JP2017179224A - Polysiloxane production method and polysiloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polysiloxane production method and a novel polysiloxane.SOLUTION: The invention provides: [1] a polysiloxane production method using a transition metal catalyst containing at least one selected from the group consisting of Ru, Fe, Pd and Mo to polymerize a hydrosilane compound (A) represented by general formula (II) in an amide-based solvent so as to obtain a polysiloxane represented by general formula (III); and [2] a polysiloxane represented by general formula (III').SELECTED DRAWING: None

Description

  The present invention relates to a method for producing polysiloxane and polysiloxane.

  Polysiloxane is a general term for compounds whose main chain skeleton is composed of oxygen and silicon and has an organic group in the side chain. It has excellent characteristics in terms of thermal stability, chemical stability, and weather resistance, and is widely used as a general-purpose and special material not only in chemistry but also in the machinery and electronics industries. So far, polysiloxanes have been synthesized by hydrolysis-dehydration condensation of chlorosilane or alkoxysilane (Non-patent Document 1).

Silicon in Organic, Organometallic, and Polymer Chemistry, Michael A. Brook, JOHN WILEY & SONS, Inc. 2000

The chlorosilane or alkoxysilane used as a raw material by conventional methods is sensitive to moisture in the air and is troublesome to handle, and it is difficult to obtain a high-purity monomer having a particularly large molecular weight. That is, there are limitations on the available organosilane monomers. In addition, as the side chain organic substituents become bulky, the reactivity decreases and it is difficult to synthesize high molecular weight polymers.
An object of the present invention is to provide a novel polysiloxane production method and a novel polysiloxane.

In this study, we found that the above problems can be solved by polymerizing in the amide solvent with a specific transition metal catalyst using a hydrosilane monomer that is stable in the air.
That is, the present invention relates to the following [1] and [2].
[1] In a amide solvent using a transition metal catalyst containing at least one selected from the group consisting of Ru, Fe, Pd and Mo,
General formula (II):

[Wherein, R ^a and R ^b are each independently an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, and optionally having 6 to 12 carbon atoms. An aromatic hydrocarbon group or a heterocyclic group having 5 to 12 ring atoms which may have a substituent is shown. The hydrosilane compound (A) represented by
General formula (III):

[Wherein, R ^a and R ^b are each independently an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or 6 to 12 carbon atoms which may have a substituent. An aromatic hydrocarbon group or a heterocyclic group having 5 to 12 ring atoms which may have a substituent. ] The manufacturing method of the polysiloxane which synthesize | combines the polysiloxane represented by these.
[2] General formula (III ′):

[Wherein, R ^{a ′} is an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, Or, it represents a heterocyclic group having 5 to 12 ring atoms which may have a substituent, and R ^{b ′} represents an aliphatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. , An aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 12 ring atoms which may have a substituent. ] The polysiloxane represented by this.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of novel polysiloxane and novel polysiloxane can be provided. Since the synthesis of polysiloxane can be performed in an amide solvent, even if a bulky organic substituent is contained in the raw hydrosilane compound (A), the reaction proceeds in a homogeneous system without precipitation in the solvent. Therefore, a relatively high molecular weight polysiloxane can be obtained in one step.

[Production method of polysiloxane]
The method for producing a polysiloxane of the present invention is represented by the general formula (II) in an amide solvent using a transition metal catalyst containing at least one selected from the group consisting of Ru, Fe, Pd and Mo. The hydrosilane compound (A) is polymerized to obtain a polysiloxane represented by the general formula (III). A polysiloxane is obtained by polymerizing the hydrosilane compound (A) in an amide solvent using the transition metal catalyst.
Thus, although the reason for obtaining polysiloxane is not clear, it is considered as follows.
Already, a reaction in which an amide compound is reduced with about 2 to 5 equivalents of a silane compound using a transition metal catalyst is known (for example, M. Beller et. Al, Angewante Chemie (2009) vol. 48, 9507- 9510). In this case, an oxidation reaction of a silane compound having two or more hydrogen atoms on a silicon atom is advanced using a transition metal catalyst in the presence of an excessive amount of an amide compound relative to the silane compound, that is, in an amide solvent. Thus, it is estimated that polysiloxane can be obtained.
The above mechanism is an estimation, and the present invention is not limited to this.

