JP2023118366A - Catalyst and method for producing polymer - Google Patents

Abstract

To provide a catalyst used for living radical polymerization which has excellent solubility in a monomer and a polymerization solvent and to provide a method for producing a polymer using the catalyst without adversely affecting the production process such as reaction vessel contamination and pipe blockage.SOLUTION: There is provided a catalyst used for a living radical polymerization method, wherein the catalyst has a structure represented by the following formula (I) and satisfies at least one of the following (i) and (ii). Formula (I): (N+R1R2R3R4)X- (wherein, X is a halogen and R1 to R4 each independently is a hydrocarbon group or a substituted hydrocarbon group). (i) X is a chlorine atom. (ii) At least one of R1 to R4 is a benzyl group and at least one of R1 to R4 is a hydrocarbon group having 4 or more carbon atoms.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a catalyst used for living radical polymerization and a method for producing a polymer using the catalyst.

A radical polymerization method is conventionally known as a method of polymerizing a vinyl monomer to obtain a vinyl polymer. However, in general, the radical polymerization method has a problem that it is difficult to control the molecular weight of the resulting vinyl polymer. Moreover, the radical polymerization method has a problem that the resulting vinyl polymer is a mixture of compounds having various molecular weights, making it difficult to obtain a vinyl polymer with a narrow molecular weight distribution.

Since around 1990, a living radical polymerization method has been developed as a method for solving such problems. According to the living radical polymerization method, it is possible to control the molecular weight of the vinyl polymer and to obtain a vinyl polymer having a narrow molecular weight distribution.

Transition metal complex-based catalysts are known as one type of catalysts used in the living radical polymerization method. As the transition metal complex-based catalyst, for example, a complex in which a ligand is coordinated to a compound having Cu, Ni, Re, Rh, Ru, or the like as a central metal is used (see, for example, Non-Patent Document 1). . However, when using such a transition metal complex-based catalyst, there is a drawback that it is not easy to completely remove the used catalyst from the product. In addition, many transition metals are highly toxic, and there is a drawback that environmental problems may occur when disposing of the catalyst that is no longer needed.

On the other hand, a method using an organic compound as a catalyst for living radical polymerization is known. For example, Patent Document 1 discloses that non-metallic compounds having ionic bonds with halide ions can be used as catalysts for living radical polymerization processes. As such a compound, for example, tetrabutylammonium iodide (BNI) and the like are known. However, this compound has poor solubility in monomers and organic solvents at room temperature, and although it partially dissolves at polymerization temperature, insoluble matter precipitates at room temperature. As a result, the reaction solution becomes slurry, and there are problems in the production process such as the catalyst adhering to the reaction vessel and contaminating it, or clogging the piping.

WO2013/027419

Journal of The American Chemical Society 117, 5614 (1995), 5614-5615

The present invention has been made in view of the above circumstances, and a catalyst used for living radical polymerization that has excellent solubility in monomers and polymerization solvents, and the production of reaction vessel contamination and piping blockage using the same. An object of the present invention is to provide a method for producing a polymer that does not adversely affect the process.

The present invention has the following aspects.
[1] A catalyst used in a living radical polymerization method,
A catalyst having a structure represented by the following formula (I) and satisfying at least one of the following (i) and the following (ii).

（式（Ｉ）中、Ｘはハロゲンであり、Ｒ１～Ｒ４はそれぞれ独立に炭化水素基または置換炭化水素基である。）
（ｉ）Ｘが塩素原子である。
（ｉｉ）Ｒ１～Ｒ４の少なくとも１つがベンジル基であり、Ｒ１～Ｒ４の少なくとも１つが炭素数４以上の炭化水素基である。

(In formula (I), X is a halogen, and R1 to R4 are each independently a hydrocarbon group or a substituted hydrocarbon group.)
(i) X is a chlorine atom;
(ii) at least one of R1 to R4 is a benzyl group, and at least one of R1 to R4 is a hydrocarbon group having 4 or more carbon atoms;

[2] The catalyst according to [1], wherein any one of R1 to R4 is a hydrocarbon group having 9 or more carbon atoms.

[3] The catalyst according to [1] or [2], wherein X is a chlorine atom and any one of R1 to R4 is a hydrocarbon group having 9 or more carbon atoms.

[4] A method for producing a polymer comprising a step of performing living radical polymerization,
A method for producing a polymer, wherein the step of carrying out living radical polymerization is carried out in the presence of the catalyst according to any one of [1] to [3].

According to the present invention, a catalyst used for living radical polymerization with excellent solubility in monomers and polymerization solvents, and a polymer that does not adversely affect the production process such as contamination of reaction vessels and clogging of piping using the same. A manufacturing method can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.
"-" indicating a numerical range means that the numerical values before and after it are included as lower and upper limits.

[catalyst]
A catalyst according to one embodiment of the present invention is a catalyst used in a living radical polymerization method, has a structure represented by the following formula (I), and satisfies at least one of the following (i) and the following (ii): .

（式（Ｉ）中、Ｘはハロゲンであり、Ｒ１～Ｒ４はそれぞれ独立に炭化水素基または置換炭化水素基である。）

(In formula (I), X is a halogen, and R1 to R4 are each independently a hydrocarbon group or a substituted hydrocarbon group.)

(i) X is a chlorine atom;
(ii) at least one of R1 to R4 is a benzyl group, and at least one of R1 to R4 is a hydrocarbon group having 4 or more carbon atoms;

X is a halogen and an element selected from fluorine, chlorine, bromine and iodine. From the viewpoint of reactivity as a catalyst and solubility in monomers and organic solvents, X is preferably bromine or chlorine, more preferably chlorine.

