Method for producing polymer and resin composition

Abstract

Provided is a method for producing a (meth) acrylic polymer having a sterically hindered secondary amino group, which does not require the protection of a secondary amine with a protecting group, is simple and has a high conversion rate. A method for producing a (meth) acrylic polymer (A), which contains a specific amount of a structural unit derived from a monomer represented by formula (1), at a polymerization conversion rate of 80% or more, said method comprising: a step (a) in which a reaction mixture containing a monomer (M) and a radical polymerization initiator is prepared; the monomer (M) comprises a secondary amino group-containing (methyl) acrylate monomer as shown in a formula (1); and a step b in which polymerization is performed at 60-120 DEG C by a batch reaction using a tank reactor until the concentration of the radical polymerization initiator in the reaction mixture reaches 1.0 * 10 <-4 > mol / L or less, a specific amount of the radical polymerization initiator is used with respect to the monomer (M), and a radical polymerization initiator having a half-life [tau] 1 / 2 of 100-3000 seconds at the polymerization temperature is used. (In the formula, R1, R2, R3, and R4 are each independently a hydrogen atom or a C1-6 alkyl group, where at least one of R1 and R2 is a C1-6 alkyl group, and at least one of R3 and R4 is a C1-6 alkyl group, R1 and R2 may be bonded to each other to form a cyclic structure, R3 and R4 may be bonded to each other to form a cyclic structure, R11 represents a hydrogen atom or a methyl group, and R4 represents a hydrogen atom or a methyl group. X1 represents a single bond or a divalent linking group, and n is 0 or 1. )

Description

TECHNICAL FIELD

[0001] The present application relates to a polymer production method and a resin composition. BACKGROUND

[0002] It is known that the light stability of a polymer can be improved by introducing a secondary amine having steric hindrance such as a hindered amine into a side chain of the polymer. It is reported that a resin emulsion obtained by copolymerizing a polymerizable hindered amine-based light stability monomer described in Patent Literature 1 forms a coating film excellent in light stability.

[0003] A polymer having a secondary amine having steric hindrance such as a hindered amine is also useful as an intermediate for obtaining a polymer containing a nitroxyl radical structure. In recent years, an electrolyte layer containing a redox compound composed of a polymer containing a nitroxyl radical structure is considered to repeatedly electrochemically undergo adsorption and desorption of carbon dioxide, and thus is attracting attention. As a redox compound used in an electrolyte layer of such a carbon dioxide separation device, poly(2,2,6,6-tetramethylpiperidinyloxymethyl methacrylate) and the like are proposed in Patent Literature 2.

[0004] However, it is known that an amino group functions as a polymerization inhibitor, a retarder, and a polymer having an amino group in a side chain cannot achieve satisfactory conversion rate, which is a problem. In order to obtain a target polymer, a purification step of removing a residual monomer is required, and there is a problem of poor efficiency.

[0005] In Non-Patent Literature 1, it is reported that, in the synthesis of poly(2,2,6,6-tetramethylpiperidyl methyl methacrylate) which is an intermediate of the aforementioned poly(2,2,6,6-tetramethylpiperidinyloxymethyl methacrylate), the conversion rate is only 40% for 48 hours. In addition, it is described that a method of protecting a secondary amine with a protecting group in order to improve the above conversion rate is effective, but there is a problem of complicated procedures.

[0006] In Patent Literature 3, as a method of not protecting a secondary amine with a protecting group, anionic polymerization is proposed. However, the molecular weight is as low as 5000 or less, and the polymerization temperature is -60°C, which is a problem in industrial production.

[0007] PRIOR ART DOCUMENTS

[0008] PATENT LITERATURE

[0009] Patent Literature 1: Japanese Patent Application Laid-Open No. 2018-172612

[0010] Patent Literature 2: Japanese Patent Application Laid-Open No. 2018-001131

[0011] Patent Literature 3: International Publication No. 2014 / 087644

[0012] NON-PATENT LITERATURE

[0013] Non-patent literature 1: Journal of Polymer Science Part A: Polymer Chemistry, 2012, Vol. 50, 1394-1407 SUMMARY

[0014] PROBLEMS TO BE SOLVED BY THE INVENTION

[0015] The present invention was achieved in view of the above-described background, and aims to provide a simple and high-conversion-rate production method of a polymer having a sterically hindered secondary amino group, which does not require protection of a secondary amine with a protecting group, and a resin composition.

