JPH07126320A - Production of brominated polystyrene - Google Patents
Production of brominated polystyreneInfo
- Publication number
- JPH07126320A JPH07126320A JP27348393A JP27348393A JPH07126320A JP H07126320 A JPH07126320 A JP H07126320A JP 27348393 A JP27348393 A JP 27348393A JP 27348393 A JP27348393 A JP 27348393A JP H07126320 A JPH07126320 A JP H07126320A
- Authority
- JP
- Japan
- Prior art keywords
- polystyrene
- brominated polystyrene
- bromine
- aluminum
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 52
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 29
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- -1 aluminum halide Chemical class 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- JWFDXKOVBQLBBL-UHFFFAOYSA-N 1,1-dibromo-1,2-dichloroethane Chemical compound ClCC(Cl)(Br)Br JWFDXKOVBQLBBL-UHFFFAOYSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はポリスチレンの臭素化方
法に関する。更に詳しくは、ハロゲン化炭化水素溶媒中
でポリスチレンと臭素とを反応させて臭素化ポリスチレ
ンを製造する方法に関する。本発明によって得られる臭
素化ポリスチレンは、プラスチック用の難燃剤として幅
広く使用されるものである。FIELD OF THE INVENTION The present invention relates to a method for brominating polystyrene. More specifically, it relates to a method for producing brominated polystyrene by reacting polystyrene and bromine in a halogenated hydrocarbon solvent. The brominated polystyrene obtained by the present invention is widely used as a flame retardant for plastics.
【０００２】[0002]
【従来の技術】従来、臭素化ポリスチレンの製造法とし
ては、臭素化スチレン単量体を重合する方法が知られて
いる。該方法によって得られる臭素化ポリスチレンは優
れた色調および熱的特性を有しており、且つ単量体に三
臭素化スチレンを用いることで高い臭素含有率の臭素化
ポリスチレンを製造できる点では優れた方法と言える。
しかしながら、該方法は原料である臭素化スチレン単量
体が高価であること、重合反応終了後、残存するモノマ
ーを除去する工程が必要になることなど経済性、実用性
に欠ける。2. Description of the Related Art Conventionally, as a method for producing brominated polystyrene, a method of polymerizing a brominated styrene monomer has been known. The brominated polystyrene obtained by the method has excellent color tone and thermal properties, and is excellent in that brominated polystyrene having a high bromine content can be produced by using tribrominated styrene as a monomer. Can be called a method.
However, this method is not economical and practical because the brominated styrene monomer as a raw material is expensive and a step of removing the residual monomer is required after the completion of the polymerization reaction.
【０００３】更に、臭素化ポリスチレンの工業的製造方
法として、ポリスチレンを臭素化する方法も知られてい
る。該方法は、経済的であるだけでなく、臭素含有率を
任意に調整できる点で優れた方法であるが、高い臭素含
有率を有しかつ優れた色調および熱的特性の臭素化ポリ
スチレンが得にくい問題点が有る。Further, a method of brominating polystyrene is also known as an industrial production method of brominated polystyrene. The method is not only economical but also an excellent method in that the bromine content can be arbitrarily adjusted, but a brominated polystyrene having a high bromine content and excellent color and thermal properties can be obtained. There are difficult problems.
【０００４】該方法によれば、通常、芳香環一個あたり
二個の臭素までは容易に置換されるが、更により高い臭
素含有率の臭素化ポリスチレンを得ようとすると、ポリ
スチレンの芳香核の臭素化のみならず、炭化水素主鎖の
臭素化、切断が副反応として起こり、得られた臭素化ポ
リスチレンの耐熱性が低下する。このような臭素化ポリ
スチレンを熱可塑性樹脂に配合した際、得られた成形品
の物性や外観が低下すること、またこのようにして得ら
れた臭素化ポリスチレンは熱分解に際して臭化水素を発
生するため成形加工時に金型を腐食する等、実用に際し
てその使用領域が極めて制限されるという欠点がある。According to this method, usually up to two bromine atoms per aromatic ring are easily replaced, but when an attempt is made to obtain a brominated polystyrene having an even higher bromine content, the bromine of the aromatic nucleus of polystyrene is In addition to oxidization, bromination and cleavage of the hydrocarbon main chain occur as side reactions, and the heat resistance of the obtained brominated polystyrene decreases. When such a brominated polystyrene is blended with a thermoplastic resin, the physical properties and appearance of the obtained molded article deteriorate, and the brominated polystyrene thus obtained generates hydrogen bromide during thermal decomposition. Therefore, there is a drawback that the usage area is extremely limited in practical use, such as corrosion of the mold during molding.
