JP2015098555A - Bromine-containing poly n-phenylacrylamide derivative and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fire retardant which has high compatibility with polyamide, has excellent heat resistance, does not cause blooming or decrease of mechanical characteristics, and can make polyamide resin flame-retardant by a small amount of addition.SOLUTION: A polymer comprises a repeating unit represented by formula (1), with bromine content of 45-80 wt.% wherein m is an integer of 2-5; k is 5-m; R1 is H or C1-4 alkyl group; R2 is H, halogen, C1-4 alkyl group, alkoxy group, alkylthio group, haloalkyl group, haloalkoxy group, vinyl group, nitro group, cyano group, aldehyde group, amino group, hydroxy group, thiol group, sulfo group, sulfonamide group, carboxyl group or ester group.

Description

  The present invention relates to a bromine-containing poly N-phenylacrylamide derivative and a method for producing the same.

  Plastic is an indispensable material in modern society. Plastic is generally a material that is weak to heat and ignites and ignites at a relatively low temperature. Therefore, electrical and electronic equipment, vehicle parts, and household items that use plastic must be made difficult to burn even when lit for fire safety, and are made flame retardant by adding a flame retardant to plastic. Yes. For these flame retardants, brominated flame retardants, phosphorus flame retardants, inorganic flame retardants and the like are mainly used.

  In particular, in brominated flame retardants, monomer type, oligomer or polymer type is used, and recently, oligomer or polymer type flame retardant having higher molecular weight is considered to have higher health and safety to the environment and human body, Furthermore, it is described that it is superior to the monomer type flame retardant in various properties (for example, non-blooming property and mechanical property) (for example, see Non-Patent Document 1 and Patent Document 1).

  However, these brominated flame retardants are not applicable to all plastics, and are blended in accordance with the characteristics of each resin, and none yet satisfy all the performances.

  For example, as the oligomer or polymer type flame retardant used in polyamide, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate oligomer, brominated epoxy and the like can be mainly mentioned (for example, see Patent Documents 2 to 4).

  The above oligomer or polymer type flame retardants are essentially incompatible with polyamide, so a large amount of addition is required for flame retardant, which impairs the original mechanical properties and surface appearance of the resin. was there.

  From this point, brominated polystyrene modified with a compound having an acid anhydride group or glycidyl group has been proposed by improving the compatibility with polyamide and suppressing the amount of addition required for improving the surface appearance and flame retardancy. (For example, refer to Patent Documents 5 and 6 and Non-Patent Document 2).

  These are reaction compatibilization methods utilizing carboxyl groups or amino groups present at both ends of the polyamide, and are not effective methods for end-capped polyamides or high molecular weight polyamides with few end groups. Moreover, since the effect is expressed by covalently bonding to the terminal portion, the molecular weight is remarkably increased, and further, a cross-linked product may be generated.

  As a method for improving the compatibility with the polyamide which improves the above problem, a method for making the solution compatible by introducing an acrylamide derivative capable of increasing the affinity by forming a hydrogen bond with the polyamide is disclosed. (For example, see Patent Documents 7 and 8).

  However, Patent Documents 7 and 8 do not contain a bromine atom having a flame retardant effect, and cannot impart flame retardancy to polyamide.

  For example, as an acrylamide polymer containing bromine, a polymer in which bromine is monosubstituted on a phenyl group is known (see, for example, Non-Patent Document 3).

  However, Non-Patent Document 3 is merely an example for comparison in describing the influence of substituents on the delocalization effect of hydrogen bonds in a polymer, and the flame retardancy is disclosed and suggested. Absent.

International Publication No. 2008/134294 Pamphlet JP-A-7-228775 International Publication No. 2011/030911 Pamphlet JP 2007-177162 A JP 2000-212435 A JP 2003-119378 A JP 58-93745 A JP-A-5-163410

“Optimum prescription of flame retardant and combustion test” Technical Information Association 2011, 79-80 Polymer Papers Vol.60, No.2, pp. 78-83 Polymer 2011, 52, 2600-2608

  The present invention relates to a bromine-containing poly-N-phenylacrylamide derivative that is excellent in compatibility with polyamide and heat stability, and that can be flame-retarded with a smaller addition amount due to a high bromine content in the polymer, and its A manufacturing method is provided.

