Living radical polymer and method for producing the same

Abstract

To provide, for example, a living radical polymer having a narrow molecular weight distribution in which a functional group-containing diacyl-type organic peroxide-derived structure is incorporated into at least one terminal.SOLUTION: A living radical polymer includes an organic compound part derived from a polymerization initiator at a terminal or main chain of the living radical polymer, and includes a predetermined terminal functional group structure in at least any terminal.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to living radical polymers having a specific terminal functional group structure, and to methods for producing the same. [Background technology]

[0002] Living radical polymerization is a groundbreaking polymerization method that leverages the advantages of radical polymerization, such as its simplicity and versatility, while overcoming its drawback of heterogeneous molecular weight. Living radical polymerization is obtained by using a polymerization initiator composed of a dormant and an organic compound moiety that generate polymerization active ends in the presence of a catalyst, along with a radically polymerizable unsaturated monomer. The ends of the resulting polymer (hereinafter referred to as the precursor) are bonded to the organic compound moiety and the dormant in the polymerization initiator, respectively. Therefore, when a new radically polymerizable monomer is added to the precursor and polymerization is carried out, copolymers with different components are obtained (block copolymers with block-like bonding, graft copolymers with branch-like bonding, and star copolymers or ladder copolymers with star-like bonding). Since the primary structure of copolymers with such different bonding states greatly affects the chemical and physical properties of the polymer, living radical polymerization is an important technology both academically and industrially.

[0003] However, the resulting precursor dormants contain sulfides, halogens, or transition metals, and therefore have drawbacks such as odor, corrosiveness, toxicity, and discoloration, which significantly limit their application to various uses. For this reason, it is necessary to remove the resulting precursor dormants.

[0004] On one hand, by bonding a functional group to the end of a precursor, for example, it becomes possible to exhibit new functions by segregating the functional group near the surface of a thin film, reacting with other polymers, adsorbing or reacting on the surface of organic or inorganic particles, and the like. As precursors with a functional group bonded to the end, there are two types: (I) a polymer in which the organic compound part of a polymerization initiator containing a functional group in advance is bonded to the precursor end, and (II) a polymer in which a dormant group at the precursor end is eliminated and at the same time a new functional group is bonded to the end using a functional group-containing compound. In the polymer of (I) described above, a dormant end exists at one end of the polymer, and from the viewpoint of safety such as toxicity as described above, it can be said that it is not preferable.

[0005] For example, in Patent Document 1, as the polymer of (II) above, a living radical polymer in which a hydrolyzable silyl group is bonded via nitrogen and sulfur is described. In addition, in Non-Patent Document 1, a polymer in which a hydroxyl group, a thiol group or an alkoxysilyl group is bonded to a precursor via nitrogen is described. However, in the polymers obtained in these documents, there was a problem that a desired chemical structure could not be bonded due to deterioration by side reactions.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Non-Patent Documents

[0007]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] The present invention has been made in view of the problems of the prior art described above, and provides a living radical polymer having a narrow molecular weight distribution and a functional group-containing diacyl-type organic peroxide-derived structure introduced at least one terminal, and a method for producing the same. [Means for solving the problem]

[0009] The present invention includes the following:

[0010] [1] A living radical polymer comprising an organic compound moiety derived from a polymerization initiator in one terminal or main chain of the living radical polymer, and comprising a terminal functional group structure represented by the following formula (1), formula (2), or formula (3) at at least one terminal. [ka] (In formula (1), R 1 Each of these is independently either a hydrogen atom or a fluorine atom, and n is an integer between 1 and 17. [ka] (In formula (2), R 2 Each of these is independently a hydrogen atom, an alkyl group, a fluorine atom, or a perfluoroalkyl group. [ka] (In formula (3), R 2 Each of these is independently a hydrogen atom, an alkyl group, a fluorine atom, or a perfluoroalkyl group. [2] The living radical polymer according to [1], wherein the organic compound moiety is derived from a polymerization initiator containing iodine as a dormant. [3] A living radical polymer according to [1] or [2], having a purity of 70-100%. [4] A living radical polymer according to any one of [1] to [3], comprising a structural unit derived from acrylate as the main structural unit. [5] A living radical polymer as described in any of [1] to [4], wherein the molecular weight distribution is between 1.0 and 1.5. [6] A method for producing a living radical polymer according to any one of [1] to [5], A polymerization step to form a precursor of a living radical polymer using a polymerization initiator containing an organic compound moiety and a dormant, and a radically polymerizable unsaturated monomer, A method for producing a living radical polymer, comprising: an introduction step of reacting a functional group-containing radical generator represented by any of the following formulas (4) to (6) with the dormant terminal derived from the dormant of the precursor, thereby introducing a terminal functional group structure derived from the radical generator in place of the dormant terminal. [ka] (In formula (4), R 1 Each of these is either a hydrogen atom or a fluorine atom, and each of these is an integer between 1 and 17. [ka] (In formula (5), R 2 Each of these is independently a hydrogen atom, an alkyl group, a fluorine atom, or a perfluoroalkyl group. [ka] (In formula (6), R 2 Each of these is independently a hydrogen atom, an alkyl group, a fluorine atom, or a perfluoroalkyl group. [7] The method for producing a living radical polymer according to [6], wherein the reaction temperature for producing the living radical polymer in the introduction step is 70 to 130°C. [8] A method for producing a living radical polymer according to [6] or [7], wherein in the polymerization step, 0.1 to 50 moles of the polymerization initiator are used per 100 moles of the radical polymerizable unsaturated monomer. [9] A method for producing a living radical polymer according to any one of [6] to [8], wherein in the introduction step, 0.5 to 30 moles of the radical generating agent are used per mole of the dormant terminal of the precursor.

[10] A method for producing a living radical polymer according to any one of [6] to [9], wherein the radical generating agent is added dropwise to the reaction system in the introduction step.

[11] A method for producing a living radical polymer according to any one of [6] to

[10] , wherein the introduction step is carried out in the presence of a nonmetallic compound having an ionic bond with an iodide ion. [Effects of the Invention]

[0011] This invention describes the effects obtained by a radical polymer having a specific functional group at at least one terminal, obtained by a functional group-containing radical generator, and by a method for producing the same. While the detailed mechanism of action of this effect remains unclear, it is presumed to be as follows. However, the present invention does not have to be interpreted as being limited to this mechanism of action.

[0012] The polymer of the present invention is characterized by a narrow molecular weight distribution and the presence of a specific functional group with high purity at at least one terminal. This facilitates the segregation of the specific functional group near the surface of the thin film, and also enables uniform and efficient adsorption and reaction to the surfaces of other polymers or organic or inorganic particles. Therefore, the polymer of the present invention can be used to obtain additives such as compatibilizers and surface modifiers, as well as polymer films or particles with functionalized surfaces.

[0013] The polymer of the present invention is obtained by reacting the dormant terminal of a polymer (precursor) obtained using a polymerization initiator containing an organic compound moiety and a dormant, and a radically polymerizable unsaturated monomer, with the above-mentioned functional group-containing radical generator. The reaction mechanism is presumed to be as follows: First, the functional group-containing radicals generated from the radical generator abstract the dormant present at the precursor terminal, thereby generating a precursor terminal radical. Meanwhile, the numerous functional group-containing radicals derived from the functional group-containing radical generator can diffuse rapidly in the reaction solution due to their low molecular weight. As a result, the functional group-containing radicals quickly bind to the precursor terminal radicals, thereby obtaining a polymer with specific functional groups attached in high purity. Furthermore, the functional group-containing radicals inhibit the binding of precursor terminal radicals to each other, which would broaden the molecular weight distribution. Therefore, the resulting polymer can maintain the narrow molecular weight distribution of the precursor.