[Transition metal catalyst]
In the method for producing polysiloxane of the present invention, the transition metal catalyst contains at least one selected from the group consisting of Ru, Fe, Pd and Mo, and preferably contains Mo.
Examples of the transition metal catalyst containing Ru include RuCl ₂ (PPh ₃ ) ₃ .
Examples of the transition metal catalyst containing Fe include Fe (acac) ₃ .
Examples of the transition metal catalyst containing Pd include Pd (dba) ₂ and Pd ₂ (dba) ₃ .
Examples of the transition metal catalyst containing Mo include transition metal complexes represented by the general formula (I). The above “acac” means an acetylacetonato ligand, and “dba” means a dibenzylideneacetone ligand.

In addition to the transition metal catalyst, a ligand may be added. Examples of the ligand include phosphine-based ligands and nitrogen-containing ligands.
Examples of the phosphine-based ligand include triphenylphosphine, tricyclohexylphosphine, bis (diphenylphosphino) ethane, bis (diphenylphosphino) butane, and the like.
Examples of nitrogen-containing ligands include 2,2′-bipyridine and 1,10-phenanthroline.
The amount of the ligand used is preferably 1 to 5 equivalents, more preferably 2 to 4 equivalents, and still more preferably 2 to 3 equivalents with respect to the transition metal of the transition metal catalyst.

<Transition metal complex>
The transition metal catalyst used in the present invention is preferably a transition metal complex represented by the following general formula (I).

In the formula, X represents a silyl group represented by the following general formula (I-1), A ¹ represents at least one atom selected from phosphorus, arsenic and nitrogen, and R ¹ may be the same. R 1 represents a hydrocarbon group having 1 to 9 carbon atoms which may be different, R ² represents a hydrocarbon group having 1 to 9 carbon atoms or a divalent hydrocarbon group having 1 to 9 carbon atoms, and R ³ represents a carbon number. 2 to 4 alkanediyl groups are shown, and a is an integer of 1 to 3. However, when R ² is a divalent hydrocarbon group, R ² has a bond with the silicon atom of the silyl group of X.
In addition, the part shown with the arrow in the general formula of this specification means a coordination bond.

In the formula, each R ⁴ may be the same or different, and one or more hydrogen represents a hydrocarbon group having 1 to 9 carbon atoms which may be substituted with a functional group or a halogen atom, and Y is A bonding site with R ² is shown, * represents a bonding site with Mo (molybdenum) atom, n is an integer of 1 to 3, p is 0 or 1, and n + p is 3 or less. However, when R ² is a divalent hydrocarbon group, p is 1, if R ² is not a divalent hydrocarbon group, p is 0.
R ⁴ is, for example, phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, aminophenyl group, 4-dimethylaminophenyl group, fluorophenyl group, perfluorophenyl group, methyl group, hexyl group and octyl group. Among these, a phenyl group is preferable. n is preferably 2.

A ¹ is preferably a phosphorus atom. R ¹ is preferably a phenyl group. R ³ is preferably an alkanediyl group having 2 carbon atoms, particularly preferably a dimethylene group. a is preferably 2 or 3, and more preferably 3. R ² is preferably a phenyl group or a divalent phenylene group, and more preferably a divalent phenylene group. The divalent phenylene group for R ² is preferably a 1,2-phenylene group.

Moreover, it is preferable that the transition metal complex used for this invention is a transition metal complex represented by the following general formula (I-3).

In the formula, A ¹ represents at least one atom selected from phosphorus, arsenic and nitrogen, R ¹ represents a hydrocarbon group having 1 to 9 carbon atoms which may be the same or different, and R ′ ² represents a divalent hydrocarbon group having 1 to 9 carbon atoms, and R ³ represents an alkanediyl group having 2 to 4 carbon atoms.
R ^'2 is preferably a phenylene group, a 1,2-phenylene group is more preferable.

Specific examples of the transition metal complex used in the present invention include the following complexes (Ia) to (Id).

  Among the above complexes (Ia) to (Id), at least one selected from the complex (Ia) and the complex (Ib) is preferable, and the complex (Ia) is more preferable.

Examples of the transition metal complex include a transition metal complex represented by the following general formula (I-4) such as a bis [bis (diphenylphosphino) ethane] molybdenum tetrahydride complex, and a general formula (I-5) below. It is obtained by reacting with a silane compound.

