JP5751698B2 - Bromine-containing organic compound, bromine-containing organic compound-containing composition and method for producing the same - Google Patents

Description

  The present invention relates to a bromine-containing organic compound capable of imparting high flame retardancy and thermal stability when blended in a resin.

Bromine-containing organic compounds are widely used as flame retardants for various resins because they can impart high flame retardancy. In particular, hexabromocyclododecane (HBCD) and tetrabromobisphenol A-bis (2-methylallyl ether) are frequently used because high flame retardancy can be imparted in a small amount.

  However, these bromine-containing organic compounds have low thermal stability, and problems such as deterioration of the resin and coloring of the resin as well as equipment corrosion due to generation of hydrogen bromide gas due to heating during production and recycling. It is known to cause.

  On the other hand, tetrabromobisphenol-A-bis (2,3-dibromopropyl ether) is also known as a bromine-containing organic compound having excellent thermal stability. However, these flame retardants have a low flame retarding effect as compared with bromine-containing compounds such as HBCD, and the addition amount needs to be greatly increased, which causes problems such as a decrease in resin physical properties and a significant increase in cost.

JP 2006-316251 A JP 2005-139356 A

This invention is made | formed in view of the said problem, The objective is to provide the bromine containing organic compound which can provide high flame retardance and heat stability, when mix | blending with resin.

The present invention is a bromine-containing organic compound represented by the following general formula 1 ,
After reacting (A) a brominated bisphenol compound, (B) a compound represented by the following general formula 2 and (C) a compound represented by the following general formula 3, the carbon derived from the (B) and the (C) -A carbon double bond is brominated, and (B) and (C) are (B) / (C) = 8/2 to 2/8 (molar ratio).
A bromine-containing organic compound-containing compound is provided.

（式中、Ａは−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−および−Ｓ−のいずれかであり、Ｒ_１およびＲ_２はそれぞれ水素または炭素数１〜６の飽和炭化水素基、Ｒ_３は炭素数１〜６の飽和炭化水素基、Ｙはハロゲン原子、ｍおよびｎはそれぞれ１〜４の整数である。）

(In the formula, A is any one of —CH ₂ —, —C (CH ₃ ) ₂ —, and —S—, and R ₁ and R ₂ are each hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, R ₃ is a saturated hydrocarbon group having 1 to 6 carbon atoms, Y is a halogen atom, and m and n are each an integer of 1 to 4.)

（式中、Ｒ_４は水素または炭素数１〜６の飽和炭化水素基であり、Ｘ_１はハロゲン原子である。）

(In the formula, R ₄ is hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, and X ₁ is a halogen atom.)

（式中、Ｒ_５は水素または炭素数１〜６の飽和炭化水素基であり、Ｒ_６は炭素数１〜６の飽和炭化水素基であり、Ｘ_２はハロゲン原子である。）

(In the formula, R ₅ is hydrogen or a saturated hydrocarbon group having 1 to ₆ carbon atoms, R ₆ is a saturated hydrocarbon group having 1 to ₆ carbon atoms, and X ₂ is a halogen atom.)

  Furthermore, in the bromine-containing organic compound-containing composition of the present invention, the sum of (B) and (C) is preferably 1.5 to 3 mol with respect to 1 mol of (A).

  The bromine-containing organic compound of the present invention can be imparted with high flame retardancy and thermal stability by blending with the resin.

2 is a high performance liquid chromatograph chart of the bromine-containing organic compound-containing composition obtained in Example 1. FIG.

The bromine-containing organic compound of the present invention is represented by the general formula 1.
A in the general formula 1 is any one of —CH ₂ —, —C (CH ₃ ) ₂ —, and —S—.

R ₁ and R ₂ in the general formula 1 are each hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, specifically hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, Examples thereof include an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, and a hexyl group. Of these, hydrogen is preferred because of its highest bromine content.

R ₃ in the general formula 1 is a saturated hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl. Group, neopentyl group and hexyl group. Of these, a methyl group is preferred because the bromine content is the highest.
Y in the general formula 1 is a halogen atom. Of these, bromine is preferred because higher flame retardancy can be expected. In addition, m and n are integers of 1 to 4, respectively, and m and n are both preferably 2 because they are easily available.

