JP5963516B2 - Method for producing polymer and polymer produced by the method - Google Patents

Description

  The present invention relates to a method for producing a polymer by a selective and highly efficient dimerization reaction at a growth end of a polymer synthesized by a living radical polymerization method, and a polymer produced by the method.

  Living radical polymerization is a polymerization method that enables control of the molecular structure while maintaining the simplicity and versatility of radical polymerization, and is very effective in the synthesis of new polymer materials. Among these, a block copolymer having a controlled structure produced by adding a different monomer to the polymerization growth terminal and polymerizing is expected to be a treasure house of functional materials.

  The present inventors have reported a living radical polymerization method using an organic tellurium compound as an initiator (Patent Document 1 and Patent Document 2). For example, in Patent Document 1, a living radical polymer whose molecular weight and molecular weight distribution (PDI) are precisely controlled is obtained by polymerization at 80 to 105 ° C. using an organic tellurium compound. Moreover, in patent document 2, the living radical polymer by which molecular weight and molecular weight distribution (PDI) were controlled precisely was obtained by superposing | polymerizing at 80-120 degreeC using an organic tellurium compound and a ditelluride compound. These polymerization methods enable the polymerization of various vinyl monomers. However, when the molecular weight increases, there is a problem that the reaction time is long and the yield is poor. Furthermore, in order to obtain a block copolymer, particularly a copolymer having more polymer blocks than a triblock copolymer, there are significant restrictions on the types of block segments that can be used.

  Furthermore, the present inventors have reported a living radical polymerization method of a vinyl monomer using an organic tellurium polymerization initiator by light irradiation (Patent Document 3). It is possible to control precise molecular weight and molecular weight distribution even under light irradiation conditions. Furthermore, the polymerization of a thermally unstable monomer is possible and the polymerization can be performed at a low temperature. Therefore, the polymerization can be performed while suppressing side reactions caused by heat. However, it has the same problem as thermal polymerization, that is, it is difficult to synthesize a high molecular weight substance, and there are restrictions on the synthesis of a block copolymer.

  Therefore, a production method capable of obtaining a high molecular weight polymer with a controlled molecular weight and molecular weight distribution in a high yield and in a short time and a production method capable of obtaining a multiblock copolymer with a high degree of freedom are desired. ing.

International Publication No. 2004/14848 Pamphlet International Publication No. 2004/14962 Pamphlet JP 2007-302737 A

  An object of the present invention is to provide a method for efficiently and selectively producing a polymer having a controlled molecular weight and molecular weight distribution by dimerization by a coupling reaction of a living radical polymer, and a block copolymer as a living radical polymer. It is to provide a multi-block copolymer by using.

  The method for producing a polymer according to the first aspect of the present invention includes a step of preparing a macro-living initiator, a step of adding a conjugated olefin compound to the macro-living initiator, and light irradiation after adding the compound. And a step of selectively dimerizing a radical having the structural unit derived from the compound as a polymerization growth terminal by a coupling reaction.

  The step of irradiating with light according to the first aspect of the present invention may be a step of adding the compound, heating and polymerizing the compound with a macro living initiator, and then irradiating with light. Thereby, the block copolymer containing the block which consists of a polymer of the said compound can be manufactured.

  In addition, the method for producing a polymer according to the second aspect of the present invention includes a step of adjusting a macro-living radical initiator having a structural unit derived from a conjugated olefin compound as a polymerization growth terminal, and irradiating the macro-living initiator with light. And a step of selectively dimerizing a radical having a structural unit derived from a conjugated olefin compound as a polymerization growth terminal, and performing dimerization.

  Hereinafter, matters common to the first and second aspects of the present invention will be described as “the present invention”.

  In the present invention, the step of irradiating light is preferably performed using a light source having a light emission distribution with a wavelength of 300 to 700 nm.

  In the present invention, the step of irradiating with light is preferably performed by irradiating with light at a temperature in the range of -70 ° C to 80 ° C.

  In the present invention, the macro living initiator is preferably prepared by polymerizing a vinyl monomer by a living radical polymerization method using an organic tellurium polymerization initiator.

In this case, the organic tellurium polymerization initiator is
(A) an organic tellurium compound represented by the general formula (1),
(B) a mixture of an organic tellurium compound represented by the general formula (1) and an azo polymerization initiator,
(C) a mixture of an organic tellurium compound represented by the general formula (1) and an organic ditellurium compound represented by the general formula (2), or (d) an organic tellurium compound represented by the general formula (1), an azo type It is preferably any one of a mixture of a polymerization initiator and an organic ditellurium compound represented by the general formula (2).

(.R shown wherein, ^{R 1} represents an alkyl group having 1 to 8 carbon atoms, .R ² and ^{R 3} represents an aryl group or an aromatic heterocyclic group, a hydrogen atom or an alkyl group having 1 to 8 carbon atoms ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group or a cyano group.

(In the formula, R ¹ represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms.)

  The polymer of the present invention is characterized by being produced by the production method of the present invention.

  According to the present invention, a polymer having a controlled molecular weight and molecular weight distribution can be produced in a high yield and in a short time by dimerization by a living radical polymer coupling reaction. Furthermore, a multi-block copolymer having a symmetrical structure can be easily produced by using a macro-living initiator composed of a block copolymer having a controlled structure as a starting substrate.

The figure which shows the GPC chart of the polymer after a dimerization reaction and the macroliving initiator before the dimerization reaction in Examples 1-3, Example 8, and Examples 11-12. The figure which shows the GPC chart of the macroliving initiator before the dimerization reaction in Example 16 and Comparative Examples 1-3 and the polymer after the dimerization reaction. The figure for demonstrating the peak division | segmentation method in a GPC chart.

  In the first aspect of the present invention, as described above, after adding a conjugated olefin compound to the macro-living initiator and then irradiating with light, a radical having the compound as a polymerization growth terminal is selectively coupled. It is dimerized by reaction.

  In the second aspect of the present invention, as described above, by irradiating the macro-living initiator with light, a radical having a constitutional unit derived from a conjugated olefin compound as a polymerization growth terminal is selectively subjected to a coupling reaction. It is quantified.

  Hereinafter, the present invention will be described in more detail.

<Preparation of macro living initiator>
In the present invention, the macro living initiator refers to a compound having a tellurium atom at the polymer terminal in the form of -TeR ¹ (R ¹ is the same as above).

  The macro living initiator can be obtained, for example, by polymerizing a vinyl monomer by a living radical polymerization method using an organic tellurium compound-based polymerization initiator described in Patent Document 1 and Patent Document 2.

In particular,
(A) an organic tellurium compound represented by the general formula (1),
(B) a mixture of an organic tellurium compound represented by the general formula (1) and an azo polymerization initiator,
(C) a mixture of an organic tellurium compound represented by the general formula (1) and an organic ditellurium compound represented by the general formula (2), or (d) an organic tellurium compound represented by the general formula (1), an azo type Polymerization is performed using an organic tellurium compound-based polymerization initiator which is any of a mixture of a polymerization initiator and an organic ditellurium compound represented by formula (2).

  Examples of the organic tellurium compound-based initiator used in the present invention include those represented by the general formula (1).

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.

