WO2017150287A1

WO2017150287A1 - Polymer production method and radical polymerization initiating group-containing compound

Info

Publication number: WO2017150287A1
Application number: PCT/JP2017/006459
Authority: WO
Inventors: 嶋中　博之; 陽一田儀; 賀一村上
Original assignee: 大日精化工業株式会社
Priority date: 2016-02-29
Filing date: 2017-02-22
Publication date: 2017-09-08

Abstract

Provided are: a novel production technique of allowing production of a polymer of which the molecular weight or the molecular weight distribution is controlled or allowing production of a desirably controlled polymer having a complicated structure, using commercially available materials without using any radical polymerization initiator or any special materials for use in living radical polymerization and without the need of strict polymerization conditions; and a radical polymerization initiating group-containing compound for use in the technique. The present invention pertains to: a polymer production method comprising a polymerization step for mixing and heating (1) a radical polymerizable monomer, (2) an organic compound having introduced in a single molecule thereof at least one group having a structure that is represented by general formula 1 and/or general formula 2 (in the formulae, X represents Cl or Br) and that functions as a group for initiating polymerization of the monomer, and (3) an iodine ion-containing compound, so that radical polymerization accompanied by termination starts from the group having the structure; and said organic compound (2) for use in the method.

Description

Polymer production method and radical polymerization-initiating group-containing compound

The present invention relates to a method for producing a new polymer using a radically polymerizable monomer having an unsaturated bond, a method for producing a polymer capable of freely obtaining a polymer having a complicated structure, and a radical capable of realizing the production method. The present invention relates to a polymerization start group-containing compound. More specifically, in addition to the industrially useful polymerization method, which is advantageous in terms of cost, can obtain a polymer without using a radical polymerization initiator, and can easily obtain a polymer having a complicated structure, In particular, the present invention relates to a technique that makes it possible to provide a polymer having a uniform molecular weight and a controlled structure in a desired state, which is difficult with conventional radical polymerization.

Conventionally, polymers obtained by polymerizing a radical polymerizable monomer having an unsaturated bond having a vinyl group, vinylidene group, vinylene group or the like (hereinafter sometimes simply referred to as “monomer”) are radical polymerization, ionic polymerization, etc. Is highly versatile and used in various places. For example, regarding radical polymerization, thermal polymerization using an azo radical polymerization initiator or peroxide polymerization initiator necessary for generating radicals, or photopolymerization using a photo radical polymerization initiator. To obtain the polymer.

On the other hand, in these radical polymerizations, the lifetime of the radicals is very short, and the polymerization is stopped by a coupling reaction between radicals or a disproportionation reaction in which radicals draw hydrogen from others and the radicals disappear. There is a problem that it ends up. Due to the termination of this reaction, it was not possible to obtain a polymer having a controlled molecular structure such as a block copolymer because the molecular weight was not uniform. On the other hand, living radical polymerization was invented to control the molecular weight and structure of polymers, and various methods have been studied (Patent Documents 1 to 7). As a result, a polymer whose molecular weight and structure are controlled to a desired state can be obtained, and is used industrially.

JP-A-8-179111 Japanese Patent Laid-Open No. 2003-227921 Special Table 2000-500516 Special Table 2000-514479 Special Table 2000-515181 International Publication No. 1999/05099 JP 2007-277533 A

As described above, although a radical polymerization method using a radical polymerization initiator is useful, for example, a polymer having a complicated structure such as a block copolymer, a graft copolymer, or a star polymer can be obtained by a method in which a monomer is subjected to normal radical polymerization. I can't. On the other hand, according to living radical polymerization, although the above-described polymer having a complicated structure can be obtained, in that case, there are the following problems. That is, in living radical polymerization, a special compound is used, or a metal catalyst is used. Therefore, it is necessary to remove those compounds and catalysts, which is complicated industrially and requires a plurality of steps. In addition, the polymerization conditions have to be strict, such as requiring purification of the monomers used or in a nitrogen atmosphere.

Therefore, the object of the present invention is to use a simple commercially available material without using a radical polymerization initiator, a special material used for living radical polymerization, or a metal-based catalyst, and requires strict polymerization conditions. It is possible to simply obtain a polymer with a controlled molecular weight or molecular weight distribution, or a polymer with a complicated structure such as a block copolymer, graft copolymer or star polymer as a polymer controlled to a desired structure by a simple method. Another object of the present invention is to provide a process for producing an industrially useful new polymer. Another object of the present invention is to provide a versatile radical polymerization initiating group-containing compound that makes it possible to realize the above-described innovative polymer production method. Furthermore, an object of the present invention is to find a method for producing such a polymer so that a useful polymer whose structure is controlled to a desired state can be stably provided industrially.

As a result of intensive studies to solve the above problems, the present inventors have found that a monomer, an organic compound into which a group having a specific structure that functions as a polymerization initiation group defined in the present invention is introduced, and a compound having iodine ions And by mixing and heating (heating) them, a radical polymerization with a termination reaction starts from the group having the specific structure and proceeds to obtain a polymer. The present invention has been accomplished by finding a polymerization method. The present inventors further provide a novel polymerization capable of controlling the structure and molecular weight of the resulting polymer to a desired state very easily by using in combination with iodine or a compound capable of liberating iodine or an organic base. I found a way. According to the new polymerization method found by the present inventors, without using a radical polymerization initiator used in the conventional polymerization method, a special material used for living radical polymerization or a metal-based catalyst, A polymer can be obtained simply by mixing and heating the necessary materials, and further, a polymer whose form and characteristics are controlled to a desired state can be obtained. The “warming” defined in the present invention means that the temperature is set to room temperature or higher, for example, 40 ° C. or higher, and the temperature may be determined in consideration of the polymerization rate.

That is, the present invention includes at least (1) a radical polymerizable monomer having an unsaturated bond, and (2) a group having a structure represented by the following general formula 1 and / or the following general formula 2 that functions as a polymerization initiating group of the monomer. Is selected from the group consisting of one or more organic compounds introduced into the molecule, and (3) metal iodide, quaternary ammonium iodide, quaternary phosphonium iodide, and quaternary ammonium triiodide. It has a polymerization step in which radical polymerization with termination reaction starts from a group of the above structure by mixing and heating one or more iodide salts or iodine compounds containing triiodide salts. A method for producing a polymer is provided.

(In General Formula 1, R ₁ represents H or any alkyl group or acyl group, R ₂ represents any alkyl group or aryl group, X represents Cl or Br, and Y represents O or NH.)

(In General Formula 2, R ₃ represents H or any alkyl group or aryl group, R ₄ represents an aryl group, cyano group, carboxyl group, ester group or amide group, and X represents Cl or Br.)

Preferred forms of the polymer production method described above include the following. Do not use any of azo radical polymerization initiator, peroxide radical polymerization initiator and photo radical polymerization initiator in the polymerization step; and (4) liberate iodine and iodine in the polymerization step. Using at least one selected from the group consisting of an iodinated organic compound and a compound having an organic base; and further using an organic solvent in the polymerization step; , A glycol group, an amide group, a sulfoxide group and an ionic liquid; the iodine organic compound capable of liberating iodine is an N-iodimide compound; -Iodoimide compounds are N-iodosuccinimide, N-iodophthalimide, N-iodo It is at least one selected from the group consisting of cyclohexanilimide, 1,3-diaiodo-5,5-dimethylhydantoin and N-iodosaccharin; the group having the structure represented by the general formula 1 is represented by the following general formula And a group having a structure represented by 3.

(In general formula 3, Y is O or NH)

Preferred forms of the polymer production method described above include the following. And although it is the simple method, it is possible to change the constitution of the organic compound (2) to any of the following, for example, ABA block copolymer, star polymer, bottle brush polymer, concentrated polymer brush, Polymers having various desired structures such as block and multi-branched polymers can be obtained.

That is, in the polymer production method described above, the organic compound (2) is a polymerization-initiating group-containing polymer in which two groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced in the molecule. If it exists, the polymer obtained by the said polymerization process turns into a polymer which has a block structure or a comb-shaped structure. In addition, when the organic compound (2) is a compound in which three or more groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced in a molecule, a polymer obtained in the polymerization step is obtained. It becomes a branched structure type polymer, a star polymer or a graft copolymer. In addition, when the organic compound (2) is a vinyl polymer in which three or more groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced in a molecule, the polymer obtained in the polymerization step is The vinyl polymer is polymerized with the monomer (1) and grafted to form a polymer or bottle brush polymer. Further, the organic compound (2) has a monomer in which one or more groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced in the molecule, and a reactive group that binds to the surface of the substrate. A copolymer with a monomer, the substrate is treated with the copolymer to modify the substrate surface, and then the monomer (1) and the (( When the iodine ion-containing compound 3) is mixed and heated, a polymer having a concentrated brush structure is produced on the surface of the substrate.

As another embodiment, the present invention provides a radical polymerizable monomer having an unsaturated bond without using any of an azo radical polymerization initiator, a peroxide radical polymerization initiator, and a photo radical polymerization initiator. A radical polymerization initiating group-containing compound for causing radical polymerization with termination reaction,
Used in combination with an iodine ion-containing compound which is one or more iodide salts or triiodide salts selected from the group consisting of metal iodide, quaternary ammonium iodide, quaternary phosphonium iodide and quaternary ammonium triiodide. Thus, at least one group having a structure represented by the following general formula 1 and / or the following general formula 2 that functions as a polymerization initiating group of the radical polymerizable monomer is introduced into the molecule. Initiating group-containing compounds for radical polymerization are provided.

