WO2017047652A1

WO2017047652A1 - Method for producing periodic polysiloxane by polycondensation of symmetric oligosiloxanes

Info

Publication number: WO2017047652A1
Application number: PCT/JP2016/077135
Authority: WO
Inventors: 一幸黒田; 敦下嶋; 島田　茂; 佐藤　一彦
Original assignee: 国立研究開発法人産業技術総合研究所
Priority date: 2015-09-18
Filing date: 2016-09-14
Publication date: 2017-03-23
Also published as: JP6550626B2; JPWO2017047652A1

Abstract

The purpose of the present invention is to provide a method for producing a polysiloxane with which it is possible to efficiently produce a polysiloxane having side-chain organic groups arranged periodically. A polysiloxane having side-chain organic groups arranged periodically can be efficiently produced by polycondensing symmetrical oligosiloxanes having the same arrangement of organic groups, such as an oligosiloxane represented by formula (I-1) and an oligosiloxane represented by formula (II-1), in the presence of a Lewis acid.

Description

Process for producing periodic polysiloxanes by polycondensation of symmetrical oligosiloxanes

The present invention relates to a method for producing polysiloxane, and more particularly to a method for producing polysiloxane capable of producing a polysiloxane in which side chain organic groups are periodically arranged.

“Polysiloxane” is a polymer material that combines the properties of inorganic and organic compounds, and its use is wide-ranging in electronic devices, chemicals, cosmetics, and the like. Polysiloxane has a structure with siloxane bonds (Si-O-Si) as the main skeleton and organic groups such as methyl and phenyl groups in the side chain, and is durable, defoaming, releasable, and hydrophobic. It is known to exhibit the following characteristics. These characteristics are derived from the side chain organic group. For example, by replacing a part of the methyl group of polydimethylsiloxane with a phenyl group, the heat resistance and viscosity can be increased. Lubricity etc. can also be provided by introduce | transducing an organic group.

As a synthesis method of polysiloxane, a method of ring-opening polymerization of cyclic siloxane, a method of copolymerizing two or more kinds of organosilane monomers, and the like are known. In recent years, attempts have been made to synthesize polysiloxanes having a periodic structure by applying these methods. For example, a method using a cyclic trisiloxane containing two kinds of organic functional groups as a raw material and using secondary butyllithium as a reaction initiator (see Non-Patent Document 1), a method using trifluoromethanesulfonic acid (Non-Patent Document 2) And a method using (Me) ₄ N [Si (Me) ₂ O] _n N (Me) ₄ (see Non-Patent Document 3) and the like have been reported.

JP 2013-209473 A

As described above, polysiloxanes are known to exhibit various properties depending on the side chain organic groups. For example, if two or more types of organic groups are randomly arranged, the target properties decrease. It has also been pointed out (see Patent Document 1).
An object of this invention is to provide the manufacturing method of polysiloxane which can manufacture efficiently the polysiloxane which the organic group of the side chain arranged periodically.

As a result of intensive investigations to solve the above problems, the present inventors have conducted polycondensation of oligosiloxanes having the same organic group arrangement and symmetric oligosaccharides in the presence of a Lewis acid. The present inventors have found that a polysiloxane in which chain organic groups are periodically arranged can be efficiently produced, and the present invention has been completed.
That is, the present invention is as follows.

<1> In the presence of a Lewis acid, an oligosiloxane represented by the following formula (I-1), an oligosiloxane represented by the following formula (II-1), and an oligosiloxane represented by the following formula (I-2) And an oligosiloxane represented by the following formula (II-2) or an oligosiloxane represented by the following formula (I-3) and an oligosiloxane represented by the following formula (II-3) A method for producing polysiloxane, comprising:

(In the formulas (I-1) to (I-3), R ¹ to R ⁸ may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. Represents a hydrocarbon group, R ^{1 to} each other, R ^{2 to} each other, R ^{8 to} each other are the same hydrocarbon group, and R ¹ to R ⁸ each represent the same or different hydrocarbon group Provided that R ¹ , R ³ , R ⁵ , and R ⁷ are all the same hydrocarbon group, and R ² , R ⁴ , R ⁶ , and R ⁸ are all the same hydrocarbon group. )

