JP6159415B2 - Bromine-containing N-phenyldiacrylimide derivative and method for producing the same - Google Patents

Description

  The present invention relates to a bromine-containing N-phenyldiacrylimide derivative useful as a reactive flame retardant and a polymer flame retardant precursor and a method for producing the same.

  Acrylic resins such as polymethyl methacrylate are used in a wide range of fields such as optical materials, household electrical appliances, office automation equipment, and automobiles, taking advantage of their transparency and dimensional stability. .

  In recent years, acrylic resins have been widely used in higher performance optical materials such as optical lenses, prisms, mirrors, optical disks, optical fibers, liquid crystal display sheets and films, light guide plates, etc. The optical properties, moldability, and heat resistance required for these products are also higher.

  However, although acrylic resin has excellent transparency and weather resistance, there is a problem that flame retardancy and heat resistance are not sufficient. Technologies for improving the flame retardancy of acrylic resins include, for example, a method of adding a phosphorus flame retardant to an acrylic resin, polymerizing a brominated monomer as a comonomer, and introducing a brominated monomer unit into the acrylic resin. The method is known. In addition, as a technique for improving the heat resistance of an acrylic resin, for example, a method of introducing a maleic anhydride monomer or a method of introducing an imide ring is known (for example, see Patent Documents 1 to 4).

  As a method for introducing an imide ring into a polymer, an acrylic amide and methyl methacrylate are copolymerized in a methanol solvent in the presence of a radical polymerization catalyst, and then the imide is heated at a temperature of 80 to 150 ° C. in the presence of a basic catalyst. There is known a production method in which an acrylic amide unit in a copolymer is converted into a glutarimide unit by carrying out a polymerization reaction (see, for example, Patent Document 5).

  Furthermore, it has been reported that a polymer having a cyclic imide structure can be obtained through intramolecular cyclization by radical polymerization of an N-substituted diacrylimide derivative (see, for example, Non-Patent Document 1).

Japanese Patent Laid-Open No. 5-230316 JP-A-6-220292 JP 2004-331915 A Japanese Patent Laid-Open No. 5-262951 Japanese Patent Laid-Open No. 2-153904

Journal of Polymer Science, Vol.46, No.9, 507-514

  The present invention is a reactive flame retardant that can easily impart excellent heat resistance, optical properties, and flame retardancy by introducing it into a polymer as a copolymerization component, or by polymerizing these as a main component. A bromine-containing N-phenyldiacrylimide derivative useful as a precursor capable of providing a heat-resistant polymer flame retardant and a method for producing the same are provided.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention is as follows.

（式中、
ｍは、２〜５の整数であり、
ｋは５−ｍであり、
Ｒ_１は、同一であっても異なっていてもよく、水素原子又は炭素数１〜４のアルキル基であり、
Ｒ_２は、水素原子、フッ素原子、塩素原子、ヨウ素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数１〜４のアルキルチオ基、炭素数１〜４のハロアルキル基、炭素数１〜４のハロアルコキシ基、ビニル基、ニトロ基、シアノ基、アルデヒド基、アミノ基、ヒドロキシル基、チオール基、スルホ基、スルホンアミド基、カルボキシル基もしくはエステル基であり、ｋが２以上の場合、Ｒ_２は同一であっても異なっていてもよい）
で表わされる含臭素Ｎ−フェニルジ（メタ）アクリルイミド誘導体、及び製造方法に関する。The following general formula (1):

(Where
m is an integer of 2 to 5,
k is 5-m,
R ₁ may be the same or different, and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ₂ is a hydrogen atom, a fluorine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a haloalkyl having 1 to 4 carbon atoms. A haloalkoxy group having 1 to 4 carbon atoms, a vinyl group, a nitro group, a cyano group, an aldehyde group, an amino group, a hydroxyl group, a thiol group, a sulfo group, a sulfonamide group, a carboxyl group, or an ester group, and k is In the case of 2 or more, R ₂ may be the same or different)
The present invention relates to a bromine-containing N-phenyldi (meth) acrylimide derivative represented by the formula:

  By using the bromine-containing N-phenyldiacrylimide derivative of the present invention as a polymerization component, a cyclic imide structure can be easily introduced into the polymer together with bromine. Therefore, the bromine-containing N-phenyldiacrylimide derivative of the present invention is expected as a reactive flame retardant capable of imparting excellent heat resistance, optical properties and flame retardancy, or as a precursor of a polymer flame retardant.

