JP2002327007A - Polymerization method of anionic polymerizable monomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anion polymerization method which can safely and in good operability perform the anion polymerization without using an organic alkali metal compound as a polymerization initiator and thereby produce rapidly and in good productivity a polymer with a given polymerization degree at high yield, and to provide the polymerization initiator for the method. SOLUTION: In the method, an anionic polymerizable monomer is subjected to the anion polymerization in the presence of (A) an organoaluminum compound having, in a molecule, a chemical structure represented by the formula: Al-O-Ar (wherein, Ar is an aromatic ring) and at least one sort of compound selected from (B1) an organic nitrogen compound in which a hydrogen atom is not directly bound to a nitrogen atom and (B2) an organophosphorus compound in which the hydrogen atom is not directly bound to a phosphorus atom. The polymerization initiator comprises (A) the organoaluminum compound and at least one sort of compound selected from (B1) the organic nitrogen compound and (B2) the organophosphorus compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for anionic polymerization and a polymerization initiator system used for the method. More specifically, the present invention relates to a method of anionically polymerizing an anionic polymerizable monomer in the presence of a specific organic aluminum compound and a compound selected from a specific organic nitrogen compound and an organic phosphorus compound, and a polymerization initiator system for the method. .
In the case of the present invention, anionic polymerization is carried out safely and with good operability without using an organic alkali metal compound as a polymerization initiator to produce a target polymer in a high yield and promptly with good productivity. can do.

[0002]

2. Description of the Related Art The anionic polymerization method is a polymerization method which has few side reactions such as polymerization deactivation and chain transfer, has high so-called living polymerizability, and is suitable for controlling the molecular weight of a polymer and designing a block copolymer. is there. Usually, anionic polymerization is performed using an organic alkali metal compound as a polymerization initiator. However, when a polymer is produced on an industrial scale using an organic alkali metal compound as a polymerization initiator, the organic alkali metal compound is a water-prohibiting reagent that may ignite due to contact with moisture. Care must be taken in the method and handling. Further, in the production process of the polymer, after the polymerization, a neutralization step with an acid and a removal step of an alkali metal salt are required, and there is a problem that a large amount of wastewater is discharged with the step. Therefore, development of a living anionic polymerization method that does not use an organic alkali metal compound as a polymerization initiator has been desired.

The following methods are known as methods for anionically polymerizing an anionic polymerizable monomer without using an organic alkali metal. A method of anionic polymerization of acrylonitrile and methyl methacrylate using a catalyst system comprising a trialkylaluminum and a Lewis base [Makromol. Ch
em. 175, 2775-2793 (1974)]. A method of anionic polymerization of methyl methacrylate using a catalyst system comprising methyl (2,6-t-butyl-4-methylphenoxy) aluminum and an enamine compound [J
ownal of Polymer Science
e: Part A: Polymer Chemistr
y, 37, 3671-3679 (1999)]. Method for producing methacrylic acid ester polymer having high stereoregularity by anionic polymerization of methacrylic acid ester using a catalyst system comprising an organoaluminum compound, a phenol and a bisoxazoline compound (JP-A-10-139822) . A method of anionically polymerizing methacrylates and acrylates using ammonium methanide as a polymerization initiator [Angew. Chem. Int. E
d. Engl. 27, 1373-1374 (198
8)]. Using a mixture of an organoaluminum compound having an alkyl group or an alkoxy group having 4 or less carbon atoms and a tertiary phosphine compound as a polymerization initiator, anionic polymerization of methacrylic acid ester, a methacrylic acid ester polymer having a narrow molecular weight distribution and A method for producing the block copolymer (JP-A-01-090209). A method of anionically polymerizing methacrylic acid ester and acrylic acid ester using a ketene silyl acetal compound as a polymerization initiator in the presence of a Lewis acid catalyst [Macromolecules, 20, 1473-1
488 (1987)].

[0004] However, the above polymerization methods (1) to (4)
In any case, since the polymerization does not proceed in a living state, it is difficult to control the molecular weight of the polymer, and further, it is not suitable for producing a block copolymer. Moreover, the above polymerization methods (1) to (4) are not suitable for anionic polymerization of acrylate. In addition, the above polymerization method requires a low temperature condition of -78 ° C, and it is impossible to perform living polymerization and block copolymerization of an acrylate ester. In the above-mentioned polymerization method, complicated synthesis and purification of a ketene silyl acetal compound used as a polymerization initiator are required, and therefore, there is an extremely large industrial restriction.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an anionically polymerizable monomer without using an organic alkali metal compound which is problematic in terms of safety and handleability, and having excellent safety and handleability. To provide an anionic polymerization method using the above polymerization initiator system. Furthermore, the object of the present invention is to maintain a high polymerization rate and a high living property at a higher polymerization temperature without employing an extremely low polymerization temperature (−78 ° C.) as in the conventional method described above. An object of the present invention is to provide an anion polymerization method capable of producing various polymers and block copolymers with high yield and high productivity. And an object of the present invention is to provide a polymerization initiator system for anionic polymerization to achieve the above-mentioned object.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object. As a result, in performing anionic polymerization using an anionic polymerizable monomer, at least one selected from a specific organic aluminum compound and a specific organic nitrogen compound and an organic phosphorus compound is used.
When used as a polymerization initiator system in combination with a compound of the species, even if an organic alkali metal compound is not used as a polymerization initiator, anionic polymerization can proceed favorably, and a polymer having a predetermined degree of polymerization can be converted into a polymer having a high polymerization degree. It has been found that it can be produced at high speed and high yield with good productivity. Further, the present inventors have found that a polymerization initiator system comprising the above-mentioned specific organoaluminum compound and at least one compound selected from a specific organic nitrogen compound and an organic phosphorus compound has excellent safety and handleability. And polymerization initiation efficiency,
It was found that the polymerization rate, living property, etc. were excellent. In addition, the present inventors have found that the use of a polymerization initiator system comprising the above-mentioned specific organoaluminum compound and at least one selected from a specific organic nitrogen compound and an organic phosphorus compound results in extremely low levels as in the prior art. Even if a higher polymerization temperature is employed without employing the polymerization temperature, it is found that the anionic polymerization proceeds favorably, and furthermore, the polymerization initiator system is suitable for producing a block copolymer, The present invention has been completed based on those findings.

That is, the present invention provides: (1) An anionically polymerizable monomer represented by the formula: Al-OA
an organic aluminum compound (A) having a chemical structure represented by r (where Ar represents an aromatic ring) in the molecule, an organic nitrogen compound (B1) having no hydrogen atom directly bonded to a nitrogen atom, and This is a method for polymerizing an anionic polymerizable monomer, which comprises performing anionic polymerization in the presence of at least one compound selected from organic phosphorus compounds (B2) having no hydrogen atom directly bonded to a phosphorus atom.