[0014] Therefore, according to the manufacturing method of the present invention, in addition to the effects described above, a polymer in which the desired functional groups are bonded can be obtained without degrading the polymer. [Brief explanation of the drawing]

[0015] [Figure 1] The MALDI-TOFMS spectrum of the precursor is shown. [Figure 2] The MALDI-TOFMS spectra of living radical polymers are shown. The spectra are based on linear mode data, while the precise molecular weights of the peaks are based on spiral mode data. Furthermore, all precise molecular weights listed in the spectra include the ionizing agent Na (precise mass = 22.99). [Modes for carrying out the invention]

[0016] The present invention will be described in detail below.

[0017] [1. Living radical polymers] (1-1. Structure of living radical derivatives) The living radical polymer of the present invention has a specific functional group at at least one end. That is, in the radical polymer of the present invention, an organic compound moiety derived from a polymerization initiator is contained at one end or in the center (in the main chain), and at least one of the ends contains a specific functional group represented by the following formula (1), formula (2) or formula (3). [Chemical formula] (In formula (1), each R 1 is independently a hydrogen atom or a fluorine atom, and n is an integer of 1 to 17.) [Chemical formula] (In formula (2), each R 2 is independently a hydrogen atom, an alkyl group, a fluorine atom or a perfluoroalkyl group.) [Chemical formula] (In formula (3), each R 2 is independently a hydrogen atom, an alkyl group, a fluorine atom or a perfluoroalkyl group.)

[0018] The structure of the living radical polymer having the above functional group mainly varies depending on the polymerization initiator, for example, depending on the number of dormant species in one molecule of the polymerization initiator. For example, in the case of a living radical polymer obtained from a monofunctional polymerization initiator having one dormant species in one molecule, an organic compound fragment of the polymerization initiator is bonded to one end of the polymer as the main chain, and a compound having a specific functional group is bonded to the other end. On the other hand, in the case of a living radical polymer obtained from a polyfunctional polymerization initiator having 2 to 4 dormant species in one molecule, an organic compound moiety derived from the polymerization initiator is arranged at the center of the main chain or at the center of the polymer molecule, and a polymer having 2 to 4 branched chains sandwiching the organic compound moiety is obtained, and a compound having a specific functional group is bonded to the end of each branched chain of the polymer.

[0019] In other words, when a monofunctional initiator represented by the formula CX (where C is the organic compound moiety and X is the dormant) is used, the structure of the resulting living radical polymer is exemplified by the formula CMX (where M is the main chain), C'-X 2~4 A polyfunctional initiator represented by (C' is the organic compound moiety, X 2~4 When using (which shows 2 to 4 dormants), the structure of the resulting living radical polymer is C'-(MX) 2~4 This is illustrated by the formula (where M is a branched chain that can form the main chain). And the above C'-(MX) 2~4 In the living radical polymer of the formula, since the lengths of each of the multiple branched chains represented by M are substantially uniform, the aforementioned organic compound moiety represented by C' is located approximately at the center of the living radical polymer. In other words, by using a polyfunctional initiator, it is possible to produce a radical polymer in which the organic compound moiety is located in the center of a main chain having multiple branched chains. Regarding these structures in living radical polymers, the most suitable one can be selected depending on the desired application. For example, if only one end needs to be reacted, a polymer obtained from a monofunctional polymerization initiator without functional groups, to which a compound having a specific functional group is bonded, is suitable. If two or more ends need to be reacted, a polymer obtained from a monofunctional polymerization initiator with functional groups, or a radical polymer obtained from a polyfunctional polymerization initiator, to which a compound having a specific functional group is bonded, is suitable.

[0020] Examples of living radical polymers before the bonding of compounds having specific functional groups, where a dormant is bonded to the terminal (hereinafter referred to as a precursor), include homopolymers of one type of radically polymerizable unsaturated monomer, random copolymers, block copolymers, graft copolymers of two or more types of radically polymerizable unsaturated monomers, and even star-shaped (co)polymers and ladder-shaped (co)polymers of one or more types of radically polymerizable unsaturated monomers. However, the present invention is not limited to these examples.

[0021] (1-2. Radical polymerizable unsaturated monomers) Radical polymerizable unsaturated monomers are used in the production of living radical polymers and refer to monomers that have unsaturated bonds capable of radical polymerization in the presence of organic radicals. More specifically, monomers known as vinyl monomers can be used to form the main chain of radical polymers. Vinyl monomers are a general term for monomers represented by formula (7). CHR 3 =CR 4 R 5 (7) (In formula (7), R 3 , R 4 and R 5 Each of these independently represents either a hydrogen atom or an organic group. In formula (7), the organic group includes optionally substituted alkyl groups having 1 to 12 carbon atoms, optionally substituted aryl groups having 6 to 18 carbon atoms, and so on.

[0022] The following are examples of vinyl monomers represented by formula (7), but the present invention is not limited to these examples.

[0023] Examples of vinyl monomers include styrene and its derivatives (R 3 and R 4 is a hydrogen atom, R 5 (a phenyl group which may have substituents), acrylic acid (R 3 and R 4 is a hydrogen atom, R 5 (Carboxyl group) and its alkali metal salts, acrylamide (R 3 and R 4 is a hydrogen atom, R 5 (CONH2 group) and its derivatives, acrylates (acrylic acid esters or acrylic acid salts), methacrylic acid (R 3 is a hydrogen atom, R 4 is a methyl group, R 5 (Carboxyl group) and its alkali metal salts, methacrylamide (R 3 is a hydrogen atom, R 4 is a methyl group, R 5Examples include the CONH2 group and its derivatives, methacrylates (methacrylate esters or methacrylate salts), etc., but the present invention is not limited to these examples.

[0024] Specific examples of styrene and its derivatives include, for example, 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-styrenesulfonic acid and its alkali metal salts, o-, m- or p-styreneboronic acid and its derivatives, but the present invention is not limited to these examples.

[0025] Specific examples of acrylamide and its derivatives include, for example, acrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, and N-hydroxyethylacrylamide, but the present invention is not limited to these examples.

[0026] Specific examples of acrylates include alkyl acrylates such as 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, decanyl acrylate, lauryl acrylate, behenyl acrylate, stearyl acrylate, aryl alkyl acrylates such as benzyl acrylate, epoxy alkyl acrylates such as tetrahydrofurfuryl acrylate, glycidyl acrylate, cycloalkyl acrylates such as cyclohexyl acrylate, alkoxyalkyl acrylates such as 2-methoxyethyl acrylate (hereinafter referred to as MEA), 2-butoxyethyl acrylate, and hydroxypropyl acrylates such as 2-hydroxyethyl acrylate. Examples of polyalkylene glycol monoacrylates such as chloroacrylate, diethylene glycol monoacrylate, and polyethylene glycol monoacrylate; alkoxy polyalkylene glycol acrylates such as methoxytetraethylene glycol acrylate and methoxy polyethylene glycol acrylate; dialkylaminoalkyl acrylates such as 2-(dimethylamino)ethyl acrylate; 3-chloro-2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate; fluoroalkyl acrylates in which a fluorine atom is substituted on the alkyl group of an alkyl acrylate; acrylates in which a tris(trialkylsiloxy)silyl group is substituted on the alkyl group of an alkyl acrylate; and acrylates in which an ethyl phosphorylcholine group is substituted on the alkyl group of an alkyl acrylate. However, the present invention is not limited to these examples.

[0027] Specific examples of methacrylamide and its derivatives include, for example, methacrylamide, N-isopropylmethacrylamide, N,N-dimethylmethacrylamide, N-methylolmethacrylamide, and N-hydroxyethylmethacrylamide, but the present invention is not limited to these examples.