The ¹ H-NMR chart of the compound obtained in Example 1 is shown. The FT-IR chart of the compound obtained in Example 1 is shown. ¹ shows a ¹ H-NMR chart of the compound obtained in Example 2. The FT-IR chart of the compound obtained in Example 2 is shown. The ¹ H-NMR chart of the compound obtained in Example 3 is shown. The FT-IR chart of the compound obtained in Example 3 is shown. ¹ shows a ¹ H-NMR chart of the compound obtained in Example 4. The FT-IR chart of the compound obtained in Example 4 is shown. ¹ shows a ¹ H-NMR chart of the compound obtained in Example 5. The FT-IR chart of the compound obtained in Example 5 is shown.

  Hereinafter, embodiments of the present invention will be described in detail.

（式中、
ｍは、２〜５の整数であり、
ｋは５−ｍであり、
Ｒ_１は、同一であっても異なっていてもよく、水素原子又は炭素数１〜４のアルキル基であり、
Ｒ_２は、水素原子、フッ素原子、塩素原子、ヨウ素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数１〜４のアルキルチオ基、炭素数１〜４のハロアルキル基、炭素数１〜４のハロアルコキシ基、ビニル基、ニトロ基、シアノ基、アルデヒド基、アミノ基、ヒドロキシル基、チオール基、スルホ基、スルホンアミド基、カルボキシル基もしくはエステル基であり、ｋが２以上の場合、Ｒ_２は同一であっても異なっていてもよい）
で表わされる含臭素Ｎ−フェニルジアクリルイミド誘導体である。The present invention provides the following general formula (1):

(Where
m is an integer of 2 to 5,
k is 5-m,
R ₁ may be the same or different, and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ₂ is a hydrogen atom, a fluorine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a haloalkyl having 1 to 4 carbon atoms. A haloalkoxy group having 1 to 4 carbon atoms, a vinyl group, a nitro group, a cyano group, an aldehyde group, an amino group, a hydroxyl group, a thiol group, a sulfo group, a sulfonamide group, a carboxyl group, or an ester group, and k is In the case of 2 or more, R ₂ may be the same or different)
A bromine-containing N-phenyldiacrylimide derivative represented by the formula:

  Here, the term “C1-C4 alkyl group” means a monovalent group of a linear or branched aliphatic saturated hydrocarbon having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, Examples include propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group and the like.

  The term “C1-C4 haloalkyl group” means a C1-C4 alkyl group substituted with one or more halogen atoms, and includes a bromomethyl group, a 2-bromoethyl group, a 3-bromopropyl group, 4 -Bromobutyl group, iodomethyl group, 2-iodoethyl group, 3-iodopropyl group, 4-iodobutyl group, fluoromethyl group, 2-fluoroethyl group, 3-fluoropropyl group, 4-fluorobutyl group, tribromomethyl group, A trichloromethyl group, a trifluoromethyl group, etc. can be illustrated. The halogen atoms of the alkyl group having 1 to 4 carbon atoms substituted with two or more halogen atoms may be the same or different.

  The term “C 1-4 alkoxy group” means the group RO— (where R is an alkyl group having 1 to 4 carbon atoms), and is a methoxy group, ethoxy group, propoxy group, isopropoxy group. , Butoxy group, isobutoxy group, s-butoxy group, t-butoxy group and the like.

  The term “C1-C4 haloalkoxy group” means a C1-C4 alkoxy group substituted with one or more halogen atoms, including bromomethoxy group, 2-bromoethoxy group, 3-bromopropyl group. Oxy group, 4-bromobutyloxy group, iodomethoxy group, 2-iodoethoxy group, 3-iodopropyloxy group, 4-iodobutyloxy group, fluoromethoxy group, 2-fluoroethoxy group, 3-fluoropropyloxy group 4-fluorobutyloxy group, tribromomethoxy group, trichloromethoxy group, trifluoromethoxy group and the like. The halogen atoms of the alkyl group having 1 to 4 carbon atoms substituted with two or more halogen atoms may be the same or different.

  The term “alkylthio group having 1 to 4 carbon atoms” means a group R′S— (wherein R ′ is an alkyl group having 1 to 4 carbon atoms), methylthio group, ethylthio group, propylthio group, Examples include isopropylthio group, butylthio group, isobutylthio group, s-butylthio group, t-butylthio group and the like.

  The terms “halogen atom” or “halo” are interchangeable and mean iodine atom, bromine atom, chlorine atom, fluorine atom.