  The bromine-containing organic compound-containing composition of the present invention comprises: (A) a halogenated bisphenol compound, (B) a compound represented by the general formula 2 and (C) a compound represented by the general formula 3; This is a reaction of bromine. The bromine-containing organic compound-containing composition of the present invention contains the bromine-containing organic compound represented by the general formula 1.

  The (A) halogenated bisphenol compound used in the present invention is a compound obtained by substituting at least one hydrogen atom on the aromatic ring with a halogen atom in bisphenol compounds such as bisphenol A, bisphenol F and bisphenol S. Here, the halogen atom is preferably bromine because it is more excellent in flame retardancy, and specific examples include tetrabromobisphenol A, tetrabromobisphenol F, and tetrabromobisphenol S.

The compound (B) used in the present invention is represented by the general formula 2. R ₄ in General Formula 2 is hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, and examples thereof are the same as R ₁ in General Formula 1. X ₁ in the general formula 2 is a halogen group, and specific examples include chlorine, bromine, and iodine. Of these, chlorine is preferred because it is readily available.

The compound (C) used in the present invention is represented by the general formula 3. R ₅ in General Formula 3 is hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, and examples thereof are the same as R ₂ in General Formula 1. R ₆ in General Formula 3 is a saturated hydrocarbon group having 1 to ₆ carbon atoms, and examples thereof are the same as R ₃ in General Formula 1. Further, X ₂ in the general formula 3 is a halogen group, and examples thereof are the same as X ₁ in the general formula 2.

  In the bromine-containing organic compound-containing composition of the present invention, the sum of (B) and (C) is preferably 1.5 to 4 mol, and 2 to 3 mol, relative to 1 mol of (A). More preferably. By setting it within the above range, the flame retardancy and the thermal stability become more excellent.

  In the bromine-containing organic compound-containing composition of the present invention, the (B) and the (C) are preferably (B) / (C) = 8/2 to 2/8 (molar ratio). 7/3 to 3/7 is more preferable. By setting it within the above range, the flame retardancy and the thermal stability become more excellent.

  The bromine-containing organic compound and bromine-containing organic compound-containing composition of the present invention can be produced according to a known method. For example, (A) a halogenated bisphenol compound alcoholated with sodium hydroxide and the like, (B ) After reacting with a compound represented by the following general formula 2 and (C) a compound represented by the following general formula 3, further bromination is carried out by reacting with bromine at 0 to 10 ° C., followed by excess Of bromine with a reducing agent and a neutralizing agent. In addition, when making said (B) and said (C) react, you may make it react simultaneously, either one may be made to react first, and the other may be made to react after that. Here, as a reducing agent, a well-known compound can be used, for example, sodium bisulfite, hydrazine, etc. can be used. Moreover, as a neutralizing agent, a well-known compound can be used, for example, sodium hydroxide, a monoethanolamine, etc. can be used.

  The flame retardant of the present invention contains a bromine-containing organic compound represented by the general formula 1, but may further contain other bromine-containing organic compounds. Examples of such bromine-containing organic compounds include tetrabromocyclooctane, hexabromocyclododecane, tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-S-bis (2,3 -Dibromopropyl ether), tetrabromobisphenol-F-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (2-bromoethyl ether), tetrabromobisphenol-S-bis (2-bromoethyl) Ether), tetrabromobisphenol-F-bis (2-bromoethyl ether), bisphenol-A-bis (2,3-dibromopropyl ether), bisphenol-S-bis (2,3-dibromopropyl ether), bisphenol- F-bi (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol-S-bis (2,3-dibromo-2-methylpropyl ether) ), Tetrabromobisphenol-F-bis (2,3-dibromo-2-methylpropyl ether), bisphenol-A-bis (2,3-dibromo-2-methylpropyl ether), bisphenol-S-bis (2, 3-dibromo-2-methylpropyl ether), bisphenol-F-bis (2,3-dibromo-2-methylpropyl ether), tris (2,3-dibromopropyl) isocyanurate, tris (2,3-dibromopropyl) ) Cyanurate, tris (2-methyl-2,3-dibromopropyl) Sosocyanurate, tris (2-methyl-2,3-dibromopropyl) cyanurate, bistribromoneopentyl malate, bistribromoneopentyl fumarate, bistribromoneopentyl adipate, bistribromoneopentyl phthalate, bistribromoneopentyl terephthalate, tris Tribromoneopentyl pyromellate, bis-2,3-dibromopropyl phthalate, bis-2,3-dibromopropyl terephthalate, tris-2,3-dibromopropyl pyromellitate, tristribromoneopentyl phosphate, tetrabromobisphenol -A, hexabromobenzene, pentabromotoluene, polybromodiphenyl ether, polybromodiphenylethane, bispolybromophenoxyethane, trispoly Examples include bromophenoxytriazine, polybromophenylindane, polypentabromobenzyl acrylate, and ethylene bistetrabromophthalimide.

