JP4539843B2 - Method for producing aqueous liquid using organic tellurium compound - Google Patents

Description

  The present invention relates to a method for producing an aqueous liquid containing a polymer.

Living radical polymerization is a polymerization method that allows precise 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. The present inventor has reported living radical polymerization using an organic tellurium compound as an initiator as an example of living radical polymerization (see, for example, Patent Document 1).
WO 2004/14848

The method of Patent Document 1 is studied in a homogeneous system using a bulk, an organic solvent, or the like, and enables control of molecular weight and molecular weight distribution. However, from an environmental and industrial viewpoint, application of these living radical polymerization techniques in an aqueous medium is desired.
The object of the present invention is to polymerize a vinyl monomer in an aqueous medium using (a) an organic tellurium compound, (b1) a surfactant and / or a dispersant, thereby obtaining a precise molecular weight and molecular weight distribution (PD = Mw). It is to provide a method for producing an aqueous liquid containing a polymer having a controlled / Mn).
Another object of the present invention is to miniemulsify a vinyl monomer in an aqueous medium using (a) an organic tellurium compound represented by formula (1), (b2) a surfactant and a co-surfactant. Therefore, it is providing the method of manufacturing the aqueous liquid containing the polymer by which precise molecular weight and molecular weight distribution (PD = Mw / Mn) were controlled.

The present invention relates to the following inventions.
1. Polymerizing a vinyl monomer in an aqueous medium using (a) an organic tellurium compound represented by formula (1), (b1) a surfactant and / or a dispersant, and (d) an azo polymerization initiator. The manufacturing method of the aqueous liquid containing the polymer characterized by these.

（式中、Ｒ^１は、Ｃ_１〜Ｃ_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Ｃ_１〜Ｃ_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、オキシカルボニル基又はシアノ基を示す。）

(In the formula, R ¹ represents a C _{1 to} C ₈ alkyl group, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₈ alkyl group. R ⁴ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an oxycarbonyl group, or a cyano group.

2 . In an aqueous medium, (a) an organic tellurium compound represented by formula (1), (b1) a surfactant and / or a dispersant, (c) a compound represented by formula (2), (d) an azo-based compound The manufacturing method of the aqueous liquid containing the polymer characterized by superposing | polymerizing a vinyl monomer using a polymerization initiator.
(R ¹ Te) ₂ (2)
(In the formula, R ¹ is the same as above.)

3 . In an aqueous medium, a vinyl monomer is miniemulsion polymerized using (a) an organic tellurium compound represented by the formula (1), (b2) a surfactant and a co-surfactant, and (d) an azo polymerization initiator. A method for producing an aqueous liquid containing a polymer.

4. In an aqueous medium, (a) an organic tellurium compound represented by formula (1), (b2) a surfactant and a co-surfactant, (c) a compound represented by formula (2), (d) an azo-based compound The manufacturing method of the aqueous liquid containing the polymer characterized by carrying out the miniemulsion polymerization of the vinyl monomer using a polymerization initiator.

5 . The manufacturing method of the aqueous liquid containing the polymer characterized by polymerizing a vinyl monomer using the aqueous liquid obtained by the manufacturing method of said 1-4 as a macro living initiator (macroinitiator).
6 . The aqueous liquid containing the polymer manufactured with the manufacturing method of said 1-5 .

  According to the present invention, there is provided a method for producing an aqueous liquid containing a polymer having a controlled molecular weight and molecular weight distribution (PD = Mw / Mn) in an aqueous medium. Further, by adding a vinyl monomer to the aqueous liquid obtained by the production method of the present invention, it is possible to produce an aqueous liquid composed of a polymer having an increased molecular weight or an arbitrary block (co) polymer. The polymer obtained can also produce products of interest in various fields of application.

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

（式中、Ｒ^１は、Ｃ_１〜Ｃ_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Ｃ_１〜Ｃ_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、オキシカルボニル基又はシアノ基を示す。）

(In the formula, R ¹ represents a C _{1 to} C ₈ alkyl group, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₈ alkyl group. R ⁴ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an oxycarbonyl group, or a cyano group.

