JP3359698B2 - Method for producing brominated polystyrene - Google Patents
Method for producing brominated polystyreneInfo
- Publication number
- JP3359698B2 JP3359698B2 JP14363693A JP14363693A JP3359698B2 JP 3359698 B2 JP3359698 B2 JP 3359698B2 JP 14363693 A JP14363693 A JP 14363693A JP 14363693 A JP14363693 A JP 14363693A JP 3359698 B2 JP3359698 B2 JP 3359698B2
- Authority
- JP
- Japan
- Prior art keywords
- organic solvent
- polystyrene
- parts
- bromine
- brominated polystyrene
- 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.)
- Expired - Fee Related
Links
- 239000004793 Polystyrene Substances 0.000 title claims description 42
- 229920002223 polystyrene Polymers 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 36
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 28
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 27
- 229910052794 bromium Inorganic materials 0.000 claims description 27
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- -1 saturated aliphatic halogenated hydrocarbons Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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
- 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
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は臭素化ポリスチレンの製
造方法に関する。更に詳しくは、色相が良好で耐熱性に
優れた臭素化ポリスチレンを製造する方法に関する。The present invention relates to a method for producing brominated polystyrene. More specifically, the present invention relates to a method for producing brominated polystyrene having good hue and excellent heat resistance.
【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、有機溶媒中で塩化アルミニウム触媒の存在下ポリス
チレンに臭素を反応させる方法が知られている。例えば
特開昭５３−６０９８６号公報、特開昭５５−１５１０
０７号公報及び特公昭６１−３４７２３号公報には、塩
化アルミニウムを有機溶媒中に分散させた不均一系でポ
リスチレンに臭素を反応させる臭素化ポリスチレンの製
造法が記載されている。しかしながら、これらの方法で
は得られる臭素化ポリスチレンは色相や耐熱性が悪化す
る。2. Description of the Related Art Conventionally, as a method for producing brominated polystyrene, a method of reacting bromine with polystyrene in an organic solvent in the presence of an aluminum chloride catalyst is known. For example, JP-A-53-60986 and JP-A-55-1510
No. 07 and Japanese Patent Publication No. 61-34723 describe a method for producing brominated polystyrene in which bromine is reacted with polystyrene in a heterogeneous system in which aluminum chloride is dispersed in an organic solvent. However, the brominated polystyrene obtained by these methods deteriorates in hue and heat resistance.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、有機
溶媒中で塩化アルミニウム触媒の存在下ポリスチレンに
臭素を反応させる臭素化ポリスチレンの製造方法によっ
て、上記欠点のない色相が良好で耐熱性に優れた臭素化
ポリスチレンを提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a brominated polystyrene production method in which polystyrene is reacted with bromine in the presence of an aluminum chloride catalyst in an organic solvent. It is to provide an excellent brominated polystyrene.
【０００４】本発明者は上記目的を達成せんとして鋭意
検討した結果、ポリスチレンの有機溶媒溶液に塩化アル
ミニウムを添加し直ちに臭素を添加せずに、有機溶媒中
で予め塩化アルミニウムとポリスチレンを充分に攪拌混
合した後臭素を添加反応させると、ラジカル反応が抑制
されて色相や耐熱性に優れた製品が得られることを見出
した。更に、臭素の添加時期について検討を重ねた結
果、有機溶媒中で塩化アルミニウムとポリスチレンを攪
拌混合すると無色透明な有機溶媒溶液が橙色に着色して
くること、着色した有機溶媒溶液に臭素を添加反応させ
るとラジカル反応が充分に抑制されて色相や耐熱性に優
れた製品が得られることを究明し、本発明に到達した。The present inventors have conducted intensive studies to achieve the above object. As a result, aluminum chloride was added to an organic solvent solution of polystyrene, and immediately without adding bromine, aluminum chloride and polystyrene were sufficiently stirred in an organic solvent in advance. It has been found that when a bromine is added and reacted after mixing, a radical reaction is suppressed and a product excellent in hue and heat resistance can be obtained. Furthermore, as a result of repeated studies on the timing of adding bromine, it was found that when aluminum chloride and polystyrene were stirred and mixed in an organic solvent, a colorless and transparent organic solvent solution turned orange, and bromine was added to the colored organic solvent solution. It has been found that the radical reaction is sufficiently suppressed to obtain a product excellent in hue and heat resistance, and arrived at the present invention.