[0016] METHOD FOR SOLVING THE PROBLEM

[0017] The present inventors have conducted intensive studies in order to achieve the above-described object, and as a result, have completed the present invention including the following means.

[0018] [1] A production method of a polymer (A) that is a production method of a polymer (A) containing 50 to 100 mass% of a structural unit derived from a monomer represented by the following formula (1) at a polymerization conversion rate of 80% or more, the production method comprising: a step a in which a reaction mixture containing a monomer (hereinafter referred to as a monomer (M)) for polymerization of the polymer (A) and a radical polymerization initiator is prepared, the monomer (M) containing a secondary amino group-containing monomer represented by the following formula (1) (hereinafter referred to as a monomer (m1)) and can contain a monomer (hereinafter referred to as a monomer (m2)) that is copolymerizable with the monomer (m1); and a step b in which polymerization is performed by batch reaction using a tank reactor at 60 to 120°C until the concentration of the radical polymerization initiator in the reaction mixture reaches 1.0 x 10 -4 mol / L or less, the radical polymerization initiator is added at the same time as the step a and during the middle of the step b, 0.01 to 1 parts by mass of the radical polymerization initiator in total is used with respect to 100 parts by mass of the monomer (M), the half-life period τ of the radical polymerization initiator at the polymerization temperature of the step b 1 / 2 is 100 to 3000 seconds.

[0019]

[0020] (In the formula, R 1 , R 2 , R 3 , and R 4each independently is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, wherein R 1 at least one of R 2 and R 3 is an alkyl group having 1 to 6 carbon atoms, and at least one of R 4 and R 1 is an alkyl group having 1 to 6 carbon atoms, R 2 and R 3 may be mutually bonded to form a ring structure, R 4 and R 11 may be mutually bonded to form a ring structure, R 1 represents a hydrogen atom or a methyl group, X 1 / 2 represents a single bond or a divalent linking group, and n is 0 or 1.

[0021] [2] The production method of the polymer (A) according to [1], wherein in the process b, the radical polymerization initiator is added in batches or continuously.

[0022] [3] The production method of the polymer (A) according to [1] or [2], wherein the final addition time TL of the radical polymerization initiator and the end time TE of the polymerization reaction satisfy the following mathematical formula (1).

[0023] TE - TL ≥ 6τ 1 Mathematical formula (1)

[0024] [4] The production method of the polymer (A) according to [1], wherein the secondary amino group-containing monomer is a secondary amino group-containing (meth)acrylate monomer represented by the following formula (2).

[0025]

[0026] (In the formula, R 2 , R 3 , R 4 , R 11 , and n are the same as in formula (1). X 2 represents a single bond or a divalent linking group.)

[0027] [5] A resin composition, wherein, in 100 mass% of the resin composition, 0.1 to 20 mass% of a secondary amino group-containing monomer represented by formula (1) (hereinafter referred to as monomer (m1)) and 80 to 99.9 mass% of a polymer (A) having 50 to 100 mass% of structural units derived from monomer (m1), no radical polymerization initiator is contained, or a radical polymerization initiator in an amount of 0.01 mass% or less is contained.

[0028]

[0029] (where R is in the formula) 1 R 2 R 3 and R 4 Each is independently an alkyl group having 1 to 6 carbon atoms, wherein R 1 and R 2 At least one of them is an alkyl group having 1 to 6 carbon atoms, and R 3 and R 4 At least one of them is an alkyl group having 1 to 6 carbon atoms, R 1 With R 2 They can bond together to form a ring structure, R 3 With R 4 They can bond together to form a ring structure, R 11 X represents a hydrogen atom or a methyl group. 1 (This represents a linking group that is either a single bond or divalent, where n is 0 or 1.)

[0030] [6]: According to the resin composition of [5], wherein the secondary amino monomer is a secondary amino (meth)acrylate monomer (hereinafter referred to as monomer (m11)) as shown in the following formula (2). The polymer (A) is a (meth)acrylic polymer (A1) having 50-100% by mass of structural units derived from monomer (m11).

[0031]

[0032] (where R is in the formula) 1 R 2 R 3 R 4 R 11 And n is the same as in equation (1). X 2 (This indicates a single bond or a divalent linking group.)

