Method for producing polymer having polymerizable multiple bond

Abstract

A method for producing a polymer having a polymerizable multiple bond, the method comprising reacting a polymer (A) having a first functional group with a compound (B) having a second functional group and a polymerizable multiple bond in a reactor in the presence of an N-oxyl-compound polymerization inhibitor and an organic solvent by reacting the first functional group with the second functional group, thereby producing the polymer having a polymerizable multiple bond.

Description

Method for producing polymers having polymerizable multiple bonds

[0001] The present invention relates to a method for producing a polymer having polymerizable multiple bonds.

[0002] A polymer having a carbon-carbon double bond can be obtained, for example, by reacting a polymer having an epoxy group with (meth)acrylic acid. For example, a method for producing an epoxy acrylate resin has been proposed, in which an epoxy resin is reacted with methacrylic acid containing 30 to 80 ppm of monomethyl ether hydroquinone in an atmosphere of a mixed gas of oxygen and nitrogen containing 1 to 10% by volume of oxygen (see Patent Document 1).

[0003] JP 2024-5441 A

[0004] When a polymer is produced in a reactor in a factory, it is required to produce the desired polymer as well as to produce the polymer safely. In order to produce the polymer safely, it is effective to lower the oxygen concentration in the reactor, but in that case, it may become difficult to produce the desired polymer.

[0005] An object of the present invention is to provide a production method that can produce a polymer having polymerizable multiple bonds even when the oxygen concentration in a reaction vessel is low.

[0006] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0007] That is, the present invention encompasses the following: [1] A method for producing a polymer having a polymerizable multiple bond, comprising reacting a polymer (A) having a first functional group with a compound (B) having a second functional group and a polymerizable multiple bond in a reaction vessel in the presence of an N-oxyl-based polymerization inhibitor and an organic solvent, by reacting the first functional group with the second functional group, to produce a polymer having a polymerizable multiple bond. [2] The method for producing a polymer having a polymerizable multiple bond according to [1], wherein the first functional group is an epoxy group and the second functional group is a carboxy group. [3] The method for producing a polymer having a polymerizable multiple bond according to [1] or [2], wherein the N-oxyl-based polymerization inhibitor has a piperidine ring. [4] The method for producing a polymer having a polymerizable multiple bond according to any one of [1] to [3], wherein the amount of the N-oxyl-based polymerization inhibitor used is 1 ppm by mass to 3,000 ppm by mass relative to the total mass of materials used in the reaction. [5] The method for producing a polymer having a polymerizable multiple bond according to any one of [1] to [4], wherein the amounts of the polymer (A) and the compound (B) used during the reaction satisfy a molar ratio (Bf / Af) of the molar amount (Bf) of the second functional group in the compound (B) to the molar amount (Af) of the first functional group in the polymer (A) of 1.00 or more. [6] The method for producing a polymer having a polymerizable multiple bond according to any one of [1] to [5], wherein the oxygen concentration of the gas in the reaction vessel is 5% by volume or less.

[0008] According to the present invention, a polymer having polymerizable multiple bonds can be produced even when the oxygen concentration in the reaction vessel is low.

[0009] (Method for producing a polymer having a polymerizable multiple bond) The method for producing a polymer having a polymerizable multiple bond of the present invention includes reacting a polymer (A) with a compound (B). The reaction between the polymer (A) and the compound (B) is carried out in a reaction vessel. The reaction between the polymer (A) and the compound (B) is carried out in the presence of an N-oxyl-based polymerization inhibitor and an organic solvent. The polymer (A) has a first functional group. The compound (B) has a second functional group and a polymerizable multiple bond. The reaction between the polymer (A) and the compound (B) is a reaction between the first functional group and the second functional group.

[0010] When a polymer is reacted with a compound having a polymerizable multiple bond to produce a polymer having a polymerizable multiple bond, a polymerization inhibitor is usually used to suppress the reaction of the polymerizable multiple bond to obtain the polymer. However, depending on the type of polymerization inhibitor, if the oxygen concentration in the atmosphere in the reaction vessel is low, the polymerization inhibitor may not function sufficiently and may not be able to suppress the reaction of the polymerizable multiple bond. On the other hand, an N-oxyl-based polymerization inhibitor functions as a polymerization inhibitor regardless of the oxygen concentration in the atmosphere in the reaction vessel, and can suppress the reaction of the polymerizable multiple bond. Therefore, by using an N-oxyl-based polymerization inhibitor when reacting a polymer with a compound having a polymerizable multiple bond, a polymer having a polymerizable multiple bond can be produced without excessively increasing the molecular weight, even if the oxygen concentration in the reaction vessel is reduced. It is known that an N-oxyl-based polymerization inhibitor functions as a polymerization inhibitor regardless of the oxygen concentration in the atmosphere in the reaction vessel (e.g., JP-A-1-165534 and JP-A-2015-086197 (e.g., paragraph

[0083] )).