【０００５】[0005]
【課題を解決するための手段】本発明は、有機溶媒中で
塩化アルミニウム触媒の存在下ポリスチレンに臭素を反
応させて臭素化ポリスチレンを製造するに当り、予め有
機溶媒中で塩化アルミニウムとポリスチレンを混合して
有機溶媒溶液が着色した後臭素を添加反応させることを
特徴とする臭素化ポリスチレンの製造方法である。The present invention relates to a method for producing brominated polystyrene by reacting bromine with polystyrene in the presence of an aluminum chloride catalyst in an organic solvent. And then reacting bromine after the organic solvent solution is colored, thereby producing a brominated polystyrene.
【０００６】本発明で使用する有機溶媒としては例えば
塩化メチレン、ジクロロエタン、トリクロロエタン、テ
トラクロロエタン、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あげられ、なかでも塩化メチレ
ンが特に好ましい。これらは無水の溶媒だけでなく、工
業的に通常行われるように回収し、水分を含有する場合
は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。Examples of the organic solvent used in the present invention include saturated aliphatic halogenated hydrocarbons such as methylene chloride, dichloroethane, trichloroethane, tetrachloroethane, dichlorodibromoethane, dibromoethane, tetrabromoethane and carbon tetrachloride. Of these, methylene chloride is particularly preferred. These may be not only an anhydrous solvent but also a solvent which is recovered as usual in an industrial practice and, when containing water, is dehydrated to a substantially anhydrous state.
【０００７】ポリスチレンとしては、通常重量平均分子
量で１０，０００〜５００，０００程度のものが使用さ
れ、２０，０００〜２５０，０００のものが好ましい。
重量平均分子量が１０，０００以下のものを使用したの
では得られる臭素化ポリスチレンの耐熱性が低下するよ
うになり、重量平均分子量が高くなるほど耐熱性はよく
なるが、実用的には５００，０００程度までである。As polystyrene, those having a weight average molecular weight of about 10,000 to 500,000 are usually used, and those having a weight average molecular weight of 20,000 to 250,000 are preferable.
When a material having a weight average molecular weight of 10,000 or less is used, the heat resistance of the resulting brominated polystyrene decreases. As the weight average molecular weight increases, the heat resistance improves, but practically about 500,000. Up to.
【０００８】臭素化剤として使用する臭素は原料ポリス
チレンのベンゼン環１モルに対し、１〜３．３モル使用
するのが好ましい。１モルよりも少ない場合は臭素化ポ
リスチレンの臭素含有量が不十分になり、３．３モルよ
り多くすると反応終了時に残余の臭素が多くなり、経済
的ではない。The bromine used as the brominating agent is preferably used in an amount of from 1 to 3.3 mol per mol of the benzene ring of the starting polystyrene. When the amount is less than 1 mol, the bromine content of the brominated polystyrene becomes insufficient. When the amount is more than 3.3 mol, the residual bromine increases at the end of the reaction, which is not economical.
【０００９】本発明で触媒として使用する塩化アルミニ
ウムの量は、あまりに少ないと反応時間が長くなり、あ
まりに多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、ポリスチレンのベンゼン環
１モル当り通常１〜１０モル％、好ましくは２〜６モル
％である。If the amount of aluminum chloride used as a catalyst in the present invention is too small, the reaction time will be prolonged, and if it is too large, the color of the resulting brominated polystyrene tends to be large. Usually, it is 1 to 10 mol%, preferably 2 to 6 mol%.