[0033] Invention Effects

[0034] According to the present invention, the following excellent effects are achieved: a simple and high-conversion manufacturing method and resin composition for polymers having sterically hindered secondary amines that do not require protection with protecting groups are provided. Detailed Implementation

[0035] The following describes one example of an embodiment of the present invention. The present invention is not limited to this embodiment; other embodiments that conform to the spirit of the present invention may also fall within its scope. Furthermore, the numerical values ​​"A to B" specified in this specification include both numerical values ​​A and B. The numerical values ​​specified in this specification are values ​​obtained through the methods disclosed in the embodiments or examples. Unless otherwise specified, each component appearing in this specification may be used independently, individually, or in combination with two or more. (Meth)acrylic acid is a general term for acrylic acid and methacrylic acid.

[0036] This invention relates to a method for manufacturing polymer (A) containing 50 to 100% by mass of structural units derived from monomers represented by formula (1) below, with a polymerization conversion rate of 80% or higher, and comprising the following steps a and b. The method for manufacturing polymer (A) (hereinafter also referred to as this manufacturing method) involves polymerization using a batch reaction in a trough reactor. It should be noted that the polymerization conversion rate refers to a value obtained by the method described in the examples below.

[0037]

[0038] In equation (1), R 1 R 2 R 3 and R 4 Each is independently an alkyl group having 1 to 6 carbon atoms, wherein R 1 and R 2 At least one of them is an alkyl group having 1 to 6 carbon atoms, and R 3 and R 4 At least one of them is an alkyl group having 1 to 6 carbon atoms, R 1 With R 2 They can bond together to form a ring structure, R 3 With R 4 They can bond together to form a ring structure, R 11 X represents a hydrogen atom or a methyl group. 1 This indicates a single bond or a divalent linker, where n is 0 or 1.

[0039] Step a is the step of preparing a reaction mixture, which contains monomers (hereinafter referred to as monomers (M)) for the polymerization of polymer (A) and a free radical polymerization initiator. The monomers (M) contain secondary amino monomers (hereinafter referred to as monomers (m1)) as shown in formula (1) above and may contain monomers (hereinafter referred to as monomers (m2)) capable of copolymerizing with monomers (m1). Here, monomer (M) is a collective term for all monomers used in the polymerization system, which is a single monomer (m1) in the case of homopolymerization and a mixture of monomers in the case of copolymerization. The copolymer contains polymers containing two or more monomers (m1). In addition to the above-described method, copolymers can also be polymers obtained by using one or more monomers (m1) and one or more monomers (m2) as a monomer mixture. The reaction mixture refers to all compounds fed into the tank reactor, which includes a monomer mixture and a free radical polymerization initiator, and may also contain any components. Any components include, for example, chain transfer agents, solvents, and additives that do not depart from the spirit of the invention.

[0040] Step b involves polymerization at 60–120°C using a batch reaction in a trough reactor until the concentration of the free radical polymerization initiator in the reaction mixture reaches 1.0 × 10⁻⁶. -4 Processes below mol / L. "Polymerization to reach 1.0 × 10⁻⁶ mol / L." -4 "Below mol / L" means that the concentration needs to be below the above concentration, and does not determine the concentration at the end of the polymerization. No monomer (M) is added in step b.

[0041] The free radical polymerization initiator is added simultaneously with step a above and midway through step b above. The concentration of the free radical polymerization initiator is calculated using the following mathematical formula (2).

[0042] I = I0 × exp(-k d t) Mathematical expression (2)

[0043] I represents the concentration of the free radical polymerization initiator at time t, I0 represents the initial concentration of the free radical polymerization initiator, and k represents the concentration of the initiator at the time of addition. d Let I be the decomposition rate constant of the free radical polymerization initiator at the polymerization temperature of process b. It should be noted that, in the case of batch or continuous addition of the free radical polymerization initiator, I is set as I0×exp(-k)2. d The sum of t).

