Polymer, oxygen absorber using the polymer, and curable composition

Abstract

A polymer represented by the following general formula (I). (In general formula (I), X 1 , X 2 and X 3 represent chalcogen atoms. R 1 and R 2 each independently represent any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an aralkyl group. R 3 and R 4 each independently represent any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 5 and R 6 each independently represent any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 7 represents a hydrogen atom or a methyl group. R 8 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. n is an arbitrary integer. R 3 , R 4 , R 5 and R 6 do not form a ring structure by being connected to each other.)

Description

Technical Field

[0001] The present invention relates to specific polymers, oxygen absorbers using the polymers, and curable compositions. Background Art

[0002] Free-radical polymerizable monomers and free-radical polymerizable resins used in coatings, adhesives, coating agents, etc. have unsaturated bonds and are cured with vinyl crosslinking agents. When these free-radical polymerizable monomers and free-radical polymerizable resins are used for applications such as coatings, adhesives, and coating agents, curing is usually carried out in an air atmosphere, so curing is likely to be hindered by oxygen in the air, and there are problems such as slower curing or stickiness on the surface. As means for preventing these problems, adding a complex other than the free-radical polymerizable resin and using a polymerization method different from free-radical polymerization have been proposed. In Patent Documents 1 and 2, a technique of adding an oxygen absorber as a complex to a free-radical polymerizable resin has been proposed. In addition, as the oxygen absorber as a complex, allyl glycidyl ether, etc. are described in Patent Documents 3 and 4. In addition, Patent Document 5 describes a technique of curing a free-radical polymerizable resin by cationic polymerization using a photoacid generator. In addition, Patent Document 6 describes a technique of adding a thiol compound to an olefin. However, for the method of using a conventional complex, a sufficient effect of preventing curing hindrance cannot be obtained. In addition, when cationic polymerization is used as the polymerization method, there are problems such as a decrease in the rate of the polymerization reaction due to moisture in the air. In addition, when a thiol compound is used as in Patent Document 6, there are problems such as the generation of a peculiar odor.

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Patent Laid-Open No. 63-130610

[0006] Patent Document 2: Japanese Patent Laid-Open No. 5-78459

[0007] Patent Document 3: Japanese Patent Laid-Open No. 61-101518

[0008] Patent Document 4: U.S. Patent No. 3,644,568 Specification

[0009] Patent Document 5: Japanese Patent Laid-Open No. 2008-308420

[0010] Patent Document 6: Japanese Patent Laid-Open No. 2004-277660 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] As described above, with respect to radically polymerizable monomers and radically polymerizable resins, the problem of curing inhibition caused by oxygen has not been solved yet.

[0013] In addition, in coating applications, styrene or the like has been mostly used as a reactive diluent in the past. However, from the viewpoint of environmental protection, there has been a growing trend to switch to less volatile (meth)acrylates. However, when using (meth)acrylates, there are problems such as that curing is more easily inhibited by oxygen compared to the case of using conventional reactive diluents.

[0014] Therefore, in curing in an environment such as under air where curing inhibition caused by oxygen is likely to occur, a method for suppressing curing inhibition is desired.

[0015] The present invention has been completed in view of the above-mentioned conventional problems, and an object thereof is to provide a polymer which can also cause a curing reaction to proceed sufficiently and suppress curing inhibition caused by oxygen when used in coatings, adhesives, coating agents, etc. Another object of the present invention is to provide an oxygen absorber containing the polymer and a curable composition containing the same.

[0016] Means for Solving the Problem

[0017] As a result of intensive studies by the present inventors, it was found that a polymer represented by the following general formula (I) or general formula (II) can stabilize the generated free radicals more than conventional oxygen absorbers and exhibits higher oxygen radical scavenging performance, that is, higher absorption performance. Based on this finding, the present invention was completed by further repeated studies.

[0018] That is, the present invention provides the following [1] to

[14] .

[0019] [1] A polymer represented by the following general formula (I).

[0020] [Chemical formula 1]

[0021]

[0022] (In general formula (I), X 1 , X 2 and X 3 represent chalcogen atoms. R 1 and R 2 each independently represent any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an aralkyl group. R 3 and R 4 each independently represent any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. R 5 and R6 Each independently represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, R 7 represents a hydrogen atom or a methyl group, R 8 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. n is an arbitrary integer. R 3 、R 4 、R 5 and R 6 do not form a ring structure by being connected to each other. )

[0023] [2] The polymer according to [1], wherein, in the above general formula (I), X 1 and X 2 are oxygen atoms.

[0024] [3] The polymer according to [1] or [2], wherein, in the above general formula (I), R 3 and R 4 are alkyl groups having 1 to 6 carbon atoms.

[0025] [4] The polymer according to any one of [1] to [3], wherein, in the above general formula (I), R 5 、R 6 and R 7 are hydrogen atoms.

[0026] [5] The polymer according to any one of [1] to [4], wherein, in the above general formula (I), R 8 is a hydrogen atom.

[0027] [6] A polymer represented by the following general formula (II).

[0028] [Chemical formula 2]

[0029]

[0030] (In the general formula (II), R 11 、R 12 、R 13 and R 14 each independently represents any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, R 15 represents a hydrogen atom or a methyl group, R 16 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. n is an arbitrary integer. )

[0031] [7] The polymer according to [6], wherein, in the above general formula (II), R16 is a hydrogen atom.