The following are mentioned as a preferable form of the above-mentioned radical polymerization start group containing compound. That is, in the radical polymerization initiating group-containing compound, the group having a structure represented by the general formula 1 is a group having a structure represented by the following general formula 3;

(In general formula 3, Y is O or NH)
A group in which two groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced in the molecule;
A compound in which three or more groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced into the molecule;
A vinyl polymer in which three or more groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced in the molecule;
The group having a structure represented by the general formula 1 and / or the general formula 2 is a copolymer of a monomer having at least one monomer introduced in the molecule and a monomer having a reactive group bonded to the surface of the substrate. ;

According to the present invention, at least a general-purpose organic compound having a specific structure functioning as a polymerization initiation group for a monomer and capable of being in various forms, a monomer, and a compound having iodine ions are mixed. Thus, there is provided a very simple polymer production method in which radical polymerization accompanied by a termination reaction starts from a group having the above structure only by heating (heating) to obtain a polymer. In addition, according to the present invention, it is possible to easily obtain a polymer whose molecular weight or structure is controlled by simply adding a compound that liberates iodine to the above system, which involves a conventional termination reaction. Provided is a method for producing a polymer that could not be achieved by radical polymerization. According to the present invention, industrial production of, for example, ABA block copolymer, star polymer, bottle brush polymer, concentrated polymer brush, heterogeneous graft / block / multi-branched polymer, etc. by utilizing the above-described excellent production method. However, it is possible to easily obtain a polymer having a complicated structure which is difficult and complicated.

The production method of the present invention is environmentally useful and advantageous in terms of cost because the types of materials used for production are reduced as compared with conventional methods. Furthermore, the polymer production method of the present invention does not require the use of explosive compounds such as the conventionally used azo polymerization initiators and peroxide polymerization initiators. And the material does not need to be frozen and refrigerated as in the case of those initiators. In addition, since the production method of the present invention uses a compound in which a chlorine atom or a bromine atom is bonded to the polymerization initiating group, the bond is relatively stable, which is very useful for living radical polymerization. Although there is no need to use a polymerization initiating compound having an iodine atom that decomposes by heat or light, there is a great merit in storing materials. These mean that the polymer production method has extremely high practical value.

The method for producing a polymer capable of obtaining the above-described various excellent effects of the present invention can be realized for the first time by the radical polymerization initiator-containing compound of the present invention. The radical polymerization initiation group-containing compound of the present invention is a general-purpose compound that is not limited as long as one or more groups having a simple structure defined by the present invention are introduced. Specifically, it can be used as a general-purpose low molecular weight compound, polymer or monomer by appropriately changing the number of groups to be introduced and the form of the organic compound into which the group has been introduced. Therefore, by using the radical polymerization initiating group-containing compound of the present invention, ABA block copolymer, star polymer, bottle brush polymer, concentrated polymer brush, heterogeneous graft / block / multi-branched polymer, etc. designed to the desired structure Various polymers can be obtained easily and economically.

It is a figure which shows IR chart of the initiating group polymer-1. FIG. 3 is a view showing an NMR chart of an initiating group polymer-1.

Next, the present invention will be described in more detail with reference to preferred embodiments.
As a result of intensive studies to achieve the object of the present invention, the present inventors have used complicated materials using simple commercially available materials without using conventional materials with problems of safety and storage. The present invention has been accomplished by finding an unprecedented and completely new polymerization method which is extremely industrially useful and can easily obtain a polymer having a structure. In the production method of the present invention, a radical polymerizable monomer, an organic compound having a specific structure group functioning as a polymerization initiating group defined in the present invention, and a compound having iodine ions are mixed. By simply heating (heating), radical polymerization with a termination reaction can easily start and proceed from a group having a specific structure to obtain a polymer. The following configuration will be described in detail below.

In the method for producing a polymer of the present invention, at least (1) a radically polymerizable monomer and (2) a group having a structure represented by the following general formula 1 and / or general formula 2 that functions as a polymerization initiating group of the monomer are molecules One or more organic compounds introduced in the inside, and (3) one or more selected from the group consisting of metal iodide, quaternary ammonium iodide, quaternary phosphonium iodide, and quaternary ammonium triiodide It is characterized by having a specific polymerization step in which radical polymerization accompanied by a termination reaction starts from the group of the above structure by mixing and heating an iodine ion-containing compound which is an iodide salt or triiodide salt. Hereafter, each material which comprises this invention is demonstrated in detail.

[(1) Radical polymerizable monomer having an unsaturated bond]
In the polymer production method of the present invention, (1) a radically polymerizable monomer having an unsaturated bond, which is a polymer forming component, is used as an essential component. Examples of the monomer having an unsaturated bond include conventionally known monomers having an unsaturated bond, such as a monomer having a vinyl group, a vinylidene group, or a vinylene group. That is, any of conventionally known monomers capable of radical polymerization can be used and is not particularly limited.

For example, styrene, vinyl toluene, vinyl hydroxybenzene, chloromethyl styrene, vinyl naphthalene, vinyl biphenyl, vinyl ethyl benzene, vinyl dimethyl benzene, α-methyl styrene, ethylene, propylene, isoprene, butene, butadiene, 1-hexene, cyclohexene, cyclodecene , Dichloroethylene, chloroethylene, fluoroethylene, tetrafluoroethylene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, isocyanatodimethylmethane isopropenylbenzene, phenylmaleimide, cyclohexylmaleimide, hydroxymethylstyrene, styrenesulfonic acid, vinylsulfone Acid, vinylamine, allylamine, aminostyrene, vinylmethylamine, allylmethylamido , Methylaminostyrene, vinylpyridine, vinylimidazole, vinylbenzotriazole, vinylcarbazole, dimethylaminostyrene, diallylmethylamine, trimethylammonium styrene chloride, dimethyllaurylaminostyrene chloride, vinylmethylpyridinyl chloride, diallyldimethylammonium chloride These monomers are mentioned.

Moreover, the following (meth) acrylate type and (meth) acrylamide type monomers are mentioned. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-methylpropane (meth) acrylate, t-butyl (meth) Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) Acrylate, tetradecyl (meth) acrylate, octadecyl (meth) acrylate, behenyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclo Xylmethyl (meth) acrylate, isobornyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, cyclodecyl (meth) acrylate, cyclodecylmethyl (meth) acrylate, benzyl (meth) acrylate, t-butylbenzotriazole phenylethyl (meth) acrylate , Phenyl (meth) acrylate, naphthyl (meth) acrylate, allyl (meth) acrylate, and the like, aliphatic, alicyclic, and aromatic alkyl (meth) acrylates.

The monomers containing hydroxyl groups are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl ( Examples thereof include mono (meth) acrylates of alkylene glycol such as (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and cyclohexanediol mono (meth) acrylate.

A monomer having a glycol group, poly (n = 2 or more, the same applies hereinafter) ethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, mono or polyethylene glycol mono or Examples include mono (meth) acrylates of polyalkylene glycols such as mono (meth) acrylates of polypropylene glycol random copolymers, mono (meth) acrylates of mono or polyethylene glycol mono or polypropylene glycol block copolymers.

Furthermore, (poly) ethylene glycol monomethyl ether (meth) acrylate, (poly) ethylene glycol monooctyl ether (meth) acrylate, (poly) ethylene glycol monolauryl ether (meth) acrylate, (poly) ethylene glycol monostearyl ether ( (Meth) acrylate, (poly) ethylene glycol monooleyl ether (meth) acrylate, (poly) ethylene glycol monostearate (meth) acrylate, (poly) ethylene glycol monononylphenyl ether (meth) acrylate, (poly) propylene glycol Monomethyl ether (meth) acrylate, (poly) propylene glycol monoethyl ether (meth) acrylate, (poly) propylene glycol mono (Polyalkylene) glycol monoalkyl, alkylene, alkyne ether such as cutyl ether (meth) acrylate, (poly) propylene glycol monolauryl ether (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol monomethyl ether (meth) acrylate Or the mono (meth) acrylate of ester is mentioned.

The following monomers which are monomers having an acid group (carboxyl group, sulfonic acid, phosphoric acid) can also be used. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, acrylic acid dimer, itaconic acid, fumaric acid, crotonic acid, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth). Examples thereof include monomers obtained by reacting a hydroxyalkyl (meth) acrylate such as acrylate with maleic anhydride, succinic anhydride, phthalic anhydride, and the like, and monoester monomers of maleic acid and itaconic acid. Examples of the monomer having a sulfonic acid group include dimethylpropylsulfonic acid (meth) acrylamide, ethyl sulfonate (meth) acrylate, and ethyl (meth) acrylamide. Examples of the monomer having a phosphoric acid group include (di, tri) methacryloyloxyethyl phosphate.

Oxygen atom-containing monomers such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, oxetanylmethyl (meth) acrylate, morpholino (meth) acrylate, methylmorpholino (meth) acrylate, methylmorpholinoethyl (meth) acrylate Etc.