[Wherein A ¹ , R ¹ and R ³ are the same as those in formula (I). ]

[Wherein, R ⁴ and n are the same as those in formula (I-1). ]

The transition metal complex represented by the general formula (I-3) includes a transition metal complex represented by the general formula (I-4) and a secondary class represented by the following general formula (I-6). It is obtained by reacting with a silane compound at 80 to 150 ° C.

[Wherein, R ⁴ is the same as in general formula (I-1). ]
By the above reaction, a dehydrogenative condensation reaction between silicon on the secondary silane compound and R ¹ in the transition metal complex occurs, and a transition metal complex represented by the general formula (I-3) is obtained.
In the production method of the present invention, the above-mentioned transition metal complex raw materials are mixed to generate the transition metal complex represented by the general formula (I) or (I-3), and the raw hydrosilane compound (A) is prepared. Polymerization may be performed.

[Fluorine anion compound]
In the production method of the present invention, polymerization is preferably performed in the presence of a fluorine anion compound from the viewpoint of enhancing the activity of the catalyst. Examples of the fluorine anion compound include alkali metal fluorides such as fluorinated cesium and fluorinated trialkylammonium.
Among these, the fluorine anion compound is preferably fluorinated tetraalkylammonium, more preferably fluorinated tetra-n-butylammonium (TBAF). The compounding amount of the fluorine anion compound is preferably 50 to 2,000 mol, more preferably 70 to 1,500 mol, and still more preferably 80 to 1,200 mol with respect to 100 mol of the transition metal of the transition metal catalyst.

[Hydrosilane Compound (A)]
The hydrosilane compound (A) used in the present invention has the general formula (II):

[Wherein, R ^a and R ^b are each independently an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, and optionally having 6 to 12 carbon atoms. An aromatic hydrocarbon group or a heterocyclic group having 5 to 12 ring atoms which may have a substituent is shown. ] Is represented.

Examples of the substituent for R ^a and R ^b include a halogen atom, an amino group, a carboxy group, an aldehyde group, a cyano group, a nitro group, and a ferrocenyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The number of substituents in R ^a and R ^b is preferably 3 or less, more preferably 1 or less, and still more preferably 0.

The aliphatic hydrocarbon group for R ^a and R ^b may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and may be a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group. It may be a hydrocarbon group or a cycloaliphatic hydrocarbon group.
Carbon number of the aliphatic hydrocarbon group of R ^a and R ^b is preferably 1 to 10, more preferably 1 to 8, and further preferably 1 to 6.
Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, octyl group, cyclohexyl group and the like. Can be mentioned.
The carbon number of the aromatic hydrocarbon group of R ^a and R ^b is preferably 6 to 12, more preferably 6 to 10, and further preferably 6 to 8.
Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, a perfluorophenyl group, an aminophenyl group, a dialkylaminophenyl group, and a ferrocenyl group.
The number of ring-forming atoms of the heterocyclic group is preferably 5 to 12, more preferably 5 to 10, and still more preferably 5 to 8.
Examples of the heterocyclic group include a pyridinyl group, a morpholyl group, a pyrazolyl group, an imidazolyl group, and the like.

Among these, in the production method of the present invention, since the reaction solvent is an organic solvent, the product polysiloxane is easily dissolved in the system. In particular, even a polysiloxane having a hydrocarbon group having a large number of carbon atoms can be easily dissolved in a reaction solvent, so that the molecular weight of the resulting polysiloxane can be increased.
Preferably, at least one of R ^a and R ^b contains a hydrocarbon group having a relatively large number of carbon atoms, specifically, R ^a is an aliphatic group having 1 to 12 carbon atoms that may have a substituent. An aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 12 ring atoms which may have a substituent, R ^b has an optionally substituted aliphatic hydrocarbon group having 6 to 12 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituent. It is preferably an optionally substituted heterocyclic group having 5 to 12 ring atoms.

  Specific examples of the hydrosilane compound (A) include dihydrosilane compounds such as dimethylsilane, diethylsilane, diphenylsilane, methylphenylsilane, dicyclohexylsilane, methylcyclohexylsilane, phenylcyclohexylsilane, and octylmethylsilane.

