WO2021049627A1

WO2021049627A1 - Polymer production method and polymerization catalyst

Info

Publication number: WO2021049627A1
Application number: PCT/JP2020/034491
Authority: WO
Inventors: 洋新納; 俊介茶谷; 書堯許; 後藤　淳; ジュンジエチャン
Original assignee: 三菱ケミカル株式会社; ナンヤンテクノロジカルユニヴァーシティー
Priority date: 2019-09-13
Filing date: 2020-09-11
Publication date: 2021-03-18
Also published as: JPWO2021049627A1

Abstract

Provided are: a polymerization catalyst formed from a polymer having nitrogen-containing functional groups; and a polymer production method having a step for obtaining a polymer by polymerizing vinyl monomers in the presence of an organic iodine compound.

Description

Polymer production method and polymerization catalyst

The present invention relates to a method for producing a polymer and a polymerization catalyst.
The present application claims priority based on Japanese Patent Application No. 2019-16772 filed on September 13, 2019, and Japanese Patent Application No. 2019-167783 filed on September 13, 2019. The contents are used here.

Conventionally, a radical polymerization method is well known as a method for obtaining a polymer by polymerizing a vinyl monomer. In general, the radical polymerization method has a problem that it is difficult to control the molecular weight of the obtained polymer. Further, the polymer obtained by the radical polymerization method is a mixture of polymers having various molecular weights, and has a problem that it is difficult to form a polymer having a narrow molecular weight distribution.

The living radical polymerization method is known as a method for solving the above-mentioned problems. In recent years, a living radical polymerization method called reversible complex formation-mediated polymerization (RCMP) has been developed (see, for example, Patent Document 1). The RCMP method is an organic catalyst type living radical polymerization method in which an iodine atom is used as a protecting group for growth radicals in living radical polymerization and an amine is used as a polymerization catalyst.

In the RCMP method, a low molecular weight amine such as triethylamine (TEA) can be used as a polymerization catalyst. Therefore, as compared with other living radical polymerization methods using a transition metal complex as a polymerization catalyst, the polymerization catalyst has features such as low cost and high environmental safety. However, when a low molecular weight amine such as TEA is used in the RCMP method, a purification step for removing the catalyst from the polymer which is a reaction product is required. Therefore, the RCMP method using a low molecular weight amine has a problem that the operation becomes complicated industrially.

Further, in a polymerization system using a catalyst, a heterogeneous catalyst in which the catalyst is supported on a solid is generally used in order to easily remove the catalyst from the reaction product. As such a polymerization system, for example, an example of using a non-uniform copper catalyst in which a copper catalyst is supported on a polymer is known (Non-Patent Document 1). However, by supporting the catalyst on a polymer, the activity and selectivity of the catalyst that was expressed in the catalyst before the support is changed, so that it has sufficient performance in the living radical polymerization of vinyl monomers so far. No heterogeneous catalyst was found.

Further, in the RCMP method, a method of adding iodine _{to generate an amine-I 2} complex acting as an inactive agent is widely used. However, in this method, iodine remains in the reaction product and causes coloring. Therefore, when iodine is added in the RCMP method, a purification step for removing iodine from the polymer which is a reaction product is required, and there is a problem that the operation becomes complicated industrially.

International Publication No. 2011/016166

The present invention has been made in view of such circumstances, and provides a polymerization catalyst having high activity in living radical polymerization without using a transition metal-based catalyst and which can be removed by a simple method. The purpose is to do. Another object of the present invention is to provide a method for producing a polymer using the polymerization catalyst, in which the molecular weight and the molecular weight distribution can be sufficiently controlled, and the residual iodine amount and the catalyst amount can be reduced.

In order to solve the above problems, the present invention includes the following aspects.

[1] A method for producing a polymer, which comprises a step of polymerizing a vinyl monomer to obtain a polymer in the presence of a polymerization catalyst composed of a polymer having a nitrogen-containing functional group and an organic iodine compound.

[2] The method for producing a polymer according to [1], wherein the polymerization catalyst further contains iodine or an iodine atom-containing ion.
[3] The method for producing a polymer according to [1] or [2], wherein the polymer is a crosslinked polymer.
[4] The method for producing a polymer according to any one of [1] to [3], wherein the polymer is a polymer capable of adsorbing iodine.
[5] The method for producing a polymer according to any one of [1] to [4], wherein the polymer mainly has a repeating unit of a vinyl monomer.
[6] The method for producing a polymer according to [5], wherein the polymer has a polystyrene skeleton or a polyacrylamide skeleton.
[7] The weight according to any one of [1] to [6], wherein the nitrogen-containing functional group is at least one selected from the group consisting of a secondary amino group, a tertiary amino group and a quaternary ammonium group. Manufacturing method of coalescence.
[8] The method for producing a polymer according to [7], wherein the nitrogen-containing functional group is a quaternary ammonium group.
[9] The method for producing a polymer according to [7] or [8], wherein the counter ion of the quaternary ammonium group is a halogen ion.
[10] The method for producing a polymer according to [9], wherein the counter ion is an iodine ion.

[11] The method for producing a polymer according to any one of [1] to [10], wherein a radical polymerization initiator is further present in the reaction system in the step of obtaining the polymer.

[12] The method for producing a polymer according to [11], wherein iodine is further present in the reaction system in the step of obtaining the polymer.
[13] [11] or [12], the molar equivalent ratio of the nitrogen-containing functional group contained in the polymerization catalyst is 0.001 to 200 with respect to the total of the organic iodine compound and the radical polymerization initiator. The method for producing a polymer according to.

[14] The weight according to any one of [1] to [13], wherein the vinyl monomer is at least one selected from the group consisting of a styrene-based monomer and a (meth) acrylate-based monomer. Manufacturing method of coalescence.

[15] The method for producing a polymer according to any one of [1] to [14], wherein the polymerization temperature in the step of obtaining the polymer is 120 ° C. or lower.

[16] A polymerization catalyst composed of a polymer having a nitrogen-containing functional group, which is used in the method for producing a polymer according to any one of [1] to [15].

According to the present invention, it is possible to provide a polymerization catalyst that is highly environmentally safe and can be removed by a simple method. Further, in the method for producing a polymer using the polymerization catalyst, the molecular weight and the molecular weight distribution can be sufficiently controlled, and the residual iodine amount and the catalyst amount can be further reduced.

FIG. 1 is an XPS chart of the reaction product obtained in the production example of the example.

(Explanation of terms)
The following definitions of terms are adopted herein.
"Vinyl monomer" means a compound containing at least one vinyl group (carbon-carbon unsaturated double bond).
"(Meta) acrylate" means "acrylate" or "methacrylate".
The "organoiodine compound" means a compound having a carbon-iodine bond in one molecule.

[Method for producing polymer]
The method for producing a polymer of the present embodiment includes a step of polymerizing a vinyl monomer in the presence of a polymerization catalyst composed of a polymer having a nitrogen-containing functional group and an organic iodine compound to obtain a polymer. ..
Hereinafter, they will be described in order.