[0011] <N-oxyl-based polymerization inhibitor> An N-oxyl-based polymerization inhibitor refers to a compound having a group with an —N—O bond that can stabilize a radical growing end. The N-oxyl-based polymerization inhibitor preferably has a piperidine ring. Examples of N-oxyl-based polymerization inhibitors having a piperidine ring include the following compounds: 4-Hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl 4-Oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl 4-Acetoxy-2,2,6,6-tetramethyl-piperidine-N-oxyl 2,2,6,6-tetramethyl-piperidine-N-oxyl Piperidine-1-oxyl 4-(Dimethylamino)-2,2,6,6-tetramethyl-piperidine-N-oxyl 4-Amino-2,2,6,6-tetramethyl-piperidine-N-oxyl 4-Ethanoloxy-2,2,6,6-tetramethyl-piperidine-N-oxyl 4-Benzoyloxy-2,2,6,6-tetramethyl-piperidine-N-oxyl 2,2,5,5-tetramethyl-piperidine-N-oxyl 3-amino-2,2,5,5-tetramethyl-piperidine-N-oxyl 4,4′,4″-tris(2,2,6,6-tetramethyl-piperidine-N-oxyl)phosphite Examples of other N-oxyl-based polymerization inhibitors include the following compounds. 3-oxo-2,2,5,5-tetramethylpyrrolidine-N-oxyl Pyrrolidine-1-oxyl 2,2,5,5-tetramethyl-1-oxa-3-azacyclopentyl-3-oxy 2,2,5,5-tetramethyl-3-pyrrolinyl-1-oxy-3-carboxylic acid 2,2,3,3,5,5,6,6-octamethyl-1,4-diazacyclohexyl-1,4-dioxy Di-tert-butyl nitroxide, di-tert-amyl nitroxide Among these, 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl and 2,2,6,6-tetramethyl-piperidine-N-oxyl are preferred. N-oxyl polymerization inhibitors can be used alone or in combination of two or more.

[0012] The amount of the N-oxyl polymerization inhibitor used is not particularly limited, but is, for example, 1 ppm by mass to 3,000 ppm by mass, preferably 5 ppm by mass to 1,500 ppm by mass, more preferably 10 ppm by mass to 1,000 ppm by mass, and most preferably 20 ppm by mass to 500 ppm by mass, relative to the total mass of the materials used in the reaction. Examples of the materials used in the reaction include the polymer (A), the compound (B), the N-oxyl polymerization inhibitor, a catalyst, and an organic solvent.

[0013] <Polymer (A) and Compound (B)> The polymer (A) has a first functional group, and the compound (B) has a second functional group and a polymerizable multiple bond.

[0014] The polymer (A) is not particularly limited as long as it has a first functional group. The amount of the first functional group in the polymer (A) is not particularly limited.

[0015] Compound (B) is not particularly limited as long as it has a second functional group and a polymerizable multiple bond. The number of second functional groups in compound (B) is not particularly limited, but is preferably one. The number of polymerizable multiple bonds in compound (B) is not particularly limited, but is preferably one or two. Examples of polymerizable multiple bonds include one or more types selected from the group consisting of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds.

[0016] The first functional group does not contain a polymerizable multiple bond. Examples of the first functional group include an epoxy group, a carboxy group, a hydroxy group, a phenolic hydroxy group, an amino group, and an isocyanate group. The second functional group does not contain a polymerizable multiple bond. Examples of the second functional group include an epoxy group, a carboxy group, a hydroxy group, a phenolic hydroxy group, an amino group, and an isocyanate group. The combination of the first functional group and the second functional group is not particularly limited as long as they react with each other, but examples include a combination of an epoxy group and a carboxy group, a combination of an epoxy group and a phenolic hydroxy group, a combination of an epoxy group and an amino group, and a combination of a hydroxy group and an isocyanate group. Among these, from the viewpoint of performing the reaction under heating conditions that require the use of a polymerization inhibitor, a combination of an epoxy group and a carboxy group, and a combination of an epoxy group and a phenolic hydroxy group are preferred as the combination of the first functional group and the second functional group. When the combination of the first functional group and the second functional group is a combination of an epoxy group and a carboxy group, for example, the first functional group may be an epoxy group and the second functional group may be a carboxy group, or the first functional group may be a carboxy group and the second functional group may be an epoxy group. Note that in this specification, the mere term "hydroxy group" refers to a non-phenolic hydroxy group.

