JP3057139B2 - Linear polyorganosiloxane and production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a linear polyorganosiloxane having a cyclic fluorinated organic group, particularly a cyclic perfluoroether group, which is excellent in releasability, gas permeability and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, heat resistance, cold resistance, chemical resistance,
As a polyorganosiloxane having excellent releasability, weather resistance, water and oil repellency, etc., those having a fluorine-containing organic group in the molecule are known. For example, JP-A-2-19829 and JP-A-2-19830 have the following formula:

[0003]

Embedded image (In the formula, a is an integer of 1 to 3, b is an integer of 1 to 5, c is an integer of 1 or 2, and R ⁴ has 3 carbon atoms.
It is an organic group containing no divalent fluorine of 10 to 10. The polyorganosiloxane having a chain-like fluorine-containing organic group represented by the formula (1) is disclosed.

[0004]

However, a linear polyorganosiloxane having a cyclic fluorine-containing organic group as a substituent bonded to a silicon atom has not yet been known. Accordingly, an object of the present invention is to provide a linear polyorganosiloxane having a cyclic fluorinated organic group as a substituent on a silicon atom, particularly a cyclic perfluoroether group, and a method for producing the same.

[0005]

According to the first aspect of the present invention, the repeating part of the main chain has substantially the following formula (1):

[0006]

Embedded image (Wherein R is an unsubstituted or substituted monovalent hydrocarbon group) and a repeating unit represented by the following formula (2):

[0007]

Embedded image (Wherein R ^{1 is a} hydrogen atom or the same or different, unsubstituted or substituted, monovalent hydrocarbon group).
A second aspect of the present invention is the following formula (3):

[0008]

Embedded image (Wherein, R and R ² are each as described above)
The method for producing a linear polyorganosiloxane described above, characterized by polymerizing an organocyclotrisiloxane compound represented by the following formula:

Hereinafter, the present invention will be described in detail. Linear polyorganosiloxane The linear polyorganosiloxane of the present invention has the above formula (1)
And the repeating unit of the main chain consists essentially of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2). The repeating unit represented by the formula (1) is less than 100 mol%, preferably 28 to 35 mol%, and the repeating unit represented by the formula (2) is more than 0 mol%, preferably 65 to 7 mol%.
And linear polyorganosiloxane containing 2 mol%.

In the repeating unit represented by the above formula (1), R is an unsubstituted or substituted monovalent hydrocarbon group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, alkyl group having 1 to 10 carbon atoms, especially 1 to 6 carbon atoms such as octyl group; phenyl group, tolyl group, An aryl group having 6 to 10 carbon atoms such as a xylyl group and a naphthyl group; a carbon atom having 6 to 10 carbon atoms such as a benzyl group, a phenylethyl group and a phenylpropyl group
And an aralkyl group having 10; an aralkyl group having no aliphatic unsaturated bond such as a fluoroalkyl group having 3 to 10 carbon atoms such as a trifluoropropyl group, a nonafluorohexyl group, and a heptadecafluorodecyl group. Among these, R is preferably a methyl group, a phenyl group, 3,3,3-trifluoropropyl group, and more preferably a methyl group, from the viewpoint of the availability of the raw materials and the ease of the reaction in the production. It is.

In the repeating unit represented by the above formula (2), a plurality of R ^{1 s} may be the same or different and each represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-
Butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group and other alkyl groups having 1 to 10 carbon atoms, especially 1 to 6 carbon atoms; vinyl group, allyl group, propenyl group Alkenyl groups having 2 to 6 carbon atoms, especially 2 to 4 carbon atoms such as isopropenyl group, butenyl group, hexenyl group and cyclohexenyl group; carbon atoms such as phenyl group, tolyl group, xylyl group and naphthyl group 6 to 10 aryl groups; benzyl group,
An aralkyl group having 6 to 10 carbon atoms such as a phenylethyl group and a phenylpropyl group; and chloromethyl in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups have been substituted with a halogen atom, a cyano group, or the like. And a substituted hydrocarbon group such as a substituted alkyl group having 1 to 10 carbon atoms such as a group, bromoethyl group, cyanoethyl group, chloropropyl group, trifluoropropyl group, nonafluorohexyl group, heptadecafluorodecyl group and the like.

