Phenothiazine derivative compounds and their production method

Abstract

To provide a phenothiazine derivative compound that can be easily copolymerized with a polymerizable unsaturated monomer, and a production method thereof.SOLUTION: The phenothiazine derivative compound is represented by general formula [I], where R1 is C1-20 monovalent hydrocarbon, and R2 and R3 are C1-5 divalent aliphatic hydrocarbon.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a phenothiazine derivative compound and a method for producing the same, and more particularly to a phenothiazine derivative compound having a polymerizable unsaturated group and a method for producing the same. [Background technology]

[0002] Regulations on the amount of carbon dioxide and NOx gas emitted by internal combustion engines, such as automobile engines, are becoming increasingly strict. As a response to these trends, automobile engines are required to have higher output, higher thermal efficiency, and reduced and harmless exhaust gases, and the temperature inside the engine compartment is on the rise. Accordingly, polymeric materials such as rubber and plastics used around the engines are required to have even higher heat resistance.

[0003] As a specific example, vehicles equipped with turbocharger systems aimed at improving engine fuel efficiency are becoming more and more common. Because the air guided from the turbocharger to the intercooler and engine is at high temperature and pressure, the rubber hose material that transports this air is required to have high heat resistance.

[0004] As described above, in response to the demand for higher temperatures and longer life for the polymeric materials used in automobile engines, it is common practice to add appropriate antioxidants to rubber product components to improve their heat resistance.

[0005] As the antioxidant, a phenol-based antioxidant or an amine-based antioxidant is used, and in particular, an amine-based antioxidant is used for rubber members used in higher temperature environments.

[0006] For example, in the case of acrylic rubber, an amine-based antioxidant, typically 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, is used as the antioxidant (Patent Documents 1 to 6).

[0007] However, even the above-mentioned amine-based antioxidants cannot fully satisfy the recent demands for heat resistance.

[0008] In recent years, phenothiazine-based antioxidants have been considered to be effective as antioxidants for rubber materials, and Patent Document 7 describes a rubber material that is excellent in vulcanization properties, mechanical properties, and heat aging properties and is particularly suitable for use as vibration-proof rubber, which contains (A) a diene rubber, (B) a bismaleimide compound, and (C) the following phenothiazine compound. TIFF0007605621000001.tif28166R 1 , R 2 : Hydrogen atom, optionally substituted with an aromatic ring C1-C8 alkyl group Alkoxy group, halogen atom, cyano group R 3 : Hydrogen atom, C1-C6 linear or cyclic alkyl group vinyl group, aromatic group m, n: 0 to 2 Phenothiazine compounds in which the sulfur atom at the 5-position is -SO2- are also known and are described in, for example, Patent Document 8.

[0009] Patent Document 8 describes a fused heterocyclic compound represented by the following general formula and an organic material composition containing the same, and states that it is possible to impart high processing stability, heat resistance, and long life to organic materials such as polymers that are susceptible to oxidative, thermal, or light-induced degradation. TIFF0007605621000002.tif30166Y: Chemical single bond, -S(=O)-, -SO2- R a , R b C1 to C which may have a substituent 30 organic group Z a , Z b : Chemical single bond, -SO2- X 1 , X 2 : Hydrogen atom, halogen atom, alkyl group, cyano group, Nitro group, -OR 1, -O-CO-R 1 , -CO-OR 1 , -O-CO-OR 1 , -NR 2 R 3 , -NR 2 -CO-R 1 , -CO-NR 2 R 3 , -O-CO-NR 2 R 3 , n, m: 0~2, but one of them is not 0

[0010] As a countermeasure, increasing the molecular weight and melting point of amine-based antioxidants has been investigated, but this approach has problems such as reduced dispersibility in rubber and reduced migration within the rubber.

[0011] Furthermore, for the purpose of preventing the volatilization of antioxidants and extending the service life of rubber parts in high-temperature environments, antioxidants having polymerizable unsaturated groups have been marketed.

