JP5555485B2 - N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide and N, N-bis- (2,2,6,6-tetramethyl- Piperidine-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer - Google Patents

Description

  The present invention relates to N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide and a process for producing the same, N, N-bis- (2,2 , 6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer and a secondary battery electrode. More specifically, N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meta) used as an electrode material for a secondary battery having a high energy density and a large capacity. ) Acrylamide and production method thereof, N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer, and The present invention relates to an electrode of a secondary battery using

  With the rapid market expansion of notebook personal computers and mobile phones, there is an increasing demand for small high-capacity secondary batteries with high energy density used for these. In order to meet this demand, a secondary battery using an alkali metal ion such as lithium ion as a charge carrier and utilizing an electrochemical reaction accompanying charge transfer has been developed. Among these, lithium ion secondary batteries are used in various electronic devices as high-capacity secondary batteries having high energy density and excellent stability. Such a lithium ion secondary battery generally uses a lithium-containing transition metal oxide as a positive electrode as an active material and carbon as a negative electrode, and utilizes insertion and desorption reactions of lithium ions into these active materials. Charging and discharging.

In recent years, for the purpose of further increasing the capacity, secondary batteries using radical compounds as electrode active materials that directly contribute to electrode reactions have been proposed.
For example, Patent Document 1 discloses poly (2,2,6,6-tetramethyl-4-piperidinoxymethacrylate), poly (2,2,5,5-tetramethyl-2-pyrrole) as radical compounds. A method using a compound having a stable radical in the side chain of a polymer such as dinoxymethacrylate) or poly (2,2,5,5-tetramethyl-2-pyrrolinoxymethacrylate) is described. Patent Document 2 describes a method using a polymer compound having a spirocyclic nitroxide structure as a radical compound having a high radical concentration.

On the other hand, in a radical compound used as an electrode active material, the radical concentration is one of the important indexes for realizing a secondary battery having a high energy density and a large capacity.
Of the radical compounds described in Patent Document 1, the radical concentration (calculated value) of poly (2,2,5,5-tetramethyl-2-pyrrolinoxymethacrylate) having the highest radical concentration is 2.69 ×. Poly (2,2,8,8,10,10-hexamethyl-1,9-diazaspiro [5, which is 10 ²¹ radicals / g and has the highest radical concentration among the polymer compounds described in Patent Document 2. , 5] -undecane acrylate oxy radical) was 3.56 × 10 ²¹ radicals / g.

JP 2002-304996 A JP 2006-45310 A

The compounds of Patent Documents 1 and 2 have a high radical concentration, but there are problems that the production method requires many steps and the yield is low.
Therefore, the advent of a radical compound that has a high radical concentration, can be suitably used as an electrode active material, and can be easily obtained with a high yield has been awaited.
The present invention relates to N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide and a process for producing the same, which can have a high radical concentration, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer, and secondary battery electrode using them The purpose is to provide.

  The present invention relates to N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide represented by the following formula (1).

式（１）中、Ｒは水素原子またはメチル基を示す。

In formula (1), R represents a hydrogen atom or a methyl group.

  In the present invention, N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine represented by the following formula (2) is used as a (meth) acrylic acid halide. The present invention relates to a method for producing N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide represented by the following formula (1).

式（１）中、Ｒは水素原子またはメチル基を示す。

In formula (1), R represents a hydrogen atom or a methyl group.

  The present invention also relates to N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide represented by the above formula (1) as a crosslinking agent. N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide obtained by polymerization in the presence of The present invention relates to a compound cross-linked polymer.

The N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer according to the present invention is used as a copolymer component. Contains (meth) acrylic acid ester.
Examples of the (meth) acrylic acid ester include hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and (meth) acrylic. It is preferably at least one selected from the group consisting of behenyl acid. Further, the content ratio of (meth) acrylic acid ester is 0 with respect to 1 mol of N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide. A ratio of ˜0.25 mol is preferred.
The crosslinking agent used in the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound crosslinked polymer according to the present invention is: For example, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate and 1,9- It is preferably at least one selected from the group consisting of nonanediol di (meth) acrylate.
The method of polymerization in the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer according to the present invention is as follows. For example, a suspension polymerization method, an emulsion polymerization method and a solution polymerization method are preferable.
The present invention also provides an N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound crosslinked polymer according to the present invention. It is related with the electrode of the used secondary battery.
In the present invention, acryl and methacryl may be collectively referred to as (meth) acryl, acrylate and methacrylate as (meth) acrylate.

  N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide according to the present invention is a novel compound represented by the following formula (1). . Hereinafter, N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide according to the present invention will be described.

式（１）中、Ｒは、水素原子またはメチル基を示す。

In formula (1), R represents a hydrogen atom or a methyl group.

  N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide represented by the following formula (1) according to the present invention is, for example, Manufactured by a method in which N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine represented by (2) is amidated with (meth) acrylic acid halide can do.

式（１）中、Ｒは、水素原子またはメチル基を示す。

In formula (1), R represents a hydrogen atom or a methyl group.

  The N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine is, for example, as shown in the following formula (3), 2,2,6,6-tetra It can be produced by a known method using methyl-4-piperidione and 4-amino-2,2,6,6-tetramethyl-piperidine (JP-A 64-50858, JP-A-1-308251). Gazette, JP-A-10-130238).

  Specific examples of the method for producing the N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine include 2,2,6,6-tetramethyl. By reacting -4-piperidione with 4-amino-2,2,6,6-tetramethyl-piperidine, 2,2,6,6-tetramethyl-4-[(2,2,6,6 -Tetramethyl-4-piperidylidene) amino] piperidine. Next, there is a method of obtaining N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine by reacting with hydrogen in the presence of a hydrogenation catalyst.

  The N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide according to the present invention is the N, N-bis- thus obtained. It can be produced by amidating with (meth) acrylic acid halide using (2,2,6,6-tetramethyl-piperidin-4-yl) -amine.

  Examples of the (meth) acrylic acid halide include (meth) acrylic acid fluoride, (meth) acrylic acid chloride, (meth) acrylic acid bromide, and (meth) acrylic acid iodide. Among these, (meth) acrylic acid chloride is preferably used because it is inexpensive.

  The ratio of the (meth) acrylic acid halide used is 0.8 to 1.5 with respect to 1 mol of N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine. A molar ratio is preferable, and a molar ratio of 0.9 to 1.1 mol is more preferable. When the use ratio of (meth) acrylic acid halide is less than 0.8 mol, the reaction may not easily proceed. Moreover, when the usage-amount of (meth) acrylic acid halide exceeds 1.5 mol, there exists a possibility that it may not become economical without the effect corresponding to the usage-amount.

  Examples of the solvent used for the amidation include ethers such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; aliphatic nitriles such as acetonitrile, propionitrile and butyronitrile; benzonitrile. , Aromatic nitriles such as tolunitrile; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol and tert-butanol; aromatic hydrocarbons such as benzene, toluene and xylene Etc. Among these, ethers such as diethyl ether and tetrahydrofuran are preferably used.

