WO2024010011A1

WO2024010011A1 - Alkoxy group-containing radical generator, radical polymer, composition, and method for producing radical polymer

Info

Publication number: WO2024010011A1
Application number: PCT/JP2023/024837
Authority: WO
Inventors: 真澄高村; 理糸山
Original assignee: 国立大学法人山形大学
Priority date: 2022-07-05
Filing date: 2023-07-04
Publication date: 2024-01-11
Also published as: JP2024007206A

Abstract

The present invention addresses the problem of providing: an alkoxy group-containing radical generator that imparts hydrophilicity to a polymer; a radical polymer that has a narrow molecular weight distribution and includes an alkoxy group at at least one terminal thereof; and a method for producing such a radical polymer.　This problem is solved by an alkoxy group-containing radical generator expressed by formula (1) (in formula (1), R1 and R1' are straight chain or branched C1-5 alkyl groups, and R2 and R2' are straight chain or branched C1-10 alkylene groups), a radical polymer having a terminal functional group structure derived from the radical generator, and a method for producing said radical polymer.

Description

Alkoxy group-containing radical generator, radical polymer, composition, and method for producing radical polymer

The present invention relates to an alkoxy group-containing radical generator, a radical polymer having a specific terminal functional group structure, a composition thereof, a method for producing the radical polymer, and the like.

Living radical polymerization is an epoch-making polymerization that can take advantage of the advantages of radical polymerization, such as simplicity and versatility, while solving the disadvantage of non-uniform molecular weight. The living radical polymerization method is obtained by using a polymerization initiator composed of a dormant that generates a polymerization active terminal in the presence of a catalyst and an organic compound moiety, and a radically polymerizable unsaturated monomer. (hereinafter referred to as precursor), the organic compound moiety in the polymerization initiator and the dormant are respectively bonded to the ends. Therefore, when a new radically polymerizable monomer is added to the precursor and polymerized, copolymers with different components (block copolymers bonded in block shapes, graft copolymers bonded in branched shapes, and even star-like copolymers) are produced. A star-shaped copolymer bonded to a star-shaped copolymer, a ladder-shaped copolymer bonded to a ladder-shaped copolymer, etc.) are obtained, respectively. Living radical polymerization is an important technology both academically and industrially because the primary structure of copolymers with different bonding states greatly influences the chemical and physical properties of the polymer.

However, the resulting precursor-terminated dormant contains sulfides, halogens, transition metals, etc., and therefore has disadvantages such as odor, corrosivity, toxicity, and coloring, and there are many limitations in developing it for various uses. There is. Therefore, it is necessary to remove the dormant at the end of the obtained precursor.

On the other hand, by bonding a functional group to the terminal end of the precursor, for example, by causing the functional group to segregate near the surface of a thin film, reacting with another polymer, adsorbing or reacting with the surface of an organic or inorganic particle, etc. It becomes possible to express new functions. As the precursor with a functional group bonded to the terminal, (I) a polymer in which an organic compound moiety of a polymerization initiator containing a functional group in advance is bonded to the precursor terminal, and (II) a functional group-containing compound, There are two types of polymers in which the dormant at the precursor end is removed and at the same time a new functional group is attached to the end. In the above-mentioned polymer (I), a dormant terminal is present at one end of the polymer, and this can be said to be unfavorable from the viewpoint of safety such as toxicity as described above.

For example, Patent Document 1 describes a living radical polymer in which a hydrolyzable silyl group is bonded via nitrogen and sulfur as the polymer (II) above. Furthermore, Non-Patent Document 1 describes a polymer in which a hydroxyl group, a thiol group, or an alkoxysilyl group is bonded to a precursor via a nitrogen link. However, the polymers obtained in these documents had the problem that a desired chemical structure could not be bonded to them due to deterioration due to side reactions.

Japanese Patent Application Publication No. 2011-74325

The present invention has been made in view of the problems of the prior art described above, and uses an alkoxy group-containing radical generator that imparts hydrophilicity to a polymer, and a radical generator that has a narrow molecular weight distribution and has an alkoxy group at at least one end. The present invention provides a polymer, a composition containing a highly pure radical polymer, a method for producing a radical polymer, and the like.

The present invention includes those described below.

[1] An alkoxy group-containing radical generator represented by the following formula (1).

(In formula (1),
R ₁ and R ₁ ' are linear or branched C _1-5 alkyl groups,
R ₂ and R ₂ ' are linear or branched C _1-10 alkylene groups. )
[2] R ₁ ' and R ₁ are linear or branched C _1-3 alkyl groups, and R ₂ ' and R ₂
The alkoxy group-containing radical generator according to [1] above, wherein is a linear or branched C _1-5 alkylene group.
[3] The alkoxy group-containing radical generator described in [1] or [2] above, for example, in [1] above, wherein R ₁ and/or R ₁ ' is a methyl group.
[4] Any one of [1] to [3] above, for example the alkoxy group-containing radical according to [1] above, wherein R ₂ and/or R ₂ ' is a methylene group, ethylene group or propylene group Generating agent.

[5] A radical polymer having a terminal functional group structure represented by the following formula (2) at least at either end.

(In formula (2), R ₁ is a linear or branched C _1-5 alkyl group,
R ₂ is a linear or branched C _1-10 alkylene group,
* is a connection site with the main chain of the radical polymer. )
[6] The radical polymer according to the above [5], which is a living radical polymer.
[7] The radical polymer according to [5] or [6] above, for example, the radical polymer according to [5] above, which contains an organic compound moiety derived from a polymerization initiator at one end or main chain of the radical polymer.
[8] The radical polymer according to [7] above, which contains the organic compound moiety derived from an organic iodine compound.
[9] The radical polymer according to any one of [5] to [8] above, for example, according to [5] above, wherein the radically unsaturated monomer constituting the main chain of the radical polymer contains an acrylate. .
[10] The radical polymer according to any one of [5] to [9] above, such as the radical polymer according to [5] above, which has a molecular weight distribution value of 1.0 to 1.5.

[11] A radical polymer composition comprising the radical polymer according to any one of [5] to [10] above and a polymer that does not contain the terminal functional group structure.

[12] A method for producing a radical polymer according to any one of [5] to [10] above, comprising:
a polymerization step of forming a precursor of a radical polymer using a polymerization initiator containing an organic compound moiety and a dormant and a radically polymerizable unsaturated monomer;
The dormant end derived from the dormant of the precursor is reacted with any one of the above [1] to [4], for example, the radical generator described in the above [1], instead of the dormant end. A method for producing a radical polymer, comprising an introduction step of introducing a terminal functional group structure derived from the radical generator.
[13] The method for producing a radical polymer according to [12] above, wherein in the introduction step, the reaction temperature for producing the radical polymer is within the range of 70°C to 130°C.
[14] The radical polymerization according to [12] or [13] above, wherein in the polymerization step, 0.5 to 30 mol of the polymerization initiator is used with respect to 100 mol of the radically polymerizable unsaturated monomer. Method of manufacturing coalescence.
[15] In the introduction step, 0.5 to 30 mol of any one of the above [1] to [4], for example the one according to the above [1], per 1 mol of the dormant end of the precursor. The method for producing a radical polymer according to any one of [12] to [14] above, for example, according to [12] above, using the radical generator.
[16] In the introduction step, any one of the above [1] to [4], for example, the radical generator described in the above [1] is added dropwise to the reaction system, the above [12] to [15] For example, the method for producing a radical polymer according to [12] above.
[17] In the introduction step, a nonmetallic compound having an ionic bond with an iodide ion is further added to any one of the above [1] to [4], for example, the radical generator described in the above [1]. , any one of [12] to [16] above, for example, the method for producing a radical polymer according to [12] above.

The alkoxy group-containing radical generator of the present invention is useful in radical polymerization, particularly in living radical polymerization, and enables the production of a radical polymer containing a hydrophilic alkoxy group-containing terminal structure by a relatively easy production method. enable.
In addition, effects obtained by the radical polymer having a specific functional group at at least one terminal obtained by the above-mentioned radical generator according to the present invention, the composition thereof, and the method for producing the radical polymer will be explained. Although some details of the mechanism of action of this effect are unclear, it is estimated as follows. However, the present invention does not need to be interpreted as being limited to this mechanism of action.

The polymer of the present invention is characterized by having a narrow molecular weight distribution and having a specific functional group present in high purity at at least one end. This makes it easy to segregate specific functional groups near the surface of the thin film, and also makes the adsorption and reaction of other polymers and organic or inorganic particles on the surface uniform and efficient. Therefore, using the polymer of the present invention, it is possible to obtain, for example, additives such as compatibilizers and surface modifiers, and polymer films or particles whose surfaces are functionalized.
In particular, the polymer of the present invention having a hydrophilic terminal functional group is useful in, for example, antifogging paints.

The method for producing a polymer of the present invention is based on the dormant end of a precursor, which is a polymer obtained by using a polymerization initiator composed of an organic compound and a dormant, and a radically polymerizable unsaturated monomer. It is obtained by reacting the above-mentioned alkoxy group-containing radical generator.
The reaction mechanism is estimated as follows. First, the alkoxy group-containing radical generated from the radical generating agent extracts the dormant present at the end of the precursor, thereby generating a radical at the end of the precursor. On the other hand, since the alkoxy group-containing radical derived from the alkoxy group-containing radical generator present in an equimolar or more amount to the dormant present at the end of the precursor has a low molecular weight, it can quickly diffuse in the reaction solution. . Therefore, the alkoxy group-containing radical quickly bonds with the terminal radical of the precursor, and as a result, a highly purified precursor to which a specific functional group-containing compound is bonded can be obtained. Furthermore, since the alkoxy group-containing radical inhibits the bonding between the terminal radicals of the precursor, which would otherwise broaden the molecular weight distribution, the resulting polymer can maintain the narrow molecular weight distribution of the precursor as it is.