  The flame retardant resin composition of the present invention contains the flame retardant and a resin. As resins that can be used, known resins such as polystyrene and polypropylene can be used. In the resin composition of the present invention, the flame retardant is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the resin.

  In the flame retardant resin composition of the present invention, additives such as phosphite compounds, thioether compounds, hindered phenol compounds, metal compounds, radical generators, and phthalocyanine metal complexes can be used.

  Phosphite compounds are generally used as heat stabilizers, such as tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl). ) Pentaerythritol diphosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetrakis (2,4-di-t-butylphenyl) [1, 1-biphenyl] -4,4′-diylbisphosphonite, bis (nonylphenyl) pentaerythritol diphosphite, bisstearyl pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methyl Phenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-di-t-butyl-1-phenyloxy) 2-ethylhexyloxy) phosphorus, tetra (tridecyl) -4,4′-butylidene-bis (2-t-butyl-5-methylphenyl) diphosphite, hexatridecyl-1,1,3-tris (3-t- Butyl-6-methyl-4-oxyphenyl) -3-methylpropane triphosphite, mono (dinonylphenyl) mono-p-nonylphenyl phosphite, tris (monononylphenyl) phosphite, tetraalkyl (C = 12- 16) -4,4'-isopropylidene- (bisphenyl) diphosphite, phosphorous mono- or diphenyl mono- or dialkyl (or alkoxyalkyl, C = 8-13), diphenylisodecyl phosphite, trisdecyl phosphite and tri And phenyl phosphite.

  The thioether compound is generally used as a heat stabilizer, such as dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3, 3'-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, and the like.

  The hindered phenol compound is generally used as a heat stabilizer, for example, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl). Propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], glycerin tris [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate], pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate, thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], , N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol Diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, calcium diethylbis [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p- Cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexa Tylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3 , 5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1, 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine 2-ylamino) phenol and the like.

  Metal compounds are commonly used to enhance flame retardancy, such as antimony trioxide, antimony pentoxide, zinc borate, hydrated aluminum oxide, molybdenum oxide, zinc sulfate and zinc stannate. Etc.

  The radical generator is generally used to enhance flame retardancy, such as cumene peroxide, cumene hydroperoxide, di-t-butyl peroxide, di-t-hexyl peroxide, Examples include 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3, dicumyl peroxide and 2,3-dimethyl-2,3-diphenylbutane.

  The phthalocyanine metal complex is generally used for enhancing flame retardancy, and examples thereof include phthalocyanine iron, phthalocyanine manganese, and phthalocyanine cobalt.

  As a compounding quantity of these additives, 0.01-10 weight part is preferable with respect to 100 weight part of resin.

  Moreover, a foaming agent, a foam nucleating agent, etc. can also be used for the flame-retardant resin composition of this invention.

  Examples of the blowing agent include propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, 1-chloro-1,1-difluoroethane, monochlorodifluoromethane, monochloro-1,2,2,2-tetrafluoroethane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,3,3,3-pentafluoropropane, dichloromethane, 1,2-dichloroethane, dimethyl ether, diethyl ether and ethyl methyl ether, etc. Examples include volatile organic foaming agents, inorganic foaming agents such as water, nitrogen and carbon dioxide, and chemical foaming agents such as azo compounds. Although the compounding quantity of a foaming agent is not specifically limited, Preferably, it is 0.01-0.5 mol with respect to 100 weight part of resin, More preferably, it is 0.05-0.3 mol.

  Examples of the foam nucleating agent include talc, bentonite, kaolin, mica, silica, clay, and diatomaceous earth. When the foam nucleating agent is used, the amount used is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the resin.

  The molded body of the present invention is formed by molding the flame retardant resin composition by a known method. The molding method is not particularly limited, and examples thereof include extrusion molding, injection molding, extrusion foam molding, and bead foam molding.

