JP5261717B2 - Block copolymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a block copolymer including a vinyl monomer having a carbazole group and a conjugated vinyl monomer, and a method for producing the same. <P>SOLUTION: The block copolymer includes a polymer block of the vinyl monomer having a carbazole group and a polymer block of the conjugated vinyl monomer. The method for producing the same is also provided. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a block copolymer and a method for producing the same. Specifically, the present invention relates to a block copolymer including a polymer block of a vinyl monomer having a carbazole group and a polymer block of a conjugated vinyl monomer, and a method for producing the same.

Block copolymers in which different types of polymer blocks are bonded are generally produced by successively polymerizing different monomers. Various polymerization methods have been developed so far, and block copolymers using them have been produced.
In the synthesis of block copolymers by Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization, which is one of the techniques of living radical polymerization, the first-stage monomer is homopolymerized using a chain transfer agent having a thiocarbonylthio group. A method of synthesizing a polymer chain transfer agent having a thiocarbonylthio group at the end (macro-chain transfer agent), isolating and purifying, and then polymerizing the next monomer in the second stage is used.

It is also important to consider the block efficiency of the two monomers. For example, the addition of a macro chain transfer agent synthesized from monomer A [ASC (= S) -Z] to monomer B may result in the addition of a macro chain transfer agent synthesized from monomer B [BSC ( = S) -Z] may be more efficient than addition to monomer A. Actually, when a block copolymer such as poly (A) -b-poly (B) is synthesized by polymerizing monomer B in the presence of a macro chain transfer agent [A-S-C (= S) -Z], The chain transfer agent [A-S-C (= S) -Z] must have a high chain transfer constant, that is, the elimination ability of the growing chain radical (A.) is higher or lower than that of the B. radical. (Non-Patent Document 1). Otherwise, it is said that block copolymers of conjugated monomers and non-conjugated monomers are generally not polymerizable.
G. Moad et al. / Polymer 49 (2008) 1079-1131

  The subject of this invention is providing the block copolymer containing the polymer block of the vinyl monomer which has a carbazole group, and the polymer block of a conjugated vinyl monomer, and its manufacturing method.

The present invention relates to the following inventions.
1. A block copolymer comprising a block (A) containing a repeating unit of a vinyl monomer having a carbazole group and a block (B) containing a repeating unit of a conjugated vinyl monomer.

2. A block copolymer comprising a block (A) containing a vinyl monomer repeating unit having a carbazole group and a block (B) containing a vinyl monomer repeating unit having a Q value of 0.2 or more in the Qe scheme, The block copolymer according to the above, having a weight average molecular weight of 2,000 to 40,000.

3. (A) an organic tellurium compound represented by formula (1),
(B) a mixture of an organic tellurium compound represented by formula (1) and an azo polymerization initiator,
(C) A mixture of an organic tellurium compound represented by formula (1) and an organic ditellurium compound represented by formula (2), or (d) an organic tellurium compound represented by formula (1), an azo polymerization initiator. And an organic tellurium compound-based polymerization initiator selected from a mixture of organic ditellurium compounds represented by the formula (2):
Process for producing a block copolymer comprising a block (A) containing a vinyl monomer having a carbazole group for polymerizing a vinyl monomer having a carbazole group and a conjugated vinyl monomer, and a block (B) containing a repeating unit of the conjugated vinyl monomer .

（式中、Ｒ^１は、炭素数１〜８のアルキル基、アリール基、置換アリール基又は芳香族ヘテロ環基を示す。Ｒ^２及びＲ^３は、水素原子又は炭素数１〜８のアルキル基を示す。Ｒ^４は、アリール基、置換アリール基、芳香族ヘテロ環基、アシル基、アミド基、オキシカルボニル基又はシアノ基を示す。）
（Ｒ^１Ｔｅ）_２ （２）
（Ｒ^１は上記に同じ）

(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ² and R ³ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group, or a cyano group.
(R ¹ Te) ₂ (2)
(R ¹ is the same as above)

  According to the present invention, a block copolymer including a polymer block of a vinyl monomer having a carbazole group and a polymer block of a conjugated vinyl monomer can be produced.