(Preparation of polymerizable composition)
In the step of obtaining a polymer, a polymerizable composition containing a polymerization catalyst composed of a polymer having a nitrogen-containing functional group and a vinyl monomer is prepared, and the polymer is polymerized by polymerizing the vinyl monomer. obtain.
Hereinafter, the components contained in the polymerizable composition will be described.

(Polymerization catalyst)
The polymerization catalyst contains a polymer having a nitrogen-containing functional group. By applying the polymerization catalyst to radical polymerization of a vinyl monomer in the presence of an organic iodine compound, the reaction progress of the radical polymerization can be promoted and the polymerization reaction can be controlled.

The polymerization catalyst preferably contains a polymer having a nitrogen-containing functional group as a main component. _{In addition to iodine (I 2} ) or iodine atom-containing ions, which will be described later, the polymerization catalyst may contain other components as long as the effects of the present invention are not significantly impaired.

The "main component" means that the ratio of the polymer to the entire polymerization catalyst exceeds 50% by mass. From the viewpoint of removing the polymerization catalyst from the reaction product, the polymer preferably contains 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more, based on the entire polymerization catalyst. ..

<Polymer>
The polymers constituting the polymerization catalyst are synthetic polymers such as polystyrene, polyacrylamide, poly (meth) acrylic acid, and poly (meth) acrylic acid ester in the molecular skeleton, and naturally produced polysaccharides such as cellulose. Has. The polymer is preferably a polymer having a repeating unit of a vinyl monomer, and more preferably a polymer having a polystyrene skeleton or a polyacrylamide skeleton.

As used herein, the term "polystyrene skeleton" means a molecular chain having a repeating unit derived from styrene or a repeating unit derived from a styrene derivative.
Further, as used herein, the term "polyacrylamide skeleton" means a molecular chain having a repeating unit derived from acrylamide or a repeating unit derived from an acrylamide derivative.

Note that "mainly" means that the ratio of the repeating unit derived from the vinyl monomer to all the repeating units of the polymer exceeds 50 mol%. The polymer constituting the polymerization catalyst preferably contains 80 mol% or more of vinyl monomer, more preferably 90 mol% or more, and further preferably 95 mol% or more, based on all the repeating units of the polymer. preferable.

The same can be considered when the polymer constituting the polymerization catalyst is a polymer having a polystyrene skeleton or a polyacrylamide skeleton. That is, "mainly" means that the ratio of the polystyrene skeleton or the polyacrylamide skeleton to all the repeating units of the polymer exceeds 50 mol%, preferably 80 mol% or more, and 90 mol% or more. Is more preferable, and 95 mol% or more is further preferable.

The polymer constituting the polymerization catalyst of the present embodiment may have a property of being difficult to dissolve in the solvent used in the radical polymerization, the dispersion medium, and the monomer used in the radical polymerization. As a result, the polymerization catalyst can be easily separated from the reaction solution after radical polymerization. “Difficult to dissolve” means that the solubility at 25 ° C. is 0 g / 100 mL to 0.3 g / 100 mL.

The upper limit of the solubility of the polymer constituting the polymerization catalyst in the solvent used for radical polymerization, the dispersion medium, and the monomer used for radical polymerization is preferably 0.2 g / 100 mL or less, and preferably 0.1 g / 100 mL or less. Is more preferable.
Specifically, when the polymer does not have a crosslinked body or a crosslinked structure, a number average molecular weight of 3000 or more is preferable because the polymer is difficult to dissolve in the reaction system of radical polymerization.

In addition, a polymer is a "crosslinked body", that is, a structure in which chemical bonds are formed between molecules of a chain polymer and are connected so as to bridge between the molecular chains of a chain polymer, that is, a crosslinked structure. It means that it is a polymer having.

It is more preferable that the number average molecular weight of the polymer is 10,000 or more. The upper limit of the number average molecular weight of the polymer is not particularly limited, but from a practical point of view, it is preferably 10,000,000 or less.

Further, the polymer constituting the polymerization catalyst is preferably a crosslinked product, more preferably a crosslinked product having a repeating unit of a vinyl monomer, and a crosslinked product of a polymer having a polystyrene skeleton or a crosslinked polymer having a polyacrylamide skeleton. The body is more preferred. In the following description, a crosslinked polymer may be referred to as a “crosslinked polymer”. In this sense, for example, a crosslinked polystyrene is sometimes referred to as “crosslinked polystyrene”.

The degree of cross-linking of the polymer is not particularly limited. Further, the molecular weight distribution of the polymer is not particularly limited.

The fact that the polymer is crosslinked can be confirmed by the fact that the sample remains undissolved when the sample of the polymer to be verified is immersed in a good solvent of the sample. At this time, it is preferable that the sample does not dissolve or only swells.
The "good solvent for the sample" can be selected by analyzing the sample by a commonly known method such as infrared spectroscopy or NMR, and inferring the molecular structure of the repeating unit of the sample from the obtained results.

The polymer according to this embodiment is not particularly limited in shape, form, size, etc., such as granular, fibrous, and film-like. The granular polymer can be obtained by appropriately cutting or pulverizing the massive polymer.

The polymer constituting the polymerization catalyst has at least one nitrogen-containing functional group. In the present invention, the nitrogen-containing functional group acts as a polymerization catalyst, and the nitrogen-containing functional group is covalently bonded to the polymer. The nitrogen-containing functional group of the polymer is not particularly limited. Further, the nitrogen-containing functional group contained in the polymer may be contained in either the main chain or the side chain of the polymer, or may be contained in both the main chain and the side chain.

Further, the polymerization catalyst may contain a low molecular weight compound having a nitrogen-containing functional group. A low molecular weight compound having a nitrogen-containing functional group also functions as a part of the polymerization catalyst, but purification for removing the low molecular weight compound from the polymer which is a reaction product is required. In order to facilitate catalyst removal, it is preferable that 99 mol% or more of the nitrogen-containing functional groups contained in the polymerization catalyst are covalently bonded to the polymer. The ratio of the nitrogen-containing functional group covalently bonded to the polymer is more preferably 99.9 mol%.

Examples of the nitrogen-containing functional group include an amino group, a quaternary ammonium group, an amide group, an imide group, a nitrile group, and a pyridyl group. Among these, the nitrogen-containing functional group is preferably an amino group or a quaternary ammonium group from the viewpoint of catalytic activity, and more preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group from the viewpoint of ease of reaction. .. The counter ion of the quaternary ammonium group is not particularly limited, and a halogen ion or a hydroxide ion can be adopted. The counter ion is preferably a halogen ion, more preferably an iodine ion.

The quaternary ammonium group may be possessed by the polymerization catalyst before the polymerization reaction using the polymerization catalyst, and is generated by the reaction of the nitrogen-containing functional group of the polymerization catalyst in the reaction system of the polymerization reaction using the polymerization catalyst. You may.
Nitrogen-containing functional groups can be identified by known analytical methods such as IR spectrum, NMR spectrum, UV spectrum, and mass spectrum.