【０００５】これらの問題を解決する方法としては、三
ハロゲン化鉄の如きより低活性の触媒を用いる方法、触
媒量を低減する方法、反応温度を下げる方法等がある
が、このような方法では反応時間が長くなる、所望の臭
素含有率が達成できない等の問題が発生する。As a method for solving these problems, there are a method of using a catalyst having a lower activity such as iron trihalide, a method of reducing the amount of catalyst, a method of lowering the reaction temperature, and the like. There are problems that the reaction time becomes long and the desired bromine content cannot be achieved.
【０００６】さらに、これらの問題を解決するための臭
素化技術が数多くの特許明細書に開示されている。例え
ば、特公平１−５７６８４号公報では、臭素化剤に塩化
臭素、触媒にハロゲン化アンチモンを用いる方法が提案
されている。しかし、該方法では塩化臭素の製造工程が
必要となること、得られる臭素化ポリスチレンが一部塩
素化されるという欠点がある。また、特公昭６１−３４
７２３号公報では、水の如き求核試剤の存在下、触媒活
性を調整しつつ臭素化する方法が提案されているが、微
量水分量の調整が必要となり実用性に問題がある。ま
た、特公昭６２−５８６０４号公報では、触媒としてア
ルカリ金属ハロゲン化物とハロゲン化鉄との複塩を用い
る方法が提案されているが、該方法では高い臭素含有率
の臭素化ポリスチレンは得ることができない。Further, a number of patent specifications disclose bromination techniques for solving these problems. For example, Japanese Patent Publication No. 1-57684 proposes a method using bromine chloride as a brominating agent and antimony halide as a catalyst. However, this method has the drawbacks that a bromine chloride production step is required and that the brominated polystyrene obtained is partially chlorinated. In addition, Japanese Examined Japanese Patent Publication 61-34
Japanese Patent No. 723 proposes a method of brominating in the presence of a nucleophilic reagent such as water while adjusting the catalytic activity, but it requires adjustment of a trace amount of water, which is problematic in practicality. Further, Japanese Patent Publication No. 62-58604 proposes a method using a double salt of an alkali metal halide and an iron halide as a catalyst, but this method can obtain a brominated polystyrene having a high bromine content. Can not.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、ポリスチレ
ンを臭素化して臭素化ポリスチレンを製造するに際し、
上記欠点が無く、色相が良好で且つ耐熱性に優れた高臭
素含有ポリスチレンを経済的に効率よく製造する方法を
提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention relates to the production of brominated polystyrene by brominating polystyrene,
It is an object of the present invention to provide a method for economically and efficiently producing a high bromine content polystyrene having the above-mentioned drawbacks, a good hue and excellent heat resistance.
【０００８】本発明者らは、上記目的を達成せんとして
鋭意検討した結果、触媒にハロゲン化アルミニウムおよ
びアルミニウム粉末を併用することにより実質的な触媒
量を低減できることに着目し、更に検討した結果、触媒
にハロゲン化アルミニウムとアルミニウム粉末を用いる
ことにより、反応時間を延長する事なく、色相も良好で
且つ耐熱性も著しく改善された臭素化ポリスチレン得る
本発明の方法に到達したものである。As a result of intensive studies aimed at achieving the above object, the present inventors have paid attention to the fact that a substantial amount of catalyst can be reduced by using aluminum halide and aluminum powder together with the catalyst, and as a result of further studies, By using aluminum halide and aluminum powder as the catalyst, the present invention has reached the method of obtaining brominated polystyrene having good hue and remarkably improved heat resistance without extending the reaction time.