Therefore, according to the production method of the present invention, in addition to the above-mentioned effects, a polymer to which a desired alkoxy group is bonded can be obtained without deteriorating the polymer.

FIG. 3 is a diagram showing MALDI-TOFMS spectrum data of a sample of the precursor of Production Example 1. FIG. 7 is a diagram showing MALDI-TOFMS spectrum data for a sample of the polymer of Example 16. In addition, in FIGS. 1 and 2, Linear mode data was used for the spectrum, and Spiral mode data was used for the exact mass of the peak. Further, the exact molecular weights described in the spectra all indicate the values to which Na (accurate mass = 22.99), which is an ionizing agent, is added.

Hereinafter, the present invention will be explained in detail.

[1. Radical generator (alkoxy group-containing radical generator)]
(1-1. Molecular structure of alkoxy group-containing radical generator)
The radical generator of the present invention is a peroxide having a molecular structure represented by the following formula (1).
In the radical generator of formula (1), R ₁ and R ₁ ' are each a linear or branched alkyl group having 1 to 5 carbon atoms (C _{1 to 5} ). R ₁ ' and R ₁ may be different or the same.
Further, R ₂ and R ₂ ' are each a linear or branched alkylene group having 1 to 10 carbon atoms (C _{1 to 10} ). R ₂ ' and R ₂ may be different or the same.
As is clear from formula (1), the radical generator has a peroxide structure (-O-O-) which is a radical generating site at the center and an alkoxy group at the end. Radicals are generated by cleavage of peroxide bonds in the radical generator having such a molecular structure.

In the radical generator, R ₁ and R ₁ ' are each preferably a linear or branched C _1-3 alkyl group. In the radical generator, R ₁ and R ₁ ′ are preferably an alkyl group having 1 or 2 carbon atoms, more preferably at least one of R ₁ and R ₁ ′ is a methyl group, and even more preferably R ₁ and R ₁ ' are both methyl groups.
R ₂ and R ₂ ' are each preferably a linear or branched C _1-5 alkylene group. Preferred specific examples of R ₂ and R ₂ ' include a methylene group, an ethylene group, and a propylene group. It is preferable that at least one of R ₂ and R ₂ ′ is a methylene group, an ethylene group, or a propylene group, and more preferably that both of R ₂ and R ₂ ′ are a methylene group, an ethylene group, or a propylene group. .
Further, R ₁ , R _{1 ′} , R ₂ and R ₂ ′ may each be substituted with a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, an acyl group, an amino group, nitro group, cyano group, mercapto group, silyl group, etc. When R ₁ , R _{1 ′} , R ₂ and R ₂ ′ are substituted with a substituent, the above-mentioned number of carbon atoms does not include the number of carbon atoms in the substituent.

(1-2. Other radical generators)
As the radical generator, other radical generators may be used in addition to the above-mentioned alkoxy group-containing radical generator. That is, a radical generator composition containing an alkoxy group-containing radical generator and a general-purpose radical generator may be used in the radical polymerization reaction.
The general-purpose radical generator is not particularly limited as long as it is a known radical generator such as an azo compound or an organic peroxide. Specific general-purpose radical generators include 4-1 below. The same radical polymerization initiators as described in the column of polymerization step can be used.

In the case of a composition in which a radical generator other than the alkoxy group-containing radical generator of formula (1) is used in combination, for example, a composition in which the alkoxy group-containing radical generator of formula (1) and a general-purpose radical generator are used in combination. In the case of a radical generator mixture, that is, based on the total weight of the composition, the alkoxy group-containing radical generator of formula (1) preferably contains 30% by weight or more, 50% by weight or more, It is more preferable that it is contained, more preferably 70% by weight or more, and particularly preferably 90% by weight or more.

(1-3. Application of radical generator)
The radical generator of the present invention is particularly suitable for use in living radical polymerization reactions. As will be described in detail later, the alkoxy group-containing radical generated from the radical generator acts on the living radical polymer precursor in which the dormant derived from the polymerization initiator is bonded to the terminal, and an alkoxy group-containing terminal structure is introduced. enables the production of living radical polymers.

In addition to the above-mentioned uses, the radical generator of the present invention can also be used as a radical generator in radical polymerization other than living radical polymerization, a crosslinking agent for synthetic resins and rubber, a degrading agent for polypropylene, an oxidizing agent, etc. .

[2. Radical polymer (living radical polymer)]
(2-1. Structure of radical polymer)
The radical polymer of the present invention, for example a living radical polymer, has a specific functional group at at least one end. That is, the terminal of the radical polymer of the present invention contains at least a specific functional group represented by the following formula (2). The terminal functional group is bonded to the main chain of the radical polymer, as shown in formula (2) below.

In formula (2), * is a linking site to the main chain of the radical polymer, and R ₁ and R ₂ are both described in 1-1 above. As stated in the column.

The structure of the radical polymer having the above-mentioned terminal functional group differs mainly depending on the polymerization initiator, for example, depending on the number of dormants in one molecule of the polymerization initiator. For example, in the case of a radical polymer obtained from a monofunctional polymerization initiator having one dormant in one molecule, an organic compound fragment of the polymerization initiator is bonded to one end of the polymer as the main chain. , a compound having a specific functional group is bonded to the other end. On the other hand, in the case of radical polymers obtained from polyfunctional polymerization initiators having 2 to 4 dormants in one molecule, organic compounds originating from the polymerization initiator occur at the center of the main chain or at the center of the polymer molecule. A polymer having two to four branched chains sandwiching the organic compound moiety is obtained by arranging the compound moieties, and a compound having a specific functional group is bonded to the end of the branched chain of each polymer. .

That is, when a monofunctional initiator represented by the formula A-X (A is an organic compound moiety and X represents a dormant) is used, the structure of the resulting radical polymer is as shown in the formula A-M-X. When using a polyfunctional initiator (M is the main chain) and represented by A'-X _{2 to 4} (A' is an organic compound moiety, and X _{2 to 4} represent 2 to 4 dormants), The structure of the resulting radical polymer is exemplified by the formulas A'-(M-X) _{2 to 4} (M is a branched chain that can form a main chain). In the radical polymers of formulas A'-(M-X) _{2 to 4} above, since the lengths of the multiple branched chains represented by M are substantially uniform, A' The above-mentioned organic compound moiety represented will be located approximately at the center of the radical polymer. That is, by using a polyfunctional initiator, it is possible to produce a radical polymer in which an organic compound moiety is located at the center of a main chain having multiple branches.
Regarding these structures in the radical polymer, the most suitable one can be used depending on the desired use. For example, if you want to react only at one end, a polymer in which a compound having a specific functional group is bonded to the end of a radical polymer obtained from a monofunctional polymerization initiator having no functional group is suitable. When it is desired to react two or more terminals, a radical polymer obtained from a monofunctional polymerization initiator having a functional group or a radical polymer obtained from a polyfunctional polymerization initiator may be reacted with a specific terminal. A polymer to which a compound having a functional group is bonded is good.

Before bonding a compound having a specific functional group, the radical polymer with a dormant bonded to the terminal (hereinafter referred to as precursor) has one type of radical polymer that constitutes the main chain. Homopolymers of polymerizable unsaturated monomers, random copolymers of two or more types of radically polymerizable unsaturated monomers, block copolymers, graft copolymers, and even one or more types of radically polymerizable unsaturated monomers. Examples include star-shaped (co)polymers and ladder-shaped (co)polymers of saturated monomers, but the present invention is not limited to these examples.

(2-2. Radical polymerizable unsaturated monomer (radical unsaturated monomer))
A radically polymerizable unsaturated monomer is a monomer that is used in the production of a radical polymer and has an unsaturated bond that can undergo radical polymerization in the presence of an organic radical. More specifically, a so-called vinyl monomer can be used to form the main chain of the radical polymer. Vinyl monomer is a general term for monomers represented by formula (3).
CHR ⁷ = CR ⁸ R ⁹ (3)
(In formula (3), R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an organic group.)
In formula (3), the organic group includes an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted aryl group having 6 to 18 carbon atoms, and the like.

Note that the vinyl monomer represented by formula (3) includes the following, but the present invention is not limited to these examples.

Examples of vinyl monomers include styrene and its derivatives (R ⁷ and R ⁸ are hydrogen atoms, R ⁹ is a phenyl group that may have a substituent), acrylic acid (R ⁷ and R ⁸ are hydrogen atoms, R ⁹ is a carboxyl group) and its alkali metal salts, acrylamide (R ⁷ and R ⁸ are hydrogen atoms, R ⁹ is a CONH ₂ group) and its derivatives, acrylate (acrylic ester or acrylate), methacrylic acid (R ⁷ is a hydrogen atom, ^R8 is a methyl group, ^R9 is a carboxyl group) and its alkali metal salts, methacrylamide ( ^R7 is a hydrogen atom, ^R8 is a methyl group, R is a _CONH2 group) and its derivatives, methacrylate (methacrylate) acid esters or methacrylates), but the present invention is not limited to these examples.

Specific examples of styrene and its derivatives include styrene (hereinafter also referred to as St), 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-styrene sulfonic acid and its alkali metal salts, o-, m- - or p-styrene boronic acid and derivatives thereof, but the present invention is not limited to these examples.

Specific examples of acrylamide and its derivatives include acrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide, etc., but the present invention is limited only to such examples. It is not something that will be done.

