JP5148974B2 - (Meth) acrylic acid diazaadamantyl compound and method for producing the same - Google Patents

Description

  The present invention relates to a diazaadamantyl (meth) acrylate compound and a method for producing the same. More specifically, the present invention relates to a (meth) acrylic acid diazaadamantyl compound that can be used for the production of a (meth) acrylic acid polymer used as an electrode material of a secondary battery and a method for producing the same.

  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, a secondary battery using a radical compound as an electrode active material that directly contributes to an electrode reaction has been proposed for the purpose of increasing the capacity (see Patent Document 1). Examples of the radical compound include poly (2,2,6,6-tetramethyl-4-piperidinoxymethacrylate) and poly (2,2,5,5-tetramethyl-2-pyrrolidinoxymethacrylate). Further, compounds having a stable radical in the side chain of a polymer such as poly (2,2,5,5-tetramethyl-2-pyrrolinoxymethacrylate) have been proposed. Among these radical compounds, for example, the radical concentration (calculated value) of poly (2,2,5,5-tetramethyl-2-pyrrolinoxymethacrylate) having the highest radical concentration is 2.69 × 10 ²¹ radicals / g.

In addition, a polymer compound having a spiro cyclic nitroxide structure has been proposed as a radical compound having a high radical concentration (see Patent Document 2). Among the polymer compounds, the radical concentration of poly (2,2,8,8,10,10-hexamethyl-1,9-diazaspiro [5,5] -undecane acrylateoxy radical) having the highest radical concentration (calculation) Value) is 3.56 × 10 ²¹ radicals / g, and Patent Document 2 describes that the radical concentration (measured value) of this polymer compound is 3.58 × 10 ²¹ radicals / g. Yes.

  The radical concentration is one of the important indexes for realizing a secondary battery having a high energy density and a large capacity. Therefore, the radical concentration is used as an electrode active material including a radical compound having a high radical concentration. The emergence of various radical compounds that can be expected is awaited.

JP 2002-304996 A JP 2006-45310 A

  The present invention provides a monomer raw material for producing a (meth) acrylic acid polymer capable of having a high radical concentration as a radical compound useful as an electrode material for a secondary battery, and a method for producing the same. With the goal.

  The present invention relates to a general formula (1):

(In the formula, R represents a hydrogen atom or a methyl group.) A (meth) acrylic acid diazaadamantyl compound represented by: The (meth) acrylic acid diazaadamantyl compound has the formula (2):

Or a method of esterifying this with (meth) acrylic acid halide using 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol represented by the formula: And transesterification.

  In the present invention, acrylic acid and methacrylic acid are referred to as (meth) acrylic acid, and methacrylate and acrylate are referred to as (meth) acrylate.

  According to the present invention, it is possible to provide a monomer raw material for producing a (meth) acrylic acid polymer that can be used as an electrode active material for a secondary battery and that can have a high radical concentration, and a method for producing the same. it can.

  The (meth) acrylic acid diazaadamantyl compound according to the present invention is a novel compound represented by the following general formula (1).

In general formula (1), R represents a hydrogen atom or a methyl group.
The (meth) acrylic acid diazaadamantyl compound according to the present invention includes, for example, the following formula (2):

A method of esterifying this with 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol represented by (meth) acrylic acid halide (hereinafter referred to as "Production Method 1") Or a method of transesterifying with a (meth) acrylic acid ester compound (hereinafter sometimes referred to as “production method 2”).

  3,5,7-trimethyl-2,6-diazaadamantane-1-methanol is, for example, 1,5,7-trimethyl-9-azabicyclo [3.3.1] nonane- It can be produced by a known method using 3-one (Bull Soc Chim Fr, 130, 299-303 (1993)) or the like.