  In the flame-retardant resin composition of the present invention, within the range not impairing the effects of the present invention, a light stabilizer, an ultraviolet absorber, an ultraviolet stabilizer, a heavy metal deactivator, an impact resistance improver, a colorant, Known resin additives such as lubricants, anti-dripping agents, crystal nucleating agents, antistatic agents and compatibilizers can be blended.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, “%” means “% by weight” and “parts” means “parts by weight”.

Example 1
In a flask equipped with a stirrer, thermometer and dropping funnel, 111 g of 10% aqueous sodium hydroxide, 11.1 g of sodium bromide, 0.1 g of sodium borohydride, 17.9 g of isopropanol and 3,3 ′, 5,5 71.45 g (0.131 mol) of '-tetrabromobisphenol A was added to make a uniform solution at 40 ° C. A mixed solution of 13.3 g (0.174 mol) of 2-chloropropene and 14.8 g (0.164 mol) of 3-methyl-2-chloropropene was dropped from the dropping funnel, and further at 65 to 70 ° C. for 4 hours. After stirring, the solvent was distilled off under reduced pressure. Further, after cooling to 35 ° C., 70 g of methylene chloride and 50 g of water were added and mixed, and then the methylene chloride layer was extracted.

  The extracted methylene chloride layer was transferred to a flask equipped with a stirrer, a thermometer and a dropping funnel, and 150 g of methylene chloride was added and cooled to 5 ° C. To this solution, 27 g of bromine was added dropwise so that the liquid temperature did not exceed 10 ° C., and the mixture was further stirred at 10 to 20 ° C. for 30 minutes after the completion of the addition. Subsequently, excess bromine was reduced with a 15% by weight aqueous sodium hydrogen sulfite solution, and then further neutralized with 20% by weight sodium hydroxide. After stirring for 30 minutes, the solution was allowed to stand to extract a methylene chloride layer, and the solvent was distilled off under reduced pressure to obtain Composition 1. ((A) 1 mol relative to (B) 2.57 mol, (B1) / (B2) = 4.8 / 5.2 (molar ratio))

  About the composition 1, the chart of the liquid chromatograph in a high performance liquid chromatograph mass spectrometry is shown in FIG. Note that peaks A, B, C, D, and E are used in order from the peak with the shortest retention time.

  Moreover, the mass spectrometry result in each peak is as follows, The structure can be attributed as follows.

<Peak A>
MS m / z: 742 [M−H] ⁻

<Peak B>
MS m / z: 756 [M−H] ⁻

<Peak C>
MS m / z: 895 [M-HBr + O ₂ ] ⁻ , 742 [M-CH ₂ CHBrCH ₂ Br] ⁻

<Peak D>
MS m / z: 909 [M-HBr + O ₂ ] ⁻ , 742 [M-CH ₂ CBr (CH ₃ ) CH ₂ Br] ⁻

<Peak E>
MS m / z: 923 [M-HBr + O ₂ ] ⁻ , 756 [M—CH ₂ CBr (CH ₃ ) CH ₂ Br] ⁻

(Example 2)
In a flask equipped with a stirrer, thermometer and dropping funnel, 111 g of 10% aqueous sodium hydroxide, 11.1 g of sodium bromide, 0.1 g of sodium borohydride, 17.9 g of isopropanol and 3,3 ′, 5,5 71.45 g (0.131 mol) of '-tetrabromobisphenol A was added to make a uniform solution at 40 ° C. Here, 8.0 g (0.105 mol) of 3-methyl-2-chloropropene was dropped from a dropping funnel, and the mixture was further stirred at 65 to 70 ° C. for 4 hours. Subsequently, 20.7 g (0.229 mol) of 2-chloropropene was dropped from the dropping funnel and further stirred at 65 to 70 ° C. for 4 hours, and then the solvent was distilled off under reduced pressure. Further, after cooling to 35 ° C., 70 g of methylene chloride and 50 g of water were added and mixed, and then the methylene chloride layer was extracted.