  The term “carboxyl group or ester group” means a group: —COOH or an ester group thereof (ie, group: —COOR ″). Here, R ″ means an alkyl group having 1 to 4 carbon atoms.

  The bromine content of the bromine-containing N-phenyldiacrylimide derivative of the present invention is 30 to 75% by weight, preferably 35 to 75% by weight, more preferably 45 to 75% by weight, and particularly preferably 50 to 75% by weight. . In addition, in this invention, a bromine content means the measured value of the method according to JISK7229 (flask combustion method).

In the general formula (1), R ₁ may be either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may include both a hydrogen atom and an alkyl group having 1 to 4 carbon atoms in the compound. A hydrogen atom or a methyl group is preferable in that the content can be further increased, and a hydrogen atom is more preferable.

In the general formula (1), R ₂ may be appropriately selected according to the availability of raw materials and the ease of synthesis, but it is more preferable that it contains one or more hydrogen atoms in terms of higher bromine content. More preferably, all are hydrogen atoms.

  In the general formula (1), the bromine atom substitution number m is 2 to 5, preferably 3 to 5, and more preferably 3 to 4 from the viewpoint of bromine content.

（式中、
ｍは、２〜５の整数であり、
ｋは５−ｍであり、
Ｒ_２は、水素原子、フッ素原子、塩素原子、ヨウ素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数１〜４のアルキルチオ基、炭素数１〜４のハロアルキル基、炭素数１〜４のハロアルコキシ基、ビニル基、ニトロ基、シアノ基、アルデヒド基、アミノ基、ヒドロキシル基、チオール基、スルホ基、スルホンアミド基、カルボキシル基もしくはエステル基であり、ｋが２以上の場合、Ｒ_２は同一であっても異なっていてもよい）
で表わされるアニリン誘導体と、一般式（３）：

（式中、
Ｒ_１は、水素原子又は炭素数１〜４のアルキル基であり、
Ｘは、塩素原子又は臭素原子である）
で表わされるアクリル酸ハライド誘導体を、塩基存在下で反応させることで、前記一般式（１）：

（式中、Ｒ_１、Ｒ_２、ｍ及びｋは前記と同義である）
で表わされる含臭素Ｎ−フェニルジアクリルイミド誘導体を得ることができる。The production method of the bromine-containing N-phenyldiacrylimide derivative of the present invention is not particularly limited, and any production method may be used. Preferably, the following general formula (2):

(Where
m is an integer of 2 to 5,
k is 5-m,
R ₂ is a hydrogen atom, a fluorine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a haloalkyl having 1 to 4 carbon atoms. A haloalkoxy group having 1 to 4 carbon atoms, a vinyl group, a nitro group, a cyano group, an aldehyde group, an amino group, a hydroxyl group, a thiol group, a sulfo group, a sulfonamide group, a carboxyl group, or an ester group, and k is In the case of 2 or more, R ₂ may be the same or different)
An aniline derivative represented by the general formula (3):

(Where
R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
X is a chlorine atom or a bromine atom)
Is reacted in the presence of a base to give the general formula (1):

(Wherein R ₁ , R ₂ , m and k are as defined above)
The bromine-containing N-phenyl diacrylimide derivative represented by this can be obtained.

  The aniline derivative represented by the general formula (2) used in the production method of the present invention is commercially available, and can be easily obtained from suppliers such as Manac Corporation and Sigma Aldrich Japan Corporation. For example, 2,4-, 2,5-, 2,6- or 3,4-dibromoaniline, 2,6-dibromo-4-methylaniline, 4-chloro-2,4-dibromoaniline, 2,6- Dibromo-4-trifluoromethylaniline, 2,6-dibromo-4-trifluoromethoxyaniline, 2,6-dibromo-4-nitroaniline, 2,4,6-tribromoaniline, 3-methyl-2,4 , 6-tribromoaniline and the like. Further, it can be synthesized according to a known method (for example, the method described in Organic Syntheses, Vol. 13, p. 93 (1933)).

  The acrylic acid halide derivative represented by the general formula (3) used in the production method of the present invention is commercially available, and can be easily obtained from suppliers such as Tokyo Chemical Industry Co., Ltd. For example, acrylic acid chloride, methacrylic acid chloride, 2-ethylacrylic acid chloride and the like can be mentioned. Further, it can be synthesized by subjecting an acrylic acid derivative to a known acid halide reaction.