  Examples of the vinyl monomer having a carbazole group include N-vinylcarbazole and N-ethyl-3-vinylcarbazole.

The conjugated vinyl monomer used in the present invention can be used without any particular limitation, and examples thereof include monomers having a Q value of 0.2 or more in the Qe scheme proposed by Alfrey and Price in 1949. The Q value of the monomer is described in various publications. For example, it is described in the section of Q and e Values for Free Radical Copolymerization of Vinyl Monomers and Telogens on the pages of POLYMER HANDBOOK fourth edition II / 309 to II / 319. Specifically styrene, alpha-methyl styrene, 4-methylstyrene, 2-methylstyrene, styrenes monomers and derivatives thereof such as 3-methylstyrene, blanking Tajien may illustrate dienes monomers such as chloroprene. In this invention, a conjugated vinyl monomer can be used individually by 1 type or 2 or more types.

The method for producing a block copolymer containing a vinyl monomer having a carbazole group and a conjugated vinyl monomer according to the present invention can be obtained by polymerization using an organic tellurium compound-based polymerization initiator. In particular,
(A) an organic tellurium compound represented by formula (1),
(B) a mixture of an organic tellurium compound represented by formula (1) and an azo polymerization initiator,
(C) A mixture of an organic tellurium compound represented by formula (1) and an organic ditellurium compound represented by formula (2), or (d) an organic tellurium compound represented by formula (1), an azo polymerization initiator. And an organic tellurium compound-based polymerization initiator selected from a mixture of organic ditellurium compounds represented by formula (2).

  The organic tellurium compound used in the present invention is represented by the formula (1).

（式中、Ｒ^１は、炭素数１〜８のアルキル基、アリール基、置換アリール基又は芳香族ヘテロ環基を示す。Ｒ^２及びＲ^３は、水素原子又は炭素数１〜８のアルキル基を示す。Ｒ^４は、アリール基、置換アリール基、芳香族ヘテロ環基、アシル基、アミド基、オキシカルボニル基又はシアノ基を示す。）

(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ² and R ³ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group, or a cyano group.

Specific examples of the group represented by R ¹ are as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclobutyl group, and n-pentyl. Examples thereof include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms such as a group, n-hexyl group, n-heptyl group and n-octyl group. A preferable alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms. More preferably, a methyl group, an ethyl group, or an n-butyl group is good.
Examples of the aryl group include a phenyl group and a naphthyl group. A preferred aryl group is a phenyl group. Examples of the substituent of the substituted aryl include an alkyl group having 1 to 8 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by —COR ^a (R ^a = carbon number). 1-8 alkyl groups, aryl groups, C1-C8 alkoxy groups, aryloxy groups), sulfonyl groups, trifluoromethyl groups, and the like.

A preferred substituted aryl group is a trifluoromethyl-substituted phenyl group.
These substituents may be substituted one or two, and the para position or ortho position is preferable.
Examples of the aromatic heterocyclic group include a pyridyl group, a pyrrole group, a furyl group, and a thienyl group.

Each group represented by R ² and R ³ is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as those described above for R ¹ .

Specific examples of each group represented by R ⁴ are as follows.
Examples of the aryl group, substituted aryl group, and aromatic heterocyclic group include the same groups as those described above for R ¹ .
Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.
Examples of the amide group include carboxylic acid amides such as acetamide, malonamide, succinamide, maleamide, benzamide, and 2-fluamide, thioamides such as thioacetamide, hexanedithioamide, thiobenzamide, and methanethiosulfonamide, selenoacetamide, hexanediselenoamide, Examples include selenoamides such as selenobenzamide and methaneselenosulfonamide, N-substituted amides such as N-methylacetamide, benzanilide, cyclohexanecarboxanilide, and 2,4′-dichloroacetanilide.
Examples of the oxycarbonyl group include a group represented by -COOR ^b (R ^b = H, an alkyl group having 1 to 8 carbon atoms, an aryl group).
Specifically, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group, etc. Can be mentioned.