The aryl group is a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, or ^a carbonyl-containing group represented by —COR ^a [R ^a = an alkyl group having 1 to 8 carbon atoms (preferably carbon A linear or branched alkyl group having 1 to 4 carbon atoms), an alkoxy group having 1 to 8 carbon atoms (preferably a linear or branched alkoxy group having 1 to 4 carbon atoms), an aryl group, and aryloxy Group], a sulfonyl group, a trifluoromethyl group and the like may have 1 to 4 substituents (preferably 1 to 3, more preferably 1, para position or ortho position). Specific examples of the aryl group include a phenyl group, a naphthyl group, a halogen atom-substituted phenyl group, and a trifluoromethyl-substituted phenyl group, and a phenyl group 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 alkyl group, aryl group, and aromatic heterocyclic group having 1 to 8 carbon atoms 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.

As the oxycarbonyl group, -COOR ^b [R ^b = H, an alkyl group having 1 to 8 carbon atoms (preferably a linear or branched alkyl group having 1 to 4 carbon atoms), or 2 to 8 carbon atoms. Alkenyl group (preferably linear or branched alkenyl group having 2 to 4 carbon atoms), alkynyl group having 2 to 8 carbon atoms (preferably linear or branched alkynyl group having 2 to 4 carbon atoms) ), An aryl group]. The alkyl group having 1 to 8 carbon atoms, the alkenyl group having 2 to 8 carbon atoms, the alkynyl group having 2 to 8 carbon atoms, and the aryl group represented by R ^b are a halogen atom, a hydroxyl group, and 1 to 8 carbon atoms at any position. Alkoxy groups, trialkylsilyl ether groups (wherein the alkyl has 1 to 8 carbon atoms), trialkylsilyl groups (the alkyl has 1 to 8 carbon atoms), amino groups, nitro groups, cyano groups, sulfonyl groups, trifluoromethyl It may have 1 to 4 substituents such as a group (preferably 1 to 3, more preferably 1). Specific examples of the oxycarbonyl group include a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an n-butoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an n-pentoxycarbonyl group, Phenoxycarbonyl group etc. can be mentioned, Preferably a methoxycarbonyl group and an ethoxycarbonyl group are good.

As each group represented by R ⁴ , an aryl group, an oxycarbonyl group or a cyano group is preferable.

As an organic tellurium compound represented by the general formula (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 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, and R ⁴ represents a phenyl group or a methoxycarbonyl group. An ethoxycarbonyl group is preferable.

  Specific examples of the organic tellurium compound represented by the general formula (1) include (methylterranylmethyl) benzene, (methylterranylmethyl) naphthalene, ethyl-2-methyl-2-methylterranyl-propionate, and ethyl-2-methyl. 2-n-butyl terranyl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methyl terranyl-propionate, (2-hydroxyethyl) -2-methyl-2-methyl terranyl-propionate, (3-trimethylsilylpropargyl) All of the organic tellurium compounds described in Patent Document 1, Patent Document 2, etc., such as 2-methyl-2-methylterranyl-propinate, can be exemplified.

  The method for producing the organic tellurium compound represented by the general formula (1) is not particularly limited, and can be produced by a known method described in Patent Document 1, Patent Document 2, and the like.

  For example, the compound of the general formula (1) can be produced by reacting the compound of the general formula (3), the compound of the general formula (4) and metal tellurium.

(In the formula, 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.

(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, M When is a copper atom, m represents 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 of the general formula (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.

  Examples of other organic tellurium compounds used in the present invention include those represented by the general formula (2).

The group represented by R ¹ is as shown in the general formula (1).

As a preferable compound represented by the general formula (2), R ¹ is preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group.

  Specific examples of the compound represented by the general formula (2) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, 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, Examples include 2'-azobis (N-butyl-2-methylpropionamide), 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 intermediate 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 In the case of 80 ° C. or higher, 1,1′-azobis (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] may be used.

  The amount of the compound of the general formula (1) may be appropriately adjusted according to the molecular weight or molecular weight distribution of the obtained macro-living initiator. Usually, the compound of the general formula (1) is 0.5% with respect to 10 mol of the vinyl monomer. It is good to set it as -200 mmol, Preferably it is 1-100 mmol.

  The ratio of the compound of the general formula (1) to the azo polymerization initiator is usually 0.01 to 100 mol, preferably 0.1 to 10 mol mol of the azo polymerization initiator with respect to 1 mol of the compound of the general formula (1). Particularly preferably, the content is 0.1 to 5 mol.

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

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

  The reaction for obtaining the macro living initiator can be carried out without a solvent, but can be carried out using an organic solvent or an aqueous solvent generally used in radical polymerization. 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, hexafluoroisopropol, chloroform, tetrachloride. Carbon, tetrahydrofuran (THF), ethyl acetate, trifluoromethylbenzene, N-methyl-N-methoxymethylpyrrolidinium tetrafluoroborate, N-methyl-N-ethoxymethyltetrafluoroborate 1-methyl 3-methylimidazolium tetra Examples thereof include ionic liquids such as fluoroborate, 1-methyl 3-methylimidazolium hexafluorophosphate, and 1-methyl 3-methylimidazolium chloride. 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, the solvent is 0.01 to 50 L, preferably 0.05 to 10 L, particularly preferably 0.0 to 10 g based on 1000 g of the obtained macro living initiator. 1-5L is good.

  A macro living initiator can be obtained by stirring a mixture of an organic tellurium compound polymerization initiator and a vinyl monomer. The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the macroliving initiator 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. Thus, even with a low polymerization temperature and a short polymerization time, a high yield and a precise molecular weight distribution can be obtained. At this time, the pressure is usually a normal pressure, but may be increased or decreased.

  After completion of the reaction, the target macro living initiator can be taken out by removing the used solvent and residual monomer under reduced pressure by a conventional method, or the target macro living initiator can be isolated by reprecipitation using an insoluble solvent. it can. The reaction treatment can be performed by any treatment method as long as there is no problem with the object. Moreover, a macro living initiator can also be used as it is, without isolating.

  The molecular weight of the macro-living initiator can be adjusted by the reaction time, the amount of the compound of the general formula (1) and the amount of the compound of the general formula (2), but is preferably in the range of 2000 to 2000000 in weight average molecular weight. More preferably, the weight average molecular weight is in the range of 5,000 to 1,000,000.

  The molecular weight distribution (PDI = Mw / Mn) of the macroliving initiator is controlled between 1.05 and 2.00. Furthermore, it is possible to obtain a macro-living initiator having a molecular weight distribution of 1.05 to 1.80, and a narrower molecular weight distribution of 1.05 to 1.50.

  The vinyl monomer used for obtaining the macro living initiator of the present invention can be used without particular limitation as long as radical polymerization is possible. These are used individually by 1 type or in mixture of 2 or more types.

  For example, the following can be mentioned as a vinyl monomer used for this invention.

  Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid-2- (Meth) acrylic acid esters such as hydroxyethyl.

  Cycloalkyl group-containing unsaturated monomers such as cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and cyclododecyl (meth) acrylate.

  (Meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride and other carboxyl group-containing unsaturated monomers.

  3 such as N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, 2- (dimethylamino) ethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, etc. Secondary amine-containing unsaturated monomer.

  Quaternary ammonium base-containing unsaturated monomers such as N-2-hydroxy-3-acryloyloxypropyl-N, N, N-trimethylammonium chloride and N-methacryloylaminoethyl-N, N, N-dimethylbenzylammonium chloride.

