ethyl group and a propyl group. Groups, an alkyl group such as a butyl group and a hexyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group and an allyl group, and an aryl group such as a phenyl group and a tolyl group. Further, as the monovalent substituted hydrocarbon group, a group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom other than fluorine, a cyano group, an amino group, and the like, for example, a chloromethyl group, a cyanomethyl group, Examples thereof include a γ-aminopropyl group. Among these, an unsubstituted hydrocarbon group is preferable, and a methyl group and a phenyl group are particularly preferable because the reaction proceeds favorably and the characteristics of the obtained fluoroalkyl group-containing siloxane can be improved.

When the obtained fluoroalkyl group-containing siloxane is used as a raw material of another material, or is blended with a paint or a resin, the fluoroalkyl group-containing siloxane in which R is a hydrogen atom or an alkenyl group is used. May be used in combination.

X in the above formula (1) represents a hydrolyzable group, such as a halogen atom such as a chlorine atom, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group, an aminooxy group such as a diethylaminooxy group, and methylethylketo. Examples thereof include an oxime group such as an oxime group, an amide group such as an acetamido group, and an alkenyloxy group such as an isopropenoxy group. Among these, a chlorine atom and an alkoxy group having 1 to 4 carbon atoms are preferable, and a chlorine atom, a methoxy group and an ethoxy group are particularly preferable because the reaction proceeds favorably.

In the above formula (1), a is an integer of 0 to 3. In particular, a is preferably 0 because it is easy to produce a fluorosiloxane-containing siloxane having desired properties such as viscosity and heat resistance.
It is preferably from 2 to 2. When a is 0, resinous fluoroalkyl group-containing siloxane is generally easily obtained, and when a is 1, an oily one having mainly a fluoroalkyl group in a side chain is obtained, and when a is 2 In this case, an oily product having a fluoroalkyl group at both ends is obtained. When a is 3, the component (A) is a non-hydrolyzable silane, and when this is used, it is mainly an oily substance having a fluoroalkyl group at a terminal and a non-hydrolyzable silane. An oily mixture is obtained.

In the present invention, the value of a is appropriately selected and used depending on the molecular structure of the desired fluoroalkyl group-containing siloxane. Further, two or more kinds of the component (A) having different values of a can be used in combination. Note that a
Is 0, the ratio of the component (B) is increased,
It may be prepared so as to obtain a liquid product, for example, by using a low-molecular-weight linear siloxane as a component.

As the other starting material, the polyorganosiloxane of the component (B) is basically a liquid having a linear structure or a cyclic structure, and has a partially branched structure. However, those having a linear structure or those having a cyclic structure are preferred. In the polyorganosiloxane having a linear structure, a triorganosilyl group or a compound in which a part of the organo group is substituted with a hydroxyl group is exemplified as a molecular chain terminal. As the component (B), a polydiorganosiloxane end-blocked by a trimethylsilyl group or a dimethylhydroxysilyl group is preferable, and a polydimethylsiloxane end-blocked by a trimethylsilyl group is particularly preferable.

In the polyorganosiloxane of the component (B), the organic group among the substituents bonded to the silicon atom includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group, and a cyclohexyl group. Alkenyl groups such as cycloalkyl group, vinyl group, allyl group,
Phenyl group, aryl group such as tolyl group, or a group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom, cyano group, amino group, etc., for example, chloromethyl group, 3,3,3-trifluoro Propyl group, cyanomethyl group,
Examples thereof include a γ-aminopropyl group. The substituent bonded to the silicon atom may include an alkoxy group, a hydroxyl group, a hydrogen atom, and the like.

Among them, the reaction with the component (A) proceeds favorably, and good properties can be imparted to the obtained fluoroalkyl group-containing siloxane, so that an alkyl group, an aryl group, a hydrogen atom, a hydroxyl group or the like can be obtained. Is preferable, and particularly preferred are polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, polydimethylsiloxane containing hydroxyl groups at both ends, polymethylphenylsiloxane containing hydroxyl groups at both ends, and the like.