  As a result of intensive studies to solve the above problems, the present inventor has 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、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）
で表わされる繰り返し単位を含み、臭素含量が４５〜８０重量％である重合体及びこれらの製造方法に関する。 The following general formula (1):

(Where
m is an integer of 2 to 5,
k is 5-m,
R ₁ 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)
And a process for producing these polymers having a bromine content of 45 to 80% by weight.

  According to the present invention, a brominated poly N-phenylacrylamide derivative useful as a flame retardant that can be expected to have good compatibility with polyamide is provided. Moreover, since these have the outstanding thermal stability, they are applicable also to polymers other than polyamide.

1 shows a ¹ H-NMR chart of a compound obtained in Synthesis Example 1. The FT-IR chart of the compound obtained by the synthesis example 1 is shown. ¹ shows a ¹ H-NMR chart of the compound obtained in Synthesis Example 2. The FT-IR chart of the compound obtained by the synthesis example 2 is shown. The FT-IR chart of the compound obtained in Example 1 is shown. The FT-IR chart of the compound obtained in Example 2 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、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）
で表わされる繰り返し単位を含み、臭素含量が４５〜８０重量％である重合体である。 The polymer of the present invention has the following general formula (1):

(Where
m is an integer of 2 to 5,
k is 5-m,
R ₁ 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)
And a bromine content of 45 to 80% by weight.

  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 term “C 1-4 alkoxy group” means a group RO— (wherein R is an alkyl group having 1 to 4 carbon atoms), and is a methoxy group, an ethoxy group, a propoxy group, an 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 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.

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 polymer. A hydrogen atom or a methyl group is preferable in that the bromine 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 the compound and the ease of synthesis, but preferably contains one or more hydrogen atoms from the viewpoint that the bromine content can be further increased. More preferably, it is a hydrogen atom.

  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.

  The bromine content of the polymer of the present invention is preferably 45 to 80% by weight, more preferably 50 to 80% by weight, and even more preferably 55 to 80% by weight from the viewpoint of reducing the amount added for imparting flame retardancy. In addition, in this invention, a bromine content means the measured value of the method according to JISK7299 (flask combustion method).

  The polymer of the present invention is not particularly limited as long as it contains the repeating unit represented by the general formula (1) and has a bromine content of 45 to 80% by weight. Components other than the repeating unit represented by the general formula (1) may be appropriately included as a copolymerization component depending on the purpose and application. Specific examples of copolymer components include, for example, styrene derivatives such as styrene, α-methylstyrene, aminated styrene, brominated styrene; (meth) acrylic acid, methyl (meth) acrylate, (meth) acrylamide, and phenyl (meth) acrylate. , (Meth) acrylic acid derivatives such as brominated phenyl (meth) acrylate, brominated benzyl (meth) acrylate, brominated phenoxyethyl (meth) acrylate; maleic acid derivatives such as maleic anhydride, phenyl maleimide, brominated phenyl maleimide Is mentioned. Of these, brominated styrene, brominated phenyl (meth) acrylate, brominated benzyl (meth) acrylate, brominated phenoxyethyl (meth) acrylate, brominated phenylmaleimide and the like containing a bromine atom are preferable from the viewpoint of bromine content. From the viewpoint of the amide bond content in the polymer, the polymer of the present invention preferably contains 30 mol% or more, more preferably 50 mol% or more of the repeating unit represented by the general formula (1), Preferably, it is a homopolymer comprising not less than 80 mol% and most preferably comprising only the repeating unit represented by the general formula (1).

  The molecular weight of the polymer of the present invention may be appropriately set according to the purpose and application, but in order to obtain good thermal stability and processability, the weight average molecular weight in terms of polystyrene is preferably 1,000 to 1, It is 1,000,000, more preferably 1,000 to 500,000, still more preferably 1,000 to 250,000.