Specific examples of the group represented by R ¹ are as follows.
Examples of the C _{1 to} C ₈ alkyl group 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 substituted aryl group include a phenyl group having a substituent and a naphthyl group having a substituent.
Examples of the substituent of the aryl group having the substituent include 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 = C ₁ alkyl group -C _8, aryl _group, alkoxy group of C 1 -C _8, an aryloxy group), a sulfonyl group, and a trifluoromethyl group.
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 C _{1 to} C ₈ alkyl group 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 oxycarbonyl group include a group represented by —COOR ^b (R ^b = H, C _{1 to} C ₈ alkyl group, aryl group).
Specifically, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, ter-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 a C _{1 to} C ₄ alkyl group, R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₄ alkyl group, R A compound in which ⁴ is an aryl group, a substituted aryl group or an oxycarbonyl group is preferable.
Particularly preferably, R ¹ represents a C _{1 to} C ₄ alkyl group, R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₄ alkyl group, and R ⁴ represents a phenyl group or a substituted phenyl group. A methoxycarbonyl group and an ethoxycarbonyl group are preferable.

Specific representative examples of the organic tellurium compound represented by the formula (1) are as follows.
(Methylterranylmethyl) benzene, (1-methylterranylethyl) benzene, 1-chloro-4- (1-methylterranylethyl) benzene, 1-trifluoromethyl-4- (1-methylterranylethyl) Benzene, 3,5-bis-trifluoromethyl-1- (1-methylteranylethyl) benzene, 1,2,3,4,5-pentafluoro-6- (1-methylterranylethyl) benzene, 2 -Methyl terranyl propionitrile, (2-methyl teranyl propyl) benzene, methyl 2-methyl teranyl-2-methyl-propionate, ethyl 2-methyl teranyl-2-methyl-propionate, 2-methyl teranyl-2-methyl-propio A nitrile etc. can be mentioned. Further, in the above, all compounds in which the methyl terranyl moiety is changed to ethyl terranyl or n-butyl terranil are also included. In addition, all of the organic tellurium compounds described in WO2004 / 014962 can be exemplified.

The organic tellurium compound represented by the formula (1) can be produced by reacting the compound of the formula (3), the compound of the formula (4) and metal tellurium.
Specific examples of the compound represented by 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。〕

(Wherein R ² , R ³ and R ⁴ are the same as above. X represents a halogen atom.)

Specific examples of the compound represented by the formula (3) are as follows.
Each group represented by R ² , R ³ and R ⁴ is as described above.
Examples of the group represented by X include halogen atoms such as fluorine, chlorine, bromine and iodine. Preferably, chlorine and bromine are good.

Specifically, the compound represented by the formula (3) is as follows.
Benzyl chloride, benzyl bromide, (1-chloroethyl) benzene, (1-bromoethyl) benzene, 1-chloro-4- (1-chloroethyl) benzene, 1-chloro-4- (1-bromoethyl) benzene, 1-trifluoro Methyl-4- (1-chloroethyl) benzene, 1-trifluoromethyl-4- (1-bromoethyl) benzene, 3,5-bis-trifluoromethyl-1- (1-chloroethyl) benzene, 3,5-bis -Trifluoromethyl-1- (1-bromoethyl) benzene, 1,2,3,4,5-pentafluoro-6- (1-chloroethyl) benzene, 1,2,3,4,5-pentafluoro-6 -(1-bromoethyl) benzene, 2-chloropropionitrile, 2-bromopropionitrile, (2-chloropropyl) benzene, (2-butyl Romopropyl) benzene, methyl 2-chloro-2-methyl-propionate, methyl 2-bromo-2-methyl-propionate, ethyl 2-chloro-2-methyl-propionate, ethyl 2-bromo-2-methyl-propionate, 2- Examples include chloro-2-methyl-propionitrile, 2-bromo-2-methyl-propionitrile, and the like. In addition, all of the compound (3) described in WO2004 / 014963 can be exemplified.