The polymer constituting the polymerization catalyst has the repeating units shown in (1'-1) to (1'-6). The polymer constituting the polymerization catalyst is preferably a crosslinked product.

In the formulas (1'-1) to (1'-6), R1 is an alkyl group having 1 to 4 carbon atoms, R2 to R4 are independently hydrogen atoms, an alkyl group having 1 to 20 carbon atoms, or the following formula. (1'-7) is shown.

In the formula (1'-7), R5 represents an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10.

In the formulas (1'-1) to (1'-7), when R1 to R5 are alkyl groups, R1 to R5 may have a substituent. The substituent is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, and an alkali metal salt of a carboxyl group.

Specific examples of the polymer constituting the polymerization catalyst include polymers having repeating units as shown in the following formulas (1-1) to (1-10).

In equation (1-3), n represents an integer of 1 to 4. Further, in the equation (1-4), n represents an integer of 1 to 10.

Polymerization catalysts having the structures of the above formulas (1-1) to (1-10) are also available as commercially available ion exchange resins and chelate resins having completely different uses from the polymerization catalysts.

Examples of commercially available ion exchange resins include SA series, PA series, and HPA series of strongly basic anion exchange resins manufactured by Mitsubishi Chemical Co., Ltd., and WA series of weakly basic anion exchange resins. Examples thereof include SAF series and PAF series of low odor and low elution anion exchange resins. In addition, Dow Chemical Company's Dowex Marathon (registered trademark) MSA Chloride, Amberlist (registered trademark) A21, and Amberlite (registered trademark) IRA-96 can be mentioned.

Examples of commercially available chelate resins include Mitsubishi Chemical's Diaion (registered trademark) iminodiacetic acid type and polyamine type CR series, and glucamine type CRB series.

All of the above commercial products are crosslinked polymers.

Further, the polymer having a nitrogen-containing functional group can be obtained by, for example, the following method.
First, crosslinked polystyrene is obtained by copolymerization of styrene and divinylbenzene.

Next, by the chloromethylation reaction of the obtained crosslinked polystyrene, a chloromethyl group is introduced into a part of the aromatic ring of the styrene unit to obtain chloromethylated crosslinked polystyrene.

Then, the obtained chloromethylated crosslinked polystyrene is reacted with dimethylamine to replace the chloro group of the chloromethyl group with a dimethylamino group.
As a result, a polymerization catalyst having the repeating unit of the above formula (1-5) can be obtained.

Further, for example, by reacting the above-mentioned chloromethylated crosslinked polystyrene with a tertiary amine, a polymerization catalyst having the repeating units of the above formulas (1-1) and (1-2) can be obtained.

The above polymer may be used alone or in combination of two or more.

<Iodine>
The polymerization catalyst preferably contains _{iodine (I 2} ) in addition to the above polymer. Iodine functions as an inactive agent that suppresses the concentration of active species, which will be described later, and suppresses the termination reaction due to the binding and disproportionation of radical species. Iodine can exist in a state of being physically adsorbed on the surface of the polymer. Iodine can be physically adsorbed on the surface of the polymer by a method such as mixing iodine in the polymerizable composition containing the polymer.

Further, the polymerization catalyst may contain iodine atom-containing ions. Here, the "iodine atom-containing ion" is an iodide ion (I ⁻ ), a triiodide ion (I ₃ ⁻ ), or a pentaiodide ion (I ₅ ⁻ ). The iodine atom-containing ion has a function of enhancing the catalytic performance of the above-mentioned polymer. The iodine atom-containing ion can exist in a state of being ionically bonded to the polymer as a counter ion of a quaternary ammonium group possessed by the polymer.

(Vinyl monomer)
Examples of the vinyl monomer to be polymerized in the method for producing the polymer of the present embodiment include, for example.
(Meta) acrylic acid;
Alkyl (meth) acrylate with 1 to 30 carbon atoms, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (Meta) acrylate, polyethylene glycol (meth) acrylate and its alkyl ether, benzyl (meth) acrylate, phenyl (meth) acrylate, 3- (triethoxysilyl) propyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) ) (Meta) acrylate-based monomer represented by acrylate and its quaternary alkylammonium salt;
Styrene-based monomers such as α-methylstyrene, vinyltoluene, and styrene;
Vinyl ether-based monomers such as methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether;
Fumaric acid, monoalkyl ester of fumaric acid, dialkyl ester of fumaric acid;
Maleic acid, monoalkyl ester of maleic acid, dialkyl ester of maleic acid;
Itaconic acid, monoalkyl ester of itaconic acid, dialkyl ester of itaconic acid;
(Meta) acrylonitrile, (meth) acrylamide, butadiene, isoprene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ketone, vinyl pyridine, vinyl carbazole;
Etc. can be exemplified.

As the vinyl monomer, at least one selected from the group consisting of a styrene-based monomer, a (meth) acrylate-based monomer, and (meth) acrylonitrile is preferable from the viewpoint of polymerization control.

The vinyl monomer may be used alone or in combination of two or more.

(Organoiodine compound)
In the method for producing a polymer of the present embodiment, an organic iodine compound (dormant species) having a carbon-iodine bond is present in the polymerizable composition, and iodine given to the growth chain from this organic iodine compound is used as a growth radical. Used as a protective radical for iodine. The organic iodine compound is not particularly limited as long as it has at least one carbon-iodine bond in the molecule and acts as a dormant species. As the organic iodine compound, a compound containing one or two iodine atoms in one molecule is preferable.

The organic iodine compound may be added as an organic iodine compound in the polymerizable composition, or may be produced by reacting a compound added as another compound in a reaction system. When added as another compound, for example, an organic iodine compound is produced by reacting at least a part of each of the radical polymerization initiator described later with iodine in the process of polymerization.

Examples of the organic iodine compound include iodotrichloromethane, dichlorodiiodomethane, iodotribromomethane, dibromodiiodomethane, bromotriiodomethane, iodoform, diiodomethane, methyl iodide, triiodoethane, ethyl iodide, and diiodopropane. Isopropyl iodide, t-butyl iodide, iododichloroethane, chlorodiiodoethane, diiodopropane, chloroiodopropane, iododibromoethane, bromoiodopropane, 2-iodo-2-polyethylene glycosylpropane, 2-iodo-2- Amidinopropane, 2-iodo-2-cyanobutane, 2-iodo-2-cyano-4-methylpentane, 2-iodo-2-cyano-4-methyl-4-methoxypentane, 4-iodo-4-cyanopentanoic acid , Methyl-2-iodoisobutyrate, 2-iodo-2-methylpropanoamide, 2-iodo-2,4-dimethylpentane, 2-iodo-2-cyanobutanol, 2-iodo-2-methyl-N- (2-Hydroxyethyl) Propionamide 4-methylpentane, 2-iodo-2-methyl-N- (1,1-bis (hydroxymethyl) -2-hydroxyethyl) Propionamide-4-methylpentane, 2-iodine -2- (2-Imidazoline-2-yl) propane, 2-iodo-2- (2- (5-methyl-2-imidazolin-2-yl) propane, iodobenzylcyanide (PhCN-I), ethyl- 2-Iodine phenylacetate (EPh-I), diethyl-2-iodo-2-methylmalonate (EEMA-I), 2-iodo-2-cyanopropane (CP-I), 1-iodo-1-cyanoethane ( CE-I), 1-iodo-1-phenylethane (PE-I), ethyl-2-iodoisobutyrate (EMA-I), ethyl-2-iodovalerate (EPA-I), ethyl-2- Iodine propionate (EA-I), ethyl-2-iodoacetate (EI), 2-iodoisobutyric acid (MAA-I), hydroxyethyl-2-iodoisobutyrate (HEMA-I), 2-iodine Propionic acid amide (AAm-I), ethylene glycol bis (2-iodoisobutyrate) (EMA-II), diethyl-2,5-diiodoadipate (EA-II), glycerol-tris (2-iodoisobutyrate) Rate) (EMA-III), 6- (2-iodo-2-isobutyroxy) hexyltriethoxysilane (IH) E) can be exemplified.