【０００９】[0009]
【課題を解決するための手段】本発明は、ハロゲン化炭
化水素溶媒中でポリスチレンと臭素とを反応させて臭素
化ポリスチレンを製造する方法において、触媒としてハ
ロゲン化アルミニウム及びアルミニウム粉末を併用する
ことを特徴とするポリスチレンの臭素化方法に係わるも
のである。The present invention provides a method for producing brominated polystyrene by reacting polystyrene and bromine in a halogenated hydrocarbon solvent, in which aluminum halide and aluminum powder are used in combination as a catalyst. It relates to a characteristic polystyrene bromination method.
【００１０】本発明で使用する溶媒としては、臭素と反
応せず、触媒を失活させないものであれば特に限定はな
いが、例えば塩化メチレン、ジクロロエタン、トリクロ
ロエタン、ジクロロジブロモエタン、ジブロモエタン、
テトラブロモエタン、四塩化炭素等の飽和脂肪族ハロゲ
ン化炭化水素が挙げられる。これらは無水の溶媒だけで
なく、回収溶剤を脱水処理して実質的に無水状態にした
溶媒であってもよい。これらのなかでも、塩化メチレン
が実用上好ましい。The solvent used in the present invention is not particularly limited as long as it does not react with bromine and does not deactivate the catalyst. For example, methylene chloride, dichloroethane, trichloroethane, dichlorodibromoethane, dibromoethane,
Examples include saturated aliphatic halogenated hydrocarbons such as tetrabromoethane and carbon tetrachloride. These may be not only anhydrous solvents but also solvents obtained by subjecting the recovered solvent to a dehydration treatment to be substantially anhydrous. Of these, methylene chloride is practically preferable.
【００１１】本発明で使用するポリスチレンとしては、
重量平均分子量で１０，０００〜５００，０００程度の
ものが使用され、中でも２０，０００〜２５０，０００
のものが好ましい。As the polystyrene used in the present invention,
A weight average molecular weight of about 10,000 to 500,000 is used, and among them, 20,000 to 250,000.
Are preferred.
【００１２】本発明で臭素化剤として使用する臭素は、
ポリスチレンのベンゼン環１モルに対し１〜３モル使用
するのが好ましいが、特に臭素含有率の高い臭素化ポリ
スチレンを製造するために２〜３モルの臭素を使用する
のが好ましい。The bromine used as the brominating agent in the present invention is
It is preferable to use 1 to 3 moles per 1 mole of benzene ring of polystyrene, but it is preferable to use 2 to 3 moles of bromine for producing brominated polystyrene having a particularly high bromine content.
【００１３】本発明の特徴は、触媒としてハロゲン化ア
ルミニウムおよびアルミニウム粉末を併用することにあ
る。ハロゲン化アルミニウムとしては、塩化アルミニウ
ム、臭化アルミニウム、ヨウ化アルミニウムが挙げられ
るが、特に塩化アルミニウムが好ましい。ハロゲン化ア
ルミニウム及び併用するアルミニウム粉末の形態として
は特に限定は無いが、副反応、反応液中での分散等を考
慮して、高純度且つ微粉末状のものが好ましい。また、
アルミニウム粉末の添加時期は、臭素滴下前にハロゲン
化アルミニウムと共に添加してもよいし、臭素滴下途
中、臭素滴下終了後何れでもよいが、実用上臭素滴下前
にハロゲン化アルミニウムと同時に添加する事が好まし
い。触媒の使用量は余りに少ないと反応時間が長くなる
ため、実用上ハロゲン化アルミニウムとアルミニウム粉
末の化学量論の和がポリスチレンの芳香環１モル当り、
通常０. １〜１０モル％、好ましくは１〜５モル％であ
る。また、ハロゲン化アルミニウムとアルミニウム粉末
との割合は、重量比で１／０. ０１〜０. ０１／１であ
るが、アルミニウムの割合を高くすると得られる臭素化
ポリスチレンの着色が大きくなる傾向があるので、好ま
しくは１／０. １〜１／１である。A feature of the present invention is that aluminum halide and aluminum powder are used together as a catalyst. Examples of aluminum halides include aluminum chloride, aluminum bromide and aluminum iodide, with aluminum chloride being particularly preferred. The form of the aluminum halide and the aluminum powder to be used in combination is not particularly limited, but in view of side reactions, dispersion in the reaction solution, etc., high purity and fine powder are preferred. Also,
The aluminum powder may be added together with the aluminum halide before the addition of bromine, or during the addition of bromine or after the end of the addition of bromine. preferable. When the amount of the catalyst used is too small, the reaction time becomes long. Therefore, in practice, the sum of the stoichiometry of aluminum halide and aluminum powder is
It is usually 0.1 to 10 mol%, preferably 1 to 5 mol%. Further, the weight ratio of aluminum halide to aluminum powder is 1 / 0.01 to 0.01 / 1, but when the proportion of aluminum is increased, the color of brominated polystyrene obtained tends to increase. Therefore, it is preferably 1 / 0.1 to 1/1.