[Amide solvent]
In the production method of the present invention, an amide solvent is used.
Examples of amide solvents include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetate, N-methylpyrrolidone, tetramethylurea and the like. Among these, N, N-dimethylformamide is preferable.

[Polysiloxane]
The polysiloxane obtained by the production method of the present invention has the general formula (III):

[Wherein, R ^a and R ^b are the same as those in the general formula (II). ] Is represented.

In the production method of the present invention, polysiloxane can be obtained using an amide solvent, so that a polymer can be obtained even if it has a substituent having a relatively large carbon number.
That is, the polysiloxane of the present invention has the general formula (III ′):

[Wherein, R ^{a ′} is an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, Or an optionally substituted heterocyclic group having 5 to 12 ring atoms, R ^{b ′} is an optionally substituted aliphatic hydrocarbon group having 6 to 12 carbon atoms, substituted An aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a group, or a heterocyclic group having 5 to 12 ring atoms which may have a substituent. ] Is represented.

Preferred examples of the substituent for R ^{a ′} , the aliphatic hydrocarbon group, the aromatic hydrocarbon group, and the heterocyclic group are the same as those in the general formula (II).
Preferred examples of the substituent for R ^{b ′} , the aromatic hydrocarbon group and the heterocyclic group are the same as those in formula (II). The carbon number of the aliphatic hydrocarbon group for R ^{b ′} is preferably 6 to 10, more preferably 6 to 8.
Examples of the aliphatic hydrocarbon group for R ^{b ′} include a hexyl group, an octyl group, and a cyclohexyl group.

R ^{b '}
General formula (R ^{b '} 1):

[In the formula, * is a binding site. Or a group represented by the general formula (R ^{b ′} 2):

[Wherein R _fu is independently at least one selected from the group consisting of an amino group, a hydroxy group, a sulfonyl group, a phosphino group, a diphenylmethyl radical group, an alkyl carbonate group, and an aryl carbonate group, when a plurality of R _fu are present. A seed, m1 is an integer from 1 to 3,
R ₁ is independently an aliphatic hydrocarbon having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a heterocyclic group having 5 to 12 ring atoms, when there are a plurality of R ₁ . , M2 is an integer from 0 to 3, and * is a binding site. Or a group represented by the general formula (R ^{b '} 3):

[In the formula, when there are a plurality of R ₁₁ and R ₁₂ , each independently represents an aliphatic hydrocarbon having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or 5 to 5 ring-forming atoms. 12 is a heterocyclic group, m3 is an integer of 0 to 3, m4 is an integer of 0 to 3, and * is a binding site. It is preferable that it is group represented by these.

In the general formula (R ^{b ′} 1), the substitution position of * is preferably the 4-position of the pyridinyl ring.
The amino group of R _fu includes a dihydroamino group (—NH ₂ group), a monoalkylamino group, a dialkylamino group, and the like, and specifically includes a dimethylamino group, a diethylamino group, and the like.
_Examples of the phosphino group of R _fu include diphenylphosphino group and ditoluylphosphino group.
m1 is preferably 1 or 2, more preferably 1.
m2, m3, and m4 are each independently preferably 0 to 2, more preferably 0 to 1, and still more preferably 0.
The carbon number of the aliphatic hydrocarbon group of R ₁ , R ₁₁ and R ₁₂ is preferably 1 to 6, more preferably 1 to 4, and further preferably 1 to 3. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, octyl group, cyclohexyl group and the like. Can be mentioned.
The aromatic hydrocarbon group having 6 to 12 carbon atoms or the heterocyclic group having 5 to 12 ring atoms of R ₁ , R ₁₁ , and R ₁₂ is the same as the preferred examples given for R ^a and R ^b .

The weight average molecular weight (Mw) of the polysiloxane is preferably 500 to 10,000, more preferably 1,000 to 10,000, still more preferably 3,000 to 8,000, and still more preferably 4,000 to 6,500.
In this specification, a weight average molecular weight (Mw) is measured by the method as described in an Example.

[Reaction conditions]
In the production method of the present invention, the blending amount of the raw hydrosilane compound (A) with respect to the amide solvent is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and more preferably 1 to 10% by mass.
In the production method of the present invention, the blending amount of the transition metal catalyst is preferably 0.01 to 20 mol%, more preferably 0.1 to 10 mol%, and 0.1 to 3 mol% with respect to the raw hydrosilane compound (A). Is more preferable.

