JP6836242B2 - A method for producing a polymer and a polymer obtained by the method for producing the polymer. - Google Patents

Description

The present invention relates to a method for producing a polymer in which a plurality of types of polymer chains are grafted and a polymer obtained by the production method. More specifically, a polymer in which a plurality of types of acrylic chains are introduced in a high mass ratio can be relatively easily introduced. It relates to an industrially useful polymerization method that can be obtained and a technique for providing a polymer whose structure is controlled to a desired state.

Conventionally, when it is desired to graft a polymer, particularly a vinyl-based polymer such as a (meth) acrylic acid-based (co) polymer in the present invention, onto one organic compound, the following method is performed. That is, a method obtained by reacting a functional group possessed by or previously introduced in the organic compound to be grafted with a polymer having a group capable of reacting with the functional group at the terminal, or an organic compound to be grafted. It is obtained by a method of introducing a group for initiating polymerization (polymerization initiating group) and polymerizing a monomer from the polymerization initiating group. The "graft" defined in the present invention indicates a structure in which the polymer extends from an arbitrary place in the structure of the organic compound, and the polymer extends from the end of the organic compound as well as the branched structure. Including the case where is generated.

More specifically, especially when the organic compound is a polymer, a polymer having a functional group or an introduced polymer (main polymer) is reacted with a polymer having a group capable of reacting with the functional group at the terminal or the like. The "grafting to" method of obtaining a polymer in which a polymer is grafted onto a main polymer, or the "grafting from" method of introducing a polymerization initiating group into the polymer and polymerizing a monomer from the polymerization initiating group to obtain a polymer. A polymer having an unsaturated bond at one end (macromonomer) and, if necessary, another monomer having an unsaturated bond are used in combination to polymerize, resulting in a polymer grafted with a polymer derived from the macromonomer. There are respective graft methods called "polymering through" methods (Patent Documents 1 to 3). In order to obtain a polymer grafted with a plurality of types of polymers by the above method, in the "grafting to" method and the "grafting flow" method, a plurality of types of polymers having a functional group or an unsaturated group at the terminal thereof are used. In the "grafting from" method, a monomer is polymerized from the introduced initiating group to obtain a polymer, and then a polymerization initiating group is further introduced into the polymer to carry out the polymerization. A method of polymerizing another monomer from the initiating group to introduce the next polymer species can be considered.

Japanese Patent No. 4758652 Japanese Patent No. 4813733 Japanese Unexamined Patent Publication No. 2008-274181

However, each of the above-mentioned graft methods has the following problems. First, in the "grafting to" method and the "grafting through" method, since the material used is a polymer having a functional group at the terminal, the reaction is a high molecular weight terminal reaction, so that the functional group concentration in the reaction system is high. Is low, the reactivity may be poor, a large amount of polymer cannot be introduced by mass, and the polymer of the material may not react and remain. Further, in the "grafting through" method, radicals at the terminals may be coupled to form a gel or have a high molecular weight, and a desired polymer may not be obtained. In addition, when attempting to graft-introduce a plurality of types of polymers by these graft methods, it may be complicated and the desired polymer may not be obtained, which is industrially or industrially unsuitable, and the method is not suitable. Not established. Therefore, there is no clear product on the market in which a vinyl polymer such as a (meth) acrylic acid-based (co) polymer is grafted onto one organic compound, which is the object of the present invention.

Therefore, an object of the present invention is to provide a technique capable of relatively easily industrially and industrially producing a polymer grafted with a plurality of desired (meth) acrylic acid-based (co) polymer chains. There is. A more specific object of the present invention is to graft a desired polymer species as a polymer chain to introduce a plurality of types of polymer chains, and further, the mass ratio of the grafted polymer chains is the graft. It is an object of the present invention to provide a technique for producing a polymer having a high mass ratio to the whole polymer produced, and as a result, the produced polymer can exhibit unprecedented performance.

（一般式１中、Ｒ１は、Ｈ又は任意のアルキル基又はアシル基又はアリール基のいずれかを表し、Ｒ２は、アルキル基又はアリール基を表し、Ｘは、Ｃｌ又はＢｒを表し、Ｙは、Ｏ又はＮＨを表す。） The above object is achieved by the following invention. That is, the present invention has the following general formula 1 which functions as (1) a radically polymerizable monomer having an unsaturated bond, a (meth) acrylic acid-based monomer, and (2) a polymerization initiating group of the monomer of (1). By mixing and heating an organic compound in which at least one group having the structure represented is introduced into one molecule and (3) an iodine ion-containing compound which is an iodide salt or a triiodide salt, the above-mentioned Two or more (meth) acrylic acid-based (co) polymer chains are grafted using a polymerization method for obtaining a polymer having a polymerization step in which radical polymerization accompanied by a termination reaction starts from a structural group (polymerization initiation group). (Co) A method for producing a polymer, wherein the polymerization step is carried out twice or more, and in the first step, two or more of the organic compounds of the above (2) are contained in one molecule. By using the organic compound in which the polymerization initiating group of (3) is introduced and using the iodine ion-containing compound of (3) in an amount less than the number of polymerization initiating groups introduced in the organic compound of (2). , The polymerization of the monomer (1), which starts from a part of the two or more polymerization initiation groups, is carried out to obtain a polymer grafted with the first kind (meth) acrylic acid-based (co) polymer chain. It is a step of purifying or not purifying the obtained polymer, and the second step is the first kind (meth) acrylic acid obtained in the first step as the organic compound of the above (2). Using a polymer grafted with a system (co) polymer chain, the iodine ion-containing compound of the above (3) was added to the residual polymerization initiating group with respect to the residual polymerization initiating group not used in the first step. (1) is different from the monomer of (1) used in the first step, which starts from a part or all of the residual polymerization initiating group by using in an amount equal to or less than the number of A polymer characterized by a step of obtaining a polymer grafted with a second type (meth) acrylic acid-based (co) polymer chain by polymerizing the monomers of the above, and purifying or not purifying the obtained polymer. Provide a manufacturing method.

(In General Formula 1, R1 represents H or any alkyl or acyl or aryl group, R2 represents an alkyl or aryl group, X represents Cl or Br, and Y represents. Represents O or NH)

（一般式２中、Ｙは、Ｏ又はＮＨを表す。） Preferred forms of the above-mentioned method for producing a polymer of the present invention include the following. That is, further, in the polymer to which the second kind (meth) acrylic acid-based (co) polymer chain obtained in the second step is grafted, the first step and the second step If there is a residual polymerization initiating group that was not used in the step, this is used as the organic compound of (2), and the same steps as in the second step are sequentially repeated until there are no residual polymerization initiating groups. , To obtain a (co) polymer having a structure in which a plurality of (meth) acrylic acid-based (co) polymer chains are grafted; in the above-mentioned polymerization step, an azo-based radical polymerization initiator and a peroxide-based radical polymerization initiator. And neither of the photopolymerization radical polymerization initiators; in the polymerization step, at least (4) iodine, an organic iodide compound capable of liberating iodine, and at least a compound having an organic base selected from the group. Use either; further (5) use an organic solvent during the polymerization step; the group consisting of alcohol-based, glycol-based, amide-based, sulfoxide-based, urea-based and ionic liquids. It is at least one selected from the above; the group represented by the general formula 1 is a group represented by the following general formula 2;

(In general formula 2, Y represents O or NH.)

Further, as a preferred embodiment of the method for producing a polymer of the present invention, in the polymerization step carried out two or more times, after obtaining the polymer in the polymerization step carried out first, the polymer is then not purified. In the polymerization step to be carried out, the polymer was used as the organic compound in (2), and the iodine ion-containing compound in (3) and the monomer (1) different from those used in the polymerization step carried out earlier were added. The organic compound of (2) used in the first step is a polymer having two or more of the polymerization initiating groups in one molecule; the polymerization initiating group is contained in one molecule. The polymer having two or more is a polymer having the polymerization initiating group and having a monomer having a radical polymerizable group as a constituent unit; the polymer having two or more of the polymerization initiating groups in one molecule is Any polymer selected from the group consisting of linear polymers, star polymers and crosslinked particle polymers; the organic compound of (2) used in the first step has 1 polymerization initiating group. Utilizing the polymerization method using a radically polymerizable monomer having one in the molecule and having a radically polymerizable group, another radically polymerizable monomer, and the iodine ion-containing compound of (3) above. It is a star-shaped polymer in which a plurality of polymerization initiation groups remain inside the branched two kinds of polymers.

In another embodiment, the present invention comprises two or more (meth) acrylic acid-based (co) polymer chains obtained by polymerizing the monomer (1) obtained by any of the above polymer production methods. Each provides a polymer characterized by being grafted from a polymerization initiator constituting the organic compound (2).

A preferred form of the polymer of the present invention is that two types of (meth) acrylic acid-based (co) polymer chains are grafted.

In another embodiment of the present invention, two or more (meth) acrylic acid-based (co) polymer chains obtained by polymerizing the monomer (1) obtained by the above-mentioned preferred polymer production method are provided. , The polymerization initiating group constituting the organic compound of (2) is grafted, and at least one of the polymer chains is an AB block copolymer chain, and the other one is the A-. Provided is a polymer characterized by being a polymer chain composed of a monomer similar to the B polymer block of a B block copolymer.

In another embodiment, the present invention has a plurality of (meth) acrylic acid-based (co) polymer chains obtained by the above-mentioned preferred polymer production method inside the star-shaped polymer. Provided is a polymer characterized by being a star-shaped polymer grafted from a polymerization initiator.

Regarding the invention of the product, the polymer of the present invention specifies the invention of the product by the production process "obtained by the method for producing the polymer according to any one of claims 1 to 12". The polymer of the present invention is obtained for the first time by using the novel production method of the present invention, and two or more desired polymer chains are used as the organic compound (2) used in the polymerization method peculiar to the above production method. It is a structure grafted from a unique group introduced, and the mass ratio of the grafted polymer chain is a high mass ratio with respect to the entire grafted polymer. Here, these plurality of polymer chains are obtained by a polymerization method peculiar to the above-mentioned production method. Specifically, the iodine ion-containing compound, which is the iodide salt or triiodide salt of (3), causes a group having a unique structure introduced into the organic compound of (2) to function as a polymerization initiation group, and the polymerization thereof. A polymer chain having a structure in which a polymer composed of the monomer of (1) is grown from the polymerization initiating group of the organic compound of (2) by radical polymerization of the monomer of (1) from the starting group. It is not possible to directly specify by structure or property, and it becomes possible to specify only by the process (manufacturing method) for obtaining the polymer described above. It is a well-known fact in the art that a polymer is an aggregate (mixture) of various polymer molecules having different molecular weights, and specifies the structure and physical properties of individual polymer molecules contained in the aggregate (mixture). It is impossible and almost impractical. For the above reasons, the polymers of the present invention are specified by the manufacturing process.

