JPH0680712A - Production of polystyrene resin - Google Patents
Production of polystyrene resinInfo
- Publication number
- JPH0680712A JPH0680712A JP23597892A JP23597892A JPH0680712A JP H0680712 A JPH0680712 A JP H0680712A JP 23597892 A JP23597892 A JP 23597892A JP 23597892 A JP23597892 A JP 23597892A JP H0680712 A JPH0680712 A JP H0680712A
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- weight
- molecular weight
- reactor
- average molecular
- aromatic vinyl
- Prior art date
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- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性及び機械的強度
に優れ、しかも、射出成形及び押出成形性が良好で、特
に、加熱二次成形性に優れたポリスチレン系樹脂の製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polystyrene resin which is excellent in heat resistance and mechanical strength, has good injection molding and extrusion moldability, and is particularly excellent in heat secondary moldability.
【０００２】[0002]
【従来の技術】ポリスチレン系樹脂は、一般に透明性、
耐熱性及び機械的強度に優れ、更に、成形性が良好なた
めに、家庭用品及び電気製品等多くの分野で使用されて
いる。また、ポリスチレン系樹脂の発泡体は、表面光沢
性、軽量性、熱遮断性及び緩衝性などの特徴を持ち、発
泡体の厚さにより使用分野が異なっている。ポリスチレ
ン系樹脂発泡体は、厚さ約３mm以下のシート状のものは
ポリスチレンペーパー（ＰＳＰ）と称され、成形が容易
であるのに加えて緩衝性や熱遮断性などの特徴を活かし
てプリパッケージを中心に弁当箱、丼、カップ及び菓子
箱の中仕切り用などに広く活用されているが、生産性の
向上等の観点から優れた加熱２次成形性が求められてい
る。2. Description of the Related Art Polystyrene resins are generally transparent,
It has excellent heat resistance and mechanical strength, and because it has good moldability, it is used in many fields such as household products and electric appliances. Further, the foam of polystyrene resin has characteristics such as surface gloss, lightness, heat insulating property and cushioning property, and its field of use varies depending on the thickness of the foam. A sheet of polystyrene-based resin foam with a thickness of about 3 mm or less is called polystyrene paper (PSP). It is easy to mold, and features such as cushioning and heat insulation are used for pre-packaging. It is widely used mainly for lunch boxes, bowls, cups, and as a partition for confectionery boxes, etc., but it is required to have excellent secondary heat moldability from the viewpoint of improving productivity.
【０００３】ポリスチレン系樹脂発泡シートは、ブタ
ンやペンタン等の脂肪族炭化水素、トリクロロモノフル
オルメタン及び塩化メチル等のハロゲン化脂肪族炭化水
素からなる発泡剤を含浸させた発泡性ポリスチレン系樹
脂の粒子を直接押出機でシート状に押出す方法、押出
機内で溶融されたポリスチレン系樹脂に前述の発泡剤を
圧入しながらシート状に押出す方法により製造されてい
る。そして、得られたポリスチレン系樹脂発泡体シート
は、まず加熱ヒーターにより二次発泡され、次いでプラ
グアシスト法等の真空成形、圧空成形又はプレス成形さ
れて容器として使用されている。一般に、ポリスチレン
系樹脂は、シート状に押出されたものを二次加工する際
に、シートへの加熱分布状態が不均一な場合及び加熱不
足で成形を行うとシートが破れたり、偏肉部分が発生し
て成形品の強度が不足することになり、美観も損ねる。A polystyrene-based resin foam sheet is a foamable polystyrene-based resin impregnated with a foaming agent composed of an aliphatic hydrocarbon such as butane and pentane, and a halogenated aliphatic hydrocarbon such as trichloromonofluoromethane and methyl chloride. It is produced by a method of directly extruding particles into a sheet by an extruder or a method of extruding the particles into a sheet while pressing the above-mentioned foaming agent into a polystyrene resin melted in the extruder. The polystyrene-based resin foam sheet thus obtained is secondarily foamed by a heater and then vacuum-molded by a plug assist method, pressure-molded or press-molded to be used as a container. In general, polystyrene-based resin, when secondary processing of the extruded sheet, when the heating distribution state to the sheet is non-uniform and when the molding is performed with insufficient heating, the sheet is torn or the uneven thickness portion is generated. If it occurs, the strength of the molded product will be insufficient, and the appearance will be impaired.
【０００４】特に、発泡シートを用いて発泡体を成形す
る際には、加熱二次発泡体成形工程において、加熱炉内
の温度分布があることや、外気温の変動のために、シー
トの一部もしくは全部が加熱不足となり、成形時にシー
トが破れたり、型決まり性が悪くなったり、逆に加熱過
剰となって、成形品表面がケロイド状になったり、成形
品の厚みが変動する等の現象が生じる。このようなケロ
イド状のヤケの発生を防ぐためには、原料ポリスチレン
系重合体の分子量を上げたり、シート表面にフィルムを
貼ったり、樹脂密度の大きい層いわゆるスキン層を形成
する等の方法が知られている。しかし、かかる方法で
は、生産性の低下を招いたり、シート押出し時にダイ及
びマンドレルでの振動やシート表面の傷つきなどの不具
合を起こすことがある。更に、この様な重合体を深絞り
用途に用いた場合は、シート破れを生じやすい。In particular, when molding a foam using a foamed sheet, in the heating secondary foam molding step, there is a temperature distribution in the heating furnace and the fluctuation of the outside air temperature causes the sheet Insufficient heating of all or part of the sheet may cause the sheet to break during molding, the mold regularity may deteriorate, or conversely, excessive heating may cause the surface of the molded product to become keloid-like, or the thickness of the molded product may fluctuate. The phenomenon occurs. In order to prevent the occurrence of such keloid-like burns, there are known methods such as increasing the molecular weight of the raw material polystyrene-based polymer, sticking a film on the surface of the sheet, and forming a layer having a high resin density, a so-called skin layer. ing. However, such a method may lead to a decrease in productivity, and may cause defects such as vibration of a die and a mandrel at the time of extruding a sheet and scratches on the sheet surface. Further, when such a polymer is used for deep drawing, sheet breakage is likely to occur.