[0028] Specific examples of methacrylates include, for example, 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, decanyl methacrylate, lauryl methacrylate, behenyl methacrylate, stearyl methacrylate, and other alkyl methacrylates, arylalkyl methacrylates such as benzyl methacrylate, epoxyalkyl methacrylates such as tetrahydrofurfuryl methacrylate and glycidyl methacrylate, cycloalkyl methacrylates such as cyclohexyl methacrylate, alkoxyalkyl methacrylates such as 2-methoxyethyl methacrylate and 2-butoxyethyl methacrylate, hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, diethylene glycol monomethacrylate, poly Examples of methacrylates include polyalkylene glycol monomethacrylates such as ethylene glycol monomethacrylate, alkoxy polyalkylene glycol methacrylates such as methoxytetraethylene glycol methacrylate and methoxy polyethylene glycol methacrylate, dialkylaminoalkyl methacrylates such as 2-(dimethylamino)ethyl methacrylate, fluoroalkyl methacrylates such as 3-chloro-2-hydroxypropyl methacrylate and 2-hydroxy-3-phenoxypropyl methacrylate, fluoroalkyl methacrylates such as 2,2,3,4,4,4-hexafluorobutyl methacrylate in which a fluorine atom is substituted on the alkyl group of the alkyl methacrylate, 3-[[triethylsiloxy)silyl]propyl methacrylate in which a tris(trialkylsiloxy)silyl group is substituted on the alkyl group of the alkyl methacrylate, and ethyl phosphorylcholine methacrylate in which an ethyl phosphorylcholine group is substituted on the alkyl group of the alkyl methacrylate, but are not limited to these examples.

[0029] R of the vinyl monomer represented by formula (7) 4 and R 5The group may also be a group having a carboxyl group or a carboxylate. Specifically, examples include itaconic acid such as itaconic acid, dimethyl itaconate, and monobutyl itaconate, as well as its monoalkyl esters and dialkyl esters, but the examples are not limited to these.

[0030] The vinyl monomer may be a vinyl monomer having two or more double bonds (vinyl groups, isopropenyl groups, etc.). Specifically, examples include 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.), and compounds having two methacrylic groups (e.g., ethylene glycol dimethacrylate, etc.), but are not limited to these examples.

[0031] Other vinyl monomers besides those mentioned above can also be used. Specifically, examples include vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl benzoate), other styrene derivatives (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.

[0032] Radical polymerizable unsaturated monomers may be used individually or in combination of two or more types.

[0033] The amount of radically polymerizable unsaturated monomer used can be adjusted as appropriate depending on the desired molecular weight and other factors.

[0034] From the viewpoint of obtaining living radical polymers having terminal functional group structures in high purity, it is preferable to use acrylate as the main radical polymerizable unsaturated monomer. In this case, the living radical polymer will contain structural units derived from acrylate as the main structural units. Here, "main" means that, based on all structural units constituting the living radical polymer, the structural units derived from acrylate account for 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more. The amount of structural units derived from acrylate can be measured using a nuclear magnetic resonance (NMR) spectrometer.

[0035] (1-3. Properties of Living Radical Polymers) The number-average molecular weight of the living 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 living radical polymer is equal to or slightly greater than the number-average molecular weight, for example, 1,000 to 240,000, preferably 1,500 to 120,000, and more preferably 3,000 to 60,000.

[0036] Living radical polymers also have the characteristic of having a narrower molecular weight distribution compared to conventional radical polymerization. The molecular weight distribution is the value obtained by dividing the weight-average molecular weight of a polymer by the number-average molecular weight. Compared to the molecular weight distribution obtained by conventional radical polymerization, which is about 2 or more, the molecular weight distribution of the radical polymer obtained in the present invention 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 1.24. However, the lower limit of the molecular weight distribution range of the radical polymer may be 1.05, 1.10, etc.

[0037] The number-average molecular weight and weight-average molecular weight of the polymer are values ​​obtained by size exclusion chromatography in accordance with general rules (JIS K 7252-1 (2016) and ISO 16014-1 (2012)) under the following measurement conditions. [Number-average molecular weight and weight-average molecular weight of polymers] • Measuring instrument: EXTREMA size exclusion chromatography (GPC / SEC) system manufactured by JASCO Corporation. • Columns: SHODEX manufactured by Showa Denko K.K., Sample side: K-803, KF-804L, KF-806F (3 columns connected), Reference side: KF-800RH • Eluent: Tetrahydrofuran (hereinafter referred to as THF) Calibration curve standard materials: Polymethyl methacrylate (excluding styrene-based polymers), polystyrene (styrene-based polymer) • Preparation of the sample for measurement: Dissolve the polymer in the eluent (THF) to prepare a solution with a polymer concentration of 0.1% by weight, and use the filtrate after filtering the solution.

[0038] The purity of the living radical polymer is preferably 70-100%, more preferably 80-100%, even more preferably 90-100%, and particularly preferably 92-100%. Purity can also be expressed as the rate of introduction of terminal functional group structures. For example, if the living radical polymer is an aggregate of 100 molecules, and terminal functional group structures are introduced in 90 molecules, the purity (introduction rate) is 90%. Purity can be measured by the method described in the following examples.

[0039] Polymers without terminal functional group structures include precursors and polymers in which the dormant of the precursor is substituted with hydrogen. The composition, primary structure, and molecular weight of these polymers without terminal functional group structures are almost the same as those with terminal functional group structures. The difference in the precise molecular weight of these polymers can only be distinguished by the MALDI-TOFMS method described above, and the difference in precise molecular weight is at most a few hundred.

[0040] (1-4. Polymerization Initiators) The polymerization initiator used in the production of the aforementioned precursor (hereinafter also referred to as the polymerization initiator for precursor production) contains an organic compound moiety and a dormant, and preferably consists only of the organic compound moiety and the dormant. Furthermore, while known methods can be used in the polymerization of precursors of living radical polymers, it is necessary to appropriately select the type of polymerization initiator depending on the polymerization method, as described below. For example, precursors of radical polymers can be produced by nitroxide-mediated radical polymerization (NMP method) using a nitroxide compound (nitroxide group) as the dormant, atom transfer radical polymerization (ATRP method) using bromine as the dormant, radical polymerization (RAFT method) utilizing a reversible addition-cleavage reaction using a thiocarbonylthio compound (thiocarbonylthio group) as the dormant, radical polymerization using organic tellurium, organic antimony, or organic bismuth as the dormant (TERP method, represented by organic tellurium), and radical polymerization using iodine as the dormant (e.g., RCMP method and RTCP method).

[0041] Typical polymerization initiators in the NMP method using a nitroxide compound as a dormant include, for example, t-butyl(1-phenyl-2-methylpropyl)(1-phenylethoxy)amine, which has a 1-phenylethyl group as the organic compound moiety and a t-butyl(1-phenyl-2-methylpropyl)nitroxide group as a dormant. However, the present invention is not limited to these examples. The NMP method and the polymerization initiators used therein are summarized in Sigma-Aldrich's "Handbook of Precision Radical Polymerization," pp. 31-34, published in July 2012; please refer to it.

[0042] Examples of typical polymerization initiators in the ATRP method using bromine as a dormant include monofunctional t-butyl-α-bromoisobutyrate having a t-butylisobutyrate group as the organic compound moiety, monofunctional 2-hydroxyethyl-2-bromoisobutyrate having a hydroxyl-containing 2-hydroxyethyl-2-isobutyrate group as the functional group-containing organic compound moiety, and bifunctional ethylenebis(2-bromoisobutyrate) having an ethylenebis(isobutyrate group) as the organic compound moiety. However, the present invention is not limited to these examples. Furthermore, examples of catalysts include amine compounds such as 2,2'-bipyridine, and examples of catalytic metal salts include halogenated transition metals such as copper(I) chloride. However, the present invention is not limited to these examples. The ATRP method and the polymerization initiators used therein are summarized on page 2-18 of Sigma-Aldrich's "Handbook of Precision Radical Polymerization," published in July 2012. Please refer to it.

