Method for using phenothiazine derivative compound

Abstract

Provided is a method for using a phenothiazine derivative compound, wherein when producing a synthetic polymer material produced by addition polymerization of a polymerizable unsaturated monomer, the polymerizable unsaturated monomer constituting the synthetic polymer material is copolymerized with a phenothiazine derivative compound represented by a general formula (R1 is a C1-10 monovalent aliphatic hydrocarbon group, and R2 is a hydrogen atom or a methyl group) to prevent the oxidative deterioration of the synthetic polymer material. This compound can be copolymerized with various polymerizable unsaturated monomers because the polymerization inhibiting effect characteristic of phenothiazine compounds is reduced.

Description

Use of phenothiazine derivative compounds

[0001] The present invention relates to a method for utilizing a phenothiazine derivative compound, and more particularly to a method for utilizing a phenothiazine derivative compound by copolymerizing it with a polymerizable unsaturated monomer that constitutes a synthetic polymer material produced by addition polymerization in order to stabilize the material against oxidative degradation.

[0002] A wide variety of synthetic polymer materials, such as synthetic rubber and synthetic resins, are manufactured from fossil resources and are used. These materials have permeated every corner of society and economy, bringing great convenience and benefits to our lives.

[0003] These synthetic polymer materials can suffer from oxidative degradation due to the actions of various factors, such as heat, light, oxygen, and ozone, either alone or in combination, resulting in the loss of their original physical properties and functions over time. To prevent this, antioxidants are added during their production and molding processes. For example, certain synthetic polymer materials are produced through processes such as polymerization of the monomers that make up the materials, recovery of unreacted monomers, removal of the polymerization medium, coagulation, drying, and granulation. To prevent deterioration of the polymer material due to the heat history during the drying and granulation processes, antioxidants are added beforehand. Phenol-based or amine-based antioxidants are used as antioxidants, and the former, with low molecular weight, are preferred when color and appearance are particularly important.

[0004] Furthermore, when synthetic polymer materials are molded into desired shapes and used under harsh conditions such as high temperatures, antioxidants are added to them during the molding process to prevent performance degradation due to thermal oxidative degradation. Phenol- or amine-based antioxidants are used as antioxidants, with relatively high molecular weights being preferred, particularly to prevent evaporation or leaching into the external environment. Generally, phenol-based antioxidants are used for resinous polymer materials, while amine-based antioxidants are often used for elastomeric polymer materials.

[0005] JP 4-264106 JP 5-230132 JP 2009-209268

[0006] Rubber Chem.Technol., Vol. 45, p. 204 (1972) Rubber Chem.Technol., Vol. 46, p. 106 (1973) Rubber Chem.Technol., Vol. 52, p. 883 (1979) Organic Letters, Vol. 23, p. 4564 (2021) Energy Environ.Sci., Vol. 10, p. 2334-2341 (2017) Macromolecules, Vol. 20, p. 978 (1987) Russian Journal of applied chem., Vol. 76, p. 1327 (2003)

[0007] The problems with stabilizing synthetic polymer materials against oxidative degradation include the need to add antioxidants twice, during the manufacturing and molding processes, and the associated equipment and costs. Furthermore, when antioxidants are used, which pose a risk to human health, occupational safety and health measures are required to prevent exposure to them.

[0008] Furthermore, when a polymeric material molded part is used, there are problems such as poor appearance due to migration of the antioxidant to the surface, volatilization of the antioxidant to the outside due to heat, or loss of the antioxidant's original function due to extraction with water, oils, solvents, etc. Furthermore, when a polymeric material molded part comes into direct contact with food or is used in medical parts, care must be taken to ensure that the amount of antioxidant elution is acceptable from a health perspective. Furthermore, in the case of large molded parts such as automobile tires, there is a risk that a large amount of antioxidant will volatilize or leach into the external environment, which is undesirable from the standpoint of environmental conservation.

[0009] From this perspective, attempts have been made to chemically bond antioxidants to synthetic polymer materials in order to reduce the cost associated with adding antioxidants and to suppress the elution and volatilization of antioxidants during use.

[0010] For example, in the case of elastomeric polymer materials, attempts have been made to chemically bond antioxidant components to polymer chains (Patent Documents 1 to 3, Non-Patent Documents 1 to 3). However, these methods require an additional modification step and are not practical in terms of production cost. Furthermore, the antioxidant having a polymerizable unsaturated group described in Non-Patent Document 2 cannot be said to be versatile.

[0011] The preparation method of the phenothiazine derivative compound [I], the use of which is proposed in the present invention, is known (Non-Patent Documents 4 and 5). In addition, the preparation of its homopolymer and copolymer with methyl methacrylate and their redox properties are also known (Non-Patent Document 6).

[0012] In relation to the present invention, Non-Patent Document 7 describes the production of a homopolymer of 2-ethenyl-10H-phenothiazine and its function as a polymeric antioxidant.

[0013] However, none of the prior art documents mentions the stabilizing effect against oxidative deterioration, that is, the efficacy as an antioxidant, when compound [I] is copolymerized with a polymerizable unsaturated monomer.

[0014] In order to solve the above problems, the present inventors have proposed a synthetic polymer material produced by addition polymerization of a polymerizable unsaturated monomer, in which the polymerizable unsaturated monomer constituting the material is added with a compound represented by the general formula (where R 1 is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R 2 The present invention proposes a method for utilizing compound [I] as an antioxidant to prevent oxidative deterioration of synthetic polymer materials by copolymerizing it with a phenothiazine derivative compound represented by the formula (I) where R is a hydrogen atom or a methyl group.

[0015] These compounds have reduced radical polymerization inhibition properties specific to phenothiazine compounds, enabling radical copolymerization with various polymerizable unsaturated monomers. Furthermore, the replacement of the hydrogen atom at the 10-position, which is active against basic compounds such as alkyllithium compounds, with an aliphatic hydrocarbon group substantially prevents hydrogen abstraction, enabling anionic copolymerization with various polymerizable unsaturated monomers such as diene monomers and vinyl monomers. For the same reason, deactivation of cationic polymerization catalysts and coordination polymerization catalysts can be prevented, enabling cationic or coordination polymerization with various polymerizable unsaturated monomers.

[0016] Furthermore, in the process of producing a synthetic polymer material, copolymerization of a smaller amount of the phenothiazine derivative compound [I] compared with the amount of conventional antioxidants can stabilize the material against oxidative degradation, and as a result, the addition of a new antioxidant in the production and molding processes of the material is not required or the amount of antioxidant used can be significantly reduced.

[0017] Furthermore, when molded parts made from synthetic polymer materials are used, problems such as poor appearance due to migration of the antioxidant to the surface, contamination of other parts in contact with the molded part, evaporation or elution of the antioxidant into the external environment, and extraction by liquid media such as oils and organic solvents can be prevented, thereby enabling the safe use and long life of polymer material molded parts in a variety of usage environments.

[0018] The synthetic polymer material copolymerized with the phenothiazine derivative compound [I] is inhibited from losing its antioxidant component over time, and the addition of a new antioxidant is unnecessary or can be significantly reduced when the synthetic polymer material is reused. Therefore, this technology is useful from the viewpoint of the recycling of plastics today.

[0019] Furthermore, this technology is also useful from the standpoint of environmental conservation, since it reduces the release of antioxidant components into the external environment from large molded parts such as automobile tires.

