JP2020125460A - Manufacturing method of stereoregular substituted polyacetylene having substituent on terminal - Google Patents

Abstract

To provide a simple and effective manufacturing method of stereoregular substituted polyacetylene having a substituent on the terminal; and to provide a polymerization initiator system of substituted acetylene used for the method.SOLUTION: There is provided a manufacturing method using a polymerization initiator system of substituted acetylene containing bicyclo[2.2.1]hepta-2,5 diene rhodium (I) chloride dimer (A-1) (component A), 4-propoxy phenylboronic acid (B-1) (component B), diphenylacetylene (C-1) (component C), triphenylphosphine (D-1) (component D) and potassium hydroxide (KOH).SELECTED DRAWING: None

Description

The present invention relates to a simple and effective method for producing a stereoregular substituted polyacetylene having a substituent at the terminal. The present invention also relates to a polymerization initiator system for substituted acetylene used in the above production method.

The substituted polyacetylene derivative is one of typical conjugated polymers, and has a structure in which various side chains are introduced into a rigid main chain, and therefore has a unique property not found in other polymer materials. In fact, much research is being conducted toward the development of materials such as gas separation membranes, organic ELs, liquid crystals, and organic diodes.

The substituted polyacetylene derivative can be obtained by chain polymerization of the corresponding acetylene derivative with a transition metal catalyst. Among transition metal catalysts, a polymerization system using a rhodium complex as a main catalyst has been reported to exhibit high activity for polymerization of monosubstituted acetylene derivatives and to proceed cis-stereoselectively. Patent Documents 1 and 2). It is also known that a cis-stereoregular substituted polyacetylene derivative forms a helical structure due to steric repulsion between side chain substituents (Non-Patent Document 3). Further, since the rhodium complex has a high tolerance to functional groups, it is possible to carry out a polymerization reaction of acetylene derivatives having various polar functional groups (Non-Patent Document 4). Therefore, taking advantage of such characteristics of rhodium complexes, substituted polyacetylene derivatives having a unidirectionally wound helical structure in which various optically active groups are introduced have been synthesized, and chiral stationary phase of an optical resolution column and asymmetric selective synthesis have been synthesized. Applications as various chiral materials including organic catalysts are expected.

In the polymerization reaction of substituted acetylene derivatives, not only stereoregularity but also control of molecular weight are important for controlling physical properties and functions of polymers.So far, living polymerization of monosubstituted acetylene derivatives using rhodium catalyst has been achieved. Some examples have been reported (Non-patent documents 2, 5 to 9). However, in the conventional precise polymerization method of mono-substituted acetylene (stereospecific living polymerization method), (1) preparation of a highly active rhodium catalyst is very complicated, (2) any functional group at the polymer end However, there is a problem that it is not possible to introduce the above (non-patent document 6, patent document 1, patent document 2).

On the other hand, it has been reported that a polar functional group can be directly introduced into the terminal of a polymer of monosubstituted acetylene by using a palladium catalyst (Non-Patent Document 10). However, in a polymerization system using a palladium catalyst, the stereoregularity of the obtained polymer is not controlled and living polymerization has not been achieved.

JP, 2004-91539, A JP, 2008-222796, A

Polym. Bull. 16, 311 (1986) J. Am. Chem. Soc., 116, 12131 (1994) Chem. Rev., 109, 6102 (2009) J. Polym. Sci., Part A: Polym. Chem. 27, 75 (1989) Macromolecules, 29, 5054 (1996) Macromolecules, 31, 7572-7573 (1998) Macromol. Chem. Phys., 201, 2239 (2000) Macromolecules, 37, 4044 (2004) Macromolecules, 33, 6636 (2000) J. Polym. Sci., Part A: Polym. Chem. 48, 5549 (2010)

Against this background, if we could develop a stereospecific living polymerization system in which various desired functional groups could be easily introduced at the ends, block polymers, star polymers, comb-shaped polymers with a precisely controlled structure could be developed. Since it is possible to freely synthesize polymers with special structures such as coalescence, fusion with different materials, and modification of various substrates, semiconductor materials for flexible electronic devices, members for display materials, substance transport films, superhydrophobic coatings. It can also be used for materials and sensors. Therefore, development of a simple and effective method for producing stereoregular substituted polyacetylene having a substituent at the terminal has been earnestly desired.

An object of the present invention is to provide a polymerization initiator system for efficiently synthesizing a stereoregularly substituted polyacetylene having a substituent at the terminal and having a narrow molecular weight distribution by a simple operation, and using it, at the terminal. An object of the present invention is to provide an effective method for producing a stereoregular substituted polyacetylene having a substituent.

The present inventors, as a result of repeated studies under such circumstances,
Component (A): Formula (I) below:

[In the formula,
-X- is the following formula:

Or -CH ₂ - represents a group represented by, and Y represents a halogen atom. ]
A rhodium complex represented by
Component (B): Formula (II) below:

[In the formula,
R ¹ represents an aryl group having one or more substituents, and X ¹ and X ² both represent a hydrogen atom or an alkyl group, or OX ¹ and OX ² are bonded to each other, and May combine with the boron atom to which is bonded to form an optionally substituted cyclic group. ]
A compound represented by
Component (C): Formula (III) below:

[In the formula,
n R ^{2 s} are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted alkylsulfanyl. A group, an optionally substituted acyl group, an optionally substituted acyloxy group, an alkoxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
m R ^{3 s} are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted alkylsulfanyl. A group, an optionally substituted acyl group, an optionally substituted acyloxy group, an alkoxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
n shows the integer of 0-3, and m shows the integer of 0-3. ]
A compound represented by
Component (D): optionally substituted triarylphosphine, and a polymerization initiator system of substituted acetylene characterized by containing a base (hereinafter, also referred to as "polymerization initiator system of the present invention"). ), the stereospecificity and the high living property are exhibited in the precise polymerization of monosubstituted acetylene by a simple operation without preparing a special catalyst, and the substituted polyacetylene having a narrow molecular weight distribution is efficiently used. For the first time, they have found that they can be obtained, and have completed the present invention.

That is, the present invention is as follows.
[1] A polymerization initiator system for substituted acetylene, comprising the following component (A), component (B), component (C) and component (D), and a base.
Component (A): Formula (I) below:

[In the formula,
-X- is the following formula:

Or -CH ₂ - represents a group represented by, and Y represents a halogen atom. ]
A rhodium complex represented by.
Component (B): Formula (II) below:

[In the formula,
R ¹ represents an aryl group having one or more substituents, and X ¹ and X ² both represent a hydrogen atom or an alkyl group, or OX ¹ and OX ² are bonded to each other, and May combine with the boron atom to which is bonded to form an optionally substituted cyclic group. ]
The compound represented by.
Component (C): Formula (III) below:

[In the formula,
n R ^{2 s} are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted alkylsulfanyl. A group, an optionally substituted acyl group, an optionally substituted acyloxy group, an alkoxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
m R ^{3 s} are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted alkylsulfanyl. A group, an optionally substituted acyl group, an optionally substituted acyloxy group, an alkoxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
n shows the integer of 0-3, and m shows the integer of 0-3. ]
The compound represented by.
Component (D): an optionally substituted triarylphosphine.
[2] -X- in the formula (I) of component (A), -CH ₂ - in which the [1] polymerization initiator system substituted acetylene according.
[3] Y in the formula (I) of the component (A) is a chlorine atom,
R ¹ in the formula (II) of the component (B) is a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkynyl group, or an optionally substituted Good alkoxy group, optionally substituted alkylsulfanyl group, optionally substituted acyl group, optionally substituted acyloxy group, alkoxy-carbonyl group, optionally substituted carbamoyl group, tri-substituted silyl group And a phenyl group having one substituent selected from the group consisting of a substituted amino group,
N and m in the formula (III) of the component (C) are both 0 or 1,
Component (D) is triphenylphosphine, tris(4-fluorophenyl)phosphine or tris(4-chlorophenyl)phosphine, and the base is potassium hydroxide,
The polymerization initiator system of the substituted acetylene according to the above [1] or [2].
[4] Y in the formula (I) of the component (A) is a chlorine atom,
R ¹ in the formula (II) of the component (B) is a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkynyl group, or an optionally substituted Good alkoxy group, optionally substituted alkylsulfanyl group, optionally substituted acyl group, optionally substituted acyloxy group, alkoxy-carbonyl group, optionally substituted carbamoyl group, tri-substituted silyl group And a phenyl group having one substituent selected from the group consisting of a substituted amino group,
N and m in the formula (III) of the component (C) are both 0,
The component (D) is triphenylphosphine, and the base is potassium hydroxide,
The polymerization initiator system of the substituted acetylene according to the above [1] or [2].
[5] The following formula (IV):

[In the formula,
R represents an aryl group or a heteroaryl group, each of which may be substituted. ]
Represented by the following formula (V): including a step of polymerizing a substituted acetylene represented by the formula [1] to [4] in the presence of the polymerization initiator system.