[0043] Typical polymerization initiators in the RAFT polymerization method using thiocarbonylthio compounds as dormants include, for example, monofunctional cyanopropylbenzothianoates (hereinafter referred to as CPBS) having a phenyldithioester group as a dithioester dormant and a cyanoisopropyl group as an organic compound moiety, monofunctional cyanopentanoic acid benzothianoates having a carboxyl group such as a cyanopentanoic acid group as a functional group-containing organic compound moiety, monofunctional cyanopropyl-n-dodecyltrithiocarbonates having an n-dodecyltrithiocarbonate group as a trithiocarbonate dormant and a cyanoisopropyl group as an organic compound moiety, and bifunctional ethylenebis(cyanopentanoic acid-n-dodecylthiocarbonate) having an ethylenebiscyanopentanoic acid group as an organic compound moiety. However, the present invention is not limited to these examples. For information on the RAFT polymerization method and the polymerization initiators used therein, please refer to pp. 19-30 of Sigma-Aldrich's "Handbook of Precision Radical Polymerization," published in July 2012.

[0044] Typical polymerization initiators in the TERP method, which uses an organic tellurium compound as the dormant, include, for example, 2-methylteranylpropionitrile, which has a methyl tellurium group as the organic tellurium dormant and a cyanoisopropyl group as the organic compound moiety. However, the present invention is not limited to these examples. The TERP method and the polymerization initiators used therein are summarized in "Living Radical Polymerization 2. Polymerization Mechanism and Method 2," pp. 365-367, of the Journal of the Rubber Association of Japan (No. 82), published in August 2009. Please refer to this for further information.

[0045] Examples of typical polymerization initiators in the RCMP and RTCP methods using iodine as a dormant include monofunctional 2-iodoisobutyronitrile (CP-I), 2-iodoisobutyrate ethyl, and 2-iodo-2-phenylethyl acetate, each having an isobutyronitrile group, an ethyl isobutyrate group, and an ethyl phenylethyl group as organic compound moieties; monofunctional 2-iodoisobutyrate and 2-iodo-2-phenylacetic acid, each having a carboxyl-containing isobutyrate group and a phenylacetic acid group as functional group-containing organic compound moieties; and bifunctional 2-iodoisobutyrate-2-hydroxyethyl and 2-iodo-2-phenylacetic acid-2-hydroxyethyl, each having an isobutyrate hydroxyethyl group and a phenylacetic acid hydroxyethyl group as organic compound moieties. However, the present invention is not limited to these examples. For details on the RCMP method, RTCP method, and the polymerization initiators used therein, please refer to pp. 6610-6618 of the journal Macromolecules (No. 47), published by ACS in September 2014, and pp. 5177-5185 of the journal Polymer (No. 49), published by ELSEVIER in September 2008.

[0046] From the viewpoint of polymerization control, the amount of polymerization initiator used to obtain a living radical polymer is preferably 0.1 to 50 moles, and more preferably 0.5 to 40 moles, per 100 moles of the radically polymerizable unsaturated monomer used. Furthermore, from the viewpoint of the degree of polymerization, it is even more preferable to use 0.5 to 10 moles of polymerization initiator per 100 moles of the radically polymerizable unsaturated monomer.

[0047] As for methods for obtaining living radical polymers, from the viewpoint of efficiency in dormant abstraction at the polymer ends and bonding of functional group-containing organic compound fragments, the RAFT method using a thiocarbonylthio compound as the dormant, the TERP method using an organic tellurium compound, and the ATRP method, RCMP method, or RTCP method using a halogen (bromine or iodine) are preferred. Among these, the ATRP method, RCMP method, or RTCP method using a halogen (bromine or iodine) are more preferred, and the RCMP method or RTCP method is most preferred from the viewpoint of low odor, low coloration, and low toxicity of the resulting polymer.

[0048] (1-5. Structure of the organic compound moiety) The living radical polymer of the present invention contains an organic compound moiety derived from the polymerization initiator used for precursor production described above. That is, the organic compound moiety introduced by the polymerization initiator to either one terminal or part of the main chain of the precursor is maintained in the living radical polymer even when a living radical polymer with altered terminal structure of the precursor is subsequently produced. Thus, the organic compound moiety contained in the living radical polymer is present either at one terminal or in the main chain of the living radical polymer.

[0049] As is evident from the fact that the organic compound moieties originate from the polymerization initiators mentioned above, specific examples of organic compound moieties include the following: For example, 1-phenylethyl group which can be introduced by the NMP method; for example, t-butylisobutyrate group, 2-hydroxyethyl-2-isobutyrate group, ethylenebis(isobutyrate group) which can be introduced by the ATRP method; for example, cyanoisopropyl group, cyanopentanoic acid group, cyanoisopropyl group, ethylenebiscyanopentanoic acid group which can be introduced by the RAFT polymerization method; for example, cyanoisopropyl group which can be introduced by the TERP method; for example, isobutyronitrile group, ethyl isobutyrate group, ethyl phenylethyl group, isobutyrate group containing a carboxyl group, phenylacetic acid group, hydroxyethyl isobutyrate group, hydroxyethyl phenylacetic acid group, etc., which can be introduced by the RCMP or RTCP method.

[0050] Examples of organic compound moieties exemplified in the above structure include alkyl or alkylate group residues (such as alkylene groups if included in the main chain of the polymer) with a total of 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, which may be substituted with phenyl groups, halogens, hydroxyl groups, cyano groups, etc., and may have organic acid groups such as carboxyl groups, acetate groups, and butyric acid groups; and aryl group residues (such as arylene groups if included in the main chain of the polymer) with a total of 6 to 24 carbon atoms, preferably 8 to 18 carbon atoms, which may be substituted with phenyl groups, halogens, hydroxyl groups, cyano groups, etc., and may have organic acid groups such as carboxyl groups, acetate groups, and butyric acid groups.

[0051] Among these, organic compound moieties that can be introduced by methods such as the ATRP method and RCMP method using polymerization initiators containing halogens such as iodine, such as t-butylisobutyrate group, 2-hydroxyethyl-2-isobutyrate group, ethylenebis(isobutyrate group); isobutyronitrile group, ethyl isobutyrate group, ethyl phenylacetate group, isobutyrate group containing a carboxyl group, phenylacetic acid group, hydroxyethyl isobutyrate group, and hydroxyethyl phenylacetic acid group, are preferred as organic compound moieties.

[0052] (1-6. Structure of terminal functional groups) In the radical polymer of the present invention, a specific functional group represented by formula (1), formula (2), or formula (3) described above is bonded to at least one end (or one or both ends if there are two ends) via an ester moiety shown in the following formula. [ka] (In formula (1), R 1 Each of these is independently either a hydrogen atom or a fluorine atom, and n is an integer between 1 and 17. [ka] (In formula (2), R 2Each of these is independently a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group), a fluorine atom, or a perfluoroalkyl group (preferably a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms, and even more preferably a trifluoromethyl group). [ka] (In formula (3), R 2 Each of these is independently a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group), a fluorine atom, or a perfluoroalkyl group (preferably a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms, and even more preferably a trifluoromethyl group).

[0053] [2. Living radical polymer composition] In addition to the living radical polymers mentioned above, known components of the living radical polymer composition include thermoplastic resins, thermosetting resins, solvents that dissolve polymers derived from precursors, and antioxidants.

[0054] The content of the living radical polymer in the living radical polymer composition is preferably 1 to 100 parts by weight per 100 parts by weight of the entire polymer composition. Furthermore, the content of polymers not derived from precursors, such as thermoplastic resins, thermosetting resins, solvents for dissolving polymers derived from precursors, and antioxidants, is preferably 0 to 99 parts by weight per 100 parts by weight of the entire polymer composition.

[0055] [3. Method for producing living radical polymers] Next, a method for producing living radical polymers according to the present invention will be described. This method is characterized by the ability to obtain polymers with a narrow molecular weight distribution and having a specific functional group at at least one polymer terminal in high purity.