【０００５】また、成形時に型決まりの良い発泡体を得
るためには、原料ポリスチレン系重合体の分子量を下げ
たり、原料ポリスチレン系重合体に可塑剤、潤滑剤を添
加する方法が知られている。しかし、この方法はシート
の機械的強度の低下を招いたり、耐熱性が低下するとい
う問題がある。一方、射出成形及び押出成形性に優れ、
しかも、発泡シートの成形に関して、加熱二次加工性の
向上対策としては、例えば、重量平均分子量Mwと数平均
分子量Mnの比Mw／Mnが3.０以上の樹脂からなる発泡体を
使用することが特開昭62-22834号公報に記載されてい
る。Further, in order to obtain a foam having good moldability during molding, a method is known in which the molecular weight of the raw polystyrene polymer is reduced or a plasticizer and a lubricant are added to the raw polystyrene polymer. . However, this method has a problem that the mechanical strength of the sheet is lowered and the heat resistance is lowered. On the other hand, it has excellent injection molding and extrusion moldability,
Moreover, regarding the molding of the foamed sheet, as a measure for improving the heating secondary processability, for example, a foam made of a resin having a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of 3.0 or more is used. Are described in JP-A-62-22834.
【０００６】しかし、単に樹脂の重量平均分子量Mwと数
平均分子量Mnの比Mw／Mnが広いということは、その平均
分子量の定義上、分子量の広がりが主に低分子量側に広
がっていることを意味し、このように低分子領域に分布
が広いポリスチレン系樹脂の発泡体は本質的に強度が弱
いという欠点を有している。しかも、特開昭62-22834号
公報の記載では、重合途中で触媒や連鎖移動剤等を追加
する等工程が複雑である。また、一般に重量平均分子量
Mwを大きくするには、低温で長時間重合を行うことが必
要となり、生産性の面から有利とはいえない。更に、特
開平3-111434号公報、特開平3-111435号公報では、長鎖
アルキルを含む開始剤を用い重合したポリスチレン系樹
脂の使用が提案されている。しかし、この開始剤の分解
温度は80℃前後と低く、商業的に使用するには重合温度
を低くせざるを得なくなり、重合液の粘度が高くなると
いう欠点とともに、実施例にあるように長い重合時間が
必要であり生産性に難点があり、実用的でない。However, the fact that the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the resin is wide means that the definition of the average molecular weight means that the broadening of the molecular weight mainly extends to the low molecular weight side. This means that the polystyrene resin foam having a wide distribution in the low-molecular region has a drawback that its strength is essentially low. Moreover, in the description of JP-A No. 62-22834, the step of adding a catalyst, a chain transfer agent, etc. during the polymerization is complicated. In addition, generally the weight average molecular weight
In order to increase Mw, it is necessary to carry out polymerization at a low temperature for a long time, which is not advantageous in terms of productivity. Further, JP-A-3-111434 and JP-A-3-111435 propose the use of a polystyrene resin polymerized with an initiator containing a long-chain alkyl. However, the decomposition temperature of this initiator is as low as around 80 ° C., and the polymerization temperature has to be lowered for commercial use, and the viscosity of the polymerization solution becomes high, and it is long as in Examples. It requires polymerization time and has a difficulty in productivity, which is not practical.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、かかる欠点
を解決するものであり、本発明の目的とするところは、
機械的強度に優れ、しかも、射出成形及び押出成形性が
良好であり、特に、発泡シートとした際の二次成形性に
優れたポリスチレン系樹脂の製造方法を見出し本発明を
完成するに至った。DISCLOSURE OF THE INVENTION The present invention solves these drawbacks, and the object of the present invention is to:
The present invention has been completed by finding a method for producing a polystyrene-based resin having excellent mechanical strength, excellent injection molding and extrusion moldability, and particularly excellent secondary moldability when used as a foamed sheet. .
【０００８】[0008]
【課題を解決するための手段】すなわち本発明は、下記
一般式〔化２〕で表される有機過酸化物の重合開始剤を
用いて芳香族ビニル系化合物または芳香族ビニル系化合
物及び芳香族ビニル系化合物と共重合可能な化合物との
混合物を重合して、ゲルパーミエイションクロマトグラ
フィーで測定した値において、Ｚ平均分子量Mzと重量平
均分子量Mwの比Mz／Mwが1.７〜2.５、重量平均分子量Mw
と数平均分子量Mnの比Mw／Mnが2.０〜3.０、しかも、重
量平均分子量Mwが20万〜60万の範囲にあることを特徴と
するポリスチレン系樹脂の製造方法である。That is, the present invention provides an aromatic vinyl compound or an aromatic vinyl compound and an aromatic vinyl compound using an organic peroxide polymerization initiator represented by the following general formula [Chemical formula 2]. A mixture of a vinyl compound and a copolymerizable compound is polymerized, and in the value measured by gel permeation chromatography, the ratio Mz / Mw of the Z average molecular weight Mz and the weight average molecular weight Mw is 1.7 to 2. 5, weight average molecular weight Mw
And a number average molecular weight Mn ratio Mw / Mn of 2.0 to 3.0 and a weight average molecular weight Mw of 200,000 to 600,000.
【０００９】[0009]
【化２】 （式中Ｒ1 、Ｒ2 は水素または炭素数１〜２のアルキル
基、Ｒ3 は炭素数１〜５のアルキル基またはフェニル基
を表す）[Chemical 2] (Wherein R 1 and R 2 represent hydrogen or an alkyl group having 1 to 2 carbon atoms, and R 3 represents an alkyl group having 1 to 5 carbon atoms or a phenyl group)
【００１０】本発明の製造法によれば、一般式〔化２〕
を重合開始剤として用いることにより、公知の重合法で
生産性を下げることなく、Ｚ平均分子量Mzと重量平均分
子量Mwの比Mz／Mwが1.７〜2.５の範囲にあり、重量平均
分子量Mwと数平均分子量Mnの比Mw／Mnが2.０〜3.０の範
囲にあり、しかも、重量平均分子量Mwが20万〜60万の範
囲にあることを特徴とするポリスチレン系樹脂が得られ
る。According to the production method of the present invention, a compound represented by the general formula:
By using as a polymerization initiator, the ratio Mz / Mw of the Z average molecular weight Mz and the weight average molecular weight Mw is in the range of 1.7 to 2.5 without decreasing the productivity by the known polymerization method, and the weight average A polystyrene resin characterized in that the ratio Mw / Mn of the molecular weight Mw to the number average molecular weight Mn is in the range of 2.0 to 3.0, and the weight average molecular weight Mw is in the range of 200,000 to 600,000. can get.