[In the formula, R represents the same meaning as described above. ]
And a repeating unit represented by the following formula (VI):

[In formula, R< ¹ >, R< ² >, R< ³ >, n and m show the same meaning as the above, and p shows the integer of 0-2. ]
A method for producing a substituted polyacetylene having a terminal group represented by (hereinafter also referred to as "the polyacetylene of the present invention") (hereinafter also referred to as "the production method of the present invention").
[6] In the production method described in [5] above, the following formula (VII):

[In the formula,
R'represents an optionally substituted aryl group or heteroaryl group. However, R′ represents a group different from R in the above formula (V). ] The following formula (V) including the process of adding the substituted acetylene represented by:

[In the formula, R represents the same meaning as described above. ]
A repeating unit represented by the following formula (VIII):

[In the formula, R'is as defined above. ]
And a repeating unit represented by the following formula (VI):

[In formula, R< ¹ >, R< ² >, R< ³ >, n and m show the same meaning as the above, and p shows the integer of 0-2. ]
A method for producing a substituted polyacetylene having a terminal group represented by:
[7] The production method according to the above [5] or [6], wherein the substituted polyacetylene has a molecular weight distribution (Mw/Mn) of 1.20 or less measured by gel permeation chromatography.

According to the polymerization initiator system of the present invention, precise polymerization (stereospecific living polymerization) of monosubstituted acetylene is possible by a simple operation without preparing a special catalyst. In addition, the polymerization initiator system of the present invention not only exhibits extremely high activity, high cis selectivity, and high living property, but also can easily synthesize a substituted polyacetylene having a substituent at the terminal, and therefore, the conventional method uses polyacetylene. It also has an advantage that a functional functional group that is difficult to introduce at the terminal can be introduced easily and freely. Furthermore, the method for producing a substituted polyacetylene using the polymerization initiator system of the present invention is extremely useful as a raw material synthesizing method for various functional polymer materials because it can be scaled up.

FIG. 1 shows the assignment of each proton of the main chain in the ¹ H NMR spectrum of the polyphenylacetylene obtained in Example 23 in Table 4. FIG. 2 shows the ¹ H NMR spectrum of the substituted polyphenylacetylene obtained in Example 1 and the assignment of protons corresponding to the terminal groups. FIG. 3 shows the size of the polyphenylacetylene obtained by further adding the same amount of phenylacetylene after the phenylacetylene (monomer) was completely consumed (after 1 hour) under the same conditions as in Example 1. The result of exclusion chromatography (SEC) measurement is shown. The broken line in FIG. 3 shows the result of the polymer obtained after 1 hour, and the solid line shows the result of the polymer obtained by adding the same amount of phenylacetylene. FIG. 4 shows the result of size exclusion chromatography (SEC) measurement of the block copolymer of two kinds of substituted phenylacetylenes obtained in Example 19. The broken line in FIG. 4 shows the result of the polymer obtained 1 hour after the addition of phenylacetylene (first monomer), and the solid line shows the addition of the same amount of 4-ethoxycarbonylphenylacetylene (second monomer). The result of the obtained polymer is shown.

Definitions of terms and symbols used in the present specification are explained below.

In the present specification, the “halogen atom” means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the present specification, the term “alkyl (group)” means a linear or branched alkyl group having 1 or more carbon atoms, and when the carbon number range is not particularly limited, it is preferably C _Of these, a C _1-6 alkyl group is more preferred, and a C _1-4 alkyl group is particularly preferred.

In the present specification, the “C _1-20 alkyl (group)” means a linear or branched alkyl group having 1 to 20 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl and isobutyl. , Sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, eicosyl and the like.

In the present specification, the “C _1-6 alkyl (group)” means a linear or branched alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl and isobutyl. , Sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc. Can be mentioned.

In the present specification, the “C _1-4 alkyl (group)” means a linear or branched alkyl group having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl and isobutyl. , Sec-butyl, tert-butyl and the like. In the present specification, the “C _1-6 alkyl group” means a linear or branched monovalent saturated hydrocarbon group having 1 to 6 carbon atoms. Examples of the “C _1-6 alkyl group” include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 4-methylpentyl, hexyl and the like. To be

In the present specification, the term “cycloalkyl (group)” means a cyclic alkyl group, and is preferably a C _3-8 cycloalkyl group, unless the carbon number range is particularly limited.

In the present specification, the “C _3-8 cycloalkyl (group)” means a cyclic alkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Is mentioned. Especially, a _C3-6 cycloalkyl group is preferable.

In the present specification, the “alkoxy (group)” means a group in which a linear or branched alkyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but is preferably C _1-20 alkoxy. It is a group, More preferably, it is a _C1-6 alkoxy group.

In the present specification, the “C _1-20 alkoxy (group)” means a straight chain or branched chain alkoxy group having 1 to 20 carbon atoms, and includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, Isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, isohexyloxy, 1,1-dimethylbutoxy, 2,2-dimethylbutoxy, 3,3-dimethylbutoxy, 2 -Ethylbutoxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, eicosyloxy and the like can be mentioned.

In the present specification, the “C _1-6 alkoxy (group)” means a linear or branched alkoxy group having 1 to 6 carbon atoms, and includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, Examples thereof include isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy and hexyloxy. Especially, a _C1-4 alkoxy group is preferable.

In the present specification, the “alkylsulfanyl (group)” means a group in which a linear or branched alkyl group is bonded to a sulfur atom, and the carbon number range is not particularly limited, but preferably C _1-6. It is an alkylsulfanyl group, and more preferably a C _1-4 alkylsulfanyl group.

In the present specification, the “C _1-6 alkylsulfanyl (group)” is a group in which the aforementioned “C _1-6 alkyl” group is bonded to a sulfur atom, that is, a straight chain or branched chain having 1 to 6 carbon atoms. It means an alkylsulfanyl group. Examples of the “C _1-6 alkylsulfanyl (group)” include methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, isobutylsulfanyl, sec-butylsulfanyl, tert-butylsulfanyl, pentylsulfanyl, isopentyl. Examples thereof include sulfanyl, neopentylsulfanyl, 1-ethylpropylsulfanyl, hexylsulfanyl and the like.

In the present specification, the “C _1-6 alkylsulfonyl (group)” is a group in which the “C _1-6 alkyl” group is bonded to a sulfonyl group, that is, a straight chain or branched chain having 1 to 6 carbon atoms. It means an alkylsulfonyl group. Examples of the "C _1-6 alkylsulfonyl (group)" include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentyl. Examples thereof include sulfonyl, neopentylsulfonyl, 1-ethylpropylsulfonyl and hexylsulfonyl.

In the present specification, the “alkoxy-carbonyl (group)” means a group in which the alkoxy group is bonded to an oxygen atom and a carbonyl group, and the carbon number range is not particularly limited, but preferably C _1-20 alkoxy. A carbonyl group, and more preferably a C _1-8 alkoxy-carbonyl group.

In the present specification, the “acyl (group)” means alkanoyl or aroyl, and the carbon number range is not particularly limited, but is preferably a C _1-7 alkanoyl group or C _7-11 aroyl.

In the present specification, the “C _1-7 alkanoyl (group)” is a linear or branched formyl or alkylcarbonyl having 1 to 7 carbon atoms (that is, C _1-6 alkyl-carbonyl). Examples include formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl and the like.

In the present specification, the “C _7-11 aroyl (group)” is arylcarbonyl having 7 to 11 carbon atoms (that is, C _6-10 aryl-carbonyl), and examples thereof include benzoyl.

In the present specification, the “acyloxy (group)” means a group in which the alkanoyl group or aroyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but preferably a C _1-7 alkanoyloxy group. Alternatively, it is a C _7-11 aroyloxy group.

In the present specification, examples of the “C _1-7 alkanoyloxy (group)” include formyloxy, acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyl. Oxy, tert-butylcarbonyloxy (pivaloyloxy), pentylcarbonyloxy, isopentylcarbonyloxy, neopentylcarbonyloxy, hexylcarbonyloxy and the like can be mentioned, with preference given to acetoxy or pivaloyloxy.

In the present specification, examples of the “C _7-11 aroyloxy (group)” include benzoyloxy, 1-naphthoyloxy, 2-naphthoyloxy and the like.

In the present specification, the “aryl (group)” means a monocyclic or polycyclic (fused) hydrocarbon group exhibiting aromaticity, and specifically, for example, phenyl, 1-naphthyl, Examples thereof include C _6-14 aryl groups such as 2-naphthyl, biphenylyl, 2-anthryl and fluorenyl, and among them, C _6-10 aryl groups are preferable.

In the present specification, examples of the “C _6-10 aryl (group)” include phenyl, 1-naphthyl and 2-naphthyl, and phenyl or 1-naphthyl is particularly preferable.