The viscosity of the polyorganosiloxane (B) is not particularly limited as long as it is liquid at room temperature.
A viscosity in the range of 0000 cP is preferred, especially in the range of 50-5000 cP. Examples of the cyclic polyorganosiloxane include trimer and heptamer such as hexaorganocyclotrisiloxane, octaorganocyclotetrasiloxane, and decaorganocyclopentasiloxane, and the viscosity is not particularly limited. If necessary, a low-molecular-weight linear siloxane such as hexorganodisiloxane or octaorganotrisiloxane may be used in combination, and the viscosity thereof is not particularly limited. Among these cyclic siloxanes and low-molecular-weight linear siloxanes, those having a methyl group as a substituent are particularly preferred.

In the process for producing a fluoroalkyl group-containing siloxane according to the present invention, 100 parts by weight of the above-mentioned component (A) -containing fluoroalkyl group-containing silane and 5-5000 parts by weight of the component (B) of the polyorganosiloxane are used. Equilibration is carried out in the presence of 0.0001 to 0.1 parts by weight of phosphorus chloronitride as the component (C). If the amount of the component (B) is less than 5 parts by weight based on 100 parts by weight of the component (A), a large amount of the hydrolysis / condensation product of the component (A) alone is generated, and the components (A) and (B) It is difficult to obtain an equilibrium product of the components, whereas if it exceeds 5000 parts by weight, a large amount of the equilibrium product of only the component (B) is produced.
In particular, it is desirable that the content be in the range of 50 to 500 parts by weight at which the reaction proceeds well.

The above-mentioned phosphorus oxynitride as the component (C) is a phosphonitrile compound having chlorine and a compound having a phosphorus-nitrogen bond. Such a phosphorus oxynitride reacts with the fluoroalkyl group-containing silane of the component (A) and the polyorganosiloxane of the component (B) to form the component (A) like a usual acidic catalyst or basic catalyst. The components (A) and (B) are well balanced, and a homogeneous reaction product is obtained. )
It proceeds well in a wide mixing ratio of the component and the component (B), and there is little difference in the reaction depending on the number of the hydrolyzable groups of the silane of the component (A). Since such an action is exhibited, for example, a fluoroalkyl group-containing siloxane in which a long-chain fluoroalkyl group is introduced at an arbitrary ratio, a high-viscosity fluoroalkyl group-containing siloxane, and a liquid having a branched structure having excellent heat resistance. Fluoroalkyl group-containing siloxane and the like can be easily synthesized.

Examples of the condensation catalyst for synthesizing the polysiloxane include basic hydroxides such as metal hydroxides such as sodium hydroxide and potassium hydroxide, organic amines such as ethylenediamine and dimethylamine, hydrochloric acid, and the like. Acidic catalysts such as sulfuric acid, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, monochloroacetic acid, and trifluoromethanesulfonic acid are known. Of these, phosphorus chloronitride is equilibrated with chlorosilane or siloxanediol and polysiloxane. It is known to be used for reactions (Japanese Patent Publication No. 45-415)
No. 99, JP-A-49-52300 and JP-A-7-1445240) do not specifically show the use of siloxanes containing fluoroalkyl groups. Nothing has been shown to exhibit the above-mentioned effective function for the production of the contained siloxane.

Examples of the phosphorus chlorinated nitride of the component (C) include phosphorous amide dichloride, phosphoric amide dichloride, and chlorine-containing polyphosphazene. In particular,
Phosphorous amide dichloride includes C ₆ H ₅ NHPCl
₂ , C ₆ H ₅ N (CH ₃ ) PCl ₂ , C ₆ H ₅ N (C _{2
H 5) PCl 2, (C} 6 H 5) 2 NPCl 2, CH 3 N
HPCl ₂ , (CH ₃ ) ₂ CHNHPCl ₂ , C ₆ H ₅
CH ₂ NHPCl _{2 and the} like, and phosphoric acid amide dichlorides include C ₆ H ₅ NHPOCl ₂ and C ₁₀ H ₇ NHPCl
₂ , CH ₃ NHPOCl ₂ , (CH ₃ ) ₂ CHNHPO
Cl ₂ and C ₂ H ₅ NHPOCl ₂ are exemplified.