According to the present invention, a novel polymerization method is used, which makes it possible to easily obtain a polymer having a structure in which a plurality of desired polymer chains are grafted, which has been difficult and complicated to manufacture industrially. A method for producing a polymer is provided. The novel polymerization method used in the present invention is simple, and comprises the organic compound of (2) having a specific structural group substituted with chlorine or bromine, which functions as a polymerization initiating group of the monomer of (1), and ( Simply by mixing and heating (heating) 1) a radically polymerizable monomer having an unsaturated bond and (3) a compound having an iodine ion, a radical that undergoes a termination reaction from a group having the above structure (polymerization initiation group). Polymerization begins and the polymer can be obtained. According to the present invention, this polymerization method is skillfully utilized, and in the first-stage polymerization step, the organic compound (2) having two or more specific structural groups is used, and this group is left over. Then, a compound having a residual polymerization initiating group (a polymer because the polymer chain was grafted in the first step) was obtained, and this polymer was used as the organic compound in (2) of the second step of polymerization. By mixing and heating the (meth) acrylic acid-based monomer as the monomer of (1) and the compound having iodine ion of (3), the polymerization starts from the polymerization initiating group, and the next polymer chain is grafted. To do. Then, by repeating the above operation in each polymerization step, a polymer grafted with a desired number of types of polymer chains can be easily obtained. That is, the number of groups having a specific structure of the organic compound (2) that functions as a polymerization initiating group is set to be equal to or greater than the number of desired polymer chain types, and the iodine (3) is mixed in each step of the polymerization step. By appropriately controlling the amount of the compound having an ion, a polymer having a versatile structure in which a plurality of desired polymer chains are grafted can be obtained. In addition, the polymers made possible by the present invention were introduced with a very high mass ratio of the polymer chains being grafted relative to the entire polymer, in addition to which multiple polymer chains were grafted. Since it is a polymer having a structure, it is considered that the properties of each grafted polymer chain will appear and the performance will be unprecedented. Therefore, the polymer provided by the present invention can be used in various ways, and since it is an unprecedented material, it is considered that it can be a technological innovation in the industrial world.

It is an image diagram for demonstrating the reaction when the polymer obtained in the 1st step is used as the organic compound of (2) in the 2nd step without purification. It is an image diagram for demonstrating the reaction when the polymer obtained in the 1st step is purified and used as the organic compound of (2) in the 2nd step.

Next, the present invention will be described in more detail with reference to preferred embodiments. As a result of diligent research to achieve the object of the present invention, the present inventors have conducted an organic compound having a group having a specific structure (polymerization initiator group) that functions as a polymerization initiator group of the above-mentioned (2). And (1), a radically polymerizable monomer having an unsaturated bond, and (3), a compound having an iodine ion, are simply mixed and heated (heated) to form a group having the above-mentioned structure (polymerization initiation group). ), A radical polymerization accompanied by a termination reaction is started, and a polymer can be obtained by finding an unprecedented polymerization method. Furthermore, by skillfully utilizing this new polymerization method, a plurality of desired polymer chains are grafted. The present invention has been achieved by finding that polymers having a wide variety of structures can be obtained.

Specifically, in the production method of the present invention, the organic compound (2) has two or more groups (polymerization initiators) having a specific structure, and is used in the first step. The first kind by polymerizing a (meth) acrylic acid-based monomer as the monomer of (1) using the compound having iodine ion of (3) so as to leave the polymerization initiation group of the organic compound of (2). Then, in the second step, the polymer chain of the first kind is grafted to the organic compound of (2), and all the remaining polymerization initiation groups are used. (1), which is different from the one previously polymerized by using the compound having iodine ions of (3) so as to leave the polymerization initiating group of the organic compound of (2) again. By polymerizing the monomer, a second type of (meth) acrylic acid-based (co) polymer chain is grafted, and if necessary, this step is repeated to perform multiple types of (meth) acrylic acid-based (co) polymer chains. Allows the polymer to be grafted. That is, the polymer production method of the present invention is characterized in that it is configured as follows.

The first feature of the present invention is that (1) a radically polymerizable monomer and (2) a group having a structure represented by the following general formula 1 which functions as a polymerization initiating group of the monomer of (1) above are contained in one molecule. By mixing and heating (heating) at least one organic compound introduced and (3) an iodine ion-containing compound which is an iodide salt or a triiodide salt, the group having the above-mentioned structure (polymerization initiation group) can be used. This is due to the use of a polymerization method for obtaining a polymer, which has a polymerization step in which radical polymerization accompanied by a termination reaction is started.
Then, at least by carrying out the above polymerization step twice or more, a (co) polymer having a structure in which two or more kinds of (meth) acrylic acid-based (co) polymer chains are grafted is produced.

（一般式１中、Ｒ１は、Ｈ又は任意のアルキル基又はアシル基又はアリール基のいずれかを表し、Ｒ２は、アルキル基又はアリール基を表し、Ｘは、Ｃｌ又はＢｒを表し、Ｙは、Ｏ又はＮＨを表す。）

(In General Formula 1, R1 represents H or any alkyl or acyl or aryl group, R2 represents an alkyl or aryl group, X represents Cl or Br, and Y represents. Represents O or NH)

（一般式２中、Ｙは、Ｏ又はＮＨを表す。） Among the groups having the structure represented by the general formula 1 described above, in the present invention, it is particularly preferable that the polymerization initiating group is a group represented by the following general formula 2.

(In general formula 2, Y represents O or NH.)

The second feature of the present invention is that in the first step, an organic compound in which two or more polymerization initiators are introduced into one molecule is used as the organic compound of (2). By using the iodine ion-containing compound of (3) in an amount less than the number of polymerization initiating groups introduced into the organic compound of (2), starting from a part of the two or more polymerization initiating groups. The above-mentioned (1) is polymerized to obtain a polymer grafted with the first kind (meth) acrylic acid-based (co) polymer chain. The polymer obtained in the first step corresponds to the organic compound (2) in the polymerization method used in the present invention in which a polymerization initiating group remains in a part of the structure.

The third feature of the present invention is the first kind (meth) acrylic acid-based (co) polymer chain obtained in the first step as the organic compound of (2) in the second step. In contrast to the residual polymerization initiating groups in the polymer that were not used in the first step, the iodine ion-containing compound of (3) was added to the number of the residual polymerization initiating groups or By using an amount of less than a few, the polymerization of the second type (1) monomer different from the monomer used in the first step, which starts from a part or all of the residual polymerization initiation group. A polymer obtained by grafting a second kind of (meth) acrylic acid-based (co) polymer chain was obtained. If the polymer obtained in the second step contains a residual polymerization initiating group that has not been used in the previous steps, the polymer obtained in the subsequent polymerization step will be continued thereafter. As the organic compound of (2), a plurality of (meth) acrylic acid-based (co) polymer chains are grafted by sequentially repeating the same steps as in the second step until the residual polymerization initiating group disappears. We have obtained a (co) polymer with the same structure.

The fourth feature of the present invention is that the polymer used as the organic compound of (2) in the polymerization step of the next step, which is obtained in each step sequentially performed from the first step described above, is used. The point is that it is either purified and used, or it is used without purification. According to the study by the present inventors, when an unpurified polymer was used, it was used from the end of the (meth) acrylic acid-based polymer chain obtained in the polymerization in the previous step, and further in the step. It has been found that polymerization with another monomer is initiated, resulting in the graft chain being an AB block copolymer. When the purified polymer is used, the polymer chain obtained in each step is composed of the monomers used in the corresponding step.

First, the polymerization method used in the present invention, which is the first feature described above, will be described. This polymerization method has a structure represented by the general formula 1 defined in the present invention, which functions as (1) a radically polymerizable monomer having an unsaturated bond and (2) a polymerization initiating group of the monomer of (1). An organic compound in which at least one group is introduced into one molecule (hereinafter, may be referred to as "organic compound of (2)") and (3) an iodine ion-containing compound which is an iodide salt or a triiodide salt. It is characterized by having a polymerization step in which radical polymerization accompanied by a termination reaction of the monomer of (1) is started from the group (polymerization initiation group) of the structure by mixing and heating. As described above, the polymerization method used in the present invention uses 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 is strict. It is a simple method that does not require various polymerization conditions, and is a useful method that solves the following problems of the prior art.

A polymer obtained by polymerizing a radically polymerizable monomer having an unsaturated bond is highly versatile because it can be efficiently obtained by radical polymerization using a radical polymerization initiator necessary for generating radicals. It is used in various places. However, although the usual radical polymerization method is useful, there is a problem that the polymerization is stopped. For example, a polymer having a complicated structure such as a block copolymer, a graft copolymer, or a star polymer is a usual radical polymerization method. Cannot be obtained by some. On the other hand, according to the living radical polymerization invented for controlling the molecular weight and structure of the polymer, the above-mentioned polymer having a complicated structure can be obtained. However, in living radical polymerization, since special compounds are used or metal catalysts are used, it is necessary to remove those compounds and catalysts, which is industrially complicated and requires a plurality of steps. In addition, there is a problem that the polymerization conditions also need to be strict, such as the need to purify the monomer to be used and the need to carry out in a nitrogen atmosphere.

The polymerization method used in the present invention is a novel one made for the above-mentioned problems, and as described above, it has a group having a specific structure that functions as a polymerization initiation group of a monomer, and has a general-purpose and various forms. By simply mixing and heating (heating) the organic compound (2), the monomer, and the compound having iodine ions (3), a radical accompanied by a termination reaction can be obtained from the group having the above structure. It is an extremely simple substance in which polymerization can be started to obtain a polymer.

In the present invention, a novel polymerization method having a structure different from that of the conventional polymerization method described above is used, and this is skillfully utilized, and the type and polymerization of the organic compound corresponding to (2) to be used without using a separate component. Industrial production was difficult and complicated by an extremely simple operation of appropriately adjusting the number of starting groups and the like and the mixing amount of the iodine ion-containing compound of (3) with respect to the organic compound of (2). It becomes possible to easily obtain a polymer having a complicated structure. Specifically, it corresponds to, for example, a multi-branched polymer in which many kinds of polymer chains are grafted in a desired amount, or a multi-branched polymer in which many kinds of polymer chains including AB block copolymer chains are grafted, (2). It is possible to obtain a graft copolymer obtained by grafting various kinds of polymer chains, a plurality of kinds of star-shaped polymers, a plurality of kinds of crosslinked acrylic fine particles, and the like, which are obtained by using a polymer having a plurality of polymerization initiation groups as an organic compound. Hereinafter, each component constituting the polymerization method used in the present invention will be described.

[(1) (Meta) acrylic acid-based monomer]
An object of the method for producing a polymer of the present invention is to produce a (co) polymer in which two or more (meth) acrylic acid-based (co) polymer chains are grafted. That is, as a result, the grafted polymer obtained by the production method of the present invention is a (meth) acrylic acid-based polymer. Therefore, in the present invention, as the radically polymerizable monomer having an unsaturated bond of (1) used in the novel polymerization method described above, a (meth) acrylic acid-based monomer (simply, "monomer of (1)"". May be described as), and many types are used. The "(meth) acrylic acid-based monomer" referred to in the present invention is generally referred to as an acid monomer such as (meth) acrylic acid, which will be described later, or a (meth) acrylate monomer. These monomers are extremely versatile, and any known monomer can be used in the present invention and is not particularly limited.

The reason for using the (meth) acrylic acid-based monomer in the present invention is that the (meth) acrylic acid-based monomer has various ester residues, and various combinations can be used to obtain a wide variety of polymers. The resulting polymer can be expected to be widely used, and the most suitable monomer for the novel polymerization method used in the present invention is a (meth) acrylic acid-based monomer, particularly a methacrylic acid-based monomer. By being. In the present invention, the monomer of (1) is limited to the (meth) acrylic acid-based monomer in consideration of the versatility of the obtained polymer, but the method for producing the polymer of the present invention can be applied to various other monomers. Can also be applied.

Examples of the (meth) acrylic acid-based monomer used in the present invention include, but are not limited to, the following. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-methylpropane (meth) acrylate, t-butyl (meth) acrylate, pentyl. (Meta) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (Meta) acrylate, octadecyl (meth) acrylate, behenyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexylmethyl (meth) acrylate, isobolonyl (meth) acrylate, trimethylcyclohexyl (Meta) acrylate, cyclodecyl (meth) acrylate, cyclodecylmethyl (meth) acrylate, benzyl (meth) acrylate, t-butylbenzotriazole phenylethyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, allyl Examples thereof include aliphatic, alicyclic, and aromatic alkyl (meth) acrylates such as (meth) acrylate.