One type of organic iodine compound may be used alone, or two or more types may be used in combination.

Among the organic iodine compounds, PhCN-I, EPh-I, EEMA-I, CP-I, CE-I, PE-I, EMA-I, EPA-I, EA-I, E from the viewpoint of polymerization control. At least one selected from the group consisting of -I, MAA-I, HEMA-I, AAm-I, EMA-II, EA-II, EMA-III, and IHE is preferred.

(Radical polymerization initiator)
In the method for producing a polymer of the present embodiment, a radical polymerization initiator may be added to the polymerizable composition. When the radical polymerization initiator polymerizes a polymerizable composition containing a polymerization catalyst, a vinyl monomer, an organic iodine compound, and iodine, the radical polymerization initiator increases the radical concentration in the polymerizable composition and increases the polymerization rate. Used for the purpose of raising.

As the radical polymerization initiator, known compounds such as an azo-based radical polymerization initiator and a peroxide-based radical polymerization initiator can be used. In the method for producing a polymer of the present embodiment, the polymerization reaction can be carried out by using the above-mentioned polymerization catalyst, and a radical polymerization initiator may not be substantially used. When a radical polymerization initiator is used in the method for producing a polymer of the present embodiment, the polymerization rate can be improved and the polymerization time can be shortened as compared with the case where the radical polymerization initiator is not used.

Examples of the azo radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 2,2'-azobis (2,4-dimethyl). Valeronitrile) and 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile).

Examples of the peroxide-based radical polymerization initiator include 2,4-dichlorobenzoyl peroxide, t-butyl peroxypivalate, o-methylbenzoyl peroxide, and bis-3,5,5-trimethylhexanoyl peroxide. , Octanoyl peroxide, t-butylperoxy-2-ethylhexanoate, cyclohexanone peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydro Examples include peroxides and di-t-butyl peroxides.

Among the above radical polymerization initiators, benzoyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,) 4-Dimethylvaleronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) and 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) are preferred in terms of availability. ..

The radical polymerization initiator may be used alone or in combination of two or more.

(Iodine)
In the method for producing a polymer of the present embodiment, iodine may be contained in the polymerization catalyst as described above, or may be added separately to the polymerizable composition. Iodine suppresses the concentration of active species, which will be described later, as an inactivating agent for the polymerization reaction, and suppresses the termination reaction due to the binding and disproportionation of radical species. Further, by using iodine and the above-mentioned radical initiator in combination, an organic iodine compound can be produced in the reaction system.

(Other additives)
In the method for producing a polymer of the present embodiment, other additives can be added as needed. Examples of other additives include chain transfer agents.

Examples of the chain transfer agent include mercaptan.
(solvent)
In the method for producing a polymer of the present embodiment, an organic solvent can be used at the time of polymerization. Examples of the organic solvent include hydrocarbon solvents such as toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as dichloromethane and chloroform; ketone solvents such as acetone; alcohol solvents such as methanol; acetonitrile. And other nitrile solvents; vinyl ester solvents such as ethyl acetate; carbonate solvents such as ethylene carbonate; and supercritical carbon dioxide can be exemplified.
As the organic solvent, one type may be used alone, or two or more types may be used in combination.
When a solvent is used, the content of the solvent is preferably more than 0% by mass and 700% by mass or less when the total amount of the polymerizable composition excluding the solvent is 100% by mass.

(Composition of polymerizable composition)
An example of the polymerizable composition is a polymerizable composition containing the above-mentioned polymerization catalyst, vinyl monomer, organic iodine compound, and iodine.

Further, as another example of the polymerizable composition, a polymerizable catalyst containing a polymer having a nitrogen-containing functional group and iodine, a vinyl monomer, an organic iodine compound, and a radical polymerization initiator. The composition is mentioned.

Further, as another example of the polymerizable composition, there is a polymerizable composition containing a polymerization catalyst containing a polymer having a nitrogen-containing functional group and iodine, a vinyl monomer, and a radical polymerization initiator. .. Such a polymerizable composition does not contain an organic iodine compound, but as described above, at least a part of each of the radical polymerization initiator and iodine reacts in the process of polymerization to form an organic iodine compound in the polymerizable composition. Generates and functions as a dormant species.

<Contents of each component in the polymerizable composition>
Next, the content of each component in the above-mentioned polymerizable composition will be described. In the following description, the "content" indicates the amount charged at the time of preparation of the polymerizable composition.

<Polymerization catalyst>
The content of the polymerization catalyst in the polymerizable composition is preferably 0.01% by mass or more and 50% by mass or less with respect to the total amount of the vinyl monomer and the polymerization catalyst. The lower limit of the content of the catalyst with respect to the total amount of the vinyl monomer and the polymerization catalyst is more preferably 0.1% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less. As for the content of the polymerization catalyst with respect to the total amount of the vinyl monomer and the polymerization catalyst described above, the upper limit value and the lower limit value can be arbitrarily combined.

The molar equivalent ratio of nitrogen atoms contained in the polymerization catalyst is preferably 0.0001 or more and 0.5 or less, and more preferably 0.0005 or more and 0.1 or less with respect to the vinyl monomer.

The molar equivalent ratio of nitrogen atoms contained in the polymerization catalyst is preferably 0.001 or more and 1000 or less, and more preferably 0.01 or more and 180 or less with respect to the added organic iodine compound. The above-mentioned upper limit value and lower limit value of the molar equivalent ratio can be arbitrarily combined.

The molar equivalent ratio of the nitrogen-containing functional group contained in the polymerization catalyst is preferably 0.001 or more and 200 or less with respect to the total of the added organic iodine compound and the radical polymerization initiator. The lower limit of the molar equivalent ratio of the nitrogen-containing functional group is more preferably 0.005 or more, and further preferably 0.01 or more. Further, the upper limit is more preferably 100 or less. The above-mentioned upper limit value and lower limit value of the molar equivalent ratio can be arbitrarily combined.

When the molar equivalent ratio of the nitrogen atom and the nitrogen-containing functional group contained in the polymerization catalyst is within the above range, the polymerization rate is sufficiently promoted, and the polymerization solution maintains an appropriate viscosity and is easy to handle.