Specific examples of acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate (hereinafter referred to as BA), t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, nonyl acrylate, Alkyl acrylates such as decanyl acrylate, lauryl acrylate, behenyl acrylate, stearyl acrylate, arylalkyl acrylates such as benzyl acrylate, epoxyalkyl acrylates such as tetrahydrofurfuryl acrylate, glycidyl acrylate, cycloalkyl acrylates such as cyclohexyl acrylate, 2-methoxyethyl Acrylate (hereinafter referred to as MEA), alkoxyalkyl acrylate such as 2-butoxyethyl acrylate, hydroxyalkyl acrylate such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polyalkylene glycol monoacrylate such as diethylene glycol monoacrylate, polyethylene glycol monoacrylate, etc. Acrylate, alkoxypolyalkylene glycol acrylate such as methoxytetraethylene glycol acrylate, methoxypolyethylene glycol acrylate, dialkylaminoalkyl acrylate such as 2-(dimethylamino)ethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxy-3 - Phenoxypropyl acrylate, fluoroalkyl acrylate in which the alkyl group of alkyl acrylate is substituted with a fluorine atom, acrylate in which the alkyl group of alkyl acrylate is substituted with a tris(trialkylsiloxy)silyl group, ethylphosphorylcholine group is substituted in the alkyl group of alkyl acrylate Examples include acrylates, but the present invention is not limited to these examples.

Specific examples of methacrylamide and its derivatives include methacrylamide, N-isopropylmethacrylamide, N,N-dimethylmethacrylamide, N-methylolmethacrylamide, N-hydroxyethylmethacrylamide, etc. is not limited to these examples.

Specific examples of methacrylate include methyl methacrylate (hereinafter referred to as MMA), ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, nonyl methacrylate, Alkyl methacrylates such as decanyl methacrylate, lauryl methacrylate, behenyl methacrylate, stearyl methacrylate, arylalkyl methacrylates such as benzyl methacrylate, epoxyalkyl methacrylates such as tetrahydrofurfuryl methacrylate, glycidyl methacrylate, cycloalkyl methacrylates such as cyclohexyl methacrylate, 2-methoxy Alkoxyalkyl methacrylates such as ethyl methacrylate and 2-butoxyethyl methacrylate; hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; polyalkylene glycol monomethacrylates such as diethylene glycol monomethacrylate and polyethylene glycol monomethacrylate; methoxytetraethylene Glycol methacrylate, alkoxypolyalkylene glycol methacrylate such as methoxypolyethylene glycol methacrylate, dialkylaminoalkyl methacrylate such as 2-(dimethylamino)ethyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, Fluoroalkyl methacrylates such as 2,2,3,4,4,4-hexafluorobutyl methacrylate in which the alkyl group of the alkyl methacrylate is substituted with a fluorine atom, and tris(trialkylsiloxy)silyl group is substituted in the alkyl group of the alkyl methacrylate. Examples include 3-[[tris(triethylsiloxy)silyl]propyl methacrylate, ethylphosphorylcholine methacrylate in which the alkyl group of alkyl methacrylate is substituted with an ethylphosphorylcholine group, but are not limited to these examples.

Both R ⁸ and R ⁹ of the vinyl monomer represented by formula (3) may be groups having a carboxyl group or a carboxylate. Specific examples thereof include itaconic acid, dimethyl itaconate, monobutyl itaconate, and its monoalkyl esters and dialkyl esters, but are not limited to these examples.

As the vinyl monomer, a vinyl monomer having two or more double bonds (vinyl group, isopropenyl group, etc.) may be used. Specifically, for example, diene compounds (e.g., butadiene, isoprene, etc.), compounds having two allyl groups (e.g., diallyl phthalate, etc.), compounds having two acrylic groups (e.g., ethylene glycol diacrylate, etc.) , compounds having two methacrylic groups (eg, ethylene glycol dimethacrylate), but are not limited to these examples.

As the vinyl monomer, vinyl monomers other than those mentioned above can also be used. Specifically, for example, vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl benzoate), styrene derivatives other than the above (e.g., α-methylstyrene), vinyl ketones (e.g., vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone), N-vinyl compounds (e.g. N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, vinyloxazoline), acrylonitrile, methacrylonitrile, maleic acid and its derivatives (e.g., maleic anhydride), vinyl halides (e.g., vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropylene, vinyl fluoride, vinylidene fluoride), olefins (e.g., ethylene, propylene, 1- or 2-butene, 1-hexene, 1-octene, cyclohexene), etc., but are not limited to these examples.

The radically polymerizable unsaturated monomers may be used alone or in combination of two or more.
As the radically polymerizable unsaturated monomer, acrylates, methacrylates, and styrenes are preferable, it is more preferable to use at least one of acrylates and methacrylates, and it is particularly preferable to use acrylates. For example, based on the total weight of all radically polymerizable unsaturated monomers used in the production of the radical polymer, it is preferable that acrylate is contained in an amount of 30% by weight or more, and preferably 50% by weight or more. It is more preferable that the content is 70% by weight or more, and it is particularly preferable that the content is 90% by weight or more.

The amount of the radically polymerizable unsaturated monomer used can be adjusted as appropriate depending on the desired molecular weight.

(2-3. Properties of radical polymer)
The number average molecular weight of the radical polymer is, for example, 1,000 to 200,000, preferably 1,500 to 100,000, and more preferably 3,000 to 50,000.
The weight average molecular weight of the radical polymer is equal to or slightly larger than the number average molecular weight, for example, 1,000 to 240,000, preferably 1,500 to 120,000, more preferably 3. 000 to 60,000.

Radical polymers are also characterized by a narrower molecular weight distribution compared to normal radical polymerization. Molecular weight distribution is the value obtained by dividing the weight average molecular weight of a polymer by the number average molecular weight, and compared to the molecular weight distribution obtained by ordinary radical polymerization, which is about 2 or more, the molecular weight distribution obtained by the present invention is The molecular weight distribution of the aggregate is preferably 1.0 to 1.5, more preferably 1.0 to 1.3, even more preferably 1.0 to 1.25, and particularly preferably 1.0 to 1.3. It is 0 to 1.24. However, the lower limit of the molecular weight distribution range of the radical polymer may be 1.05, 1.10, or the like.

The number average molecular weight and weight average molecular weight of the polymer were measured by size exclusion chromatography according to the general rules (JISK 7252-1 (2016) and ISO 16014-1 (2012)) under the following measurement conditions. This is the value at the time.
[Number average molecular weight and weight average molecular weight of polymer]
・Measuring equipment: EXTREMA size exclusion chromatography (GPC/SEC) system manufactured by JASCO Corporation ・Column: SHODEX manufactured by Showa Denko Co., Ltd. Sample side: 3 K-803, KF-804L, KF-806F connected , Reference side: KF-800RH
・Eluent: Tetrahydrofuran (hereinafter referred to as THF)
・Calibration curve standard material: Polymethyl methacrylate (other than styrene polymers), polystyrene (styrene polymers)
- Preparation of sample for measurement: Dissolve the polymer in an eluent (THF) to prepare a solution with a polymer concentration of 0.1% by weight, and use the filtrate after filtering the solution with a filter.

(2-4. Polymerization initiator)
The polymerization initiator used for producing the above-mentioned precursor (hereinafter also referred to as a polymerization initiator for producing the precursor) contains an organic compound part and a dormant, and preferably consists of only an organic compound part and a dormant.
Further, in the polymerization of the radical polymer precursor, although already known methods can be utilized, it is necessary to appropriately select the type of polymerization initiator depending on the polymerization method as described below. For example, nitroxide-mediated radical polymerization method (NMP method) using a nitroxide compound (nitroxide group) as a dormant, atom transfer radical polymerization method (ATRP method) using bromine as a dormant, thiocarbonylthio compound (thiocarbonylthio group) as a dormant, ) radical polymerization method using reversible addition-fragmentation reaction (RAFT method), radical polymerization method using organic tellurium, organic antimony, or organic bismuth, etc. as a dormant (TERP method using organic tellurium as a representative), as a dormant A radical polymer precursor can be produced by a radical polymerization method using iodine (eg, RCMP method or RTCP method).

Typical polymerization initiators in the NMP method using a nitroxide compound as a dormant include, for example, a polymer having a 1-phenylethyl group as an organic compound moiety and a t-butyl (1-phenyl-2-methylpropyl) nitroxide group as a dormant. Examples include t-butyl(1-phenyl-2-methylpropyl)(1-phenylethoxy)amine, but the present invention is not limited to such examples. The NMP method and the polymerization initiator used therein are summarized in Sigma-Aldrich's "Precision Radical Polymerization Handbook" published in July 2012, pages 31-34, so please refer to it.

Typical polymerization initiators in the ATRP method using bromine as a dormant include, for example, monofunctional type t-butyl-α-bromoisobutyrate having a t-butyl isobutyrate group as an organic compound moiety, and t-butyl-α-bromoisobutyrate containing a functional group. Monofunctional 2-hydroxyethyl-2-bromoisobutyrate has a hydroxyl-containing 2-hydroxyethyl-2-isobutyrate group as an organic compound moiety, and bifunctional 2-hydroxyethyl-2-bromoisobutyrate has an ethylenebis(isobutyrate group) as an organic compound moiety. Examples include ethylene bis(2-bromoisobutyrate), but the present invention is not limited to such examples. Further, examples of catalysts include amine compounds such as 2,2'-bipyridine, and examples of metal salts for catalysts include transition metal halides such as copper(I) chloride, but in the present invention, only such examples are used. It is not limited to. The ATRP method and the polymerization initiator used therein are summarized in Sigma-Aldrich's "Precision Radical Polymerization Handbook", p. 2-18, published in July 2012, so please refer to it.