[0012] For example, Nocrac G-1 (Ouchi Shinko Chemical Industry Co., Ltd.) and APMA (Seiko Chemical Industry Co., Ltd.) are exemplified as such compounds (Non-Patent Documents 1 and 2). TIFF0007605621000003.tif33170Nocrac G-1 APMA

[0013] However, in the case of the above antioxidants, the radical polymerization inhibitory effect of the diphenylamino group makes it practically difficult to carry out radical copolymerization with a polymerizable unsaturated monomer (Patent Document 9).

[0014] In addition, several methods have been disclosed for introducing a diphenylamino structure into a polymer by a modification reaction of an elastomeric polymer. For example, a method of hydroformylating the side chain of an elastomer having an olefin-based unsaturated group and then introducing a diphenylamino group (Patent Document 10) and a method of adding maleic anhydride to a diene copolymer in the presence of a free radical generator and then introducing a diphenylamino group (Patent Document 11) are known. However, these methods require an additional modification step of introducing a diphenylamino group after producing the base copolymer, and are not practical in terms of production costs. [Prior art documents] [Patent documents]

[0015] [Patent Document 1] Japanese Patent Application Publication No. 11-21411 [Patent Document 2] WO 2007 / 005458 A1 [Patent Document 3] JP 2010-254579 A [Patent Document 4] WO 2006 / 001299 A1 [Patent Document 5] JP 2011-032390 A [Patent Document 6] WO 2011 / 58918 A1 [Patent Document 7] JP2015-227402A [Patent Document 8] WO 2011 / 093443 A1 [Patent Document 9] JP 2009-209268 A [Patent Document 10] Japanese Patent Application Publication No. 4-264106 [Patent Document 11] Japanese Patent Application Publication No. 5-230132 [Non-patent literature]

[0016] [Non-Patent Document 1] Rubber Chem Technol., Vol. 46, p. 106(1973) [Non-Patent Document 2] Rubber Chem Technol., Vol. 52, p. 883 (1979) Summary of the Invention [Problem to be solved by the invention]

[0017] An object of the present invention is to provide a novel phenothiazine derivative compound which can be easily copolymerized with a polymerizable unsaturated monomer and a process for producing the same. [Means for solving the problem]

[0018] The first object of the present invention is to provide a compound represented by the general formula TIFF0007605621000004.tif34166 (where R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each of the above formulas is independently a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms.

[0019] The second object of the present invention is to provide a compound represented by the general formula TIFF0007605621000005.tif36166 (where R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 2 is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms) is treated with a compound represented by the general formula TIFF0007605621000006.tif35159 (where X is a chlorine atom, a bromine atom, or an iodine atom, and R 3 The above-mentioned object can be attained by a method for producing a phenothiazine derivative compound, comprising reacting a compound represented by the following formula (I): Effect of the Invention

[0020] Unlike conventional polymerizable amine-based antioxidants, the phenothiazine derivative compound [I] according to the present invention has an alkylated amino group (NHAr2) at the 10-position, and thus inhibits radical polymerization, facilitating copolymerization with various polymerizable unsaturated monomers.

[0021] It is also speculated that during the processing stage (primary crosslinking, secondary crosslinking) or during actual use after processing, the alkyl group at the 10-position decomposes, liberating the amino group (HNAr2), which exerts an anti-thermal aging effect.

[0022] The elastomeric polymer material in which the phenothiazine derivative compound of the present invention is copolymerized can prevent the volatilization of the anti-aging component due to heat or the extraction of the anti-aging component by a liquid medium such as oils and fats or organic solvents, and as a result, enables the rubber parts to have a longer life under various deterioration environments.

[0023] In addition, compared to conventional amine-based antioxidants, it can also suppress the decrease in elongation at break (hardening deterioration) that accompanies crosslinking or changes in the molecular structure of various elastomeric polymer materials in high-temperature environments. Loss of rubber elasticity, as typified by elongation at break, can lead to reduced sealing performance, destruction, and surface cracks in rubber parts, so maintaining elongation is important.