Examples of monomers having amino groups include the following. Examples of the monomer having a primary amino group include 2-aminoethyl (meth) acrylate and 2-aminopropyl (meth) acrylamide. Examples of the monomer having a secondary amino group include t-butylaminoethyl (meth) acrylate. , Tetramethylpiperidyl (meth) acrylate, t-butylaminopropyl (meth) acrylamide and the like. Examples of the monomer having a tertiary amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, pentamethylpiperidyl (meth) acrylate, N-ethylmorpholino (meth) acrylate, dimethylpropyl (meth) acrylamide and the like. Can be mentioned. Examples of monomers having a quaternary amino group include trimethylaminoethyl (meth) acrylate chloride, diethylmethylaminoethyl chloride (meth) acrylate, benzyldimethylaminoethyl chloride (meth) acrylate, and trimethylaminoethyl (meth) acrylate methyl sulfate. Is mentioned. In addition, examples include monomers obtained by reacting primary and secondary amines with glycidyl group-containing monomers such as glycidyl (meth) acrylate.

Nitrogen atom-containing monomers, for example, (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, and blocked isocyanate-containing (meth) acrylates blocked with isocyanates such as caprolactone, Ethyleneiminoethyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, etc. Amide monomers, N-vinylpyrrolidone, N-vinylacetamide, N-vinylcaprolactam and the like.

Furthermore, the following can be used as other monomers. Obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-butyrolactone using the (poly) alkylene glycol mono (meth) acrylic acid ester such as (meth) acryloyloxyethyl mono or polycaprolactone as an initiator. Polyester-based mono (meth) acrylic acid ester; 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl succinate, etc. (poly) An ester-based (meth) acrylate obtained by reacting an alkylene glycol mono (meth) acrylic acid ester with a dibasic acid to form a half ester and then reacting the other carboxylic acid with an alcohol or an alkylene glycol;

Mono (meth) acrylates of polyfunctional hydroxyl compounds having three or more hydroxyl groups such as glycerol mono (meth) acrylate and dimethylolpropane mono (meth) acrylate; 3-chloro-2-hydroxypropyl (meth) acrylate, octafluoro Halogen atom-containing (meth) acrylates such as octyl (meth) acrylate and tetrafluoroethyl (meth) acrylate; silicon atom-containing monomers having a trimethoxysilyl group and a dimethylsilicone chain; 2- (4-benzoxy-3-hydroxyphenoxy ) UV-absorbing monomers such as ethyl (meth) acrylate, 2- (2′-hydroxy-5- (meth) acryloyloxyethylphenyl) -2H-benzotriazole; and ethyl-α-hydroxymethyl acrylate α-position hydroxyl-substituted acrylates, and the like.

Furthermore, a cyclic vinyl monomer can be used, and a monomer having two or more addition polymerizable groups can be used as necessary. For example, divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, (meth) acrylic acid ester of polyalkylene glycol adduct of trimethylolpropane, (meth) acrylic acid of alkylene oxide adduct of bisphenol A Examples include esters. One or more kinds of the above-mentioned radical polymerizable monomers having an unsaturated bond can be used. Since the present invention aims to easily obtain an ABA block copolymer, a star polymer, a bottle brush polymer, a concentrated polymer brush, a heterogeneous graft / block / multi-branched polymer, etc., it is usually used in two or more kinds. Hereinafter, these monomers may be referred to as “monomer of (1)”.

[(2) Organic compound having at least one group having a structure represented by general formula 1 and / or general formula 2 in the molecule]
Next, the organic compound (2) (radical polymerization initiating group-containing compound) that functions as a polymerization initiating group for the monomer (1), which characterizes the present invention, will be described. According to the study by the present inventors, in the presence of a group having a structure represented by the following general formula 1 or 2 (hereinafter also referred to as “group of

formula

1 or 2”), the monomer of (1) and When the mixture is heated with the iodine ion-containing compound of 3), as a result, radical polymerization accompanied by termination reaction is initiated from the group having the above-mentioned specific structure characterizing the present invention, and various structures with controlled structures are obtained. A polymer is obtained.

The organic compound (2) used in the present invention and characterizing the present invention only needs to have the following structure introduced into the molecule, and this structure serves as a polymerization initiating group for the monomer (1). Function. The organic compound (2) is safer than conventional azo polymerization initiators and peroxide polymerization initiators, and the material is frozen and refrigerated like conventional initiators. There is no need to do. In addition, since a compound having a chlorine atom or bromine atom bonded thereto is used in the structure, the bond is relatively stable. Like a polymerization initiating compound having an iodine atom bonded in living radical polymerization, it can be heated or lighted. It won't break down.

The “group of

formula

1 or 2” defined in the present invention has a chlorine atom (also referred to as chloro) or a bromine atom (also referred to as bromo) bonded as X in the structure, and these atoms are reactive. Further, it is a group that can be eliminated or substituted, and furthermore, at least one or more electron withdrawing groups, carbon, to which these atoms are bonded, an ester group, an amide group, a cyano group, A carboxyl group or an aryl group is bonded. In the present invention, any organic compound having a structure in which one or more such groups are introduced into the molecule can be used. As the organic compound (2), for example, any form such as a low molecular weight compound, a monomer, and a polymer can be used. Hereinafter, “group of formula 1” and “group of formula 2” will be described.

First, “group of formula 1” is specifically exemplified, but is not limited to the following. Examples of the “group of formula 1” include those having an ester bond or an amide bond in the structure thereof as shown below. As shown below, an organic compound having one or more “groups of formula 1” used in the present invention introduced through an ester bond or an amide bond, as shown below, is a chlorine atom (Cl) or a bromine atom ( Br) is bound.

Examples thereof include groups having an ester bond or an amide bond of β-chloro or bromoalkanoic acid as described below.

Examples thereof include groups having an ester bond or an amide bond of β-chloro or bromoaryl-substituted alkanoic acid as described below.

Examples thereof include groups having an ester bond or an amide bond of chloro or bromo-substituted acetoalkanoic acid as described below.

Next, the “group of formula 2” is specifically exemplified, but is not limited to the following. Examples of the “group of formula 2” include the following groups, and those in which these groups are directly bonded to the organic compound can be used as the organic compound (2) defined in the present invention. .

For example, the following chloro or bromo substituted aryl substituted alkyl groups and the like can be mentioned.

Examples thereof include chloro- or bromo-substituted cyano group-containing alkyl groups as described below.

For example, the following chloro or bromo substituted alkanoic acid groups, esterified products of these carboxylic acids and the like can be mentioned.

Examples thereof include chloro or bromo-substituted alkanoic acid amides, alkyl mono-substituted and di-substituted groups of the nitrogen thereof, and the like.

The introduction of the “group of

formula

1 or 2” as exemplified above into the organic compound can be any method and is not particularly limited. For example, when the “group of formula 1” is introduced, it can be obtained by esterifying or amidating the corresponding carboxylic acid group-containing compound. Further, it can be obtained by reacting a compound having an “epoxy group” with a compound having “group of formula 1”. Further, X in the structure of the above-mentioned “group of

formula

1 or 2”, that is, a compound in which a hydroxyl group is bonded to a group to which chlorine or bromine is bonded, phosphorus halide, concentrated hydrochloric acid or bromide is used. You may introduce | transduce by substituting the hydroxyl part of this compound to chlorine and a bromine using a hydrogen acid. In addition, using a compound having an unsaturated bond at the C—X portion in the structure of the above “group of

formula

1 or 2,” hydrogen chloride or hydrogen bromide is added to the unsaturated bond to introduce chloro or bromo. May be. The above-mentioned method is an illustration, and is not particularly limited thereto, and conventionally known compounds and organic reactions are used.

As the organic compound (2) characterizing the present invention, any organic compound may be used as long as the “group of

formula

1 or 2” described above is introduced. According to the study by the present inventors, among the “groups of the formula 1,” a group having a structure represented by the following general formula 3 can be used because the initiation polymerization reaction rate is high and the synthesis can be easily performed with a commercially available compound. It is preferable to use an organic compound into which (hereinafter referred to as “group of formula 3”) is introduced.

(Y is O or NH)

The above-mentioned “group of formula 3” can be obtained by conventionally known materials and methods, and various forms of organic compounds into which “group of formula 3” is introduced can be easily obtained. It is not limited. Hereinafter, an example in which an organic compound having the “group of formula 3” introduced therein can be easily synthesized will be described. Using a 2-bromoisobutyric acid compound as a raw material, an organic compound having a group capable of reacting with its carboxy group and its derivative is used as the organic compound into which the “group of formula 3” is introduced, and these are reacted. The compound used in that case is not specifically limited. Examples of 2-bromoisobutyric acid compounds include 2-bromoisobutyric acid, 2-bromoisobutyric acid bromide, and anhydrous 2-bromoisobutyric acid. And these compounds and organic compounds having a reactive group that can react with a carboxyl group-based compound such as a hydroxyl group, an amino group, an epoxy group, a carbodiimide group, an oxazoline group, an isocyanate group, and an ethyleneimine group Can be introduced into an organic compound through an ester bond or an amide bond.