The polyphosphazene includes a general formula: OCl ₂ P (NPCl ₂ ) _d NPCl _3-e (A) _e (4) a general formula: OCl ₂ P (NPCl ₂ ) _d N (H) P ( O) Cl _2-f (A) _f ... (5) General formula: Cl ₃ P (NPCl ₂ ) _g NPCl ₃ · PCl ₆ ... (6) (where d is an integer of 0 to 10 and e is 0 An integer from 2 to f
Is 0 or 1, g is an integer of 0 to 10, A is OH, OR
Or a straight-chain phosphonitrile chloride represented by O (O) CR, and R represents an alkyl group or an aryl group). Among these, since the reaction can proceed well, d is 1-3, g is 1, and e is
1, f is preferably 0, and A is preferably OH.

As the polyphosphazenes represented by the above formulas (4) to (6), specifically, OCl ₂ P (NPCl ₂ ) _d NPCl ₂ (OH) (4a) OCl ₂ P (NPCl ₂ ) _{d NPCl 3 ... (4b) OCl} 2 P (NPCl 2) d N (H) P (O) Cl 2 ... (5a) Cl 3 P (NPCl 2) NPCl 3 · PCl 6 ... (6a) , and the like.

In the compound represented by the above formula (4b), d is
The compound 0 or 1 is soluble in an organic solvent such as an ether such as diethyl ether, an ester such as ethyl acetate, or an aromatic hydrocarbon such as toluene, and has a feature that it is easy to handle.

When using the component (C) as described above,
Further, it may be used as a compound reacted with carboxylic acid, sulfonic acid, alcohol, phenol, water and the like. The component (C) of the present invention can be produced by a known method as shown in the above-mentioned literature. For example, in the case of polyphosphazene, phosphorus pentachloride and ammonium chloride are reacted preferably by heating to reflux in tetrachloroethane or the like, phosphorus pentachloride and ammonia are reacted, phosphorus pentachloride is reacted with mercuric chloride amide, Alternatively, it can be produced by a method such as reacting phosphorus nitride with chlorine. Component (C) is used in an amount of 0.1 parts by weight per 100 parts by weight of the fluoroalkyl group-containing silane of component (A).
0001 to 0.1 part by weight, preferably 0.005 to 0.
It is in the range of 05 parts by weight. For a good equilibration reaction,
It is necessary to use 0.0001 parts by weight or more, but after deactivation of the catalyst by neutralization after the reaction, the amount of the remaining catalyst or neutralizing agent can be reduced, and the heat resistance of the resulting fluoroalkyl group-containing siloxane can be reduced. It is necessary that the content be 0.1 part by weight or less because the properties and the like are excellent.

The component (C) is preferably used by dissolving or dispersing it in an organic solvent in order to improve the dispersibility of the component (A) or the component (B) and to exert a satisfactory catalytic action. In particular, it is preferable to use it diluted to 0.5 to 5.0% by weight. As the organic solvent for dilution, in addition to the aforementioned ethers, esters, and aromatic hydrocarbons, halogenated hydrocarbons such as methylene chloride, trichloroethane, and 1,3,5-trichlorobenzene, or liquid siloxanes such as polydimethylsiloxane May be used, or may be used after being diluted with a part of the component (B).

The equilibration reaction uses a fluoroalkyl group-containing silane as the component (A), a liquid polyorganosiloxane as the component (B), phosphorus chloronitride as a catalyst as the component (C), and, if necessary, a solvent. After mixing these at a predetermined ratio, the mixing is performed at room temperature or by heating and mixing and stirring. This reaction is preferably carried out at a temperature in the range of 293 to 393K, and more preferably, by heating at 333 to 373K and stirring for 10 minutes to 25 hours, preferably 1 to 10 hours. The pressure may be normal pressure, but may be reduced or increased. Generally, immediately after mixing the components, the solution becomes cloudy, but becomes transparent as the reaction proceeds. The degree of progress of the reaction can be easily examined by measuring the consumption of the fluoroalkyl group-containing silane as the component (A) as a raw material by a method such as gas chromatography. After performing the equilibration reaction, a basic compound is added and stirred to neutralize the component (C) of the acidic catalyst.

