JP2007211048A - Method for manufacturing vinyl polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method which prevents an acid from mixing into a vinyl polymer produced by atom transfer radical polymerization and efficiently removes transition metal. <P>SOLUTION: The method for manufacturing a vinyl polymer comprises a step of bringing a vinyl polymer polymerized by the atom transfer radical polymerization of a vinyl monomer with the use of a transition metal complex as a polymerization catalyst into contact with a cation-exchange resin and a solid acid absorber to purify the polymer. The method for manufacturing a vinyl polymer comprises using a sulfonic acid type cation-exchange resin as the cation-exchange resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a vinyl polymer, and more particularly to a method for producing a vinyl polymer that can efficiently remove a transition metal used for polymerization.

  It has been reported that an atom transfer radical polymerization method in which an organic halide or a sulfonyl halide compound is used as an initiator and a metal complex having a transition metal as a central metal is used as a catalyst is a living polymerization (for example, non-patent literature) 1-4, and Patent Documents 3 to 5), by utilizing this polymerization method, not only the control of the molecular weight and molecular weight distribution of the polymer, but also the precision of the polymer structure such as block copolymer and star polymer, etc. Control became possible.

  However, since a transition metal complex as a polymerization catalyst remains in a vinyl polymer produced by atom transfer radical polymerization, when the vinyl polymer obtained by the above polymerization is used as a coloring material such as a dispersion resin, When it is applied to a display material, it causes a problem that a trace amount of metal ions causes a display defect.

  So far, for example, a method using an inorganic adsorbent such as activated carbon or hydrotalcites has been proposed as a method for purifying a vinyl polymer used in this atom transfer radical polymerization (Patent Document 1 or 2). However, in this method, not only the removal efficiency of the transition metal from the polymer solution is bad, but also a large amount of inorganic powder and activated carbon are used, so special filtration equipment is required for removing the powder from the polymer solution. there were.

  Further, a method of removing a metal in a polymer solution by bringing a vinyl polymer obtained by atom transfer radical polymerization into contact with an ion exchange resin is exemplified (see Patent Document 3). This method can remove the transition metal in a short time, and the ion exchange resin is an industrially useful purification method because it can be easily separated from the polymer solution.

However, in this method, for example, when a cation exchange resin is used as the ion exchange resin, an acid is generated in the system by ion exchange between the cation exchange resin and the transition metal. This generated acid not only causes corrosion of the polymerization equipment, but also (1) causes degradation of the resin itself (2) reduces the exchange capacity of the cation exchange resin itself (3) inhibits the reaction when the resin is subsequently modified. Caused problems. Furthermore, when only the cation exchange resin was used alone, the transition metal removal efficiency was not sufficient.
Fukuda et al., Prog. Polym. Sci. 2004, 29, 329. Matyjaszewski et al., Chem. R ev. 2001, 101, 2921. Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614. Macromolecules 1995, 28, 7901, Science 1996, 272, 866. JP 2001-323016 A JP 2001-323012 A International Publication No. 96/30421 Pamphlet International Publication No. 97/18247 Pamphlet Special Table 2002-540234

  An object of this invention is to provide the manufacturing method which prevents mixing of the acid in the polymer solution of the vinyl-type polymer manufactured by atom transfer radical polymerization, and removes a transition metal efficiently.

The present invention is a method for producing a vinyl polymer polymerized by atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst,
The present invention relates to a method for producing a vinyl polymer, which includes a step of bringing a cation exchange resin and a solid acid adsorbent into contact with a system containing the vinyl polymer for purification.

  Furthermore, the present invention relates to a method for producing a vinyl polymer, wherein the cation exchange resin is a sulfonic acid type cation exchange resin.

  Furthermore, the present invention relates to a method for producing a vinyl polymer, wherein the solid acid adsorbent is an anion exchange resin.

  Furthermore, the present invention relates to a method for producing a vinyl polymer, wherein the solid acid adsorbent is an inorganic powder.

  Furthermore, the present invention relates to a method for producing a vinyl polymer, wherein the inorganic powder is selected from the group consisting of zeolite adsorbents, hydrotalcites, and alkaline earth metal salts.

  The present invention further relates to a method for producing a vinyl polymer, wherein the polymer after purification has a pH of 5 or more.

  Furthermore, the present invention relates to a method for producing a vinyl polymer, wherein the concentration of transition metal ions remaining in the polymer after purification is 100 ppm or less.

