JPH07116257B2 - Method for producing styrene polymer - Google Patents

Method for producing styrene polymer

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Publication number
JPH07116257B2
JPH07116257B2 JP62121745A JP12174587A JPH07116257B2 JP H07116257 B2 JPH07116257 B2 JP H07116257B2 JP 62121745 A JP62121745 A JP 62121745A JP 12174587 A JP12174587 A JP 12174587A JP H07116257 B2 JPH07116257 B2 JP H07116257B2
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JP
Japan
Prior art keywords
circulation system
styrene
reaction
circulation
producing
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 - Lifetime
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JP62121745A
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Japanese (ja)
Other versions
JPS63286406A (en
Inventor
貞 松井
雅治 畑
弘師 稲留
和成 稲熊
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Kao Corp
Original Assignee
Kao Corp
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Priority to JP62121745A priority Critical patent/JPH07116257B2/en
Publication of JPS63286406A publication Critical patent/JPS63286406A/en
Publication of JPH07116257B2 publication Critical patent/JPH07116257B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、スチレン系重合体の製造方法に関するもの
で、本発明によれば、特に電子写真用トナーバインダー
樹脂として有用な、低分子量域と高分子量域に分子量分
布のピークがあり、分子量分布がワイド（分布範囲が広
い）で且つ任意の平均分子量を有する、ポリスチレン又
はスチレンとアクリル酸エステル（スチレン／アクリ
ル）共重合体等のスチレン系重合体を安定に且つ連続的
に製造することができる。The present invention relates to a method for producing a styrene-based polymer, and according to the present invention, a low molecular weight region particularly useful as a toner binder resin for electrophotography is used. A styrene-based polymer such as polystyrene or a styrene-acrylic acid ester (styrene / acrylic) copolymer having a molecular weight distribution peak in a high molecular weight region, a wide molecular weight distribution (wide distribution range) and an arbitrary average molecular weight. The coalescence can be manufactured stably and continuously.

〔従来の技術〕[Conventional technology]

一般に、スチレン系重合体は、平均分子量が高いほど、
また分子量分布が狭いほど、引貼り強さや耐衝撃性等の
機械的性質及び加工性がすぐれている。そして、この様
なスチレン系重合体を連続的に製造する方法としては、
特開昭59−1515号公報に開示された方法がある。Generally, the higher the average molecular weight of the styrene-based polymer,
Further, the narrower the molecular weight distribution, the better the mechanical properties such as pulling strength and impact resistance, and the workability. And, as a method for continuously producing such a styrene-based polymer,
There is a method disclosed in JP-A-59-1515.

一方、電子写真用トナーバインダー樹脂として用いられ
るスチレン系重合体、特にスチレン／アクリル系共重合
体は、ヒートロール定着向けの場合、その要求される物
性から分子量分布がワイドである必要がある。また、ス
チレン系重合体は、従来、主にバッチ式で製造されてい
る。On the other hand, a styrene polymer used as a toner binder resin for electrophotography, particularly a styrene / acrylic copolymer, is required to have a wide molecular weight distribution in view of required physical properties in the case of heat roll fixing. Further, styrene-based polymers have hitherto been mainly produced in a batch system.

〔発明が解決しようとする問題点〕[Problems to be solved by the invention]

スチレン系モノマーを、必要に応じ該スチレン系モノマ
ーと重合可能なモノマーと共に重合又は共重合させて、
スチレン系重合体を製造する場合、重合開始剤として有
機過酸化物及びアゾ系有機化合物を使用することができ
る。この有機過酸化物及びアゾ系有機化合物の使用は、
重合温度を比較的低い温度にして高分子量のスチレン系
重合体を製造する際にその生産性を向上することができ
るので好ましい。また、上記有機過酸化物及びアゾ系有
機化合物は、重合温度を比較的高い温度にして低分子量
のスチレン系重合体を製造する際に、その低分子化を容
易にさせる効果がある。A styrene-based monomer is polymerized or copolymerized with a monomer that is polymerizable with the styrene-based monomer, if necessary,
When producing a styrene polymer, an organic peroxide and an azo organic compound can be used as a polymerization initiator. The use of this organic peroxide and azo organic compound,
When the polymerization temperature is set to a relatively low temperature, the productivity can be improved when producing a high molecular weight styrene polymer, which is preferable. Further, the above-mentioned organic peroxide and azo organic compound have an effect of facilitating the reduction of the molecular weight when a low molecular weight styrene polymer is produced at a relatively high polymerization temperature.

しかし乍ら、前記の特開昭59−1515号公報に記載の方法
において、ポリスチレン等を製造する場合、有機過酸化
物やアゾ系有機化合物を使用した系では、重合開始剤の
分解によるガス（窒素、炭酸ガス又はメタン等の低沸点
ガス）の発生及びモノマー蒸気の発生（特に重合温度が
モノマーの沸点以上の場合に発生）のため、循環する反
応混合物中に多量の気泡が混入し、循環系内に滞留して
装置効率を低下させると共に、系内圧力の異常上昇ひい
ては運転停止をもたらす問題（第１の問題点）がある。However, in the method described in the above-mentioned JP-A-59-1515, when polystyrene or the like is produced, in a system using an organic peroxide or an azo organic compound, a gas ( Due to the generation of nitrogen, carbon dioxide or low boiling point gas such as methane) and the generation of monomer vapor (especially when the polymerization temperature is higher than the boiling point of the monomer), a large amount of air bubbles are mixed in the circulating reaction mixture, and the gas is circulated. There is a problem (first problem) of staying in the system to reduce the efficiency of the apparatus and causing abnormal increase of the system pressure and eventually stop of operation.