Of these, R ¹ is a hydrogen atom, a methyl group, a vinyl group, a phenyl group, 3,3,3-trifluoro, in view of the availability of raw materials or the ease of reaction during production. A propyl group is preferred, and a methyl group is more preferred. Further, the terminal of the linear polyorganosiloxane of the present invention is appropriately selected as needed, for example,

[0013]

Embedded image (In each of the above formulas, R ¹ is as described above.) And the like.

The degree of polymerization of the linear polyorganosiloxane of the present invention is usually from 3 to 500, especially from 5 to 3
00 is preferred.

Production Method The linear organopolysiloxane of the present invention can be produced, for example, by the following method.

Method 1 The first method uses the following formula (4):

[0017]

Embedded image (Wherein R is as defined above) and the following formula (5): (R ¹ ) ₂ SiCl ₂ (5) (wherein R ¹ is as defined above. This is a method of co-hydrolyzing with dichlorosilane represented by the formula (1) and polymerizing the same.

The dichlorosilane represented by the above formula (4) is
For example, an organodichlorosilane represented by the following general formula (6): Cl ₂ (R) SiH (6) (where R is as described above), and the following formula (7):

Embedded image And a hydrosilylation reaction in the presence of a catalyst.

Examples of the catalyst used in the hydrosilylation reaction include transition metal metals such as Pt, Rh, and Pd and compounds of these transition metals. Specifically, for example, H ₂
Modified complex of PtCl ₆ with olefins, modified complex of H ₂ PtCl ₆ with alcohols, modified complex of H ₂ PtCl ₆ with vinyl siloxanes, RhCl ₃ , Rh (CH ₃ COCHCOCH ₃ ) ₃ , Rh (PPh ₃ ) ₃ C
l, Rh (PPh ₃ ) ₃ Br, Rh ₂ (AcO) ₄ , Rh (PPh ₃ ) ₂ (CO) Cl, Rh
(η ⁴ -C ₇ H ₈ ) Cl, Rh (CH ₃ COCHCOCH ₃ ) (CO) ₂ , Rh ₄ (C
_{O) 12, Rh 4 (CO} ) 16, Rh (PPh 3) 3 (CO) H, (NH 4) 2 PdCl 6,
(NH ₄ ) ₂ PdCl ₄ , Pd (CH ₃ COCHCOCH ₃ ) ₂ , Pd (PhCN) ₂ Cl ₂ , Pd
(PPh ₃ ) ₂ Cl ₂ , Pd (PPh ₃ ) ₄ (where Ph is a phenyl group, Ac
Represents an acetyl group. ) And the like.

In order to carry out the reaction between the organodichlorosilane of the formula (6) and the allyl ether of the formula (7), the allyl ether and the hydrosilylation catalyst are charged into a reaction vessel and maintained at a predetermined reaction temperature. The organodichlorosilane may be added dropwise while doing so. The reaction temperature is usually 30-15
0 ° C, preferably 60-130 ° C.

The progress of the reaction can be monitored by measuring the consumption of organodichlorosilane and allyl ether as reaction components and the amount of reaction product formed by gas chromatography analysis. The addition reaction is completed by performing the reaction for about an hour. When the consumption of the reaction components stops during the reaction, the reaction can be restarted by adding a catalyst. After the reaction,
The fluorine-containing organosilicon compound of the present invention can be isolated and purified by distilling the reaction mixture.

In the above reaction, the organodichlorosilane of the formula (6) is preferably used in a ratio of 0.8 to 2 mol, more preferably 1 to 1.5 mol, per mol of the allyl ether of the formula (7). The amount of the catalyst used is usually from 1 × 10 ⁻⁶ to 1 × 10 ⁻² per mole of organodichlorosilane.
Mol, preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol.