[0056] The present invention provides a method for producing a polymer, comprising a polymerization step to form a precursor of a living radical polymer and an introduction step to introduce a specific functional group structure to the terminal end of the precursor. In the polymerization step, the precursor is polymerized 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. In the introduction step, a specific functional group-containing radical generator is reacted with the dormant terminal end of the precursor obtained in the polymerization step at a predetermined temperature to introduce a terminal functional group structure derived from the functional group-containing radical generator. Each step will be described below.

[0057] (3-1. Polymerization process) In the polymerization process, the aforementioned NMP method, ATRP method, RAFT polymerization method, TERP method, RCMP method, or RTCP method may be used. As polymerization initiators for precursor production, the polymerization initiators described in the explanation of these production methods can be used, but it is particularly preferable to use an organiodine compound as the polymerization initiator, which can efficiently detach and bond the dormant at the end of the precursor using a functional group-containing radical generator. For this reason, the RCMP method, which has a high content of radical polymer-terminated iodines, among the RCMP and RTCP methods that use at least an organiodine compound as the polymerization initiator, will be explained in more detail.

[0058] While organiodine compounds that can be suitably used as polymerization initiators for precursor production were described in detail in the previous section, in addition to methods using already manufactured polymerization initiators, it is also possible to use polymerization initiator raw materials, such as azo compounds and iodine, by introducing them into the initial stages of polymerization and generating an in-situ polymerization initiator consisting of an organiodine compound through the reaction of the two.

[0059] Examples of azo compounds used to produce organoiodine compounds include functional group-free azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonnitrile), and 2,2'-azobis(2,4,4-trimethylpentane), as well as functional group-containing azo compounds such as 4,4'-azobis-4-cyanovaleric acid (ACVA) having a carboxyl group, 2,2'-azobis{2-methyl-N-(2-hydroxyethyl)propionamide} having a hydroxyl group, and 2-2'-azobis{2-(2-imidazolin-2-yl)propane} having an amino group. However, the present invention is not limited to these examples.

[0060] The amount of azo compound used to generate the polymerization initiator described above is preferably 1 to 5 moles, and more preferably 1.3 to 3 moles, per mole of iodine.

[0061] To efficiently polymerize the aforementioned polymerization initiator, it is desirable to use a catalyst in addition to the polymerization initiator. Examples of catalysts include known compounds that coordinate to and abstract iodine, but the present invention is not limited to such examples.

[0062] Examples of catalysts include organic amine compounds and nonmetallic compounds having ionic bonds with iodide ions, where the nonmetallic atoms in the nonmetallic compound are in a cationic state and form ionic bonds with iodide ions. However, the present invention is not limited to these examples.

[0063] Examples of catalysts consisting of organic amine compounds include triethylamine, tributylamine, 1,1,2,2-tetrakis(dimethylamino)ethene, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, ethylenediamine, tetramethylethylenediamine, tetramethyldiaminomethane, tris(2-aminoethyl)amine, tris(2-(methylamino)ethyl)amine, and hematoporphyrin. These catalysts may be used individually or in combination of two or more types.

[0064] Catalysts that have an ionic bond with an iodide ion, wherein the nonmetallic atom in the nonmetallic compound is in a cationic state and forms an ionic bond with the iodide ion, include, specifically, ammonium salts, imidazolium salts, pyridinium salts, phosphonium salts, sulfonium salts, and iodonium salts. More specifically, examples include tetrabutylammonium iodide, tetrabutylammonium triiodide, tetrabutylammonium bromodiodide, 1-methyl-3-methylimidazolium iodide, 2-chloro-1-methylpyridinium iodide, methyltributylphosphonium iodide (hereinafter referred to as PMBI), tetraphenylphosphonium iodide, tributylsulfonium iodide, and diphenyliodonium iodide. These catalysts may be used individually or in combination of two or more types.

[0065] From the viewpoint of increasing the polymerization rate and reducing the amount of unreacted monomers remaining, the amount of catalyst is preferably 0.01 to 50 moles, more preferably 0.05 to 30 moles, even more preferably 0.1 to 20 moles, and even more preferably 0.5 to 10 moles per 100 moles of the above-mentioned organic iodine compound.

[0066] In addition to the catalysts mentioned above, a small amount of a general-purpose radical polymerization initiator may be used as needed to accelerate the polymerization rate. The type of general-purpose radical polymerization initiator does not need to be selected as strictly as the type of polymerization initiator used for precursor production mentioned above; one can be used as appropriate depending on the polymerization temperature and polymerization time.

[0067] 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 individually or in combination of two or more types.

[0068] Examples of azo compounds include those similar to those mentioned above. These azo compounds may be used individually or in combination of two or more types.

[0069] Examples of organic peroxides include, in addition to the aforementioned diacyl peroxides containing specific functional groups, general-purpose organic peroxides that do not contain functional groups, such as diacyl peroxides like di-(3,5,5-trimethylhexanoyl) peroxide and benzoyl peroxide, peroxy dicarbonates like di-n-propyl peroxy dicarbonate and di-isopropyl peroxy dicarbonate, dialkyl peroxides like dicumyl peroxide and di-t-butyl peroxide, peroxy esters like t-butyl peroxy pivalate and t-butyl peroxy-2-ethylhexanoate, and peroxyketals like 1,1-bis(t-butylperoxy)cyclohexane. However, the present invention is not limited to these examples. These organic peroxides may be used individually or in combination of two or more types.

[0070] Furthermore, if it is not necessary to use a general-purpose radical polymerization initiator, it is preferable to substantially omit the use of a general-purpose radical polymerization initiator, and more preferably to omit it entirely, from the viewpoint of avoiding adverse effects caused by the general-purpose radical polymerization initiator. Here, "substantially omitted" means an amount of general-purpose radical polymerization initiator such that there is substantially no influence on the polymerization reaction by the polymerization initiator. 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.

[0071] The amount of general-purpose radical polymerization initiator per 100 moles of total radical polymerizable unsaturated monomer components is preferably 0.005 to 30 moles, more preferably 0.01 to 20 moles, and even more preferably 0.02 to 15 moles, from the viewpoint of increasing the polymerization rate and reducing the amount of unreacted radical polymerizable unsaturated monomers remaining.

[0072] As described in detail in the previous section, the polymerization conditions for polymerizing radically polymerizable unsaturated monomers are not particularly limited and can be set appropriately according to the polymerization method of the radically polymerizable unsaturated monomer. The polymerization temperature is preferably room temperature to 200°C, more preferably 30 to 140°C. Furthermore, the atmosphere when polymerizing radically polymerizable unsaturated monomers is preferably an inert gas such as nitrogen gas or argon gas. The reaction time should be set appropriately so that the polymerization reaction of the radically polymerizable unsaturated monomer is completed.

[0073] Polymerization of radically polymerizable unsaturated monomers may be carried out by bulk polymerization without the use of solvents, or by solution polymerization using a solvent that dissolves in the radically polymerizable unsaturated monomer or the polymer obtained thereby. Furthermore, emulsion polymerization, dispersion polymerization, suspension polymerization, etc., can be carried out by using a solvent that does not dissolve in the radically polymerizable unsaturated monomer or the polymer obtained thereby.

[0074] Solvents used in solution polymerization of radically polymerizable unsaturated monomers include, for example, aromatic solvents such as water, benzene, toluene, xylene, and ethylbenzene; alcoholic solvents such as methanol, ethanol, isopropanol, n-butanol, and t-butyl alcohol; halogen-containing solvents such as dichloromethane, dichloroethane, and chloroform; linear or branched aliphatic ether solvents such as propylene glycol methyl ether, dipropylene glycol methyl ether, ethyl cellsolve, butyl cellsolve, diglyme, and propylene glycol monomethyl ether acetate; alicyclic ether solvents such as tetrahydrofuran, 1,2-dioxane, 1,3-dioxane, and 1,4-dioxane; esteric solvents such as ethyl acetate, butyl acetate, cellosolve acetate, and cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diacetone alcohol; amide solvents such as dimethylformamide; and sulfoxide solvents such as dimethyl sulfoxide. However, the present invention is not limited to these examples. These solvents may be used individually or in combination of two or more. The amount of solvent should be determined appropriately, taking into account the polymerization conditions, monomer composition, and the concentration of the resulting polymer.