In the present specification, the “aralkyl (group)” means a group in which an aryl group is substituted on an alkyl group, and the carbon number range is not particularly limited, but is preferably C _7-14 aralkyl.

In the present specification, the “C _7-22 aralkyl (group)” means a group in which a “C _1-4 alkyl group” is substituted with a “C _6-18 aryl group”, and examples thereof include benzyl and 1-phenyl. Ethyl, 2-phenylethyl, (naphthyl-1-yl)methyl, (naphthyl-2-yl)methyl, 1-(naphthyl-1-yl)ethyl, 1-(naphthyl-2-yl)ethyl, 2-( Examples include naphthyl-1-yl)ethyl, 2-(naphthyl-2-yl)ethyl, diphenylmethyl, fluorenylmethyl, trityl and the like.

In the present specification, the “arylsulfonyl (group)” means a group in which an aryl group is bonded to a sulfonyl group, and the carbon number range is not particularly limited, but is preferably a C _6-10 arylsulfonyl group.

In the present specification, the “C _6-10 arylsulfonyl (group)” means a group in which a “C _6-10 aryl group” is bonded to a sulfonyl group, and for example, phenylsulfonyl, 1-naphthylsulfonyl, 2- Naphthyl sulfonyl etc. are mentioned.

In the present specification, the “alkylsulfonyloxy (group)” means a group in which an alkylsulfonyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but is preferably a C _1-6 alkylsulfonyloxy group. Is.

In the present specification, the “C _1-6 alkylsulfonyloxy (group)” means a group in which a C _1-6 alkylsulfonyl group is bonded to an oxygen atom, and examples thereof include methylsulfonyloxy, ethylsulfonyloxy and propylsulfonyl. Oxy, isopropyl sulfonyloxy, butyl sulfonyloxy, etc. are mentioned.

In the present specification, the “arylsulfonyloxy (group)” means a group in which an arylsulfonyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but preferably a C _6-10 arylsulfonyloxy group. Is.

In the present specification, the “C _6-10 arylsulfonyloxy (group)” means a group having a C _6-10 arylsulfonyl group bonded to an oxygen atom, and examples thereof include phenylsulfonyloxy, 1-naphthylsulfonyloxy, 2-naphthyl sulfonyloxy etc. are mentioned.

In the present specification, the “heteroaryl (group)” means a monocyclic, bicyclic or polycyclic aromatic group in which at least one ring atom is a hetero atom and the remaining ring atoms are carbon. means. Monocyclic heteroaryl groups include, but are not limited to, cyclic aromatic groups having 5 or 6 ring atoms, at least one ring atom being a heteroatom and the remaining ring atoms being carbon. Examples include cyclic aromatic groups. The nitrogen atom may be optionally quaternized and the sulfur atom may be optionally oxidized. Examples of the heteroaryl group of the present invention include furan, imidazole, isothiazole, isoxazole, oxadiazole, oxazole, 1,2,3-oxadiazole, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrroline, thiazole, 1 , 3,4-thiadiazole, triazole, and tetrazole, but are not limited to these. “Heteroaryl” means one or two heteroaryl rings independently selected from the group consisting of aryl rings, cycloalkyl rings, cycloalkenyl rings, and other monocyclic heteroaryl or heterocycloalkyl rings. Also included, but not limited to, bicyclic or tricyclic rings fused to one ring. Examples of these bicyclic or tricyclic heteroaryl include benzo[b]furan, benzo[b]thiophene, benzimidazole, imidazo[4,5-c]pyridine, quinazoline, thieno[2,3-c]. Pyridine, thieno[3,2-b]pyridine, thieno[2,3-b]pyridine, indolizine, imidazo[1,2-a]pyridine, quinoline, isoquinoline, phthalazine, quinoxaline, naphthyridine, quinolidine, indole, iso Indole, indazole, indoline, benzoxazole, benzopyrazole, benzothiazole, imidazo[1,5-a]pyridine, pyrazolo[1,5-a]pyridine, imidazo[1,2-a]pyrimidine, imidazo[1,2] -C]pyrimidine, imidazo[1,5-a]pyrimidine, imidazo[1,5-c]pyrimidine, pyrrolo[2,3-b]pyridine, pyrrolo[2,3-c]pyridine, pyrrolo[3,2 -C] pyridine, pyrrolo[3,2-b]pyridine, pyrrolo[2,3-d]pyrimidine, pyrrolo[3,2-d]pyrimidine, pyrrolo[2,3-b]pyrazine, pyrazolo[1,5 -A] pyridine, pyrrolo[1,2-b]pyridazine, pyrrolo[1,2-c]pyrimidine, pyrrolo[1,2-a]pyrimidine, pyrrolo[1,2-a]pyrazine, triazo[1,5 -A] pyridine, pteridine, purine, carbazole, acridine, phenazine, phenothiazene, phenoxazine, 1,2-dihydropyrrolo[3,2,1-hi]indole, pyrido[1,2-a]indole, and 2( Examples include, but are not limited to, those derived from 1H)-pyridinone. Suitable heteroaryl (group) is, for example, one derived from pyridine (pyridyl (group)), one derived from pyrimidine (pyrimidyl (group)), one derived from pyrazole (pyrazolyl (group)). And a 5- or 6-membered heteroaryl (group).

In the present specification, the “substituted amino group” means a group in which at least one of the two hydrogen atoms of the amino group is substituted with a group other than hydrogen atom, and both of the two hydrogen atoms are When substituted with a substituent, the substituents may be the same or different.

In the present specification, the “tri-substituted silyl (group)” means a silyl group substituted with the same or different three substituents (eg, C _1-6 alkyl group, C _6-10 aryl group, etc.). Examples of the group include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group (preferably triC _1-6 alkylsilyl group), tert-butyldiphenylsilyl group. Groups and triphenylsilyl groups are preferred.

In the present specification, the “tri-substituted silyloxy (group)” means a group in which a tri-substituted silyl group is bonded to an oxygen atom, and examples of the group include a trimethylsilyloxy group, a triethylsilyloxy group and a triisopropylsilyloxy group. , A tert-butyldimethylsilyloxy group and other trialkylsilyloxy groups (preferably tri-C _1-6 alkylsilyloxy groups), a tert-butyldiphenylsilyloxy group, a triphenylsilyloxy group and the like are preferable.

In the present specification, as the substituent constituting the “substituted amino group”, for example, a protecting group for an amino group described in Protective Groups in Organic Synthesis, John Wiley and Sons (3rd edition, 1999) is used. obtained, for _{example, C 1-6 alkyl, C 1-6 alkylsulfonyl, C 7-22} aralkyl _{groups, C 6-10} aryl _{group, C 1-7} alkanoyl _{group, C 7-11} aroyl _{group, C 7 - 14} aralkyl - carbonyl _{group, C 1-6} alkoxy - carbonyl _{group, C 7 - 14} aralkyloxy - carbonyl _{group, C 6-10} arylsulfonyl, tri _{C 1-6} alkylsilyl group (e.g., _{tri--C 1-6} alkylsilyl And a protecting group such as trimethylsilyl, tert-butyl(dimethyl)silyl, etc. The above protecting group is further substituted with a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group or a nitro group. Specific examples of the amino-protecting group include methyl (monomethyl or dimethyl), benzyl, trityl, acetyl, trifluoroacetyl, pivaloyl, tert-butoxycarbonyl, benzyloxycarbonyl, trifluoromethanesulfonyl, p-toluene sulfonyl etc. are mentioned.

The "optionally substituted" means that it has 1 to 5 (preferably 1 to 3) substituents at a substitutable position, which is unsubstituted, and each substituent is the same. Or may be different.

Examples of the “optionally substituted” substituent include, for example, (1) halogen atom, (2) hydroxy group, (3) cyano group, (4) nitro group, (5) azido group, and (6) substitution group. Amino group, (7) C _1-6 alkyl group, (8) C _1-6 alkoxy group, (9) C _3-8 cycloalkyl group, (10) C _6-10 aryl group, (11) C _{7- 22} aralkyl group, (12) C _1-7 alkanoyl group, (13) C _7-11 aroyl group, (14) C _1-7 alkanoyloxy group, (15) C _7-11 aroyloxy group, (16) C _{1 -6} alkoxy-carbonyl group, (17) C _1-6 alkyl group, carbamoyl group which may be mono- or di-substituted, (18) C _1-6 alkylsulfonyloxy group, (19) C _6-10 aryl Examples thereof include a sulfonyloxy group, (20) C _1-6 alkylsulfanyl, (21) tri-substituted silyl group and (22) tri-substituted silyloxy group. Among them, halogen atom, C _1-6 alkyl, C _1-6 alkoxy, acetyl, formyl, carbamoyl, azide, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, tert-butyldimethylsilyloxy, phenyl, cyclohexyl. , Dimethylamino, acetylamino, tert-butoxycarbonylamino, benzyloxycarbonylamino, methoxycarbonyl, methylsulfanyl and the like are preferable.