Examples of the basic compound for neutralization include inorganic alkaline compounds such as lithium hydroxide, sodium hydroxide, calcium oxide, calcium hydroxide, magnesium oxide, sodium carbonate, sodium hydrogen carbonate, ethylamine, diethylamine, triethylamine, and the like. Aliphatic organic amines such as propylamine, silazane such as hexamethyldisilazane, ammonia and the like are exemplified, and among these, removal from the product is easy, and it has a preferable action such as silylation of a silanol group. Silazane is preferably used.

The amount of the basic compound used as the neutralizing agent is sufficient for neutralization, and is used in a range where the stability of the obtained product is good. A basic compound is used in an amount of about 1 to 1.2 times the theoretical amount required for the addition, but the excess of silazane, ammonia, and the like can be easily removed by leaving at room temperature, heating, or gas replacement. It may be several times to several hundred times the theoretical amount of the sum,
For example, 50 to 500 times the amount of the component (C) can be used.

The product obtained by performing the equilibration reaction as described above generally has a hydrolyzable group remaining. Therefore, in order to hydrolyze the hydrolyzable group, water is added to the above product, if necessary, using an organic solvent, followed by stirring and mixing. When chlorosilane or the like is used as a raw material, an acid such as hydrochloric acid is generated by hydrolysis. Therefore, if necessary, a basic compound is added to neutralize.

The conditions for the hydrolysis are not particularly limited, and the amount of water and the like may be appropriately selected and used. For example, about 10 to 1000 parts by weight of water is added to 100 parts by weight of the product of the equilibration reaction. Preferably, about 40 to 200 parts by weight, and if necessary, an organic solvent is used in an amount of about 0 to 80% by weight, preferably about 40 to 60% by weight based on the total amount with water, for example, room temperature to 373K,
Preferably, the hydrolysis reaction is performed by heating to 333 to 368K.
Neutralization when an acid is generated as a hydrolysis product may be achieved by adding a basic compound, mixing and stirring. On this occasion,
Although a basic compound as a neutralizing agent for the above-mentioned catalyst can be used, generally, a weakly basic inorganic alkaline compound such as sodium carbonate or sodium hydrogen carbonate may be used.

As the organic solvent, ketones such as acetone, methyl ethyl ketone and diethyl ketone, esters such as methyl acetate, ethyl acetate and n-butyl acetate, n-hexane, gasoline, rubber volatile oil, mineral spirit, Aliphatic hydrocarbons such as kerosene, benzene, toluene, aromatic hydrocarbons such as xylene are exemplified, and can be used for both the equilibration reaction and the hydrolysis reaction.
When water is distilled off after the hydrolysis reaction, toluene, xylene and the like are preferably used since water can be satisfactorily distilled off by azeotropic distillation or the like.

The product obtained by performing the above-described equilibration reaction and, if necessary, the hydrolysis reaction is subjected to an operation of distilling off water, an organic solvent, unreacted low-boiling components, and the like. A desired fluoroalkyl group-containing siloxane, for example,

Embedded image And a fluoroalkyl group-containing polyorganosiloxane represented by the following formula: The low-boiling components may be distilled off simultaneously with the mixing and stirring of the basic compound for neutralizing the acid after hydrolysis.

According to the production method of the present invention, a liquid polyorganosiloxane containing a fluoroalkyl group at an arbitrary ratio can be easily produced using relatively easily available raw materials. In particular, it is characterized in that a fluoroalkyl group-containing polyorganosiloxane having a branched structure in a liquid state, which has not been easily synthesized until now, can be obtained relatively easily. As described above, in the fluoroorganic group-containing polyorganosiloxane having a branched structure obtained by the production method of the present invention, Z in the above formula (7) is represented by the formula (8). Liquid fluoroalkyl group-containing polyorganosiloxanes having such a branched structure have better heat resistance, are less likely to gel, and have a higher solvent resistance than those known so far. It is also excellent in oil resistance and the like.