Specific examples of the compound represented by the formula (4) are as follows.
M (R ¹ ) m (4)
(In the formula, 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, and when M is an alkaline earth metal, m is 2. When M is a copper atom, m represents 1 or 2.)

The group represented by R ¹ is as described above.
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 a chloro atom or a bromo atom.

  Specific examples of the compound include methyl lithium, ethyl lithium, n-butyl lithium, phenyl lithium, p-chlorophenyl lithium, p-methoxyphenyl lithium, and p-nitrophenyl lithium. Preferably, methyl lithium, ethyl lithium, n-butyl lithium, and phenyl lithium are good.

Specifically as a manufacturing method of the compound represented by Formula (1), it is as follows.
Metal tellurium is suspended in a solvent. Solvents that can be used include polar solvents such as N, N-dimethylformamide (DMF) and tetrahydrofuran (THF), aromatic solvents such as toluene and xylene, aliphatic hydrocarbons such as hexane, ethers such as dialkyl ether, and the like. Can be mentioned. Preferably, THF is good. The amount of the solvent used may be adjusted as appropriate, but is usually 1 to 100 ml, preferably 5 to 20 ml with respect to 1 g of metal tellurium.
The compound (4) is slowly added dropwise to the suspension solution and then stirred. While the reaction time varies depending on the reaction temperature and pressure, it is usually 5 minutes to 24 hours, preferably 10 minutes to 2 hours. The reaction temperature is -20 ° C to 80 ° C, preferably -10 ° C to 40 ° C, more preferably -5 ° C to 40 ° C. The pressure is usually normal pressure, but may be increased or decreased.

Next, the compound (3) is added to the reaction solution and stirred. While the reaction time varies depending on the reaction temperature and pressure, it is usually 5 minutes to 24 hours, preferably 10 minutes to 2 hours. The reaction temperature is -20 ° C to 80 ° C, preferably -10 ° C to 40 ° C, more preferably -5 ° C to 40 ° C. The pressure is usually normal pressure, but may be increased or decreased.
As a use ratio of the metal tellurium, the compound (3) and the compound (4), the compound (3) is 0.5 to 1.5 mol and the compound (4) is 0.5 to 1.5 mol with respect to 1 mol of the metal tellurium. Preferably, the compound (3) is 0.8 to 1.2 mol and the compound (4) is 0.8 to 1.2 mol. After completion of the reaction, the solvent is concentrated and the target compound is isolated and purified. The purification method can be appropriately selected depending on the compound, but usually vacuum distillation, recrystallization purification and the like are preferable.

The (b1) surfactant and / or dispersant used in the present invention is as follows.
The surfactant is not particularly limited, and specifically, dodecylbenzene sulfonate, lauryl sulfate, dioctyl sulfosuccinate, dioctyl succinate, lauryl methyl taurate, polyoxyethylene alkyl ether sulfate Anionic compounds such as lauryl phosphate, cationic compounds such as octadecylamine acetate, tetradecylamine acetate, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, tetradecyldimethylbenzylammonium chloride, oxyethylene dodecylamine; Nonionic compounds such as polyoxyethylene alkyl ethers; reactive surfactants and the like.

  The dispersant is not particularly limited, and specifically, nonionic polymer compounds such as polyvinyl alcohol, polyethylene oxide, and cellulose derivatives; polyacrylic acid and its salt, polymethacrylic acid and its salt, methacrylic acid ester and methacrylic acid Examples include anionic polymer compounds such as copolymers with acids and / or salts thereof; poorly water-soluble inorganic compounds such as calcium phosphate, calcium carbonate, and aluminum hydroxide. These may be used alone or in combination.

(B2) Surfactant and cosurfactant used in the present invention are as follows.
Examples of the surfactant include the same ones as described above.
The co-surfactant is not particularly limited, and specifically, a higher alcohol substantially insoluble in water such as 1-pentanol or 1-hexadecanol, or a long chain such as hexadecane or octadecane. Examples include alkanes.