  Furthermore, the present invention relates to a vinyl polymer purified by the production method described above.

  According to the present invention, it was possible to provide a production method for efficiently removing a transition metal without mixing an acid into a vinyl polymer produced by atom transfer radical polymerization.

  The present invention relates to a method for producing a vinyl polymer that is polymerized by atom transfer radical polymerization of a vinyl monomer using a transition metal complex as a polymerization catalyst, the system comprising the vinyl polymer comprising a cation exchange resin and It is a manufacturing method of a vinyl polymer including the process of making a solid acid adsorbent contact and refine | purify.

  First, a method for synthesizing a vinyl polymer by atom transfer radical polymerization will be described.

  In atom transfer radical polymerization, in order to suppress side reactions that occur during general radical polymerization, the molecular weight of the polymer and the monomer to be block copolymerized depend on the charge ratio between the polymerization initiator added during polymerization and the vinyl monomer. Can be freely controlled, and can be used for the production of block polymers, gradient polymers, star polymers, comb polymers, and terminal functional polymers.

As the vinyl monomer capable of atom transfer radical polymerization, any monomer that does not cause deactivation of the polymerization catalyst may be used.
Dienes such as ethylene, buta-1,3-diene, 2-methylbuta-1,3-diene, 2-chlorobuta-1,3-diene;
Styrenes such as styrene and α-methylstyrene;
Methyl acrylate, normal butyl acrylate, tertiary butyl acrylate, benzyl acrylate, ethyl hexyl acrylate, paracumylphenol EO modified acrylate, nonylphenol EO modified acrylate, 2-vinyloxyethyl acrylate, 2- (2'-vinyl) Roxyethoxy) ethyl, acrylic acid esters such as lauryl acrylate, glyceryl acrylate, methoxypolyethylene glycol acrylate, phenoxypolyethylene glycol acrylate;
Methyl methacrylate, ethyl methacrylate, normal butyl methacrylate, tertiary butyl methacrylate, stearyl methacrylate, ethyl hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, lauryl methacrylate, glyceryl methacrylate, methoxypolyethylene glycol methacrylate, methacrylic acid Methacrylic acid esters such as acid phenoxypolyethylene glycol, glycidyl methacrylate, dimethylaminoethyl methacrylate, 2-vinyloxyethyl methacrylate, 2- (2′-vinyloxyethoxy) ethyl methacrylate, cyclopentadienyl methacrylate;
(Meth) acrylic acid derivatives such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate;
Vinyl ethers such as vinyl methyl ether and vinyl ethyl ether;
N-vinyl compounds such as vinyl methyl ketone, vinyl hexyl ketone, vinyl ketones, N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone;
Allyl compounds such as allyl alcohol, allyl chloride, allyl acetate, vinyl chloride, vinylidene chloride;
(Meth) acrylic acid esters having a fluorine alkyl group such as vinyl fluoride and vinylidene fluoride;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate,
Glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-vinyl-1-cyclohexene 1,2 epoxide, glycidyl cinnamate, 1,3-butadiene monoepoxide, Celoxide 2000 (manufactured by Daicel Chemical Industries, Ltd.),
Methacryloyloxyethyl isocyanate (MOI), acryloyloxyethyl isocyanate (AOI), methacryloyloxyethyl isothiocyanate, acryloyloxyethyl isothiocyanate, methacryloyl isothiocyanate, acryloyl isothiocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate (MAI) And isopropenyl-α, α-dimethylbenzyl isocyanate (TMI).

  Two or more types of the above-mentioned vinyl monomers may be used and random copolymerization or block copolymerization may be performed, and gradient polymerization may be performed by gradually adding another type of vinyl monomer during the polymerization.

  In addition, after polymerizing a vinyl monomer having a reactive functional group among the vinyl monomers exemplified above, the polymer can be modified using a functional group remaining in the polymer. For example, after atom transfer radical polymerization of a monomer having a hydroxyl group, a hydroxyl group in the polymer and an acid anhydride are reacted in the presence of a basic catalyst to obtain a polymer having an acid group.

  Since the polymer in the present invention is produced by a living polymerization method, its molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is usually 2.0 or less, preferably 1.5 or less. Is 1.3 or less.

  In the atom transfer radical polymerization method, a transition metal complex such as copper, ruthenium, iron or nickel is used as a redox polymerization catalyst. Specific examples of the transition metal complex include low-valent halogenated transition metals such as copper (I) chloride and copper (I) bromide. In order to control the polymerization rate, a well-known method is used. High valent transition metals such as copper (II) chloride and copper (II) bromide may be added to the polymerization system.