(In the formulas (II-1) to (II-3), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R ¹ to R ⁸ are selected from the group consisting of an oxygen atom and a halogen atom. represents a hydrocarbon group having at least one atom of carbon atoms which may contain an ^1-20, respectively the same R 1 ~ ^{R 8} is a ^R 1 ~ ^{R 8} of formula (I-1) ~ (I -3) Represents a hydrocarbon group of
<2> In the presence of a Lewis acid, an oligosiloxane represented by the following formula (III-1), an oligosiloxane represented by the following formula (IV-1), and an oligosiloxane represented by the following formula (III-2) And a reaction step of polycondensing an oligosiloxane represented by the following formula (IV-2) or an oligosiloxane represented by the following formula (III-3) and an oligosiloxane represented by the following formula (IV-3): A method for producing polysiloxane, comprising:

(In the formulas (III-1) to (III-3), R ¹ to R ⁸ may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. Represents a hydrocarbon group, R ^{1 to} each other, R ^{2 to} each other, R ^{8 to} each other are the same hydrocarbon group, and R ¹ to R ⁸ each represent the same or different hydrocarbon group Provided that R ¹ , R ³ , R ⁵ , and R ⁷ are all the same hydrocarbon group, and R ² , R ⁴ , R ⁶ , and R ⁸ are all the same hydrocarbon group. )

(In the formulas (IV-1) to (IV-3), each R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R ¹ to R ⁸ are selected from the group consisting of an oxygen atom and a halogen atom. represents a hydrocarbon group having at least one atom of carbon atoms which may contain an ^1-20, respectively the same R 1 ~ ^{R 8} is a ^R 1 ~ ^{R 8} of formula (III-1) ~ (III -3) Represents a hydrocarbon group of
<3> The oligosiloxane represented by the formula (I-1) is an oligosiloxane represented by the following formula (I-1-1), and the oligosiloxane represented by the formula (II-1) The method for producing a polysiloxane according to <1>, in which is an oligosiloxane represented by the following formula (II-1-1).

(In the formula (I-1-1), R ¹ and R ³ represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. And R ¹ and R ³ are the same hydrocarbon group, and R ¹ and R ³ are different hydrocarbon groups.)

(In the formula (II-1-1), each R independently represents a hydrocarbon group having 1 to 6 carbon atoms, and R ¹ and R ³ are at least one selected from the group consisting of an oxygen atom and a halogen atom. Represents a hydrocarbon group having 1 to 20 carbon atoms which may contain an atom, and R ¹ and R ³ are the same hydrocarbon groups as R ¹ and R ³ in the formula (I-1-1), respectively. To express.)
<4> The oligosiloxane represented by the formula (III-1) is an oligosiloxane represented by the following formula (III-1-1), and the oligosiloxane represented by the formula (IV-1) Is the oligosiloxane represented by the following formula (IV-1-1):

(In the formula (III-1-1), R ¹ and R ³ represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. And R ¹ and R ³ are the same hydrocarbon group, and R ¹ and R ³ are different hydrocarbon groups.)

(In the formula (IV-1-1), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R ¹ and R ³ are at least one selected from the group consisting of an oxygen atom and a halogen atom. Represents a hydrocarbon group having 1 to 20 carbon atoms which may contain an atom, and R ¹ and R ³ are the same hydrocarbon groups as R ¹ and R ³ in formula (III-1-1), respectively. To express.)
<5> The Lewis acid is tris (pentafluorophenyl) borane (B (C ₆ F ₅ ) ₃ ), boron trifluoride (BF ₃ ), iron chloride (III) (FeCl ₃ ), aluminum chloride (III) The method for producing a polysiloxane according to any one of <1> to <4>, which is at least one selected from the group consisting of (AlCl ₃ ) and zinc chloride (II) (ZnCl ₂ ). <6> The method for producing a polysiloxane according to any one of <1> to <5>, wherein the produced polysiloxane is a linear polysiloxane in which organic groups are periodically arranged.