[0020] 1 is a diagram showing the change over time in the rate of change in strength at break of a cross-linked acrylic rubber product at 190°C (Example 16: --●-, Comparative Example 5: --●--, Comparative Example 6--▲--, Comparative Example 7--◆--; common to Figures 1 and 2). This diagram shows the change over time in the rate of change in elongation at break of a cross-linked acrylic rubber product at 190°C. For Examples 17 to 19 and Comparative Examples 8 and 9, the change in elongation at break after an air heating aging test (175°C, 300 hours) (white bars) is compared with the change in elongation at break when immersed in IRM903 oil (150°C, 168 hours) and then subjected to an air heating aging test (175°C, 300 hours) (black bars).

[0021] The present invention relates to a compound of the general formula (where R 1 is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R 2 is a hydrogen atom or a methyl group). Specifically, the present invention relates to a method for utilizing a phenothiazine derivative compound [I], which is copolymerized with a polymerizable unsaturated monomer constituting a synthetic polymer material produced by addition polymerization in order to prevent the material from oxidative deterioration.

[0022] R 1 Specific examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, isopropyl, 2-butyl, 2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, 4-heptyl, 2-octyl, 3-octyl, 4-octyl, tertiary butyl, and 1,1-dimethyl-1 1-propyl group, 1,1-dimethyl-1-butyl group, 1,1-dimethyl-1-pentyl group, 1,1-dimethyl-1-hexyl group, 3-methyl-3-pentyl group, 3-ethyl-3-pentyl group, 3-methyl-3-hexyl group, etc., or cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1-methyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1-adamantyl group, etc.

[0023] Specific examples of the phenothiazine derivative compound [I] include 2-ethenyl-10-methyl-10H-phenothiazine, 2-(1-methylethenyl)-10-methyl-10H-phenothiazine, 3-ethenyl-10-methyl-10H-phenothiazine, 3-(1-methylethenyl)-10-methyl-10H-phenothiazine, etc.

[0024] There is no particular limitation on the method for producing the phenothiazine derivative compound [I], and it can be produced using inexpensive diphenylamine or 10H-phenothiazine as a starting material. For example, Non-Patent Documents 4 and 5 describe methods for producing 2-(1-methylethenyl)-10-methyl-10H-phenothiazine and 3-ethenyl-10-methyl-10H-phenothiazine, respectively.

[0025] In copolymerizing the phenothiazine derivative compound [I] with a polymerizable unsaturated monomer, the phenothiazine derivative compound [I] is used in an amount of about 0.001 to 2.0 parts by weight, preferably about 0.01 to 1.0 part by weight, per 100 parts by weight of the monomer mixture. If the amount is less than this, a sufficient antioxidant effect cannot be expected, while if the amount is greater than this, no improvement in the antioxidant effect can be expected, which is uneconomical.

[0026] The synthetic polymer material referred to in the present invention is a material produced by addition polymerization of polymerizable unsaturated monomers, and there are no particular limitations on the type thereof.

[0027] The synthetic polymer material may be in any physical form, such as a resin, elastomer, or viscous liquid.

[0028] When producing synthetic polymer materials, radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, etc. can be used from the viewpoint of the active species in the polymerization reaction, and solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, gas phase polymerization, etc. can be used from the viewpoint of the phase state of the polymerization reaction. A polymerization method suitable for the type and application of each synthetic polymer material is used as appropriate.

[0029] There are no particular limitations on the polymerizable unsaturated monomer that constitutes the synthetic polymer material, and it may be either a homopolymer produced from one type of polymerizable unsaturated monomer or a copolymer produced from multiple polymerizable unsaturated monomers.

[0030] The polymerization form of the copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer.

[0031] Examples of the polymerizable unsaturated monomer include chain olefins having 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene, and isobutylene; cyclic olefins, such as cyclopentene and cyclohexene; diene monomers, such as 1,3-butadiene, isoprene, chloroprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, and 2-phenyl-1,3-butadiene; styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, and 1,4 Examples of the vinyl monomer include aromatic vinyl monomers such as divinylbenzene, nitrile-containing unsaturated monomers such as acrylonitrile and methacrylonitrile, chlorine-containing unsaturated monomers such as vinyl chloride and vinylidene chloride, alkyl vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether, alkyl (meth)acrylate monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate, alkoxyalkyl (meth)acrylate monomers such as methoxyethyl (meth)acrylate and methoxypropyl (meth)acrylate, aralkyl (meth)acrylate trilate monomers such as benzyl (meth)acrylate, and vinyl acetate. Note that (meth)acrylate refers to acrylate or methacrylate.

[0032] In addition to the main polymerizable unsaturated monomers constituting the synthetic polymer material, a small amount of polymerizable unsaturated monomers having reactive groups may be copolymerized to impart functions such as adhesiveness, crosslinkability, etc. Examples of reactive groups include vinyl groups, epoxy groups, acryloyl groups, isocyanate groups, hydroxyl groups, chlorine-containing alkyl groups, and carboxyl groups.

[0033] Specific examples of synthetic polymer materials in which the phenothiazine derivative compound [I] can be copolymerized in the molecule include polyethylene, polypropylene, poly-4-methylpentene, ethylene-propylene copolymer, 1-butene-propylene copolymer, polystyrene, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, methacrylic acid-styrene copolymer, acrylonitrile-styrene graft copolymer of butadiene rubber, acrylonitrile-styrene graft copolymer of styrene-butadiene rubber, poly-1,3-butadiene, Examples of the polyisobutylene copolymer include isobutylene-isoprene copolymer, 1,3-butadiene-isobutylene copolymer, polyisoprene, polychloroprene, 1,3-butadiene-styrene copolymer, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, polyethyl acrylate, poly-n-butyl acrylate, n-butyl acrylate-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, n-butyl acrylate-ethyl acrylate-ethylene copolymer, and the like.

[0034] The present invention will now be described in detail with reference to examples, although the present invention, including its effects, is not limited to these examples.

[0035] Reference Example 1 - Preparation of phenothiazine derivative compound [IA] -

[0036] [Step 1] [PTZ] → (a): 2.0 L of thoroughly dehydrated N,N-dimethylformamide was placed in a 5 L five-neck flask equipped with a stirrer, thermometer, dropping funnel, nitrogen gas inlet, and outlet tube. The system was cooled to below 10°C under a nitrogen atmosphere. 103.4 g (2.59 mol) of sodium hydride (60% purity) was added and stirred for 10 minutes. After this, 312.3 g (2.2 mol) of phenothiazine [PTZ] was added in several portions and reacted for 30 minutes while maintaining the system temperature below 10°C. 312.3 g (2.20 mol) of iodomethane was added dropwise while maintaining the system temperature below 10°C, and the reaction was continued for an additional hour. After the reaction was complete, the reaction mixture was added to 4 L of 10% aqueous sodium chloride solution. The colorless solid precipitated was filtered and washed with 4 L of distilled water. The resulting solid was dissolved in 2.5 L of warm ethyl acetate at approximately 50°C, and the lower layer (aqueous layer) was separated. The upper layer (organic layer) was dried over anhydrous magnesium sulfate, and then insoluble matter was filtered off. Volatile components were removed from the filtrate by distillation under reduced pressure to obtain 451.4 g of crude product (crude yield 105%). This was washed (defatted) with 0.7 L of isooctane to obtain 421.2 g of 10-methyl-10H-phenothiazine (a) as a slightly grayish crystalline solid (yield 98.2%). 1 H NMR (400MHz, Acetone-d6, δ ppm): 3.39 (s, 3H, N-CH3) 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)