  When the polymer of the present invention is used as, for example, a flame retardant, stability at the processing temperature is required. Therefore, the 5% weight loss temperature in thermogravimetric analysis (TGA) is preferably 200 to 450 ° C., 250 to More preferably, it is 450 degreeC.

（式中、
ｍは、２〜５の整数であり、
ｋは５−ｍであり、
Ｒ_１は、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）
で表わされる単量体を重合させることで下記一般式（１）：

（式中、Ｒ_１、Ｒ_２、ｍ及びｋは前記と同義である）
で表わされる繰り返し単位を含み、臭素含量が４５〜８０重量％である重合体を得ることができる。 The manufacturing method of the polymer of this invention is not specifically limited, You may manufacture using what kind of manufacturing method. Preferably, that is, the following general formula (2):

(Where
m is an integer of 2 to 5,
k is 5-m,
R ₁ 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 following general formula (1):

(Wherein R ₁ , R ₂ , m and k are as defined above)
A polymer having a bromine content of 45 to 80% by weight can be obtained.

  The monomer represented by the general formula (2) used in the production method of the present invention is a known method using a brominated aniline derivative and an acrylic acid halide derivative (for example, International Publication No. 2009/047514, Assiut University Journal). of Chemistry, 38 (1), 27-39; 2009)).

  As the polymerization method of the monomer, a polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization and the like can be used, and may be appropriately selected according to the purpose and use, but solution polymerization is industrially advantageous, Structural adjustment such as molecular weight is easy and preferable. As the polymerization mechanism, a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used, but the polymerization method based on the radical polymerization mechanism is also industrially advantageous. ,preferable.

  When the monomer is polymerized by a radical polymerization mechanism, it is industrially advantageous and preferable to use a polymerization initiator that generates radicals by heat. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy, depending on the polymerization conditions such as polymerization temperature, solvent, type of monomer to be polymerized, etc. And may be selected as appropriate.

  Examples of the polymerization initiator include 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, α-cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecane. Noate, t-amylperoxyneodecanoate, t-butylperoxyneodecanoate, di (2-ethylhexyl) peroxydicarbonate, di (secondary butyl) peroxydicarbonate, t-butylperoxyneo Heptanoate, t-amyl peroxypivalate, t-butyl peroxypivalate, diisononanoyl peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexa Noate, dibenzoyl peroxide, t-amylperoxy-2-ethyl Sanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, 1,1-di (t-amylperoxy) cyclohexane, t-amylperoxyisononanoate, t-amyl Peroxynormal octoate, 1,1-di (t-butylperoxy) cyclohexane, t-amyl peroxyisopropyl carbonate, t-butyl peroxyisopropyl carbonate, t-amyl peroxy 2-ethylhexyl carbonate, t-butyl peroxy Oxy 2-ethylhexyl carbonate, t-amyl peroxybenzoate, t-amyl peroxyacetate, t-butyl peroxyacetate, t-butyl peroxyisononanoate, t-butyl peroxybenzoate, 2,2-di (t -Butylpa Oxy) butane, n-butyl 4,4-di (t-butylperoxy) valerate, methyl ethyl ketone peroxide, ethyl 3,3-di (t-butylperoxy) butyrate, 1,3-di (2-t- Butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-amyl peroxide, di-t-butyl peroxide, 1,1 , 3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, t-amyl hydroperoxide, t-butyl hydroperoxide, peroxidation Peroxides such as hydrogen and persulfate; 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2 ′ -Azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1- Carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′- Azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis ( 2-Amidinopropane) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n-hydrate, 2,2′- Zobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (N-butyl) -2-methylpropionamide), dimethyl 2,2′-azobis (isobutyrate), 4,4′-azobis (4-cyanopentanoic acid), 1,1-azobis (1-acetoxy-1-phenylethane), etc. Azo compounds and the like, preferably 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyro) Nitrile), 1,1-azobis (1-acetoxy-1-phenylethane), dibenzoyl peroxide, and dilauroyl peroxide. These may be used alone or in combination of two or more. Moreover, you may use together reducing agents, such as a transition metal salt and amines, with a polymerization initiator.