According to the present invention, polysiloxane in which side chain organic groups are periodically arranged can be efficiently produced.

It is the schematic diagram showing the functional group exchange reaction etc. which arise in the polycondensation reaction for obtaining polysiloxane. 1 is a ¹ H NMR spectrum of the product obtained in Example 1. 3 is a ¹³ C NMR spectrum of the product obtained in Example 1. 2 is a ²⁹ Si NMR spectrum of the product obtained in Example 1. 2 is a MALDI-TOFMS spectrum of the product obtained in Example 1. 2 is a ¹ H NMR spectrum of the product obtained in Example 2. 3 is a ¹³ C NMR spectrum of the product obtained in Example 2. 2 is a ²⁹ Si NMR spectrum of the product obtained in Example 2. 2 is a MALDI-TOFMS spectrum of the product obtained in Example 2. A ¹ H NMR spectrum of the product obtained in Comparative Example. It is a ¹³ C NMR spectrum of the product obtained in the comparative example. It is a ²⁹ Si NMR spectrum of the product obtained by the comparative example. It is a MALDI-TOFMS spectrum of the product obtained in the comparative example.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Details of the present invention will be described with specific examples. However, the present invention is not limited to the following contents without departing from the gist of the present invention, and can be implemented with appropriate modifications.

<Method for producing polysiloxane>
A method for producing a polysiloxane which is one embodiment of the present invention includes an oligosiloxane represented by the following formula (I-1), an oligosiloxane represented by the following formula (II-1), The oligosiloxane represented by (I-2) and the oligosiloxane represented by the following formula (II-2), or the oligosiloxane represented by the following formula (I-3) and the following formula (II-3) And a reaction step of polycondensation of the oligosiloxane.

(In the formulas (II-1) to (II-3), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R ¹ to R ⁸ are selected from the group consisting of an oxygen atom and a halogen atom. represents a hydrocarbon group having at least one atom of carbon atoms which may contain an ^1-20, respectively the same R 1 ~ ^{R 8} is a ^R 1 ~ ^{R 8} of formula (I-1) ~ (I -3) Represents a hydrocarbon group of
In another embodiment of the present invention, a method for producing a polysiloxane includes an oligosiloxane represented by the following formula (III-1), an oligosiloxane represented by the following formula (IV-1) in the presence of a Lewis acid, An oligosiloxane represented by the formula (III-2) and an oligosiloxane represented by the following formula (IV-2), or an oligosiloxane represented by the following formula (III-3) and the following formula (IV-3): It includes a reaction step of polycondensing the represented oligosiloxane.

(In the formulas (IV-1) to (IV-3), each R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R ¹ to R ⁸ are selected from the group consisting of an oxygen atom and a halogen atom. represents a hydrocarbon group having at least one atom of carbon atoms which may contain an ^1-20, respectively the same R 1 ~ ^{R 8} is a ^R 1 ~ ^{R 8} of formula (III-1) ~ (III -3) Represents a hydrocarbon group of

As described above, polysiloxanes are known to exhibit various properties depending on the side chain organic groups. For example, if two or more types of organic groups are randomly arranged, the target properties decrease. It has also been pointed out.
In particular, in the polycondensation reaction for obtaining polysiloxane, a “cyclization reaction” or a “functional group exchange reaction” may proceed as a side reaction, which is a polycyclic structure in which side chain organic groups are periodically arranged. This makes it difficult to obtain siloxane efficiently.
The “cyclization reaction” occurs, for example, when a disiloxane having two hydrosilyl groups (Si—H) and a silane having two alkoxysilyl groups (Si—OR) are condensed as shown in the following formula: In some cases, polysiloxane cannot be obtained efficiently.

