JP2017200882A - Organic tellurium compound and method for producing the same, and living radical polymerization initiator and method for producing vinyl polymer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic tellurium compound that has versatility to be applied to the polymerization of various kinds of vinyl monomers, when used as a living radical polymerization initiator, and can be recovered as an organic ditellurium compound with high efficiency after the polymerization reaction and a method for producing the same, and a living radical polymerization initiator prepared with the organic tellurium compound and a method for producing a vinyl polymer using the same.SOLUTION: The present invention provides an organic tellurium compound represented by formula (1) [Ris a C1-C20 fluorine-containing alkyl group; Rand Rindependently represent H or a C1-C8 alkyl group; Ris a C1-C8 alkyl group, an aryl group, a substituted aryl group, an aromatic heterocycle group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group].SELECTED DRAWING: None

Description

  The present invention relates to an organic tellurium compound, a method for producing the same, a living radical polymerization initiator, and a method for producing a vinyl polymer using the same.

  The living radical polymerization method is a polymerization method that enables precise control of the molecular structure and the production of a polymer with a uniform composition while maintaining the simplicity and versatility of the conventional radical polymerization method. Demonstrate great power. Therefore, in recent years, the development of living radical polymerization technology has been remarkable, and living radical polymerization methods using various techniques have been reported. Among them, TERP (organotellium-mediated radical polymerization), which is a living radical polymerization method using an organic tellurium compound, is versatile and applicable to polymerization of various types of vinyl monomers, and practically the same as ordinary radical polymerization. This is a polymerization method that has attracted particular attention in that the molecular weight and molecular weight distribution of the polymer can be highly controlled under reaction conditions (see Patent Documents 1 to 4).

  In general, the growth terminal of a polymer obtained by a living radical polymerization method is called a dormant terminal in which a radical is reversibly protected with an appropriate protecting group, and the growth terminal of a polymer obtained by a TERP method is polymer- Te-R form. A polymer obtained by chemically removing the dormant end is used as a product.

On the other hand, since tellurium is a rare element having a Clark number of 2 × 10 ⁻⁷ %, it is required to recover the tellurium removed from the polymerization terminal. For example, in Patent Document 5, when a living radical polymer synthesized by the TERP method is irradiated with light in the presence of a diene, a coupling reaction of polymerization terminal radicals selectively proceeds and an organic ditellurium compound is quantitatively produced as a by-product. It is disclosed that it can be recovered. Patent Document 2 discloses the use of an organic ditellurium compound in the TERP method.

International Publication No. 2004/014848 International Publication No. 2004/014962 International Publication No. 2004/072126 International Publication No. 2004/096870 JP 2012-236984 A

  However, Patent Document 5 does not discuss any specific method for recovering the organic ditellurium compound. Further, since the polymer dimerization reaction is essential, there is a problem that the design of the polymer is limited.

  It is an object of the present invention to have versatility applicable to the polymerization of various types of vinyl monomers when used as a living radical polymerization initiator, and can be recovered as an organic ditellurium compound with high efficiency after the polymerization reaction. An organic tellurium compound and a method for producing the same, and a living radical polymerization initiator using the organic tellurium compound and a method for producing a vinyl polymer using the same.

  The present inventors have found that by using a tellurium compound having a structure in which a fluorine-containing alkyl group is bonded to a tellurium atom as a living radical polymerization initiator, the used organic tellurium compound can be recovered as an organic ditellurium compound with high efficiency. The present invention has been completed.

  That is, the present invention provides the following organic tellurium compound and a method for producing the same, a living radical polymerization initiator, a method for producing a vinyl polymer using the same, and a vinyl polymer.

  Item 1 An organic tellurium compound represented by the following general formula (1).

[Wherein, R ¹ represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group. ]

  Item 2 A method for producing the organic tellurium compound according to Item 1, wherein the compound represented by the following general formula (4) is reacted with a base, the compound obtained by the reaction and the following general formula ( A process for reacting the compound represented by 5) with a method for producing an organic tellurium compound.

[Wherein, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group. ]

[Wherein, R ¹ represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. X represents a halogen atom. ]

  Item 3 A method for producing the organic tellurium compound according to Item 1, wherein the organic ditellurium compound represented by the following general formula (6) is reacted with a reducing agent, and the compound obtained by the reaction step: The manufacturing method of an organic tellurium compound including the process with which the compound represented by following General formula (7) is made to react.

[Wherein, R ¹ represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. ]

[Wherein, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group. X represents a halogen atom. ]

  Item 4 A living radical polymerization initiator comprising the organic tellurium compound according to Item 1.

Item 5: A step of living radical polymerization of a vinyl monomer using the organic tellurium compound of Item 1 to synthesize a vinyl polymer (A);
A step (B) in which a reducing agent is allowed to act on the vinyl polymer obtained in the step (A);
And (C) a step of washing the vinyl polymer obtained in the step (B) with a fluorinated solvent.

  Item 6. The method for producing a vinyl polymer according to Item 5, wherein the cleaning in the step (C) is a separation cleaning.

  Item 7 A vinyl polymer produced by the method according to Item 5 or 6.

  According to the present invention, when used as a living radical polymerization initiator, it has versatility applicable to the polymerization of various types of vinyl monomers and can be recovered as an organic ditellurium compound with high efficiency after the polymerization reaction. An organic tellurium compound and a method for producing the same, a living radical polymerization initiator using the organic tellurium compound, and a method for producing a vinyl polymer using the same can be provided.

  The recovered organic ditellurium compound containing the rare element tellurium can be reused for living radical polymerization.

  Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiments are merely examples. The present invention is not limited to the following embodiments.

<Organic tellurium compound>
The organic tellurium compound of the present invention is represented by the following general formula (1).

[Wherein, R ¹ represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group. ]

Specific examples of the group represented by R ¹ are as follows.

  In the fluorine-containing alkyl group having 1 to 20 carbon atoms, part or all of the hydrogen atoms bonded to the carbon atoms constituting the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms are substituted with fluorine atoms. Suitable specific examples include, for example, a group represented by the following general formula (2), a group represented by the general formula (3), and the like.

  [In formula, n represents the integer of 0-5, m represents the integer of 1-15. ]

  n preferably represents 0 to 3, and m preferably represents 6 to 10.

  Examples of the group represented by the general formula (2) include (1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8). -Septadecafluorooctyl) group, (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-septadecafluorononyl) group, (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) group, (3,3,4,4,5,5,6,6) , 7,7,8,8,9,9,10,10,10-septadecafluorodecyl) group, (4,4,5,5,6,6,7,7,8,8,9,9) , 10,10,11,11,11-septadecafluoroundecyl) group, (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10, 10, 11, 11, 12, 12, 13, 13, 13-f It can be exemplified Eiko Saka fluoro dodecyl) groups. Preferably, (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) group, (3,3,4,4,5,5,6) , 6,7,7,8,8,9,9,10,10,10-septadecafluorodecyl) group, more preferably (3,3,4,4,5,5,6,6, 7, 7, 8, 8, 9, 9, 10, 10, 10-septadecafluorodecyl) group.

