JP2005105265A - Polymer and its preparing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer containing less content of transition metal components and its preparing method which can solve the problems that, in living radical polymerization using a transition metal catalyst, the metal catalyst remains in the polymer, causes stains or decrease in properties, and can not put the living radical polymerization using a transition metal catalyst to practical use, and which removes transition metal components from a polymer obtained by atom transfer radical polymerization of monomers that is polymerized by addition polymerization. <P>SOLUTION: The polymer can be obtained by purification of polymerization reaction liquid, which is obtained by applying the atom transfer radical polymerization using a transition metal complex as a catalyst to monomers that is polymerized by addition polymerization, or the polymer obtained from the polymerization reaction liquid using a water-insoluble solvent and a complexing agent solution. The complexing agent solution is a complexing agent aqueous solution, a complexing agent aqueous solution containing electrolytes or a solution in which the complexing agent is dissolved in a precipitant. The concentration of the transfer metal components in the polymer is ≤10 ppm to the whole amount of the polymer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for purifying an addition polymer obtained by atom transfer radical polymerization using a transition metal complex and a purified polymer obtained thereby.

  In recent years, with the development of advanced science and technology, polymer materials have come to be used in various fields not only as general-purpose structure-forming materials but also as high-value-added materials having advanced functions and performance. . Along with this, it is becoming more important to manufacture polymer materials based on precise design. In order to obtain such a material, it is extremely important to synthesize a polymer having a clear structure. Otherwise, it is difficult to precisely analyze the molecular properties of the polymer and the properties of the molecular assembly, and thus the function of the polymer material cannot be optimized for the purpose. The atom transfer radical polymerization method (Atom Transfer Radical Polymerization Method) using transition metal complexes described in Non-Patent Documents 1 and 2 exhibits excellent living polymerizability as radical polymerization, narrow molecular weight distribution, and molecular weight. However, it is possible to obtain a polymer in which is strictly controlled. As a result, it is possible to obtain a polymer having a clear structure represented by a block copolymer, a terminal functionalized polymer, or the like, which has been extremely difficult with conventional radical polymerization.

Living radical polymerization using a transition metal catalyst is very excellent in terms of broad adaptability to polymerizable monomers and molecular structure control, but it is inevitable that the metal catalyst used remains in the polymer. This causes problems such as coloring and deterioration of physical properties, and is a major obstacle to practical use. In order to solve these problems, removal of transition metal components using an inorganic adsorbent or an ion exchange resin has been studied (see Patent Document 1, Patent Document 2, and Non-Patent Document 3). However, in any case, a solid-liquid separation process is required, and a long processing time is required when an adsorbent packed column is used. When an ion exchange resin is used, there is a possibility that a soluble resin component contained in the ion exchange resin may be mixed into the polymer.
JP 2001-323012 A JP 2001-323015 A Chem. Rev., 101, 2921-2990 (2001) Chem. Rev., 101, 3689-3745 (2001) Macromolecules, 33, 1476-1478 (2000)

  In order to solve the above problems, an object of the present invention is to provide a method for removing a transition metal component from a polymer obtained by atom transfer radical polymerization of an addition polymerizable monomer using a transition metal complex as a polymerization catalyst, and the method. It is to provide a polymer having a low content of a transition metal component obtained by the method.

  The present inventors have found that by using a solution of a complexing agent as a treating agent, it is possible to reduce the content of a transition metal component in a polymer obtained using a transition metal complex as a polymerization catalyst. That is, the present invention has the following configuration.

[1] A polymerization reaction solution obtained by applying an atom transfer radical polymerization method using a transition metal complex as a catalyst to an addition-polymerizable monomer, or a polymer obtained from this polymerization reaction solution as a water-insoluble solution as an optional component A polymer obtained by purification using a basic solvent and a complexing agent solution as an essential component; the complexing agent solution is a complexing agent aqueous solution, a complexing agent aqueous solution containing an electrolyte component, or a precipitating agent. A polymer in which a complexing agent is dissolved, and the concentration of the transition metal component contained in the polymer is 10 ppm or less with respect to the total amount of the polymer.

[2] An atom transfer radical polymerization method using a transition metal complex as a catalyst is applied to an addition polymerizable monomer to obtain a polymerization reaction solution, and a polymer obtained from the polymerization reaction solution is converted into a water-insoluble solvent and a complexing agent. The polymer according to the item [1], which is obtained by purification using an aqueous solution.

[3] An atom transfer radical polymerization method using a transition metal complex as a catalyst is applied to an addition polymerizable monomer to obtain a polymerization reaction solution, and a polymer obtained from the polymerization reaction solution is mixed with a water-insoluble solvent and an electrolyte component. The polymer according to item [1], which is obtained by purification using an aqueous complexing agent solution.

[4] A polymerization reaction solution obtained by applying an atom transfer radical polymerization method using a transition metal complex as a catalyst to an addition polymerizable monomer, a solution in which a complexing agent is dissolved in a precipitating agent, and a water-insoluble solution as an optional component The polymer according to item [1], which is obtained by purification using an organic solvent.

[5] The complexing agent is carboxylic acid and its salt, amine and its salt, aminocarboxylic acid and its salt, amino acid and its salt, phosphoric acid and its salt, phosphonic acid and its salt, inorganic halide, inorganic cyanide, [1] to [4], which are at least one compound selected from the group consisting of ammonium salts, sulfites, thiocyanates, thiosulfates, polythionates, dithionites, and dithionates. The polymer according to any one of the above.

[6] At least one compound in which the complexing agent is selected from the group consisting of carboxylic acids and salts thereof, amines and salts thereof, aminocarboxylic acids and salts thereof, amino acids and salts thereof, phosphoric acid and salts thereof, and inorganic cyanides. The polymer according to any one of [1] to [4], wherein

[7] Complexing agent is carboxylic acid and its salt, amine and its salt, aminocarboxylic acid and its salt, amino acid and its salt, phosphoric acid and its salt, phosphonic acid and its salt, inorganic cyanide, sulfite, thiocyan At least one compound selected from the group consisting of acid salts, thiosulfates, polythionates, dithionites and dithionates, and the electrolyte component is an inorganic halide or ammonium salt [3 ] The polymer of description.

[8] At least one compound in which the complexing agent is selected from the group consisting of carboxylic acids and salts thereof, amines and salts thereof, aminocarboxylic acids and salts thereof, amino acids and salts thereof, phosphoric acid and salts thereof, and inorganic cyanides. The polymer according to item [3], wherein the electrolyte component is an inorganic halide or an ammonium salt.

[9] The polymer according to any one of [1] to [8], wherein the central metal of the transition metal complex is an element of Group 8, Group 9, Group 10, or Group 11 of the Periodic Table. .

[10] The polymer described in the item [9], wherein the central metal of the transition metal complex is iron, nickel, ruthenium or copper.

[11] The polymer according to item [9], wherein the central metal of the transition metal complex is copper.

[12] The polymer according to any one of [1] to [11], wherein the addition polymerizable monomer is at least one selected from the group consisting of a (meth) acrylic acid derivative and a styrene derivative.

[13] An atom transfer radical polymerization method using a transition metal complex as a catalyst is applied to an addition polymerizable monomer to obtain a polymerization reaction solution, and a polymer obtained from the polymerization reaction solution is dissolved in a water-insoluble solvent. A polymer solution, and by adding a complexing agent aqueous solution or an aqueous complexing agent solution further containing an electrolyte component to the polymer solution and stirring, the transition metal component is extracted from this solution into an aqueous layer, The method for producing a polymer according to item [1].

[14] An atom transfer radical polymerization method using a transition metal complex as a catalyst is applied to an addition polymerizable monomer to obtain a polymerization reaction solution, and a solution in which a complexing agent is dissolved in a precipitant is added to the polymerization reaction solution. The method for producing a polymer as described in the item [1], wherein the polymer is precipitated while the transition metal component is extracted into the complexing agent solution.

  According to the present invention, a polymer in which the content of the transition metal complex is significantly reduced can be easily obtained. That is, the coloration and physical property degradation, which are problems of the polymer obtained using the transition metal complex, are improved. Since the polymer of the present invention is based on atom transfer radical polymerization using a transition metal complex as a catalyst, the molecular structure can be easily controlled. Therefore, the polymer of the present invention can be put into practical use as a high-performance polymer material capable of optimizing the function according to the purpose.

First, terms used in the present invention will be described. “Arbitrary” means that not only the position but also the number can be arbitrarily selected, but the case where the number is 0 is not included. The description that any —CH ₂ — may be replaced by —O— does not include the case where a plurality of consecutive —CH ₂ — are replaced by —O—. The expression that any A may be replaced by B or C means that any A is replaced by B in addition to any A being replaced by B and any A being replaced by C. , It means that any A in the remaining A is replaced by C. For example, alkyl where any —CH ₂ — may be replaced by —O— or —CH═CH— includes alkyl, alkoxy, alkoxyalkyl, alkenyl, alkyloxyalkenyl and alkenyloxyalkyl. Alkyl and alkylene may both be straight-chain groups or branched groups. This also applies when any —CH ₂ — is replaced by another divalent group. For example, all of alkyl, alkenylene, alkenyl and alkylene in the above-mentioned alkyloxyalkenyl and alkenyloxyalkyl may be a straight-chain group or a branched group. Both cycloalkyl and cycloalkenyl may or may not be a bridged ring structure group. (Meth) acrylic acid is used as a general term for acrylic acid and methacrylic acid. (Meth) acrylate is used as a general term for acrylate and methacrylate. (Meth) acryloyloxy is used as a general term for acryloyloxy and methacryloyloxy.

ここに、Ｒ^１およびＲ^２は水素、Ｘ、および炭素原子の数が１〜２０であって任意の−ＣＨ_２−が−Ｏ−またはシクロアルキレンで置き換えられてもよいアルキルから独立して選択される基であり、Ｘは塩素、臭素またはヨウ素である。

ここに、Ｒ^３、Ｒ^４およびＲ^５は、独立して水素、炭素数１〜２０のアルキル、炭素数６〜１２のアリールまたは炭素数７〜２０のアリールアルキルであり、Ｒ^３およびＲ^４が共に水素であることはなく、そしてＸは塩素、臭素またはヨウ素である。 Next, atom transfer radical polymerization will be described. This polymerization method is one of living radical polymerization methods, using a living polymerization initiator, and using a metal complex having a central metal of group 8, 9, 10, or 11 of the periodic table as a catalyst. is there. Examples of living polymerization initiators are organic halides and halogenated sulfonyl compounds. Examples of the organic halide include a benzyl derivative represented by the formula (1) and a compound having an α-haloester group represented by the formula (2).