The present invention provides: (2) an organoaluminum compound (A) and at least one compound selected from an organic nitrogen compound (B1) and an organic phosphorus compound (B2), which are previously mixed or reacted. (3) at least one compound selected from the group consisting of an organoaluminum compound (A), an organic nitrogen compound (B1), and an organic phosphorus compound (B2), in which anion polymerization is carried out in the presence of a mixture or a reactant; And the polymerization method according to the above (1), wherein anionic polymerization is carried out in the presence of a mixture or a reaction product obtained by previously mixing or reacting an acrylic acid ester; (4) the α, β-unsaturated carboxylic acid ester An α, β-unsaturated carboxylic acid amide,
(1) which is at least one monomer selected from α, β-unsaturated ketones and α, β-unsaturated nitriles
(5) the polymerization method according to any one of the above (1) to (4), wherein the anionic polymerization is block copolymerization; and (6) a copolymerization monomer for block copolymerization. Wherein the at least one is an acrylate ester.

Further, the present invention provides an organoaluminum compound (A) having a chemical structure represented by the formula: Al—O—Ar (where Ar represents an aromatic ring) in a molecule; An organic nitrogen compound (B1) having no hydrogen atom directly bonded to a nitrogen atom and an organic phosphorus compound (B1) having no hydrogen atom directly bonded to a phosphorus atom
A polymerization initiator system for anionic polymerization, comprising at least one compound selected from 2).

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, an organoaluminum compound (A) having a chemical structure represented by the formula: Al—O—Ar (where Ar represents an aromatic ring) in a molecule, and a hydrogen atom directly bonded to a nitrogen atom At least one compound selected from an organic nitrogen compound (B1) having no hydrogen atom and an organic phosphorus compound (B2) having no hydrogen atom directly bonded to a phosphorus atom;
An anionically polymerizable monomer is anionically polymerized by using as a polymerization initiator system.

In the present invention, the above-mentioned formula: Al—O—Ar is used according to the kind of the anionic polymerizable monomer used.
Suitable compounds can be selected from the organoaluminum compounds (A) having the chemical structure represented by the following formula in the molecule, and the organoaluminum compounds (A) generally have the following general formula (I) );

[0012]

## STR1 ## ^{AlR 1 R 2 R 3 (I} ) ( In the formula, R ¹ 1 may have a substituent monovalent saturated hydrocarbon group, a monovalent aromatic which may have a substituent Group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group or N, N-
A disubstituted amino group, R ² and R ³ are each independently an aryloxy group which may have a substituent, or R ² and R ³ may have a substituent by bonding It forms a good arylenedioxy group. An organoaluminum compound [hereinafter may be referred to as “organoaluminum compound (AI)”]; or the following general formula (II);

[0013]

Embedded image AlR^FourR^FiveR⁶ (II) (wherein, R^FourIs an aryloxy optionally having a substituent
Represents a group, R^FiveAnd R ⁶Each independently represents a substituent
Optionally having a monovalent saturated hydrocarbon group and a substituent
Optionally having a monovalent aromatic hydrocarbon group and a substituent
Optionally substituted alkoxy or N, N-disubstituted amino groups
It is. ) Represented by an organoaluminum compound (hereinafter, referred to as
Sometimes referred to as "organoaluminum compound (A-II)"
Is preferably used.

In the above general formulas (I) and (II), R ¹ , R ⁵ and R ⁶ each have a monovalent saturated hydrocarbon group which may have a substituent or a substituent. 1
When it is a monovalent aromatic hydrocarbon group, an alkoxy group which may have a substituent or an N, N-disubstituted amino group, examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, alkyl groups such as n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, n-octyl group and 2-ethylhexyl group; cycloalkyl groups such as cyclohexyl group; An aryl group such as a phenyl group; an aralkyl group such as a benzyl group; an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group and a t-butoxy group; a dimethylamino group, a diethylamino group, a diisopropylamino group;
Examples include N, N-disubstituted amino groups such as bis (trimethylsilyl) amino group. Examples of the substituent which these groups may have include an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group and a t-butoxy group; and a halogen atom such as chlorine and bromine.

In the above formulas (I) and (II), when R ¹ , R ² , R ³ and R ⁴ are an aryloxy group which may have a substituent, examples thereof include a phenoxy group , 2-methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, 2,4-di-t-
Butylphenoxy group, 2,6-di-t-butylphenoxy group, 2,6-di-t-butyl-4-methylphenoxy group, 2,6-di-t-butyl-4-ethylphenoxy group, 2, 6-diphenylphenoxy group, 1-naphthoxy group, 2-naphthoxy group, 9-phenanthryloxy group,
Examples thereof include a 1-pyrenyloxy group, an aryloxy group, and a 7-methoxy-2-naphthoxy group. These aryloxy groups can have a substituent such as an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group, and a t-butoxy group, and a halogen atom such as chlorine and bromine.

In the above general formula (I), examples of the case where R ² and R ³ combine to form an arylenedioxy group which may have a substituent include 2,2′- Biphenol, 2,2'-methylenebisphenol, 2,2 '
-Methylenebis (6-t-butyl-4-methylphenol), (R)-(+)-1,1′-bi-2-naphthol,
And groups derived from (S)-(-)-1,1′-bi-2-naphthol and the like. These arylenedioxy groups can have a substituent such as an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group and a t-butoxy group, and a halogen atom such as chlorine and bromine.

In the organoaluminum compound (AI) represented by the general formula (I), R ¹ , R ² and R ³ may be the same or different as long as they are the groups defined above. You may. In the organoaluminum compound (A-II) represented by the general formula (II), R ⁵ and R ⁶ may be the same or different as long as they are the groups defined above.

A typical example of the organoaluminum compound (AI) is ethylbis (2,6-di-tert-butyl-4).
-Methylphenoxy) aluminum, ethylbis (2,
6-di-t-butylphenoxy) aluminum, ethyl [2,2′-methylenebis (6-t-butyl-4-methylphenoxy)] aluminum, isobutylbis (2
6-di-t-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-di-t-butylphenoxy) aluminum, isobutyl [2,2′-methylenebis (6-t-butyl-4-methylphenoxy) )] Aluminum, n-octylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, n-octylbis (2,6-di-t-butylphenoxy) aluminum, n-octyl [2,2 ′ -Methylenebis (6-t-
Butyl-4-methylphenoxy)] aluminum, methoxybis (2,6-di-t-butyl-4-methylphenoxy) aluminum, methoxybis (2,6-di-t-
Butylphenoxy) aluminum, methoxy [2,2 ′
-Methylenebis (6-t-butyl-4-methylphenoxy)] aluminum, ethoxybis (2,6-di-t-
Butyl-4-methylphenoxy) aluminum, ethoxybis (2,6-di-t-butylphenoxy) aluminum, ethoxy [2,2′-methylenebis (6-t-butyl-4-methylphenoxy)] aluminum, isopropoxybis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isopoloxybis (2,6
-Di-t-butylphenoxy) aluminum, isopropoxy [2,2'-methylenebis (6-t-butyl-4)
-Methylphenoxy)] aluminum, t-butoxybis (2,6-di-t-butyl-4-methylphenoxy)
Aluminum, t-butoxybis (2,6-di-t-butylphenoxy) aluminum, t-butoxy [2,
2′-methylenebis (6-t-butyl-4-methylphenoxy)] aluminum, tris (2,6-di-t-butyl-4-methylphenoxy) aluminum, tris (2,6-diphenylphenoxy) aluminum and the like Can be mentioned.