Preferred oxycarbonyl groups are a methoxycarbonyl group and an ethoxycarbonyl group.
Each group represented by R ⁴ is preferably an aryl group, a substituted aryl group, an oxycarbonyl group or a cyano group.
A preferred aryl group is a phenyl group.
Preferred examples of the substituted aryl group include a halogen atom substituted phenyl group and a trifluoromethyl substituted phenyl group.
In addition, in the case of a halogen atom, these substituents are preferably substituted by 1 to 5 pieces.
In the case of an alkoxy group or a trifluoromethyl group, one or two substituents may be substituted. In the case of one substitution, the para position or the ortho position is preferable, and in the case of two substitutions, the meta position is preferable. .
Preferred oxycarbonyl groups are a methoxycarbonyl group and an ethoxycarbonyl group.

As the preferred organic tellurium compound represented by (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , R ⁴ is preferably an aryl group, a substituted aryl group, or an oxycarbonyl group.
Particularly preferably, R ¹ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴ represents a phenyl group, A substituted phenyl group, a methoxycarbonyl group, and an ethoxycarbonyl group are preferable.

The organic tellurium compound represented by the formula (1) is specifically as follows.
(Methylterranylmethyl) benzene, (methylterranylmethyl) naphthalene, ethyl-2-methyl-2-methylterranyl-propionate, ethyl-2-methyl-2-butylterranyl-propionate, and Patent Documents 1 and 2 All of the organic tellurium compounds can be exemplified.

The production method of the organic tellurium compound represented by the formula (1) is not particularly limited, and can be produced by a known method described in Patent Documents 1 and 2 and the like.
WO 2004/14848 WO 2004/14962

For example, the compound of formula (1) can be produced by reacting a compound of formula (3), a compound of formula (4) and metal tellurium.
Specific examples of the compound of the formula (3) are as follows.

〔式中、Ｒ^２、Ｒ^３及びＲ^４は、上記と同じ。Ｘは、ハロゲン原子を示す。〕
Ｘで示される基としては、フッ素、塩素、臭素又はヨウ素等のハロゲン原子を挙げることができる。好ましくは、塩素、臭素が良い。
Ｍ（Ｒ^１）ｍ （４）
〔Ｒ^１は、上記と同じ。Ｍは、アルカリ金属、アルカリ土類金属又は銅原子を示す。Ｍがアルカリ金属の時、ｍは１、Ｍがアルカリ土類金属の時、ｍは２、Ｍが銅原子の時、ｍは１または２を示す。〕

[Wherein R ² , R ³ and R ⁴ are the same as above. X represents a halogen atom. ]
Examples of the group represented by X include halogen atoms such as fluorine, chlorine, bromine and iodine. Preferably, chlorine and bromine are good.
M (R ¹ ) m (4)
[R ¹ is the same as above. M represents an alkali metal, alkaline earth metal or copper atom. When M is an alkali metal, m is 1, when M is an alkaline earth metal, m is 2, and when M is a copper atom, m is 1 or 2. ]

Examples of M include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, and copper. Lithium is preferable.
When M is magnesium, the compound (4) may be Mg (R ¹ ) ₂ or a compound represented by R ¹ MgX (X is a halogen atom) (Grignard reagent). X is preferably chlorine or bromine.

The organic ditellurium compound used in the present invention is represented by the formula (2).
(R ¹ Te) ₂ (2)
(R ¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, or an aromatic heterocyclic group.)
The group represented by R ¹ is as shown in Formula (1).
Preferred compounds represented by the formula (2) are compounds in which R ¹ is an alkyl group having 1 to 4 carbon atoms and a phenyl group.

  Specifically, the compound represented by the formula (2) includes dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, dicyclopropylditelluride, di-n- Butyl ditelluride, di-sec-butyl ditelluride, di-tert-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis- (p -Nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthylditelluride, dipyridylditelluride and the like. Preferred are dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride, and diphenyl ditelluride.

  In the present invention, an azo polymerization initiator may be used for the purpose of accelerating the polymerization rate. The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization.

  For example, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid) (ACVA) 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methylbutyramide), 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (2-methylamidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [ 2-Methyl-N- 2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2-methyl) Propionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) and the like.