The compound of (2) characterizing the present invention is the above-mentioned “group of

formula

1 or 2” functioning as a polymerization initiating group of the monomer of (1), more preferably “group of formula 3” (these are (Sometimes collectively referred to as “groups of Formulas 1 to 3”) are organic compounds having one or more introduced in the molecule. As described above, the organic compound to be used may be in any form, and conventionally known organic compounds are used. There are so many kinds of conventionally known organic compounds that cannot be exemplified. In the following, by using the organic compound (2) that characterizes the present invention, an azo radical polymerization initiator, a peroxide radical polymerization initiator, and a photo radical polymerization initiator that are conventionally used in polymerization are used. It will be described that the monomer (1) can be polymerized and polymers having various structures can be formed without using any of them.

Using the organic compound of (2) in which one “group of formulas 1 to 3” defined in the present invention is introduced into the molecule, in combination with the iodine ion-containing compound of (3) described later, When the monomer of 1) is mixed and heated, polymerization starts with the organic compound of (2) as an initiating group and proceeds to obtain a linear polymer having a radical polymerizable monomer as a constituent component. . In addition, when the organic compound of (2) in which two “groups of formulas 1 to 3” are introduced in the molecule, a structure in which polymerization starts in a form in which two chains extend from the organic compound, Become. For this reason, when the form of the organic compound (2) used is a polymer component, if there are “groups of formulas 1 to 3” at both ends of the organic compound, the polymer is defined as B. When the monomer polymerization product is A, it can be an ABA block copolymer. Further, in this case, when the polymer form of the organic compound (2) to be used has two “groups of formulas 1 to 3” hanging in the molecule, the resulting polymer is converted into two comb structures. The polymer can be

(2) As the polymer as the organic compound, a conventionally known polymer can be used and is not particularly limited. Examples thereof include polymers such as polyether, polyester, polyamide, polyurethane, polyolefin, polyimide, polyacryl, polymethacryl, polystyrene, polycarbonate, polysilicone, polyhalogenated olefin, and polyvinyl alcohol. These may be polymers having any structure of homopolymers, copolymers, graft copolymers, and block copolymers.

In the production method of the present invention, when an organic compound having three or more “groups of formulas 1 to 3” introduced therein is used as the organic compound (2), a branched structure type polymer Or a star polymer or a graft polymer can be obtained. Among them, it is preferable to use a polymer of a vinyl monomer into which three or more “groups of formulas 1 to 3” are introduced as the organic compound (2). That is, when a vinyl polymer having “groups of formulas 1 to 3” introduced into the organic compound of (2) is used, the polymer obtained by polymerizing the monomer of (1) becomes the organic compound of (2). It becomes a bottle brush polymer having a structure grafted to a certain vinyl polymer or a bottle-like structure. By configuring the production method of the present invention as described above, a useful polymer having specific properties can be obtained industrially simply and inexpensively.

The above-mentioned vinyl polymer having the “groups of formulas 1 to 3” introduced therein may be obtained by polymerizing a monomer having the “groups of formulas 1 to 3” introduced therein, or a monomer having a hydroxyl group or the like in advance. After polymerization, “groups of formulas 1 to 3” may be introduced. Further, the copolymer may be obtained by copolymerizing a monomer having “groups of formulas 1 to 3” and the other monomer described above. In this case, the amount of the monomer into which the “group of formulas 1 to 3” is introduced is arbitrary and is not particularly limited.

Further, the polymer introduced with the above-mentioned “groups of formulas 1 to 3” used as the organic compound (2) is more preferably obtained by living radical polymerization because the molecular weight distribution becomes narrow. In the living radical polymerization method, a nitroxide method using a nitroxide radical (NMP method), a dithioester compound, or the like is used using a monomer in which “groups of formulas 1 to 3” are introduced. A reversible addition-cleavage chain transfer polymerization (RAFT method), a reversible transfer catalyst polymerization using an iodine compound and an organic catalyst (RTCP method), and the like are used, and are not particularly limited. However, atom transfer radical polymerization utilizing redox is not preferred because it may cause gelation because of polymerization of monomers and initiation of polymerization from chloro or bromo groups.

Further, a monomer having the “groups of formulas 1 to 3” introduced therein and a reactive monomer as another monomer component, in particular, are copolymerized, and a copolymer having this reactive group is used. Then, the surface of the article is treated, and then the polymer of (1) is polymerized using the “groups of formulas 1 to 3” constituting the copolymer as a polymerization initiating group, thereby grafting the polymer onto the article surface. Can be introduced. That is, the surface of the article can be modified by the polymer introduced by grafting. Furthermore, when the polymerization method using the monomer having the “groups of formulas 1 to 3” is living radical polymerization, the introduction rate of the specific monomer into the copolymer is constant and stopped. Since there is no reaction, it is possible to introduce a dense polymer brush structure in which the polymer is an extended chain and the molecular weight is uniform.

Specifically, in this case, for example, the organic compound (2) is used as a polymer component as described below. First, a polymer in which a “group of formulas 1 to 3” is introduced and a vinyl monomer having an alkoxysilyl group is copolymerized with a vinyl monomer having an alkoxysilyl group and having an alkoxysilyl group As a component, this is applied to the surface of a substrate such as glass, metal, plastic and the like, surface-modified, and then the “groups of formulas 1 to 3” characterizing the present invention function as a polymerization initiating group. By performing radical polymerization of the monomer 1), a rich brush structure can be easily introduced into the article.

As described above, in the production method of the present invention, as the organic compound (2), an organic compound into which one or more “groups of formulas 1 to 3” are introduced can be used. However, more preferably, a compound having two or more “groups of the formulas 1 to 3” is used. By comprising in this way, the polymer of the structure which was not able to be obtained easily with the prior art can be obtained simply. That is, when the number of “groups of formulas 1 to 3” is 1, the polymer obtained by the production method of the present invention is linear as described above. Since a linear polymer can be obtained by ordinary radical polymerization or living radical polymerization, it is compared with the production method of the present invention using an organic compound in which two or more “groups of formulas 1 to 3” are introduced. And the benefits are not so great.

In addition, the molecular weight of the resulting polymer may be controlled by adjusting the amount of the “group of formulas 1 to 3” introduced into the organic compound (2). This is also the case with the production method of the present invention. It is a feature. In the production method of the present invention, the polymerization is started from the “groups of formulas 1 to 3” introduced into the organic compound of (2). Therefore, with respect to 1 mol of the compound containing “groups of formulas 1 to 3”, The molecular weight of the polymer to be produced can be adjusted by adjusting the amount of the monomer 1). However, this polymerization is accompanied by a termination reaction such as radical polymerization, and there are cases in which a high molecular weight can be obtained by coupling. In this case, adjustment cannot be made by the amount of the initiating group. In this case, it can be avoided by adding a catalyst described later.

[(3) Iodine ion-containing compound which is iodide salt or triiodide salt]
In the method for producing a polymer of the present invention, (3) one or more iodide salts selected from the group consisting of metal iodide, quaternary ammonium iodide, quaternary phosphonium iodide and quaternary ammonium triiodide. Alternatively, it is essential to use an iodine ion-containing compound that is a triiodide salt. Hereinafter, these compounds will be described. The details of the action of these compounds have not been elucidated. According to the study by the present inventors, it is considered that by using these compounds, bromine in the above-mentioned “groups of formulas 1 to 3” is replaced with iodine, and polymerization in which iodine moves occurs. In addition, these compounds may act as a redox catalyst to promote polymerization. Hereinafter, the above-described iodine ion-containing compound may be referred to as “iodination agent” or (3) compound.

The compound (3) is a compound having iodine ions, and is selected from the group consisting of metal iodide, quaternary ammonium iodide, quaternary phosphonium iodide, and quaternary ammonium triiodide. The compounds which are the above-described iodide salts or triiodide salts, and conventionally known compounds can be used, and are not particularly limited. Specifically, examples of the metal iodide include lithium iodide, sodium iodide, potassium iodide, calcium iodide, magnesium iodide and the like. Examples of the quaternary ammonium iodide include tetramethylammonium iodide, tetraethylammonium iodide, and tetrabutylammonium iodide. Examples of the quaternary phosphonium iodide include tetrabutylphosphonium iodide, tributylmethylphosphonium iodide, triphenylmethylphosphonium iodide, and the like. Examples of the quaternary ammonium triiodide include tributylmethylammonium triiodide. Any compound can be used as long as it has iodine ions.

The amount of the iodinating agent in (3) is preferably about equimolar to the “groups of formulas 1 to 3” in (2) to be used in combination, but the amount used may be determined according to the polymer to be produced. There is no particular limitation. For example, if the number of moles of “groups of formulas 1 to 3” to be substituted with iodine is added, iodinated, and subjected to the polymerization step specified in the present invention, polymerization is performed with the amount of the iodinating agent of (3). You can adjust the number of chains. Further, since the remaining “groups of formulas 1 to 3” are the starting groups of atom transfer radical polymerization which is redox living radical polymerization, as described above, by this atom transfer radical polymerization, other polymerization is performed. The vinyl polymer can be introduced by the method.