  The amount of the solvent used is N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) from the viewpoint of smoothly proceeding the reaction and obtaining an effect corresponding to the amount used. ) -Preferably 50 to 5000 parts by mass, more preferably 100 to 3000 parts by mass with respect to 100 parts by mass of amine.

  A base may be added for the purpose of allowing the amidation to proceed more smoothly. Examples of the base include amine compounds such as trimethylamine, triethylamine, triphenylamine, and 4-dimethylaminopyridine. These bases may be used individually by 1 type, or may use 2 or more types together.

  The base is preferably used in a proportion of 1.5 mol or less per 1 mol of N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine. More preferably, the ratio is 1.1 mol or less.

Examples of the amidation operation method include a predetermined amount of N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine, a solvent, and, if necessary, a base. And a method of reacting with stirring while adding (meth) acrylic acid halide dropwise. According to this method, the reaction can be easily performed with a high yield.
As reaction temperature, 0-100 degreeC is preferable and 20-80 degreeC is more preferable. Although there is no restriction | limiting in particular as reaction time, Usually, it is 1 to 20 hours, Preferably it is 5 to 20 hours.
The N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide thus obtained can be easily isolated by filtration or concentration. .

  N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide according to the present invention is a high radical useful as an electrode active material for a secondary battery. N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer having a concentration It can be used as a monomer raw material.

  The N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound crosslinked polymer according to the present invention is prepared as described above. The obtained N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide represented by the above formula (1) is obtained in the presence of a crosslinking agent. A polymerization reaction product can be prepared by polymerization with a nitroxide, and further produced by nitroxide formation.

  N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide represented by the above formula (1) has a relatively low molecular weight and is a nitroxide. Since it can have a plurality of radical sites, N, N-bis- (2,2,6,6-tetramethyl-piperidine-N-oxyl-4 according to the present invention having this as a repeating unit can be obtained. The -yl) -amine- (meth) acrylamide compound cross-linked polymer can have a high radical concentration.

  In such a crosslinked polymer, a polymer having no crosslinked structure, that is, N, N-bis- (2,2,6,6-tetramethyl-piperidine-N-oxyl) obtained without using a crosslinking agent -4-yl) -amine- (meth) acrylamide compound polymers can also have high radical concentrations. However, N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound polymer not having such a crosslinked structure is In secondary batteries, etc., secondary batteries using this as an electrode active material have sufficient performance because they are easily dissolved in a solvent that constitutes an electrolyte solution that transports charge carriers between the positive electrode and the negative electrode. There is a risk that it can no longer be exhibited. In contrast, the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound crosslinked polymer according to the present invention is: By having a crosslinked structure, solubility in the solvent constituting the electrolytic solution is suppressed, and the solvent has excellent characteristics in terms of solvent stability.

  The N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer according to the present invention is used as a copolymer component. It is preferable to contain (meth) acrylic acid ester. N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide containing the (meth) acrylic acid ester as a copolymer component The compound cross-linked polymer not only has excellent solvent stability, but also has high coatability. That is, the cross-linked polymer can be formed into a paint with a relatively small amount of solvent in a coating process required when applied as an electrode active material for a secondary battery or the like. Cracks are less likely to occur. If cracks occur in an electrode manufactured by applying the paint to a current collector and drying it, the workability of the electrode in subsequent secondary battery manufacturing will be impaired, or the capacity of the secondary battery will be reduced. May occur. In the cross-linked polymer, the reason why it has such a high coating property and can suppress cracking during drying is not clear, but the repulsion between the introduced alkyl groups causes the solvent to move between the molecular chains. This is considered to be because the fluidity of the slurry is improved from before the introduction of the alkyl group.

Although it does not specifically limit as said (meth) acrylic acid ester, For example, (meth) acrylic-acid alkylester, polyalkylene glycol mono (meth) acrylate, etc. are mentioned.
Although it does not specifically limit as said (meth) acrylic-acid alkylester, For example, (meth) acrylic acid methyl, (meth) acrylic-acid ethyl, (meth) acrylic-acid propyl, (meth) acrylic-acid isopropyl, Butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate Can be mentioned.
The polyalkylene glycol mono (meth) acrylate is not particularly limited, and examples thereof include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Moreover, as a molecule | numerator size of a polyalkylene glycol part, the thing whose repeating number of an alkylene glycol part is 1-100 is mentioned, for example. Among these, when the obtained N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer is made into a paint (Meth) acrylic acid alkyl ester is preferably used because of its excellent coating ease. Among these, hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, (meth) Lauryl acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate are preferably used, and hexyl (meth) acrylate and stearyl (meth) acrylate are particularly preferably used. In addition, these (meth) acrylic acid ester can be used individually by 1 type or in combination of 2 or more types, respectively.

  The N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer according to the present invention is a copolymer component. The content ratio in the case of containing (meth) acrylic acid ester is N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth). From the viewpoint of obtaining a good coated surface of the acrylamide compound cross-linked polymer and obtaining an effect corresponding to the amount used, the N, N-bis- (2,2,6,6-tetramethyl-piperidine-4- Yl) -amine- (meth) acrylamide is preferably in a proportion of 0.25 mol or less, more preferably in the proportion of 0.00005-0.1 mol, and 0.001-0. 0 And more preferably a ratio of moles.

As a crosslinking agent used in the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound crosslinked polymer according to the present invention, Any compound having a plurality of polymerizable unsaturated groups in the molecule is not particularly limited, and examples thereof include (meth) acrylic acid polyfunctional compounds, allyl ether polyfunctional compounds, and vinyl polyfunctional compounds. It is done.
Examples of the (meth) acrylic acid polyfunctional compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, 7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, glyce Nji (meth) acrylate and 2-hydroxy-3- (meth) acryloyloxy propyl (meth) acrylate.
Examples of the allyl ether polyfunctional compound include diethylene glycol diallyl ether and dibutylene glycol diallyl ether. Examples of the vinyl polyfunctional compound include divinylbenzene. Among these, from the viewpoint of having high polymerization reactivity, a (meth) acrylic acid polyfunctional compound is preferably used, and in particular, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate are preferably used. In addition, these crosslinking agents can be used individually by 1 type or in combination of 2 or more types, respectively.

  The proportion of the crosslinking agent used is N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) having excellent solvent stability. From the viewpoint of obtaining an acrylamide compound cross-linked polymer and obtaining an effect corresponding to the amount used, the above N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- The ratio is preferably 0.00001 to 0.25 mol, more preferably 0.00005 to 0.1 mol, and 0.0001 to 0.05 mol per mol of (meth) acrylamide. More preferably, the ratio is

  As a polymerization method used in the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer according to the present invention. Is not particularly limited, and for example, methods such as a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method can be used.