【００１４】本発明にあっては、通常上記有機溶媒にポ
リスチレンを溶解し、次いで所定量のハロゲン化アルミ
ニウムおよびアルミニウム粉末を投入した後、臭素を滴
下する。臭素化反応は温度を０〜３０℃、好ましくは５
〜２０℃に保持しながら臭素を滴下することによって行
う。反応温度が０℃未満では反応速度が遅くなり、３０
℃より高いと得られる臭素化ポリスチレンの着色が大き
くなる傾向がある。滴下終了後更に５〜１５℃に保持し
て１０分〜２時間攪拌を継続して反応を完結させる。反
応終了後、反応溶液を水中に投入するか反応溶液に水を
投入して触媒を失活させ、水層を分離し、有機溶媒層を
水で洗浄して不純物を除去する。洗浄後の有機溶媒層に
含まれる臭素化ポリスチレンを単離するには任意の方
法、例えばメタノール等の低級アルコール類、炭素数５
〜８の飽和脂肪族炭化水素中に有機溶媒層を注いで析出
させてもよいし、温水中に反応溶媒層を注ぎ、溶媒を蒸
発させて析出させてもよい。また、スプレー乾燥の如き
真空下で溶媒を留去する方法によってもよい。In the present invention, usually, polystyrene is dissolved in the above organic solvent, and then a predetermined amount of aluminum halide and aluminum powder are added, and then bromine is added dropwise. The bromination reaction has a temperature of 0 to 30 ° C., preferably 5
Performed by dropwise addition of bromine while maintaining ~ 20 ° C. If the reaction temperature is lower than 0 ° C, the reaction rate becomes slow,
If the temperature is higher than ° C, the color of the brominated polystyrene obtained tends to increase. After completion of the dropping, the temperature is further maintained at 5 to 15 ° C. and stirring is continued for 10 minutes to 2 hours to complete the reaction. After completion of the reaction, the reaction solution is poured into water or water is added to the reaction solution to deactivate the catalyst, the aqueous layer is separated, and the organic solvent layer is washed with water to remove impurities. Any method can be used to isolate the brominated polystyrene contained in the organic solvent layer after washing, for example, lower alcohols such as methanol, carbon number 5 and the like.
The organic solvent layer may be poured into the saturated aliphatic hydrocarbon of ~ 8 for precipitation, or the reaction solvent layer may be poured into warm water and the solvent may be evaporated for precipitation. Alternatively, the solvent may be distilled off under vacuum such as spray drying.
【００１５】本発明の方法で得られる臭素化ポリスチレ
ンは、ポリスチレンの芳香環１個当り１〜３個の臭素原
子を有し、色相や耐熱性に優れているので例えばポリカ
ーボネート、ポリエステル、ポリプロピレン、スチレン
系樹脂、ポリアミド等のプラスチック用難燃剤として幅
広く使用できる。The brominated polystyrene obtained by the method of the present invention has 1 to 3 bromine atoms per aromatic ring of polystyrene and is excellent in hue and heat resistance, and therefore, for example, polycarbonate, polyester, polypropylene, styrene. It can be widely used as a flame retardant for plastics such as resin and polyamide.
