JP2023104691A - Method for production of substituted poly(diphenylacetylene) using molybdenum pentachloride catalyst system - Google Patents

Abstract

To provide a method for producing linear substituted poly(diphenylacetylene), which enables polymerization reaction of diphenylacetylenes with various functional groups under relaxed conditions.SOLUTION: This invention relates to a method for producing linear substituted poly(diphenyl)acetylene having repeating units represented by the formula (II) in the figure, the method comprising the step of polymerizing a compound represented by the formula (I) in the figure in the presence of molybdenum pentachloride and a co-catalyst acting as an arylating agent.SELECTED DRAWING: None

Description

The present invention relates to a new method for producing linear substituted poly(diphenylacetylene)s having various functional groups, which can be polymerized in a wide temperature range from room temperature to high temperature, and which has good yields.

Substituted polyacetylene derivatives are one of the representative conjugated polymers. They have a structure in which various side chains are introduced into a rigid main chain, so they have unique properties not found in other polymer materials. In fact, many studies are being conducted toward the development of materials for gas separation membranes, organic ELs, liquid crystals, organic diodes, and the like. Among them, substituted poly(diphenylacetylene)s are high molecular compounds that are expected to have practical applications because they not only have extremely high thermal stability compared to other substituted polyacetylene derivatives but also exhibit strong luminescence properties. is.

Substituted poly(diphenylacetylene)s can be synthesized by chain polymerization of the corresponding diphenylacetylenes using a transition metal catalyst. It is often more difficult than other general polymerization methods of this kind. So far, as a polymerization method for diphenylacetylenes, a method using a catalyst system combining tantalum pentachloride (TaCl ₅ ) and an organotin reagent, or a catalyst system combining tungsten hexachloride (WCl ₆ ) and an organotin reagent has been used. However, these polymerization methods are limited in the range of applicable monomers, i.e., diphenylacetylenes, and yield poly(diphenylacetylene)s with desired molecular weights and functional groups. It was difficult to obtain it efficiently (Patent Documents 1 and 2, Non-Patent Documents 1 and 3).

By using tungsten oxytetrachloride (WOCl ₄ ) as a catalyst instead of WCl ₆ , the present inventors found poly(diphenylacetylene) with various functional groups such as alkoxy-carbonyl groups, halogen atoms, and alkoxy groups. (Non-Patent Document 4). However, the upper limit of the molecular weight of the poly(diphenylacetylene)s obtained by this method is about 20,000, and it is difficult to obtain functionalized poly(diphenylacetylene)s having a higher molecular weight. It was difficult.

Patent Document 3 describes an example of a polymerization reaction of phenylacetylenes using molybdenum pentachloride (MoCl ₅ ) as a catalyst, but there is no example of polymerization of diphenylacetylenes. Generally, diphenylacetylenes and phenylacetylenes are known to have dramatically different reactivities as monomers in polymerization reactions. It has been confirmed that the polymerization reaction of diphenylacetylenes does not proceed at all in the polymerization method.

JP-A-5-271338 JP-A-6-107737 JP-A-4-212205

Handbook of Metathesis, Grubbs, R. H., Ed. Wiley-VCH: Weinheim, 2003; Vol. 3, pp 375-406 J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 165-180 Polymer Reviews 2017, 57, 175-199 Angew. Chem. Int. Ed. 2020, 59, 14772-14780

Against this background, an effective method for producing linear substituted poly(diphenylacetylene)s, which can be applied to a wide range of monomers having desired functional groups and can be polymerized even at room temperature. development is desired.

An object of the present invention is to provide a linear polymer having various functional groups under mild polymerization reaction conditions and capable of controlling the molecular weight to some extent in a relatively high molecular weight range (about 30,000 to 3,500,000). An object of the present invention is to provide a method for producing substituted poly(diphenylacetylene)s with good yield.

Under such circumstances, the present inventors have made intensive studies and found that, in the presence of molybdenum pentachloride and a cocatalyst functioning as an arylating agent, the formula (I):

[In the formula,
n R ¹ 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, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group, a trisubstituted silyl group, or a substituted amino group,
m R ² 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, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group, a trisubstituted silyl group, or a substituted amino group,
n represents an integer of 0-3, and m represents an integer of 0-3. ]
Formula (II), comprising a step of polymerizing a compound represented by (hereinafter sometimes referred to as "compound (I)"):

[Each symbol in the formula has the same meaning as described above. ]
A method for producing a linear substituted poly(diphenylacetylene) (hereinafter sometimes referred to as "compound (II)") having a repeating unit represented by ), the polymerization reaction proceeds rapidly under mild reaction conditions, and the molecular weight can be controlled to some extent even in a relatively high molecular weight range (about 30,000 to 3,500,000), and the production method It was found for the first time that the substituted poly(diphenylacetylene) obtained by has a linear structure and a functional group derived from the cocatalyst can be introduced as a terminal group, leading to the completion of the present invention.

That is, the present invention is as follows.
[1] In the presence of molybdenum pentachloride and a cocatalyst that functions as an arylating agent, formula (I):

[In the formula,
n R ¹ 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, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group, a trisubstituted silyl group, or a substituted amino group,
m R ² 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, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group, a trisubstituted silyl group, or a substituted amino group,
n represents an integer of 0-3, and m represents an integer of 0-3. ]
comprising the step of polymerizing a compound represented by formula (II):

[Each symbol in the formula has the same meaning as described above. ]
A method for producing a linear substituted poly(diphenylacetylene) having repeating units represented by
[2] A co-catalyst that functions as an arylating agent is optionally substituted tetraaryltin, optionally substituted aryl(tri-n-butyl)tin, and optionally substituted heteroaryl (tri-n -butyl) tin, the production method according to the above [1].
[3] The production method according to the above [1] or [2], wherein the step of polymerizing is performed at room temperature.
[4] Formula (II):

[In the formula,
n R ¹ 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, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group, a trisubstituted silyl group, or a substituted amino group;
m R ² 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, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group, a trisubstituted silyl group, or a substituted amino group;
n represents an integer from 0 to 3; and
m represents an integer of 0 to 3; ]
A linear substituted poly(diphenylacetylene) having a repeating unit represented by and a number average molecular weight of 30,000 or more.
[5] The substitution according to [4] above, wherein one terminal group is an optionally substituted aryl group or an optionally substituted heteroaryl group, and the other terminal group is a hydrogen atom. Poly(diphenylacetylene).