  Examples of the suspension polymerization method include a predetermined amount of N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide, a crosslinking agent, and oil solubility. A radical polymerization initiator and, if necessary, a (meth) acrylic acid ester mixed with an inert hydrocarbon solvent and a surfactant mixed with water which is inert to the reaction and dispersed, then nitrogen A method of deoxygenating with gas and heating with stirring can be mentioned.

  The oil-soluble radical polymerization initiator used in the suspension polymerization method is not particularly limited, and examples thereof include benzoyl peroxide, tert-butyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and the like. Peroxide-based polymerization initiators of α, α′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2′-azobisisobutyrate, etc. Azo polymerization initiators; redox polymerization initiators such as benzoyl peroxide / dimethylaniline, di-tert-butyl peroxide / dimethylaniline, and lauroyl peroxide / dimethylaniline. Among these, an azo polymerization initiator such as α, α'-azobisisobutyronitrile, which is inexpensive and easy to handle, is preferably used.

  The amount of the oil-soluble radical polymerization initiator used in the suspension polymerization method varies depending on the type of the oil-soluble radical polymerization initiator used and the reaction temperature, but usually N, N-bis- (2,2,6 , 6-Tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide is 0.005 to 5 parts by mass with respect to 100 parts by mass.

  The inert hydrocarbon solvent used in the suspension polymerization method is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as benzene, toluene and xylene; acyclic rings such as n-hexane, n-heptane and ligroin. Formula saturated hydrocarbon solvents; cyclic saturated hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; halogenated hydrocarbon solvents such as dichloromethane, chloroform, dichloroethane, and the like. Among these, an aromatic hydrocarbon solvent and an acyclic saturated hydrocarbon solvent are preferable from the viewpoint of being easily available industrially, inexpensive, and stabilizing the quality of the obtained polymerization reaction product. Toluene and n-hexane are preferably used.

  The amount of the inert hydrocarbon solvent used in the suspension polymerization method is N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide. N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) from the viewpoint of sufficiently dissolving the polymer and proceeding the polymerization reaction smoothly and obtaining an effect sufficient for the amount used -It is preferable that it is 50-300 mass parts with respect to 100 mass parts of amine- (meth) acrylamide, and it is more preferable that it is 75-200 mass parts.

As the surfactant used in the suspension polymerization method, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used.
Examples of the anionic surfactant include fatty acid sodium, aliphatic potassium, sodium alkyl sulfate, sodium alkylbenzene sulfonate, sodium alkane sulfonate, sodium alkyl phosphate, acyloyl methyl taurate, N-methyl-N-acyl. Sodium amidopropionate, sodium monoalkylbiphenyl ether disulfonate, sodium naphthalene sulfonate-formalin condensate, sodium acylglutamate, sodium polyoxyethylene alkylphenyl ether alkylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether Sodium methylcarboxylate and sodium polyoxyethylene alkyl ether ethanesulfonate, etc. And the like.
Examples of the cationic surfactant include monoalkyl trimethyl ammonium methosulfate, cationized cellulose, alkyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, dialkyl dimethyl benzyl ammonium chloride, and alkyl pyridinium chloride. It is done.
Examples of the nonionic surfactant include fatty acid monoglyceride, sorbitan fatty acid partial ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid monoglyceride, polyoxyethylene sorbitol fatty acid partial ester, and polyoxyethylene sorbitan. Fatty acid partial ester, polyoxyethylene lanolin alcohol ether, polyethylene glycol fatty acid monoester, polyethylene glycol fatty acid diester, polyoxyethylene fatty acid amine, polyglycerin fatty acid partial ester, bis (2-hydroxyethyl) alkylamine, alkyldimethylamine oxide, fatty acid Alkylolamide, ω-methoxypolyoxyethylene-α-alkyl ether, poly Examples include reoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene acetylene glycol, sugar fatty acid partial ester, polyvinyl alcohol, and partially saponified polyvinyl alcohol.
Examples of the amphoteric surfactant include N-acylamidopropyl-N, N-dimethylammoniobetaine, N-acylamidopropyl-N ′, N′-dimethyl-N′-β-hydroxypropylammoniosulfobetaine. N-acylamidoethyl-N′-hydroxyethyl-N′-carboxymethylammoniobetaine, N-alkyl-N-dimethyl-N-carboxymethylammoniobetaine, alkyldiaminoethylglycine, acylated polypeptide, etc. It is done.
Among these surfactants, industrially easy to obtain, inexpensive, and from the viewpoint of stabilizing the quality of the resulting polymerization reaction product, sodium alkylbenzene sulfonate, sodium polyoxyethylene alkylphenyl ether alkylbenzene sulfonate, Polyvinyl alcohol and partially saponified polyvinyl alcohol are preferably used. Among sodium alkylbenzenesulfonates, sodium dodecylbenzenesulfonate is preferable, and among sodium polyoxyethylene alkylphenylether alkylbenzenesulfonates, sodium polyoxyethylenenonylphenylether dodecylbenzenesulfonate is preferable.

  The amount of the surfactant used in the suspension polymerization method is 0.05 to 10 masses with respect to 100 parts by mass of water from the viewpoint of smoothly proceeding the reaction and obtaining an effect that is commensurate with the usage amount. Part is preferable, and 0.1 to 5 parts by mass is more preferable.

  The amount of water used in the suspension polymerization method is N, N-bis- (2,2,6,6-tetramethyl-) from the viewpoint of sufficiently removing the heat of polymerization and from the viewpoint of easily controlling the polymerization temperature. It is preferable that it is 100-3000 mass parts with respect to 100 mass parts of piperidin-4-yl) -amine- (meth) acrylamide, and it is more preferable that it is 200-2000 mass parts.

In the suspension polymerization method, additives such as a chain transfer agent such as isopropyl alcohol and a polymerization terminator such as methanol may be added as necessary.
As reaction temperature in the said suspension polymerization method, 30-100 degreeC is preferable and 40-80 degreeC is more preferable. Since the reaction time varies depending on the reaction temperature, it cannot be generally specified, but is usually 0.5 to 10 hours.
Since the polymerization reaction product thus obtained exists in a particle state in the reaction solvent, it can be isolated by filtering the reaction solution. Furthermore, it can be purified by removing unreacted substances, washing and drying using water, methanol, hexane or the like.

  Another polymerization used in the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer according to the present invention. Examples of the emulsion polymerization method include a predetermined amount of N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide, a crosslinking agent, and an interface. After the activator and, if necessary, (meth) acrylic acid ester are mixed and dispersed in an inert solvent, water, deoxygenated with nitrogen gas, a water-soluble radical polymerization initiator is added, and the mixture is stirred. The method of heating is mentioned.