Further, (meth) acrylic acid-based monomers containing a hydroxyl group, (meth) acrylic acid-based monomers having a glycol group, (polyalkylene) glycol monoalkyl, alkylene, alkin ether or ester mono (meth) acrylates, It has (meth) acrylic acid-based monomers having an acid group (carboxyl group, sulfonic acid, phosphoric acid) containing acrylic acid or acrylic acid dimer, (meth) acrylic acid-based monomers containing an oxygen atom, and an amino group. (Meta) acrylic acid-based monomers, nitrogen atom-containing (meth) acrylic acid-based monomers, and the like can be used. Furthermore, it has mono (meth) acrylates having three or more hydroxyl groups, halogen atom-containing (meth) acrylates, silicon atom-containing (meth) acrylic acid-based monomers, and a group that absorbs ultraviolet rays. (Meta) acrylic acid-based monomers, α-position hydroxyl group methyl-substituted acrylates, and the like can also be used. Further, a (meth) acrylic having two or more addition-polymerizable groups such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and (meth) acrylic acid ester of a polyalkylene glycol adduct of trimethylolpropane. Acid-based monomers can also be used as needed. It may be appropriately selected from the above-mentioned general-purpose monomers and used according to the required performance of the polymer finally obtained by the production method of the present invention.

[Organic compound of (2)]
In the method for producing a polymer of the present invention, as the organic compound of (2), a group having a structure represented by the general formula 1 (polymerization starting group) that functions as a polymerization initiating group of the monomer of (1) is contained in one molecule. By using two or more organic compounds introduced into the above, it is possible to produce a polymer by the above-mentioned new polymerization method. As a result of diligent studies to achieve the object of the present invention, the present inventors first mixed and heated the organic compound (2) with the iodine ion-containing compound (3) described later. It has been found that radical polymerization accompanied by a termination reaction starts from a group having a structure constituting the organic compound (2) (polymerization initiator group) and functions as a polymerization initiator group of the monomer of (1) described above to obtain a polymer. .. Specifically, the monomer (1) and the iodine ion-containing compound (3) are mixed and added in the presence of a group having a structure represented by the following general formula 1 (hereinafter, also referred to as “group of formula 1”). When heated, polymerization starts from these groups, resulting in a (meth) acrylic acid-based polymer obtained by radical polymerization of the monomer (1).

In the present invention, by skillfully utilizing the above polymerization method, it is possible to obtain a polymer grafted with a plurality of (meth) acrylic acid-based polymer chains. In the method for producing a polymer of the present invention, first, as the organic compound of (2), a polymer having a structure in which two or more polymerization initiating groups are present in one molecule is used, and in the first step, "formula 1 An amount of the iodine ion-containing compound (3) adjusted so that only a part of the "groups" functions as a polymerization initiating group is mixed and heated, and the polymerization is started from the group. A polymer to which the first kind (meth) acrylic acid-based polymer chain is grafted is obtained. Next, the iodine ion-containing (3) is contained so that all or a part of the "groups of the formula 1" remaining in the polymer obtained in the first-stage polymerization step function as the polymerization initiation group. The compounds are mixed and heated, and the second-stage polymerization step is carried out to obtain a polymer having a structure in which two or more kinds of polymer chains are grafted and the second kind (meth) acrylic acid-based polymer chains are grafted. Further, when the "group of the formula 1" remains in the obtained polymer, by sequentially performing the same operation as above, the group functioning as the polymerization initiator group is selected from the groups different from those described above. A polymer in which the (meth) acrylic acid-based polymer chain is grafted is obtained.

The organic compound of (2) used in the present invention and characterizing the present invention may have a structure represented by the following general formula introduced into the molecule, and these structures are the polymerization of the monomer of (1). Act as a starting point.

（一般式１中、Ｒ１は、Ｈ又は任意のアルキル基又はアシル基又はアリール基のいずれかを表し、Ｒ２は、アルキル基又はアリール基を表し、Ｘは、Ｃｌ又はＢｒを表し、Ｙは、Ｏ又はＮＨを表す。）

(In General Formula 1, R1 represents H or any alkyl or acyl or aryl group, R2 represents an alkyl or aryl group, X represents Cl or Br, and Y represents. Represents O or NH)

The "group of formula 1" defined in the present invention has a chlorine atom (also called chloro) or a bromine atom (also called bromo) bonded as X in its structure, and these atoms react with each other. It is characterized by being a group that can be eliminated or substituted, and further, at least one or more electron attracting groups such as an ester group and an amide group are bonded to the carbon to which these atoms are bonded. It is a thing.

The reaction mechanism of the polymerization method of the present invention is not clear. Iodine of the iodine ion-containing compound of (3) described later is substituted (halogen substituted) with chlorine or bromine of the polymerization initiating group, and the polymerization initiating group becomes an iodine group, followed by heat and other ionic components. Is desorbed as iodine radicals by the action of oxidative reduction reaction, and then the monomer is polymerized, and the polymer may be grafted and polymerized, such as conventionally known iodine transfer polymerization and reversible transfer catalyst polymerization. May be obtained at. The reaction mechanism is not particularly limited, and the production method of the present invention includes the monomer of (1), the organic compound having the group of the structure represented by the general formula 1 of (2), and (3) described later. ), It is characterized in that it is possible to produce a polymer in which a plurality of types of (meth) acrylic acid-based polymer chains are grafted only by mixing and heating the iodine ion-containing compound. That is, as described above, in the present invention, by controlling the number of reactions of the "group of formula 1" existing in the organic compound (2) of (2) or more, which functions as a polymerization initiating group. It makes it possible to appropriately graft a plurality of desired polymer chains into a desired state. Further, the electron attracting group in the structure of the "group of the formula 1" is necessary for promoting the above-mentioned halogen substitution, facilitating the desorption of iodine as a radical, and stabilizing the radical slightly. It is believed that there is.

In the production method of the present invention, any organic compound having a structure in which two or more such "groups of formula 1" are introduced into the molecule can be used. Further, as the organic compound (2), for example, any form such as a low molecular weight compound, a monomer, or a polymer can be used. Hereinafter, the "group of Equation 1" will be described.

Examples of the "group of the formula 1" include those having an ester bond or an amide bond in the structure as shown below. As shown below, the organic compound (2) in which the "group of formula 1" used in the present invention is introduced into the molecule has a chlorine atom (Cl) or a bromine atom via an ester bond or an amide bond. (Br) is combined.

Examples of the "group of the formula 1" include the following groups of β-chloro or bromoalkanoic acid having an ester bond or an amide bond.

For example, the following groups of β-chloro or bromoaryl substituted alkanoic acids having an ester bond or an amide bond can be mentioned.

For example, the following groups of chloro or bromo-substituted acetoalkanoic acids having an ester bond or an amide bond can be mentioned.

The introduction of the "group of formula 1" 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 a "group of formula 1". Further, using a compound in which a hydroxyl group is bonded to X in the structure of the above "group of formula 1," that is, a group to which chlorine or bromine is bonded, phosphorus halide, concentrated hydrochloric acid or hydrobromic acid is used. May be introduced by substituting the hydroxyl portion of the compound with chlorine or bromine. Further, a compound having an unsaturated bond in the CX portion in the structure of the above "group of formula 1" is used, and hydrogen chloride or hydrogen bromide is added to the unsaturated bond to introduce chloro or bromo. May be good.

（一般式２中、Ｙは、Ｏ又はＮＨを表す。） As the organic compound (2) used in the present invention, any organic compound may be used as long as the "group of formula 1" is introduced. According to the studies by the present inventors, among the "groups of the formula 1", the rate of the initiation polymerization reaction is particularly high, and the synthesis can be easily performed with a commercially available compound. Therefore, a group having a structure represented by the following general formula 2 It is preferable to use an organic compound into which (hereinafter, referred to as “group of formula 2”) has been introduced.

(In general formula 2, Y represents O or NH.)

The above-mentioned "group of formula 2" can be obtained by a conventionally known material or method, and various forms of organic compounds into which the "group of formula 2" has been introduced can also be easily obtained. An example in which an organic compound into which the "group of the formula 2" has been introduced can be easily synthesized will be described below. It is obtained by using a 2-bromoisobutyric acid-based compound as a raw material and using an organic compound having a carboxy group thereof and a group capable of reacting with a derivative thereof as an organic compound into which the "group of formula 2" is introduced, and reacting them. The compound used at that time is not particularly limited. Examples of the 2-bromoisobutyric acid-based compound include 2-bromoisobutyric acid, 2-bromoisobutyric acid bromide, and 2-bromoisobutyric anhydride. Then, these compounds and an organic compound having a reactive group which is a pair capable of reacting 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. By reacting with, the "group of formula 2" can be introduced into the organic compound by an ester bond or an amide bond.

The organic compound (2) used in the production method of the present invention functions as a polymerization initiating group for the monomer (1) described above, and is the above-mentioned "group of formula 1", and more preferably "group of formula 2" (these). Are collectively referred to as "groups of formula 1 or 2"), which are organic compounds in which two or more are introduced into 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 many types of conventionally known organic compounds that cannot be exemplified, but specific examples include ethylene bis (2-bromoisobutyrate) and bis (2- (2'-bromoisobutyryloxy) ethyl. ) Disulfide, bis (2- (2'-bromoisobutyryloxy) undecyl) disulfide, polyethylene glycol bis (2-bromoisobutyrate), 1,1,1-tris (2-bromoisobutyryloxymethyl) ethane , Tetrakiss (2-bromoisobutyryloxymethyl) pentaerythritol, hexakis (2-bromoisobutyryloxymethyl) dipentaerythritol, and the like.

In addition, a polymer can be mentioned as a suitable organic compound (2) used in the production method of the present invention. That is, by using a polymer having two or more polymerization initiator groups, more kinds of (meth) acrylic acid-based polymer chains can be introduced, and the obtained graft copolymer is considered to exhibit various performances. .. As the polymer used as the organic compound of (2), conventionally known polymers can be used. Examples thereof include polymers such as polyether, polyester, polyamide, polyurethane, polyolefin, polyimide, polyacrylic, polymethacrylic, polystyrene, polycarbonate, polysilicone, polyhalogenated olefin, polyvinyl alcohol, cellulose and chitosan. These may be polymers having any structure such as homopolymers, copolymers of monomer units of these polymers, graft copolymers, block copolymers and the like. In the present invention, a polymer in which two or more of the above-mentioned "groups of formula 1 or 2" are introduced into these polymers is used by a conventionally known method. As a specific example, the above-mentioned 2-bromoisobutyric acid is reacted with glyzidol to synthesize a glycerol monoester having the structure of the formula 2 as one of the diol components, and the polyurethane or polyester is used. By incorporating the carboxylic acid itself into polyamide or polyimide, a polymer corresponding to the organic compound (2) can be obtained, but the present invention is not limited to this.

Further, as the organic compound (2) used in the production method of the present invention, a polymer having a polymerization initiating group of "group of formula 1 or 2" and having a radically polymerizable group as a constituent unit is used. Use is also a preferred embodiment of the present invention. When a polymer obtained by polymerizing a monomer having such a polymerization initiating group is used as the organic compound of (2), the finally obtained polymer has a structure in which the polymer chain is branched from the polymer of (2). It can be a so-called graft copolymer. As a result, a polymer having a structure in which the mass ratio of the grafted polymer chains is a high mass ratio to the entire polymer and the grafted polymer chains are a plurality of types, which has not been easily obtained until now, is obtained. , It becomes possible to obtain it industrially easily and inexpensively.

Further, as the organic compound (2), it is also a preferable form to use a star-shaped polymer obtained as described below in which a plurality of polymerization initiation groups remain. In such a star-shaped polymer, a monomer having one polymerization initiating group in one molecule and having a radically polymerizable group and another radically polymerizable monomer in an appropriate amount (3). ) Can be obtained by mixing and heating with an iodine ion-containing compound.