The allyl ether of the formula (7) used as a starting material in the above reaction is represented by the following formula (8):

[0024]

Embedded image And a halogenated allyl compound such as allyl bromide in the presence of a fluorine anion source such as cesium fluoride in a solvent inert to these reaction components (for example, (Glyme). The perfluorocyclic ketone of the formula (8) used is known from JP-A-4-316576. Allyl compound per mole of the cyclic ketone
The fluorine anion source may be used in the range of 1.0 to 1.5 mol per mol of the cyclic ketone, and the reaction is preferably carried out under anhydrous conditions at 30 to 150 ° C. with stirring.
After completion of the reaction, the allyl ether of the formula (7) can be isolated by distillation or the like. Co-hydrolysis of the dichlorosilane represented by the formula (4) and the dichlorosilane represented by the formula (5)
It is carried out by reacting with water at 10 to 90 ° C.
This ends the

[0025]

Embedded image (Wherein R ¹ is as defined above). Also, for example,

[0026]

Embedded image (R ³ is a hydrogen atom, a methyl group or a vinyl group) in order to obtain a linear polysiloxane, which is obtained by dehydrating and neutralizing the polysiloxane produced by this hydrolysis, and then adding, for example, trifluoromethanesulfonic acid. And a catalyst represented by the general formula (9):

[0027]

Embedded image (Wherein, R ³ is as described above, and n is an integer of 1 to 6).

Method 2 In the second method, a repeating unit represented by the above (2) and the following formula (10):

Embedded image (CH ₃ ) ₃ SiO—, (R ¹ ) ₂
(HO) SiO -, (CH 2 = CH) (R 1) 2 SiO -, (R 1) 2 ClSiO
-, A linear organohydrogenpolysiloxane in which both ends of a molecular chain are blocked with siloxy units (R ¹ is as described above) such as (CH ₃ ) ₂ (H) SiO-, and the following formula (7): :

[0029]

Embedded image Is a method of adding an allyl ether compound represented by

The allyl ether compound represented by the above formula (7) is obtained by mixing the perfluorocyclic ketone represented by the formula (8) with an allyl halide compound such as allyl bromide as described in the above method 1. It can be obtained by reacting in the presence of a fluorine anion source such as cesium bromide.

In this addition reaction, the above-mentioned linear organohydrogenpolysiloxane and the allyl ether compound represented by the formula (7) are usually reacted at 40 to 150 ° C., preferably in the presence of a catalyst for the hydrosilylation reaction. Is 60 to 130
The reaction is carried out by conducting a hydrosilylation reaction at a temperature of about 10 minutes to 10 hours.

As the catalyst used for the hydrosilylation reaction, the same catalyst as that used in the above method 1 can be used.

The amount of catalyst used is usually 1 × 10 ^-6 ~1 × 10 relative to the hydrosilyl group in the organohydrogenpolysiloxane (≡Si-H) ^{- 2} mol / mol, preferably 1 × 10 ^{- 5} ~ It can be added at a rate of 1 × 10 ⁻³ mol / mol.

Method 3 In the third method, the repeating unit represented by the above formula (1) is represented by 2
This is a method for producing a linear polyorganosiloxane containing 8 to 35 mol% and 65 to 72 mol% of a repeating unit represented by the above formula (2), and comprises the following formula (3):

[0035]

Embedded image (Wherein R and R ² are each as defined above) by homopolymerization to produce such a linear polyorganosiloxane. Here, R ² is a lower alkyl group, a halogen-substituted lower alkyl group or a phenyl group which may be the same or different. Examples of the lower alkyl group include a methyl group,
Those having 1 to 4 carbon atoms such as ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and tert-butyl group, and the halogen-substituted lower alkyl group include chloromethyl group, bromoethyl group and chloropropyl group. Examples thereof include those having 1 to 3 carbon atoms such as a group and a trifluoropropyl group. Among them, R ² is preferably a methyl group, a phenyl group, a 3,3,3-trifluoropropyl group, and the polymerization for producing the linear organopolysiloxane of the present invention is preferred. From the viewpoint of ease of reaction, a methyl group is more preferred. When a linear polyorganosiloxane is produced by this method, this method is particularly effective because the cyclic fluorine-containing organic group is uniformly and efficiently introduced into the polymer.