The molar equivalent ratio of nitrogen atoms contained in the polymerization catalyst can be determined by an elemental analysis method.

The molar equivalent ratio of nitrogen atoms in the polymer contained in the polymerization catalyst can also be determined by the following method.
First, the excess amount of the organic iodine compound having a known molecular weight is completely reacted with the polymer in the polymerization catalyst. Next, the amount of substance (mol) of the organic iodine compound that has reacted with the nitrogen-containing functional group is determined from the reaction rate of the organic iodine compound, and the amount of substance (mol) of the nitrogen-containing functional group is determined from the amount of substance of the reacted organic iodine compound. From the amount of substance of the obtained nitrogen-containing functional group, the molar equivalent ratio of nitrogen atoms is calculated.

More specifically, the molar equivalent ratio of the nitrogen-containing functional groups contained in the polymerization catalyst can be calculated by, for example, the following method.
2.0 g of the polymerization catalyst and 1.21 g (5.61 mmol) of 1-iodohexane are mixed and uniformly dispersed in 8 ml of tetrahydrofuran. The dispersion solution is reacted in a reflux state for 24 hours with heating and stirring. An internal standard having a known concentration is added to the obtained reaction solution, ¹ H-NMR is measured, and the amount of decrease in 1-iodohexane is determined from the amount of remaining 1-iodohexane. The molar equivalent ratio of 1-iodohexane decreased at this time is equal to the molar equivalent ratio of the nitrogen-containing functional groups contained in the polymerization catalyst.

When the polymerization catalyst contains iodine, the molar equivalent ratio of iodine contained in the polymerization catalyst is arbitrary. However, the amount of the vinyl monomer is preferably 0.0001 or more and 0.5 or less, and more preferably 0.0005 or more and 0.1 or less. When the molar equivalent ratio of iodine is in the above range, the polymerization rate can be sufficiently promoted.

In the present specification, the molar equivalent ratio of iodine contained in the polymerization catalyst is a value obtained by elemental analysis of the polymerization catalyst or a value obtained from the amount charged when synthesizing the polymerization catalyst.

<Organoiodine compound>
When the polymerizable composition contains an organic iodine compound, the content of the organic iodine compound in the polymerizable composition is arbitrary. The content of the organic iodine compound in the polymerizable composition is preferably 0.001 mol or more and 0.5 mol or less per 1 mol of the vinyl monomer, and the amount is 0.002 mol or more and 0.1 mol or less. More preferred. When the content of the organic iodine compound in the polymerizable composition is within the above range, it is sufficient to provide the iodine atom as a protecting group from the organic iodine compound to the growth chain of the polymerization reaction, and the polymerization rate is extremely high. Do not lower.

<Radical polymerization initiator>
When the organic iodine compound is produced by adding the radical polymerization initiator to the polymerizable composition without adding the organic iodine compound, the content of the radical polymerization initiator in the polymerizable composition is arbitrary. The content of the radical polymerization initiator in the polymerizable composition is preferably 0.0001 mol or more and 0.05 mol or less, and 0.0002 mol or more and 0.02 mol or less per mol of the vinyl monomer. Is more preferable. When the content of the radical polymerization initiator in the polymerizable composition is within the above range, an appropriate polymerization rate can be obtained.

(Reaction mechanism)
The nitrogen-containing functional group of the polymerization catalyst has an action of promoting a redox reaction in the living radical polymerization of a vinyl monomer having a carbon-iodine bond as a dormant species. Therefore, in the method for producing a polymer of the present embodiment, the polymerization catalyst extracts iodine atoms from the organic iodine compound to generate radicals derived from the organic iodine compound.

The method for producing the polymer of the present embodiment is not particularly bound by theory, but the presumed mechanism will be described below.

Scheme 1 below shows the reaction formula of the RCMP method, which is generally known.

In Scheme 1, A is a polymerization catalyst having a redox ability, and I is an iodine atom. The polymerization catalyst A is in a reduced state on the left side of the reaction formula and in an oxidized state on the right side. When the polymerization catalyst A is in the oxidizing state, radicals of the polymer which is an active species are generated, and when the polymerization catalyst A is in the reducing state, the ends of the polymer are protected by iodine atoms. "Polymer-I" on the left side is a dormant species in the reaction system, and "Polymer." On the right side is an active species in the reaction system.

Then, the polymerization catalyst A reversibly undergoes a redox reaction between the reduced state (left side) and the oxidized state (right side). Further, as shown in Scheme 1, Scheme 1 is an equilibrium reaction, and the equilibrium is biased to the left side. That is, active species are present in low concentrations in the reaction system.

Therefore, first, when the polymerization catalyst A is in the reduced state, the dormant species (Polymer-I) shown on the left side is protected at the end by an iodine atom and the reaction is stopped.

Further, when the polymerization catalyst A is in an oxidized state, the active species (radicals of the polymer) shown on the right side radically polymerize with the vinyl monomer to generate a polymer.

Furthermore, since the equilibrium of Scheme 1 is biased to the left side, the concentration of active species can be suppressed to a low level, and the termination reaction due to the binding and disproportionation of radical species can be suppressed. Therefore, the equilibrium reaction of Scheme 1 lasts for a long time, and the active species will be present in the reaction system for a long time. Furthermore, it is easy to make the molecular weight distribution of the resulting polymer uniform.

As a result, the polymer terminal always keeps its activity (living room), and the molecular weight distribution can be made uniform.

Based on the above mechanism, in the method for producing a polymer of the present embodiment, for example, when a crosslinked polymer having a tertiary amino group which is a nitrogen-containing functional group in the side chain of crosslinked polystyrene is used as the polymerization catalyst, the polymerization catalyst The reaction formula for the reaction is considered to be as shown in Scheme 2 below. On the right side of the equation below, it can be in the state of a salt in which one electron is transferred between the tertiary amino group and the iodine atom, or in the state of a complex in which the partial charge is transferred between the tertiary amino group and iodine. The polymerization catalyst is in an oxidized state because electrons are supplied from the nitrogen atom of the tertiary amino group to the radical of iodine on the right side of the following formula. In relative terms, the polymerization catalyst is in a reduced state on the left side.

On the right side of the above scheme 2, the above formula is the above-mentioned "state of a salt in which one electron is transferred between a tertiary amino group and an iodine atom", and the lower formula after dimerization is the above-mentioned "class 3". "A complex in which a partial charge is transferred between an amino group and iodine" is shown. The dimerization shown on the right side may occur between different nitrogen-containing functional groups existing in continuous molecular chains, or may occur between different nitrogen-containing functional groups existing in different molecular chains.

Also in the method for producing a polymer of the present embodiment, the polymerization catalyst reversibly undergoes a redox reaction between the reduced state (left side) and the oxidized state (right side), so that the radical of the polymer shown on the right side is a single amount of vinyl. It is considered that the polymer is polymerized with the body to obtain the desired polymer.