[0024] Thus, the acrylic rubber copolymerized with the phenothiazine derivative compound of the present invention, particularly the acrylic rubber containing ethyl acrylate as the main component, effectively solves the above problem and has improved resistance to heat aging. [Brief description of the drawings]

[0025] [Figure 1] 1 is a diagram showing the 100% modulus change rate of a cross-linked acrylic rubber (solid line: Example 3, dashed line: Comparative Example 2, and dashed dotted line: Comparative Example 3). [Diagram 2] 1 is a diagram showing the rate of change in strength at break of a cross-linked acrylic rubber (solid line: Example 3, dashed line: Comparative Example 2, dashed dotted line: Comparative Example 3). [Diagram 3]1 is a diagram showing the rate of change in elongation at break of a cross-linked acrylic rubber (solid line: Example 3, dashed line: Comparative Example 2, dashed dotted line: Comparative Example 3). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] In the phenothiazine derivative compound represented by the general formula [I], R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0027] Specific examples of the aliphatic hydrocarbon group include primary hydrocarbon groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-undecyl group, an n-pentadecyl group, and an n-heptadecyl group; secondary hydrocarbon groups such as an isopropyl group, a 2-butyl group, a 2-pentyl group, a 3-pentyl group, a 2-hexyl group, a 3-hexyl group, a 2-heptyl group, a 3-heptyl group, a 4-heptyl group, a 2-octyl group, a 3-octyl group, and a 4-octyl group; tertiary hydrocarbon groups such as a tertiary butyl group, a 1,1-dimethyl-1-propyl group, a 1,1-dimethyl-1-butyl group, a 1,1-dimethyl-1-pentyl group, a 1,1-dimethyl-1-hexyl group, a 3-methyl-3-pentyl group, a 3-ethyl-3-pentyl group, and a 3-methyl-3-hexyl group; alicyclic hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-methyl-1-cyclopentyl group, and a 1-methyl-1-cyclohexyl group; Examples of the alkyl group include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, such as a 1-adamantyl group.

[0028] Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, and an anthranyl group.

[0029] R 2 and R 3are each independently a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group.

[0030] The method for producing the compound represented by the general formula [I] is not particularly limited, but it can be easily produced from inexpensive raw materials, for example, by the following method. TIFF0007605621000007.tif49166

[0031] [Step 1] N-alkylation reaction of phenothiazine: (A) → (B) In the N-alkylation of phenothiazine, an alkyl halide can be used as the alkylating agent, such as an alkyl chloride, an alkyl bromide, or an alkyl iodide.

[0032] The amount of the alkyl halide used is in the range of about 1 to 2 moles per mole of phenothiazine.

[0033] The reaction is carried out by reacting phenothiazine with a base such as potassium tert-butoxide or sodium hydride, followed by the reaction with an alkylating agent. Potassium tert-butoxide or sodium hydride is used in an amount of about 1 to 2 moles per mole of phenothiazine.

[0034] As the reaction solvent, N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, dimethylsulfoxide, etc. can be used.

[0035] The reaction of phenothiazine with a base is carried out at about 0 to 10°C, and the N-alkylation is carried out at about 0 to 60°C.

[0036] [Step 2] Introduction of a hydroxyalkyl group: (B) → (C) There is no particular limitation on the method for introducing a hydroxyalkyl group into phenothiazine, but it can be carried out, for example, by formylation followed by reduction.

[0037] As the formylating agent, N-monoalkylformamide / phosphoryl chloride, N,N-dialkylformamide / phosphoryl chloride, N-methylformanilide / phosphoryl chloride, etc. can be used, and N,N-dimethylformamide / phosphoryl chloride [POCl3] is commonly used.