【００１６】[0016]
【実施例】以下に実施例をあげて本発明を更に説明す
る。なお、実施例中の色相および耐熱性は下記の方法に
より評価した。EXAMPLES The present invention will be further described with reference to the following examples. The hue and heat resistance in the examples were evaluated by the following methods.
【００１７】色 相：得られた臭素化ポリスチレンを
０．１０ｇ秤量後、５０ｍｌの塩化メチレンに溶解し、
この溶液をハーゼン色数標準液と比較して色相（ＡＰＨ
Ａ）を測定した。値は小さい程色相が良いことを示す。Hue: 0.10 g of the obtained brominated polystyrene was weighed and then dissolved in 50 ml of methylene chloride,
This solution is compared with Hazen color standard solution
A) was measured. The smaller the value, the better the hue.
【００１８】耐熱性：ＴＡインスツルメント社製１０９
０Ｂ型熱分析システム９５１型ＴＧＡにより、窒素雰囲
気中昇温速度２０℃／ｍｉｎで３％減量温度にて評価し
た。Heat resistance: 109 manufactured by TA Instruments
Evaluation was carried out by a 0B type thermal analysis system 951 TGA at a temperature increase rate of 20 ° C./min in a nitrogen atmosphere at a 3% weight loss temperature.
【００１９】[0019]
【実施例１】温度計、滴下ロートおよび冷却管を付した
容量１ｌの四つ口フラスコに塩化メチレン５３０ｇ及び
ポリスチレン［大日本インキ（株）製エラスチレン２０
０、重量平均分子量５５，０００］３４ｇを仕込み、５
〜７℃に保持して攪拌下塩化アルミニウム１．１５ｇお
よびアルミニウム粉末０．０７ｇを投入した後、５〜１
０℃にて臭素１３９ｇを４５分間かけて滴下した。滴下
終了後更に１時間攪拌して反応を完結した。得られた反
応溶液を２５０ｍｌの水中へ１０分かけて滴下して触媒
を失活させた。水層を除去し、更に有機溶媒層を４００
ｍｌの水で２回洗浄、濾過後４００ｍｌの温水中（５０
〜８０℃）へ攪拌下１時間かけて滴下し、析出した固体
を濾別、乾燥して白色の臭素化ポリスチレン（臭素含有
率６７％、２．６５Ｂｒ体）９４ｇを得た。得られた臭
素化ポリスチレンの色相、耐熱性の評価結果を表１に示
した。Example 1 In a four-necked flask having a capacity of 1 liter equipped with a thermometer, a dropping funnel and a cooling tube, 530 g of methylene chloride and polystyrene [Elaststyrene 20 manufactured by Dainippon Ink and Chemicals, Inc.]
0, weight average molecular weight 55,000] 34 g was charged, and 5
After maintaining at -7 ° C and adding 1.15 g of aluminum chloride and 0.07 g of aluminum powder under stirring, 5-1
At 0 ° C., 139 g of bromine was added dropwise over 45 minutes. After completion of dropping, the reaction was completed by further stirring for 1 hour. The resulting reaction solution was added dropwise to 250 ml of water over 10 minutes to deactivate the catalyst. The water layer is removed, and an organic solvent layer is further added to 400
After washing twice with ml of water and filtering, 400 ml of warm water (50
To 80 ° C.) with stirring over 1 hour, the precipitated solid was separated by filtration and dried to obtain 94 g of white brominated polystyrene (bromine content 67%, 2.65 Br body). The evaluation results of hue and heat resistance of the obtained brominated polystyrene are shown in Table 1.
【００２０】[0020]
【実施例２〜４】塩化アルミニウムおよびアルミニウム
粉末の使用量を変更した以外は実施例１と同様な方法に
より検討を行った。その際に得られた臭素化ポリスチレ
ンの色相、耐熱性の評価結果を併せて表１に示した。Examples 2 to 4 Examination was conducted in the same manner as in Example 1 except that the amounts of aluminum chloride and aluminum powder used were changed. The evaluation results of the hue and heat resistance of the brominated polystyrene obtained at that time are also shown in Table 1.