In addition, many polymers exist in the reaction system in a state where the ends are protected by iodine atoms as shown on the left side of Scheme 2. Therefore, in the method for producing a polymer of the present embodiment, the radical concentration in the reaction system can be suppressed to a low level, and the termination reaction due to the binding or disproportionation of radical species can be suppressed.

(Polymerization conditions)
The polymerization method in the method for producing the polymer of the present embodiment is not particularly limited, and examples thereof include a massive polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.

The polymerization reaction may be carried out in the presence of air, but from the viewpoint of the efficiency of radical polymerization, it is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon.

The polymerization temperature is preferably 0 ° C. or higher and 150 ° C. or lower because an appropriate polymerization rate can be easily obtained. Further, since polymerization control is easy, 20 ° C. or higher and 120 ° C. or lower is more preferable. Further, when the polymerization temperature is 120 ° C. or lower, the activity of the polymerization catalyst can be easily maintained, which is preferable.

The polymerization time is not particularly limited, and can be, for example, 0.5 hours or more and 24 hours or less.

(Polymer)
The polymer produced by the method for producing a polymer of the present embodiment has an iodine atom at the end of the main chain. I of "Polymer-I" shown in the above scheme 1 corresponds. The iodine atom at the terminal can be removed by treating at a high temperature. In addition, a functional group derived from the nucleophile can be introduced by reacting the iodine atom at the terminal with the nucleophile.

The molecular weight distribution (Mw / Mn) of the polymer obtained by a known typical controlled polymerization is generally less than 1.5. Here, Mw is a weight average molecular weight and Mn is a number average molecular weight.

According to the method for producing a polymer of the present embodiment, the Mw / Mn of the obtained polymer can be less than 1.5. In the method for producing a polymer of the present embodiment, the molecular weight may be larger than the target Mw / Mn depending on the dispersed state of the polymerization catalyst. In that case, Mw / Mn can be reduced by satisfactorily dispersing the polymerization catalyst in the reaction system. Examples of a method for satisfactorily dispersing the polymerization catalyst in the reaction system include a method of adding a solvent to reduce the viscosity, an increase in the stirring speed, and a method of reducing the particle size of the polymer constituting the polymerization catalyst.

From these, it is considered that the method for producing the polymer of the present embodiment causes a redox reaction similar to the case where the organic compound catalyst used in the generally known RCMP method is used. As a result, it is considered that the method for producing a polymer of the present embodiment can control the molecular weight and obtain a polymer having a narrow molecular weight distribution.

(Removal of polymerization catalyst)
The polymerization catalyst used in the method for producing a polymer of the present embodiment does not contain a transition metal, is inexpensive, and has high environmental safety. On the other hand, there is a concern that the residual polymerization catalyst may cause coloring or deterioration of durability due to remaining in the polymer. Therefore, it is preferable to remove the polymerization catalyst from the reaction product.

The conventional organic compound catalyst can be dissolved during the reaction not only as a solvent-soluble organic compound catalyst but also as an organic compound catalyst supported on a carrier. Therefore, it was difficult to remove the organic compound catalyst from the reaction product. On the other hand, the polymerization catalyst used in the method for producing a polymer of the present embodiment contains a polymer having a nitrogen-containing functional group. Since such a polymer is difficult to dissolve in the reaction system in which the polymerization reaction is carried out, it is difficult to remain in the reaction product.

In such a method for producing a polymer of the present embodiment, the polymerization catalyst used can be easily removed from the reaction product after the polymerization reaction by a simple method. That is, in the method for producing a polymer of the present embodiment, it is preferable to have a step of removing the polymerization catalyst after the polymerization reaction of the vinyl monomer is carried out. Examples of the removal method include centrifugation and filtration.

The polymerization catalyst removed from the reaction product by the above method can be reused as a polymerization catalyst by appropriately washing with an organic solvent and drying.

The organic solvent used for cleaning includes a hydrocarbon solvent such as toluene; an ether solvent such as diethyl ether and tetrahydrofuran; a halogenated hydrocarbon solvent such as dichloromethane and chloroform; a ketone solvent such as acetone; an alcohol solvent such as methanol. Examples thereof include a solvent; a nitrile solvent such as acetonitrile; a vinyl ester solvent such as ethyl acetate; a carbonate solvent such as ethylene carbonate; and supercritical carbon dioxide.

As the organic solvent used for cleaning, one type may be used alone, or two or more types may be used in combination.

According to the above-mentioned polymerization catalyst, it is possible to provide a polymerization catalyst having high activity in living radical polymerization without using a transition metal-based catalyst and which can be removed by a simple method.

The polymer produced by the method for producing a polymer of the present embodiment is not particularly limited in use because the polymerization catalyst that causes coloring and deterioration of durability can be removed by a simple method as described above. Specific examples thereof include dispersants, resin additives, coating compositions, and lithographic polymers.

Although the preferred embodiment of the present invention has been described above, the present invention is not limited to such an example. The combination of each configuration shown in the above-mentioned example is an example, and can be variously changed based on the design requirements and the like without departing from the gist of the present invention.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following description.

In the following explanation, "eq" indicates "molar equivalent".

[Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer obtained by the polymerization are measured by GPC (manufactured by Tosoh Corporation, "HLC-8220"), and the calibration curve of PMMA (polymethylmethacrylate) is used. Obtained using.
The measurement conditions were as follows.
(Measurement condition)
Column: TSK GUARD COLUMN SUPER HZ-L (manufactured by Tosoh Corporation, 4.6 mm x 35 mm)
And TSK-GEL SUPER HZM-N (manufactured by Tosoh Corporation, 6.0 mm x 150 mm) in series Eluent: tetrahydrofuran Measurement temperature: 40 ° C
Flow velocity: 0.6 mL / min

The molecular weight distribution (Mw / Mn) was calculated using Mn and Mw obtained by the above method.

[Polymer conversion rate]
The monomer conversion rate (%) of Examples and Comparative Examples is a measured value of ¹ H-NMR measurement using a nuclear magnetic resonance apparatus (Bruker, "BBF0400", 400 MHz) and CDCl _{3 as a measurement solvent.} I asked for it. Specifically, using the integrated value of the peak derived from the residual monomer and the integrated value of the peak derived from the produced polymer, the amount of the produced polymer relative to the total amount of the residual monomer amount and the produced polymer amount. Calculated as a ratio.

[Detection of iodine atom]
Iodine or iodine atom-containing ions contained in the polymerization catalyst were detected by XPS (X-ray photoelectron spectroscopy, SPECS, "Phoibos 100", monochromatic X-ray light source) measurement.

[Polymer YI]
The spectral light transmittance of a solution obtained by dissolving 1.0 g of the polymer obtained in Examples and Comparative Examples in 10 mL of chloroform at 380 nm to 780 nm was measured using U-3300 (trade name) manufactured by Hitachi High-Tech Fielding Co., Ltd. Then, the yellow index (YI) was calculated.

YI was calculated by the following formula described in JIS K7105 based on the tristimulus values X, Y, and Z. The larger the value of YI, the stronger the yellowness and the higher the degree of coloring.
Yellow index (YI) = 100 (1.28X-1.06Z) / Y

The abbreviations in this example are as follows.