  The amount of the acrylic acid halide derivative represented by the general formula (3) is 1.0 to 10 moles, preferably 1.5 to 8 moles, more preferably 1 mole relative to 1 mole of the aniline derivative represented by the general formula (2). Is 2.0-5.0 mol.

  As the base used in the production method of the present invention, any of inorganic bases, organic bases and metal alkoxides can be used, and one kind or a combination of two or more kinds can also be used. The inorganic base is not particularly limited. For example, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydride, sodium hydride, potassium hydride, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, Examples thereof include sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, disodium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, metal lithium, metal sodium, and metal potassium. Examples of the organic base include, but are not limited to, pyridine, 4-dimethylaminopyridine (DMAP), lutidine, collidine, trimethylamine, dimethylamine, triethylamine, diethylamine, N, N-diisopropylethylamine, N, N-diisopropylpentylamine. , Morpholine, piperidine, pyrrolidine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), 1 , 4-diazabicyclo [2.2.2] octane (DABCO). Although it does not specifically limit as a metal alkoxide, For example, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, t-butoxy sodium, t-butoxy potassium, etc. are mentioned. Of these, organic bases are preferable, and pyridine, 4-dimethylaminopyridine (DMAP), and triethylamine are more preferable.

  The usage-amount of a base is 0.5-20 mol with respect to 1 mol of aniline derivatives represented by General formula (2), Preferably it is 0.5-15 mol, More preferably, it is 0.8-10 mol.

  In the production method of the present invention, the order of addition of the aniline derivative represented by the general formula (2), the acrylic acid halide derivative represented by the general formula (3) and the base is not particularly limited. These three types may be added and mixed simultaneously to start the reaction, or after mixing any two types, the remaining one type may be added at once or dividedly to start and proceed the reaction.

  The production method of the present invention may be carried out without a solvent or using a solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction, and is appropriately selected depending on the desired reaction temperature and the like. Specific examples include aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, monochlorobenzene, monobromobenzene, dichlorobenzene, and trichlorobenzene; n-hexane, n-heptane, n-octane, and cyclopentane. , Cyclohexane, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, ethylene dichloride, aliphatic hydrocarbon solvents such as 1,1,1-trichloroethane, trichloroethylene, dimethyl ether, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran Ether solvents such as 1,4-dioxane and cyclopentyl methyl ether, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, γ-butyrolactone and γ-valerolactone, acetone, methyl Examples thereof include ketone solvents such as ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, sulfur-containing solvents such as dimethyl sulfoxide, nitrogen-containing solvents such as picoline and pyridine, and nitrile solvents such as acetonitrile and benzonitrile. These may be used alone or in combination of two or more. Among these solvents, toluene, xylene, monochlorobenzene, methylene chloride, tetrahydrofuran, cyclopentyl methyl ether, acetone, methyl ethyl ketone, due to the solubility of raw materials, little influence on human body and environment, and easy industrial availability. , Methyl isobutyl ketone, dimethyl sulfoxide, and acetonitrile are preferable.

  The amount of the solvent used is preferably 0 to 20 times (weight basis), more preferably 0 to 10 times (weight basis) based on 1 g of the compound represented by the general formula (2). .

  The reaction temperature in the production method of the present invention is preferably in the range of 0 to 200 ° C. The reaction temperature is more preferably in the range of 0 to 150 ° C. from the viewpoint of suppressing side reactions.

  The reaction time in the production method of the present invention can be appropriately set according to the conditions such as the amount and type of the starting material used, the presence or absence of a solvent, the type thereof, and the reaction temperature. Usually, it is preferably 1 minute to 336 hours, and more preferably 10 minutes to 168 hours from the viewpoint of workability.

  After completion of the reaction, the by-product inorganic salt may be removed from the resulting reaction solution using a general method. The method for removing the by-product inorganic salt is not particularly limited. For example, washing with water, an aqueous acid solution (such as an aqueous hydrochloric acid solution) and / or an alkaline aqueous solution (such as an aqueous sodium hydroxide solution or an aqueous sodium hydrogen carbonate solution) can be mentioned. It is done.

  The compound represented by the general formula (1) can be isolated from the reaction solution thus obtained by performing general operations such as liquid separation and concentration. The isolated compound can be further purified by recrystallization, column chromatography or the like, if necessary.

  Hereinafter, the present invention will be illustrated by specific examples, but the present invention is not limited to the contents of the examples. In addition, the measuring method of melting | fusing point of the compound obtained in the Example, bromine content, NMR, and an infrared absorption spectrum is as follows.