The cyclotrisiloxane represented by the above formula (3) is, for example, a compound represented by the following formula (4):

[0037]

Embedded image (Wherein R is as defined above) and the following general formula (11):

[0038]

Embedded image (Wherein R ² is as defined above), and can be produced by a method of reacting with a tetraorganodisiloxane diol represented by the formula:

This reaction is carried out by reacting Si in dichlorosilane of the formula (4)
It proceeds by condensing -Cl and Si-OH in the tetraorganodisiloxane diol of the formula (11) by removing HCl. This condensation can usually be carried out smoothly in the presence of an HCl scavenger such as an amine. Examples of amines include triethylamine, pyridine, dimethylaniline, and the like.

In order to carry out this reaction, it is preferable to separately dissolve the compounds of the formulas (4) and (11) in a solvent to form a solution, which is then simultaneously added dropwise to the amine-containing solution.
Preferred as the solvent for the disiloxane diol and amine of the formula (11) are aprotic polar solvents, such as acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone, and esters such as ethyl acetate.
Particularly, methyl ethyl ketone and methyl isobutyl ketone are preferred. Examples of the solvent for the dichlorosilane of the formula (4) include those exemplified as the solvent for the disiloxane diol and the amine of the above formula (11), and further include n-pentane and n-pentane.
-Hexane, cyclohexane, aliphatic hydrocarbons such as petroleum ether, ethers such as diethyl ether, tetrahydrofuran, dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform,
Chlorinated hydrocarbon solvents such as carbon tetrachloride, meta- or para-
Xylene hexafluoride, benzotrifluoride, perfluorobutyltetrahydrofuran, perfluoro-n-
A fluorinated solvent such as octane is also exemplified. In particular, meta- or para-xylene hexafluoride can be suitably used. If the amount of these solvents is too small, undesired chain-like by-products increase during the condensation reaction between the dichlorosilane of the formula (4) and the disiloxane diol of the formula (11), The hydrochloride increases the solution viscosity and reduces the efficiency of stirring. Conversely, if the amount of the solvent is too large, the cost associated with the amount of the consumed solvent increases and the pot yield decreases, which is not industrially preferable. Suitable amounts of solvent are based on the total amount of dichlorosilane of formula (4), disiloxane diol of formula (11) and amine, on a weight basis.
5 to 4 times.

Formula (4) Formula (11) for the amount of dichlorosilane
The amount of the disiloxane diol on a molar basis is usually from 1 to
It is 1.5 times, preferably 1-1.2 times. The amount of amine is usually 2 to 3 times, preferably 2 to 2.2 times on a molar basis, based on the amount of dichlorosilane of the formula (4).

The reaction temperature is 30-80 ° C., preferably 35
６５65 ° C. The dropping time may be usually from 15 minutes to 5 hours. The progress of the reaction is determined by gas chromatographic analysis using Equation (4),
It can be confirmed by monitoring the consumption of the compound (11) and the production of the target compound. After the reaction, the amine hydrochloride is removed from the reaction mixture by means such as washing with water and the solvent is distilled off, and then the desired product can be isolated by distillation.
The dichlorosilane of the formula (4) used as a starting material in the above-mentioned production method is, for example, as described above, an organodichlorosilane represented by the above formula (6) and an allyl ether represented by the formula (7). Can be obtained by a hydrosilylation reaction in the presence of a catalyst.

