JP2023014604A - Block copolymer and method for producing the same - Google Patents

Abstract

To provide a novel block copolymer or the like that can improve the mechanical properties of polythiophene.SOLUTION: A block copolymer comprises a polythiophene block comprising polythiophene, and a polymer block that comprises a polymer of a radical polymerizable monomer comprising a methacrylic acid compound.SELECTED DRAWING: Figure 1A

Description

The present invention relates to block copolymers and methods for producing the same.

As flexible organic electronic materials, π-conjugated polymer materials such as polythiophenes exhibiting conductor properties or semiconducting properties have attracted attention.
However, π-conjugated polymer materials have a problem of trade-off between electronic properties and mechanical properties. In particular, π-conjugated polymer thin films with high crystallinity are prone to cracking due to stress deformation of only a few percent to several tens of percent, resulting in significant degradation of electronic properties and brittleness of the film. In order to improve the mechanical strength, there has been a demand for a method of introducing nano-level stress relaxation units into π-conjugated polymer thin films.

For example, a blend of poly(3-hexylthiophene) and syndiotactic polystyrene has been proposed (see Non-Patent Document 1).
Also AB, BAB, B ₂ AB ₂ and B ₃ AB ₃ (A: P3HT, B: PDL) molecules of poly(3-hexylthiophene)-block-poly(δ-decanolactone) (P3HT-b-PDL) The structure has been investigated (see Non-Patent Document 2).

Intermingled Network of Syndiotactic Polystyrene/Poly(3-hexylthiophene), Macromolecules 2019, 52, 8569-8576 Highly Stretchable Semiconductor Polymers for Field-Effect Transistors through Branched Soft-Hard-Soft Type Triblock Copolymers, Macromolecules 2020, 53-7, 71496

An object of the present invention is to provide a novel block copolymer capable of improving the mechanical properties of polythiophene.

The present inventors have made intensive studies to solve the above problems, and as a result, polythiophene is block-copolymerized with a polymer of a radically polymerizable monomer containing a (meth)acrylic acid compound to solve the above problems. can be solved, and the present invention has been completed.

That is, the present invention includes the following aspects.
[1] a polythiophene block containing polythiophene;
a polymer block containing a polymer of radically polymerizable monomers containing a (meth)acrylic acid compound;
A block copolymer characterized by having
[2] The block copolymer according to [1], wherein the polythiophene has an alkyl group.
[3] The block copolymer according to [1] or [2], wherein the polymer is obtained by living radical polymerization.
[4] The block copolymer according to any one of [1] to [3], wherein the radically polymerizable monomer contains two or more (meth)acrylic acid compounds.
[5] The block copolymer according to any one of [1] to [4], wherein the polythiophene block and the polymer block are linked by a linking group having a triazole ring.
[6] The block copolymer according to any one of [1] to [5], wherein the polymer is a star polymer.
[7] A method for producing a block copolymer for producing the block copolymer according to [5],
A method for producing a block copolymer, comprising the step of linking the polythiophene block and the polymer block by the following reaction (I) or (II).
(I) a reaction of forming the triazole ring between the azide group of the polythiophene block having an azide group and the alkynyl group of the polymer block having an alkynyl group;
(II) Reaction of the alkynyl group of the polythiophene block having an alkynyl group and the azide group of the polymer block having an azide group to form the triazole ring.
[8] the polymer is produced by reversible addition-fragmentation chain transfer polymerization (RAFT polymerization);
During the reaction (I), the alkynyl group is bound to the cleavage residue of the chain transfer agent,
During the reaction of (II), the azide group is bound to the cleavage residue of the chain transfer agent.
A method for producing a block copolymer according to [7].

INDUSTRIAL APPLICABILITY According to the present invention, a novel block copolymer capable of improving the mechanical properties of polythiophene can be provided.

1 is an AFM image (height image) of a film obtained by heat-treating at 150° C. for 5 minutes using block copolymer 4 obtained in Example 4 (No. 1). 2 is an AFM image (height image) of a film obtained by heat-treating 150° C. for 5 minutes using block copolymer 4 obtained in Example 4 (No. 2). 1 is an AFM image (phase contrast image) of a film obtained by heat-treating at 150° C. for 5 minutes using block copolymer 4 obtained in Example 4 (No. 1). FIG. 2 is an AFM image (phase contrast image) of a film obtained by heat-treating 150° C. for 5 minutes using block copolymer 4 obtained in Example 4 (No. 2). 1 is an AFM image (height image) of a film obtained by heat-treating at 200° C. for 5 minutes using block copolymer 4 obtained in Example 4 (No. 1). 2 is an AFM image (height image) of a film obtained by heat-treating at 200° C. for 5 minutes using block copolymer 4 obtained in Example 4 (No. 2). 1 is an AFM image (phase contrast image) of a film obtained by heat-treating at 200° C. for 5 minutes using block copolymer 4 obtained in Example 4 (No. 1). 2 is an AFM image (phase contrast image) of a film obtained by heat-treating at 200° C. for 5 minutes using block copolymer 4 obtained in Example 4 (No. 2).

Hereinafter, the block copolymer and the method for producing the block copolymer of the present invention will be described in detail. is not specified.

(Block copolymer)
The block copolymer of the present invention has a polythiophene block and a polymer block.

<Polythiophene block>
A polythiophene block includes polythiophene.

Polythiophenes, for example, have alkyl groups.
Examples of alkyl groups include alkyl groups having 1 to 20 carbon atoms.
Alkyl groups may be linear, branched, or cyclic.
Examples of alkyl groups include methyl, ethyl, n-propyl, iso-propyl, 2-methylpropyl, tert-butyl, pentyl, hexyl, octyl and decyl groups.
As the alkyl group, an alkyl group having 5 to 20 carbon atoms is preferable from the viewpoint of conductor properties and semiconductor properties.

（式（Ｐｔ１）中、Ａｒ^１は、置換基を有していてもよい１価の芳香族環基を表し、
Ｒ^１は、水素原子、又は炭素数１～２０のアルキル基を表し、
Ａｒ^２は、単結合、又は置換基を有していてもよい２価の芳香族複素環基を表し、
Ｌ^１は、単結合、又は２価の連結基を表し、
ｎは、正の整数を表し、
＊は、結合手を表す。
式（Ｐｔ２）中、Ｒ^１１は、水素原子、又は炭素数１～２０のアルキル基を表し、
Ａｒ^１１は、単結合、又は置換基を有していてもよい２価の芳香族環基を表し、
Ｌ^１１は、単結合、又は２価の連結基を表し、
ｎは、正の整数を表し、
＊は、結合手を表す。） A polythiophene block is represented, for example, by the following formula (Pt1) or (Pt2).

(In formula (Pt1), Ar ¹ represents a monovalent aromatic ring group which may have a substituent,
R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
Ar ² represents a single bond or a divalent aromatic heterocyclic group optionally having a substituent,
L ¹ represents a single bond or a divalent linking group,
n represents a positive integer,
* represents a bond.
In formula (Pt2), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
Ar ¹¹ represents a single bond or a divalent aromatic ring group optionally having a substituent,
L ¹¹ represents a single bond or a divalent linking group,
n represents a positive integer,
* represents a bond. )

Specific examples and preferred carbon numbers of the alkyl groups having 1 to 20 carbon atoms in R ¹ and R ¹¹ include the aforementioned specific examples and preferred carbon numbers of the alkyl groups.

Aromatic rings for Ar ¹ and Ar ¹¹ include, for example, aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, and phenanthrene ring; Aromatic heterocycles substituted with and the like can be mentioned. The heteroatom in the aromatic heterocycle includes, for example, oxygen atom, sulfur atom, nitrogen atom and the like. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings.
Specific examples of the aromatic ring for Ar ¹ include a monovalent group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the above aromatic hydrocarbon ring or aromatic heterocyclic ring; A monovalent group obtained by removing one hydrogen atom from a ring-containing aromatic compound (eg, biphenyl, fluorene, etc.) can be mentioned.
Specific examples of the aromatic ring for Ar ¹¹ include a divalent group (arylene group or heteroarylene group) obtained by removing two hydrogen atoms from the above aromatic hydrocarbon ring or aromatic heterocyclic ring; A divalent group obtained by removing two hydrogen atoms from an aromatic compound containing a ring (eg, biphenyl, fluorene, etc.) can be mentioned.
Examples of substituents that Ar ¹ and Ar ¹¹ may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.
The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
The alkoxy group as a substituent includes an alkoxy group having 1 to 5 carbon atoms, and includes a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group.
A halogen atom as a substituent includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Examples of halogenated alkyl groups as substituents include groups in which some or all of the hydrogen atoms of the above alkyl groups are substituted with halogen atoms.
When Ar ¹ has a substituent, the number of substituents is not particularly limited.
When Ar ¹¹ has a substituent, the number of substituents is not particularly limited.

Examples of the divalent linking group for L ¹ and L ¹¹ include an alkylene group.
Although the number of carbon atoms in the alkylene group is not particularly limited, 1 to 6 are preferable.
The alkylene group includes, for example, a linear alkylene group and a branched alkylene group.
Linear alkylene groups include, for example, a methylene group [--CH.sub.2--], an ethylene group [-- ₍ CH.sub.2) _.sub.2-- ], a trimethylene group [-- ₍ CH.sub.2) _.sub.3-- ] _, a tetramethylene group [--( CH ₂ ) ₄ -], pentamethylene group [-(CH ₂ ) ₅ -] and the like.
Examples of branched alkylene groups include -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )- , -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - and other alkylmethylene groups; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH Alkylethylene groups such as (CH ₃ )—, —C(CH ₃ ) ₂ CH ₂ —, —CH(CH ₂ CH ₃ )CH ₂ —, —C(CH ₂ CH ₃ ) ₂ —CH ₂ —; —CH Alkyltrimethylene groups such as (CH ₃ )CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ )CH ₂ —; —CH(CH ₃ )CH ₂ CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ ) and alkyltetramethylene groups such as CH ₂ CH ₂ —.
The methylene group of the alkylene group in the divalent linking group of L ¹ and L ¹¹ may be substituted with an oxygen atom.