The compound represented by the formula (2) used in the present invention is as follows.
(R ¹ Te) ₂ (2)
(In the formula, R ¹ is the same as above.)

The group represented by R ¹ is as described above.
As a preferable compound represented by the formula (2), R ¹ is preferably a C _{1 to} C ₄ alkyl group or 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. Particularly preferred are dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride and di-n-butyl ditelluride.

Specific examples of the method for producing the compound represented by the formula (2) include a method of reacting metal tellurium with the compound represented by the formula (4).
Metal tellurium is suspended in a solvent. Solvents that can be used include polar solvents such as dimethylformamide (DMF) and tetrahydrofuran (THF), aromatic solvents such as toluene and xylene, aliphatic hydrocarbons such as hexane, and ethers such as dialkyl ether. Can be mentioned. Preferably, THF is good. The amount of the organic solvent used may be appropriately adjusted, but is usually 1 to 100 ml, preferably 5 to 20 ml, based on 1 g of metal tellurium.
The compound represented by the formula (4) is slowly added dropwise to the suspension solution, followed by stirring. While the reaction time varies depending on the reaction temperature and pressure, it is usually 5 minutes to 24 hours, preferably 10 minutes to 2 hours. The reaction temperature is −20 ° C. to 80 ° C., preferably −10 ° C. to 40 ° C., more preferably −5 to 40 ° C. The pressure is usually normal pressure, but may be increased or decreased.

Next, water (neutral water such as saline, alkaline water such as aqueous ammonium chloride, or acidic water such as hydrochloric acid) may be added to the reaction solution and stirred. While the reaction time varies depending on the reaction temperature and pressure, it is usually 5 minutes to 24 hours, preferably 10 minutes to 2 hours. As reaction temperature, -20 degreeC-80 degreeC, Preferably, 0 degreeC-40 degreeC, More preferably, 15-40 degreeC is good. The pressure is usually normal pressure, but may be increased or decreased.
Regarding the usage ratio of the metal tellurium and the compound of the formula (4), the compound of the formula (4) is 0.5 to 1.5 mol, preferably 0.8 to 1.2 mol with respect to 1 mol of the metal tellurium. Is good.
After completion of the reaction, the solvent is concentrated and the target compound is isolated and purified. The purification method can be appropriately selected depending on the compound, but usually vacuum distillation, reprecipitation purification and the like are preferable.

The azo polymerization initiator used in the present invention 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, 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN) in the case of low temperature polymerization, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) in the case of low temperature polymerization, 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], 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 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] may be used.

The vinyl monomer used in the present invention can be used without particular limitation as long as it is capable of radical polymerization. These are used individually by 1 type or in mixture of 2 or more types.
For example, (meth) acrylic acid ester, cycloalkyl group-containing unsaturated monomer, aromatic unsaturated monomer (styrene monomer), (meth) acrylamide monomer, (meth) acrylonitrile, methyl vinyl ketone, etc. are described in WO 2004/014962. All the vinyl monomers that have been produced can be exemplified.
Specific examples include the following monomers.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid-2- Cycloalkyl group-containing unsaturated monomers such as (meth) acrylic acid esters such as hydroxyethyl, 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) , Pt-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) acrylamide monomers such as (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide. 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 esters, cycloalkyl group-containing unsaturated monomers, aromatic unsaturated monomers (styrene monomers), (meth) acrylamide monomers, (meth) acrylonitrile, and methyl vinyl ketone are preferable.
Preferred (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Can be mentioned. Particularly preferred are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate.
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, p-chlorostyrene is mentioned. Particularly preferred are styrene and p-chlorostyrene.
Preferable (meth) acrylamide monomers include N-isopropyl (meth) acrylamide. Particularly preferred is N-isopropylmethacrylamide.
The above “(meth) acryl” is a general term for “acryl” and “methacryl”.