[0017] The weight average molecular weight of the polymer (A) is not particularly limited, but may be, for example, 1,000 to 30,000 or 1,500 to 20,000. The weight average molecular weight in the present invention is a weight average molecular weight measured by gel permeation chromatography.

[0018] The molecular weight of the compound (B) is not particularly limited, and may be, for example, not more than 500 or not more than 300. The lower limit of the molecular weight of the compound (B) is, for example, 72 (the molecular weight of acrylic acid).

[0019] The amounts of polymer (A) and compound (B) used during the reaction are not particularly limited, but it is preferable that the molar ratio (Bf / Af) of the molar amount (Bf) of the second functional group of compound (B) to the molar amount (Af) of the first functional group of polymer (A) is 1.00 times or more, more preferably 1.01 times or more. That is, the molar ratio (Bf / Af) is preferably 1.00 times or more, more preferably 1.01 times or more. The upper limit of the molar ratio (Bf / Af) is not particularly limited, but for example, the molar ratio (Bf / Af) may be 1.20 times or less, or 1.10 times or less. The molar amount (Af) is the molar amount of the first functional group of the total amount of polymer (A) used in the reaction. The molar amount (Bf) is the molar amount of the second functional group of the total amount of compound (B) used in the reaction.

[0020] The amounts of polymer (A) and compound (B) used during the reaction are, for example, preferably 0.1 parts by mass to 150 parts by mass, more preferably 1 part by mass to 100 parts by mass, and particularly preferably 2 parts by mass to 50 parts by mass, relative to 100 parts by mass of the organic solvent.

[0021] Polymer (A1) as an example of polymer (A) will be described below, and compound (B1) as an example of compound (B) will be described below.

[0022] <<Polymer (A1)>> The polymer (A1) may be a homopolymer or a copolymer. Examples of the polymer (A1) include a polymer having a structural unit represented by the following formula (A1): (In formula (A1), A represents a trivalent group having one or more carbon atoms. X １ represents a monovalent group having a first functional group.

[0023] In the present invention, the monovalent group having a first functional group may be the first functional group itself, or may be a monovalent group containing the first functional group. Examples of the monovalent group containing the first functional group include monovalent groups containing an alicyclic epoxy group. The number of carbon atoms in the monovalent group having the first functional group is, for example, 0 to 10.

[0024] An example of the polymer (A1) is a polymer (A1-1) having a structural unit represented by the following formula (A1-1). (In formula (A1-1), R １ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. １ represents a single bond or a linking group. １ represents a monovalent group having a first functional group.

[0025] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, and a 1-ethyl-n-propyl group. cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2, 2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include a 3-trimethylcyclopropyl group, a 1-ethyl-2-methylcyclopropyl group, a 2-ethyl-1-methylcyclopropyl group, a 2-ethyl-2-methylcyclopropyl group, a 2-ethyl-3-methylcyclopropyl group, an n-heptyl group, a cycloheptyl group, a norbornyl group, an n-octyl group, a cyclooctyl group, an n-nonyl group, an isobornyl group, a tricyclononyl group, an n-decyl group, an adamantyl group, and a tricyclodecyl group. Of these, a methyl group is preferred.

[0026] Y １ When is a linking group, the number of carbon atoms in the linking group is not particularly limited, but may be, for example, 1 to 10.

[0027] "-Y" in formula (A1-1) １ -X １ Examples of " include the following groups: (* represents a bond.)

[0028] The proportion of the structural unit represented by formula (A1-1) in polymer (A1-1) is not particularly limited, but the mass ratio of the structural unit represented by formula (A1-1) relative to all structural units of polymer (A1) may be, for example, 20% by mass to 100% by mass, or 20% by mass or more but less than 100% by mass.