The divalent aromatic heterocyclic group for Ar ² includes a divalent group obtained by removing two hydrogen atoms from a pyridine ring or a thiophene ring.
Specific examples of the substituent that Ar ² may have include specific examples of the substituent that Ar ¹ and Ar ¹¹ may have.
When Ar ² has a substituent, the number of substituents is not particularly limited.

Polythiophene blocks have different charge mobilities depending on their molecular weight. When the block copolymer is used as an opto-electronic functional material, the number average molecular weight of the polythiophene block is preferably 2,500 or more, more preferably 5,000 or more, more preferably 9,000, because good charge mobility can be obtained. More preferably, 10,000 or more is particularly preferable. Although the upper limit of the number average molecular weight of the polythiophene block is not particularly limited, for example, the number average molecular weight of the polythiophene block is preferably 100,000 or less.

Such a number average molecular weight is a number average molecular weight (polystyrene equivalent) measured by gel permeation chromatography (GPC). Tetrahydrofuran (THF) is preferably used as a solvent for the measurement.

If the molecular weight distribution of the polythiophene block is wide, it may contain particles with molecular weights smaller than the desired range, making it impossible to obtain the desired charge mobility.
Therefore, the molecular weight distribution (Mw/Mn) of the polythiophene block is preferably about 1.0 to 4.0, more preferably about 1.0 to 3.0, and particularly preferably about 1.0 to 2.0. . In addition, Mw shows a weight average molecular weight. Mn indicates number average molecular weight.
In the present invention, the polythiophene block preferably has a small molecular weight dispersity and a number average molecular weight of 10,000 or more.

The content of the polythiophene block in the block copolymer is preferably 5 to 70% by mass, more preferably 10 to 65% by mass, and even more preferably 20 to 60% by mass, based on the total mass of the polythiophene block and the polymer block. 25 to 55% by weight is particularly preferred.
If the polythiophene block content is at least the above lower limit, the block copolymer will have good conductive properties.
If the content of the polythiophene block is equal to or less than the above upper limit, the mechanical properties of the block copolymer will be good.

<Polymer block>
The polymer block contains a polymer of radically polymerizable monomers containing (meth)acrylic acid compounds.

<<Polymer>>
The polymer is a polymer of radically polymerizable monomers containing (meth)acrylic acid compounds.

<<<radical polymerizable monomer>>>
The radically polymerizable monomer contains a (meth)acrylic acid compound and, if necessary, other radically polymerizable monomers.

The radically polymerizable monomer preferably contains two or more (meth)acrylic acid compounds. There are many types of (meth)acrylic acid compounds, and the glass transition temperatures of homopolymers vary widely depending on the types. Therefore, if the radically polymerizable monomer contains two or more (meth)acrylic acid compounds, it becomes easier to adjust the mechanical properties.

-(Meth)acrylic acid compound-
Examples of (meth)acrylic acid compounds include (meth)acrylic acid and (meth)acrylic acid esters.
Examples of (meth)acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, Isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, (meth)acrylic heptyl acid, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-(meth)acrylate -decyl, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, n-octadecyl (meth)acrylate, (meth)acrylate Aliphatic (meth)acrylic acid esters such as isooctadecyl acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth) ) Alicyclic (meth)acrylates such as dicyclopentenyloxyethyl acrylate; Aromatic (meth)acrylic acids such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenyl (meth)acrylate and esters.
Further, as (meth)acrylic acid esters having an amino group, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, (meth)acryloxyethyltrimethylammonium chloride etc.

A (meth)acrylic acid compound is a monofunctional vinyl compound having one radically polymerizable vinyl group.

-Other radically polymerizable monomers-
Other radically polymerizable monomers are compounds having a radically polymerizable vinyl group.
As used herein, the radically polymerizable vinyl group includes, for example, a vinyl group, an acryloyloxy group, a methacryloyloxy group, an allyl group, and the like.
Other radically polymerizable monomers are not particularly limited as long as they are radically polymerizable monomers other than (meth)acrylic acid compounds. Examples include (meth)acrylamide compounds, styrenes, allyl esters, vinyl ethers, and vinyl esters. and crotonate esters.
The (meth)acrylamide compounds, styrenes, allyl esters, vinyl ethers, vinyl esters, and crotonic acid esters exemplified here are monofunctional vinyl compounds having one radically polymerizable vinyl group.

(Meth)acrylamide compounds include, for example, (meth)acrylamide; (meth)acrylonitrile; N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-isopropyl ( N-monosubstituted (meth)acrylamide monomers such as meth)acrylamide and dimethylaminopropyl (meth)acrylamide; N-(meth)acryloylmorpholine, N-(meth)acryloylpyrrolidone, N-(meth)acryloylpiperidine, N -N,N-disubstituted (meth)acrylamide units such as (meth)acryloylpyrrolidine, N-(meth)acryloyl-4-piperidone, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide and the like.

Examples of styrenes include styrene, tert-butoxystyrene, α-methyl-tert-butoxystyrene, 4-(1-methoxyethoxy)distyrene, 4-(1-ethoxyethoxy)distyrene, tetrahydropyranyloxystyrene, adamantyloxy Styrene, 4-(2-methyl-2-adamantyloxy)styrene, 4-(1-methylcyclohexyloxy)styrene, trimethylsilyloxystyrene, dimethyl-tert-butylsilyloxystyrene, tetrahydropyranyloxystyrene, benzylstyrene, trifluoro methylstyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoro methylstyrene, 4-fluoro-3-trifluoromethylstyrene, vinylnaphthalene and the like.

Examples of allyl esters include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and allyloxyethanol.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxy Ethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinylphenyl ether, vinyltolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, and the like.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate and the like.

Examples of crotonates include butyl crotonate, hexyl crotonate, glycerin monocrotonate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dimethyl maleate, dibutyl fumarate, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleironitrile and the like.

Further, other radically polymerizable monomers may contain polyfunctional vinyl compounds having two or more radically polymerizable vinyl groups.

Examples of polyfunctional vinyl compounds include the following compounds.
(1) Aromatic vinyl hydrocarbons (2) Vinyl hydrocarbons (3) Ester group-containing vinyl monomers (4) Sulfone group-containing vinyl monomers, vinyl sulfate monoesters and their salts ( 5) Phosphate group-containing vinyl monomers (6) Hydroxyl group-containing vinyl monomers (7) Nitrogen-containing vinyl monomers (8) Halogen element-containing vinyl monomers (9) Carboxyl group-containing vinyl monomers Monomers and their salts (10) Silicon-containing vinyl monomers

Examples of aromatic vinyl hydrocarbons in (1) include o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, divinyltoluene, 1,4-diisopropenylbenzene and trivinylbenzene.

Vinyl hydrocarbons in (2) include, for example, isoprene, butadiene, 3-methyl-1,2-butadiene, 2,3-dimethyl-1,3-butadiene, pentadiene, hexadiene, octadiene, 1,3,5- hexatriene, cyclopentadiene, cyclohexadiene, trivinylcyclohexane and the like.

Examples of the ester group-containing vinyl monomer in (3) include diallyl maleate, diallyl phthalate, divinyl adipate, diallyl adipate, divinyl fumarate, divinyl maleate, divinyl itaconate, vinyl cinnamate, and croton. Vinyl acid, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate ) acrylate, pentaerythritol tetra(meth)acrylate, 1,2-cyclohexanediol di(meth)acrylate, 1,3-cyclohexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, vinyl (meth)acrylate ) acrylate, polyethylene glycol (molecular weight 300) di(meth)acrylate, polypropylene glycol (molecular weight 500) diacrylate, and the like.

Examples of the sulfone group-containing vinyl monomers, vinyl sulfate monoesters, and salts thereof in (4) include divinyl sulfide, divinyl sulfone, divinyl sulfoxide, and diallyl disulfide.

Examples of the phosphoric acid group-containing vinyl monomer in (5) include triallyl phosphate, tri(4-vinylphenyl) phosphate, tri(4-vinylbenzyl) phosphate, diallylmethyl phosphate, di(4- vinylphenyl)methyl phosphate, di(4-vinylbenzyl)methyl phosphate, diallylphenyl phosphate and the like.

Examples of hydroxyl group-containing vinyl monomers in (6) include divinyl glycol (1,5-hexadiene-3,4-diol), 1,2-divinyloxy-3-propanol, 1,3-divinyloxy -2-propanol and the like.

Examples of nitrogen-containing vinyl monomers in (7) include diallylamine, triallylamine, diallyl isocyanurate, diallyl cyanurate, 1-cyanobutadiene, methylenebisacrylamide and bismaleimide.

Examples of halogen-containing vinyl monomers in (8) include 1,4-divinylperfluorobutane, chloroprene, and diallylamine hydrochloride.

Examples of the carboxyl group-containing vinyl monomer and its salt in (9) include carboxyl group-containing vinyl monomers such as monoallyl maleate, monoallyl phthalate, monovinyl fumarate, monovinyl maleate, and monovinyl itaconate; and alkali metal salts and alkaline earth metal salts thereof. Alkali metal salts include, for example, sodium salts, potassium salts and the like. Alkaline earth metal salts include, for example, calcium salts and magnesium salts.

Specific examples of the silicon-containing vinyl monomer in (10) include divinyldimethylsilane, 1,3-divinyltetramethyldisiloxane, 1,1,3,3-tetramethyl-1,3- and divinyldisiloxane.