[0032] [8] The polymer according to any one of [1] to [7] has a polystyrene-reduced weight-average molecular weight (Mw) of 300 to 50,000 and a molecular weight distribution (Mw / Mn) of 1.05 to 10.0.

[0033] [9] An oxygen absorber comprising the polymer according to any one of [1] to [8].

[0034]

[10] The oxygen absorber according to [9] comprises 0.001 to 10 mol% of a transition metal salt relative to the vinyl group of the above polymer.

[0035]

[11] A curable composition comprising the oxygen absorber according to [9] or

[10] , a polymerizable monomer, and / or a polymerizable resin.

[0036]

[12] In the curable composition according to

[11] , the above polymerizable monomer and / or polymerizable resin is a radical polymerizable monomer and / or a radical polymerizable resin.

[0037]

[13] A method for producing a polymer composition containing the following general formula (V), the polymer composition being obtained by reacting a compound represented by the following general formula (III), a compound represented by the following general formula (IV), and a base.

[0038] [Chemical formula 3]

[0039]

[0040] (In general formula (III), R 21 and R 22 each independently represent any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group.)

[0041] [Chemical formula 4]

[0042]

[0043] (In general formula (IV), R 23 represents a hydrogen atom or a methyl group.)

[0044] [Chemical formula 5]

[0045]

[0046] (In general formula (V), R 21 , R 22 and R 23 are synonymous with the above, and R 24represents an optional member selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an aryl group, and an aralkyl group. n is an arbitrary integer.) 2 ~6, an alkenyl group having 1 to 6 carbon atoms, an aryl group, and an aralkyl group. n is an arbitrary integer.)

[0047]

[14] The method for producing a polymer composition containing the general formula (V) according to

[13] , wherein the ratio of the compound represented by the general formula (III) to the compound represented by the general formula (IV) is compound (III) / compound (IVIV) = 1 / 2 to 2 / 1.

[0048] Advantages of the Invention

[0049] According to the present invention, it is possible to provide a polymer having oxygen absorption performance, which can cause a curing reaction to proceed sufficiently even in a low-temperature environment such as room temperature when used in paints, adhesives, coating agents, etc., and can suppress curing inhibition caused by oxygen. In addition, it is possible to provide an oxygen absorber containing the polymer and a curable composition containing the same. Detailed Description of the Invention

[0050] Regarding the polymer represented by the general formula (I) or the general formula (II) of the present invention, by coexisting it with a polymerizable monomer such as a curable (meth)acrylate or a polymerizable resin such as an unsaturated polyester resin, curing inhibition caused by oxygen can be suppressed. As a result, an excellent cured product can be provided. The mechanism of this action has not been determined, but it is presumed that in the polymerization reaction, for the hydrogen atom bonded to the carbon of the double bond constituting the polymer represented by the general formula (I) or the general formula (II) of the present invention, which is activated by heat or active energy rays, it will react preferentially with oxygen that hinders the polymerization reaction or with peroxy radicals generated from oxygen due to the polymerization reaction, thereby consuming oxygen or peroxy radicals. In addition, according to the production method of the present invention, the polymer represented by the general formula (I) or the general formula (II) can be produced from available raw materials by a simple method, and the obtained polymer composition can be used without purification. Therefore, the cost spent in the process can be reduced and the price can be lowered, making it suitable for coating applications and the like that require a low price.

[0051] In addition, since the polymer represented by the general formula (I) or the general formula (II) of the present invention is a high molecular compound, it is easy to remain in the cured product and difficult to elute.

[0052] [Polymer Represented by the General Formula (I)]

[0053] The polymer of the present invention is a polymer represented by the following general formula (I).

[0054] [Chemical Formula 6]

[0055]

[0056] In general formula (I), X 1 、X 2 and X 3 each independently represents a chalcogen atom. From the viewpoints of ease of polymer production and improvement of oxygen absorption performance, X 1 、X 2 and X 3 are preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

[0057] R 1 、R 2 in general formula (I) each independently represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an aralkyl group.

[0058] Examples of the alkyl group having 1 to 18 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, isobornyl, adamantyl, and the like.

[0059] Examples of the alkenyl group having 2 to 18 carbon atoms include: vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, octadecenyl, iso-3-hexenyl, cyclohexenyl, norbornenyl, isobornenyl, and the like.

[0060] Examples of the aralkyl group include: benzyl, 2-phenylethyl, 2-naphthylethyl, diphenylmethyl, and the like.

[0061] Among these, R 1 、R 2 are preferably a hydrogen atom.

[0062] R 3 、R 4 in general formula (I) each independently represents any one of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group.

[0063] Examples of the alkyl group having 1 to 6 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0064] As the alkenyl group having 2 to 6 carbon atoms, for example, vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, iso-3-hexenyl, cyclohexenyl and the like can be mentioned.

[0065] As the aryl group, for example, phenyl, tolyl, xylyl, naphthyl and the like can be mentioned.

[0066] As the aralkyl group, for example, benzyl, 2-phenylethyl, 2-naphthylethyl, diphenylmethyl and the like can be mentioned.

[0067] Among these, R 3 and R 4 are each independently preferably any one of an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably methyl.

[0068] R 5 and R 6 in the general formula (I) each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group or an aralkyl group.

[0069] As the alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like can be mentioned.

[0070] As the alkenyl group having 2 to 6 carbon atoms, for example, vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, iso-3-hexenyl, cyclohexenyl and the like can be mentioned.