The polymerization of the cyclotrisiloxane represented by the above formula (3) is specifically carried out as follows. One method is to use a low polymerization degree siloxane or an alkali metal silanolate of silane as a polymerization initiator. This initiator constitutes one end of the linear polyorganosiloxane to be produced, and can be selected according to a desired end. For example,

[0044]

Embedded image To produce a terminal linear polyorganosiloxane, the formula:

[0045]

Embedded image (Wherein L is an integer of 0 to 5, m is an integer of 0 to 2, Rf is a monovalent fluorine-substituted alkyl group, and M is an alkali metal). Used as an initiator,

[0046]

Embedded image When the terminal linear polyorganosiloxane is produced, the following general formula (12):

[0047]

Embedded image (Where p is an integer of 0 to 5, q is an integer of 0 to 2, Rf and M are as described above), and the like may be used as the initiator. Equation (12) above
Medium, following unit

[0048]

Embedded image Are particularly exemplified as those having an advantage that the compatibility with the cyclotrisiloxane of the formula (3) is increased and the polymerization can be carried out more smoothly. In the above formula, the fluorine-substituted monovalent alkyl group represented by _{Rf, -CH 2 CH 2 C k} F 2 k + 1 (k is an is an integer from 1 to 12) were obtained those represented by Preferred in terms of ease, specifically, for example, CF ₃ CH ₂ CH
₂ −, C ₂ F ₅ CH ₂ CH ₂ −, C ₃ F ₇ CH ₂ CH ₂ −, C ₄ F ₉ CH ₂ CH ₂ , C ₅ F
₁₁ CH ₂ CH ₂ −, C ₆ F ₁₃ CH ₂ CH ₂ −, C ₈ F ₁₇ CH ₂ CH ₂ −, C ₁₀ F
₂₁ CH ₂ CH ₂ —, C ₁₂ F ₂₅ CH ₂ CH ₂ — and the like. In the above formula, examples of the alkali metal represented by M include Li,
Na, K and the like are mentioned, and Li is particularly preferable.

The polymerization is carried out by mixing and stirring the cyclotrisiloxane of the formula (3) and the above-mentioned polymerization initiator in the absence of water, at a temperature of 70 to 130 ° C. and usually for 1 to 1 hour.
24 hours. The molar ratio between the polymerization initiator and the cyclotrisiloxane substantially determines the degree of polymerization. The other end during polymerization is

[0050]

Embedded image It is also necessary if necessary

[0051]

Embedded image (The polymer may be hydrolyzed),

[0052]

Embedded image (After polymerization,

[0053]

Embedded image as well as

[0054]

Embedded image And silylate. ),

[0055]

Embedded image (After polymerization,

[0056]

Embedded image as well as

[0057]

Embedded image To silylate).

The above (CH ₃ ) ₃ SiCl, (CH ₂ = CH) (CH ₃ )
₂ Monochlorosilane such as SiCl is sufficiently blocked at its terminals by using 1.2 to 2.0 times the molar amount of the polymerization initiator used, and

[0059]

Embedded image Is used in an amount of 1.2 to 2.0 times on a molar basis with respect to monochlorosilane added in combination, to neutralize excess monochlorosilane and to assist in forming a desired terminal. This post-treatment with monochlorosilane and disilazane is performed under stirring at 30 to 60 ° C. for 30 minutes to 5 hours, and the generated salt is filtered off, and excess disilazane and low-molecular products are removed by a strip to remove the residual product. The linear organopolysiloxane of the invention can be obtained.

Another method is to carry out the polymerization using a strong acid, particularly trifluoromethanesulfonic acid as a catalyst. The amount of the catalyst is usually 10% by weight based on the cyclotrisiloxane of the formula (3).
-10,000 ppm. Also in this case, a means for obtaining a desired end can be taken. End

[0061]

Embedded image To do so, for example,

[0062]

Embedded image (Wherein, i is an integer of 0 to 4), and polymerization may be performed by adding a siloxane oligomer represented by the following formula:

[0063]

Embedded image To do so, for example,

[0064]

Embedded image (Wherein, j is an integer of 0 to 4), and the polymerization may be performed by adding a siloxane oligomer represented by the formula: The amount of addition of these oligosiloxanes corresponds to the desired degree of polymerization.
It is determined by the molar ratio of (3) to cyclotrisiloxane. The polymerization is carried out at 30-100 ° C in the absence of water
The reaction may be performed for 24 hours, and after polymerization, neutralize with a base such as ammonia, sodium carbonate, sodium hydrogen carbonate, and the like.
The linear polyorganosiloxane of the present invention can be obtained by removing the low molecular weight components by stripping.