The radically polymerizable group of the monomer having the polymerization initiation group of the "group of formula 1 or 2" used above and having the radically polymerizable group is not particularly limited, but for example, a vinyl group or a vinylidene group. , Acrylic group, methacryl group and other unsaturated double bonds. Hereinafter, the above-mentioned monomer may be referred to as a vinyl-based monomer having a "group of formula 1 or 2". Specific examples include 2- (2-bromoisobutyryloxy) ethyl (meth) acrylate and vinyl 2-bromoisobutyric acid ester. A polymer corresponding to the organic compound of (2) used in the present invention by polymerizing a vinyl-based monomer having such a "group of formula 1 or 2" or copolymerizing with another vinyl-based monomer. Can be suitably used as. Not limited to this method, even if a monomer having a hydroxyl group or the like is polymerized in advance and then the “group of formula 1 or 2” is introduced, the same polymer can be obtained as a result. In the case of copolymerizing with other vinyl-based monomers, the blending amount of the monomer into which the "group of formula 1 or 2" is introduced is arbitrary and is not particularly limited.

As the other monomer, those listed below can be appropriately used. For example, (meth) acrylic acid-based monomers used as the monomer of (1) above; 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, isocyanatodimethylmethaneiso Propenylbenzene, phenylmaleimide, cyclohexylmaleimide, hydroxymethylstyrene, styrene styreneic acid, vinylsulfonic acid, vinylamine, allylamine, aminostyrene, vinylmethylamine, allylmethylamine, methylaminostyrene, vinylpyridine, vinylimidazole, vinylbenzotriazole, Monomers such as vinylcarbazole, dimethylaminostyrene, diallylmethylamine, trimethylammonium styrene chloride, dimethyllaurylaminostyrene chloride, vinylmethylpyridinyl chloride, diallyldimethylammonium salt chloride, (meth) acrylamide, and dimethyl (meth) acrylamide. Be done.

The polymer corresponding to the organic compound of (2) may be obtained by a conventionally known radical polymerization method, or may be obtained by a method such as ionic polymerization or coordination polymerization in some cases. Usually, the above-mentioned monomer may be used, and a polymer obtained by conventional radical polymerization using an azo compound or a peroxide may be used. Furthermore, when the polymer corresponding to the organic compound of (2) is obtained by living radical polymerization, the molecular weight distribution can be narrowed, and various structures such as block copolymers and star polymers (star-shaped polymers) can be obtained. Therefore, depending on the polymer finally desired, it is preferable to use the polymer obtained by radical polymerization. Among the methods of living radical polymerization, a monomer having a "group of formula 1 or 2" introduced therein is used, and a nitroxide method (NMP method) using a nitroxide radical, a reversible method using a dithioester compound, or the like is used. Target addition cleavage type chain transfer polymerization (RAFT method), reversible mobile catalyst polymerization using an iodine compound and an organic catalyst (RTCP method), and the like can be used. However, atom transfer radical polymerization utilizing redox is not preferable because there is a possibility of gelation due to polymerization of the monomer and initiation of polymerization from a chloro group or a bromo group.

When a polymer is used as the organic compound of (2), the structure of the polymer is particularly preferably any one of a linear polymer, a star polymer, and a crosslinked particle polymer. According to the production method of the present invention, a plurality of types of (meth) acrylic acid-based polymers can be easily introduced into these polymers having various structures, so that they can be used in various industrial applications. It can be expected to produce a polymer having a structure, which is very preferable.

The linear polymer mentioned above is a homopolymer, a copolymer, or an AB block copolymer, ABA or AB-of a monomer having the above-mentioned "group of formula 1 or 2". Also includes C triblock copolymers and the like. Further, the star-shaped polymer refers to a conventionally known dendrimer, a multi-branched polymer, or the like. The crosslinked fine particle type polymer is a vinyl-based monomer having two or more unsaturated bonds, which is obtained by a conventionally known method such as suspension polymerization, emulsification polymerization, or miniemulsion polymerization, or two or more kinds having a group that reacts with each other. It is a polymer obtained by polymerizing a monomer and a monomer having a "group of formula 1 or 2" as at least a material.

When a linear polymer is used as the organic compound of (2), the (meth) acrylic acid-based polymer finally obtained by the production method of the present invention has a grafted structure. In addition, when a star-shaped polymer is used, it has a structure in which a polymer such as a dendrimer is used as a core and a plurality of types of (meth) acrylic acid-based polymer chains are bonded as an arm. When a crosslinked fine particle type polymer is used, it can be a core-shell type polymer in which a polymer chain is bonded to the surface of the particles.

As described above, in the present invention, as the organic compound (2), an organic compound in which two or more "groups of formula 1 or 2" are introduced is used. According to the studies by the present inventors, it is preferable to use an organic compound in which three or more "groups of formula 1 or 2" (polymerization initiating groups) are introduced, because the amount of impurity polymer can be reduced. When the organic compound (2) having two polymerization initiation groups is used and polymerized by the polymerization method of the present invention, a polymer having a structure in which only one (meth) acrylic acid-based polymer chain is bonded in the first-stage polymerization. A polymer in which both (meth) acrylic acid-based polymer chains are bonded or a polymer having a structure in which no polymer chain is attached can be obtained. Then, when the monomer is polymerized in the second step, the polymer of the present invention in which two types of polymer chains are bonded can be obtained, but the polymer of impurities in which the two types of polymer chains are not bonded may be contained. On the other hand, when the organic compound (2) in which three or more polymerization initiating groups are introduced is used and polymerized by the polymerization method of the present invention, an impurity polymer in which two types of polymer chains are not bonded is used. Is preferable because the amount of With this configuration, it is possible to easily and more reliably obtain a polymer having a structure that could not be easily obtained by conventional techniques.

Further, the molecular weight of the obtained polymer may be controlled by adjusting the amount of the polymerization initiating group introduced into the organic compound (2), which is also a feature of the polymerization method used in the present invention. In this polymerization method, since the polymerization is started from the "group of formula 1 or 2" introduced into the organic compound of (2), (1) is applied to 1 mol of the compound containing the "group of formula 1 or 2". By adjusting the amount of the monomer of, the molecular weight of the polymer to be produced can be adjusted. However, the polymerization by this polymerization method involves a termination reaction such as radical polymerization, and may be coupled to form a high molecular weight, in which case the amount of the initiating group cannot be adjusted.

[(3) Iodine ion-containing compound]
In the method for producing a polymer of the present invention, it is necessary to use (3) an iodine ion-containing compound which is an iodide salt or a triiodide salt in addition to the above-mentioned monomer (1) and organic compound (2). The details of the action of these compounds have not been elucidated, but by using this compound, bromine or chlorine of the above-mentioned "group of formula 1 or 2" is replaced with iodine, and polymerization in which iodine is transferred occurs. it is conceivable that. In addition, this compound may act as a catalyst for redox to promote polymerization. Hereinafter, the above-mentioned compound may be referred to as an "iodizing agent".

Specifically, one or more iodide salts or triiodide salts selected from the group consisting of metals iodide, quaternary ammonium iodides, quaternary phosphonium iodides and quaternary ammonium triiodides. Use the contained compound. Conventionally known compounds can be used as these compounds, and the present invention is not particularly limited. For example, 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, and triphenylmethylphosphonium iodide. Examples of the quaternary ammonium triiodide include tributylmethylammonium triiodide. Not limited to the above, any compound can be used as long as it has an iodine ion.

[(4) Iodine or an organic iodide compound capable of liberating iodine or a compound having an organic base]
In the method for producing a polymer of the present invention, the materials (1) to (3) described above are used, and if they are mixed and heated, the polymerization proceeds and a plurality of types of polymer chains are grafted to each other. E) Polymers can be obtained. According to the study by the present inventors, in addition to the above materials, any one selected from (4) iodine, an iodinated organic compound capable of liberating iodine, and a compound having an organic base such as an organic amine. Is also a preferable form to carry out the polymerization step. According to the studies by the present inventors, by further adding these components, it is possible to prevent the radical polymerization termination reaction that occurs in the polymerization method used in the present invention, and prevent high molecular weight and gelation. be able to. Its action is unknown, but it is thought that iodine and amino groups become radicals and contribute to the prevention of coupling of growth radicals. Hereinafter, the component (4) may be simply referred to as "catalyst of (4)".

The catalyst of (4) may be iodine, an organic compound iodide capable of liberating iodine, or a compound having an organic base, and conventionally known compounds are used, and they are not particularly limited. As the iodinated organic compound capable of liberating iodine, any compound can be used because iodine is liberated by heat or light if iodine is bound. It is preferably an N-iodoimide-based compound, and more preferably N-iodosuccinylimide, N-iodophthalimide, N-iodocyclohexanylimide, 1,3-diaiodo-5, which are commercially available. , 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 in (4) is arbitrary and is not particularly limited. Preferably, it is used in the range of 0.001 mol times to 0.1 mol times of the "group of formula 1 or 2" of the organic compound (2) that functions as a polymerization initiator to be used in combination. If the amount used is too large, the action as a catalyst is not sufficiently exhibited, and side reactions may occur, which is not preferable.

[(5) Organic solvent]
Hereinafter, other materials that can be used in the method for producing a polymer of the present invention will be described. The polymerization step of the method for producing a polymer of the present invention is preferably solution polymerization in which the polymer is polymerized using an organic solvent. This may mean that it may not be possible to dissolve an ionic material such as the iodinating agent of (3) in the monomer material of (1), while the organic compound of (2) "formula 1 or 2". The exchange of chlorine or bromine in the structure of the "group" with the iodine ion of the iodinating agent of (3) needs to be carried out by dissolving the iodizing agent as described above, and for that purpose, as described below. It is preferable to use a highly polar organic solvent in part or in whole. Specifically, it is preferable to use an alcohol-based, glycol-based, amide-based, sulfoxide-based, urea-based, or ionic liquid solvent. However, these solvents are not always necessary. For example, when a monomer that dissolves an iodizing agent is used as the monomer of (1), polymerization can be carried out without using an organic solvent. Commonly used organic solvents include conventionally known non-polar solvents such as hydrocarbon-based, halogen-based, ketone-based, ester-based, and glycol-based solvents, which can be used in combination with the above-mentioned polar solvents. Higher solvents may be used. In that case, the ratio of the highly polar solvent is arbitrary, and the solvent is selected so as to dissolve the polymer of the present invention obtained by polymerizing the monomers.

Specifically, alcoholic solvents such as methanol, ethanol and isopropanol; glycol solvents such as ethireglycol, propylene glycol, glycerin, diethylene glycol and propylene glycol monomethyl ether; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 3- Amide solvents such as methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide; sulfoxide solvents such as dimethyl sulfoxide; urea solvents such as tetramethylurea and dimethylimidazolidinone; imidazo Examples thereof include ionic liquids such as urium salt and quaternary ammonium salt, which can be used alone or in two or more kinds.

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% on a mass basis. If it is less than 30%, the solid content may be too high and the viscosity may be high, and if it is more than 80%, the monomer concentration may be too low and the polymerization rate may not increase. More preferably, it is 40% to 70%.

The polymer production method of the present invention is basically characterized in that it does not require the use of a radical polymerization initiator that generates radicals. Conventionally, when a monomer having an unsaturated bond is polymerized, the polymerization has been carried out using an azo-based or peroxide-based compound, or a compound that generates radicals such as thiol. However, in the polymerization method used in the present invention, even if such a radical polymerization initiator is not used, the above-mentioned materials (1) to (3) are mixed and the polymerization easily proceeds by heat. In some cases, it is expected that a polymer produced by the polymerization method of the present invention can be obtained by using a radical polymerization initiator in combination, but in that case, polymerization from the radical polymerization initiator may also start, which is desired. It is not preferable for the purpose of stably obtaining a polymer having a complicated structure. In the production method of the present invention, it is preferable to carry out polymerization without using a radical polymerization initiator such as an azo radical polymerization initiator, a peroxide radical polymerization initiator and a photopolymerization radical polymerization initiator.