  [In formula, q represents the integer of 0-3, p represents the integer of 1-9. ]

  Examples of the group represented by the general formula (3) include (1,2,2,3,3,4,4,5,5,6,6-undecafluorocyclohexyl) ethyl group. it can.

The groups represented by R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is specifically as follows.

  Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. Group, a linear or branched alkyl group such as an octyl group, and a cyclic alkyl group such as a cyclohexyl group. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.

The group represented by R ⁴ is a C 1-8 alkyl group, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, acyl group, amide group, oxycarbonyl group, cyano group, allyl group or A propargyl group, specifically as follows.

  Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. Group, a linear or branched alkyl group such as an octyl group, and a cyclic alkyl group such as a cyclohexyl group. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.

  Examples of the aryl group include a phenyl group and a naphthyl group. A phenyl group is preferred.

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 above 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 ⁴¹ (R ⁴¹ is the number of carbon atoms). 1-8 alkyl groups, aryl groups, C1-C8 alkoxy groups or aryloxy groups), sulfonyl groups, trifluoromethyl groups, and the like. These substituents may be substituted by one or two.

  Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.

  The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tet- A butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and the like can be given.

  Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.

As the amide group, —CONR ⁴²¹ R ⁴²² (R ⁴²¹ and R ⁴²² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group) can be exemplified.

As the oxycarbonyl group, a group represented by —COOR ⁴³ (R ⁴³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group) is preferable. For example, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, propoxy A carbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, ter-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group, and the like can be given. Preferred oxycarbonyl groups are a methoxycarbonyl group and an ethoxycarbonyl group.

As an allyl group, —CR ⁴⁴¹ R ⁴⁴² —CR ⁴⁴³ = CR ⁴⁴⁴ R ⁴⁴⁵ (R ⁴⁴¹ and R ⁴⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁴³ , R ⁴⁴⁴ and R ⁴⁴⁵ are And each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and each substituent may be linked by a cyclic structure).

As the propargyl group, —CR ⁴⁵¹ R ⁴⁵² —C≡CR ⁴⁵³ (R ⁴⁵¹ and R ⁴⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁵³ is a hydrogen atom and an alkyl group having 1 to 8 carbon atoms) , Aryl group or silyl group).

  Specifically, the organic tellurium compound represented by the general formula (1) is ethyl-2-methyl-2- (1,1,2,2,3,3,4,4,5,5,6,6). , 7,7,8,8,8-septadecafluorooctylteranyl) -propionate, ethyl-2-methyl-2- (2,2,3,3,4,4,5,5,6,6) 7,7,8,8,9,9,9-septadecafluorononylterranyl) -propionate, ethyl-2-methyl-2- (3,3,4,4,5,5,6,6,7 , 7,8,8,8-tridecafluorooctylterranyl) -propionate, ethyl-2-methyl-2- (3,3,4,4,5,5,6,6,7,7,8, 8,9,9,10,10,10-septadecafluorodecylterranyl) propionate, ethyl-2-methyl-2- (4,4,5,5 6,6,7,7,8,8,9,9,10,10,11,11,11-septadecafluoroundecylteranyl) -propionate, methyl-2-methyl-2- (3,3 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecylterranyl) -propionate, diethylamino-2-methyl-2- (3 , 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecylterranyl) -propionate, 2-methyl-2- ( 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecylteranyl) ru-propionitrile, methyl-2 -(3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10 Septadecafluorodecylterranyl) propionate, 1-phenylethyl 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadedecafluoro Decyl telluride, 3- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecylterranyl) -2- Methyl-1-propene, 4- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecylterranyl) Examples include -3-methyl-1-butyne. Preferably, ethyl-2-methyl- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylterranyl) -propionate, ethyl-2- Methyl- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecylterranyl) -propionate, Preferably ethyl-2-methyl- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecylteranyl) -Propionate.

(Method 1 for producing organic tellurium compound)
The organic tellurium compound represented by the general formula (1) includes, for example, a step of reacting a compound represented by the following general formula (4) and a base, a compound obtained by the above reaction, and the following general formula (5) It can manufacture from the 1st method including the process with which the compound represented by these is made to react.

[Wherein, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group. ]

Each group represented by R ² , R ³ and R ⁴ is as described above. Preferably, in the first production method of the present invention, R ⁴ is an acyl group, an amide group, an oxycarbonyl group or a cyano group.

  Specific examples of the compound represented by the general formula (4) include ethyl-2-methyl-propionate, methyl-2-methyl-propionate, diethylamino-2-methyl-propionate and the like.

  The compound represented by the general formula (5) is as follows.

[Wherein, R ¹ represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. X represents a halogen atom. ]

Each group represented by R ¹ is as described above.

  Examples of the group represented by X include a halogen atom such as a fluorine atom, chlorine, bromine or iodine. Of these, chlorine and bromine are preferable.

  Specific examples of the compound represented by the general formula (5) include (1, 1, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8 -Septadecafluorooctylterranyl) chloride, (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-Septadecafluorononylterra) Nyl) bromide, (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylterranyl) bromide, (3,3,4,4,5) , 5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecylterranyl) chloride, (3,3,4,4,5,5,6,6) , 7,7,8,8,9,9,10,10,10-septadecafluorodecylteranyl) bromide, (4,4,5,5,6,6,7,7,8,8, , 9,10,10,11,11,11-septadecafluoroundecylteranyl) rubromide, (3,3,4,4,5,5,6,6,7,7,8,8,9) , 9, 10, 10, 11, 11, 12, 12, 13, 13, 13-heneicosacafluorododecyl teranyl) bromide. Preferably, (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylteranyl) bromide, (3,3,4,4,5,5) 5,6,6,7,7,8,8,9,9,10,10,10-septadedecafluorodecylteranyl) bromide is preferred.

  As the base, lithium diisopropylamide, hexamethyldisilazane lithium, lithium tetramethylpiperidine, lithium amide, potassium diisopropylamide, potassium amide, sodium isopropylamide, sodium amide and the like can be used. Among these, lithium diisopropylamide is preferable.

  The first production method of the organic tellurium compound represented by the general formula (1) is specifically as follows.

  The base is prepared in a solvent. Solvents that can be used include polar solvents such as dimethylformamide (DMF), aromatic solvents such as toluene and xylene, aliphatic hydrocarbons such as hexane and dimethoxyethane, and ether solvents such as diethyl ether and tetrahydrofuran (THF). Can be mentioned. Preferably, THF is good. The amount of the solvent used may be adjusted as appropriate, but is usually 5 to 500 ml, preferably 10 to 100 ml, with respect to 1 g of the base.