A typical example of the organoaluminum compound (A-II) is diethyl (2,6-di-tert-butyl-4-).
Methylphenoxy) aluminum, diethyl (2,6-
Di-t-butylphenoxy) aluminum, diisobutyl (2,6-di-t-butyl-4-methylphenoxy)
Aluminum, diisobutyl (2,6-di-t-butylphenoxy) aluminum, di-n-octyl (2,6-
Di-t-butyl-4-methylphenoxy) aluminum, di-n-octyl (2,6-di-t-butylphenoxy) aluminum, and the like.

In the present invention, as the organoaluminum compound (A), only one kind of the organoaluminum compound may be used, or two or more kinds of the organoaluminum compounds may be used in combination. Among them, in the present invention, as the organoaluminum compound (A), diisobutyl (2,6-
Di-t-butyl-4-methylphenoxy) aluminum and isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum are preferably used in terms of high polymerization rate and high living property.

In the present invention, the amount of the organoaluminum compound (A) used can be adjusted according to the kind of the anionic polymerizable monomer to be used. 1 × 10
^{-8 to} 5 × 10 ^-1 mol, preferably 1 × 10 ^-4 mol
More preferably, it is モ ル 1 × 10 ⁻¹ mol. The method for producing the organoaluminum compound (A) is not particularly limited, and can be produced according to a known method, or a commercially available product may be purchased and used.

In the present invention, at least one compound selected from an organic nitrogen compound (B1) and an organic phosphorus compound (B2) is used together with the above-mentioned organic aluminum compound (A). The organic nitrogen compound (B1) may be any organic nitrogen compound that does not have a hydrogen atom directly bonded to a nitrogen atom and has an organic group bonded to a nitrogen atom.
Examples include aliphatic amines and aromatic amines having no hydrogen atom directly bonded to a nitrogen atom.
In the organic nitrogen compound (B1), the organic group bonded to the nitrogen atom may have a hetero atom such as oxygen, sulfur, nitrogen, phosphorus, and halogen, as the case may be. Among them, the organic group bonded to nitrogen is preferably an alkyl group.

Specific examples of the organic nitrogen compound (B) include:
Trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-octylamine, tri-2-ethylhexylamine, tribenzylamine, tribenzylamine Allylamine, N, N-dimethylethylamine, N, N-diisopropylethylamine, N, N-dimethylisopropylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethylallylamine,
N-diethylmethylamine, N, N-diisopropylmethylamine, N-methylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N, N, N ', N'-tetramethyldiaminomethane, N, N, N' , N'-tetramethylethylenediamine, N, N, N ', N'-tetraethylethylenediamine, N, N, N', N'-tetraisopropylethylenediamine, N, N, N ', N'
-Tetramethyl-1,3-propanediamine, N, N,
N ′, N′-tetramethyl-1,6-hexanediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriamine Ethylenetetramine, 1,4-diazabicyclo [2.2.2] octane, hexamethylenetetramine,
N, N, N ', N'-tetramethyl-1,3-diaminopropane, 1- (2-dimethylaminoethyl) -4-methylpiperazine, N, N'-dimethylpiperazine, pyridine, 2,2'- Dipyridyl, 2,4'-dipyridyl,
4,4'-dipyridyl, N, N-dimethyl-2-methoxyethylamine, 1-methylpyrrolidine, 1-methylpiperidine, N-methylmorpholine and the like can be mentioned.

The organic phosphorus compound (B2) may be any organic phosphorus compound having no hydrogen atom directly bonded to a phosphorus atom and having an organic group bonded to a phosphorus atom.
For example, phosphine having no hydrogen atom directly bonded to a phosphorus atom can be given. In the organic phosphorus compound (B2), the organic group bonded to the phosphorus atom may have a hetero atom such as oxygen, sulfur, nitrogen, phosphorus, or halogen, as the case may be. Among them, the organic group bonded to the phosphorus atom is preferably a monovalent aromatic group such as an alkyl group or a phenyl group. Organic phosphorus compound (B)
Specific examples include triethylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, and 1,2-bis (diphenylphosphino) ethane.

In the present invention, the organic nitrogen compound (B
Only one of 1) and the organic phosphorus compound (B2) may be used, or two or more thereof may be used. Among them, in the present invention, as the organic nitrogen compound (B1),
N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N-dimethylethylamine, 1-methylpyrrolidine, tricyclohexylphosphine, triphenylphosphine, as an organic phosphorus compound (B2)
1,2-bis (diphenylphosphino) ethane is preferably used in view of a high polymerization rate and a high living property.

In the present invention, the organic nitrogen compound (B1)
And at least one selected from organic phosphorus compounds (B2)
The amount of one compound used depends on the species of the anionic polymerizable monomer.
Can be adjusted according to the kind, but generally, a monomer,
1 × 10 per liter of polymerization system including solvent^-8~
1 mol, preferably 1 × 10^-Four~ 1 × 10 ^-1
More preferably, it is molar. Organic aluminum compound
(A) and organic nitrogen compound (B1) and organic phosphorus compound
Use of at least one compound selected from compounds (B2)
The ratio is adjusted according to the type of anionic polymerizable monomer, etc.
Although it can be knotted, generally, [organoaluminum compound
(A)]: [organic nitrogen compound (B1) and organic phosphation
At least one compound selected from compound (B2)] =
Preferably, the mass ratio is 95: 5 to 5:95, and 8
More preferably, the mass ratio is 0:20 to 20:80.
No.

The organic aluminum compound (A) and at least one compound selected from the organic nitrogen compound (B1) and the organic phosphorus compound (B2) may be separately added to the polymerization system. (A) and at least one compound selected from an organic nitrogen compound (B1) and an organic phosphorus compound (B2) are mixed or reacted in advance to prepare a mixture or a reaction product,
The mixture or reactant may be added to the reaction system. Among them, the latter method of adding a mixture or a reaction product which has been mixed or reacted in advance to the polymerization system is preferable in terms of smooth progress of the anionic polymerization reaction and high polymerization initiation efficiency. When a mixture of the organoaluminum compound (A) and at least one compound selected from the organic nitrogen compound (B1) and the organic phosphorus compound (B2) is used in advance, the same organic compound as used in the polymerization is used. It is preferable to mix them in a solvent and add the mixture to the polymerization system. When a reactant obtained by previously reacting an organoaluminum compound (A) with at least one compound selected from an organic nitrogen compound (B1) and an organic phosphorus compound (B2) is used, it is used for polymerization. It is preferable to react these by heating in an organic solvent of the same kind as necessary, and to add the reaction product to the polymerization system.