The above-mentioned substituent may be further substituted with one or more hydroxy group, C _1-6 alkyl group, C _1-6 alkoxy group, halogen atom, cyano group, nitro group, phenyl group and the like. Good.

In the present specification, the “triarylphosphine” means a compound in which three identical or different aryl groups are bonded to a phosphorus atom. The “optionally substituted triarylphosphine” is not particularly limited, and examples thereof include triphenylphosphine, tris(methylphenyl)phosphine, tris(fluorophenyl)phosphine, tris(chlorophenyl)phosphine, and the like. Among them, triphenylphosphine, tris(4-fluorophenyl)phosphine or tris(4-chlorophenyl)phosphine is preferable.

In the present specification, in the definition of the above formula (II), “OX ¹ and OX ² are bonded to each other to form a cyclic group which may be substituted together with a boron atom to which they are bonded”. The “cyclic group” is not particularly limited, but for example, the following formula:

And a group represented by the following formula:

The group represented by is preferable. The cyclic group may further have one or more substituents (eg, C _1-6 alkyl group, C _1-6 alkoxy group, etc.) at substitutable positions.

In the present specification, the “repeating unit” means a partial unit structure constituting a polymer compound (polyacetylene of the present invention). A plurality of repeating units are continuously present in the polyacetylene of the present invention. When a plurality of types of repeating units are present in the polyacetylene of the present invention, these plurality of types of repeating units are present in the polyacetylene, each forming a plurality of blocks.

In the present specification, “initiator efficiency (IE)” is an index showing how much of the initiator (initiator system) added to the polymerization reaction is effectively used. The initiator efficiency (IE) can be calculated by the following formula.
Initiator efficiency (IE) (%)={[molecular weight of monomer×(mol number of monomer/mol number of catalyst)+molecular weight of terminal group]/[number average molecular weight of obtained polymer]}×100

In the present specification, the “molecular weight distribution” means a value (Mw/Mn) (hereinafter also referred to as “PDI”) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn), and this The closer the value is to 1, the more uniform the molecular weight of the polymer compound. The molecular weight distributions described in the examples below are estimated by gel permeation chromatography equipped with a refractive index detector and calibrated with polystyrene standards.

(Polymerization initiator system of the present invention)
The polymerization initiator system of the present invention comprises a component (A): the following formula (I):

[In the formula,
-X- is the following formula:

Or -CH ₂ - represents a group represented by, and Y represents a halogen atom. ]
A rhodium complex represented by
Component (B): Formula (II) below:

[In the formula,
R ¹ represents an aryl group having one or more substituents, and X ¹ and X ² both represent a hydrogen atom or an alkyl group, or OX ¹ and OX ² are bonded to each other, and May combine with the boron atom to which is bonded to form an optionally substituted cyclic group. ]
A compound represented by
Component (C): Formula (III) below:

[In the formula,
n R ^{2 s} are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted alkylsulfanyl. A group, an optionally substituted acyl group, an optionally substituted acyloxy group, an alkoxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
m R ^{3 s} are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted alkylsulfanyl. A group, an optionally substituted acyl group, an optionally substituted acyloxy group, an alkoxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
n shows the integer of 0-3, and m shows the integer of 0-3. ]
A compound represented by
Component (D): It is characterized by containing an optionally substituted triarylphosphine and a base.

As the rhodium complex (rhodium catalyst) according to the component (A), X in the above formula (I) is preferably —CH ₂ — and Y is preferably a chlorine atom (that is, bicyclo[2 1.2.1] hepta-2,5-diene rhodium (I) chloride dimer ([RhCl(nbd)] ₂ )(A-1)).

As another preferable embodiment of the rhodium complex (rhodium catalyst) according to the component (A), X in the above formula (I) is preferably the following formula:

And Y is preferably a chlorine atom (ie, tetrafluorobenzovalerene rhodium(I) chloride dimer ([RhCl(tfb)] ₂ )(A-2)).

As the rhodium complex according to the component (A), a commercially available product may be used as it is, or by a method known per se (for example, see DM Roe, AG Massey, J. Organomet. Chem. 1971, 28, 273-279). What was prepared can be used.

Preferred embodiments of the compound according to the component (B) will be described below.
As the component (B), R ¹ in the formula (II) is preferably a phenyl group having one or more substituents, more preferably a halogen atom, a hydroxy group, a cyano group, a nitro group, Optionally substituted alkyl group, optionally substituted alkynyl group, optionally substituted alkoxy group, optionally substituted alkylsulfanyl group, optionally substituted acyl group, optionally substituted A phenyl group having one substituent selected from the group consisting of an acyloxy group, an alkoxy-carbonyl group, an optionally substituted carbamoyl group, a tri-substituted silyl group and a substituted amino group, and particularly preferably Halogen atom, cyano group, C _1-4 alkyl group _optionally substituted by a halogen atom (eg, methyl, ethyl, isopropyl, trifluoromethyl), optionally substituted C _2-6 alkynyl group (eg, Tri(isopropyl)silylethynyl), a C _1-4 alkoxy group optionally substituted by a halogen atom (eg, methoxy, ethoxy, propoxy, trifluoromethoxy), C _1-6 optionally substituted by a phenyl group. Alkylsulfanyl group (eg, tritylsulfanyl), C _1-7 alkanoyl group optionally substituted by a halogen atom (eg acetyl, trifluoroacetyl), C _1-7 alkanoyloxy optionally substituted by a halogen atom. Group (eg, acetoxy, trifluoroacetoxy), C _1-6 alkoxy-carbonyl group, tri C _1-4 alkylsilyl group, and C _1-6 alkylsulfonyl, C _1-7 alkanoyl group, C _7-11 aroyl Group, an amino group substituted with a group selected from the group consisting of a C _7-14 aralkyl-carbonyl group, a C _1-6 alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and a C _6-10 arylsulfonyl. A phenyl group having one substituent selected from the group consisting of:
X ¹ and X ² are preferably both hydrogen atoms or C _1-4 alkyl groups, or OX ¹ and OX ² are bound to each other and together with the boron atom to which they are bound. The following formula:

More preferably both are hydrogen atoms, or OX ¹ and OX ² are bonded to each other and together with the boron atom to which they are bonded, formula:

To form a cyclic group.

The following compounds are mentioned as a compound which concerns on a suitable component (B).
[Compound II-1]
R ¹ in the above formula (II) is a phenyl group having one or more substituents;
X ¹ and X ² are both a hydrogen atom or a C _1-4 alkyl group, or OX ¹ and OX ² are bonded to each other and together with the boron atom to which they are bonded, formula:

To form a cyclic group represented by
A compound according to component (B).

[Compound II-2]
R ¹ in the formula (II) is a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkynyl group, an optionally substituted alkoxy group, Alkylsulfanyl group which may be substituted, acyl group which may be substituted, acyloxy group which may be substituted, alkoxy-carbonyl group, carbamoyl group which may be substituted, tri-substituted silyl group and substituted amino group A phenyl group having one substituent selected from the group consisting of:
X ¹ and X ² are both hydrogen atoms, or OX ¹ and OX ² are bound to each other and together with the boron atom to which they are bound, the following formula:

To form a cyclic group represented by
A compound according to component (B).

[Compound II-3]
R ¹ in the above formula (II) is substituted with a halogen atom, a cyano group, or a C _1-4 alkyl group _optionally substituted with a halogen atom (eg, methyl, ethyl, isopropyl, trifluoromethyl), C _2-6 alkynyl group (eg, tri(isopropyl)silylethynyl), C _1-4 alkoxy group optionally substituted by a halogen atom (eg, methoxy, ethoxy, propoxy, trifluoromethoxy), phenyl group A C _1-6 alkylsulfanyl group optionally substituted by (eg tritylsulfanyl), a C _1-7 alkanoyl group optionally substituted by a halogen atom (eg acetyl, trifluoroacetyl), substituted by a halogen atom C _1-7 alkanoyloxy groups (eg, acetoxy, trifluoroacetoxy), C _1-6 alkoxy-carbonyl groups, tri-C _1-4 alkylsilyl groups, and C _1-6 alkylsulfonyl, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 aralkyloxy-carbonyl group and C _6-10 arylsulfonyl group A phenyl group having one substituent selected from the group consisting of amino groups substituted with a more selected group;
X ¹ and X ² are both hydrogen atoms, or OX ¹ and OX ² are bound to each other and together with the boron atom to which they are bound, the following formula:

To form a cyclic group represented by
A compound according to component (B).

Specific preferred examples of the compound relating to the component (B) include, for example, the following formulas:

And the like.