[0029] An example of the polymer (A1-1) is polyglycidyl (meth)acrylate.

[0030] An example of the polymer (A1) is a polymer (A1-2) having a structure represented by the following formula (A1-2). (In formula (A1-2), Ar represents a benzene ring, a naphthalene ring, or an anthracene ring. R １ represents a hydroxy group, a mercapto group which may be protected by a methyl group, an amino group which may be protected by a methyl group, a halogeno group, or an alkyl group having 1 to 10 carbon atoms which may be substituted or interrupted by a heteroatom and which may be substituted by a hydroxy group. n1 represents an integer of 0 to 3. Y １represents a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by the following formula (Y1-1). n2 represents 1 or 2. E １ represents a group having an epoxy group or a group having an oxetanyl group. １ When n2=1, represents a single bond or an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond or an amide bond. １ represents a nitrogen atom or an amide bond when n2=2. * represents a bond. (In formula (Y1-1), T ２ represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms. １ represents a group having an epoxy group or a group having an oxetanyl group. * represents a bond.

[0031] The above phrase "optionally interrupted" means, in the case of an alkylene group having 2 to 10 carbon atoms, that any carbon-to-carbon bond in the alkylene group is interrupted by a heteroatom (i.e., an ether bond in the case of oxygen, or a sulfide bond in the case of sulfur), an ester bond, or an amide bond; and in the case of an alkylene group having one carbon atom (i.e., a methylene group), that either one of the carbons of the methylene group has a heteroatom (i.e., an ether bond in the case of oxygen, or a sulfide bond in the case of sulfur), an ester bond, or an amide bond.

[0032] Examples of the polymer (A1-2) having a structure represented by formula (A1-2) include polymers having structures represented by the following formulas (A1-2-1) to (A1-2-8).

[0033] The polymer (A1-2) may be a commercially available product, such as EOCN-104S, NC-2000L, NC-3000L, NC-7000L, NC-73000L, EPPN-201, EPPN-501H, or XD-1000-H (manufactured by Nippon Kayaku Co., Ltd.), or ECN-1229 (manufactured by Asahi Kasei Corporation).

[0034] An example of the polymer (A1) is a polymer (A1-3) having a structure represented by the following formula (A1-3). (In formula (A1-3), * represents a bond.)

[0035] The polymer (A1-3) may be a commercially available product, such as EHPE-3150 (manufactured by Daicel Corporation).

[0036] <<Compound (B1)>> The compound (B1) is represented by the following formula (B1). (In formula (B1), X ２ represents a monovalent group having a second functional group. ２ represents a monovalent group having a polymerizable multiple bond.

[0037] The monovalent group having a second functional group may be the second functional group itself, or may be a monovalent group containing the second functional group. Examples of the monovalent group containing a second functional group include a monovalent group containing an alicyclic epoxy group. The number of carbon atoms in the monovalent group having a second functional group may be, for example, 0 to 10.

[0038] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1). (In formula (B1-1), L ２ represents a monovalent group having a polymerizable multiple bond.

[0039] L ２ Examples of the group include the following monovalent groups (L2-1) to (L2-32). (In the formula, * represents a bond.)

[0040] <Organic Solvent> The organic solvent is not particularly limited, and examples thereof include alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

[0041] Examples of the alkylene group of the alkylene glycol monoalkyl ether include alkylene groups having 2 to 4 carbon atoms. Examples of the alkyl group of the alkylene glycol monoalkyl ether include alkyl groups having 1 to 4 carbon atoms. Examples of the number of carbon atoms of the alkylene glycol monoalkyl ether include 3 to 8. Examples of the alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0042] Examples of the alkylene group of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include alkylene groups having 2 to 4 carbon atoms. Examples of the alkyl group of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include alkyl groups having 1 to 4 carbon atoms. Examples of the monocarboxylic acid of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include saturated monocarboxylic acids having 2 to 4 carbon atoms. Examples of saturated monocarboxylic acids having 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid. Examples of the number of carbon atoms of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include those having 5 to 10 carbon atoms. Examples of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate.

[0043] Other organic solvents include, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0044] Among these organic solvents, alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers are preferred.

[0045] These organic solvents may be used alone or in combination of two or more.