  The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the type and amount of the monomer used, the polymerization temperature, the polymerization conditions such as the polymerization concentration, the molecular weight of the target polymer, etc. In order to obtain a polymer having a polystyrene-equivalent weight average molecular weight of 1,000 to 1,000,000, 0.01 to 20 parts by weight is preferable with respect to 100 parts by weight of all monomers, and 0.05 to 15 Part by weight is more preferable, and 0.1 to 10 parts by weight is more preferable.

  When the monomer is polymerized by a radical polymerization mechanism, a chain transfer agent may be used as necessary, and it is more preferable to use the monomer in combination with a radical polymerization initiator. When a chain transfer agent is used at the time of polymerization, there is a tendency that increase in molecular weight distribution and gelation can be suppressed. Specific examples of such chain transfer agents include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, N-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), di Mercaptocarboxylic esters such as pentaerythritol hexakis (3-mercaptopropionate); ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane, etc. Alkyl mercaptans; mercaptoalcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; tris [(3 -Mercaptopropionyloxy) -ethyl] mercaptoisocyanurates such as isocyanurate; disulfides such as 2-hydroxyethyl disulfide and tetraethylthiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; simple units such as α-methylstyrene dimer Monomeric dimers; halogenated alkyls such as carbon tetrabromide; and the like. Among these, mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans; mercaptoisocyanurates in terms of availability, ability to prevent crosslinking, and low degree of polymerization rate reduction. Compounds having a mercapto group such as alkyls are preferred, and alkyl mercaptans, mercaptocarboxylic acids, and mercaptocarboxylic esters are most preferred. These may be used alone or in combination of two or more.

  The amount of chain transfer agent used is not particularly limited as long as it is appropriately set according to the type and amount of monomers used, the polymerization temperature, the polymerization conditions such as the polymerization concentration, the molecular weight of the target polymer, etc. In order to obtain a polymer having a polystyrene-equivalent weight average molecular weight of 1,000 to 1,000,000, 0.01 to 20 parts by weight is preferable with respect to 100 parts by weight of all monomers, and 0.05 to 15 Part by weight is more preferable, and 0.1 to 10 parts by weight is more preferable.

  The polymerization temperature when the above monomer is polymerized using a radical polymerization mechanism and a polymerization initiator that generates radicals by heat is the type and amount of the monomer used, the type and amount of the polymerization initiator, etc. Although it may set suitably according to this, 30-200 ° C is preferred and 70-150 ° C is more preferred.

  When the monomer is polymerized by a solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization reaction. The polymerization mechanism, the type of monomer used, It may be appropriately set according to the polymerization conditions such as the amount, polymerization temperature and polymerization concentration, and is not particularly limited. For example, fragrance such as benzene, toluene, xylene, mesitylene, monochlorobenzene, monobromobenzene, dichlorobenzene, trichlorobenzene, etc. Group hydrocarbon solvents: n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, ethylene dichloride, 1,1,1-trichloroethane, trichloroethylene, etc. Aliphatic hydrocarbon solvents; dimethyl ether, diethyl ether, 1,2-dimethyl Ether solvents such as xylene, tetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether; N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazo Amide solvents such as lydinone, tetramethylurea, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone; methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutanol, alcohol solvents such as n-butyl alcohol, sec-butanol, t-butanol, ethylene glycol; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, γ-butyrolactone, γ-valerolactone; acetone, Methyl ethyl ketone, Sulfur-containing solvents such as dimethyl sulfoxide; picoline, nitrogen-containing solvent such as pyridine; chill isobutyl ketone, cyclopentanone, ketone solvents such as cyclohexanone acetonitrile, and nitrile-based solvents such as 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, N, due to the solubility of the monomer, little influence on the human body and the environment, and easy industrial availability. -Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfoxide, acetonitrile are preferred. .