[0071] As the aryl group, for example, phenyl, tolyl, xylyl, naphthyl and the like can be mentioned.

[0072] As the aralkyl group, for example, benzyl, 2-phenylethyl, 2-naphthylethyl, diphenylmethyl and the like can be mentioned.

[0073] Among these, R 5 and R 6 are each independently preferably any one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, and an aryl group, more preferably a hydrogen atom, methyl, and still more preferably a hydrogen atom. Among them, from the viewpoint of improving the oxygen absorption performance of the polymer, R 5 is preferably a hydrogen atom, R 6 is preferably a hydrogen atom or methyl, and more preferably both are hydrogen atoms.

[0074] R 3 , R 4 , R 5 and R6 Do not form a contraction ring structure by connecting to each other.

[0075] R in the general formula (I) 7 represents a hydrogen atom or a methyl group. R 7 is preferably a hydrogen atom.

[0076] R in the general formula (I) 8 represents any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group.

[0077] Examples of the alkyl group having 1 to 6 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, etc.

[0078] Examples of the alkenyl group having 2 to 6 carbon atoms include: vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, iso-3-hexenyl, and cyclohexenyl, etc.

[0079] Examples of the aryl group include: phenyl, tolyl, xylyl, and naphthyl, etc.

[0080] Examples of the aralkyl group include: benzyl, 2-phenylethyl, 2-naphthylethyl, and diphenylmethyl, etc.

[0081] Among these, R 8 is preferably any one of a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms, and more preferably a hydrogen atom.

[0082] In the general formula (I), n is an arbitrary integer. From the viewpoint of oxygen absorption performance, n is preferably 2 to 150, and more preferably 2 to 50.

[0083] As a specific example of the polymer represented by the general formula (I), for example, the following polymers, etc. can be cited. From the viewpoint of oxygen absorption performance, a polymer represented by the following general formula (II) is preferred.

[0084] [Chemical formula 7]

[0085]

[0086] [Chemical formula 8]

[0087]

[0088] (In the general formula (II), R 11 , R 12 , R 13 and R 14Each independently represents any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, R 15 represents a hydrogen atom or a methyl group, R 16 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. n is an arbitrary integer.)

[0089] In the general formula (II), R 11 , R 12 , R 13 and R 14 each independently represents any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, and the preferred mode is the same as that of R 3 and R 4 in the above general formula (I).

[0090] In the general formula (II), R 15 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. R 16 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, preferably a hydrogen atom.

[0091] In the general formula (II), n is an arbitrary integer. From the viewpoint of oxygen absorption performance, n is preferably 2 to 150, more preferably 2 to 50.

[0092] The weight average molecular weight (Mw) in terms of standard polystyrene of the polymers represented by the general formula (I) and the general formula (II) is preferably 300 to 50,000. The weight average molecular weight (Mw) in terms of standard polystyrene of the polymer represented by the general formula (I) is more preferably 300 to 1,000, and further preferably 330 to 500. The weight average molecular weight (Mw) in terms of standard polystyrene of the polymer represented by the general formula (II) is more preferably 1,000 to 25,000, and further preferably 3,000 to 10,000.

[0093] It should be noted that the "weight average molecular weight (Mw)", the "number average molecular weight (Mn)" described later, and the "molecular weight distribution (Mw / Mn)" described in this specification are all the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) in terms of standard polystyrene obtained by gel permeation chromatography (GPC) measurement, and more specifically, the values measured according to the methods described in the examples.

[0094] The molecular weight distribution (Mw / Mn) in terms of standard polystyrene of the polymers represented by the general formula (I) and the general formula (II) is preferably 1.05 to 10.00, more preferably 1.05 to 5.00, and further preferably 1.10 to 3.00.

[0095] [Oxygen absorbent]

[0096] The oxygen absorbent of the present invention contains a polymer represented by the above general formula (I) or general formula (II). As described above, the polymer of the present invention has excellent oxygen absorption performance. Therefore, when the oxygen absorbent containing the same is used in coatings, adhesives, coating agents, etc., the curing reaction can proceed sufficiently.

[0097] The oxygen absorbent of the present invention contains the polymer of the present invention and thus has sufficient oxygen absorption performance. However, a transition metal salt may be further contained to further improve the oxygen absorption performance.

[0098] Examples of the transition metal constituting the above transition metal salt include iron, nickel, copper, manganese, cobalt, rhodium, titanium, chromium, vanadium, ruthenium, etc. Among these, from the viewpoint of improving the oxygen absorption performance of the oxygen absorbent, iron, nickel, copper, manganese, and cobalt are preferred, and cobalt is more preferred.

[0099] As the counter ion of the transition metal in the above transition metal salt, from the aspect of compatibility, an anion species derived from an organic acid is preferred. Examples of the organic acid include acetic acid, stearic acid, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, oleic acid, capric acid, naphthenic acid, etc.

[0100] For the transition metal salt used in the present invention, any transition metal salt combining the above transition metal and the above counter ion can be used. However, from the viewpoint of the balance between manufacturing cost and oxygen absorption performance, cobalt 2-ethylhexanoate, cobalt neodecanoate, and cobalt stearate are preferred.

[0101] When the oxygen absorbent contains a transition metal salt, its content is preferably 0.001 to 10 mol% relative to the vinyl group in the polymer, more preferably 0.005 to 5 mol%, further preferably 0.01 to 1 mol%, and even more preferably 0.1 to 1 mol%.