[0075] (3-2.Introduction process) In the introduction step of the polymer production method of the present invention, a polymer with a modified terminal structure is obtained by reacting the dormand terminal of a precursor obtained from a polymerization initiator and a radically polymerizable unsaturated monomer with a specific functional group-containing radical generator and applying heat. As the functional group-containing radical generator, at least a compound having a functional group represented by formulas (1), (2), and (3) described above is used.

[0076] The introduction step is preferably carried out in the presence of a nonmetallic compound having an ionic bond with an iodide ion. In the presence of a specific functional group-containing radical generator, the nonmetallic compound having an ionic bond with an iodide ion efficiently abstracts the dormant at the precursor terminal, and the resulting precursor terminal radical rapidly reacts with the specific functional group-containing radical to generate the specific terminal functional group.

[0077] As the radical generators mentioned above, diacyl-type organic peroxides having functional groups represented by the following formulas (4), (5), and (6) are used. In the structures of formulas (4) to (6), the right-hand structure and the left-hand structure centered on the oxygen-oxygen bond (-OO-) may be the same or different. [ka] (In formula (4), R 1 Each of these is either a hydrogen atom or a fluorine atom, and each of these is an integer between 1 and 17. [ka] (In formula (5), R 2 Each of these is independently a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group), a fluorine atom, or a perfluoroalkyl group (preferably a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms, and even more preferably a trifluoromethyl group). [ka] (In formula (6), R 2 Each of these is independently a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group), a fluorine atom, or a perfluoroalkyl group (preferably a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms, and even more preferably a trifluoromethyl group).

[0078] The diacyl-type organic peroxide having the functional group represented by formula (4) above is not particularly limited as long as it is known, for example, R in formula (4) above 1 When the atom is a hydrogen atom, examples include diacetoxy peroxide (n=1), di-n-propoyl peroxide (n=2), diisopropoyl peroxide (n=2), di-n-butyroyl peroxide (n=3), di-3,5,5-trimethylhexanoyl peroxide (n=8), dilauroyl peroxide (n=11, hereafter referred to as LPO), dimyristyroyl peroxide (n=13), dipalmitiroyl peroxide (n=15), distearoyl peroxide (n=17), etc. On the other hand, R in equation (4) above 1 When the atom is a fluorine atom, examples include ditrifluoroacetoxy peroxide (n=1), diperfluoropropoloyl peroxide (n=2), and diperfluorobutyroyl peroxide (n=3, hereafter referred to as PFB).

[0079] The diacyl-type organic peroxide having the functional group represented by formula (5) above is not particularly limited as long as it is known, for example, R in formula (5) above 2 When the atom is a hydrogen atom or a methyl group, examples include dibenzoyl peroxide (hereinafter referred to as BPO), di-p-methylbenzoyl peroxide, di-o-methylbenzoyl peroxide, di-m-methylbenzoyl peroxide, etc. On the other hand, R in equation (5) above 2 When the atom is a fluorine atom or a trifluoromethyl group, examples include diperfluorobenzoyl peroxide, di-p-perfluoromethylbenzoyl peroxide, di-o-perfluoromethylbenzoyl peroxide, and di-m-perfluoromethylbenzoyl peroxide.

[0080] The diacyl-type organic peroxide having the functional group represented by formula (6) above is not particularly limited as long as it is known, for example, R in formula (6) above 2When the atom is a hydrogen atom or a methyl group, examples include dicyclohexyl peroxide, di-p-methylcyclohexyl peroxide, di-o-methylcyclohexyl peroxide, and di-m-methylcyclohexyl peroxide. On the other hand, R in equation (6) above 2 When the atom is a fluorine atom or a trifluoromethyl group, examples include diperfluorocyclohexyl peroxide, di-p-perfluoromethylcyclohexyl peroxide, di-o-perfluoromethylcyclohexyl peroxide, and di-m-perfluoromethylcyclohexyl peroxide.

[0081] The amount of radical generator added is preferably 0.5 to 30 moles, more preferably 0.5 to 20 moles, even more preferably 1 to 10 moles, and most preferably 1 to 5 moles, per mole of the precursor-termining dormant. Furthermore, in the introduction step, from the viewpoint of further increasing purity, it is preferable to gradually add the radical generator to the reaction system dropwise. The dropping rate (supply rate) of the radical generator to the reaction system in the introduction step is, for example, 2 to 20 ml / min, preferably 5 to 10 ml / min, per liter of reaction system, using a 10% diluted product in the reaction solvent.

[0082] The reaction conditions for reacting a specific functional group-containing radical generator with the precursor terminal dormant can be set appropriately according to the conditions for the decomposition of the functional group-containing radical generator, and are not particularly limited. The reaction temperature is preferably 70°C to 130°C, more preferably 80°C to 110°C when the main radical polymerizable unsaturated monomer constituting the precursor is styrene and its derivatives, 110°C to 130°C when the main radical polymerizable unsaturated monomer constituting the precursor is acrylamide and its derivatives or acrylate, and 70°C to 100°C when the main radical polymerizable unsaturated monomer constituting the precursor is methacrylate. Furthermore, the atmosphere during the reaction is preferably an inert gas such as nitrogen gas or argon gas. The reaction time should be set appropriately so that the decomposition of the functional group-containing radical generator is completed. In addition, a solvent may be used as appropriate to ensure homogeneity of the reaction. Any solvent that can dissolve the radical polymer can be used, for example, the same solvents used when polymerizing the radical polymerizable unsaturated monomers described above can be suggested.

[0083] As mentioned above, the reaction mechanism of the polymer production method of the present invention is presumed to be as follows. First, the functional group-containing radicals generated from the functional group-containing radical generator abstract the dormant present at the precursor terminal, thereby generating the precursor terminal radical. On the other hand, the numerous functional group-containing radicals derived from the functional group-containing radical generator have low molecular weight and can diffuse rapidly in the reaction solution. Therefore, the functional group-containing radicals quickly bind to the precursor terminal radicals, and this results in the acquisition of a polymer with specific functional groups bonded to it in high purity. Furthermore, the functional group-containing radicals inhibit the bonding of precursor terminal radicals, which would broaden the molecular weight distribution, so the resulting polymer can maintain the narrow molecular weight distribution of the precursor. Furthermore, by using a compound that abstracts the dormant present at the precursor terminal faster than the functional group-containing radical, the dormant present at the precursor terminal is abstracted faster than the functional group-containing radical, thereby rapidly generating the precursor terminal radical. On the other hand, the functional group-containing radical generated from the functional group-containing radical generator is low molecular weight and an oxygen radical, so it can diffuse rapidly in the reaction solution and bind to the precursor terminal radical, resulting in the production of a polymer with higher purity and efficiency.

[0084] As mentioned above, examples of compounds that extract radicals from precursors include nonmetallic compounds that have an ionic bond with an iodide ion.

[0085] 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, examples include tetrabutylammonium iodide (hereinafter referred to as BNI), tetrabutylammonium triiodide, tetrabutylammonium bromodiodide, 1-methyl-3-methylimidazolium iodide, 2-chloro-1-methylpyridinium iodide, methyltributylphosphonium iodide, tetraphenylphosphonium iodide, tributylsulfonium iodide, and diphenyliodonium iodide. These catalysts may be used individually or in combination of two or more types.

[0086] From the viewpoint of increasing the reaction rate, the amount of compound used to extract radicals from the aforementioned precursor is 0.5 to 20 moles, preferably 1 to 10 moles, per mole of terminal dormant of the radical polymer precursor. [Examples]

[0087] The present invention will be described in more detail below with reference to examples. First, an example of the production of a living radical polymer precursor is shown below.