Wherein R ¹ and R ² are independently selected from hydrogen, X, and alkyl having 1 to 20 carbon atoms, wherein any —CH ₂ — may be replaced by —O— or cycloalkylene X is chlorine, bromine or iodine.

Here, R ³ , R ⁴ and R ⁵ are independently hydrogen, alkyl having 1 to 20 carbons, aryl having 6 to 12 carbons or arylalkyl having 7 to 20 carbons, and R ³ and R ⁴ Are not both hydrogen and X is chlorine, bromine or iodine.

ここに、Ｒ^６は水素、炭素数１〜２０のアルキル、炭素数６〜１２のアリールまたは炭素数７〜２０のアリールアルキルであり、Ｘは塩素、臭素またはヨウ素である。 Examples of the halogenated sulfonyl compound include a compound represented by the formula (3).

Here, R ⁶ is hydrogen, alkyl having 1 to 20 carbons, aryl having 6 to 12 carbons or arylalkyl having 7 to 20 carbons, and X is chlorine, bromine or iodine.

これらの式において、Ｐは付加重合性単量体の重合によって得られる構成単位の連鎖であり、Ｒ^１〜Ｒ^６およびＸは式（１）〜式（３）におけるそれぞれの記号と同じ意味を有する。 That is, when atom transfer radical polymerization is performed using these initiators, polymers represented by formulas (1-1) to (3-1) can be obtained.

In these formulas, P is a chain of structural units obtained by polymerization of addition polymerizable monomers, R ¹ to R ⁶ and X are the same meaning as each of the symbols in the formula (1) to (3) Have.

  Accordingly, an organic halide or halogenated sulfonyl compound having a functional group that initiates atom transfer radical polymerization and a specific functional group that does not initiate atom transfer radical polymerization is used as an initiator for atom transfer radical polymerization. A polymer having a specific functional group that does not initiate atom transfer radical polymerization at one end thereof and X (chlorine, bromine, or iodine) at the other end can be obtained. Examples of such specific functional groups are alkenyl groups, hydroxyl groups, epoxy groups, amino groups and amide groups. Specific examples of the organic halide or halogenated sulfonyl compound having such a specific functional group include the aforementioned Patent Documents 1 and 2, Non-Patent Documents 1 and 2, and Progress In Polymer Science, 26, 337-377 (2001). ).

  In the atom transfer radical polymerization in the present invention, a compound called a macroinitiator can also be used as an initiator. Specifically, the polymers represented by the respective formulas (1-1), (2-1), and (3-1) are used as macroinitiators, and various addition polymerizable monomers are subsequently used as atom transfer radicals. By polymerization, it can be derived into a block copolymer or the like. In the present invention, a macroinitiator obtained by a polymerization method different from atom transfer radical polymerization can also be used. For example, polydimethylsiloxane obtained by the living anion polymerization method, polyethylene glycol, or polypropylene glycol introduced with an atom transfer radical polymerization initiation group such as an α-bromoester group at the terminal can be used as a macroinitiator, Furthermore, an atom transfer radical polymerization initiator which is a silsesquioxane derivative can also be used.

  Furthermore, in the present invention, fine particles having an atom transfer radical polymerization initiator immobilized thereon can also be used as the initiator. For example, the above initiator is immobilized on metal fine particles (eg, gold, silver, platinum, palladium, nickel, iron, etc.), silica fine particles, silsesquioxane fine particles, polymer fine particles, etc. Can be grafted.

Specific examples of the atom transfer radical polymerization initiator used in the present invention are shown below. The meanings of symbols in the specific examples are as follows.
Me: methyl Et: ethyl Bu: butyl iBu: isobutyl Oc: octyl iOc: isooctyl Ph: phenyl Cp: cyclopentyl Ch: cyclohexyl TFP: 3,3,3-trifluoropropyl

  In addition to the above examples, a ladder-type silsesquioxane derivative, which is a compound in which one or more initiators are introduced toward the main chain instead of a terminal group, or an amorphous silsesquioxane in which an initiator is introduced Derivatives can also be mentioned.

  The atom transfer radical polymerization method used in the present invention includes a so-called reverse atom transfer radical polymerization method. Reverse atom transfer radical polymerization is a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, a peroxide or the like with respect to Cu (II) when Cu (I) is used as a catalyst. In this method, an equilibrium state similar to that of atom transfer radical polymerization is produced as a result (see Macromolecules, 32, 2872 (1999)).

Next, an addition polymerizable monomer that can be used for atom transfer radical polymerization will be described. This addition polymerizable monomer is a monomer having at least one addition polymerizable double bond. One example of a monofunctional monomer having one addition polymerizable double bond is a (meth) acrylic acid monomer. Specific examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl ( ) Acrylate, 3-methoxypropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) Acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 2- (meth) acryloyloxyethyl isocyanate, (meth) acrylate 2-aminoethyl, 2- (2-bromopropionyloxy) ethyl (meth) acrylate, 2- (2-bromoisobutyryloxy) ethyl (meth) acrylate, 1- (meth) acryloxy-2-phenyl-2- (2,2,6,6-tetramethyl-1-piperidinyloxy) ethane , (1- (4-((4- (meta) Kurirokishi) ethoxyethyl) phenylethoxy) piperidine, .gamma. (methacryloyloxypropyl) trimethoxysilane, 3- (3,5,7,9,11,13,15- hepta ethylpentamethylene cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15- hepta isobutyl - pentacyclo [9 .5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15- hepta isooctyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7, , 11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^{3, 9.} 1 ^5,15 . 1 ^7,13] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15- heptaphenyl penta cyclo [9.5.1.1 ^{3, 9 .1,5,15.1,7,13} ] ^{octasiloxane-} 1-yl) propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15-heptaethylpentacyclo [9.5]. .1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3,5,7,9,11,13, 15 hepta isobutyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3, 5,7 9,11,13,15- hepta isooctyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate , 3 - [(3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane -1- yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3,5,7,9,11,13,15- heptaphenyl penta cyclo ^[9.5.1.1 3,9 ^{.1 5,15. 1713} ]] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) ) Acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) Acrylate, trifluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2- Perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, 2- (meth) acryloyloxyethylphosphorylcholine, and the like.

Another example of a monofunctional monomer is a styrenic monomer. Specific examples thereof include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, m-chloromethylstyrene, o-aminostyrene, p-styrene chlorosulfonic acid, styrenesulfonic acid and salts thereof. , Vinylphenylmethyldithiocarbamate, 2- (2-bromopropionyloxy) styrene, 2- (2-bromoisobutyryloxy) styrene, 1- (2-((4-ethenylphenyl) methoxy) -1-phenyl Ethoxy) -2,2,6,6-tetramethylpiperidine, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15- heptaphenyl penta cyclo [9.5.1.1 ^{3, 9.} 1 ^5,15 . 1 ^7,13] octasiloxane, 3- (3,5,7,9,11,13,15- hepta ethylpentamethylene cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13} ] octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9,11,13,15- hepta isobutyl penta cyclo ^[9.5.1.1 3,9 ^{.1 5,15 .1 7,13]} octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9,11,13,15- hepta isooctyl penta cyclo ^[9.5.1.1 3,9 .1 ^{5 ,} 15.1 ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] oct-siloxane -1 Yl) ethyl styrene, 3- (3,5,7,9,11,13,15- heptaphenyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane 1-yl) ethyl styrene, 3 - ((3,5,7,9,11,13,15- hepta ethylpentamethylene cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7, 13]} octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5,7,9,11,13,15- hepta isobutyl penta cyclo ^[9.5.1.1 3, 9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5,7,9,11,13,15- hepta isooctyl penta cyclo [9.5. 1.1 ^3,9 .1 ^5,15 1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^{3, 9} .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5,7,9,11,13,15- heptaphenyl penta cyclo [9. 5.1.1 ^3,9 .1 ^5,15 .1 ^7,13], and the like octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene.

  Examples of other monofunctional monomers include fluorine-containing vinyl monomers (perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc.), silicon-containing vinyl monomers (vinyltrimethoxysilane, vinyltriethoxysilane) Maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, maleimide monomers (maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, Butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc.), nitrile group-containing monomers (acrylonitrile, methacrylonitrile, etc.), Mido group-containing monomers (acrylamide, methacrylamide, etc.), vinyl ester monomers (vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc.), olefins (ethylene, propylene, etc.) , Conjugated diene monomers (butadiene, isoprene, etc.), vinyl halides (vinyl chloride, etc.), vinylidene halides (vinylidene chloride, etc.), allyl halides (eg, allyl chloride), allyl alcohol, vinyl pyrrolidone, vinyl pyridine, N-vinyl carbazole, methyl vinyl ketone, vinyl isocyanate and the like. Furthermore, it has one polymerizable double bond per molecule, and the main chain is styrene, (meth) acrylic acid ester, siloxane (for example, polydimethylsiloxane), polyethylene glycol, polypropylene glycol, polyethylene glycol-block-polypropylene. A macromonomer such as glycol is also included.

  Examples of polyfunctional monomers having two addition polymerizable double bonds are 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalic acid Ester neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, bis [(meth) acryloyloxyethoxy] bisphenol A, bis [(meth) acryloyloxyethoxy] tetrabro Bisphenol A, bis [(meth) acryloxypolyethoxy] bisphenol A, 1,3-bis (hydroxyethyl) 5,5-dimethylhydantoin, 3-methylpentanediol di (meth) acrylate, hydroxypivalate ester neopentyl glycol Di (meth) acrylates of derivatives, di (meth) acrylate monomers such as bis [(meth) acryloyloxypropyl] tetramethyldisiloxane, and divinylbenzene. Furthermore, it has two polymerizable double bonds in the molecule, and the main chain is styrene, (meth) acrylic acid ester, siloxane (such as polydimethylsiloxane), polyethylene glycol, polypropylene glycol, polyethylene glycol) -block-polypropylene There are also macromonomers such as glycol.