[Polymerization process]
The above are the materials required for the method for producing a polymer of the present invention. In the present invention, the above-mentioned materials (1) to (3) are mixed and heated (heated) to obtain the above (2). Polymerization of the monomer of (1) proceeds from the "group of formula 1 or 2" of the organic compound, and the polymerization is repeated to obtain a polymer in which two or more (meth) acrylic acid-based polymer chains are grafted. be able to. The polymerization conditions are not particularly limited, and conventionally known methods are used. To list preferable specific conditions, it is better to use a nitrogen or argon atmosphere or bubbling without the influence of oxygen, and the polymerization proceeds better. The temperature may be room temperature or higher, for example, 40 ° C. or higher, but since the polymerization time is long at room temperature or higher, polymerization is preferably performed at 60 ° C. or higher, further 70 ° C. or higher. Is suitable for the manufacturing time of practical manufacturing. Further, the stirring speed does not particularly affect the polymerization, and shading is not always necessary. The polymerization rate is also arbitrary, and the monomer does not have to be completely consumed.

In the method for producing a polymer of the present invention, the first step of obtaining a polymer grafted with the first type of polymer chain and the polymer obtained in the first step are used as the organic compound of (2). It is characterized by having at least two polymerization steps of the second step of initiating the polymerization of the second type of monomer (1). In the production method of the present invention, at that time, the polymer obtained in the first step may be used as it is as the organic compound of (2) used in the next second step, or a poor solvent. The purified polymer component may be used by adding to and precipitating. That is, the usage form, usage method, post-treatment, etc. of the polymer obtained after each polymerization step are arbitrary, and conventionally known methods are used depending on the respective uses. As described below, the structure of the polymer to which two or more (meth) acrylic acid-based polymer chains finally obtained are grafted, particularly depending on whether or not the obtained polymer is purified by post-treatment. Will be different, so it is preferable to take this point into consideration.

According to the study by the present inventors, when the unpurified polymer was used as the organic compound of (2) in the second step, the (meth) acrylic acid system obtained by the first step polymerization was used. Polymerization with the second type of monomer used in the second stage is also started from the end of the polymer chain. As a result, the polymer chains obtained in the second step are formed at least with the first type polymer chain (referred to as A chain) formed in the first step and in the second step. The second type of polymer chain (referred to as B chain) and the AB block copolymer chain obtained by initiating the polymerization of the second type of monomer from the end of the A chain, which is the first type of polymer chain. Will have. On the other hand, when the purified polymer is used as the organic compound of (2) in the second step to initiate the polymerization, the (meth) acrylic acid-based polymer chain obtained in the second step is , It does not become a block copolymer chain, but becomes a polymer chain composed of a second kind of monomer. Therefore, in the third step, when the polymer obtained in the second step is used as the organic compound of (2) without purification, the ABC block copolymer chain or AB A polymer obtained by grafting a -A block copolymer chain is obtained.

[Method of introducing multiple types of (meth) acrylic acid-based polymer chains]
In the production method of the present invention, a (co) polymer in which two or more (meth) acrylic acid-based (co) polymer chains are grafted, that is, a (meth) acrylic acid-based polymer is converted into the organic compound of (2). The purpose is to produce polymers in which multiple types are introduced. A specific method for introducing the plurality of types of polymer chains will be described below. First, in the first step, the iodine ion-containing compound of (3) is added in an appropriate amount with respect to n polymerization initiation groups (n is an integer of 2 or more) existing in one molecule of the organic compound of (2). It is used to react n1 polymerization initiators (n1 is an integer less than n) so that n1 functions as a polymerization initiator of the monomer, and the monomer of (1) is polymerized from here. The polymer obtained by grafting the first kind (meth) acrylic acid-based polymer chain is obtained. This is called polymer A. Then, in the second step, the iodine ion-containing compound of (3) was used in an appropriate amount with respect to n1 of the residual polymerization initiating groups in the obtained polymer A, and n2 (n2). Reacts less than n-1 if you want to leave more polymerization initiators, or nn1) if you do not want to leave more polymerization initiators, so that n2 functions as the polymerization initiators of the monomer. Then, the monomer of (1) is polymerized from here to obtain a polymer grafted with a second kind (meth) acrylic acid-based polymer chain. This is called polymer B. Further, when the obtained polymer B has a polymerization initiating group remaining, a plurality of types of (meth) acrylic acid-based compounds are formed as a whole by repeating the same operation as in the second step described above. A polymer with a polymer chain grafted can be obtained.

More specifically, it is assumed that one molecule of the organic compound (2) has n polymerization initiating groups (n is an integer of 2 or more). In the polymerization method used in the present invention, it is considered that the compound having the iodine ion of (3) is used to replace the bromine and chlorine of the polymerization initiating group with iodine, and the polymerization proceeds from the iodine. Therefore, out of the above n amounts of the polymerization initiators of chlorine or bromine, only some of the above-mentioned polymerization initiators are replaced with iodine, and the polymerization initiators substituted with chlorine or bromine are left behind and substituted with iodine. The polymerization of the monomer is started from the above, and the polymer is graft-introduced. For the polymerization initiating group remaining substituted with chlorine or bromine, the compound having the iodine ion of (3) is used, and the polymerization is started from a part thereof, and the polymerization initiating group is left over. , It is configured to perform the operation of being used for the next polymerization.

In the above, when it is desired to replace n1 chlorine or bromine among the n polymerization initiation groups of the organic compound corresponding to (2), the iodine ion-containing compound of (3) having the same molar amount or less of n1 is used. It is common and preferable to use it in combination. However, even if the iodine ion-containing compound of (3) is added in an amount of this molar amount or more, the chlorine or bromine and iodide ion may be affected by the influence of ion dissociation based on the temperature, the solubility of the solvent, and the polarity or dielectric constant of the solvent. In some cases, the reaction may not proceed entirely, in which case the desired partial initiation of polymerization is carried out by tracking the amount of iodine ions by NMR measurement, ion chromatography, etc. and quantifying the substituted functional groups. It can be performed. Therefore, the number of moles of the compound having iodine ions with respect to the polymerization initiation group is not limited. Preferably, as described above, when the organic compound corresponding to (2) has n polymerization initiating groups, the iodine ion-containing compound of (3) having a molar equivalent of less than n is used.

From the above, a part of the polymerization initiating group to which chlorine or bromine was bonded was substituted with iodine to initiate polymerization to obtain a polymer, and the polymerization initiating group in which the polymerization initiating group to which chlorine or bromine was bonded was left over was used. By carrying out the production method of the present invention in which the polymer having the polymer is sequentially used, the (meth) acrylic acid-based polymer chain grafted in the first polymerization step, and the (meth) acrylic acid-based polymer chain grafted in the second polymerization step, A polymer having a polymerization initiating group to which residual chlorine or bromine is bonded is obtained, and by repeating this polymerization step until there are no residual polymerization initiating groups, a polymer in which a plurality of (meth) acrylic acid-based polymer chains are bonded is obtained. When introducing this final polymer chain, preferably, the number of residual polymerization initiating groups used as the organic compound corresponding to (2) in the final polymerization step so as not to leave the polymerization initiating groups. A compound having a molar equivalent or more, for example, a large excess of iodine ions bound thereto may be added. By making a large excess, chlorine or bromine is completely replaced with iodine, and all the residual polymerization initiating groups contribute to the polymerization.

In the present invention, the polymer obtained in the first-stage polymerization step is precipitated in a poor solvent or the like of the polymer and purified to obtain the first-stage polymer, and then this polymer is used in the second-stage. Two or more kinds of polymers are introduced by introducing a second kind of polymer chain in the polymerization step of the eye, and purifying this to obtain the second kind of polymer, and repeating the purification to polymerize the next monomer. Produce the polymer of the present invention in which the chains are grafted. In the present invention, after the polymer is obtained by the first polymerization, the second polymer is obtained by polymerizing by adding a monomer to the compound having iodine ions as described above without performing a purification operation. The polymer may be polymerized, and this operation may be repeated in one pot to obtain the polymer of the present invention. In this case, as described above, iodine may be at the end of the polymerization, possibly chlorine or bromine, but if it is substituted, the polymerization proceeds again from that part. Therefore, it can be introduced as a block copolymer. In the case of this one pot, the monomer and the iodinating agent may be added after the previous monomer is almost polymerized and consumed, or the monomer and the iodinating agent may be added and polymerized in the middle of the polymerization. May be good. In particular, in the case of the latter one pot described above, since post-treatment such as precipitation is not performed, there is a high possibility that the end is alive, and therefore it is considered that it is easily introduced as a block copolymer. The block copolymer can also have a structure of triblock or tetrapod, and can be a polymer to which various (meth) acrylic acid-based polymers are bonded.

The number of two or more (meth) acrylic acid-based polymer chains introduced into the finally obtained polymer, which is the object of the present invention, is not particularly limited, and the polymerization operation is repeated by the method as described above. Therefore, many kinds of (meth) acrylic acid-based polymer chains can be introduced. However, the number of industrially realistic introductions is 10 or less, more preferably 5 or less, depending on the number of steps and the like. Particularly preferably, it is a polymer obtained by two polymerization operations of introducing the first kind (meth) acrylic acid-based polymer chain and then adding the second kind of monomer in this step. Among them, more preferable is a polymer in which at least two kinds of polymer chains are grafted, which is carried out in one pot without the step of purifying the polymer obtained in the first polymerization described above, in terms of practicality and productivity. It is considered to be suitable in terms of cost performance.

A polymer in which at least two types of polymer chains are grafted can be obtained by the method of performing the polymerization twice, that is, the first step and the second step. Specifically, in the first polymerization, a polymer obtained by polymerizing one kind of (meth) acrylic acid-based polymer chain is obtained, and then a compound having iodine ions and a monomer are added to the reaction system to polymerize, and one pot is obtained. If the end is alive, the next monomer can be polymerized from the end of the polymer produced in the first step to polymerize it into a block copolymer. For convenience, if the first polymer is an A polymer and then the polymer obtained by polymerizing the next monomer is a B polymer, the block copolymer described above is an AB block copolymer. Then, when the polymerization is started from the residual polymerization initiating group, the B polymer is grafted. Therefore, at least two types of A-B block copolymers and B polymers are grafted polymers. However, in some cases, the terminal may not be halogen, in which case the polymerization does not proceed, so that the polymer of A is only polymerized, and in some cases, despite the use of the iodinating agent and the monomer twice. Instead, it may be a polymer in which three kinds of (meth) acrylic acid-based polymers are bonded.

[polymer]
In the method for producing a polymer of the present invention, under the above conditions, each of the materials described above is prepared so that the polymerization initiating group is left under the conditions such as the formulation described above. , Mixing and heating to polymerize, and then using the residual polymerization initiator group to polymerize from the polymerization initiator group, the following types of polymer chains are introduced, and by repeating this, a plurality of polymer chains are introduced. A polymer to which a (meth) acrylic acid-based polymer chain is bonded can be easily produced.