[(4) Iodine or an iodine iodide organic compound or organic base compound capable of liberating iodine]
In the method for producing a polymer of the present invention, the materials (1) to (3) described above are used, and when these are mixed and heated, radical polymerization starts and proceeds to obtain a polymer. According to the study by the present inventors, in addition to the above-mentioned materials, further, from the compound having an organic base such as an iodine iodide, an organic compound capable of liberating iodine, and an organic amine as described in (4). It is preferable to add any one selected and perform the polymerization step. According to the study by the present inventors, by further adding these components, the radical polymerization termination reaction described above can be prevented, and high molecular weight and gelation can be prevented. Although its action is unclear, the present inventors believe that iodine or amino groups become radicals and contribute to the prevention of growth radical coupling. Hereinafter, the component (4) may be simply referred to as “catalyst (4)”.

The catalyst of (4) may be iodine, an organic iodide compound capable of liberating iodine and a compound having an organic base, and conventionally known compounds are used, and they are not particularly limited. Examples other than iodine are specifically exemplified. Any compound can be used as the iodinated organic compound capable of releasing iodine since iodine is released by heat or light as long as iodine is bonded. N-iodoimide-based compounds are preferable, and N-iodosuccinimide, N-iodophthalimide, N-iodocyclohexanilimide, and 1,3-diaiodo-5 which are easily available as commercial products are preferable. , 5-dimethylhydantoin, N-iodosaccharin and the like. As the compound having an organic base, conventionally known compounds such as triethylamine, tributylamine, diazabicycloundecene (DBU), diazabicyclooctane (DABCO), and phosphazene base can be used.

The amount of the catalyst (4) is arbitrary and is not particularly limited. Preferably, it is used in the range of 0.001 to 0.1 mol times the “group of formulas 1 to 3” of (2) which functions as a polymerization initiating group to be used in combination. If the amount used is too large, the effect as a catalyst is not sufficiently exhibited, and a side reaction or the like may occur.

[solvent]
Below, the other material which can be used for the manufacturing method of the polymer of this invention is demonstrated. The polymerization step of the method for producing a polymer of the present invention is preferably solution polymerization in which polymerization is performed using an organic solvent. This is because an ionic material such as (3) cannot be dissolved in the monomer material of (1), and chlorine in the structure of “groups of formulas 1 to 3” of (2) Alternatively, the exchange of bromine and iodine ion of the iodinating agent of (3) must be performed by dissolving the iodinating agent as described above. For this purpose, an organic solvent having a high polarity as listed below is used. It is preferable to use for part or all. Specifically, it is preferable to use a solvent that is an alcohol, glycol, amide, sulfoxide, or ionic liquid. However, these solvents are not always necessary. For example, when a monomer that dissolves an iodinating agent is used, polymerization can be performed without using an organic solvent. Commonly used organic solvents include conventionally known nonpolar solvents such as hydrocarbons, halogens, ketones, esters, glycols, etc., in combination with these solvents, A high solvent may be used. In that case, the ratio of the solvent having high polarity is arbitrary, and the solvent is selected so as to dissolve the polymer of the present invention obtained by polymerizing the monomer.

As described above, conventionally known solvents can be used, and preferable solvents include alcohols, glycols, amides, sulfoxides, and ionic liquids. Specific examples include alcohol solvents such as methanol, ethanol and isopropanol; glycol solvents such as ethylene glycol, propylene glycol, glycerin, diethylene glycol and propylene glycol monomethyl ether; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 3- Amide solvents such as methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide; sulfoxide solvents such as dimethyl sulfoxide; ionic liquids such as imidazolium salts and quaternary ammonium salts Can be used alone or in combination of two or more.

The amount of these solvents used during polymerization is not particularly limited as long as the iodinating agent (3) is dissolved. Preferably, it is 30% to 80% by mass. If it is less than 30%, the solid content may be too high, resulting in a high viscosity. If it is more than 80%, the monomer concentration may be too low to increase the polymerization rate. More preferably, it is 40% to 70%.

The polymer production method of the present invention is basically characterized in that it is not necessary to use a radical polymerization initiator that generates radicals. Conventionally, when a monomer having an unsaturated bond is polymerized, the polymerization is performed using a compound that generates a radical such as azo, peroxide, or thiol. However, in the production method of the present invention, without using such a radical polymerization initiator, the above-described materials (1) to (3) are mixed and polymerization proceeds easily by heat. In some cases, it is expected that a polymer by the polymerization method of the present invention can be obtained even if a radical polymerization initiator is used in combination. However, in that case, since polymerization from a radical polymerization initiator may also start, it is not preferable for the purpose of obtaining a polymer having a desired complicated structure. In the production method of the present invention, it is preferable to perform polymerization without using a radical polymerization initiator. That is, since radical polymerization starts from the structure of “groups of formulas 1 to 3”, as described above, the amount of the organic compound into which “groups of formulas 1 to 3” are introduced, and (3) Since the molecular weight can be controlled by the amount of the iodinating agent, and a polymer derived from a radical initiator cannot be produced, normal radical polymerization is controlled, and only a polymer using “groups of formulas 1 to 3” is obtained. Can do.

[Polymerization process]
The above are the materials necessary for the production method of the polymer according to the present invention. In the present invention, these materials are mixed and heated (heated), so that the radicals of the monomer can be converted from “groups of formulas 1 to 3”. Polymerization starts and proceeds to obtain a polymer. The polymerization conditions are not particularly limited, and conventionally known methods are used. When more preferable specific conditions are listed, in a nitrogen or argon atmosphere or bubbling, there is no influence of oxygen and the polymerization proceeds well. Further, the temperature may be room temperature or higher, for example, 40 ° C. or higher, but if it is about room temperature, it takes a lot of polymerization time. This is suitable in that a preferable production time can be realized in practical production. Further, the stirring speed does not particularly affect the polymerization, and light shielding is not always necessary. The polymerization rate is also arbitrary, and the monomer may not be completely consumed.

[polymer]
In the polymer production method of the present invention, the respective materials described above are prepared, mixed, and heated under the above conditions, whereby the polymer can be easily produced. Furthermore, by appropriately designing the form of the radical polymerization initiating group-containing compound (2) that characterizes the present invention, it is easier to use the catalyst (4) as required. A polymer having a desired specific (complex) structure can be obtained industrially. Specifically, by using the production method of the present invention, a desired polymer controlled in various forms as described below can be easily provided. Polymers provided include linear polymers, AB block polymers, ABA block polymers, branched polymers, graft polymers, star polymers, concentrated polymer brushes, bottle brush polymers, and the like.

According to the production method of the present invention using the radical polymerization initiating group-containing compound (2) that characterizes the present invention, it is possible to synthesize various polymers as described above in a simpler manner than ever before. Can do. To describe a specific example, a bottle brush polymer, which is a dense graft polymer, can be synthesized using a conventionally known commercially available material without purification and in some cases in one pot. More specifically, first, glycidyl methacrylate and bromoisobutyric acid are reacted with tetraethylammonium bromide as a catalyst in an amide solvent to open an epoxy group and introduce an “ester of formula 3” as an ester. The obtained monomer is obtained. Next, radical polymerization with an azo initiator added to the system, or in addition, polymerization with reversible transfer catalyst polymerization using iodine, azo initiator, diphenylmethane as a catalyst, A polymer which is an organic compound of (2) in which “group 3” is introduced. Next, tributylammonium iodide as the iodinating agent of (3), the monomer of (1), and N-iodosuccinimide as the catalyst of (4) as a preferred form are added to this, and this is mixed and heated. By carrying out the polymerization step defined in the invention, a bottle brush can be synthesized in one pot without purifying each material.

The polymer obtained as described above may be used as it is, or may be added to a poor solvent, precipitated, purified, and a polymer component may be used.

The use of the obtained polymer can be used for conventionally known applications and is not particularly limited. For example, the present invention can be applied to various fields such as inks, paints, coatings, plastics, inkjet inks, color filter materials, energy-related materials, mechanical component-related materials, medical devices, medical materials, and pharmaceuticals.

Hereinafter, the present invention will be described in more detail with reference to Examples, Synthesis Examples and Comparative Examples, but the present invention is not limited to these Examples. Hereinafter, “parts” and “%” in the text are based on mass unless otherwise specified. Hereinafter, an example of the method for producing a polymer of the present invention is referred to as an example, and an example of a radical polymerization-initiating group-containing compound of the present invention is referred to as a synthesis example.

[Example 1]
To a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 100.0 parts of 3-methoxy-N, N-dimethylpropanamide (hereinafter abbreviated as MDPA) as a solvent, As an organic compound, 4.0 parts of ethyl 2-bromoisobutyrate, 100.0 parts of methyl methacrylate (hereinafter abbreviated as MMA) as a monomer of (1), sodium iodide as an iodinating agent of (3) 3.0 parts was charged, heated to 75 ° C. while bubbling nitrogen, and polymerized for 7 hours. The polymerization rate of the obtained polymer was 95%, the number average molecular weight (hereinafter abbreviated as Mn) was 7600, and the molecular weight distribution (weight average molecular weight / number average molecular weight, hereinafter abbreviated as PDI) was 1.87. From the above, it was confirmed that according to the production method of the present invention, a polymer can be obtained without using a conventionally used azo-based or peroxide-based radical generator.

The polymerization rate in the above was calculated by drying the solution at 180 ° C. and measuring the nonvolatile content. In the following examples, the same method was used. The molecular weight is measured by gel permeation chromatograph (GPC), and the solvent is tetrahydrofuran (THF) unless otherwise specified, and has a molecular weight in terms of polystyrene. In the following examples, the measurement was performed in the same manner.