  Melting point: Using a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation), the temperature was raised to 40 to 400 ° C. at 10 ° C. per minute, and measurement was performed. The melting point was calculated from the extrapolation point of the DSC curve by analysis software.

  Bromine content: Measured by a method according to JIS K 7229 (flask combustion method).

NMR: A solution in which a compound and deuterated chloroform (chloroform-d ₁ 0.05% TMS produced by Cambrige Isotope Laboratories, Inc.) was mixed was prepared, and ¹ H- was obtained by NMR (JNM-AL400, manufactured by JEOL Ltd.). NMR measurement was performed.

  Infrared absorption spectrum: Using an IR measuring apparatus (Spectrum 100 FT-IR Spectrometer manufactured by PerkinElmer Co., Ltd.), an infrared absorption spectrum was measured by the KBr method.

  HPLC purity: Measured using high performance liquid chromatography (HPLC) and calculated by area percentage. The measurement conditions are as follows.

Sample preparation: 1.0 mg sample dissolved in 1.0 mL acetonitrile Detector: SPD-10AVP (manufactured by Shimadzu Corporation)
Oven: CTO-10AVP (manufactured by Shimadzu Corporation)
Pump: LC-10ADVP (manufactured by Shimadzu Corporation)
Column: ODS-80TM (manufactured by Tosoh Corporation)
Eluent: acetonitrile / water / phosphoric acid = 600/400 / 0.5
Column temperature: 40 ° C
Flow rate: 1.0 mL / min
Wavelength: 254 nm

[Example 1]
Synthesis of N- (2,4,6-tribromophenyl) dimethacrylamide The eggplant flask equipped with a condenser was charged with 1.65 g (5.00) of 2,4,6-tribromoaniline (manac). Mmol), 5.00 mL of dichloromethane, 0.09 g (0.736 mmol) of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.52 g (15. 0 mmol) was added, and 1.57 g (15.0 mmol) of methacryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added dropwise in an ice bath, followed by stirring at room temperature for 6 days. After completion of the reaction, the reaction solution was distilled off under reduced pressure and recrystallized with a mixed solvent of hexane / ethyl acetate. The obtained white crystals were dried under vacuum to obtain 1.49 g (3.20 mmol) of the target compound, yield 64%, HPLC purity 100.0%, bromine content 51.5%, melting point 139 ° C. Obtained. ¹ H-NMR of the target product is shown in FIG. 1, and an FT-IR chart is shown in FIG.

[Example 2]
Synthesis of N- (2,4,6-tribromophenyl) diacrylimide Into a 500 mL four-necked flask equipped with a condenser, a thermometer and a gas absorber, 2,4,6-tribromoaniline (Manac Co., Ltd.) 50.0 g (150 mmol), 4-dimethylaminopyridine (Tokyo Chemical Industry Co., Ltd.) 1.03 g (8.43 mmol), monochlorobenzene 289 mL, triethylamine 17.2 g (170 mmol) were added, To this, 20.6 g (227 mmol) of acryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, stirred at an internal temperature of 40 ° C. for 24 hours, and then 17.6 g of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 174 mmol) was further added, and 19.9 g (219 mmol) of acryloyl chloride was further added dropwise, followed by stirring for 1 hour. After returning to room temperature, 200 mL of water was injected to wash and separate the organic layer. After separation, the reaction solution was concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by column purification (heptane: ethyl acetate = 5: 1) to obtain 49.8 g (114 mmol) of the desired product, yield 75%, HPLC purity 93.7%, bromine content 54.8%, melting point Obtained at 93 ° C. The ¹ H-NMR of the target product is shown in FIG. 3, and the FT-IR chart is shown in FIG.

[Example 3]
Synthesis of N- (2,6-dibromo-4-nitrophenyl) dimethacrylimide To an eggplant flask equipped with a condenser, 3.00 g of 2,6-dibromo-4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) (10.1 mmol), monochlorobenzene 20.2 mL, 4-dimethylaminopyridine (Tokyo Chemical Industry Co., Ltd.) 0.06 g (0.491 mmol), triethylamine (Tokyo Chemical Industry Co., Ltd.) 2 .45 g (24.2 mmol) was added, 2.53 g (24.2 mmol) of methacryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added dropwise, and the mixture was stirred at an internal temperature of 70 ° C. for 17 hours. After completion of the reaction, the reaction solution was filtered, and then the mother liquor was concentrated under reduced pressure to obtain a crude product. The obtained crude product was recrystallized from methanol, and the crystals were collected by filtration. The obtained white crystals were blown and dried at 60 ° C. to obtain 3.55 g (8.22 mmol) of the desired product, yield 81%, HPLC purity 99.6%, bromine content 36.6%, melting point 141 ° C. Got in. FIG. 5 shows the ¹ H-NMR of the target product, and FIG. 6 shows the FT-IR chart.