The water-soluble radical polymerization initiator used in the emulsion polymerization method is not particularly limited, and examples thereof include peroxide polymerization initiators such as ammonium persulfate, sodium persulfate, and potassium persulfate; ferrous ammonium sulfate / ammonium persulfate And redox polymerization initiators such as ethanolamine / potassium persulfate. Among these, peroxide polymerization initiators such as potassium persulfate, which are inexpensive and easy to handle, are preferably used.
In addition, the type and amount of surfactant used in the emulsion polymerization method, the amount used of the polymerization initiator, the amount of water used as the inert solvent, the reaction temperature and the reaction time are the same as those in the suspension polymerization method. Things can be applied.
In the emulsion polymerization method, it is used in the suspension polymerization method in order to dissolve N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide. An inert hydrocarbon solvent similar to the above may be added as appropriate, and an additive such as a chain transfer agent such as isopropyl alcohol and a polymerization terminator such as methanol may be added as necessary.
The polymerization reaction product thus obtained can be isolated, for example, by mixing the reaction solution with a large amount of cold water and precipitating the polymerization reaction product, followed by filtration. Furthermore, it can be purified by removing unreacted substances, washing and drying using water, methanol, hexane or the like.

  Still another polymerization used in the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound crosslinked polymer according to the present invention. Examples of the solution polymerization method are, for example, a predetermined amount of N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide, a crosslinking agent, An example is a method in which an inert solvent and, if necessary, (meth) acrylic acid ester are charged, deoxygenated with nitrogen gas, and then a polymerization initiator is added with stirring.

  The inert solvent used in the solution polymerization method is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; acyclic saturated hydrocarbons such as n-hexane, n-heptane, and ligroin. Examples of the solvent include cyclic saturated hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; and inert solvents such as ether solvents such as diethyl ether and tetrahydrofuran. Among these, aromatic hydrocarbon solvents and acyclic saturated hydrocarbon solvents are preferred from the viewpoint of being easily available industrially, inexpensive, and stabilizing the quality of the resulting polymerization reaction product. , Tetrahydrofuran and n-hexane are preferably used.

  The use amount of the inert solvent used in the solution polymerization method is N, N-bis- (2,2,6,6-) from the viewpoint of smoothly proceeding the reaction and obtaining an effect sufficient for the use amount. It is preferable that it is 50-2000 mass parts with respect to 100 mass parts of tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide.

It does not specifically limit as a polymerization initiator used for the said solution polymerization method, It can superpose | polymerize using a radical polymerization initiator and an anionic polymerization initiator. Examples of the radical polymerization initiator include peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide, and potassium persulfate; α, α′-azobis Azo polymerization initiators such as isobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2′-azobisisobutyrate; ferrous ammonium sulfate / ammonium persulfate, ethanol Examples include redox polymerization initiators such as amine / potassium persulfate and sodium bromate / sulfur dioxide. Among these, an azo polymerization initiator such as α, α′-azobisisobutyronitrile, which is inexpensive and easy to handle, is preferably used. Examples of the anionic polymerization initiator include Grignard reagents (n-butylmagnesium bromide, isobutylmagnesium bromide, tert-butylmagnesium bromide, n-butylmagnesium chloride, isobutylmagnesium chloride, tert-butylmagnesium chloride) and alkyls. And lithium (n-butyllithium, tert-butyllithium, 1,1, -diphenylhexyllithium, etc.) and the like. Among these, alkyllithium such as tert-butyllithium and α, α′-azobisisobutyronitrile are preferably used from the viewpoint of stabilizing the quality of the obtained polymerization reaction product.
The amount of the polymerization initiator used in the solution polymerization method varies depending on the type of polymerization initiator used and the reaction temperature, but usually N, N-bis- (2,2,6,6-tetramethyl-piperidine- It is 0.005-5 mass parts with respect to 100 mass parts of 4-yl) -amine- (meth) acrylamide.
In the solution polymerization reaction, additives such as a chain transfer agent such as isopropyl alcohol and a polymerization terminator such as methanol may be added as necessary.

The reaction temperature in the solution polymerization method varies depending on the type of polymerization initiator used, but is usually preferably −100 to 100 ° C., more preferably −50 to 80 ° C. Although the reaction time varies depending on the reaction temperature, it cannot be generally stated, but it is usually 2 to 10 hours.
The polymerization reaction product thus obtained can be isolated by mixing the reaction solution with a solvent such as an aliphatic hydrocarbon such as hexane to precipitate the polymerization reaction product, followed by filtration. Furthermore, it can refine | purify by removing unreacted substances etc. using methanol, hexane, etc., washing, and drying.

The N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound crosslinked polymer according to the present invention is prepared as described above. The resulting polymerization reaction product can be produced by nitroxidation.
The method for nitrating the polymerization reaction product is not particularly limited. For example, a compound having a corresponding nitroxide free group is produced by oxidizing a secondary amine having steric hindrance using an oxidizing agent. The publicly known method etc. which can be mentioned can be mentioned. Specifically, for example, after mixing the polymerization reaction product and an inert solvent, the polymerization reaction product can be converted into a nitroxide by reacting with stirring while adding an oxidizing agent.

  Examples of the inert solvent used for the nitroxidation include halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; aliphatic nitriles such as acetonitrile, propionitrile and butyronitrile; aromatic nitriles such as benzonitrile and tolunitrile. Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol and tert-butanol; aromatic hydrocarbons such as benzene, toluene and xylene, and water . Among these, halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane and alcohols such as methanol, ethanol and tert-butanol are preferably used.

  The amount of the inert solvent used for the nitroxide formation is 50 to 5000 parts by mass with respect to 100 parts by mass of the polymerization reaction product from the viewpoint of smoothly proceeding the reaction and obtaining an effect sufficient for the amount of use. It is preferable that it is 100-3000 mass parts.

  Examples of the oxidizing agent used for the nitroxidation include peroxides such as hydrogen peroxide, performic acid, peracetic acid, perbenzoic acid and perphthalic acid, halides thereof, silver oxide, lead tetraacetate, hexacyanoiron. (III) Oxides such as potassium acid and potassium permanganate can be mentioned.

  The proportion of the oxidizing agent used for the nitroxide formation is determined from the viewpoint of smoothly proceeding the reaction and obtaining an effect sufficient for the amount used, and N, N-bis- ( 2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide is preferably in a ratio of 1 to 200 mol, and 1.5 to 100 mol. Is more preferable.

  In the nitroxide formation, a catalyst can be used as necessary. As a catalyst, the catalyst currently used for normal nitroxide formation can be mentioned. Specific examples of the catalyst used for nitroxidation include a compound containing a metal element selected from Group 6 of the Group 18 element periodic table such as tungsten and molybdenum, and examples thereof include tungstic acid, phosphotungstic acid, and paratungsten. Acids and alkali metal salts thereof (sodium salt, potassium salt, etc.) and ammonium salts, tungsten oxides such as tungsten oxide and tungsten carbonyl; molybdic acid, phosphomolybdic acid, paramolybdic acid and alkali metal salts thereof (sodium salt, potassium salt) Salts) and ammonium compounds, and molybdenum compounds such as molybdenum oxide and molybdenum carbonyl. More specifically, ammonium paratungstate, sodium tungstate, phosphotungstic acid, sodium molybdate, and the like. Arm, molybdenum trioxide and molybdenum hexacarbonyl, and the like.