[0102] If the content of the transition metal salt is within the above range, sufficient oxygen absorption performance can be imparted to the oxygen absorbent.

[0103] The content of the polymer represented by the general formula (I) or general formula (II) in the oxygen absorbent of the present invention is not particularly limited. However, from the viewpoint of effectively absorbing oxygen, it is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 85% by mass or more, and even more preferably 90% by mass or more. In addition, from the viewpoint of the manufacturing cost of the oxygen absorbent, it is preferably substantially 100% by mass, more preferably 99.9% by mass or less, and further preferably 99.8% by mass or less.

[0104] In addition to the polymers and transition metal salts represented by General Formula (I) or General Formula (II), the oxygen absorbent of the present invention may also contain various additives within the range that does not impair the effects of the present invention. Specifically, it may contain fillers, ultraviolet absorbers, pigments, thickeners, low shrinkage agents, anti-aging agents, plasticizers, aggregates, flame retardants, stabilizers, fiber reinforcing materials, dyes, antioxidants, leveling agents, and anti-sagging agents, etc.

[0105] The oxygen absorbent of the present invention also exhibits excellent oxygen absorption performance at room temperature. Specifically, regarding the oxygen absorption amount of the oxygen absorbent of the present invention at 20 °C without a transition metal salt, the value 15 days after the date of starting to be used as an oxygen absorbent is preferably 1.5 mL / g or more, more preferably 2 mL / g or more, and further preferably 3.5 mL / g or more.

[0106] In addition, regarding the oxygen absorption amount of the oxygen absorbent of the present invention at 60 °C without a transition metal salt, the value 5 days after the date of starting to be used as an oxygen absorbent is preferably 45 mL / g or more, more preferably 48 mL / g or more, and further preferably 50 mL / g or more.

[0107] It should be noted that there is no limit to the upper limit of the oxygen absorption amount of the oxygen absorbent, and the oxygen absorption amount can be measured by the method described in the examples.

[0108] The oxygen absorbent of the present invention can be obtained by mixing the polymer represented by General Formula (I) or General Formula (II) with a transition metal salt and / or various additives as required. Specifically, it can be obtained by stirring and mixing the polymer represented by General Formula (I) or General Formula (II) with a transition metal salt.

[0109] [Curable Composition]

[0110] The curable composition of the present invention contains: the oxygen absorbent of the present invention, and a polymerizable monomer and / or a polymerizable resin. Regarding the polymer represented by General Formula (I) or General Formula (II), it itself has a polymerizable group and a reactive group, and even when incorporated into a polymerizable monomer and / or resin, it is difficult to hinder crosslinking reactions, polymerization reactions, etc. Therefore, the curable composition of the present invention is difficult to affect the crosslinking reaction and polymerization reaction of the polymerizable monomer and the polymerizable resin even in the presence of oxygen, and it is excellent in this regard.

[0111] There are no particular limitations on the polymerizable monomer for the curable composition of the present invention as long as it can be used in coatings, adhesives, coating agents, etc. The polymerizable monomer may be a thermosetting free-radical polymerizable monomer, or may also be a polymerizable monomer for active energy ray-curable resins such as UV-curable resins. Although it also depends on the use, etc., from the aspect of more significantly exhibiting the effects of the present invention, the resin is preferably a thermosetting free-radical polymerizable monomer.

[0112] Examples of the free-radical polymerizable monomer for the present invention and the polymerizable monomer for the active energy ray-curable resin include monofunctional compounds and polyfunctional compounds.

[0113] Examples of the monofunctional compound include vinyl compounds such as styrene, vinyl ethers, vinyl esters, and N-vinylpyrrolidone; (meth)acryloyl compounds such as (meth)acrylic acid and (meth)acrylates; and allyl compounds such as allyl alcohol and allyl esters.

[0114] Examples of the polyfunctional compound include poly(meth)acrylates having one or more (preferably two or more) (meth)acryloxy groups in the molecule, unsaturated polyester resins, etc. Among these, poly(meth)acrylates having one or more (preferably two or more) (meth)acryloxy groups in the molecule are preferred, and urethane (meth)acrylate and epoxy (meth)acrylate are particularly preferred from the viewpoints of the curing rate of the resulting curable composition and the properties of the cured coating film. In the curable composition of the present invention, the polyfunctional compound may contain only one kind or may contain two or more kinds.

[0115] Examples of the urethane (meth)acrylate include urethane (meth)acrylate obtained by adding a (meth)acrylate containing a hydroxyl group to a polymer having an isocyanate group remaining after synthesis using a polyol and an excessive polyisocyanate.

[0116] Examples of the polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, hydrogenated bisphenol A, hydrogenated bisphenol F, etc.

[0117] Examples of the polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, etc. Among these, hexamethylene diisocyanate having excellent curability is preferred.

[0118] As the urethane (meth) acrylate, a urethane (meth) acrylate obtained by reacting hexamethylene diisocyanate as a polyisocyanate with pentaerythritol tri (meth) acrylate as a (meth) acrylate containing a hydroxyl group is preferred.

[0119] Examples of the epoxy (meth) acrylate include epoxy (meth) acrylates obtained by adding (meth) acrylic acid to the terminals of bisphenol A type epoxy resins, and epoxy (meth) acrylates obtained by adding (meth) acrylic acid to epoxy resins.