Typical polymerization initiators in the RAFT polymerization method using a thiocarbonylthio compound as a dormant include, for example, a phenyldithioester group as a dithioester dormant, and a monofunctional cyanopropyl group having a cyanoisopropyl group as an organic compound moiety. trithiocarbonates, such as benzothyanoate (hereinafter referred to as CPBS), monofunctional cyanopentanoic acid benzothyanoate, etc., which has a carboxyl group such as a cyanopentanoic acid group as a functional group-containing organic compound moiety; monofunctional cyanopropyl-n-dodecyltrithiocarbonate having an n-dodecyltrithiocarbonate group as a system dormant and a cyanoisopropyl group as an organic compound moiety, and an ethylenebiscyanopentanoic acid group as an organic compound moiety. Examples include bifunctional ethylene bis(cyanopentanoic acid-n-dodecylthiocarbonate) having the following, but the present invention is not limited to such examples. The RAFT polymerization method and the polymerization initiator used therein are summarized in Sigma-Aldrich's "Precision Radical Polymerization Handbook", pages 19-30, published in July 2012, so please refer to it.

Typical polymerization initiators in the TERP method using an organic tellurium compound as a dormant include, for example, 2-methyltellanylpropionitrile having a methyltellurium group as an organic tellurium dormant and a cyanoisopropyl group as an organic compound moiety. However, the present invention is not limited to these examples. The TERP method and the polymerization initiators used in it are summarized in "Living Radical Polymerization 2. Polymerization Mechanism and Method 2" pages 365-367 of the Japan Rubber Association Journal (No. 82) published in August 2009. So please refer to it.

Typical polymerization initiators used in the RCMP method and RTCP method that use iodine as a dormant include, for example, monofunctional diamines having an isobutyronitrile group, an ethyl isobutyrate group, or an ethyl phenylacetate group as an organic compound moiety. -Iodoisobutyronitrile (CP-I), ethyl 2-iodoisobutyrate, ethyl 2-iodo-2-phenylacetate (PAME), etc., and as a functional group-containing organic compound moiety, isobutyric acid group containing a carboxyl group, phenyl Monofunctional 2-iodoisobutyric acid and 2-iodo-2-phenylacetic acid each having an acetate group, and difunctional 2-iodoisobutyric acid-2- each having a hydroxyethyl isobutyrate group and a hydroxyethyl phenylacetate group as organic compound moieties. Examples include hydroxyethyl, 2-hydroxyethyl 2-iodo-2-phenylacetate, but the present invention is not limited to these examples. Regarding the RCMP method and RTCP method and the polymerization initiators used therein, please refer to pages 6610-6618 of Macromolecules (No. 47) published by ACS Publishing in September 2014 and ELSEVIER Publishing published in September 2008, respectively. Please refer to the magazine Polymer (No. 49), pages 5177-5185.

From the viewpoint of polymerization control, the amount of the polymerization initiator used to obtain the radical polymer is preferably 0.1 to 50 moles, and 0.1 to 50 moles per 100 moles of the radically polymerizable unsaturated monomer used. More preferably, it is 5 to 40 moles. Further, from the viewpoint of the degree of polymerization, it is more preferable to use 0.5 to 10 moles of the polymerization initiator per 100 moles of the radically polymerizable unsaturated monomer.

Methods for obtaining radical polymers include the RAFT method using a thiocarbonylthio compound as a dormant and the use of an organic tellurium compound, from the viewpoint of the efficiency of dormant extraction from the polymer terminal and bonding of functional group-containing organic compound fragments. TERP method, ATRP method using halogen (bromine or iodine), RCMP method or RTCP method is preferable, and among them, ATRP method, RCMP method or RTCP method using halogen (bromine or iodine) is more preferable, and the resulting polymer has low odor. , RCMP method or RTCP method is most preferred from the viewpoint of low coloring and low toxicity.

(2-5. Structure of organic compound part)
The radical polymer of the present invention contains an organic compound moiety derived from the above-mentioned polymerization initiator for producing the precursor. In other words, the organic compound moiety introduced into one end or main chain of the precursor by the polymerization initiator will not undergo radical polymerization even if a radical polymer with a changed terminal structure of the precursor is subsequently produced. Maintained during coalescence. In this way, the organic compound moiety contained in the radical polymer exists either at one end of the radical polymer or in the main chain. As is clear from the fact that the organic compound moiety is derived from the above-mentioned polymerization initiator, specific examples of the organic compound moiety include the following. For example, 1-phenylethyl group that can be introduced by NMP method, t-butyl isobutyrate group, 2-hydroxyethyl-2-isobutyrate group, ethylene bis (isobutyrate group) that can be introduced by ATRP method, for example, by RAFT polymerization method. Cyanoisopropyl group, cyanopentanoic acid group, cyanoisopropyl group, ethylenebiscyanopentanoic acid group that can be introduced, for example, cyanoisopropyl group that can be introduced by TERP method, for example, isobutylene group that can be introduced by RCMP method or RTCP method. It is an organic compound moiety having a structure such as a lonitrile group, an ethyl isobutyrate group, an ethyl phenylacetate group, a carboxyl group-containing isobutyric acid group, a phenylacetate group, a hydroxyethyl isobutyrate group, or a hydroxyethyl phenylacetate group.
The organic compound moiety exemplified in the above structure may be substituted with a phenyl group, halogen, hydroxyl group, cyano, etc., and may have an organic acid group such as a carboxyl group, an acetate group, a butyrate group, etc. Residues of alkyl groups or alkylate groups having a total number of carbon atoms of 1 to 20, preferably 1 to 12 (alkylene groups, etc. when included in the main chain of the polymer); phenyl groups, halogens, hydroxyl groups Aryl having 6 to 24 carbon atoms in total, preferably 8 to 18 carbon atoms in total, which may be substituted with Examples include residues of groups (arylene groups when included in the main chain of the polymer).
Among these, organic compound moieties that can be introduced by ATRP method, RCMP method, etc. using a polymerization initiator containing halogen such as iodine, such as t-butyl isobutyrate group, 2-hydroxyethyl-2-isobutyrate group, ethylene Bis (isobutyrate group): Residues such as isobutyronitrile group, ethyl isobutyrate group, ethyl phenylacetate group, isobutyric acid group containing carboxyl group, phenylacetate group, hydroxyethyl isobutyrate group, hydroxyethyl phenylacetate group, etc. , preferred as an organic compound moiety.

(2-6. Structure of terminal functional group)
In the radical polymer of the present invention, a functional group containing an alkoxy group represented by formula (2) is bonded to at least one end, ie, one end or both ends, via an ester moiety. The terminal functional group of formula (2) is derived from an alkoxy group-containing radical generator, and has a structure corresponding to formula (1) representing an alkoxy group-containing radical generator as shown below.

In formula (2), R ₁ and R ₂ are as described above.
That is, R ₁ is preferably an alkyl group having 1 or 2 carbon atoms, more preferably a methyl group.
R ₂ is preferably an alkylene group having 1 or 2 carbon atoms, more preferably an ethylene group.
Furthermore, R ₁ and R ₂ contained in the terminal functional group may each be independently substituted with a substituent, and examples of substituents contained in R ₁ and R ₂ include a halogen atom, a hydroxyl group, an alkoxy group. , carboxyl group, acyl group, amino group, nitro group, cyano group, mercapto group, silyl group, etc. When R ₁ and R ₂ are substituted with a substituent, the number of carbon atoms in the substituent is not included in the above number of carbon atoms.

[3. Radical polymer composition (living radical polymer composition)]
Next, the radical polymer composition of the present invention, for example a living radical polymer composition, will be explained. The living radical polymer composition includes at least the above-mentioned living radical polymer and the above-mentioned polymer that does not contain a terminal functional group (a polymer that does not contain a specific terminal functional group, such as a living radical polymer). radical polymers such as coalescence).

The radical polymer to which a compound having a functional group containing an alkoxy group is not bonded to the terminal thereof preferably includes a precursor and a radical polymer in which the dormant of the precursor is replaced with hydrogen by some reaction. It will be done. The composition, primary structure and molecular weight of these polymers, which do not contain specific terminal functional groups, are almost the same, with little change compared to those of radical polymers. That is, the radical polymer that may be included in the radical polymer composition preferably differs primarily only in the terminal structure from a radical polymer having a specific terminal functional group.
In addition to the above-mentioned polymers derived from precursors, polymers that can be included in the radical polymer composition include thermoplastic resins, thermosetting resins, and polymers derived from precursors that are not derived from precursors. Known solvents such as soluble solvents and antioxidants can be used.

The above-mentioned radical polymer having a terminal functional group containing an alkoxy group is the entire mixture of polymers derived from a precursor, that is, a precursor in which a dormant such as a halogen such as iodine is introduced at the terminal end, and a precursor terminal having a dormant such as halogen such as iodine. It preferably accounts for 50 to 100 parts by weight, more preferably 70 to 100 parts by weight, and even more preferably It accounts for 90 to 100 parts by weight. According to the method for producing a radical polymer of the present invention, a radical polymer contained in a high content (purity) in a mixture derived from a precursor can be efficiently produced without the need for a special purification process. Obtainable.