[0038] As the solvent, a chlorine-containing hydrocarbon solvent such as metadichlorobenzene, chloroform, or 1,2-dichloroethane, or N,N-dimethylformamide is used. The reaction is carried out at about 0 to 100°C.

[0039] The reduction reaction of the aldehyde group is carried out using sodium borohydride, which is used in an amount of about 1 to 10 moles, preferably about 1 to 5 moles, per mole of the aldehyde group-containing compound.

[0040] As the solvent, methanol, ethanol, tetrahydrofuran, etc. can be used.

[0041] The reaction temperature is about 0 to 50°C, preferably about 0 to 30°C.

[0042] [Step 3] Oxidation of sulfur atom: (C) → (II) The oxidizing agent used in the oxidation reaction is metachloroperbenzoic acid, peracetic acid, or acetic acid / hydrogen peroxide. The amount of the oxidizing agent used is about 2 to 10 moles per mole of compound (C).

[0043] Examples of reaction solvents include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane and octane, chlorine-containing solvents such as dichloromethane and chlorobenzene, acetic acid, etc. These solvents can be used alone or in combination of two or more.

[0044] The reaction is carried out at a temperature within the range of about 0 to 150°C, preferably about 20 to 100°C.

[0045] [Step 4] Introduction of a polymerizable unsaturated group: (II) → (I) The desired phenothiazine derivative compound (I) can be produced by reacting compound (II) with compound (III).

[0046] The amount of compound (III) used is within the range of about 1 to 3 moles, preferably about 1 to 2 moles, per mole of compound (II).

[0047] 1 mole of compound (II) is reacted with 1 to 2 moles of a basic compound such as sodium hydride or potassium tert-butoxide, and then 1 mole of compound (II) is reacted with 1 to 2 moles of compound (III).

[0048] As the reaction solvent, N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, dimethylsulfoxide, etc. can be used.

[0049] The first stage reaction is carried out at about 0 to 20° C., preferably 0 to 10° C. The second stage reaction is carried out at about 0 to 100° C., preferably about 20 to 80° C.

[0050] In copolymerization of the phenothiazine derivative compound [I] of the present invention with other polymerizable unsaturated monomers, the compound [I] is used in an amount of about 0.1-5 parts by weight, preferably about 0.3-3 parts by weight, based on 100 parts by weight of the polymerizable unsaturated monomer. If the amount is less than this amount, sufficient antiaging effect cannot be expected. On the other hand, if the amount is more than this amount, the improvement of antiaging effect cannot be expected, and it is uneconomical.

[0051] The application range of the above phenothiazine derivative compound [I] is not particularly limited so long as it is an elastomeric polymer material produced by radical polymerization.

[0052] Acrylic copolymers are produced by a general copolymerization method for acrylic rubber. The copolymerization reaction can be carried out by any method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, etc., but the emulsion polymerization or suspension polymerization is preferably used, and the reaction is carried out at a temperature of about -10 to 100°C, preferably about 5 to 80°C.

[0053] As the polymerization initiator for the reaction, organic peroxides or hydroperoxides such as benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, and p-methylene hydroperoxide, diazo compounds such as azobisisobutyronitrile and azobisisobutylamidine, and peroxide salts such as ammonium salts represented by ammonium persulfate, sodium salts, and potassium salts are used alone or as redox systems.

[0054] As an emulsifier particularly preferred for use in emulsion polymerization, an anionic or nonionic surfactant is used in the form of an aqueous solution, the pH of which is adjusted with an acid or base as necessary, and which is buffered with an inorganic salt.

[0055] The polymerization reaction is continued until the conversion rate of the monomer mixture reaches 90% or more. The obtained aqueous latex is coagulated by a salt-acid coagulation method, a method using a salt such as calcium chloride, magnesium sulfate, sodium sulfate, or ammonium sulfate, a method using a boron compound such as boric acid or borax, a thermal coagulation method, or a freeze coagulation method, and the obtained copolymer is thoroughly washed with water and dried. This acrylic rubber has a Mooney viscosity ML of about 5 to 100, preferably about 20 to 80. 1+4 (100°C).