  That is, first, 1,5,7-trimethyl-9-azabicyclo [3.3.1] nonane-3-one is reacted with a cyanide compound such as potassium cyanide and sodium cyanide in the presence of a base such as ammonium carbonate. 1,5,7-trimethylspiro [9-azabicyclo (3.3.1) nonane-3,4′-imidazolidine-2 ′, 5′-dione] is obtained. Next, by reacting this with a base such as barium hydroxide, 3-amino-1,5,7-trimethyl-9-azabicyclo [3.3.1] -nonane-, which is a ring-opened amino acid compound, is obtained. 3-carboxylic acid is obtained. Further, this is reacted with methanol in the presence of an acid such as hydrochloric acid to give methyl ester of 3-amino-1,5,7-trimethyl-9-azabicyclo [3.3.1] -nonane-3-carboxylic acid. And then ring-closing by reacting with a halogen compound such as bromine in the presence of a base such as sodium hydroxide to produce 3,5,7-trimethyl-2,6-diazaadamantane-1-carboxylic acid. Get the acid. Then, 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol can be obtained by reducing this using a reducing agent such as lithium aluminum hydride and lithium borohydride.

  The (meth) acrylic acid diazaadamantyl compound according to the present invention uses the 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol thus obtained, for example, the following 2 It can be manufactured by various methods.

Manufacturing method 1
In this production method, a 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol is esterified with a (meth) acrylic acid halide to produce a (meth) acrylic acid diazaadamantyl compound. be able to.

  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 proportion of (meth) acrylic acid halide used is preferably 0.8 to 1.5 moles per mole of 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol. The 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 esterification include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; aliphatic nitriles such as acetonitrile, propionitrile and butyronitrile; Aromatic nitriles such as nitrile 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 the like. Among these, ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran are preferably used.

  The amount of the solvent used is 100 parts by weight of 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol, from the viewpoint of smoothly proceeding the reaction and obtaining an effect sufficient for the amount of use. The amount is preferably 50 to 5000 parts by weight, and more preferably 100 to 3000 parts by weight.

  Moreover, you may add a base in order to advance esterification more smoothly. Examples of the base include amine compounds such as trimethylamine, triethylamine, and triphenylamine. These bases may be used individually by 1 type, or may use 2 or more types together. The use ratio of the base is preferably 1.5 mol or less, and 1.1 mol or less with respect to 1 mol of 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol. It is more preferable that

  As an operation method of esterification, for example, a predetermined amount of 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol, a solvent and, if necessary, a base are mixed and then stirred. Examples include a method of reacting while dropping (meth) acrylic acid halide. 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 thus obtained (meth) acrylic acid diazaadamantyl compound can be easily isolated by filtration, concentration or the like.

Manufacturing method 2
In this production method, 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol is transesterified with a (meth) acrylic acid ester compound to produce a (meth) acrylic acid diazaadamantyl compound. can do.

  Examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl and (meth) acrylic acid-n-butyl. Among these, methyl (meth) acrylate and ethyl (meth) acrylate are preferably used.

  The use ratio of the (meth) acrylic acid ester compound is preferably 1 to 10 moles per mole of 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol.

  In transesterification, hydrocarbons such as benzene, toluene, xylene, hexane, octane, isooctane and cyclohexane can be used as a solvent, but these solvents are not used, and the resulting alcohol is a (meth) acrylic acid ester. The reaction can be completed easily by reacting while taking out from the system by azeotropy with the compound.

  Moreover, you may use a catalyst for the purpose of advancing transesterification more smoothly. Examples of the catalyst include tetramethyl titanate, tetraethyl titanate, dibutyltin oxide and dioctyltin oxide. These catalysts may be used individually by 1 type, or may use 2 or more types together. The catalyst is used in a proportion of preferably 0.05 mol or less, and 0.005 mol or less with respect to 1 mol of 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol. It is more preferable that

  As reaction temperature, 50-160 degreeC is preferable and 80-140 degreeC is more preferable. The reaction time can be appropriately selected depending on the reaction temperature, the type of catalyst, and the like, but is usually 1 to 48 hours.

  The diazaadamantyl (meth) acrylate compound thus obtained can be easily isolated by removing the catalyst by filtration or the like and further distilling off the solvent when a solvent is used.

  The (meth) acrylic acid diazaadamantyl compound according to the present invention is a simple substance for producing a (meth) acrylic acid adamantyl polymer useful as an electrode active material for a secondary battery and having a high radical concentration. It can be used as a body material.