The production method of the present invention is preferably performed in an inert gas atmosphere in order to maintain the catalytic activity of the transition metal catalyst. Examples of the inert gas include nitrogen, argon, helium, and the like. Among these, argon is preferable because it has little effect on the transition metal catalyst.
The reaction temperature in the production method of the present invention is preferably 50 to 150 ° C., more preferably 60 to 110 ° C., and still more preferably 70 to 100 ° C. in order to prevent reaction activity and catalyst deactivation.

  As described above, by the production method of the present invention, the hydrosilane compound (A) is polymerized to obtain polysiloxane. According to this method, polysiloxane can be obtained using an amide solvent.

  Examples of the present invention will be described below, but the present invention is not limited to them.

[Measurement of weight average molecular weight]
Measurement was performed at room temperature using the following two devices.
(Device 1)
Tosoh GPC8020 system
RI detector: RI-8021
Pump: DP-8020
Solvent: THF
Elution rate: 1000μl / min
Polystyrene conversion (apparatus 2)
Tosoh HPLC CCP & 8020 Series
RI detector: RI-8021
UV detector: UV-8020
Deaerator: SD-8022
Pump: DP-8020
Solvent: DMF (5.21 g of lithium bromide and 11.76 g of phosphoric acid added to 2 L)
Elution rate: 1000μl / min
Polystyrene conversion

[Production example of transition metal complex]
Production Example 1: Complex (Ia)
Molybdenum tetrahydride complex (MoH ₄ (dppe) ₂ , 0.255 mmol) and diphenylsilane (Ph ₂ SiH ₂ , 1.53 mmol) are dissolved in toluene (20 ml) and heated under reflux in an argon atmosphere for 5 hours. The reaction solution is cooled to room temperature and the solvent is removed under reduced pressure. Dissolve the residue in benzene (10 ml), add hexane (25 ml) to it, and let stand at room temperature overnight. The resulting yellow precipitate was filtered off, washed with hexane (5 ml × 3), and then vacuum dried to obtain the transition metal complex of formula (Ia) (complex (Ia)) (0.239 g, 87% yield). It was. (Reference: 1. “5th edition, Experimental Chemistry Course 21” (2004), p. 136. 2. Organometallics, (2005), vol. 24, 3434.)

[Production method of polysiloxane]
Example 1
After adding the complex (Ia) (60 mg, 0.06 mmol) obtained in Production Example 1 and N, N-dimethylformamide (DMF) (10 mL) to a Schlenk flask substituted with an argon atmosphere, phenylmethylsilane was added. _{(PhMeSiH 2, 0.41 mL, 3} mmol), was added fluoride tetra -n- butylammonium (TBAF) (0.6 mL, 0.6 mmol). The mixture was stirred at room temperature, then moved to a pressure-resistant tube replaced with an argon atmosphere, and heated at 90 ° C. for 24 hours. Thereafter, the mixture was cooled to room temperature, and an appropriate amount of water was added to terminate the reaction.
The reaction solution was extracted with methylene chloride in a separatory funnel, and the resulting organic layer was dried over magnesium sulfate, and then the solvent was removed under reduced pressure to obtain polymethylphenylsiloxane (yield 99%). The weight average molecular weight of the obtained polysiloxane was measured and shown in Table 1.

Examples 2-11, Comparative Examples 1-2
Polysiloxane was obtained in the same manner as in Example 1 except that phenylmethylsilane was changed to the compound (A) shown in Table 1, transition metal catalyst, and additive. The obtained polysiloxane yield and the weight average molecular weight are shown in Table 1.

In the table, the meanings of the abbreviations are as follows.
Me: Methyl group
Et: Ethyl group
Ph: Phenyl group
Cy: cyclohexyl group
p-Me ₂ NC ₆ H ₄ : pN, N-dimethylaminophenyl group

  As described above, according to the method shown in the examples, polysiloxane can be obtained by reacting the hydrosilane compound represented by the general formula (II) in an amide solvent using a specific transition metal catalyst. I understand.