  The amount of the catalyst used for the nitroxide formation is 0.001 to 20 parts by mass with respect to 100 parts by mass of the polymerization reaction product from the viewpoint of smoothly proceeding the reaction and obtaining an effect that is commensurate with the amount of use. It is preferable that it is 0.01-10 mass parts.

The reaction temperature for the nitroxidation is preferably 0 to 100 ° C, more preferably 20 to 80 ° C.
Examples of the operation method of the nitroxidation include a method in which a predetermined amount of a polymerization reaction product, an inert solvent and, if necessary, a catalyst are mixed, and then reacted while an oxidizing agent is added with stirring. It is done. According to this method, the reaction can be easily performed with a high yield. In this method, the reaction time while adding the oxidizing agent is not particularly limited, but is usually 1 to 10 hours, preferably 2 to 6 hours. Further, usually, after the addition of the oxidizing agent is completed, the reaction is completed by maintaining at the above temperature for 1 to 10 hours.
Thus obtained N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer according to the present invention is obtained as follows. It can isolate from the said reaction liquid combining filtration, drying, etc. In the nitroxidation, the polymerization reaction product does not necessarily need to be dissolved in an inert solvent. For example, the nitroxidation easily proceeds even in a swollen state.
The reaction rate of nitroxide formation is usually 90% or more, and the reaction rate is a method for analyzing the residual amount of the oxidizing agent used in the reaction, an imino group remaining in the reaction product using an NMR method or the like. Can be calculated by a method of quantifying the spin concentration in the reaction product using the ESR method or the like.

The N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer according to the present invention is a current collector. Can be used as an electrode of a secondary battery.
The current collector is an electrode component that collects electric charges generated from the electrodes of the secondary battery and is made of a conductor. Examples of the member used for the current collector usually include metal stays such as nickel, aluminum, copper, gold, silver, aluminum alloy, and stainless steel, metal flat plates and metal meshes, and carbon bars.
Examples of the method for producing the electrode of the secondary battery according to the present invention include the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- Examples thereof include a method including a coating step for forming a (meth) acrylamide compound cross-linked polymer and a coating step for applying the coating to a current collector. There is no restriction | limiting in particular in the method of the said coating-izing and the method of application | coating, It can carry out using a well-known method and apparatus.

Examples of the coating method include N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer. After mixing a binder, the method of adding a solvent and making it a slurry form etc. are mentioned. Specific examples of the binder include, for example, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, polypropylene, polyethylene, polyimide, and various polyurethanes. And a resin binder. Specific examples of the solvent include dimethylformamide and N-methylpyrrolidone.
In addition, as a coating method, for example, the slurry obtained by the above coating is dropped on the surface of the current collector, developed with a wire bar so that the entire thickness is uniform, and then dried to remove the solvent. The method of removing is mentioned.

It should be noted that N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound is used for the purpose of lowering impedance when forming the above-mentioned paint. You may add an auxiliary electrically conductive material and an ion conduction auxiliary agent to a crosslinked polymer suitably. Specific examples of the auxiliary conductive material include carbonaceous fine particles such as graphite, carbon black, and acetylene black, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyacene. Specific examples of the ionic conduction aid include a polymer gel electrolyte and a polymer solid electrolyte.
Coating obtained by applying the above-mentioned coated N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer The film thickness is preferably 10 to 1000 μm, and more preferably 50 to 300 μm.

  When the electrode of the secondary battery according to the present invention is used as an electrode of a secondary battery having a high energy density and a large capacity, such as a lithium ion secondary battery, the solubility in the solvent constituting the electrolytic solution is suppressed. Since it has excellent properties with respect to solvent, it can be used particularly preferably.

  Examples of the solvent constituting the electrolytic solution include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxofuran, sulfolane, dimethylformamide, dimethylacetamide, and N-methyl-2- An organic solvent such as pyrrolidone is used alone or in admixture of two or more.

When a radical compound is used as the electrode active material of the secondary battery, the capacity is given by the following formula (4). For example, the capacity of the active material of the lithium ion secondary battery is assumed to be 130 to 160 Ah / kg, and N, N-bis- (2,2,6,6-tetramethyl-piperidine-N according to the present invention). -Oxyl-4-yl) -amine-acrylamide compound crosslinked polymer and N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -methacrylamide compound crosslinked polymer The radical concentration of the coalescence is 1.73 × 10 ²¹ radicals / g (calculated value) and 1.59 × 10 ²¹ radicals / g (calculated value), so that it is approximately 153 Ah / kg (calculated value) and 141 Ah / kg. Realization of a large-capacity electrode active material (calculated value) can be expected.

C (Ah / kg) = N _A · e / (3600 · M / 1000) (4)
Wherein (4), C is the capacitance, the N _A molar constant, e is the electronic charge, M denotes a molecular weight per radical.

According to the present invention, N, N-bis- (2,2,6,6-tetramethyl-piperidine-N-oxyl-4-4, which is useful as an electrode active material of a secondary battery and can have a high radical concentration. N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) which is a monomer raw material for easily producing a crosslinked polymer of yl) -amine- (meth) acrylamide compound -Amine- (meth) acrylamide and its manufacturing method can be provided.
Further, according to the present invention, N, N-bis- (2,2,6,6-tetramethyl-piperidine-N-oxyl-) having a high radical concentration, which is useful as an electrode active material of a secondary battery. A 4-yl) -amine- (meth) acrylamide compound cross-linked polymer and a secondary battery electrode having a high energy density and a large capacity can be easily provided.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

[Example 1]
In a 1000 mL autoclave equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 77.62 g (0.50 mol) of 2,2,6,6-tetramethyl-4-piperidione, 4-amino- 85.95 g (0.55 mol) of 2,2,6,6-tetramethyl-piperidine was added. After removing oxygen in the reaction system through nitrogen gas, the mixture was reacted at 50 ° C. for 4 hours with stirring. After completion of the reaction, 750 mL of petroleum ether was added and dissolved, and then cooled to 0 ° C. to give crude 2,2,6,6-tetramethyl-4-[(2,2,6,6-tetramethyl-4-piperidylidene. ) Amino] piperidine was precipitated. This was filtered, washed with 100 mL of petroleum ether, and then dried under reduced pressure to give white 2,2,6,6-tetramethyl-4-[(2,2,6,6-tetramethyl-4-piperidylidene). 109.88 g (yield 75%) of amino] piperidine were obtained.
The obtained 2,2,6,6-tetramethyl-4-[(2,2,6,6-tetramethyl-4-piperidylidene) amino] piperidine was subjected to mass spectrometry by an atmospheric pressure ionization method. 293. The measured _{C-NMR (CDCl 3),} 168.28,54.07,53.72,52.26,51.40,50.51,46.05,42.11,35.06, Peaks were observed at 31.87, 31.45, and 28.76 ppm.