  As a method for producing a (meth) acrylic acid adamantyl polymer, for example, a mixture of the above (meth) acrylic acid diazaadamantyl compound and a polymerization initiator in a solvent such as toluene or n-hexane, and a surfactant. A method of mixing and dispersing in water and then heating under stirring to obtain a polymerization reaction product, which is reacted with an oxidizing agent such as peroxide to form a nitroxide can be mentioned. Moreover, the (meth) acrylic acid adamantyl polymer thus obtained can be used as an electrode of a secondary battery by binding it to a current collector such as a metal.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Production Example 1
To a 250 mL four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, was added 1,5,7-trimethyl-9-azabicyclo [3.3.1] nonan-3-one 9 .1 g (50 mmol) and 18 mL of ethanol were charged to obtain a homogeneous solution. Then, 9.6 g (100 mmol) of ammonium carbonate dissolved in 30 mL of water and 4.5 g (70 mmol) of potassium cyanide dissolved in 18 mL of water were added thereto. After removing oxygen in the system through nitrogen gas, the mixture was reacted at 50 ° C. for 144 hours, filtered, washed with 50 mL of ethanol and 50 mL of diethyl ether, dried under reduced pressure, and 1,5,7-trimethylspiro [9- 11.6 g of azabicyclo (3.3.1) nonane-3,4'-imidazolidine-2 ', 5'-dione] was obtained (yield 92%). The obtained 1,5,7-trimethylspiro [9-azabicyclo (3.3.1) nonane-3,4′-imidazolidine-2 ′, 5′-dione] was subjected to mass spectrometry by atmospheric pressure ionization. The molecular weight was 251.

Along with 5.2 g (20 mmol) of 1,5,7-trimethylspiro [9-azabicyclo (3.3.1) nonane-3,4′-imidazolidine-2 ′, 5′-dione] obtained, After charging 51 g (300 mmol) of barium oxide and 120 mL of water into a 500 mL four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, and removing oxygen in the system through nitrogen gas Reaction at 100 ° C. for 72 hours, further filtration and evaporation to dryness to give 3-amino-1,5,7-trimethyl-9-azabicyclo [3.3.1] -nonane-3-carboxylic acid. 5 g was obtained (yield 99%). The obtained 3-amino-1,5,7-trimethyl-9-azabicyclo [3.3.1] -nonane-3-carboxylic acid was measured by H-NMR (D ₂ O) to be 2.36,2 .14, 1.93, 1.52, 1.35, and 1.07 ppm, and peaks were recognized.

The obtained 3-amino-1,5,7-trimethyl-9-azabicyclo [3.3.1] -nonane-3-carboxylic acid (4.5 g, 20 mmol) and methanol (150 mL) were mixed with a stirrer and nitrogen gas. A 500 mL four-necked flask equipped with an inlet tube, a thermometer and a reflux condenser was charged, and after removing oxygen in the system through nitrogen gas, the system was saturated at 65 ° C. with saturated hydrochloric acid gas. The mixture was reacted for 5 hours and evaporated to dryness to obtain 3.3 g of methyl ester of 3-amino-1,5,7-trimethyl-9-azabicyclo [3.3.1] -nonane-3-carboxylic acid (yield). Rate 68%). The methyl ester of 3-amino-1,5,7-trimethyl-9-azabicyclo [3.3.1] -nonane-3-carboxylic acid thus obtained was measured by H-NMR (CDCl ₃ ). 1.46, 1.23, 1.02, 0.79, and 0.50 ppm, the peaks were recognized.

The resulting 3-amino-1,5,7-trimethyl-9-azabicyclo [3.3.1] -nonane-3-carboxylic acid methyl ester 2.9 g (12 mmol) and 12 wt% sodium hydroxide 16 mL And 100 mL of cyclohexane were charged into a 500 mL four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, and oxygen in the system was removed through nitrogen gas, and then dissolved in 100 mL of cyclohexane. Bromine 3.8 g (24 mmol) was added dropwise at 0 ° C. over 1 hour 30 minutes. Then, it was reacted at 50 ° C. for 72 hours and evaporated to dryness to obtain 2.6 g of 3,5,7-trimethyl-2,6-diazaadamantane-1-carboxylic acid (yield 96%). The obtained 3,5,7-trimethyl-2,6-diazaadamantane-1-carboxylic acid was measured by H-NMR (CDCl ₃ ) and found to be 3.68, 2.16, 1.23, 1.18 ppm. It was identified from the fact that a peak was observed.