  Epoxy group-containing unsaturated monomers such as (meth) glycidyl acrylate.

  Styrene, α-methylstyrene, 4-methylstyrene (p-methylstyrene), 2-methylstyrene (o-methylstyrene), 3-methylstyrene (m-methylstyrene), 4-methoxystyrene (p-methoxystyrene) P-tert-butylstyrene, pn-butylstyrene, p-tert-butoxystyrene, 2-hydroxymethylstyrene, 2-chlorostyrene (o-chlorostyrene), 4-chlorostyrene (p-chlorostyrene), Aromatic unsaturated monomers (styrene monomers) such as 2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, p-styrenesulfonic acid or alkali metal salts thereof (sodium salt, potassium salt, etc.).

  Heterocycle-containing unsaturated monomers such as 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine and 4-vinylpyridine.

  Vinylamides such as N-vinylformamide and N-vinylacetamide.

  (Meth) acrylamides such as (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like.

  Α-olefins such as 1-hexene, 1-octene and 1-decene.

  Dienes such as butadiene, isoprene, 4-methyl-1,4-hexadiene and 7-methyl-1,6-octadiene.

Carboxylic acid vinyl esters such as vinyl acetate and vinyl benzoate.
Hydroxyethyl (meth) acrylate. (Meth) acrylonitrile. Methyl vinyl ketone. Vinyl chloride. Vinylidene chloride.

  Among these, (meth) acrylic acid ester, cycloalkyl group-containing unsaturated monomer, aromatic unsaturated monomer (styrene monomer), (meth) acrylamide, (meth) acrylonitrile, and methyl vinyl ketone are preferable.

  Preferred (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. It is done. Particularly preferred are methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and 2-hydroxyethyl methacrylate.

  Preferred cycloalkyl group-containing unsaturated monomers are cyclohexyl (meth) acrylate and isobornyl (meth) acrylate. Particularly preferred are cyclohexyl methacrylate and isobornyl methacrylate.

  Preferred styrenic monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-methoxystyrene, pt-butylstyrene, pn-butylstyrene, p-tert-butylstyrene, Examples include p-chlorostyrene, p-styrenesulfonic acid or alkali metal salts thereof (sodium salt, potassium salt, etc.). Particularly preferred are styrene and p-chlorostyrene.

  Preferable (meth) acrylamide includes N-isopropyl (meth) acrylamide. Particularly preferred is N-isopropylmethacrylamide.

  The above “(meth) acryl” is a general term for “acryl” and “methacryl”.

  The macro-living initiator can obtain a polymer based on the order of the vinyl monomers to be reacted, regardless of the type of monomer. When the vinyl monomer A and the vinyl monomer B are reacted to obtain a block copolymer, either AB or BA can be obtained depending on the order of reaction. In the above, after manufacturing each block, the reaction of the next block may be started as it is, or the reaction of the next block may be started after purification after finishing the reaction once. Isolation of the block copolymer can be performed by a usual method.

<Dimerization reaction>
The dimerization reaction can be performed by mixing a conjugated olefin compound with a macro living initiator and irradiating with light. Specifically, the macro-living initiator and the conjugated olefin compound are mixed in a container substituted with an inert gas. In this case, examples of the inert gas include nitrogen, argon, helium, carbon dioxide and the like. Argon and nitrogen are preferable.

  The container can be used without any particular limitation. For example, UV glass, hard glass such as Pyrex (registered trademark) glass, or soft glass such as quartz glass can be used.

  The light irradiation method is not particularly limited, and the polymerization can be performed by irradiating light to an immersion type photoreaction apparatus or a normal reaction vessel.

  The amount of the macro-living initiator and the conjugated olefin compound used may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the dimer to be obtained. Usually, the conjugated olefin compound is 1 to 1 mol per 1 mol of the macro-living polymerization initiator. The amount is 20000 mol, preferably 10 to 10000 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, N-methyl-N-methoxymethylpyrrolidinium tetrafluoroborate, N-methyl-N-ethoxymethyltetrafluoroborate 1-methyl 3-methylimidazolium tetrafluoroborate And ionic liquids such as 1-methyl 3-methylimidazolium hexafluorophosphate and 1-methyl 3-methylimidazolium chloride. 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, the solvent is 0.01 to 50 L, preferably 0.05 to 10 L, particularly preferably 0.1 to 5 L with respect to 1000 g of the macro living initiator. good.

  Further, when the reaction is carried out without isolating the macro living initiator, it is usually carried out without a solvent, but an organic solvent or an aqueous solvent generally used in radical polymerization may be used (added). 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, N-methyl-N-methoxymethylpyrrolidinium tetrafluoroborate, N-methyl-N-ethoxymethyltetrafluoroborate 1-methyl 3-methylimidazolium tetrafluoroborate And ionic liquids such as 1-methyl 3-methylimidazolium hexafluorophosphate and 1-methyl 3-methylimidazolium chloride. 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, but the solvent is 0.01 to 50 L, preferably 0.05 to 10 L, particularly preferably 0.1 to 5 L with respect to 1000 g of the macro living initiator.

  Light irradiation, reaction temperature, and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the dimer obtained. In addition, the organic ditellurium compound (2) is quantitatively by-produced by the reaction, and the organic ditellurium compound (2) precipitates metal tellurium by photolysis and blocks light, so that the reaction can be performed with high efficiency and in a short time. May be appropriately adjusted under the following reaction conditions.

  For light irradiation, lamps used for light irradiation are preferably those having a light emission distribution at a light wavelength of 300 to 700 nm. Examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, and an ultrahigh pressure lamp. Examples include mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, xenon lamps, krypton lamps, LED lamps, and organic EL lamps.

  Further, the irradiation wavelength region can be controlled by combining a light source to be irradiated with a glass cut-off filter, a neutral density filter, and a solvent filter. As a preferable irradiation wavelength, it is preferable to use a light source having a light emission distribution in the range of 300 to 600 nm, and it is more preferable to irradiate light having a wavelength in the range of 300 to 450 nm.

  The reaction temperature is preferably -70 ° C to 80 ° C, preferably -70 to 60 ° C, more preferably 0 to 35 ° C.

  The reaction time is not particularly limited because it varies depending on the light irradiation intensity and the irradiation wavelength. Usually, it can be performed in about 1 minute to 100 hours. Preferably 0.1 to 30 hours is good. More preferably, it is 0.1 to 15 hours.

  After the 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.

  In the first aspect of the present invention, the dimerization reaction proceeds as a result of a coupling reaction caused by a radical generated by the reaction of a polymerization growth terminal radical derived from a macro-living initiator with a conjugated olefin compound. Further, as in the second aspect of the present invention, when a macro-living initiator having a structural unit derived from a conjugated olefin compound as a polymerization growth terminal is used for the dimerization reaction, the conjugated olefin compound is not mixed. Quantification reactions can be performed. The conjugated olefin compound used for these reactions can be used without particular limitation as long as it is a conjugated olefin compound that causes radical coupling, and these are used singly or in combination of two or more.

  For example, examples of the conjugated olefin compound used in the present invention include conjugated polyene compounds such as conjugated dienes and conjugated trienes, and olefin compounds conjugated with aromatic groups such as styrene derivatives. Specific examples include the following, but are not limited to these compounds.