  An organic ligand is used for the transition metal complex. Organic ligands are used to allow for reversibility of the solubility in the polymerization solvent and the redox polymerization catalyst. Examples of the coordination atom of the transition metal include a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom, and a nitrogen atom or a phosphorus atom is preferable. Specific examples of organic ligands include sparteine, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, tris (dimethylaminoethyl) amine, triphenyl Examples include phosphine and tributylphosphine.

  The transition metal and the organic ligand may be added separately to form a metal complex in the polymer, or the metal complex may be synthesized in advance and added to the polymerization system. In particular, when the transition metal is copper, the former method is preferable, and for the ruthenium, iron, and nickel, the latter method is preferable.

Specific examples of ruthenium, iron and nickel complexes synthesized in advance include tristriphenylphosphinoniruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ), bistrisphenylphosphinoniiron chloride (FeCl ₂ (PPh ₃ ) ₂ ), Nickel bistrisphenylphosphinonichloride (NiCl ₂ (PPh ₃ ) ₂ ), nickel bistributylphosphinonibromide (NiBr ₂ (PBu ₃ ) ₂ ), and the like.

  Moreover, the amount of the transition metal to be used can be reduced by combining these transition metal catalysts and reducing agents by a known method.

As the initiator used in the atom transfer radical polymerization method, known initiators can be used, and organic halides and sulfonyl halide compounds having a highly reactive carbon halogen bond are mainly used. Specific examples include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, paratoluenesulfonic acid chloride, 1-bromoethylbenzene, chloroethylbenzene, and the like. These are used alone or in combination.

In the atom transfer radical polymerization, the atom transfer radical polymerization initiator is used in a proportion of 0.01 to 10 mol%, preferably 0.1 to 2 mol%, based on the total amount of the vinyl monomer.
Moreover, the usage-amount of a transition metal is 0.03-3 mol with respect to 1 mol of initiators as forms, such as a halide, Preferably it is used in the ratio of 0.1-2 mol. Further, the organic ligand is usually used in a ratio of 1 to 5 mol, preferably 2 to 3 mol, per 1 mol of the above transition metal (form of halide or the like). When the initiator for the atom transfer radical polymerization, the transition metal, and the organic ligand are used in such ratios, it is preferable in terms of the reactivity of the living radical polymerization, the molecular weight of the produced polymer, and the like.

  In addition, due to the characteristics of atom transfer radical polymerization, the resulting polymer has an active carbon-halogen bond at the terminal end, which can be modified by a known method to introduce a functional group.

  Atom transfer radical polymerization can be carried out without solvent, but hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole, and dimethoxybenzene, methylene chloride, chloroform, chloro Halogenated hydrocarbon solvents such as benzene, ketone solvents such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone, alcohol solvents such as methanol, ethanol, and propanol, and nitrile systems such as acetonitrile, propionitrile, and benzonitrile Solvents, ester solvents such as ethyl acetate and butyl acetate, carbonate solvents such as ethylene carbonate and propylene carbonate, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide alone or It may be used in combination. In the case of using a solvent, in order to prevent a decrease in polymerization rate, the amount of the solvent used after the polymerization is preferably 50% by weight or less. Even if there is no solvent or a small amount of solvent, there is no particular safety problem with respect to the control of the heat of polymerization. Rather, the solvent reduction is preferable in terms of economic efficiency and environmental measures.

  As polymerization conditions, from the point of polymerization rate and catalyst deactivation, a polymerization temperature of 60 to 130 ° C. depends on the final molecular weight and polymerization temperature, but a polymerization time of about 1 to 100 hours may be used. . The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon in order to prevent the polymerization catalyst from being deactivated by oxygen.

  Next, the purification process in the production method of the present invention will be described. The purification step of the present invention is a step of purifying a vinyl polymer produced by atom transfer radical polymerization using a transition metal complex as a polymerization catalyst by contacting with a cation exchange resin and a solid acid adsorbent. In the case of the present invention, the vinyl polymer to be purified is synthesized using atom transfer radical polymerization. However, the purification method of the present invention is not limited to the polymerization method of the present invention, and other syntheses. It can also be used for vinyl polymers obtained by the method.