[0046] <Catalyst> The reaction between the polymer (A) and the compound (B) may be carried out in the presence of a catalyst, for example. The catalyst is not particularly limited as long as it is a catalyst for the reaction between the first functional group and the second functional group. Examples of the catalyst include quaternary phosphonium salts and quaternary ammonium salts. Examples of quaternary phosphonium salts include tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide. Examples of quaternary ammonium salts include benzyltriethylammonium chloride. These catalysts are suitable for use when the combination of the first functional group and the second functional group is a combination of an epoxy group and a carboxy group. The amount of catalyst used is not particularly limited, but can be selected from the range of 0.1% by mass to 10% by mass, for example, based on the total mass of the polymer (A) and the compound (B).

[0047] <Reaction Temperature and Reaction Time> The reaction temperature between the polymer (A) and the compound (B) is not particularly limited, but may be, for example, 50° C. to 150° C. The reaction time between the polymer (A) and the compound (B) is not particularly limited, but may be, for example, 1 hour to 48 hours.

[0048] Before the reaction, it is preferable to replace the gas in the reaction vessel with an inert gas. Examples of inert gases include nitrogen gas and argon gas, with nitrogen gas being preferred. A method of replacement includes, for example, reducing the pressure of the gas in the reaction vessel and restoring the pressure with an inert gas. Restoring the pressure means returning the pressure of the gas in the reaction vessel to the state before the pressure reduction (for example, about 1 atmosphere). The number of times the pressure is reduced and restored may be one or more times.

[0049] The oxygen concentration of the gas in the reaction vessel is not particularly limited, but from the viewpoint of safety, it is preferably 5% by volume or less, more preferably 3% by volume or less. The lower limit of the oxygen concentration of the gas in the reaction vessel is not particularly limited, but for example, the oxygen concentration of the gas in the reaction vessel may be 0% by volume or more, or 1% by volume or more.

[0050] The reaction may be carried out, for example, by placing all of the materials to be used in the reaction in a reaction vessel to prepare an organic solvent solution containing the polymer (A), the compound (B), an N-oxyl-based polymerization inhibitor, and, if necessary, a catalyst, and then heating the organic solvent solution. The reaction may be carried out, for example, by placing the organic solvent solution containing the polymer (A), the N-oxyl-based polymerization inhibitor, and, if necessary, a catalyst in a reaction vessel, heating the solution, and then dropping the compound (B) (or a diluted solution (organic solvent solution) of the compound (B)) into the reaction vessel.

[0051] The amount of polymerizable multiple bonds in the produced polymer (polymer having polymerizable multiple bonds) is not particularly limited.

[0052] The weight average molecular weight of the produced polymer (polymer having polymerizable multiple bonds) is not particularly limited, but is, for example, 1.0 to 5.0 times, preferably 1.0 to 3.0 times, and more preferably 1.0 to 2.0 times the weight average molecular weight of polymer (A).

[0053] The weight average molecular weight of the produced polymer (polymer having polymerizable multiple bonds) is not particularly limited, and may be, for example, 2,000 to 30,000, or 2,000 to 20,000.

[0054] In the production method of the present invention, after the reaction, an organic solvent solution containing a polymer having a polymerizable multiple bond is obtained. The content of the polymer having a polymerizable multiple bond in the organic solvent solution containing the polymer having a polymerizable multiple bond is not particularly limited and may be, for example, 10% by mass to 50% by mass, preferably 15% by mass to 40% by mass, and more preferably 15% by mass to 30% by mass.

[0055] The amount of the organic solvent solution containing the polymer having polymerizable multiple bonds obtained by one reaction in the production method of the present invention is not particularly limited and may be, for example, 50 L to 2,000 L or 100 L to 1,000 L.

[0056] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The apparatus used is as follows.

[0057] <GPC-1> The weight average molecular weight Mw and polydispersity Mw / Mn of the polymer were calculated from each peak of a chromatogram obtained by measurement by gel permeation chromatography (GPC) based on a calibration curve. The measurement conditions were as follows. <Measurement conditions> Apparatus: HLC-8320GPC (manufactured by Tosoh Corporation) Column: GF-510 HQ (Asahipak) (manufactured by Shodex) Eluent: 10 mM lithium bromide / dimethylformamide Flow rate: 0.6 mL / min Column temperature: 40°C Detector: RI Standard sample: polystyrene