Examples of polyfunctional monomers having three or more addition polymerizable double bonds are trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy Penta (meth) acrylate, tris (2-hydroxyethylisocyanate) tri (meth) acrylate, tris (diethylene glycol) trimaleate tri (meth) acrylate, 3,7,14-tris [(((meth) acryloyloxypropyl) dimethylsiloxy )] - 1,3,5,7,9,11,14- hept ethyl tricyclo ^{[7.3.3.1 5 and 11]} hept siloxane, 3,7,14- tris [(((meth) acryloyl Oxypropyl) dimethylsiloxy) -1,3,5,7,9,11,14- hepta isobutyl tricyclo ^{[7.3.3.1 5 and 11]} hept siloxane, 3,7,14- tris [(((meth) acryloyloxy propyl ) dimethylsiloxy)] - 1,3,5,7,9,11,14- hept isooctyl tricyclo ^{[7.3.3.1 5 and 11]} hept siloxane, 3,7,14- tris [(( (meth) acryloyloxy propyl) dimethylsiloxy)] - 1,3,5,7,9,11,14- hept cyclopentanol tilt Li cyclo ^{[7.3.3.1 5 and 11]} hept siloxanes, 3, 7, 14 - tris [(((meth) acryloyloxy propyl) dimethylsiloxy)] - 1,3,5,7,9,11,14- heptaphenyl tricyclo ^{[7.3.3.1 5 and 11]} Heputashiroki Emissions, and the like octakis (3- (meth) acryloyloxy propyl dimethylsiloxy) octasilsesquioxane, octakis (3- (meth) acryloyloxy propyl) octasilsesquioxane. Furthermore, it has two or more polymerizable double bonds in the molecule, and the main chain is styrene, (meth) acrylic acid ester, siloxane (such as polydimethylsiloxane), polyethylene glycol, polypropylene glycol, polyethylene glycol-block-polypropylene. A macromonomer such as glycol is also included.

  These monomers may be used alone or a plurality may be copolymerized. The copolymerization may be random copolymerization or block copolymerization.

  Next, a method for atom transfer radical polymerization of an addition polymerizable monomer using a transition metal complex as a catalyst will be described. The atom transfer radical polymerization method in the present invention is one of living radical polymerization methods, and is a method of radical polymerization of an addition polymerizable monomer using an organic halide or a halogenated sulfonyl compound as an initiator. For this method, reference can be made to J. Am. Chem. Soc., 117, 5614 (1995), Macromolecules, 28, 7901 (1995), and Science, 272, 866 (1996).

A preferred example of the transition metal complex used as the polymerization catalyst is a metal complex having a group 7 element, group 8, group 9, group 10, or group 11 element of the periodic table as a central metal. Further preferred catalysts are zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel complex. Of these, a copper complex is preferable. Examples of monovalent copper compounds are cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. For the metal complex, ligands described in Non-Patent Documents 1 and 2 are used. More specifically, 2,2′-bipyridyl or a derivative thereof (2,2′-bipyridine, 4,4′-di-n-heptyl-2,2′-bipyridine, etc.), 1,10-phenanthroline or a derivative thereof Derivatives, pyridylmethanimine (such as N- (n-propyl) -2-pyridylmethanimine), polyamine (such as tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine), or L-(- ) -Polycyclic alkaloids such as sparteine are added as ligands. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistributylphosphine complex ( NiBr ₂ (PBu ₃ ) ₂ ) and the like are also suitable as the catalyst.

A solvent may be used for the polymerization reaction. Examples of solvents used include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (methylene chloride, chloroform, chlorobenzene, etc.) ), Ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, etc.), nitrile solvents (acetonitrile, propionitrile, Benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N) Dimethylformamide, N, N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (HFCs having 2 to 4, 5 and 6 or more carbon atoms), perfluorocarbon Solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol), water, etc. It is. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium. In addition, the solvent which can be used is not restrict | limited to these examples.

  Atom transfer radical polymerization can be performed under reduced pressure, normal pressure, or increased pressure, depending on the type of addition polymerizable monomer and the type of solvent. Transition metal complexes and generated radicals may be deactivated when they come into contact with oxygen. In such a case, it is important to perform the polymerization in an inert gas atmosphere such as nitrogen or argon because the polymerization rate decreases or a good living polymer cannot be obtained. In this reaction, it is necessary to previously remove dissolved oxygen in the polymerization system under reduced pressure. And it is also possible to transfer to a superposition | polymerization process as it is under reduced pressure after the removal process of dissolved oxygen. A conventional method can be adopted for the atom transfer radical polymerization, and it is not particularly limited by the polymerization method. For example, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a bulk-suspension polymerization method, or the like can be employed. And polymerization temperature is the range of 0-200 degreeC, and preferable polymerization temperature is the range of room temperature-150 degreeC.

  When a normal addition polymerizable monomer is polymerized, a compound having a polymerizable functional group and also a function as an initiator, such as 2- (2-bromopropionyloxy) ethyl (meth) acrylate, 2- ( Highly branched polymers can be bonded by using 2-bromoisobutyryloxy) ethyl (meth) acrylate, 2- (2-bromopropionyloxy) styrene, 2- (2-bromoisobutyryloxy) styrene, etc. The obtained polymer can be obtained. In addition, by using together a compound having a polymerizable functional group such as a (meth) acryl group or a styryl group, such as trialkoxysilane, polydimethylsiloxane, silsesquioxane, etc., a silicon atom is contained in the structure of the polymer. A structural unit containing can be introduced. Addition polymerizable monomers having an initiating group not involved in atom transfer radical polymerization, such as 1- (2- (4-ethenylphenylmethoxy) -1-phenylethoxy) -2,2,6,6-tetramethylpiperidine 1- (meth) acryloyloxy-2-phenyl-2- (2,2,6,6-tetramethyl-1-piperidinyloxy) ethane, 1- (4- (4- (meth) acryloyloxyethoxy) After copolymerization of ethyl) phenylethoxy) piperidine, vinylphenylmethyldithiocarbamate, etc., the resulting polymer is used as an initiator, and addition polymerization is performed in another polymerization mode (for example, nitroxyl polymerization or photoinifer polymerization). The body can be polymerized to form a graft copolymer.

  Thermally latent or photolatent cationic polymerization into a polymer obtained by copolymerizing an addition polymerizable monomer with a monomer having a glycidyl group, a monomer having an oxetanyl group, or a monomer having a dioxolane If an aliphatic sulfonium salt, an aromatic sulfonium salt or an aromatic iodonium salt is added as an initiator and subjected to cationic polymerization, a crosslinked polymer having a three-dimensional network structure can be obtained. In this case, it is preferable to remove the transition metal complex of the radical polymerization catalyst prior to the cationic polymerization. An example of a monomer having a glycidyl group is glycidyl (meth) acrylate. An example of a monomer having an oxetanyl group is 3-ethyl-3- (meth) acryloyloxymethyloxetane. An example of a monomer having dioxolane is 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane. Examples of aliphatic sulfonium salts are 3-methyl-2-butenyltetramethylenesulfonium hexafluoroantimonate and 2-butenyltetramethylenesulfonium hexafluoroantimonate. Examples of aromatic sulfonium salts are Sun Aid SI-15, SI-20, SI-25, SI-40, SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI -100, SI-100L, SI-145, SI-150, SI-160 (all manufactured by Sanshin Chemical Industry Co., Ltd.), Adeka optomer SP-172, Adeka optomer SP-152 (all Asahi Denka Kogyo) Co., Ltd.), diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate. An example of an aromatic iodonium salt is (4-pentadecyloxyphenyl) phenyl iodonium hexafluoroantimonate. When performing photolatent cationic polymerization, you may use together a photosensitizer, for example, Adeka optomer SP-100 (Asahi Denka Kogyo Co., Ltd. product). Further, when obtaining a crosslinked polymer having a three-dimensional network structure by cationic polymerization, a monofunctional or polyfunctional glycidyl-based crosslinking agent or a monofunctional or polyfunctional oxetane-based crosslinking agent may coexist.

  In the following description, the polymer obtained as described above is referred to as a polymer (1). In order to isolate the polymer (1) from the polymerization reaction solution, it is necessary to efficiently remove the unreacted addition polymerizable monomer. For this purpose, a purification method by reprecipitation operation is preferred. This purification method is performed as follows. First, only the polymer (1) is precipitated by mixing the polymer (1) and a polymerization reaction solution containing an unreacted monomer and a precipitant. This precipitating agent means a solvent that does not dissolve the polymer (1) but dissolves unreacted monomers. A preferred amount of the precipitating agent is 20 to 50 times based on the weight of the polymerization reaction solution. The selection conditions for the precipitating agent are that it is compatible with the solvent used in the polymerization, does not dissolve the polymer (1) at all, dissolves only the unreacted monomer, and has a relatively low boiling point. Examples of preferred precipitating agents are lower alcohols and aliphatic hydrocarbons. Particularly preferred precipitants are methanol and hexane. And in order to raise the removal efficiency of an unreacted monomer further, what is necessary is just to increase the repetition frequency of reprecipitation operation. By this method, only the polymer (1) can be precipitated in a poor solvent, and the unreacted monomer and the polymer can be easily separated by a filtration operation.

  Since the transition metal complex which is a polymerization catalyst remains in the polymer (1) isolated by the above method, problems such as coloration of the polymer, influence on physical properties and environmental safety are likely to occur. Therefore, it is necessary to remove this residual catalyst after completion of the polymerization reaction. In the present invention, the transition metal component is removed by purification using a water-insoluble solvent and a complexing agent solution. Examples of the complexing agent solution are a complexing agent aqueous solution, a complexing agent aqueous solution containing an electrolyte component, and a solution in which a complexing agent is dissolved in a precipitant. That is, after the polymer (1) is dissolved in a water-insoluble solvent, a complexing agent aqueous solution or a complexing agent aqueous solution containing an electrolyte component is added to the polymer (1) solution, and the mixture is stirred and mixed. Is converted to a complex with this complexing agent and extracted into an aqueous layer. After the separated polymer (1) solution is separated from the aqueous layer, a precipitant is added thereto to isolate the polymer (1). In this way, the concentration of the catalyst component remaining in the polymer (1) can be significantly reduced. If the polymer (1) is dissolved in a water-insoluble solvent and then added to a solution in which a complexing agent is dissolved in a precipitant, the transition metal complex is extracted into the precipitant layer and at the same time the polymer (1) is precipitated. Can be made.

  You may refine | purify a polymerization reaction liquid as object. When the viscosity of the polymerization reaction solution is high, a purification treatment may be performed after adding a non-aqueous solvent to obtain a suitable solution viscosity. That is, after completion of the polymerization reaction, the polymerization reaction solution containing the polymer (1) is diluted with a water-insoluble solvent as necessary, and then a complexing agent aqueous solution or a complexing agent aqueous solution containing an electrolyte component is added to this solution. Stirring and mixing, complexing the transition metal component and transferring it to the aqueous layer, and then separating the aqueous solution and the water-insoluble solvent including the polymer (1) by physical operation such as centrifugation or stationary separation . And by putting the solution containing this polymer (1) into the precipitant, the polymer (1) can be precipitated while removing unreacted monomers. By such a purification treatment, the concentration of the catalyst component remaining in the polymer (1) can be significantly reduced.

  The operation procedure of this purification process does not necessarily have to be as described above. For example, the water-insoluble solvent may be added after adding the complexing agent or the complexing agent and the electrolyte component to the polymer (1) or the polymerization reaction solution containing the polymer (1), and water may be further added. Regardless of the operation procedure, the purification process is finally the same extraction process as the operation procedure described first, and the same effect can be obtained.