The aqueous liquid of the present invention is an emulsion or a suspension.
Examples of the method for producing the aqueous liquid of the present invention include an emulsion polymerization method, a suspension (suspension) polymerization method, and a miniemulsion polymerization method.
The emulsion polymerization method in the present invention 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.

The suspension polymerization method in the present invention uses a dispersant and performs polymerization mainly without passing through 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 dispersant used is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, and particularly preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total monomers. Part. 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 a dispersing agent, a polymerization initiator, etc. Preferably within 24 hours.

  In the miniemulsion polymerization method in the present invention, a surfactant and a co-surfactant are used, and after the monomer is forcibly dispersed using a homogenizer or an ultrasonic device, the polymerization is mainly performed without using 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.

The molecular weight of the polymer in the aqueous liquid obtained in the present invention can be adjusted by the amount of the tellurium compound, the reaction time and the polymerization temperature, but a living radical polymer having a number average molecular weight of 500 to 1000000 can be obtained. It is particularly suitable for obtaining a living radical polymer having a number average molecular weight of 1,000 to 500,000.
The molecular weight distribution (PD = MW / Mn) of the polymer in the aqueous liquid obtained in the present invention can be controlled between 1.02 and 1.50. Furthermore, a narrower polymer having a molecular weight distribution of 1.02 to 1.30, further 1.02 to 1.20, and further 1.02 to 1.10 can be obtained.

Since the polymer in the aqueous liquid obtained by the present invention proceeds by living radical polymerization, it functions as a macro-living initiator (macro-initiator). In other words, by adding the same or different vinyl monomer to the aqueous liquid obtained in the present invention, it is possible to produce an aqueous liquid composed of a polymer having an increased molecular weight or an arbitrary block and graft (co) polymer. is there.
The aqueous liquid obtained in the present invention may be used alone as it is, but depending on the application, known additives such as various antioxidants, viscosity modifiers, pigments, dyes, crosslinking agents, plasticizers, UV absorption You may add and use an agent, a light stabilizer, etc.
From the aqueous liquid obtained in the present invention, the polymer can be taken out from the aqueous liquid by techniques such as centrifugation, salting out, filtration, and drying, as necessary. Moreover, the taken-out polymer can be made into a pellet shape or the like by a method such as extrusion molding according to the purpose.

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: ¹ H-NMR: Varian Gemini 2000 (300 MHz for ¹ H), JEOL JNM-A400 (400 MHz for ¹ H)
¹³ C-NMR: Varian Gemini 2000, JEOL JNM-A400
HRMS: JEOL JMS-300
Gas chromatography: Shimadzu GC-14B
Gel permeation chromatography: TOSOH Corporation, TSKgel GMHhr-H

Synthesis Example 1 (Ethyl-2-methyl-2-methylterranyl-propionate)
6.38 g (50 mmol) of metal tellurium (manufactured by Aldrich, trade name: Tellurium (−40 mesh)) was suspended in 50 ml of THF, and 52.9 ml (1.04 M diethyl ether solution, 55 mmol) of methyllithium (same as above) was suspended therein. ) Was slowly added dropwise at room temperature (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 6.53 g (yield 51%) of a yellow oil.
It was confirmed to be ethyl-2-methyl-2-methylterranyl-propionate by HRMS, ¹ H-NMR, and ¹³ C-NMR.
HRMS (EI) m / z: Calcd for C ₇ H ₁₄ O ₂ Te (M) ⁺ , 260.0056; Found 260.0053
¹ H-NMR (300 MHz, CDCl ₃ )
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 ) -17.38, 13.89, 23.42, 27.93, 60.80, 176.75