【００１０】本発明にあっては、まず上記有機溶媒にポ
リスチレンを溶解し、得られたポリスチレンの有機溶媒
溶液に所定量の塩化アルミニウムを加えて攪拌する。こ
の攪拌時間は通常５分以上、好ましくは１０分以上であ
る。ポリスチレンの有機溶媒溶液に塩化アルミニウムを
加えて攪拌すると、一部塩化アルミニウム懸濁物を含む
有機溶媒溶液は橙色に着色してくる。有機溶媒溶液が着
色した時点以降に臭素を添加反応させる。有機溶媒溶液
が着色する以前に臭素を添加したのでは色相、耐熱性の
いずれも満足できる臭素化ポリスチレンは得られない。
臭素の添加時期は有機溶媒溶液が着色した時点以降であ
れば特に制限されないが、有機溶媒溶液が着色してから
臭素の添加まで長時間保持すると有機溶媒溶液がゲル化
して反応が不可能になるので、有機溶媒溶液がゲル化す
る以前、通常有機溶媒溶液が着色してから６０分以内、
好ましくは３０分以内に臭素を添加する。In the present invention, first, polystyrene is dissolved in the organic solvent, and a predetermined amount of aluminum chloride is added to the obtained organic solvent solution of polystyrene, followed by stirring. The stirring time is usually at least 5 minutes, preferably at least 10 minutes. When aluminum chloride is added to the organic solvent solution of polystyrene and stirred, the organic solvent solution partially containing the aluminum chloride suspension is colored orange. Bromine is added and reacted after the organic solvent solution is colored. If bromine is added before the organic solvent solution is colored, a brominated polystyrene satisfying both hue and heat resistance cannot be obtained.
The timing of adding bromine is not particularly limited as long as it is after the time when the organic solvent solution is colored, but if the organic solvent solution is colored and held for a long time until the addition of bromine, the organic solvent solution gels and the reaction becomes impossible. So, before the organic solvent solution gelled, usually within 60 minutes after the organic solvent solution was colored,
Preferably, the bromine is added within 30 minutes.
【００１１】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１〜２時間攪拌を継続して反応を完結させる。反
応終了後、反応溶液中の触媒を失活させ、水相を分離
し、有機溶媒相を水で洗浄して不純物を除去する。有機
溶媒相に臭素が残存している場合には、例えばチオ硫酸
ナトリウムや亜硫酸ナトリウムの如き還元剤を配合した
水で洗浄することが好ましい。洗浄後の有機溶媒相に含
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又は炭素数５〜
８の飽和脂肪族炭化水素に有機溶媒相を注ぎ析出させて
もよいし、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。The bromination reaction is carried out by dropping bromine while maintaining the temperature at 0 to 30 ° C, preferably 5 to 20 ° C. If the reaction temperature is lower than 0 ° C., the reaction rate becomes slow,
If the temperature is higher than 30 ° C., the obtained brominated polystyrene tends to be more colored. After completion of the dropwise addition, the mixture is further kept at 5 to 15 ° C. and stirring is continued for 1 to 2 hours to complete the reaction. After completion of the reaction, the catalyst in the reaction solution is deactivated, the aqueous phase is separated, and the organic solvent phase is washed with water to remove impurities. When bromine remains in the organic solvent phase, it is preferable to wash with water containing a reducing agent such as sodium thiosulfate or sodium sulfite. Any method for isolating brominated polystyrene contained in the organic solvent phase after washing,
For example, lower alcohols such as methanol or C5-C5
The organic solvent phase may be poured into the saturated aliphatic hydrocarbon of No. 8 and precipitated, or a method of removing the solvent under vacuum such as spray drying.
【００１２】本発明の方法で得られる臭素化ポリスチレ
ンは、ベンゼン環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の難燃剤として極めて有用
である。The brominated polystyrene obtained by the method of the present invention has 1 to 3 bromine atoms per benzene ring,
Excellent in hue and heat resistance, for example, polycarbonate, polyester, polypropylene, styrene resin,
It is extremely useful as a flame retardant for plastics such as polyamide.