Further, in the present invention, from the viewpoint of obtaining a smooth progress of the anionic polymerization reaction and a higher polymerization initiation efficiency, the organic aluminum compound (A), the organic nitrogen compound (B1) and the organic phosphorus compound (B2) Preparing a mixture or a reactant by previously mixing or reacting at least one compound selected from and an acrylate ester, and further adding an anionic polymerizable monomer in the presence of the mixture or the reactant to continue the polymerization. Can be. As the acrylate used before mixing or reacting, an alkyl acrylate is preferably used. The amount of the acrylate ester may be a small amount that does not affect the structure of the target polymer. For example, at least one acrylate selected from an organic nitrogen compound (B1) and an organic phosphorus compound (B2) may be used. 0.1 to 10 times the molar amount of the compound is used. An organic aluminum compound (A) and an organic nitrogen compound (B
When a mixture or a reaction product obtained by adding an acrylate ester to at least one compound selected from 1) and the organic phosphorus compound (B2) and mixing or reacting in advance is used, the efficiency of polymerization initiation is improved. This method is effective not only when the polymerization is carried out by further supplying an acrylate ester into the system, but also when the polymerization is carried out by supplying another anionic polymerizable monomer such as a methacrylate ester into the system. .

In the present invention, since the organic alkali metal compound is not used as the polymerization initiator, the organic group in the organic alkali metal compound does not bind to the starting terminal during or after the polymerization of the anionic polymerizable monomer. Further, in the present invention, together with the organoaluminum compound (A) and at least one compound selected from the organonitrogen compound (B1) and the organophosphorus compound (B2), it is necessary to use an additive that is not introduced at the initiation terminal of the polymerization. Can be used accordingly. Examples of such additives include inorganic salts such as lithium chloride, alkoxide compounds such as lithium methoxyethoxy ethoxide and potassium t-butoxide; organic quaternary salts such as tetraethylammonium chloride and tetraethylphosphonium bromide; diethyl ether; Examples include ether compounds such as 2-dimethoxyethane and 1,2-diethoxyethane.

In the present invention, as the anionic polymerizable monomer, any of the monomers conventionally known to undergo anionic polymerization can be used. For example, α, β-unsaturated carboxylate, α, β-unsaturated Carboxamide,
α, β-unsaturated ketone, α, β-unsaturated nitrile, 2-
Α, β-unsaturated carbonyl monomers having a polar group such as vinylpyridine, α, β-unsaturated nitrile monomers having a polar group such as 2-vinylpyridine, and lactone compounds such as ε-caprolactone. it can. Among them, in the present invention, α, β-unsaturated carboxylic acid ester, α, β-unsaturated carboxylic acid amide,
At least one anion-polymerizable monomer selected from α, β-unsaturated ketones and α, β-unsaturated nitriles is preferably used.

Preferred examples of the α, β-unsaturated carboxylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, allyl acrylate, n-butyl acrylate and t-acrylate.
-Butyl, cyclohexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, glycidyl acrylate, trimethoxysilyl acrylate, methoxyethyl acrylate, N, N-dimethylaminoethyl acrylate, N acrylate , N-
Acrylic esters such as diethylaminoethyl; methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, allyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate, glycidyl methacrylate, trimethoxysilyl propyl methacrylate, methoxyethyl methacrylate,
Methacrylic esters such as N, N-dimethylaminoethyl methacrylate and N, N-diethylaminoethyl methacrylate; α-alkoxyacrylic esters such as α-methyl methacrylate and α-ethoxy methacrylate; methyl crotonate; Examples thereof include crotonic esters such as ethyl crotonate; and 3-alkoxyacrylic esters such as 3-methoxyacrylic ester.

Preferred examples of the α, β-unsaturated carboxylic acid amide include N-isopropylacrylamide and N-isopropylacrylamide.
Acrylamide compounds such as t-butylacrylamide, N, N-dimethylacrylamide and N, N-diethylacrylamide can be mentioned. Preferred examples of the α, β-unsaturated ketone include methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, ethyl isopropenyl ketone, and the like.
Preferred examples of the α, β-unsaturated nitrile include acrylonitrile and methacrylonitrile.

In the present invention, one or more of the above-mentioned anionic polymerizable monomers can be used. In the present invention, as a part of the anionic polymerizable monomer, a polyfunctional monomer having two or more polymerizable groups such as a vinyl group in a molecule can be used, if necessary. Among the above-mentioned anionic polymerizable monomers, at least one of acrylates, methacrylates and acrylamides is particularly preferably used.

The anionic polymerizable monomer to be used is preferably subjected to a sufficient drying treatment in advance under an inert gas stream or the like, if necessary, from the viewpoint that the polymerization reaction proceeds smoothly. In the drying treatment, a dehydrating / drying agent such as calcium hydride, molecular sieves and activated alumina is preferably used.

The anionic polymerization reaction in the present invention can be carried out without using an organic solvent. However, the polymerization temperature can be controlled, the conditions in the polymerization system can be made uniform, and the polymerization can proceed smoothly. It is preferable to carry out the reaction in an organic solvent from the viewpoint that the reaction can be performed. As an organic solvent, generally, toluene, from the viewpoint of relatively high safety in handling chemicals, hardly mixed into wastewater, and easy recovery and purification of the solvent, etc.
Hydrocarbon solvents such as xylene, cyclohexane and methylcyclohexane; halogenated hydrocarbon solvents such as chloroform, methylene chloride and carbon tetrachloride; ethyl acetate;
Ester solvents such as dimethyl phthalate are preferably used. These organic solvents may be used alone or in combination of two or more. It is preferable that the organic solvent used for the polymerization is purified by degassing and dehydrating in advance.

The amount of the organic solvent used depends on the degree of polymerization of the desired polymer, the type of anionic polymerizable monomer, the type of the organic aluminum compound (A) used, and the organic nitrogen compound (B
It can be adjusted according to 1) and / or the type of the organic phosphorus compound (B2), the type of the organic solvent, and the like. However, the polymerization proceeds smoothly, the obtained polymer can be easily separated and obtained, and the waste liquid treatment burden and the like can be adjusted. From the point of view, generally, the monomer used 100
It is preferable to use 100 to 10000 parts by mass of the organic solvent with respect to parts by mass.

Organic Aluminum Compound (A) for Polymerization
And an organic nitrogen compound (B1) and an organic phosphorus compound (B
The method of adding at least one compound selected from 2) and the anionic polymerizable monomer to the polymerization system is not particularly limited, and a suitable method can be appropriately employed as desired. Among them, as described above, as a polymerization initiator system, an organic aluminum compound (A) and at least one compound selected from an organic nitrogen compound (B1) and an organic phosphorus compound (B2) are previously mixed or reacted. It is preferable to prepare a mixture or a reactant, and add the mixture or the reactant to the polymerization system to carry out the polymerization, from the viewpoint of smooth progress of the anionic polymerization reaction and high polymerization initiation efficiency. At that time, as described above, if a small amount of an acrylate ester is added in advance to the mixture or the reactant forming the polymerization initiator system, the anionic polymerization reaction proceeds more smoothly, and a higher polymerization initiation efficiency is obtained. can get.

In the present invention, when anionic polymerization is carried out using two or more kinds of anionic polymerizable monomers, a copolymer can be obtained. In this case, a copolymer in any copolymer form such as random, block, or tapered block can be produced depending on the method of adding the monomer, the combination of types of the monomer, and the like. In the case of the polymerization method of the present invention, a high living property can be exhibited. Therefore, the polymerization method of the present invention is particularly suitable for producing a block copolymer requiring high blocking efficiency.