  The present invention is a method for producing a vinyl polymer comprising a step of efficiently removing a transition metal used in the synthesis of a vinyl polymer and simultaneously removing an acid generated in the system. In this step, the transition metal is adsorbed on the cation exchange resin, but an acid is generated from the cation exchange resin instead. The generated acid is further adsorbed on the solid acid adsorbent, whereby a vinyl polymer containing almost no transition metal or acid can be obtained.

  The cation exchange resin used in the present invention is not particularly limited as long as it is a cation exchange resin capable of adsorbing transition metals, and includes sulfonic acid type, carboxylic acid type, sulfonate type, carboxylate type, etc. Sulphonic acid type ion exchange resins that generally exhibit excellent adsorption rates are preferred. In the present invention, since a solvent is used as necessary, an ion exchange resin excellent in solvent resistance and heat resistance is preferable, and it is desirable to select a porous or high porous ion exchange resin. Specifically, commercially available products include “Diaion PK228LH”, “Diaion PK220LH”, “Diaion PK216LH” manufactured by Mitsubishi Chemical, “Amberlist 15” manufactured by Rohm and Haas, and “Dautex” manufactured by Dow Chemical. Marathon MSC "can be used, but it is not limited to this.

  The amount of the cation exchange resin used must be appropriately selected according to the amount of the transition metal used in the atom transfer radical polymerization and the cation exchange capacity of the cation exchange resin, but is 1000 to 20000 per 100 parts by weight of the transition metal used. It is desirable to use parts by weight. If the amount is less than 1000 parts by weight with respect to the transition metal, a sufficient metal removal effect may not be obtained, and if it is used in excess of 20000 parts by weight, it will not affect the removal of the metal, but will later be separated from the polymer. Can be difficult.

  The solid acid adsorbent of the present invention is not particularly limited as long as it is insoluble in the polymer solution and adsorbs the acid in the solution. Among them, anion exchange resins and inorganic powders are preferably used, and in the subsequent steps. It is desirable that the particle size and shape be easily solid-liquid separated from the polymerization solution by filtration or the like.

  As the anion exchange resin used in the present invention, an ion exchange resin excellent in solvent resistance and heat resistance is preferable. Among them, a regenerated form (OH form) of a styrenic strong base anion exchange resin having a quaternary ammonium base as an exchange group is preferably used. Specifically, commercially available products include “Diaion SANUP”, “Diaion SA10A”, “Diaion SA11A” manufactured by Mitsubishi Chemical, “Amberlite MB-1” manufactured by Rohm and Haas, and Dow Chemical Examples include “Dawex Marathon MSA”, but are not limited thereto.

  The amount of the anion exchange resin used depends on the anion exchange capacity of the anion exchange resin, but is preferably 10 to 400 parts by weight with respect to the cation exchange resin used. If the amount is less than 10 parts by weight, the acid produced by the exchange reaction between the cation exchange resin and the transition metal may not be sufficiently adsorbed, and even if added in an amount of more than 400 parts by weight, the acid adsorption is not affected. Separation from the polymer may be difficult.

  As the inorganic powder used in the present invention, those having a large adsorptive capacity for acidic compounds are preferable, and zeolite-based adsorbents and hydrotalcites generally named in hydrous aluminosilicate mineral groups such as activated alumina and sodium aluminum silicate. And alkaline earth metal salts.

  The amount of the inorganic powder to be used needs to be appropriately selected depending on the acid adsorption capacity of the inorganic powder to be used, but is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the cation exchange resin to be used.

  As hydrotalcites, “Kyoward 300”, “Kyoward 500”, “Kyoward 1000”, and “Kyoward 2000”, which are solid bases made of aluminum, magnesium hydroxide and carbonate, are preferably used. It is not limited to this.

  Known alkaline earth metal salts can be used, but magnesium oxide, calcium carbonate, calcium hydroxide, and calcium oxide are preferred.

  In the purification step of the present invention, the contact of the polymer with the cation exchange resin and the solid acid adsorbent is as follows: (2) A moving bed system in which a liquid is passed through a moving bed of a cation exchange resin and a solid acid adsorbent, (3) a fluidized bed type in which adsorption is performed by fluidizing a cation exchange resin and a solid acid adsorbent with a liquid, (4 ) A known method such as a batch method in which a polymer or polymer solution, a cation exchange resin and a solid acid adsorbent are mixed with stirring and then solid-liquid separation is performed can be used. In particular, when considering large-scale industrial production, it is preferable to use the batch system of (4) because it is efficient in the process.