As the compound of component (B), a commercially available product can be easily obtained and used as is, or a method known per se (for example, Ishiyama, T. et al., J. Org. Chem. 1995, 60, 7508; Murata, M. et al., J. Org. Chem. 1997, 62, 6458; Ishiyama, T. et al., Angew. Chem., Int. Ed. 2002, 41, 3056, etc.), Alternatively, it can be manufactured according to a method similar thereto.

Preferred embodiments of the compound according to the component (C) will be described below.
As the component (C), n R ^{2 s} in the formula (III) are preferably each independently a halogen atom, a cyano group, or a C _1-4 alkyl group _optionally substituted with a halogen atom. (Eg, methyl, ethyl, isopropyl, trifluoromethyl), C _1-4 alkoxy group optionally substituted by a halogen atom (eg, methoxy, ethoxy, propoxy, trifluoromethoxy), substituted by a halogen atom good _{C 1-7} alkanoyl group (e.g., acetyl, trifluoroacetyl), optionally _{C 1-7} alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, _{trifluoroacetoxy), C 1-8} alkoxy - Carbonyl group, tri C _1-4 alkylsilyl group, or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy- A carbonyl group, an amino group substituted with a group selected from the group consisting of a C _7-14 aralkyloxy-carbonyl group and a C _6-10 arylsulfonyl, more preferably, each independently a halogen atom, a halogen atom. Optionally substituted by C _1-4 alkyl group (eg, methyl, ethyl, isopropyl, trifluoromethyl), C _1-4 alkoxy group (eg, methoxy, ethoxy, propoxy) or C _1-8 alkoxy-carbonyl. A group (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl);
m R ^3's are preferably each independently a halogen atom, a cyano group, a C _1-4 alkyl group _optionally substituted by a halogen atom (eg, methyl, ethyl, isopropyl, trifluoromethyl), C _1-4 alkoxy group optionally substituted with a halogen atom (eg, methoxy, ethoxy, propoxy, trifluoromethoxy), C _1-7 alkanoyl group optionally substituted with a halogen atom (eg, acetyl, trifluoro). Fluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (eg, acetoxy, trifluoroacetoxy), a C _1-8 alkoxy-carbonyl group, a tri-C _1-4 alkylsilyl group, or C _1-6 alkylsulfonyl, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 aralkyloxy-carbonyl group and C _6-10 arylsulfonyl is an amino group substituted with a group selected from the group consisting of, more preferably, each independently a halogen atom, a C _1-4 alkyl group optionally substituted by a halogen atom ( (Eg, methyl, ethyl, isopropyl, trifluoromethyl), C _1-4 alkoxy group (eg, methoxy, ethoxy, propoxy) or C _1-6 alkoxy-carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl) And
n is preferably 0 or 1; and m is preferably 0 or 1.

The following compounds are mentioned as a compound which concerns on a suitable component (C).
[Compound III-1]
N R ^{2 s} in the formula (III) are each independently a halogen atom, a cyano group, or a C _1-4 alkyl group which may be substituted with a halogen atom (eg, methyl, ethyl, isopropyl, tri). Fluoromethyl), a C _1-4 alkoxy group optionally substituted by a halogen atom (eg, methoxy, ethoxy, propoxy, trifluoromethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (eg , Acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (eg, acetoxy, trifluoroacetoxy), a C _1-8 alkoxy-carbonyl group, a tri-C _1-4 alkylsilyl group. Group, or C _1-6 alkylsulfonyl, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 aralkyloxy- group. An amino group substituted with a group selected from the group consisting of a carbonyl group and a C _6-10 arylsulfonyl;
m R ³ are each independently a halogen atom, a cyano group, a C _1-4 alkyl group which may be substituted with a halogen atom (eg, methyl, ethyl, isopropyl, trifluoromethyl), a halogen atom, C _1-4 alkoxy group which may be substituted (eg, methoxy, ethoxy, propoxy, trifluoromethoxy), C _1-7 alkanoyl group which may be substituted by a halogen atom (eg, acetyl, trifluoroacetyl) , A C _1-7 alkanoyloxy group which may be substituted with a halogen atom (eg, acetoxy, trifluoroacetoxy), a C _1-8 alkoxy-carbonyl group, a tri-C _1-4 alkylsilyl group, or C _{1- 6} alkylsulfonyl, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 aralkyloxy-carbonyl group and C _6-10 An amino group substituted with a group selected from the group consisting of arylsulfonyl;
n is 0 or 1; and m is 0 or 1.
A compound according to component (C).

[Compound III-2]
The n R ^{2 s} in the formula (III) are each independently a halogen atom or a C _1-4 alkyl group _optionally substituted by a halogen atom (eg, methyl, ethyl, isopropyl, trifluoromethyl). A C _1-4 alkoxy group (eg, methoxy, ethoxy, propoxy) or a C _1-8 alkoxy-carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl);
m R ^{3 s} are each independently a halogen atom, a C _1-4 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, isopropyl, trifluoromethyl), a C _1-4 alkoxy group. (Eg, methoxy, ethoxy, propoxy) or a C _1-8 alkoxy-carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl);
n is 0 or 1; and m is 0 or 1.
A compound according to component (C).

Specific preferred examples of the compound relating to the component (C) include, for example, the following formulas:

And the like.

As the compound of component (C), a commercially available product can be easily obtained and used as is, or a method known per se (eg, Coleman, GH et al., J. Am, Chem. Soc., 1936, 58, 2310; Sonogashira, K. et al., Tetrahedron Lett. 1975, 4467; Sonogashira, K. In Metal-Catalyzed Cross-Coupling Reactions, Diederich, F. and Stang, PJ, Eds., Wiley-VCH: Weinheim, 1998, Chapter 5, pp 203-229, etc.) or a method analogous thereto.

Examples of the optionally substituted triarylphosphine of the component (D) include triphenylphosphine, tris(methylphenyl)phosphine, tris(fluorophenyl)phosphine, tris(chlorophenyl)phosphine and the like. Among them, triphenylphosphine, tris(4-fluorophenyl)phosphine or tris(4-chlorophenyl)phosphine is particularly preferable.

As the optionally substituted triarylphosphine of the component (D), a commercially available product can be used as it is.

Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, calcium hydroxide, calcium carbonate, barium hydroxide and lithium hydroxide; trimethylamine, Triethylamine, N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine, N,N'-dimethylpiperazine, N,N-dimethylaniline, N,N-diethylaniline, N,N,N',N'- Tetramethyl-1,3-propanediamine, pyridine, α-picoline, β-picoline, γ-picoline, 4-ethylmorpholine, triethylenediamine, 1,
5-diazabicyclo[4,3,0]-5-nonene, 1,3-diazabicyclo[5,4,0]undecene, 1,8-diazabicyclo[5,4,0]-7-undecene, N-ethylpiperidine , Quinoline, isoquinoline, N,N-dimethylpiperazine, N,N-diethylpiperazine, quinaldine, 2-ethylpyridine, 4-ethylpyridine, 3,5-lutidine, 2,6-lutidine, 4-methylmorpholine, 2, Organic bases such as 4,6-collidine and the like can be mentioned, but potassium hydroxide is preferable.

The mixing ratio of each component in the polymerization initiator system of the substituted acetylene was 1 mol of the rhodium complex of the component (A) (the number of rhodium catalysts was converted to a mononuclear complex by doubling the number of mols of the binuclear complex. Component), component (B) is 1.0 to 2.0 mol (preferably 1.2 to 1.8 mol, more preferably 1.4 to 1.6 mol, particularly preferably, 1.5 mol), and the component (C) is 1.0 to 5.0 mol (preferably 2.0 to 4.5 mol, more preferably 2.5 to 4.0 mol, and particularly preferably). Is 3.0 mol), and the component (D) is 1.0 to 5.0 mol (preferably 2.0 to 4.0 mol, more preferably 2.5 to 3.5 mol, And particularly preferably 3.0 mol, and the base is 2.0 to 3.0 mol (preferably 2.2 to 2.8 mol, more preferably 2.4 to 2.6 mol, It is particularly preferably 2.5 mol).

(Method for producing polyacetylene of the present invention)
The method for producing polyacetylene of the present invention is represented by the above formula (V) by polymerizing the substituted acetylene represented by the above formula (IV) in the presence of the above-mentioned polymerization initiator system of the present invention. It is characterized by including a step of obtaining a substituted polyacetylene having a repeating unit and an end group represented by the formula (VI).

The substituted acetylene used in the polymerization reaction has the following formula (IV):

[In the formula,
R represents an aryl group or a heteroaryl group, each of which may be substituted. ]
It is a substituted acetylene represented by.