  When the above monomer is polymerized by the solution polymerization method, the amount of the solvent used is preferably 10 to 5,000 parts by weight, more preferably 50 to 1,000 parts by weight with respect to 100 parts by weight of the total monomers. preferable.

  The polymerization time in the production method of the present invention can be appropriately set depending on conditions such as the amount and type of the starting material to be used, the presence or absence of a solvent, its type, reaction temperature and the like. Usually, it is preferably 1 minute to 72 hours, and more preferably 10 minutes to 48 hours from the viewpoint of workability.

  After completion of the polymerization, the compound represented by the general formula (1) can be isolated from the obtained reaction solution using a general method. The isolation method is not particularly limited, and examples thereof include a method of concentrating the polymerization solvent and / or a method of depositing a solid by adding it to a poor solvent.

  The isolated polymer can be further purified by column chromatography, reprecipitation method or the like, if necessary, and can be dried and / or heated and melted and pelletized as 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 5% weight reduction | decrease temperature, melting | fusing point, a weight average molecular weight, a bromine content, NMR, and an infrared absorption spectrum of the compound obtained by the Example and the synthesis example is as follows.

  5% weight reduction temperature: The temperature was increased from 40 to 500 ° C. at a rate of temperature increase of 10 ° C./min in a nitrogen stream with a differential heat / thermogravimetric simultaneous measurement device (DTG-60, manufactured by Shimadzu Corporation). The temperature was the time when the weight decreased by 5% from the start of measurement.

  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.

  Weight average molecular weight: Measured by gel permeation chromatography. A calibration curve with a molecular weight of up to about 1.2 million was prepared in advance using Tosoh standard polystyrene. Next, 0.01 g of a sample was dissolved in 10 ml of tetrahydrofuran, and 10 μl thereof was injected into a Tosoh CCPM system. The weight average molecular weight in terms of standard polystyrene was calculated using a data processor. The analysis conditions are as follows. Column (Tosoh TSK-Gel G4000Hxl × 1, G3000Hxl × 1, G2000Hxl × 24 linked), mobile phase (tetrahydrofuran), flow rate (1.0 ml / min.), Column temperature (40 ° C.), detection wavelength (UV254 nm) .

  Bromine content: Measured by a method according to JIS K 7299 (flask combustion method).

NMR: A solution in which a compound and heavy DMSO (containing DMSO-d ₆ 0.05% TMS manufactured by Cambrige Isotope Laboratories, Inc.) was mixed was prepared, and ¹ H- 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.

[Synthesis Example 1]
Synthesis of N- (2,4,6-tribromophenyl) acrylamide 2,4,6-tribromoaniline (manac) manufactured in a eggplant flask equipped with a condenser, thermometer and gas absorber. 65 g (5.00 mmol) and 5.00 mL of dichloromethane were added, and 1.36 g (15.0 mmol) of acryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added dropwise in an ice bath, and then at room temperature for 24 hours. Stirring was performed. After completion of the reaction, the reaction solution was distilled off under reduced pressure and recrystallized with toluene. The obtained white crystals were dried under vacuum to obtain 1.14 g (2.97 mmol) of the desired N- (2,4,6-tribromophenyl) acrylamide in a yield of 59% and a bromine content of 62.3. %, Melting point 195 ° C. ¹ H-NMR of the target product is shown in FIG. 1, and an FT-IR chart is shown in FIG.

[Synthesis Example 2]
Synthesis of N- (2,4,6-tribromophenyl) methacrylamide In a 500 mL four-necked flask equipped with a condenser, thermometer and gas absorber, 2,4,6-tribromoaniline (manac Co., Ltd.) ) 52.1 g (158 mmol), 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.965 g (7.90 mmol), monochlorobenzene 230 mL, triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 15 0.9 g (158 mmol) was added, and 19.8 g (190 mmol) of methacryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto. A reflux tube was attached and the mixture was heated to reflux. After stirring for 18 hours, the temperature was returned to room temperature, 200 mL of water was injected, and the organic layer was washed and separated. When the reaction solution was allowed to stand after separation, a solid was deposited, and was collected by filtration (44.5 g). Further, 95.0 g of heptane was added to the solution after filtration to precipitate a solid, which was collected by filtration (8.46 g). The obtained crude product (50.3 g, 126 mmol) was recrystallized from toluene. The crystals obtained were dried to yield 44.3 g (111 mmol) of the desired N- (2,4,6-tribromophenyl) methacrylamide, yield 70%, bromine content 60.1%, melting point 159 ° C. Got in. The ¹ H-NMR of the target product is shown in FIG. 3, and the FT-IR chart is shown in FIG.