Synthesis Example 2 (Ethyl-2-methyl-2-n-butylteranyl-propionate)
6.38 g (50 mmol) of metal tellurium (same as above) was suspended in 50 ml of THF, and 34.4 ml (55 mmol) of n-butyllithium (manufactured by Aldrich, 1.6M hexane solution) was slowly added dropwise at room temperature. (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 8.98 g (yield 59.5%) of a yellow oil.
It was confirmed by ¹ H-NMR that it was ethyl-2-methyl-2-n-butylteranyl-propionate.
¹ H-NMR (300 MHz, CDCl ₃ )
0.93 (t, J = 7.5 Hz, 3H), 1.25 (t, J = 7.2 Hz, 3H), 1.37 (m, 2H), 1.74 (s, 6H), 1. 76 (m, 2H), 2.90 (t, J = 7.5 Hz, 2H, CH ₂ Te), 4.14 (q, J = 7.2 Hz, 2H)

Synthesis Example 3 (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 methyl lithium (manufactured by Kanto Chemical Co., Inc., diethyl ether solution) 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 sodium sulfate and concentrated under reduced pressure to obtain 2.69 g (9.4 mmol: yield 75%) of a black purple oily substance.

Example 1
Synthesis of aqueous solution of polymethyl methacrylate In a glove box substituted with nitrogen, 23 μL (0.10 mmol) of ethyl-2-methyl-2-butylterranyl-propionate prepared in Synthesis Example 2 and 1.00 g (10 mmol) of methyl methacrylate Dibutyl ditelluride prepared in Synthesis Example 3 12.4 μL (0.05 mmol), 2,2′-azobis (isobutyronitrile) 8.2 mg (0.05 mmol), sodium dodecylsulfonate 0.1 g and nitrogen bubbling A mixed liquid consisting of 15 g of sufficiently degassed distilled water was prepared and reacted at 60 ° C. for 24 hours to obtain an aqueous liquid (emulsion) of polymethyl methacrylate.
The polymerization rate calculated by the weight method was 77%.
By GPC [TOSOH Corporation, TSKgel GMHhr-H, 7.8 mm (id.) × 30 cm] analysis (based on the molecular weight of polystyrene standard sample), Mn = 20,900 and PD = 1.36.
The average particle diameter measured by a dynamic light scattering method (DLS-700, Otsuka Electronics Co., Ltd.) was 29 nm.

Example 2
Synthesis of polymethyl methacrylate aqueous solution Except that the amount of sodium dodecyl sulfonate added in Example 1 was changed to 0.45 g, the reaction was carried out in the same manner as in Example 1 to prepare an aqueous solution (emulsion) of polymethyl methacrylate. Obtained.
The polymerization rate calculated by the weight method was 91%.
By GPC [TOSOH Corporation, TSKgel GMHhr-H, 7.8 mm (id.) × 30 cm] analysis (based on the molecular weight of a polystyrene standard sample), Mn = 14,600 and PD = 1.20.
The average particle diameter measured by a dynamic light scattering method (DLS-700, Otsuka Electronics Co., Ltd.) was 26 nm.

Example 3
Synthesis of aqueous solution of polymethyl methacrylate In a glove box substituted with nitrogen, 23 μL (0.10 mmol) of ethyl-2-methyl-2-butylterranyl-propionate prepared in Synthesis Example 2 and 1.00 g (10 mmol) of methyl methacrylate 12.4 μL (0.05 mmol) of dibutyl ditelluride prepared in Synthesis Example 3, 8.2 mg (0.05 mmol) of 2,2′-azobis (isobutyronitrile), 0.05 g of hexadecane, and sodium dodecylsulfonate A liquid mixture consisting of 01 g and 15 g of distilled water sufficiently deaerated by nitrogen bubbling was prepared, and the mixture was uniformly dispersed by irradiating with ultrasonic waves for 30 seconds using an ultrasonic homogenizer. The dispersion was reacted at 60 ° C. for 24 hours in a nitrogen purged glass tube to obtain an aqueous liquid (emulsion) of polymethyl methacrylate.
From the gas chromatography analysis, the polymerization rate was 100%.
By GPC [TOSOH Corporation, TSKgel GMHhr-H, 7.8 mm (id.) × 30 cm] analysis (based on the molecular weight of polystyrene standard sample), Mn = 9,300 and PD = 1.37.
The average particle diameter by the dynamic light scattering method (Otsuka Electronics Co., Ltd. DLS-700) was 151 nm.