  The compound represented by the general formula (4) is slowly added dropwise to the base prepared above and stirred. While the reaction time varies depending on the reaction temperature, it is usually 5 minutes to 24 hours, preferably 10 minutes to 3 hours. The reaction temperature is preferably −150 to 50 ° C., and preferably −80 to 0 ° C.

  Next, the compound represented by the general formula (5) is added to the reaction solution and stirred. While the reaction time varies depending on the reaction temperature, it is usually 5 minutes to 24 hours, preferably 10 minutes to 3 hours. The reaction temperature is −150 to 50 ° C., preferably −80 to 20 ° C.

  After completion of the reaction, the solvent is concentrated and the desired product is isolated and purified. Prior to solvent concentration, washing with water, saline, or the like may be performed as appropriate. The purification method can be appropriately selected depending on the compound, but vacuum distillation, recrystallization and the like are usually preferred.

(Method 2 for producing organic tellurium compound)
The organic tellurium compound represented by the general formula (1) includes a step of reacting an organic ditellurium compound represented by the following general formula (6) with a reducing agent, a compound obtained by the above reaction step, and the following general formula ( It can also manufacture from the 2nd method including the process of reacting with the compound represented by 7).

[Wherein, R ¹ represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. ]

[Wherein, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group. X represents a halogen atom. ]

Each group represented by R ¹ , R ² , R ³ , R ⁴ and X is as described above.

  Specific examples of the compound represented by the general formula (7) include ethyl-2-methyl-2-chloro-propionate, ethyl-2-methyl-2-bromo-propionate, ethyl-2-methyl-2-iodo- Propionate, methyl-2-methyl-2-bromo-propionate, diethylamino-2-methyl-2-bromo-propionate, 2-methyl-2-bromo-propionitrile, (1-bromo-ethyl) benzene, 1-bromo -1-methoxyhexane, 4-bromo-2-pentene, crotyl bromide, 3-bromo-2-methyl-1-propene, 3-bromo-1-trimethylsilylpropyne, 4-bromo-3-methyl-1- Butin and the like can be mentioned. Preferred are ethyl-2-methyl-2-bromo-propionate and (1-bromo-ethyl) benzene.

  Examples of the reducing agent used for producing the compound represented by the general formula (7) include lithium metal, sodium metal, potassium metal, naphthalenide of these metals, sodium borohydride, lithium borohydride, and potassium borohydride. , Lithium triethylborohydride, lithium naphthalenide, or the like can be used. Among these, lithium triethylborohydride is preferable.

  The second production method of the organic tellurium compound represented by the general formula (1) is specifically as follows.

  The organic ditellurium compound represented by the general formula (6) is dissolved in a solvent. Solvents that can be used include polar solvents such as dimethylformamide (DMF), aromatic solvents such as toluene and xylene, aliphatic hydrocarbons such as hexane and dimethoxyethane, and ether solvents such as diethyl ether and tetrahydrofuran (THF). Can be mentioned. Preferably, THF is good. The amount of the solvent used may be appropriately adjusted, but is usually 5 to 500 ml, preferably 10 to 100 ml, with respect to 1 g of the organic ditellurium compound.

  An organic reducing agent is slowly dropped into the solvent and stirred. While the reaction time varies depending on the reaction temperature, it is usually 5 minutes to 24 hours, preferably 10 minutes to 3 hours. As reaction temperature, -40-80 degreeC is good, Preferably 0-50 degreeC is good.

  Next, the compound represented by the general formula (7) is added to the reaction solution and stirred. While the reaction time varies depending on the reaction temperature, it is usually 5 minutes to 24 hours, preferably 10 minutes to 3 hours. As reaction temperature, -40-100 degreeC is good, Preferably 0-50 degreeC is good.

  After completion of the reaction, the solvent is concentrated and the desired product is isolated and purified. Prior to solvent concentration, washing with water, saline, or the like may be performed as appropriate. The purification method can be appropriately selected depending on the compound, but vacuum distillation, recrystallization and the like are usually preferred.

(Method for producing compound represented by general formula (5))
The compound represented by the general formula (5) can be produced by reacting an organic ditellurium compound represented by the following general formula (6) with a halogenating agent.

[Wherein, R ¹ represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. ]

Each group represented by R ¹ is as described above.

  Specific examples of the organic ditellurium compound represented by the general formula (6) include di-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8, 8,8-septadecafluorooctyl ditelluride, di-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-septadeca Fluorononyl ditelluride, di-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl ditelluride, di-3,3,4, 4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecyl ditelluride, di-4,4,5,5,6,6 7,7,8,8,9,9,10,10,11,11,11-septadecafluoroundecylteranyl) ruditelluride, di-3,3,4,4,5,5,6,6 7, 7, 8, 8 9,9,10,10,11,11,12,12,13,13,13- can be mentioned Heng Eiko Saka fluoro dodecyl ditelluride like. Preferably, di-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl ditelluride, di-3,3,4,4,5 5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecyl ditelluride.

  Examples of the halogenating agent include chlorine, bromine and iodine. Bromine is preferable.

  The method for producing the compound represented by the general formula (5) is specifically as follows.

  The organic ditellurium compound represented by the general formula (6) is dissolved in a solvent. Solvents that can be used include polar solvents such as dimethylformamide (DMF), aromatic solvents such as toluene and xylene, aliphatic hydrocarbons such as hexane and dimethoxyethane, and ether solvents such as diethyl ether and tetrahydrofuran (THF). Can be mentioned. Preferably, THF is good. The amount of the solvent used may be appropriately adjusted, but is usually 5 to 500 ml, preferably 10 to 100 ml, with respect to 1 g of the organic ditellurium compound represented by the general formula (6).

  Add the halogenating agent to the solvent and stir. While the reaction time varies depending on the reaction temperature, it is usually 5 minutes to 24 hours, preferably 10 minutes to 3 hours. As reaction temperature, -50-50 degreeC is good, Preferably -20-30 degreeC is good.

  The solution of the compound represented by the general formula (5) obtained as described above may be used as it is for the production of the organic tellurium compound represented by the general formula (1), or may be used after being isolated and purified. Also good.

(Method for producing organic ditellurium compound)
The organic ditellurium compound represented by the general formula (6) includes a ditelluride dianion obtained by reducing metal tellurium and a compound R ¹ -X (wherein R ¹ is a fluorine-containing alkyl having 1 to 20 carbon atoms). And a group X represents a halogen atom).

  Examples of the reducing agent that can be used include metallic sodium, metallic lithium, metallic potassium, naphthalenide of these metals, and the like. Metal sodium is preferable.

  Metal tellurium is suspended in a solvent. Examples of the solvent that can be used include ether solvents such as tetrahydrofuran (THF), ethylenediamine, and the like. Ethylenediamine is preferable. The amount of the solvent used may be adjusted as appropriate, but is usually 5 to 500 ml, preferably 10 to 100 ml, with respect to 1 g of metal tellurium.