[0044] Free radical polymerization initiators are compounds that generate reactive free radicals through irradiation with ultraviolet or visible light or heating, thus initiating polymerization reactions. Importantly, the half-life τ at the polymerization temperature in step b is used. 1 / 2 It is a free radical polymerization initiator with a half-life of 100–3000 seconds. This free radical polymerization initiator can be determined by measuring its half-life τ at the reaction temperature. 1 / 2Alternatively, it can be easily selected based on literature. Throughout all steps, a total of 0.01 to 1 part by mass of free radical polymerization initiator is used relative to 100 parts by mass of monomer (M). The initial amount of free radical polymerization initiator added in step a is preferably 0.005 to 0.5 parts by mass relative to 100 parts by mass of monomer (M).

[0045] To obtain a polymer (A) containing 50–100% by mass of structural units derived from the monomers shown in formula (1), in step a, the molar ratio of monomers (m1) and (m2) is determined, taking into account the polymerization rates of monomers (m1) and (m2). When the polymerization rate is substantially the same regardless of the type of monomer used, the ratio is adjusted so that 50–100% by mass of the monomer (m1) shown in formula (1) is included in 100% by mass of monomer (M).

[0046] Polymer (A) can be a homopolymer or a copolymer. In the case of copolymers, its form is not limited. For example, block copolymers and random copolymers can be listed.

[0047] The content of structural units derived from monomer (m1) in polymer (A) is 50-100% by mass as described above, preferably 60% by mass, more preferably 70% by mass, and even more preferably 90% by mass. In 100% by mass of polymer (A), the content of structural units derived from monomer (m1) can be 100% by mass.

[0048] In 100% by mass of polymer (A), the structural units derived from monomer (m2) are 50% by mass or less, with an upper limit of 40% by mass, more preferably 30% by mass, and even more preferably 10% by mass.

[0049] The monomer (m1) content in the monomer mixture is 50-100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more, provided that the polymerization rate is substantially the same as that of the monomer (m2) used. 100% by mass of monomer (m1) can be used. The monomer (m2) content in the monomer mixture (in multiple cases, the total amount) is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 10% by mass or less.

[0050] Preferred examples of monomers (m1) include: monomers containing secondary amino (meth)acrylates such as 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine; monomers containing secondary amino (meth)acrylamides such as 4-(meth)acrylamide-2,2,6,6-tetramethylpiperidine; monomers containing secondary amino vinyl ethers such as 4-(vinyloxy)-2,2,6,6-tetramethylpiperidine; and monomers containing secondary amino vinyl groups such as 2,2,6,6-tetramethyl-4-vinylpiperidine.

[0051] The secondary amino-containing monomer of the present invention is preferably the secondary amino (meth)acrylate monomer (hereinafter referred to as monomer (m11) shown in the following formula (2).

[0052]

[0053] (where R is in the formula) 1 R 2 R 3 R 4 R 11 And n is the same as in equation (1). X 2 (This indicates a single bond or a divalent linking group.)

[0054] The monomer (m11) content in the monomer mixture is 50-100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more, provided that the polymerization rate is substantially the same as that of the monomer (m2) used. 100% by mass of monomer (m11) can be used. The monomer (m2) content in the monomer mixture (in multiple cases, the total amount) is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 10% by mass or less.

[0055] Preferred examples of monomers (m11) include: 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 6,6-Tetramethylpiperidine, 4-crotonylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonyl-4-crotonyloxy-2,2,6,6-tetramethylpiperidine, etc.

[0056] Preferred examples of monomers (m2) include: alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate, which have alkyl groups having two or more carbon atoms; aryl methacrylates such as phenyl methacrylate; cyclohexyl methacrylate and norbornyl methacrylate; alkyl methacrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; aryl acrylates such as phenyl acrylate; cyclohexyl acrylate and norbornyl acrylate; styrene, α-methylstyrene, p-methylstyrene, and m-methylstyrene; acrylamide and methacrylamide; acrylonitrile and methacrylonitrile; and vinyl monomers such as methacrylic acid and acrylic acid, which have only one polymerizable alkenyl group in one molecule.

[0057] Preferred examples of free radical polymerization initiators include tert-hexyl peroxyisopropyl carbonate, tert-hexyl peroxy2-ethylhexanoate, 1,1,3,3-tetramethyl butyl peroxy2-ethylhexanoate, tert-butyl peroxypentanoate, tert-hexyl peroxypentanoate, tert-butyl peroxyneodecanate, tert-hexyl peroxyneodecanate, 1,1,3,3-tetramethyl butyl peroxyneodecanate, 1,1-bis(tert-hexyl peroxy)cyclohexane, benzoyl peroxy, 3,5,5-trimethylhexanoyl peroxy, lauroyl peroxy, 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), and dimethyl 2,2'-azobis(2-methylpropionic acid); examples include tert-hexyl peroxy2-ethylhexanoate, 1,1-bis(tert-hexyl peroxy)cyclohexane, and dimethyl 2,2'-azobis(2-methylpropionic acid). Free radical polymerization initiators can be used alone or in combination with two or more.