[0088] Manufacturing Example 1 19.23 g of n-butyl acrylate (BA; distilled and purified by conventional method from Fujifilm Wako Pure Chemical Industries, Ltd.), 0.172 g of 2-iodoisobutyronitrile (CP-I; manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.303 g of tetrabutylammonium iodide (BNI; manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 30 ml Schlenk tube, 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 reprecipitation by dropping it into a mixed solution of 180 ml of deionized water and 720 ml of methanol, and the polymer precipitated in the deionized water and methanol mixed solution was vacuum dried at 60°C for 18 hours to obtain a BA polymer (hereinafter referred to as PBA) having iodine at one molecular end. This reaction is represented by the following formula (i). [ka] 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. Furthermore, when the obtained polymer was dissolved in deuterated chloroform and analyzed by 13C-NMR, the integral value of the quaternary carbon (number of carbon atoms: 1) in CP-I and the integral value of the tertiary carbon (number of carbon atoms: 1) in the BA1 molecule immediately adjacent to the iodine atom were 1:0.99, confirming that 99.0% of the iodine present at the polymer ends was introduced. The results are shown in Table 1.

[0089] Manufacturing Example 2 PBA having iodine at one molecular end was obtained using the same method as in Production Example 1, 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. The obtained polymer had a number-average molecular weight of 3,360 and a Mw / Mn ratio of 1.18. Furthermore, 13C-NMR spectroscopy confirmed that 99.2% of the iodine present at the polymer ends was incorporated. The results are shown in Table 1.

[0090] Manufacturing Example 3 PBA having iodine at one molecular end was obtained using the same method as in Production Example 1, except that the amount of CPI added was changed from 0.172 g to 0.073 g, the amount of BNI added was changed from 1.303 g to 8.688 g, and the polymerization conditions were changed from 9 hours at 110°C to 18 hours at 110°C. The obtained polymer had a number-average molecular weight of 26,000 and a Mw / Mn ratio of 1.19. Furthermore, 13C-NMR spectroscopy confirmed that 99.1% of the iodine present at the polymer ends was incorporated. The results are shown in Table 1.

[0091] Manufacturing Example 4 PMEA having iodine at one molecular terminus was obtained by the same method as in Production Example 2, except that 19.53 g of 2-methoxyethyl acrylate (MEA; manufactured by Tokyo Chemical Industry Co., Ltd. and purified by distillation using a conventional method) was used instead of 19.23 g of BA as the radical polymerizable unsaturated monomer, and the polymerization conditions were changed from 6 hours at 110°C to 10 hours at 110°C. The obtained polymer had a number-average molecular weight of 4,910 and a Mw / Mn ratio of 1.12. Furthermore, 13C-NMR spectroscopy confirmed that 99.6% of the iodine present at the polymer ends was incorporated. The results are shown in Table 1.

[0092] Manufacturing Example 5 PSt having iodine at one molecular terminus was obtained by the same method as in Production Example 2, except that instead of using 19.23 g of BA as the radical polymerizable unsaturated monomer, 15.63 g of styrene (St; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. and distilled and purified by conventional methods) was used, the amount of BNI added 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. The obtained polymer had a number-average molecular weight of 6,060 and a Mw / Mn ratio of 1.21. Furthermore, 13C-NMR spectroscopy confirmed that 98.1% of the iodine present at the polymer ends was incorporated. The results are shown in Table 1.

[0093] Manufacturing Example 6 PMMA having iodine at one molecular terminus was obtained by the same method as in Production Example 2, except that 15.02 g of methyl methacrylate (MMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. and purified by conventional distillation) was used instead of 19.23 g of BA as the radical polymerizable unsaturated monomer, the amount of BNI 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. The obtained polymer had a number-average molecular weight of 6,600 and a Mw / Mn ratio of 1.19. Furthermore, 13C-NMR spectroscopy confirmed that 98.4% of the iodine present at the polymer ends was incorporated. The results are shown in Table 1.

[0094] Manufacturing example 7 PBA having a phenyldithioester group at one molecular terminus was obtained by the same method as in Production Example 3, except that 0.073 g of the organioidone compound CP-I was used instead of 0.083 g of the RAFT agent 2-cyano-2-propylbenzodithianoate (manufactured by Sigma-Aldrich Japan, hereinafter referred to as CPBD), 0.812 g of AIBN was used instead of BNI, and the polymerization conditions were changed from 18 hours at 110°C to 1 hour at 70°C. The obtained polymer had a number-average molecular weight of 5,500 and a Mw / Mn ratio of 1.15. Furthermore, 1H-NMR results confirmed that 98.8% of the phenyl dithioester at the polymer ends were introduced. The results are shown in Table 1.

[0095] [Table 1]

[0096] Next, an example in which a terminal structure derived from a specific functional group-containing compound is attached to the precursor obtained in the above-described manufacturing example will be explained below.

[0097] The identification and purity of the polymers containing specific functional groups obtained in the examples described later were investigated based on the following method.

[0098] (Sample adjustment) A sample solution was prepared by adding 1 ml of THF to 0.01 g of the obtained polymer, a matrix solution was prepared by adding 1 ml of THF to 0.02 g of the matrix trans-2-{3-(4-t-butylphenyl)-2-methyl-2-propenylidene}malononitrate (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as DCTB), and an ionizing agent solution was prepared by adding 1 ml of THF to 0.001 g of the ionizing agent sodium trifluoroacetate (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as NaTFA). 100 μl of the matrix solution, 20 μl of the ionizing agent solution, and 20 μl of the sample solution were mixed in a 2 ml sample bottle, 1 μl of the mixture was spotted onto a sample plate, and the THF was dried at room temperature for about 5 minutes to prepare the sample.

[0099] (Identification of polymer terminal groups) MS spectra obtained by irradiating the sample with a 50kV laser were analyzed using a JEOL Ltd. JMS-S3000 SpiralTOF. In the precursor's MS spectrum, the MS spectra of the precursor PBA-I and PBA-H (where the iodine at the precursor's end is removed) appeared in almost the same position and were indistinguishable. However, since PBA-I was present in high purity from the precursor's NMR measurement, the main peak was expected to be PBA-I. On the other hand, in the sample's MS spectrum, both PBA-I and PBA-H, or either one of them, were present in very small amounts. The sample's MS spectrum contained a main spectrum that did not correspond to the spectra derived from PBA-I and PBA-H, and its total molecular weight matched the total molecular weight obtained by adding the molecular weight of the PBA with a specific functional group attached and the molecular weight of the ionizing agent Na. Therefore, it was confirmed that a specific functional group was directly bonded to the PBA end.

[0100] (Purity measurement of polymers having compounds derived from functional group-containing radical generators at their termini) The purity of polymers in the sample that have compounds derived from functional group-containing radical generators at their termini was calculated by dividing the area of ​​the MS spectrum of polymers with compounds derived from functional group-containing radical generators at their termini, along with the area of ​​other spectra, by the total area of ​​all MS spectra present in the sample.

[0101] Example 1 In a 30 ml Schlenk tube, 0.3 g of the polymer obtained in Production Example 1, 0.034 g of LPO as a radical generator, 0.079 g of BNI, and 2.7 ml of toluene (manufactured by Kanto Chemical Co., Ltd.) as a solvent were added and dissolved. After dissolving, the internal space of the Schlenk tube was replaced with nitrogen gas. The contents of the Schlenk tube were reacted at 110°C for 1 hour in Example 1. After rapid cooling to room temperature, centrifugation was performed at 3000 rpm for 5 minutes to remove unreacted BNI. The polymer obtained by distilling off toluene under reduced pressure using an evaporator was vacuum-dried at 60°C for 1 hour, thereby removing the dormant from the polymer ends, and C 11 H 23 A polymer with a COO group attached was obtained. The number-average molecular weight, Mw / Mn ratio, and purity of the polymer with the attached functional group were calculated and the results are shown in Table 2. This reaction is represented by the following formula (ii). [ka]

[0102] Examples 2-3 The polymer was produced in the same manner as in Example 1, except that the amount of LPO used was changed to 0.5 moles in Example 2 and 10 moles in Example 3 per 1 mole of the iodine-terminated precursor. As a result, the dormant at the precursor terminal was eliminated, and C 11 H 23 A polymer with a COO group attached was obtained. The number-average molecular weight, Mw / Mn ratio, and purity of the polymer with the attached functional group were calculated, and the results are shown in Table 2.