[0120] There is no particular limitation on the polymerizable resin used in the curable composition of the present invention as long as it is a resin that can be used in coatings, adhesives, coating agents, etc. The resin may be a free radical polymerizable resin, or may be an active energy ray curable resin such as a UV curable resin. Although it also depends on the use and the like, from the aspect of more significantly exhibiting the effects of the present invention, the resin is preferably a free radical polymerizable resin. In addition, since the oxygen absorber of the present invention has excellent oxygen absorption performance, it can be preferably used for the purpose of absorbing oxygen already contained in the resin in an oxygen barrier resin that requires low oxygen permeability.

[0121] Specific examples of the resin include free radical polymerizable resins such as unsaturated polyester resins, vinyl ester resins, (meth) acrylic resins having a polymerizable group, and urethane (meth) acrylate resins; resins that require oxygen barrier properties such as polyvinyl alcohol, ethylene-vinyl acetate copolymers, partially or completely saponified ethylene-vinyl acetate copolymers, epoxy resins, polyester resins, polyolefin resins, and cyclic polyolefin resins.

[0122] In addition to the above resins, fluororesins, polyamide resins such as polyamide 66, polycarbonate resins, polyurethane resins, etc. may also be used as needed.

[0123] Examples of the unsaturated polyester resin include copolymers of polyol compounds such as propylene glycol-phthalic anhydride-maleic anhydride copolymers and ethylene glycol-phthalic anhydride-maleic anhydride copolymers with α,β-unsaturated polyacid compounds and other polyacid compounds, and unsaturated polyester resins obtained by adding a free radical polymerizable monomer such as styrene to the copolymer.

[0124] Examples of the above polyol compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, hydrogenated bisphenol A, and hydrogenated bisphenol F.

[0125] Examples of the α,β-unsaturated polybasic acid compounds include maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc. Examples of the other polybasic acid compounds include phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, chlorendic acid, adipic acid, sebacic acid, etc. They may be used alone or in combination of two or more.

[0126] These copolymers may further contain a glycidyl compound of an unsaturated alcohol such as allyl glycidyl ether as one of the copolymer components.

[0127] Examples of the vinyl ester resin include vinyl ester resins obtained by adding (meth)acrylic acid to the terminals of bisphenol A type epoxy resins, vinyl ester resins obtained by adding (meth)acrylic acid to epoxy resins, etc.

[0128] Examples of the urethane (meth)acrylate resin include urethane (meth)acrylates obtained by adding (meth)acrylic acid to a polymer having isocyanate groups remaining after synthesis using a polyol compound and an excessive polyisocyanate compound. The above polyol compound may be the same as the polyol compound in the description of the above unsaturated polyester resin. Examples of the above polyisocyanate compound include toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.

[0129] The content of the polymer represented by the general formula (I) or the general formula (II) in the curable composition of the present invention is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 40 parts by mass, and still more preferably 0.5 to 30 parts by mass relative to 100 parts by mass of the resin.

[0130] The curable composition of the present invention may appropriately contain pigments, dyes, fillers, ultraviolet absorbers, thickeners, low shrinkage agents, anti-aging agents, plasticizers, aggregates, flame retardants, stabilizers, fiber reinforcing materials, antioxidants, leveling agents, anti-sagging agents, etc. In addition, the curable composition of the present invention may also contain, for example, styrene, (meth)acrylate, etc. as diluents. From the viewpoint of polymerizability, the effect of the present invention is more significantly exhibited when (meth)acrylate is contained, and thus it is particularly preferred.

[0131] Examples of the pigment include titanium oxide, iron oxide red, aniline black, carbon black, cyanine blue, chrome yellow, etc. Examples of the filler include talc, mica, kaolin, calcium carbonate, clay, etc.

[0132] The curable composition of the present invention can be obtained by mixing a polymerizable monomer and / or a polymerizable resin with the oxygen absorbent of the present invention. Specifically, it can be obtained by mixing the oxygen absorbent, resin, and optional components as needed using stirring or the like.

[0133] The curable composition of the present invention can be preferably used for applications such as coatings, adhesives, inks, sealants, resist materials, and coating agents. In particular, it can be preferably used in applications where curing is liable to be hindered by oxygen, such as in air, and in curing in a state where dissolved oxygen is present in the curable composition.

[0134] [Method for producing a polymer composition containing a compound of general formula (V)]

[0135] The method for producing a polymer composition containing a compound of general formula (V) according to the present invention is a method for producing a polymer composition containing a compound of general formula (V) obtained by reacting a compound represented by the following general formula (III) and a compound represented by the following general formula (IV) with a base.

[0136] [Chemical formula 9]

[0137]

[0138] [Chemical formula 10]

[0139]

[0140] [Chemical formula 11]

[0141]

[0142] In general formula (III), R 21 and R 22 each independently represent any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. The preferred mode is the same as R 3 and R 4 in the above general formula (I).

[0143] In general formula (IV), R 23 represents a hydrogen atom or a methyl group.

[0144] In general formula (V), R 21 , R 22 and R 23 have the same meanings as above, and R 24 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. The preferred mode is the same as R 16The same. n is an arbitrary integer, and preferably the same as n in the above general formula (I).