In addition to the above-mentioned radical polymer having an alkoxy group-containing terminal functional group and the above-mentioned polymer not containing an alkoxy group-containing terminal functional group, the radical polymer composition includes a thermoplastic polymer which is a polymer not derived from a precursor. The resin, thermosetting resin, a solvent that dissolves the polymer derived from the precursor, an antioxidant, and the like may be included. The content of the above-mentioned radical polymer having an alkoxy group-containing terminal functional group in the radical polymer composition is preferably 1 to 100 parts by weight based on 100 parts by weight of the entire polymer composition. On the other hand, the content of the polymer that does not contain a specific alkoxy group-containing terminal functional group is preferably 0 to 50 parts by weight based on 100 parts by weight of the entire polymer composition. In addition, the content of thermoplastic resins and thermosetting resins that are polymers not derived from precursors, solvents that dissolve polymers derived from precursors, antioxidants, etc. is 100 parts by weight of the entire polymer composition. The amount is preferably 0 to 99 parts by weight.

[4. Method for producing radical polymer (living radical polymer)]
Next, a method for producing a radical polymer such as a living radical polymer according to the present invention will be explained. The production method is characterized in that a highly purified polymer having a narrow molecular weight distribution and having the above-mentioned alkoxy group-containing functional group at at least one polymer terminal is obtained.

The method for producing a polymer of the present invention includes a polymerization step of forming a radical polymer precursor and an introduction step of introducing an alkoxy group-containing functional group structure to the terminal end of the precursor. In the polymerization step, a precursor can be formed by using a polymerization initiator containing an organic compound moiety and a dormant, or preferably a polymerization initiator consisting only of an organic compound moiety and a dormant, and a radically polymerizable unsaturated monomer. polymerize. In the introduction step, an alkoxy group-containing radical generator is reacted with the dormant end of the precursor obtained in the polymerization step at a predetermined temperature to form a terminal functional group structure derived from the alkoxy group-containing radical generator. Introduce. Each step will be explained below.

(4-1. Polymerization step)
In the polymerization step, the aforementioned NMP method, ATRP method, RAFT polymerization method, TERP method, RCMP method, RTCP method, etc. can be used. As the polymerization initiator for producing the precursor, the above-mentioned polymerization initiators shown in the explanation of these production methods can be used, but in particular, the dormant at the terminal end of the precursor can be efficiently eliminated by using an alkoxy group-containing radical generator. Preference is given to using organic iodine compounds capable of binding as polymerization initiators. For this reason, of the RCMP method and RTCP method using at least an organic iodine compound as a polymerization initiator, the RCMP method in which the content of radical polymer terminal iodine is high will be explained in more detail.

The organic iodine compound that can be suitably used as a polymerization initiator for producing a precursor was described in detail in the previous section, but in addition to the method using an already produced polymerization initiator, there are also methods that use a polymerization initiator raw material. For example, an azo compound and iodine may be charged at the initial stage of polymerization, and a polymerization initiator made of an organic iodine compound may be generated in-situ by the reaction of the two.

Examples of azo compounds used to generate organic iodine compounds include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile) (AIBN ), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4,4-trimethylpentane), etc. Azo compounds containing no functional group, such as 4,4-azobis-4-cyanovaleric acid (ACVA) having a carboxyl group, and 2,2'-azobis{2-methyl-N-(2-hydroxyethyl) having a hydroxyl group. ) propionamide}, 2-2'-azobis{2-(2-imidazolin-2-yl)propane} having an amino group, and other functional group-containing azo compounds, but the present invention is limited only to such examples. It's not something you can do.

The amount of the azo compound used to produce the above-mentioned polymerization initiator is preferably 1 to 5 mol, more preferably 1.3 to 3 mol, per 1 mol of iodine.

In order to efficiently polymerize the above-mentioned polymerization initiator, it is desirable to use a catalyst in addition to the polymerization initiator. Examples of the catalyst include known compounds that coordinate to iodine and extract iodine, but the present invention is not limited to such examples.

Examples of catalysts include organic amine compounds and nonmetallic compounds that have ionic bonds with iodide ions, in which the nonmetallic atoms in the nonmetallic compound are in a cation state and form ionic bonds with iodide ions. However, the present invention is not limited to only such examples.

Specific examples of catalysts made of organic amine compounds include triethylamine, tributylamine, 1,1,2,2-tetrakis(dimethylamino)ethene, 1,4,8,11-tetramethyl-1,4,8, Examples include 11-tetraazacyclotetradecane, ethylenediamine, tetramethylethylenediamine, tetramethyldiaminomethane, tris(2-aminoethyl)amine, tris(2-(methylamino)ethyl)amine, hematoporphyrin, and the like. These catalysts may be used alone or in combination of two or more.

Specific examples of catalysts that are nonmetallic compounds that have ionic bonds with iodide ions, in which the nonmetallic atoms in the nonmetallic compounds are in a cation state and form ionic bonds with iodide ions, include: Examples include ammonium salts, imidazolium salts, pyridinium salts, phosphonium salts, sulfonium salts, iodonium salts, and more specifically, tetrabutylammonium iodide, tetrabutylammonium triiodide, tetrabutylammonium bromodiiodide, 1-Methyl-3-methyl-imidazolium iodide, 2-chloro-1-methylpyridinium iodide, methyltributylphosphonium iodide (hereinafter referred to as PMBI), tetraphenylphosphonium iodide, tributylsulfonium iodide, diphenyliodonium iodide Examples include de. These catalysts may be used alone or in combination of two or more.

The amount of the catalyst is preferably 0.01 to 50 mol, more preferably 0.05 mol, per 100 mol of the organic iodine compound, from the viewpoint of increasing the polymerization rate and reducing the residual amount of unreacted monomers. ~30 moles, more preferably 0.1 moles to 20 moles, even more preferably 0.5 to 10 moles.

In addition to the above-mentioned catalysts, a small amount of a general-purpose radical polymerization initiator may be used, if necessary, for the purpose of increasing the polymerization rate. Regarding the type of general-purpose radical polymerization initiator, it is not necessary to select it as strictly as the type of polymerization initiator for producing the precursor described above, and it is appropriately selected depending on the polymerization temperature, polymerization time, etc.

Examples of general-purpose radical polymerization initiators include azo compounds and organic peroxides, but the present invention is not limited to these examples. These general-purpose radical polymerization initiators may be used alone, or two or more types may be used in combination.

As the azo compound, the same azo compounds as mentioned above can be exemplified. These azo compounds may be used alone or in combination of two or more.

Examples of organic peroxides include, in addition to the above-mentioned specific functional group-containing diacyl peroxides, general-purpose organic peroxides that do not contain functional groups, such as di-(3,5,5-trimethylhexanoyl) peroxide and benzoyl peroxide. diacyl peroxides such as di-n-propyl peroxydicarbonate, di-isopropyl peroxydicarbonate, dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, and t-butyl peroxide. Examples include peroxyesters such as peroxypivalate and t-butylperoxy-2-ethylhexanoate, and peroxyketals such as 1,1-bis(t-butylperoxy)cyclohexane. It is not limited to only. These organic peroxides may be used alone or in combination of two or more.

In addition, if there is no need to use a general-purpose radical polymerization initiator, it is preferable not to use the general-purpose radical polymerization initiator substantially from the viewpoint of avoiding the adverse effects of the general-purpose radical polymerization initiator. It is more preferable not to use it at all. Here, "substantially not used" means an amount of the general-purpose radical polymerization initiator such that the polymerization initiator does not substantially affect the polymerization reaction. More specifically, the amount of general-purpose radical polymerization initiator per mole of catalyst is preferably 10 mmol or less, more preferably 1 mmol or less, and even more preferably 0.1 mmol or less.

The amount of the general-purpose radical polymerization initiator per 100 moles of all radically polymerizable unsaturated monomer components is preferably from the viewpoint of increasing the polymerization rate and reducing the remaining amount of unreacted radically polymerizable unsaturated monomers. The amount is 0.005 to 30 mol, more preferably 0.01 to 20 mol, and even more preferably 0.02 to 15 mol.

The radically polymerizable unsaturated monomer was described in detail in the previous section, but the polymerization conditions when polymerizing the radically polymerizable unsaturated monomer depend on the polymerization method of the radically polymerizable unsaturated monomer. It may be set as appropriate and is not particularly limited. The polymerization temperature is preferably room temperature (eg, 10-25°C, 20°C, etc.) to 200°C, more preferably 30-140°C. Further, the atmosphere during polymerization of the radically polymerizable unsaturated monomer is preferably an inert gas such as nitrogen gas or argon gas. The reaction time may be appropriately set so that the polymerization reaction of the radically polymerizable unsaturated monomer is completed.

The polymerization of the radically polymerizable unsaturated monomer may be bulk polymerization without using a solvent, or solution polymerization using a solvent that dissolves in the radically polymerizable unsaturated monomer or the polymer obtained thereby. Good too. Furthermore, by using a solvent that does not dissolve in the radically polymerizable unsaturated monomer or the polymer obtained thereby, emulsion polymerization, dispersion polymerization, suspension polymerization, etc. can be performed.

Examples of solvents used in solution polymerization of radically polymerizable unsaturated monomers include water, aromatic solvents such as benzene, toluene, xylene, and ethylbenzene, methanol, ethanol, isopropanol, n-butanol, and t-butanol. Alcohol-based solvents such as butyl alcohol, halogen atom-containing solvents such as dichloromethane, dichloroethane, and chloroform, and linear solvents such as propylene glycol methyl ether, dipropylene glycol methyl ether, ethyl cellosolve, butyl cellosolve, diglyme, and propylene glycol monomethyl ether acetate. aliphatic or branched aliphatic ether solvents, alicyclic ether solvents such as tetrahydrofuran, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, ethyl acetate, butyl acetate, cellosolve acetate, cellosolve acetate Examples thereof include ester solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as diacetone alcohol, amide solvents such as dimethylformamide, and sulfoxide solvents such as dimethyl sulfoxide. It is not limited to only. These solvents may be used alone or in combination of two or more. The amount of the solvent may be appropriately determined in consideration of the polymerization conditions, monomer composition, concentration of the resulting polymer, and the like.