[0103] Example 4 The polymer was prepared in the same manner as in Example 1, except that the amount of BNI used was changed to 1 mole per mole of iodine-terminated precursor. As a result, the dormant at the precursor terminal was eliminated, and C 11 H 23 A polymer with a COO group attached was obtained. The number-average molecular weight, Mw / Mn ratio, and purity of the polymer with the attached functional group were calculated, and the results are shown in Table 2.

[0104] Implementation 5-6 The polymer was produced in the same manner as in Example 1, except that the precursor was changed in Example 5 to the precursor from Production Example 2 (Mn: 3,360 g / mol), and in Example 6 to the precursor from Production Example 3 (Mn: 26,000 g / mol). As a result, the dormant at the polymer end was removed, and C 11 H 23 A polymer with a COO group attached was obtained. The number-average molecular weight, Mw / Mn ratio, and purity of the polymer with the attached functional group were calculated, and the results are shown in Table 2.

[0105] Examples 7-8 Polymers were produced in the same manner as in Example 1, except that the radical generator was changed to BPO in Example 7 and PFB in Example 8. As a result, the dormant at the polymer ends was eliminated, and polymers with benzoyl groups were obtained in Example 7, and polymers with perfluorobutyroyl groups were obtained in Example 8. The number-average molecular weight, Mw / Mn, and purity of the polymers to which the obtained functional groups were attached were calculated, and the results are shown in Table 2.

[0106] Example 9 The polymer was produced in the same manner as in Example 1, except that the precursor was changed to the precursor of Production Example 4 (PMEA having iodine at the molecular end). As a result, the dormant at the polymer end was removed, and C 11 H 23 A polymer with a COO group attached was obtained. The number-average molecular weight, Mw / Mn ratio, and purity of the polymer with the attached functional group were calculated, and the results are shown in Table 2.

[0107] Example 10 The polymer was produced in the same manner as in Example 1, except that the amount of BNI used was changed to 2 moles per 1 mole of the iodine-terminated precursor, and the reaction temperature was changed from 110°C to 130°C. As a result, the dormant at the precursor terminal was eliminated, and C 11 H 23 A polymer with a COO group attached was obtained. The number-average molecular weight, Mw / Mn ratio, and purity of the polymer with the attached functional group were calculated, and the results are shown in Table 2.

[0108] Examples 11-12 In Example 11, the precursor was changed to the precursor of Production Example 5 (PSt with iodine at the molecular end), and the reaction conditions were changed to 80°C for 4 hours. In Example 12, the precursor was changed to the precursor of Production Example 6 (PMMA with iodine at the molecular end), and the reaction conditions were changed to 70°C for 8 hours. The polymer was produced in the same manner as in Example 10. As a result, the dormant at the precursor end was eliminated, and C 11 H 23 A polymer with a COO group attached was obtained. The number-average molecular weight, Mw / Mn ratio, and purity of the polymer with the attached functional group were calculated, and the results are shown in Table 2.

[0109] Example 13 The polymer was produced in the same manner as in Example 1, except that the amount of toluene added was changed from 2.7 ml to 2.4 ml, and 0.340 g of a toluene solution of LPO, prepared by adjusting the concentration of LPO to 10% by weight with 0.306 g of toluene, was added dropwise over approximately 30 minutes. As a result, the dormant at the precursor end was eliminated, and C 11 H 23 A polymer with a COO group attached was obtained. The number-average molecular weight, Mw / Mn ratio, and purity of the polymer with the attached functional group were calculated, and the results are shown in Table 2.

[0110] Comparative Example Polymers were produced in the same manner as in Example 4, except that the precursor from Production Example 7 was used and 2,2'-azobis(isobutyronitrile) (AIBN; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) that does not contain specific functional groups was used. The number-average molecular weight, Mw / Mn, and purity of the polymers to which the alkoxy groups were bonded were calculated, and the results are shown in Table 2.

[0111] [Table 2]

[0112] The results in Table 2 show that the living radical polymers in which a specific functional group is introduced to the dormant side of the polymer terminals in the present invention, that is, living radical polymers in which a specific functional group is bonded in place of the eliminated dormant, have a narrow molecular weight distribution and high purity. Furthermore, according to the production method of the present invention, by reacting a radical polymerization initiator having a specific functional group with the dormant at the terminal of the precursor, a living radical polymer with a narrow molecular weight distribution and high purity can be obtained.

Claims

1. A composition comprising a living radical polymer having an organic compound moiety derived from a polymerization initiator in one end or main chain of the living radical polymer, and having a terminal functional group structure represented by the following formula (1), formula (2), or formula (3) in at least one of its ends, The purity of the living radical polymer is 70-100%. A composition containing a living radical polymer. 【Chemistry 1】 (In formula (1), R 1 Each of these is independently either a hydrogen atom or a fluorine atom, and n is an integer from 1 to 17. 【Chemistry 2】 (In formula (2), R 2 Each of these is independently a hydrogen atom, an alkyl group, a fluorine atom, or a perfluoroalkyl group. 【Transformation 3】 (In formula (3), R 2 Each of these is independently a hydrogen atom, an alkyl group, a fluorine atom, or a perfluoroalkyl group.

2. A composition comprising the living radical polymer according to claim 1, wherein the organic compound moiety is derived from a polymerization initiator containing iodine as a dormant.

3. A composition comprising the living radical polymer according to Claim 1, wherein the living radical polymer includes structural units derived from acrylate as the main structural units.

4. A composition comprising the living radical polymer according to claim 1, wherein the molecular weight distribution (weight average molecular weight / number average molecular weight) of the living radical polymer is 1.0 to 1.

5.

5. A method for producing a composition containing a living radical polymer according to any one of claims 1 to 4, A polymerization step to form a precursor of a living radical polymer using a polymerization initiator containing an organic compound moiety and a dormant, and a radically polymerizable unsaturated monomer, A method for producing a composition containing a living radical polymer, comprising: an introduction step of reacting a functional group-containing radical generator represented by any of the following formulas (4) to (6) with the dormant terminal derived from the dormant of the precursor, thereby introducing a terminal functional group structure derived from the radical generator in place of the dormant terminal. 【Chemistry 4】 (In formula (4), R 1 (Each of these is independently a hydrogen atom or a fluorine atom, and each of these is independently an integer from 1 to 17.) 【Transformation 5】 (In formula (5), R 2 Each of these is independently a hydrogen atom, an alkyl group, a fluorine atom, or a perfluoroalkyl group. 【Transformation 6】 (In formula (6), R 2 Each of these is independently a hydrogen atom, an alkyl group, a fluorine atom, or a perfluoroalkyl group.

6. The method for producing a composition containing a living radical polymer according to claim 5, wherein the reaction temperature for producing the composition containing the living radical polymer in the introduction step is 70 to 130°C.

7. A method for producing a composition containing a living radical polymer according to claim 5, wherein in the polymerization step, 0.1 to 50 moles of the polymerization initiator are used per 100 moles of the radical polymerizable unsaturated monomer.

8. A method for producing a composition containing a living radical polymer according to claim 5, wherein in the introduction step, 0.5 to 30 moles of the radical generating agent are used per mole of the dormant terminal of the precursor.

9. A method for producing a composition containing a living radical polymer according to claim 5, wherein in the introduction step, the radical generating agent is added dropwise to the reaction system.

10. A method for producing a composition containing a living radical polymer according to claim 5, wherein the introduction step is carried out in the presence of a nonmetallic compound having an ionic bond with an iodide ion.

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