The liquid fluoroalkyl group-containing siloxane obtained by the production method of the present invention has heat resistance, cold resistance,
Because of its excellent lubricity, it can be applied to hydraulic oil of various machines, and because of its low surface tension, various release agents, release agents, roll compositions for copiers and electrophotographic machines, or roll surfaces It can be applied to processing agents, etc.
Because of its excellent flexibility and low surface tension, it can be applied to cosmetic compositions such as skin cosmetics, make-up cosmetics, hair cosmetics, etc., or fiber treatment agents.
It can also be applied to surface modifiers such as glass and various powders by utilizing oil repellency.

[0041]

Next, specific examples of the present invention will be described. In the following Examples and Comparative Examples, “parts” are all “parts by weight”, “%” are all “% by weight”, and the viscosity is
Shows the value at 298K.

[0042] Example 1 stirrer, reflux condenser, after a four-necked flask equipped with a thermometer was purged with _{nitrogen, C 8 F 17 C 2 H} 4 Si (CH 3) Cl
80 parts of a fluoroalkyl group-containing silane represented by ₂ , viscosity
80 parts of 500 cSt polydimethylsiloxane was charged and mixed and stirred. The temperature was raised to 353K while stirring, and Cl ₃ P
0.45 parts of a 2% solution of (NPCl ₂ ) NPCl ₃ .PCl ₆ in methylene chloride was added, and mixing and stirring were continued. The cloudy mixed solution became transparent after 10 minutes, and after 2 hours, the concentration of silane as a raw material was measured by gas chromatography (GC). As a result, it was completely consumed. Here, in order to stop the reaction, 1.0 part of hexamethyldisilazane was added, mixed and stirred, and cooled to room temperature.

Next, 100 parts of toluene was added and mixed at room temperature, and 100 parts of water was further added and mixed. 36 with stirring
The temperature was raised to 3K for hydrolysis, 30 parts of powdered sodium hydrogencarbonate was added, and the mixture was heated and stirred at 393K for 1 hour, and neutralized and dehydrated by distilling off water and the like. Then 473K,
The low boiling point was removed under heating and reduced pressure of 267 Pa, and the mixture was cooled to room temperature to obtain 135 parts of a product having a viscosity of 560 cSt (yield
89%).

The product obtained has a specific gravity of 1.210 (298K),
The gelation time at a surface tension of 18.0 dyn / cm, a refractive index of 1.3753, and 473K was 250 hours. Incidentally, the raw material dimethylpolysiloxane (500 cSt) had a specific gravity of 0.971 (298K), a surface tension of 21.0 dyn / cm, a refractive index of 1.404, and a gelation time of 120 hours at 473K. This product has IR, NMR,
From the GPC measurement,

Embedded image It was confirmed that it was a fluoroalkyl group-containing polydimethylsiloxane represented by the following formula:

Example 2 The mixing amount of the fluoroalkyl group-containing silane and polydimethylsiloxane was changed to 40 parts of silane and polydimethylsiloxane.
The reaction was carried out in the same manner as in Example 1 except that the amount was changed to 120 parts, whereby 130 parts of a product having a viscosity of 250 cSt was obtained (yield: 83%). The resulting product has a specific gravity of 1.054 (298 K) and a surface tension of 18.9.
The gelation time at dyn / cm, refractive indexes of 1.3922 and 473K was 250 hours.

Example 3 The mixing amount of a fluoroalkyl group-containing silane and polydimethylsiloxane was 96 parts with silane and polydimethylsiloxane.
The reaction was conducted in the same manner as in Example 1 except that the amount was changed to 64 parts.
130 parts of a product having a viscosity of 670 cSt were obtained (86% yield). The resulting product has a specific gravity of 1.240 (298K) and a surface tension of 17.9 dyn /
The gelation time at cm, refractive index of 1.3724 and 473K was 280 hours.

Examples 1 to 3 show that the characteristics of the obtained product can be adjusted by changing the ratio of the raw material fluoroalkyl group-containing silane and polydimethylsiloxane.