[0056] Other specific examples of elastomeric copolymers include styrene-butadiene rubber (SBR), chloroprene rubber (CR), acrylic rubber (ACM), ethylene-vinyl acetate rubber (EVA), nitrile rubber (NBR), hydrogenated nitrile rubber (H-NBR), ethylene-methyl acrylate rubber (AEM), and the like. EXAMPLES

[0057] The present invention will now be described with reference to examples.

[0058] Example 1 Preparation of compound (f) TIFF0007605621000008.tif38170Compound (f) was produced by the following method. TIFF0007605621000009.tif48166 [1st step] (a) → (b): In a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, a dropping funnel, a nitrogen gas inlet tube and an outlet tube, 40.0 g (201 mmol) of phenothiazine and 200 ml of N,N-dimethylformamide were added, and the temperature in the system under a nitrogen atmosphere was cooled to 5°C or less. While keeping the temperature in the system at 10°C or less, 7.2 g (300 mmol) of sodium hydride was added and reacted for 1 hour. While keeping the temperature in the system at 20°C or less, 34.2 g (241 mmol) of iodomethane was added dropwise, and the reaction was continued for another 1 hour. After the reaction was completed, the reaction mixture was added to a saturated aqueous sodium chloride solution. The precipitated colorless solid was filtered and dissolved in ethyl acetate. After washing with a saturated aqueous sodium chloride solution, the organic layer was dried over anhydrous magnesium sulfate, and then the insoluble matter was filtered. Volatile components were distilled off from the filtrate under reduced pressure, and 45.9 g of crude product was obtained (crude yield 107%). Recrystallization from ethanol gave 40.5 g (yield 94%) of 10-methyl-10H-phenothiazine (b) as colorless needle crystals. TIFF0007605621000010.tif32170 1 H NMR (400MHz, Acetone-d6, δ ppm): 3.39 (s, 3H, NC H 3) 6.91-6.98 (m, 4H, Ar) 7.14 (dd, J=7.6Hz, J=1.6Hz, 2H, Ar) 7.21 (td, J=7.6Hz, J=1.6Hz, 2H, Ar)

[0059] [Second step] (b) → (c): 210 ml of N,N-dimethylformamide was added to a 500 ml four-neck flask equipped with a magnetic stirrer, a dropping funnel, a thermometer, a gas inlet, a gas outlet, and a reflux condenser. While maintaining the internal temperature of the system under a nitrogen atmosphere at 10°C or less, 129.4 g (844 mmol) of phosphoryl chloride was added dropwise, and the reaction was continued for another 30 minutes. Next, 30 g (141 mmol) of N-methyl-10H-phenothiazine obtained in the first step was added, and the reaction was continued at 60°C for 24 hours. After the reaction was completed, the contents were poured into an aqueous sodium acetate solution, and sodium bicarbonate was added for neutralization. The product was extracted from the resulting aqueous solution using ethyl acetate, and the organic layer was washed once with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate, and insoluble matter was filtered off, and then volatile components were distilled off from the filtrate under reduced pressure to obtain 33.5 g of crude product (crude yield 98%) as a red oily substance. The low Rf components were removed by column chromatography (carrier: Wakogel C300) using ethyl acetate as an eluent to obtain 33.2 g (98% yield) of the crude product as a yellow solid. Further recrystallization using ethyl acetate gave 30.1 g (88% yield) of 10-methyl-10H-phenothiazine-3-carbaldehyde as a yellow crystal. TIFF0007605621000011.tif38170 1 H NMR (400MHz, Acetone d6, δ ppm): 3.49 (s, 3H, NC H 3) 7.00-7.06 (m, 2H, Ar) 7.10 (d, J=8.4Hz, 1H, Ar) 7.15-7.19(m, 1H, Ar) 7.22-7.28(m, 1H, Ar) 7.61(d, J=1.6Hz, 1H, Ar) 7.75(dd, J=8.4Hz, J=1.6Hz, 1H, Ar) 9.85(s, 1H, -C H O)

[0060] [3rd step] (c)→(d): In a 2000 ml four-neck flask equipped with a magnetic stirrer, a thermometer, a gas outlet, and a reflux condenser, 20 g (83 mmol) of the compound (c) obtained in the above second step and 800 ml of methanol were placed. While maintaining the internal temperature at 30° C. or less, 3.1 g (83 mmol) of sodium borohydride was slowly added and reacted for another hour. Methanol was distilled off under reduced pressure, and the residue was dissolved in methyl isobutyl ketone. The organic layer was washed once with a saturated aqueous sodium chloride solution, and then the organic layer was dried over anhydrous magnesium sulfate, after which the insoluble matter was filtered off. Volatile components were distilled off from the filtrate under reduced pressure, and 19.9 g (crude yield 99%) of the crude product was obtained as a pale yellow solid. Recrystallization was performed using methanol, and 18.3 g (yield 91%) of 3-hydroxymethyl-10-methyl-10H-phenothiazine (d) was obtained as a pale yellow solid. TIFF0007605621000012.tif32170 1 H NMR (400MHz, Acetone d6, δ ppm): 3.38 (s, 3H, NC H 3) 4.08 (t, J=6.0Hz, 1H, -CH2O H ) 4.53 (d, J=6.0Hz, 2H, -C H 2OH) 6.87-6.98 (m, 3H, Ar) 7.10-7.23 (m, 4H, Ar)

[0061] [4th step] (d)→(e): Into a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a reflux condenser, 17.0 g (70 mmol) of the compound (d) obtained in the third step, 150 ml of acetic acid, and 19.0 g (168 mmol) of 30% hydrogen peroxide were added, and the mixture was reacted at 60° C. for 1 hour and at 80° C. for 1 hour. Acetic acid was distilled off from the reaction mixture under reduced pressure, and the residue was recrystallized using methanol to obtain 17.8 g (yield 92%) of 3-hydroxymethyl-10-methyl-10H-phenothiazine-5,5-dioxide (e) as a pale yellow solid. TIFF0007605621000013.tif381701 H NMR (400MHz, Acetone d6, δ ppm): 3.80 (s, 3H, -NC H 3) 4.43 (t, J=6.0Hz, 1H, -CH2O H ) 4.75 (d, J=6.0Hz, 2H, -C H 2OH) 7.35 (t, J=7.6Hz, 1H, Ar) 7.56 (t, J=8.4Hz, 2H, Ar) 7.68-7.76 (m, 2H, Ar) 8.00-8.05 (m, 2H, Ar)

[0062] [5th ​​step] (e) → (f): In a 300 ml four-neck flask equipped with a magnetic stirrer, a thermometer, a reflux condenser, a gas inlet tube, and a gas outlet tube, 12.0 g (52 mmol) of compound (e) and 120 ml of N,N-dimethylformamide were placed, and the internal temperature was cooled to 10°C or less under a nitrogen atmosphere. 1.9 g (79 mmol) of sodium hydride was added and reacted for 1 hour, then 9.5 g (62 mmol) of 4-chloromethylstyrene was added and reacted at 60°C for 1 hour. The resulting reaction mixture was added to a saturated aqueous sodium chloride solution, and the product was extracted with ethyl acetate. The organic layer was washed once with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. After filtering off the insoluble matter, volatile components were distilled off from the filtrate under reduced pressure to obtain 22.1 g of crude product. Column chromatography (carrier: Wakogel C300) was performed using a first eluent (n-hexaneacetic acid) and a second eluent (ethyl acetate) to obtain 15.6 g (yield 86%) of compound (f) as a pale yellow viscous liquid. TIFF0007605621000014.tif38170 1 H NMR (400MHz, Acetone d6, δ ppm): 3.59 (s, 3H, NC H 3) 4.54 (d, 2H, J=7.6Hz, PTZ-CH2O-C H 2-Ph) 4.60 (d, 2H, J=6.0Hz, PTZ-C H 2O-CH2-Ph) 5.16-5.23 (m, 1H, C H 2=CH-Ph (for phenyl group) Trans)) 5.73-5.82 (m, 1H, C H 2=CH-Ph (for phenyl group) sis)) 6.66-6.76 (m, 1H, CH2=C H -Ph) 7.22-7.46 (m, 7H, Ar) 7.55-7.62 (m, 2H, Ar) 7.97-8.06 (m, 2H, Ar)

[0063] Example 2 A separable flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube, and a Dimroth condenser Inside, Water 187 parts by weight Sodium lauryl sulfate 2 〃 Polyoxyethylene lauryl ether 2 Same Charged monomer mixture Ethyl acrylate [EA] 97.4 〃 Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (f) of Example 1 1.0 After thoroughly removing oxygen from the system by replacing the chamber gas, Sodium formaldehyde sulfoxylate 0.008 parts by weight (Fujifilm Wako Pure Chemical products Rongalit) Tertiary butyl hydroperoxide 0.0047 〃 (NOF Products Perbutyl H-69) The polymerization reaction was started at room temperature by adding the above, and the reaction was continued until the polymerization conversion rate reached 90% or more. The obtained aqueous latex was coagulated with a 10% by weight aqueous solution of sodium sulfate, washed with water, and dried to obtain acrylic rubber A. The Mooney viscosity PML of the obtained acrylic rubber A was l+4(100℃) was 34.

[0064] The mole fraction composition is: l The formula was calculated from H-NMR (400 MHz, Acetone d6, δ ppm) using the following equation: Compound (f): 0.23 mol%, EA+MBF: 99.77 mol% It was. A: integral value of the signal from 6.7 to 8.3 ppm B: Integrated value of the signal from 3.2 to 5.0 ppm Compound (f) (mol%)=200×A / (11B-5A) EA+MBF(mol%)=100-compound (f)(mol%) The approximate weight fraction composition is calculated using the following formula: Compound (h): 0.9% by weight, EA+MBF: 99.1% by weight. Compound (f) (weight%)=(Compound (f) (mol%)×391.5×100) / [Compound (f) (mol%) × 391.5 + (EA + MBF (mol%)) × 100.8)] EA+MBF(wt%)=100-compound(f)(wt%)

[0065] Comparative Example 1 A copolymerization reaction was carried out in the same manner as in Example 2, except that the following monomer mixture was used, to obtain an acrylic rubber B. Mooney viscosity PML of the obtained acrylic rubber B l+4 (100℃) was 33. Charged monomer mixture Ethyl acrylate [EA] 98.4 parts by weight Mono-n-butyl fumarate [MBF] 1.6 〃

[0066] Example 3 Acrylic rubber A 100 parts by weight FEF Carbon Black (Tokai Carbon Products Seast GS0) 60 〃 Stearic acid (Miyoshi Oil Products TST) Polyoxyethylene stearyl ether phosphate 0.5 〃 (Toho Chemical Industry Co., Ltd. Phosphanol RL-210) Crosslinking accelerator (Vulcofac ACT55, Safic-Alcan) 1 Same Hexamethylenediamine carbamate 0.6 〃 (Unimatec product Cheminox AC6F) Of the above components, acrylic rubber A, FEF carbon black, stearic acid and polyoxyethylene stearyl ether phosphate were mixed in a bumper mixer. The remaining components were mixed with the above hydrate using an open roll to obtain an acrylic rubber composition.