In the present invention, the temperature of the reaction system at the time of polymerization is not particularly limited, and suitable temperature conditions can be selected according to the kind of the anionic polymerizable monomer to be used. , A temperature in the range of -60 ° C to + 100 ° C is preferably employed, and a temperature in the range of -40 ° C to + 50 ° C is more preferably employed. The polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen, argon, and helium. Further, it is preferable to carry out the polymerization under sufficient stirring conditions so that the reaction system becomes uniform.

In the present invention, the time required for the polymerization can be selected, but in the case of the present invention, the polymerization can proceed at a high speed. Although it depends on the conditions employed, for example, when methacrylic acid ester is used as the anionic polymerizable monomer, the polymerization can be completed within several minutes. When an acrylate is used as the anionic polymerizable monomer, the polymerization can be completed within several tens of seconds. Therefore, in the present invention, the polymerization reaction can be carried out by a so-called “tubular continuous polymerization method” having high productivity and good cooling efficiency.

In the present invention, at the stage when the desired polymer is formed by the polymerization reaction, the polymerization reaction can be stopped by adding a polymerization terminator to the reaction mixture. As the polymerization terminator, for example, a protic compound such as a methanol solution of methanol, acetic acid, or hydrochloric acid can be used. Although the amount of the polymerization terminator used is not particularly limited, generally, the used organic nitrogen compound (B
It is preferable to use the compound in an amount of 1 to 100 mol per 1 mol of at least one compound selected from 1) and the organic phosphorus compound (B2). The method for separating and obtaining the polymer from the reaction mixture after the termination of the polymerization is not particularly limited, and any method according to a known method can be adopted. For example, a method in which the reaction mixture is poured into a poor solvent for the polymer to precipitate the polymer, a method in which the solvent is distilled off from the reaction mixture to obtain the polymer, and the like can be adopted.

If the metal component derived from the organoaluminum compound (A) used as the polymerization initiator system remains in the polymer separated and obtained from the reaction mixture after the termination of the polymerization,
Depending on the intended use of the polymer, a metal compound derived from the organoaluminum compound (A) may be polymerized after the polymerization, depending on the intended use of the polymer. It is preferred to remove it from the coalescence.
As a method for removing the organoaluminum compound (A) from the polymer, a method of washing the polymer using an acidic aqueous solution,
A method of cleaning the polymer using an adsorbent such as an ion exchange resin is effective. Here, as the above-mentioned acidic aqueous solution, for example, hydrochloric acid, sulfuric acid aqueous solution, nitric acid aqueous solution, acetic acid aqueous solution, propionic acid aqueous solution, citric acid aqueous solution and the like can be used.

According to the present invention, a polymer having an arbitrary molecular weight can be produced. The molecular weights of the polymers that can be produced vary widely, but generally the number average molecular weight is 100
It is preferable to produce a polymer in the range of 0 to 1,000,000 in view of handleability, fluidity, mechanical properties, and the like of the obtained polymer. Furthermore, in the case of the present invention, a polymer having a narrow molecular weight distribution and a high molecular weight uniformity is obtained,
A polymer having a molecular weight distribution (Mw / Mn) of 1.5 or less can be produced. However, by controlling the rate of addition of the anionic polymerizable monomer to the polymerization system, the rate of diffusion of the anion polymerizable monomer in the polymerization system, and the like,
A polymer having a wide molecular weight distribution can be obtained.

[0044]

EXAMPLES The present invention will be described below more specifically with reference to examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, the chemicals used were purified and prepared as follows. Also,
Operations such as transfer and supply of chemicals were all performed in a nitrogen or argon atmosphere. (1) Toluene: A commercially available product was subjected to simple distillation, dried with molecular sieve 4A, added with metallic sodium, and vacuum distilled immediately before use. (2) n-butyl acrylate and methyl methacrylate: A commercially available product was washed with an aqueous solution of NaHSO ₄ and an aqueous solution of NaOH, and then calcium hydride was added to the distilled product.
Vacuum distilled immediately before use was used. (3) Organic nitrogen compounds and organic phosphorus compounds: Commercial products were used as they were or as toluene solutions. (4) isobutyl bis (2,6-di-t-butyl-4-
Methylphenoxy) aluminum: Commercially available triisobutylaluminum is added to a 2-fold molar amount of a toluene solution of 2,6-di-t-butyl-4-methylphenol, and the mixture is added overnight.
The product reacted by heating was recrystallized three times in heptane.
Purified and used as a toluene solution. (5) Triisobutylaluminum: A commercially available product was used as a toluene solution.

[0045] In the following Examples and Comparative Examples, the polymerization conversion ratio of anionic polymerizable monomers by using a deuterated chloroform as a deuterated solvent, by ¹ H- nuclear magnetic resonance ⁽¹ H-NMR) measurement of the reaction solution I asked. The block efficiency of the block copolymer was determined by high performance liquid chromatography (HPLC). Separation and recovery of the polymer from the reaction solution were performed by the following method. (1) Recovery of n-butyl polyacrylate (Examples 1 to 3)
9): After separating and washing the reaction solution with a 3% aqueous sulfuric acid solution, the organic phase was poured into a mixed solution of methanol: distilled water = 90: 10 (mass ratio), and the polymer was recovered as an insoluble precipitate (oily substance). did. (2) Recovery of n-butyl polyacrylate-block-polymethyl methacrylate (Example 10): 3% of the reaction solution
After separating and washing with a sulfuric acid aqueous solution, the organic phase is poured into methanol,
The precipitated insoluble matter (solid substance) was recovered as a polymer. Also, the molecular weight of the obtained polymer (number average molecular weight Mn
And weight average molecular weight (Mw) were determined by gel permeation chromatography (GPC) in terms of molecular weight in terms of polystyrene.

The measuring apparatus and conditions used above are as follows. (1) ¹ H-Nuclear Magnetic Resonance ( ¹ H-NMR): Apparatus: Nuclear magnetic resonance apparatus “JNM-” manufactured by JEOL Ltd.
LA400 "・ Heavy solvent: deuterated chloroform (2) High performance liquid chromatography (HPLC): ・ Equipment: Shimadzu high performance liquid chromatograph equipped with an evaporative detector“ PL-EMD960 ”manufactured by Polymer Laboratories HPLC10Avp ”・ Separation column:“ SUPELCOS ”manufactured by SUPELCO
IL LC-3-Si "・ Eluent: mixed solvent of ethyl acetate and cyclohexane [Ethyl acetate: cyclohexane = 50: 2 minutes after the start of measurement]
50 (volume ratio), and thereafter, the composition ratio was changed from ethyl acetate: cyclohexane = 50: 50 (volume ratio) to ethyl acetate: cyclohexane = 100: 0 (volume ratio) over 18 minutes, and further 10 minutes thereafter Was fixed at ethyl acetate: cyclohexane = 100: 0 (volume ratio). Eluent flow rate: 1.0 ml / min Column temperature: 40 ° C. (3) Gel permeation chromatography (GP
C): ・ Equipment: GPC unit “HLC-802” manufactured by Tosoh Corporation
• Separation column: “TSKgel” manufactured by Tosoh Corporation
GMHXL "," G4000HXL "and" G500
0HXL "connected in series ・ Eluent: tetrahydrofuran ・ Eluent flow rate: 1.0 ml / min ・ Column temperature: 40 ° C.