R1 to R4 are each independently a hydrocarbon group or a substituted hydrocarbon group.
As the hydrocarbon group, a straight-chain or branched-chain hydrocarbon group, a cyclic hydrocarbon group, or the like can be used. A straight or branched chain hydrocarbon group is generally represented by C _k H _2k+1 , where k is a positive integer. The cyclic hydrocarbon group may be composed only of a cyclic structure, or may be a structure in which a chain alkyl is further bonded to the cyclic structure. The number of carbon atoms in the hydrocarbon group can be any natural number. The number of carbon atoms in the hydrocarbon group is preferably 1-30, more preferably 1-20. R1 to R4 may all be the same hydrocarbon group, or all may be different. From the viewpoint of reactivity as a catalyst and solubility in monomers and organic solvents, at least one hydrocarbon group preferably has 4 or more carbon atoms.
Any one of R1 to R4 is preferably a hydrocarbon group having 9 or more carbon atoms. Moreover, it is preferable that X is a chlorine atom and any one of R1 to R4 is a hydrocarbon group having 9 or more carbon atoms.

Substituted hydrocarbon groups include those in which one or more hydrogen atoms of the aforementioned hydrocarbon groups have been replaced with a substituent. The number of hydrogen atoms to be substituted may be one or more, and for example, 2 to 5 hydrogen atoms may be substituted. Here, as a substituent, halogen, hydroxyl group, cyano group, amino group, nitro group, alkoxy group, alkylcarboxyl group (ester group), alkylcarbonyl group (ketone group), aryl group, etc. can be used. Furthermore, when these substituents contain hydrogen atoms, one or more of the hydrogen atoms may be replaced with similar substituents. From the viewpoint of reactivity as a catalyst and solubility in monomers and organic solvents, at least one substituted hydrocarbon group is preferably a benzyl group.

These compounds function as catalysts for the living radical polymerization method, and are very useful in that they have excellent solubility in the monomers and organic solvents described below. Since these compounds are highly soluble even at room temperature, precipitation of the catalyst is less likely to occur, and production process problems such as contamination of the reaction vessel, transportation of the polymer solution, and clogging of piping during transportation are less likely to occur.

(Specific example of catalyst compound)
Preferred specific examples of the catalyst compound having the structure represented by the above formula (I) include benzyldimethyldodecylammonium chloride (BDDAC), benzyldimethyldodecylammonium iodide (BDDAI), tetrabutylammonium chloride (BNC), and benzyltributylammonium. chloride (BBAC), benzyltriethylammonium chloride (BTEAC), acetylcholine chloride (ACC), methyltrioctylammonium chloride (MOAC), didecyldimethylammonium chloride (DDAC), benzethonium chloride (BTC), cetyltrimethylammonium bromide (CTAB) is mentioned.
Particularly preferred examples include benzyldimethyldodecylammonium chloride (BDDAC), benzyldimethyldodecylammonium iodide (BDDAI), tetrabutylammonium chloride (BNC), benzyltributylammonium chloride (BBAC), and methyltrioctylammonium chloride (MOAC). is mentioned.

(Method for producing catalyst)
Many of the compounds used as the catalyst of the present invention are known compounds, and those commercially available from reagent sales companies can be used as they are, or they can be synthesized by known methods. be. Compounds existing in natural products can also be obtained by methods such as extraction from the natural products.

[Polymer production method]
A method for producing a polymer according to one embodiment of the present invention is a polymerization method including a step of performing living radical polymerization, wherein the step of performing living radical polymerization is performed in the presence of the catalyst of the present invention.

(monomer and organic solvent that dissolves the catalyst)
The organic compound used as a catalyst for the living radical polymerization method is dissolved in a monomer and an organic solvent before use. As the monomer, a radically polymerizable monomer is selected, for example, (meth)acrylate-based monomer, styrene-based monomer, vinyl ester-based monomer, vinyl ketone-based monomer, N-vinyl-based monomer, (meth)acrylamide-based monomer and derivatives thereof, (Meth)acrylonitrile, maleic acid and derivatives thereof, vinyl halide monomers, 1-olefin monomers, and the like. Specific examples of these monomers will be described later.

An organic solvent can be used for the purpose of ensuring the fluidity of the polymer solution and imparting workability such as coating of the polymer. Examples of organic solvents include aromatic hydrocarbon solvents (toluene, ethylbenzene, xylene, etc.), aliphatic hydrocarbon solvents (pentane, hexane, heptane, octane, cyclohexane, etc.), ketone solvents (acetone, methyl isobutyl ketone, etc.). , methyl ethyl ketone, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ether solvents (tetrahydrofuran, diethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, methyl cellosolve, etc.), alcohol solvents (methanol, ethanol, isopropanol, etc.) ), halogen-based solvents (dichloromethane, chloroform, etc.), and aprotic polar solvents (acetonitrile, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, etc.).

The organic compound used as a catalyst for living radical polymerization preferably has high solubility in the monomer and organic solvent. Specifically, the solubility (g/L) at 20°C is preferably 0.5 or more, more preferably 1.0 or more.

(Amount of catalyst used)
In the method for producing the polymer of the present invention, the catalyst should be used in an amount sufficient to catalyze the living radical polymerization, and no further addition is required. Specifically, for example, in a preferred embodiment, the amount of the catalyst used can be 80 millimoles or less, or 40 millimoles or less, or even 10 millimoles or less, per liter of the reaction solution. . On a mass basis, the amount of the catalyst used can be 8% by mass or less, 4% by mass or less, or 1% by mass or less in the total mass of the reaction solution.

The amount of the catalyst used is preferably 0.02 millimoles or more, more preferably 0.1 millimoles or more, and still more preferably 0.5 millimoles or more, per liter of the reaction solution. . On a mass basis, the amount of the catalyst used is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.02% by mass, based on the total mass of the reaction solution. That's it. If the amount of catalyst used is too small, the molecular weight distribution tends to become broad.