  The conjugated polyene compound may have 1 to 4 substituents (preferably 1 to 3, more preferably 1) described later at an arbitrary position. Specifically, 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 2,3-dimethyl -1,3-butadiene, 2,4-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene 2-methyl-1,3-octadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3 -Cyclooctadiene, 1,3-tricyclodecadiene, myrcene, chloroprene, 1,3,5-hexatriene, 1,3,5-heptatriene, trans-2,4-hexadien-1-ol, ethyl sorbate Etc.

  The olefin compound conjugated with the aromatic group may have 1 to 4 substituents (preferably 1 to 3, more preferably 1) described later at an arbitrary position. Specifically, styrene, α-methylstyrene, 4-methylstyrene (p-methylstyrene), 2-methylstyrene (o-methylstyrene), 3-methylstyrene (m-methylstyrene), 4-methoxystyrene ( p-methoxystyrene), p-tert-butylstyrene, pn-butylstyrene, p-tert-butoxystyrene, 2-hydroxymethylstyrene, 2-chlorostyrene (o-chlorostyrene), 4-chlorostyrene (p -Chlorostyrene), 2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, p-styrenesulfonic acid or alkali metal salts thereof (sodium salt, potassium salt, etc.), 2-vinylpyridine, 4-vinylpyridine and the like. Can be mentioned.

Conjugated polyene compound, the substituent of the olefin compound conjugated with an aromatic group, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, a carbonyl-containing group represented by -COR ^c [R ^{c =} carbon 1-8 An alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms), an aryl group], -COOR ^d [R ^d = H, an alkyl group having 1 to 8 carbon atoms (preferably a carbon number) 1-4 linear or branched alkyl group), aryl group], trialkylsilyl ether group (wherein the alkyl has 1 to 8 carbon atoms), trialkylsilyl group (wherein the alkyl has 1 to 8 carbon atoms) , An amino group, a nitro group, a cyano group, a sulfonyl group, a trifluoromethyl group and the like may have 1 to 4 substituents (preferably 1 to 3, more preferably 1).

  Preferred conjugated polyene compounds include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 2,3. -Dimethyl-1,3-butadiene, 2,4-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3 -A linear, branched or cyclic conjugated polyene compound having 1 to 10 carbon atoms such as hexadiene, 2-methyl-1,3-octadiene, myrcene and the like is preferable.

  Preferred olefin compounds conjugated with an aromatic group include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-methoxystyrene, pt-butylstyrene, pn-butylstyrene, p- Examples thereof include tert-butyl styrene, p-chlorostyrene, p-styrene sulfonic acid or alkali metal salts thereof (sodium salt, potassium salt, etc.). Particularly preferred are styrene and p-chlorostyrene.

  In the production method of the present invention, the segment of the macro-living initiator and the segment of the conjugated olefin compound are selectively coupled and then dimerized to double the molecular weight. A block copolymer can be easily obtained. Furthermore, ABCBA pentablock copolymer etc. can be obtained by using the macro living initiator which is a block copolymer.

  In the production method of the present invention, the molecular weight can be easily doubled and the organic ditellurium compound (2) is quantitatively by-produced during the process, so that the organic ditellurium compound (2) is recovered. it can. Further, there is an advantage that it is not necessary to perform a treatment for removing tellurium from the polymer terminal of the obtained block copolymer.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these at all.

  The following apparatus was used for the dimerization reaction.

Equipment: USHIO Optical Modex SX-UI 501HQ type Mercury lamp: Ultra-high pressure mercury lamp 500W (BA-H501)
LED lamp: 365 nm LED lamp (1200 mW, manufactured by Nichia Corporation)
Filter A: L-39 (50% light blocking wavelength 390 nm, manufactured by Asahi Techno Glass)
Filter B: Y-42 (50% light blocking wavelength 420 nm, manufactured by Asahi Techno Glass)

  For the number average molecular weight (Mn) and molecular weight distribution (PDI), GPC [Shodex GPC-104 (column: Shodex LF-604x2), Shodex GPC-101 (column: Shodex LF804, K-805F, K-800RL)] is used. The molecular weight of a polystyrene standard sample (Tosoh TSK Standard) or a polymethyl methacrylate standard sample (Shodex PMMS Standard) was obtained as a reference.

The coupling reaction efficiency (x _c ) of the dimerization reaction was determined by the peak resolution method in GPC analysis. In Examples 1 to 3, 8, 12, and 16 and Comparative Examples 1 to 3, calculation was performed from the formula x _c = 2 * (1-Mn (macroliving initiator) / Mn (product)).

  The peak splitting method in GPC analysis is a comparison of GPC charts before and after the reaction, by measuring the polymer concentration at a constant level to estimate how many components of the curve before the reaction are in the curve after the reaction. This is a method for calculating how much of the polymer before the reaction (that is, the polymer that has not reacted) is contained in the product.

  Specifically, the following procedure can be used.

  1. A predetermined amount (Amg) of the reaction solution before the reaction is taken, and a Bg solvent is added thereto to perform GPC measurement.

  2. A certain amount (Cmg) of the solution after the reaction is taken, and a Dg solvent is added thereto to perform GPC measurement.

  3. The RI intensity is divided by A / B or C / D for each GPC measurement.

  FIG. 3 is a GPC chart for explaining the peak splitting method, and shows the peak converted from the RI intensity. (1) is the curve before the reaction, and (2) is the curve after the reaction.

  4). The peak is reduced by multiplying the curve (1) before the reaction by a coefficient X, and the amount contained in the curve (2) after the reaction is estimated. In the example shown in FIG. 3, X = 0.08 (that is, the remaining amount is 8% and the coupling efficiency is 92%). (3) is a curve obtained by reducing the curve (1) before the reaction by applying the coefficient X as described above. (4) is obtained by subtracting the component of the curve (3) from the curve (2) after the reaction. By subtracting the component (3), the curve (4) has a shape close to a Gaussian distribution curve.

<Manufacture of organic tellurium compounds>
Synthesis example 1 (CTA1)
6.38 g (50 mmol) of metal tellurium (trade name: Tellurium (−40 mesh)) manufactured by Aldrich was suspended in 50 mL of THF, and 52.9 mL of methyllithium (1.04 M diethyl ether solution, 55 mmol) was added to room temperature. Was slowly added dropwise (10 minutes). The reaction solution was stirred until the metal tellurium disappeared completely (20 minutes). To this reaction solution, 10.7 g (55 mmol) of ethyl-2-bromo-isobutyrate was added at room temperature and stirred for 2 hours. After completion of the reaction, the solvent was concentrated under reduced pressure, followed by distillation under reduced pressure to obtain a yellow oil (6.53 g, yield 51%).