[0037] [Step 2] (a) → (b): 0.7 L of thoroughly dehydrated N,N-dimethylformamide was placed in a 3 L five-neck flask equipped with a stirrer, dropping funnel, thermometer, gas inlet, gas outlet, and reflux condenser. Under a nitrogen atmosphere, 509 g (3.32 mol) of phosphoryl chloride was added dropwise while maintaining the internal temperature of the system below 10°C, and the reaction was continued for an additional 30 minutes. Next, 291.2 g (1.37 mol) of 10-methyl-10H-phenothiazine (a) obtained in Step 1 above was added, and the reaction was continued at 60°C for 17 hours. After completion of the reaction, the contents were poured into 2.3 kg of 50% aqueous sodium acetate solution cooled in an ice-water bath, and 194 g of sodium hydroxide was added to adjust the pH to 6 or higher. The resulting solution was allowed to stand for 2 hours while cooling in an ice-water bath. The precipitated solid was filtered and washed with 3 L of distilled water to dissolve the inorganic electrolytes. The remaining brown solid was dissolved in 1.5 L of warm ethyl acetate at approximately 50°C. The lower layer (aqueous layer) was separated, and the organic layer was dried over anhydrous magnesium sulfate. After filtering off the insoluble material, the volatile components were removed from the filtrate under reduced pressure, yielding 329.0 g of crude product (99.9% crude yield) as a reddish-brown oil. The crude product was dissolved in approximately 1 L of ethyl acetate and passed through a silica gel (carrier: Wakogel C300) column to remove low-Rf components. The volatile components were removed from the eluate under reduced pressure, yielding 321.6 g of a yellow solid (97.6% yield). Further recrystallization using 320 mL of ethyl acetate yielded 308.2 g of 10-methyl-10H-phenothiazine-3-carbaldehyde (b) as yellow crystals (93.6% yield). 1 H NMR (400MHz, Acetone d6, δ ppm): 3.49 (s, 3H, N-CH3) 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, -CHO)

[0038] [Step 3] (b) → [I-A]: 2.3 L of tetrahydrofuran was placed in a 5 L five-neck flask equipped with a stirrer, magnetic stirrer, thermometer, gas inlet tube, and gas outlet tube. The reaction vessel was cooled to below 10°C while purging with nitrogen. 175.0 g (1.56 mol) of potassium tert-butoxide was added, followed by 557.3 g (1.56 mol) of methyltriphenylphosphonium bromide, and the reaction was carried out for 30 minutes. 313.7 g (1.30 mol) of compound (b) was added, and the reaction was carried out at -10 to 40°C for 1 hour to obtain a reaction mixture. The reaction mixture was then added to 1.7 L of 10% aqueous sodium chloride solution to quench the reaction. The organic layer was recovered, while the aqueous layer was extracted with ethyl acetate and combined with the previous organic layer. To this mixture, 0.35 g of p-methoxyphenol was added, dried over anhydrous magnesium sulfate, and then insoluble matter was filtered off. Volatile components were removed from the filtrate by distillation under reduced pressure, yielding 718.4 g of a pale yellow solid. This was then pulverized in a mortar to form a powder. The powdered pale yellow solid was dissolved in 2.1 L of ethanol, and a small amount of insoluble matter was filtered off. The filtrate was then left overnight at 5°C or below to crystallize [I-A]. The resulting yellow crystals weighed 286.3 g (yield 92.0%). The same procedure was repeated using 3.3 L of ethanol with 286.3 g of the precipitated yellow crystals, yielding 259.2 g (yield 83.3%) of pale yellow crystals [I-A]. Melting point: 102°C 1H NMR (400 MHz, CDCl3, δ ppm): 3.37 (s, 3H, N-CH3), 5.14 (d, J = 10.8 Hz, 1H, CH2 = CH-PTZ (trans to the phenothiazine group)), 5.61 (d, J = 17.6 Hz, 1H, CH2 = CH-PTZ (cis to the phenothiazine group)), 6.59 (dd, J = 10.8 Hz, 17.6 Hz, 1H, CH2 = CH-PTZ), 6.75 (d, J = 8.4 Hz, 1H, Ar), 6.81 (d, J = 9.2 Hz, 1H, Ar), 6.92 (td, J = 7.6 Hz, 1.2 Hz, 1H, Ar), 7.11-7.23 (m, 4H, Ar).

[0039] Reference Example 2 - Preparation of phenothiazine derivative compound [IB] -

[0040] [Step 1] (A-PTZ) → (c): 16.4 g (68.0 mmol) of 2-acetylphenothiazine (A-PTZ), 400 mL of toluene, 36 g of ethylene glycol, and 0.70 g of p-toluenesulfonic acid monohydrate were placed in a 1 L four-neck flask equipped with a magnetic stirrer, thermometer, nitrogen gas inlet, outlet, and reflux condenser, and refluxed for 10 hours under a nitrogen atmosphere. The reaction mixture was added to 600 mL of 10% aqueous sodium chloride solution. This was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. Insoluble matter was then filtered off. Volatile components were removed from the filtrate by distillation under reduced pressure to obtain 16.3 g (84% crude yield) of compound (c) as a brown solid.

[0041] [Step 2] (c) → (d): 200 ml of thoroughly dehydrated N,N-dimethylformamide was placed in a 500 ml four-neck flask equipped with a magnetic stirrer, thermometer, dropping funnel, nitrogen gas inlet, and outlet tube. The system was cooled to below 10°C under a nitrogen atmosphere. 4.6 g (115 mmol) of sodium hydride (60% purity) was added and stirred for 10 minutes. After stirring, 16.3 g (57.1 mmol) of compound (c) was added while maintaining the system temperature below 10°C, and the reaction was continued for 30 minutes. While maintaining the system temperature below 10°C, 12.2 g (86 mmol) of iodomethane was added dropwise, and the reaction was continued for an additional hour. After completion of the reaction, the reaction mixture was added to 600 ml of 10% aqueous sodium chloride solution. After extraction with ethyl acetate, the upper layer (organic layer) was dried over anhydrous magnesium sulfate, and then insoluble matter was filtered off. Volatile components were distilled off from the filtrate under reduced pressure to obtain 17.2 g of compound (d) as a yellow solid (crude yield from compound (c) 101%).

[0042] [Step 3] (d) → (e): 17.2 g of compound (d), 40 ml of distilled water, and 160 ml of acetic acid were placed in a 500 ml four-neck flask equipped with a magnetic stirrer and a thermometer, and the reaction was carried out at 90°C for 2 hours. The reaction mixture was added to 600 ml of 10% aqueous sodium chloride solution. This was extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and then the insoluble matter was filtered off. Volatile components were removed from the filtrate under reduced pressure, yielding 15.4 g of compound (e) as a brown liquid (crude yield from compound (c) 106%).