The obtained 3,5,7-trimethyl-2,6-diazaadamantane-1-carboxylic acid (2.2 g, 10 mmol) and tetrahydrofuran (200 mL) were mixed with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser. Into a 500 mL four-necked flask to obtain a homogeneous solution. Next, 3.8 g (100 mmol) of lithium aluminum hydride dissolved in 50 mL of tetrahydrofuran was added thereto. After removing the oxygen in the system through nitrogen gas, the mixture was reacted at 65 ° C. for 144 hours, concentrated under reduced pressure, dissolved in 50 mL of a chloroform-methanol mixture (volume ratio 5/1), and further dissolved in silica gel (Daiso). Made by Co., Ltd., IR-60-63 / 210) 300 mL of chloroform-methanol mixture (volume ratio 5/1) suspended in 1.2 L and purified by passing through a 1 L column, dried at 25 ° C. under reduced pressure As a result, 1.3 g of 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol was obtained (yield 60%). When the obtained 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol was measured by H-NMR (CDCl ₃ ), peaks were observed at 3.25, 1.30, and 1.20 ppm. Further, mass spectrometry by atmospheric pressure ionization method revealed that the molecular weight was 210, so that identification was possible.

Example 1
3,5,7-trimethyl-2,6 obtained in the same manner as in Production Example 1 was added to a 100 mL four-necked flask equipped with a stirrer, nitrogen gas introduction tube, thermometer, reflux condenser and dropping funnel. -Diazaadamantane-1-methanol (2.10 g, 10 mmol), triethylamine (1.11 g, 11 mmol) and diethyl ether (30 mL) 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 1.05 g (10 mmol) of methacrylic acid chloride was added dropwise over 3 hours with stirring. Subsequently, after maintaining 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 purified by passing through a 1 L column packed with 1.2 mL of a chloroform-methanol mixture (volume ratio 5/1) 300 mL of silica gel (Daiso Co., Ltd., IR-60-63 / 210). did. The target product fraction was collected and dried under reduced pressure at 25 ° C. until a constant weight was obtained, thereby obtaining 2.64 g (yield 94.8%) of a diazaadamantyl methacrylate compound.

  When the obtained diazaadamantyl methacrylate compound was subjected to mass spectrometry by the atmospheric pressure ionization method, the molecular weight was 278.

Example 2
To a 100 mL four-necked flask with a side tube, 2.10 g (10 mmol) of 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol obtained in the same manner as in Production Example 1, After charging 4.00 g (40 mmol) of methyl acid and 0.00086 g (0.005 mmol) of tetramethyl titanate and removing oxygen in the reaction system through nitrogen gas, a reflux apparatus equipped with a 20-stage Oldershaw distillation column was prepared. Used for 6 hours transesterification. During this time, methanol produced by the reaction was removed out of the system by azeotropy with methyl methacrylate. Moreover, the temperature of the reaction liquid rose from 105 ° C to 118 ° C.

  After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 100 mL of hexane was added to the obtained crystals. Further, an appropriate amount of water was added to deactivate tetramethyl titanate, and this was filtered, and further hexane was reduced under reduced pressure. By removing, 2.75 g (yield 99.0%) of diazaadamantyl methacrylate compound was obtained.

  When the obtained diazaadamantyl methacrylate compound was subjected to mass spectrometry by the atmospheric pressure ionization method, the molecular weight was 278.

Claims (3)

General formula (1):

(In the formula, R represents a hydrogen atom or a methyl group.) A (meth) acrylic acid diazaadamantyl compound represented by: Formula (2):

General formula (1) characterized in that 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol represented by formula (1) is esterified with (meth) acrylic acid halide:

(In formula, R shows a hydrogen atom or a methyl group.) The manufacturing method of the (meth) acrylic-acid diaza adamantyl compound represented by these. Formula (2):

General formula (1) characterized by transesterifying 3,5,7-trimethyl-2,6-diazaadamantane-1-methanol represented by formula (1):

(In formula, R shows a hydrogen atom or a methyl group.) The manufacturing method of the (meth) acrylic-acid diaza adamantyl compound represented by these.