^{From 1} H-NMR, ¹³ C-NMR, HRMS, and IR, it was confirmed to be ethyl-2-methyl-2-methylterranyl-propinate.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 1.27 (t, J = 6.9 Hz, 3H), 1.74 (s, 6H), 2.15 (s, 3H, TeCH ₃ ), 4.16 (Q, J = 7.2 Hz, 2H); ¹³ C-NMR (75 MHz, CDCl ₃ ): δ-17.38, 13.89, 23.42, 27.93, 60.80, 176.75; HRMS (EI) m / z: found 260.0053, calcd for C ₇ H ₁₄ O ₂ Te [M] ⁺ 260.0056; IR (neat, cm ⁻¹ ): 1700, 1466, 1385, 1296, 1146, 1111 1028

Synthesis example 2 (CTA2)
Metal tellurium (trade name: Tellurium (-200 mesh) manufactured by Aldrich, Inc.) 2.57 g (20 mmol) was suspended in 15 mL of THF, and 15.4 mL of methyllithium (1.15 M diethyl ether solution, 21.3 mmol) was added thereto. The solution was slowly added dropwise at room temperature (10 minutes). The reaction solution was stirred until the metal tellurium disappeared (30 minutes). The reaction solution was cooled in an ice bath, 6.0 g (21.3 mmol) of (2-trimethylsiloxyethyl) -2-bromo-isobutyrate was added, and the mixture was stirred at 40 ° C. for 4.5 hours. After completion of the reaction, the reaction solution was washed with an aqueous ammonia chloride solution and an aqueous sodium chloride solution and dehydrated with anhydrous magnesium sulfate. The solvent was concentrated under reduced pressure, followed by distillation under reduced pressure to give a yellow oil (3.48 g, yield 50%).

^{From 1} H-NMR, ¹³ C-NMR, HRMS, and IR, it was confirmed to be (2-trimethylsiloxyethyl) -2-methyl-2-methylterranyl-propinate.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.14 (s, 9H), 1.75 (s, 6H), 2.17 (s, 3H), 3.79 (t, J = 5.2 Hz, 2H), 4.17 (t, J = 5.2 Hz, 2H); ¹³ C-NMR (400 MHz, CDCl ₃ ): δ-17.13, −0.53, 23.18, 27.97, 60. _{31,66.05,176.92; HRMS (FAB) m /} z: found 348.0399, calcd for C 10 H 22 O 3 SiTe [M] + 348.0401; IR (neat, cm -1): 2957 , 1717, 1466, 1252, 1152, 1105

Synthesis example 3 (CTA3)
To a solution of CTA2 (1.28 g, 3.7 mmol) in methanol (18 mL) was slowly added 1.3 mL (22.7 mmol) of acetic acid, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was washed with an aqueous sodium bicarbonate solution and dehydrated with anhydrous sodium sulfate. The solvent was concentrated under reduced pressure, followed by distillation under reduced pressure to give a yellow oil (0.71 g, 70% yield).

^{From 1} H-NMR, ¹³ C-NMR, HRMS, IR, it was confirmed to be (2-hydroxyethyl) -2-methyl-2-methylterranyl-propinate.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.76 (s, 6H), 2.16 (s, 3H), 3.84 (br, 2H), 4.26 (t, J = 4.6 Hz, ¹³ C-NMR (CDCl ₃ ): δ-16.89, 23.63, 27.67, 61.12, 66.42, 177.01; HRMS (FAB) m / z: found 276.0005 , Calcd for C ₇ H ₁₄ O ₃ Te [M] ⁺ 276.0005; IR (neat, cm ⁻¹ ): 3437 (br), 2957, 1710, 1466, 1387, 1260, 1150, 1113, 1080, 1026

Synthesis example 4 (CTA4)
Metal tellurium (trade name: Tellurium (-200 mesh) manufactured by Aldrich, Inc.) 1.23 g (9.5 mmol) was suspended in 7.5 mL of THF, and 7.25 mL of methyllithium (1.38 M diethyl ether solution, 10 mmol) was added thereto. ) Was slowly added dropwise at room temperature (10 minutes). The reaction solution was stirred until the metal tellurium disappeared completely (40 minutes). The reaction solution was cooled in an ice bath, 2.76 g (10 mmol) of (3-trimethylsilylpropargyl) -2-bromo-isobutyrate was added, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was washed with an aqueous ammonia chloride solution and an aqueous sodium chloride solution and dehydrated with anhydrous magnesium sulfate. The solvent was concentrated under reduced pressure followed by distillation under reduced pressure to give a yellow oil (1.74 g, 54% yield).

^{From 1} H-NMR, it was confirmed that it was (3-trimethylsilylpropargyl) -2-methyl-2-methylterranyl-propinate.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.18 (s, 9H), 1.76 (s, 6H), 2.18 (s, 3H), 4.70 (s, 2H)
The structural formulas of CTA1 to CTA4 are as shown below.

<Production of organic ditellurium compound>
Synthesis Example 5 (Dimethylditelluride)
3.19 g (25 mmol) of metal tellurium (same as above) was suspended in 25 mL of THF, and 25 mL (28.5 mmol) of methyllithium (same as above) was slowly added at 0 ° C. (10 minutes). The reaction solution was stirred until the metal tellurium disappeared completely (10 minutes). To this reaction solution, 20 mL of ammonium chloride solution was added at room temperature and stirred for 1 hour. The organic layer was separated and the aqueous layer was extracted 3 times with diethyl ether. The collected organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a black purple oil (2.69 g, yield 75%).

^{From 1} H-NMR and MS (HRMS), it was confirmed to be dimethylditelluride.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 2.67 (s, 6H); HRMS (EI) m / z: found 289.8593, calcd for C ₂ H ₆ Te ₂ (M) ⁺ 289.8594

<Preparation of macro living initiator>
Synthesis Example 6 (PIp1)
In a nitrogen-substituted Pyrex (registered trademark) glass tube, 3.0 mL (30 mmol) of isoprene, 38.7 mg (0.15 mmol) of CTA1 and 42.8 mg (0.15 mmol) of dimethylditelluride were charged. The reaction solution was stirred at 120 ° C. for 10 hours, and the reaction solution was allowed to cool to room temperature to terminate the polymerization, thereby obtaining a PIp1 solution.

  From GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 1770 and PDI = 1.15.

Synthesis Example 7 (PIp2)
In a Pyrex (registered trademark) glass tube substituted with nitrogen, 3.0 mL (30 mmol) of isoprene, 8.3 mg (0.03 mmol) of CTA1 and 8.6 mg (0.03 mmol) of dimethylditelluride were charged. The reaction solution was stirred at 120 ° C. for 12 hours, and the reaction solution was allowed to cool to room temperature to terminate the polymerization to obtain a PIp2 solution.

  From GPC analysis (based on the molecular weight of the polystyrene standard sample), Mn = 9680 and PDI = 1.09.

Synthesis Example 8 (PIp3)
In a Pyrex (registered trademark) glass tube purged with nitrogen, 2.0 mL (20 mmol) of isoprene, 18 μL (0.067 mmol) of CTA2 and 6 μL (0.067 mmol) of dimethylditelluride were charged. The reaction solution was stirred at 120 ° C. for 8 hours, and the reaction solution was allowed to cool to room temperature to terminate the polymerization, thereby obtaining a PIp3 solution.

  From GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 2300 and PDI = 1.11.

Synthesis Example 9 (PIp4)
In a Pyrex (registered trademark) glass tube purged with nitrogen, 2.3 mL (23 mmol) of isoprene, 20 μL (0.11 mmol) of CTA3 and 12 μL (0.11 mmol) of dimethylditelluride were charged. The reaction solution was stirred at 120 ° C. for 12 hours, and the reaction solution was allowed to cool to room temperature to terminate the polymerization, thereby obtaining a PIp4 solution.

  From GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 3200 and PDI = 1.09.