【００１３】[0013]
【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、実施例中の部及び％は重量部及び重量％であ
り、耐熱性及び色相は強化ポリエチレンテレフタレート
樹脂［帝人（株）製 C−３０３０］１００部に臭素化ポ
リスチレン１０部及び三酸化アンチモン［日本精鉱
（株）製 ATOX-S]５部をドライブレンドして押出してペ
レット化し、このペレットを射出成形機によりシリンダ
ー温度２９０℃で厚さ３．２mmの試験片を成形し、成形
中成形を一旦停止し、２９０℃で１５分間滞留させた後
成形を再開し、滞留前後の試験片のｂ値をカラーメータ
ーで測定して評価した。滞留前後のｂ値の差が大きい程
耐熱性が悪く、ｂ値は小さい程色相がよいことを示す。The present invention will be further described with reference to the following examples. In the examples, parts and% are parts by weight and% by weight, and the heat resistance and the hue are 100 parts of reinforced polyethylene terephthalate resin [C-3030 manufactured by Teijin Limited] and 10 parts of brominated polystyrene and antimony trioxide [ 5 parts of ATOX-S manufactured by Nippon Seiko Co., Ltd. are dry-blended, extruded and pelletized, and the pellets are molded into a 3.2 mm-thick test piece at a cylinder temperature of 290 ° C. using an injection molding machine. Was stopped once, kept at 290 ° C. for 15 minutes, and the molding was restarted. The b value of the test piece before and after the stay was measured and evaluated by a color meter. The larger the difference between the b values before and after the stay, the worse the heat resistance, and the smaller the b value, the better the hue.
【００１４】[0014]
【実施例１】反応釜に塩化メチレン２６０部及びポリス
チレン［大日本インキ（株）製エラスチレン２００、重
量平均分子量５５，０００］１７部を仕込み、１０℃に
保持して攪拌下塩化アルミニウム０．７部を投入し、２
６分間攪拌したところ溶液の色相は無色透明から橙色透
明に変化した。この時点から臭素５５部を２時間かけて
滴下し、滴下終了後更に１時間攪拌して反応を完結し
た。得られた反応溶液に水５０部を９０分かけて滴下し
て触媒を失活させた。水相を除去し、有機溶媒相を４０
０部の水で２回洗浄した。有機溶媒相を６００部のメタ
ノールに攪拌下３時間かけて滴下し、析出した固体を遠
心分離機により分離し、乾燥して白色の臭素化ポリスチ
レン（臭素含有量６２％）３９．９部を得た。その色
相、耐熱性の評価結果を表１に示した。Example 1 A reaction kettle was charged with 260 parts of methylene chloride and 17 parts of polystyrene [Erastyrene 200, manufactured by Dainippon Ink and Co., Ltd., weight average molecular weight: 55,000]. Part
After stirring for 6 minutes, the hue of the solution changed from colorless and transparent to orange and transparent. From this point, 55 parts of bromine was added dropwise over 2 hours, and after completion of the addition, the mixture was further stirred for 1 hour to complete the reaction. 50 parts of water was added dropwise to the obtained reaction solution over 90 minutes to deactivate the catalyst. The aqueous phase is removed and the organic solvent phase is
Washed twice with 0 parts of water. The organic solvent phase was added dropwise to 600 parts of methanol with stirring over 3 hours. The precipitated solid was separated by a centrifuge and dried to obtain 39.9 parts of white brominated polystyrene (bromine content: 62%). Was. The evaluation results of the hue and heat resistance are shown in Table 1.