(4-2. Introduction process)
In the introduction step of the method for producing a polymer of the present invention, an alkoxy group-containing radical generator is reacted with the dormant end of a precursor obtained from a polymerization initiator and a radically polymerizable unsaturated monomer, and the temperature is lowered. By applying this method, a polymer with a changed terminal structure can be obtained. As the functional group-containing radical generator, at least a compound having an alkoxy group represented by the above formula (1) is used.

The amount of the above-mentioned alkoxy group-containing radical generator to be added is preferably 0.5 to 30 mol, more preferably 0.5 to 20 mol, and even more preferably 1 to 10 mol, per 1 mol of the dormant at the terminal end of the precursor. , more preferably 1 to 5 mol. Moreover, in the introduction step, it is preferable to gradually add the radical generator to the reaction system while dropping it. The dropping rate (supply rate) of the radical generator into the reaction system in the introduction step is, for example, 2 to 20 (ml/min), preferably 5 to 10 per liter of the reaction system as a product diluted with a reaction solvent at a concentration of 10% by mass. (ml/min).

The reaction conditions for reacting the alkoxy group-containing radical generator with the dormant at the terminal end of the precursor may be appropriately set depending on the conditions for decomposing the alkoxy group-containing radical generator, and are not particularly limited.
However, the reaction temperature is, for example, 70°C to 140°C, preferably 80°C to 110°C when the main radically polymerizable unsaturated monomer constituting the precursor is styrene and its derivatives. When the main radically polymerizable unsaturated monomer constituting the precursor is acrylamide and its derivatives or acrylates, the temperature is 110°C to 130°C. In this case, the temperature is 70°C to 100°C. Further, the atmosphere during the reaction is preferably an inert gas such as nitrogen gas or argon gas. The reaction time may be appropriately set so that the decomposition of the alkoxy group-containing radical generator is completed, but for example, it may be 50 minutes to 200 minutes, 60 minutes to 150 minutes, 70 minutes to 120 minutes, 80 minutes to 100 minutes, etc. can be selected from the range of . Further, in order to make the reaction uniform, a solvent can be used as appropriate. As the solvent, any solvent can be used as long as it can dissolve the radical polymer, and for example, the same solvents as those used in polymerizing the above-mentioned radically polymerizable unsaturated monomer can be used.

As mentioned above, the reaction mechanism of the method for producing a polymer of the present invention is estimated to be as follows. First, the alkoxy group-containing radical generated from the alkoxy group-containing radical generating agent extracts the dormant present at the end of the precursor, thereby generating a precursor end radical. On the other hand, since the alkoxy group-containing radical derived from the alkoxy group-containing radical generator present in an equimolar or more amount to the dormant present at the end of the precursor has a low molecular weight, it can quickly diffuse in the reaction solution. . Therefore, the alkoxy group-containing radical quickly bonds with the terminal radical of the precursor, and as a result, a highly purified precursor to which a specific functional group-containing compound is bonded can be obtained. Furthermore, since the alkoxy group-containing radical inhibits the bonding between the terminal radicals of the precursor, which would otherwise broaden the molecular weight distribution, the resulting polymer can maintain the narrow molecular weight distribution of the precursor as it is.
Furthermore, if a nonmetallic compound having an ionic bond with an iodide ion or the like is used as a compound that extracts the dormant present at the end of the precursor faster than the alkoxy group-containing radical, the dormant present at the end of the precursor can be extracted by the alkoxy group-containing radical. , thereby rapidly generating precursor terminal radicals. On the other hand, alkoxy-containing radicals generated from alkoxy-containing radical generators have a low molecular weight and are oxygen radicals, so they can diffuse quickly in the reaction solution, and the alkoxy-containing terminal functional groups have higher purity and higher efficiency. is generated.

As mentioned above, examples of compounds that extract radicals from precursors include nonmetallic compounds that have an ionic bond with iodide ions.

Specific examples of nonmetallic compounds having an ionic bond with iodide ions include ammonium salts, imidazolium salts, pyridinium salts, phosphonium salts, sulfonium salts, and iodonium salts. More specifically, tetrabutyl Ammonium iodide, tetrabutylammonium triiodide, tetrabutylammonium bromodiiodide, 1-methyl-3-methyl-imidazolium iodide, 2-chloro-1-methylpyridinium iodide, methyltributylphosphonium iodide (hereinafter referred to as BMPI), tetraphenylphosphonium iodide, tributylsulfonium iodide, diphenyliodonium iodide, and the like. These catalysts may be used alone or in combination of two or more.

The amount of the compound that extracts radicals from the above-mentioned precursor is 0.5 to 20 mol, preferably 1 to 10 mol, per mol of the terminal dormant of the radical polymer precursor, from the viewpoint of increasing the reaction rate.

The present invention will be explained in more detail with reference to Examples below. First, examples of methoxy group-containing radical polymerization initiators are shown below.

Example 1
(Synthesis of methoxy group-containing raw material acid chloride)
3-Methoxypropionic acid (3-MPA; manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was placed in a 30 ml eggplant flask equipped with a 1.5 mm long rugby ball stirrer, a thermometer, a reflux condenser, and a calcium tube. 3.75 g (36 mmol) was charged, and 6.85 g (54 mmol) of oxanyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 20 minutes at room temperature while rotating a stirrer at 500 rpm. Thereafter, the temperature inside the 30 ml eggplant flask was raised to 80° C. in an oil bath, and the reaction was carried out for 2 hours. The temperature in the eggplant flask containing the obtained reaction solution was raised to 95°C in an oil bath and distilled under normal pressure to remove unreacted oxanyl chloride (boiling point: 63°C), thereby producing 3-methoxypropionic acid chloride. 4.61 g (3-MP-Cl) (yield 105% based on the amount of 3-MPA charged) was obtained.
When the alkali consumption and chlorine content of the obtained 3-MP-Cl were measured by chemical titration, they were 0.365 g/g (theoretical alkali consumption = 0.326 g/g) and 31.5% (theoretical chlorine consumption), respectively. amount = 28.9%). Furthermore, when ¹ H-NMR (solvent: CDCl ₃ , TMS included) of the obtained 3-MP-CL was measured, the following results were obtained, and it was assigned to be 3-MP-Cl.
3.10-3.13 ppm (t, j = 1.96, -CH ₂ - CO (Cl)), 3.37 ppm (s, j = 3.37, -O-CH ₃ ), 3.68-3 .71ppm (t,j=2.01, -O-CH ₂ -).

(Synthesis of methoxy group-containing radical generator)
In a 50 ml three-necked flask equipped with a glass rod with a 38 mm long crescent blade, a thermometer, and a stirrer, add 10% by weight of sodium hydroxide aqueous solution (NaOH; manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) with water. ) 14.5 g (36.3 mmol), 60% by weight hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 0.94 g (16.5 mmol) and toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 6.19 g of each was charged and stirred for about 30 minutes at a temperature of 20° C. or less and a rotation speed of 400 rpm. While adjusting the temperature of the liquid to 5±2° C., 3.68 g (30 mmol) of 3-MP-Cl synthesized earlier was added dropwise over 30 minutes, followed by further reaction for 60 minutes. The obtained reaction solution was transferred to a 50 ml separatory funnel, left to stand for 5 minutes, and only the upper layer remained, to which was added 25 g of 3.3% by weight saline solution, which had been adjusted to 0 to 5°C in advance. Thereafter, the reaction solution was washed by shaking the separatory funnel, and the mixture was allowed to stand for 5 minutes to separate. The same washing operation was repeated using 25 g of 3.3% by weight saline solution, which had been adjusted to 0 to 5°C in advance. After confirming with pH test paper that the waste liquid in the lower layer has changed from alkaline to neutral, take out the upper layer after static separation, dehydrate the system using anhydrous magnesium sulfate, and filter it. -Methoxypropionyl peroxide (3-MPPO) 5.04 g of toluene solution was obtained.
The active oxygen content and chlorine content of the obtained 3-MPPO toluene solution were measured by chemical titration and were found to be 3.24% (theoretical active oxygen content = 7.76%) and 0.03%, respectively.
Therefore, the purity determined from the theoretical amount of active oxygen was 41.8%, and the yield calculated from the purity and yield based on the amount of 3-MP-Cl charged was 82%.

In addition, toluene was added to the obtained 3-MPPO toluene solution to dilute 3-MPPO to 0.1 mol/L, and 3-MPPO was decomposed by differential scanning calorimetry (DSC). The 10 hour half-life temperature of MPPO was approximately 60°C.
Furthermore, when the obtained 3-MPPO toluene solution product was measured by ¹ H-NMR (solvent: CDCl ₃ with TMS), the following results were obtained, and it was assigned to be 3-MPPO.
2.69-2.72ppm (t, j = 4.01, -CH ₂ -CO(O)-), 3.37ppm (s, j = 6.00, -O-CH ₃ ), 3.70- 3.73ppm (t,j=4.03, -O-CH ₂ -).

Example 2
(Synthesis of methoxy group-containing raw material acid chloride)
2 was prepared in the same manner as in Example 1, except that 3.75 g (36 mmol) of 3-MPA was changed to 3.24 g (36 mmol) of 2-methoxyacetic acid (2-MAA; manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). -Methoxyacetic acid chloride (2-MA-Cl) 5.76 g (yield 100% based on the amount of 2-MAA charged) was obtained.
(Synthesis of methoxy group-containing radical generator)
A toluene solution product of di-2-methoxyacetyl peroxide (2-MAPO) was prepared in the same manner as in Example 1 except that 3.68 g (30 mmol) of 3-MP-Cl was changed to 4.80 g (30 mmol) of 2-MA-Cl. 10.14g was obtained. The 10-hour half-life temperature and 2-MAPO purity in the resulting 2-MAPO toluene solution were calculated to be approximately 54° C. and 41.1%, respectively. Further, the yield based on the amount of 2-MA-Cl charged was 78%.