[0043] [Step 4] (e) → [IB]: 150 ml of tetrahydrofuran was placed in a 500 ml four-neck flask equipped with a magnetic stirrer, thermometer, gas inlet, and gas outlet tubes. The reaction vessel was cooled to below 10°C while purging with nitrogen. 8.3 g (74.0 mmol) of potassium tert-butoxide was added, followed by 25.6 g (74.2 mmol) of methyltriphenylphosphonium bromide, and the reaction was carried out for 30 minutes. 15.4 g (approximately 57.1 mmol) of compound (e) was then added and the reaction was carried out at -10 to 40°C for 1 hour. The reaction mixture was then quenched by adding 700 ml of 10% aqueous sodium chloride solution. The organic layer was then recovered, while the aqueous layer was extracted with ethyl acetate and mixed with the previous organic layer. 0.02 g of p-methoxyphenol was added to the mixture, which was then dried over anhydrous magnesium sulfate and filtered to remove any insoluble material. The volatile components were distilled off from the filtrate under reduced pressure to obtain 32.2 g of a brown liquid. This was then subjected twice to column chromatography (stationary phase: Wakogel C300, φ60 mm, L=80 mm) using dichloromethane as an eluent to remove triphenylphosphine oxide. The volatile components were then distilled off from the eluate under reduced pressure to obtain 13.0 g of compound [IB] as a pale yellow solid (yield from compound (c) 90%). 1 H NMR (400 MHz, acetone-d6, δ ppm): 2.13 (s, 3H, CH═C(CH═)-PTZ), 3.42 (s, 3H, N-CH═), 5.08 (m, 1H, CH═C(CH═)-PTZ (trans to the phenothiazine group), 5.41 (m, 1H, CH═C(CH═)-PTZ (cis to the phenothiazine group), 6.91-7.23 (m, 7H, Ar).

[0044] Example 1 A separable flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube, and a Dimroth condenser was charged with the following: 187 parts by weight of water, 2 parts by weight of sodium lauryl sulfate, 2 parts by weight of polyoxyethylene lauryl ether, a monomer mixture of 98.2 parts by weight of ethyl acrylate [EA], 97.9 parts by weight of ethyl acrylate [EA], 1.6 parts by weight of mono-n-butyl fumarate [MBF], and 0.5 parts by weight of compound [IA] of Reference Example 1. The system was then thoroughly purified by nitrogen gas substitution, and 0.008 parts by weight of sodium formaldehyde sulfoxylate (Rongalite, a product of Fujifilm Wako Pure Chemical Industries, Ltd.) and 0.0047 parts by weight of tert-butyl hydroperoxide (Perbutyl H-69, a product of NOF Corp.) were added to initiate the polymerization reaction at room temperature and continued until the polymerization conversion rate reached 90% or more. The obtained aqueous latex was coagulated with a 10% aqueous solution of sodium sulfate, then 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 30.

[0045] Its mole fraction composition is: l The ratios were determined from H-NMR (400 MHz, Acetone d6, δ ppm) using the following formula: Compound [I-A]: 0.20 mol %, EA + MBF: 99.80 mol %. α: integral value of signals from 6.5 to 7.5 ppm β: integral value of signals from 3.2 to 5.0 ppm Compound [I-A] (mol %) = 200 × α / (2α + 7β) EA + MBF (mol %) = 100 - Compound [I-A]

[0046] The approximate weight fraction composition was calculated from the following formula: Compound [I-A]: 0.48 wt %, EA + MBF: 99.52 wt %. Compound [I-A] (wt %) = (Compound (e) (mol %) x 239.34 x 100) / [Compound [I-A] (mol %) x 239.34 + (EA + MBF (mol %)) x 100.8)] EA + MBF (wt %) = 100 - Compound [I-A] (wt %)

[0047] Example 2 A copolymerization reaction was carried out in the same manner as in Example 1, 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°C) was 32. Charged monomer mixture: Ethyl acrylate [EA] 98.2 parts by weight Mono-n-butyl fumarate [MBF] 1.6 parts by weight Compound [IA] of Reference Example 1 0.2 parts by weight

[0048] The molar fraction composition was Compound [IA]: 0.085 mol %, EA + MBF: 99.915 mol %, and the approximate weight fraction composition was Compound [IA]: 0.20 wt %, EA + MBF: 99.80 wt %.

[0049] Example 3 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain an acrylic rubber C. Mooney viscosity PML of the obtained acrylic rubber C l+4 (100°C) was 32. Charged monomer mixture: Ethyl acrylate [EA] 98.3 parts by weight Mono-n-butyl fumarate [MBF] 1.6 parts by weight Compound [IA] of Reference Example 1 0.1 parts by weight

[0050] The molar fraction composition was Compound [IA]: 0.047 mol %, EA + MBF: 99.953 mol %, and the approximate weight fraction composition was Compound [IA]: 0.11 wt %, EA + MBF: 99.89 wt %.

[0051] Comparative Example 1 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain an acrylic rubber D. Mooney viscosity PML of the obtained acrylic rubber D l+4 (100°C) was 32. Charged monomer mixture: Ethyl acrylate (EA) 98.4 parts by weight Mono-n-butyl fumarate (MBF) 1.6 parts by weight

[0052] Example 4 Acrylic rubbers A, B, C and D obtained in Examples 1 to 3 and Comparative Example 1 were subjected to heating tests in air at 100°C (50 hours, 100 hours), 150°C (3 hours) and 200°C (10 minutes), and the Mooney viscosity PML before and after the tests was measured. 1+4 (100°C) and stress relaxation coefficient MSR(100°C) were measured.

[0053] The results obtained are shown in Table 1 below. Table 1 Acrylic rubber A B C D Amount of compound [IA] charged (parts by weight) 0.50 0.20 0.10 0 Before test PML 1+4 30 32 32 32 MSR 0.149 0.045 0.025 0.023 PML after heating test at 100°C for 50 hours 1+4 30 27 31 14 MSR 0.038 0.051 0.083 0.578 PML after heating test at 100°C for 100 hours 1+4 26 28 32 4 MSR 0.045 0.055 0.086 0.230 PML after heating test at 150°C for 3 hours 1+4 32 29 32 9 MSR 0.074 0.082 0.096 0.573 PML after heating test at 200°C for 10 minutes 1+430 30 34 24 MSR 0.084 0.038 0.042 0.515

[0054] Example 5 A copolymerization reaction was carried out in the same manner as in Example 1, 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 The temperature (100°C) was 35. Charged monomer mixture Ethyl acrylate [EA] 53.2 parts by weight Butyl acrylate [BA] 45.0 parts by weight Mono-n-butyl fumarate [MBF] 1.6 parts by weight Compound [IA] of Reference Example 1 0.2 parts by weight n-Dodecyl mercaptan 0.035 parts by weight

[0055] Its mole fraction composition is: l The molecular weights were determined from H-NMR (400 MHz, Acetone d6, δ ppm) according to the following formula: Compound [I-A]: 0.090 mol %, EA + BA + MBF: 99.910 mol %. α: integral value of signals from 6.5 to 7.5 ppm β: integral value of signals from 3.2 to 5.0 ppm Compound [I-A] (mol %) = 200 × α / (2α + 7β) EA + BA + MBF (mol %) = 100 - Compound [I-A]

[0056] The approximate weight fraction composition was calculated from the following formula: Compound [I-A]: 0.19 wt %, EA+BA+MBF: 99.81 wt %. Compound [I-A] (wt %) = (Compound [I-A] (mol %) x 239.34 x 100) / [Compound [I-A] (mol %) x 239.34 + (EA+BA+MBF (mol %)) x 110.6)] EA+BA+MBF (wt %) = 100 - Compound [I-A] (wt %)