【００１１】そして、このポリスチレン系樹脂から得ら
れるポリスチレン系発泡体は、原料樹脂の重量平均分子
量が大きいため機械的強度に優れている。また、Ｚ平均
分子量Mzと重量平均分子量Mwの比Mz／Mwが1.７より大き
いため、従来のポリスチレン系樹脂に比べ、高分子量重
合体の割合が高くなっており、機械的強度を損なわず
に、特に発泡シートとした際の深絞り成形時に優れた成
形性を発揮する。The polystyrene foam obtained from this polystyrene resin is excellent in mechanical strength because the raw material resin has a large weight average molecular weight. Further, since the ratio Mz / Mw of the Z-average molecular weight Mz and the weight-average molecular weight Mw is larger than 1.7, the ratio of the high-molecular weight polymer is higher than that of the conventional polystyrene resin, and the mechanical strength is not impaired. In particular, it exhibits excellent formability during deep drawing, especially when used as a foamed sheet.
【００１２】以下、本発明について詳しく説明する。本
発明の芳香族ビニル化合物とは、例えばスチレン、α−
メチルスチレン、ｐ−メチルスチレン及びｐ−tert−ブ
チルスチレン等の核アルキル置換スチレンやｏ−クロル
スチレン、ｐ−ブロモスチレン及び２，４−ジブロモス
チレン等の核ハロゲン化スチレン等であり、単独又は２
種以上の混合物として用いることができる。The present invention will be described in detail below. Examples of the aromatic vinyl compound of the present invention include styrene and α-
Nuclear alkyl-substituted styrenes such as methylstyrene, p-methylstyrene and p-tert-butylstyrene, and nuclear halogenated styrenes such as o-chlorostyrene, p-bromostyrene and 2,4-dibromostyrene, which may be used alone or in combination with 2
It can be used as a mixture of two or more species.
【００１３】更に、上述の芳香族ビニル系化合物と共重
合可能なビニル単量体としては、アクリロニトリルやメ
タクリロニトリル等のシアン化ビニル化合物、アクリル
酸メチルやアクリル酸エチル等のアクリル酸エステル系
化合物、メタクリル酸メチル、メタクリル酸エチル及び
メタクリル酸プロピル等のメタクリル酸エステル系化合
物並びにアルリルアミド誘導体等が使用できる。これら
の化合物は、単独でも、２種以上を組み合わせて使用し
ても良い。Further, as the vinyl monomer copolymerizable with the above-mentioned aromatic vinyl compound, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and acrylic ester compounds such as methyl acrylate and ethyl acrylate are used. , Methacrylic acid ester compounds such as methyl methacrylate, ethyl methacrylate and propyl methacrylate, and allyl amide derivatives can be used. These compounds may be used alone or in combination of two or more.
【００１４】また、これらの単量体に、ポリブタジエン
やスチレン−ブタジエンブロック共重合体に代表され
る、いわゆるゴム状物質を溶解して使用することもでき
る。Further, a so-called rubber-like substance typified by polybutadiene or styrene-butadiene block copolymer may be dissolved and used in these monomers.
【００１５】本発明の製造方法においては、溶剤として
例えばベンゼン、トルエン、エチルベンゼン及びキシレ
ン等のアルキルベンゼン類やアセトンやメチルエチルケ
トン等のケトン類、ヘキサンやシクロヘキサン等の脂肪
族炭化水素等が使用できる。In the production method of the present invention, as the solvent, for example, alkylbenzenes such as benzene, toluene, ethylbenzene and xylene, ketones such as acetone and methylethylketone, and aliphatic hydrocarbons such as hexane and cyclohexane can be used.
【００１６】更に、連鎖移動剤としては、脂肪族メルカ
プタン、芳香族メルカプタン、ペンタフェニルエタン、
α−メチルスチレンダイマー及びテルピノーレン等も使
用できる。Further, as the chain transfer agent, aliphatic mercaptan, aromatic mercaptan, pentaphenylethane,
α-Methylstyrene dimer and terpinolene can also be used.
【００１７】本発明の製造方法に用いる重合開始剤は、
〔化３〕に表される有機過酸化物である。The polymerization initiator used in the production method of the present invention is
It is an organic peroxide represented by [Chemical Formula 3].
【００１８】[0018]
【化３】 （式中Ｒ1 、Ｒ2 は水素または炭素数１〜２のアルキル
基、Ｒ3 は炭素数１〜５のアルキル基またはフェニル基
を表す）[Chemical 3] (Wherein R 1 and R 2 represent hydrogen or an alkyl group having 1 to 2 carbon atoms, and R 3 represents an alkyl group having 1 to 5 carbon atoms or a phenyl group)
【００１９】そして、具体的な有機過酸化物としては、
例えば２，２−ビス（４，４−ジターシャリーブチルパ
ーオキシシクロヘキシル）プロパンや２，２−ビス
（４，４−ジターシャリーオクチルパーオキシシクロヘ
キシル）プロパンなどが挙げられるが、これに限定され
るものではなく、単独でも２種以上の複数で使用しても
良い。And as a concrete organic peroxide,
Examples include 2,2-bis (4,4-ditertiarybutylperoxycyclohexyl) propane and 2,2-bis (4,4-ditertiaryoctylperoxycyclohexyl) propane, but are not limited thereto. Instead, they may be used alone or in combination of two or more.
【００２０】この重合開始剤の使用量は、芳香族ビニル
化合物及び該化合物と共重合可能な化合物との混合物 1
00重量部に対して0.00１〜0.１重量部、好ましくは0.00
2 〜0.05重量部、更に好ましくは0.005 〜 0.05 重量部
使用するのがよい。0.001 重量部未満では効果が少な
く、0.１重量部を越えると生成する重合体の分子量の制
御及び重合速度の制御が困難となり、また、Ｚ平均分子
量Mzと重量平均分子量Mwの比Mz／Mwが2.５を越えること
となる。Mz／Mwが2.５を越えるということは、重量平均
分子量Mwを目的の大きさにするには、高分子量領域のみ
ならず低分子量領域の分子量分布も広がることとなり、
得られた発泡体の機械的強度が損なわれる。The amount of this polymerization initiator used is 1% by weight of the aromatic vinyl compound and a mixture of the compound and a compound copolymerizable therewith.