  Further, at that time, a method of simultaneously adding a cation exchange resin and a solid acid adsorbent to the polymer and stirring and mixing may be used, or after adding a cation exchange resin and stirring and mixing for a certain time, the solid acid adsorbent is added. In addition, a method of stirring and mixing may be used.

  The contact between the polymer, the cation exchange resin and the solid acid adsorbent may be carried out in the absence of a solvent or in a state diluted with a solvent. In the separation step, it is preferably carried out in a state diluted with a solvent, and in particular, the solid content of the polymer solution during purification is preferably 10 to 40% by weight. Although it does not specifically limit as a kind of solvent, Adsorption efficiency of a transition metal can be raised by using a highly hydrophilic thing. In addition, when the atom transfer radical polymerization is performed in the presence of a solvent, it is preferable to add the cation exchange resin and the solid acid adsorbent directly to the polymer solution after polymerization. At this time, the removal efficiency of the transition metal can be increased by adding a hydrophilic solvent according to a known method.

  The contact temperature between the polymer, the cation exchange resin and the solid acid adsorbent is not particularly limited, but is generally 0 to 100 ° C., preferably room temperature to 60 ° C.

Separation of the cation exchange resin and the solid acid adsorbent from the polymer can be carried out by a known solid-liquid separation method such as filtration, decantation, and centrifugation alone or in combination.
In particular, after the purification treatment, simple filtration with decantation or filter cloth is performed to remove the cation exchange resin, and then the solid acid adsorbent is removed by a known method such as a single plate pressure filtration device, a cartridge filter, or centrifugation. The desired clear polymer can be obtained by diluting and washing with water as necessary.

  Furthermore, it is preferable to use a filter aid such as diatomaceous earth for filtration of the solid acid adsorbent based on a known method. As a filter aid, diatomaceous earth, perlite, etc. are used suitably. From the viewpoint of achieving both particle capturing properties and filtration speed, the filter aid is preferably one having an average particle size of 10 to 100 μm, more preferably 20 to 50 μm. If the average particle size is less than 10 μm, the filtration rate may decrease due to the large resistance of the filter cake. If the average particle size exceeds 100 μm, the solid content having a small particle size in the gap between the filter aids generates a cake layer with high resistance. In some cases, the effect of improving filterability cannot be obtained.

  As a method of filtration, generally known methods such as a filter press as a batch method, a pressure Nutsche, a pressure leaf filter, and a drum filter as a continuous method are used.

  In many cases, the cation exchange resin or anion exchange resin used in the present invention is in a water-containing state, and when there is a concern about water mixing in the polymer or polymer solution, a desiccant is added to the polymer solution after purification. Water in the resin solution can be removed by a known method such as stirring. Further, the cation exchange resin itself has a property of absorbing moisture, and it can adsorb moisture in the polymer or the polymer solution by using it after air drying.

  In the production method of the present invention, the transition metal removal step may be repeated a plurality of times as necessary. Furthermore, a known transition metal removal method may be used in combination.

  The amount of transition metal contained in the polymer can be quantified by ICP mass spectrometry, and the concentration of transition metal contained in the vinyl polymer produced by the production method of the present invention is 100 ppm or less, preferably 50 ppm or less. be able to.

  In addition, since the acid generated by ion exchange between the transition metal and the cation exchange resin is adsorbed by the solid acid adsorbent, the pH of the polymer solution is affected by acidic groups and basic groups contained in the polymer itself. Although there is a thing, it becomes about 5 or more preferably, preferably pH = 5-9.

  The use of the polymer obtained in the present invention is not limited, but the removal of the transition metal catalyst improves the coloration of the polymer or polymer solution, so it is suitable for use as a coloring material such as a pigment dispersant. Application to flat color material is expected.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example shows a weight part and% shows weight%.

(Synthesis example)
A four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas inlet tube is charged with 200 parts of methyl ethyl ketone, 200 parts of normal butyl methacrylate, 2.8 parts of ethyl bromoisobutyrate, and 3.7 parts of tetramethylethylenediamine. The temperature was raised to 40 ° C. and nitrogen was introduced for 30 minutes. 1.0 part of cuprous chloride was added and the temperature was raised to 70 ° C. under a nitrogen stream to initiate polymerization. After polymerization for 7 hours, the polymerization yield was confirmed to be 98% or more from the solid content of the polymerization solution obtained by sampling the polymerization solution, and the polymerization was stopped by cooling to 0 ° C. As a result of GPC measurement, the polymer Mn was 15600, and Mw / Mn = 1.3. The non-volatile content of the solution after polymerization was 49.4%.