[0057] Example 6 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain acrylic rubber F. Mooney viscosity PML of the obtained acrylic rubber F l+4The temperature (100°C) was 39. Charged monomer mixture: Ethyl acrylate [EA] 53.2 parts by weight Butyl acrylate [BA] 45.0 parts by weight Mono-n-butyl fumarate [MBF] 1.6 parts by weight Compound [IB] of Reference Example 2 0.2 parts by weight n-Dodecyl mercaptan 0.035 parts by weight

[0058] Its mole fraction composition is: l The molecular weights were determined from H-NMR (400 MHz, Acetone d6, δ ppm) according to the following formula: Compound [IB]: 0.085 mol %, EA + BA + MBF: 99.915 mol %. α: integral value of signals from 6.5 to 7.5 ppm β: integral value of signals from 3.2 to 5.0 ppm Compound [IB] (mol %) = 200 × α / (2α + 7β) EA + BA + MBF (mol %) = 100 - Compound [IB]

[0059] The approximate weight fraction composition was calculated from the following formula: Compound [IB]: 0.19 wt %, EA + BA + MBF: 99.81 wt %. Compound [IB] (wt %) = (Compound [IB] (mol %) x 253.37 x 100) / [Compound [IB] (mol %) x 253.37 + (EA + BA + MBF (mol %)) x 110.6] EA + BA + MBF (wt %) = 100 - Compound [IB] (wt %)

[0060] Comparative Example 2 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain an acrylic rubber G. Mooney viscosity PML of the obtained acrylic rubber G l+4 (100°C) was 36. Ethyl acrylate [EA] 53.4 parts by weight Butyl acrylate [BA] 45.0 parts by weight Mono-n-butyl fumarate [MBF] 1.6 parts by weight n-Dodecyl mercaptan 0.035 parts by weight

[0061] Example 7 Acrylic rubbers E, F and G obtained in Examples 5 and 6 and Comparative Example 2 were subjected to a heating test at 150°C (3 hours) in air, and the Mooney viscosity PML before and after the test was measured. 1+4 The PML (100°C) and stress relaxation coefficient MSR (100°C) were measured. The results are shown in Table 2 below. Table 2 Acrylic rubber E F G Amount of compound [IA] charged (parts by weight) 0.20 0 0 Amount of compound [IB] charged (parts by weight) 0 0.20 0 Before test PML 1+4 35 39 36 MSR 0.254 0.238 0.255 PML after heating test at 150℃ for 3 hours 1+4 37 41 19 MSR 0.249 0.198 0.505

[0062] Example 8 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following monomer mixture was used, to obtain an acrylic rubber H. Mooney viscosity PML of the obtained acrylic rubber H l+4 The temperature (100°C) was 26. Charged monomer mixture: Ethyl acrylate [EA] 47.9 parts by weight Butyl acrylate [BA] 30.0 parts by weight Methoxyethyl acrylate [MEA] 20.0 parts by weight Mono-n-butyl fumarate [MBF] 1.6 parts by weight Compound [IA] of Reference Example 1 0.5 parts by weight

[0063] Example 9 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain an acrylic rubber I. Mooney viscosity PML of the obtained acrylic rubber I l+4The temperature (100°C) was 28. Charged monomer mixture: Ethyl acrylate [EA] 48.2 parts by weight Butyl acrylate [BA] 30.0 parts by weight Methoxyethyl acrylate [MEA] 20.0 parts by weight Mono-n-butyl fumarate [MBF] 1.6 parts by weight Compound [IA] of Reference Example 1 0.2 parts by weight

[0064] Example 10 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following monomer mixture was used, to obtain an acrylic rubber J. Mooney viscosity PML of the obtained acrylic rubber J l+4 The temperature (100°C) was 28. Charged monomer mixture: Ethyl acrylate [EA] 48.3 parts by weight Butyl acrylate [BA] 30.0 parts by weight Methoxyethyl acrylate [MEA] 20.0 parts by weight Mono-n-butyl fumarate [MBF] 1.6 parts by weight Compound [IA] of Reference Example 1 0.1 parts by weight

[0065] Comparative Example 3 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain acrylic rubber K. Mooney viscosity PML of the obtained acrylic rubber K l+4 The temperature (100°C) was 27. Charged monomer mixture Ethyl acrylate [EA] 48.4 parts by weight Butyl acrylate [BA] 30.0 parts by weight Methoxyethyl acrylate [MEA] 20.0 parts by weight Mono-n-butyl fumarate [MBF] 1.6 parts by weight

[0066] Example 11 Acrylic rubbers H, I, J and K obtained in Examples 8 to 10 and Comparative Example 3 were subjected to a heating test at 150°C (3 hours) in air, and the Mooney viscosity PML before and after the test was 1+4The PML (100°C) and stress relaxation coefficient MSR (100°C) were measured. The results are shown in Table 3 below. Table 3 Acrylic rubber H I J K Amount of compound [IA] charged (parts by weight) 0.50 0.20 0.10 0 Before test 1+4 26 28 28 27 MSR 0.081 0.073 0.063 0.061 PML after heating test at 150°C for 3 hours 1+4 31 33 30 26 MSR 0.078 0.074 0.062 0.281

[0067] Example 12 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following monomer mixture was used, to obtain an acrylic rubber L. The Mooney viscosity PML of the obtained acrylic rubber L was l+4 The temperature (100°C) was 37. Charged monomer mixture: Ethyl acrylate [EA] 97.0 parts by weight Vinyl chloroacetate [VCA] 2.5 parts by weight Compound [IA] of Reference Example 1 0.5 parts by weight

[0068] Example 13 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following monomer mixture was used, to obtain an acrylic rubber M. Mooney viscosity PML of the obtained acrylic rubber M l+4 (100°C) was 38. Charged monomer mixture: Ethyl acrylate [EA] 97.3 parts by weight Vinyl chloroacetate [VCA] 2.5 parts by weight Compound [IA] of Reference Example 1 0.2 parts by weight

[0069] Example 14 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following monomer mixture was used, to obtain Acrylic Rubber N. Mooney viscosity PML of the obtained Acrylic Rubber N l+4(100°C) was 36. Charged monomer mixture: Ethyl acrylate [EA] 97.4 parts by weight Vinyl chloroacetate [VCA] 2.5 parts by weight Compound [IA] of Reference Example 1 0.1 parts by weight

[0070] Comparative Example 4 A copolymerization reaction was carried out in the same manner as in Example 1, except that the following charged monomer mixture was used, to obtain an acrylic rubber P. Mooney viscosity PML of the obtained acrylic rubber P l+4 (100°C) was 36. Charged monomer mixture: Ethyl acrylate (EA) 97.5 parts by weight Vinyl chloroacetate (VCA) 2.5 parts by weight

[0071] Example 15 The acrylic rubbers L, M, N and P obtained in Examples 12 to 14 and Comparative Example 4 were subjected to a heating test in air at 150°C for 3 hours, and the Mooney viscosity PML before and after the test was 1+4 The PML (100°C) and stress relaxation coefficient MSR (100°C) were measured. The results are shown in Table 4 below. Table 4 Acrylic rubber L M N P Amount of compound [IA] charged (parts by weight) 0.50 0.20 0.10 0 Before test PML 1+4 36 36 38 37 MSR 0.081 0.073 0.063 0.061 PML after heating test at 150°C for 3 hours 1+4 34 34 38 8 MSR 0.064 0.066 0.080 0.538

[0072] Example 16 Acrylic Rubber A 100 parts by weight SRF carbon black (Tokai Carbon's Seast GS) 70 parts by weight Stearic acid (Miyoshi Oil & Fats' TST) 1 part by weight Polyoxyethylene stearyl ether phosphate 0.5 parts by weight (Toho Chemical Industry's Phosphanol RL-210) Stearylamine (Kao's Farmin 80S) 1 part by weight Crosslinking accelerator (Safic-Alcan's Vulcofac ACT55) 1 part by weight Hexamethylenediamine carbamate 0.6 parts by weight (Unimatec's Cheminox AC6F) Of the above ingredients, Acrylic Rubber A, SRF carbon black, stearic acid, and polyoxyethylene stearyl ether phosphate were mixed in a Banbury mixer. The remaining ingredients were mixed with the resulting mixture using an open roll mill to obtain an acrylic rubber composition.