Specifically, by utilizing the method of the present invention, (meth) acrylic acid-based polymers (hereinafter, may be simply referred to as polymers) chains having various properties are introduced, and polymers having various properties (hereinafter, referred to as polymers) are introduced. , Called a graft copolymer) can be obtained. For example, a graft copolymer in which a plurality of polymer chains having different soft and hard properties are introduced; a graft copolymer in which a polymer chain having a different Tg type such as a glass transition point (Tg) of room temperature or lower, room temperature, room temperature or higher, etc. is introduced; Graft copolymers with different polymer chains introduced; Graft copolymers with different polymer chains introduced; Graft copolymers with non-reactive polymer chains and reactive polymer chains; Water-soluble polymer chains and water Graft copolymers with insoluble polymer chains introduced into them; Graft copolymers with polymer chains that are incompatible with each other introduced into them; Polymers that are compatible with some substances but not with some substances, but with different compatibility Graft copolymer with introduced chains; Graft copolymer with introduced hydrophilic and hydrophobic polymer chains; Graft copolymer with introduced water-repellent and hydrophilic polymer chains; Water-repellent and oil-repellent polymer chains Introduced graft copolymer; graft copolymer in which a water-absorbent polymer chain and a polymer chain having no affinity for water are introduced; a graph copolymer in which polymer chains having different bulk densities of monomers such as low shrinkage rate and high shrinkage rate are introduced; Graft copolymers with ionic and nonionic polymer chains introduced; Graf copolymers with anionic and cationic polymer chains introduced; Graft copolymers with polymer chains with different light absorption wavelengths introduced; Graft copolymers with polymer chains to be crosslinked; Graf copolymers with groups that decompose and hydrolyze with heat or light and have different decomposition rates; Graf copolymers with dye-bonded polymer chains and non-dye-bonded polymer chains; Inorganic Graft copolymers with polymer chains with and without sex groups; graft copolymers with polymer chains with different gas permeabilitys; graft copolymers with polymer chains with different thermal conductivity, etc. It is not limited to, and a combination of each property is also possible.

In addition, by changing the functional group, type, number, ratio, number of monomer species to be introduced, etc. of each polymer chain to be introduced, or by changing the molecular weight even if the polymer to be introduced is the same monomer type. Alternatively, by changing the type, molecular weight, etc. of the main polymer into which the polymer chain is introduced, or by making a block copolymer as in the present invention, various polymer properties can be obtained by using the present invention. It is possible.

The use of the obtained polymer can be used for conventionally known applications and is not particularly limited. For example, it can be applied to various fields such as ink, paint, coating, plastic, inkjet ink, color material related materials such as color filter materials, energy related materials, machine parts related materials, medical device materials, drug related, etc. Be expected.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Hereinafter, "part" and "%" in the text are based on mass unless otherwise specified.

[Synthesis Example 1: Synthesis of a multi-branched polymer in which two types of polymer chains are grafted-1]
150 parts of 3-methoxy-N, N-dimethylpropanamide (hereinafter abbreviated as MDPA) as a solvent, the organic compound of (2) in a reaction device equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube. 2.74 parts of pentaerythritol tetrakis (2-bromoisobutyrate) having four polymerization initiation groups, and 50.0 parts of methyl methacrylate (hereinafter abbreviated as MMA) as the monomer of (1). As the compound of 3), 3.04 parts of tetrabutylammonium iodide (hereinafter abbreviated as TBAI) was charged. Then, nitrogen was heated to 75 ° C. while bubbling, and then 0.37 parts of triethylamine (hereinafter abbreviated as TEA) was added as an organic base, and the mixture was polymerized for 7 hours. The polymerization rate of the obtained polymer was 98.5%.

As a result of measuring the molecular weight of the polymer of the obtained polymer with a GPC apparatus using a differential refractometer of a tetrahydrofuran (hereinafter abbreviated as THF) solvent, the number average molecular weight (hereinafter abbreviated as Mn) was obtained as the molecular weight in terms of polystyrene. The molecular weight distribution was 12500, and the molecular weight distribution (weight average molecular weight / number average molecular weight, hereinafter abbreviated as PDI) was 1.46. Hereinafter, unless otherwise specified, the molecular weight is a polystyrene-equivalent molecular weight value obtained by a GPC apparatus of a differential refractometer using this THF solvent. Further, as a result of GPC measurement having an ultraviolet detector having a measurement wavelength of 254 nm (hereinafter, abbreviated as UV detector), only a minute peak was observed. It is considered that this polymer has weak absorption at that wavelength. Hereinafter, the measurement with the UV detector of GPC was performed at the measurement wavelength of 254 nm.

The obtained polymer was put into 1 L of methanol to precipitate the polymer. The precipitated polymer was filtered, washed with water, and then sufficiently dried in a dryer at 70 ° C. for purification. The obtained dry polymer is a multi-branched polymer composed of MMA of the first type of monomer, and has a residual polymerization initiating group that is not used in the above-mentioned polymerization step. This is called PBR-1.

Then, using the reactor of Synthesis Example 1, 200 parts of MDPA was used as the solvent, 50 parts of PBR-1 corresponding to the organic compound of (2) was used, and benzyl methacrylate, which was the second monomer, was used as the monomer of (1). (Hereinafter abbreviated as BzMA) was charged in 50.0 parts, and TBAI was charged in 3.04 parts as the compound of (3). Then, nitrogen was heated to 75 ° C. while bubbling, and then 0.37 part of TEA was added as an organic base, and the mixture was polymerized for 7 hours. The polymerization rate of the obtained polymer was 96.2%, Mn was 26400, and PDI was 1.52. The molecular weight value of the UV detector was 25700, and the PDI was 1.56. In PBR-1, which was confirmed earlier, almost no peak was obtained by the UV detector, whereas in this polymer, UV absorption was large, so the polymerization of the second type of monomer (BzMA) was PBR-. It is considered that a multi-branched polymer (4 branches in this example) composed of 2 kinds of monomers was obtained starting from the polymerization initiating group remaining in 1.

[Synthesis Example 2: Synthesis of a multi-branched polymer in which two types of polymer chains are grafted-2]
Using the reaction apparatus of Synthesis Example 1, 150 parts of MDPA was used as a solvent, and 2.87 parts of dipentaerythritol hexakis (2-bromoisobutyrate) having 6 polymerization initiation groups was used as the organic compound of (2). , 50 parts of MMA was charged as the monomer of (1), and 3.04 parts of TBAI was charged as the compound of (3). Then, nitrogen was heated to 75 ° C. while bubbling, and then 0.37 part of TEA was added as an organic base, and the mixture was polymerized for 7 hours. The polymerization rate of the obtained polymer was 95.8%, Mn was 21400, and PDI was 1.47.

The obtained polymer was put into methanol to precipitate the polymer. The precipitated polymer was filtered, washed with water, and then sufficiently dried in a dryer at 70 ° C. for purification. The obtained dry polymer is a multi-branched polymer composed of MMA of the first type of monomer, and has a residual polymerization initiating group that is not used in the above-mentioned polymerization step. This is called PBR-2.

Then, using the reaction apparatus of Synthesis Example 1, 200 parts of MDPA was used as a solvent, 50 parts of PBR-2 corresponding to the organic compound of (2) was used, and 50.0 parts of BzMA was used as the monomer of (1). As the compound of 3), 3.04 parts of TBAI was charged. Then, nitrogen was heated to 75 ° C. while bubbling, and then 0.37 part of TEA was added as an organic base, and the mixture was polymerized for 7 hours. The polymerization rate of the obtained polymer was 95.8%, Mn was 46700, and PDI was 1.59. The molecular weight value of the UV detector was 46100, and the PDI was 1.61. While PBR-2 showed almost no peak in the UV detector, this polymer showed large UV absorption, so the polymerization of the second type of monomer (BzMA) remained in PBR-1. It is considered that a multi-branched polymer (6 branches in this example) composed of two types of monomers was obtained, starting from the polymerization initiating group.

[Synthesis Example 3-Synthesis of Graft Copolymer Using Polymer with Multiple Polymerization Initiators-1]
(A1) Preparation of Polymer Initiating Group-Containing Polymer Using the same apparatus as in Synthesis Example 1, 561.0 parts of MDPA, 1.0 part of iodine, and 2,2'-azobis (radical polymerization initiator) as a solvent. 4-methoxy-2,4-dimethylvaleronitrile) [trade name: V-70, manufactured by Wako Pure Chemical Industries, Ltd.] 3.7 parts, 2-hydroxyethyl methacrylate 208.0 parts, N-iodoscusinimide 0.113 parts were added and polymerized at 65 ° C. for 7 hours while bubbling nitrogen. As a result, the polymerization rate was almost 100%, and as a result of measuring the molecular weight with a GPC apparatus of N, N-dimethylformamide solvent, Mn was 18500 and PDI was 1.35.

Then, 189.5 parts of pyridine was added and cooled to 5 ° C. in an ice bath. 459.8 parts of 2-bromoisobutyric acid bromide was charged into the dropping funnel, attached to the apparatus, dropped over 3 hours so as not to exceed 10 ° C., and then left at that temperature for 2 hours. Then, it was heated to 45 degreeC and reacted for 1 hour. Then, after cooling to room temperature, 561 parts of methanol was added and stirred. Then, 5000 g of methanol was prepared in a separate container, and the above solution was gradually added while stirring with a disper. The polymer was precipitated to give a soft polymer. The polymer was separated, added to a large amount of water with stirring with a disper, washed, filtered, washed with water, and dried in a blower dryer at 50 ° C. until the volatile matter disappeared. As a result, a white powdery solid was obtained.

As shown in Scheme I below, the white powdery solid obtained above becomes a polymer in which the group having the structure of the general formula 2 defined in the present invention is bonded to the side chain. It was confirmed by identifying with an infrared spectrophotometer (IR) and a nuclear magnetic resonance apparatus (NMR) that the powdery solid is a polymer in which a plurality of "groups of formula 2" are introduced into its side chain. did it. This is referred to as an initiating group polymer-1. Moreover, when the molecular weight of the initiating group polymer-1 was measured by the THF solvent GPC, Mn was 26000 and PDI was 1.41.

(B1) Preparation of Graft Copolymer with Grafted Two Polymer Chains Using the same equipment as in Synthesis Example 1, 200 parts of MDPA, 30 parts of MMA as the monomer of (1), and (a1) were prepared. 5.5 parts of the initiating group polymer-1 having a plurality of "groups of the formula 2" introduced into the side chain, 3.33 parts of TBAI as the compound of (3), and 0.5 parts of TEA as the organic amine were added. , 75 ° C. for 8 hours. Since the polymerization proceeded and the liquid became a highly viscous liquid, it was sampled and the polymerization rate was measured and found to be 82%. Further, Mn was 661000 and PDI was 1.43.

The obtained polymer was put into methanol to precipitate the polymer. The precipitated polymer was filtered, washed with water, and then sufficiently dried in a dryer at 70 ° C. for purification. The obtained dry polymer is a copolymer grafted with a polymer chain consisting of MMA of the first type of monomer, and has a residual polymerization initiating group in the main chain structure which is not used in the above polymerization step. This is called PBR-3.

Then, using the reactor of Synthesis Example 1, 200 parts of MDPA was used as a solvent, 30 parts of PBR-3 corresponding to the organic compound of (2) was used, and 30 parts of BzMA was used as the monomer of (1), (3). As a compound of, 3.33 parts of TBAI was charged. Then, nitrogen was heated to 75 ° C. while bubbling, and then 0.5 part of TEA was added as an organic base, and the mixture was polymerized for 7 hours. The polymerization rate of the obtained polymer was 97.2%, Mn was 1050400, and PDI was 1.82. The molecular weight value of the UV detector was 1020300, and the PDI was 1.88. While PBR-3 showed almost no peak in the UV detector, this polymer showed large UV absorption, so the polymerization of the second type of monomer (BzMA) remained in PBR-3. It is considered that a graft copolymer having a structure in which polymer chains composed of two kinds of monomers were grafted, starting from the polymerization initiating group, was obtained.