【００２１】[0021]
【比較例１】温度計、滴下ロートおよび冷却管を付した
容量１ｌの四つ口フラスコに塩化メチレン５３０ｇ及び
ポリスチレン［大日本インキ（株）製エラスチレン２０
０、重量平均分子量５５，０００］３４ｇを仕込み、５
〜７℃に保持して攪拌下塩化アルミニウム１．７０ｇを
投入した後、５〜１０℃にて臭素１３９ｇを４５分間か
けて滴下した。滴下終了後更に１時間攪拌して反応を完
結した。得られた反応溶液を２５０ｍｌの水中へ１０分
かけて滴下して触媒を失活させた。水層を除去し、更に
有機溶媒層を４００ｍｌの水で２回洗浄、濾過後４００
ｍｌの温水中（５０〜８０℃）へ攪拌下１時間かけて滴
下し、析出した固体を濾別、乾燥して白色の臭素化ポリ
スチレン（臭素含有率６７％、２．６５Ｂｒ体）９２ｇ
を得た。得られた臭素化ポリスチレンの色相、耐熱性の
評価結果を表１に実施例と共に併記した。Comparative Example 1 530 g of methylene chloride and polystyrene [Elaststyrene 20 manufactured by Dainippon Ink and Chemicals, Inc.] were placed in a four-necked flask having a capacity of 1 liter equipped with a thermometer, a dropping funnel and a cooling tube.
0, weight average molecular weight 55,000] 34 g was charged, and 5
After maintaining at -7 ° C and adding 1.70 g of aluminum chloride with stirring, 139 g of bromine was added dropwise at 5-10 ° C over 45 minutes. After completion of dropping, the reaction was completed by further stirring for 1 hour. The resulting reaction solution was added dropwise to 250 ml of water over 10 minutes to deactivate the catalyst. The water layer was removed, and the organic solvent layer was washed twice with 400 ml of water, filtered, and washed with 400
92 g of white brominated polystyrene (bromine content 67%, 2.65 Br body) was dropped into 1 ml of warm water (50 to 80 ° C.) with stirring over 1 hour, and the precipitated solid was separated by filtration and dried.
Got The evaluation results of hue and heat resistance of the obtained brominated polystyrene are shown in Table 1 together with the examples.
【００２２】[0022]
【比較例２】温度計、滴下ロートおよび冷却管を付した
容量１ｌの四つ口フラスコに塩化メチレン５３０ｇ、及
びポリスチレン［大日本インキ（株）製エラスチレン２
００、重量平均分子量５５，０００］３４ｇを仕込み、
７℃に保持して攪拌下塩化アルミニウム１．４９ｇを投
入した後、５〜１０℃にて臭素１３９ｇを４５分間かけ
て滴下した。滴下終了後更に１時間攪拌して反応を完結
した。得られた反応溶液を２５０ｍｌの水中へ１０分か
けて滴下して触媒を失活させた。この時、水層は褐色に
帯色しており、未反応臭素の残存が確認された。水層を
除去し更に有機溶媒層を４００ｍｌの水で２回洗浄、濾
過後４００ｍｌの温水中（５０〜８０℃）へ攪拌下１時
間かけて滴下し、析出した固体を濾別、乾燥して白色の
臭素化ポリスチレン（臭素含有率６５％、２．３５Ｂｒ
体）８８ｇを得た。得られた臭素化ポリスチレンの色
相、耐熱性の評価結果を表１に併記した。[Comparative Example 2] 530 g of methylene chloride and polystyrene [Elaststyrene 2 manufactured by Dainippon Ink and Chemicals, Inc.] were placed in a four-necked flask having a capacity of 1 liter equipped with a thermometer, a dropping funnel and a cooling tube.