According to the present invention, under mild reaction conditions of about room temperature to about 110° C., the molecular weight is controlled in a relatively high molecular weight range of about 30,000 to about 3,500,000, and various functional groups are rapidly obtained with good yield. , linear substituted poly(diphenylacetylene)s can be produced. Further, according to the production method of the present invention, not only does it have a desired functional group, but also a functional group derived from a cocatalyst (specifically, an aryl group, a heteroaryl group, etc.), and high-molecular-weight substituted poly(diphenylacetylene)s can be obtained by controlling the molecular weight to some extent. be.

A to C in FIG. 1 show compound (II-1) coated on a highly oriented pyrolytic graphite substrate under an atomic force microscope (AFM) (Cypher (registered trademark)) manufactured by Asylum Research Inc. or Hitachi High An image measured using AFM5000II SPA-400 manufactured by Technologies, Inc. and a partially enlarged image are shown.

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

As used herein, "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the present specification, "alkyl (group)" means a linear or branched alkyl group having 1 or more carbon atoms, and when there is no particular limitation on the carbon number range, preferably C It is a _1-20 alkyl group, and more preferably a C _1-6 alkyl group.

As used herein, "C _1-20 alkyl (group)" means a linear or branched alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, 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.

As used herein, "C _1-6 alkyl (group)" means a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl , sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl and the like. mentioned.

As used herein, “cycloalkyl (group)” means a cyclic alkyl group, preferably a C _3-8 cycloalkyl group, unless the carbon number range is particularly limited.

As used herein, "C _3-8 cycloalkyl (group)" means a cyclic alkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. are mentioned. Among them, a C _3-6 cycloalkyl group is preferred.

As used herein, the term "alkoxy (group)" means a group in which a straight-chain or branched-chain alkyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but preferably C _1-20 alkoxy group, more preferably a C _1-8 alkoxy group, still more preferably a C _1-6 alkoxy group.

As used herein, "C _1-20 alkoxy (group)" means a linear or branched alkoxy group having 1 to 20 carbon atoms, such as 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.

As used herein, "C _1-6 alkoxy (group)" means a linear or branched alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy and the like.

As used herein, the term "alkylsulfanyl (group)" means a group in which a straight-chain or branched-chain 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, more preferably a C _1-4 alkylsulfanyl group.

As used herein, the term "C _1-6 alkylsulfanyl (group)" refers to a group in which the above "C _1-6 alkyl" group is bonded to a sulfur atom, i.e., a linear or branched chain having 1 to 6 carbon atoms. means an alkylsulfanyl group. The "C _1-6 alkylsulfanyl (group)" includes, for example, methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, isobutylsulfanyl, sec-butylsulfanyl, tert-butylsulfanyl, pentylsulfanyl, isopentyl sulfanyl, neopentylsulfanyl, 1-ethylpropylsulfanyl, hexylsulfanyl and the like.

As used herein, the term "C _1-6 alkylsulfonyl (group)" refers to a group in which the above "C _1-6 alkyl" group is bonded to a sulfonyl group, i.e., a linear or branched chain having 1 to 6 carbon atoms. means an alkylsulfonyl group. The "C _1-6 alkylsulfonyl (group)" includes, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentyl sulfonyl, neopentylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl and the like.

As used herein, "alkoxy-carbonyl (group)" means a group in which the alkoxy group is bonded to a carbonyl group, and the carbon number range is not particularly limited, but preferably a C _1-20 alkoxy-carbonyl group and more preferably a C _1-8 alkoxy-carbonyl group.

As used herein, "acyl (group)" means alkanoyl or aroyl, and although the carbon number range is not particularly limited, it is preferably a C _1-7 alkanoyl group or a C _7-11 aroyl group.

As used herein, "C _1-7 alkanoyl (group)" is a linear or branched chain formyl or alkylcarbonyl having 1 to 7 carbon atoms (that is, C _1-6 alkyl-carbonyl). , for example, formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl and the like.

As used herein, "C _7-11 aroyl (group)" is an arylcarbonyl having 7 to 11 carbon atoms (ie, C _6-10 aryl-carbonyl), and includes benzoyl and the like.

As used herein, "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 or a C _7-11 aroyloxy group.

In the present specification, "C _1-7 alkanoyloxy (group)" includes, for example, formyloxy, acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyl oxy, tert-butylcarbonyloxy (pivaloyloxy), pentylcarbonyloxy, isopentylcarbonyloxy, neopentylcarbonyloxy, hexylcarbonyloxy and the like, preferably acetoxy or pivaloyloxy.

As used herein, “C _7-11 aroyloxy (group)” includes, for example, benzoyloxy, 1-naphthoyloxy, 2-naphthoyloxy and the like.

As used herein, the term "aryl (group)" means a monocyclic or polycyclic (condensed) hydrocarbon group exhibiting aromaticity, and specifically includes, for example, phenyl, 1-naphthyl, Examples thereof include C _6-14 aryl groups such as 2-naphthyl, biphenylyl, 2-anthryl and fluorenyl, with C _6-10 aryl groups being preferred.

As used herein, “C _6-10 aryl (group)” includes, for example, phenyl, 1-naphthyl and 2-naphthyl, with phenyl and 1-naphthyl being particularly preferred.

As used herein, "aryloxy (group)" means a group in which the above aryl group is bonded to an oxygen atom, preferably a C _6-14 aryloxy group, more preferably a C _6-10 It is an aryloxy group.

As used herein, "aryloxy-carbonyl (group)" means a group in which the above aryloxy group is bonded to a carbonyl group, and the carbon number range is not particularly limited, but preferably C _6-14 aryloxy -carbonyl group, more preferably C _6-10 aryloxy-carbonyl group, particularly preferably phenoxy-carbonyl group.

As used herein, “aralkyl (group)” means a group in which an alkyl group is substituted with an aryl group, and although the carbon number range is not particularly limited, it is preferably C _7-14 aralkyl.

As used herein, "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", such as benzyl, 1-phenyl ethyl, 2-phenylethyl, (naphthyl-1-yl)methyl, (naphthyl-2-yl)methyl, 1-(naphthyl-1-yl)ethyl, 1-(naphthyl-2-yl)ethyl, 2-( naphthyl-1-yl)ethyl, 2-(naphthyl-2-yl)ethyl, diphenylmethyl, fluorenylmethyl, trityl and the like.