When the polymer constituting the polymer block is a polymer of two or more radically polymerizable monomers, the polymer may be a random copolymer or a block copolymer.
Also, the polymer constituting the polymer block may be a so-called star polymer. Since the polymer is a star-shaped polymer, a π-conjugated polymer block (polythiophene block) having electrical properties is arranged in the outer part of the star-shaped polymer, and a polymer block expected to have high polymer properties is arranged in the inner part. can be done. By doing so, when a film is formed, the outer π-conjugated polymer blocks of adjacent star-shaped polymers are more likely to come into contact with each other, and it can be expected that even a small amount of star-shaped polymer will provide excellent electrical properties. .

<<<star polymer>>>
A star polymer has a core and arms.
The arm portion is coupled to the core portion.
Typically, in a star polymer, multiple arms are attached to the core. The plurality of arm portions, for example, radially extend from the core portion.

The core part has, for example, a polyfunctional vinyl compound as a constituent. The core portion is, for example, a reaction product of a vinyl compound with a polyfunctional vinyl compound. In other words, the core portion has structural units derived from a polyfunctional vinyl compound.
Examples of polyfunctional vinyl compounds include the aforementioned polyfunctional vinyl compounds.

The core portion can contain other vinyl compounds as constituents in addition to the polyfunctional vinyl compound. Other vinyl compounds include, for example, the aforementioned (meth)acrylic acid compounds, (meth)acrylamide compounds, styrenes, allyl esters, vinyl ethers, vinyl esters, and crotonate esters.

The ratio of the polyfunctional vinyl compound to the vinyl compound having a radically polymerizable vinyl group, which constitutes the core portion, is not particularly limited, but is preferably 5 to 100 mol%, more preferably 20 to 100 mol%, and more preferably 50 to 100. Mole % is particularly preferred. Within such a range, the core portion of the star-shaped polymer takes a spherical shape that is advantageous in suppressing entanglement between molecules constituting the core portion of the star-shaped polymer, which is preferable.

The ratio of the monomers constituting the core portion in the star polymer is not particularly limited, but is preferably 10 to 99 mol % with respect to the total monomers constituting the star polymer.

The arms are polymer chains. Polymer chains are generally linear.
The arm portion has, for example, a monofunctional vinyl compound having one radically polymerizable vinyl group as a constituent component, preferably a (meth)acrylic acid compound as a constituent component. In other words, the arm portion has a structural unit derived from a monofunctional vinyl compound.
The arm portion may have one type of monofunctional vinyl compound as a constituent, or may have two or more types of monofunctional vinyl compounds as constituents.

Examples of monofunctional vinyl compounds include the aforementioned (meth)acrylic acid compounds, (meth)acrylamide compounds, styrenes, allyl esters, vinyl ethers, vinyl esters, and crotonate esters.

The number average molecular weight (Mn) of the arm portion measured by gel permeation chromatography (GPC (RI)) is not particularly limited, but is preferably 10,000 or more from the viewpoint of obtaining a membrane having excellent mechanical properties. 15,000 or more is more preferred, 20,000 or more is even more preferred, and 25,000 or more is particularly preferred.
The upper limit of the number average molecular weight (Mn) is not particularly limited, but the number average molecular weight (Mn) may be 100,000 or less, may be 60,000 or less, or may be It may be below.

[GPC (RI) measurement]
The number average molecular weight (Mn) and weight average molecular weight (Mw) by the GPC (RI) measurement method can be obtained by the following GPC (RI) measurement method.
Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column; guard column HXL-H manufactured by Tosoh Corporation
+ TSKgel G5000HXL manufactured by Tosoh Corporation
+ TSKgel G4000HXL manufactured by Tosoh Corporation
+ TSKgel G3000HXL manufactured by Tosoh Corporation
+ TSKgel G2000HXL manufactured by Tosoh Corporation
Detector; RI (differential refractometer)
Data processing: SC-8010 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40°C
Solvent Tetrahydrofuran
Flow rate 1.0 ml/min Standard; Polystyrene Sample; A tetrahydrofuran solution of 0.5% by mass in terms of resin solid content filtered through a microfilter (100 μl)

It is difficult to measure only the molecular weight of the arms in a star polymer. Therefore, the number average molecular weight of the arm portion can be determined, for example, by subjecting the arm portion alone to the above-described method when the arm portion is synthesized by living radical polymerization.

The mass ratio between the core portion and the arm portion (core portion:arm portion) is not particularly limited, but is preferably 1:99 to 99:1, more preferably 1:99 to 50:50, and 3:97 to 40. :60 is even more preferred, and 5:95 to 20:80 is particularly preferred.

The weight average molecular weight (Mw) of the star polymer measured by gel permeation chromatography (GPC (RI)) is, for example, 10,000 or more, and from the viewpoint of obtaining a coating film having better mechanical properties, 40 ,000 or more is preferable, 100,000 or more is more preferable, and 200,000 or more is particularly preferable.
In order to obtain coatings with good mechanical properties, the weight average molecular weight (Mw) of the star polymer is 10,000 or more. If the weight average molecular weight (Mw) of the star polymer is less than 10,000, it is not possible to obtain a coating film with excellent mechanical properties.
The upper limit of the weight average molecular weight (Mw) is not particularly limited, but the weight average molecular weight (Mw) may be 5,000,000 or less, or 4,500,000 or less. , 4,000,000 or less.

The number average molecular weight (Mn) of the star polymer measured by gel permeation chromatography (GPC (RI)) is, for example, 5,000 or more, and from the viewpoint of obtaining a coating film having better mechanical properties, it is 20 ,000 or more is preferable, 50,000 or more is more preferable, and 100,000 or more is particularly preferable.
In order to obtain coatings with good mechanical properties, the number average molecular weight (Mn) of the star polymer is 5,000 or more. If the number average molecular weight (Mn) of the star polymer is less than 5,000, it is not possible to obtain a coating film with excellent mechanical properties.
The upper limit of the number average molecular weight (Mn) is not particularly limited, but the number average molecular weight (Mn) may be 3,000,000 or less, or 2,500,000 or less. , 2,000,000 or less.

The number of arm portions of the star polymer is not particularly limited, but the number of arm portions determined by the following formula is preferably 3 or more, more preferably 5 or more, even more preferably 10 or more, and 20. The above are particularly preferred. Also, the number is preferably 150 or less, more preferably 100 or less, and particularly preferably 50 or less.

The method for producing the polymer constituting the polymer block and the star polymer is not particularly limited, but the polymer constituting the polymer block and the star polymer are preferably produced by controlled radical (living radical) polymerization. In particular, it is preferably produced by ATRP (Atom Transfer Radical Polymerization) or RAFT polymerization (Reversible Addition/Fragmentation Chain Transfer Polymerization). Controlled radical (living radical) polymerization such as ATRP and RAFT polymerization allows the polymerization to proceed linearly while preventing recombination and disproportionation of growing radicals, thereby enabling the precise synthesis of polymers with a narrow molecular weight distribution.

The tip of the arm portion of the star polymer has, for example, a polymerization initiation end in living radical polymerization. Here, the “tip” refers to the end opposite to the end on the core portion side among both ends of the arm portion.
For example, when a star polymer is produced by ATRP, the ends of the arms have residues upon radical cleavage of the organohalogen compound.
Further, for example, when a star polymer is produced by RAFT polymerization, the tip of the arm part is either a residue when the radical polymerization initiator is thermally cleaved or a residue when the chain transfer agent is cleaved. have. In addition, the "polymerization initiation terminal in living radical polymerization" includes not only the initiation terminal of the polymer chain obtained by the growth reaction caused by the radical generated by thermal cleavage of the radical polymerization initiator, but also the polymerization initiation terminal generated by the cleavage of the chain transfer agent. Also included are starting ends of polymer chains resulting from radical-induced propagation reactions.

The molecular weight of the polymer block is not particularly limited, but when the polymer block contains a polymer other than the star polymer, the number average molecular weight of the polymer block is preferably 10,000 or more, more preferably 20,000 or more. Although the upper limit of the number average molecular weight of the polymer block is not particularly limited, the number average molecular weight of the polymer block is preferably 100,000 or less.
When the polymer block contains a star polymer, the number average molecular weight of the polymer block is preferably 20,000 or more, more preferably 50,000 or more, and particularly preferably 100,000 or more. The upper limit of the number average molecular weight of the polymer block is not particularly limited, but the number average molecular weight of the polymer block may be 3,000,000 or less, or 2,500,000 or less. It may be 2,000,000 or less.

Such a number average molecular weight is a number average molecular weight (polystyrene equivalent) measured by gel permeation chromatography (GPC). Tetrahydrofuran (THF) is preferably used as a solvent for the measurement.

If the molecular weight distribution of the polymer blocks is wide, it may include those with molecular weights lower than the desired range, and the extent to which the mechanical properties of the block copolymer are improved may not be small.
Therefore, the molecular weight distribution (Mw/Mn) of the polymer block is preferably about 1.0 to 4.0, more preferably about 1.0 to 3.0, and particularly preferably about 1.0 to 2.0. .
In the present invention, the polymer block preferably has a small molecular weight distribution and a number average molecular weight of 10,000 or more.

The content of the polymer block in the block copolymer is preferably 30 to 95% by mass, more preferably 35 to 90% by mass, and even more preferably 40 to 80% by mass, based on the total mass of the polythiophene block and the polymer block. 45 to 75% by weight is particularly preferred.
If the polymer block content is equal to or less than the above upper limit, the block copolymer will have good conductive properties.
If the polymer block content is at least the above lower limit, the block copolymer will have good mechanical properties.

<Binding Mode of Block Copolymer>
The bonding mode of the polythiophene block and the polymer block in the block copolymer may be linear, branched, radial, or any combination thereof. A combination is preferred.
For example, when the polythiophene block is represented by A and the polymer block is represented by B, AB type diblock copolymer, ABA type triblock copolymer, and ABAB type tetrablock copolymer polymers, star [(A)mB] type block copolymers (m is an integer of 3 or more), and the like.
When the polymer constituting the polymer block is a star-shaped polymer and the polythiophene block is bonded to the tip of the arm of the star-shaped polymer, the block copolymer itself can be said to be a star-shaped polymer.