R in the formula (IV) is preferably a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkoxy group optionally substituted with a halogen atom, an alkoxy-carbonyl group, and a mono- or di-substituted group. Is an aryl group which may be substituted with a substituent selected from the group consisting of an optionally substituted carbamoyl group, and more preferably a C _1-6 alkyl group which may be substituted with a halogen atom (eg, Methyl, trifluoromethyl), a C _1-6 alkoxy group (eg, methoxy), a C _1-6 alkoxy-carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), and a mono- or di-substituted carbamoyl group ( For example, a phenyl group which may be substituted with a substituent selected from the group consisting of desiloxyalanylcarbamoyl).

The addition amount of the polymerization initiator system in the main polymerization step is 1 mol of the polymerization initiator system of the present invention (the number of rhodium catalysts is converted to a mononuclear complex by doubling the number of moles of the binuclear complex. The molar ratio ([monomer]/[Rh]) of the substituted acetylene (monomer) to (.)) is 10 to 1000, preferably 50 to 500.

As the solvent used in the main polymerization step, any solvent can be used without particular limitation as long as it can dissolve the raw materials and is inert to the reaction. Examples thereof include tetrahydrofuran, toluene, dichloromethane, chloroform, N,N-dimethylformamide and the like, and these may be used alone or in combination of two or more. Of these, tetrahydrofuran is preferable.

The temperature at the time of preparing the polymerization initiator system in the main polymerization step is preferably selected from suitable temperature conditions depending on the components (A) to (D) and the type of base used, but is usually -30°C to 50°C. C., preferably -20.degree. C. to 40.degree. C., more preferably -10.degree. C. to 30.degree. The time required for preparing the polymerization initiator system varies depending on the components (A) to (D) used, the type of base, the concentration of the reaction solution, and the like, but in most cases is 10 minutes or less.

Regarding the temperature of the polymerization reaction in the main polymerization step, it is preferable to appropriately select suitable temperature conditions depending on the type of the substituted acetylene (monomer) to be polymerized, but it is usually 0°C to 60°C, preferably 10°C to 50°C. , And more preferably 20°C to 40°C. In addition, the polymerization reaction time from the addition of the substituted acetylene to the completion of the polymerization after the polymerization initiator system is prepared varies depending on the type of the substituted acetylene to be polymerized, the concentration of the reaction solution, etc., but in most cases is within 1 hour. is there.

After completion of the polymerization reaction, an excess amount of acid (eg, acetic acid, hydrochloric acid, etc.) is added to the reaction solution to stop the polymerization, and then the solution is poured into a large amount of poor solvent (eg, methanol, diethyl ether, etc.). By performing precipitation or the like, the following target formula (V):

[In the formula, R represents the same meaning as described above. ]
And a repeating unit represented by the following formula (VI):

[In formula, R< ¹ >, R< ² >, R< ³ >, n and m show the same meaning as the above, and p shows the integer of 0-2. ]
A substituted polyacetylene having a terminal group represented by can be obtained.

The concentration of the substituted acetylene (monomer) in the reaction solution of the polymerization reaction in the main polymerization step can be appropriately optimized depending on the solubility of the substituted acetylene in the reaction solvent and is not particularly limited, but is usually 0.1 M to 1. Within the concentration range of 0M, the polymerization reaction is completed within a short time (within 1 hour).

In the production method of the present invention, the polymerization reaction of the substituted acetylene represented by the formula (IV) is living polymerization and proceeds cis-specifically. Moreover, the production efficiency of the present invention has an extremely high initiator efficiency (IE) of 95% or more.

The substituted polyacetylene obtained by the production method of the present invention has a number average molecular weight (Mn) of 1,000 to 100,000, preferably 5,000 to 50,000, and a molecular weight distribution (Mw/Mn) measured by gel permeation chromatography is: It is 1.20 or less (preferably 1.10 or less).

(Method for producing block copolymer of substituted acetylene according to the present invention)
In the production method of the present invention, after confirming that the substituted acetylene represented by the formula (IV) (first monomer) is consumed, the substituted acetylene represented by the formula (VII) (second monomer). Is added to the reaction solution and mixed to give the following formula (V):

[In the formula, R represents the same meaning as described above. ]
A repeating unit represented by the following formula (VIII):

[In the formula, R'is as defined above. ]
And a repeating unit represented by the following formula (VI):

[In formula, R< ¹ >, R< ² >, R< ³ >, n and m show the same meaning as the above, and p shows the integer of 0-2. ]
And a substituted acetylene (first monomer) represented by the formula (IV) and a substituted acetylene (second monomer) represented by the formula (VII). Can be produced.

The second substituted acetylene (second monomer) used in the copolymerization reaction is represented by the following formula (VII):

[In the formula,
R'represents an optionally substituted aryl group or heteroaryl group. However, R′ represents a group different from R in the above formula (V). ]
It is a substituted acetylene represented by.

R'in the formula (VII) is preferably a halogen atom, an alkyl group optionally substituted by a halogen atom, an alkoxy group optionally substituted by a halogen atom, an alkoxy-carbonyl group, and a mono- or di-group. An aryl group which may be substituted with a substituent selected from the group consisting of an optionally substituted carbamoyl group, and more preferably a C _1-6 alkyl group which may be substituted with a halogen atom (eg, , Methyl, trifluoromethyl), a C _1-6 alkoxy group (eg, methoxy), a C _1-6 alkoxy-carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), and a mono- or di-substituted carbamoyl group. A phenyl group which may be substituted with a substituent selected from the group consisting of (eg, desyloxyalanylcarbamoyl).

Whether or not the substituted acetylene (first monomer) represented by the formula (IV) has been consumed in the polymerization reaction in the production method of the present invention can be easily confirmed by thin layer chromatography or gas chromatography. Is.

By repeating the same operation as above, it is possible to produce a block copolymer composed of plural kinds of substituted acetylene and having a uniform molecular weight.

The features of the manufacturing method of the present invention are as follows.
1. In the present invention, it is not necessary to prepare a special polymerization catalyst, each component contained in the polymerization initiator system of the present invention is stable and easy to handle, and a commercially available product or a method known per se from a commercially available product. Is a compound that can be easily obtained.

2. In the step of preparing the polymerization initiator system of the present invention and the step of polymerizing a substituted acetylene (monomer), the polymerization reaction is efficient and stereospecific (cis-specific) by simply adding and mixing each component and the monomer in order. ), the operation is extremely simple and can be performed with good reproducibility.

3. The polymerization reaction in the production method of the present invention is living polymerization. Therefore, the initiator efficiency of the polymerization initiator system of the present invention is extremely high (99% or more), the molecular weight distribution is narrow, and it is suitable for the production of a wide range of polyacetylene from a polymer having a relatively low degree of polymerization to a polymer having a high degree of polymerization. It can be used and scaled up easily. It is also possible to obtain a block copolymer having a uniform molecular weight by sequentially adding a plurality of types of substituted acetylene.

4. In the polymer obtained by the production method of the present invention, any functional group derived from the arylboronic acid derivative (component (B)) used in the polymerization initiator system of the present invention can be introduced at the polymer end, Thereby, it is possible to fuse with various organic materials and/or inorganic materials by using the functional group as a foothold.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples and test examples, and may be changed without departing from the scope of the present invention. Further, the reagents and raw material compounds used in the present invention are commercially available, unless otherwise specified.

Further, in each step, the treatment after the reaction may be carried out by a commonly used method, and the isolation and purification may be performed by crystallization, recrystallization, distillation, liquid separation, silica gel chromatography, preparative HPLC, etc., if necessary. The conventional method may be appropriately selected and combined.

Reagents and raw material compounds used in the following Examples, phenylacetylene and various boronic acid derivatives (manufactured by Tokyo Chemical Industry Co., Ltd. (TCI)), bicyclo[2.2.1]hepta-2,5-dienrhodium( I) Chloride dimer (manufactured by Sigma-Aldrich or Umicore), diphenylacetylene and potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), triphenylphosphine (manufactured by Nacalai Tesque), tris(4-fluorophenyl)phosphine (sum) Commercially available products were used as they were for Kojunkaku Co., Ltd.), tris(4-chlorophenyl)phosphine (Wako Pure Chemical Industries, Ltd.), and tetrahydrofuran (dehydrated) (Kanto Chemical Co., Inc.).

% Indicates mol/mol% for yield, and indicates% by weight unless otherwise specified. Further, the room temperature refers to a temperature of 15 to 30° C. unless otherwise specified.
^{The 1} H-NMR spectrum was measured using JEOL ECA500 with deuterated chloroform as a solvent. Data for ¹ H-NMR are chemical shift (δ ppm), multiplicity (s=singlet, d=doublet, t=triplet, q=quartet, quint=quintet, m=multiplet, dd=double doublet, dt= Report as double triplet, brs = broad singlet), coupling constant (Hz), integral and assignment. The infrared spectrum was measured using a Fourier transform infrared spectrophotometer IR-460 manufactured by JASCO Corporation. The average molecular weight is determined by gel permeation chromatography (JASCO high performance liquid chromatography pump PU-2080, JASCO UV-visible detector UV-970, JASCO column oven CO-1560, Shodex column KF-805L). Calculated by conversion.