0.001-0.1 parts by weight, preferably 0.00, relative to 00 parts by weight
It is preferable to use 2 to 0.05 parts by weight, and more preferably 0.005 to 0.05 parts by weight. If it is less than 0.001 part by weight, the effect is small, and if it exceeds 0.1 part by weight, it becomes difficult to control the molecular weight and the polymerization rate of the resulting polymer, and the ratio of Z average molecular weight Mz to weight average molecular weight Mw Mz / Mw. Will exceed 2.5. Mz / Mw exceeding 2.5 means that the molecular weight distribution of not only the high molecular weight region but also the low molecular weight region is widened in order to achieve the target weight average molecular weight Mw.
The mechanical strength of the obtained foam is impaired.
【００２１】また、本発明は、アゾビスイソブチロニト
リルに代表されるアゾ系化合物、ベンゾイルパーオキサ
イド、ターシャリーブチルパーオキシベンゾエート及び
ターシャリーブチルパーオキシシクロヘキシルイソプロ
ピルカーボネートに代表されるいわゆる単官能性の過酸
化物や、１，１−ビス（ターシャリーブチルパーオキ
シ）３，３，５−トリメチルシクロヘキサンのような２
官能の過酸化物を重合開始剤として、単独又は２種以上
の複数で一般式〔化３〕で表せる過酸化物と併用でき
る。The present invention also provides a so-called monofunctional compound represented by azo compounds represented by azobisisobutyronitrile, benzoyl peroxide, tertiary butyl peroxybenzoate and tertiary butyl peroxycyclohexyl isopropyl carbonate. Peroxides and 2 such as 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane
As a polymerization initiator, a functional peroxide can be used alone or in combination with two or more kinds of peroxides represented by the general formula [Chemical Formula 3].
【００２２】本発明のポリスチレン系樹脂の重量平均分
子量Mwは、20万〜60万、好ましくは25〜50万、更に、好
ましくは28〜40万が望ましい。Mwが20万未満では、成形
体の機械的強度が弱くなり、実用に耐える成形品を得る
ことはできない。また、60万を越えると、原料樹脂ペレ
ットを押出す際の負荷が大きく、生産性が著しく低くな
り、更に、押出成形したシート及び発泡シートを加熱二
次成形した際の金型への賦型性が著しく悪くなる。The weight average molecular weight Mw of the polystyrene resin of the present invention is 200,000 to 600,000, preferably 250,000 to 500,000, and more preferably 280 to 400,000. If the Mw is less than 200,000, the mechanical strength of the molded product will be weak and a molded product that can be used practically cannot be obtained. Further, if it exceeds 600,000, the load when extruding the raw material resin pellets is large and the productivity is remarkably reduced, and further, the sheet to be extruded and the foamed sheet are imprinted on the mold when the secondary molding is performed by heating. The remarkably poor quality.
【００２３】本発明の製造方法は、懸濁重合、塊状重合
と懸濁重合の組み合わせたもの、乳化重合、懸濁乳化重
合及び連続重合装置による連続重合等の公知の重合方法
を用いて、ポリスチレン系樹脂を重合することができ
る。The production method of the present invention uses a known polymerization method such as suspension polymerization, a combination of bulk polymerization and suspension polymerization, emulsion polymerization, suspension emulsion polymerization, and continuous polymerization with a continuous polymerization apparatus. A system resin can be polymerized.
【００２４】本発明の製造方法により製造したポリスチ
レン系樹脂は、射出成形性、押出成形性及び真空成形性
に優れるものであり、更に、発泡剤を加えた発泡体とし
ての性能にも優れるものである。The polystyrene resin produced by the production method of the present invention is excellent in injection moldability, extrusion moldability and vacuum moldability, and is also excellent in performance as a foam containing a foaming agent. is there.
【００２５】次に、実施例に基づき本発明を具体的に説
明するが、これらは本発明の範囲を制限するものではな
い。 実施例１ 原料ポリスチレンの製造 容積約20リットルの完全混合型撹拌槽である第一反応器
と容積約15リットルの完全混合撹拌槽である第二反応器
及び容積約７リットルの撹拌機付搭式プラグフロー型反
応器からなる第三反応器を直列に接続して重合工程を構
成した。スチレンモノマー83重量部及びエチルベンゼン
17重量部を混合した液に２，２−ビス（４，４−ジター
シャリーブチルパーオキシシクロヘキシル）プロパンを
0.013 重量部、およびターシャリーブチルパーオキシイ
ソプロピルカーボネートを0.013 重量部を混合し原料溶
液とした。この原料溶液を毎時4.3 リットルの割合で第
一反応器へ連続供給した。各反応器での反応温度は、第
一反応器で111 ℃、第二反応器で125 ℃となるように調
整し、第三反応器では流れの方向に沿って125 ℃から14
5 ℃の勾配がつくように調整した。各々の反応器の出口
でのスチレンモノマーのポリマーへの転化率は、第一反
応器で約30％、第二反応器で約65％、第三反応器で約80
％であった。第三反応器より連続的に取り出した重合液
は、常法に従い高温減圧下で未反応モノマー及びエチル
ベンゼンを重合体より分離した後、ストランド状に押出
して冷却した後、切断してペレットとした。表１に重合
条件、表２に得られたペレットのゲルパーミエイション
クロマトグラフィー測定結果及び物性評価結果を示し
た。ブタンガスを発泡剤として、上記ポリマーを押出し
発泡させ、厚さ約 2.5mm、密度約0.07ｇ／ccの発泡シー
トを得た。この発泡シートを加熱二次発泡させ、直ちに
真空成形機により容器を成形した。得られた容器の亀裂
状態、ケロイド状の発生状態及び発泡シートの脆性強度
を評価した結果を表２に示した。Next, the present invention will be specifically described based on examples, but these do not limit the scope of the present invention. Example 1 Production of Raw Polystyrene A first reactor which is a complete mixing type stirring tank with a volume of about 20 liters, a second reactor which is a complete mixing stirring tank with a volume of about 15 liters, and a stirrer with a volume of about 7 liters The polymerization process was constituted by connecting a third reactor consisting of a plug flow type reactor in series. 83 parts by weight of styrene monomer and ethylbenzene
2,2-bis (4,4-ditertiary butylperoxycyclohexyl) propane was added to a mixture of 17 parts by weight.