Example 1 (1) The inside of a 100 ml Schlenk tube with a three-way cock was evacuated and replaced with argon, and then 43.5 toluene was used.
ml, isobutyl bis (2,6-di-t-butyl-4-
1.3 ml of a toluene solution containing 0.78 mmol of methylphenoxy) aluminum, and N, N, N ',
N '', N ''-pentamethyldiethylenetriamine
7 mg was added, and the mixture was cooled to -20 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. The solution initially colored yellow and became colorless one minute after the end of the dropping. Three minutes after the completion of the dropwise addition, 0.2 ml of methanol was added to stop the polymerization reaction. The polymerization conversion of the monomer was determined by ¹ H-NMR measurement of the reaction solution, and as a result, the polymerization conversion was 100%. (2) About a part of the reaction solution generated in the above (1),
The molecular weight in terms of polystyrene of the polymer (n-butyl polyacrylate) obtained by removing the toluene solvent was determined by the GPC method using the above-described apparatus and conditions, and the Mn (number average molecular weight) was 35700. And Mw / Mn
(Molecular weight distribution) was 1.20. (3) After separating and washing the reaction solution produced in the above (1) with a 3% aqueous sulfuric acid solution, the organic phase was methanol: distilled water = 90: 1.
The mixture was poured into a mixed solution of 0 (mass ratio), and a polymer was recovered as an insoluble precipitate (oil). The polymerization conditions and results are shown in Table 1 below.

Example 2 (1) The inside of a 100 ml Schlenk tube equipped with a three-way cock was degassed and purged with argon, and then 43.5 toluene was used.
ml, isobutyl bis (2,6-di-t-butyl-4-
1.3 ml of a toluene solution containing 0.78 mmol of methylphenoxy) aluminum, and N, N, N ',
N ″, N ″ -pentamethyldiethylenetriamine 14
9.4 mg was added and cooled to -20 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. The solution initially colored yellow and became colorless one minute after the end of the dropping. After 3 minutes from the end of dropping, add 0.2 ml of methanol.
The addition stopped the polymerization reaction. The polymerization conversion of the monomer was determined by ¹ H-NMR measurement of the reaction solution, and as a result, the polymerization conversion was 100%. (2) About a part of the reaction solution generated in the above (1),
The polystyrene-equivalent molecular weight of the polymer (n-butyl polyacrylate) obtained by removing the toluene solvent was determined by the GPC method using the above-described apparatus and conditions, and the Mn (number average molecular weight) was 25200. And Mw / Mn
(Molecular weight distribution) was 1.21. (3) After separating and washing the reaction solution produced in the above (1) with a 3% aqueous sulfuric acid solution, the organic phase was methanol: distilled water = 90: 1.
The mixture was poured into a mixed solution of 0 (mass ratio), and a polymer was recovered as an insoluble precipitate (oil). The polymerization conditions and results are shown in Table 1 below.

Example 3 (1) The inside of a 100 ml Schlenk tube with a three-way cock was degassed and replaced with argon, and then 43.5 toluene was used.
ml, isobutyl bis (2,6-di-t-butyl-4-
1.3 ml of a toluene solution containing 0.78 mmol of methylphenoxy) aluminum, and N, N, N ',
N '', N ''-pentamethyldiethylenetriamine
7 mg was added and cooled to -40 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. The solution initially colored yellow and became colorless 10 minutes after the end of the dropping. 13 minutes after the completion of dropping, 0.2 ml of methanol was added.
The addition stopped the polymerization reaction. The polymerization conversion of the monomer was determined by ¹ H-NMR measurement of the reaction solution, and as a result, the polymerization conversion was 100%. (2) About a part of the reaction solution generated in the above (1),
The molecular weight in terms of polystyrene of the polymer (n-butyl polyacrylate) obtained by removing the toluene solvent was determined by the GPC method using the above-described apparatus and conditions, and the Mn (number average molecular weight) was 8850. And Mw / Mn
(Molecular weight distribution) was 1.19. (3) After separating and washing the reaction solution produced in the above (1) with a 3% aqueous sulfuric acid solution, the organic phase was methanol: distilled water = 90: 1.
The mixture was poured into a mixed solution of 0 (mass ratio), and a polymer was recovered as an insoluble precipitate (oil). The polymerization conditions and results are shown in Table 1 below.

Example 4 (1) The inside of a 100 ml Schlenk tube with a three-way cock was degassed and replaced with argon, and then 43.5 toluene was used.
ml, isobutyl bis (2,6-di-t-butyl-4-
1.3 ml of a toluene solution containing 0.78 mmol of methylphenoxy) aluminum and 32.0 mg of N, N-dimethylethylamine were added, and the mixture was cooled to -20 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. The solution initially colored yellow and became colorless one minute after the end of the dropping. Three minutes after the completion of the dropwise addition, 0.2 ml of methanol was added to stop the polymerization reaction. The polymerization conversion of the monomer was determined by ¹ H-NMR measurement of the reaction solution, and as a result, the polymerization conversion was 100%. (2) About a part of the reaction solution generated in the above (1),
The molecular weight in terms of polystyrene of the polymer (n-butyl polyacrylate) obtained by removing the toluene solvent was determined by the GPC method using the above-described apparatus and conditions, and the Mn (number average molecular weight) was 42000. And Mw / Mn
(Molecular weight distribution) was 1.31. (3) After separating and washing the reaction solution produced in the above (1) with a 3% aqueous sulfuric acid solution, the organic phase was methanol: distilled water = 90: 1.
The mixture was poured into a mixed solution of 0 (mass ratio), and a polymer was recovered as an insoluble precipitate (oil). The polymerization conditions and results are shown in Table 1 below.

Example 5 (1) The inside of a 100 ml Schlenk tube equipped with a three-way cock was degassed and purged with argon, and then 43.5 toluene was used.
ml, isobutyl bis (2,6-di-t-butyl-4-
1.3 ml of a toluene solution containing 0.78 mmol of methylphenoxy) aluminum and 44.0 mg of triethylamine were added, and the mixture was cooled to -20 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. The solution initially colored yellow and became colorless 30 minutes after the end of the dropping. Thirty-three minutes after the completion of the dropwise addition, 0.2 ml of methanol was added to stop the polymerization reaction.
The polymerization conversion of the monomer was determined by ¹ H-NMR measurement of the reaction solution, and as a result, the polymerization conversion was 100%. (2) About a part of the reaction solution generated in the above (1),
The polystyrene-equivalent molecular weight of the polymer (n-butyl polyacrylate) obtained by removing the toluene solvent was determined by the GPC method using the above-described apparatus and conditions, and as a result, the Mn (number average molecular weight) was 21,4000. And Mw / M
n (molecular weight distribution) was 1.40. (3) After separating and washing the reaction solution produced in the above (1) with a 3% aqueous sulfuric acid solution, the organic phase was methanol: distilled water = 90: 1.
The mixture was poured into a mixed solution of 0 (mass ratio), and a polymer was recovered as an insoluble precipitate (oil). The polymerization conditions and results are shown in Table 1 below.