[0058] <GPC-2> The weight average molecular weight Mw and polydispersity Mw / Mn of the polymer were calculated from each peak of a chromatogram obtained by measurement by gel permeation chromatography (GPC) based on a calibration curve. The measurement conditions were as follows. <Measurement conditions> Apparatus: ACQUITY Advanced Polymer Chromatography System (manufactured by Waters) Column: ACQUITY APC XT (manufactured by Waters) Eluent: 0.1% by mass phosphoric acid / tetrahydrofuran Flow rate: 0.5 mL / min Column temperature: 40°C Detector: RI Standard sample: polystyrene

[0059] Example 1 58.46 g of polyglycidyl methacrylate (Mw: 9600, 30% by mass propylene glycol monomethyl ether acetate solution) (manufactured by Maruzen Petrochemical Co., Ltd.), 10.34 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.41 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.), and 0.015 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 6.78 g of propylene glycol monomethyl ether acetate and 72.00 g of propylene glycol monomethyl ether. The gas in the reaction vessel was replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas three times, and the mixture was then reacted at 85°C for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. Analysis by GPC-1 revealed that the polymer in the resulting solution had a weight-average molecular weight of 15,700 in terms of standard polystyrene.

[0060] Example 2 58.46 g of polyglycidyl methacrylate (Mw: 9600, 30% by mass propylene glycol monomethyl ether acetate solution) (manufactured by Maruzen Petrochemical Co., Ltd.), 10.34 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.41 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.), and 0.0075 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 6.78 g of propylene glycol monomethyl ether acetate and 72.00 g of propylene glycol monomethyl ether. The gas in the reaction vessel was replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas three times, and the mixture was then reacted at 85°C for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. Analysis by GPC-1 revealed that the polymer in the resulting solution had a weight-average molecular weight of 16,500 in terms of standard polystyrene.

[0061] Example 3 58.46 g of polyglycidyl methacrylate (Mw: 9600, 30% by mass propylene glycol monomethyl ether acetate solution) (manufactured by Maruzen Petrochemical Co., Ltd.), 10.34 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.41 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.), and 0.0045 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 6.78 g of propylene glycol monomethyl ether acetate and 72.00 g of propylene glycol monomethyl ether. The gas in the reaction vessel was replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas three times, and the mixture was then reacted at 85°C for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. Analysis by GPC-1 revealed that the polymer in the resulting solution had a weight-average molecular weight of 16,000 in terms of standard polystyrene.

[0062] Example 4 58.46 g of polyglycidyl methacrylate (Mw: 9600, 30% by mass propylene glycol monomethyl ether acetate solution) (Maruzen Petrochemical Co., Ltd.), 10.34 g of methacrylic acid (Tokyo Chemical Industry Co., Ltd.), 2.41 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 0.0075 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 6.78 g of propylene glycol monomethyl ether acetate and 72.00 g of propylene glycol monomethyl ether. The gas in the reaction vessel was rigorously replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas 20 times, and the mixture was then reacted at 85°C for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. Analysis by GPC-1 revealed that the polymer in the resulting solution had a weight-average molecular weight of 16,900 in terms of standard polystyrene.

[0063] Comparative Example 1 58.46 g of polyglycidyl methacrylate (Mw: 9600, 30% by mass propylene glycol monomethyl ether acetate solution) (Maruzen Petrochemical Co., Ltd.), 10.34 g of methacrylic acid (Tokyo Chemical Industry Co., Ltd.), and 2.41 g of tetrabutylphosphonium bromide (Hokuko Chemical Co., Ltd.) were added to 6.78 g of propylene glycol monomethyl ether acetate and 72.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The gas in the reaction vessel was replaced with nitrogen by repeating the process of reducing the pressure and restoring the pressure with nitrogen gas three times, and then the reaction was carried out at 85°C for 1 hour, at which point the polymer solution became cloudy, probably due to the progress of molecular weight increase.

[0064] Example 5 70.01 g of polyglycidyl methacrylate (Mw: 9600, 30% by mass propylene glycol monomethyl ether acetate solution) (manufactured by Maruzen Petrochemical Co., Ltd.), 16.45 g of sorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.89 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.), and 0.0194 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 30.63 g of propylene glycol monomethyl ether acetate and 80.00 g of propylene glycol monomethyl ether. The gas in the reaction vessel was replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas three times, and the mixture was then reacted at 85°C for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. Analysis by GPC-2 revealed that the polymer in the resulting solution had a weight-average molecular weight of 13,600 in terms of standard polystyrene.