[0145] In the production method of the present invention, a polymer can be easily obtained by reacting the compound represented by the above general formula (III) with the compound represented by the general formula (IV) in the presence of a base. Examples of the base that can be used include inorganic bases such as alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides, and organic bases such as triethylamine, diisopropylamine, pyrimidine, diazabicycloundecene, pyridine, triphenylphosphine, and metal alkoxides. These can be used alone or in combination of two or more. From the viewpoints of solubility and activity in the reaction substrate, sodium hydroxide or potassium hydroxide is preferred.

[0146] In the production method of the present invention, the ratio of the compound represented by the above general formula (III) (hereinafter, also referred to as compound (III)) to the compound represented by the general formula (IV) (hereinafter, also referred to as compound (IV)) is not particularly limited, but from the viewpoint of forming a polymer, it is preferably compound (III) / compound (IV) = 2 / 1 to 1 / 2. If it is greater than 2 / 1, the reaction will stop and the amount of polymer formed will be significantly reduced. If it is less than 1 / 2, side reactions will occur and the yield will be significantly reduced.

[0147] As a specific example of the production method of the present invention, for example, in the case of producing a polymer represented by the following formula (A-1), it can be produced by reacting a compound capable of forming a polymerizable site such as epichlorohydrin with 3-methyl-2-buten-1-ol as the corresponding alcohol in the presence of a base such as potassium hydroxide. As the reaction conditions, from the viewpoint of sufficient reaction, it is preferably stirred at a temperature of about 60 to 150 °C for about 0.5 to 20 hours. In addition, in purification, the reaction solution after polymerization can be directly used, or a desired purity can be obtained by combining known methods such as silica gel column, activated carbon column, and distillation operation.

[0148] [Chemical formula 12]

[0149]

[0150] Examples

[0151] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. It should be noted that the physical property values in the examples, reference examples, and comparative examples were measured by the following methods.

[0152] 1 H-NMR measurement conditions]

[0153] ​In 4 g of deuterated chloroform, 20 mg of the oxygen absorbent obtained in the examples, reference examples, and comparative examples was respectively added to prepare a homogeneous solution, and this solution was subjected to 1 1H-NMR measurement.

[0154] Apparatus: "ULTRASHIELD 400 PLUS" manufactured by Bruker Co., Ltd.

[0155] Reference substance: Tetramethylsilane

[0156] Measurement temperature: 25 °C

[0157] Number of accumulations: 16 times

[0158] [Gel Permeation Chromatography (GPC) Measurement]

[0159] In 2 g of tetrahydrofuran (THF), 200 mg of the oxygen absorbent obtained in the examples or comparative examples was respectively added to prepare a homogeneous solution, and this solution was subjected to gel permeation chromatography analysis under the following measurement conditions. The weight average molecular weight number (Mw) and number average molecular weight (Mn) were determined in terms of standard polystyrene conversion, and the molecular weight distribution (Mw / Mn) was calculated.

[0160] Apparatus: "HLC-8220GPC" manufactured by Tosoh Corporation

[0161] Column: Three "TSKgel SuperHM-N (inner diameter 6 mm, effective length 15 cm)" manufactured by Tosoh Corporation were connected in series.

[0162] Eluent: THF was passed at a flow rate of 0.6 mL / minute.

[0163] Sample injection volume: 10 μL

[0164] Detector: RI

[0165] Detector temperature: 40 °C

[0166] [Method for Measuring Oxygen Absorption Amount (at 20 °C)]

[0167] 100 mg of the oxygen absorbent obtained in the examples or comparative examples was accurately weighed and placed in a sample bottle with an internal volume of 20 mL. Subsequently, in order to adjust the humidity inside the sample bottle, a vial containing 0.5 mL of ion-exchanged water was placed in this sample bottle, and the opening of the sample bottle was blocked with a rubber cap and an aluminum cap sealed with polytetrafluoroethylene resin.

[0168] The sample bottle was placed statically in a thermostat at 20°C. After 1 day, 5 days, and 15 days from the date when it started to be used as an oxygen absorbent, the residual oxygen amount in the sample bottle was measured respectively using a residual oxygen meter ("PACK MASTER RO-103" manufactured by Iijima Electronics Industry Co., Ltd.).

[0169] For control, except for not putting the oxygen absorbents obtained in the examples and comparative examples, the residual oxygen amount was measured under the same conditions, and the difference (oxygen absorption amount) between the measured values obtained in the examples and comparative examples and the measured values obtained in the control was calculated. The oxygen absorption amount per 1 g of the oxygen absorbent was calculated as the oxygen absorption amount (20°C) [mL / g] of the oxygen absorbent. It should be noted that the same test was carried out 3 times, and the average value was adopted.

[0170] [Method for Measuring Oxygen Absorption Amount (60°C)]

[0171] Except for changing the temperature of the thermostat in the measurement of the oxygen absorption amount (20°C) from 20°C to 60°C, the oxygen absorption amount (60°C) [mL / g] (average value of 3 tests) of the oxygen absorbent was measured in the same way.