In the block copolymer, the polythiophene block and the polymer block are preferably linked by a linking group having a triazole ring from the viewpoint of facilitating the production of the block copolymer.

The block copolymer is preferably, for example, a block copolymer represented by the following formula (X).

（式（Ｘ）中、ＰｔＢは、ポリチオフェンブロックを表し、
ＰＢは、ポリマーブロックを表し、
Ｌ_ｘは、連結基を表し、
ｍは、正の整数を表す。）

(In formula (X), PtB represents a polythiophene block,
PB represents a polymer block,
L _x represents a linking group,
m represents a positive integer. )

A triazole ring is preferable as the linking group of _Lx .
Although m is not particularly limited as long as it is a positive integer, 1 to 150 is preferable.
When the polymer constituting the polymer block is a star polymer, m is usually 2 or more.

(Method for producing block copolymer)
The method for producing a block copolymer of the present invention includes a step of linking a polythiophene block and a polymer block by the following reaction (I) or (II).
(I) A reaction of forming a triazole ring between an azide group of a polythiophene block having an azide group and an alkynyl group of a polymer block having an alkynyl group.
(II) A reaction to form a triazole ring between an alkynyl group of a polythiophene block having an alkynyl group and an azide group of a polymer block having an azide group.

The above reaction (I) or (II) utilizes a click reaction between an azide and an alkyne. A click reaction is a reaction in which an azide (N ₃ ) compound reacts with an alkynyl group to form a 1,2,3-triazole ring. The click reaction can be performed applying or employing any Huisgen experimental procedure commonly known to those skilled in the art. Generally, the click reaction is carried out according to the Huisgen reaction either in the presence of an organic solvent or in the presence of an aqueous solvent. In the presence of an organic solvent, the click reaction is typically carried out in the presence of copper(I) bromide (CuBr) and N,N,N',N',N''-pentamethyldiethylenetriamine (PMDETA). be. This reaction is preferably carried out in an organic solvent (e.g., dimethylformamide (DMF), tetrahydrofuran (THF), toluene, dimethylsulfoxide (DMSO)) at temperatures including between room temperature and the reflux temperature of the reaction mixture, preferably anhydrous. It should be done under certain conditions.

Preferably the polymer is made by reversible addition-fragmentation chain transfer polymerization (RAFT polymerization). In that case, during the reaction of (I), the alkynyl group is preferably bound to the cleavage residue of the chain transfer agent (RAFT agent). Also, in the reaction of (II), the azide group is preferably bound to the cleavage residue of the chain transfer agent. Cleavage residues are usually at the ends of the polymer.
Examples of chain transfer agents include thiocarbonylthio compounds such as dithioesters, dithiocarbamates, trithiocarbonates, and xanthates, and halogen compounds having chloro (Cl), bromo (Br), and iodo (I) groups. is preferred.

（式（Ｐｔ１１）及び（Ｐｔ１３）中、Ａｒ^１、Ｒ^１、Ａｒ^２、Ｌ^１、及びｎは、式（Ｐｔ１）中の、Ａｒ^１、Ｒ^１、Ａｒ^２、Ｌ^１、及びｎとそれぞれ同じである。
式（Ｐｔ１２）及び（Ｐｔ１４）中、Ｒ^１１、Ａｒ^１１、Ｌ^１１、及びｎは、式（Ｐｔ２）中の、Ｒ^１１、Ａｒ^１１、Ｌ^１１、及びｎとそれぞれ同じである。） <Polythiophene Block Having Azide Group, Polythiophene Block Having Alkynyl Group>
A polythiophene block having an azide group is represented, for example, by the following formula (Pt11) or (Pt12).
A polythiophene block having an alkynyl group is represented, for example, by the following formula (Pt13) or (Pt14).

(In formulas (Pt11) and (Pt13), Ar ¹ , R ¹ , Ar ^{2 , L 1 , and n correspond to Ar 1 , R 1 , Ar 2 , L 1 , and} n in formula (Pt1), respectively. are the same.
R ¹¹ , Ar ¹¹ , L ¹¹ and n in formulas (Pt12) and (Pt14) are the same as R ¹¹ , Ar ¹¹ , L ¹¹ and n in formula (Pt2), respectively. )

A polythiophene block having an azide group can be obtained, for example, by converting a hydroxyl group of polythiophene having a terminal hydroxyl group into an azide group. A specific example is given in Synthesis Example 1 described later.
A polythiophene having a terminal hydroxyl group can be obtained, for example, by polymerization of a dihalogenated thiophene using magnesium and a metal complex having a hydroxyl group. A hydroxyl group may be protected by a protective group during polymerization. Examples of metal complexes include nickel complexes.

A polythiophene block having an azide group can be obtained, for example, by polymerizing a dihalogenated thiophene using magnesium and a metal complex to obtain a polythiophene, and then adding an azide group to the growing end of the polythiophene. . A specific example is given in Synthesis Example 8 described later.

A polythiophene block having an alkynyl group can be obtained, for example, by polymerizing a dihalogenated thiophene using magnesium and a metal complex to obtain a polythiophene, and then adding an alkynyl group to the growing end of the polythiophene. A specific example is given in Synthesis Example 2 described later.
An alkynyl group can be attached to the growing terminal of polythiophene by, for example, reacting the growing terminal with alkynylmagnesium halide.
Alkynylmagnesium halides include, for example, ethynylmagnesium bromide.

（式（ＰＢ１）及び式（ＰＢ２）中、ＢＰは、ポリマーブロックを表す。ｍは、正の整数を表す。）
ｍとしては、正の整数であれば、特に限定されないが、１～１５０が好ましい。 <Polymer Block Having Azide Group, Polymer Block Having Alkynyl Group>
A polymer block having an azide group is represented, for example, by the following formula (PB1).
A polymer block having an alkynyl group is represented, for example, by the following formula (PB2).

(In formulas (PB1) and (PB2), BP represents a polymer block. m represents a positive integer.)
Although m is not particularly limited as long as it is a positive integer, 1 to 150 is preferable.

A polymer block having an azide group can be obtained, for example, by polymerizing a radically polymerizable monomer containing a (meth)acrylic acid compound using a polymerization initiation component having an azide group. Polymerization initiation components having an azide group include chain transfer agents having an azide group.
When the polymer constituting the polymer block is a star-shaped polymer, the azide group of the polymer block having an azide group is arranged, for example, at the tip of the arm portion of the star-shaped polymer.
A polymer block having an alkynyl group can be obtained, for example, by polymerizing a radically polymerizable monomer containing a (meth)acrylic acid compound using a polymerization initiation component having an alkynyl group. A chain transfer agent having an alkynyl group is exemplified as the polymerization initiation component having an alkynyl group.
When the polymer constituting the polymer block is a star-shaped polymer, the alkynyl group of the polymer block having an alkynyl group is arranged, for example, at the tip of the arm portion of the star-shaped polymer.

<<Method for producing star polymer>>
A method for producing a star polymer includes steps in which a living polymer is synthesized, reacted, and optionally other steps.
The method for producing a star polymer is a method for producing a star polymer by living radical polymerization.

<<<Process of Synthesizing Living Polymer>>>
In the step of synthesizing the living polymer, the living polymer to be the arm portion is synthesized.
Synthesis of living polymers is carried out, for example, by ATRP or RAFT polymerization, which are living radical polymerizations.

ATRP uses an organic halogen compound as a polymerization initiator and a transition metal complex such as a copper (I) complex as a catalyst. Moreover, a ligand is used as needed.
In ATRP, the carbon-halogen bond of the organohalogen compound is radically cleaved, the halogen atom moves onto the metal atom of the catalyst, and the resulting polymerization initiator radical adds to the double bond of the vinyl monomer. Radical active species newly generated by the addition become dormant species by abstracting halogen atoms on the metal atoms of the catalyst. The radical active species and the dormant species are in an equilibrium state, but the equilibrium is largely biased toward the dormant species, and the terminal of the radical active species present at a low concentration adds to the vinyl monomer to grow the polymer.
Examples of catalysts include copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, chloro(indenyl)bis(triphenylphosphine)ruthenium(II) (dichloromethane adduct ), chloro(indenyl)bis(η5-pentamethylcyclopentadiene)[bis(triphenylphosphine)]ruthenium (II), and the like.
Ligands are used, for example, to enhance the catalytic activity of copper compounds. Ligands include, for example, 2,2'-bipyridyl and derivatives thereof; 1,10-phenanthroline and derivatives thereof; polyamines such as tetramethylethylenediamine, pentamethyldiethylenetriamine, tris[2-(dimethylamino)ethyl]amine, etc. is mentioned.
Commercially available reagents such as those manufactured by Sigma-Aldrich, Tokyo Chemical Industry Co., and Fujifilm Wako Pure Chemical Industries, Ltd. can be used as these organic halogen compounds and catalysts.

In RAFT polymerization, a reaction related to RAFT equilibrium is added to the general free radical polymerization of substituted monomers, and the polymerization reaction proceeds by a reversible chain transfer reaction via a chain transfer agent (RAFT agent).
Chain transfer agents (RAFT agents) used in RAFT polymerization include, for example, dithioesters, dithiocarbamates, trithiocarbonates, thiocarbonylthio compounds such as xanthates, chloro (Cl) groups, bromo (Br) groups, iodine ( It is preferred to use halogen compounds having the group I).
Radical polymerization initiators used in RAFT polymerization include, for example, azobisisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2-methylpropionitrile). , 4,4′-azobis(4-cyanopropionic acid), (2RS,2′RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) and other azo compound polymerization initiators, benzoyl peroxide, etc. and polymerization initiators for peroxides.