Example 4
Synthesis of poly (n-butyl methacrylate) aqueous liquid The reaction was conducted in the same manner as in Example 3 except that methyl methacrylate in Example 3 was changed to 1.42 g (10 mmol) of n-butyl methacrylate. An aqueous liquid (emulsion) of butyl was obtained.
From the gas chromatography analysis, the polymerization rate was 96%.
By GPC [TOSOH Corporation, TSKgel GMHhr-H, 7.8 mm (id.) × 30 cm] analysis (based on molecular weight of polystyrene standard sample), Mn = 13,700 and PD = 1.18.
The average particle size by dynamic light scattering method (Otsuka Electronics Co., Ltd. DLS-700) was 466 nm.

Example 5
Synthesis of polystyrene aqueous liquid In a nitrogen-substituted glove box, 23 μL (0.10 mmol) of ethyl-2-methyl-2-butylterranyl-propionate prepared in Synthesis Example 2, 1.00 g (10 mmol) of styrene and 2,2′- A mixed liquid consisting of 8.2 mg (0.05 mmol) of azobis (isobutyronitrile), 0.05 g of hexadecane, 0.01 g of sodium dodecylsulfonate, and 15 g of distilled water sufficiently deaerated by nitrogen bubbling was prepared. Using a homogenizer, ultrasonic waves were applied for 30 seconds for uniform dispersion. The dispersion was reacted in a glass tube purged with nitrogen at 60 ° C. for 24 hours to obtain an aqueous polystyrene solution (emulsion).
From the gas chromatography analysis, the polymerization rate was 93%.
According to GPC [[TOSOH Corporation, TSKgel GMHhr-H, 7.8 mm (id.) × 30 cm] analysis (based on the molecular weight of polystyrene standard sample), Mn = 16,600 and PD = 1.46.
The average particle diameter according to a dynamic light scattering method (DLS-700, Otsuka Electronics Co., Ltd.) was 166 nm.

Example 6
Polymethyl methacrylate-polystyrene diblock polymer Synthesis of aqueous liquid 4 g of polymethyl methacrylate aqueous liquid (0.25 g of polymethyl methacrylate component) and styrene as a macroinitiator synthesized in Example 3 in a nitrogen-substituted glove box A mixture consisting of 0.25 g (2.5 mmol) was prepared.
The mixed solution was sealed in a glass tube purged with nitrogen and reacted at 60 ° C. for 12 hours to obtain an aqueous solution (emulsion) of polymethyl methacrylate-polystyrene diblock polymer.

Example 7
Polymethyl methacrylate-polystyrene diblock polymer Synthesis of aqueous liquid Reaction of Example 6 using polymethyl methacrylate aqueous liquid (Mn = 7,500, PD = 1.37) prepared in the same manner as in Example 3. A reaction was carried out in the same manner as in Example 6 except that the temperature was changed to 80 ° C. to obtain an aqueous liquid (emulsion) of polymethyl methacrylate-polystyrene diblock polymer.

Example 8
Polymethyl methacrylate-polystyrene diblock polymer Synthesis of aqueous liquid 4 g of polymethyl methacrylate aqueous liquid (0.25 g of polymethyl methacrylate component) and styrene as a macroinitiator synthesized in Example 3 in a nitrogen-substituted glove box A liquid mixture consisting of 0.25 g (2.5 mmol) and 2,2′-azobis (isobutyronitrile) 2.05 mg (0.0125 mmol) was prepared.
The mixed solution was sealed in a glass tube purged with nitrogen and reacted at 60 ° C. for 12 hours to obtain an aqueous solution (emulsion) of polymethyl methacrylate-polystyrene diblock polymer.

Example 9
Polymethyl methacrylate-polystyrene diblock polymer Synthesis of aqueous liquid Reaction of Example 8 using polymethyl methacrylate aqueous liquid (Mn = 7,500, PD = 1.37) prepared in the same manner as in Example 3. A reaction was carried out in the same manner as in Example 8 except that the temperature was changed to 80 ° C., to obtain an aqueous liquid (emulsion) of polymethyl methacrylate-polystyrene diblock polymer. Table 1 shows the experimental results of Examples 6 to 9.