[Example 1]
Polymerization of N- (2,4,6-tribromophenyl) acrylamide N- (2,4,6-tribromophenyl) acrylamide 193 mg (0.502 mmol) synthesized in Synthesis Example 1 was converted to N, N-dimethylformamide. It melt | dissolved in 1.00 mL, and 4.10 mg of 2,2'- azobisisobutyronitrile (made by Wako Pure Chemical Industries Ltd.) was added there. The reaction vessel was purged with argon and stirred at 60 ° C. for 22 hours. The reaction solution was added to 50 mL of methanol, and the formed precipitate was filtered by suction and dried in vacuo to obtain a polymer as a white solid (155 mg, yield 80%, bromine content 61.5%, 5% weight loss temperature 290). ° C, weight average molecular weight 24000 (Mw / Mn = 2.80)). The FT-IR chart of the object is shown in FIG.

¹ H-NMR (DMSO-d ₆ , at 70 ° C.) δ (ppm): 10-8.5 (1H, br), 8.0-7.4 (2H, br), 3.4-1.6 (3H, br).

[Example 2]
Polymerization of N-2,4,6-tribromophenylmethacrylamide 3.99 g (10.0 mmol) of N-2,4,6-tribromophenylmethacrylamide synthesized in Synthesis Example 2 was added to 10.0 mL of monochlorobenzene. After dissolution, 80.0 mg of 2,2′-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The reaction vessel was purged with argon and stirred at 80 ° C. for 48 hours. The reaction solution was added to 300 mL, and the formed precipitate was filtered by suction and dried in vacuo to obtain a polymer as a white solid (2.46 g, yield 62%, bromine content 59.4%, 5% weight loss temperature). 289 ° C., weight average molecular weight 7300 (Mw / Mn = 1.83)). The FT-IR chart of the target product is shown in FIG.

¹ H-NMR (DMSO-d ₆ , at 25 ° C.) δ (ppm): 9.7-8.5 (1H, br), 8.3-7.4 (2H, br), 3.4-0.8 (5H, br).

  The bromine-containing poly N-phenylacrylamide derivative of the present invention is useful as a flame retardant because of its excellent thermal stability and high bromine content.

Claims (8)

The following general formula (1):

(Where
m is an integer of 2 to 5,
k is 5-m,
R ₁ 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)
And a bromine content of 45 to 80% by weight.   The polymer according to claim 1, wherein the bromine content is from 55 wt% to 80 wt%. The polymer according to claim 1 or 2, wherein R ₂ is a hydrogen atom.   The polymer according to any one of claims 1 to 3, wherein m is an integer of 3 to 5.   The polymer according to any one of claims 1 to 4, wherein a 5% weight loss temperature in thermogravimetric analysis (TGA) is 200 ° C to 450 ° C. The following general formula (2):

(Where
m is an integer of 2 to 5,
k is 5-m,
R ₁ 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)
Including the step of polymerizing the monomer represented by the following general formula (1):

(Wherein R ₁ , R ₂ , m and k are as defined above)
The manufacturing method of the polymer which contains the repeating unit represented by and whose bromine content is 45 to 80 weight%.   The method for producing a polymer according to any one of claims 1 to 5, comprising carrying out the polymerization step in the presence of a radical initiator.   The radical initiator is 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1 , 1-azobis (1-acetoxy-1-phenylethane), dibenzoyl peroxide, or dilauroyl peroxide.

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