A polymerization initiator, which is an initiator component used in ATRP polymerization, has, for example, an azide group or an alkynyl group at a site that becomes a polymerization initiation terminal when polymerized.
A chain transfer agent, which is an initiator component used in RAFT polymerization, has, for example, an azide group or an alkynyl group at a site that becomes a polymerization initiation terminal when polymerized.
Azide groups or alkynyl groups can be introduced at the tips of the arm portions of the star polymer by synthesizing the living polymer that will be the arm portion by living radical polymerization using such a polymerization initiator and chain transfer agent. .
The polymerization initiator and chain transfer agent, which are the initiator components used, may be synthesized or commercially available.
A specific example of the chain transfer agent having an azide group is given in Synthesis Example 3B below.
Specific examples of the chain transfer agent having an alkynyl group are given in Synthesis Example 4 below.

In the step of synthesizing the living polymer, for example, a monofunctional vinyl compound is polymerized by heating in the presence of a solvent by precision radical polymerization such as ATRP or RAFT polymerization described above to obtain the living polymer that will form the arm portion. can.
In the polymerization, for example, nitrogen is introduced at room temperature to deoxygenate, then the temperature in the system is raised to 50 to 100° C. with stirring, and maintained at 50 to 100° C. for 3 to 24 hours. can be done by

When the step of synthesizing the living polymer is performed by ATRP, the step of synthesizing the living polymer can be performed, for example, as follows. First, an organic halogen compound, a catalyst, a ligand, a monofunctional vinyl compound, and a solvent are added and mixed in a reactor. Subsequently, nitrogen is blown into the system to remove dissolved oxygen in the system, and then the system is heated to polymerize the monofunctional vinyl compound to obtain a living polymer.
When the step of synthesizing the living polymer is performed by RAFT polymerization, the step of synthesizing the living polymer can be performed, for example, as follows. First, a RAFT agent, a radical polymerization initiator (for example, an azo polymerization initiator), a monofunctional vinyl compound, and a solvent are added and mixed in a reactor. Subsequently, nitrogen is blown into the system to remove dissolved oxygen in the system, and then the system is heated to polymerize the monofunctional vinyl compound to obtain a living polymer.

The monofunctional vinyl compound that constitutes the living polymer may be of one kind, or may be of two or more kinds.

The monofunctional vinyl compound includes, for example, the monofunctional vinyl compounds exemplified in the explanation of the polymer block.

<Reacted step>
In the reacted step, the polyfunctional vinyl compound and the living polymer are reacted.
The reacted step is performed, for example, as follows. A polyfunctional vinyl compound is added into the reactor in a state in which the growing terminal of the living polymer is not deactivated, and the living polymer and the polyfunctional vinyl compound are reacted. By polymerizing the polyfunctional vinyl compound in the presence of the living polymer, a core portion is formed, and the living polymer is bonded to the core portion at the growth terminal to obtain a star-shaped polymer.
Examples of polyfunctional vinyl compounds include the monofunctional vinyl compounds exemplified in the explanation of the polymer block.

In ATRP polymerization, the tip of the arm usually has a residue from the radical cleavage of the organohalogen compound. When the residue has an azide group, the azide group is introduced at the tip of the arm portion of the resulting star polymer. When the residue has an alkynyl group, the alkynyl group is introduced at the tip of the arm portion of the resulting star polymer.
In RAFT polymerization, the tip of the arm usually has a group derived from a radical polymerization initiator or a chain transfer agent (RAFT agent). When the group has an azide group, the azide group is introduced at the tip of the arm portion of the resulting star polymer. When the group has an alkynyl group, the alkynyl group is introduced at the tip of the arm portion of the resulting star polymer.

(Block copolymer composition)
The block copolymer of the present invention may be mixed with other components to form a block copolymer composition.
There are no particular restrictions on the method for producing the block copolymer composition, and various conventional production methods can be used.
For example, after blending a block copolymer, a softening agent and other components used as necessary, melt-kneading using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or a roll. By doing so, a block copolymer composition can be suitably produced.
Moreover, the block copolymer composition may be a composition containing a block copolymer and an organic solvent. The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbon solvents, ester solvents, glycol solvents, ketone solvents, amine solvents, and halogen solvents.

(Molded body)
The molded article made of the block copolymer or block copolymer composition of the present invention is not particularly limited as long as it can be produced using the block copolymer or block copolymer composition of the present invention. Each member of organic electronic devices such as films, actuators and connectors can be mentioned.

INDUSTRIAL APPLICABILITY The block copolymer of the present invention has excellent electrical conductivity and a polymer block capable of adjusting mechanical properties, so it can be widely applied to organic electronic devices that require flexibility, deformation, folding, and stretchability. .

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the scope of the present invention is not limited to these Examples.

(Synthesis Example 1: Preparation of P3HT modified with an azide group)
P3HT modified with an azide group was prepared with reference to the following non-patent literature.
- Van Den Eede, M.; -P. De Winter, J.; Gerbaux, P.; Teyssandier, J.; De Feyter, S.; Van Goethem, C.; Vankelecom, I.; F. J. Koeckelberghs, G.; , Controlled Synthesis and Supramolecular Organization of Conjugated Star-Shaped Polymers. , Macromolecules 2018, 51, 8689-8697,, DOI: 10.1021/acs. macromol. 8b01777.

<Synthesis Example 1A: Synthesis of 4-Bromo-3-methylbenzyloxy-tert-butyldimethylsilane>

1.04 g (5.2 mmol) of 4-bromo-3-methylbenzoylalcohol and 0.75 g (11 mmol) of imidazole were weighed into a 100 ml two-necked flask, purged with nitrogen, and dissolved in 50 ml of DMF. Subsequently, 0.92 g (6.1 mmol) of tert-butyldimethylsilyl chloride was added and reacted overnight. Subsequently, liquid separation and washing using water and dichloromethane were performed, and after dehydrating the organic layer with magnesium sulfate, magnesium sulfate was removed by filtration. The filtrate was then concentrated by an evaporator and dried under reduced pressure by a vacuum pump. Finally, the desired product was obtained by purification by silica gel column chromatography.
Yield: 1.3g, 80%
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.47 (d, J=8.2 Hz, 1 H), 7.18 (s, 1 H), 7.00 (d, J=10.0 Hz, 1 H), 4. 65 (s, 2H), 2.39 (s, 3H), 0.94 (s, 9H), 0.09 (s, 6H)

<Synthesis Example 1B: Synthesis of Bromo-(2-methyl-2-(tert-butyldimethylsilyloxymethylphenyl)-bis(triphenylphosphine) nickel (II)>

In a nitrogen-purged glove box, 1.13 g (4.0 mmol) of triphenylphosphine and 0.50 g (1.6 mmol) of 4-bromo-3-methylbenzyloxy-tert-butyldimethylsilane obtained in Synthesis Example 1A were weighed into a 50 ml sample tube. After adding 25 ml of toluene, the mixture was stirred at room temperature for 10 minutes. Subsequently, 0.3 g (1.1 mmol) of Ni(COD) ₂ [Bis(1,5-cyclooctadiene)nickel(0)] was added and stirred at room temperature for 60 minutes. After that, the sample tube was taken out from the glove box, 100 ml of toluene was added, and the insoluble matter was filtered. The solvent of the filtrate was concentrated by an evaporator and precipitated in hexane to precipitate a solid. A solid was collected by filtration, washed with hexane, and freeze-dried to obtain a yellow powder.
Yield: 0.17g, 12%
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.55 (d, J=65.9 Hz, 13 H), 7.19-6.84 (m, 13 H), 6.22 (s, 1 H), 5.87 ( s, 1H), 4.25 (s, 2H), 2.03 (s, 2H), 0.87 (s, 9H), 0.02 (s, 6H)

<Synthesis Example 1C: Synthesis of P3HT (poly(3-hexylthiophene-2,5-diyl)) having a benzyl alcohol group at the chain end>

1.8 g (4.9 mmol) of 2-bromo-5-iodo-3-hexylthiophene was added to a 30 ml two-necked flask, the pressure was reduced with a vacuum pump, and the inside of the container was replaced with nitrogen. After adding 100 ml of THF (tetrahydrofuran), the mixture was cooled to 0° C., 3.7 ml (4.9 mmol) of a 1.3 M ⁱ PrMgCl.LiCl THF solution was added, and the mixture was stirred for 30 minutes to prepare a monomer solution.
On the other hand, 0.14 g (0.16 mmol) of bromo-(2-methyl-2-(tert-butyldimethylsilyloxymethylphenyl)-bis(triphenylphosphine)nickel (II) obtained in Synthesis Example 1B and 1, 0.15 g (0.37 mmol) of 2-bis(diphenylphosphino)ethane was weighed out, depressurized with a vacuum pump, and then replaced with nitrogen, then 5.8 ml of THF was added, and the initiator solution was stirred for 15 minutes. was prepared.
Polymerization was initiated by adding 5 ml of this initiator solution to the monomer solution and quenched after 1 hour by adding 5M aqueous HCl. Solid precipitated when the resulting solution was poured into a mixed solvent of water/methanol (100 ml/200 ml). After filtering this, it was vacuum-dried to obtain a purple polymer.
Subsequently, after dissolving the polymer in 100 ml of chloroform, deprotection was performed using 1 M×2 ml=2 mmol of THF solution of tetrabutylammonium fluoride (TBAF). The resulting solution was poured into a mixed solvent of water/methanol (100 ml/200 ml) to precipitate the polymer. After filtering it, it was dried in vacuum to obtain P3HT with a benzyl alcohol group at the chain end in purple color.
Yield: 0.72 g, 88%, Mn ( ¹ H NMR) = 5,500
Mn (GPC; polystyrene equivalent) = 8,500, D _M (polydispersity) = 1.10.
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.44 (d, J=8.2 Hz), 7.29-7.22 (m), 6.98 (s), 6.91 (m), 4.71 (s), 2.81 (t, J = 7.7 Hz), 2.51 (s), 1.75-1.67 (m), 1.49-1.41 (m), 1.35 ( q, J = 3.3 Hz), 0.92 (t, J = 6.8 Hz)