On the other hand, the “functional group exchange reaction” is a reaction in which a hydrosilyl group and an alkoxysilyl group are exchanged as shown in FIG. 1, thereby disturbing the arrangement of organic groups of the resulting polysiloxane. It becomes.
Based on the fact that the “cyclization reaction” is particularly easy to produce a 6-membered siloxane, the present inventors pay attention to the fact that the siloxane cyclization reaction is less likely to occur as the number of silicon atoms increases. By arranging polycondensation of symmetric oligosiloxanes with the same sequence, it is possible to prevent disturbance of the organic group sequence even when a "functional group exchange reaction" occurs. Was found.
Hereinafter, R ¹ to R ⁸ , R, etc. in “oligosiloxane represented by formula (I-1)”, etc., “Lewis acid”, reaction conditions, etc. will be described in detail.

In formulas (I-1) to (I-3), (II-1) to (II-3), (III-1) to (III-3), (IV-1) to (IV-3), R ¹ to R ⁸ represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. “May contain at least one atom selected from the group consisting of” includes a functional group containing an oxygen atom or a halogen atom such as a chloro group (—Cl) or a fluoro group (—F). In addition, it means that a linking group containing an oxygen atom or a halogen atom such as an ether group (—O—) may be contained inside or at the terminal of the carbon skeleton. Further, the “hydrocarbon group” is not limited to a linear saturated hydrocarbon group, and may mean that each may have a carbon-carbon unsaturated bond, a branched structure, or a cyclic structure.
R ^{1 s} , R ^{2 s} ,..., R ⁸ are the same hydrocarbon group, and R ¹ to R ⁸ are the same or different hydrocarbon groups. In addition, oligosiloxanes in which R ¹ , R ³ , R ⁵ , and R ⁷ are all the same hydrocarbon group and R ² , R ⁴ , R ⁶ , and R ⁸ are all the same hydrocarbon group are represented by the formula: It is excluded from “oligosiloxane represented by (I-1)”. This indicates that “oligosiloxanes represented by the formula (I-1)” and the like are symmetrical oligosiloxanes having different organic groups.
Further, ^R 1 ~ ^{R 8} of formula (II-1) ~ (II -3) are each the ^R 1 ~ ^{R 8} identical hydrocarbon radical of the formula (I-1) ~ (I -3), ^R 1 ~ ^{R 8} of formula (IV-1) ~ (IV -3) represents that are respectively the same hydrocarbon group as ^R 1 ~ ^{R 8} of formula (III-1) ~ (III -3) ing. For example, the organic groups of “oligosiloxane represented by formula (I-1)” and “oligosiloxane represented by formula (II-1)” have the same sequence, This means that the arrangement of the organic groups of the “oligosiloxane represented” and the “oligosiloxane represented by the formula (IV-1)” are the same.
The carbon number of the hydrocarbon group of R ¹ to R ⁸ is preferably 12 or less, more preferably 6 or less.
Examples of the functional group contained in the hydrocarbon group of R ¹ to R ⁸ include an ether group (—O—), a fluoro group (—F), a chloro group (—Cl), and the like.
The ^R ¹ ~ R ^8, methyl group (-Me), ethyl (-Et), a vinyl group (-CH ₌ CH 2), n- propyl ^(- n Pr), i- propyl ^(- i Pr ), N-butyl group ( ^-n Bu), t-butyl group ( ^-t Bu), phenyl group (-Ph) and the like.

In the formulas (II) and (IV), R each independently represents a hydrocarbon group having 1 to 6 carbon atoms, and the “hydrocarbon group” has the same meaning as R ¹ to R ⁸ .
The carbon number of the hydrocarbon group of R is preferably 3 or less, more preferably 2 or less.
R includes a methyl group (—Me), an ethyl group (—Et), a vinyl group (—CH═CH ₂ ), an n-propyl group ( ^—n Pr), an i-propyl group ( ^—i Pr), an n— Examples thereof include a butyl group ( ^-n Bu), a t-butyl group ( ^-t Bu), and a phenyl group (-Ph).