  When purifying the polymerization reaction liquid as a target, the polymerization reaction liquid is diluted with a water-insoluble solvent as necessary, for example, to reduce its viscosity, and then the complexing agent is dissolved in the precipitant. If put in the solution, the polymer (1) can be precipitated at the same time as the transition metal complex is extracted into the precipitant layer. The selection conditions for the precipitant used in this purification treatment method are to dissolve the complexing agent and to precipitate the polymer (1). Also in this case, examples of preferable precipitants are the same lower alcohols and aliphatic hydrocarbons as described above. Particularly preferred precipitants are methanol and hexane. And in order to raise the removal efficiency of a transition metal component further, what is necessary is just to increase the repetition frequency of reprecipitation operation. By this method, it is possible to precipitate only the polymer (1), and the unreacted monomer and transition metal complex can be easily separated from the polymer by a filtration operation.

  Examples of the water-insoluble solvent used in the present invention are anisole, benzene, carbon tetrachloride, chlorobenzene, chloroform, 1-chloronaphthalene, dibenzylnaphthalene, o-dichlorobenzene, m-dichlorobenzene, 1,1-dichloroethane, 1 , 2-dichloroethane, dichloromethane, diisopropyl ether, N, N-dimethylaniline, diphenyl ether, ethyl acetate, mesitylene, methyl acetate, isoamyl acetate, cyclohexanone, cyclopentanone, nitrobenzene, nitromethane, tetrachloroethylene, tetralin, toluene, trichloroethylene and xylene is there. More preferred examples are chloroform, ethyl acetate and toluene.

  In the present invention, carboxylic acid and its salt, amine and its salt, aminocarboxylic acid and its salt, amino acid and its salt, phosphoric acid and its salt, phosphonic acid and its salt, inorganic halide, inorganic cyanide, ammonium salt, At least one compound selected from the group consisting of sulfites, thiocyanates, thiosulfates, polythionates, dithionites and dithionates is used as the complexing agent. Examples of carboxylic acids are aliphatic carboxylic acids and aromatic carboxylic acids. Examples of acid salts are alkali metal salts such as sodium, potassium and lithium, alkaline earth metal salts such as calcium and barium, and heavy metal salts such as iron (III) and vanadium, and metal to the carboxyl group. Alternatively, a partially neutralized salt having a basic substance in an equivalent amount or less or a mixture of these salts can also be used. An example of an amine salt is a salt with a fatty acid such as acetic acid.

  Examples of aliphatic carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, adipic acid, fumaric acid, citraconic acid , Itaconic acid, tricarbazic acid, propane-1,1,2,3-tetracarboxylic acid, butane-1, glycolic acid, lactic acid, β-hydroxypropionic acid, malic acid, tartaric acid, citric acid, alloisocitric acid, gluconic acid Pyruvic acid, oxalic acid, diglycolic acid and thiodiglycolic acid. Examples of aromatic carboxylic acids are benzoic acid, phthalic acid, isophthalic acid, mandelic acid, salicylic acid, 5-sulfosalicylic acid, α-carboxy-o-anisic acid and o- (carboxymethylthio) benzoic acid.

  Examples of amines are diethylamine, methylamine, ethylamine, propylamine, triethylamine, morpholine, piperidine, ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, Nn-propylethylenediamine, N-isopropylethylenediamine, N- (2 -Hydroxyethyl) ethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine, N, N'-di-n-propylethylenediamine, N, N-di (2-hydroxyethyl) ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-diaminopropane, meso-2,3-diaminobutane, rac-2,3 Diaminobutane, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, triethylenediamine, diethylenetriamine, 3,3'-diaminodipropylamine, triethylenetetraamine, 2-hydroxyethylamine, 2-methoxyethylamine, 2,2'- Dihydroxydiethyleneamine and polyamidoamine.

  Examples of aminocarboxylic acids or salts thereof include iminodiacetic acid, iminodipropionic acid, N-methyliminodiacetic acid, N- (3,3′-dimethylbutyl) iminodiacetic acid, phenyliminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethyl Iminodipropionic acid, hydroxypropyliminodiacetic acid, 2-hydroxycyclohexyliminodiacetic acid, methoxyethyliminodiacetic acid, 2-hydroxybenzyliminodiacetic acid, N- (o-carboxyphenyl) iminodiacetic acid, N- (m-carboxy Phenyl) iminodiacetic acid, N- (p-carboxyphenyl) iminodiacetic acid, N- (carbamoylmethyl) iminodiacetic acid, cyanomethyliminodiacetic acid, aminoethyliminodiacetic acid, 2-ethoxycarbonylaminoethyliminodiacetic acid, phosphonomethyl Iminodi vinegar Phosphonoethyliminodiacetic acid, sulfoethyliminodiacetic acid, o-sulfophenyliminodiacetic acid, m-sulfophenyliminodiacetic acid, nitrilotriacetic acid, carboxyethyliminodiacetic acid, carboxymethyliminodipropionic acid, nitrilotripropionic acid, N, N′-ethylenediamine, ethylenediamine-N, N′-dipropionic acid, N, N′-di (hydroxyethyl) ethylenediaminediacetic acid, Nn-butylethylenediaminetriacetic acid, N-cyclohexylethylenediaminetriacetic acid, N ′ -Hydroxyethyl-N, N, N'-triacetic acid, benzylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid-zinc, ethylenediaminetetraacetic acid-2sodium, ethylenediaminetetraacetic acid-calci Ethylenediaminetetraacetic acid-magnesium, ethylenediaminetetraacetic acid-2 potassium, ethylenediamine-N, N'-diacetic acid N, N'-dipropionic acid, ethylenediamine-N, N'-di (2-propionic acid), ethylenediamine- N, N′-disuccinic acid, ethylenediamine-N, N′-diglutaric acid, ethylenediaminetetrapropionic acid, 1,2-propylenediaminetetraacetic acid, trimethylenediaminetetraacetic acid, tetramethylenediaminetetraacetic acid, pentamethylenediaminetetraacetic acid, Hexamethylenediaminetetraacetic acid, octamethylenediaminetetraacetic acid, 1,2-cyclopentanediaminetetraacetic acid, trans-cyclohexane-1,2-diaminetetraacetic acid, cyclohexane-1,4-diaminetetraacetic acid, 1 , 3,5-triaminocyclohexaacetic acid, o-phenylenediaminetetraacetic acid, 2-hydroxytrimethylenediaminetetraacetic acid, ethyl ether diaminetetraacetic acid, hydantoic acid, (S, S) -ethylenediamine disuccinic acid, (S, S) -ethylenediamine diglutaric acid, (S) -aspartic acid-N, N-diacetic acid, (S, S) -iminodisuccinic acid, (S) -glutamic acid-N, N-diacetic acid, (S) -α- Alanine-N, N-diacetic acid, taurine-N, N-diacetic acid, and salts thereof.

  Examples of amino acids are glycine, sarcoxin, glycine methyl ester, valine, alanine, β-alanine, norleucine, leucine, isoleucine, phenylalanine, tyrosine, cysteine, methionine, serine, threonine, asparagine, glutamine, lysine, ε-polylysine, histidine Arginine, glutamic acid, polyglutamic acid, aspartic acid, 1,2-diaminopropionic acid, proline, tryptophan and N-ethylglycine.

  Examples of phosphoric acids are hexametaphosphoric acid, tetrametaphosphoric acid and condensed phosphoric acid. Examples of phosphonic acids are ethylidene diphosphonic acid, diethylenetriaminepenta (methylenephosphonic acid), methyldiphosphonic acid, nitrilotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1,2-propylenediaminetetra (methylenephosphonic). Acid).

Examples of inorganic sulfur compounds, thiosulfates (e.g. sodium thiosulfate), polythionates _{(eg: SO 3 - (S) n} -SO 3 (n = 1~4)), dithionite (eg : Sodium dithionate), sulfites (eg sodium sulfite) and dithionates (eg sodium dithionate).

  Preferred examples of the complexing agent when the complexing agent is used as an aqueous solution include alkali metal salts of aliphatic carboxylic acids, fatty acid salts of amines, alkali metal salts of aminocarboxylic acids, inorganic cyanides, thiosulfates and phosphoric acids. Alkali metal salt. A more preferable example of the complexing agent is an alkali metal salt of aminocarboxylic acid, and disodium ethylenediaminetetraacetate is particularly preferable.

  Preferred examples of the complexing agent when the complexing agent is used as a precipitant solution include aliphatic carboxylic acids, aromatic carboxylic acids, amines and fatty acid salts thereof, aminocarboxylic acids, and amino acids. Of these, aminocarboxylic acids are more preferred, and ethylenediaminetetraacetic acid is particularly preferred.

  There is no selection condition for water to be used other than considering prevention of contamination of the polymer. Water through a filter of 50 μm or less is preferable, and pure water treated with an ion exchange resin is more preferable.

  Examples of electrolyte components are sodium chloride, ammonium chloride, ammonium phosphate, ammonium sulfate, ammonium acetate, sodium acetate, sodium phosphate, sodium citrate, sodium tartrate, sodium benzoate, sodium sorbate, sodium phthalate and Sodium bisulfite. These sodium salts may be potassium salts. Among the compounds used in the above complexing agent aqueous solution, those that can be used as electrolyte components are included. Preferred examples of the electrolyte component are inorganic halides and ammonium salts among these compounds, and sodium chloride, potassium chloride and ammonium chloride are more preferred.

  In the following description, a solution obtained by dissolving the polymer (1) with a water-insoluble solvent, a polymerization reaction solution or a solution obtained by diluting the polymerization reaction solution with a water-insoluble solvent may be referred to as a polymer (1) solution. The mixing and contacting of the polymer (1) solution with the complexing agent aqueous solution or the complexing agent aqueous solution further containing an electrolyte component is preferably stirred in a batch-type tank-type treatment tank equipped with a stirrer. A shaking tank type treatment tank may be used. The polymer concentration in the polymer (1) solution is a uniform solution and is a viscosity that allows stirring and mixing with the complexing agent aqueous solution, but it is preferably 40% by weight or less. When the polymer concentration in the polymer (1) solution is increased, precipitation and thickening of the polymer may be a problem. In this case, the steam coil can be heated to about 70 to 100 ° C. Or what is necessary is just to process under a heating using the processing tank provided with heating apparatuses, such as a steam jacket. If the polymer concentration in the polymer (1) solution is low and the solution is homogeneous at room temperature, stirring and contact can be performed at room temperature.