[0073] This was subjected to primary crosslinking at 180°C for 8 minutes and oven crosslinking (secondary crosslinking) at 175°C for 4 hours using a 100-ton press molding machine, resulting in 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.

[0074] The physical properties of the crosslinked acrylic rubber composition were measured as follows: Physical properties at normal state: According to JIS K6251 corresponding to ISO 37 and JIS K6253 corresponding to ISO 7619-1 Air heating aging test: According to JIS K6257 corresponding to ISO 188 (190°C: 100 hours, 200 hours, 300 hours, 400 hours, 500 hours) Compression set test: According to JIS K6262 corresponding to ISO 815-1 (175°C: 70 hours)

[0075] Comparative Example 5 In Example 16, acrylic rubber D was used in place of acrylic rubber A.

[0076] Comparative Example 6 In Comparative Example 5, 0.5 parts by weight of the compound (b) prepared in Reference Example 1 was further mixed with acrylic rubber D together with other additives in the composition preparation step.

[0077] Comparative Example 7 In Comparative Example 5, 0.5 parts by weight of the compound [IA] was further mixed with the acrylic rubber D together with other additives in the composition preparation step.

[0078] The results obtained in Example 16 and Comparative Examples 5 to 7 are shown in Table 5 below. Table 5 Measurement Results Actual 16 Ratio 5 Ratio 6 Ratio 7 Physical Properties in Ordinary State Hardness (Duro A) 70 70 69 70 100% Modulus (MPa) 5.1 5.6 6.0 5.5 Strength at Break (MPa) 15.5 15.3 15.4 14.6 Elongation at break (%) 270 240 240 260 Heat aging test (190℃, 100 hours) Change in hardness (Duro A) +10 +7 +6 +9 Change in 100% modulus (%) +27 -38 -42 -24 Change in strength at break (%) -9 -47 -49 -29 Change in elongation at break (%) -20 +7 +6 -1 Heat aging test (190℃, 200 hours) Change in hardness (Duro A) +9 +9 +11 +10 Change in 100% modulus (%) +10 -29 -37 -38 Change in strength at break (%) -25 -59 -59 -58 Change in elongation at break (%) -14 -10 -9 -3 Heat aging test (190℃, 300 hours) Change in hardness (Duro A) +15 +20 +23 +21 100% Change in Modulus (%) -2 +7 Change in Strength at Break (%) -49 -56 -55 -57 Change in Elongation at Break (%) -22 -66 -62 -55 Heat Aging Test (190℃, 400hrs) Change in Hardness (Duro A) +17 +25 +24 +23 100% Change in Modulus (%) +10 Change in Strength at Break (%) -54 -29 -32 -37 Change in Elongation at Break (%) -37 -86 -86 -82 Heat Aging Test (190℃, 500hrs) Change in Hardness (Duro A) +21 +25 +28 +24 100% Change in Modulus (%) +41 Change in Strength at Break (%) -52 +11 +5 +0 Elongation change at break (%) -60 -96 -96 -95 Compression set test (175°C, 70 hours) (%) 21 20 20 21.

[0079] Example 17 In Example 16, the following ingredients were used: Acrylic rubber L 100 parts by weight FEF carbon black (Seast GSO) 60 parts by weight Stearic acid (TST) 1 part by weight Sodium fatty acid (Kao Chemical product Na-soap) 3 parts by weight Potassium fatty acid (NOF product Nonsal SK-1) 0.25 parts by weight Sulfur (Hosoi Chemical product precipitated sulfur) 0.3 parts by weight

[0080] The physical properties of the crosslinked acrylic rubber composition were measured as follows. Ordinary physical properties: Conforming to JIS K6251 and JIS K6253. Air heating aging test: Conforming to JIS K6257 (175°C: 300 hours). Oil immersion-air heating aging combined test: An oil (IRM903 oil) immersion test was carried out at 150°C for 168 hours in accordance with JIS K6258, which corresponds to ISO 1817, and then an air heating aging test was carried out at 175°C for 300 hours in accordance with JIS K6257, which corresponds to ISO 188. Compression set test: Conforming to JIS K6262, which corresponds to ISO 815-1, (175°C: 70 hours).

[0081] Example 18 In Example 17, acrylic rubber M was used in place of acrylic rubber L.

[0082] Example 19 In Example 17, acrylic rubber N was used in place of acrylic rubber L.

[0083] Comparative Example 8 In Example 17, acrylic rubber P was used in place of acrylic rubber L.

[0084] Comparative Example 9 In Comparative Example 8, 2.0 parts by weight of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Nocrac CD) was further added.

[0085] The results obtained in Examples 17 to 19 and Comparative Examples 8 and 9 are shown in Table 6 below. Table 6 Measurement results Ex. 17 Ex. 18 Ex. 19 Ratio 8 Ratio 9 Physical properties at normal state Hardness (Duro A) 69 68 67 69 66 100% modulus (MPa) 6.0 6.0 5.7 5.5 5.2 Strength at break (MPa) 15.9 15.6 15.3 14.9 14.5 Elongation at break (%) 280 290 300 280 290 Heat aging test (175°C, 300 hours) Change in hardness (Duro A) +9 +8 +9 +10 +8 Change in 100% modulus (%) -34 -58 -61 -42 -64 Change in strength at break (%) -49 -72 -78 -72 -74 Change in elongation at break (%) -3 +25 +27 -19 +67 Combined oil immersion and heat aging test Hardness change (Duro A) +9 +10 +10 +17 +17 100% modulus change (%) -26 -55 -56 -13 -25 Strength at break change (%) -49 -71 -76 -66 -69 Elongation at break change (%) -18 +8 +3 -60 -51 Compression set test (150°C, 70 hours) (%) 32 33 31 32 32

[0086] Example 20: A 200 ml borosilicate glass flask was charged with 30 g of styrene, 30 mg of compound [I-A], and 90 mg of azobisisobutyronitrile. The mixture was subjected to three cycles of freeze-degassing and then polymerized at 80°C for 24 hours. The contents were slightly yellow at the beginning of the polymerization, but became a colorless solid at the end of the polymerization. This was dissolved in toluene and removed from the reaction vessel. The monomer conversion determined by evaporation to dryness was 96%. The toluene solution of the copolymer was heated on a hot plate at 150°C for 1 hour to remove volatile components. Further drying at 100°C for 1.5 hours under reduced pressure yielded a resinous copolymer Q of styrene and compound [I-A].

[0087] A portion of the toluene solution of the copolymer removed from the reaction vessel was added to methanol to precipitate the copolymer, which was then dried under reduced pressure at 60°C for 3 hours. 1 It was used for H-NMR and GPC measurements.