In the reaction system carried out above, the same operation as above was carried out for each of the cases where (3) sodium iodide was not used and (2) ethyl 2-bromobutyrate was not used. . However, in either case, the polymerization did not proceed and a polymer could not be obtained. On the other hand, when tetrabutylammonium iodide is used instead of sodium iodide of (3), tributylmethylphosphonium iodide is used, and when tetrabutylammonium triiodide is used, the same as above. As a result, the same polymer as in the case where sodium iodide was used could be obtained.

[Example 2]
In the same manner as in Example 1, 0.2 part of N-iodosuccinimide (hereinafter abbreviated as NIS) was further added to the system of Example 1 as the component (4) defined in the present invention. Polymerized for 7 hours. When sampled at this time, the polymerization rate was 68%, Mn was 5200, and PDI was 1.43. Then, when further polymerizing for 5 hours under the same conditions, the polymerization rate reached 95%, Mn was 8700, and PDI was 1.47. From comparison with the polymer obtained in Example 1, it was confirmed that by adding an N-iodide compound as a catalyst in the system, the polymerization was controlled and the particle size distribution of the obtained polymer was narrowed.

[Example 3]
To the system of Example 2, 1.0 part of triethylamine was further added as a compound having an organic base as the component (4) defined in the present invention, and polymerization was carried out in the same manner. When sampled after 7 hours, the polymerization rate reached 91%, Mn was 7800, and PDI was 1.61. From the comparison with Example 2, it was confirmed that the polymerization rate was increased, and from the comparison with Example 1, it was confirmed that a polymer whose particle size distribution was controlled to some extent could be obtained.

[Examples 4 and 5]
In the system of Example 2, when 2.8 parts of ethyl 2-chloroisopropionate was used instead of 4.0 parts of ethyl 2-bromoisobutyrate in (2) (Example 4), When 3.3 parts of ethyl onate were used (Example 5), a polymer was prepared in the same manner as in Example 2 except that the heating conditions were changed. Polymerization was carried out at 85 ° C. in Example 4 using ethyl 2-chloroisopropionate and 80 ° C. in Example 5 using ethyl 2-bromoisopropionate. Sampling was conducted after 7 hours, and the polymerization rate and molecular weight were measured. In the case of Example 4, the polymerization rate was 82%, Mn was 7600, and PDI was 1.65. In the case of Example 5, the polymerization rate was Was 79%, Mn was 6900, and PDI was 1.56. From the above, it was confirmed that each compound used above also functions as a polymerization initiation group.

[Synthesis Example 1-Preparation of Initiating Group-Containing Polymer for Radical Polymerization]
Using the same reaction apparatus as in Example 1, 561.0 parts of MDPA and 1.0 part of iodine as solvents, 2,2′-azobis (4-methoxy-2,4-dimethyl) as an azo polymerization initiator Valeronitrile) [trade name: V-70 (hereinafter abbreviated as V-70), manufactured by Wako Pure Chemical Industries, Ltd.] 3.7 parts, 2-hydroxyethyl methacrylate 208.0 parts, and NIS 0.113. Then, polymerization was carried out at 65 ° C. for 7 hours while bubbling nitrogen. As a result, the polymerization rate of the obtained polymer was approximately 100%, and the molecular weight of the polymer was measured with a GPC apparatus using a dimethyl sulfoxide solvent. As a result, Mn was 18500 and PDI was 1.35.

Next, 189.5 parts of pyridine was added to the above reaction system and cooled to 5 ° C. in an ice bath. To the dropping funnel was charged 459.8 parts of 2-bromoisobutyric acid bromide, and the dropping funnel was attached to the above apparatus. The dropping funnel was dropped in 3 hours so as not to exceed 10 ° C., and left at that temperature for 2 hours. Then, it heated at 45 degreeC and made it react for 1 hour. And after cooling to room temperature, 561 parts of methanol was added and stirred. Next, 5000 g of methanol was prepared in a separate container, and the above solution was gradually added while stirring with a disper. The polymer precipitated and a soft polymer was obtained. The polymer was collected, added to a large amount of water while stirring with a disper, washed, filtered, washed with water, and dried with a blow dryer at 50 ° C. until there was no volatile matter. As a result, a white powdery solid was obtained.

The white powdery solid obtained by the above operation becomes a polymer in which a group having the structure of the general formula 3 defined by the present invention (“group of formula 3”) is bonded to a side chain, as shown below. A powdered solid can be confirmed by identification with an infrared spectrophotometer (IR) or nuclear magnetic resonance apparatus (NMR) to be a polymer having a plurality of “groups of formula 3” introduced in the side chain. It was. Hereinafter, this is referred to as initiating group polymer-1. The IR chart of this starting group polymer-1 is shown in FIG. 1, and the NMR chart is shown in FIG. Further, when the molecular weight of the initiating group polymer-1 was measured with a THF solvent GPC, Mn was 26000 and PDI was 1.41.

[Synthesis Example 2, 3-Preparation of radical-containing polymerization initiator group-containing polymer]
Two types of initiator polymers having different molecular weights were synthesized in the same manner as in Synthesis Example 1 except that the amounts of iodine and V-70 used in Synthesis Example 1 were changed. Specifically, the amount of iodine was 1.2 parts, the amount of V-70 was 4.4 parts, and Synthesis Example 2 was obtained, the amount of iodine was 0.75 parts, and V-70 was 2. 8 parts were used as Synthesis Example 3, and the resulting white powdery solids were used as initiator group polymers-2 and -3, respectively. The structure of the synthesized product was confirmed using IR and NMR as in Synthesis Example 1. As a result, all were polymers in which the “group of formula 3” was introduced into the side chain. As a result of measuring the molecular weight in the same manner as in Synthesis Example 1, the initiating group polymer-2 had Mn of 14500 and PDI of 1.38, and the initiating group polymer-3 had Mn of 31400 and PDI of 1.55. Met.

[Example 6]
Using the same reaction apparatus as in Example 1, 200 parts of MDPA as a solvent, 200 parts of MMA of (1), 6 parts of initiating group polymer-1 prepared in Synthesis Example 1 of (2), (3 ) Was charged with 7.9 parts of tetrabutylammonium iodide (hereinafter abbreviated as TBAI), 0.3 parts of NIS as the component (4) was added, and polymerization was carried out at 75 ° C. for 8 hours. Since the polymerization progressed to become a highly viscous liquid, it was sampled and the polymerization rate was measured and found to be 87%. Moreover, Mn was 2970000 and PDI was 1.48. From this, as described above, when polymerizing in the presence of the initiator polymer-1 in which the “group of formula 3” is introduced into the side chain, the resulting polymer has a structure in which the main chain has a side chain. It was confirmed that a high molecular weight polymer can be obtained.

[Examples 7 and 8]
Instead of the initiating group polymer-1 used in Example 6, initiating group polymer-2 was used in Example 7, initiating group polymer-3 was used in Example 8, and the others were the same as in Example 6. Each was polymerized. As a result, the polymer obtained using Initiator Polymer-2 having a molecular weight smaller than that of Initiator Polymer-1 used in Example 6 had a polymerization rate of 95%, Mn of 1870000, and PDI of 1.45. there were. On the other hand, the polymer obtained using Initiator Polymer-3 having a molecular weight larger than that of Initiator Polymer-1 used in Example 6 had a polymerization rate of 80%, Mn of 330000, and PDI of 1.72. Met. From this, it was confirmed that the molecular weight of the finally obtained polymer can be adjusted by the difference in the molecular weight of the starting group polymer used.

[Example 9]
Polymerization was carried out in the same manner as in Example 6 except that 6 parts of the used amount of the starting group polymer-1 was changed to 4 parts and 8 parts, respectively. As a result, when 4 parts of the starting group polymer-1 were used, the polymerization rate was 71%, Mn was 3210000, and PDI was 1.56. When 8 parts of the starting group polymer-1 were used, the polymerization rate was It was 89%, Mn was 190000, and PDI was 1.42. From the above results, it was found that the molecular weight of the finally obtained polymer can be adjusted also by the amount of the starting group polymer used, that is, the amount of the starting group.

[Comparative Example 1]
Using the same reaction apparatus as in Example 1, 200 parts of MDPA as a solvent, 0.29 parts of first copper bromide, 0.52 parts of pentamethyldiethylenetriamine, obtained in Synthesis Example 1 (2) 6 parts of the initiating group polymer-1, 200 parts of MMA of (1) and 0.22 part of tin dioctanoate were added and mixed well while bubbling nitrogen. The temperature was then raised to 65 ° C. As a result, the viscosity increased during heating, causing gelation, and the polymerization was stopped. The reason is that the reaction in this case is atom transfer radical polymerization, and the polymerization proceeds by oxidation-reduction, but the side reaction is terminated, and the solid content concentration is high. This is probably because the gelation of the polymer by Polymer-1 was remarkable.