The polymerization rate was calculated by a weight method.
The number average molecular weight (Mn) and molecular weight distribution (PD) were measured by GPC [TOSOH Corporation, TSKgel GMHhr-H, 7.8 mm (id.) × 30 cm] analysis (based on the molecular weight of a polystyrene standard sample).

Example 10
N-butyl polyacrylate Synthesis of aqueous liquid In a glove box substituted with nitrogen, 1.28 g (10 mmol) of n-butyl acrylate (manufactured by Sigma-Aldrich Japan) and polyvinyl alcohol (saponification degree 80%, Nippon Synthetic Chemical Industry Co., Ltd.) ), Product name: Gohsenal KH-17] A mixed solution consisting of 3.8 mg and 4.3 mL of distilled water sufficiently deaerated by nitrogen bubbling was prepared and stirred for 1 hour.
2.25 μL (0.013 mmol) of ethyl-2-methyl-2-methylterranyl-propionate prepared in Synthesis Example 1 and 2,2′-azobis (isobutyronitrile) (manufactured by Otsuka Chemical Co., Ltd.) Name: AIBN) 1.05 mg (0.006 mmol) was added and reacted at 60 ° C. for 7 hours to obtain a poly (n-butyl acrylate) aqueous solution (suspension).
By GPC analysis (based on the molecular weight of a polystyrene standard sample), Mn = 88000 PD = 1.18.

Claims (6)

Polymerizing a vinyl monomer in an aqueous medium using (a) an organic tellurium compound represented by formula (1), (b1) a surfactant and / or a dispersant, and (d) an azo polymerization initiator. The manufacturing method of the aqueous liquid containing the polymer characterized by these.

(In the formula, R ¹ represents a C _{1 to} C ₈ alkyl group, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₈ alkyl group. R ⁴ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an oxycarbonyl group, or a cyano group. In an aqueous medium, (a) an organic tellurium compound represented by formula (1), (b1) a surfactant and / or a dispersant, (c) a compound represented by formula (2), (d) an azo-based compound The manufacturing method of the aqueous liquid containing the polymer characterized by superposing | polymerizing a vinyl monomer using a polymerization initiator.

(In the formula, R ¹ represents a C _{1 to} C ₈ alkyl group, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₈ alkyl group. R ⁴ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an oxycarbonyl group, or a cyano group.
(R ¹ Te) ₂ (2)
(In the formula, R ¹ is the same as above.) In an aqueous medium, a vinyl monomer is miniemulsion polymerized using (a) an organic tellurium compound represented by the formula (1), (b2) a surfactant and a co-surfactant, and (d) an azo polymerization initiator. A method for producing an aqueous liquid containing a polymer.

(In the formula, R ¹ represents a C _{1 to} C ₈ alkyl group, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₈ alkyl group. R ⁴ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an oxycarbonyl group, or a cyano group. In an aqueous medium, (a) an organic tellurium compound represented by formula (1), (b2) a surfactant and a co-surfactant, (c) a compound represented by formula (2), (d) an azo-based compound The manufacturing method of the aqueous liquid containing the polymer characterized by carrying out the miniemulsion polymerization of the vinyl monomer using a polymerization initiator.

(In the formula, R ¹ represents a C _{1 to} C ₈ alkyl group, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₈ alkyl group. R ⁴ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an oxycarbonyl group, or a cyano group.
(R ¹ Te) ₂ (2)
(In the formula, R ¹ is the same as above.) With an aqueous solution obtained by the process according to any one of claims 1 to 4 macro living initiator as (macroinitiator), preparation of an aqueous solution containing a polymer characterized by polymerizing a vinyl monomer Method. The aqueous liquid containing the polymer manufactured with the manufacturing method in any one of Claims 1-5.
It was.