Synthesis Example 10 (PMMA-b-PIp1)
In a Pyrex (registered trademark) glass tube substituted with nitrogen, 3.0 mL (28 mmol) of methyl methacrylate, 32 μL (0.19 mmol) of CTA1, 20 μL (0.19 mmol) of dimethylditelluride, and 6 mg (0.037 mmol) of AIBN are charged. It is. The reaction solution was stirred at 55 ° C. for 9 hours. After the reaction, 10 mL of chloroform was added. The obtained solution was poured into 500 mL of stirring hexane, and the precipitated polymer was suction filtered and dried to obtain 2.4 g (yield 86%) of the macro living initiator.

  From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn = 13700 and PDI = 1.16.

  In a Pyrex (registered trademark) glass tube purged with nitrogen, 200 mg (0.015 mmol) of the obtained macro living initiator, 0.6 mL (6.0 mmol) of isoprene and 0.6 mL of benzene were charged. The reaction solution was stirred at 120 ° C. for 8 hours, and the reaction solution was allowed to cool to room temperature to stop the polymerization to obtain a PMMA-b-PIp1 solution.

  From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn = 16600 and PDI = 1.18.

Synthesis Example 11 (PSt-b-PIp1)
In a Pyrex (registered trademark) glass tube purged with nitrogen, 7.5 mL (65 mmol) of styrene and 228 μL (1.3 mmol) of CTA1 were charged. The reaction solution was stirred at 110 ° C. for 19.5 hours. After the reaction, 20 mL of α, α, α-trifluoromethyltoluene was added. The obtained solution was poured into 700 mL of stirred methanol, and the precipitated polymer was suction filtered and dried to obtain 6.2 g of macro-living initiator (yield 92%).

  From GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 5900 and PDI = 1.15.

  In a Pyrex (registered trademark) glass tube purged with nitrogen, 354 mg (0.06 mmol) of the obtained macro-living initiator, 3.0 mL (30 mmol) of isoprene and 6.5 μL (0.06 mmol) of dimethylditelluride were charged. . The reaction solution was stirred at 120 ° C. for 10 hours, and the reaction solution was allowed to cool to room temperature to stop the polymerization, thereby obtaining a PSt-b-PIp1 solution.

  From GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 9700 and PDI = 1.12.

Synthesis Example 12 (PSt1)
In a Pyrex (registered trademark) glass tube purged with nitrogen, 2.0 mL (17.5 mmol) of styrene, 96.3 mg (0.35 mmol) of CTA1 and 29.0 mg (0.175 mmol) of AIBN were charged. The reaction solution was stirred at 60 ° C. for 13.5 hours. After the reaction was completed, 4 mL of DMF was added. The obtained solution was poured into 400 mL of stirring methanol, and the precipitated polymer was filtered by suction and dried to obtain PSt1 (1.57 g, yield 85%).

  By GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 4700 and PDI = 1.15.

Synthesis Example 13 (PSt2)
In a Pyrex (registered trademark) glass tube substituted with nitrogen, styrene 2.13 mL (19 mmol), CTA1 100 μL (0.53 mmol), dimethylditelluride 18 μL (0.53 mmol) and ACHN 39 mg (0.16 mmol) were charged. It is. The reaction solution was stirred at 80 ° C. for 7 hours. After the reaction, 10 mL of chloroform was added. The obtained solution was poured into 400 mL of stirring methanol, and the precipitated polymer was suction filtered and dried to obtain PSt2 (1.52 g, yield 79%).

  From GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 3500 and PDI = 1.08.

Synthesis Example 14 (PAN1)
In a Pyrex (registered trademark) glass tube purged with nitrogen, 1.23 mL (19 mmol) of acrylonitrile, 100 μL (0.53 mmol) of CTA1, 39 mg (0.16 mmol) of ACHN, and 4 mL of DMF were charged. The reaction solution was stirred at 60 ° C. for 6 hours. After the reaction, 4 mL of DMF was added. The obtained solution was poured into 300 mL of stirring methanol, and the precipitated polymer was suction filtered and dried to obtain PAN1 (870 mg, yield 82%).

  From GPC analysis (based on the molecular weight of the polymethyl methacrylate standard sample), Mn = 4700 and PDI = 1.20.

Synthesis Example 15 (PNVP1)
In a Pyrex (registered trademark) glass tube substituted with nitrogen, 1.5 mL (14.1 mmol) of N-vinylpyrrolidone, 120.5 mg (0.47 mmol) of CTA1 and 38.0 mg (0.23 mmol) of AIBN were charged. The reaction solution was stirred at 50 ° C. for 3 hours. After completion of the reaction, 5 mL of chloroform was added. The obtained solution was poured into 300 mL of stirring hexane, and the precipitated polymer was suction filtered and dried to obtain PNVP1 (1.21 g, yield 80%).

  From GPC analysis (based on the molecular weight of the polymethyl methacrylate standard sample), Mn = 2250 and PDI = 1.10.

Synthesis Example 16 (PNVP2)
In a Pyrex (registered trademark) glass tube purged with nitrogen, 2.1 mL (20.0 mmol) of N-vinylpyrrolidone, 102.9 mg (0.40 mmol) of CTA1 and 32.8 mg (0.20 mmol) of AIBN were charged. The reaction solution was stirred at 50 ° C. for 3 hours. After completion of the reaction, 5 mL of chloroform was added. The obtained solution was poured into 300 mL of stirring hexane, and the precipitated polymer was suction filtered and dried to obtain PNVP2 (2.06 g, yield 89%).

  By GPC analysis (based on the molecular weight of a polymethylmethacrylate standard sample), Mn = 4440 and PDI = 1.11.

Synthesis example 17 (PMMA1)
In a nitrogen-substituted Pyrex (registered trademark) glass tube, 2.25 g (22.4 mmol) of methyl methacrylate, 103 mg (0.37 mmol) of CTA1, 106 mg (0.37 mmol) of dimethylditelluride and 17.2 mg (0.1. 075 mmol) was charged. The reaction solution was stirred at 60 ° C. for 3.5 hours. After completion of the reaction, 8 mL of chloroform was added. The obtained solution was poured into 350 mL of stirring hexane, and the precipitated polymer was suction filtered and dried to obtain PMMA1 (1.88 g, yield 82%).

  From GPC analysis (based on the molecular weight of a polymethylmethacrylate standard sample), Mn = 5700 and PDI = 1.19.

Synthesis Example 18 (PMMA2)
In a Pyrex (registered trademark) glass tube purged with nitrogen, 1.98 mL (19 mmol) of methyl methacrylate, 100 μL (0.53 mmol) of CTA1, 56 μL (0.53 mmol) of dimethylditelluride and 24 mg (0.11 mmol) of AIBN were charged. It is. The reaction solution was stirred at 60 ° C. for 8.5 hours. After the reaction, 8 mL of chloroform was added. The obtained solution was poured into 500 mL of stirring hexane, and the precipitated polymer was suction filtered and dried to obtain PMMA2 (1.72 g, yield 90%).

  From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn = 4300 and PDI = 1.16.

Synthesis Example 19 (PMMA3)
In a Pyrex (registered trademark) glass tube substituted with nitrogen, 1.07 mL (10 mmol) of methyl methacrylate, 27 μL (0.10 mmol) of CTA2 and 11 μL (0.1 mmol) of dimethylditelluride were charged. The reaction solution was stirred at 80 ° C. for 34 hours, and the reaction solution was allowed to cool to room temperature to stop the polymerization to obtain a PMMA3 solution.