As used herein, “arylsulfonyl (group)” means a group in which an aryl group is bonded to a sulfonyl group, and although the carbon number range is not particularly limited, it is preferably a C _6-10 arylsulfonyl group.

As used herein, “C _6-10 arylsulfonyl (group)” means a group in which “C _6-10 aryl group” is bonded to a sulfonyl group, such as phenylsulfonyl, 1-naphthylsulfonyl, 2- and naphthylsulfonyl.

As used herein, "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 preferably a C _1-6 alkylsulfonyloxy group is.

As used herein, "C _1-6 alkylsulfonyloxy (group)" means a group in which a C _1-6 alkylsulfonyl group is bonded to an oxygen atom, such as methylsulfonyloxy, ethylsulfonyloxy, propylsulfonyl oxy, isopropylsulfonyloxy, butylsulfonyloxy and the like.

As used herein, "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.

As used herein, "C _6-10 arylsulfonyloxy (group)" means a group in which a C _6-10 arylsulfonyl group is bonded to an oxygen atom, such as phenylsulfonyloxy, 1-naphthylsulfonyloxy, 2-naphthylsulfonyloxy and the like.

As used herein, the term "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 a hydrogen atom, and both of the two hydrogen atoms are When substituted by substituents, the substituents may be the same or different.

As used herein, "trisubstituted silyl (group)" means a silyl group substituted with three identical or different substituents (e.g., C _1-6 alkyl group, C _6-10 aryl group, etc.) The group includes a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group (preferably a tri-C _1-6 alkylsilyl group, more preferably a tri-C _1-4 alkylsilyl group), tert-butyldiphenylsilyl group, triphenylsilyl group and the like are preferred.

As used herein, the term "trisubstituted silyloxy (group)" means a group in which a trisubstituted silyl group is bonded to an oxygen atom, and the group includes a trimethylsilyloxy group, a triethylsilyloxy group, and a triisopropylsilyloxy group. , a trialkylsilyloxy group such as a tert-butyldimethylsilyloxy group (preferably a tri-C _1-6 alkylsilyloxy group, more preferably a tri-C _1-4 alkylsilyloxy group), tert-butyldiphenylsilyloxy groups, triphenylsilyloxy groups and the like are preferred.

In the present specification, the substituents constituting the "substituted amino group" include, for example, protective groups for amino groups described in Protective Groups in Organic Synthesis, John Wiley and Sons (3rd edition, 1999). For example, C _1-6 alkyl group, C _1-6 alkylsulfonyl group, C _7-22 aralkyl group, 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 group, tri-C _1-6 alkylsilyl group (e.g., tri-C _1-6 alkylsilyl protecting groups such as groups (eg, trimethylsilyl, tert-butyl(dimethyl)silyl)). The protecting groups above may be 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-toluenesulfonyl and the like. mentioned.

"Optionally substituted" means having 1 to 5 (preferably 1 to 3) substituents at unsubstituted or substitutable positions, and each substituent is the same may be different.

Examples of substituents "optionally substituted" include (1) a halogen atom, (2) a hydroxy group, (3) a cyano group, (4) a nitro group, (5) an azide group, and (6) a substituted 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) carbamoyl group optionally mono- or di-substituted with C _1-6 alkyl group, (18) C _1-6 alkylsulfonyloxy group, (19) C _6-10 aryl sulfonyloxy group, (20) C _1-6 alkylsulfanyl, (21) tri-substituted silyl group, (22) tri-substituted silyloxy group, (23) C _6-10 aryloxy-carbonyl group and the like. Among them, halogen atoms, 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 preferred.
Substituents of "optionally substituted alkyl" or "optionally substituted alkoxy" include "(7) C _1-6 alkyl group" and "(11) C _7-22 Substituents other than "aralkyl group" can be mentioned.

Each of the above substituents may be further substituted with one or more of hydroxy group, C _1-6 alkyl group, C _1-6 alkoxy group, halogen atom, cyano group, nitro group, phenyl group, etc. good.

As used herein, the term "co-catalyst that functions as an arylating agent" does not itself have the ability to promote the polymerization reaction, but when used with molybdenum pentachloride, it improves the catalytic action of molybdenum pentachloride. It means a compound that is both a catalyst and has the function of arylating (or heteroarylating) the polymerization initiation terminal.

As used herein, the term "repeating unit" means a partial unit structure that constitutes a polymer compound. A plurality of such repeating units are continuously present in the substituted poly(diphenylacetylene) obtained by the production method of the present invention. When multiple types of repeating units are present in the polyacetylene of the present invention, these multiple types of repeating units are present forming multiple blocks in the substituted poly(diphenylacetylene).

In the present specification, "linear substituted poly(diphenylacetylene)" means a substituted poly(diphenylacetylene) in which the above repeating units are linked together in a one-dimensional chain and bonded.

In the present specification, "molecular weight distribution" means the value ( _Mw / _Mn ) obtained by dividing the weight average molecular weight ( _Mw ) by the number average molecular weight ( _Mn ), and the closer to 1 , meaning that the molecular weight of the polymer compound (ie, the substituted poly(diphenylacetylene)) is consistent. Molecular weight distributions given in the examples below were estimated by gel permeation chromatography with a UV-visible detector and calibrated with polystyrene standards.

As used herein, "somewhat controlled molecular weight" means that there is a substantial correlation between the molar ratio of catalyst to monomer used and the molecular weight (M _n ) of the polymer produced. In the production method of the present invention, the molecular weight (M _n ) of the substituted poly(diphenylacetylene) obtained varies depending on the types of monomers and co-catalysts used in a wide molecular weight range from about 30,000 to about 3,500,000. They can be produced differently by changing the molar ratio of the catalyst and the monomer. Thus, any molecular weight (M _n ) that can be obtained with relatively high accuracy is referred to herein as a "somewhat controlled molecular weight."

(Manufacturing method of the present invention)
The production method of the present invention is
In the presence of molybdenum pentachloride and a promoter functioning as an arylating agent, formula (I):

n R ¹ 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, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group, a trisubstituted silyl group, or a substituted amino group,
m R ² 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, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group, a trisubstituted silyl group, or a substituted amino group,
n represents an integer of 0-3, and m represents an integer of 0-3. ]
It is characterized by including a step of polymerizing a compound represented by (compound (I)).