Example 4 After replacing a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer with nitrogen, 100 parts of a fluoroalkyl group-containing silane represented by C ₆ F ₁₃ C ₂ H ₄ SiCl ₃ , 200 parts of methyldisiloxane and Cl ₃ P (NPCl ₂ ) NP
0.45 part of a 2% solution of Cl ₃ .PCl ₆ in methylene chloride was charged and mixed and stirred. When the temperature was raised to 363 K with stirring, generation of trimethylchlorosilane was confirmed by gas chromatography analysis, and heating and stirring were continued for 1 hour while continuously distilling this out of the reaction system. At the stage when the temperature in the flask reached 376 K, the distillation of trimethylchlorosilane was stopped, so the heating was stopped, and the mixture was cooled and stirred.

Then, low boiling point components were removed under heating and reduced pressure conditions of 333 K and 4000 Pa, followed by cooling to room temperature to obtain 114 parts of the product (86% yield based on fluorosilane). This product includes C ₆ F ₁₃ C ₂ H ₄ Si (OSi (C
H _{3) 3)} Compounds represented by ₃ was found to contain 60%.

[0050] Example 5 stirrer, reflux condenser, after a four-necked flask equipped with a thermometer was purged with _{nitrogen, C 8 F 17 C 2 H} 4 Si (CH 3) Cl
70 parts of a fluoroalkyl group-containing silane represented by ₂ , C ₈
10 parts of a fluoroalkyl group-containing silane represented by F ₁₇ C ₂ H ₄ Si (OCH ₃ ) ₃ , 80 parts of polydimethylsiloxane having a viscosity of 100 cSt, and Cl ₃ P (NPCl ₂ ) NPCl ₃
• 0.45 parts of a 2% methylene chloride solution of PCl ₆ was charged and mixed and stirred. The mixture was heated to 353K with stirring, 0.45 parts of a 2% solution of Cl ₃ P (NPCl ₂ ) NPCl ₃ · PCl ₆ in methylene chloride was added, and the mixture was heated to 373K and stirred for 2 hours. Hexamethyldisilazane was added to stop the reaction because the silane compound was consumed.
Then, the mixture was cooled to room temperature and stirred. The viscosity of the reaction solution was 20 cSt.

Next, 100 parts of toluene was added and mixed at room temperature, and 100 parts of water was further added and mixed. 36 with stirring
The temperature was raised to 3 K to carry out hydrolysis, 30 parts of powdered sodium hydrogen carbonate was added, and the mixture was heated and stirred at 393 K for 1 hour, followed by neutralization and dehydration by distilling off water and the like. Then 473K,
The low boiling point was removed under heating and reduced pressure conditions of 267 Pa, and the mixture was cooled to room temperature to obtain 115 parts of a product having a viscosity of 1000 cSt (yield: 76%).

The obtained product has a specific gravity of 1.250 (298K),
The gelation time at a surface tension of 18.5 dyn / cm, a refractive index of 1.3772, and 473K was 340 hours.

Example 6 A four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was purged with nitrogen, and then C ₈ F ₁₇ C ₂ H ₄ Si (CH ₃ ) Cl
80 parts of a fluoroalkyl group-containing silane represented by ₂ , viscosity
80 parts of 450 cSt polydiphenylsiloxane was charged and mixed and stirred. The temperature was raised to 363 K while stirring, and Cl ₃
2.0 parts of a 2% dispersion of P (NPCl ₂ ) NPCl ₃ .PCl ₆ in 2% diphenylpolysiloxane was added, and mixing and stirring were further continued. When stirring was continued for 2 hours, silane as a raw material was consumed. To stop the reaction, 2.0 parts of hexamethyldisilazane was added, mixed, stirred and cooled to room temperature.

Next, 100 parts of toluene was added and mixed at room temperature, and 100 parts of water was further added and mixed. 36 with stirring
The temperature was raised to 3K for hydrolysis, 30 parts of powdered sodium hydrogencarbonate was added, and the mixture was heated and stirred at 393K for 1 hour, and neutralized and dehydrated by distilling off water and the like. Then 473K,
The low boiling point was removed under heating and reduced pressure of 267 Pa, and the mixture was cooled to room temperature to obtain 130 parts of a product having a viscosity of 590 cSt (yield: 85%).

The obtained product has a specific gravity of 1.277 (298K),
The gelation time at a surface tension of 20.8 dyn / cm, a refractive index of 1.4440, and 473K was 320 hours.