  These azo initiators are preferably selected as appropriate according to the reaction conditions. For example, in the case of low temperature polymerization (40 ° C. or lower), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), In the case of medium temperature polymerization (40-80 ° C.), 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), dimethyl-2,2 '-Azobisisobutyrate (MAIB), 1,1'-azobis (1-acetoxy-1-phenylethane), 4,4'-azobis (4-cyanovaleric acid) (ACVA), 2,2'- Azobis (2-methylbutyramide), 2,2′-azobis (2-methylamidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], high temperature polymerization ( 1,1'- in the case of 80 ° C or higher) Zobis (1-cyclohexanecarbonitrile) (ACHN), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl) 2-methylpropionamide), 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] Is good.

  The proportion of the vinyl monomer and the compound of formula (1) used may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the copolymer to be obtained. Usually, the vinyl monomer is added to 20 mol of the compound of formula (1). ˜4,000 mol, preferably 40 to 400 mol.

  The use ratio of the compound of formula (1) and the azo polymerization initiator is usually 0.01-100 mol, preferably 0.1-10 mol, particularly azo polymerization initiator, with respect to 1 mol of the compound of formula (1). Preferably it is 0.1-5 mol.

  When the compound of the formula (1) and the compound of the formula (2) are used in combination, the use amount thereof is usually 0.01 to 100 mol of the compound of the formula (2) with respect to 1 mol of the compound of the formula (1), preferably Is 0.05 to 10 mol, particularly preferably 0.1 to 5 mol.

  When the compound of the formula (1), the compound of the formula (2) and the azo polymerization initiator are used in combination, the amount used is usually 1 mol of the total of the compound of the formula (1) and the compound of the formula (2). The azo polymerization initiator may be 0.01 to 100 mol, preferably 0.1 to 10 mol, and particularly preferably 0.1 to 5 mol.

  The reaction is usually carried out without a solvent, but an organic solvent or an aqueous solvent generally used in radical polymerization may be used. Examples of the organic solvent that can be used include benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, hexafluoroisopropanol, chloroform, carbon tetrachloride, Tetrahydrofuran (THF), ethyl acetate, trifluoromethylbenzene and the like can be mentioned. Examples of the aqueous solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, diacetone alcohol and the like. The amount of the solvent used may be adjusted as appropriate. For example, 0.01 to 50 ml, preferably 0.05 to 10 ml, particularly preferably 0.1 to 1 ml of the solvent is used per 1 g of the vinyl monomer. good.

  Next, the mixture is stirred. The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the copolymer to be obtained, but are usually stirred at 0 to 150 ° C. for 1 minute to 100 hours. Preferably, stirring is performed at 20 to 100 ° C. for 0.1 to 30 hours. More preferably, stirring is performed at 20 to 80 ° C. for 0.1 to 15 hours. It is a feature of the present invention that a high yield and a precise molecular weight distribution can be obtained even at such a low polymerization temperature and a short polymerization time. At this time, the pressure is usually a normal pressure, but may be increased or decreased.

  After completion of the reaction, the solvent or residual monomer is removed under reduced pressure by a conventional method to take out the target polymer, or the target product is isolated by reprecipitation using a target polymer insoluble solvent. The reaction treatment can be performed by any treatment method as long as there is no problem with the object.

Moreover, since the organic tellurium compound used as an initiator in the present invention is stable to water, the copolymer of the present invention can be synthesized by an aqueous polymerization method described in Patent Document 3 and the like shown below.
That is, the emulsion polymerization method uses a surfactant and polymerizes mainly in micelles. You may use dispersing agents, such as water-soluble polymers, such as polyvinyl alcohol, as needed. These surfactants can be used alone or in combination of two or more. The amount of the surfactant used is preferably 0.3 to 50 parts by weight, more preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of the total monomers. Moreover, it is preferable that the usage-amount of water is 50-2000 weight part with respect to 100 weight part of all the monomers, More preferably, it is 70-1500 weight part. Although superposition | polymerization temperature is not specifically limited, It is preferable to carry out in the range of 0-100 degreeC, More preferably, it is 40-90 degreeC. What is necessary is just to set reaction time suitably so that a polymerization reaction may be completed according to reaction temperature or the composition of the monomer composition to be used, the kind of surfactant or a polymerization initiator, etc. Preferably within 24 hours.