A commercially available product of molybdenum pentachloride can be used as it is.

The co-catalyst that functions as an arylating agent is not particularly limited as long as it is a compound that has the ability to activate molybdenum pentachloride by arylating it and functions as an arylating agent at the polymerization initiation terminal. organic tin compounds, organic lithium compounds, organic magnesium compounds (Grignard reagents), organic aluminum compounds, organic zinc compounds, organic bismuth compounds, etc., having a group or heteroaryl group. Among them, preferably from the group consisting of optionally substituted tetraaryltin, optionally substituted aryl(tri-n-butyl)tin, and optionally substituted heteroaryl(tri-n-butyl)tin Selected organotin compounds, more preferably tetraphenyltin, phenyl(tri-n-butyl)tin (trade name: tributylphenylstannane), 4-methoxyphenyl(tri-n-butyl)tin, 2,4 ,6-trimethylphenyl(tri-n-butyl)tin, 4-ethoxycarbonylphenyl(tri-n-butyl)tin, and furan-2-yl(tri-n-butyl)tin (trade name: tributyl(2-furyl)tin ) is a promoter selected from the group consisting of As the cocatalyst, a commercially available product may be used as it is, or one prepared by a method known per se (see, for example, J. Am. Chem. Soc., 2010, 132, 12150-12154) may be used. can be done.

As the solvent used in the production method of the present invention, any solvent can be used without particular limitation as long as it can dissolve the raw materials and is inert to the reaction. For example, ethers such as ethyl tert-butyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; hydrogen halides such as dichloromethane and chloroform; N,N-dimethylformamide, N,N-dimethylacetamide and the like. These amides can be used singly or in combination of two or more. Among them, toluene is preferred.

In the production method of the present invention, the blending ratio of molybdenum pentachloride and the co-catalyst that functions as an arylating agent varies depending on the type of the co-catalyst. Per 1 mol of molybdenum, the cocatalyst that functions as an arylating agent is 1.0 to 5.0 mol (preferably 1.0 to 3.0 mol, more preferably 1.0 to 1.5 mol ).

The amount of compound (I) added in the production method of the present invention can be arbitrarily set according to the molecular weight of the desired compound (II) (polymer), but usually the compound ( I) The (monomer) molar ratio ([monomer]/[molybdenum pentachloride]) is 5-100, preferably 20-50.

In the production method of the present invention, suitable reaction conditions can be appropriately selected depending on the type of co-catalyst or solvent that functions as the arylating agent to be used. The reaction (polymerization reaction) is preferably carried out for 0.5 to 24 hours (preferably 1 to 12 hours) within the range of room temperature to the reflux temperature of the solvent used (preferably room temperature to about 110° C.).

The concentration of compound (I) (monomer) in the reaction solution of the polymerization reaction can be appropriately optimized depending on the solubility of compound (I) in the reaction solvent, and is not particularly limited, but is usually 0.1M to 2M. 0M concentration range, preferably 0.5M to 1.2M.

After completion of the polymerization reaction, an excess amount of a poor solvent (eg, methanol) is poured into the reaction solution for precipitation or the like, whereby the target compound (II) can be obtained.

Compound (II) obtained by the production method of the present invention has a number average molecular weight (M _n ) of 30,000 or more and 3,500,000 or less, preferably 30,000 or more and 1,500,000 or less, measured by gel permeation chromatography. The molecular weight distribution (M _w /M _n ) is about 1.5 to 6 (preferably 1.5 to 4.5).

Generally, in the polymerization reaction of diphenylacetylenes, heating is essential, but in the production method of the present invention, the polymerization reaction proceeds rapidly even under mild reaction conditions such as room temperature, It is characterized in that high-molecular-weight substituted poly(diphenylacetylene)s can be obtained in good yield.

In addition, in the production method of the present invention, molybdenum pentachloride and a co-catalyst functioning as an arylating agent are premixed and stirred before adding diphenylacetylenes (monomers), thereby increasing the molecular weight of the product. Substituted poly(diphenylacetylene)s can be obtained.

(Compound (I))
Preferred embodiments of the raw material monomer, that is, the compound (I) are described below.
As the compound (I), n R ^1s in the formula (I) are preferably each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy , hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), C _1-7 alkanoyl groups optionally substituted by halogen atoms (e.g., acetyl, trifluoroacetyl), substituted by halogen atoms optionally C _1-7 alkanoyloxy group (e.g., acetoxy, trifluoroacetoxy), C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), an arylsulfonyloxy group (e.g., benzenesulfonyloxy, 4- _{fluorobenzenesulfonyloxy} , 2- nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl optionally substituted by halogen atoms group (e.g., pentafluorophenoxy-carbonyl), tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C by a group selected from the group consisting of _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 substituted amino group,
More preferably, each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _{1- 6} alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl) or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl);
m R ² are preferably each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl , hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy , trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of groups (eg, benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _{1- 8} alkoxy-carbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl groups optionally substituted by halogen atoms (eg, pentafluorophenoxy-carbonyl), tri-C _{1 -6} alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group , a C _1-6 alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and an amino group substituted by a group selected from the group consisting of a C _6-10 arylsulfonyl group,
More preferably, each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _{1- 6} alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl);
n is preferably an integer from 0 to 2, more preferably 0 or 1; and m is preferably an integer from 0 to 2, more preferably 0 or 1.
In addition, it is preferable that n R ¹ and m R ² are each independently absent or present in the meta-position and/or para-position relative to the phenylethynyl group, absent or It is more preferred to be in the meta or para position relative to the phenylethynyl group.

Suitable compounds (I) include the following compounds.
[Compound IA]
n R ¹ in the above formula (I) are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl , butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and C an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of _1-6 alkyl groups (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy) , C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl groups optionally substituted by halogen atoms (e.g. pentafluorophenoxy-carbonyl) , tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 an amino group substituted by a group selected from the group consisting of an aralkyl-carbonyl group, a C _1-6 alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and a C _6-10 arylsulfonyl group;
m R ² are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy ), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoro acetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl group an arylsulfonyloxy group optionally substituted by a group selected from the group (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy- carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (eg, pentafluorophenoxy-carbonyl), tri-C _1-6 alkyl silyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), 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} an alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and an amino group substituted by a group selected from the group consisting of a C _6-10 arylsulfonyl group;
n is an integer from 0 to 2;
m is an integer of 0 to 2; and n R ¹ and m R ² are each independently absent or present in meta and/or para positions relative to the phenylethynyl group. do,
Compound (I).