[0058] The total amount of free radical polymerization initiator used is 0.01 to 1 part by mass relative to 100 parts by mass of monomer (M). Preferably, it is 0.02 to 0.9 parts by mass, more preferably 0.03 to 0.8 parts by mass, and even more preferably 0.05 to 0.7 parts by mass. When the total amount of the aforementioned free radical polymerization initiator used is less than 0.01 parts by mass, the polymerization conversion rate becomes low. On the other hand, when the total amount of the aforementioned free radical polymerization initiator used exceeds 1 part by mass, there is concern that side reactions caused by residual free radical polymerization initiator may occur when the obtained polymer (A) is used as a component of an electrochemical device.

[0059] In this manufacturing method, the polymerization temperature in step b refers to the temperature of the liquid inside the trough reactor during the polymerization reaction, which is 60–120°C, preferably 65–115°C, and particularly preferably 70–110°C. By keeping the polymerization temperature within the above range, the polymerization conversion rate can be increased in a short time.

[0060] The half-life τ of the free radical polymerization initiator at the above polymerization temperature 1 / 2 The half-life τ of the free radical polymerization initiator is 100–3000 seconds, preferably 150–2800 seconds, and more preferably 200–2700 seconds. 1 / 2 The value is calculated using the following mathematical formulas (3) and (4).

[0061] τ 1 / 2 =[ln(2)] / k d Mathematical formula (3)

[0062] k d =A×exp(-E a / RT) Mathematical formula (4)

[0063] It should be noted that mathematical formula (3) is obtained by substituting I=(1 / 2)I0 into mathematical formula (2) and converting it to the natural logarithm. A is the frequency factor, E a R is the activation energy, R is the gas constant, T is the polymerization temperature (absolute temperature (K)), and k is the polymerization temperature. d is the decomposition rate constant of the free radical polymerization initiator at absolute temperature T.

[0064] In this manufacturing method, the concentration of the free radical polymerization initiator in the reaction mixture at the end of the polymerization reaction is set to 1.0 × 10⁻⁶ as described above. -4 Below mol / L. The preferred concentration of the above-mentioned free radical polymerization initiator is 0.9 × 10⁻⁶ mol / L. -4 Below mol / L, more preferably 0.8 × 10⁻⁶ -4Below mol / L. This is achieved by setting the concentration of the free radical polymerization initiator in the reaction mixture at the end of the polymerization reaction to 1.0 × 10⁻⁶ mol / L. -4 Below mol / L, the amount of free radical polymerization initiator in the obtained polymer (A) is reduced, which is useful for its use as a component in electrochemical devices. It should be noted that the end of the polymerization reaction refers to the moment when heating is stopped in this manufacturing method to conclude the polymerization reaction within the tank reactor. That is, it refers to the moment when cooling of the liquid in the tank begins.

[0065] Chain transfer agents are preferably used as any component of the reaction mixture. Examples of chain transfer agents include: alkyl thiols such as n-octylthiol, n-dodecylthiol, tert-dodecylthiol, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol dithiopropionate, butanediol dithioglycolate, hexanediol dithioglycolate, hexanediol dithiopropionate, trimethylolpropane tri-(β-thiopropionate), pentaerythritol tetrathiopropionate; α-methylstyrene dimers; and terpinene. Monofunctional alkyl thiols such as n-octylthiol and n-dodecylthiol are preferred. These chain transfer agents can be used alone or in combination of two or more. The amount of chain transfer agent used is preferably 0.1 to 1 part by mass relative to 100 parts by mass of the monomer mixture, more preferably 0.012 to 0.48 parts by mass, and even more preferably 0.3 to 0.6 parts by mass.