(protecting group)
In the method for producing the polymer of the present invention, a protective group that protects a growing chain during the reaction of living radical polymerization is used. As such a protecting group, it is possible to use various protecting groups known as protecting groups conventionally used for living radical polymerization. Halogen is preferably used as the protective group because the special protective group has drawbacks such as being very expensive.

(organic halide)
In the method for producing the polymer of the present invention, an organic halide having a carbon-halogen bond is preferably added to the reaction material, and the halogen given to the growing chain from this organic halide is used as a protecting group. Such organic halides are relatively inexpensive, which is an advantage over other known compounds used for protecting groups used in living radical polymerizations. Also, if necessary, it is possible to use an organic halide in which a halogen is bonded to an element other than carbon.

The organic halide is not particularly limited as long as it has at least one carbon-halogen bond in the molecule and acts as a dormant species. However, in general, the organic halides preferably contain one or two halogen atoms per molecule.

Here, in the organic halide, it is preferable that the carbon radical is unstable when the halogen is eliminated and the carbon radical is generated. Therefore, as the organic halide, those in which two or more substituents for stabilizing a carbon radical are bonded to the carbon atom forming the carbon radical when the halogen is eliminated to generate the carbon radical are not suitable. However, those in which one substituent that stabilizes the carbon radical is bonded to the carbon atom serving as the carbon radical often exhibit moderate radical stability and can be used as a dormant species.

The carbon to which the halogen of the organic halide is bonded (hereinafter, for convenience, referred to as the "1-position carbon of the organic halide") has preferably two or less hydrogens, more preferably one or less, It is even more preferred to have no hydrogen. The number of halogens bonded to the 1-position carbon of the organic halide is preferably 3 or less, more preferably 2 or less, and even more preferably 1. In particular, when the halogen bonded to the 1-position carbon of the organic halide is chlorine, the number of chlorine atoms is very preferably 3 or less, more preferably 2 or less, One is particularly preferred.

It is preferable that one or more carbon atoms are bonded to the 1-position carbon of the organic halide, and it is particularly preferable that two or three carbon atoms are bonded.

The halogen atom of the organic halide is preferably chlorine, bromine or iodine. Bromine or iodine is more preferred. Iodine is most preferable from the viewpoint of narrowing the molecular weight distribution. Bromine can also be preferably used in one embodiment. Advantages of bromine compounds are that they are generally more stable and easier to store than iodine compounds, and that the need to remove terminal halogens from the resulting polymer is relatively low. Furthermore, many compounds having multiple bromine groups can be commercially available or easily synthesized, and various branched polymers such as star-shaped, comb-shaped, and surface-grafted polymers can be easily synthesized. Another advantage is that a block copolymer can be easily synthesized from a bromine-terminated compound.

Also, the halogen atom in the organic halide may be the same as or different from the halogen atom in the catalyst. This is because even if the halogen atoms are different, the halogen atoms can be exchanged between the organic halide and the catalyst compound.

In one embodiment, the organic halide has a structure represented by general formula (II) below.

^{CR12R13R14X13 ( II )}
where R ¹² is halogen, hydrogen or alkyl. Hydrogen or lower alkyl is preferred. Hydrogen or methyl is more preferred.

R ¹³ may be the same as or different from R ¹² and is halogen, hydrogen or alkyl. Hydrogen or lower alkyl is preferred. Hydrogen or methyl is more preferred.

R ¹⁴ is halogen, hydrogen, alkyl, aryl, heteroaryl, alkylcarboxyl, or cyano. Preferred are aryl, heteroaryl, alkylcarboxyl, or cyano. When R ¹⁴ is halogen, hydrogen or alkyl, R ¹⁴ may be the same as or different from R ¹² or R ¹³ .

X ¹³ is halogen. Chlorine, bromine or iodine is preferred. Bromine or iodine is more preferred, and iodine is most preferred. When halogen is present in R ¹² to R ¹⁴ , X ¹³ may be the same as or different from the halogen in R ¹² to R ¹⁴ . In one embodiment, the halogen at X ¹³ can be the same halogen contained in the catalyst compound. However, the halogen may be different from the halogen contained in the catalyst compound.

The above R ¹² to R ¹⁴ and X ¹³ are each selected independently of each other, provided that 0 or 1 halogen atom is present among R ¹² to R ¹⁴ (i.e., as an organic halide, the presence of 1 or 2 halogen atoms) is preferred.

In one preferred embodiment, the organic halide is a halogenated alkyl or halogenated substituted alkyl. More preferred is halogenated substituted alkyl. Here, alkyl is preferably secondary alkyl, more preferably tertiary alkyl. In the halogenated alkyl or halogenated substituted alkyl, the alkyl preferably has 2 or 3 carbon atoms. Therefore, the organic halide is more preferably halogenated-substituted ethyl or halogenated-substituted isopropyl. Substituents on halogenated substituted alkyl include, for example, phenyl, cyano, and the like.

Preferred specific examples of organic halides include 2-iodo-2-cyanopropane and 1-iodo-1-phenylethane.

Other specific examples of organic halides include methyl chloride, dichloromethane, chloroform, chloroethane, dichloroethane, trichloroethane, bromomethyl, dibromomethane, bromoform, bromoethane, dibromoethane, tribromoethane, tetrabromoethane, bromotrichloromethane, Dichlorodibromomethane, chlorotribromomethane, iodotrichloromethane, dichlorodiiodomethane, iodotribromomethane, dibromodiiodomethane, bromotriiodomethane, iodoform, diiodomethane, methyl iodide, isopropyl chloride, t-butyl chloride, odor Isopropyl bromide, t-butyl bromide, triiodoethane, ethyl iodide, diiodopropane, isopropyl iodide, t-butyl iodide, bromodichloroethane, chlorodibromoethane, bromochloroethane, iododichloroethane, chlorodiiodoethane, di iodopropane, chloroiodopropane, iododibromoethane, bromoiodopropane, 2-iodo-2-polyethyleneglycosylpropane, 2-iodo-2-amidinopropane, 2-iodo-2-cyanopropane, 2-iodo-2-cyanobutane , 2-iodo-2-cyano-4-methylpentane, 2-iodo-2-cyano-4-methyl-4-methoxypentane, 4-iodo-4-cyano-pentanoic acid, methyl-2-iodoisobutyrate, 2-iodo-2-methylpropanamide, 2-iodo-2,4-dimethylpentane, 2-iodo-2-cyanobutanol, 4-methylpentane, cyano-4-methylpentane, 2-iodo-2-methyl- N-(2-hydroxyethyl)propionamide 4-methylpentane, 2-iodo-2-methyl-N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)propionamide 4-methylpentane, 2- iodo-2-(2-imidazolin-2-yl)propane, 2-iodo-2-(2-(5-methyl-2-imidazolin-2-yl)propane, etc. These halides are may be used, or may be used in combination.