  Add the reducing agent to the suspension and stir. While the reaction time varies depending on the reaction temperature, it is usually 5 minutes to 24 hours, preferably 10 minutes to 6 hours. The reaction temperature is preferably 0 to 150 ° C, and preferably 60 to 130 ° C.

To the resulting Tae Ruri blunder anion solution was slowly added dropwise a compound R ¹ -X, stirred. While the reaction time varies depending on the reaction temperature, it is usually 5 minutes to 24 hours, preferably 10 minutes to 3 hours. As reaction temperature, -50-50 degreeC is good, Preferably -20-20 degreeC is good.

  After completion of the reaction, the solvent is concentrated and the desired product is isolated and purified. Prior to solvent concentration, washing with water, saline, or the like may be performed as appropriate. The purification method can be appropriately selected depending on the compound, but vacuum distillation, recrystallization and the like are usually preferred.

<Manufacture of vinyl polymer>
The method for producing a vinyl polymer of the present invention includes a step (A) of synthesizing a vinyl polymer by subjecting a vinyl monomer to living radical polymerization using the organic tellurium compound represented by the above general formula (1), A step (B) in which a reducing agent is allowed to act on the vinyl polymer obtained in the step (A), and a step (C) in which the vinyl polymer obtained in the step (B) is washed with a fluorine-based solvent. It is a manufacturing method.

  The living radical polymerization in the above-mentioned step (A) is a living radical polymerization using the organic tellurium compound represented by the general formula (1) as a living radical polymerization initiator, promoting the reaction according to the type of vinyl monomer, and controlling the molecular weight. For the purpose of, for example, an azo polymerization initiator and / or an organic ditellurium compound represented by the general formula (6) may be added for polymerization.

  Specifically, a method of producing a vinyl polymer by polymerizing a vinyl monomer using any of the following (a) to (d) can be mentioned.

(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 (6).
(D) A mixture of an organic tellurium compound represented by the general formula (1), an azo polymerization initiator, and an organic ditellurium compound represented by the general formula (6).

  The organic tellurium compound represented by the general formula (1) used in the step (A) is as described above.

  The organic ditellurium compound represented by the general formula (6) used in the step (A) is as described above.

  The azo polymerization initiator used in the step (A) 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) (V-70), 2,2′-azobis (2-methylamidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propyl Pan], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2-cyano-2-propyl Azoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) and the like can be mentioned.

  The vinyl monomer used in the step (A) is not particularly limited as long as it can be radically polymerized, and specific examples thereof include the following vinyl monomers.

  Further, the vinyl polymer obtained by the production method of the present invention may be a copolymer composed of a plurality of vinyl monomers including the following vinyl monomers. In the present invention, the “vinyl monomer” refers to a monomer having a carbon-carbon double bond capable of radical polymerization in the molecule. “(Meth) acryl” means “at least one of acrylic and methacrylic”, “(meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”, and “(meth) acrylate” means “ “At least one of acrylate and methacrylate”.

  Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, (meth ) (Meth) acrylates having an aliphatic alkyl group such as tert-butyl acrylate and 2-ethylhexyl (meth) acrylate.

  (Meth) acrylates having an alicyclic alkyl group such as (meth) acrylic acid cyclohexyl, (meth) acrylic acid methylcyclohexyl, (meth) acrylic acid cyclododecyl, (meth) acrylic acid bornyl, (meth) acrylic acid isobornyl.

  (Meth) acrylate having an aromatic ring group such as benzyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate.

  (Meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

  Diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxy (Meth) acrylate having a polyethylene glycol structural unit such as tetraethylene glycol (meth) acrylate and methoxypolyethylene glycol (meth) acrylate.

  Aromatic vinyl monomers such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene and 1-vinylnaphthalene.

  (Meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, maleic anhydride, succinic anhydride, anhydrous A vinyl monomer having a carboxyl group, such as a monomer obtained by reacting an acid anhydride such as phthalic acid.

  Vinyl monomers having a sulfonic acid group such as styrene sulfonic acid, dimethylpropyl sulfonic acid (meth) acrylamide, ethyl sulfonate (meth) acrylate, ethyl sulfonate (meth) acrylamide, and vinyl sulfonic acid.

  Vinyl monomers having a phosphate group such as methacryloyloxyethyl phosphate.

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

  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.

  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, N-vinylacetamide, N-vinyl-ε-captolactam.

  Vinyl carboxylates such as vinyl acetate, vinyl pivalate and vinyl benzoate. 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.

  Among these, (meth) acrylate having an aliphatic alkyl group, (meth) acrylate having an alicyclic alkyl group, (meth) acrylate having a hydroxyl group, aromatic vinyl monomer, (meth) acrylamide, tertiary amine Containing unsaturated monomers, heterocyclic containing unsaturated monomers, and vinylamide monomers are preferred.

  The step (A) is a container substituted with an inert gas. For the purpose of promoting the reaction, controlling the molecular weight, etc., depending on the type of the vinyl monomer and the organic tellurium compound represented by the general formula (1) and the vinyl monomer, An azo polymerization initiator and / or an organic ditellurium compound represented by the general formula (6) is mixed. At this time, examples of the inert gas include nitrogen, argon, helium, and the like. Argon and nitrogen are preferable. Nitrogen is particularly preferable.

  The amount of vinyl monomer used in the above (a), (b), (c) and (d) can be appropriately adjusted depending on the physical properties of the intended vinyl polymer. Usually, a vinyl monomer can be 5-10,000 mol with respect to 1 mol of organic tellurium compounds represented by General formula (1). Preferably, the amount is 50 to 5,000 mol.

  When the organic tellurium compound represented by the general formula (1) and the azo polymerization initiator are used in combination, the amount of the azo polymerization initiator used is usually 1 mol of the organic tellurium compound represented by the general formula (1). On the other hand, an azo polymerization initiator can be 0.01-10 mol. Preferably, it is 0.05-2 mol.

  When the organic tellurium compound represented by the general formula (1) and the organic ditellurium compound represented by the general formula (6) are used in combination, the amount of the organic ditellurium compound represented by the general formula (6) is usually used. The organic ditellurium compound represented by the general formula (6) can be 0.01 to 100 mol per 1 mol of the organic tellurium compound represented by the general formula (1). Preferably, it is 0.1-10 mol.

  When the organic tellurium compound represented by the general formula (1), the organic ditellurium compound represented by the general formula (6) and the azo polymerization initiator are used in combination, An azo polymerization initiator can be 0.01-100 mol with respect to 1 mol in total of the organic tellurium compound represented by General formula (1) and the organic ditellurium compound represented by General formula (6). Preferably, it is 0.05-2 mol.

  The step (A) can be performed without a solvent, but it is preferable to use an aprotic solvent or a protic solvent that can be phase-separated from a fluorine-based solvent among solvents generally used in radical polymerization. Is carried out with stirring.