The oligosiloxane represented by the formula (I) is preferably an oligosiloxane represented by the following formula (I-1-1).

(In the formula (I-1-1), R ¹ and R ³ represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. And R ¹ and R ³ are the same hydrocarbon group, and R ¹ and R ³ are different hydrocarbon groups.)
Specific examples of the oligosiloxane represented by the formula (I-1) include those represented by the following formula.

The oligosiloxane represented by the formula (II-1) is preferably an oligosiloxane represented by the following formula (II-1-1).

(In the formula (II-1-1), each R independently represents a hydrocarbon group having 1 to 6 carbon atoms, and R ¹ and R ³ are at least one selected from the group consisting of an oxygen atom and a halogen atom. Represents a hydrocarbon group having 1 to 20 carbon atoms which may contain an atom, wherein R ¹ and R ³ are the same hydrocarbon group, and R ¹ and R ³ are different hydrocarbon groups. Represents that.)
Specific examples of the oligosiloxane represented by the formula (II-1) include those represented by the following formula.

The oligosiloxane represented by the formula (III-1) is preferably an oligosiloxane represented by the following formula (III-1-1).

(In the formula (III-1-1), R ¹ and R ³ represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. And R ¹ and R ³ are the same hydrocarbon group, and R ¹ and R ³ are different hydrocarbon groups.)
Specific examples of the oligosiloxane represented by the formula (III-1) include those represented by the following formula.

The oligosiloxane represented by the formula (IV-1-1) is preferably an oligosiloxane represented by the following formula (IV-1-1).

(In the formula (IV-1-1), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R ¹ and R ³ are at least one selected from the group consisting of an oxygen atom and a halogen atom. Represents a hydrocarbon group having 1 to 20 carbon atoms which may contain an atom, wherein R ¹ and R ³ are the same hydrocarbon group, and R ¹ and R ³ are different hydrocarbon groups. Represents that.)
Examples of the oligosiloxane represented by the formula (IV-1) include those represented by the following formula.

The amount of the oligosiloxane represented by the formula (I-1) and the oligosiloxane represented by the formula (II-1) in the reaction step can be appropriately selected according to the target polysiloxane, etc. The amount of the oligosiloxane represented by the formula (II-1) is preferably the same amount ([mol]) as the amount of the oligosiloxane represented by the formula (I-1). Polysiloxane can be more efficiently produced when the same amount of material is used.

The Lewis acid is not particularly limited as long as it is a known compound having Lewis acidity, but tris (pentafluorophenyl) borane (B (C ₆ F ₅ ) ₃ ), boron trifluoride (BF ₃ ), Examples thereof include iron (III) chloride (FeCl ₃ ), aluminum (III) chloride (AlCl ₃ ), and zinc (II) chloride (ZnCl ₂ ).

The amount of Lewis acid used in the reaction step can be appropriately selected depending on the purpose, but the amount of substance ([mol]) relative to the amount of oligosiloxane used represented by formula (I-1) is: Usually it is 0.001 times or more and usually 0.05 times or less. Within the above range, polysiloxane can be produced more efficiently.

The reaction step may or may not use a solvent, but it is preferable not to use a solvent. Further, when a solvent is used, the type of the solvent is not particularly limited and can be appropriately selected according to the purpose. Specifically, hydrocarbon solvents such as hexane, benzene, and toluene, methylene chloride, chloroform And halogen-based solvents such as

The reaction temperature in the reaction step is usually 10 ° C. or higher, preferably 25 ° C. or higher, and is usually 60 ° C. or lower, preferably 30 ° C. or lower. Within the above range, polysiloxane can be produced more efficiently.
The reaction time in the reaction step is usually 30 minutes or longer, preferably 1 hour or longer, usually 2 hours or shorter, preferably 1 hour or shorter.
The reaction step is usually performed under an inert atmosphere such as nitrogen or argon.