The process for producing a linear organopolysiloxane by polymerizing the compound of the formula (3) described herein additionally comprises

[0066]

Embedded image (Where h is 3 or 4 and R ¹ is as described above). This is an effective method for producing a linear polyorganosiloxane in which a desired amount of a group other than a methyl group is introduced into the main chain of the polymer when at least one of R ¹ is a group other than a methyl group. is there.

The linear polyorganosiloxane of the present invention is a novel compound having a cyclic fluorinated organic group, particularly a cyclic perfluoroether group. The chain polyorganosiloxane of the present invention is expected to be used as oils, rubbers, coating materials, and the like, which are excellent in release properties, gas permeability and the like.

[0068]

【Example】

Example 1 A 300 ml flask equipped with a stirrer, a Dimroth condenser, a thermometer and a dropping funnel was charged with 120 g of water, and then the following formula was used.

[0070]

Embedded image 37.5 g (0.070 mol) of (CH ₃ ) ₂ Si
A mixture of 81.3 g (0.630 mol) of Cl _{2 was} added dropwise over 1 hour. Thereafter, the mixture in the flask was continuously stirred at 55 ° C. for 2 hours. The obtained reaction mixture was washed twice with water,
Dehydration and neutralization were performed by adding 3.5 g and 3.5 g of sodium bicarbonate. After completion of dehydration and neutralization, the reaction mixture was charged into a 200 ml flask equipped with a stirrer, a Dimroth condenser, and a thermometer.

[0071]

Embedded image 2.2 g (0.0071 mol) of the compound represented by and 0.1 g of trifluoromethanesulfonic acid were added, and the mixture was stirred at 110 ° C. for 5 hours.
Next, 0.5 g of sodium sulfate and 0.5 g of sodium bicarbonate were added, and neutralization was performed at 25 ° C. for 4 hours. After that, both ends of the molecular chain, which are colorless and transparent by filtration,

[0072]

Embedded image 62 g of a linear organopolysiloxane oil blocked in units were obtained. The oil has a viscosity of 235 cSt (25 ° C),
The specific gravity was 1.23 (25 ° C) and the refractive index was 1.3815 (25 ° C).

Further, regarding the obtained oil,

Embedded image The F content was determined by ¹⁹ F-NMR based on
%, From which about 12 mol% of the repeating unit represented by the above formula (1) (where R is a methyl group),

[0074]

Embedded image Was found to be contained in each of about 88 mol%. The molecular weight was found to be about 5,000 by GPC (gel permeation chromatography) analysis.

Example 2 200 m equipped with a stirrer, Dimroth condenser and thermometer
l 80 g of cyclotrisiloxane represented by the above formula (3) (where R and R ² are methyl groups) (0.127
Mol) and the following formula:

[0076]

Embedded image Compound represented by 1.47 g (0.00193 mol) were charged, N ₂
The polymerization reaction was carried out at 100 ° C. for 5 hours under air flow. Furthermore, the following formula is added to the flask at 50 ° C .:

[0077]

Embedded image 0.35 g (0.00290 mol) of the compound represented by the following formula:

[0078]

Embedded image 0.81 g (0.00437 mol) of the compound represented by the formula was added, and the mixture was stirred for 2 hours to neutralize and silylate. After removing the salt from the obtained reaction product by filtration, the mixture was heated at 180 ° C. for 2 hours.
A vacuum strip was performed for hours. 75 g of the thus obtained colorless and transparent molecular chain terminal is represented by the formula:

[0079]

Embedded image The linear organopolysiloxane oil blocked by the unit (1) had a viscosity of 8200 cSt (25 ° C.), a specific gravity of 1.39 (25 ° C.), and a refractive index of 1.3728 (25 ° C.).

When the F content was determined in the same manner as in Example 1, it was 37.9%. From this, about 30 mol% of the repeating units in which R was a methyl group in the formula (1) were obtained.

[0081]

Embedded image Was confirmed to be contained in about 70 mol% of each.