[0172] [Example 1]

[0173] Synthesis of α-(3-methyl-2-butenyloxy)-ω-hydroxy poly[oxy(3-methyl-2-butenyloxymethylethane-1,2-diyl)] (A-1)

[0174] [Chemical Formula 13]

[0175]

[0176] In a reactor equipped with a stirrer, a thermometer, and a dropping funnel, under a nitrogen stream, 1654 g (manufactured by Kuraray Co., Ltd., 19.2 mol) of 3-methyl-2-buten-1-ol, 1842 g (manufactured by Kanto Denka Kogyo Co., Ltd., 23.0 mol) of 50% aqueous sodium hydroxide solution, and 28 g (manufactured by Tokyo Chemical Industry Co., Ltd., 0.084 mol) of dodecylbenzyldimethylammonium chloride were charged. While maintaining the internal temperature below 60 °C, 1776 g (manufactured by Fujifilm Wako Pure Chemical Corporation, 19.2 mol) of epichlorohydrin was added dropwise with stirring. After the addition was completed, the temperature was raised to 90 °C. Stirring was carried out at an internal temperature of 90 °C for 9 hours, and then it was cooled to 25 °C. After washing the reaction solution with 5000 g of 7.5% aqueous sodium bicarbonate solution, the upper layer was washed with 5000 mL of ion-exchanged water. Water and unreacted 3-methyl-2-buten-1-ol were distilled off from the obtained organic layer by distillation to obtain 1996 g (yield 73%) of α-(3-methyl-2-butenyloxy)-ω-hydroxypoly[oxy(3-methyl-2-butenyloxymethylethane-1,2-diyl)] represented by the above general formula (A-1). The following shows its 1 measurement results of 1H-NMR and GPC measurement results.

[0177] 1 1H-NMR (270 MHz, CDCl 3 , TMS) δ: 5.37 - 5.32 (m, 5H), 4.02 - 3.99 (brd, 10H), 3.68 - 3.56 (m, 4H), 3.55 - 3.40 (m, 10H), 2.54 (d, J = 3.8 Hz, 1H), 1.74 (brs, 15H), 1.66 (brs, H)

[0178] GPC measurement: weight-average molecular weight (Mw) = 360, number-average molecular weight (Mn) = 300, molecular weight distribution (Mw / Mn) = 1.2 (in terms of polystyrene)

[0179] [Reference Example 1]

[0180] Synthesis of 1-(3-methyl-2-butenyloxy)-2,3-epoxypropane (A-2)

[0181] [Chemical Formula 14]

[0182]

[0183] In a reactor equipped with a stirrer, a thermometer, and a dropping funnel, under a nitrogen stream, 324 g (manufactured by Kuraray Co., Ltd., 3.77 mol) of 3-methyl-2-buten-1-ol, 2300 mL of cyclohexane, 226 g (manufactured by Fujifilm Wako Pure Chemical Corporation, 5.65 mol) of sodium hydroxide, 15.2 g (manufactured by Tokyo Chemical Industry Co., Ltd., 37.3 mmol) of trioctylmethylammonium chloride, and 226 mL of purified water were charged. While maintaining the internal temperature below 25°C and stirring, 698 g (manufactured by Fujifilm Wako Pure Chemical Corporation, 7.54 mol) of epichlorohydrin was added dropwise over 90 minutes. After the addition was completed, the temperature was raised to 40°C over 30 minutes. The mixture was stirred at an internal temperature of 40°C for 3 hours and then cooled to 25°C. The upper layer of the reaction solution was washed 5 times with 670 mL of saturated brine, and the organic layer was dried with sodium sulfate. The sodium sulfate was filtered off, and the filtrate was concentrated to obtain 536 g of a concentrate. The concentrate was purified by distillation to obtain 242 g (1.67 mol; yield 44%) of 1-(3-methyl-2-butenyloxy)-2,3-epoxypropane represented by the above formula (A-2). The following shows its 1 measurement results of 1H-NMR.

[0184] 1 1H-NMR (400 MHz, CDCl 3 , TMS) δ: 5.35 (tquin, J = 6.8, 1.2 Hz, 1H), 4.03 (ddd, J = 19.6, 12.0, 7.2 Hz, 2H), 3.68 (dd, J = 11.6, 3.2 Hz, 1H), 3.99 (dd, J = 11.2, 5.6 Hz, 1H), 3.17 - 3.13 (m, 1H), 2.79 (dd, J = 4.8, 4.0 Hz, 1H), 2.60 (dd, J = 5.2, 2.8 Hz, 1H), 1.75 (s, 3H), 1.68 (s, 3H).

[0185] [Example 2]

[0186] Synthesis of α-methoxy-ω-hydroxy poly[oxy(3-methyl-2-butenyloxymethylethane-1,2-diyl)] (A-3)

[0187] [Chemical formula 15]

[0188]

[0189] In a reactor equipped with a stirrer, a thermometer, and a dropping funnel, 20 g (manufactured by Kuraray Co., Ltd., 0.14 mol) of 3-methyl-2-buten-1-ol and 76 mg (manufactured by Fujifilm Wako Pure Chemical Corporation, 1.4 mmol) of sodium methoxide were charged under a nitrogen stream. The internal temperature was raised to 110 °C and stirred for 9 hours, and then cooled to 25 °C. After adding 1 mL of acetic acid to the reaction solution, low-boiling components were removed by evaporation to obtain 18.8 g (yield 94%) of α-methoxy-ω-hydroxy poly[oxy(3-methyl-2-buteneoxymethylethane-1,2-diyl)] represented by the above general formula (A-3). The following shows its 1 1H-NMR measurement results and GPC measurement results.