0.013 parts by weight and 0.013 parts by weight of tertiary butyl peroxyisopropyl carbonate were mixed to prepare a raw material solution. This raw material solution was continuously fed to the first reactor at a rate of 4.3 liters per hour. The reaction temperature in each reactor was adjusted to 111 ℃ in the first reactor and 125 ℃ in the second reactor, and in the third reactor from 125 ℃ to 14 ℃ along the flow direction.
It was adjusted so that a gradient of 5 ° C was created. The conversion of styrene monomer to polymer at the outlet of each reactor was about 30% in the first reactor, about 65% in the second reactor and about 80% in the third reactor.
%Met. The polymer solution continuously taken out from the third reactor was separated into unreacted monomer and ethylbenzene from the polymer under a high temperature and reduced pressure according to a conventional method, then extruded in a strand form and cooled, and then cut into pellets. Table 1 shows the polymerization conditions, and Table 2 shows the gel permeation chromatography measurement results of the obtained pellets and the physical property evaluation results. The above polymer was extruded and foamed using butane gas as a foaming agent to obtain a foamed sheet having a thickness of about 2.5 mm and a density of about 0.07 g / cc. This foam sheet was subjected to secondary foaming by heating, and a container was immediately molded by a vacuum molding machine. Table 2 shows the results of evaluation of the cracked state, keloid-shaped generation state and brittleness strength of the foamed sheet of the obtained container.
【００２６】実施例２ 実施例１と同じ重合工程を利用した。スチレンモノマー
80重量部及びエチルベンゼン20重量部に対して２，２−
ビス（４，４−ジターシャリーブチルパーオキシシクロ
ヘキシル）プロパンを0.01重量部混合したものを原料溶
液として、毎時4.4 リットルの割合で第一反応器に供給
した。各反応器での反応温度は、第一反応器で116 ℃、
第二反応器で135 ℃となるように調整し、第三反応器で
は流れの方向に沿って135 ℃から150 ℃の勾配がつくよ
うに調整した。各々の反応器の出口でのスチレンモノマ
ーのポリマーへの転化率は、第一反応器で約30％、第二
反応器で約62％、第三反応器で約78％であった。第三反
応器より連続的に取り出した重合液を、実施例１と同様
の処理を行いポリスチレンペレットを得た。以下実施例
１と同様の方法で発泡体の成形を行った。重合条件を表
１に、得られたペレット及び発泡成形体の評価を表２に
示した。Example 2 The same polymerization process as in Example 1 was utilized. Styrene monomer
2,2-based on 80 parts by weight and 20 parts by weight of ethylbenzene
A mixture of 0.01 parts by weight of bis (4,4-ditertiarybutylperoxycyclohexyl) propane was used as a raw material solution and fed to the first reactor at a rate of 4.4 liters per hour. The reaction temperature in each reactor is 116 ℃ in the first reactor,
The second reactor was adjusted to 135 ° C, and the third reactor was adjusted to have a gradient of 135 ° C to 150 ° C along the flow direction. The conversion of styrene monomer to polymer at the outlet of each reactor was about 30% in the first reactor, about 62% in the second reactor and about 78% in the third reactor. The polymerization liquid continuously taken out from the third reactor was treated in the same manner as in Example 1 to obtain polystyrene pellets. The foam was molded in the same manner as in Example 1 below. The polymerization conditions are shown in Table 1, and the evaluation of the obtained pellets and foamed molded products is shown in Table 2.
【００２７】実施例３ 内容積30リットルのジャケット、撹拌機付反応機にスチ
レンモノマー12kg及びスチレンモノマー100 重量部に対
して懸濁安定剤として第三燐酸カルシウム0.05重量部、
界面活性剤としてドデシルベンゼンスルホン酸ナトリウ
ム0.005 重量部を含む水120 重量部を仕込み、撹拌下に
溶液を懸濁させた。この懸濁液にスチレンモノマー100
重量部に対して重合開始剤として２，２，−ビス（４，
４−ジターシャリーブチルパーオキシシクロヘキシル）
プロパンを0.045 重量部、１，１−ビス（ターシャリー
ブチルパーオキシ）３，３，５−トリメチルシクロヘキ
サンを0.08重量部、エチル３，３−ジ（ターシャリーブ
チルパーオキシ）ブチレートを0.02重量部、更に、連鎖
移動剤としてアルファメチルスチレンダイマーを0.03重
量部添加した。この懸濁液を撹拌しつつ105 ℃にて４時
間、130 ℃にて３時間加熱して重合した。得られたビー
ズ状の樹脂をろ別した後、熱風乾燥し、次いで押出機を
用いてペレット化した。以下実施例１と同様の方法で発
泡体の成形を行った。重合条件を表１に、得られたペレ
ット及び発泡成形体の評価を表２に示した。Example 3 A jacket having an inner volume of 30 liters, a reactor equipped with a stirrer, and 12 parts of styrene monomer and 100 parts by weight of styrene monomer were used as a suspension stabilizer, and 0.05 part by weight of calcium triphosphate was added as a suspension stabilizer.
120 parts by weight of water containing 0.005 parts by weight of sodium dodecylbenzenesulfonate was charged as a surfactant, and the solution was suspended with stirring. Add styrene monomer 100 to this suspension.
2,2, -bis (4,4 as a polymerization initiator relative to parts by weight
4-ditertiary butylperoxycyclohexyl)
0.045 parts by weight of propane, 0.08 parts by weight of 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, 0.02 parts by weight of ethyl 3,3-di (tert-butylperoxy) butyrate, Further, 0.03 part by weight of alpha methyl styrene dimer was added as a chain transfer agent. The suspension was heated with stirring at 105 ° C. for 4 hours and at 130 ° C. for 3 hours to polymerize. The obtained bead-like resin was filtered off, dried with hot air, and then pelletized using an extruder. The foam was molded in the same manner as in Example 1 below. The polymerization conditions are shown in Table 1, and the evaluation of the obtained pellets and foamed molded products is shown in Table 2.