Example 3
(Synthesis of methoxy group-containing raw material acid chloride)
In the same manner as in Example 1, except that 3.75 g (36 mmol) of 3-MPA was changed to 4.25 g (36 mmol) of 4-methoxybutanoic acid (4-MBA; manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), -Methoxybutanoic acid chloride (4-MB-Cl) 6.78 g (yield 103% based on the amount of 4-MBA charged) was obtained.
(Synthesis of methoxy group-containing radical generator)
4-methoxybutanoyl peroxide (4-MBPO) toluene solution product 14 was prepared in the same manner as in Example 1 except that 3.68 g (30 mmol) of 3-MP-Cl was changed to 5.64 g (30 mmol) of 4-MB-Cl. .19g was obtained. The 10-hour half-life temperature and 4-MBPO purity of the obtained 4-MBPO toluene solution product were calculated to be approximately 64° C. and 42.1%, respectively. Further, the yield based on the amount of 4-MB-Cl charged was 85%.

Next, an example of producing a living radical polymer precursor is shown below.

Manufacturing example 1
In a 30 ml Schlenk tube, 19.23 g of n-butyl acrylate (BA; manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., purified by distillation using a conventional method), 2-iodoisobutyronitrile (CP-I, Tokyo Chemical Industry Co., Ltd.) Co., Ltd.) and 1.303 g of tetrabutylammonium iodide (BNI; manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the internal space of the Schlenk tube was replaced with nitrogen gas. The contents of the Schlenk tube were stirred at 110° C. for 9 hours and then rapidly cooled to room temperature. The polymerization solution was reprecipitated by dropping it into a mixed solution of 180 ml of ion-exchanged water and 720 ml of methanol, and the polymer precipitated in the mixed solution of ion-exchanged water and methanol was vacuum-dried at 60°C for 18 hours. A BA polymer having iodine at the end (hereinafter referred to as PBA) was obtained. This reaction is represented by the following formula (i).

The number average molecular weight of the obtained polymer was 6,340, and the molecular weight distribution (weight average molecular weight/number average molecular weight, hereinafter referred to as Mw/Mn) was 1.17. In addition, when the obtained polymer was dissolved in deuterated chloroform and analyzed by ¹³ C-NMR, it was found that the integral value of carbon (carbon number: 1) of the quaternary carbon in CP-I and one BA molecule immediately adjacent to iodine. Since the integral value of carbon (carbon number: 1) of tertiary carbon was 1:0.99, it was confirmed that 99.0% of iodine present at the end of the polymer was introduced. The results are shown in Table 1.

Manufacturing example 2
Production example except that the amount of CPI added was changed from 0.172 g to 0.292 g, the amount of BNI added was changed from 1.303 g to 2.172 g, and the polymerization conditions were changed from 9 hours at 110°C to 6 hours at 110°C. PBA having iodine at one molecule end was obtained in the same manner as in Example 1.
The number average molecular weight of the obtained polymer was 3,360, and Mw/Mn was 1.18. Furthermore, from the results of ¹³ C-NMR, it was confirmed that 99.2% of iodine present at the polymer terminals was introduced. The results are shown in Table 1.

Manufacturing example 3
Production example except that the amount of CPI added was changed from 0.172g to 0.073g, the amount of BNI added was changed from 1.303g to 8.688g, and the polymerization conditions were changed from 9 hours at 110°C to 18 hours at 110°C. PBA having iodine at one molecule end was obtained in the same manner as in Example 1.
The number average molecular weight of the obtained polymer was 26,000, and Mw/Mn was 1.19. Furthermore, from the results of ¹³ C-NMR, it was confirmed that 99.1% of iodine present at the ends of the polymer was introduced. The results are shown in Table 1.

Production example 4
Instead of using 19.23 g of BA as a radically polymerizable unsaturated monomer, 19.53 g of 2-methoxyethyl acrylate (MEA; manufactured by Tokyo Kasei Kogyo Co., Ltd., purified by distillation using a conventional method) was used for polymerization. PMEA having iodine at one molecular end was obtained in the same manner as in Production Example 2, except that the conditions were changed from 110°C for 6 hours to 110°C for 10 hours.
The number average molecular weight of the obtained polymer was 4,910, and Mw/Mn was 1.12. Furthermore, from the results of ¹³ C-NMR, it was confirmed that 99.6% of iodine present at the ends of the polymer was introduced. The results are shown in Table 1.

Manufacturing example 5
Instead of using 19.23 g of BA as a radically polymerizable unsaturated monomer, 15.63 g of styrene (St; manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., purified by distillation by a conventional method) was used, and BNI was added. PSt having iodine at one molecule end was obtained in the same manner as Production Example 2, except that the amount was changed from 2.172 g to 0.543 g and the polymerization conditions were changed from 110 °C for 6 hours to 80 °C for 18 hours. Ta.
The number average molecular weight of the obtained polymer was 6,060, and Mw/Mn was 1.21. Furthermore, from the results of ¹³ C-NMR, it was confirmed that 98.1% of iodine present at the ends of the polymer was introduced. The results are shown in Table 1.

Manufacturing example 6
Instead of using 19.23 g of BA as a radically polymerizable unsaturated monomer, 15.02 g of methyl methacrylate (MMA; manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., purified by distillation using a conventional method) was used, and BNI PMMA having iodine at one molecular end was prepared in the same manner as in Production Example 2, except that the amount added was changed from 2.172 g to 0.543 g and the polymerization conditions were changed from 110° C. for 6 hours to 70° C. for 3 hours. Obtained.
The number average molecular weight of the obtained polymer was 6,600, and Mw/Mn was 1.19. Furthermore, from the results of ¹³ C-NMR, it was confirmed that 98.4% of the iodine present at the ends of the polymer was introduced. The results are shown in Table 1.

Manufacturing example 7
Instead of using 0.073 g of CP-I, which is an organic iodine compound, 0.083 g of 2-cyano-2-propyl benzodithianoate (manufactured by Sigma-Aldrich Japan, hereinafter referred to as CPBD), which is a RAFT agent, was used. PBA having a phenyldithioester group at one molecular end was prepared in the same manner as in Production Example 3, except that 0.812 g of AIBN was used and the polymerization conditions were changed from 110°C for 18 hours to 70°C for 1 hour. Obtained.
The number average molecular weight of the obtained polymer was 5,500, and Mw/Mn was 1.15. Furthermore, from the results of ¹ H-NMR, it was confirmed that 98.8% of the phenyl dithioester present at the polymer terminal had been introduced. The results are shown in Table 1.

Next, an example in which a terminal structure derived from a specific functional group-containing compound was bonded to the precursor obtained in the above production example will be described below.

Incidentally, the identity and purity of the polymer having a specific functional group-containing compound obtained in the Examples described below was confirmed based on the following method.

(sample preparation)
A sample solution obtained by adding 1 ml of THF to 0.01 g of the obtained polymer, matrix trans-2-{3-(4-t-butylphenyl)-2-methyl-2-propenylidene}malononitrate (manufactured by Tokyo Kasei Kogyo Co., Ltd., hereinafter referred to as DCTB) and a matrix solution obtained by adding 1 ml of THF to 0.02 g, and an ionizing agent, sodium trifluoroacetate (manufactured by Tokyo Kasei Kogyo Co., Ltd., hereinafter referred to as An ionizing agent solution was prepared by adding 1 ml of THF to 0.001 g of NaTFA. A sample was prepared by mixing 100 μl of the matrix solution, 20 μl of the ionizing agent solution, and 20 μl of the sample solution in a 2 ml sample bottle, spotting 1 μl of the mixed solution onto the sample plate, and drying the THF at room temperature for about 5 minutes.

(Identification of polymer terminal groups)
Using JMS-S3000 SpiralTOF manufactured by JEOL Ltd., a 50 kV laser was applied to the sample prepared according to the method described above (sample preparation) for the precursor of Production Example 1 and the above-mentioned sample for the polymer. The MS spectra obtained by each irradiation were analyzed. In the MS spectrum of the precursor, the MS spectra of the precursor PBA-I and PBA-H, in which the iodine at the end of the precursor was removed, appeared at almost the same position and could not be distinguished, but from NMR measurements of the precursor, PBA- The main peak was expected to be PBA-I since I was present in high purity (see Figure 1).
On the other hand, in the MS spectrum of the sample, PBA-I and/or PBA-H were present in extremely small amounts (see FIG. 2). In the MS spectrum shown in Figure 2 of the sample, there is a main spectrum that does not fit the spectra derived from PBA-I and PBA-H, and its total molecular weight is the molecular weight of the 3-methoxypropionyloxy group added to PBA. and the Na molecular weight of the ionizing agent. Therefore, it was confirmed that the 3-methoxypropionyloxy group was directly bonded to the PBA terminal.

(Purity measurement of a polymer having a compound derived from an alkoxy group-containing radical generator at its terminal)
Divide the area of the MS spectrum of the polymer having a compound derived from an alkoxy group-containing radical generator at the end and the area of other spectra present in the sample by the total area of all MS spectra present in the sample. Then, the purity of the polymer having a compound derived from an alkoxy group-containing radical generator at its terminal in the sample was calculated.