The 2,2,6,6-tetramethyl-4-[(2,2,6,6-tetramethyl-4] obtained as described above was added to a 1000 mL autoclave equipped with a stirrer, a nitrogen gas inlet tube, and a thermometer. -Piperidylidene) amino] piperidine (4.0 g, 13.6 mmol), Raney nickel (2.0 g) and methanol (20 mL) were added. After removing oxygen in the reaction system through nitrogen gas, the pressure was adjusted to 20 atm (gauge pressure) with hydrogen, and heated to 90 ° C. with stirring to raise the hydrogen pressure to 100 atm (gauge pressure). The reaction was continued for 8 hours, and then cooled and decompressed. Add 100 mL of petroleum ether and dissolve at 50 ° C., then cool to 0 ° C. to precipitate crude N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine I let you. This was filtered, washed with 20 mL of petroleum ether, and dried under reduced pressure to give 2.77 g of white N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine ( Yield 69%).
The obtained N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine was identified by mass analysis by an atmospheric pressure ionization method and a molecular weight of 295. did it.

Next, in a 500 mL five-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a reflux condenser, and a dropping funnel, 70.60 g (100 mL) of diethyl ether, N, Charge 14.78 g (50 mmol) of N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine and 1.6 g (13 mmol) of 4-dimethylaminopyridine to obtain a homogeneous solution. Obtained. While maintaining this solution at 25 ° C., oxygen in the reaction system was removed through nitrogen gas, and then 4.8 g (53 mmol) of acrylic acid chloride adjusted to 0 to 2 ° C. was added dropwise over 4 hours with stirring. Subsequently, after holding at 25 ° C. for 8 hours, the reaction solution was filtered, the filtrate was concentrated under reduced pressure at 25 ° C., and the concentrate was dissolved in 50 mL of a chloroform / methanol mixture (volume ratio 5/1). This solution was passed through a 1 L column in which 300 mL of silica gel (IR-60-63 / 210, manufactured by Daiso Corporation) was suspended and packed in 1.2 L of a chloroform / methanol mixture (volume ratio 5/1). And purified. The target fraction was collected and dried under reduced pressure at 25 ° C. until a constant weight was obtained, whereby white N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- 15.53 g (89% yield) of acrylamide was obtained.
The obtained N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine-acrylamide was analyzed by mass analysis by the atmospheric pressure ionization method and found to have a molecular weight of 349. We were able to identify from.

[Example 2]
To an Erlenmeyer flask having an internal volume of 250 mL, 3.49 g of N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine-acrylamide obtained in the same manner as in Example 1 ( 10 mmol), 0.09 g (0.1 mmol) of 1,9-nonanediol dimethacrylate, 0.0115 g (0.07 mmol) of α, α′-azobisisobutyronitrile and 3.03 g of toluene (3. 5 mL) was added and mixed to obtain a homogeneous solution.
Next, a 250 mL four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with 20 g of water (20 mL) and 0.03 g of sodium dodecylbenzenesulfonate as a surfactant. While maintaining this solution at 25 ° C., the homogeneous solution in the Erlenmeyer flask was added and dispersed with stirring. Subsequently, oxygen in the reaction system was removed through nitrogen gas, followed by suspension polymerization reaction at 60 ° C. with stirring for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, filtered, washed with 500 mL of water and then with 500 mL of hexane, and dried under reduced pressure to obtain 3.45 g of a white powder polymerization reaction product (yield 98). .1%).
The polymerization reaction product obtained white powder was measured for _{C-NMR (CDCl 3),} 167.28,55.02,54.02,52.72,52.16,46.05,41 .11, 34.06, 31.45, and 28.89 ppm were observed.
Next, in a 250 mL five-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, a reflux condenser, and a dropping funnel, 2 g of the polymerization reaction product obtained in the same manner as above (into the polymerization reaction product) The used N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine-acrylamide: 5.7 mmol) and 39.55 g (50 mL) of methanol were charged. After removing the oxygen in the reaction system through nitrogen gas while maintaining this at 25 ° C., 5.04 g (44.5 mmol) of a 30 mass% hydrogen peroxide solution was added dropwise over 3 hours. Subsequently, after maintaining at 25 ° C. for 8 hours, the reaction solution was filtered, washed with 500 mL of methanol and then with 500 mL of water, and then dried under reduced pressure to obtain N, N-bis- (2,2,6) of red powder. , 6-Tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound crosslinked polymer 2.0g was obtained.
The radical conversion rate of the obtained N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound crosslinked polymer was measured. 1%.
The radical conversion rate was first measured in the range of 335.9 mT ± 5 mT using a JES-FR30EX free radical monitor (manufactured by JEOL Ltd.) under conditions of a microwave output of 4 mW, a modulation frequency of 100 kHz and a modulation width of 79 μT The first-order differential type ESR spectrum thus obtained was integrated twice to determine the absorption area intensity. Next, it computed by comparing with the absorption area intensity | strength of the known sample (4-hydroxy-2,2,6,6-tetramethyl piperidinooxy free radical (4-TEMPOL)) measured on the same conditions.

[Example 3]
To an Erlenmeyer flask having an internal volume of 250 mL, 3.49 g of N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine-acrylamide obtained in the same manner as in Example 1 ( 10 mmol), 1,9-nonanediol dimethacrylate 0.03 g (0.1 mmol), methacrylic acid-n-stearyl 0.07 g (0.2 mmol), α, α′-azobisisobutyronitrile 0 0.0115 g (0.07 mmol) and 4.33 g (5.0 mL) of toluene were charged and mixed to obtain a homogeneous solution.
Next, a 250 mL four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with 20 g of water (20 mL) and 0.03 g of sodium dodecylbenzenesulfonate as a surfactant. While maintaining this solution at 25 ° C., the homogeneous solution in the Erlenmeyer flask was added and dispersed with stirring. Subsequently, oxygen in the reaction system was removed through nitrogen gas, followed by suspension polymerization reaction at 60 ° C. with stirring for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, filtered, washed with 500 mL of water and then with 500 mL of hexane, and dried under reduced pressure to obtain 3.46 g of a white powder polymerization reaction product (yield 96). .3%).
The polymerization reaction product obtained white powder was measured for _{C-NMR (CDCl 3),} 167.28,55.02,54.02,52.72,52.16,46.05,41 .11, 34.06, 31.45, 28.89, 20.55, and 18.67 ppm.
Next, in a 250 mL five-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, a reflux condenser, and a dropping funnel, 2 g of the polymerization reaction product obtained above (used for the polymerization reaction product). N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine-acrylamide: 5.7 mmol) and 39.55 g (50 mL) of methanol were charged. After removing the oxygen in the reaction system through nitrogen gas while maintaining this at 25 ° C., 5.04 g (44.5 mmol) of a 30 mass% hydrogen peroxide solution was added dropwise over 3 hours. Subsequently, after maintaining at 25 ° C. for 8 hours, the reaction solution was filtered, washed with 500 mL of methanol and then with 500 mL of water, and then dried under reduced pressure to obtain N, N-bis- (2,2,6) of red powder. , 6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound crosslinked polymer 1.9 g was obtained.
The radical conversion rate of the obtained N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound crosslinked polymer was the same as in Example 2. It was 98.5% when measured by the method.