[Synthesis Example 4-Synthesis of Graft Copolymer Using Polymer with Multiple Polymerization Initiators-2]
(A2) Preparation of Polymer Initiating Group-Containing Polymer Using the same apparatus as in Synthesis Example 1, 281.6 parts of MDPA and 70.4 parts of Poval 105 (manufactured by Kuraray, saponification degree 98 mol%) were added and dissolved. I let you. Then, 189.5 parts of pyridine was added and cooled to 5 ° C. in an ice bath. 459.8 parts of 2-bromoisobutyric acid bromide was charged into the dropping funnel, attached to the apparatus, dropped over 3 hours so as not to exceed 10 ° C., and then left at that temperature for 2 hours. Then, it was heated to 45 degreeC and reacted for 1 hour. Then, after cooling to room temperature, 561 parts of methanol was added and stirred. Then, 5000 g of methanol was prepared in a separate container, and the above solution was gradually added while stirring with a disper. The polymer was precipitated to give a soft polymer. The polymer was separated, added to a large amount of water with stirring with a disper, washed, filtered, washed with water, and dried in a blower dryer at 50 ° C. until the volatile matter disappeared. As a result, a white powdery solid was obtained.

As shown in Scheme II below, the white powdery solid obtained above becomes a polymer in which the group having the structure of the general formula 2 defined in the present invention is bonded to the side chain. It can be confirmed by identifying with an infrared spectrophotometer (IR) and a nuclear magnetic resonance apparatus (NMR) that the powdery solid is a polymer in which a plurality of "groups of formula 2" are introduced into its side chain. It was. This is referred to as initiating group polymer-2. Moreover, when the molecular weight of the initiating group polymer-2 was measured by the THF solvent GPC, Mn was 98600 and PDI was 1.46.

(B2) Preparation of Graft Copolymer with Grafted Two Polymer Chains Using the same equipment as in Synthesis Example 1, 280 parts of MDPA, 20 parts of MMA as the monomer of (1), and the side prepared in (a2). 27.5 parts of the initiating group polymer-2 having a plurality of "groups of formula 2" introduced into the chain, 6.66 parts of TBAI as the compound of (3), and 1.0 part of TEA as the organic amine were added. Polymerization was carried out at 75 ° C. for 8 hours. Since the polymerization proceeded and the liquid became a highly viscous liquid, it was sampled and the polymerization rate was measured and found to be 79%. The Mn was 521000 and the PDI was 1.96.

The obtained polymer was put into methanol to precipitate the polymer. The precipitated polymer was filtered, washed with water, and then sufficiently dried in a dryer at 70 ° C. for purification. The obtained dry polymer is a copolymer grafted with a polymer chain consisting of MMA of the first type of monomer, and has a residual polymerization initiating group in the main chain structure which is not used in the above polymerization step. This is called PBR-4.

Then, using the reactor of Synthesis Example 1, 360 parts of MDPA as a solvent, 20 parts of PBR-4 corresponding to the organic compound of (2), 20 parts of BzMA as a monomer of (1), (3). As a compound of, 3.33 parts of TBAI was charged. Then, nitrogen was heated to 75 ° C. while bubbling, and then 0.5 part of TEA was added as an organic base, and the mixture was polymerized for 7 hours. The polymerization rate of the obtained polymer was 96.2%, Mn was 1034500, and PDI was 2.16. The molecular weight value of the UV detector was 1020300, and the PDI was 2.18. While PBR-4 showed almost no peak in the UV detector, this polymer showed large UV absorption, so the polymerization of the second type of monomer (BzMA) remained in PBR-4. It is considered that a graft copolymer having a structure in which polymer chains composed of two kinds of monomers were grafted, starting from the polymerization initiating group, was obtained.

(B3) Preparation of Graft Copolymer with Grafts of Three Polymer Chains Using the same equipment as in Synthesis Example 1, 200 parts of MDPA, 30 parts of MMA, and the side chain prepared in (a1) were charged with "Formula 2". 5.5 parts of the initiating group polymer-1 into which a plurality of "groups" were introduced, 2.22 parts of TBAI as the compound of (3), and 0.33 parts of TEA as an organic amine were added, and the mixture was polymerized at 75 ° C. for 8 hours. Since the polymerization proceeded and the liquid became a highly viscous liquid, it was sampled and the polymerization rate was measured and found to be 89%. The Mn was 435,000 and the PDI was 1.41.

The obtained polymer was put into methanol to precipitate the polymer. The precipitated polymer was filtered, washed with water, and then sufficiently dried in a dryer at 70 ° C. for purification. The obtained dry polymer is a copolymer grafted with a polymer chain consisting of MMA of the first type of monomer, and has a residual polymerization initiating group in the main chain structure which is not used in the above polymerization step. This is called PBR-5.

Then, using the reaction apparatus of Synthesis Example 1, 340 parts of MDPA was used as a solvent, 30 parts of PBR-5 corresponding to the organic compound of (2) was used, and 30 parts of BzMA was used as the monomer of (1), (3). As a compound of, 2.22 parts of TBAI was charged. Then, nitrogen was heated to 75 ° C. while bubbling, and then 0.33 part of TEA was added as an organic base, and the mixture was polymerized for 7 hours. The polymerization rate of the obtained polymer was 98.2%, Mn was 880400, and PDI was 1.67. The molecular weight value of the UV detector was 871300, and the PDI was 1.71. While PBR-5 showed almost no peak in the UV detector, this polymer showed large UV absorption, so the polymerization of the second type of monomer (BzMA) remained in PBR-5. It is considered that a graft copolymer having a structure in which polymer chains composed of two kinds of monomers were grafted, starting from the polymerization initiating group, was obtained. This copolymer has a residual polymerization initiating group in its main chain structure that is not used in the polymerization step. This is called PBR-6.

Further, using the reaction apparatus of Synthesis Example 1, 340 parts of MDPA was used as a solvent, 60 parts of PBR-6 corresponding to the organic compound of (2) was used, and 30 parts of lauryl methacrylate was used as the monomer of (1). 2.22 parts of TBAI was charged as the compound of 3). Then, nitrogen was heated to 75 ° C. while bubbling, and then 0.33 part of TEA was added as an organic base, and the mixture was polymerized for 7 hours. The polymerization rate of the obtained polymer was 91.5%, Mn was 1253400, and PDI was 1.95. The molecular weight value of UV was 1196300, and the PDI was 1.99. From the above, it is considered that a graft copolymer having a structure in which polymer chains composed of three types of monomers are grafted is obtained.

(B4) Preparation of Graft Copolymer with Grafted Two Polymer Chains Using the same equipment as in Synthesis Example 1, 300 parts of MDPA, 30 parts of MMA as the monomer of (1), and the side prepared in (a1). 5.5 parts of the initiating group polymer-1 having a plurality of "groups of the formula 2" introduced into the chain, 3.33 parts of TBAI as the compound of (3), and 0.5 part of TEA as the organic amine were added. Polymerization was carried out at 75 ° C. for 8 hours. Since the polymerization proceeded and the liquid became a highly viscous liquid, it was sampled and the polymerization rate was measured and found to be 81%. The Mn was 658,000 and the PDI was 1.42. The obtained polymer solution was used as it was for the next polymerization without being precipitated in methanol (without purification operation). A copolymer grafted with a polymer chain consisting of MMA of the first type of monomer, which has a residual polymerization initiating group in its main chain structure that is not used in the above polymerization step, but since purification was not manipulated, other than that, the side chain It is considered that the polymerization initiation group remains at the terminal of. This polymer solution is referred to as PBR-7.

Then, as the monomer of (1), 10 parts of BzMA and 20 parts of 2-dimethylaminoethyl methacrylate (hereinafter abbreviated as DMAEMA) were charged, and 3.33 parts of TBAI was charged as the compound of (3). .. Then, nitrogen was heated to 75 ° C. while bubbling, and then 0.5 part of TEA was added as an organic base, and the mixture was polymerized for 7 hours. The polymerization rate of the obtained polymer was 98.6%, Mn was 973100, and PDI was 1.89. The molecular weight value of the UV detector was 967500, and the PDI was 1.92. The PBR-7 showed almost no peak in the UV detector, whereas this polymer showed a large amount of UV absorption. Therefore, the polymerization of the added mixed monomer (BzMA / DMAEMA) was carried out on the PBR-7. Copolymers grafted with these polymer chains, starting from the remaining polymerization initiating group, the graft chain consisting of an AB block copolymer chain consisting of MMA and BzMA / DMAEMA and a random copolymer chain of BzMA / DMAEMA. Is considered to have been obtained. FIG. 1 shows an image diagram of this reaction. FIG. 2 shows an image of the reaction when the purification operation is performed at the end of the first stage step.

[Synthesis Example 5: In the first step, a core polymer having a plurality of polymerization initiators was obtained using a polymerization initiator monomer, and finally a graft copolymer in which two kinds of polymer chains were grafted (multiple kinds). Synthesis of star-shaped polymer)]
First, the following substances were charged into the same reaction apparatus as in Synthesis Example 1, and the core polymer was synthesized as follows. 200 parts of MDPA as an organic solvent, 10 parts of 2- (2-bromoisobutyryloxy) ethyl methacrylate (abbreviated as BEMA) as a radically polymerizable monomer having one polymerization initiating group of "group of formula 2", ( 90 parts of MMA was charged as the monomer of 1) and 7.28 parts of TBAI was charged as the compound of (3), and the mixture was stirred and heated to 75 ° C. After TBAI was dissolved and the whole became uniform, 0.36 part of TEA was added as an organic base, and the above temperature was maintained for 7 hours of polymerization. When the sample was sampled and the polymerization rate was measured, it was almost 100%. When the molecular weight was measured by GPC, Mn was 4700 and PDI was 1.52. In addition, no peak was observed with the UV detector of GPC (absorption wavelength 254 nm). The core polymer solution was obtained as described above.

The polymer obtained above was put into methanol to precipitate the polymer. The precipitated polymer was filtered, washed with water, and then sufficiently dried in a dryer at 70 ° C. for purification. The obtained dry polymer is a branched polymer that serves as a core in a state in which a plurality of "groups of formula 2" (bromo-initiating group) remain inside, and this is referred to as C-1. That is, the core polymer C-1 is a bifunctional monomer in which the BEMA used as a material has two polymerizable groups, a radical polymerization group and a polymerization initiation group specified in the present invention. , C-1 is prepared by polymerizing this BEMA with a monomer MMA and an iodinating agent to carry out two polymerizations, radical polymerization and polymerization from a polymerization initiating group. It is considered that the polymer has a multi-layered structure composed of and MMA, and has a plurality of residual "groups of formula 2" inside the polymer. Moreover, when the obtained polymer C-1 was measured by NMR, it was converted from the number of protons of the methyl group (around 3.6 ppm) of MMA and the number of protons of the ethylene group (around 4.2, 4.4 ppm) of BEMA. Then, the contained polymerization initiating group was calculated to be 0.0174 mol in 100 g of the polymer as the BEMA monomer.

In the same reaction apparatus as above, 500 parts of MDPA and 50 parts of C-1 corresponding to the organic compound of (2) were charged and heated to 80 ° C. to dissolve all C-1. Then, 1.60 parts of TBAI was added as the compound of (3) and dissolved, and then 176 parts of BzMA and then 0.18 parts of TEA were added as the monomer of (1) to maintain the above temperature. Then polymerized for 6 hours. When the sample was sampled and the polymerization rate was measured, it was 80.6%. Moreover, when the molecular weight was measured by GPC, Mn was 21000 and PDI was 1.98. The molecular weight value of the UV detector was 21400, and the PDI was 2.011. While C-1 showed almost no peak in the UV detector, this polymer showed large UV absorption, so the polymerization of the first type of monomer (BzMA) was the core polymer C. It is considered that it is started from the polymerization initiation group remaining in -1.