[Example 1]
Bicyclo[2.2.1]hepta-2,5-diene rhodium (I) chloride dimer (A-1) (component (A)), 4-propoxyphenylboronic acid (B-1) (component (B)) , A diphenylacetylene (C-1) (component (C)), a triphenylphosphine (D-1) (component (D)) and potassium hydroxide (KOH) are used. Synthesis of functionalized substituted polyphenylacetylene

In a 10-mL single-necked eggplant flask under a nitrogen atmosphere, bicyclo[2.2.1]hepta-2,5-diene rhodium(I) chloride dimer ([RhCl(nbd)] ₂ )(A-1) (9.2 mg, 0.02 mmol (converted to mononuclear complex 0.04 mmol)), diphenylacetylene (C-1) (21.6 mg, 0.12 mmol), 4-propoxyphenylboronic acid (B-1) (10.8 mg, 0.06 mmol) and tetrahydrofuran ( THF) (0.2 mL) and 50% aqueous potassium hydroxide solution (11 μL) were added, and the mixture was stirred at 0° C. for 5 min. Then, triphenylphosphine (D-1) (31.5 mg, 0.12 mmol) and THF (3.8 mL) were added, and phenylacetylene (IV-1) (204 mg, 2 mmol) was added thereto, and then at 30°C. It was stirred for 1 hour. After the excess amount of acetic acid was added to the reaction solution to terminate the polymerization, the solution was poured into a large amount of methanol to produce a yellow precipitate. The supernatant was removed and the precipitate was dried under reduced pressure to obtain a yellow powdery solid of polyphenylacetylene (204 mg, >90% yield).
The polystyrene equivalent number average molecular weight ( _Mn ) of polyphenylacetylene determined by gel permeation chromatography measurement was 4,600, and the molecular weight distribution ( _Mw / _Mn ) was 1.07. Further, the molecular weight estimated by the end group quantification method by ¹ H NMR was about 5,700. Since the catalyst/monomer molar ratio ([Rh]/[monomer]) under this condition is 1/50, the initiator efficiency (IE) estimated from these molecular weights is 95% or more. It was Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) was performed using a polymer with a molecular weight of about 3000 obtained by increasing the amount of catalyst. Multiple peaks having repeating units were observed. From the peak, a peak was observed that was consistent with the composition formula in which two molecules of diphenylacetylene units were introduced in addition to the 4-propoxyphenyl group at the end (eg, calcd for C ₂₂₁ H ₁₇₀ OAg [M+Ag] ⁺ 2946.2303). , found 2946.2299; corresponding to 23-mer).
IR (KBr, cm ^-1 ): 3053, 3020, 1596, 1489, 1444, 738, 696.
¹ H NMR (500 MHz, CDCl ₃ , 20 °C): δ 6.94 (d, J = 6.9 Hz, 3H), 6.64 (d, J = 6.9 Hz, 2H), 5.84 (s, 1H), 3.65-3.69 ( m, terminal O CH ₂ CH ₂ CH ₃ ), 1.60-1.70 (m, terminal OCH ₂ CH ₂ CH ₃ ), 0.92 (t, J = 7.5 Hz, terminal OCH ₂ CH ₂ CH ₃ ).

[Examples 2 to 10]
Instead of 4-propoxyphenylboronic acid (B-1) as the compound of the component (B), the following formula:

Polymerization reaction of phenylacetylene (IV-1) under the same reaction conditions as in Example 1 except that the arylboronic acid derivative represented by (any of (B-2) to (B-10)) was used. Was carried out (the polymerization initiator system was prepared at room temperature). The yield, number average molecular weight ( _Mn ), molecular weight distribution ( _Mw / _Mn ), and initiator efficiency (IE) of each of the obtained substituted polyacetylenes are shown below in Table 1.

[Examples 11 to 14]
Instead of phenylacetylene (IV-1), the following formula:

The polymerization reaction was carried out under the same reaction conditions as in Example 1 except that the substituted phenylacetylene represented by (any one of (IV-2) to (IV-5)) was used as a monomer (rhodium catalyst. The polymerization reaction was carried out using 4 equivalents of diphenylacetylene (C-1) and 100 equivalents of substituted phenylacetylene with respect to (A-1)). The yield, number average molecular weight ( _Mn ), molecular weight distribution ( _Mw / _Mn ), and initiator efficiency (IE) of each of the obtained substituted polyacetylenes are shown in Table 2 below.

[Example 15]
As the compound relating to the component (A), instead of the bicyclo[2.2.1]hepta-2,5-diene rhodium (I) chloride dimer (A-1), the following formula:

A tetrafluorobenzovalerene rhodium (I) chloride dimer (A-2) represented by the following formula is used instead of 4-propoxyphenylboronic acid (B-1) as the compound relating to the component (B). A polymerization reaction was performed under the same reaction conditions as in Example 1 except that the compound (4-methylphenylboronic acid) represented by B-2) was used (for the rhodium catalyst (A-2), The polymerization reaction was carried out using 100 equivalents of phenylacetylene (IV-1) as a monomer). As a result, the yield of the obtained polyacetylene was >90%, the number average molecular weight (M _n ) was 4,600, the molecular weight distribution (M _w /M _n ) was 1.06, and the initiator efficiency was (IE) was >95%.

[Examples 16 to 17]
As the compound relating to the component (A), instead of the bicyclo[2.2.1]hepta-2,5-diene rhodium (I) chloride dimer (A-1), the following formula:

A tetrafluorobenzovalerene rhodium (I) chloride dimer (A-2) represented by the following formula is used instead of 4-propoxyphenylboronic acid (B-1) as the compound relating to the component (B). A compound represented by B-2) (4-methylphenylboronic acid) is used, and as the compound relating to the component (D), instead of triphenylphosphine (D-1), the following formula:

Polymerization was carried out under the same reaction conditions as in Example 1 except that the substituted triphenylphosphine represented by ((D-2: Example 16) or (D-3: Example 17)) was used. (Polymerization reaction was carried out using 100 equivalents of phenylacetylene (IV-1) as a monomer relative to the rhodium catalyst (A-2)). The yield, number average molecular weight (M _n ), molecular weight distribution (M _w /M _n ), and initiator efficiency (IE) of each of the obtained substituted polyacetylenes are shown in Table 3 below.

[Example 18]
As the compound relating to the component (C), instead of diphenylacetylene (C-1), the following formula:

The polymerization reaction was carried out under the same reaction conditions as in Example 1 except that the substituted diphenylacetylene (C-5) represented by the following formula was used (rhodium catalyst (A-1), phenylacetylene (IV- The polymerization reaction was carried out using 100 equivalents of 1) as a monomer). As a result, the yield of the obtained polyacetylene was >90%, the number average molecular weight (M _n ) was 4,500, the molecular weight distribution (M _w /M _n ) was 1.09, and the initiator efficiency was (IE) was >95%.

[Example 19]
Synthesis of terminally functionalized block copolymers of two substituted phenylacetylenes using the polymerization initiator system of the present invention

In a 10-mL single-necked eggplant flask under a nitrogen atmosphere, bicyclo[2.2.1]hepta-2,5-diene rhodium(I) chloride dimer ([RhCl(nbd)] ₂ )(A-1) (9.2 mg, 0.02 mmol.), diphenylacetylene (C-1) (21.6 mg, 0.12 mmol), 4-propoxyphenylboronic acid (B-1) (10.8 mg, 0.06 mmol) in tetrahydrofuran (THF) (0.2 mL) and 50% water. A potassium oxide aqueous solution (11 μL) was added, and the mixture was stirred at 0° C. for 5 minutes. Then, triphenylphosphine (D-1) (31.5 mg, 0.12 mmol) and THF (3.8 mL) were added, and phenylacetylene (IV-1) (204 mg, 2 mmol) was added thereto, and then at 30°C. It was stirred for 1 hour. Then, 4-ethoxycarbonylphenylacetylene (IV-2) (348 mg, 2 mmol) was added as a second monomer (compound of formula (VII) above), and the mixture was further stirred at 30° C. for 1 hour. After the excess amount of acetic acid was added to the reaction solution to terminate the polymerization, the solution was poured into a large amount of methanol to produce a yellow precipitate. The supernatant was removed and the precipitate was dried under reduced pressure to obtain a yellow-orange powdery solid (524 mg, >90% yield) of the block copolymer. The polystyrene-equivalent number average molecular weight ( _Mn ) of the block copolymer determined by gel permeation chromatography was 12,000, and the molecular weight distribution ( _Mw / _Mn ) was 1.08. In addition, the molecular weight estimated by the end group quantification method by ¹ H NMR was about 14,000.
IR (KBr, cm ^-1 ): 2982, 1718, 1274, 698.
¹ H NMR (500 MHz, CDCl ₃ , 20 °C): δ 7.63 (d, J = 7.4 Hz, 2H), 6.88-7.04 (m, 3H), 6.58-6.71 (m, 4H), 5.77-5.91 (m , 2H), 4.24-4.33 (m, 2H), 3.66 (td, J = 14.9, 7.3 Hz, terminal O CH ₂ CH ₂ CH ₃ ), 1.32 (t, J = 6.9 Hz, 3H), 0.90 (t, J = 7.4 Hz, terminal OCH ₂ CH ₂ CH ₃ ), terminal OCH ₂ CH ₂ CH ₃ signals overlap with the 1.32 ppm signal.