Therefore, the amount of MDPA was increased from 200 parts to 600 parts, and the polymerization was carried out by lowering the viscosity. Although the temperature reached 65 ° C., gelation did not occur and polymerization proceeded. After 7 hours, the viscosity became high, and when sampled, the polymerization rate was 45%. Further, in order to measure GPC, when dissolved in a THF solution and applied with a 0.45 μm filter, clogging occurred. And when the molecular weight of the filtration part was measured, the high molecular weight body had arisen, Mn was 5400000, and the particle size distribution was a 2 Cobb peak. From the above, although the polymerization has progressed, it has become a high molecular weight and is a step before gelation, and when this situation occurs industrially, it becomes difficult to use the reactor, accidents, etc. It cannot be used industrially because it may cause danger. On the other hand, as shown in the previous Examples 6 to 8, according to the production method of the present invention, it has a high solid content, a high molecular weight without gelation even at a high polymerization rate, and a multi-branched type. Since a polymer having a structure can be obtained, this is a useful method that can be used industrially to obtain various polymers.

[Examples 10 and 11]
Instead of the MMA (1) used in Example 6, Example 10 used lauryl methacrylate (hereinafter abbreviated as LMA) as the monomer (1), and Example 11 used cyclohexyl methacrylate (hereinafter CHMA). The abbreviation was used for the monomer of (1), and polymerization was carried out in the same manner as in Example 6 except that. As a result, in Example 10 using LMA, the polymerization rate of the obtained polymer was 95%, Mn was 350,000, and PDI was 1.32. The obtained polymer was precipitated in methanol, and the polymer content was collected and dried to remove methanol. As a result, it was a viscous liquid and was a liquid despite having a high molecular weight. In Example 11 using CHMA, the polymerization rate of the obtained polymer was 70%, Mn was 181000, and PDI was 1.78. From these facts, it was confirmed that the production method of the present invention is not limited to MMA but can be applied to polymerization of other methacrylate monomers.

[Example 12]
Instead of the MMA (1) used in Example 6, butyl acrylate was used and the temperature was set to 120 ° C. to carry out the polymerization. As a result, at 7 hours, the polymerization rate was 57%, the molecular weight was 114,000, and the PDI was 1.89. From this, it was confirmed that the production method of the present invention can be applied to the polymerization of acrylate monomers.

[Synthesis Example 4-Preparation of Polymer Initiating Group for Radical Polymerization]
Using the same reaction apparatus as in Example 1, 370.2 parts of solvent propylene glycol monomethyl ether (hereinafter abbreviated as PGM), 85.1 parts of glycidyl methacrylate, 100 parts of 2-bromoisobutyric acid, methoxyphenol 1.0 part and 4.6 parts of tetraethylammonium bromide were mixed and reacted at 90 ° C. for 8 hours. When the acid value of the obtained reaction product was measured, it was 0.4 mgKOH / g, and most of 2-bromoisobutyric acid was reacted. Further, the generation of hydroxyl groups and the disappearance of epoxy groups were confirmed by IR. From this, it can be seen that the obtained reaction product is a methacrylate having a “group of formula 3” introduced by reacting an epoxy group of glycidyl methacrylate with a carboxylic acid.

Next, this solution was cooled to 65 ° C., and in another container, 185.1 parts of benzyl methacrylate (BzMA), 2,2′-azobis (2,4-dimethylvaleronitrile) (hereinafter referred to as V-65). ) 5.6 parts were mixed and the homogenized one was charged into a dropping funnel, one third of the mixture was added, and then dropped over 1 hour. Furthermore, polymerization was continued for 7 hours at that temperature. When the polymerization rate was measured by sampling at that time, it was almost 100%, and the nonvolatile content was 50.3%. Moreover, Mn was 8900 and PDI was 2.31. The resulting polymer is referred to as initiator group polymer-4, and this solution is referred to as initiator group polymer-4 solution.

[Example 13]
Using the same reactor as in Example 1, 194 parts of PGM as the solvent, 100 parts of MMA as the monomer of (1), 100 parts of butyl methacrylate (BMA), the start of (2) obtained above 12 parts of the base polymer-4 solution and 7.4 parts of (3) tributylmethylphosphonium iodide were added, and polymerization was carried out at 80 ° C. for 7 hours. When the solid content was measured after the completion of the polymerization, it was 96.1%, Mn was 198000, and PDI was 2.6. As a result, it was confirmed that a graft polymer could be formed without refining each material, and that the initiator polymer-4 could be used for polymerization even with a random copolymer.

[Example 14]
Using the same reactor as in Example 1, 200 parts of MDPA, 100 parts of MMA of (1), 6 parts of initiator group polymer-1 of (2) prepared in Synthesis Example 1, and TBAI of (3) Was added as a component of (4), 0.3 parts of NIS and 1 part of triethylamine were added and polymerized at 75 ° C. for 5 hours. Polymerization progressed to become a highly viscous liquid. Sampling was performed at that time, and the polymerization rate was measured and found to be 68%. Moreover, Mn was 154000 and PDI was 1.59. Subsequently, 100 parts of polyethylene glycol monomethyl ether methacrylate (1) (molecular weight of about 400, hereinafter referred to as PME) was added, and polymerization was further performed for 6 hours. When the molecular weight was measured after the polymerization, Mn was 387000 and PDI was 2.45, and it was confirmed that the molecular weight was increased from the time point measured previously. From this, from the polymerization of MMA at the time when the polymerization rate was 68%, it was presumed that the added PME and the residual monomer MMA were polymerized into a block copolymer to obtain a block copolymer having a multi-branched structure. I was able to. When this was precipitated in water, it became a slimy sloppy polymer.

[Synthesis Example 5-Preparation of radical-initiating group-containing polymer having alkoxysilyl group as reactive group]
An initiating group polymer was obtained according to the following formulation. In the same reactor as in Example 1, 50.0 parts of MDPA, 20.8 parts of 2-hydroxyethyl methacrylate, and 18.9 parts of pyridine were added and cooled to 5 ° C. in an ice bath. The dropping funnel was charged with 45.9 parts of 2-bromoisobutyric acid bromide and attached to the apparatus, and dropped in 3 hours so as not to exceed 10 ° C. Then, after dropping, the mixture was allowed to stand at that temperature for 2 hours, and then heated to 45 ° C. and reacted for 1 hour. After cooling to room temperature, 200 parts of ethyl acetate was added, then a large amount of water was added, and the monomer obtained in a separatory funnel was extracted. Next, after washing several times with a large amount of water and drying with anhydrous magnesium chloride, the solvent was removed with an evaporator, and the target product 2- (2-bromomethacrylate), which was the target product, was obtained with a fractionator. -2methylpropionyloxy) ethyl ester (hereinafter abbreviated as BMPMA).

Next, using the same reaction apparatus as in Example 1, 100 parts of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMAc) was charged and heated to 85 ° C. In a separate container, 80 parts of BMPMA obtained above, 20 parts of 3-methacryloxypropyltriethoxysilane, 3 parts of 2,2′-azobis (isobutyric acid) dimethyl (V-601), and 100 parts of PGMAc A monomer mixed solution was prepared. And 1/3 of said monomer mixed solution was added into the reaction apparatus which prepared PGMAc using the dripping apparatus, and the remaining solution was dripped over 3 hours then. Subsequently, polymerization was carried out at a temperature of 85 ° C. for 7 hours. As a result, a polymer having a polymerization rate of almost 100%, Mn of 12000, and PDI of 2.21 was obtained. Subsequently, the obtained polymer was cooled, and PGMAc was added to obtain a polymer solution having a solid content concentration of 5%. This is an initiating group polymer-5 having a “group of formula 3” functioning as a polymerization initiating group and having an alkoxysilyl group as a reactive group. This solution is referred to as initiator group polymer-5 solution.

[Example 15]
10 parts of the initiator group polymer-5 solution having an alkoxysilyl group in the reactive group obtained in Synthesis Example 5, 10 parts of ethanol, and 2 g of 25% aqueous ammonia were mixed to obtain an initiator group polymer mixed solution. Next, a silicon substrate cut into 5 cm squares was prepared, and the above initiator group polymer mixed solution was spin-coated on one surface (hereinafter referred to as the front surface) of the substrate with a spin coater. Thereafter, it was dried and baked at 80 ° C. for 10 minutes and at 150 ° C. for 10 minutes. As a result, in the silicon substrate, the polymerization initiating group is surely introduced into the front surface of the substrate. That is, in the substrate obtained as described above, a group that initiates polymerization exists in the form of a polymer film in a high concentration state on the front surface of the substrate, and the alkoxysilyl group is firmly bonded to the silicon substrate. It will be in the state.

Next, in the same reaction apparatus as used in Example 1, 100.0 parts of the above-obtained silicon substrate and MDPA as a solvent, 0.04 part of (2-) ethyl 2-bromoisobutyrate, (1) 100.0 parts of MMA and 1 part of TBAI of (3) were charged, heated to 75 ° C. while bubbling nitrogen, and polymerized for 14 hours. After the reaction, the silicon substrate was taken out to obtain a polymer-treated silicon substrate in which polymethyl methacrylate (PMMA) was grafted on the front surface of the substrate into which the polymerization initiating group had been introduced. The polymer of ethyl 2-bromoisobutyrate that functions as the above polymerization initiating group has Mn of 28700 and PDI of 1.67, and this polymer is considered to be introduced on the surface of the silicon substrate. If the technique of this embodiment is utilized, it is possible to grow a polymer brush on the surface of a substrate made of various materials, and the material surface can be variously modified. Be expected.