[0066] When it is necessary to adjust the viscosity of the liquid in the tank reactor where the raw materials are dissolved, the reactants may contain a solvent. Aromatic hydrocarbons such as benzene, toluene, and ethylbenzene are preferred as solvents. These solvents may be used alone or in combination of two or more. The amount of solvent used relative to 100 parts by mass of the monomer mixture (M) is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and even more preferably 300 parts by mass or less. As long as the above principles are met, there is no limitation on the lower limit of the amount of solvent used; from the viewpoint of the solubility of the monomers in the solvent, a lower limit of 50 parts by mass is preferred.

[0067] In this manufacturing method, there are no particular limitations on the method of adding the free radical polymerization initiator, but it is preferred to add it in batches or continuously in step b.

[0068] When adding the free radical polymerization initiator in batches, there are no particular restrictions on the number of batches or the amount added each time. From the viewpoint of efficiently improving the polymerization conversion rate, it is preferable that the concentration of the first added free radical polymerization initiator in the tank is 1.0 × 10⁻⁶. -4 The next free radical polymerization initiator is added before the concentration drops below mol / L. The concentration of the previously added free radical polymerization initiator in the tank is calculated using the above mathematical formula (2).

[0069] The polymerization conversion rate at the end of the polymerization reaction in this manufacturing method is 80% or more, preferably 85% or more, and more preferably 90% or more. According to this manufacturing method, since polymerization is carried out through steps a and b, the secondary amine does not need to be protected with a protecting group. Furthermore, a polymer with sterically hindered secondary amines can be obtained with high conversion rate without a monomer removal step. It should be noted that steps other than steps a and b (e.g., purification steps, monomer removal steps) may be included without departing from the spirit of the invention. It should also be noted that steps involving protecting the secondary amine with a protecting group and removing monomers are not excluded.

[0070] In this manufacturing method, the final addition time TL of the free radical polymerization initiator in step b and the polymerization reaction end time TE preferably satisfy the following mathematical formula (1).

[0071] TE-TL≥6τ 1 / 2 Mathematical formula (1)

[0072] By setting TE-TL to the above range, the amount of free radical polymerization initiator in the resulting resin composition is reduced, which is useful for use as a component of an electrochemical device.

[0073] The weight-average molecular weight (Mw) of the polymer (A) obtained by this manufacturing method is not particularly limited, but is preferably 1,000 to 200,000. The lower limit of the above-mentioned Mw is more preferably 2,000, further preferably 3,000, particularly preferably 4,000, and most preferably 5,000. The upper limit of the above-mentioned Mw is more preferably 180,000, further preferably 150,000, particularly preferably 130,000, and most preferably 100,000. If the above-mentioned Mw is 1,000 or more, the electrochemical stability of the polymer (A) is improved. If the above-mentioned Mw is 200,000 or less, the film-forming properties when the polymer (A) is used as a component of an electrochemical device are improved.

[0074] The resin composition of the present invention contains 0.1 to 20% by mass of a secondary amino monomer (hereinafter referred to as monomer (m1)) as shown in formula (1) and 80 to 99.9% by mass of a polymer (A) having 50 to 100% by mass of structural units derived from monomer (m1) in 100% by mass of the resin composition, and does not contain a free radical polymerization initiator, or contains less than 0.01% by mass of a free radical polymerization initiator.

[0075] In the resin composition of the present invention, the secondary amino monomer is preferably a secondary amino (meth)acrylate monomer (monomer (m11)) as shown in formula (2), and the polymer (A) is a (meth)acrylate polymer (A1) having 50 to 100% by mass of structural units derived from monomer (m11).

[0076] The content of monomer (m11) in the resin composition of the present invention is preferably 0.1 to 20% by mass, and the content of (meth)acrylic polymer (A1) is preferably 80 to 99.9% by mass.

[0077] Example

[0078] Next, embodiments will be shown to illustrate the invention in more detail. It should be noted that the invention is not limited to these embodiments. Measurements of physical properties, etc., are performed by the following methods.