[Compound IB]
n R ¹ in the above formula (I) are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxy carbonyl), a C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropyl Cyril);
m R ² are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl) which may be optionally
n is 0 or 1;
m is 0 or 1; and n R ¹ and m R ² are each independently absent or are meta or para to the phenylethynyl group,
Compound (I).

Preferable specific examples of compound (I) include the following formula:

Compounds represented by and the like.

Compound (I) can be easily obtained commercially and used as it is, or by a method known per se (e.g., Molecules 2016, 21, 1487; Chem. Lett. 2016, 45, 1063-1065; Angew. Chem. Int. Ed. 2020, 59, 14772-14780, etc.) or a method equivalent thereto.

(Compound (II))
The compound obtained by the production method of the present invention has the following formula (II):

[Each symbol in the formula has the same meaning as described above. ]
Linear substituted poly(diphenylacetylene) (compound (II)) having a repeating unit represented by

Preferred embodiments of compound (II) are described below.
As the compound (II), n R ^1s in the formula (II) are preferably each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted with a halogen atom (e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy , hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), C _1-7 alkanoyl groups optionally substituted by halogen atoms (e.g., acetyl, trifluoroacetyl), substituted by halogen atoms optionally C _1-7 alkanoyloxy group (e.g., acetoxy, trifluoroacetoxy), C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), an arylsulfonyloxy group (e.g., benzenesulfonyloxy, 4- _{fluorobenzenesulfonyloxy} , 2- nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl optionally substituted by halogen atoms group (e.g., pentafluorophenoxy-carbonyl), tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C by a group selected from the group consisting of _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 substituted amino group,
More preferably, each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _{1- 6} alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl);
m R ² are preferably each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl , hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy , trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of groups (eg, benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _{1- 8} alkoxy-carbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl groups optionally substituted by halogen atoms (eg, pentafluorophenoxy-carbonyl), tri-C _{1 -6} alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group , a C _1-6 alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and an amino group substituted by a group selected from the group consisting of a C _6-10 arylsulfonyl group,
More preferably, each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _{1- 6} alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl);
n is preferably an integer from 0 to 2, more preferably 0 or 1; and m is preferably an integer from 0 to 2, more preferably 0 or 1.
In addition, it is preferred that n R ¹ and m R ² are each independently absent or present in the meta-position and/or para-position relative to the substituted styryl group, absent or It is more preferred to be in the meta or para position relative to the substituted styryl group.

Suitable compounds (II) include the following compounds.
[Compound II-A]
n R ¹ in the above formula (II) are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl , butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and C an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of _1-6 alkyl groups (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy) , C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl groups optionally substituted by halogen atoms (e.g. pentafluorophenoxy-carbonyl) , tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 an amino group substituted by a group selected from the group consisting of an aralkyl-carbonyl group, a C _1-6 alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and a C _6-10 arylsulfonyl group;
m R ² are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy ), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoro acetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl group an arylsulfonyloxy group optionally substituted by a group selected from the group (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy- carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (eg, pentafluorophenoxy-carbonyl), tri-C _1-6 alkyl silyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), 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} an alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and an amino group substituted by a group selected from the group consisting of a C _6-10 arylsulfonyl group;
n is an integer from 0 to 2;
m is an integer of 0 to 2; and n R ¹ 's and m R ² 's are each independently absent or present in meta and/or para positions relative to the substituted styryl group. has a repeating unit,
Compound (II).

[Compound II-B]
n R ¹ in the formula (II) are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxy carbonyl), a C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropyl Cyril);
m R ² are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl) which may be optionally
n is 0 or 1;
m is 0 or 1; and n R ¹ and m R ² are each independently absent or present at the meta-position or para-position relative to the substituted styryl group. has a
Compound (II).

Preferable specific examples of compound (II) include the following formula:

Linear substituted poly(diphenylacetylene) (compound (II)) having a repeating unit represented by

Compound (II) obtained by the production method of the present invention has a number average molecular weight (M _n ) of 30,000 or more and 3,500,000 or less, preferably 30,000 or more and 1,500,000 or less, measured by gel permeation chromatography. The molecular weight distribution (M _w /M _n ) is about 1.5 to 6 (preferably 1.5 to 4.5).

Among compound (II), one terminal group is an optionally substituted aryl group or an optionally substituted heteroaryl group derived from the cocatalyst functioning as an arylating agent, and the other terminal group is A linear substituted poly(diphenylacetylene) whose terminal group is a hydrogen atom and/or whose number average molecular weight (M _n ) is 30,000 or more and 3,500,000 or less, preferably 30,000 or more and 1,500,000 or less ) is a novel compound.

The optionally substituted aryl group or optionally substituted heteroaryl group includes a phenyl group, a 4-methoxyphenyl group, a 2,4,6-trimethylphenyl group, a 4-ethoxycarbonylphenyl group, or a furan group. -2-yl groups are preferred.

More suitable compounds (II) include the following compounds.
[Compound II-C]
n R ¹ in the above formula (II) are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl , butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and C an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of _1-6 alkyl groups (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy) , C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl groups optionally substituted by halogen atoms (e.g. pentafluorophenoxy-carbonyl) , tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 an amino group substituted by a group selected from the group consisting of an aralkyl-carbonyl group, a C _1-6 alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and a C _6-10 arylsulfonyl group;
m R ² are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy ), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoro acetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl group an arylsulfonyloxy group optionally substituted by a group selected from the group (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy- carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (eg, pentafluorophenoxy-carbonyl), tri-C _1-6 alkyl silyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), 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} an alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and an amino group substituted by a group selected from the group consisting of a C _6-10 arylsulfonyl group;
n is an integer from 0 to 2;
m is an integer from 0 to 2;
n R ¹ 's and m R ² 's each independently have a repeating unit that is absent or is meta- and/or para-positioned relative to the substituted styryl group; Compound (II), wherein the group is an optionally substituted aryl group or an optionally substituted heteroaryl group, and the other terminal group is a hydrogen atom.