【００２８】実施例４ 実施例１と同じ重合工程を利用した。スチレンモノマー
88.6重量部、エチルベンゼン9.０重量部及びパラフィン
2.４重量部に対して２，２−ビス（４，４−ジターシャ
リーブチルパーオキシシクロヘキシル）プロパンを0.01
重量部混合したものを原料溶液として、毎時3.０リット
ルの割合で第一反応器に供給した。各反応器での反応時
間は、第一反応器で119 ℃、第二反応器で117 ℃となる
ように調整し、第三反応器では流れの方向に沿って117
℃から151 ℃の勾配がつくように調整した。各々の反応
器の出口でのスチレンモノマーのポリマーへの転化率
は、第一反応器で約47％、第二反応器で約67％、第三反
応器で約76％であった。第三反応器より連続的に取り出
した重合液を、実施例１と同様の処理を行いポリスチレ
ンペレットを得た。以下実施例１と同様の方法で発泡体
の成形を行った。また、射出成型機を用いて長さ120mm
×幅40mm×高さ１，２及び３mmの３段プレートを成型し
た。重合条件を表１に、得られたペレット、発泡成形体
及びプレートの評価を表２に示した。Example 4 The same polymerization process as in Example 1 was utilized. Styrene monomer
88.6 parts by weight, ethylbenzene 9.0 parts by weight and paraffin
0.01% of 2,2-bis (4,4-ditertiarybutylperoxycyclohexyl) propane to 2.4 parts by weight
The mixture of parts by weight was fed as a raw material solution to the first reactor at a rate of 3.0 liters per hour. The reaction time in each reactor was adjusted so that it was 119 ° C in the first reactor and 117 ° C in the second reactor, and the reaction time in the third reactor was 117 ° C along the flow direction.
The gradient was adjusted from ℃ to 151 ℃. The conversion of styrene monomer to polymer at the outlet of each reactor was about 47% in the first reactor, about 67% in the second reactor, and about 76% in the third reactor. The polymerization liquid continuously taken out from the third reactor was treated in the same manner as in Example 1 to obtain polystyrene pellets. The foam was molded in the same manner as in Example 1 below. Also, using an injection molding machine, length 120 mm
A three-stage plate having a width of 40 mm, a height of 1, 2 and 3 mm was molded. Polymerization conditions are shown in Table 1, and evaluations of the obtained pellets, foamed molded products and plates are shown in Table 2.
【００２９】比較例１ 実施例１と同じ重合工程を利用した。スチレンモノマー
85重量部及びエチルベンゼン15重量部に対してターシャ
リーブチルパーオキシイソプロピルカーボネートを0.03
0 重量部混合したものを原料溶液として、毎時3.９リッ
トルの割合で第一反応器に供給した。各反応器での反応
温度は、第一反応器で112 ℃、第二反応器で124 ℃とな
るように調整し、第三反応器では流れの方向に沿って12
4 ℃から147 ℃の勾配がつくように調整した。各々の反
応器の出口でのスチレンモノマーのポリマーへの転化率
は、第一反応器で約30％、第二反応器で約64％、第三反
応器で約77％であった。第三反応器より連続的に取り出
した重合液を、実施例１と同様の処理を行いポリスチレ
ンペレットを得た。以下実施例１と同様の方法で発泡体
の成形を行った。重合条件を表３に、得られたペレット
及び発泡成形体の評価を表４に示した。Comparative Example 1 The same polymerization process as in Example 1 was used. Styrene monomer
To 85 parts by weight and 15 parts by weight of ethylbenzene, 0.03 of tertiary butyl peroxyisopropyl carbonate was added.
A mixture of 0 parts by weight was fed as a raw material solution to the first reactor at a rate of 3.9 liters per hour. The reaction temperature in each reactor was adjusted to be 112 ° C in the first reactor and 124 ° C in the second reactor, and 12 ° C in the third reactor along the flow direction.
The gradient was adjusted from 4 ° C to 147 ° C. The conversion of styrene monomer to polymer at the outlet of each reactor was about 30% in the first reactor, about 64% in the second reactor and about 77% in the third reactor. The polymerization liquid continuously taken out from the third reactor was treated in the same manner as in Example 1 to obtain polystyrene pellets. The foam was molded in the same manner as in Example 1 below. Polymerization conditions are shown in Table 3, and evaluations of the obtained pellets and foamed molded products are shown in Table 4.
【００３０】比較例２ 実施例１と同じ重合工程を利用した。スチレンモノマー
88重量部及びエチルベンゼン12重量部を混合し、過酸化
物等の重合開始剤を添加せずに原料溶液として、毎時4.
０リットルの割合で第一反応器に供給した。各反応器で
の反応温度は、第一反応器で120 ℃、第二反応器で135
℃となるように調整し、第三反応器では流れの方向に沿
って135 ℃から155 ℃の勾配がつくように調整した。各
々の反応器の出口でのスチレンモノマーのポリマーへの
転化率は、第一反応器で約30％、第二反応器で約64％、
第三反応器で約82％であった。第三反応器より連続的に
取り出した重合液を、実施例１と同様の処理を行いポリ
スチレンペレットを得た。以下実施例１と同様の方法で
発泡体の成形を行った。重合条件を表３に、得られたペ
レット及び発泡成形体の評価を表４に示した。Comparative Example 2 The same polymerization process as in Example 1 was used. Styrene monomer
88 parts by weight and 12 parts by weight of ethylbenzene are mixed, and a raw material solution is added without adding a polymerization initiator such as a peroxide, and every hour 4.
The first reactor was fed at a rate of 0 liter. The reaction temperature in each reactor was 120 ° C in the first reactor and 135 ° C in the second reactor.
The temperature was adjusted so that the temperature became ℃, and the third reactor was adjusted so that there was a gradient of 135 ℃ to 155 ℃ along the flow direction. The conversion of styrene monomer to polymer at the outlet of each reactor was about 30% in the first reactor, about 64% in the second reactor,
About 82% in the third reactor. The polymerization liquid continuously taken out from the third reactor was treated in the same manner as in Example 1 to obtain polystyrene pellets. The foam was molded in the same manner as in Example 1 below. Polymerization conditions are shown in Table 3, and evaluations of the obtained pellets and foamed molded products are shown in Table 4.