  Examples of aprotic solvents that can be used include benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, hexafluoroisopropaol, chloroform, Examples thereof include carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, trifluoromethylbenzene, propylene glycol monomethyl ether acetate and the like.

  Examples of protic solvents that can be used include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, diacetone alcohol, and the like.

  The above-mentioned solvents may be used as a mixture, or a fluorine-based solvent described later may be used as a mixture at the time of polymerization.

  What is necessary is just to adjust suitably the usage-amount of a solvent, for example, it is the range of 0.01-100 ml normally with respect to 1g of vinyl monomers, Preferably it is the range of 0.05-10 ml, More preferably, it is 0.00. It is in the range of 1-5 ml.

  What is necessary is just to adjust reaction temperature and reaction time suitably with the molecular weight or molecular weight distribution of the target vinyl polymer, and it normally stirs in the range of 0 degreeC-150 degreeC for 1 minute-100 hours.

The growth terminal of the vinyl polymer obtained by the step (A) is -TeR ¹ derived from an organic tellurium compound represented by the general formula (1) (wherein R ¹ is the same as above, and hereinafter referred to as a tellurium group). .)), It can be used as a macro-living radical polymerization initiator. In other words, an AB block copolymer, an ABA triblock copolymer, an ABC triblock copolymer, and the like can be produced using a macro living radical polymerization initiator.

  After completion of the step (A), the solvent or residual monomer is removed from the polymerization solution under reduced pressure to take out the target vinyl polymer, or the target vinyl polymer is simply removed by reprecipitation using an insoluble solvent. Can be separated.

  After the completion of the step (A), the growth end of the obtained vinyl polymer is converted into a tellurium group at the growth end of the vinyl polymer by the step (B) in which a reducing agent is allowed to act on the vinyl polymer after the completion of the polymerization reaction. The tellurium group is removed from the growing terminal of the vinyl polymer as an organic ditellurium compound. By subsequent washing in step (C), it can be recovered with high efficiency as an organic ditellurium compound.

  The step (B) can be performed on the solution after the living radical polymerization, even if the vinyl polymer is isolated from the polymerization solution after the completion of the step (A) and dissolved in an appropriate solvent capable of phase separation with the fluorinated solvent. However, from the viewpoint of shortening the process, it is preferable to add a reducing agent to the polymerization solution after the completion of the process (A) to cause the reaction. Further, when a vinyl polymer is obtained by mixing a fluorinated solvent at the time of polymerization, a reducing agent can be added to the solution after living radical polymerization and reacted.

  As a reducing agent that can be used in the step (B), a compound that exhibits a reducing property with respect to a tellurium group at the vinyl polymer growth terminal, and generally known as a reducing agent can be used. For example, at least one selected from a borohydride compound, an aluminum hydride compound, and an organic tellurol compound can be used.

  Examples of borohydride compounds include borane complexes (borane / dimethyl sulfide complex, borane / tetrahydrofuran complex), diborane, lithium borohydride, sodium borohydride, potassium borohydride, calcium borohydride, triacetoxy hydrogen Sodium borohydride, sodium cyanoborohydride, lithium tri (sec-butyl) borohydride, potassium tri (sec-butyl) borohydride, lithium triethylborohydride, zinc borohydride, tetramethylammonium borohydride, Examples thereof include tetraethylammonium borohydride, tetrabutylammonium borohydride, trimethyloctylammonium borohydride, trimethylbenzylammonium borohydride, and the like. Among these, sodium borohydride and lithium triethylborohydride are preferable from the viewpoints of safety, economy, and handleability.

  Examples of the aluminum hydride compound include lithium aluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, and the like.

  Examples of the organic tellurol compound include an organic tellurium compound represented by the following general formula (8).

[Wherein, R ¹ represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. ]

Each group represented by R ¹ is as described above.

  Examples of the organic tellurol compound represented by the general formula (8) include 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-ceptor. Decafluorooctyl tellurol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-septadecafluorononyl tellurol, 3,3 , 4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl tellurol, 3,3,4,4,5,5,6,6,7,7, 8,8,9,9,10,10,10-septadecafluorodecyl tellurol, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11 , 11,11-Septadecafluoroundecylterol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12 , 1 , 13,13,13- Heng Eiko Saka fluoro dodecyl ether roll, and the like. Preferably 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl tellurol, 3,3,4,4,5,5,6,6 , 7,7,8,8,9,9,10,10,10-septadecafluorodecyl tellurol, more preferably 3,3,4,4,5,5,6,6,7,7. , 8,8,9,9,10,10,10-septadecafluorodecyl tellurol.

  The organic tellurium compound represented by the general formula (8) can be produced by reducing the organic ditellurium compound represented by the general formula (6) with a borohydride compound or the like.

  The organic tellurol compound represented by the general formula (8) may be produced in the reaction system. For example, in a reaction system by using a mixture of a tellurium compound and an alcohol represented by the following general formula (9), a mixture of an organic ditellurium compound and a borohydride compound represented by the general formula (6), There is a method of generating an organic tellurol compound represented by the general formula (8).

[Wherein, R ¹ represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. Y represents a leaving group. ]

Each group represented by R ¹ is as described above.

  The leaving group represented by Y is not particularly limited as long as it can be eliminated in the polymer solution to produce the organic tellurol compound represented by the general formula (8), such as a trimethylsilyl (TMS) group. An organic tellurium compound represented by the general formula (8) can be generated by elimination of the TMS group by reaction with an alcohol such as methanol.

  Examples of the tellurium compound represented by the general formula (9) include 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- Septadecafluorooctyl-trimethylsilyl telluride, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-septadecafluorononyl-trimethylsilyl telluride Lido, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl-trimethylsilyl telluride, 3,3,4,4,5,5,6 , 6,7,7,8,8,9,9,10,10,10-septadecafluorodecyl-trimethylsilyl telluride, 4,4,5,5,6,6,7,7,8,8, 9,9,10,10,11,11,11-septadecafluoroundecyl-trimethylsilyl telluride, 3,3 4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosacafluorododecyl-trimethylsilyl telluride Etc. Preferred is 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecyl-trimethylsilyl telluride.

  The tellurium compound represented by the general formula (9) can be produced by reacting the organic ditellurium compound represented by the general formula (6) with a reducing agent and subsequently reacting with a silylating agent.

  Examples of the reducing agent used for producing the tellurium compound represented by the general formula (9) include lithium metal, sodium metal, potassium metal and naphthalenide of these metals, sodium borohydride, lithium borohydride, borohydride. Metal hydrides such as potassium, lithium triethylborohydride, sodium cyanoborohydride and the like can be used. Among these, lithium triethylborohydride is preferable.

  Examples of the silylating agent include trimethylsilyl chloride, trimethylsilyl bromide, triethylsilyl bromide, and the like, preferably trimethylsilyl bromide.