In addition, since the molecular weight was large and the peak of the core polymer had disappeared, the bromo group inside the core polymer was converted into an iodo group, and the generated polymerization initiation group and the surface surface. From the iod group, it was found that the polymer chain was further extended.

Then, 1.60 parts of TBAI was added as the compound of (3), and 100 parts of MMA was further added, and the above temperature was maintained for 6 hours of polymerization. When a part was sampled and the polymerization rate was measured, it was 87.2%. Moreover, when GPC measurement was performed, Mn was 31500 and PDI was 2.39. Further, when the sample was purified in the same manner as described above and NMR was measured, the peak of the starting group of BEMA was not detected. Due to the increased molecular weight and the loss of the polymerization initiating group, that is, this polymer is introduced by grafting BzMA from C-1, a branched core polymer having an initiating group, and then purifying. It is presumed that by polymerizing MMA without doing so, a star-shaped polymer obtained by introducing a second type of polymer and having many types of polymer chains grafted is obtained.

[Synthesis Example 6: Synthesis of Multiple Crosslinked Acrylic Fine Particles Using Polymer Fine Particles Having Multiple Polymerization Initiating Groups]
In a 2-liter 3-neck round flask reactor equipped with a thermometer, 670 parts of ethyl acetate, 65 parts of diethylene glycol dimethacrylate (hereinafter abbreviated as DEGDMA), and a polymerization initiation group (bromo group) of the "group of formula 2" were added. 5.7 parts of BEMA, which is a radically polymerizable monomer having one, was added, loosely plugged, and immersed in a hot water bath at 70 ° C. Start for preparing polymer fine particles of the organic compound corresponding to (2) by dissolving 20 parts of ethyl acetate and 2.2 parts of 2,2'-azobisisobutyronitrile, which is a radical polymerization initiator, in a separate container. An initiator solution was prepared. Then, when the whole system of the glass bottle (round flask) reached 65 ° C., the initiator solution was added from another container and reacted at that temperature for 10 hours. As a result, the system became cloudy and the particles aggregated and precipitated. After the polymerization was completed, it was cooled. The solution was filtered, washed well with ethyl acetate, and dried in a blower dryer at 70 ° C. to obtain 69.7 parts of a white powder.

The white powder obtained was in the form of fine particles. Further, since it is considered that almost all the monomers have reacted from the yield, the content of BEMA in the weight of the obtained white powder is 8.1% and that of DEGDMA is 91.9%. Moreover, when the obtained fine particles were measured with a Coulter counter (manufactured by Beckman Coulter), the weight average particle diameter was 1.84 μm. Hereinafter, unless otherwise specified, the average particle size was measured by this method. The white powder obtained above was pulverized by a pulverizer and allowed to pass 100 mesh. The white powder made of a polymer obtained by polymerizing a radically polymerizable monomer having one polymerization initiating group of the "group of the formula 2" is referred to as fine particles B-1.

In a 500 ml separable flask equipped with a nitrogen introduction device and a cooling tube, 200 parts of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) as an organic solvent and 20 fine particles B-1 corresponding to (2) were added. Then, 1.18 parts of TBAI was added as the compound of (3), and the mixture was heated to 75 ° C. for 30 minutes. Then, when the temperature reached 75 ° C., 40 parts of MMA was added as the monomer of (1) and 0.1 part of TEA was added as an organic base, and the mixture was polymerized at 75 ° C. for 8 hours and cooled.

The polymerization solution obtained above was diluted with methyl ethyl ketone (hereinafter abbreviated as MEK) and filtered through a 10 μm pressure filter to remove a solid substance. Further, 1500 g of methanol was charged in a 3000 ml flask, attached to a stirrer, and stirred. The above-mentioned filtrate is added to the methanol while stirring, and the mixture is filtered, washed well with methanol, dried at 25 ° C. (room temperature) for 12 hours and at 80 ° C. for 24 hours, purified and white. A lump was obtained. The weight average particle size of the obtained white mass (fine particles) was 2.38 μm. This is a crosslinked acrylic fine particle in which a bromo group remains inside the structure. This is referred to as fine particles A-1.

Next, in a 500 ml separable flask equipped with a nitrogen introduction device and a cooling tube, 200 parts of NMP, 30 parts of fine particle A-1 corresponding to (2), and TBAI as the compound of (3) were added to 0. 59 parts were added and heated to 75 ° C. for 30 minutes. Then, when the temperature reached 75 ° C., 30 parts of BzMA was added as the monomer of (1) and 0.1 part of TEA was added as an organic base, and the mixture was polymerized at 75 ° C. for 8 hours and cooled.

The polymerization solution obtained above was diluted with MEK and filtered through a 10 μm pressure filter to remove a solid substance. Further, 1500 g of methanol was charged in a 3000 ml flask, attached to a stirrer, and stirred. The above-mentioned filtrate is added to the methanol while stirring, and the mixture is filtered, washed well with methanol, dried at 25 ° C. (room temperature) for 12 hours and at 80 ° C. for 24 hours, purified and white. A lump was obtained. The weight average particle size of the obtained white mass (fine particles) was 2.95 μm. The particle size is larger than that of the fine particle B-1 before polymerization, the polymerization initiating group generated by converting the bromo group remaining inside the fine particle B-1 into an iodo group, and the iodine on the surface of the fine particle B-1. From the group, it was found that the polymer was further extended. From the above, it is considered that a plurality of types of crosslinked acrylic fine particles were obtained.

As an example of utilization of the present invention, since an unprecedented novel method capable of industrially and easily producing polymers having various structures is provided, it can be used in fields that could not be used until now. Innovative technological development can be expected by providing it as a material. Specifically, a polymer material having peculiar properties such as adhesiveness, friction property, abrasion resistance, wettability, barrier property, adsorption / separation / transport property of a specific substance, or a polymer having such peculiar property as a base material. Various materials with treated surfaces have been provided and are expected to be used.

Claims (16)

A group having a structure represented by the following general formula 1 that functions as (1) a (meth) acrylic acid-based monomer as a radically polymerizable monomer having an unsaturated bond and (2) a polymerization initiating group of the monomer of (1) above. However, by mixing and heating an organic compound in which at least two of them are introduced into one molecule and (3) an iodine ion-containing compound which is an iodide salt or a triiodide salt, the group having the above-mentioned structure (polymerization initiation). Using a polymerization method to obtain a polymer having a polymerization step in which radical polymerization accompanied by a termination reaction starts from the group), a (co) polymer in which two or more (meth) acrylic acid-based (co) polymer chains are grafted is used. A method for producing a polymer to be produced.
The polymerization step is carried out twice or more,
In the first step, as the organic compound of (2), two or more groups having a structure represented by the following general formula 1 functioning as a polymerization initiating group are introduced as polymerization initiating groups in one molecule. using the organic compounds are, the the use in an amount which leftover the polymerization initiation group introduced into the organic compounds of iodine ion-containing compound (2) in (3), wherein two or more polymerization initiation group The monomer of (1) above is polymerized starting from a part of (1) to obtain a polymer grafted with the first (meth) acrylic acid-based (co) polymer chain, and the obtained polymer is purified or purified. It is a process that does not
In the second step, as the organic compound of the above (2), a polymer grafted with the first kind (meth) acrylic acid-based (co) polymer chain obtained in the first step was used. to polymerization initiation group remaining which has not been used leftover in the first stage of step, the (3) of by using the iodide ion-containing compound, part or all of the polymerization initiator group of the remaining The monomer of (1), which is different from the monomer of (1) used in the first step, was polymerized starting from, and the second kind (meth) acrylic acid-based (co) polymer chain was grafted. A method for producing a polymer, which is a step of obtaining a polymer and purifying or not purifying the obtained polymer.

(In General Formula 1, R1 represents H or any alkyl or acyl or aryl group, R2 represents an alkyl or aryl group, X represents Cl or Br, and Y represents. Represents O or NH) Further, in the polymer grafted with the second type (meth) acrylic acid-based (co) polymer chain obtained in the second step, in the first step and the second step. When there is a residual polymerization initiating group that has not been used, this is used as the organic compound of (2), and the same steps as those in the second step are sequentially repeated until there are no residual polymerization initiating groups. The method for producing a polymer according to claim 1, wherein a (co) polymer having a structure in which a seed (meth) acrylic acid-based (co) polymer chain is grafted is obtained. The method for producing a polymer according to claim 1 or 2, wherein none of the azo-based radical polymerization initiator, the peroxide-based radical polymerization initiator, and the photopolymerization radical polymerization initiator is used in the polymerization step. In the polymerization step, at least one of (4) iodine other than the iodide salt or triiodide salt of (3), an organic iodide compound capable of liberating iodine, and a compound having an organic base. The method for producing a polymer according to any one of claims 1 to 3. The method for producing a polymer according to any one of claims 1 to 4, wherein (5) an organic solvent is further used in the polymerization step. The method for producing a polymer according to claim 5, wherein the organic solvent is at least one selected from the group consisting of alcohol-based, glycol-based, amide-based, sulfoxide-based, urea-based and ionic liquids. The method for producing a polymer according to any one of claims 1 to 6, wherein the group represented by the general formula 1 is a group represented by the following general formula 2.

(In general formula 2, Y represents O or NH.) In the polymerization step carried out two or more times, after obtaining the polymer in the polymerization step carried out first, the polymer is used as the organic compound of (2) in the next polymerization step carried out without purifying the polymer. The invention according to any one of claims 1 to 7, wherein the polymer is polymerized by adding the iodine ion-containing compound of (3) and the monomer of (1) different from that used in the polymerization step previously carried out. How to make a polymer. The production of the polymer according to any one of claims 1 to 8, wherein the organic compound of (2) used in the first step is a polymer having two or more polymerization initiating groups in one molecule. Method. The production of the polymer according to claim 9, wherein the polymer having two or more polymerization initiating groups in one molecule is a polymer having the monomer having the polymerization initiating group and having a radical polymerizable group as a constituent unit. Method. The production of the polymer according to claim 9, wherein the polymer having two or more polymerization initiating groups in one molecule is any polymer selected from the group consisting of linear polymers, star polymers and crosslinked particle polymers. Method. The organic compound of (2) used in the first step is radically polymerizable having one polymerization initiating group having a structure represented by the general formula 1 in one molecule and having a radically polymerizable group. By mixing and heating the monomer, another radically polymerizable monomer, and the iodine ion-containing compound of (3) above, radical polymerization accompanied by a termination reaction starts from the polymerization initiating group of the structure. obtained by polymerization proposed method of obtaining a polymer having a step, two polymers according to any one of claims 1 to 8 the polymer is a star polymer remaining plurality polymerization initiation groups in the interior which is branched Manufacturing method. Two or more (meth) acrylic acid-based (co) polymer chains obtained by polymerizing the monomer of (1) obtained by the method for producing a polymer according to any one of claims 1 to 12 are each described above. A polymer characterized by being grafted from a polymerization initiator constituting the organic compound of (2). The polymer according to claim 13, wherein two types of (meth) acrylic acid-based (co) polymer chains are grafted. Two or more (meth) acrylic acid-based (co) polymer chains obtained by polymerizing the monomer of (1) obtained by the method for producing a polymer according to claim 8 each contain the organic compound of (2). It is grafted from the constituent polymerization initiating group, and at least one of the polymer chains is an AB block copolymer chain, and the other one is a B polymer block of the AB block copolymer. A polymer characterized by being a polymer chain composed of a monomer similar to a monomer for its composition. A star in which two or more (meth) acrylic acid-based (co) polymer chains obtained by the method for producing a polymer according to claim 12 are grafted from a plurality of polymerization initiators inside the star-shaped polymer. A polymer characterized by being a type polymer.

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