[0088] The mole fraction composition of copolymer Q is l The results were obtained by H-NMR (400 MHz, CDCl3, δ ppm) according to the following formula: Compound [I-A]: 0.037 mol %, Styrene: 99.963 mol %. α: Integrated value of signals from 3.1 to 3.4 ppm β: Integrated value of signals from 5.9 to 7.7 ppm Compound [I-A] (mol %) = 500 × α / (5α + 3β) Styrene (mol %) = 100 - Compound [I-A] (mol %)

[0089] The weight fraction composition was calculated from the following formula: Compound [I-A]: 0.09% by weight, Styrene: 99.91% by weight. Compound [I-A] (wt%) = (Compound [I-A] (mol%) x 239.34 x 100) / [Compound [I-A] (mol%) x 239.34 + (Styrene (mol%)) x 104.15] Styrene (wt%) = 100 - Compound [I-A] (wt%)

[0090] The weight-average molecular weight (Mw) and Z-average molecular weight (Mz) were measured by gel permeation chromatography (GPC) under the following conditions: Mw, Mz, and Mz / Mw were 3.56 × 10 5 , 1.84×106 , 5.16. Equipment: Shimadzu HPLC system 20A Column: Shodex GPC KF-807L x 4 Detector: RI Measurement temperature: 40°C Sample concentration: 0.4% Carrier (THF) flow rate: 1.0 ml / min

[0091] Example 21 In Example 20, the amount of compound [IA] was changed to 15 mg, and a resinous copolymer R of styrene and compound [IA] was obtained. The polymerization rate of the monomers was 95%, and the weight fraction composition was compound [IA]: 0.05 wt % and styrene: 99.95 wt %. The Mw, Mz, and Mz / Mw were each 2.55 × 10 5 , 1.06×10 6 , was 4.17.

[0092] Example 22 In Example 20, 30 mg of compound [IB] was used instead of compound [IA] to obtain a resinous copolymer S of styrene and compound [IB]. The conversion of the monomers was 96%, and Mw, Mz, and Mz / Mw were 3.33 × 10 5 , 1.64×10 6 , was 4.92.

[0093] In addition, l Attempts to determine the amount of compound [IB] copolymerized in the resulting copolymer using H-NMR (400 MHz, CDCl3, δ ppm) from the following formula were impossible because no signal was detected at 3.1-3.4 ppm. This is presumably due to the loss of methyl groups on the nitrogen atoms due to thermal history. However, judging from the weight fraction composition of the amounts of styrene and compound [IB] added, the weight fraction of compound [IB] in the copolymer is presumed to be in the range of 0.05-0.10 wt%. α: integral value of the signal at 3.1-3.4 ppm β: integral value of the signal at 5.9-7.7 ppm Compound [IB] (mol%) = 500 × α / (5α + 3β) (mol%) Styrene (mol%) = 100 - Compound [IB] (mol%)

[0094] Comparative Example 10 In Example 20, the compound [IA] was not used, and a resinous styrene homopolymer T was obtained. The polymerization rate of styrene was 96%, and Mw, Mz, and Mz / Mw were 3.36×10 5 , 1.67×10 6 , was 4.97.

[0095] Reference Example 3 To the toluene solution of the styrene homopolymer obtained in Comparative Example 10, 0.1 parts by weight of a phenolic antioxidant, 2,6-di-tert-butyl-4-methylphenol (BHT: a product of Tokyo Chemical Industry Co., Ltd.), was added per 100 parts by weight of solid content, and the volatile components were then removed and the mixture was dried under reduced pressure under the same conditions as in Example 20 to obtain a styrene resin composition.

[0096] Reference Example 4 In Reference Example 3, the same amount (0.1 part by weight) of Irganox 1010 manufactured by BASF was used as the phenolic antioxidant in place of 2,6-di-tert-butyl-4-methylphenol to obtain a styrene resin composition.

[0097] Comparative Example 11 In Reference Example 3, the same amount (0.1 part by weight) of compound [IA] was used in place of the phenolic antioxidant 2,6-di-tert-butyl-4-methylphenol to obtain a styrene resin composition.

[0098] Comparative Example 12 In Reference Example 3, the same amount (0.1 part by weight) of compound (a) of Reference Example 1 was used in place of the phenolic antioxidant 2,6-di-tert-butyl-4-methylphenol to obtain a styrene resin composition.

[0099] Example 23: In Example 20, the amount of styrene was changed to 27.0 g, and 3.0 g of methyl methacrylate was newly added to obtain a resinous copolymer U of styrene, methyl methacrylate, and compound [IA]. The polymerization rate of the monomers was 94%, and the weight fraction composition excluding compound [IA] was 90.63% by weight of styrene and 9.37% by weight of methyl methacrylate. Mw, Mz, and Mz / Mw were each 2.57 x 10 5 , 9.48×10 6, 3.69. Since the signal at 3.1-3.4 ppm derived from compound [IA] overlapped with the signal derived from methyl methacrylate, the weight fraction of compound [IA] could not be determined.

[0100] Comparative Example 13 In Example 23, compound [IA] was not used, and a resinous styrene-methyl methacrylate copolymer V was obtained. The polymerization rate of the monomers was 95%, and the weight fraction composition was 90.63% by weight of styrene and 9.37% by weight of methyl methacrylate. Mw, Mz, and Mz / Mw were each 2.56 × 10 5 , 9.96×10 5 , was 3.9.

[0101] Example 24 In Example 20, the amount of styrene was changed to 27.0 g, and 3.0 g of acrylonitrile was newly used to obtain a resinous copolymer W of styrene, acrylonitrile, and compound [I-A]. The polymerization rate of the monomers was 97%, and the weight fraction composition was 90.14% by weight of styrene, 9.77% by weight of acrylonitrile, and 0.09% by weight of compound [I-A]. Mw, Mz, and Mz / Mw were each 3.75 x 10 5 , 2.04 × 10 6 , 5.45.

[0102] Comparative Example 14 In Example 24, compound [IA] was not used, and a resinous copolymer X was obtained. The monomer polymerization rate was 91%, and the weight fraction composition was 90.23% by weight of styrene and 9.77% by weight of acrylonitrile. Mw, Mz, and Mz / Mw were each 3.90×10 5 , 1.77×10 6 , was 4.55.

[0103] Example 25: In Example 20, the amount of styrene was changed to 29.4 g, and 0.6 g of methacrylic acid was newly added to obtain a resinous copolymer Y of styrene, methacrylic acid, and compound [I-A]. The monomer polymerization rate was 87%, and the weight fraction composition was 98.15% by weight of styrene, 1.78% by weight of methacrylic acid, and 0.07% by weight of compound [I-A]. Mw, Mz, and Mz / Mw were each 4.96 x 10 5, 2.14 × 10 6 , was 4.32.

[0104] Comparative Example 15 In Example 25, compound [IA] was not used, and a resinous copolymer Z of styrene and methacrylic acid was obtained. The polymerization rate of the monomers was 91%, and the weight fraction composition was 98.06% by weight of styrene and 1.94% by weight of methacrylic acid. Mw, Mz, and Mz / Mw were each 4.06×10 5 , 1.85×10 6 , was 4.51.