<Polymerization catalyst (A)>
WA-30: Polystyrene ion exchange resin (manufactured by Mitsubishi Chemical Corporation, Diaion (registered trademark) WA-30)
WA-21J: Polystyrene ion exchange resin (manufactured by Mitsubishi Chemical Corporation, Diaion (registered trademark) WA-21J)
HP-20: Polystyrene-based synthetic adsorbent (manufactured by Mitsubishi Chemical Corporation, Diaion (registered trademark) HP-20)
MSA Chloride: Polystyrene ion exchange resin (Dow Chemical Company, Dowex Marathon (registered trademark))
A21: Polystyrene ion exchange resin (Amberlist (registered trademark) manufactured by Dow Chemical Company, Ltd.)
IRA-96: Polystyrene ion exchange resin (Amberlite (registered trademark) manufactured by Dow Chemical Company, Ltd.)
BNI: Tetrabutylammonium iodide (manufactured by Tokyo Chemical Industry Co., Ltd.)

HP-20 is a polymer having a repeating unit represented by the following formula (2-1) and does not have a nitrogen-containing functional group.

It was confirmed by the following method that the polymer used as the polymerization catalyst was crosslinked.
When 2 g of the polymer was added to 8 ml of tetrahydrofuran, immersed, and heated for 24 hours while refluxing at 70 ° C., if the polymer remained undissolved, it was determined that the polymer was crosslinked.

<Vinyl monomer (B)>
MMA: Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
EHMA: 2-ethylhexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
LMA: Lauryl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Organoiodine compound (C)>
CP-I: 2-iodine-2-cyanopropane (manufactured by Tokyo Chemical Industry Co., Ltd.)
EPh-I: Ethyl-2-iodophenyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.)
PMMA-I: Iodinated terminal polymethylmethacrylate PMMA-I was synthesized and used according to a conventional method.

<Radical polymerization initiator (D)>
AIBN: 2,2'-azobis (isobutyronitrile) (manufactured by Tokyo Chemical Industry Co., Ltd.)
V-65: 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Iodine>
I ₂ : Iodine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Manufacturing example: Synthesis of quaternized WA-30]
2.0 g of WA-30 and 1.21 g (5.61 mmol) of 1-iodohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and uniformly dispersed in 8 ml of tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.). .. This dispersion solution was transferred to a glass reaction vessel and reacted for 24 hours with heating and stirring in a reflux state to obtain a reaction solution.

Benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was precisely added to the obtained reaction solution as an internal standard, and the amount of 1-iodohexane in tetrahydrofuran was compared before and after the reaction to determine the reaction rate. The reaction rate of iodine was 83% (4.74 mmol).

When the nitrogen-containing functional group of WA-30 reacts with excess 1-iodohexane, unreacted 1-iodohexane remains in the reaction solution. An internal standard having a known concentration (benzene, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution, and ¹ H-NMR of the reaction solution was measured to determine the amount of 1-iodohexane remaining.

Subsequently, the residual amount was subtracted from the amount of 1-iodohexane added first to determine the amount of 1-iodohexane that reacted with WA-30.

Since WA-30 has a dimethylamino group as a nitrogen-containing functional group, the molar equivalent of nitrogen atom can be calculated from the amount of 1-iodohexane reacted per 1 g of WA-30.

FIG. 1 is an XPS chart of the obtained reaction product. The chart on the left shown in FIG. 1 shows the result of wide scan analysis, and the chart on the right shows the result of narrow scan analysis.

As shown in FIG. 1, in the reaction products, peaks derived from the 3d electron of the iodine atom were detected at 629 eV and 617 eV, which were not detected by WA-30, and the peak derived from the nitrogen atom changed from 399 eV to 402 eV. I confirmed that it had shifted. From the above results, it was determined that the product obtained by the above reaction was a compound in which 1-iodohexane was reacted with the nitrogen-containing functional group of WA-30 to quaternize it, and iodine ion was bound as a counter ion.

The reaction product was recovered by filtration, washed repeatedly with tetrahydrofuran, and then dried under reduced pressure.

In the following description, the obtained product will be referred to as "quaternized WA-30". The obtained quaternized WA-30 has a number average molecular weight of 10,000 or more.

[Example 1]
A quaternized WA-30 as the polymerization catalyst (A), MMA as the vinyl monomer (B), and CP-I as the organic iodine compound (C) were weighed with the compositions shown in Table 1 to prepare a polymerizable composition. ..

The composition unit (eq / mass%) of the polymerization catalyst (A) shown in Table 1 is the mass of the polymerization catalyst with respect to the equivalent number of nitrogen atoms contained in the polymerization catalyst and the total mass of the polymerization catalyst and the vinyl monomer (B). Means ratio. The same applies to Tables 2 and 3 described later.

The obtained polymerizable composition was transferred to a glass reaction vessel, the gas phase was replaced with nitrogen, and then the polymerization reaction was carried out at 70 ° C. for the time shown in Table 1 with stirring, and then the polymer was filtered. Got

The amounts of the polymerization catalyst (A), the organic iodine compound (C), and the radical polymerization initiator (D) shown in Table 1 mean the molar equivalents used with respect to 8000 molar equivalents of the vinyl monomer (B). .. Further, the molar equivalent ratio of the nitrogen-containing functional group contained in the polymerization catalyst means the molar equivalent ratio to the total of the added organic iodine compound and the radical polymerization initiator. The same applies to Table 2 described later.

[Example 2]
A polymer was obtained in the same manner as in Example 1 except that the composition of the polymerizable composition was set to the composition shown in Table 1 and a polymerization catalyst containing a polymer having a nitrogen-containing functional group and iodine was used.

[Examples 3 to 4]
A polymer was obtained in the same manner as in Example 2 except that the composition of the polymerizable composition was the composition shown in Table 1 and V-65 was used as the radical polymerization initiator (D).

[Examples 5 to 6]
A polymer was obtained in the same manner as in Example 3 except that the composition of the polymerizable composition was the composition shown in Table 1 and AIBN was used as the radical polymerization initiator (D).

[Examples 7 to 8]
A polymer was obtained in the same manner as in Example 5 except that the composition of the polymerizable composition was the composition shown in Table 1 and toluene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a solvent.

The composition unit (mass%) of the solvent shown in Table 1 means the ratio of the solvent when the total amount including the solvent is 100% by mass. The same applies to Tables 2 and 3 described later.

[Examples 9 to 10]
A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 1 and EHMA was used as the vinyl monomer (B).

[Examples 11 to 12]
A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 1 and LMA was used as the vinyl monomer (B).

[Examples 13 to 15]
A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 2 and WA-30 was used as the polymerization catalyst (A).

[Examples 16 to 17]
A polymer was obtained in the same manner as in Example 11 except that the composition of the polymerizable composition was the composition shown in Table 2 and EPh-I was used as the organic iodine compound (C).

[Example 18]
A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 2.