[0079] (Weight-average molecular weight (Mw), Number-average molecular weight (Mn), Molecular weight distribution (Mw / Mn))

[0080] The average molecular weights (Mw, Mn) and molecular weight distribution (Mw / Mn) of the polymer were determined by GPC (gel permeation chromatography). As the eluent, a solution of triethylamine mixed in tetrahydrofuran at a concentration of 200 mM / L was used. As the column, a column consisting of two TSKgel SuperMultipore HZM-M columns (manufactured by Tosoh Corporation) connected in series with a SuperHZ4000 was used. As the GPC apparatus, an HLC-8320 (model) (manufactured by Tosoh Corporation) equipped with a differential refractive index detector (RI detector) was used. 8 mg of the analyte resin was dissolved in 5 mL of a mixture of tetrahydrofuran and triethylamine to prepare the sample solution. The column oven temperature was set to 40°C, and 20 μL of the sample solution was injected into the apparatus at an eluent flow rate of 0.35 mL / min. The chromatogram was then measured. GPC was performed on 10 sites of standard polymethyl methacrylate with molecular weights ranging from 400 to 5,000,000 to create a standard curve showing the relationship between retention time and molecular weight. Based on this standard curve, the average molecular weights (Mw, Mn) and molecular weight distributions (Mw / Mn) of the polymers being tested were determined.

[0081] (Aggregation Conversion Rate)

[0082] Dissolve 1 mg of the reaction mixture after polymerization in 2 mL of deuterated chloroform and determine the reaction mixture. 1 Using H-NMR, the integral values ​​(IM) of the protons (6.0-6.2 ppm) of the vinyl double bonds of the LA-87 monomer and the integral values ​​(IP) of the protons (5.0-5.3 ppm) adjacent to the methylene carbon of the side chain of the polyLA-87 polymer are obtained, and the polymerization conversion rate is calculated using the following formula.

[0083] Conversion rate (%) = IP / (IM + IP) × 100

[0084] (raw material)

[0085] In the following examples and comparative examples, the following raw materials were used as raw materials.

[0086] LA-87: "ADK STAB LA-87" (compound name: 2,2,6,6-tetramethyl-4-piperidinyl methacrylate) manufactured by ADEKA Co., Ltd. PERBUTYL D: "PERBUTYL D" (compound name: di-tert-butyl peroxide) manufactured by Nippon Oil Co., Ltd.

[0087] (Example 1)

[0088] In a high-pressure reactor equipped with a stirrer, thermometer, nitrogen inlet pipe, monomer inlet pipe, and collection pipe, 100 parts by mass of toluene and 100 parts by mass of LA-87 were added, and the reactor was purged with nitrogen. The reactor was heated to 100°C, and a solution containing 0.02 parts by mass of azobisisobutyronitrile (AIBN) dissolved in 0.05 parts by mass of toluene was introduced under nitrogen pressure to initiate polymerization. One hour after the start of polymerization, a solution containing 0.02 parts by mass of AIBN dissolved in 0.05 parts by mass of toluene was introduced under nitrogen pressure. This process of adding the initiator solution was repeated four times every hour (a total of five times, including the initial addition). The reaction was then continued for another hour, after which heating was stopped, and this point was considered the end of the polymerization reaction. The reaction vessel was then cooled to room temperature. The evaluation results are shown in Table 1.

[0089] (Examples 2-7, Comparative Examples 1-6)

[0090] Except for the changes in formulation and conditions shown in Table 1, the polymerization reaction was carried out in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0091]

[0092] When the free radical polymerization initiator is added in a single step at a rate exceeding 1 part by mass relative to 100 parts by mass of monomer (M), as shown in Comparative Examples 1-3, the polymerization conversion rate is low and the productivity is poor. The low conversion rate of Comparative Example 4 was confirmed. Furthermore, when the polymerization temperature in step b exceeds 120°C, as shown in Comparative Example 5, the polymerization conversion rate is low and the productivity is poor. Furthermore, the half-life τ of the free radical polymerization initiator... 1 / 2 When the value exceeds 3000, as shown in Comparative Example 6, the polymerization conversion rate is low and the productivity is poor. On the other hand, according to the present manufacturing method, as shown in Examples 1-7, it has been confirmed that the polymerization conversion rate can be improved in a shorter time and the productivity is excellent. In addition, according to the present manufacturing method, as shown in Examples 1-7, the amount of residual free radical polymerization initiator in the reaction solution after the polymerization reaction is completed is low. Therefore, it has been confirmed that the polymer obtained by the present manufacturing method has fewer concerns about side reactions when used as a component of an electrochemical device, which is useful.