[Compound II-D]
n R ¹ in the formula (II) are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxy carbonyl), a C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropyl Cyril);
m R ² are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl) which may be optionally
n is 0 or 1;
m is 0 or 1;
n R ¹ 's and m R ² 's each independently have a repeating unit that is absent or is meta- or para-positioned relative to the substituted styryl group; , a phenyl group, a 4-methoxyphenyl group, a 2,4,6-trimethylphenyl group, a 4-ethoxycarbonylphenyl group, or a furan-2-yl group, and the other terminal group is a hydrogen atom. (II).

[Compound II-E]
n R ¹ in the above formula (II) are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl , butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and C an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of _1-6 alkyl groups (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy) , C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl groups optionally substituted by halogen atoms (e.g. pentafluorophenoxy-carbonyl) , tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 an amino group substituted by a group selected from the group consisting of an aralkyl-carbonyl group, a C _1-6 alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and a C _6-10 arylsulfonyl group;
m R ² are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy ), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoro acetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl group an arylsulfonyloxy group optionally substituted by a group selected from the group (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy- carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (eg, pentafluorophenoxy-carbonyl), tri-C _1-6 alkyl silyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), 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} an alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and an amino group substituted by a group selected from the group consisting of a C _6-10 arylsulfonyl group;
n is an integer from 0 to 2;
m is an integer from 0 to 2;
n R ¹ 's and m R ² 's each independently have a repeating unit that is absent or is meta- and/or para-positioned relative to the substituted styryl group; is an optionally substituted aryl group or an optionally substituted heteroaryl group, and the other terminal group is a hydrogen atom; and the number average molecular weight (M _n ) is 30,000 or more and 3,500,000 Compound (II), which is

[Compound II-F]
n R ¹ in the formula (II) are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxy carbonyl), a C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropyl Cyril);
m R ² are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl) which may be optionally
n is 0 or 1;
m is 0 or 1;
n R ¹ 's and m R ² 's each independently have a repeating unit that is absent or is meta- or para-positioned relative to the substituted styryl group;
one terminal group is a phenyl group, 4-methoxyphenyl group, 2,4,6-trimethylphenyl group, 4-ethoxycarbonylphenyl group, or furan-2-yl group, and the other terminal group is hydrogen and a number average molecular weight (M _n ) of 30,000 or more and 1,500,000 or less.

Preferable specific examples of compound (II) include, for example,
having repeating units represented by formulas (II-1) to (II-8);
one terminal group is a phenyl group, 4-methoxyphenyl group, 2,4,6-trimethylphenyl group, 4-ethoxycarbonylphenyl group, or furan-2-yl group, and the other terminal group is hydrogen is an atom;
The number average molecular weight (M _n ) is 30,000 or more and 1,500,000 or less; and the molecular weight distribution (M _w /M _n ) measured by gel permeation chromatography is about 1.5 to 6 (preferably 1.5 to 4.5), a linear substituted poly(diphenylacetylene) (compound (II)).

The production method of the present invention provides a high yield of substituted poly (poly( diphenylacetylene) can be produced. Further, the substituted poly(diphenylacetylene)s obtained by the production method of the present invention have no weight loss observed up to at least around 200° C. in thermogravimetric analysis, and are excellent in thermal stability. It is also extremely useful as a raw material polymer for

Hereinafter, the present invention will be described in more detail based on Examples and Test Examples, but the present invention is not limited by Examples and Test Examples, and can be changed without departing from the scope of the present invention. good too. In addition, reagents and starting compounds used in the present invention are commercially available unless otherwise specified.

Molybdenum pentachloride (manufactured by Sigma-Aldrich), tetraphenyltin (manufactured by Tokyo Chemical Industry Co., Ltd. (TCI)), tributylphenylstannane (manufactured by Sigma-Aldrich), which are reagents and starting compounds used in the following examples ), tributyl(2-furyl)tin (manufactured by Tokyo Chemical Industry Co., Ltd. (TCI)), and toluene (dehydrated) (manufactured by Kanto Kagaku Co., Ltd.) were used as commercially available products.

% indicates mol/mol % for yields, otherwise indicates weight % unless otherwise specified. Further, room temperature indicates a temperature of 15 to 30° C. unless otherwise specified.
¹ H-, ¹³ C- and ¹⁹ F-NMR spectra were measured using JEOL JNM-ECA 500 with deuterated chloroform as a solvent. Data for ¹ H-NMR are given in terms of chemical shift (δ ppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, quint = quintet, m = multiplet, dd = double doublet, dt = Reported as double triplet, br=broad), integral and assignment. The infrared spectrum was measured using a Fourier transform infrared spectrophotometer IR-4700 manufactured by JASCO Corporation. The average molecular weight and molecular weight distribution were determined by gel permeation chromatography (high-performance liquid chromatography pump PU-4180 manufactured by JASCO Corporation, ultraviolet-visible detector MD-4010 manufactured by JASCO Corporation, column oven CO-4060 manufactured by JASCO Corporation, It was calculated in terms of polystyrene using a column KF-805L manufactured by Shodex or a column TSKgel GMHHR-H(S) manufactured by Tosoh Corporation. Using an atomic force microscope (AFM) Cypher (registered trademark) manufactured by Asylum Research, a sample coated on a highly oriented pyrolytic graphite substrate was measured.