  From GPC analysis (based on the molecular weight of the polymethyl methacrylate standard sample), Mn = 9500 and PD = 1.14.

Synthesis Example 20 (PMMA4)
In a Pyrex (registered trademark) glass tube substituted with nitrogen, 0.59 ml (5.5 mmol) of methyl methacrylate, 29 μL (0.11 mmol) of CTA4 and 5.8 μL (0.055 mmol) of dimethylditelluride were charged. This reaction solution was stirred at 80 ° C. for 32 hours, and the reaction solution was allowed to cool to room temperature to terminate the polymerization to obtain a PMMA4 solution.

  From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn = 5100 and PDI = 1.20.

Synthesis example 21 (PMMA5)
In a nitrogen-substituted Pyrex (registered trademark) glass tube, 0.79 ml (7.4 mmol) of methyl methacrylate, 43 μL (0.25 mmol) of CTA1, 26 μL (0.25 mmol) of dimethylditelluride and 21 mg (0.13 mmol) of AIBN Was charged. The reaction solution was stirred at 60 ° C. for 6 hours. After the reaction, 3 mL of chloroform was added. The obtained solution was poured into 300 mL of stirring hexane, and the precipitated polymer was suction filtered and dried to obtain PMMA5 (671 mg, yield 88%).

  From GPC analysis (based on the molecular weight of the polymethyl methacrylate standard sample), Mn = 3300 and PD = 1.21.

Synthesis example 22 (PMMA6)
In a nitrogen-substituted Pyrex (registered trademark) glass tube, 2.2 mL (20.5 mmol) of methyl methacrylate, 120 μL (0.68 mmol) of CTA1, 65 μL (0.68 mmol) of dimethylditelluride, and 23 mg of AIBN (0. 141 mmol). The reaction solution was stirred at 60 ° C. for 5.2 hours. After the reaction, 10 mL of chloroform was added. The obtained solution was poured into 500 mL of stirring hexane, and the precipitated polymer was suction filtered and dried to obtain PMMA6 (2.1 g, yield 98%).

  From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn = 3800 and PDI = 1.17.

Synthesis example 23 (PMMA7)
In a Pyrex (registered trademark) glass tube purged with nitrogen, 1.98 ml (19 mmol) of methyl methacrylate, 70 μL (0.37 mmol) of CTA1, 39 μL (0.37 mmol) of dimethylditelluride and 17 mg (0.074 mmol) of AIBN were charged. It is. The reaction solution was stirred at 60 ° C. for 4.5 hours. After the reaction, 8 mL of chloroform was added. The obtained solution was poured into 500 mL of stirring hexane, and the precipitated polymer was suction filtered and dried to obtain PMMA7 (1.96 g, yield 89%).

  From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn = 5100 and PDI = 1.19.

<Dimerization reaction>
Example 1
Without removing the PIp1 solution from the prepared container, light irradiation was performed through the filter A at 20 ° C. for 1 hour. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 3500, PDI = 1.13, and x _c = 0.99.

Example 2
Without taking out the PIp1 solution from the prepared container, light irradiation was performed at 20 ° C. for 3 hours. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 3100, PDI = 1.20, and x _c = 0.85. Further, metal tellurium was deposited on the inner surface of the reaction tube.

Example 3
Without removing the PIp2 solution from the prepared container, light irradiation was performed through the filter A at 20 ° C. for 3 hours. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of the polystyrene standard sample), Mn = 17200, PDI = 1.11, and x _c = 0.87.

Example 4
Without removing the PIp3 solution from the adjusted container, light irradiation was performed through the filter A at room temperature for 2 hours. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn was 4450, PDI was 1.11 and x _c was 0.93.

Example 5
The PIp4 solution was irradiated with light through the filter A at room temperature for 2 hours without removing it from the adjusted container. A mercury lamp was used as the light source.

From GPC analysis (based on molecular weight of polystyrene standard sample), Mn = 6400, PDI = 1.10, x _c = 0.96.

Example 6
The PMMA-b-PIp1 solution was irradiated with light through the filter A at room temperature for 2 hours without removing it from the adjusted container. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn was 28900, PDI was 1.15, and x _c was 0.88.

Example 7
The PSt-b-PIp1 solution was irradiated with light through the filter A at room temperature for 2 hours without removing it from the adjusted container. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 17000, PDI = 1.18, and x _c = 0.86.

Example 8
In a Pyrex (registered trademark) glass tube purged with nitrogen, 380 mg of PSt1 and 1 mL of benzene were charged. The reaction solution was irradiated with light through filter A at 20 ° C. for 11 hours. A mercury lamp was used as the light source.

By GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 7200, PDI = 1.27, and x _c = 0.72.

Example 9
In a Pyrex (registered trademark) glass tube purged with nitrogen, 80 mg of PSt2, 90 μL (0.90 mmol) of isoprene and 0.4 mL of benzene were charged. The reaction solution was irradiated with light through filter A at 20 ° C. for 1.5 hours. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 7100, PDI = 1.13, and x _c = 0.91.

Example 10
In a Pyrex (registered trademark) glass tube purged with nitrogen, 80 mg of PAN1, 92 μL (0.92 mmol) of isoprene and 1.0 mL of DMF were charged. The reaction solution was irradiated with light through a filter B at 20 ° C. for 1.5 hours. A mercury lamp was used as the light source. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn was 9700, PDI was 1.17, and x _c was 0.89.

Example 11
In a Pyrex (registered trademark) glass tube purged with nitrogen, 100 mg of PNVP1, 0.22 mL (2.2 mmol) of isoprene and 0.22 mL of DMF were charged. This reaction solution was irradiated with light through a filter A at 20 ° C. for 30 minutes. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn was 5050, PDI was 1.12 and x _c was 0.94.

Example 12
In a Pyrex (registered trademark) glass tube purged with nitrogen, 100 mg of PMMA1, 82 μL (0.82 mmol) of isoprene and 0.4 mL of DMF were charged. The reaction solution was irradiated with light through filter A at 20 ° C. for 1.5 hours. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn was 10100, PDI was 1.22, and x _c was 0.87.

Example 13
In a Pyrex (registered trademark) glass tube purged with nitrogen, 74 mg of PMMA2, 90 μL (0.90 mmol) of isoprene and 0.7 mL of benzene were charged. This reaction solution was irradiated with light at 20 ° C. for 4 hours. An LED lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polymethylmethacrylate standard sample), Mn = 7200, PDI = 1.19, x _c = 0.80.

Example 14
Isoprene 0.5 mL (5.0 mmol) and 1,4-dioxane 1 mL were added to the reaction vessel in which the PMMA 3 solution was prepared. The reaction solution was irradiated with light through filter A at room temperature for 2 hours. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn was 15200, PD was 1.21, and x _c was 0.86.

Example 15
To a reaction vessel in which the PMMA4 solution was prepared, 0.09 mL (0.9 mmol) of isoprene and 0.2 mL of 1,4-dioxane were added. The reaction solution was irradiated with light through filter A at room temperature for 2 hours. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn = 8700, PDI = 1.21, and x _c = 0.86.