In the method for producing the polymer of the present invention, the organic halide should be able to provide a sufficient amount of halogen to the growing chain. Specifically, for example, in the method for producing a polymer of the present invention, the amount of the organic halide used is preferably 0.05 mol or more per 1 mol of the nonmetallic compound as a catalyst in the polymerization reaction system, and more It is preferably 0.5 mol or more, more preferably 1 mol or more. Also, it is preferably 100 mol or less, more preferably 30 mol or less, still more preferably 5 mol or less per 1 mol of the non-metallic compound as a catalyst in the polymerization system. Furthermore, it is preferably 0.0001 mol or more, more preferably 0.0005 mol or more, per 1 mol of the monomer. Further, it is preferably 0.5 mol or less, more preferably 0.4 mol or less, still more preferably 0.3 mol or less, and particularly preferably 0.2 mol or less per 1 mol of the monomer, Most preferably, it is 0.1 mol or less. Further, if necessary, 0.07 mol or less, 0.05 mol or less, 0.03 mol or less, 0.02 mol or less, 0.01 mol or less, 0.005 mol or less, or 0.001 mol or less per 1 mol of monomer It is also possible to make it mol or less.

Many of the above organic halides are known compounds, and reagents commercially available from reagent sales companies can be used as they are. Alternatively, it may be synthesized using a conventionally known synthesis method.

The organic halide can also be used as the organic halide in this polymerization method by charging the starting material and generating the organic halide in situ during the polymerization, that is, in the reaction solution. For example, an azo-based radical reaction initiator (e.g., 2,2'-azobis(isobutyronitrile)) and a halogen molecule (e.g., iodine) are charged as raw materials, and the reaction of the two produces an organic halide (e.g., 2-iodo-2-cyanopropane) can be generated in situ during the polymerization and used as the dormant species in this polymerization process.

As organic halides, those immobilized on surfaces such as inorganic or organic solid surfaces and inorganic or organic molecule surfaces can also be used. For example, an organic halide immobilized on the surface of a silicon substrate, the surface of a polymer film, the surface of inorganic or organic fine particles, the surface of a pigment, or the like can be used. For immobilization, for example, chemical bonding or physical bonding can be used.

As the organic halide, a compound having a plurality of halogenated alkyl moieties can also be used. From a compound having two halogenated alkyl moieties, for example, a BAB-type triblock copolymer can be synthesized by block copolymerizing two types of monomers A and B. Furthermore, as the compound having a plurality of halogenated alkyl moieties, a compound having a structure in which a halogen is bonded to an alkyl in an organic compound can be preferably used. Compounds with structures can also be used. A compound having a plurality of halogenated alkyl moieties may be a compound with a low molecular weight or a compound with a high molecular weight. Thus, macromolecular or supramolecular compounds can also be used. Further, as a compound having a plurality of alkyl halide moieties, a compound that is not dissolved in the reaction solution can be used as a solid, and a polymer chain can be grown from the solid surface. Thus, compounds having various structures can be used as compounds having multiple alkyl halide moieties. By using compounds having various structures, various branched polymers such as star-shaped, comb-shaped, and surface-grafted polymers can be synthesized.

A block copolymer can also be synthesized using a polymer compound having an alkyl halide moiety at its terminal. According to this method, for example, a block copolymer of a polymer synthesized by a method other than living radical polymerization and a polymer synthesized by living radical polymerization can be synthesized.

(monomer)
A radically polymerizable monomer is used as a monomer in the method for producing the polymer of the present invention. A radically polymerizable monomer refers to a monomer having an unsaturated bond capable of undergoing radical polymerization in the presence of an organic radical. Such unsaturated bonds may be double bonds or triple bonds. That is, in the method for producing the polymer of the present invention, any monomer that is conventionally known to undergo living radical polymerization can be used. For example, (meth)acrylate monomers, styrene monomers, carbonyl group-containing unsaturated monomers, (meth)acrylonitrile, (meth)acrylamide monomers, diene monomers, vinyl ester monomers, N-vinyl monomers, (meth)acrylic acid Monomers, vinyl halide monomers, 1-olefin monomers, and the like can be used.

Specific examples of methacrylate-based monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, nonyl methacrylate, benzyl methacrylate, glycidyl methacrylate, Cyclohexyl methacrylate, lauryl methacrylate, 2-methoxyethyl methacrylate, butoxyethyl methacrylate, methoxytetraethylene glycol methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro 2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, 2- Hydroxy 3-phenoxypropyl methacrylate, diethylene glycol methacrylate, polyethylene glycol methacrylate and its alkyl ethers, 2-(dimethylamino)ethyl methacrylate and the like. Methacrylic acid can also be used. Also, 2-(N,N-diethyl-N-methylamino)ethyl methacrylate ⁺ /trifluorosulfonyliminium (N(CF ₃ SO ₂ ) ²⁻ ) salt, 2-(N-ethyl-N-methyl-N - hydrogenated amino)ethyl methacrylate ⁺ / trifluorosulfonyliminium (N(CF ₃ SO ₂ ) ^2- ) salt, 1-ethyl-3-methylimidazolium methacrylate ⁺ /fluorohydrogenation ((FH) _n F ^- ) salts, N-ethyl-N-methylpyrrolidinium methacrylate ⁺ /fluorohydrogenation ((FH) _n F ⁻ ) salts can be used.