  For oil-water separation of the polymer (1) solution and the complexing agent aqueous solution or further the complexing agent aqueous solution containing the electrolyte component, centrifugal separation or static separation utilizing the difference in specific gravity, or static utilizing the difference in electrical properties. Electric oil can be used. In the present invention, since two-phase oil-water separation is required, the use of a two-phase separation type decanter is most suitable, but it is naturally possible to use other centrifuges. When an inorganic adsorbent is used in combination, solid content such as sludge is included, so a three-phase separation type decanter will be used. In this case, the use of other centrifuges is also natural. Is possible. And the polymer processed by the said process can be isolated by making it precipitate in a poor solvent, or distilling off volatile components, such as a solvent, under reduced pressure.

  The mixing / contacting of the polymer (1) solution with the complexing agent aqueous solution or the complexing agent aqueous solution further containing the electrolyte component and the number of oil-water separation steps significantly reduce the concentration of the catalyst component remaining in the polymer (1). If possible, there is no particular limitation. That is, when the mixing / contacting and oil / water separation step is one step, the transition metal component in the polymer (1) is analyzed for each step to reduce the content to the target level. It may be the number of times.

  About the addition ratio of the complexing agent with respect to the transition metal component contained in the polymer (1), it is generally preferable that the molar ratio of the complexing agent to the transition metal component is 1-1000 equivalents. Since the transition metal content in the polymer (1) can be predicted in advance at the time of charging the polymerization reaction solution, the complexing agent described above depends on the transition metal content contained in the polymer (1) to be treated. The amount can be determined. The concentration of the complexing agent in the complexing agent aqueous solution is preferably in the range of 0.001 to 20% by weight.

  Furthermore, in the complexing agent aqueous solution containing the electrolyte component, the main purpose is to improve the oil-water separation efficiency by increasing the specific gravity of the aqueous solution. It is not limited. In general, it can be used after being saturated or half saturated.

  Such a step may be performed on the polymer (1) which is the final product, but may be performed on an intermediate product for producing the polymer. For example, in each polymerization stage of the block copolymer obtained by atom transfer radical polymerization, the polymer can be isolated and subjected to such treatment.

  By the above purification treatment, the content of the transition metal component in the polymer of the present invention can be made 10 ppm or less with respect to the total amount of the polymer. And it is also possible to make this content into 5 ppm or less, and also 1 ppm or less.

  In order to remove the residual catalyst, an adsorption treatment using activated carbon or the like may be used in combination with the above method. Examples of adsorbents other than activated carbon are ion exchange resins (acidic, basic or chelate type), and inorganic adsorbents. Examples of the inorganic adsorbent include silica, magnesium oxide, activated alumina, acidic clay, activated clay, zeolite, kaolin, bentonite, diatomaceous earth and the like. When the solid-liquid contact between the ion exchange resin or inorganic adsorbent and the polymer solution is used in combination, a batch method in which stirring and mixing and solid-liquid separation are performed by a batch operation can be used. In addition to this, a fixed bed system in which a container is filled with an adsorbent and the polymer solution is passed, a moving bed system in which the liquid is passed through the moving bed of the adsorbent, a fluidized bed system in which the adsorbent is fluidized with liquid and adsorbed, etc. The continuous method can also be used. Furthermore, if necessary, operations for improving dispersion efficiency, such as shaking of a container or use of ultrasonic waves, can be combined with the mixing and dispersing operation by stirring. After the polymer solution is brought into contact with the adsorbent, the adsorbent is removed by a method such as filtration, centrifugation, sedimentation separation, etc., and a washing treatment is performed as necessary to further increase the degree of purification.

  When an atom transfer radical polymerization initiator that is a silsesquioxane derivative is used, since the terminal portion of the polymer (1) has a silsesquioxane structure, it is easily decomposed under acidic conditions or basic conditions. be able to. That is, by separating the addition polymer from the silsesquioxane structure portion and then measuring the molecular weight, the accuracy of the molecular weight analysis of the polymer portion can be further improved. When decomposing the polymer (1) under acidic conditions, it is preferable to use hydrofluoric acid. When decomposing the polymer (1) under basic conditions, potassium hydroxide is preferably used. The polymer (1) can be decomposed in either a homogeneous system or a heterogeneous system. For example, the silsesquioxane portion of the polymer (1) can be separated by a homogeneous mixed system of an organic solvent (tetrahydrofuran, acetonitrile, etc.) that can dissolve the polymer (1) and hydrofluoric acid. Even in a heterogeneous mixed system of toluene and hydrofluoric acid, the silsesquioxane moiety can be decomposed. In this case, a phase transfer catalyst is preferably used in combination. Examples of phase transfer catalysts are benzyltrimethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium bromide, trioctylammonium chloride, dioctylmethylammonium chloride, triethylamine, dimethylaniline and the like. When potassium hydroxide is used, it can be decomposed in a mixed solvent of tetrahydrofuran, ethanol and water. “Silsesquioxane” is a class name indicating a compound in which each silicon atom is bonded to three oxygen atoms, and each oxygen atom is bonded to two silicon atoms. Sesquioxane has a general meaning of a silsesquioxane structure and a silsesquioxane-like structure in which a part thereof is deformed.

  A method for analyzing the molecular weight and molecular weight distribution of the obtained polymer will be described. Usually, the molecular weight of an addition polymer can be measured by gel permeation chromatography (GPC) using a calibration curve using a linear polymer such as polystyrene or poly (methyl methacrylate) as a standard sample. . The molecular weight and molecular weight distribution of the polymer (1) can also be analyzed by GPC. It is also possible to determine the molecular weight of the polymer (1) by using a universal calibration curve obtained from the viscosity and GPC data. The absolute molecular weight of the polymer (1) can also be determined by a terminal group determination method, a membrane osmotic pressure method, an ultracentrifugation method, a light scattering method, or the like.

  The preferred molecular weight of the polymer (1) is in the range of 500 to 1,000,000 in terms of number average molecular weight in terms of polystyrene. A more preferable range is 1000 to 100,000. However, the upper limit and the lower limit of this range do not have any special meaning. The molecular weight distribution is preferably in the range of 1.01 to 2.0 in terms of dispersity (Mw / Mn).

The molecular weight of the polymer (1) can be adjusted by the ratio of the addition polymerizable monomer and the initiator. That is, the theoretical molecular weight of the polymer (1) can be predicted from the addition polymerizable monomer / initiator molar ratio and the monomer consumption rate using the following calculation formula.
Mn _T = (Consumption rate of monomer (mol%) / 100) × MW _M × molar ratio + MW _I
In this calculation formula, Mn _T is the theoretical number average molecular weight, MW _M is the molecular weight of the addition polymerizable monomer, MW _I is the molecular weight of the initiator, and the molar ratio is the molar ratio of the addition polymerizable monomer to the initiator. .

In order to obtain a polymer having the above number average molecular weight range, the molar ratio of the addition polymerizable monomer to the initiator is set to about 2 to about 40,000. A preferred range for this molar ratio is from about 10 to about 5,000. The number average molecular weight can also be adjusted by changing the polymerization time. Consumption of the monomer (hereinafter sometimes referred to as "conversion".) To determine the can GPC, 1 ^H-NMR, any method of gas chromatography employing.

The present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.
The meanings of symbols used in the examples are as follows.
Mn: number-average molecular weight Mw: weight average molecular weight Mw / Mn: molecular weight distribution ^Cu I Br: cuprous bromide MMA: Methyl methacrylate PMMA: Poly (methyl methacrylate)
St: Styrene PSt: Polystyrene EDTA · 2Na: Disodium ethylenediaminetetraacetate dihydrate

そして、実施例中のＰＳｔおよびＰＭＭＡの分子量データは、すべてゲルパ−ミエーションクロマトグラフィー（ＧＰＣ）によって求めた値である。

The molecular weight data of PSt and PMMA in the examples are all values obtained by gel permeation chromatography (GPC).

Next, analysis conditions in the examples are shown.
<GPC>
Device: 8020 Series, manufactured by Tosoh Corporation (detector: differential refractometer)
Solvent: Tetrahydrofuran Flow rate: 0.8 ml / min
Column temperature: 40 ° C
Column used: Showa Denko KK, Shodex KF-LG (GUARDCOLUMN) + Shodex KF-804L (exclusion limit molecular weight (PSt) = 400,000) x 2 standard samples for calibration curve: Polymer Standards (PL), Poly, manufactured by Polymer Laboratories (methylmethacrylate), Polymer Standards (PL), Polystyrene, manufactured by Polymer Laboratories

<High-frequency inductively coupled plasma emission analysis>
The amount of copper remaining in the polymer was determined by adding ultrapure nitric acid to the obtained polymer and subjecting it to thermal decomposition, followed by thermal decomposition by adding ultrapure perchlorine to obtain high purity hydrochloric acid and ultrapure. Water was added and dissolved by heating using a high frequency inductively coupled plasma emission spectrometer (ICP-AES, Kyoto Koken UOP-1 MARKII, measurement wavelength: 324.754 nm).

<Preparation of MMA polymerization solution>
Within draft ultraviolet is cut, introducing ^Cu I Br (36mg) in heat-resistant glass ampoule, further added MMA (5g) / EBIB (49mg ) / Sp (117mg) / anisole (4.8 g) solution, Cooled quickly using liquid nitrogen. Thereafter, freeze vacuum deaeration (pressure: 1.0 Pa) was performed three times in a vacuum apparatus equipped with an oil rotary pump, and the ampule was quickly sealed using a hand burner while maintaining the vacuum state. At this time, the ratio of MMA, EBIB, Cu ¹ Br and Sp in this polymerization solution is 199: 1: 1: 2 in this order, and the concentration of MMA is 50.0% by weight.

<MMA polymerization>
The sealed heat-resistant glass ampoule was set in a constant temperature shaking bath and polymerized to obtain a brown and viscous solution of the polymer (1a). At this time, the polymerization temperature was 80 ° C., and the polymerization time was 3.0 hours. Thereafter, the polymer (1a) solution was sampled and diluted with tetrahydrofuran, and then GPC measurement was performed. In addition, the monomer conversion rate in this polymerization reaction system was analyzed on the basis of the peak area obtained from the GPC measurement value of the PMMA solution having a known concentration. Table 1 shows the analysis results of the monomer conversion rate, the theoretical number average molecular weight, the number average molecular weight (PMMA conversion value) measured by GPC measurement, and the molecular weight distribution in this polymerization reaction system.