Example 7 A four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was purged with nitrogen, and then replaced with C ₈ F ₁₇ C ₂ H ₄ Si (CH ₃ ) Cl.
50 parts of a fluoroalkyl group-containing silane represented by ₂ , viscosity
50 parts of 500 cSt polydimethylsiloxane and 50 parts of 25 cSt viscosity polymethylhydrogensiloxane were charged and mixed and stirred. The temperature was raised to 353 K while stirring, and Cl ₃
2.0 parts of a 2% dispersion of P (NPCl ₂ ) NPCl ₃ .PCl ₆ in polydimethylsiloxane was added, and mixing and stirring were continued. When stirring was continued for 2 hours, the starting material, silane, was consumed. To stop the reaction, 1.0 part of hexamethyldisilazane was added, mixed, stirred, and cooled to room temperature.

Next, 200 parts of toluene was added and mixed at room temperature, and 500 parts of water was further added and mixed. 36 with stirring
The temperature was raised to 3K for hydrolysis, 30 parts of powdered sodium hydrogencarbonate was added, and the mixture was heated and stirred at 393K for 1 hour, and neutralized and dehydrated by distilling off water and the like. Then, 423K,
The low-boiling point was removed under heating and reduced pressure conditions of 267 Pa, and cooled to room temperature to obtain 128 parts of a product having a viscosity of 280 cSt (yield
88%).

The obtained product has a specific gravity of 1.215 (298K),
The gelation time at a surface tension of 21.5 dyn / cm, a refractive index of 1.3820, and 473K was 230 hours. Note that the obtained product was colorless and transparent, and was analyzed by infrared absorption (IR) analysis.
The presence of H was confirmed. Incidentally, in order to confirm the reactivity of Si—H, the product was reacted with allyl glycidyl ether using a platinum catalyst.
The analysis confirmed the consumption of allyl glycidyl ether and Si-H, and the ¹ H-NMR analysis
The reactivity of -H was confirmed.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that trifluoromethanesulfonic acid was used as a catalyst.
130 parts were obtained. Of this product, the same copolymer as in Example 1 was 50%, and the remainder was an unreacted dimethylpolysiloxane as a raw material and a hydrolyzed condensate of a fluoroalkyl group-containing silane as a raw material.

Comparative Example 2 In place of the fluoroalkyl group-containing silane, (C ₈ F ₁₇ C
_The reaction was carried out in the same manner as in Example 1 except that 80 parts of the cyclic trisiloxane represented by ₂ H ₄ Si (CH ₃ ) O) ₃ was used to obtain 130 parts of a cloudy product. Of this product, 30% was the same copolymer as in Example 1, and the rest was unreacted dimethylpolysiloxane as the raw material and ring-opened polymer of the cyclic trisiloxane as the raw material.

[0061]

As described above, according to the process for producing a fluoroalkyl group-containing siloxane of the present invention, a target liquid siloxane can be easily prepared by a simple operation using relatively easily available raw materials. Obtainable. For example, the ratio of the fluoroalkyl group in the substituent can be introduced in an arbitrary range, and a residual siloxane component and the like can be obtained, and a liquid siloxane excellent in properties such as heat resistance can be obtained. Fluoroalkyl group-containing siloxane excellent in the above can be easily obtained.

[0062]

Claims (2)

[Claims] (1) In producing a fluoroalkyl group-containing siloxane, (A) a general formula: R ^f SiR _a ^f
_3-a (wherein, R ^f represents a fluoroalkyl group, R represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, X represents a hydrolyzable group, and a represents an integer of 0 to 3. 100 parts by weight of a fluoroalkyl group-containing silane represented by
(B) 5 to 5000 parts by weight of a polyorganosiloxane,
(C) A method for producing a fluoroalkyl group-containing siloxane, which comprises equilibrating in the presence of 0.0001 to 0.1 part by weight of phosphorus chloronitride. 2. The method for producing a fluoroalkyl group-containing siloxane according to claim 1, wherein A process for producing a fluoroalkyl group-containing siloxane represented by the formula: