Phenothiazine derivative compounds and their production method

Abstract

To provide a novel phenothiazine derivative compound that can be easily copolymerized with polymerizable unsaturated monomer, and a manufacturing method thereof.SOLUTION: The invention provides a phenothiazine derivative compound represented by the general formula [I] in the figure. The phenothiazine derivative compound is manufactured by converting the carbonyl group of a compound represented by the general formula [II] into the vinyl group. (In the formula, R1 is a C1-20 aliphatic hydrocarbon group or aralkyl group; and R2 is H or a methyl group.)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 emissions of carbon dioxide, NOx gas, and other gases emitted by internal combustion engines, such as automobile engines, are becoming increasingly strict. In response to these trends, automobile engines are being required to have higher output, higher thermal efficiency, and reduced and harmless exhaust gases, which has resulted in a tendency for the temperature inside the engine compartment to rise. Accordingly, polymeric materials, such as rubber and plastics, used in the vicinity of engines are being 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] Here, 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 such as 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] 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.

[0009] Patent Document 7 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. TIFF0007611076000001.tif28165Y: 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] In recent years, phenothiazine-based antioxidants have been considered to be effective as antioxidants for rubber materials, and Patent Document 8 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. TIFF0007611076000002.tif27165R 1 , R 2 : Hydrogen atom, optionally substituted with an aromatic ring C1 to C8 alkyl group, Alkoxy group, halogen atom, cyano group R 3 : a hydrogen atom, a 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.

[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). TIFF0007611076000003.tif50168

[0013] However, in the case of the above antioxidants, radical copolymerization with polymerizable unsaturated monomers is practically difficult due to the radical polymerization inhibitory effect of the diphenylamino group (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.

[0015] Furthermore, a method is known in which acrylic rubber is crosslinked in the presence of 4-aminodiphenylamine (Patent Document 12). In this method, there is concern that 4-aminodiphenylamine may inhibit polyamine crosslinking to some extent. [Prior art documents] [Patent documents]

[0016] [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] WO 2011 / 093443 A1 [Patent Document 8] JP2015-227402A [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 [Patent Document 12] WO 2020 / 158132 A1 [Non-patent literature]

[0017] [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]

[0018] 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]

[0019] The object of the present invention is to provide a compound represented by the general formula [I] TIFF0007611076000004.tif29129 (where R 1 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, R 2 is a hydrogen atom or a methyl group), and this phenothiazine derivative compound is represented by the general formula [II] TIFF0007611076000005.tif28129 (where R 1 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, R 2 It is produced by converting the carbonyl group of a compound represented by the formula (wherein x is a hydrogen atom or a methyl group) into a vinyl group. Effect of the Invention

[0020] The amino group (NHAr2) at the 10-position of the phenothiazine derivative compound according to the present invention is alkylated, and therefore, unlike conventional polymerizable amine-based antioxidants, the compound has the effect of suppressing the radical polymerization inhibitory action and facilitating copolymerization with various polymerizable unsaturated monomers.

[0021] In addition, it is presumed that during the processing stage (primary crosslinking, secondary crosslinking) or during actual use after processing, the alkyl group at the 10th 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. [Brief description of the drawings]

[0023] [Figure 1] 1 is a graph showing the elongation at break of an acrylic rubber over time (solid line: Example 8, two-dot chain line: Comparative Example 2, long dashed line: Comparative Example 3). [Diagram 2] 1 is a graph showing the elongation at break of an acrylic rubber over time (solid line: Example 10, dashed dotted line: Comparative Example 4, dotted line: Example 9). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] In the phenothiazine derivative compound represented by the general formula [I], R 1 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.

[0025] 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. Examples of the aralkyl group include a benzyl group and a 1-phenylethyl group.

[0026] In the phenothiazine derivative compound represented by the general formula [I], R 2 is a hydrogen atom or a methyl group.

[0027] There is no particular limitation on the method for producing the compound represented by the general formula [I]. 2 When is a hydrogen atom, it can be easily produced from inexpensive raw materials, for example, by the following method. TIFF0007611076000006.tif82154

[0028] [Step 1] N-alkylation reaction of phenothiazine: (A) → (B) In the N-alkylation of phenothiazine, an alkyl halide such as an alkyl chloride, alkyl bromide, or alkyl iodide is used as the alkylating agent.

[0029] The amount of the alkyl halide used is in the range of about 1 to 2 moles per mole of phenothiazine.

[0030] The reaction is carried out by reacting phenothiazine with a base such as sodium amide, potassium tert-butoxide, sodium hydride, sodium hydroxide, or potassium hydroxide, and then reacting with an alkylating agent. Sodium amide, potassium tert-butoxide, or sodium hydride is used in the range of about 1 to 2 moles per mole of phenothiazine. Sodium hydroxide or potassium hydroxide is used as a highly concentrated aqueous solution, and the amount is in large excess relative to phenothiazine. In this case, benzyltriethylammonium chloride or the like may be allowed to coexist.

[0031] As the reaction solvent, for example, N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, dimethylsulfoxide, etc. can be used.

[0032] 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 80°C.

[0033] [Step 2] Introduction of formyl group: (B) → (C) There is no particular limitation on the method for introducing a formyl group into phenothiazine, but examples thereof include the Vilsmeire-Haack reaction.

[0034] As the formylating agent, for example, N-monoalkylformamide / phosphorus oxytrichloride, N,N-dialkylformamide / phosphorus oxytrichloride, N-methylformanilide / phosphorus oxytrichloride, etc. can be used, and N,N-dimethylformamide / phosphorus oxytrichloride is generally used.

[0035] As the solvent, for example, a chlorine-containing hydrocarbon solvent such as metadichlorobenzene, chloroform, 1,2-dichloroethane, or an aprotic polar solvent such as N,N-dimethylformamide is used. These solvents can be used alone or in combination of two or more. The reaction is carried out at about 0 to 100°C.

[0036] [Step 3] Reduction of formyl group: (C) → (D) The reduction reaction of the formyl group is carried out by a metal hydride or catalytic hydrogenation. Examples of metal hydrides include lithium aluminum hydride, sodium borohydride, lithium borohydride, magnesium borohydride, aluminum borohydride, calcium borohydride, and zinc borohydride. The metal hydride is used in a ratio of about 0.5 to 5 moles, preferably about 1 to 3 moles, per mole of (C). For catalytic hydrogenation, hydrogen / palladium, hydrogen / palladium carbon, hydrogen / platinum, etc. are used.

[0037] As the solvent, for example, methanol, ethanol, tetrahydrofuran, etc. can be used.

[0038] The reaction temperature is about 0 to 100°C, preferably about 0 to 60°C.

[0039] [Step 4] Oxidation of sulfur atom: (D) → (E) The oxidizing agent used in the oxidation reaction is, for example, metachloroperbenzoic acid, peracetic acid, acetic acid / hydrogen peroxide, etc. The amount of the oxidizing agent used is about 2 to 6 moles per mole of compound (C).

[0040] 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.

[0041] The reaction is carried out at a temperature within the range of about 0 to 150°C, preferably about 20 to 100°C.

[0042] The oxidation of the sulfur atom can also be carried out on phenothiazine or its alkylated derivatives, followed by the introduction of a formyl group and its reduction in the same manner.

[0043] [Step 5] Conversion of hydroxymethyl group to formyl group: (E) → (F) The conversion of a hydroxymethyl group to a formyl group can be carried out using a mild oxidizing agent. For example, it can be carried out by Swern oxidation, PCC oxidation, PDC oxidation, TPAP oxidation, Dess-Martin oxidation, TEMPO oxidation, Mukaiyama oxidation, etc. In the case of Swern oxidation, oxalyl chloride / dimethyl sulfoxide is used as the oxidizing agent. Dichloromethane is used as the solvent, and the reaction is carried out at about -80 to -60°C, and then the conversion to a formyl group is achieved by the action of a basic nitrogen-containing compound that does not have active hydrogen, such as triethylamine.

[0044] [Step 6] Conversion of formyl group to vinyl group: (F) → (G) The conversion reaction of a formyl group to a vinyl group is not particularly limited, and can be carried out by the Wittig reaction, the Peterson reaction, or the like.

[0045] In the case of the Wittig reaction, compound (F) is reacted with a phosphorus ylide compound generated from a base such as potassium tert-butoxide and an alkyltriphenylphosphonium halide such as methyltriphenylphosphonium bromide in an amount of 1 to 2 moles per mole of compound (F) at about 0 to 60° C. Tetrahydrofuran, etc. can be used as the reaction solvent.

[0046] Also, R 2 When is a methyl group, it can be easily produced from inexpensive raw materials, for example, by the following method. TIFF0007611076000007.tif80154

[0047] [Step 1] Acetylation reaction of phenothiazine: (A) → (H) Acetylation can be achieved using acetyl chloride in the presence of a Lewis acid catalyst, typically aluminum chloride.

[0048] [Step 2] Reduction of acetyl group: (H) → (I) This can be carried out in the same manner as in the reduction of formyl group (C) → (D) above.

[0049] [Step 3] Acetylation of hydroxyl group: (I) → (J) The reaction can be carried out using acetyl chloride in the presence of a basic compound, such as a nitrogen-containing compound having no active hydrogen, for example, pyridine, 4-N,N-dimethylaminopyridine, triethylamine, etc.

[0050] [Step 4] N-alkylation of phenothiazine: (J) → (K) This can be done in the same manner as above (A) → (B).

[0051] [Step 5] Oxidation of sulfur atom: (K) → (L) This can be done in the same manner as above (D) → (E).

[0052] [Step 6] Ester hydrolysis: (L) → (M) This can be done using an alkali metal hydroxide, and a mixed solvent of water / methanol can be used as the solvent.

[0053] [Step 7] Oxidation of 1-hydroxyethyl group to acetyl group: (M) → (N) This can be done in the same manner as above (E) → (F).

[0054] [Step 8] Conversion of carbonyl group to olefin: (N) → (O) This can be done in the same manner as above (F) → (G).

[0055] 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, per 100 parts by weight of the other polymerizable unsaturated monomers. 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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 heat 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 PML of about 5 to 100, preferably about 20 to 80. 1+4 (100°C).

[0061] Other specific examples of elastomeric copolymers include styrene-butadiene rubber (SBR), chloroprene rubber (CR), ethylene-vinyl acetate rubber (EVA), nitrile rubber (NBR), hydrogenated nitrile rubber (H-NBR), ethylene-methyl acrylate rubber (AEM), and the like. EXAMPLES

[0062] The present invention will now be described with reference to examples.

[0063] Example 1 Preparation of compound (g) TIFF0007611076000008.tif29129Compound (g) was produced by the following method. TIFF0007611076000009.tif79154

[0064] [1st step] (a) → (b): In a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, a dropping funnel, and a nitrogen gas inlet / outlet, 40.0 g (201 mmol) of phenothiazine and 200 ml of N,N-dimethylformamide were placed, and the temperature in the system was cooled to 5°C or less under a nitrogen atmosphere. While maintaining 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 maintaining the temperature in the system at 20°C or less, 34.2 g (241 mmol) of methyl iodide 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. TIFF0007611076000010.tif25129 1 H NMR (400MHz, Acetone-d6) δ ppm (TMS): 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)

[0065] [Second step] (b)→(c): 210 ml of N,N-dimethylformamide was placed in a 500 ml four-neck flask equipped with a magnetic stirrer, a dropping funnel, a thermometer, a gas inlet / outlet, and a reflux condenser. Under a nitrogen atmosphere, while maintaining the internal temperature of the system at 10°C or less, 129.4 g (844 mmol) of phosphorus oxytrichloride was added dropwise, and the reaction was continued for another 30 minutes. Next, 30 g (141 mmol) of compound (b) obtained in the first step above 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 (c) as a yellow crystal. TIFF0007611076000011.tif29129 1 H NMR (400MHz, Acetone d6) δ ppm (TMS): 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)

[0066] [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, 30 g (124 mmol) of the compound (c) obtained in the above-mentioned second step and 1200 ml of methanol were placed. While maintaining the internal temperature at 30°C or less, 4.7 g (124 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 29.4 g (crude yield 97%) of the crude product was obtained as a pale yellow solid. Recrystallization was performed using ethyl acetate, and 28.2 g (yield 93%) of 3-hydroxymethyl-10-methyl-10H-phenothiazine (d) was obtained as a pale yellow solid. TIFF0007611076000012.tif25129 1 H NMR (400MHz, Acetone d6) δ ppm (TMS): 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)

[0067] [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 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. TIFF0007611076000013.tif29129 1 H NMR (400MHz, Acetone d6) δ ppm (TMS): 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)

[0068] [5th ​​step] (e) → (f): In a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, a dropping funnel, and a gas inlet / outlet, add 15.3 g (121 mmol) of oxalyl chloride and 225 ml of dichloromethane. The mixture was cooled to -80 to -70°C under a nitrogen atmosphere. 14.1g (181mmol) of dimethylsulfoxide was slowly added dropwise, and the mixture was allowed to react for another 30 minutes. 16.5g (60mmol) of compound (e) dissolved in 8g of dimethylsulfoxide was added dropwise, and the mixture was allowed to react for another 2 hours at -80 to -70°C. Next, 36.6g of triethylamine was added, and the mixture was allowed to rise to room temperature. A saturated aqueous sodium chloride solution was added to the reaction mixture, and the product was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. The volatile components were removed from the filtrate under reduced pressure to obtain 28.0g of crude product (94% crude yield). Column chromatography (carrier: Wakogel C300) using dichloromethane as an eluent was performed, and 15.4g (94% yield) of compound (f) was obtained as a pale yellow solid. TIFF0007611076000014.tif29129 1 H NMR (400MHz, Chloroform-d) δ ppm (TMS): 3.79 (s, 3H, NC H 3) 7.35-7.45 (m, 3H, Ar) 7.66-7.73 (m, 1H, Ar) 8.11-8.16 (m, 2H, Ar) 8.58 (d, J=1.6Hz, 1H, Ar) 10.00 (s, 1H, -C H O)

[0069] [6th step] (f)→(g): 250 ml of tetrahydrofuran was placed in a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a gas inlet / outlet, and the inside temperature was cooled to 10°C or less while replacing the inside of the reaction vessel with nitrogen. 11.2 g (99.7 mmol) of potassium tert-butoxide and then 35.6 g (99.7 mmol) of methyltriphenylphosphonium bromide were added and reacted for 30 minutes. 22.7 g (83.1 mmol) of compound (f) obtained in the fifth step above was added to this and reacted at 10 to 30°C for 2 hours. The resulting reaction mixture was added to a saturated aqueous sodium chloride solution, and the product was extracted with dichloromethane. After drying with anhydrous magnesium sulfate, insoluble matter was filtered off, and volatile components were distilled off from the filtrate under reduced pressure to obtain 47.5 g of residue. Column chromatography (carrier: Wakogel C300) using dichloromethane as an eluent was performed to remove triphenylphosphine oxide, and then recrystallization was performed using acetone to obtain 8.8 g (yield 39%) of compound (g) as a colorless solid. TIFF0007611076000015.tif29129 1 H NMR (400MHz, Chloroform-d) δ ppm (TMS): 3.71 (s, 3H, NC H 3) 5.31 (d, J=11.2Hz, 1H, trans-C to Ar H 2=CH-Ph) 5.79 (d, J=17.6Hz, 1H, cis-C for Ar H 2=CH-Ph) 6.74 (dd, J=11.2Hz, 17.6Hz, 1H, CH2=C H -Ph) 7.23-7.34 (m, 3H, Ar) 7.59-7.69 (m, 2H, Ar) 8.09-8.15 (m, 2H, Ar)

[0070] Example 2 Preparation of compound (n) TIFF0007611076000016.tif27129Compound (n) was produced by the following method. TIFF0007611076000017.tif81159

[0071] [1st step] (h)→(i): Using 38.7 g (194 mmol) of phenothiazine, 7.0 g (292 mmol) of sodium hydride, 28.6 g (233 mmol) of 1-bromopropane, and 200 ml of N,N-dimethylformamide, a reaction was carried out in the same manner as in the first step of Example 1. The resulting crude product was recrystallized using ethanol to obtain 42.1 g (yield 90%) of compound (i) as a colorless solid. TIFF0007611076000018.tif23129 1 H NMR (400MHz, Acetone-d6) δ ppm (TMS): 0.98 (t, J=7.2Hz, 3H, -CH2CH2C H 3) 1.79 (sext, J=7.2Hz, 2H, -CH2C H 2CH3) 3.90 (t, J=7.2Hz, 2H, -C H 2CH2CH3) 6.93 (td, J=7.6, 1.2Hz, 2H,Ar) 7.00 (d, J=8.0Hz, 2H, Ar) 7.13 (dd, J=7.6Hz, 1.6Hz, 2H, Ar) 7.16-7.22 (m, 2H, Ar)

[0072] [Second step] (i)→(j): Using 34 g (141 mmol) of compound (i), 129.4 g (844 mmol) of phosphorus oxytrichloride, and 210 ml of N,N-dimethylformamide, a reaction was carried out in the same manner as in the second step of Example 1 to obtain 35.8 g (yield 94%) of compound (j). TIFF0007611076000019.tif27129 1 H NMR (400MHz, Acetone-d6) δppm (TMS): 1.01 (t, J=7.2Hz, 3H, NCH2CH2CH 3) 1.83 (sext, J=7.2Hz, 2H, NCH2C H 2CH3) 3.99 (t, J=7.2Hz, 2H, NC H 2CH2CH3) 7.01 (td, J=8.0Hz, 1.2Hz, 1H, Ar) 7.08 (d, J=7.6Hz, 1H, Ar) 7.12-7.18 (m, 2H, Ar) 7.20-7.26 (m, 1H, Ar) 7.60 (d, J=2.4Hz, 1H, Ar) 7.73 (dd, J=8.4Hz,2.0Hz, 1H, Ar) 9.83 (s, 1H, -C H O)

[0073] [3rd step] (j)→(k): As in the third step of Example 1, 35.8 g (133 mmol) of compound (j), 5.0 g (133 mmol) of sodium borohydride, and 400 ml of tetrahydrofuran were used and reacted at 60° C. for 2 hours to obtain 36.1 g (yield 100%) of compound (k). TIFF0007611076000020.tif23129

[0074] [4th step] (k)→(l): Similar to the fourth step of Example 1, a reaction was carried out using 36.1 g (133 mmol) of compound (k), 45.6 g (402 mmol) of 30% aqueous hydrogen peroxide solution, and 200 ml of acetic acid to obtain 40.6 g (yield 100%) of compound (l). TIFF0007611076000021.tif27129

[0075] [5th ​​step] (l)→(m): Similarly to the fifth step of Example 1, a reaction was carried out using a solution of 40.6 g (134 mmol) of compound (l) dissolved in 50 g of dimethyl sulfoxide, 33.9 g (268 mmol) of oxalyl chloride, 31.4 g (402 mmol) of dimethyl sulfoxide, 300 ml of dichloromethane, and 81.2 g (804 mmol) of triethylamine to obtain 40.6 g (yield 97%) of compound (m). TIFF0007611076000022.tif27129

[0076] [6th step] (m)→(n): As in the sixth step of Example 1, 39.2 g (130 mmol) of compound (m), 17.5 g (156 mmol) of potassium tert-butoxide, 55.7 g (156 mmol) of methyltriphenylphosphonium bromide, and 350 ml of tetrahydrofuran were used to carry out the reaction, and 73.9 g of crude product was obtained. Column chromatography (carrier: Wakogel C300) using dichloromethane as an eluent was performed to remove triphenylphosphine oxide, and 18.0 g (46% yield) of compound (n) was obtained as a yellow solid. Further, recrystallization using ethyl acetate gave 16.3 g (42% yield) of compound (n). TIFF0007611076000023.tif27129 1 H NMR (400MHz, Chloroform-d) δppm (TMS): 1.07 (t, J=7.6Hz, 3H, NCH2CH2C H 3) 1.95 (sext, J=7.6Hz, 2H, NCH2C H 2CH3) 4.11 (t, J=7.6Hz, 2H, NC H 2CH2CH3) 5.30 (d, J=11.2Hz, 1H, trans-C to Ar H 2=CH-Ph) 5.78 (d, J=17.6Hz, 1H, cis-C for Ar H 2=CH-Ph) 6.73 (dd, J=11.2Hz, 17.6Hz, 1H, CH2=C H -Ph) 7.23-7.35 (m, 3H, Ar) 7.58-7.68 (m, 2H, Ar) 8.10-8.16 (m, 2H, Ar)

[0077] Example 3 Preparation of compound (v) TIFF0007611076000024.tif33129Compound (v) was prepared by the following method. TIFF0007611076000025.tif93134

[0078] [1st step] (o)→(p): 25.0g (104mmol) of 2-acetylphenothiazine (p) (Tokyo Chemical Industry Co., Ltd. product) and 1000ml of methanol were placed in a 2000ml four-neck flask equipped with a magnetic stirrer, a thermometer, a gas outlet and a reflux condenser. 19.6g (518mmol) of sodium borohydride was slowly added while maintaining the internal temperature at 45-55℃, and the mixture was allowed to react for another hour. Methanol was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate. The organic layer was washed once with a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. Volatile components were distilled off from the filtrate under reduced pressure, and 30.0g of crude product was obtained as a pale yellow solid. Recrystallization was performed using 85% by weight ethanol, and 23.6g (94% yield) of 2-(1-hydroxyethyl)-10H-phenothiazine (p) was obtained as a pale yellow solid. TIFF0007611076000026.tif25129

[0079] [Second step] (p)→(q): In a 500 ml four-neck flask equipped with a magnetic stirrer and a thermometer, 21.4 g (87.9 mmol) of compound (p), 48.7 g (615 mmol) of pyridine, and 200 ml of dichloromethane were added. While maintaining the internal temperature at 15°C or less, 34.5 g (440 mmol) of acetyl chloride was added dropwise, and the reaction was continued for another hour. The reaction mixture was added to a saturated aqueous sodium chloride solution, and the product was extracted with dichloromethane. The mixture was then dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. Volatile components were distilled off from the filtrate under reduced pressure, and 23.7 g (yield 94%) of 2-(1-acetoxyethyl)-10H-phenothiazine (q) was obtained. TIFF0007611076000027.tif25129

[0080] [3rd step] (q)→(r): In a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a gas inlet / outlet, 23.7 g (83.0 mmol) of compound (q) and 170 ml of N,N-dimethylformamide were placed. While maintaining the internal temperature below 5°C under a nitrogen atmosphere, 3.0 g (125 mmol) of sodium hydride was added and reacted for 1 hour. Furthermore, 14.7 g (116 mmol) of benzyl chloride was added and reacted at 60°C for 1 hour. The reaction mixture was added to a saturated aqueous sodium chloride solution, and the product was extracted with ethyl acetate. Next, after drying with anhydrous magnesium sulfate, the insoluble matter was filtered off. Volatile components were distilled off from the filtrate under reduced pressure, and 34.9 g of crude 2-(1-acetoxyethyl)-10-benzyl-10H-phenothiazine (r) was obtained. TIFF0007611076000028.tif30129

[0081] [4th step] (r)→(s): In a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer and a reflux condenser, 34.9 g (about 83.0 mmol) of the crude compound (r) obtained in the third step, 50 g of acetic acid, 56 g (494 mmol) of 30% hydrogen peroxide and 300 ml of toluene were added. The reaction was carried out at 50°C, 60°C and 70°C for 1 hour each, and then at 80°C for 2 hours. The upper layer of the reaction mixture was taken out, and the volatile components were distilled off under reduced pressure to obtain 34.0 g of a crude product. The product was recrystallized using a toluene / ethanol mixed solvent (v / v=1 / 1) to obtain 27.3 g of 2-(1-acetoxyethyl)-10-benzyl-10H-phenothiazine-5,5-dioxide (s) (yield from compound (q) 81%). TIFF0007611076000029.tif33129 1 H NMR (400MHz, Acetone-d6) δppm (TMS): 1.31 (d, J=6.8Hz, 3H, C H 3CH(OCOCH3)-Ar) 1.85 (s, 3H, CH3CH(OCOC H 3)-Ar 5.66 (s, 2H, Ar-C H 2) 5.78 (q, J=6.8Hz, 1H, CH3C H (OCOCH3)-Ar) 7.23-7.42 (m, 9H, Ar) 7.62 (t, J=8.4Hz, 1H, Ar) 8.04 (d, J=8.4Hz, 1H, Ar) 8.06 (dd, J=8.4Hz, 1H, Ar)

[0082] [5th ​​step] (s)→(t): In a 1000ml four-neck flask equipped with a magnetic stirrer, a thermometer and a reflux condenser, 26.9g (66.0mmol) of compound (s), 18.5g (330mmol) of potassium hydroxide, 500ml of methanol and 150ml of water were added and reacted at 70°C for 2 hours. After the reaction was completed, the volatile components were distilled off under reduced pressure, water was added to the residue and the product was extracted with dichloromethane. The mixture was then dried over anhydrous magnesium sulfate and the insoluble matter was filtered off. The volatile components were distilled off from the filtrate under reduced pressure to obtain 23.4g of crude product. Recrystallization was carried out using methanol to obtain 22.2g (yield 92%) of 2-(1-hydroxyethyl)-10-benzyl-10H-phenothiazine-5,5-dioxide (t) as a pale yellow solid. TIFF0007611076000030.tif33129 1 H NMR (400MHz, Acetone-d6) δppm (TMS): 1.31 (d, J=6.8Hz, 3H, C H 3CH(OH)-Ar) 4.40 (d, J=4.0Hz, 1H, CH3CH(O H )-Ar) 4.86 (quint, J=6.0Hz, 1H, CH3C H (OH)-Ar) 5.63 (s, 2H, Ar-C H 2) 7.24-7.45 (m, 9H, Ar) 7.57-7.63 (m, 1H, Ar) 8.01 (d, J=8.0Hz, 1H, Ar) 8.07 (dd, J=8.4Hz, 2.0Hz, 1H, Ar)

[0083] [6th step] (t)→(u): 330 ml of dichloromethane and 14.4 g (113 mmol) of oxalyl chloride were placed in a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a gas inlet and outlet. After cooling the temperature in the reaction vessel to -70 to -80°C under a nitrogen atmosphere, 13.3 g (170 mmol) of dimethyl sulfoxide was slowly added dropwise and the temperature was maintained for 1 hour. 20.7 g (56.7 mmol) of compound (t) dissolved in 22 g of dimethyl sulfoxide was added, and the reaction was carried out at the same temperature for 2 hours. After adding 34 g (337 mmol) of triethylamine, the temperature was slowly raised to room temperature, and the reaction mixture was added to a saturated aqueous sodium chloride solution. The product was extracted with dichloromethane, then dried with anhydrous magnesium sulfate, and insoluble matter was filtered off. Volatile components were distilled off from the filtrate under reduced pressure to obtain 29.2 g of crude product. Column chromatography using dichloromethane as an eluent gave 17.8 g (yield 86%) of 2-acetyl-10-benzyl-10H-phenothiazine-5,5-dioxide (u) as a pale yellow solid. TIFF0007611076000031.tif33129 1 H NMR (400MHz, Chloroform-d) δppm (TMS): 2.50 (s, 3H, C H 3(C=O)-Ar) 5.48 (s, 2H, Ar-C H 2) 7.19 (d, J=8.8Hz, 3H, Ar) 7.28-7.40 (m, 4H, Ar) 7.52 (t,J=7.6Hz, 1H, Ar) 7.73 (s, 1H, Ar) 7.78 (d, J=8.4Hz, 1H, Ar) 8.15 (d, J=9.2Hz, 1H, Ar) 8.23 (d, J=8.4Hz, 1H, Ar)

[0084] [Step 7] (u)→(v): 200 ml of tetrahydrofuran was placed in a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a gas inlet / outlet, and the temperature inside the container was cooled to 0°C or lower under a nitrogen atmosphere. 8.2 g (73.5 mmol) of potassium tert-butoxide was added and the temperature was maintained for 10 minutes, then 26.3 g (73.5 mmol) of methyltriphenylphosphonium bromide was added and the temperature was maintained for 30 minutes. 17.8 g (49.0 mmol) of compound (u) was added to the mixture, and the reaction was carried out for 2 hours from 0°C or lower to room temperature. The reaction mixture was added to a saturated aqueous sodium chloride solution, and the product was extracted with dichloromethane. Next, it was dried over anhydrous magnesium sulfate, and insoluble matter was filtered off, and volatile components were distilled off from the filtrate under reduced pressure to obtain a crude product. Column chromatography (carrier: Wakogel C-300) using dichloromethane as an eluent and recrystallization using ethyl acetate gave 8.4 g (yield 47%) of 2-(1-methylethenyl)-10-benzyl-10H-phenothiazine-5,5-dioxide (v) as a colorless solid. TIFF0007611076000032.tif33129 1 H NMR (400MHz, Chloroform-d) δppm (TMS): 1.96 (s, 3H, CH2=CH(C H 3)-Ar) 5.10 (s, 1H, trans-C for Ar H 2=C(CH3)-Ar) 5.22 (cis-C for s, 1H, Ar H 2=C(CH3)-Ar) 5.43 (s, 2H, Ar-C H 2-) 7.12-7.42 (m, 9H, Ar) 7.49 (t, J=8.8Hz, 1H, Ar) 8.08 (d, J=8.4Hz, 1H, Ar) 8.15 (d, J=7.6Hz, 1H, Ar)

[0085] Example 4 In a separable flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube, and a Dimroth condenser, Water 187 parts by weight Sodium lauryl sulfate 2 〃 Polyoxyethylene lauryl ether 2 Same Charged monomer mixture Ethyl acrylate [EA] 97.9 〃 Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (g) of Example 1 0.5 〃 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 and continued until the polymerization conversion rate reached 90% or more. The resulting 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 resulting acrylic rubber A was l+4 (100℃) was 36.

[0086] The mole fraction composition is: l Calculation from the following formula using 1 H-NMR (400 MHz, Acetone d6, δ ppm) revealed that the compound (g) was 0.19 mol %, and EA+MBF was 99.81 mol %. α: integral value of signal from 7.0-8.2 ppm β: integral value of signals from 3.2 to 5.0 ppm Compound (g) (mol%)=200×α / (2α+7β) EA + MBF (mol%) = 100 - compound (g) (mol%) The approximate weight fraction composition was calculated from the following formula: Compound (g): 0.5% by weight; EA+MBF: 99.5% by weight. Compound (g) (wt%)=(Compound (g) (mol%)×271.34×100) / [Compound (g) (mol%) x 271.34 + (EA + MBF (mol%)) x 100.8)] EA+MBF(wt%)=100-compound(g)(wt%)

[0087] Example 5 An acrylic rubber B was obtained by carrying out a copolymerization reaction in the same manner as in Example 4, except that the following charged monomer mixture was used. Charged monomer mixture Ethyl acrylate [EA] 97.4 〃 Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (g) of Example 1 1.0

[0088] Mooney viscosity PML of the obtained acrylic rubber B l+4 (100℃) was 27. The molar fraction composition was compound (g): 0.34 mol %, and EA+MBF: 99.66 mol %. The approximate weight fraction composition is compound (g): 1.0% by weight, EA+MBF: 99.0% by weight. It was.

[0089] Example 6 A copolymerization reaction was carried out in the same manner as in Example 4, except that the following monomer mixture was used, to obtain an acrylic rubber C. Mooney viscosity PML of the obtained acrylic rubber C l+4 (100℃) was 31. Charged monomer mixture Ethyl acrylate [EA] 97.4 〃 Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (n) of Example 2 1.0 Same

[0090] The mole fraction composition is l 1 H-NMR (400 MHz, Acetone d6, δ ppm) was used to calculate from the following formula, which revealed that the compound (n): 0.34 mol %, and EA+MBF: 99.66 mol %. α: integral value of signal from 7.0-8.2 ppm β: integral value of signals from 3.2 to 5.0 ppm Compound (n) (mol%)=200×α / (2α+7β) EA+MBF(mol%)=100-compound (n)(mol%) The approximate weight fraction composition was calculated from the following formula: Compound (n): 1.0% by weight; EA+MBF: 99.0% by weight. Compound (n) (wt%) = (Compound (n) (mol%) × 299.39 × 100) / [Compound (n) (mol%) x 299.39 + (EA + MBF (mol%)) x 100.8)] EA+MBF(wt%)=100-compound(n)(wt%)

[0091] Example 7 A copolymerization reaction was carried out in the same manner as in Example 4, except that the following monomer mixture was used, to obtain an acrylic rubber D. Mooney viscosity PML of the obtained acrylic rubber D l+4 (100℃) was 25. Charged monomer mixture Ethyl acrylate [EA] 97.9 〃 Mono-n-butyl fumarate [MBF] 1.6 〃 Compound (v) of Example 3 0.5 〃

[0092] The mole fraction composition is l Calculation from the following formula using 1 H-NMR (400 MHz, Acetone d6, δ ppm) revealed that the compound (v) was 0.14 mol %, and EA+MBF was 99.86 mol %. α: integral value of signal from 7.0-8.2 ppm β: integral value of signals from 3.2 to 5.0 ppm Compound (v) (mol%)=100×α / (α+6β) EA+MBF(mol%)=100-compound (v)(mol%) The approximate weight fraction composition was calculated from the following formula, and was found to be compound (v): 0.5% by weight, and EA+MBF: 99.5% by weight. Compound (v) (wt%)=(Compound (v) (mol%)×361.34×100) / [Compound (v) (mol%) x 361.34 + (EA + MBF (mol%)) x 100.8)] EA+MBF(wt%)=100-compound(v)(wt%)

[0093] Comparative Example 1 A copolymerization reaction was carried out in the same manner as in Example 4, except that the following monomer mixture was used, to obtain an acrylic rubber E. Mooney viscosity PML of the obtained acrylic rubber E l+4 (100℃) was 33. Charged monomer mixture Ethyl acrylate [EA] 98.4 parts by weight Mono-n-butyl fumarate [MBF] 1.6 〃

[0094] Example 8 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.

[0095] 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 (MLmin) 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 (190℃: 100 hours, 200 hours, 300 hours, 400 hours, 500 hours) Compression set: JIS K6262 compliant (175℃: 70 hours)

[0096] Example 9 In Example 8, acrylic rubber B was used instead of acrylic rubber A.

[0097] Example 10 In Example 8, Acrylic Rubber C was used instead of Acrylic Rubber A.

[0098] Comparative Example 2 In Example 8, Acrylic Rubber E was used instead of Acrylic Rubber A.

[0099] Comparative Example 3 In Comparative Example 2, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Da Of this, 0.5 parts by weight of Nocrac CD (a product of Shinko Chemical Industry) was added.

[0100] Comparative Example 4 In Comparative Example 2, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Da Of which, 1.0 part by weight of Shinko Chemical Industry's product Nocrac CD was added.

[0101] The results obtained in the above Examples 8 to 10 and Comparative Examples 2 to 4 are shown in the following table. table Measurement results Fruit 8 Fruit 9 Fruit 10 ratio 2 ratio 3 ratio 4 Mooney scorch test (125℃) ML min (pts) 66 69 62 71 69 68 t5 (min) 2.7 3.3 2.6 2.6 3.1 3.1 Cross-linking test (180℃) tc(10) (min) 0.50 0.53 0.51 0.49 0.49 0.48 tc(90) (min) 5.15 5.07 5.10 4.77 4.82 4.81 ML (N m) 0.29 0.30 0.30 0.27 0.29 0.28 MH (N m) 1.00 1.02 1.00 1.04 1.05 1.03 Normal physical properties Hardness (Duro A) 68 68 69 68 67 68 100% Modulus (MPa) 5.5 6.0 5.6 5.6 6.0 5.2 Breaking strength (MPa) 18.3 17.4 17.8 17.2 17.4 17.5 Elongation at break (%) 254 245 264 242 236 241 Heat aging test (190℃, 100 hours) Hardness change (Duro A) 72 76 76 71 71 72 100% Modulus (MPa) 3.3 4.1 3.7 3.0 3.6 3.7 Breaking strength (MPa) 7.5 8.6 8.5 7.4 10.1 10.9 Elongation at break (%) 301 268 294 297 293 296 Heat aging test (190℃, 200 hours) Hardness change (Duro A) 79 82 80 82 78 77 100% Modulus (MPa) 3.4 3.8 3.5 3.9 3.0 2.9 Breaking strength (MPa) 5.4 6.0 5.7 5.7 5.8 6.3 Elongation at break (%) 275 264 284 200 293 309 Heat aging test (190℃, 300 hours) Hardness change (Duro A) 88 88 88 92 87 82 100% Modulus (MPa) 5.0 5.2 4.5 5.3 4.2 Breaking strength (MPa) 5.4 5.8 5.3 6.9 5.4 5.3 Elongation at break (%) 135 157 181 51 111 184 Heat aging test (190℃, 400 hours) Hardness change (Duro A) 90 90 89 94 92 88 100% Modulus (MPa) 6.3 5.8 5.3 Breaking strength (MPa) 6.6 6.3 6.0 8.8 6.4 5.4 Elongation at break (%) 82 103 125 23 62 103 Heat aging test (190℃, 500 hours) Hardness change (Duro A) 96 95 94 96 93 90 100% Modulus (MPa) Breaking strength (MPa) 10.0 8.5 8.1 9.3 10.6 8.2 Elongation at break (%) 29 40 45 1 17 36 Compression set 175℃, 70 hours (%) 16 16 16 16 15 15

[0102] From the above results, the following can be concluded: (1) The thianothiazine derivative compound of the present invention can be easily copolymerized with a polymerizable unsaturated monomer. (2) During processing or during actual use after processing, the alkyl or aralkyl group at the 10-position decomposes to release an amino group, thereby exerting an anti-thermal aging effect. (3) The elastomeric polymer material in which the phenothiazine derivative compound of the present invention is copolymerized has excellent heat aging resistance in terms of various properties of the elastomeric polymer material, particularly in terms of elongation at break which indicates elastomeric properties.

Claims

1. General formula [I] (where R 1 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, R 2 is a hydrogen atom or a methyl group).

2. General formula [II] (where R 1 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, R 2 The process for producing a phenothiazine derivative compound according to claim 1, characterized in that the carbonyl group of the compound represented by the formula (I) is a hydrogen atom or a methyl group, is converted into a vinyl group.

3. 3. The process for producing a phenothiazine derivative compound according to claim 2, wherein the vinylation reaction is carried out in the presence of an alkyltriphenylphosphonium halide.

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

5. 5. The phenothiazine derivative compound according to claim 4, wherein the phenothiazine derivative compound is used in a ratio of 0.1 to 5 parts by weight based on 100 parts by weight of the other polymerizable unsaturated monomer.

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

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