[0065] Example 6 70.01 g of polyglycidyl methacrylate (Mw: 9600, 30% by mass propylene glycol monomethyl ether acetate solution) (manufactured by Maruzen Petrochemical Co., Ltd.), 16.45 g of sorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.89 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.), and 0.0097 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 30.63 g of propylene glycol monomethyl ether acetate and 80.00 g of propylene glycol monomethyl ether. The gas in the reaction vessel was replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas three times, and the mixture was then reacted at 85°C for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. Analysis by GPC-2 revealed that the polymer in the resulting solution had a weight-average molecular weight of 13,700 in terms of standard polystyrene.

[0066] Example 7 70.01 g of polyglycidyl methacrylate (Mw: 9600, 30% by mass propylene glycol monomethyl ether acetate solution) (manufactured by Maruzen Petrochemical Co., Ltd.), 16.45 g of sorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.89 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.), and 0.0061 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 30.63 g of propylene glycol monomethyl ether acetate and 80.00 g of propylene glycol monomethyl ether. The gas in the reaction vessel was replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas three times, and the mixture was then reacted at 85°C for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. Analysis by GPC-2 revealed that the polymer in the resulting solution had a weight-average molecular weight of 13,400 in terms of standard polystyrene.

[0067] Example 8 70.01 g of polyglycidyl methacrylate (Mw: 9600, 30% by mass propylene glycol monomethyl ether acetate solution) (manufactured by Maruzen Petrochemical Co., Ltd.), 16.45 g of sorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.89 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.), and 0.0097 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 30.63 g of propylene glycol monomethyl ether acetate and 80.00 g of propylene glycol monomethyl ether. The gas in the reaction vessel was rigorously replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas 20 times, and the mixture was then reacted at 85°C for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. Analysis by GPC-2 revealed that the polymer in the resulting solution had a weight-average molecular weight of 13,800 in terms of standard polystyrene.

[0068] Comparative Example 2 70.01 g of polyglycidyl methacrylate (Mw: 9600, 30% by mass propylene glycol monomethyl ether acetate solution) (manufactured by Maruzen Petrochemical Co., Ltd.), 16.45 g of sorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2.89 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.) were added to 30.63 g of propylene glycol monomethyl ether acetate and 80.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved therein. The gas in the reaction vessel was replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas three times, and the mixture was then reacted at 85° C. for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy or the like even when cooled to room temperature, and had good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. However, analysis by GPC-2 revealed that the polymer in the obtained solution had a weight average molecular weight of 22,300 in terms of standard polystyrene, indicating that the polymer had a high molecular weight.

[0069] Example 9 13.24 g of EOCN-104S (Mw: 3500 (reference value), manufactured by Nippon Kayaku Co., Ltd.), 5.51 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.25 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.), and 0.010 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 40.00 g of propylene glycol monomethyl ether acetate and 40.00 g of propylene glycol monomethyl ether. The gas in the reaction vessel was replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas three times, and then the reaction was carried out at 100°C for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and showed good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. Analysis by GPC-1 revealed that the polymer in the obtained solution had a weight average molecular weight of 5,200 in terms of standard polystyrene.

[0070] Example 10 13.24 g of EOCN-104S (Mw: 3500 (reference value), manufactured by Nippon Kayaku Co., Ltd.), 5.51 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.25 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.), and 0.005 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 40.00 g of propylene glycol monomethyl ether acetate and 40.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. The gas in the reaction vessel was replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas three times, and then the reaction was carried out at 100°C for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. Analysis by GPC-1 revealed that the polymer in the obtained solution had a weight average molecular weight of 5,200 in terms of standard polystyrene.

[0071] Comparative Example 3 13.24 g of EOCN-104S (Mw: 3500 (reference value), manufactured by Nippon Kayaku Co., Ltd.), 5.51 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.25 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.) were added to 40.00 g of propylene glycol monomethyl ether acetate and 40.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved therein. After the gas in the reaction vessel was replaced with nitrogen by repeating the process of reducing the pressure and restoring the pressure with nitrogen gas three times, the reaction was carried out at 100°C for 4 hours, at which point the polymer solution became cloudy, possibly due to the progress of molecular weight increase. Analysis by GPC-1 revealed that the polymer in the resulting solution had a weight average molecular weight of 128,900 in terms of standard polystyrene.