【００１５】[0015]
【実施例２】反応釜に塩化メチレン２６０部及びポリス
チレン［大日本インキ（株）製エラスチレン２００、重
量平均分子量５５，０００］１７部を仕込み、１０℃に
保持して攪拌下塩化アルミニウム０．７部を投入し、１
４分間攪拌したところ溶液の色相は無色透明から薄橙色
透明に変化した。この時点から臭素６６部を２時間かけ
て滴下し、滴下終了後更に１時間攪拌して反応を完結し
た。得られた反応溶液に水５０部を９０分かけて滴下し
て触媒を失活させた。水相を除去し、有機溶媒相を４０
０部の水で２回洗浄した。有機溶媒相を６００部のメタ
ノールに攪拌下３時間かけて滴下し、析出した固体を遠
心分離機により分離し、乾燥して白色の臭素化ポリスチ
レン（臭素含有量６６％）４７．９部を得た。その色
相、耐熱性の評価結果を表１に示した。EXAMPLE 2 A reaction kettle was charged with 260 parts of methylene chloride and 17 parts of polystyrene [Erastyrene 200, manufactured by Dainippon Ink and Co., Ltd., weight average molecular weight: 55,000]. Parts
After stirring for 4 minutes, the hue of the solution changed from colorless and transparent to light orange and transparent. From this point, 66 parts of bromine was added dropwise over 2 hours, and after the completion of the addition, the mixture was further stirred for 1 hour to complete the reaction. 50 parts of water was added dropwise to the obtained reaction solution over 90 minutes to deactivate the catalyst. The aqueous phase is removed and the organic solvent phase is
Washed twice with 0 parts of water. The organic solvent phase was added dropwise to 600 parts of methanol with stirring over 3 hours, and the precipitated solid was separated by a centrifugal separator and dried to obtain 47.9 parts of white brominated polystyrene (bromine content: 66%). Was. The evaluation results of the hue and heat resistance are shown in Table 1.
【００１６】[0016]
【比較例１】反応釜に塩化メチレン２６０部及びポリス
チレン［大日本インキ（株）製エラスチレン２００、重
量平均分子量５５，０００］１７部を仕込み、１０℃に
保持して攪拌下塩化アルミニウム０．７部を投入して１
分間攪拌した。次いで臭素５５部を２時間かけて滴下
し、滴下終了後更に１時間攪拌して反応を完結した。得
られた反応溶液に水５０部を９０分かけて滴下して触媒
を失活させた。水相を除去し、有機溶媒相を４００部の
水で２回洗浄した。有機溶媒相を６００部のメタノール
に攪拌下３時間かけて滴下し、析出した固体を遠心分離
機により分離し、乾燥して白色の臭素化ポリスチレン
（臭素含有量６２％）３９．３部を得た。その色相、耐
熱性の評価結果を表１に示した。COMPARATIVE EXAMPLE 1 A reaction vessel was charged with 260 parts of methylene chloride and 17 parts of polystyrene [Erastyrene 200, manufactured by Dainippon Ink and Co., Ltd., weight average molecular weight 55,000]. 1
Stirred for minutes. Next, 55 parts of bromine was added dropwise over 2 hours, and after completion of the addition, the mixture was further stirred for 1 hour to complete the reaction. 50 parts of water was added dropwise to the obtained reaction solution over 90 minutes to deactivate the catalyst. The aqueous phase was removed and the organic solvent phase was washed twice with 400 parts of water. The organic solvent phase was added dropwise to 600 parts of methanol with stirring over 3 hours, and the precipitated solid was separated by a centrifuge and dried to obtain 39.3 parts of white brominated polystyrene (bromine content: 62%). Was. The evaluation results of the hue and heat resistance are shown in Table 1.