【００３１】比較例３ 実施例１と同じ重合工程を利用した。スチレンモノマー
93.1重量部、エチルベンゼン4.5 重量部及び流動パラフ
ィン2.４重量部を原料溶液として、毎時2.９リットルの
割合で第一反応器に供給した。各反応器での反応温度
は、第一反応器で122 ℃、第二反応器で118 ℃となるよ
うに調整し、第三反応器では流れの方向に沿って118 ℃
から153 ℃の勾配がつくように調整した。各々の反応器
の出口でのスチレンモノマーのポリマーへの転化率は、
第一反応器で約48％、第二反応器で約65％、第三反応器
で約78％であった。第三反応器より連続的に取り出した
重合液を、実施例１と同様の処理を行いポリスチレンペ
レットを得た。以下実施例１と同様の方法で発泡体の成
形を行った。また、射出成型機を用いて長さ120mm ×幅
40mm×高さ１，２及び３mmの３段プレートを成型した。
重合条件を表３に、得られたペレット、発泡成形体及び
プレートの評価を表４に示した。Comparative Example 3 The same polymerization process as in Example 1 was used. Styrene monomer
93.1 parts by weight, 4.5 parts by weight of ethylbenzene and 2.4 parts by weight of liquid paraffin were used as raw material solutions and fed to the first reactor at a rate of 2.9 liters per hour. The reaction temperature in each reactor was adjusted to 122 ° C in the first reactor and 118 ° C in the second reactor, and 118 ° C along the flow direction in the third reactor.
The temperature was adjusted so that a gradient of 1 to 153 ° C could be obtained. The conversion of styrene monomer to polymer at the outlet of each reactor is
It was about 48% in the first reactor, about 65% in the second reactor, and about 78% in the third reactor. The polymerization liquid continuously taken out from the third reactor was treated in the same manner as in Example 1 to obtain polystyrene pellets. The foam was molded in the same manner as in Example 1 below. Also, using an injection molding machine, length 120 mm × width
A three-stage plate having a size of 40 mm × height 1, 2, and 3 mm was molded.
Polymerization conditions are shown in Table 3, and evaluations of the obtained pellets, foamed molded products and plates are shown in Table 4.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【表２】 [Table 2]
【００３４】[0034]
【表３】 [Table 3]
【００３５】[0035]
【表４】 [Table 4]
【００３６】重合開始剤は、以下のとおりである。 開始剤Ｉ ：２，２−ビス（４，４−ジターシャリ
ーブチルパーオキシシクロヘキシル）プロパン 開始剤II ：ターシャリーブチルパーオキシイソプ
ロピルカーボネート 開始剤III ：１，１ービス（ターシャリーブチルパ
ーオキシ）３，３，５−トリメチルシクロヘキサン 開始剤IV ：エチル−３，３−ジ（ターシャリーブ
チルパーオキシ）ブチレート α−ＭＳＤ：アルファメチルスチレンダイマーThe polymerization initiator is as follows. Initiator I: 2,2-bis (4,4-ditert-butylperoxycyclohexyl) propane Initiator II: Tertiarybutylperoxyisopropyl carbonate Initiator III: 1,1-bis (tert-butylperoxy) 3,3 3,5-Trimethylcyclohexane Initiator IV: Ethyl-3,3-di (tert-butylperoxy) butyrate α-MSD: Alphamethylstyrene dimer
【００３７】分子量及び分子量分布の測定 ゲルパーミエイションクロマトグラフィーによる分子量
及び分子量分布は、東レ（株）製、ＨＬＣ−８０２Ａ型
ＧＰＣを用い、次の条件で測定した。 カラム：東レ（株）カラム 移動相：テトラヒドロフラン 試料濃度：0.３重量％ 測定温度: ３８℃ 検出器：示差屈折計Measurement of molecular weight and molecular weight distribution The molecular weight and molecular weight distribution by gel permeation chromatography were measured under the following conditions using HLC-802A type GPC manufactured by Toray Industries, Inc. Column: Toray column Mobile phase: Tetrahydrofuran Sample concentration: 0.3 wt% Measurement temperature: 38 ° C Detector: Differential refractometer
【００３８】物性測定 １） プレート脆性強度：長さ120mm ×幅40mm×高さ
１，２及び３mmの３段プレート３mm中央部分に重さ５０
ｇの錘を高さを変えて落下させ、プレートが割れた５０
％破壊の高さを示した。 ２） 発泡シート脆性強度：重さ３００ｇの球を高さを
変えて落下させ、発泡シートが割れた５０％破壊の高さ
を示した。 ３） 成形物の亀裂及びケロイド状：成形された容器１
０個について肉眼で亀裂の状態及びケロイド状の発生具
合を５段階表示法で判定した。 亀裂、ケロイド状が全くない・・・５ 亀裂、ケロイド状がほとんどない・４ 亀裂、ケロイド状が少しある・・・３ 亀裂、ケロイド状が多い・・・・・２ 亀裂、ケロイド状が非常に多い・・１Measurement of physical properties 1) Plate brittleness strength: length 120 mm × width 40 mm × height 1, 2 and 3 mm 3-stage plate 3 mm weight 50 at the central part
The weight of g dropped at different heights and the plate broke 50
% Destruction height was indicated. 2) Foamed sheet brittleness strength: A sphere having a weight of 300 g was dropped while changing the height, and the height at which the foamed sheet was broken at 50% was shown. 3) Cracks and keloids of molded product: molded container 1
With respect to 0, the state of cracks and the degree of occurrence of keloids were visually determined by the 5-step display method. There are no cracks or keloids ... 5 Almost no cracks or keloids.-4 Some cracks or keloids ... 3 Many cracks or keloids ... 2 Very many cracks or keloids. Many ... 1
【００３９】[0039]
【発明の効果】以上の通り、本発明の方法により製造し
たポリスチレン系樹脂は、機械的強度に優れ、しかも、
射出成形性、押出成形性及び真空成形性が良好であり、
特に、発泡シートの原料に用いると、ポリスチレン系樹
脂の分子量分布に特徴があるため、成形性が非常に良好
であり、脆性強度及び外観に優れた成形体を得ることが
できる。As described above, the polystyrene resin produced by the method of the present invention has excellent mechanical strength and
Good injection moldability, extrusion moldability and vacuum moldability,
In particular, when it is used as a raw material for a foamed sheet, it has a very good moldability because of the characteristic of the molecular weight distribution of the polystyrene-based resin, and a molded product excellent in brittle strength and appearance can be obtained.