Specific examples of acrylate monomers include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, nonyl acrylate, benzyl acrylate, glycidyl acrylate, cyclohexyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, butoxyethyl acrylate, methoxytetraethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2- Hydroxy 3-phenoxypropyl acrylate, diethylene glycol acrylate, polyethylene glycol acrylate and its alkyl ethers, 2-(dimethylamino)ethyl acrylate and the like. Acrylic acid can also be used. Also, 2-(N,N-diethyl-N-methylamino)ethyl acrylate ⁺ /trifluorosulfonyliminium (N(CF ₃ SO ₂ ) ^2- ) salt, 2-(N-ethyl-N-methyl-N - hydrogenated amino) ethyl acrylate ⁺ / trifluorosulfonyliminium (N(CF ₃ SO ₂ ) ^2- ) salt, 1-ethyl-3-methylimidazolium acrylate ⁺ / fluorohydrogenation ((FH) _n F ^- ) salts, N-ethyl-N-methylpyrrolidinium acrylate ⁺ /fluorohydrogenation ((FH) _n F ⁻ ) salts can be used.

Specific examples of styrenic monomers include styrene, α-methylstyrene, o-, m- or p-methylstyrene, o-, m- or p-methoxystyrene, o-, m- or pt-butoxystyrene. , o-, m- or p-chloromethylstyrene, o-, m- or p-chlorostyrene, o-, m- or p-hydroxystyrene, o-, m- or p-styrenesulfonic acid and derivatives thereof, Examples include sodium o-, m- or p-styrenesulfonate, o-, m- or p-styrene boronic acid and derivatives thereof.

Monomers with two or more vinyl groups can also be used in the method of making the polymers of the present invention. Specifically, for example, diene compounds (e.g., butadiene, isoprene, etc.), compounds having two allyl groups (e.g., diallyl phthalate, etc.), dimethacrylates having two methacryl groups (e.g., ethylene glycol dimethacrylate), acrylic are diacrylates having two (eg, ethylene glycol diacrylate).

Vinyl monomers other than those mentioned above can also be used in the method of making the polymers of the present invention. Specifically, for example, vinyl ester-based monomers (eg, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate), vinyl ketone-based monomers (eg, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone), N - Vinyl-based monomers (e.g., N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole), (meth)acrylamide-based monomers and derivatives thereof (e.g., N-isopropylacrylamide, N-isopropylmethacrylamide , N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methylol acrylamide, N-methylol methacrylamide), acrylonitrile, methacrylonitrile, maleic acid and its derivatives (e.g., maleic anhydride), vinyl halides monomers (eg, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropylene, vinyl fluoride), 1-olefinic monomers (eg, ethylene, propylene, 1-hexene, cyclohexene), and the like.

These may be used alone or in combination of two or more.

The combination of the types of the monomers described above and the types of the catalyst of the present invention is not particularly limited, and an arbitrarily selected catalyst of the present invention can be used for any arbitrarily selected monomer.

(radical reaction initiator)
By using the catalyst of the present invention, a living radical polymerization reaction can be carried out without using a radical reaction initiator. However, in the method for producing the polymer of the present invention, if necessary, a small amount of radical reaction initiator may be used. As such a radical reaction initiator, a known initiator used for radical reaction can be used. For example, azo-based radical reaction initiators and peroxide-based radical reaction initiators can be used. Specific examples of azo-based radical reaction initiators include azobis(isobutyronitrile) (AIBN), azobis(2,4-dimethylvaleronitrile) (V65), 2,2′-azobis(4-methoxy-2 ,4-dimethylvaleronitrile) (V70). Specific examples of peroxide-based radical reaction initiators include benzoyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate (BPB), di (4-tert-butylcyclohexyl) peroxydicarbonate (PERKADOX16), and potassium peroxide disulfate. are mentioned.

When it is not necessary to use a radical reaction initiator, in order to maximize the effect of avoiding the adverse effects of the radical reaction initiator, it is preferable not to use the radical reaction initiator substantially, and the amount used is Zero is most preferred. Here, "substantially not used" means that the amount of the radical reaction initiator is so small that the polymerization reaction is not substantially affected by the radical reaction initiator. Specifically, for example, the amount of the radical reaction initiator is preferably 10 millimoles or less, preferably 1 millimoles or less, and preferably 0.1 millimoles or less per 1 mol of the catalyst of the present invention. More preferred.

On the other hand, in the method for producing the polymer of the present invention, it is possible to use a radical reaction initiator, if necessary. If a radical reaction initiator is used, the amount of radicals in the reaction solution will increase, and the polymerization rate can be increased.

When using a radical reaction initiator, the amount used is not particularly limited. It is preferably 0.1 millimoles or more, more preferably 0.5 millimoles or more, still more preferably 1 millimoles or more, per 1 liter of the reaction solution. Further, it is preferably 500 millimoles or less, more preferably 100 millimoles or less, still more preferably 50 millimoles or less, per 1 liter of the reaction solution. Particularly preferably, it is 10 millimoles or less.

(solvent)
If the reaction mixture, such as the monomers, is liquid at the reaction temperature, it is not necessary to use a solvent. A solvent may be used as necessary. As the solvent, it is possible to use the solvent that has been conventionally used for living radical polymerization as it is. Specifically, it is possible to use the above-described organic solvent or the like. When a solvent is used, the amount used is not particularly limited as long as the polymerization reaction is appropriately carried out, but it is preferable to use 1 part by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the monomer. , more preferably 50 parts by mass or more. If the amount of solvent used is too small, the viscosity of the reaction solution may become too high. Also, it is preferably 2000 parts by mass or less, more preferably 1000 parts by mass or less, and even more preferably 500 parts by mass or less, relative to 100 parts by mass of the monomer. If the amount of solvent used is too large, the concentration of the monomer in the reaction solution may become too thin.