<Preparation of MMA polymerization solution>
In a draft cut with ultraviolet rays, Cu ^I Br (36 mg) was introduced into a heat-resistant glass ampoule, and a MMA (5 g) / EBIB (49 mg) / PrPI (74 mg) / toluene (4.8 g) solution was added. Cooled quickly using liquid nitrogen. Thereafter, freeze vacuum deaeration (pressure: 1.0 Pa) was performed three times in a vacuum apparatus equipped with an oil rotary pump, and the ampule was quickly sealed using a hand burner while maintaining the vacuum state. At this time, the ratio of MMA, EBIB, Cu ¹ Br and PrPI in this polymerization solution is 199: 1: 1: 2 in this order, and the concentration of MMA is 50.2% by weight.

<MMA polymerization>
The sealed heat-resistant glass ampoule was set in a constant temperature shaking bath and polymerized to obtain a brown and viscous solution of the polymer (2a). At this time, the polymerization temperature was 90 ° C., and the polymerization time was 5.0 hours. Thereafter, the solution of the polymer (2a) was sampled and diluted with tetrahydrofuran, and then GPC measurement was performed. In addition, the monomer conversion rate in this polymerization reaction system was analyzed on the basis of the peak area obtained from the GPC measurement value of the PMMA solution having a known concentration. Table 1 shows the analysis results of the monomer conversion rate, the theoretical number average molecular weight, the number average molecular weight (PMMA conversion value) measured by GPC measurement, and the molecular weight distribution in this polymerization reaction system.

<Preparation of MMA polymerization solution>
Within draft ultraviolet is cut, introducing ^Cu I Br (36mg) in heat-resistant glass ampoule, further added MMA (5g) / EBIB (49mg ) / dHbpy (176mg) / diphenyl ether (4.7 g) solution, Cooled quickly using liquid nitrogen. Thereafter, freeze vacuum deaeration (pressure: 1.0 Pa) was performed three times in a vacuum apparatus equipped with an oil rotary pump, and the ampule was quickly sealed using a hand burner while maintaining the vacuum state. At this time, the ratio of MMA, EBIB, Cu ¹ Br and dHbpy in this polymerization solution is 199: 1: 1: 2 in this order, and the concentration of MMA is 50.2% by weight.

<MMA polymerization>
The sealed heat-resistant glass ampoule was set in a constant temperature shaking bath and polymerized to obtain a brown and viscous solution of the polymer (3a). At this time, the polymerization temperature was 90 ° C., and the polymerization time was 2.0 hours. Thereafter, the solution of the polymer (3a) was sampled and diluted with tetrahydrofuran, and then GPC measurement was performed. In addition, the monomer conversion rate in this polymerization reaction system was analyzed on the basis of the peak area obtained from the GPC measurement value of the PMMA solution having a known concentration. Table 1 shows the analysis results of the monomer conversion rate, the theoretical number average molecular weight, the number average molecular weight (PMMA conversion value) measured by GPC measurement, and the molecular weight distribution in this polymerization reaction system.

<Preparation of MMA polymerization solution>
In a draft cut with ultraviolet rays, Cu ^I Br (36 mg) was introduced into a heat-resistant glass ampoule, and a MMA (5 g) / EBIB (49 mg) / bpy (78 mg) / diphenyl ether (4.8 g) solution was added, Cooled quickly using liquid nitrogen. Thereafter, freeze vacuum deaeration (pressure: 1.0 Pa) was performed three times in a vacuum apparatus equipped with an oil rotary pump, and the ampule was quickly sealed using a hand burner while maintaining the vacuum state. At this time, the ratio of MMA, EBIB, Cu ^I Br and bpy in this polymerization solution is 199: 1: 1: 2 in this order, and the concentration of MMA is 50.2% by weight.

<MMA polymerization>
The sealed heat-resistant glass ampoule was set in a constant temperature shaking bath and polymerized to obtain a brown and viscous solution of the polymer (4a). At this time, the polymerization temperature was 90 ° C., and the polymerization time was 2.0 hours. Thereafter, the polymer (4a) solution was sampled and diluted with tetrahydrofuran, and then GPC measurement was performed. In addition, the monomer conversion rate in this polymerization reaction system was analyzed on the basis of the peak area obtained from the GPC measurement value of the PMMA solution having a known concentration. Table 1 shows the analysis results of the monomer conversion rate, the theoretical number average molecular weight, the number average molecular weight (PMMA conversion value) measured by GPC measurement, and the molecular weight distribution in this polymerization reaction system.

<Table 1>

  The brown and viscous liquid (2 g) of the polymer (1a) obtained in Example 1 was dissolved in toluene (100 ml) and added to a 300 ml-separation funnel together with an EDTA · 2Na aqueous solution (concentration 2 wt%, 100 ml). Flushing was performed. The light yellow organic layer quickly turned transparent and the aqueous layer turned light blue. Further, the organic layer was recovered, concentrated under reduced pressure using a rotary evaporator, and then purified by reprecipitation with hexane to recover a white polymer (1a-1). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 2.

  A white polymer (1a-2) was recovered in the same manner as in Example 5 except that toluene (100 ml) was replaced with ethyl acetate (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 2.

  A white polymer (1a-3) was recovered in the same manner as in Example 5 except that toluene (100 ml) was replaced with chloroform (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 2.

  The brown and viscous liquid (2 g) of the polymer (2a) obtained in Example 2 was dissolved in toluene (100 ml) and added to a 300 ml-separation funnel together with an EDTA · 2Na aqueous solution (concentration 2 wt%, 100 ml). Flushing was performed. The light yellow organic layer quickly turned transparent and the aqueous layer turned light blue. Further, the organic layer was recovered, concentrated under reduced pressure using a rotary evaporator, and then purified by reprecipitation with hexane to recover the white polymer (2a-1). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 2.

  A white polymer (2a-2) was recovered in the same manner as in Example 8, except that toluene (100 ml) was replaced with ethyl acetate (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 2.

  A white polymer (2a-3) was recovered in the same manner as in Example 8 except that toluene (100 ml) was replaced with chloroform (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 2.

  The brown and viscous liquid (2 g) of the polymer (3a) obtained in Example 3 was dissolved in toluene (100 ml) and added to a 300 ml-separation funnel together with an EDTA · 2Na aqueous solution (concentration 2 wt%, 100 ml). Flushing was performed. The light yellow organic layer quickly turned transparent and the aqueous layer turned light blue. Further, the organic layer was recovered, concentrated under reduced pressure using a rotary evaporator, and then purified by reprecipitation with hexane to recover a white polymer (3a-1). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 2.

  A white polymer (3a-2) was recovered in the same manner as in Example 11 except that toluene (100 ml) was replaced with ethyl acetate (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 2.

  A white polymer (3a-3) was recovered in the same manner as in Example 11 except that the toluene (100 ml) was changed to chloroform (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 2.

  The brown and viscous liquid (2 g) of the polymer (4a) obtained in Example 4 was dissolved in toluene (100 ml) and added to a 300 ml-separation funnel together with an EDTA · 2Na aqueous solution (concentration 2 wt%, 100 ml). Flushing was performed. The light yellow organic layer quickly turned transparent and the aqueous layer turned light blue. Further, the organic layer was recovered, concentrated under reduced pressure using a rotary evaporator, and then purified by reprecipitation with hexane to recover a white polymer (4a-1). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 2.

  A white polymer (4a-2) was recovered in the same manner as in Example 14 except that toluene (100 ml) was replaced with ethyl acetate (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 2.

  A white polymer (4a-3) was recovered in the same manner as in Example 14 except that toluene (100 ml) was replaced with chloroform (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 2.

<Table 2>

<Comparative Example 1>
The brown and viscous liquid of the polymer (1a) obtained in Example 1 was reprecipitated using hexane, and a pale yellow polymer (1a) was recovered. The analysis result of the copper content in the polymer using ICP-AES is as shown in Table 2, which clearly showed a high copper content as compared with the EDTA · 2Na aqueous solution treated.

<Comparative example 2>
The brown and viscous liquid of the polymer (2a) obtained in Example 2 was reprecipitated using hexane, and a pale yellow polymer (2a) was recovered. The analysis result of the copper content in the polymer using ICP-AES is as shown in Table 2, which clearly showed a high copper content as compared with the EDTA · 2Na aqueous solution treated.

<Comparative Example 3>
The brown and viscous liquid of the polymer (3a) obtained in Example 3 was reprecipitated using hexane, and a pale yellow polymer (3a) was recovered. The analysis result of the copper content in the polymer using ICP-AES is as shown in Table 2, which clearly showed a high copper content as compared with the EDTA · 2Na aqueous solution treated.

<Comparative example 4>
The brown and viscous liquid of the polymer (4a) obtained in Example 4 was reprecipitated using hexane, and a pale yellow polymer (4a) was recovered. The analysis result of the copper content in the polymer using ICP-AES is as shown in Table 2, which clearly showed a high copper content as compared with the EDTA · 2Na aqueous solution treated.

<Preparation of St polymerization solution>
In a draft cut with ultraviolet rays, Cu ^I Br (34 mg) was introduced into a heat-resistant glass ampoule, a St (5 g) / BEB (44 mg) / Sp (113 mg) solution was added, and liquid nitrogen was used promptly. Cooled down. Thereafter, freeze vacuum deaeration (pressure: 1.0 Pa) was performed three times in a vacuum apparatus equipped with an oil rotary pump, and the ampule was quickly sealed using a hand burner while maintaining the vacuum state. At this time, the ratio of St, BEB, Cu ^I Br and Sp in this polymerization solution is 202: 1: 1: 2 in this order.

<St polymerization>
The sealed heat-resistant glass ampoule was set in a constant temperature shaking bath and polymerized to obtain a brown and viscous solution of the polymer (1b). At this time, the polymerization temperature was 120 ° C., and the polymerization time was 3.0 hours. Thereafter, the solution of the polymer (1b) was sampled and diluted with tetrahydrofuran, and then GPC measurement was performed. The monomer conversion rate in this polymerization reaction system was analyzed on the basis of the peak area obtained from the GPC measurement value of a PSt solution having a known concentration. Table 3 shows the analysis results of the monomer conversion rate, the theoretical number average molecular weight, the number average molecular weight (PSt conversion value) measured by GPC measurement, and the molecular weight distribution in this polymerization reaction system.

<Preparation of St polymerization solution>
In a draft cut with ultraviolet rays, Cu ^I Br (34 mg) was introduced into a heat-resistant glass ampoule, a St (5 g) / BEB (44 mg) / PrPI (71 mg) solution was added, and liquid nitrogen was used promptly. Cooled down. Thereafter, freeze vacuum deaeration (pressure: 1.0 Pa) was performed three times in a vacuum apparatus equipped with an oil rotary pump, and the ampule was quickly sealed using a hand burner while maintaining the vacuum state. At this time, the ratio of St, BEB, Cu ^I Br and PrPI in this polymerization solution is 202: 1: 1: 2 in this order.