When the vinyl group was quantified by the Hanus method, it was 0.0050 mol / 100 g.
205.

Example 3 In a 100 ml flask equipped with a stirrer, a Dimroth condenser, a dropping funnel and a thermometer, the following formula was added.

[0084]

Embedded image 50 g of a linear polyorganosiloxane represented by
(078 mol) and 0.037 g (3.9 × 10 ^-6 mol) of an n-butanol-modified complex of chloroplatinic acid (Pt concentration: 2%), and the liquid in the flask was heated to 75 ° C. 65.4 g of the allyl ether compound of the formula (7) was added to the dropping funnel.
(0.16 mol), and added dropwise over 30 minutes.
During this time, the liquid temperature in the flask rose to 79 ° C. After completion of the dropwise addition, the temperature in the flask was maintained at 75 ° C. for another 30 minutes, and activated carbon was added thereto, followed by stirring and filtration.
Strip at reduced pressure for 1 hour at
44.9 g were obtained. The viscosity was 6.7 cSt (25 ° C.), the specific gravity was 1.29 (25 ° C.), and the refractive index was 1.3474 (25 ° C.).

When the F content was determined in the same manner as in Example 1, it was 31.8%, and the average structural formula of the oil obtained therefrom was:

Embedded image Turned out to be.

Example 4 20 equipped with a stirrer, a Dimroth condenser and a thermometer
In a 0 ml flask, 80 g of cyclotrisiloxane represented by the formula (3) (where R and R ² are methyl groups)
(0.127 mol), formula:

[0087]

Embedded image 1.72 g of cyclotrisiloxane represented by
67 mol), the formula:

[0088]

Embedded image 0.39 g of decamethyltetrasiloxane represented by
(0.00126 mol) and 0.008 g of trifluoromethanesulfonic acid, and polymerized at 50 ° C. for 10 hours. Thereafter, sodium bicarbonate was added to neutralize the mixture, the mixture was further treated with activated carbon, filtered, and then stripped under vacuum at 200 ° C. for 1 hour to obtain 67.1 g of a colorless and transparent oil. Viscosity (25 ° C) 1410 cSt, specific gravity (25 ° C) 1.3
8 The refractive index (25 ° C.) was 1.3716.

When the F content was determined by the same method as in Example 1, it was 38.2%, and when the vinyl group was quantified by the same method as in Example 2, it was 0.026 mol / 100 g. Thus, this oil has about 31 mol% of repeating units represented by the formula (1) (where R is a methyl group):
formula:

[0090]

Embedded image About 5 mol% of a repeating unit represented by the following formula:

[0091]

Embedded image It was found to contain about 64 mol% of repeating units represented by According to GPC analysis, the molecular weight was about 65,000.
It turned out to be.

[0092]

The linear polyorganosiloxane of the present invention has a cyclic fluorinated organic group as a substituent on a silicon atom,
Especially because it has a cyclic perfluoroether group,
It is expected to be used as oils, rubbers, coating materials, etc., which have excellent release properties and gas permeability. Further, according to the production method of the present invention, the cyclic fluorinated organic group can be uniformly introduced into the molecule.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A 8-27169 (JP, A) JP-A 8-27164 (JP, A) (58) Fields studied (Int. Cl. ⁷ , DB name) C08G 77/24 CA (STN)

Claims (3)

(57) [Claims] The main chain is substantially the following formula (1): (Wherein, R is an unsubstituted or substituted monovalent hydrocarbon group)
And a repeating unit represented by the following formula (2): Wherein R ¹ is a hydrogen atom or a repeating unit represented by the same or different unsubstituted or substituted monovalent hydrocarbon group. 2. A repeating unit represented by the formula (1):
35 mol% and the repeating unit 65 to 72 represented by the above formula (2)
The linear polyorganosiloxane according to claim 1, comprising mol%. 3. The following formula (3): Wherein R is as described above, and R ² is the same or different lower alkyl group, halogen-substituted lower alkyl group or phenyl group. Item 3. The method for producing a linear polyorganosiloxane according to Item 1 or 2.