[Example 4]
In Example 3, instead of 0.03 g of sodium dodecylbenzenesulfonate, 0.03 g of polyvinyl alcohol (degree of polymerization: 2000) was used in the same manner as in Example 3, except that polymerization reaction product 3 of white powder was used. .27 g was obtained (91.0% yield).
The polymerization reaction product obtained white powder was measured for _{C-NMR (CDCl 3),} 167.38,55.00,54.12,52.67,52.15,46.03,41 .10, 34.03, 31.44, 28.89, 20.55, and 18.66 ppm.
Next, in a 250 mL five-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, a reflux condenser, and a dropping funnel, 2 g of the polymerization reaction product obtained above (used for the polymerization reaction product). N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine-acrylamide: 5.7 mmol), sodium tungstate dihydrate as catalyst 0.14 g (0 .44 mmol) and 39.55 g (50 mL) of methanol were charged. After removing the oxygen in the reaction system through nitrogen gas while maintaining this at 25 ° C., 5.04 g (44.5 mmol) of a 30% by mass hydrogen peroxide solution was added dropwise over 3 hours. For 8 hours, the reaction solution is filtered, washed with 500 mL of methanol and then with 500 mL of water, and dried under reduced pressure to give red powder N, N-bis- (2,2,6,6-tetra 2.0 g of a methyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound crosslinked polymer was obtained.
The radical conversion rate of the obtained N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound crosslinked polymer was the same as in Example 2. It was 98.4% when measured by the method.

[Example 5]
N, N-bis- (2,2,6,6-) obtained in the same manner as in Example 1 was added to a 500 mL four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. Tetramethyl-piperidin-4-yl) -amine-acrylamide 6.98 g (20 mmol), 1,9-nonanediol dimethacrylate 0.13 g (0.4 mmol), methacrylic acid-n-stearyl 0.07 g (0 .2 mmol), 0.03 g of sodium polyoxyethylene nonylphenyl ether dodecylbenzenesulfonate as a surfactant, and 14 g (14 mL) of water were added, followed by stirring at 65 ° C. for 1 hour to obtain a uniform solution. . Subsequently, after removing oxygen in the reaction system through nitrogen gas, 0.0190 g (0.07 mmol) of potassium persulfate as a polymerization initiator was added, and an emulsion polymerization reaction was performed at 70 ° C. for 6 hours with stirring. It was. After completion of the reaction, the reaction solution was cooled to room temperature, added to 200 mL of cold water at 5 ° C., filtered, washed with 500 mL of water, and dried under reduced pressure to obtain 6.54 g of a polymerization reaction product as a white powder. (Yield 91.1%).
The polymerization reaction product of the obtained white powder was measured for C-NMR (CDCl ₃ ). As a result, 167.37, 55.00, 54.02, 52.66, 52.15, 46.13, 41 .10, 34.09, 31.48, 28.89, 20.55, and 18.56 ppm.
Next, in a 250 mL five-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, a reflux condenser, and a dropping funnel, 2 g of the polymerization reaction product obtained above (used for the polymerization reaction product). N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine-acrylamide: 5.7 mmol) and 39.55 g (50 mL) of methanol were charged. After removing the oxygen in the reaction system through nitrogen gas while maintaining this at 25 ° C., 5.04 g (44.5 mmol) of a 30 mass% hydrogen peroxide solution was added dropwise over 3 hours. Subsequently, after maintaining at 25 ° C. for 8 hours, the reaction solution was filtered, washed with 500 mL of methanol and then with 500 mL of water, and then dried under reduced pressure to obtain N, N-bis- (2,2,6) of red powder. , 6-Tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound crosslinked polymer 2.1 g was obtained.
The radical conversion rate of the obtained N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound crosslinked polymer was the same as in Example 2. It was 98.9% when measured by this method.

[Example 6]
N, N-bis- (2,2,6,6-) obtained in the same manner as in Example 1 was added to a 250 mL four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser. Tetramethyl-piperidin-4-yl) -amine-acrylamide 10.82 g (31.1 mmol), 0.10 g (0.31 mmol) 1,9-nonanediol dimethacrylate, 0.11 g methacrylic acid-n-stearyl (0.31 mmol) and 44.45 g (50 mL) of tetrahydrofuran were charged to obtain a homogeneous solution. While maintaining this solution at 25 ° C., oxygen in the reaction system was removed through nitrogen gas, and then 0.0358 g (0.22 mmol) of α, α′-azobisisobutyronitrile as a polymerization initiator was added. The solution polymerization reaction was carried out at 50 ° C. for 6 hours under stirring. After completion of the reaction, the reaction solution was cooled to room temperature, added to 1000 mL of hexane, filtered, washed with 500 mL of hexane, and dried under reduced pressure to obtain 10.91 g of a white powder polymerization reaction product (yield) 98.9%).
The polymerization reaction product of the obtained white powder was measured for C-NMR (CDCl ₃ ). As a result, it was 167.35, 55.02, 54.02, 52.66, 52.12, 46.13, 41. Peaks were observed at 0.08, 34.12, 31.45, 28.89, 20.51, and 18.56 ppm.
Next, in a 500 mL five-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, a reflux condenser, and a dropping funnel, 5 g of the polymerization reaction product obtained above (used for the polymerization reaction product). N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine-acrylamide: 5.7 mmol) and 66.25 g (50 mL) of dichloromethane were charged. After removing oxygen in the reaction system through nitrogen gas while maintaining this at 25 ° C., 47.28 g (pure content 65% by mass, 178 mmol) of m-chloroperbenzoic acid dissolved in 132.50 g (100 mL) of dichloromethane. ) Was added dropwise over 5 hours. Subsequently, after maintaining at 25 ° C. for 6 hours, the white precipitate was separated and removed from the reaction solution by centrifugation. The remaining upper layer was washed with 150 mL of a 10% by mass aqueous potassium carbonate solution and then with 150 mL of saturated brine. The organic layer is dehydrated with an appropriate amount of magnesium sulfate, magnesium sulfate is removed, and then dried under reduced pressure to give red powder N, N-bis- (2,2,6,6-tetramethyl-piperidine-N-oxyl). 4.19 g of -4-yl) -amine-acrylamide compound cross-linked polymer was obtained.
The radical conversion rate of the obtained N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound crosslinked polymer was the same as in Example 2. It was 98.3% when measured by the method.

[Comparative Example 1]
In Example 2, red powder N, N-bis- (2,2,6,6-tetra) was obtained in the same manner as in Example 2 except that 0.03 g of 1,9-nonanediol dimethacrylate was not used. 1.9 g of methyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound polymer was obtained.
The radical conversion rate of the obtained N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound polymer is the same as in Example 2. It was 98.2% when measured by the method.