  The extracted methylene chloride layer was transferred to a flask equipped with a stirrer, a thermometer and a dropping funnel, and 150 g of methylene chloride was added and cooled to 5 ° C. To this solution, 27 g of bromine was added dropwise so that the liquid temperature did not exceed 10 ° C., and the mixture was further stirred at 10 to 20 ° C. for 30 minutes after the completion of the addition. Subsequently, excess bromine was reduced with a 15% by weight aqueous sodium hydrogen sulfite solution, and then further neutralized with 20% by weight sodium hydroxide. After stirring for 30 minutes, the solution was allowed to stand to extract a methylene chloride layer, and the solvent was distilled off under reduced pressure to obtain Composition 2. ((A) per mole of (B) 2.54 mol, (B1) / (B2) = 6.9 / 3.1 (molar ratio))

  Moreover, when the high performance liquid chromatograph mass spectrometry of the composition 2 was performed, all the peaks AE in Example 1 were detected.

(Example 3)
In a flask equipped with a stirrer, thermometer and dropping funnel, 111 g of 10% aqueous sodium hydroxide, 11.1 g of sodium bromide, 0.1 g of sodium borohydride, 17.9 g of isopropanol and 3,3 ′, 5,5 71.45 g (0.131 mol) of '-tetrabromobisphenol A was added to make a uniform solution at 40 ° C. Here, 8.9 g (0.098 mol) of 2-chloropropene was dropped from the dropping funnel, and the mixture was further stirred at 65 to 70 ° C. for 4 hours. Subsequently, 18.7 g (0.244 mol) of 3-methyl-2-chloropropene was dropped from the dropping funnel and further stirred at 65 to 70 ° C. for 4 hours, and then the solvent was distilled off under reduced pressure. Further, after cooling to 35 ° C., 70 g of methylene chloride and 50 g of water were added and mixed, and then the methylene chloride layer was extracted.

  The extracted methylene chloride layer was transferred to a flask equipped with a stirrer, a thermometer and a dropping funnel, and 150 g of methylene chloride was added and cooled to 5 ° C. To this solution, 27 g of bromine was added dropwise so that the liquid temperature did not exceed 10 ° C., and the mixture was further stirred at 10 to 20 ° C. for 30 minutes after the completion of the addition. Subsequently, excess bromine was reduced with a 15% by weight aqueous sodium hydrogen sulfite solution, and then further neutralized with 20% by weight sodium hydroxide. After stirring for 30 minutes, the solution was allowed to stand to extract a methylene chloride layer, and the solvent was distilled off under reduced pressure to obtain Composition 3. ((A) per mole of (B) 2.54 mol, (B1) / (B2) = 6.9 / 3.1 (molar ratio))

  Moreover, when the high performance liquid chromatograph mass spectrometry of the composition 3 was performed, all the peaks AE in Example 1 were detected.

(Comparative Example 1)
Composition 4 was obtained by making it react like Example 1 except having made 2-chloropropene 29g (0.32 mol) and not using 3-methyl-2-chloropropene. Moreover, when the composition 4 was subjected to high performance liquid chromatograph mass spectrometry, only peak A and peak C in Example 1 were detected.

(Comparative Example 2)
Composition 5 was obtained by reacting in the same manner as in Example 1 except that 26 g (0.34 mol) of 3-methyl-2-chloropropene was used and 2-chloropropene was not used. Further, when the composition 5 was subjected to high performance liquid chromatography / mass spectrometry, only peak B and peak E in Example 1 were detected.

<Measurement conditions for high performance liquid chromatograph mass spectrometry>
The high performance liquid chromatograph was performed under the following conditions.
Equipment Agilent 1100 (manufactured by Agilent Technologies)
Column inertsil ODS-3, 3.0 mm × 50 mm (manufactured by GL Sciences Inc.)
Eluent water / acetonitrile = 10/90
Flow rate 1 ml / min Column temperature 40 ° C
Moreover, mass spectrometry was measured by connecting a mass spectrometer to the high performance liquid chromatograph.

Resin compositions were prepared using the flame retardant compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2, and the flame retardancy and thermal stability were evaluated. In addition, the used raw material is as follows.
(resin)
PSJ polystyrene G9401 (polystyrene resin made by PS Japan)
(Foaming agent)
Heptane (foam nucleating agent)
Talc MS (Nippon Talc Industry Co., Ltd.)