  The method for producing the tellurium compound represented by the general formula (9) is specifically as follows.

  The organic ditellurium compound represented by the general formula (6) is dissolved in a solvent. Solvents that can be used include polar solvents such as dimethylformamide (DMF), aromatic solvents such as toluene and xylene, aliphatic hydrocarbons such as hexane and dimethoxyethane, and ether solvents such as diethyl ether and tetrahydrofuran (THF). Can be mentioned. Preferably, THF is good. The amount of the solvent used may be appropriately adjusted, but is usually 1 to 500 ml, preferably 10 to 100 ml, based on 1 g of the organic ditellurium compound represented by the general formula (6).

  A reducing agent is slowly dropped into the solvent and stirred. While the reaction time varies depending on the reaction temperature, it is usually 5 minutes to 24 hours, preferably 10 minutes to 3 hours. As reaction temperature, -20-80 degreeC is good, Preferably 0-50 degreeC is good.

  Next, a silylating agent is added to the reaction solution and stirred. While the reaction time varies depending on the reaction temperature, it is usually 5 minutes to 24 hours, preferably 10 minutes to 3 hours. As reaction temperature, 0-80 degreeC is good, Preferably 10-50 degreeC is good.

  After completion of the reaction, the solvent is concentrated and the desired product is isolated and purified. Prior to solvent concentration, washing with water, saline, or the like may be performed as appropriate. The purification method can be appropriately selected depending on the compound, but vacuum distillation, recrystallization and the like are usually preferred.

  What is necessary is just to adjust suitably as the usage-amount of the solvent in a process (B), for example, it is the range of 0.01-100 ml normally with respect to 1 g of vinyl polymers, Preferably 0.1-10 ml is good.

  The temperature and time of a process (B) are normally 5-100 minutes in the range of 0-100 degreeC. Preferably, it is 20 to 80 ° C. and 10 minutes to 3 hours is good.

  The usage-amount of the reducing agent in a process (B) can be 0.5-10.0 mol with respect to 1 mol of organic tellurium compounds represented by General formula (1). Preferably, 1.0-3.0 mol is good.

  The production method of the present invention includes a step (C) of washing the vinyl polymer obtained in the step (B) with a fluorinated solvent. As the washing, a known washing method can be used, but separation washing is preferable, and an appropriate polymer capable of isolating the vinyl polymer from the solution after the completion of the step (B) and phase-separating with the fluorinated solvent can be used. A solution dissolved in a solvent or a solution after completion of the step (B) is used.

  As a specific example of the liquid separation cleaning, a solution in which a vinyl polymer is dissolved and a fluorinated solvent are mixed, and then the separated fluorinated solvent is extracted. By this operation, it is possible to remove the organic ditellurium compound from the vinyl polymer, and there is a further effect by repeating the liquid separation washing. Since the organic ditellurium compound removed from the vinyl polymer has a fluorine-containing alkyl group, the organic ditellurium compound is selected as the fluorine-based solvent by separating and washing the vinyl polymer solution using the fluorine-based solvent. It can be extracted and recovered. After separating and washing, the solvent of each phase is removed under reduced pressure, whereby the vinyl polymer and the organic ditellurium compound can be separated and recovered.

  The solvent that can be phase-separated from the above-described fluorine-based solvent may be an aprotic solvent, a protic solvent, or a mixed solvent thereof that can dissolve the vinyl polymer.

  Examples of aprotic solvents that can be used include benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, hexafluoroisopropaol, chloroform, Examples thereof include carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, trifluoromethylbenzene, propylene glycol monomethyl ether acetate and the like.

  Examples of protic solvents that can be used include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, diacetone alcohol, and the like.

  As the fluorine-based solvent, linear or branched fluorine atom-substituted alkanes, fluorine atom-substituted alkylamines, fluorine atom-substituted cycloalkanes, fluorine atom-substituted aromatics, and the like can be used. Specifically, 2H, 3H-decafluoropentane, tetradecafluorohexane, octadecafluorofluorooctane, eicosafluorononane, hexacosafluorododecane, hexafluoroisopropyl methyl ether, heptacosafluorotributylamine, pentadecafluorotri Examples include triethylamine, octadecafluorocyclopentane, tetradecafluoromethylcyclohexane, hexafluorobenzene, octafluorotoluene, octadecafluorodecanaphthalene and the like. Tetradecafluorohexane and tetradecafluoromethylcyclohexane are preferable.

  In the liquid separation washing, the fluorinated solvent is usually added in an amount of 0.1 to 10 times, preferably 0.5 to 3 times the amount of the organic solvent, the aqueous solvent or the mixed solvent thereof. Separation washing is usually performed at 10 to 60 ° C., preferably room temperature (20 ° C.). Moreover, you may add another solvent and water suitably.

  The molecular weight of the vinyl polymer obtained by the production method of the present invention can be appropriately adjusted depending on the reaction time and the amount of the organic tellurium compound, but a vinyl polymer having a number average molecular weight (Mn) of 500 to 1,000,000 is used. Can be obtained. It is particularly suitable for obtaining a vinyl polymer having Mn of 1,000 to 50,000. Mn can be measured by a gel permeation chromatography (hereinafter referred to as “GPC”) method.

  The molecular weight distribution (PDI) of the vinyl polymer obtained by the production method of the present invention can be controlled to 1.5 or less. The molecular weight distribution (PDI) is obtained by (weight average molecular weight (Mw) of vinyl polymer) / (number average molecular weight (Mn) of vinyl polymer). The smaller the PDI, the narrower the molecular weight distribution. When the value is 1.0, the width of the molecular weight distribution is the narrowest. Conversely, the larger the PDI, the smaller the molecular weight and the larger the molecular weight of the vinyl polymer designed.

  In the production method of the present invention, since the used organic tellurium compound can be recovered with high efficiency as an organic ditellurium compound, the resulting vinyl polymer has a low tellurium content. For example, optical use, medical use, electrical use -It can be suitably used for electronic applications, energy material applications, and the like.

  Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples, and can be implemented with appropriate modifications without departing from the scope of the invention.

<Synthesis of organic ditellurium compound>
(Synthesis Example 1)
Di-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecyl ditelluride was synthesized by the following method. .

Ethylenediamine (75 mL) was added to metal tellurium (2.55 g, 20 mmol) and metal sodium (0.51 g, 22 mmol) in a 200 mL three-necked glass container, and the mixture was refluxed for 3 hours with stirring. The reaction solution was allowed to cool to room temperature, and then a mixed solution of C ₈ F ₁₇ C ₂ H ₄ I (11.5 g, 20 mmol) and THF (25 mL) was added dropwise over 30 minutes. Stir for hours. The reaction solution was cooled in an ice bath, and 30 mL of water was slowly added, followed by extraction with diethyl ether. The organic phase was dehydrated with magnesium sulfate and then passed through a short column of celite. The crude product obtained by distilling off the solvent was washed with methanol, and recrystallized using chloroform as a solvent to obtain an orange solid (7.3 g, yield 65%). ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR confirmed the desired product.