[Comparative Example 2]
In Example 3, red powder N, N-bis- (2,2,6,6-tetra) was obtained in the same manner as in Example 3 except that 0.03 g of 1,9-nonanediol dimethacrylate was not used. 1.8 g of methyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound polymer was obtained.
The radical conversion rate of the obtained N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound polymer is the same as in Example 2. It was 98.1% when measured by the method.

(1) Evaluation of N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound cross-linked polymer Obtained in Examples 2-6 N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound cross-linked polymer, and N, obtained in Comparative Examples 1 and 2 For N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide polymer, mixed solvent of propylene carbonate, diethyl carbonate and ethylene carbonate / diethyl carbonate (mass The solubility in each solvent of the ratio: 3/7) was evaluated. After mixing for each solvent so that the polymer concentration is 10% by mass and stirring for 24 hours at room temperature, the filtrate obtained by filtration was dried under reduced pressure at 150 ° C. and 10 mmHg for 15 hours, Crude dissolution was obtained. This coarsely dissolved component was washed with pure water, and dried under reduced pressure at 150 ° C. and 10 mmHg for 3 hours to obtain a dissolved component to determine the solubility. These results are shown in Table 1.

  From the results shown in Table 1, N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide obtained in Examples 2-6 The compound cross-linked polymer has a solubility in all solvents used for evaluation of less than 1%, indicating that it is excellent in solvent stability.

(2) Evaluation of long-term solvent stability N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound obtained in Example 3 The crosslinked polymer was mixed at 10% by mass with respect to each solvent used in the above evaluation, and then stored at 40 ° C. with stirring for 10 days, 20 days, and 50 days. After elapse of a predetermined period, the filtrate obtained by filtration was dried under reduced pressure at 150 ° C. and 10 mmHg for 15 hours to obtain a coarsely dissolved component. This coarsely dissolved component was washed with pure water, and dried under reduced pressure at 150 ° C. and 10 mmHg for 3 hours to obtain a dissolved component to determine the solubility. The results are shown in Table 2.

  From the results shown in Table 2, N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound crosslinking obtained in Example 3 Since the polymer has a solubility in all the solvents used for evaluation of less than 1% over a storage period of 50 days, it can be seen that the polymer is excellent in solvent stability over a long period of time.

[Example 7] (Production of electrode of lithium ion secondary battery)
Using the agate mortar, the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound crosslinked polymer obtained in Example 3 was used. By pulverizing to a particle size of 100 μm or less, 0.5 g thereof, 10 g of N-methylpyrrolidone as a solvent, 0.1 g of polyvinylidene fluoride as a binder, and 0.4 g of graphite powder as an auxiliary conductive material Mixing and stirring gave a black slurry. 2 g of this slurry was dropped on the surface of an aluminum foil (area: 1.5 cm × 1.5 cm, thickness: 100 μm) provided with a lead wire, and developed so as to have a uniform thickness with a wire bar. N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide obtained in Example 3 by drying under reduced pressure at 120 ° C. for 6 hours An electrode in which the compound cross-linked polymer was bound to a current collector was produced. When the coated surface of the current collector was visually observed, no cracks were observed. In addition, about the coating film which consists of N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound crosslinked polymer, it is a film | membrane using a micrometer. It was 150 micrometers when thickness was measured.

[Example 8]
In Example 7, the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound cross-linked polymer obtained in Example 3 was used instead. Except for using the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound cross-linked polymer obtained in Example 4. When electrodes were produced in the same manner as in Example 7, no cracks were observed on the coated surface of the current collector. In addition, it was 140 micrometers when the film thickness was measured like Example 7.

[Example 9]
In Example 7, the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound cross-linked polymer obtained in Example 3 was used instead. Except for using the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound cross-linked polymer obtained in Example 5. When electrodes were produced in the same manner as in Example 7, no cracks were observed on the coated surface of the current collector. In addition, it was 145 micrometers when the film thickness was measured like Example 7.

[Example 10]
In Example 7, the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound cross-linked polymer obtained in Example 3 was used instead. Except for using the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine-acrylamide compound cross-linked polymer obtained in Example 6. When electrodes were produced in the same manner as in Example 7, no cracks were observed on the coated surface of the current collector. In addition, it was 150 micrometers when the film thickness was measured like Example 7.

[Example 11]
In Example 7, an electrode was produced in the same manner as in Example 7 except that 4 g of N-methylpyrrolidone was used in place of 10 g of N-methylpyrrolidone, and no crack was observed on the coated surface of the current collector. It was. In addition, it was 268 micrometers when the film thickness was measured like Example 7.

[Example 12]
In Example 11, instead of the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -acrylamide compound crosslinked polymer obtained in Example 3, Example 11 except that the N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -acrylamide compound crosslinked polymer obtained in Example 2 was used. When an electrode was produced in the same manner as described above, very small cracks were observed on a part of the coated surface of the current collector. In addition, it was 272 micrometers when the film thickness was measured like Example 7. FIG.

  According to the present invention, N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide capable of having a high radical concentration, and a method for producing the same, Provided are an N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer, and an electrode for a secondary battery. be able to.

Claims (8)

N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide represented by the following formula (1) , ethylene glycol di (meth) acrylate, Group consisting of 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate N, N-bis- (2,2,6,6-tetramethyl-piperidine-N-oxyl-) obtained by polymerizing in the presence of at least one cross-linking agent selected from nitroxides 4-yl) -amine- (meth) acrylamide compound cross-linked polymer.

In formula (1), R represents a hydrogen atom or a methyl group. As a copolymer component (meth) N according to claim 1, containing an acrylic acid ester, N- bis - (2,2,6,6-tetramethyl - piperidine -N- oxyl-4-yl) - amine - (Meth) acrylamide compound cross-linked polymer. (Meth) acrylic acid ester from hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate The N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) according to claim 2 , which is at least one selected from the group consisting of Acrylamide compound cross-linked polymer. The content ratio of (meth) acrylic acid ester is 0 to 0 with respect to 1 mol of N, N-bis- (2,2,6,6-tetramethyl-piperidin-4-yl) -amine- (meth) acrylamide. 4. N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound according to claim 2 or 3 in a proportion of .25 mol Cross-linked polymer. The N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) according to any one of claims 1 to 4 , which is polymerized by a suspension polymerization method. -Amine- (meth) acrylamide compound cross-linked polymer. N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl)-according to any one of claims 1 to 4 , which is polymerized by an emulsion polymerization method. Amine- (meth) acrylamide compound cross-linked polymer. N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl)-according to any one of claims 1 to 4 , which is polymerized by a solution polymerization method. Amine- (meth) acrylamide compound cross-linked polymer. N, N-bis- (2,2,6,6-tetramethyl-piperidin-N-oxyl-4-yl) -amine- (meth) acrylamide compound cross-linked polymer according to any one of claims 1 to 7. Rechargeable battery electrode.