[Example 19]
The quaternized WA-30 used in Example 18 was recovered by centrifugation. The solid content was washed three times, with the recovery of the recovered solid content in 10 ml of tetrahydrofuran and then recovery by centrifugation as one wash. Then, the recovered solid content was dried under reduced pressure to obtain quaternized WA-30 (first reuse).

The polymer was prepared in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 2 and the quaternized WA-30 (first reuse) was used as the polymerization catalyst (A). Obtained.

[Example 20]
The quaternized WA-30 used in Example 19 was recovered by centrifugation, washed three times in the same manner as in Example 19, and then dried under reduced pressure to obtain the quaternized WA-30 (second reuse). Obtained.
The polymer was prepared in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 2 and the quaternized WA-30 (second reuse) was used as the polymerization catalyst (A). Obtained.

[Example 21]
The quaternized WA-30 used in Example 20 was recovered by centrifugation, washed three times in the same manner as in Example 19, and then dried under reduced pressure to obtain the quaternized WA-30 (third reuse). Obtained.

The polymer was prepared in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 2 and the quaternized WA-30 (third reuse) was used as the polymerization catalyst (A). Obtained.

[Example 22]
The quaternized WA-30 used in Example 21 was recovered by centrifugation, washed three times in the same manner as in Example 19, and then dried under reduced pressure to obtain the quaternized WA-30 (fourth reuse). Obtained.

The polymer was prepared in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 2 and the quaternized WA-30 (fourth reuse) was used as the polymerization catalyst (A). Obtained.

[Example 23]
A polymer was obtained in the same manner as in Example 11 except that the composition of the polymerizable composition was the composition shown in Table 2 and PMMA-I was used as the organic iodine compound (C). The obtained polymer was a block copolymer composed of PMMA and PLMA (polylauryl methacrylate).
[Example 24]
A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 3 and a mixture of MSA Chloride and iodine was used as the polymerization catalyst (A).
[Example 25]
A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 3 and a mixture of A21 and iodine was used as the polymerization catalyst (A).
[Example 26]
A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 3 and a mixture of IRA-96 and iodine was used as the polymerization catalyst (A).
[Example 27]
Examples except that the composition of the polymerizable composition was the composition shown in Table 3, the polymerization catalyst (A) was changed to a mixture of WA-21J and iodine, and the amount of iodine was the amount shown in Table 3. A polymer was obtained in the same manner as in 1.

[Comparative Example 1]
The composition of the polymerizable composition was set to the composition shown in Table 2, and the same procedure as in Example 7 was carried out except that the quaternized WA-30 was not used.

[Comparative Example 2]
The composition of the polymerizable composition was the composition shown in Table 2, and the same procedure as in Example 7 was carried out except that HP-20 was used as the polymerization catalyst (A).
[Comparative Example 3]
The composition of the polymerizable composition was the composition shown in Table 3, and the same procedure as in Example 1 was carried out except that BNI was used as the polymerization catalyst (A) and toluene was used as the solvent.

Tables 1 to 3 show the measurement results of the composition, polymerization conditions, Mn, Mw / Mn, monomer conversion rate and YI of the polymerizable compositions of each Example and Comparative Example.

As shown in Tables 1 to 3, Examples 1 to 3 obtained by polymerizing a vinyl monomer (B) in the presence of an organic iodine compound using a polymer having a nitrogen-containing functional group as a polymerization catalyst (A). For 18 and 23 to 26, a constant monomer conversion rate could be obtained within a predetermined polymerization time. Further, in the obtained polymer, the molecular weight and the molecular weight distribution were controlled, and Mw / Mn became a small value.

Comparing these results with Comparative Example 3 using BNI, which is a small molecule having a nitrogen-containing functional group as the polymerization catalyst (A), Examples 1 to 18 and 23 to 26 are heterogeneous catalysts that can be easily removed. Although the above is used, a polymer having a molecular weight and a molecular weight distribution controlled in the same manner as when a low molecular weight catalyst is used is obtained. Furthermore, it was shown that in Example 17, a polymer having a lower YI and a lower coloration was obtained as compared with Comparative Example 3.

Furthermore, from the results of Examples 19 to 22, it was shown that even when the polymer having a nitrogen-containing functional group is reused, it has the same catalytic ability as that of Example 18 before the reuse.

Further, from the results of Example 23, it was shown that a polymerization catalyst composed of a polymer having a nitrogen-containing functional group is also useful for the production of block copolymers.

On the other hand, in Comparative Example 1 in which the polymerization catalyst (A) was not used, the monomer conversion rate was 0%, and the polymerization did not proceed at all.

Further, in Comparative Example 2 in which HP-20, which is a polymer having no nitrogen-containing functional group, was used as the polymerization catalyst (A), the monomer conversion rate was 0%, and the polymerization did not proceed at all. ..

From the above results, it was found that the present invention is useful.

Claims

A method for producing a polymer, which comprises a step of polymerizing a vinyl monomer in the presence of a polymerization catalyst composed of a polymer having a nitrogen-containing functional group and an organic iodine compound to obtain a polymer.
The method for producing a polymer according to claim 1, wherein the polymerization catalyst further contains iodine or an iodine atom-containing ion.
The method for producing a polymer according to claim 1 or 2, wherein the polymer is a crosslinked polymer.
The method for producing a polymer according to any one of claims 1 to 3, wherein the polymer is a polymer capable of adsorbing iodine.
The method for producing a polymer according to any one of claims 1 to 4, wherein the polymer mainly has a repeating unit of a vinyl monomer.
The method for producing a polymer according to claim 5, wherein the polymer has a polystyrene skeleton or a polyacrylamide skeleton.
The production of the polymer according to any one of claims 1 to 6, wherein the nitrogen-containing functional group is at least one selected from the group consisting of a secondary amino group, a tertiary amino group and a quaternary ammonium group. Method.
The method for producing a polymer according to claim 7, wherein the nitrogen-containing functional group is a quaternary ammonium group.
The method for producing a polymer according to claim 7 or 8, wherein the counter ion of the quaternary ammonium group is a halogen ion.
The method for producing a polymer according to claim 9, wherein the counter ion is an iodine ion.
The method for producing a polymer according to any one of claims 1 to 10, wherein a radical polymerization initiator is further present in the reaction system in the step of obtaining the polymer.
The method for producing a polymer according to claim 11, wherein iodine is further present in the reaction system in the step of obtaining the polymer.
The weight according to claim 11 or 12, wherein the molar equivalent ratio of the nitrogen-containing functional group contained in the polymerization catalyst is 0.001 to 200 with respect to the total of the organic iodine compound and the radical polymerization initiator. Method of manufacturing coalescence.
The production of the polymer according to any one of claims 1 to 13, wherein the vinyl monomer is at least one selected from the group consisting of a styrene-based monomer and a (meth) acrylate-based monomer. Method.
The method for producing a polymer according to any one of claims 1 to 14, wherein the polymerization temperature in the step of obtaining the polymer is 120 ° C. or lower.
A polymerization catalyst composed of a polymer having a nitrogen-containing functional group, which is used in the method for producing a polymer according to any one of claims 1 to 15.