(Other additives, etc.)
A required amount of a known additive or the like may be added to the various materials for the living radical polymerization described above, if necessary. Examples of such additives include polymerization inhibitors.

(raw material composition)
By mixing the various raw materials described above, a raw material composition suitable as a material for living radical polymerization can be obtained. The obtained composition can be used in a conventionally known living radical polymerization method.

The raw material composition contains the following ingredients:
(1) a catalyst; and (2) a monomer having a radically reactive unsaturated bond.

The raw material composition can optionally further comprise one or more ingredients selected from:
(3) low-molecular-weight dormant species (eg, organic halides with carbon-halogen bonds);
(4) raw materials for generating organic halides in the reaction solution (for example, a combination of halogen molecules and an azo radical reaction initiator);
(5) a solvent; and (6) a radical initiator.

The raw material composition may contain all of the above components (1) to (6). However, components (3)-(6) are not essential. However, the reaction requires the presence of a low-molecular-weight dormant species in addition to the catalyst and monomer. Therefore, it is preferable to include at least one of component (3) or (4) in the raw material composition. However, low-molecular-weight dormant species may be generated in the reaction solution from components (1) and (2), etc. without using components (3) or (4). It is usually sufficient to use one of component (3) or component (4) above, ie either the low-molecular-weight dormant species or its source. Also, if no solvent is required, no solvent may be used. Further, if no radical initiator is required, no radical initiator may be used.

(reaction temperature)
The reaction temperature in the method for producing the polymer of the present invention is not particularly limited. The temperature is preferably 10° C. or higher, more preferably 20° C. or higher, still more preferably 30° C. or higher, still more preferably 40° C. or higher, and particularly preferably 50° C. or higher. Also, it is preferably 130° C. or lower, more preferably 110° C. or lower, even more preferably 100° C. or lower, and particularly preferably 90° C. or lower.

If the temperature is too high, it may be difficult to obtain very high molecular weight polymer produced. Moreover, if the temperature is too high, there is a drawback that the equipment for heating is costly. If the temperature is below room temperature, there is a drawback that the equipment for cooling is costly. In addition, if the reaction mixture is prepared so as to polymerize at room temperature or lower, the reaction mixture is unstable and reacts at room temperature, which makes storage of the reaction mixture difficult. Therefore, the temperature range just above room temperature but not too high (for example, 30° C. to 100° C.) is very suitable in a practical sense.

In the method for producing the polymer of the present invention, it is possible to carry out the reaction at relatively low temperatures. For example, it is possible to carry out the reaction at 30°C to 80°C. If the reaction is carried out at such a low temperature, it is possible to carry out the reaction while suppressing the iodine detachment from the terminal of the dormant species, which is a side reaction.

(reaction time)
The reaction time in the method for producing the polymer of the present invention is not particularly limited. It is preferably 15 minutes or longer, more preferably 30 minutes or longer, and still more preferably 1 hour or longer. In one embodiment, it is 5 days or less, preferably 3 days or less, more preferably 2 days or less, and even more preferably 1 day or less.

If the reaction time is too short, it will be difficult to obtain a sufficient molecular weight (or monomer conversion rate). If the reaction time is too long, the efficiency of the whole process is poor. By setting the reaction time appropriately, excellent performance (appropriate polymerization rate and reduction of side reactions) can be achieved.

(atmosphere)
The polymerization reaction in the method for producing a polymer of the present invention may be carried out under conditions in which air is present in the reaction vessel. In addition, if necessary, the air may be replaced with an inert gas such as nitrogen or argon.

The method for producing a polymer of the present invention can be applied to homopolymerization, that is, to produce a homopolymer, but it is also possible to produce a copolymer using the method for producing a polymer of the present invention for copolymerization. . The copolymerization may be random copolymerization or block copolymerization.

The block copolymer may be a copolymer in which two or more types of blocks are bonded, or may be a copolymer in which three or more types of blocks are bonded.

In the case of block copolymerization consisting of two types of blocks, for example, a block copolymer can be obtained by a method including a step of polymerizing a first block and a step of polymerizing a second block. In this case, the method for producing the polymer of the present invention may be used for the step of polymerizing the first block, and the method for producing the polymer of the present invention may be used for the step of polymerizing the second block. It is preferable to use the method for producing the polymer of the present invention for both the step of polymerizing the first block and the step of polymerizing the second block.

More specifically, for example, a block copolymer can be obtained by polymerizing the first block and then polymerizing the second block in the presence of the obtained first polymer. The first polymer can be subjected to polymerization of the second block after being isolated and purified, or the first polymer can be subjected to polymerization during or at the completion of the polymerization of the first polymer without isolating and purifying the first polymer. Block polymerization can also be achieved by adding a second monomer to the polymerization.

In the case of producing a block copolymer having three types of blocks, a step of polymerizing each block is carried out in the same manner as in the case of producing a copolymer in which two or more types of blocks are bonded to obtain the desired copolymerization. You can get a union. Then, it is preferable to use the polymerization method of the present invention in the polymerization of all blocks.

A compound having a plurality of halogenated alkyl moieties can also be used as the dormant species. From a compound having two halogenated alkyl moieties, for example, a BAB-type triblock copolymer can be synthesized by block copolymerization of monomer A and monomer B. Furthermore, various branched polymers such as star-shaped, comb-shaped, and surface-grafted polymers can be synthesized from inorganic/organic low-molecular-weights/polymers/super-molecular-weights/solids having multiple alkyl halide moieties. Block copolymers can also be synthesized from polymer compounds having alkyl halide moieties at their terminals. Thereby, for example, a block copolymer of a polymer synthesized by a method other than living radical polymerization and a polymer synthesized by living radical polymerization can be synthesized.