  In the suspension polymerization method, a dispersant is used, and polymerization is mainly performed without using micelles. If necessary, a dispersing aid such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, or manganese sulfate may be used in combination with these dispersing agents. The amount of the water dispersion stabilizer used is preferably from 0.01 to 30 parts by weight, more preferably from 0.05 to 10 parts by weight, particularly preferably from 0.1 to 100 parts by weight based on 100 parts by weight of the total monomers. 5 parts by weight. Moreover, it is preferable that the usage-amount of water is 50-2000 weight part with respect to 100 weight part of all the monomers, More preferably, it is 70-1500 weight part. Although superposition | polymerization temperature is not specifically limited, It is preferable to carry out in the range of 0-100 degreeC, More preferably, it is 40-90 degreeC. What is necessary is just to set reaction time suitably so that a polymerization reaction may be completed according to reaction temperature or the composition of the monomer composition to be used, the kind of water dispersion stabilizer, a polymerization initiator, etc. Preferably within 24 hours.

In the miniemulsion polymerization method, a surfactant and a co-surfactant are used, and after the monomers are forcibly dispersed using a homogenizer or an ultrasonic device, the polymerization is performed mainly without passing through micelles. The amount of the surfactant or cosurfactant used is 0.3 to 50 parts by weight, particularly preferably 0.5 to 50 parts by weight, based on the total monomers. The ultrasonic irradiation time is 0.1 to 10 minutes, particularly preferably 0.2 to 5 minutes.
JP 2006-225524 A

The molecular weight of the copolymer can be adjusted by the reaction time, the amount of the compound of the formula (1) and the amount of the compound of the formula (2), but a living radical polymer having a weight average molecular weight of 2,000 to 40,000 is used. Can be obtained.
In the present invention, the proportion of the block (A) is 10 to 90% by weight, more preferably 20 to 80% by weight, and the proportion of the block (B) is 90 to 10% by weight, more preferably 80 to 20% by weight. Is good.

  The molecular weight distribution (PD = Mw / Mn) of the copolymer is controlled between 1.0 and 2.0. Furthermore, it is possible to obtain a copolymer having a narrower molecular weight distribution of 1.05 to 1.90, more preferably 1.05 to 1.80.

As a method for producing the block copolymer of the present invention, a vinyl monomer (a) having vinyl carbazole is polymerized, and then a conjugated monomer (b) is polymerized. If the order of reaction is reversed, the segment (b) -segment (a) can also be obtained.
In the above, after the production of each segment, the reaction of the next block may be started as it is, or after the reaction is finished once, the reaction of the next segment may be started after purification. Isolation of the block copolymer can be performed by a usual method.

  The block polymer of the present invention uses a hole-injecting material, a hole-injecting material, a hole-transporting material, a hole-transporting material, a hole-transporting property, a high refractive index, and a nano-sized phase separation structure construction characteristic by self-organization of the block polymer It can be used in organic EL materials such as transport materials, light emitting layer materials, electron transport materials, organic transistor materials, hologram recording materials, electrophotographic photoreceptors, optical film materials, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, it is not limited to these at all. In Examples and Comparative Examples, various physical properties were measured using the following equipment.
¹ H NMR: JNM-ECX400 (400 MHz)
Molecular weight and molecular weight distribution: Tosoh pump DP-8020, Viscotek triple detector (refractive detector, viscosity detector, light scattering detector: 630 nm) TDA model-301 (column: TSK-GEL guard column H _XL- H and TSK-GEL GMH _XL + G4000H _XL + G3000H _XL + G2500H _XL , polystyrene standard: TOSOH TSK Standard) THF solvent elemental analysis: Perkin-Elmer 2400II CHNS / O analyzer