[Example 1]
Molybdenum pentachloride (MoCl ₅ ) (27.3 mg, 0.1 mmol) and formula (I-1):

Toluene (2 mL) and tributylphenylstannane (36.7 mg (32.6 μl), 0.1 mmol) were added to a mixture of the compound (compound (I-1); monomer) (925 mg, 2.0 mmol) represented by After that, the pressure tube was sealed and the mixture was stirred at 30°C for 5 hours. The resulting reaction mixture was poured into an excess amount of methanol, and the resulting precipitate dissolved in tetrahydrofuran (20 ml) was poured into an excess amount of methanol/tetrahydrofuran mixed solution (3/1, v/v) to precipitate. Obtained. This precipitate is washed with a methanol/tetrahydrofuran mixed solution (4/1, v/v) and dried under reduced pressure to obtain formula (II-1):

A polymer (compound (II-1)) having a repeating unit represented by (904 mg, yield calculated from the yield of the polymer relative to the charged amount of monomer: 98%) was obtained as a yellow solid. The number average molecular weight (M _n ) and molecular weight distribution (M _w /M _n ) estimated from gel permeation chromatography of the resulting compound (II-1) were M _n of 776,000 and M _w / _Mn was 2.80.
¹ H NMR (500 MHz, CDCl ₃ , 20° C.): δ 7.0-7.3 (br, 4H), 6.4-6.7 (br, 2H), 5.8-6.2 (br, 2H), 4.0-4.4 (br-d, 4H), 1.6-1.9 (br, 4H), 1.1-1.7 (br, 16H), 0.7-1.0 (br, 6H);
¹³ C NMR (126 MHz, CDCl ₃ , 20° C.): δ 165.6, 146.0-147.0 (br), 125.0-131.0 (br), 65.4, 31.9, 29.2, 28.7, 26.0, 22.7, 14.2;
IR (KBr, cm ⁻¹ ): 2929, 1722, 1274, 1105;
Anal. Calculated for ( _C30H38O4 ) _n : C, 77.89; H, 8.28 _, N, 0.00. Found: C, 77.67 _; H, 8.52; N, 0.12.

Compound (II-1) was coated on a highly oriented pyrolytic graphite substrate and measured using an atomic force microscope (AFM) (Cypher (registered trademark)) manufactured by Asylum Research Inc. Image and partial enlargement The image is shown in FIG.
As shown in FIG. 1, the linear compound (II-1) was observed, indicating that in the polymerization reaction of diphenylacetylenes using a molybdenum pentachloride catalyst, the polymerization reaction proceeds via a transcalation mechanism. , it is presumed that a substituted poly(diphenylacetylene) having a linear structure was produced.

[Examples 2 to 5]
The reaction temperature in Example 1 (60°C, 80°C, 110°C) or the mixing order of the monomer and catalyst system (molybdenum pentachloride and the co-catalyst tributylphenylstannane ( ^nBu3SnPh ) prior to adding the _monomer ) The mixture was stirred in toluene for 90 minutes), under the same reaction conditions as in Example 1, the polymerization reaction of compound (I-1) was carried out. Table 1 below shows the yield, number average molecular weight (M _n ) and molecular weight distribution (M _w /M _n ) of compound (II-1) obtained in Examples 1 to 5.

From the results in Table 1, it was confirmed that the higher the polymerization temperature, the lower the number average molecular weight of the resulting polymer. It was also confirmed that a high-molecular-weight polymer was produced by mixing and stirring molybdenum pentachloride and the co-catalyst before adding the monomer.

[Examples 6 to 10]
Under _{the same reaction conditions as in Example 1, except that the cocatalyst in Example 1 was changed from tributylphenylstannane (nBu3SnPh} ⁾ to another organotin compound (Examples 6, 9 and 10 were (Also changed), the polymerization reaction of compound (I-1) was carried out. Table 2 below shows the yield, number average molecular weight (M _n ) and molecular weight distribution (M _w /M _n ) of compound (II-1) obtained in Examples 6 to 10.
In the compounds (II-1) obtained in Examples 6 to 10, an aryl group (4-methoxyphenyl group, 2,4,6- A trimethylphenyl group, or a 4-ethoxycarbonylphenyl group) or a heteroaryl group (2-furyl group) is introduced, and a hydrogen atom is introduced at the terminal end (the other terminal).

[Examples 11 to 17]
As a monomer, instead of compound (I-1), the following formula:

Diphenylacetylene represented by (Compound (I-2) (Example 11), Compound (I-3) (Example 12), Compound (I-4) (Example 13), Compound (I-5) ( Example 14), compound (I-6) (Example 15), compound (I-7) (Example 16), or compound (I-8) (Example 17)), except that A polymerization reaction of diphenylacetylene was carried out under the same reaction conditions as in Example 1. Table 3 shows the monomer used, the structural formula of the repeating unit of the obtained substituted poly(diphenylacetylene), the yield, the number average molecular weight (M _n ) and the molecular weight distribution (M _w /M _n ).

The instrumental analysis data of each polymer (compound (II)) obtained are shown below.

Compound (II-2) (Example 11):
¹ H NMR (500 MHz, CDCl ₃ , 20° C.): δ 5.3-7.5 (br, 9H), 3.3-4.5 (br, 2H), 1.6-1.9 (br, 2H), 1.0-1.5 (br, 8H). , 0.7-1.0 (br, 3H);
¹³ C NMR (126 MHz, CDCl ₃ , 20° C.): δ 166.3, 124.0-150.0 (br) 65.2, 31.8, 29.1, 28.8, 26.0, 22.7, 14.1;
IR (KBr, cm ^-1 ): 2929, 1720, 1271, 1103.
Anal. Calculated for ( _{C22H24O2 ) n} : C, 82.46; H, 7.55; N, 0.00. Found: C, 82.32 _; H, 7.74; N, 0.14.

Compound (II-3) (Example 12):
¹ H NMR (500 MHz, CDCl ₃ , 20° C.): δ 5.3-8.0 (br, 8H), 3.5-4.6 (br, 2H), 1.6-1.9 (br, 2H), 1.1-1.5 (br, 8H) , 0.7-1.0 (br, 3H);
¹³ C NMR (126 MHz, CDCl ₃ , 20° C.): δ 165.8, 120.0-150.0 (m), 65.5, 31.9, 29.1, 28.7, 26.0, 22.7, 14.2;
IR (KBr, cm ^-1 ): 2927, 1721, 1272, 1105.
Anal. Calculated for ( _{C22H23BrO2 ) n :} C, 66.17; H, 5.81; N, 0.00. Found: C, 65.88; H, 5.95; N, 0.11.

Compound (II-4) (Example 13):
¹ H NMR (500 MHz, CDCl ₃ , 20° C.): δ 5.3-8.0 (br, 8H), 3.8-4.7 (br, 2H), 1.5-1.9 (br, 2H), 1.1-1.5 (br, 8H) , 0.7-1.0 (br, 3H);
^13C NMR (126 MHz, _CDCl3 , 20°C): δ 165.5, 120.0-150.0 (m), 65.6, 31.8, 28.9, 29.0, 25.7-26.0 (m), 22.7, 14.1;
¹⁹ F NMR (470 MHz, _CDCl3 , 20°C): δ -64.0- -62.5 (m);
IR (KBr, cm ^-1 ): 2930, 1723, 1274, 1169, 1128.
Anal. Calculated for ( _C23H23F3O2 ) _n : C, 71.12; H, 5.97; N, _0.00 . Found: C _, 70.98 _; H, 6.17; N, 0.00.