(Removal of Halogen Bonded to End of Generated Polymer)
The polymer produced by the method for producing a polymer of the present invention has a halogen (eg, iodine) at its terminal. When using this polymer for products, if necessary, the terminal halogen can be removed before use. In addition, a terminal halogen can be positively utilized and converted to another functional group to bring out a new function. Terminal halogens are generally highly reactive and can be removed or transformed by a wide variety of reactions.

(Use of polymer)
According to the above-described method for producing a polymer of the present invention, a polymer with a narrow molecular weight distribution can be obtained. For example, it is possible to obtain a polymer having a weight-average molecular weight (Mw) to number-average molecular weight (Mn) ratio (PDI) of 1.5 or less by appropriately selecting reaction materials and reaction conditions. Furthermore, by appropriately selecting the reaction material formulation and reaction conditions, it is possible to obtain a polymer having a PDI of 1.4 or less, 1.3 or less, or even 1.2 or less.

A polymer obtained by the method for producing a polymer of the present invention can be used for various purposes. Examples include resists, adhesives, lubricants, paints, inks, dispersants, packaging materials, chemicals, personal care products (hair styling products, cosmetics, etc.), elastomers (automotive materials, industrial products, sporting goods, electric wire covering materials, construction materials etc.), coatings (such as powder coating), etc. It can also be used to create new electronic, optical, mechanical, crystal, separation, lubrication, and medical materials.

The catalyst used in the method for producing the polymer of the present invention is a quaternary ammonium salt, and compounds exhibiting properties such as bactericidal and antibacterial properties are known. That is, the polymer containing the catalyst of the present invention can be used for paints, elastomers, etc. having bactericidal and antibacterial properties.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited by the following description. In addition, "eq" shows "molar equivalent". The amount of solvent is represented by the amount of solvent (% by mass) when the total amount including the solvent is 100% by mass.

(solubility)
The solubility of the catalyst in various monomers and organic solvents was calculated by the following method. After weighing a certain amount of catalyst in an air-conditioned room, add a small amount of various monomers and organic solvents and apply ultrasonic waves to promote dissolution. The amount of catalyst/(amount of monomer and organic solvent) (g/L)" was taken as the solubility.

(Number average molecular weight (Mn) and molecular weight distribution (PDI))
The number average molecular weight (Mn) and molecular weight distribution (PDI) of the polymer were measured under the following conditions.
<When the eluent is tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.)>
Measuring device: LC-2030C (manufactured by Shimadzu Corporation)
Column: Series connection of Shodex KF-804L MIXED GEL COLUMN (300 mm x 8.0 mm) and Shodex LF-804 MIXED GEL COLUMN (300 mm x 8.0 mm) Measurement temperature: 40°C
Flow rate: 0.7mL/min
Reference material: Polymethyl methacrylate <When the eluent is dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.)>
Measuring device: LC-2030C (manufactured by Shimadzu Corporation)
Column: Series connection of two Shodex LF-804 MIXED GEL COLUMN (300 mm × 8.0 mm) and Shodex KD-802 (300 mm × 8.0 mm) Measurement temperature: 40 ° C.
Flow rate: 0.34 mL/min
Additive: containing 10 mM lithium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) in dimethylformamide Standard substance: polymethyl methacrylate

(Monomer conversion rate)
The monomer conversion rate was calculated by performing ¹ H NMR measurement using an NMR spectrometer "AV500" (manufactured by Bruker, 500 MHz) and calculating the ratio of the amount of polymer produced to the sum of the amount of residual monomer and the amount of polymer produced.

(abbreviation)
Abbreviations used in this embodiment are as follows.

<Monomer>
MMA: methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
BzMA: benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
LMA: Lauryl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
MEMA: 2-methoxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
PEGMA: polyethylene glycol methacrylate (Mn=300) (manufactured by Sigma-Aldrich)
DMAEMA: 2-(dimethylamino)ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
St: styrene (manufactured by Tokyo Chemical Industry Co., Ltd.)
BA: n-butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Catalyst>
BDDAI: benzyldimethyldodecylammonium iodide BDDAC: benzyldimethyldodecylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
BNC: Tetrabutylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
BBAC: benzyltributyl ammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
MOAC: methyltrioctylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
BNI: Tetrabutylammonium iodide (manufactured by Tokyo Chemical Industry Co., Ltd.)
ONI: Tetra (n-octyl) ammonium iodide (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Organic halide>
CP-I: 2-iodo-2-cyanopropane (manufactured by Tokyo Chemical Industry Co., Ltd.)
PMMA-I: terminal iodinated polymethyl methacrylate <radical reaction initiator>
AIBN: 2,2'-azobis(isobutyronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
V65: 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
<Other compounds>
I ₂ : iodine (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Solvent>
BuAc: butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.)
Diglyme: diethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Synthesis example)
[Synthesis of BDDAI]
2.13 g (5.67 mmol) of BDDAC, 2.34 g (14.1 mmol) of potassium iodide (manufactured by Kanto Chemical Co., Ltd.), and 30 mL of ethanol (manufactured by Fisher Scientific) were mixed and reacted at 75° C. for 4 hours. . After the reaction, the reaction solution was cooled to room temperature to precipitate unreacted potassium iodide and formed potassium chloride, which were removed by filtration. After ethanol was distilled off under reduced pressure, crude BDDAI was dissolved in toluene (manufactured by TEDIA) and insoluble matter was removed by filtration. After that, toluene was distilled off under reduced pressure to obtain BDDAI.