[Example 16: Synthesis of hyperbranched polymer-1]
Using the same reaction apparatus as in Example 1, 100.0 parts of MDPA as a solvent, and 1. pentaerythritol tetrakis (2-bromoisobutyrate) having 4 polymerization initiating groups as an organic compound of (2) 83 parts, 100.0 parts of MMA of (1) and 4.1 parts of TBAI of (3) were charged and heated to 75 ° C. while bubbling nitrogen, and then 0.74 of triethylamine of (4) Part was added and polymerized for 7 hours. The polymerization rate of the obtained polymer was 94.8%, Mn was 26000, and PDI was 1.49. From this, it was confirmed that a 4-chain multi-branched polymer was obtained.

[Example 17: Synthesis of hyperbranched polymer-2]
Using the same reaction apparatus as in Example 1, 100.0 parts of MDPA as a solvent and dipentaerythritol hexakis (2-bromoisobutyrate) having 6 polymerization initiating groups as an organic compound of (2) 1.91 parts, 100.0 parts of MMA of (1), 4.1 parts of TBAI of (3), were charged, heated to 75 ° C. while bubbling nitrogen, then triethylamine 0 of (4) .74 parts were added and polymerized for 7 hours. The polymerization rate of the obtained polymer was 93.3%, Mn was 44500, and PDI was 1.46. From this, it was confirmed that a 6-chain multi-branched polymer was obtained.

[Synthesis Example 6-Preparation of Initiating Group-Containing Polymer for Radical Polymerization]
An initiating group polymer was obtained according to the following formulation. In the same reactor as in Example 1, 50.0 parts of MDPA as a solvent, 25.9 parts of 4-tert-butylcalix [8] arene, and 18.9 parts of pyridine were added, and the temperature was adjusted to 5 ° C. with an ice bath. Cooled down. A dropping funnel was charged with 45.9 parts of 2-bromoisobutyric acid bromide and mounted on the apparatus, and dropped in 3 hours so as not to exceed 10 ° C. Then, after dropping, the mixture was allowed to stand at that temperature for 2 hours, and then heated to 45 ° C. and reacted for 1 hour. After cooling to room temperature, 200 parts of ethyl acetate was added, then a large amount of water was added, and the monomer obtained in a separatory funnel was extracted. Next, after washing with a large amount of water several times and drying with anhydrous magnesium chloride, the solvent was removed with an evaporator, and then 4-tert-butylcalix [8] arene, the target product, was obtained with a fractionator. A compound having 8 polymerization initiating groups in which all of the hydroxyl groups were substituted with 2-bromoisobutyryl groups was obtained. This is referred to as C8AMA.

[Example 18: Synthesis of hyperbranched polymer-3]
Using the same reaction apparatus as in Example 1, 100.0 parts of MDPA as a solvent, 3.1 parts of C8AMA having 8 polymerization initiation groups obtained in Synthesis Example 6 as an organic compound of (2), ( Charge 100.0 parts of MMA of 1) and 4.1 parts of TBAI of (3), warm to 75 ° C. while bubbling nitrogen, then add 0.74 part of triethylamine of (4). For 7 hours. The polymerization rate of the obtained polymer was 91.1%, Mn was 63600, and PDI was 1.49. From this, it was confirmed that an 8-chain multi-branched polymer was obtained.

As an application example of the present invention, by using radical polymerization initiator-containing compounds that can be formed in various forms, various radicals can be initiated and advanced without termination using conventional radical polymerization initiators. As a new polymerization method capable of industrially and easily producing a polymer with a simple structure is provided, innovative technological development has been achieved by providing it as a material to fields that could not be used so far. I can expect. Specifically, polymer materials with specific properties such as adhesion, friction properties, wear resistance, wettability, barrier properties, adsorption / separation / transport properties of specific substances, and substrates with such specific properties of polymers Various materials whose surfaces have been treated are provided and their use is expected.

Claims

At least (1) a radically polymerizable monomer having an unsaturated bond, and (2) a group having a structure represented by the following general formula 1 and / or the following general formula 2 that functions as a polymerization initiating group of the monomer is 1 in the molecule. At least one organic compound, and (3) one or more iodides selected from the group consisting of (3) metal iodide, quaternary ammonium iodide, quaternary phosphonium iodide, and quaternary ammonium triiodide. A method for producing a polymer comprising a polymerization step in which radical polymerization with termination reaction starts from a group of the above structure by mixing and heating an iodine ion-containing compound that is a salt or a triiodide salt.

(In General Formula 1, R 1 represents H or any alkyl group or acyl group, R 2 represents any alkyl group or aryl group, X represents Cl or Br, and Y represents O or NH.)

(In General Formula 2, R 3 represents H or any alkyl group or aryl group, R 4 represents an aryl group, cyano group, carboxyl group, ester group or amide group, and X represents Cl or Br.)
The method for producing a polymer according to claim 1, wherein none of the azo radical polymerization initiator, the peroxide radical polymerization initiator, and the photo radical polymerization initiator is used in the polymerization step.
The polymer according to claim 1 or 2, wherein at least one selected from the group consisting of (4) iodine, an iodine iodide organic compound capable of liberating iodine and a compound having an organic base is used in the polymerization step. Manufacturing method.
The method for producing a polymer according to any one of claims 1 to 3, wherein an organic solvent is further used in the polymerization step.
The method for producing a polymer according to claim 4, wherein the organic solvent is at least one selected from the group consisting of alcohols, glycols, amides, sulfoxides and ionic liquids.
The method for producing a polymer according to any one of claims 3 to 5, wherein the organic iodide compound capable of liberating iodine is an N-iodimide compound.
The N-iodoimide compound is a group consisting of N-iodosuccinimide, N-iodophthalimide, N-iodocyclohexanilimide, 1,3-diaiodo-5,5-dimethylhydantoin and N-iodosaccharin. The method for producing a polymer according to claim 6, which is at least one selected from the group consisting of:
The method for producing a polymer according to any one of claims 1 to 7, wherein the group represented by the general formula 1 is a group represented by the following general formula 3.

(In general formula 3, Y is O or NH)
The organic compound (2) is a polymerization initiating group-containing polymer in which two groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced in the molecule, and the polymer obtained in the polymerization step is The method for producing a polymer according to any one of claims 1 to 8, wherein the polymer has a block structure or a comb structure.
The organic compound (2) is a compound in which three or more groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced in a molecule, and the polymer obtained in the polymerization step has a branched structure. The method for producing a polymer according to any one of claims 1 to 8, which is a mold polymer, a star polymer or a graft copolymer.
The organic compound (2) is a vinyl polymer in which three or more groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced in the molecule, and the polymer obtained in the polymerization step is The method for producing a polymer according to any one of claims 1 to 8, wherein the monomer (1) is polymerized and grafted onto a vinyl polymer to form a polymer or a bottle brush polymer.
The organic compound (2) is a monomer having at least one group having a structure represented by the general formula 1 and / or the general formula 2 and a reactive group that binds to the surface of the substrate. The substrate is treated with the copolymer to modify the surface of the substrate, and then the monomer (1) and the (3) are formed on the modified substrate surface. The method for producing a polymer according to any one of claims 1 to 8, wherein a polymer having a concentrated brush structure is produced on the surface of the substrate by mixing and heating with an iodine ion-containing compound.
Without using any of azo radical polymerization initiator, peroxide radical polymerization initiator and photo radical polymerization initiator, radical polymerization with termination reaction of radical polymerizable monomer having unsaturated bond A radical polymerization initiating group-containing compound for
Used in combination with an iodine ion-containing compound which is one or more iodide salts or triiodide salts selected from the group consisting of metal iodide, quaternary ammonium iodide, quaternary phosphonium iodide and quaternary ammonium triiodide. Thus, at least one group having a structure represented by the following general formula 1 and / or the following general formula 2 that functions as a polymerization initiating group of the radical polymerizable monomer is introduced into the molecule. Initiating group-containing compound for radical polymerization.

(In General Formula 1, R 1 represents H or any alkyl group or acyl group, R 2 represents any alkyl group or aryl group, X represents Cl or Br, and Y represents O or NH.)

(In General Formula 2, R 3 represents H or any alkyl group or aryl group, R 4 represents an aryl group, cyano group, carboxyl group, ester group or amide group, and X represents Cl or Br.)
The radical polymerization initiating group-containing compound according to claim 13, wherein the group having a structure represented by the general formula 1 is a group having a structure represented by the following general formula 3.

(In general formula 3, Y is O or NH)
14. The radical polymerization initiating group-containing compound according to claim 13, which is a polymer in which two groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced into a molecule.
14. The radical polymerization initiating group-containing compound according to claim 13, which is a compound in which three or more groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced in a molecule.
14. The radical polymerization initiating group-containing compound according to claim 13, which is a vinyl polymer in which three or more groups having a structure represented by the general formula 1 and / or the general formula 2 are introduced in a molecule.
A copolymer of a monomer having a structure represented by the general formula 1 and / or the general formula 2 and one or more monomers introduced into the molecule and a monomer having a reactive group bonded to the substrate surface. Item 14. A radical polymerization initiating group-containing compound according to Item 13.