[0093] Industrial availability

[0094] The polymer and resin compositions of the present invention are suitable for use as coatings with excellent light stability. Furthermore, the polymers of the present invention are also useful as intermediates for obtaining polymers containing nitrile radical structures. It should be noted that electrolyte layers containing redox compounds formed from polymers containing nitrile radical structures are of interest due to their ability to repeatedly electrochemically adsorb and desorb carbon dioxide.

[0095] This application claims priority based on Japanese Application Special Hoc 2023-174711 filed on October 6, 2023, and incorporates all of its disclosures into this application.

Claims

1. A method for manufacturing a polymer (A), comprising producing a polymer (A) containing 50 to 100% by mass of structural units derived from monomers represented by the following formula (1) at a polymerization conversion rate of 80% or higher, the method comprising: Step a, wherein a reaction mixture comprising a monomer (hereinafter referred to as monomer (M)) for the polymerization of polymer (A) and a free radical polymerization initiator is prepared, wherein the monomer (M) comprises a secondary amino-containing monomer (hereinafter referred to as monomer (m1)) as shown in formula (1) and may comprise a monomer capable of copolymerizing with monomer (m1) (hereinafter referred to as monomer (m2)); and Step b, wherein polymerization is carried out at 60–120°C via a batch reaction using a trough reactor, until the concentration of the free radical polymerization initiator in the reaction mixture reaches 1.0 × 10⁻⁶. -4 Below mol / L, The free radical polymerization initiator is added simultaneously with step a and midway through step b. Using a total of 0.01 to 1 part by mass of the aforementioned free radical polymerization initiator relative to 100 parts by mass of monomer (M), The half-life τ of the free radical polymerization initiator at the polymerization temperature in step b. 1 / 2 The duration is 100 to 3000 seconds. In equation (1), R 1 R 2 R 3 and R 4 Each is independently an alkyl group having 1 to 6 carbon atoms, wherein R 1 and R 2 At least one of them is an alkyl group having 1 to 6 carbon atoms, and R 3 and R 4 At least one of them is an alkyl group having 1 to 6 carbon atoms, R 1 With R 2 They can bond together to form a ring structure, R 3 With R 4 They can bond together to form a ring structure, R 11 X represents a hydrogen atom or a methyl group. 1 This indicates a single bond or a divalent linker, where n is 0 or 1.

2. The method for manufacturing polymer (A) according to claim 1, wherein, In step b, the free radical polymerization initiator is added in batches or continuously.

3. The method for manufacturing polymer (A) according to claim 1, wherein, The final addition time TL of the free radical polymerization initiator and the polymerization reaction end time TE satisfy the following mathematical formula (1) relationship. TE-TL≥6τ 1 / 2 Mathematical formula (1).

4. The method for manufacturing polymer (A) according to claim 1, wherein, The secondary amino-containing monomer is a secondary amino (meth)acrylate monomer as shown in formula (2) below. In equation (2), R 1 R 2 R 3 R 4 R 11 And n is the same as in equation (1), X 2 This indicates a single bond or a divalent linker.

5. A resin composition, wherein, In 100% by mass of the resin composition The polymer (A) comprising 0.1–20% by mass of the secondary amino monomer (hereinafter referred to as monomer (m1)) shown in formula (1) and 80–99.9% by mass of structural units derived from monomer (m1) having 50–100% by mass. It does not contain free radical polymerization initiators, or contains less than 0.01% by mass of free radical polymerization initiators. In equation (1), R 1 R 2 R 3 and R 4 Each is independently an alkyl group having 1 to 6 carbon atoms, wherein R 1 and R 2 At least one of them is an alkyl group having 1 to 6 carbon atoms, and R 3 and R 4 At least one of them is an alkyl group having 1 to 6 carbon atoms, R 1 With R 2 They can bond together to form a ring structure, R 3 With R 4 They can bond together to form a ring structure, R 11 X represents a hydrogen atom or a methyl group. 1 This indicates a single bond or a divalent linker, where n is 0 or 1.

6. The resin composition according to claim 5, wherein, The secondary amino-containing monomer is a secondary amino (meth)acrylate monomer (hereinafter referred to as monomer (m11)) as shown in formula (2) below. The polymer (A) is a (meth)acrylic acid polymer having 50-100% by mass of structural units derived from monomer (m11). In equation (2), R 1 R 2 R 3 R 4 R 11 And n is the same as in equation (1), X 2 This indicates a single bond or a divalent linker.

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