Example 4
In a 30 ml Schlenk tube, 0.3 g of the polymer obtained in Production Example 1, 0.041 g of 3-MPPO (concentration = 43.1% by weight toluene solution) as a radical generator, 0.079 g of BNI, and After adding and dissolving 2.442 g of toluene (manufactured by Kanto Kagaku Co., Ltd.) as a solvent (2.7 ml of toluene was used when using pure PO), the internal space of the Schlenk tube was replaced with nitrogen gas. . In Example 1, the contents of each Schlenk tube were reacted at 110° C. for 1 hour. Thereafter, the mixture was rapidly cooled to room temperature, and centrifuged at 3000 rpm for 5 minutes to remove unreacted BNI. By vacuum drying the polymer obtained by distilling off toluene contained in the supernatant under reduced pressure using an evaporator at 60°C for 1 hour, the dormant at the terminal of the polymer is removed and the alkoxy group-containing compound is released. A polymer having a structure (3-methoxypropionyloxy group) bonded thereto was obtained. The number average molecular weight, Mw/Mn, and purity of the obtained alkoxy group-bonded polymer were calculated, and the results are shown in Table 2. This reaction is represented by the following formula (ii).

Examples 5-6
In Example 4, 2 mol of 3-MPPO was added per 1 mol of iodine terminal in the precursor, but in Example 5, 0.5 mol was added, and in Example 6, 10 mol was added. Except for this, a polymer was produced in the same manner as in Example 4. As a result, the dormant at the terminal end of the precursor was removed, yielding a polymer to which a structure having an alkoxy group-containing compound (3-methoxypropionyloxy group) was bonded. The number average molecular weight, Mw/Mn, and purity of the obtained alkoxy group-bonded polymer were calculated, and the results are shown in Table 2.

Example 7
In Example 4, a polymer was produced in the same manner as in Example 4 except that 2 mol of BNI was added per 1 mol of iodine end of the precursor, but the addition was changed to 1 mol. As a result, the dormant at the terminal end of the precursor was removed, yielding a polymer to which a structure having an alkoxy group-containing compound (3-methoxypropionyloxy group) was bonded. The number average molecular weight, Mw/Mn, and purity of the obtained alkoxy group-bonded polymer were calculated, and the results are shown in Table 2.

Examples 8-9
Polymers were produced in the same manner as in Example 4, except that Mn in the precursor in Example 4 was changed to 3,360 g/mol in Example 8 and 26,000 g/mol in Example 9. As a result, the dormant at the end of the polymer was removed, yielding a polymer to which a structure having an alkoxy group-containing compound (3-methoxypropionyloxy group) was bonded. The number average molecular weight, Mw/Mn, and purity of the obtained alkoxy group-bonded polymer were calculated, and the results are shown in Table 2.

Examples 10-11
Same as Example 4 except that the radical generator in Example 4 was changed to 2-MAPO obtained in Example 2 in Example 10 and 4-MBPO obtained in Example 3 in Example 11. The polymer was produced by the method described in the following. As a result, the dormant at the end of the polymer was removed, yielding a polymer to which a structure having an alkoxy group-containing compound (2-methoxyacetoxyoxy group) was bonded. The number average molecular weight, Mw/Mn, and purity of the obtained alkoxy group-bonded polymer were calculated, and the results are shown in Table 2.

Example 12
A polymer was produced in the same manner as in Example 4, except that the precursor in Example 4 was changed to PMEA having iodine at the molecular terminal obtained in Production Example 4. As a result, the dormant at the end of the polymer was removed, yielding a polymer to which a structure having an alkoxy group-containing compound (3-methoxypropionyloxy group) was bonded. The number average molecular weight, Mw/Mn, and purity of the obtained alkoxy group-bonded polymer were calculated, and the results are shown in Table 2.

Example 13
In Example 4, 2 moles of BNI was added per mole of iodine terminal in the precursor, but the same procedure as in Example 4 was carried out except that the addition was increased to 2 moles and the reaction temperature was changed from 110°C to 130°C. The polymer was prepared by the method. As a result, the dormant at the terminal end of the precursor was removed, yielding a polymer to which a structure having an alkoxy group-containing compound (3-methoxypropionyloxy group) was bonded. The number average molecular weight, Mw/Mn, and purity of the obtained alkoxy group-bonded polymer were calculated, and the results are shown in Table 2.

Examples 14-15
Polymers of Examples 14 and 15 were obtained according to Example 13. That is, in Example 14, the polymer was produced in the same manner as in Example 4, except that the precursor was PSt having iodine at the molecular end obtained in Production Example 5, and the reaction conditions were changed to 80°C for 4 hours. Manufactured. In Example 15, the polymer was produced in the same manner as in Example 13, except that the precursor was PMMA having iodine at the molecular end obtained in Production Example 6, and the reaction conditions were changed to 70°C for 8 hours. did. As a result, the dormant at the terminal end of the precursor was removed, yielding a polymer to which a structure having an alkoxy group-containing compound (3-methoxypropionyloxy group) was bonded. The number average molecular weight, Mw/Mn, and purity of the obtained alkoxy group-bonded polymer were calculated, and the results are shown in Table 2.

Example 16
The amount of toluene added in Example 4 was changed from 2.442 g to 2.306 g, and in place of 0.041 g of 3-MPPO (concentration = 43.1% by weight toluene solution) used in Example 4, toluene was added. A polymer was produced in the same manner as in Example 4, except that 0.177 g of a toluene solution of 3-MPPO adjusted to a concentration of 10% by weight was added dropwise over about 30 minutes. As a result, the dormant at the terminal end of the precursor was removed, yielding a polymer to which a structure having an alkoxy group-containing compound (3-methoxypropionyloxy group) was bonded. The number average molecular weight, Mw/Mn, and purity of the obtained alkoxy group-bonded polymer were calculated, and the results are shown in Table 2.

Comparative Example The RAFT polymerization method was adopted as a living radical polymerization method to produce a precursor, and 2,2'-azobis(isobutyronitrile) (AIBN; Fujifilm Wa A polymer was produced in the same manner as in Example 4, except that Hikari Junyaku Co., Ltd.) was used. As a result, the dormant at the terminal end of the precursor was removed, yielding a polymer to which a structure having an alkoxy group-containing compound (3-methoxypropionyloxy group) was bonded. The number average molecular weight, Mw/Mn, and purity of the obtained alkoxy group-bonded polymer were calculated, and the results are shown in Table 2.

From the results in Table 2, it is clear that the alkoxy-containing radical generator of the present invention is a living radical polymer in which a structure having an alkoxy group-containing compound is introduced on the dormant side of the polymer terminal, that is, the alkoxy group-containing compound replaces the eliminated dormant. It can be seen that the living radical polymer to which the compound is bonded has a narrow molecular weight distribution and high purity. Furthermore, according to the production method of the present invention, a living radical polymer with a narrow molecular weight distribution and high purity is obtained by reacting a radical polymerization initiator having a specific functional group-containing compound with the terminal dormant of the precursor. be able to.

Claims

An alkoxy group-containing radical generator represented by the following formula (1).

(In formula (1),
R 1 and R 1 ' are linear or branched C 1-5 alkyl groups,
R 2 and R 2 ' are linear or branched C 1-10 alkylene groups. )
According to claim 1, R 1 and R 1 ' are linear or branched C 1-3 alkyl groups, and R 2 and R 2 ' are linear or branched C 1-5 alkylene groups. The alkoxy group-containing radical generator described above.
The alkoxy group-containing radical generator according to claim 2, wherein R 1 and/or R 1 ' is a methyl group.
The alkoxy group-containing radical generator according to claim 2, wherein R 2 and/or R 2 ' are a methylene group, an ethylene group, or a propylene group.
A radical polymer having a terminal functional group structure represented by the following formula (2) at least at either terminal.

(In formula (2), R 1 is a linear or branched C 1-5 alkyl group,
R 2 is a linear or branched C 1-10 alkylene group,
* is a connection site with the main chain of the radical polymer. )
The radical polymer according to claim 5, which is a living radical polymer.
The radical polymer according to claim 5, which contains an organic compound moiety derived from a polymerization initiator at one end or main chain of the radical polymer.
The radical polymer according to claim 7, which contains the organic compound moiety derived from an organic iodine compound.
The radical polymer according to claim 5, wherein the radically unsaturated monomer constituting the main chain of the radical polymer contains acrylate.
The radical polymer according to claim 5, which has a molecular weight distribution value of 1.0 to 1.5.
A radical polymer composition comprising the radical polymer according to any one of claims 5 to 10 and a polymer that does not contain the terminal functional group structure.
A method for producing a radical polymer according to any one of claims 5 to 10, comprising:
a polymerization step of forming a precursor of a radical polymer using a polymerization initiator containing an organic compound moiety and a dormant and a radically polymerizable unsaturated monomer;
An introduction step of reacting the radical generator according to claim 1 with the dormant end derived from the dormant of the precursor to introduce a terminal functional group structure originating from the radical generator instead of the dormant end. A method for producing a radical polymer, comprising:
The method for producing a radical polymer according to claim 12, wherein in the introduction step, the reaction temperature for producing the radical polymer is 70 to 130°C.
The method for producing a radical polymer according to claim 12, wherein in the polymerization step, 0.1 to 50 mol of the polymerization initiator is used per 100 mol of the radically polymerizable unsaturated monomer.
The method for producing a radical polymer according to claim 12, wherein in the introduction step, 0.5 to 30 mol of the radical generator according to claim 1 is used per 1 mol of the dormant end of the precursor. .
The method for producing a radical polymer according to claim 12, wherein in the introduction step, the radical generator according to claim 1 is added dropwise to the reaction system.
The method for producing a radical polymer according to claim 12, wherein in the introduction step, a nonmetallic compound having an ionic bond with an iodide ion is further added to the radical generator according to claim 1.