<Synthesis of organic tellurium compound (living radical polymerization initiator)>
Example 1
Ethyl-2-methyl-2- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecylterranil) Propionate was synthesized by the following method.

  Diisopropylamine (2.5 mL, 18 mmol) and THF (50 mL) were added to a 500 mL three-necked glass container, and the solution was cooled in an ice bath with stirring. A butyllithium-hexane solution (10.5 mL, 16.5 mmol) was added dropwise thereto over 10 minutes, and the mixture was stirred for 20 minutes while attached to an ice bath. After cooling this solution with a dry ice / acetone bath, ethyl-2-methylpropionate (2.22 mL, 16.5 mmol) was slowly added dropwise, and the mixture was further stirred for 1.5 hours.

Di-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadedecafluorodecyl ditel in a 200 mL 3-neck glass container Lido (8.4 g, 7.5 mmol) and THF (150 mL) were added and cooled in an ice bath with stirring. Bromine (0.403 mL, 7.9 mmol) was added dropwise to this solution, and the mixture was further stirred for 1 hour. This reaction solution was added dropwise to a solution prepared in a 500 mL three-necked glass vessel cooled in a dry ice / acetone bath. The cooling bath was replaced with an ice bath, the temperature of the reaction solution was raised, and the mixture was further stirred for 30 minutes. The reaction solution was washed successively with a saturated aqueous ammonium chloride solution and saturated brine, and then the organic phase was dehydrated with magnesium sulfate. After the solvent was distilled off, distillation under reduced pressure gave an orange oily product (8.4 g, yield 82%). ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR confirmed the desired product.

(Example 2)
Methyl-2-methyl-2- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecylterranil) Propionate was synthesized by the following method.

  Diisopropylamine (2.48 mL, 17.7 mmol) and THF (50 mL) were added to a 500 mL three-necked reaction vessel, and the solution was cooled in a dry ice / acetone bath with stirring. A butyllithium-hexane solution (10.1 mL, 16.1 mmol) was added dropwise thereto over 20 minutes, and the mixture was stirred for 20 minutes while attached to a dry ice / acetone bath. Methyl 2-methylpropionate (1.85 mL, 16.1 mmol) was slowly added dropwise to this solution, and the mixture was further stirred for 1.5 hours.

Di-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadedecafluorodecyl ditel in a 300 mL three-necked glass container Lido (8.40 g, 7.31 mmol) and THF (150 mL) were added and cooled in an ice bath with stirring. Bromine (0.40 mL, 7.67 mmol) was added dropwise to this solution, and the mixture was further stirred for 45 minutes. This reaction solution was added dropwise to a 500 mL reaction vessel cooled in the previously prepared dry ice / acetone bath. After stirring for 40 minutes, the cooling bath was replaced with an ice bath and further stirred. After 30 minutes, the ice bath was removed and the mixture was further stirred for 10 minutes. The reaction solution was washed successively with a saturated aqueous ammonium chloride solution and saturated brine, and then the organic phase was dehydrated with magnesium sulfate. After the solvent was distilled off, distillation under reduced pressure gave the target compound as an orange oil (6.18 g, yield 64%). ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR confirmed the desired product.

(Example 3)
Methyl-2- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecylterranyl) propionate The method was synthesized.

  Diisopropylamine (0.34 mL, 0.24 mmol) and THF (10 mL) were added to a 100 mL three-necked glass container, and the solution was cooled in an ice bath with stirring. A butyllithium-hexane solution (1.42 mL, 0.26 mmol) was added dropwise thereto over 10 minutes, and the mixture was stirred for 20 minutes while attached to an ice bath. After this solution was cooled in a dry ice / acetone bath, methyl propionate (0.21 mL, 0.22 mmol) was slowly added dropwise, and the mixture was further stirred for 1.5 hours.

Di-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadedecafluorodecyl ditel in a 100 mL 3-neck glass container Lido (1.12 g, 1.0 mmol) and THF (30 mL) were added and cooled in an ice bath with stirring. Bromine (0.052 mL, 1.0 mmol) was added dropwise to this solution, and the mixture was further stirred for 30 minutes. This reaction solution was added dropwise to a solution prepared in a 100 mL three-necked glass vessel cooled in a dry ice / acetone bath. The cooling bath was replaced with an ice bath, the temperature of the reaction solution was raised, and the mixture was further stirred for 30 minutes. The reaction solution was washed successively with a saturated aqueous ammonium chloride solution and saturated brine, and then the organic phase was dehydrated with magnesium sulfate. After the solvent was distilled off, distillation under reduced pressure gave the target compound as an orange oil (0.56 g, yield 42%). ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR confirmed the desired product.

Example 4
1-Phenylethyl 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadedecafluorodecyl telluride was synthesized by the following method. did.

In a 300 mL three-necked glass container, di-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadedecafluorodecyldi Telluride (6.2 g, 5.39 mmol) and THF (100 mL) were added. Lithium triethylborohydride-THF solution (11.3 mL, 11.3 mol) was added thereto, and the mixture was stirred at room temperature for 10 minutes. 1-Phenyl-1-bromoethane (1.50 mL, 10.8 mmol) was added, and the mixture was further stirred for 1 hr. The reaction solution was washed successively with a saturated aqueous ammonium chloride solution and saturated brine, and then the organic phase was dehydrated with magnesium sulfate. After the solvent was distilled off under reduced pressure, tetradecafluorocyclohexane (2 mL) and methanol (3 mL) were added and stirred, and then allowed to stand until the two phases separated, and then the upper layer methanol solution was removed. Methanol (3 mL) was added thereto, and the operation of stirring and removing was repeated 4 times in total. The solvent of the tetradecafluorocyclohexane solution was distilled off under reduced pressure to obtain an orange oil (5.84 g, yield 78%). ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR confirmed the desired product.

<Synthesis of reducing agent>
(Synthesis Example 2)
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecyl trimethylsilyl telluride was synthesized by the following method.

Di-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadedecafluorodecyl ditel in a 300 mL three-necked glass container Lido (8.0 g, 6.8 mmol) and THF (150 mL) were added, and then lithium triethylborohydride THF solution (15.6 mL, 15.6 mmol) was added. Trimethylsilyl bromide (5.4 mL, 40.8 mmol) was added to this solution, and the mixture was stirred at room temperature (20 ° C.) for 5 minutes. After THF was distilled off under reduced pressure, hexane was added, and the resulting solid was removed by filtration. Hexane was distilled off from the filtrate under reduced pressure, followed by distillation under reduced pressure to obtain a yellow liquid (5.9 g, yield 67%). ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR confirmed the desired product.