Example 1
In a test tube for poly N-vinylcarbazole-styrene diblock polymer, 3.0 mg (0.018 mmol) of AIBN as an initiator and 0.350 g (1.8 mmol) of N-vinylcarbazole, 0.53 ml of 1,4-dioxane After replacing with nitrogen, 11 mg (0.036 mmol) of ethyl-2-methyl-2-n-butylterranyl-propionate was added and reacted at 60 ° C. for 5 hours. After the reaction, a small amount was taken out and subjected to ¹ H NMR and SEC (size exclusion chromatography) analysis, and it was confirmed that the conversion rate was 98%, M _n = 6700, M _{n, RALLS} = 10800, PD = 1.08. . Subsequently, 0.17 g (1.7 mmol) of styrene was added to the reaction solution and reacted at 60 ° C. for 24 hours. After completion of the reaction, the reaction solution was diluted with a small amount of chloroform, and then the solution was added dropwise to stirring methanol. The precipitated polymer was suction filtered and dried to obtain 0.44 g (yield 86%) of poly N-vinylcarbazole-styrene diblock polymer. From the SEC analysis, it was _Mn = 9700, _{Mn, RALLS} = 13900, PD = 1.18. The composition ratio was calculated from the absolute molecular weight ( _{Mn, RALLS} ) of the poly (NVC) prepolymer and the elemental analysis of the block copolymer, and it was poly (NVC): poly (St) = 59: 41. .

Example 2
In a test tube for poly N-vinylcarbazole-styrene diblock polymer, 3.0 mg (0.018 mmol) of AIBN as an initiator and 0.350 g (1.8 mmol) of N-vinylcarbazole, 0.53 ml of 1,4-dioxane After replacing with nitrogen, 11 mg (0.036 mmol) of ethyl-2-methyl-2-n-butylterranyl-propionate was added and reacted at 60 ° C. for 5 hours. After the reaction, a small amount was taken out and subjected to ¹ H NMR and SEC analysis, and it was confirmed that the conversion rate was 97%, M _n = 7100, M _{n, RALLS} = 9500, PD = 1.09. Subsequently, 0.37 g (3.5 mmol) of styrene was added to the reaction solution and reacted at 60 ° C. for 24 hours. After completion of the reaction, the reaction solution was diluted with a small amount of chloroform, and then the solution was added dropwise to stirring methanol. The precipitated polymer was suction filtered and dried to obtain 0.57 g (yield 79%) of poly N-vinylcarbazole-styrene diblock polymer. From the SEC analysis, it was _Mn = 14400, _{Mn, RALLS} = 17800, PD = 1.26. The composition ratio was calculated from the absolute molecular weight ( _{Mn, RALLS} ) of the prepolymer poly (NVC) and the elemental analysis of the block copolymer, and it was poly (NVC): poly (St) = 40: 60. .

2 is a SEC chart of Example 1. The chart on the right side shows the first stage poly N-vinyl carbazole, and the chart on the left side shows the poly N-vinyl carbazole-styrene diblock polymer. 6 is a SEC chart of Example 2. The chart on the right side shows the first stage poly N-vinyl carbazole, and the chart on the left side shows the poly N-vinyl carbazole-styrene diblock polymer. 2 is a ¹ H NMR chart of a poly N-vinylcarbazole-styrene diblock polymer obtained in Example 1. FIG.

Claims (2)

(A) an organic tellurium compound represented by formula (1),
(B) a mixture of an organic tellurium compound represented by formula (1) and an azo polymerization initiator,
(C) A mixture of an organic tellurium compound represented by formula (1) and an organic ditellurium compound represented by formula (2), or (d) an organic tellurium compound represented by formula (1), an azo polymerization initiator. And an organic tellurium compound-based polymerization initiator selected from a mixture of organic ditellurium compounds represented by the formula (2):
A block containing a repeating unit of a vinyl monomer having a carbazole group (A) and a block containing a repeating unit of a conjugated vinyl monomer (B) , characterized by polymerizing a vinyl monomer having a carbazole group and then polymerizing a conjugated vinyl monomer ) Containing a block copolymer.

(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ² and R ³ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group, or a cyano group.
(R ¹ Te) ₂ (2)
(R ¹ is the same as above) The method for producing a block copolymer according to claim 1 , wherein the conjugated vinyl monomer is a vinyl monomer having a Q value of 0.2 or more in the Qe scheme.

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