(Test Examples 1-3, Comparative Test Examples 1-3)
By introducing the raw materials shown in Table 1 excluding the foaming agent into a two-stage extruder having a diameter of 65 mm to a diameter of 90 mm and connected in series, heating to 200 ° C., melting, plasticizing, and kneading A resin composition was obtained. Subsequently, a predetermined amount of foaming agent is press-fitted in a separate line at the tip of the 65 mm extruder (opposite to the die of the 90 mm diameter extruder), and the resin temperature is cooled to 120 ° C. with a 90 mm diameter extruder, and the diameter is 90 mm. A rectangular parallelepiped resin foam (test piece) was obtained by extruding into the atmosphere from a die lip having a rectangular section of 2.5 mm in the thickness direction and 45 mm in the width direction provided at the end of the extruder.

  Using the obtained test piece, flame retardancy and thermal stability were evaluated by the following methods. The results are shown in Table 1.

<Flame retardance>
The oxygen index was measured according to JIS K-7201.
○: Oxygen index is 26 or more ×: Oxygen index is less than 26

<Thermal stability>
The obtained test piece was cut finely, 3 g of the test piece was taken in a 12 × 120 mm test tube and left in an aluminum block bath adjusted to 220 ° C. for 20 minutes, and then 2.00 g of a molten test piece was collected. After cooling, the product was dissolved in 50 ml of toluene, and the absorbance at a wavelength of 360 nm was measured using a spectrophotometer (trade name: Hitachi spectrophotometer U-1800, manufactured by Hitachi High-Technologies Corporation) and evaluated as follows.
○: Less than 0.8 Δ: 0.8 or more and less than 1.5 ×: 1.5 or more

<Moldability>
The state of the foamed molded product was visually evaluated as follows.
○: No cracks, cracks and voids were observed in the foam, and a good foam was obtained.
X: A crack, a crack, or a void is seen in a foam. Alternatively, gas ejection from the die is observed during production, and a good foam cannot be obtained.

  As is clear from Table 1, it can be seen that the molded bodies of Test Examples 1 to 3 are excellent in any of the items of flame retardancy, thermal stability and moldability. On the other hand, as in Comparative Test Examples 1 to 4, when the composition of the present invention was not used as a flame retardant, none satisfying all of flame retardancy, thermal stability and moldability was obtained.

  The bromine-containing organic compound of the present invention can impart high flame retardancy and thermal stability when blended in a resin. Therefore, it can be used for various applications including heat insulation applications such as home appliances and building materials and civil engineering applications such as embankment methods.

Claims (6)

A bromine-containing organic compound represented by the following general formula 1 ,
After reacting (A) a brominated bisphenol compound, (B) a compound represented by the following general formula 2 and (C) a compound represented by the following general formula 3, the carbon derived from the (B) and the (C) -A carbon double bond is brominated, and (B) and (C) are (B) / (C) = 8/2 to 2/8 (molar ratio).
Bromine-containing organic compound-containing compound.

(In the formula, A is any one of —CH ₂ —, —C (CH ₃ ) ₂ —, and —S—, and R ₁ and R ₂ are each hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, R ₃ is a saturated hydrocarbon group having 1 to 6 carbon atoms, Y is a halogen atom, and m and n are each an integer of 1 to 4.)

(In the formula, R ₄ is hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, and X ₁ is a halogen atom.)

(In the formula, R ₅ is hydrogen or a saturated hydrocarbon group having 1 to ₆ carbon atoms, R ₆ is a saturated hydrocarbon group having 1 to ₆ carbon atoms, and X ₂ is a halogen atom.) Wherein (A) 1 mole of the (B) and the sum claim 1 Symbol placement bromine-containing organic compound containing compound is 1.5 to 3 moles of (C). (A) brominated bisphenol compound, (B) a step of reacting a compound represented by the following general formula 2 and (C) a compound represented by the following general formula 3 to obtain an intermediate, and bromination of the obtained intermediate A process for producing a bromine-containing organic compound-containing compound according to claim 1 .

(In the formula, R ₄ is hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, and X ₁ is a halogen atom.)

(In the formula, R ₅ is hydrogen or a saturated hydrocarbon group having 1 to ₆ carbon atoms, R ₆ is a saturated hydrocarbon group having 1 to ₆ carbon atoms, and X ₂ is a halogen atom.) Flame retardants containing bromine-containing organic compound according to claim 1 or 2. A flame retardant resin composition comprising the flame retardant according to claim 4 and a resin. The molded object formed by shape | molding the resin composition of Claim 5 .

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