Example 6 (1) The inside of a 100 ml Schlenk tube equipped with a three-way cock was degassed and purged with argon, and then 43.5 toluene was used.
ml, isobutyl bis (2,6-di-t-butyl-4-
1.3 ml of a toluene solution containing 0.78 mmol of methylphenoxy) aluminum and 36.8 mg of 1-methylpyrrolidine were added, and the mixture was cooled to -20 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. The solution initially colored yellow and became colorless a few seconds after the end of the addition. Three minutes after the end of the dropwise addition, 0.2 m of methanol was added.
The polymerization reaction was stopped by adding 1 l. The polymerization conversion of the monomer was determined by ¹ H-NMR measurement of the reaction solution, and as a result, the polymerization conversion was 100%. (2) About a part of the reaction solution generated in the above (1),
The polystyrene-equivalent molecular weight of the polymer (n-butyl polyacrylate) obtained by removing the toluene solvent was determined by the GPC method using the above-described apparatus and conditions, and as a result, the Mn (number average molecular weight) was 17,400. And Mw / Mn
(Molecular weight distribution) was 1.23. (3) After separating and washing the reaction solution produced in the above (1) with a 3% aqueous sulfuric acid solution, the organic phase was methanol: distilled water = 90: 1.
The mixture was poured into a mixed solution of 0 (mass ratio), and a polymer was recovered as an insoluble precipitate (oil). The polymerization conditions and results are shown in Table 1 below.

Example 7 (1) The inside of a 100 ml Schlenk tube equipped with a three-way cock was degassed and purged with argon, and then 42.7 toluene was used.
ml, isobutyl bis (2,6-di-t-butyl-4-
1.3 ml of a toluene solution containing 0.78 mmol of methylphenoxy) aluminum and 0.1 ml of a toluene solution containing 0.43 mmol of triphenylphosphine.
84 ml was added and cooled to -20 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. The solution initially colored yellow and became colorless upon completion of the dropping. Three minutes after the completion of the dropwise addition, 0.2 ml of methanol was added to stop the polymerization reaction. The polymerization conversion of the monomer was determined by ¹ H-NMR measurement of the reaction solution, and as a result, the polymerization conversion was 100%. (2) About a part of the reaction solution generated in the above (1),
The molecular weight in terms of polystyrene of the polymer (n-butyl polyacrylate) obtained by removing the toluene solvent was determined by the GPC method using the above-described apparatus and conditions, and the Mn (number average molecular weight) was 6120. And Mw / Mn
(Molecular weight distribution) was 1.08. (3) After separating and washing the reaction solution produced in the above (1) with a 3% aqueous sulfuric acid solution, the organic phase was methanol: distilled water = 90: 1.
The mixture was poured into a mixed solution of 0 (mass ratio), and a polymer was recovered as an insoluble precipitate (oil). The polymerization conditions and results are shown in Table 1 below.

Example 8 (1) The inside of a 100 ml Schlenk tube equipped with a three-way cock was evacuated and replaced with argon, and then toluene 41.1 was used.
ml, isobutyl bis (2,6-di-t-butyl-4-
1.3 ml of a toluene solution containing 0.78 mmol of methylphenoxy) aluminum and 2.4 ml of a toluene solution containing 0.43 mmol of 1,2-bis (diphenylphosphino) ethane were added, and the mixture was cooled to -20 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. The solution initially colored yellow and became colorless upon completion of the dropping. Three minutes after the completion of the dropwise addition, 0.2 ml of methanol was added to stop the polymerization reaction. The polymerization conversion of the monomer was determined by ¹ H-NMR measurement of the reaction solution, and as a result, the polymerization conversion was 100%. (2) About a part of the reaction solution generated in the above (1),
The molecular weight in terms of polystyrene of the polymer (n-butyl polyacrylate) obtained by removing the toluene solvent was determined by the GPC method using the apparatus and conditions described above, and the Mn (number average molecular weight) was 4300. And Mw / Mn
(Molecular weight distribution) was 1.14. (3) After separating and washing the reaction solution produced in the above (1) with a 3% aqueous sulfuric acid solution, the organic phase was methanol: distilled water = 90: 1.
The mixture was poured into a mixed solution of 0 (mass ratio), and a polymer was recovered as an insoluble precipitate (oil). The polymerization conditions and results are shown in Table 1 below.

Example 9 (1) The inside of a 100 ml Schlenk tube equipped with a three-way cock was degassed and purged with argon, and then toluene 42.6 was used.
ml, isobutyl bis (2,6-di-t-butyl-4-
1.3 ml of a toluene solution containing 0.78 mmol of (methylphenoxy) aluminum and 0.91 ml of a toluene solution containing 0.43 mmol of trisictohexylphosphine were added and cooled to -20 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. The solution initially colored yellow and became colorless upon completion of the dropping. Three minutes after the end of the dropwise addition, 0.2 m of methanol was added.
The polymerization reaction was stopped by adding 1 l. The polymerization conversion of the monomer was determined by ¹ H-NMR measurement of the reaction solution, and as a result, the polymerization conversion was 100%. (2) About a part of the reaction solution generated in the above (1),
The polystyrene-equivalent molecular weight of the polymer (n-butyl polyacrylate) obtained by removing the toluene solvent was determined by the GPC method using the above-described apparatus and conditions, and as a result, the Mn (number average molecular weight) was 6370. And Mw / Mn
(Molecular weight distribution) was 1.10. (3) After separating and washing the reaction solution produced in the above (1) with a 3% aqueous sulfuric acid solution, the organic phase was methanol: distilled water = 90: 1.
The mixture was poured into a mixed solution of 0 (mass ratio), and a polymer was recovered as an insoluble precipitate (oil). The polymerization conditions and results are shown in Table 1 below.

Comparative Example 1 The inside of a 100-ml Schlenk tube with a three-way cock was degassed and replaced with argon.
44.8 ml of toluene and N, N, N ′, N ″,
N ″ -pentamethyldiethylenetriamine 74.7 mg
And cooled to -20 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. Two hours later, the polymerization conversion of the monomer was determined by ¹ H-NMR measurement of the reaction solution. As a result, the polymerization conversion was 0%. The polymerization conditions and results are shown in Table 1 below.

Comparative Example 2 The inside of a 100 ml Schlenk tube with a three-way cock was degassed and replaced with argon.
43.5 ml of toluene and isobutyl bis (2,6
1.3 ml of a toluene solution containing 0.78 mmol of -di-t-butyl-4-methylphenoxy) aluminum
And cooled to -20 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. The solution turned yellow. After 2 hours, the polymerization conversion of the monomer
As a result of ¹ H-NMR measurement, the polymerization conversion was 0%.
%Met. The polymerization conditions and results are shown in Table 1 below.