【００１７】[0017]
【比較例２】反応釜に塩化メチレン２６０部及びポリス
チレン［大日本インキ（株）製エラスチレン２００、重
量平均分子量５５，０００］１７部を仕込み、１０℃に
保持して攪拌下塩化アルミニウム０．７部を投入し、攪
拌した。塩化アルミニウム投入後６５分経過した時点で
有機溶媒溶液は橙色透明のゲル状物になり、ここで更に
塩化メチレン２００部を追加して仕込んだが、ゲル状物
は溶解しなかった。Comparative Example 2 A reaction kettle was charged with 260 parts of methylene chloride and 17 parts of polystyrene [Erastyrene 200 manufactured by Dai Nippon Ink Co., Ltd., weight average molecular weight 55,000]. Was charged and stirred. 65 minutes after the addition of aluminum chloride, the organic solvent solution became an orange transparent gel-like substance. Here, 200 parts of methylene chloride was further added, but the gel-like substance was not dissolved.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【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、難燃剤として極め
て有用であり、本発明の奏する効果は格別なものであ
る。The brominated polystyrene obtained by the method of the present invention is excellent in both hue and heat resistance, is extremely useful as a flame retardant, and the effect of the present invention is outstanding.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤井 孝司 東京都港区西新橋１丁目６番21号 帝人 化成株式会社内 (56)参考文献 特開 平２−215807（ＪＰ，Ａ) 特開 昭59−102903（ＪＰ，Ａ) 特開 昭55−151007（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 8/00 - 8/50 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Fujii 1-6-21 Nishishinbashi, Minato-ku, Tokyo Teijin Chemicals Co., Ltd. (56) References JP-A-2-215807 (JP, A) JP-A Sho 59-102903 (JP, A) JP-A-55-151007 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08F 8/00-8/50
Claims (1)
在下ポリスチレンに臭素を反応させて臭素化ポリスチレ
ンを製造するに当り、予め有機溶媒中で塩化アルミニウ
ムとポリスチレンを混合して有機溶媒溶液が着色した後
臭素を添加反応させることを特徴とする臭素化ポリスチ
レンの製造方法。When producing brominated polystyrene by reacting bromine with polystyrene in the presence of an aluminum chloride catalyst in an organic solvent, aluminum chloride and polystyrene are mixed in an organic solvent in advance to color the organic solvent solution. A method for producing brominated polystyrene, comprising adding and reacting post-bromine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14363693A JP3359698B2 (en) | 1993-06-15 | 1993-06-15 | Method for producing brominated polystyrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14363693A JP3359698B2 (en) | 1993-06-15 | 1993-06-15 | Method for producing brominated polystyrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH072930A JPH072930A (en) | 1995-01-06 |
| JP3359698B2 true JP3359698B2 (en) | 2002-12-24 |
Family
ID=15343377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14363693A Expired - Fee Related JP3359698B2 (en) | 1993-06-15 | 1993-06-15 | Method for producing brominated polystyrene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3359698B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518368B2 (en) | 1996-06-14 | 2003-02-11 | Albemarle Corporation | Brominated polystyrene having improved thermal stability and color and process for the preparation thereof |
| US5637650A (en) | 1996-06-14 | 1997-06-10 | Ferro Corporation | Brominated polysytrene having improved thermal stability and color and process for the preparation thereof |
| US6326439B1 (en) | 1996-09-26 | 2001-12-04 | Albemarle Corporation | Process for brominating polystyrenic resins |
| CA2265642C (en) | 1996-09-26 | 2006-03-14 | Albemarle Corporation | Process for brominated styrenic polymers |
| US6235831B1 (en) | 1996-09-26 | 2001-05-22 | Albemarle Corporation | Polymer compositions containing brominated polystyrenic resins |
| US6232393B1 (en) | 1996-09-26 | 2001-05-15 | Albemarle Corporation | Polymers flame retarded with brominated polystyrenic resins |
| US6232408B1 (en) | 1996-09-26 | 2001-05-15 | Albemarle Corporation | Brominated polstyrenic resins |
| US6521714B2 (en) | 1996-09-26 | 2003-02-18 | Albemarle Corporation | Brominated polystyrenic resins |
| US6235844B1 (en) | 1996-09-26 | 2001-05-22 | Albemarle Corporation | Brominated polystyrenic resins |
| JP5116670B2 (en) | 2005-06-30 | 2013-01-09 | アルベマール・コーポレーシヨン | Brominated styrenic polymers and their production |
-
1993
- 1993-06-15 JP JP14363693A patent/JP3359698B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH072930A (en) | 1995-01-06 |
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