[0190] 1 1H-NMR (270 MHz, CDCl 3 , TMS) δ: 5.34 (t, J = 13.0 Hz, 47H), 4.05 - 3.90 (brd, 94H), 3.77 - 3.35 (m, 235H), 2.61 (brs, 1H), 1.74 (brs, 282H), 1.67 (brs, 282H)

[0191] GPC measurement: weight-average molecular weight (Mw) = 7600, number-average molecular weight (Mn) = 4800, molecular weight distribution (Mw / Mn) = 1.58 (in terms of polystyrene)

[0192] [Example 3]

[0193] In a glass sample bottle, 5.00 g of compound (A-1) was added and stirred well to obtain an oxygen absorber. The evaluation results are shown in Table 1.

[0194] [Example 4]

[0195] An oxygen absorber was obtained in the same manner as in Example 3, except that compound (A-1) in Example 3 was changed to compound (A-3). The evaluation results are shown in Table 1.

[0196] [Comparative Example 1]

[0197] An oxygen absorber was obtained in the same manner as in Example 3, except that 5.00 g (manufactured by Tokyo Chemical Industry Co., Ltd.; purity 99%; 29.0 mmol) of the compound (E-1) represented by the following formula was used instead of compound (A-1) in Example 1. The evaluation results are shown in Table 1.

[0198] [Chemical Formula 16]

[0199]

[0200] [Table 1]

[0201]

[0202] As shown in Table 1, it can be seen that the polymer of the present invention has excellent oxygen absorption ability even at normal temperature. Additionally, surprisingly, it can be seen that oxygen can be absorbed even without using a transition metal salt, and the curing reaction of the curable composition can be fully exhibited.

Claims

1. A curable composition comprising an oxygen absorber represented by the following general formula (I), a polymerizable monomer and / or a polymerizable resin. In general formula (I), X 1 , X 2 and X 3 represent chalcogen atoms; R 1 and R 2 represent hydrogen atoms, R 3 and R 4 each independently represents any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, R 5 and R 6 each independently represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, R 7 represents a hydrogen atom or a methyl group, R 8 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; n is an integer of 2 to 150; R 3 , R 4 , R 5 and R 6 do not form a ring structure by being connected to each other.

2. The curable composition according to claim 1. Wherein, In the general formula (I), X 1 and X 2 are oxygen atoms.

3. The curable composition according to claim 1 or 2. Wherein, In the general formula (I), R 3 and R 4 are alkyl groups having 1 to 6 carbon atoms.

4. The curable composition according to any one of claims 1 to 3. Wherein, In the general formula (I), R 5 , R 6 and R 7 are hydrogen atoms.

5. The curable composition according to any one of claims 1 to 4. Wherein, In the general formula (I), R 8 is a hydrogen atom.

6. The curable composition according to any one of claims 1 to 5. Wherein, The polystyrene-reduced weight average molecular weight Mw of the oxygen absorber is 300 to 50,000, and the molecular weight distribution Mw / Mn is 1.05 to 10.

0.

7. The curable composition according to any one of claims 1 to 6. Wherein, The polymerizable monomer and / or the polymerizable resin is a radical polymerizable monomer and / or a radical polymerizable resin.

8. A curable composition comprising a polymer represented by the following general formula (II), a polymerizable monomer and / or a polymerizable resin. In general formula (II), R 11 , R 12 , R 13 and R 14 each independently represent any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, R 15 represents a hydrogen atom or a methyl group, and R 16 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; n is an integer of 2 to 150.

9. The curable composition according to claim 8. Wherein, In the general formula (II), R 16 is a hydrogen atom.

10. The curable composition according to claim 8 or 9, wherein the polystyrene-reduced weight average molecular weight Mw of the polymer is 300 to 50,000, and the molecular weight distribution Mw / Mn is 1.05 to 10.

0.

11. The curable composition according to any one of claims 8 to 10, which contains a transition metal salt in an amount of 0.001 mol% to 10 mol% relative to the vinyl groups of the polymer.

12. The curable composition according to any one of claims 8 to 11. Wherein, The polymerizable monomer and / or the polymerizable resin is a radical polymerizable monomer and / or a radical polymerizable resin.

13. An oxygen absorber comprising a polymer represented by the following general formula (II). In general formula (II), R 11 , R 12 , R 13 and R 14 each independently represent any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group, R 15 represents a hydrogen atom or a methyl group, R 16 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; n is an integer of 2 to 150.

14. The oxygen absorber according to claim 13. Wherein, In the general formula (II), R 16 is a hydrogen atom.

15. The oxygen absorber according to claim 13 or 14, wherein the polystyrene-reduced weight average molecular weight Mw of the polymer is 300 to 50,000, and the molecular weight distribution Mw / Mn is 1.05 to 10.

0.

16. The oxygen absorber according to any one of claims 13 to 15, which contains a transition metal salt in an amount of 0.001 mol% to 10 mol% relative to the vinyl groups of the polymer.

17. A method for producing a polymer composition containing the following general formula (V), the polymer composition being obtained by reacting a compound represented by the following general formula (III), a compound represented by the following general formula (IV) and a base. In general formula (III), R 21 and R 22 each independently represents any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group. In general formula (IV), R 23 represents a hydrogen atom or a methyl group, In general formula (V), R 21 , R 22 and R 23 are as defined above, and R 24 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; n is an integer of 2 to 150.

18. The method for producing a polymer composition containing the general formula (V) according to claim 17. Wherein, The ratio of the compound represented by the general formula (III) to the compound represented by the general formula (IV) is compound (III) / compound (IV) = 1 / 2 to 2 / 1.

Images