00, weight average molecular weight 55,000] 34 g,
After maintaining at 7 ° C and adding 1.49 g of aluminum chloride with stirring, 139 g of bromine was added dropwise at 5 to 10 ° C over 45 minutes. After completion of dropping, the reaction was completed by further stirring for 1 hour. The resulting reaction solution was added dropwise to 250 ml of water over 10 minutes to deactivate the catalyst. At this time, the aqueous layer was colored brown, and it was confirmed that unreacted bromine remained. The water layer was removed, and the organic solvent layer was washed twice with 400 ml of water, filtered, and then added dropwise to 400 ml of warm water (50 to 80 ° C.) over 1 hour with stirring. The precipitated solid was filtered and dried. White brominated polystyrene (bromine content 65%, 2.35Br
88 g of a body was obtained. The evaluation results of hue and heat resistance of the obtained brominated polystyrene are also shown in Table 1.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【発明の効果】本発明の方法によって得られる臭素化ポ
リスチレンは色相、耐熱性共に優れており難燃剤として
幅広く使用することができる。特に、本発明の方法はポ
リスチレンを臭素化するに際し、得られる臭素化ポリス
チレンの耐熱性改善に著しい効果を発揮する。The brominated polystyrene obtained by the method of the present invention has excellent hue and heat resistance and can be widely used as a flame retardant. In particular, the method of the present invention exerts a remarkable effect in improving the heat resistance of the obtained brominated polystyrene when brominating polystyrene.
Claims (1)
ンと臭素とを反応させて臭素化ポリスチレンを製造する
方法において、触媒としてハロゲン化アルミニウムおよ
びアルミニウム粉末を用いることを特徴とする臭素化ポ
リスチレンの製造方法。1. A method for producing brominated polystyrene by reacting polystyrene and bromine in a halogenated hydrocarbon solvent, wherein aluminum halide and aluminum powder are used as catalysts. .
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27348393A JP3333604B2 (en) | 1993-11-01 | 1993-11-01 | Method for producing brominated polystyrene |
| US08/200,454 US5446109A (en) | 1993-02-23 | 1994-02-23 | Polyamide/aliphatic polyester block copolymer, process for the production thereof, and blend containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27348393A JP3333604B2 (en) | 1993-11-01 | 1993-11-01 | Method for producing brominated polystyrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07126320A true JPH07126320A (en) | 1995-05-16 |
| JP3333604B2 JP3333604B2 (en) | 2002-10-15 |
Family
ID=17528541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27348393A Expired - Fee Related JP3333604B2 (en) | 1993-02-23 | 1993-11-01 | Method for producing brominated polystyrene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3333604B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7202296B2 (en) | 2003-12-19 | 2007-04-10 | Albemarle Corporation | Flame retardant compositions and their use |
| JP2009079232A (en) * | 1998-09-10 | 2009-04-16 | Albemarle Corp | Polymer composition containing brominated polystyrenic resin |
| US7632893B2 (en) | 2005-06-30 | 2009-12-15 | Albemarle Corporation | Brominated styrenic polymers and their preparation |
| US7666943B2 (en) | 2004-01-21 | 2010-02-23 | Albemarle Corporation | Flame retarded fibers and filaments and process of production therefor |
| US7666944B2 (en) | 2004-01-21 | 2010-02-23 | Albemarle Corporation | Flame retarded fibers and filaments and process of production therefor |
-
1993
- 1993-11-01 JP JP27348393A patent/JP3333604B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009079232A (en) * | 1998-09-10 | 2009-04-16 | Albemarle Corp | Polymer composition containing brominated polystyrenic resin |
| US7202296B2 (en) | 2003-12-19 | 2007-04-10 | Albemarle Corporation | Flame retardant compositions and their use |
| US7405254B2 (en) | 2003-12-19 | 2008-07-29 | Albemarle Corporation | Flame retardant compositions and their use |
| US7666943B2 (en) | 2004-01-21 | 2010-02-23 | Albemarle Corporation | Flame retarded fibers and filaments and process of production therefor |
| US7666944B2 (en) | 2004-01-21 | 2010-02-23 | Albemarle Corporation | Flame retarded fibers and filaments and process of production therefor |
| US7632893B2 (en) | 2005-06-30 | 2009-12-15 | Albemarle Corporation | Brominated styrenic polymers and their preparation |
| US8168723B2 (en) | 2005-06-30 | 2012-05-01 | Albemarle Corporation | Brominated styrenic polymers and their preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3333604B2 (en) | 2002-10-15 |
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