[0067] This was subjected to primary crosslinking at 180°C for 8 minutes using a 100-ton press molding machine and oven crosslinking (secondary crosslinking) at 175°C for 4 hours, yielding a sheet-like crosslinked product with a thickness of approximately 2 mm and a cylindrical crosslinked product with a diameter of approximately 29 mm and a height of approximately 12.5 mm. The crosslinking characteristics of the acrylic rubber composition and the physical properties of the crosslinked product were measured as follows. Mooney scorch test: JIS K6300 compliant (125℃) Using a Mooney Viscometer AM-3 manufactured by Toyo Seiki Seisakusho, Measure Mooney viscosity (ML, min) and scorch time (t5) values Cross-linking test: JIS K6300-2 compliant (180°C, 12 minutes) Using a rotorless rheometer RLR-3 manufactured by Toyo Seiki Seisakusho, ML, MH, Measure the values ​​of tc(10) and tc(90) ML: Minimum torque MH: Maximum torque tc(10): Time required for the cross-linking torque to reach ML + (MH-ML) × 0.1 tc(90): Time required for the cross-linking torque to reach ML+(MH-ML)×0.9 Normal state physical properties: Compliant with JIS K6251 and JIS K6253 Air heating aging test: JIS K6257 compliant (175℃: 70 hours, 250 hours, 500 hours, 750 hours, 1000 hours) Compression set: JIS K6262 compliant (175℃: 70 hours)

[0068] Comparative Example 2 In Example 3, acrylic rubber B was used instead of acrylic rubber A.

[0069] Comparative Example 3 In Comparative Example 2, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Da Of this, 1 part by weight of Nocrac CD (a Shinko Chemical Industry product) was added.

[0070] The results obtained in Example 3 and Comparative Examples 2 and 3 above are shown in the following table. table Measurement results Fruit-3 ratio-2 ratio-3 Mooney scorch test (125℃) ML min (pts) 71 72 70 t5 (min) 3.2 3.0 3.5 Cross-linking test (180℃) tc(10) (min) 0.55 0.51 0.51 tc(90) (min) 5.65 5.31 5.30 ML (N m) 0.28 0.27 0.27 MH (N m) 0.96 1.04 1.02 Normal physical properties Hardness (Duro A) 66 67 66 100% Modulus (MPa) 5.6 5.6 5.1 Breaking strength (MPa) 17.7 16.8 16.0 Elongation at break (%) 240 230 240 Heat aging test (175℃, 70 hours) Hardness change (Duro A) +7 +8 +6 100% Modulus Change (%) +7 -13 -17 Breaking strength change rate (%) -10 -13 -14 Elongation change at break (%) -1 +10 +15 Heat aging test (175℃, 250 hours) Hardness change (Duro A) +7 +8 +6 100% Modulus Change (%) -20 -39 -37 Breaking strength change rate (%) -38 -43 -37 Elongation change at break (%) +6 +29 +36 Heat aging test (175℃, 500 hours) Hardness Change (Duro A) +16 +11 +13 100% Modulus Change (%) -21 -39 -43 Breaking strength change rate (%) -60 -67 -61 Elongation change at break (%) +3 +12 +46 Heat aging test (175℃, 750 hours) Hardness Change (Duro A) +22 +25 +19 100% Modulus Change (%) +11 +2 -29 Breaking strength change rate (%) -62 -64 -70 Elongation change at break (%) -35 -37 +17 Heat aging test (175℃, 1000 hours) Hardness Change (Duro A) +31 +29 +24 100% Modulus Change (%) +18 Breaking strength change rate (%) -44 -40 -62 Elongation change at break (%) -76 -79 -42 Compression set 175℃, 70 hours (%) 17 16 20

Claims

1. general formula (where R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 are each independently a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms.

2. general formula (where R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 2 is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms) with a compound represented by the following general formula (wherein X is a chlorine atom, a bromine atom or an iodine atom, and R 3 is a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms).

3. 2. The phenothiazine derivative compound according to claim 1, which is used as a polymerizable unsaturated monomer for an elastomeric copolymer.

4. The phenothiazine derivative compound according to claim 3, wherein the elastomer copolymer is an acrylic elastomer copolymer.

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