<Synthesis Example 1D: Synthesis of P3HT (P3HT-N ₃ ) having an azide group at the chain end>

In a 100 ml two-necked flask, 0.523 g (95 μmol) of P3HT (Mn=5,500, D _M =1.10) having a benzyl alcohol group at the chain end obtained in Synthesis Example 1C and 0 diphenyl phosphate azide were added. 0.41 ml (1.9 mmol) was measured and decompressed with a vacuum pump, and then the inside of the container was replaced with nitrogen. After adding 60 ml of THF, the mixture was cooled to 0° C., 0.28 ml (1.9 mmol) of diazabicycloundecene (DBU) was added dropwise, and the mixture was allowed to react overnight. Solid precipitated when the resulting solution was poured into a mixed solvent of water/methanol (100 ml/200 ml). After filtering this, it was vacuum-dried to obtain purple P3HT (P3HT-N ₃ ) having an azide group at the chain end.
Yield: 0.42 g, 81%, Mn ( ^1H NMR) = 5,500.
Mn (GPC; polystyrene equivalent) = 8,000, D _M = 1.13.
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.45 (d, J=7.8 Hz), 7.24-7.13 (m), 6.98 (s), 6.91 (d, J=8. 2 Hz), 4.34 (s), 2.80 (t, J = 7.5 Hz), 2.51 (s), 1.72 (q, J = 7.3 Hz), 1.44 (s), 1.35 (d, J = 6.4 Hz), 0.91 (t, J = 6.6 Hz)

(Synthesis Example 2: Preparation of alkyne-modified P3HT)

3.0 g (8.2 mmol) of 2-bromo-5-iodo-3-hexylthiophene was added to a 200 ml two-necked flask, the pressure was reduced with a vacuum pump, and the inside of the container was replaced with nitrogen. After adding 15 ml of THF, the mixture was cooled to 0° C., 6.0 ml (7.8 mmol) of a 1.3 M ⁱ PrMgCl.LiCl THF solution was added, and the mixture was stirred for 30 minutes to prepare a monomer solution.
Separately, 0.12 g (0.16 mmol) of bromo(o-tolyl)bis(triphenylphosphine) nickel (II) and 0.18 g (0.43 mmol) of 1,2-bis(diphenylphosphino)methane were weighed into a 20 ml two-necked flask. It was taken out, decompressed with a vacuum pump, and then replaced with nitrogen. Subsequently, 5.8 ml of THF was added and stirred for 15 minutes to prepare an initiator solution.
Polymerization was initiated by adding 5 ml of this initiator solution to the monomer solution, and after stirring for 10 minutes, 1 ml (0.5 mmol) of ethyl magnesium bromide was added. After reacting at 0° C. for 10 minutes, the resulting solution was poured into 500 ml of cold methanol for purification. After filtering this, it was vacuum-dried to obtain purple P3HT (P3HT-Alkyne) having an alkyne group at the chain end.
Yield: 1.1 g, 91%, Mn (1H NMR) = ^10,000 .
Mn (GPC; polystyrene equivalent) = 15,000, D _M = 1.09.
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.44-7.42 (m), 6.98 (s, ), 3.52 (s), 2.80 (t, J=7.5 Hz); 49 (s,), 1.74-1.66 (m), 1.43 (d, J = 6.8 Hz), 1.34 (t, J = 3.4 Hz), 0.91 (t, J = 6.8Hz)

(Synthesis Example 3: Preparation of RAFT agent modified with azide group)
<Synthesis Example 3A: Synthesis of 8-Azido-1-octanol>

1.2 g (18.2 mmol) of sodium azide, 2.01 g (6.1 mmol) of 8-chloro-1-octanol, and 30 ml of water were weighed into a 50 ml two-necked flask and reacted overnight under reflux conditions. Subsequently, liquid separation and washing using water and dichloromethane were performed, the organic layer was dehydrated with magnesium sulfate, and then magnesium sulfate was removed by filtration. Next, the filtrate was concentrated with an evaporator and dried under reduced pressure with a vacuum pump to obtain the desired product, 8-azido-1-octanol.
Yield: 1.8g, 67%.
¹ H NMR (400 MHz, CDCl ₃ ) δ 3.64 (t, J = 6.6 Hz, 2H), 3.25 (t, J = 6.8 Hz, 2H), 1.63-1.53 (m, 4H ), 1.34 (s, 8H)

<Synthesis Example 3B: Synthesis of RAFT agent (2-(Dodecylsulfanylthiocarbonyl)sulfanyl) propionic acid 8-azidooctyl ester) modified with an azide group>

8-azido-1-octanol 2 g (12 mmol), 2-((dodecylsulfanylthiocarbonyl) sulfanyl) propanoic acid 5.03 g (14 mmol), and 4-dimethylaminopyridine 89.3 mg (0.073 mmol) were weighed into a 30 ml two-necked flask. It was taken out and replaced with nitrogen. Subsequently, 20 ml of dichloromethane and 2.30 g (12 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were added and allowed to react overnight. Subsequently, liquid separation and washing using water and dichloromethane were performed, the organic layer was dehydrated with magnesium sulfate, and then magnesium sulfate was removed by filtration. The filtrate was then concentrated by an evaporator and dried under reduced pressure by a vacuum pump. Finally, purification by silica gel column chromatography was performed to obtain the desired product, 2-((dodecylsulfanylthiocarbonyl)sulfanyl)propionic acid 8-azidooctyl ester.
Yield: 1.9g, 32%.
¹ H NMR (400 MHz, CDCl ₃ ) δ 4.80 (q, J = 7.4 Hz, 1 H), 4.17-4.07 (m, 2 H), 3.34 (t, J = 7.5 Hz, 2 H ), 3.25 (t, J=6.8 Hz, 2H), 1.67 (td, J=14.7, 7.4 Hz, 3H), 1.58 (dd, J=7.5, 2. 5Hz, 4H), 1.28 (d, J = 28.1Hz, 24H), 0.87 (t, J = 6.8Hz, 3H)

(Synthesis Example 4: Preparation of alkyne-modified RAFT agent)
<2-Synthesis of ((Dodecylsulfanylthiocarbonyl)sulfanyl)propionic acid propagyl ester>

2-(dodecylthiocarbonothioylthio) propionic acid 2.02 g (5.8 mmol), propargyl alcohol 0.41 g (7.3 mmol), and 4-dimethylaminopyridine 0.035 g (0.29 mmol) were added to a 50 ml two-necked flask, and a vacuum pump was added. After the pressure was reduced by , the inside of the container was replaced with nitrogen. After adding 50 ml of dichloromethane and cooling to 0° C., 1.2 ml (8.8 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide was added dropwise, and the mixture was allowed to react overnight after returning to room temperature. Subsequently, liquid separation and washing using water and dichloromethane were performed, and after dehydrating the organic layer with magnesium sulfate, magnesium sulfate was removed by filtration. The filtrate was then concentrated by an evaporator and dried under reduced pressure by a vacuum pump. Finally, the desired product, 2-((Dodecylsulfanylthiocarbonyl)sulfanyl)propionic acid propagyl ester, was obtained by purification by silica gel column chromatography.
Yield: 1.06g, 47%
¹ H NMR (400 MHz, CDCl ₃ ) δ 4.82 (q, J=7.4 Hz), 4.71 (t, J=2.5 Hz), 3.33 (t, J=7.5 Hz), 2. 48 (t, J=2.5 Hz), 1.71-1.63 (m), 1.59 (d, J=7.7 Hz), 1.36 (q, J=6.8 Hz), 1. 24 (s), 0.86 (t, J = 6.8 Hz)

(Synthesis Example 5: Preparation of random copolymer using RAFT agent modified with azide group)
2-((Dodecylsulfanylthiocarbonyl)sulfanyl)propionic acid obtained in Synthesis Example 3 0.105 g (0.21 mmol), nBA (n-butyl acrylate) 6.65 g (52 mmol), azobisisobutyronitrile 4.2 mg (0.026 mmol) of (AIBN) and 1.64 g (13 mmol) of tBA (t-butyl acrylate) were placed in a 50 ml flask and nitrogen bubbling was performed for 15 minutes. Subsequently, the temperature was raised to 65° C. to initiate polymerization. After reacting overnight, the reaction was terminated by cooling with liquid nitrogen. Subsequently, the polymer was purified by dialysis through a semipermeable membrane (Spectrapore 6 dialysis membrane (fractional molecular weight = 1,000)) using acetone. Acetone was distilled off under reduced pressure to obtain the target random copolymer (N ₃ -PnBA-r-P ^t BA) using the RAFT agent modified with an azide group.
Yield: 5.56g, 67%
Mn (GPC; polystyrene equivalent) = 33,000, D _M = 1.08.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 4.97-4.90 (m), 4.82 (d, J = 11.3 Hz), 4.23 (t, J = 6.6 Hz), 3.72 -3.64 (m), 3.55-3.48 (m), 3.38-3.35 (m), 3.32 (d, J = 7.2 Hz), 2.28 (s), 1.89 (s), 1.59 (s), 1.42 (s), 1.37 (t, J=6.8 Hz), 1.26 (s, 0.93 (t, J=7. 0 Hz)

(Synthesis Example 6: Preparation of random copolymer using alkyne-modified RAFT agent)
2-((Dodecylsulfanylthiocarbonyl)sulfanyl)propionic acid propagyl ester 0.66 g (1.7 mmol), nBA 7.2 g (52 mmol), AIBN 2.8 mg (0.017 mmol), and tBA obtained in Synthesis Example 4. 8 g (13 mmol) was put into a 50 ml flask and nitrogen bubbling was performed for 15 minutes. Subsequently, the temperature was raised to 65° C. to initiate polymerization. After reacting for 12 hours, the mixture was cooled with liquid nitrogen to terminate the polymerization. Subsequently, purification was performed by dialysis using a semipermeable membrane (Spectrapore 6 dialysis membrane (fractional molecular weight = 1,000)) using acetone. -P ⁿ BA-r-P ^t BA.
Yield: 5.8g, 65%.
Mn (GPC; polystyrene equivalent) = 56,000, D _M = 1.22.
¹ H NMR (400 MHz, CDCl ₃ ) δ 3.97 (s), 2.22 (s), 1.84 (s), 1.53 (s), 1.36 (s), 1.31 (t, J = 6.6 Hz), 0.87 (t, J = 7.0 Hz)