Claims (11)

In a amide solvent using a transition metal catalyst containing at least one selected from the group consisting of Ru, Fe, Pd and Mo,
General formula (II):

[Wherein, R ^a and R ^b are each independently an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or 6 to 12 carbon atoms which may have a substituent. An aromatic hydrocarbon group or a heterocyclic group having 5 to 12 ring atoms which may have a substituent. The hydrosilane compound (A) represented by
General formula (III):

[Wherein, R ^a and R ^b are each independently an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or 6 to 12 carbon atoms which may have a substituent. An aromatic hydrocarbon group or a heterocyclic group having 5 to 12 ring atoms which may have a substituent. ] The manufacturing method of polysiloxane which obtains polysiloxane represented by these.   The method for producing a polysiloxane according to claim 1, wherein the transition metal catalyst contains Mo. The transition metal catalyst has the general formula (I):

[Wherein, X represents the general formula (I-1):

(In the formula, each R ⁴ may be the same or different, and one or more hydrogen represents a hydrocarbon group having 1 to 9 carbon atoms which may be substituted with a functional group or a halogen atom; , R ² represents a bonding site, * represents a bonding site with Mo atom, n is an integer of 1 to 3, p is 0 or 1, and n + p is 3 or less, provided that R ² Is a divalent hydrocarbon group, p is 1, and when R ² is not a divalent hydrocarbon group, p is 0.), A ¹ is phosphorus, Represents at least one atom selected from arsenic and nitrogen, R ¹ represents a hydrocarbon group having 1 to 9 carbon atoms which may be the same or different, and R ² represents a carbon atom having 1 to 9 carbon atoms represents a hydrogen group or a divalent hydrocarbon group having 1 to 9 carbon atoms, R ³ represents an alkanediyl group having 2 to 4 carbon atoms, a is is an integer from 1 to 3 However, when R ² is a divalent hydrocarbon group, R ² has a bond with the silicon atom of the silyl group of X. ] The manufacturing method of the polysiloxane of Claim 1 or 2 which is a transition metal complex represented by these.   The method for producing a polysiloxane according to any one of claims 1 to 3, wherein the amide solvent is N, N-dimethylformamide.   The manufacturing method of the polysiloxane in any one of Claims 1-4 superposed | polymerized in presence of a fluorine anion compound. The method for producing a polysiloxane according to any one of claims 1 to 5, wherein the transition metal catalyst is at least one selected from the following complex (Ia) and complex (Ib).
R ^a represents an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituent. An optionally substituted heterocyclic group having 5 to 12 ring atoms, and R ^b having an optionally substituted aliphatic hydrocarbon group having 6 to 12 carbon atoms and a substituent. The aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted, or a heterocyclic group having 5 to 12 ring atoms which may have a substituent, according to any one of claims 1 to 6. A method for producing polysiloxane.   The method for producing a polysiloxane according to any one of claims 1 to 7, wherein the polysiloxane has a weight average molecular weight (Mw) of 500 to 10,000. General formula (III '):

[Wherein, R ^{a ′} is an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, Or an optionally substituted heterocyclic group having 5 to 12 ring atoms, R ^{b ′} is an optionally substituted aliphatic hydrocarbon group having 6 to 12 carbon atoms, substituted An aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a group, or a heterocyclic group having 5 to 12 ring atoms which may have a substituent. ] The polysiloxane represented by this. R ^{b '}
General formula (R ^{b '} 1):

[In the formula, * is a binding site. Or a group represented by the general formula (R ^{b ′} 2):

[Wherein R _fu is independently at least one selected from the group consisting of an amino group, a hydroxy group, a sulfonyl group, a phosphino group, a diphenylmethyl radical group, an alkyl carbonate group, and an aryl carbonate group, when a plurality of R _fu are present. M1 is an integer of 1 to 3, and R ₁ is independently an aliphatic hydrocarbon having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, when there are a plurality of R _{1 s} , Alternatively, it is a heterocyclic group having 5 to 12 ring atoms, m2 is an integer of 0 to 3, and * is a bonding site. Or a group represented by the general formula (R ^{b '} 3):

[In the formula, when there are a plurality of R ₁₁ and R ₁₂ , each independently represents an aliphatic hydrocarbon having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or 5 to 5 ring-forming atoms. 12 is a heterocyclic group, m3 is an integer of 0 to 3, m4 is an integer of 0 to 3, and * is a binding site. The polysiloxane of Claim 9 which is group represented by these.   The polysiloxane according to claim 9 or 10, having a weight average molecular weight (Mw) of 500 to 10,000.