<St polymerization>
The sealed heat-resistant glass ampoule was set in a constant temperature shaking bath and polymerized to obtain a brown and viscous solution of the polymer (2b). At this time, the polymerization temperature was 120 ° C., and the polymerization time was 4.0 hours. Thereafter, the solution of the polymer (2b) was sampled and diluted with tetrahydrofuran, and then GPC measurement was performed. The monomer conversion rate in this polymerization reaction system was analyzed on the basis of the peak area obtained from the GPC measurement value of a PSt solution having a known concentration. Table 3 shows the analysis results of the monomer conversion rate, the theoretical number average molecular weight, the number average molecular weight (PSt conversion value) measured by GPC measurement, and the molecular weight distribution in this polymerization reaction system.

<Preparation of St polymerization solution>
In a draft cut with ultraviolet rays, Cu ^I Br (34 mg) was introduced into a heat-resistant glass ampoule, a St (5 g) / BEB (44 mg) / dHbpy (169 mg) solution was added, and liquid nitrogen was used promptly. Cooled down. Thereafter, freeze vacuum deaeration (pressure: 1.0 Pa) was performed three times in a vacuum apparatus equipped with an oil rotary pump, and the ampule was quickly sealed using a hand burner while maintaining the vacuum state. At this time, St in the polymerization solution, BEB, ^Cu I Br and proportions of dHbpy in molar ratio of the order 202: 1: 1: 2.

<St polymerization>
The sealed heat-resistant glass ampoule was set in a constant temperature shaking bath and polymerized to obtain a brown and viscous solution of the polymer (3b). At this time, the polymerization temperature was 120 ° C., and the polymerization time was 4.0 hours. Thereafter, the solution of the polymer (3b) was sampled and diluted with tetrahydrofuran, and then GPC measurement was performed. The monomer conversion rate in this polymerization reaction system was analyzed on the basis of the peak area obtained from the GPC measurement value of a PSt solution having a known concentration. Table 3 shows the analysis results of the monomer conversion rate, the theoretical number average molecular weight, the number average molecular weight (PSt conversion value) measured by GPC measurement, and the molecular weight distribution in this polymerization reaction system.

<Preparation of St polymerization solution>
In a draft cut with ultraviolet rays, Cu ^I Br (34 mg) was introduced into a heat-resistant glass ampoule, a St (5 g) / BEB (44 mg) / bpy (75 mg) solution was added, and liquid nitrogen was used promptly. Cooled down. Thereafter, freeze vacuum deaeration (pressure: 1.0 Pa) was performed three times in a vacuum apparatus equipped with an oil rotary pump, and the ampule was quickly sealed using a hand burner while maintaining the vacuum state. At this time, the ratio of St, BEB, Cu ^I Br and bpy in this polymerization solution is 202: 1: 1: 2 in this order.

<St polymerization>
The sealed heat-resistant glass ampoule was set in a constant temperature shaking bath and polymerized to obtain a brown and viscous solution of the polymer (4b). At this time, the polymerization temperature was 120 ° C., and the polymerization time was 5.0 hours. Thereafter, the polymer (4b) solution was sampled and diluted with tetrahydrofuran, and then GPC measurement was performed. The monomer conversion rate in this polymerization reaction system was analyzed on the basis of the peak area obtained from the GPC measurement value of a PSt solution having a known concentration. Table 3 shows the analysis results of the monomer conversion rate, the theoretical number average molecular weight, the number average molecular weight (PSt conversion value) measured by GPC measurement, and the molecular weight distribution in this polymerization reaction system.

<Table 3>

  The brown and viscous liquid (2 g) of the polymer (1b) obtained in Example 17 was dissolved in toluene (100 ml) and added to a 300 ml-separation funnel together with an EDTA · 2Na aqueous solution (concentration 2 wt%, 100 ml). Flushing was performed. The light yellow organic layer quickly turned transparent and the aqueous layer turned light blue. Further, the organic layer was recovered, concentrated under reduced pressure using a rotary evaporator, and then purified by reprecipitation with methanol to recover a white polymer (1b-1). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 4.

  A white polymer (1b-2) was recovered in the same manner as in Example 21, except that toluene (100 ml) was replaced with ethyl acetate (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 4.

  A white polymer (1b-3) was recovered in the same manner as in Example 21 except that toluene (100 ml) was replaced with chloroform (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 4.

  The brown and viscous liquid (2 g) of the polymer (2b) obtained in Example 18 was dissolved in toluene (100 ml) and placed in a 300 ml-separation funnel together with an EDTA · 2Na aqueous solution (concentration 2 wt%, 100 ml). Flushing was performed. The light yellow organic layer quickly turned transparent and the aqueous layer turned light blue. Further, the organic layer was recovered, concentrated under reduced pressure using a rotary evaporator, and then purified by reprecipitation with methanol to recover a white polymer (2b-1). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 4.

  A white polymer (2b-2) was recovered in the same manner as in Example 24, except that toluene (100 ml) was replaced with ethyl acetate (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 4.

  A white polymer (2b-3) was recovered in the same manner as in Example 24, except that toluene (100 ml) was replaced with chloroform (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 4.

  The brown and viscous liquid (2 g) of the polymer (3b) obtained in Example 19 was dissolved in toluene (100 ml) and placed in a 300 ml-separating funnel together with an EDTA · 2Na aqueous solution (concentration 2 wt%, 100 ml). Flushing was performed. The light yellow organic layer quickly turned transparent and the aqueous layer turned light blue. Further, the organic layer was recovered, concentrated under reduced pressure using a rotary evaporator, and then purified by reprecipitation with methanol to recover a white polymer (3b-1). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 4.

  A white polymer (3b-2) was recovered in the same manner as in Example 27 except that toluene (100 ml) was replaced with ethyl acetate (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 4.

  A white polymer (3b-3) was recovered in the same manner as in Example 27, except that toluene (100 ml) was replaced with chloroform (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 4.

  The brown and viscous liquid (2 g) of the polymer (4b) obtained in Example 20 was dissolved in toluene (100 ml) and placed in a 300 ml-separation funnel together with an EDTA · 2Na aqueous solution (concentration 2 wt%, 100 ml). Flushing was performed. The light yellow organic layer quickly turned transparent and the aqueous layer turned light blue. Further, the organic layer was recovered, concentrated under reduced pressure using a rotary evaporator, and then purified by reprecipitation with methanol to recover a white polymer (4b-1). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 4.

  A white polymer (4b-2) was recovered in the same manner as in Example 30 except that toluene (100 ml) was replaced with ethyl acetate (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 4.

  A white polymer (4b-3) was recovered in the same manner as in Example 30 except that toluene (100 ml) was replaced with chloroform (100 ml). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 4.

<Table 4>

<Comparative Example 5>
The brown and viscous liquid of the polymer (1b) obtained in Example 17 was reprecipitated using methanol, and the pale yellow polymer (1b) was recovered. The analysis result of the copper content in the polymer using ICP-AES is as shown in Table 4, which clearly showed a high copper content as compared with the EDTA · 2Na aqueous solution treatment.

<Comparative Example 6>
The brown and viscous liquid of the polymer (2b) obtained in Example 18 was reprecipitated using hexane, and a pale yellow polymer (2b) was recovered. The analysis result of the copper content in the polymer using ICP-AES is as shown in Table 4, which clearly showed a high copper content as compared with the EDTA · 2Na aqueous solution treatment.

<Comparative Example 7>
The brown and viscous liquid of the polymer (3b) obtained in Example 19 was reprecipitated using hexane, and a pale yellow polymer (3b) was recovered. The analysis result of the copper content in the polymer using ICP-AES is as shown in Table 4, which clearly showed a high copper content as compared with the EDTA · 2Na aqueous solution treatment.

<Comparative Example 8>
The brown and viscous liquid of the polymer (4b) obtained in Example 20 was reprecipitated using hexane, and a pale yellow polymer (4b) was recovered. The analysis result of the copper content in the polymer using ICP-AES is as shown in Table 4, which clearly showed a high copper content as compared with the EDTA · 2Na aqueous solution treatment.

The white polymer (1a-2) obtained in Example 6 was dissolved in propylene glycol monomethyl ether acetate and applied onto a glass substrate using a YBA-1 type baker applicator (manufactured by Yoshimitsu Seiki Co., Ltd.). Then, after drying at 90 ° C. for 10 minutes, the polymer (1a-2) film was obtained by further heating at 180 ° C. for 30 minutes. As shown in FIG. 1A, the polymer (1a-2) film was a transparent film in which no coloration was observed, and the result of the total light transmittance was as shown in FIG. The conditions for measuring the total light transmittance are as shown below.
<Measurement conditions>
Equipment: Micro Color Analyzer (TC-1800M) manufactured by Tokyo Denshoku Technology Center
Light source: 3-wavelength daylight white,
Irradiation window measurement diameter: 500μm

As a result of measuring the thermal decomposition temperature of the white polymer (1a-2) obtained in Example 6 using a thermogravimetric apparatus, it is as shown in FIG. The value was higher than. The thermogravimetric conditions are as shown below.
<Measurement conditions>
Device: Thermogravimetric measuring device TGA7 manufactured by PerkinElmer
Temperature increase rate: 20 ° C / min
Measurement temperature range: 50 ~
Measurement atmosphere: He

<Comparative Example 9>
The pale yellow polymer (1a) obtained in Comparative Example 1 was dissolved in propylene glycol monomethyl ether acetate and applied onto a glass substrate using a YBA-1 type baker applicator (manufactured by Yoshimitsu Seiki Co., Ltd.). Then, after drying at 90 ° C. for 10 minutes, the polymer (1a) film was obtained by further heating at 180 ° C. for 30 minutes. The film of the polymer (1a) was a markedly colored film as shown in FIG. 1 (b), and the result of the total light transmittance was as shown in FIG.

<Comparative Example 10>
As a result of measuring the pyrolysis temperature of the pale yellow polymer (1a) obtained in Comparative Example 1 using a thermogravimetric apparatus, it is as shown in FIG. Compared to the lower value.

<Preparation of MMA polymerization solution>
In a draft cut with ultraviolet rays, a MMA (20 g) / EBIB (195 mg) / Sp (470 mg) / anisole (19.2 g) solution was placed in a 100 ml three-necked flask equipped with a reflux condenser, a thermometer and a stirrer. In addition, argon bubbling was performed for 5 minutes at room temperature. Thereafter, Cu ¹ Br (143 mg) was introduced into the three-necked flask, and argon bubbling was continued for 10 minutes. At this time, the ratios of MMA, EBIB, Cu ^I Br and Sp in this polymerization solution are 200: 1: 1: 2 in this order, and the concentration of MMA is 50% by weight.