Compound (II-5) (Example 14):
¹ H NMR (500 MHz, CDCl ₃ , 20° C.): δ 5.3-7.5 (br, 9H), -0.1-0.3 (br, 9H);
¹³ C NMR (126 MHz, CDCl ₃ , 20° C.): δ 145.0-147.3 (br), 143.0-145.0 (br), 136.0-137.0 (br), 130.0-132.5 (br), 127.1-128.0 (br), 125.8-127.0 (br), 124.5-125.7 (br), -1.1- -0.4 (m);
IR (KBr, cm ^-1 ): 2954, 1248, 1117.
Anal. Calculated for ( _C17H18Si ) _n : C, 81.54; H, 7.25; N, 0.00. Found: C, 81.30; H _, 7.32; N, 0.13.

Compound (II-6) (Example 15):
¹ H NMR (500 MHz, CDCl ₃ , 20° C.): δ 5.1-7.5 (br, 8H), 3.2-3.9 (br, 3H), 2.0-2.5 (br, 2H), 1.0-1.6 (br, 6H). , 0.7-1.0 (br, 3H);
¹³ C NMR (126 MHz, CDCl ₃ , 20° C.): δ 157.3, 145.2, 141.5, 139.3, 137.5, 130.0-133.0 (br), 128.6, 127.3, 126.1, 124.9, 109.0-114.5 (br), 55.1-55.3 (m), 35.7, 31.5-32.5 (m), 22.6-22.9 (m), 14.1;
IR (KBr, cm ^-1 ): 2927, 1510, 1245.
Anal. Calculated for ( _C20H22O ) _n : C, 86.29; H, 7.97; _N , 0.00. Found: C, 86.22; H, 8.17; N, 0.10.

Compound (II-7) (Example 16):
¹ H NMR (500 MHz, CDCl ₃ , 20° C.): δ 5.6-7.5 (br, 8H), 3.4-4.5 (br, 4H), 1.0-1.9 (br, 20H), 0.7-1.0 (br, 6H) ;
¹³ C NMR (126 MHz, CDCl ₃ , 20° C.): δ 165.0-167.0 (m), 145.0-148.5 (br), 142.0-144.5 (br), 124.0-134.0 (br), 64.4, 31.8-32.1 (m ), 28.7-29.3 (m), 25.9-26.2 (m), 22.8, 14.2;
IR (KBr, cm ^-1 ): 2928, 1720, 1285, 1109;
Anal. Calculated for ( _C30H38O4 ) _n : C, 77.89; H, 8.28; N, 0.00. Found: C _, 77.68 _; H, 8.20; N, 0.10.

Compound (II-8) (Example 17):
¹ H NMR (500 MHz, CDCl ₃ , 20° C.): δ 5.7-7.8 (br, 9H);
¹³ C NMR (126 MHz, CDCl ₃ , 20° C.): δ 161.9, 144.3-150.0 (br), 142.3, 140.4, 138.8, 137.0, 126.0-132.5 (m), 125.4;
¹⁹ F NMR (470 MHz, _CDCl3 , 20°C): δ -153.2, -157.2, -158.1, -162.1, -163.1 (m);
IR (KBr, cm ^-1 ): 3057, 1765, 1522, 1050;
Anal. Calculated for ( _C21H9F5O2 ) _n : C, 64.96; H, 2.34; N _{, 0.00} . Found: C _, 64.64; H, 2.50; N, 0.11.

From the above results, it was found that the substituted poly(diphenylacetylene) (compound (II)), which could only be obtained with a low molecular weight (molecular weight up to about 20,000) and in a low yield by the conventional method, can be obtained in high yield under mild reaction conditions. It was confirmed that the molecular weight (molecular weight of 30,000 or more, preferably 100,000 or more) and high yield can be obtained.

According to the present invention, under mild reaction conditions of about room temperature to about 110° C., the molecular weight is controlled in a relatively high molecular weight range of about 30,000 to about 3,500,000, and various functional groups are rapidly obtained with good yield. , linear substituted poly(diphenylacetylene)s can be produced. Further, according to the production method of the present invention, not only does it have a desired functional group, but also a functional group derived from a cocatalyst (specifically, an aryl group, a heteroaryl group, etc.), and high-molecular-weight substituted poly(diphenylacetylene)s can be obtained by controlling the molecular weight to some extent. be.

Claims (5)

In the presence of molybdenum pentachloride and a promoter functioning as an arylating agent, formula (I):


[In the formula,
n R ¹ 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, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group, a trisubstituted silyl group, or a substituted amino group,
m R ² 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, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group, a trisubstituted silyl group, or a substituted amino group,
n represents an integer of 0-3, and m represents an integer of 0-3. ]
comprising the step of polymerizing a compound represented by formula (II):


[Each symbol in the formula has the same meaning as described above. ]
A method for producing a linear substituted poly(diphenylacetylene) having repeating units represented by The cocatalyst that functions as an arylating agent is optionally substituted tetraaryltin, optionally substituted aryl(tri-n-butyl)tin, and optionally substituted heteroaryl(tri-n-butyl)tin. 2. The manufacturing method of claim 1, wherein the tin is selected from the group consisting of tin. 3. The production method according to claim 1 or 2, wherein the step of polymerizing is performed at room temperature. Formula (II):

[In the formula,
n R ¹ 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, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group, a trisubstituted silyl group, or a substituted amino group;
m R ² 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, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group, a trisubstituted silyl group, or a substituted amino group;
n represents an integer from 0 to 3; and
m represents an integer of 0 to 3; ]
A linear substituted poly(diphenylacetylene) having a repeating unit represented by and a number average molecular weight of 30,000 or more. 5. The substituted poly(diphenyl) according to claim 4, wherein one terminal group is an optionally substituted aryl group or an optionally substituted heteroaryl group, and the other terminal group is a hydrogen atom. acetylene).