[Example 4]
Synthesis of N- (2,6-dibromo-4-methylphenyl) dimethacrylimide Instead of 3.00 g (10.1 mmol) of 2,6-dibromo-4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) The same procedure as in Example 3 was conducted, except that 3.04 g (11.5 mmol) of 2,6-dibromo-4-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. The obtained crude product was recrystallized with a mixed solvent of heptane / monochlorobenzene, and the crystals were collected by filtration. The white crystals obtained were blown and dried at 60 ° C. to obtain 2.15 g (5.36 mmol) of the desired product, yield 47%, HPLC purity 10.0%, bromine content 39.7%, melting point 137 ° C. Got in. FIG. 7 shows the ¹ H-NMR of the target product, and FIG. 8 shows the FT-IR chart.

[Example 5]
Synthesis of N- (2,6-dibromo-4-trifluoromethoxyphenyl) dimethacrylimide 2,6-dibromo instead of 2,6-dibromo-4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) The procedure was the same as in Example 3 except that 3.00 g (8.96 mmol) of -4-trifluoromethoxyaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. The obtained crude product was recrystallized with a mixed solvent of heptane / monochlorobenzene, and the crystals were collected by filtration. The obtained white crystals were blown and dried at 60 ° C. to obtain 1.05 g (2.23 mmol) of the desired product, yield 25%, HPLC purity 99.7%, bromine content 33.1%, melting point 94 ° C. Got in. FIG. 9 shows the ¹ H-NMR of the target product, and FIG. 10 shows the FT-IR chart.

  By using the bromine-containing N-phenyldiacrylimide derivative of the present invention as a polymerization component, a cyclic imide structure can be easily introduced into the polymer together with bromine. Therefore, the bromine-containing N-phenylacrylamide derivative of the present invention can be polymerized as a reactive flame retardant capable of imparting heat resistance, optical properties and flame retardancy to the polymer by using as a copolymerization component, or as a main component thereof. Therefore, it is expected to be useful as a precursor of a polymer flame retardant capable of providing a high heat resistant polymer flame retardant.

Claims (6)

The following general formula (1):

(Where
m is an integer of 3 to 5,
k is 5-m,
R ₁ may be the same or different, and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ₂ is a hydrogen atom, a fluorine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a haloalkyl having 1 to 4 carbon atoms. A haloalkoxy group having 1 to 4 carbon atoms, a vinyl group, a nitro group, a cyano group, an aldehyde group, an amino group, a hydroxyl group, a thiol group, a sulfo group, a sulfonamide group, a carboxyl group, or an ester group, and k is In the case of 2 or more, R ₂ may be the same or different)
A bromine-containing N-phenyldiacrylimide derivative represented by:   The bromine-containing N-phenyl diacrylimide derivative according to claim 1, having a bromine content of 45 wt% to 75 wt%. The bromine-containing N-phenyl diacrylimide derivative according to claim 1 or 2, wherein R ₂ is a hydrogen atom. The following general formula (2):

(Where
m is an integer of 3 to 5,
k is 5-m,
R ₂ is a hydrogen atom, a fluorine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a haloalkyl having 1 to 4 carbon atoms. A haloalkoxy group having 1 to 4 carbon atoms, a vinyl group, a nitro group, a cyano group, an aldehyde group, an amino group, a hydroxyl group, a thiol group, a sulfo group, a sulfonamide group, a carboxyl group, or an ester group, and k is In the case of 2 or more, R ₂ may be the same or different)
An aniline derivative represented by the general formula (3):

(Where
R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
X is a chlorine atom or a bromine atom)
The following general formula (1), comprising reacting an acrylic acid halide derivative represented by the following formula in the presence of a base:

(Wherein R ₁ , R ₂ , m and k are as defined above)
The manufacturing method of the bromine-containing N-phenyl diacrylimide derivative represented by these. The method for producing a bromine-containing N-phenyldiacrylimide derivative according to claim 4 , wherein the base is an organic base. The method for producing a bromine-containing N-phenyldiacrylimide derivative according to claim 5 , wherein the organic base is at least one compound selected from the group consisting of triethylamine, pyridine and 4-dimethylaminopyridine.

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