[0072] Example 11 12.24 g of EHPE-3150 (Mw: 2500 (reference value), manufactured by Daicel Corporation), 6.32 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.43 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.), and 0.010 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 40.00 g of propylene glycol monomethyl ether acetate and 40.00 g of propylene glycol monomethyl ether. The gas in the reaction vessel was replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas three times, and then the reaction was carried out at 90°C for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. Analysis by GPC-1 revealed that the polymer in the obtained solution had a weight average molecular weight of 3,000 in terms of standard polystyrene.

[0073] Example 12 12.24 g of EHPE-3150 (Mw: 2500 (reference value), manufactured by Daicel Corporation), 6.32 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.43 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.), and 0.005 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel and dissolved in 40.00 g of propylene glycol monomethyl ether acetate and 40.00 g of propylene glycol monomethyl ether. The gas in the reaction vessel was replaced with nitrogen by repeatedly reducing the pressure and restoring the pressure with nitrogen gas three times, and then the reaction was carried out at 90°C for 22 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, and had good solubility in a propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent. Analysis by GPC-1 revealed that the polymer in the obtained solution had a weight average molecular weight of 3,000 in terms of standard polystyrene.

[0074] Comparative Example 4 12.24 g of EHPE-3150 (Mw: 2500 (reference value), manufactured by Daicel Corporation), 6.32 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.43 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.) were added to 40.00 g of propylene glycol monomethyl ether acetate and 40.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved therein. The gas in the reaction vessel was replaced with nitrogen by repeating the process of reducing the pressure and restoring the pressure with nitrogen gas three times, and then the reaction was carried out at 90°C for 22 hours, at which point the polymer solution became cloudy, presumably due to the progression of polymerization.

[0075] Examples 1 to 12 and Comparative Examples 1 to 4 are summarized in the table.

[0076]

[0077] In Table 1, the abbreviations represent the following: MA: methacrylic acid SorA: sorbic acid pGMA: polyglycidyl methacrylate (manufactured by Maruzen Petrochemical Co., Ltd.) EOCN: EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.) EHPE: EHPE-3150 (manufactured by Daicel Corporation) HTEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate

[0078] In Table 1, "Substrate [charge molar ratio]" represents the ratio of the molar amount of carboxy groups in compound (B) to the molar amount of epoxy groups in polymer (A). In Table 1, the amount of polymerization inhibitor (ppm) represents the mass ratio of the polymerization inhibitor to the total mass of materials used in the reaction (the total mass of polymer (A), compound (B), polymerization inhibitor, reaction catalyst, and organic solvent).

[0079] From the results of Examples 1 to 12, it was confirmed that when an N-oxyl-based polymerization inhibitor was used as a polymerization inhibitor in the reaction of the polymer (A) with the compound (B) having a polymerizable multiple bond, a polymer having a polymerizable multiple bond was obtained without an excessively large molecular weight, even when the oxygen concentration in the reaction vessel was low.

Claims

1. A method for producing a polymer having a polymerizable multiple bond, comprising reacting a polymer (A) having a first functional group with a compound (B) having a second functional group and a polymerizable multiple bond in a reaction vessel in the presence of an N-oxyl-based polymerization inhibitor and an organic solvent, thereby reacting the first functional group with the second functional group to produce a polymer having a polymerizable multiple bond.

2. The method for producing a polymer having polymerizable multiple bonds according to claim 1, wherein the first functional group is an epoxy group and the second functional group is a carboxy group.

3. The method for producing a polymer having polymerizable multiple bonds according to claim 1, wherein the N-oxyl-based polymerization inhibitor has a piperidine ring.

4. The method for producing a polymer having polymerizable multiple bonds according to claim 1, wherein the amount of the N-oxyl polymerization inhibitor used is 1 ppm by mass to 3,000 ppm by mass based on the total mass of the materials used in the reaction.

5. The method for producing a polymer having a polymerizable multiple bond according to claim 1, wherein the amounts of the polymer (A) and the compound (B) used in the reaction satisfy a molar ratio (Bf / Af) of the molar amount (Bf) of the second functional group of the compound (B) to the molar amount (Af) of the first functional group of the polymer (A) of 1.00 or more.

6. The method for producing a polymer having polymerizable multiple bonds according to claim 1, wherein the oxygen concentration in the gas in the reaction vessel is 5% by volume or less.

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