Claims (2)
化物の重合開始剤を用いて芳香族ビニル系化合物又は芳
香族ビニル系化合物及び芳香族ビニル系化合物と共重合
可能な化合物との混合物を重合して、ゲルパーミエイシ
ョンクロマトグラフィーで測定した値において、Ｚ平均
分子量Mzと重量平均分子量Mwの比Mz／Mwが1.７〜2.５、
重量平均分子量Mwと数平均分子量Mnの比Mw／Mnが2.０〜
3.０、しかも、重量平均分子量Mwが20万〜60万であるこ
とを特徴とするポリスチレン系樹脂の製造方法。 【化１】 （式中Ｒ1 、Ｒ2 は水素または炭素数１〜２のアルキル
基、Ｒ3 は炭素数１〜５のアルキル基またはフェニル基
を表す）1. An aromatic vinyl compound or an aromatic vinyl compound and a compound copolymerizable with an aromatic vinyl compound using a polymerization initiator of an organic peroxide represented by the following general formula [Chemical Formula 1] In the value measured by gel permeation chromatography by polymerizing a mixture with and, the ratio Mz / Mw of Z average molecular weight Mz and weight average molecular weight Mw is 1.7 to 2.5,
The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is 2.0 to
3. A method for producing a polystyrene resin, which has a weight average molecular weight Mw of 200,000 to 600,000. [Chemical 1] (Wherein R 1 and R 2 represent hydrogen or an alkyl group having 1 to 2 carbon atoms, and R 3 represents an alkyl group having 1 to 5 carbon atoms or a phenyl group)
の使用量が、芳香族ビニル系単量体又は芳香族ビニル系
単量体及び芳香族ビニル系単量体と共重合可能な化合物
との混合物 100重量部に対して0.001 〜0.１重量部の範
囲であることを特徴とする請求項１記載のポリスチレン
系樹脂の製造方法。2. The use amount of the organic peroxide represented by the general formula [Chemical Formula 1] is such that an aromatic vinyl monomer or an aromatic vinyl monomer and an aromatic vinyl monomer are copolymerized. The method for producing a polystyrene resin according to claim 1, wherein the content is in the range of 0.001 to 0.1 part by weight with respect to 100 parts by weight of the mixture with the possible compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4235978A JP2931162B2 (en) | 1992-09-03 | 1992-09-03 | Method for producing polystyrene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4235978A JP2931162B2 (en) | 1992-09-03 | 1992-09-03 | Method for producing polystyrene resin |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12984394A Division JPH07278218A (en) | 1994-05-20 | 1994-05-20 | Production of polystyrene resin |
| JP32351798A Division JP3271753B2 (en) | 1998-11-13 | 1998-11-13 | Polystyrene resin and foamed molded article thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0680712A true JPH0680712A (en) | 1994-03-22 |
| JP2931162B2 JP2931162B2 (en) | 1999-08-09 |
Family
ID=16994015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4235978A Expired - Lifetime JP2931162B2 (en) | 1992-09-03 | 1992-09-03 | Method for producing polystyrene resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2931162B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001085802A1 (en) * | 2000-05-08 | 2001-11-15 | Asahi Kasei Kabushiki Kaisha | Process for producing styrene resin reduced in content of low-molecular ingredient |
| JP2001354718A (en) * | 2000-06-14 | 2001-12-25 | Idemitsu Petrochem Co Ltd | Styrene resin and molded product thereof |
| KR100424209B1 (en) * | 1995-09-06 | 2004-06-16 | 스미또모 가가꾸 고교 가부시끼가이샤 | METHOD FOR PREPARING STYRENE POLYMER, STYRENE POLYMER, STYRENE RESIN COMPOSITION, AND PRODUCTION THEREOF |
| JP2005281475A (en) * | 2004-03-30 | 2005-10-13 | Toyo Styrene Co Ltd | Styrene polymer and its production method |
| US20140045961A1 (en) * | 2012-08-09 | 2014-02-13 | Americas Styrenics Llc | Styrenic resin having improved extensional viscosity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0232107A (en) * | 1988-07-22 | 1990-02-01 | Kayaku Akzo Kk | Production of alpha-methylstyrene-acrylonitrile copolymer |
| JPH0232108A (en) * | 1988-07-22 | 1990-02-01 | Kayaku Akzo Kk | Production of copolymer |
-
1992
- 1992-09-03 JP JP4235978A patent/JP2931162B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0232107A (en) * | 1988-07-22 | 1990-02-01 | Kayaku Akzo Kk | Production of alpha-methylstyrene-acrylonitrile copolymer |
| JPH0232108A (en) * | 1988-07-22 | 1990-02-01 | Kayaku Akzo Kk | Production of copolymer |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100424209B1 (en) * | 1995-09-06 | 2004-06-16 | 스미또모 가가꾸 고교 가부시끼가이샤 | METHOD FOR PREPARING STYRENE POLYMER, STYRENE POLYMER, STYRENE RESIN COMPOSITION, AND PRODUCTION THEREOF |
| WO2001085802A1 (en) * | 2000-05-08 | 2001-11-15 | Asahi Kasei Kabushiki Kaisha | Process for producing styrene resin reduced in content of low-molecular ingredient |
| US6759498B2 (en) | 2000-05-08 | 2004-07-06 | Asahi Kadei Kabushiki Kaisha | Process for producing styrene resin reduced in content of low-molecular ingredient |
| JP2001354718A (en) * | 2000-06-14 | 2001-12-25 | Idemitsu Petrochem Co Ltd | Styrene resin and molded product thereof |
| JP2005281475A (en) * | 2004-03-30 | 2005-10-13 | Toyo Styrene Co Ltd | Styrene polymer and its production method |
| US20140045961A1 (en) * | 2012-08-09 | 2014-02-13 | Americas Styrenics Llc | Styrenic resin having improved extensional viscosity |
| US9115228B2 (en) * | 2012-08-09 | 2015-08-25 | Americas Styrenics, LLC | Styrenic resin having improved extensional viscosity |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2931162B2 (en) | 1999-08-09 |
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