[0105] Example 26: A 200 ml borosilicate glass flask was charged with 15 g of methyl methacrylate, 15 g of ethyl acrylate, 30 mg of compound [I-A], 30 mg of azobisisobutyronitrile, and 30 g of ethyl acetate. The mixture was subjected to three cycles of freeze-degassing and then polymerized at 70°C for 24 hours. The monomer conversion determined by evaporation to dryness was 91%. The ethyl acetate solution of the copolymer was heated on a hot plate at 150°C for 0.5 hours to remove volatile components. Further removal of volatile components under reduced pressure (100°C, 1 hour) and atmospheric pressure (150°C, 2 hours) yielded a resinous copolymer ME1 of methyl methacrylate, ethyl acrylate, and compound [I-A].

[0106] Comparative Example 16 The polymerization reaction and devolatilization procedure were carried out in the same manner as in Example 26, but without using compound [IA], to obtain a resinous copolymer ME2. The polymerization rate of the monomers was 87%.

[0107] The resins or resin compositions obtained in each of the Examples, Comparative Examples, and Reference Examples were used to measure the melt flow rate (MFR), yellowness index (YI), and thermal stability. MFR: Measured at 200°C under a 5.0 kg load in accordance with JIS K7210-1, which corresponds to ISO 1133-1 (2011). (However, measurements were made under loads of 7.2 kg and 13.7 kg in Example 25, Comparative Example 15, and Example 26 and Comparative Example 16, respectively.) YI: A 30 mm x 50 mm, 1 mm thick plate was heated in an air-circulating oven at 150°C for a specified time, and then measured using a Nippon Denshoku Kogyo colorimeter ZE6000 in accordance with ASTM D1925, which corresponds to ISO 13468-1 (2019). Thermal stability: A circular plate with a diameter of 30 mm and a thickness of 2 mm was clamped at the top with a clip (clamp margin 15 mm wide x 5 mm long) and heated in an air-circulating oven at 140°C. As thermal oxidative degradation progressed, the test piece gradually melted and deformed, and the time it took for it to break free from the clip and fall was measured.

[0108] The results obtained in Examples 20 to 26, Comparative Examples 10 to 16, and Reference Examples 3 and 4 are shown in Tables 7 to 11. Table 7 Example 20 Example 21 Example 22 Resin Q R S Amount of compound [I-A] charged (parts by weight) 0.10 0.05 - Amount of compound [I-B] charged (parts by weight) - - 0.10 Melt flow rate (g / 10 min) 8.6 14.9 8.9 YI before test -2.7 -3.7 -0.3 YI after 150°C heating test 1 day 0.5 -0.7 0.7 2 days -3.2 -1.0 1.5 3 days 1.1 1.4 3.6 4 days 1.6 1.8 4.4 5 days -2.7 -2.9 0.2 6 days 0.9 -0.3 2.3 Test piece drop time (hours) 280 260 170 Table 8 Comparison 10 Reference 3 Reference 4 Ratio 11 Ratio 12 Resin T T T T T T Amount of compound [I-A] charged (parts by weight) - - - - - Amount of compound [I-B] charged (parts by weight) - - - - - [Compounding ingredients (parts by weight)] BHT - 0.1 - - - Irganox 1010 - - 0.1 - - Compound [I-A] - - - 0.1 Compound (a) (Reference Example 1) - - - - 0.1 Melt flow rate (g / 10 min) 23.8 10.2 11.2 10.2 19.1 YI before test -2.7 -3.3 -2.7 -3.2 3.3 YI after 150℃ heating test 1 day 9.6 0.6 0.4 9.0 0.1 2 days 17.0 -2.4 -1.3 16.6 2.8 3 days 30.0 1.9 1.8 20.9 2.8 4 days 36.4 2.4 0.4 22.5 5.1 5 days 46.7 -0.4 -2.2 24.8 6.6 6 days 56.5 3.9 0.0 27.3 6.2 Time to drop test piece (hours) 20 240 200 180 200 Table 9 Actual 23 Ratio 13 Actual 24 Ratio 14 Resin U V W X Compound [I-A] charge amount (parts by weight) 0.10 - 0.10 - Melt flow rate (g / 10 min) 9.0 22.6 13.7 21.1 YI before test -0.9 -2.0 -3.4 -1.5 YI after 150°C heating test 1 day 0.6 6.7 0.4 32.1 2 days -0.4 13.7 3.0 48.0 3 days 0.0 18.5 3.1 55.9 4 days 2.1 23.2 5.8 60.3 5 days 3.9 35.4 8.1 64.0 6 days 3.8 42.2 6.3 81.9 Time to drop test piece (hours) 70 20 130 20 Table 10 Actual 25 Ratio 15 Resin Y Z Amount of compound [I-A] charged (parts by weight) 0.10 - Melt flow rate [load 7.2 kg] (g / 10 min) 10.9 18.5 YI before test -6.8 -2.2 YI after 150°C heating test 1 day -3.7 13.6 2 days -3.3 35.8 3 days 2.5 52.7 4 days 6.8 66.1 5 days 3.3 65.4 6 days 6.1 110.9 Time to drop test piece (hours) >500 80 Table 11 Actual 26 Ratio 16 Resin ME1 ME2 Amount of compound [I-A] charged (parts by weight) 0.10 - Melt flow rate [13.7 kg load] (g / 10 min) 6.4 13.7 Test piece drop time (hours) 50 20.

[0109] The above results suggest the following: (1) Examples 1 to 15 show that copolymers copolymerized with phenothiazine derivative compound [I] are stabilized against oxidative degradation. (2) Comparisons between Example 16 and Comparative Examples 5 to 7 and Example 20 and Comparative Examples 11 to 12 show that copolymerization of phenothiazine derivative compound [I] with other polymerizable unsaturated monomers exhibits superior oxidative degradation prevention effects. (3) Comparisons between Examples 17 to 19 and Comparative Examples 8 and 9 show that synthetic polymer materials copolymerized with the phenothiazine derivative compound of the present invention are less susceptible to extraction of antioxidant components from molded articles by oil immersion, thereby maintaining their functionality (Figure 3). (4) The amount of phenothiazine derivative compound [I], a copolymerizable antioxidant, can be significantly reduced compared to conventional additive-type antioxidants. (5) By copolymerizing the phenothiazine derivative compound [I], it is possible to suppress an increase in the melt viscosity (melt flow rate) of the resinous polymer due to the thermal history in the post-polymerization treatment step (Examples 20 to 26). (6) It is possible to suppress yellowing of the resinous molded product under thermal oxidative degradation conditions (Examples 20 to 25). (7) It is possible to suppress deformation of the resinous molded product due to thermal oxidative degradation under thermal oxidative degradation conditions, thereby maintaining the original functions and physical properties of the resin for a long period of time (Examples 20 to 26).

Claims

1. In synthetic polymer materials produced by addition polymerization of polymerizable unsaturated monomers, the polymerizable unsaturated monomers constituting the material during production have the general formula (where R 1 is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R 2 A method for using a phenothiazine derivative compound [I], which comprises copolymerizing a synthetic polymer material with a phenothiazine derivative compound represented by the formula (I) represented by the formula (I):

2. A method for utilizing a phenothiazine derivative compound according to claim 1, wherein the phenothiazine derivative compound [I] is 3-ethenyl-10-methyl-10H-phenothiazine.

3. A method for utilizing a phenothiazine derivative compound according to claim 1, wherein the phenothiazine derivative compound [I] is 2-(1-methylethenyl)-10-methyl-10H-phenothiazine.

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