(Synthesis Example 7: Preparation of Star-P ⁿ BA having an ethynyl group at the chain end)
44.0 g (0.34 mol) of nBA and 2-((Dodecylsulfanylthiocarbonyl)sulfanyl)propionic acid propagyl obtained in Synthesis Example 4 were placed in a reaction apparatus equipped with a stirrer, a reflux condenser, a temperature sensor, a dropping funnel and a nitrogen inlet tube. Add 0.47 g (1.21 mmol) of ester, 0.0702 g (0.43 mmol) of azobisisobutyronitrile as a radical polymerization initiator, and 44.0 g of toluene as a solvent, and blow nitrogen into the system. Dissolved oxygen was removed from the system by After confirming that the oxygen concentration in the system had become sufficiently low, polymerization was carried out at 60° C. for 3 hours. As a result of measuring the molecular weight of the obtained arm polymer by GPC, it was found to be Mn=26,008.
Next, 84 g of toluene was added to the dropping funnel, and after removing dissolved oxygen by bubbling with nitrogen, it was added into the reactor. Thereafter, 4.4 g of trimethylolpropane triacrylate (Viscoat 295, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a polyvinyl monomer was added into the reactor while blowing nitrogen and taking care not to introduce air into the reactor. The reaction temperature was raised to 70° C. and the reaction was continued for 24 hours.
After the polymerization, 50 g of a solution having a solid concentration of 15% by mass was prepared by adding toluene to a portion of the polymerization liquid. In a 1 L flask, while stirring with a stirrer piece, a mixed solution of 420 g of cyclohexane and 80 g of isopropanol was added to the solution, and after the liquid became uniform, 100 g of cyclohexane was added to obtain a white precipitate. After filtering this solution and drying the precipitate, the precipitate was dissolved in a liquid consisting of 40 g of toluene and 5 g of isopropyl alcohol to obtain a star polymer solution.
As a result of measuring the molecular weight of the resulting star polymer by GPC (RI), it was found to be Mw=511,579 and Mn=316,501. The number of branch arms of the star-shaped polymer obtained from this result was 11.1 as a result of calculation by the following formula.

(Synthesis Example 8: Preparation of P3HT (P3HT-Th-C ₄ -N ₃ ) modified with an azide group)
P3HT modified with an azide group was prepared with reference to the following non-patent literature.
・Ｔｏｍｏｙａ Ｈｉｇａｓｈｉｈａｒａ， Ｓｈｏｔａｒｏ Ｉｔｏ， Ｓｅｉｊｉｒｏ Ｆｕｋｕｔａ， Ｓａｔｏｓｈｉ Ｍｉｙａｎｅ， Ｙｕｔｏ Ｏｃｈｉａｉ， Ｔａｋａｓｈｉ Ｉｓｈｉｚｏｎｅ， Ｍｉｔｓｕｒｕ Ｕｅｄａ， ａｎｄ Ａｋｉｒａ Ｈｉｒａｏ， Ｓｙｎｔｈｅｓｉｓ ａｎｄ Ｃｈａｒａｃｔｅｒｉｚａｔｉｏｎ ｏｆ Ｍｕｌｔｉｃｏｍｐｏｎｅｎｔ ＡＢＣ－ ａｎｄ ＡＢＣＤ－Ｔｙｐｅ Ｍｉｋｔｏａｒｍ Ｓｔａｒ－Ｂｒａｎｃｈｅｄ Ｐｏｌｙｍｅｒｓ Ｃｏｎｔａｉｎｉｎｇ ａ Ｐｏｌｙ（３－ｈｅｘｙｌｔｈｉｏｐｈｅｎｅ） Segment, ACS Macro Lett. 2016, 5, 631-635. , DOI: 10.1021/acsmacrolett. 6b00207

2.1 g (5.6 mmol) of 2-bromo-5-iodo-3-hexylthiophene was weighed into a 200 ml two-necked flask, dried under reduced pressure with a vacuum pump, and then the inside of the container was replaced with nitrogen. After 150 ml of THF was added and dissolved, the solution was cooled to 0° C., 4.4 ml (5.7 mmol) of a 1.3 M ⁱ PrMgCl.LiCl THF solution was added, and the mixture was stirred for 30 minutes to prepare a monomer solution.
On the other hand, 0.090 g (0.12 mmol) of bromo (tolyl) bis (triphenylphosphine) nickel (II) and 0.098 g (0.2 mmol) of 1,2-bis (diphenylphosphino) methane were weighed into a 20 ml two-necked flask, After drying under reduced pressure with a vacuum pump, it was replaced with nitrogen. Subsequently, 12.4 ml of THF was added and stirred for 15 minutes to prepare an initiator solution.
Polymerization was initiated by adding 10 ml of this initiator solution to the previous monomer solution (polymerization solution).
On the other hand, 0.300 g (1.0 mmol) of 2-bromo-5-(4-bromobutyl)thiophene was weighed into a 20 ml two-necked flask, dried under reduced pressure with a vacuum pump, and then replaced with nitrogen. After 15 ml of THF was added and dissolved, the solution was cooled to 0° C., 7.4 ml (9.6 mmol) of a 1.3 M iPrMgCl·LiCl solution in THF was added, and stirred for 30 minutes to prepare a terminator solution.
This terminator solution was added to the polymerization solution after 10 minutes had passed since the initiation of polymerization so that the obtained terminator was 10 equivalents to the initiator, and the mixture was stirred for 1 hour. Finally, the reaction was stopped by adding 1 ml of 5M hydrochloric acid aqueous solution. Solid precipitated when the resulting solution was poured into a mixed solvent of water/methanol (100 ml/200 ml). After filtering this, it was vacuum-dried to obtain P3HT (P3HT-Th-C 4 -Br) having a bromobutyl group at the chain end (P3HT-Th-C ₄ -Br) as a purple solid.
Yield: 0.87 g, 91%, Mn (1H NMR) = ^11,000 .
Mn (GPC; polystyrene equivalent) = 16,000, D _M = 1.07.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.52 (s), 7.44 (t, J = 4.3 Hz), 7.23-7.21 (m), 6.98 (s), 6. 91 (s), 6.76 (t, J = 3.2 Hz), 3.45 (t, J = 6.3 Hz), 2.80 (t, J = 7.5 Hz), 2.49 (s) , 1.96 (dd, J=13.1, 7.7 Hz), 1.91-1.83 (m), 1.44-1.34 (m), 0.92 (t, J=6. 8Hz)

Next, 0.2 g (0.0013 mmol) of P3HT-Th-C ₄ -Br was weighed into a 30 ml two-necked flask, dried under reduced pressure with a vacuum pump, and then the inside of the container was replaced with nitrogen. Subsequently, 0.07 ml (0.78 mmol) of trimethylsilyl azide and 10 ml of THF were added and dissolved, then 0.6 ml (0.60 mmol) of 1.0 M TBAF solution in THF was added and stirred overnight. Solid precipitated when the resulting solution was poured into a mixed solvent of water/methanol (100 ml/200 ml). After filtering this, it was vacuum-dried to obtain P3HT (P3HT-Th-C 4 -N 3 ) having an azide group at the chain end (P3HT-Th-C ₄ -N ₃ ) as a purple solid.
Yield: 0.173 g, 87%, Mn (1H NMR) = ^10,000 .
Mn (GPC; polystyrene equivalent) = 15,000, D _M = 1.09.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.52 (s), 7.43 (dd, J = 8.9, 5.7 Hz), 7.23 (d, J = 2.7 Hz), 6.98 (s), 6.91 (s), 6.77-6.75 (m), 3.33 (t, J=6.6 Hz), 2.81 (t, J=7.5 Hz), 2. 49 (s), 2.49 (s), 1.75-1.67 (m), 1.46-1.35 (m), 0.92 (t, J = 6.4 Hz), 0.92 (t, J = 6.4 Hz,)

(Example 1: Synthesis of P3HT-b-(P ⁿ BA-r-P ^t AA) (block copolymer 1))
1.05 g (0.032 mmol) of the N ₃ —P ⁿ BA-r—P ^t BA (Mn=33,000, D _M =1.08) obtained in Synthesis Example 5 was placed in a 10 ml flask. The obtained P3HT-Alkyne (Mn( ¹ H NMR)=10,000) 0.10 g (0.010 mmol) and PMDETA (N,N,N′,N″,N″-Pentamethyldiethylenetriamine) 61 mg (0.010 mmol). 35 mmol), and 5 ml of THF were measured and freeze-degassed three times. Subsequently, 65 mg (0.45 mmol) of CuBr was added and reacted overnight at 60°C. The resulting solution was poured into a mixed solvent of water/methanol (100 ml/200 ml) to precipitate the polymer. After filtering this, it was purified by Soxhlet extraction using acetone, hexane, and chloroform. Subsequently, chloroform was distilled off under reduced pressure, and the obtained solid was dissolved in benzene and freeze-dried to obtain a purple polymer P3HT-b-(P ⁿ BA-r-P ^t BA).
Crude Yield: 0.13g, 30%.
Mn (GPC; polystyrene equivalent) = 43,000, D _M = 1.13.
¹ H NMR (400 MHz, CDCl ₃ ) δ 6.98 (s), 4.03 (s), 2.80 (t, J = 7.5 Hz), 2.49 (s), 2.28 (s), 1.93-1.89 (m,), 1.74-1.67 (m), 1.58 (d, J=10.5Hz), 1.42 (s), 1.35 (t, J = 6.9 Hz), 0.92 (q, J = 7.3 Hz)