Example 1
409 parts of the polymer solution obtained in the synthesis example was diluted with 267 parts of methyl ethyl ketone, and 100 parts of styrene sulfonic acid type strongly acidic cation exchange resin “Diaion PK228LH (manufactured by Mitsubishi Chemical Corporation)” as a cation exchange resin, 200 parts of “Diaion SANUP (Mitsubishi Chemical Corporation)” was added as an anion exchange resin and stirred at room temperature for 2 hours.

(Example 2)
409 parts of the polymer solution obtained in the synthesis example was diluted with 267 parts of methyl ethyl ketone, 100 parts of Diaion PK228LH and 10 parts of Kyoward 500SN as an inorganic adsorbent were added and stirred at room temperature for 2 hours.

(Comparative Example 1)
409 parts of the polymer solution obtained in the synthesis example was diluted with 267 parts of methyl ethyl ketone, 100 parts of Diaion PK228LH was added, and the mixture was stirred at room temperature for 2 hours.

(Comparative Example 2)
409 parts of the polymer solution obtained in the synthesis example was diluted with 267 parts of methyl ethyl ketone, 200 parts of Diaion SANUP was added, and the mixture was stirred at room temperature for 2 hours.

(Comparative Example 3)
409 parts of the polymer solution obtained in the synthesis example was diluted with 267 parts of methyl ethyl ketone, 10 parts of Kyoward 500SN was added, and the mixture was stirred at room temperature for 2 hours.

(Comparative Example 4)
409 parts of the polymer solution obtained in the synthesis example was diluted with 267 parts of toluene, 10 parts of Kyoward 500SN was added, and the mixture was stirred at 100 ° C. for 2 hours.

(Comparative Example 5)
409 parts of the polymer solution obtained in the synthesis example was diluted with 267 parts of methyl ethyl ketone.

  The ion exchange resin and the solid acid adsorbent were filtered off from the polymer solutions of Examples 1-2 and Comparative Examples 1-4, respectively. All filtrates were uniform.

  The hue and pH of the purified polymer solutions of Examples 1-2 and Comparative Examples 1-5 are shown in the table.

  Ultrahigh-purity nitric acid is mixed with the treated polymers of Examples 1 and 2 and Comparative Examples 1 to 5 and subjected to microwave decomposition, and then decomposed using an ICP mass spectrometer (SPS4000 manufactured by Seiko Instruments Inc.). The amount of copper remaining therein was measured, and the amount of copper remaining in the polymer was quantified. The results are shown in Table 1.

From the above results, according to the production method of the present invention, the transition metal is efficiently removed from the polymerization solution, the coloration of the polymer is improved, and no acid is mixed into the polymer solution. On the other hand, in the production method of the comparative example, the removal of the transition metal from the polymer solution is insufficient, the coloration of the polymer solution is not sufficiently improved, or the polymer solution is mixed with an acid.

  According to the production method described above, the metal catalyst used in the atom transfer radical polymerization method has been improved so that it can be efficiently and simply removed. In particular, the polymer produced by atom transfer radical polymerization can be easily colored. Since this is improved, the application of the polymer to a coloring material is expected, and the industrial value of the invention is great.

Claims (8)

A method for producing a vinyl polymer polymerized by atom transfer radical polymerization of a vinyl monomer, using a transition metal complex as a polymerization catalyst,
A method for producing a vinyl polymer comprising a step of bringing a cation exchange resin and a solid acid adsorbent into contact with a system containing the vinyl polymer for purification.   The method for producing a vinyl polymer according to claim 1, wherein the cation exchange resin is a sulfonic acid type cation exchange resin.   3. The method for producing a vinyl polymer according to claim 1, wherein the solid acid adsorbent is an anion exchange resin.   3. The method for producing a vinyl polymer according to claim 1, wherein the solid acid adsorbent is an inorganic powder.   The method for producing a vinyl polymer according to claim 4, wherein the inorganic powder is selected from the group consisting of zeolite adsorbents, hydrotalcites, and alkaline earth metal salts.   The method for producing a vinyl polymer according to any one of claims 1 to 5, wherein the pH of the polymer after purification is 5 or more.   The method for producing a vinyl polymer according to any one of claims 1 to 6, wherein the concentration of transition metal ions remaining in the polymer after purification is 100 ppm or less.   The vinyl polymer refine | purified by the manufacturing method in any one of Claims 1-7.