The polysiloxane produced by the production method of the present invention can be appropriately selected according to the purpose, and the kind thereof is not particularly limited, but is preferably a linear polysiloxane. If it is a linear polysiloxane, it can be used for a wide range of applications.
The degree of polymerization of the polysiloxane produced by the production method of the present invention is usually n = 2 or more and usually n = 140 or less.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

The inside of the 50 mL Schlenk flask was purged with nitrogen. The flask was charged with 332 mg (1 mmol) of 1,1,3,3-tetramethyl-2,2-diphenyltrisiloxane and 1,3-diethoxy-1,1,3,3-tetramethyl-2,2-diphenyltrisiloxane. 420 mg (1 mmol) was added. To prevent air from entering the flask, 26 mg (0.05 mmol) of tris (pentafluorophenyl) borane was added while flowing nitrogen, and the mixture was stirred at room temperature for 1 hour to be reacted. An exotherm with gas evolution was observed at the beginning of the reaction.
When ¹ H, ¹³ C, ²⁹ Si NMR of the obtained transparent viscous material was measured, a signal that could be assigned to the ABA period was observed. In addition, it was confirmed that a polysiloxane in which the structure of -SiMe ₂ OSiPh ₂ OSiMe ₂ O- was periodically arranged was generated because the increase in mass of the repetitive structure could be observed by MALDI-TOFMS.

The inside of the 30 mL Schlenk flask was purged with nitrogen. The flask was charged with 531 mg (1 mmol) of 1,1,7,7-tetramethyl-3,3,5,5-tetraphenyltetrasiloxane and 1,7-diethoxy-1,1,7,7-tetramethyl-3, Add 618 mg (1 mmol) of 3,5,5-tetraphenyltetrasiloxane and 200 μL of dehydrated toluene, and add 5 mg (0.01 mmol) of tris (pentafluorophenyl) borane while flowing nitrogen so that air does not enter the flask. The reaction was stirred for 1 hour at room temperature. An exotherm with gas evolution was observed at the beginning of the reaction.
When ¹ H, ¹³ C, ²⁹ Si NMR of the obtained transparent viscous material was measured, a signal that could be assigned to the ABA period was observed. In addition, it was confirmed that a polysiloxane in which the structure of —SiMe ₂ OSiPh ₂ OSiPh ₂ OSiMe ₂ O— was periodically arranged was generated because the mass increase of the repetitive structure could be observed by MALDI-TOFMS. .

<Comparative example: Production of polysiloxane>
A 50 ml flask was charged with 10 g of dry toluene and 5.0 × 10 ⁻³ mmol of B (C ₆ F ₅ ) ₃ . The resulting mixture was heated to 50 ° C., and a mixture of 2.68 g (20 mmol) 1,1,3,3-tetramethyldisiloxane and 4.88 g (20 mmol) diphenyldimethoxysilane was added dropwise over 30 minutes. did. After the first few drops, an exotherm with gas evolution was observed. After completion of the addition, the resulting mixture was heated at 50 ° C. for an additional 60 minutes. As a result of measuring ¹ H, ¹³ C, ²⁹ Si NMR of the obtained viscous liquid containing a white solid, a signal that could not be assigned to the periodic structure was observed.

The polysiloxane produced by the production method of the present invention is useful as silicone oil, silicone rubber, etc. used in electronic equipment, electric machines, automobiles, cosmetics and the like.

Claims

In the presence of a Lewis acid, an oligosiloxane represented by the following formula (I-1) and an oligosiloxane represented by the following formula (II-1), an oligosiloxane represented by the following formula (I-2) and the following formula A reaction step of polycondensing the oligosiloxane represented by (II-2) or the oligosiloxane represented by the following formula (I-3) and the oligosiloxane represented by the following formula (II-3): A method for producing a polysiloxane.