Example 16
In a Pyrex (registered trademark) glass tube purged with nitrogen, 100 mg of PMMA1, 93 μL (0.82 mmol) of 2,3-dimethyl-1,3-butadiene and 0.4 mL of DMF were charged. This reaction solution was irradiated with light through a filter A at 20 ° C. for 30 minutes. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn = 10700, PDI = 1.20, and x _c = 0.93.

Example 17
In a Pyrex (registered trademark) glass tube purged with nitrogen, 58 mg of PMMA5, 102 μL (0.10 mmol) of 2,3-dimethyl-1,3-butadiene and 0.4 mL of benzene were charged. The reaction solution was irradiated with light through filter A at 20 ° C. for 1.5 hours. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn = 6500, PDI = 1.15, and x _c = 0.95.

Example 18
In a Pyrex (registered trademark) glass tube purged with nitrogen, 58 mg of PMMA5, 34 μL (0.36 mmol) of 1,3-cyclohexadiene and 0.4 mL of benzene were charged. The reaction solution was irradiated with light through a filter A at 20 ° C. for 2 hours. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn = 5300, PDI = 1.26, and x _c = 0.77.

Example 19
In a Pyrex (registered trademark) glass tube substituted with nitrogen, 58 mg of PMMA5, 88 mg (0.90 mmol) of trans-2,4-hexadien-1-ol and 0.4 mL of benzene were charged. The reaction solution was irradiated with light through filter A at 20 ° C. for 1.5 hours. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of the polymethyl methacrylate standard sample), Mn = 5000, PDI = 1.24, and x _c = 0.63.

Example 20
In a Pyrex (registered trademark) glass tube substituted with nitrogen, 60 mg of PMMA6, 134 μL (0.90 mmol) of ethyl sorbate and 0.4 mL of benzene were charged. This reaction solution was irradiated with light through a filter A at 20 ° C. for 30 minutes. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn = 5200, PDI = 1.28, and x _c = 0.62.

Example 21
In a Pyrex (registered trademark) glass tube substituted with nitrogen, 80 mg of PMMA7, 186 μL (1.62 mmol) of styrene and 0.5 mL of 1,4-dioxane were charged. The reaction solution was irradiated with light through filter A at 20 ° C. for 3 hours. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of the polymethyl methacrylate standard sample), Mn was 10200, PDI was 1.24, and x _c was 0.90.

Example 22
PMMA2 60 mg, 4-vinylpyridine 74 μL (0.70 mmol) and benzene 0.4 mL were charged in a nitrogen-substituted Pyrex (registered trademark) glass tube. The reaction solution was irradiated with light through a filter A at 20 ° C. for 4 hours. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample), Mn = 6400, PD = 1.27, and x _c = 0.70.

Comparative Example 1
Without removing the PIp2 solution from the prepared container, this reaction solution was stirred at 140 ° C. for 24 hours under light shielding conditions, and the reaction solution was allowed to cool to room temperature to stop the reaction.

From the GPC analysis (based on the molecular weight of the polystyrene standard sample), Mn = 1800, PDI = 1.19, x _c = 0.37, and a polymer whose molecular weight did not change was the main product.

Comparative Example 2
In a Pyrex (registered trademark) glass tube purged with nitrogen, 100 mg of PNVP2 and 0.22 mL of DMF were charged. This reaction solution was irradiated with light through a filter A at 20 ° C. for 30 minutes. A mercury lamp was used as the light source.

From GPC analysis (based on the molecular weight of polymethyl methacrylate standard sample), it has the same molecular weight as that of the macro living initiator (Mn = 4400, PDI = 1.12), x _c = 0.00, and the dimerization reaction proceeds. I did not.

Comparative Example 3
In a Pyrex (registered trademark) glass tube purged with nitrogen, 100 mg of PMMA1 and 0.4 mL of DMF were charged. The reaction solution was irradiated with light through filter A at 20 ° C. for 1.5 hours. A mercury lamp was used as the light source.

From the GPC analysis (based on the molecular weight of the polymethylmethacrylate standard sample), Mn = 6400, PDI = 1.27, x _c = 0.22, and the polymer whose molecular weight did not change was the main product.

<GPC chart>
FIGS. 1-2 are the macroliving initiator before dimerization reaction in Example 1-3, Example 8, Example 11-12, Example 16, and Comparative Example 1- Comparative Example 3, and the polymer after dimerization reaction. It is a figure which shows the GPC chart.

  1-2, the solid line shows the chart after the reaction, and the broken line shows the chart before the reaction. 1-2, the molecular weight increases as it approaches the left side of the drawing, and the molecular weight decreases as it approaches the right side of the drawing. That is, the shorter the time, the higher the molecular weight, and the longer the time, the lower the molecular weight.

  In the Examples, the peak is almost completely shifted after the dimerization reaction, and it can be seen that the reaction occurs efficiently and selectively.

  On the other hand, in Comparative Example 1 and Comparative Example 3, a shoulder peak is formed in the GPG chart after the dimerization reaction, and the largest peak exists at the same position as the peak before the dimerization reaction. . Therefore, it can be seen that a large amount of the molecular weight before the reaction remains because the reaction efficiency is low. In Comparative Example 2, it can be seen that no reaction occurred since the peak did not change after the dimerization reaction.

Claims (6)

A step of preparing a macro living initiator by polymerizing a vinyl monomer by a living radical polymerization method using an organic tellurium polymerization initiator;
Adding a conjugated olefin compound to the macro-living initiator;
And a step of selectively dimerizing a radical having a structural unit derived from the compound as a polymerization growth terminal by adding light after the compound is irradiated. Method.   The method for producing a polymer according to claim 1, wherein the light irradiation step is a step of heating the polymerized compound with a macro-living initiator after the addition of the compound, followed by light irradiation. . A step of adjusting a macro-living initiator having a constituent unit derived from a conjugated olefin compound as a polymerization growth terminal by polymerizing a vinyl monomer by a living radical polymerization method using an organic tellurium-based polymerization initiator;
And a step of selectively dimerizing a radical having a structural unit derived from a conjugated olefin compound as a polymerization growth terminal by irradiating the macro-living initiator with light. .   The method for producing a polymer according to any one of claims 1 to 3, wherein the light irradiation step is performed using a light source having an emission distribution with a wavelength of 300 to 700 nm.   The method for producing a polymer according to any one of claims 1 to 4, wherein the light irradiation step is performed by light irradiation at a temperature in the range of -70 ° C to 80 ° C. Organic tellurium compound polymerization initiator,
(A) an organic tellurium compound represented by the general formula (1),
(B) a mixture of an organic tellurium compound represented by the general formula (1) and an azo polymerization initiator,
(C) a mixture of an organic tellurium compound represented by the general formula (1) and an organic ditellurium compound represented by the general formula (2), or (d) an organic tellurium compound represented by the general formula (1), an azo type The method for producing a polymer according to any one of claims 1 to 5, wherein the polymer is a mixture of a polymerization initiator and an organic ditellurium compound represented by the general formula (2).

(.R shown wherein, ^{R 1} represents an alkyl group having 1 to 8 carbon atoms, .R ² and ^{R 3} represents an aryl group or an aromatic heterocyclic group, a hydrogen atom or an alkyl group having 1 to 8 carbon atoms ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group or a cyano group.

(In the formula, R ¹ represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms.)

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