  3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecyl trimethylsilyl telluride, methanol in deuterated chloroform As a result, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadedecafluorodecyl-tellol was produced. This 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecyl shows a reducing action.

(Examples 5-10 and Comparative Examples 1-2)
As shown in Table 1 below, Step (A), Step (B), and Step (C) were performed.

  The azo polymerization initiator, vinyl monomer and polymerization solvent shown in Table 1 are as follows.

AIBN: 2,2′-azobis (isobutyronitrile)
MMA: Methyl methacrylate MA: Methyl acrylate St: Styrene VP: N-Vinyl-2-pyrrolidone DMAEMA: 2- (dimethylamino) ethyl methacrylate THF: Tetrahydrofuran PMA: Propylene glycol monomethyl ether acetate TFC: Tetradecafluoromethylcyclohexane AcOEt: ethyl acetate

  Compounds # 1) to # 5) shown in Table 1 are as follows.

# 1) Ethyl-2-methyl-2- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecyl Terranyl) propionate # 2) Ethyl-2-methyl-2-n-butylterranyl-propionate # 3) Di-3,3,4,4,5,5,6,6,7,7,8,8,9 , 9,10,10,10-septadecafluorodecyl ditelluride # 4) dibutyl ditelluride # 5) 3,3,4,4,5,5,6,6,7,7,8,8, 9,9,10,10,10-septadecafluorodecyl trimethylsilyl telluride

<Process (A)>
Using the organic tellurium compound, the azo polymerization initiator, the vinyl monomer, and the polymerization solvent shown in Table 1, the vinyl monomer was subjected to living radical polymerization under the polymerization conditions shown in Table 1. In Table 1, each equivalent is equivalent to the organic tellurium compound. In Examples 5 and 6 and Comparative Example 2, an organic ditellurium compound is used in combination.

<Process (B)>
The treatment agent shown in Table 1 was added to the solution after completion of the polymerization, and the solution was treated under the treatment conditions shown in Table 1. In Examples 5 and 7 to 10, compound # 5) showing a reducing action was used as a treating agent. In this case, methanol was used as the protecting group leaving agent. In Example 6, NaBH ₄ showing a reducing action was used as a treating agent. In Comparative Examples 1 and 2, thiophenol which does not substantially exhibit a reducing action was used as a treating agent. Note that “6W LED” in the processing conditions of Comparative Example 1 means that a 6 W LED lamp was irradiated.

<Process (C)>
Using the cleaning solvent shown in Table 1, the vinyl polymer obtained in the step (B) was subjected to liquid separation cleaning. The recovery rate and purity of the recovered tellurium compound are shown in Table 1. The recovery rate indicates the ratio of the recovered tellurium compound to the total amount of the tellurium compound (organic tellurium compound, organic ditelluride compound and tellurium-based reducing agent) used. The purity indicates the purity of the organic ditellurium compound in the recovered tellurium compound.

  The number average molecular weight (Mn) and molecular weight distribution (PDI) of Examples 5 to 9 are GPC [Shodex GPC-104 (column: Shodex LF-604x2), Shodex GPC-101 (column: Shodex LF804 · K-805F · K). -800RL)] was determined based on the molecular weight of a polymethyl methacrylate standard sample (Shodex PMMS Standard).

  The number average molecular weight (Mn) and molecular weight distribution (PDI) of Example 10, Comparative Example 1 and Comparative Example 2 are GPC [Shodex GPC-104 (column: Shodex LF-604x2), Shodex GPC-101 (column: Shodex LF804). · K-805F · K-800RL)] was used to determine the molecular weight of a polystyrene standard sample (TSK Standard manufactured by Tosoh Corporation).

  As a typical example, Example 5 is specifically shown below.

  In a glass tube, ethyl-2-methyl-2- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluoro Decylteranyl) propionate (40 μL, 0.1 mmol), MMA (0.5 mL, 5 mmol), di-3,3,4,4,5,5,6,6,7,7,8,8,9, 9,10,10,10-Septadecafluorodecyl ditelluride (115 mg, 0.1 mmol), AIBN (3.3 mg, 0.02 mmol), THF (1 mL) were added. This solution was stirred at 60 ° C. for 18 hours in a nitrogen atmosphere to obtain polymethyl methacrylate having an organic tellurium group at the end. From GPC analysis (polymethyl methacrylate standard), Mn = 5200 and Mw / Mn = 1.12 (0.45 g, yield 89%).

  The obtained polymer was added to 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecyl-trimethylsilyl telluride (44 μL). 0.11 mmol) and methanol (49 μL, 1.2 mmol) were added, and the mixture was stirred at room temperature (20 ° C.) for 5 minutes.

To this solution was added TFC (1 mL) and stirred. After allowing to stand until the two phases separated, the TFC phase was removed. This separation washing operation was repeated 6 times. The solvent was distilled off from the collected TFC phase to obtain an orange solid. It is di-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-septadecafluorodecyl ditelluride from ¹ H-NMR. It was confirmed that the purity was 100%. From the weight measurement, the recovery rate of the tellurium compound was 93%.

  On the other hand, the solvent was distilled off from the separated THF phase to recover polymethyl methacrylate. From GPC analysis (polymethyl methacrylate standard), Mn = 5100 and Mw / Mn (PDI) = 1.12. From the weight measurement, the polymer recovery rate was 99%.

  As shown in Table 1, it can be seen that in Examples 5 to 10 using the organic tellurium compound according to the present invention, the used organic tellurium compound can be recovered as an organic ditellurium compound with a high recovery rate and high purity.

Claims (7)

An organic tellurium compound represented by the following general formula (1).

[Wherein, R ¹ represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group. ] A method for producing the organic tellurium compound according to claim 1,
An organic tellurium comprising a step of reacting a compound represented by the following general formula (4) with a base, and a step of reacting a compound obtained by the above reaction with a compound represented by the following general formula (5) Compound production method.

[Wherein, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group. ]

[Wherein, R ¹ represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. X represents a halogen atom. ] A method for producing the organic tellurium compound according to claim 1,
A step of reacting an organic ditellurium compound represented by the following general formula (6) with a reducing agent, and a step of reacting the compound obtained by the reaction step with a compound represented by the following general formula (7). A method for producing an organic tellurium compound.

[Wherein, R ¹ represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. ]

[Wherein, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group. X represents a halogen atom. ]   A living radical polymerization initiator comprising the organic tellurium compound according to claim 1. (A) a step of living radical polymerization of a vinyl monomer using the organic tellurium compound according to claim 1 to synthesize a vinyl polymer;
A step (B) in which a reducing agent is allowed to act on the vinyl polymer obtained in the step (A);
And (C) a step of washing the vinyl polymer obtained in the step (B) with a fluorinated solvent.   6. The method for producing a vinyl polymer according to claim 5, wherein the cleaning in the step (C) is a separation cleaning.   A vinyl polymer produced by the method according to claim 5 or 6.