(In the formulas (I-1) to (I-3), R 1 to R 8 may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. Represents a hydrocarbon group, R 1 to each other, R 2 to each other, R 8 to each other are the same hydrocarbon group, and R 1 to R 8 each represent the same or different hydrocarbon group Provided that R 1 , R 3 , R 5 , and R 7 are all the same hydrocarbon group, and R 2 , R 4 , R 6 , and R 8 are all the same hydrocarbon group. )

(In the formulas (II-1) to (II-3), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 to R 8 are selected from the group consisting of an oxygen atom and a halogen atom. represents a hydrocarbon group having at least one atom of carbon atoms which may contain an 1-20, respectively the same R 1 ~ R 8 is a R 1 ~ R 8 of formula (I-1) ~ (I -3) Represents a hydrocarbon group of
In the presence of a Lewis acid, an oligosiloxane represented by the following formula (III-1) and an oligosiloxane represented by the following formula (IV-1), an oligosiloxane represented by the following formula (III-2) and the following formula A reaction step of polycondensing the oligosiloxane represented by (IV-2) or the oligosiloxane represented by the following formula (III-3) and the oligosiloxane represented by the following formula (IV-3): A method for producing a polysiloxane.

(In the formulas (III-1) to (III-3), R 1 to R 8 may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. Represents a hydrocarbon group, R 1 to each other, R 2 to each other, R 8 to each other are the same hydrocarbon group, and R 1 to R 8 each represent the same or different hydrocarbon group Provided that R 1 , R 3 , R 5 , and R 7 are all the same hydrocarbon group, and R 2 , R 4 , R 6 , and R 8 are all the same hydrocarbon group. )

(In the formulas (IV-1) to (IV-3), each R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 to R 8 are selected from the group consisting of an oxygen atom and a halogen atom. represents a hydrocarbon group having at least one atom of carbon atoms which may contain an 1-20, respectively the same R 1 ~ R 8 is a R 1 ~ R 8 of formula (III-1) ~ (III -3) Represents a hydrocarbon group of
The oligosiloxane represented by the formula (I-1) is an oligosiloxane represented by the following formula (I-1-1), and the oligosiloxane represented by the formula (II-1) is The method for producing a polysiloxane according to claim 1, which is an oligosiloxane represented by the formula (II-1-1).

(In the formula (I-1-1), R 1 and R 3 represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. And R 1 and R 3 are the same hydrocarbon group, and R 1 and R 3 are different hydrocarbon groups.)

(In the formula (II-1-1), each R independently represents a hydrocarbon group having 1 to 6 carbon atoms, and R 1 and R 3 are at least one selected from the group consisting of an oxygen atom and a halogen atom. Represents a hydrocarbon group having 1 to 20 carbon atoms which may contain an atom, and R 1 and R 3 are the same hydrocarbon groups as R 1 and R 3 in the formula (I-1-1), respectively. To express.)
The oligosiloxane represented by the formula (III-1) is an oligosiloxane represented by the following formula (III-1-1), and the oligosiloxane represented by the formula (IV-1) is The method for producing a polysiloxane according to claim 2, which is an oligosiloxane represented by the formula (IV-1-1).

(In the formula (III-1-1), R 1 and R 3 represent a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. And R 1 and R 3 are the same hydrocarbon group, and R 1 and R 3 are different hydrocarbon groups.)

(In the formula (IV-1-1), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and R 1 and R 3 are at least one selected from the group consisting of an oxygen atom and a halogen atom. Represents a hydrocarbon group having 1 to 20 carbon atoms which may contain an atom, and R 1 and R 3 are the same hydrocarbon groups as R 1 and R 3 in formula (III-1-1), respectively. To express.)
The Lewis acid is tris (pentafluorophenyl) borane (B (C 6 F 5 ) 3 ), boron trifluoride (BF 3 ), iron (III) chloride (FeCl 3 ), aluminum chloride (III) (AlCl 3 ) And zinc chloride (II) (ZnCl 2 ), at least one selected from the group consisting of zinc chloride (II) (ZnCl 2 ).
The method for producing a polysiloxane according to any one of claims 1 to 5, wherein the produced polysiloxane is a linear polysiloxane in which organic groups are periodically arranged.