0.13 g (Mn=43,000, D _M =1.13, 3.0 μmol) of the obtained P3HT-b-(P ⁿ BA-r-P ^t BA) was weighed into a 30 ml two-necked flask, 25 ml of CHCl ₃ and 1 ml of trifluoroacetic acid were added and allowed to react overnight at room temperature. The resulting solution was poured into a mixed solvent of water/methanol (100 ml/200 ml) to precipitate the polymer. After filtering this, Soxhlet extraction was performed using acetone, hexane, and chloroform, and purification was performed. Subsequently, chloroform was distilled off under reduced pressure, and the obtained solid was dissolved in benzene and freeze-dried to obtain a purple polymer P3HT-b-(P ⁿ BA-r-PAA) (block copolymer 1). got
Yield: 97 mg.
¹ H NMR (400 MHz, CDCl ₃ ) δ 6.98 (s), 4.04 (s,), 2.80 (t, J = 7.1 Hz), 2.50 (s), 1.70 (d, J = 6.9 Hz), 1.43 (d, J = 5.9 Hz), 1.35 (d, J = 2.7 Hz), 1.25 (s), 0.93-0.84 (m)

(Example 2: Synthesis of P3HT-b-(P ⁿ BA-r-P ^t BA) (block copolymer 2))
Alkyne-P ⁿ BA-r-P ^t BA 0.84 g (Mn = 56,000, D _M = 1.22, 15 µmol) obtained in Synthesis Example 6 and P3HT obtained in Synthesis Example 1 were placed in a 10 ml flask. —N ₃ (Mn( ¹ H NMR)=5,500) 61 mg (11 μmol), PMDETA 26 mg (0.18 mmol), and THF 5 ml were weighed and freeze degassed three times. Subsequently, 31 mg (0.18 mmol) of CuBr was added and reacted overnight at 60°C. The resulting solution was poured into a mixed solvent of water/methanol (100 ml/200 ml) to precipitate the polymer. After filtering this, it was purified by Soxhlet extraction using acetone, hexane and chloroform to obtain a purple polymer P3HT-b-(P ⁿ BA-r-P ^t BA) (block copolymer 2). rice field.
Crude Yield: 0.49g, 84%.
Mn (GPC; polystyrene equivalent) = 66,000, D _M = 1.15.
¹ H NMR (400 MHz, CDCl ₃ ) δ 6.98 (s), 4.03 (s), 2.80 (m), 2.27 (m), 2.17 (m), 1.89 (s) , 1.60 (s), 1.42 (s), 1.35 (m), 1.25 (s), 0.93 (t, J = 7.1 Hz)

(Example 3: Synthesis of P3HT-b-(P ⁿ BA-r-PAA) (block copolymer 3))
In a 10 ml flask, 0.2 g (3 μmol) of P3HT-b-(P ⁿ BA-r-P ^t BA) (Mn=66,000, D _M =1.15) obtained in Example 2 and CHCl ₃ After 2 ml was added and dissolved, 2 ml of trifluoroacetic acid was added and stirred for 1 hour. The resulting solution was poured into 300 ml of hexane to precipitate the polymer. The precipitate was collected and freeze-dried to obtain the desired product P3HT-b-(P ⁿ BA-r-PAA) (block copolymer 3).
Yield: 0.17g, 92%.
¹ H NMR (400 MHz, THF-D ₈ ) δ 6.88 (s), 4.01 (t, J = 6.4 Hz), 2.82 (t, J = 7.5 Hz), 2.32 (m) , 1.86 (m), 1.58 (t, J=6.9 Hz), 1.58 (t, J=6.9 Hz), 1.41 (s), 1.36 (q, J=7 .5 Hz), 0.92 (t, J = 7.1 Hz)

(Example 4: Synthesis of Star-(P3HT-bP ⁿ BA) (block copolymer 4))
0.47 g of a 29.7 wt% toluene solution of Star-P ⁿ BA (11.1 arm, Mn ( ¹ H NMR) = 320,000) having an ethynyl group at the chain end obtained in Synthesis Example 7 was placed in a 10 ml flask. (0.44 μmol, 5.2 μmol for alkyne groups), P3HT-Th-C ₄ -N ₃ obtained in Synthesis Example 8 (Mn (GPC; polystyrene conversion) = 10,000, D _M = 1.09, chain Terminal functionalization rate = 60%) 99 mg (9.9 μmol, 5.9 μmol for N ₃ groups), PMDETA 79 mg (0.45 mmol), and THF 5 ml were added, and freeze degassing was performed three times. Subsequently, 65 mg (0.45 mmol) of CuBr was added and reacted overnight at 60°C. The resulting solution was poured into a mixed solvent of water/methanol (100 ml/200 ml) to precipitate the polymer. After filtering this, it was purified by Soxhlet extraction using acetone, hexane, and chloroform, and block copolymer 4 was obtained.
Crude Yield: 0.113 g.
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.44-7.41 (m), δ 6.98 (s), 4.05-4.00 (m), 2.80 (t, J = 7.8 Hz) , 2.50 (s), 2.35-2.27 (m), 1.97-1.84 (m,), 1.74-1.67 (m), 1.60 (d, J= 6.9Hz, 4H), 1.44 (t, J = 6.9Hz), 1.37-1.34 (m), 0.93 (q, J = 7.5Hz)

(Comparative example 1)
P3HT (P3HT-N ₃ ) having an azide group at the chain end obtained in Synthesis Example 1D was used as Comparative Polymer 1.

(Preparation of cast film)
Block copolymers 1 to 4 obtained in Examples 1 to 4 and P3HT (comparative polymer 1) having an azide group at the chain end obtained in Synthesis Example 1D were dissolved in tetrahydrofuran to a concentration of 5 mg/ml. of the polymer solution was obtained. The resulting polymer solution was drop-cast onto a glass substrate and allowed to air dry. Next, heat treatment was performed at 150° C. for 30 minutes in a nitrogen atmosphere. Finally, the film was allowed to stand overnight in a petri dish with a lid filled with iodine vapor for iodine doping to prepare a cast film (2.5 cm×2.5 cm).

The thickness of the obtained film was measured. Table 1 shows the results.
In addition, whether or not the obtained film had cracks was visually confirmed. Table 1 shows the results.
Further, the obtained film was measured for sheet resistance (Ω) and resistivity (Ωcm) using a 4-probe measuring jig (manufactured by Kyowa Riken) and a semiconductor parameter analyzer (Model 4155C manufactured by Agilent). Table 1 shows the results.

The block copolymers of Examples 1 to 4 had good sheet resistance and resistivity in addition to no film cracks.
In the block copolymers of Examples 2 and 3, although the ratio of polythiophene was 13 to 14% by mass, the rate of increase in sheet resistance and resistivity was 2 to 3 times that of Comparative Example 1. It was within the range, and the result was very good.
Furthermore, the block copolymer of polythiophene and star polymer of Example 4 had excellent sheet resistance and resistivity.
Comparative polymer 1 (polythiophene) of Comparative Example 1 was found to have film cracks.

(Confirmation of phase separation structure)
Block copolymer 4 obtained in Example 4 was dissolved in tetrahydrofuran to obtain a polymer solution having a concentration of 5 mg/ml. The resulting polymer solution was drop-cast onto a glass substrate and allowed to air dry. Next, heat treatment was performed at 150° C.×5 minutes or 200° C.×5 minutes in a nitrogen atmosphere. The surface state of the obtained film was observed with an atomic force microscope (AFM) to obtain a height image and a phase contrast image. The results are shown in FIGS. 1A-1D and 2A-2D.
1A and 1B are height images of the film after heat treatment at 150° C. for 5 minutes.
1C and 1D are phase-contrast images of the film after heat treatment at 150° C. for 5 minutes.
2A and 2B are height images of the film after heat treatment at 200° C. for 5 minutes.
2C and 2D are phase contrast images of the film after heat treatment at 200° C. for 5 minutes.
No nanocracks or voids were confirmed from the AFM images of the surfaces of all the thin films obtained, regardless of the heat treatment conditions. Furthermore, it was clarified that a nano-level phase separation structure was formed. It is presumed that such a nano-level ordered structure acts as a conductive path and contributes to the development of low sheet resistance and resistivity.

Claims (8)

a polythiophene block comprising polythiophene;
a polymer block containing a polymer of radically polymerizable monomers containing a (meth)acrylic acid compound;
A block copolymer characterized by having 2. The block copolymer according to claim 1, wherein said polythiophene has an alkyl group. 3. The block copolymer according to claim 1 or 2, wherein the polymer is obtained by living radical polymerization. The block copolymer according to any one of claims 1 to 3, wherein the radically polymerizable monomer contains two or more (meth)acrylic acid compounds. 5. The block copolymer according to any one of claims 1 to 4, wherein the polythiophene block and the polymer block are linked by a linking group having a triazole ring. 6. A block copolymer according to any preceding claim, wherein the polymer is a star polymer. A block copolymer production method for producing the block copolymer according to claim 5,
A method for producing a block copolymer, comprising the step of linking the polythiophene block and the polymer block by the following reaction (I) or (II).
(I) a reaction of forming the triazole ring between the azide group of the polythiophene block having an azide group and the alkynyl group of the polymer block having an alkynyl group;
(II) Reaction of the alkynyl group of the polythiophene block having an alkynyl group and the azide group of the polymer block having an azide group to form the triazole ring. the polymer is prepared by reversible addition-fragmentation chain transfer polymerization (RAFT polymerization);
During the reaction (I), the alkynyl group is bound to the cleavage residue of the chain transfer agent,
During the reaction of (II), the azide group is bound to the cleavage residue of the chain transfer agent.
A method for producing the block copolymer according to claim 7 .

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