[Examples 20 to 23]
Phenylacetylene under the same reaction conditions as in Example 1 except that the equivalent number (molar ratio) of phenylacetylene (IV-1) to rhodium catalyst (A-1) ([monomer]/[Rh]) was changed. When the polymerization reaction of (IV-1) was carried out, polyphenylacetylene was obtained almost quantitatively. The number average molecular weight ( _Mn ) and molecular weight distribution ( _Mw / _Mn ) of each of the obtained substituted polyacetylenes are shown below in Table 4.

According to Table 4, the initiator efficiency estimated from the number average molecular weight is very high (up to 99% or more), and the degree of polymerization of polyphenylacetylene should correspond to the molar ratio of [monomer]/[Rh]. I understood. Therefore, according to the production method of the present invention, the molecular weight can be controlled by arbitrarily selecting the [monomer]/[Rh] molar ratio.

[Example 24]
Confirmation of stereoregularity (cis specificity)

In the ¹ H NMR spectrum (FIG. 1) of polyphenylacetylene having a number average molecular weight of 50,000 of Example 23 in Table 4, a sharp signal derived from the protons of the main chain was observed at around 5.8 ppm, which indicates that the present polymerization catalyst system It was suggested that the polyphenylacetylene synthesized in 1. had a very high stereoregularity (cis-transoid structure). It has been reported that the cis content of polyphenylacetylene can be calculated by the formula:% cis = [A _a /{(A _a + A _b +A _c )/6}] × 100 (A is the area of each peak) (See CI Simionescu, V. Percec, S. Dumitrescu. J. Polym. Sci., Part A: Polym. Chem. 15, 2497 (1977)), the cis content of the polyacetylene obtained by the production method of the present invention. Was calculated to be approximately 100%.

[Example 25]
Confirmation of introduction of functional group at the end of polyacetylene

From the ¹ H NMR spectrum of the polyphenylacetylene obtained in Example 1, signals a, b and c derived from the propoxy group were observed at around 0.9 ppm, 1.65 ppm and 3.7 ppm, respectively (FIG. 2).
In addition, it was confirmed that the integral ratio of the peaks of the olefin portion of the polymer main chain and the proton derived from the propoxy group was almost the same as the number average molecular weight calculated by gel permeation chromatography (GPC).

[Example 26]
Confirmation of maintaining polymerization activity at the terminal end of the polymer (living polymerization)

Under the same conditions as in Example 1, the result of SEC measurement of polyphenylacetylene obtained by further adding the same amount of phenylacetylene 1 hour after the initiation of polymerization when phenylacetylene (monomer) was completely consumed is shown. It is shown in FIG.
According to FIG. 3, polyphenylacetylene (solid line in FIG. 3) obtained by adding the same amount of phenylacetylene to the polymer obtained 1 hour after the initiation of polymerization (dashed line in FIG. 3). The number average molecular weight was about double and the molecular weight distribution remained as narrow as 1.1 or less. From the above results, it was confirmed that in the present polymerization system, the polymer terminal end maintains the polymerization activity even after the monomer is completely consumed, that is, living polymerization.

Further, as shown in FIG. 4, in the preparation of the block copolymer of the two types of substituted phenylacetylenes shown in Example 19, the same behavior, that is, the polymer terminal end maintains the polymerization activity. Was confirmed.

According to the polymerization initiator system of the present invention, precise polymerization (stereospecific living polymerization) of monosubstituted acetylene is possible by a simple operation without preparing a special catalyst. In addition, the polymerization initiator system of the present invention not only exhibits high activity, high cis selectivity (cis specificity), and high living property, but also can easily synthesize substituted polyacetylene having a substituent at the end, The method also has an advantage that a functional functional group that is difficult to introduce at the polyacetylene terminal can be introduced easily and freely. Furthermore, in the method for producing a substituted polyacetylene using the polymerization initiator system of the present invention, it is possible to obtain a block copolymer by combining a plurality of types of monomers, the molecular weight distribution is narrow, and scale-up is also possible. Therefore, it is extremely useful as a raw material synthesis method for various functional polymer materials.

Claims (7)

A polymerization initiator system for substituted acetylene, comprising the following component (A), component (B), component (C) and component (D), and a base.
Component (A): Formula (I) below:

[In the formula,
-X- is the following formula:

Or -CH ₂ - represents a group represented by, and Y represents a halogen atom. ]
A rhodium complex represented by.
Component (B): Formula (II) below:

[In the formula,
R ¹ represents an aryl group having one or more substituents, and X ¹ and X ² both represent a hydrogen atom or an alkyl group, or OX ¹ and OX ² are bonded to each other, and May combine with the boron atom to which is bonded to form an optionally substituted cyclic group. ]
The compound represented by.
Component (C): Formula (III) below:

[In the formula,
n R ^{2 s} are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted alkylsulfanyl. A group, an optionally substituted acyl group, an optionally substituted acyloxy group, an alkoxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
m R ^{3 s} are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted alkylsulfanyl. A group, an optionally substituted acyl group, an optionally substituted acyloxy group, an alkoxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
n shows the integer of 0-3, and m shows the integer of 0-3. ]
The compound represented by.
Component (D): an optionally substituted triarylphosphine. -X- in formula (I) of component (A), -CH ₂ - is, polymerization initiator system substituted acetylene of claim 1. Y in the formula (I) of the component (A) is a chlorine atom,
R ¹ in the formula (II) of the component (B) is a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkynyl group, or an optionally substituted Good alkoxy group, optionally substituted alkylsulfanyl group, optionally substituted acyl group, optionally substituted acyloxy group, alkoxy-carbonyl group, optionally substituted carbamoyl group, tri-substituted silyl group And a phenyl group having one substituent selected from the group consisting of a substituted amino group,
N and m in the formula (III) of the component (C) are both 0 or 1,
Component (D) is triphenylphosphine, tris(4-fluorophenyl)phosphine or tris(4-chlorophenyl)phosphine, and the base is potassium hydroxide,
3. The substituted acetylene polymerization initiator system according to claim 1 or 2. Y in the formula (I) of the component (A) is a chlorine atom,
R ¹ in the formula (II) of the component (B) is a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkynyl group, or an optionally substituted Good alkoxy group, optionally substituted alkylsulfanyl group, optionally substituted acyl group, optionally substituted acyloxy group, alkoxy-carbonyl group, optionally substituted carbamoyl group, tri-substituted silyl group And a phenyl group having one substituent selected from the group consisting of a substituted amino group,
N and m in the formula (III) of the component (C) are both 0,
The component (D) is triphenylphosphine, and the base is potassium hydroxide,
3. The substituted acetylene polymerization initiator system according to claim 1 or 2. Formula (IV) below:

[In the formula,
R represents an aryl group or a heteroaryl group, each of which may be substituted. ]
A substituted acetylene represented by the formula (V) below, which comprises a step of polymerizing the substituted acetylene in the presence of the polymerization initiator system according to any one of claims 1 to 4.

[In the formula, R represents the same meaning as described above. ]
And a repeating unit represented by the following formula (VI):

[In formula, R< ¹ >, R< ² >, R< ³ >, n and m show the same meaning as the above, and p shows the integer of 0-2. ]
A method for producing a substituted polyacetylene having a terminal group represented by: The manufacturing method according to claim 5, further comprising the following formula (VII):

[In the formula,
R'represents an optionally substituted aryl group or heteroaryl group. However, R′ represents a group different from R in the above formula (V). ] The following formula (V) including the process of adding the substituted acetylene represented by:

[In the formula, R represents the same meaning as described above. ]
A repeating unit represented by the following formula (VIII):

[In the formula, R'is as defined above. ]
And a repeating unit represented by the following formula (VI):

[In formula, R< ¹ >, R< ² >, R< ³ >, n and m show the same meaning as the above, and p shows the integer of 0-2. ]
A method for producing a substituted polyacetylene having a terminal group represented by: The production method according to claim 5 or 6, wherein the substituted polyacetylene has a molecular weight distribution (Mw/Mn) measured by gel permeation chromatography of 1.20 or less.