<MMA polymerization>
A three-necked flask sealed with argon was set in an oil bath and polymerized to obtain a brown and viscous solution of the polymer (5a). At this time, the polymerization temperature was 80 ° C., and the polymerization time was 5 hours. Thereafter, the solution of the polymer (5a) was sampled and diluted with tetrahydrofuran, and then GPC measurement was performed. In addition, the monomer conversion rate in this polymerization reaction system was analyzed on the basis of the peak area obtained from the GPC measurement value of the PMMA solution having a known concentration. Analysis results of the monomer conversion rate, the theoretical number average molecular weight, the number average molecular weight (PMMA conversion value) measured by GPC measurement, and the molecular weight distribution in this polymerization reaction system are as shown below.
Monomer conversion = 80.3%, theoretical number average molecular weight = 16,200, number average molecular weight (PMMA conversion value) = 17,300, molecular weight distribution = 1.33

  The brown and viscous solution (40 g) of the polymer (5a) obtained in Example 35 was diluted with ethyl acetate (360 g) to adjust the viscosity, and the resulting solution (40 g) was added to an EDTA · 2Na aqueous solution ( Flushing was performed with a 100 ml separatory funnel (concentration of 0.19 wt%, 40 ml) (Cu / EDTA molar ratio = 1/2). The light yellow organic layer quickly turned transparent and the aqueous layer turned light blue. Further, the organic layer was recovered, concentrated under reduced pressure using a rotary evaporator, and then purified by reprecipitation with hexane to recover a white polymer (5a-1). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 5.

  The brown and viscous solution (40 g) of the polymer (5a) obtained in Example 35 was diluted with ethyl acetate (360 g) to adjust the viscosity, and the resulting solution (40 g) was added to an EDTA · 2Na aqueous solution ( Flushing was performed in a 100 ml-separation funnel with a concentration of 0.09 wt% (40 ml) (Cu / EDTA molar ratio = 1/1). The light yellow organic layer quickly turned transparent and the aqueous layer turned light blue. Further, the organic layer was recovered, concentrated under reduced pressure using a rotary evaporator, and then purified by reprecipitation with hexane to recover a white polymer (5a-2). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 5.

  The brown and viscous solution (40 g) of the polymer (5a) obtained in Example 35 was diluted with ethyl acetate (360 g) to adjust the viscosity, and the resulting solution (40 g) was added to an EDTA · 2Na aqueous solution ( Flushing was performed with a 100 ml separatory funnel together with a concentration of 0.05% by weight (40 ml) (Cu / EDTA molar ratio = 1 / 0.5). The light yellow organic layer quickly turned transparent and the aqueous layer turned light blue. Further, the organic layer was recovered, concentrated under reduced pressure using a rotary evaporator, and then purified by reprecipitation with hexane to recover a white polymer (5a-3). The analysis result of the copper content in the polymer using ICP-AES was as shown in Table 5.

  The brown and viscous solution (40 g) of the polymer (5a) obtained in Example 35 was diluted with ethyl acetate (360 g) to adjust the viscosity, and the resulting solution (40 g) was added to an EDTA · 2Na aqueous solution ( Flushing was performed in a 100 ml-separation funnel together with a concentration of 0.01% by weight (40 ml) (Cu / EDTA molar ratio = 1 / 0.1). The light yellow organic layer quickly turned transparent and the aqueous layer turned light blue. Further, the organic layer was recovered, concentrated under reduced pressure using a rotary evaporator, and then purified by reprecipitation with hexane to recover a white polymer (5a-4). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 5.

<Comparative Example 11>
The brown and viscous solution (40 g) of the polymer (5a) obtained in Example 35 was diluted with ethyl acetate (360 g) to adjust the viscosity, and the resulting solution (40 g) was added with hexane (800 ml). And reprecipitation to recover a pale yellow polymer (5a). The analysis result of the copper content in the polymer using ICP-AES is as shown in Table 5, which clearly showed a high copper content as compared with the EDTA · 2Na aqueous solution treated. As in Example 34, the obtained pale yellow polymer (5a) was measured for the thermal decomposition temperature using a thermogravimetric apparatus, and as shown in Table 6, it was clearly shown in Examples 36 to The value was lower than the thermal decomposition temperature of 39.

The brown and viscous solution (40 g) of the polymer (5a) obtained in Example 35 was diluted with ethyl acetate (360 g) to adjust the viscosity, and the resulting solution (40 g) was added with a precipitant (ethylenediamine / The solution was poured into a methanol solution (ethylenediamine concentration: 5% by weight, 800 ml). The precipitate layer quickly changed to light blue, and a white solid component was deposited. This solid component was subjected to solid-liquid separation by suction filtration to recover a white polymer (6a-1). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 6.
The obtained white polymer (6a-1) was measured for the thermal decomposition temperature using a thermogravimetric measurement apparatus in the same manner as in Example 34, and the result was as shown in Table 6.

A solution obtained by diluting the polymer (6a-1) (0.5 g) obtained in Example 40 with ethyl acetate (9.5 g) was added to a precipitant (ethylenediamine / methanol solution (ethylenediamine concentration 5 wt%, 200 ml)). The white solid component was deposited. This solid component was subjected to solid-liquid separation by suction filtration to recover a white polymer (6a-2). The analysis results of the copper content in the polymer using ICP-AES are as shown in Table 6.
The obtained white polymer (6a-2) was measured for the thermal decomposition temperature using a thermogravimetric measurement apparatus in the same manner as in Example 34, and the result was as shown in Table 6.

<Comparative Example 12>
The brown and viscous solution (40 g) of the polymer (5a) obtained in Example 35 was diluted with ethyl acetate (360 g) to adjust the viscosity, and the resulting solution (40 g) was diluted with methanol (800 ml). And reprecipitation to recover a pale yellow polymer (6a). The analysis result of the copper content in the polymer using ICP-AES is as shown in Table 6, which clearly showed a high copper content as compared with the one treated with ethylenediamine / methanol.
In the same manner as in Example 34, the obtained white polymer (6a) was measured for the thermal decomposition temperature using a thermogravimetric apparatus, and as shown in Table 6, it was clearly shown in Examples 40 and 41. The value was lower than the thermal decomposition temperature.

<Table 5>

<Table 6>

Photographs of coating films obtained in Example 33 and Comparative Example 9 Total light transmittance of the coatings obtained in Example 33 and Comparative Example 9 Thermal decomposition temperature measurement results in Example 34 and Comparative Example 10

Claims (14)

  A polymerization reaction solution obtained by applying an atom transfer radical polymerization method using a transition metal complex as a catalyst to an addition polymerizable monomer, or a polymer obtained from this polymerization reaction solution, and a water-insoluble solvent as an optional component are essential. A polymer obtained by purification using a complexing agent solution as a component; the complexing agent solution is a complexing agent aqueous solution, a complexing agent aqueous solution containing an electrolyte component, or a precipitating agent with a complexing agent A polymer which is a dissolved solution and has a transition metal component concentration of 10 ppm or less based on the total amount of the polymer.   An atom transfer radical polymerization method using a transition metal complex as a catalyst is applied to an addition polymerizable monomer to obtain a polymerization reaction solution, and a polymer obtained from the polymerization reaction solution is mixed with a water-insoluble solvent and an aqueous complexing agent solution. The polymer according to claim 1, which is obtained by purification using the polymer.   An atom transfer radical polymerization method using a transition metal complex as a catalyst is applied to an addition polymerizable monomer to obtain a polymerization reaction solution, and a polymer obtained from the polymerization reaction solution is complexed with a water-insoluble solvent and an electrolyte component. The polymer according to claim 1, which is obtained by purification using an aqueous agent solution.   A polymerization reaction solution obtained by applying an atom transfer radical polymerization method using a transition metal complex as a catalyst to an addition polymerizable monomer, a solution in which a complexing agent is dissolved in a precipitant, and a water-insoluble solvent as an optional component The polymer according to claim 1, obtained by purification using   Complexing agent is carboxylic acid and its salt, amine and its salt, aminocarboxylic acid and its salt, amino acid and its salt, phosphoric acid and its salt, phosphonic acid and its salt, inorganic halide, inorganic cyanide, ammonium salt, The compound according to any one of claims 1 to 4, which is at least one compound selected from the group consisting of sulfite, thiocyanate, thiosulfate, polythionate, dithionite and dithionate. The polymer described.   The complexing agent is at least one compound selected from the group consisting of carboxylic acids and salts thereof, amines and salts thereof, aminocarboxylic acids and salts thereof, amino acids and salts thereof, phosphoric acid and salts thereof, and inorganic cyanides, The polymer of any one of Claims 1-4.   The complexing agent is carboxylic acid and its salt, amine and its salt, aminocarboxylic acid and its salt, amino acid and its salt, phosphoric acid and its salt, phosphonic acid and its salt, inorganic cyanide, sulfite, thiocyanate, The at least one compound selected from the group consisting of thiosulfate, polythionate, dithionite and dithionate, and the electrolyte component is an inorganic halide or ammonium salt. Polymer.   The complexing agent is at least one compound selected from the group consisting of carboxylic acids and salts thereof, amines and salts thereof, aminocarboxylic acids and salts thereof, amino acids and salts thereof, phosphoric acid and salts thereof, and inorganic cyanides, The polymer according to claim 3, wherein the electrolyte component is an inorganic halide or an ammonium salt.   The polymer according to any one of claims 1 to 8, wherein the central metal of the transition metal complex is an element of Group 8, Group 9, Group 10 or Group 11 of the Periodic Table.   The polymer according to claim 9, wherein the central metal of the transition metal complex is iron, nickel, ruthenium or copper.   The polymer according to claim 9, wherein the central metal of the transition metal complex is copper.   The polymer according to any one of claims 1 to 11, wherein the addition polymerizable monomer is at least one selected from the group consisting of a (meth) acrylic acid derivative and a styrene derivative.   An atom transfer radical polymerization method using a transition metal complex as a catalyst is applied to an addition polymerizable monomer to obtain a polymerization reaction solution, and a polymer solution obtained by dissolving the polymer obtained from this polymerization reaction solution in a water-insoluble solvent is used. The transition metal component is extracted from the solution by adding a complexing agent aqueous solution or a complexing agent aqueous solution further containing an electrolyte component to the polymer solution and stirring the polymer solution. A method for producing the polymer described in 1. An atom transfer radical polymerization method using a transition metal complex as a catalyst is applied to an addition polymerizable monomer to obtain a polymerization reaction solution, and a solution obtained by dissolving a complexing agent in a precipitant is added to the polymerization reaction solution and stirred. The method for producing a polymer according to claim 1, wherein the transition metal component is extracted into the complexing agent solution simultaneously with the precipitation of the polymer.

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