[Synthesis of PMMA-I]
MMA 30 g (300 mmol), CP-I 0.584 g (3.0 mmol), BDDAC 1.13 g (3.0 mmol), V65 0.372 g (1.5 mmol), _I2 0.019 g (0 .075 mmol) and 20 g (217 mmol) of BuAc were mixed to prepare a reaction solution. The reaction solution was heated to 60° C. under an argon atmosphere and polymerized for 2 hours to obtain a polymer solution with a conversion rate of 59%. This polymer solution was reprecipitated in cold methanol and recovered to obtain PMMA-I (Mn=7,800, PDI=1.16).

(Catalyst solubility)
The solubility of the catalyst used in the present invention was measured and summarized in Table 1. Also, the chemical structural formula of the catalyst is shown in Formula (III) below.

From the solubility in Table 1, it has a structure represented by the following formula (I), (i) X is a chlorine atom, (ii) at least one of R1 to R4 is a benzyl group, and at least one has 4 carbon atoms. It was shown that the catalysts (catalyst examples 1 to 5) satisfying either or both of the above hydrocarbon groups have excellent solubility (>1.0 g/L) in various monomers and organic solvents. On the other hand, even among catalysts having a structure represented by the following formula (I), catalysts (catalyst examples 6 and 7) that do not satisfy both the above (i) and the above (ii) are shown to have remarkably low solubility. was done.

[Example 1]
(MMA polymerization using BDDAI as a catalyst)
CP-I was used as an alkyl halide serving as a dormant species, and BDDAI was used as a catalyst. These materials were dissolved in MMA at the equivalent ratio shown in Table 2 to prepare a reaction solution. BDDAI had good solubility and formed a homogeneous solution at room temperature. A polymerization reaction was carried out by replacing residual oxygen with argon and heating the reaction solution to 70°C. The reaction time was 24 hours. The monomer conversion rate of the reaction solution, Mn and molecular weight distribution of the polymer were measured as described above and shown in Table 2. The molecular weight (Mn=10,400) of the produced polymer was close to the theoretical molecular weight (Mn, theo=9,300), and the PDI was as small as 1.26, indicating that the living polymerization was well controlled.

[Examples 2 to 5]
(MMA polymerization using BDDAC as a catalyst)
Examples 2-5 used BDDAC as the catalyst. In Example 2, the polymerization reaction was carried out under the same conditions as in Example 1, except that AIBN and _I2 were further added. In Example 3, the polymerization reaction was carried out under the same conditions as in Example 1, except that V65 and _I2 were further added, the polymerization temperature was 60° C., and the polymerization time was 6 hours. In Example 4, the polymerization reaction was carried out under the same conditions as in Example 1, except that V65, _I2 and BuAc were further added and the polymerization temperature was 60°C. In Example 5, the polymerization reaction was carried out under the same conditions as in Example 4, except that the amounts of CP-I and _I2 used were changed.

[Examples 6 to 8]
(MMA polymerization using various catalysts)
The polymerization reaction was carried out under the same conditions as in Example 4 except that BNC was used as the catalyst in Example 6, BBAC was used as the catalyst in Example 7, and MOAC was used as the catalyst in Example 8.

[Examples 9 and 10]
(Polymerization of BzMA and LMA with BDDAC)
The polymerization reaction was carried out under the same conditions as in Example 4, except that BzMA was used as the monomer in Example 9, and LMA was used as the monomer in Example 10.

[Examples 11 and 12]
(Polymerization of MEMA and PEGMA with BDDAC)
In Example 11, the polymerization reaction was carried out under the same conditions as in Example 4, except that MEMA was used as the monomer and Diglyme was used as the solvent. In Example 12, the polymerization reaction was carried out under the same conditions as in Example 4, except that PEGMA was used as the monomer and Diglyme was used as the solvent.

[Example 13]
(Polymerization of DMAEMA using BDDAC)
In Example 13, the polymerization reaction was carried out under the same conditions as in Example 4, except that DMAEMA was used as the monomer, Diglyme was used as the solvent, and the polymerization time was 4 hours.

[Example 14]
In Example 14, a block copolymer was synthesized by using PMMA-I as the alkyl halide and BzMA as the monomer. Polymerization conditions are as shown in Table 2. The resulting block copolymer had a low PDI (1.26) and well controlled living polymerization.

[Example 15]
In Example 15, a block copolymer was synthesized by using PMMA-I as the alkyl halide and MEMA as the monomer. Polymerization conditions are as shown in Table 2.

[Example 16]
In Example 16, a block copolymer was synthesized by using PMMA-I as the alkyl halide and PEGMA as the monomer. Polymerization conditions are as shown in Table 2.

As described above, the examples show that the catalyst of the present invention is excellent in dissolving in monomers and organic solvents, and functions well as a catalyst for living radical polymerization.

According to the present invention, by having a structure represented by the above formula (I) and satisfying at least one of the above (i) and the above (ii), living radical polymerization with excellent solubility in monomers and polymerization solvents It is possible to provide a catalyst to be used and a polymerization method using the same that does not adversely affect the production process such as contamination of reaction vessels and clogging of piping.

Claims (4)

A catalyst used in a living radical polymerization method,
A catalyst having a structure represented by the following formula (I) and satisfying at least one of the following (i) and the following (ii).

(In Formula (1), X is a halogen, and R1 to R4 are each independently a hydrocarbon group or a substituted hydrocarbon group.)
(i) X is a chlorine atom;
(ii) at least one of R1 to R4 is a benzyl group, and at least one of R1 to R4 is a hydrocarbon group having 4 or more carbon atoms; The catalyst according to claim 1, wherein any one of R1 to R4 is a hydrocarbon group having 9 or more carbon atoms. 3. The catalyst according to claim 1, wherein said X is a chlorine atom and any one of said R1 to R4 is a hydrocarbon group having 9 or more carbon atoms. A method for producing a polymer comprising a step of performing living radical polymerization,
A method for producing a polymer, wherein the step of carrying out living radical polymerization is carried out in the presence of the catalyst according to any one of claims 1 to 3.