Comparative Example 3 The inside of a 100 ml Schlenk tube with a three-way cock was degassed and replaced with argon.
43.8 ml of toluene, 0.97 ml of a toluene solution containing 0.78 mmol of triisobutylaluminum,
And 74.7 mg of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, and the mixture was cooled to −20 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. The solution turned yellow. Two hours later, the polymerization conversion of the monomer was determined by ¹ H-NMR measurement of the reaction solution. As a result, the polymerization conversion was 0%. The polymerization conditions and results are shown in Table 1 below.

[0059]

[Table 1]

As shown in Table 1 above, an anionically polymerizable monomer (n-butyl acrylate) was anionized in the presence of an organic aluminum compound (A) and an organic nitrogen compound (B1) or an organic phosphorus compound (B2). Example 1 of polymerization
In Nos. To 9, a polymer having a predetermined molecular weight and a molecular weight distribution can be obtained at a high polymerization conversion rate at a relatively high polymerization temperature (-20 ° C. or -40 ° C.) and a short polymerization time.

Example 10 (1) The inside of a 100 ml Schlenk tube with a three-way cock was degassed and replaced with argon, and then toluene 42.2 was used.
ml, isobutyl bis (2,6-di-t-butyl-4-
2.6 ml of a toluene solution containing 1.56 mmol of methylphenoxy) aluminum, and N, N, N ',
N '', N ''-pentamethyldiethylenetriamine
7 mg was added, and the mixture was cooled to -20 ° C. To this, 0.98 g of n-butyl acrylate was added dropwise over about 1 minute. The solution initially colored yellow and became colorless one minute after the end of the dropping. At this time, the polymerization conversion of the monomer was determined by the ¹ H-N
As a result of an MR measurement, the polymerization conversion was 100%. (2) Part of the reaction solution generated in (1) above (1 ml)
, The molecular weight in terms of polystyrene of the polymer (n-butyl polyacrylate) obtained by removing the toluene solvent was determined by the GPC method using the above-described apparatus and conditions, and the Mn (number average molecular weight) was obtained. Was 23300, and Mw / Mn (molecular weight distribution) was 1.23. The obtained GPC chart is shown in FIG. In addition, HPLC analysis was performed using the above-described apparatus and conditions, and the chart shown in FIG. 2A was obtained.

(3) 1.03 g of methyl methacrylate was added dropwise to the remaining portion of the reaction solution produced in the above (1) at -20 ° C over about 1 minute. The solution turned yellow. After stirring at -20 ° C for 1 hour, the temperature was raised to room temperature, and the color became colorless after about 2 hours. Methanol to 0.
The polymerization reaction was stopped by adding 2 ml. The polymerization conversion of the monomer was determined by ¹ H-NMR measurement of the reaction solution, and as a result, the polymerization conversion was 100%. (4) About a part of the reaction solution generated in the above (3),
Polymer obtained by removing toluene solvent (poly (n-butyl acrylate-block-polymethyl methacrylate))
Was determined by GPC using the apparatus and conditions described above. As a result, the Mn (number average molecular weight) was 43700, and Mw / Mn (molecular weight distribution) was obtained.
Was 1.09. The obtained GPC chart is shown in FIG. In addition, HPLC analysis was performed using the above-described apparatus and conditions, and the chart shown in FIG. 2B was obtained. As a result of determining the block efficiency by the HPLC method, the block efficiency was 99% or more. (5) The reaction solution produced in the above (3) was separated and washed with a 3% aqueous sulfuric acid solution, and then the organic phase was poured into methanol, and an insoluble precipitate (solid substance) was recovered as a polymer.

[0063]

According to the present invention, the above-mentioned organoaluminum compound (A) and organic nitrogen compound (B1) are used as anionic polymerizable monomers.
In the case of the polymerization method of the present invention in which anion polymerization is performed in the presence of at least one compound selected from organic and organic phosphorus compounds (B2), the method lacks safety and is inferior in handling properties.
Moreover, even without using a conventionally widely used organic alkali metal compound as a polymerization initiator, which required neutralization treatment and removal of salts after polymerization, anionic polymerization proceeds favorably,
A polymer having a predetermined degree of polymerization can be produced at a high polymerization rate and a high yield with good productivity. The polymerization initiator system of the present invention comprising an organoaluminum compound (A) and at least one compound selected from an organic nitrogen compound (B1) and an organic phosphorus compound (B2) has excellent safety and handleability, Moreover, it is excellent in polymerization results such as polymerization initiation efficiency, polymerization rate, and living property. In the case of the present invention, even if a higher polymerization temperature is employed without employing an extremely low polymerization temperature as in the prior art,
Anionic polymerization proceeds favorably.

[Brief description of the drawings]

FIG. 1 shows a GPC chart (A) of n-butyl polyacrylate obtained in step (1) of Example 10, and FIG.
N-butyl-b polyacrylate obtained in step (3) of
FIG. 4 is a view showing a GPC chart (B) of lock-polymethyl methacrylate.

FIG. 2 shows an HPLC chart (A) of n-butyl polyacrylate obtained in step (1) of Example 10 and Example 1;
N-butyl acrylate obtained in step (3)
It is a figure which shows the HPLC chart (B) of block-polymethyl methacrylate.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J015 DA05 DA33 4J026 HA11 HA19 HA25 HA32 HA39 HB11 HB25 HB32 HB39 HB45 HB48 HE01

Claims (7)

[Claims] 1. An anionically polymerizable monomer having the formula:
Organoaluminum compound (A) having in its molecule a chemical structure represented by O-Ar (where Ar represents an aromatic ring)
And at least one compound selected from an organic nitrogen compound (B1) having no hydrogen atom directly bonded to a nitrogen atom and an organic phosphorus compound (B2) having no hydrogen atom directly bonded to a phosphorus atom, A method for polymerizing an anionic polymerizable monomer, comprising performing anionic polymerization. 2. In the presence of a mixture or reactant obtained by previously mixing or reacting an organoaluminum compound (A) with at least one compound selected from an organic nitrogen compound (B1) and an organic phosphorus compound (B2). The polymerization method according to claim 1, wherein the anion polymerization is carried out. 3. A mixture or reaction product obtained by previously mixing or reacting at least one compound selected from an organoaluminum compound (A), an organic nitrogen compound (B1) and an organic phosphorus compound (B2), and an acrylate ester. The polymerization method according to claim 1, wherein anionic polymerization is performed in the presence of. 4. An anionically polymerizable monomer comprising at least one selected from α, β-unsaturated carboxylic acid esters, α, β-unsaturated carboxylic acid amides, α, β-unsaturated ketones and α, β-unsaturated nitriles. The polymerization method according to any one of claims 1 to 3, wherein the polymerization method is one kind of monomer. 5. The polymerization method according to claim 1, wherein the anionic polymerization is block copolymerization. 6. The polymerization method according to claim 5, wherein at least one of the copolymerized monomers in the block copolymerization is an acrylate ester. 7. An organoaluminum compound (A) having a chemical structure represented by the formula: Al—O—Ar (where Ar represents an aromatic ring) in a molecule, and hydrogen directly bonded to a nitrogen atom. Polymerization initiation for anionic polymerization, comprising at least one compound selected from an organic nitrogen compound having no atom (B1) and an organic phosphorus compound having no hydrogen atom directly bonded to a phosphorus atom (B2). Agent system.