また、電子写真用トナーバインダー樹脂として用いられ
るスチレン系重合体、特にスチレン／アクリル系共重合
体は、定着性、粉砕性の観点から低分子量成分、耐オフ
セット性の観点から高分子量成分があることが好まし
く、言いかえれば中間分子量域のものは重要な意味を待
たないので低分子量域と高分子量域に分子量分布のピー
クがあるものが好ましい。Further, the styrene-based polymer used as a toner binder resin for electrophotography, particularly the styrene / acrylic copolymer, has a low molecular weight component from the viewpoint of fixability and pulverizability, and a high molecular weight component from the viewpoint of offset resistance. In other words, those having an intermediate molecular weight range do not have an important meaning, and therefore those having a peak of the molecular weight distribution in the low molecular weight range and the high molecular weight range are preferable.

しかし、前記の特開昭59−1515号公報に記載の方法によ
りスチレン系重合体を製造すると、高分子量域で分子量
分布がシャープなものが得られる問題（第２の問題点）
がある。However, when a styrene-based polymer is produced by the method described in JP-A-59-1515, a polymer having a sharp molecular weight distribution in a high molecular weight range can be obtained (second problem).
There is.

〔問題点を解決するための手段〕[Means for solving problems]

本発明者らは、上記の問題点を解決することを目的とし
て種々検討した結果、スチレン系モノマーの１種又は２
種以上を必須成分とするモノマーを、循環系を形成した
反応装置を用いて重合又は共重合させる際に、循環系の
上部に混合物抜き出し部を設け、そのすぐ下流に背圧弁
と気液分離器を配し、該背圧弁で循環系内の圧力をモノ
マー等の蒸気圧力以上になる様に設定してモノマー蒸気
の発生を押え、さらに循環系内で発生し混合物抜き出し
部から反応混合物と共に出てくる気泡（多くは重合開始
剤の分解により生成する窒素、炭酸ガス、又はメタン等
の低沸点ガス）を上記気液分離器で分離して取り除き乍
ら反応混合物を循環系に再循環させることにより、前記
の第１の問題点を解決できることを知見した。ここで、
混合物抜き出し部を循環系の上部に設けてあるのは、循
環系から気泡をスムーズに排出させるためである。ま
た、気液分離器を循環系の途中でなく混合物抜き出し部
のすぐ下流に設けてあるのは、反応混合物が高粘度であ
り、循環系の途中に配するのが実質上不可能であったか
らである。また、循環系内を減圧にして脱気する方法で
は、モノマー等の蒸発が促進されるおそれがあり、好ま
しくなかった。As a result of various investigations aimed at solving the above problems, the present inventors have found that one or two styrene-based monomers are used.
When polymerizing or copolymerizing monomers containing at least one species as essential components using a reactor that forms a circulation system, a mixture withdrawal section is provided at the upper part of the circulation system, and a back pressure valve and a gas-liquid separator immediately downstream thereof. The pressure in the circulation system is set to be equal to or higher than the vapor pressure of the monomer by the back pressure valve to suppress the generation of the monomer vapor, and further generated in the circulation system and discharged from the mixture withdrawing part together with the reaction mixture. The air bubbles (mostly nitrogen, carbon dioxide gas, or low boiling point gas such as methane generated by decomposition of the polymerization initiator) are separated and removed by the gas-liquid separator, and the reaction mixture is recirculated to the circulation system. Have found that the first problem described above can be solved. here,
The reason why the mixture withdrawing portion is provided above the circulation system is to allow the bubbles to be smoothly discharged from the circulation system. Further, the gas-liquid separator is provided immediately downstream of the mixture withdrawal section, not in the circulation system, because the reaction mixture has a high viscosity and it was practically impossible to dispose it in the circulation system. Is. Further, the method of degassing by reducing the pressure in the circulation system is not preferable because the evaporation of monomers and the like may be promoted.

そして、本発明者らは、上記知見に基づき、前記の第１
の問題点を解決すると共に前記の第２の問題点も併せて
解決することを目的として更に検討を重ねた結果、２つ
の循環系を具備した反応器を用い、先ず第１の循環系に
原料モノマー及び反応に必要な成分を供給し、該第１の
循環系における反応条件を、比較的低温で、高分子量で
分子量分布のシャープなスチレン系重合体を含む反応混
合物が得られるように操作し、次いで、この反応混合物
を第１の循環系から抜き出し第２の循環系に供給すると
共に新たに原料モノマー及び反応に必要な成分を第２の
循環系に供給し、これらを比較的高温の第２の循環系で
再循環させることにより、前記の第２の問題点も解決で
きることを知見した。Then, the present inventors based on the above findings,
As a result of further studies aimed at solving the above-mentioned problem as well as the above-mentioned second problem, as a result, a reactor equipped with two circulation systems was used, and first the raw material was supplied to the first circulation system. The monomers and the components necessary for the reaction are supplied, and the reaction conditions in the first circulation system are controlled so that a reaction mixture containing a styrene polymer having a high molecular weight and a sharp molecular weight distribution is obtained at a relatively low temperature. Then, this reaction mixture is withdrawn from the first circulation system and fed to the second circulation system, and at the same time, raw material monomers and components necessary for the reaction are newly fed to the second circulation system. It was found that the second problem can be solved by recirculating in the second circulation system.

本発明は、上記の２つの知見に基づきなされたもので、
下記のスチレン系重合体の製造方法を提供するものであ
る。The present invention is based on the above two findings,
The following method for producing a styrene-based polymer is provided.

（ａ）スチレン系モノマーの１種又は２種以上を必須成
分とするモノマーを重合又は共重合させる際に、混合部
及び循環用ポンプを具備した第１の循環系を形成し、原
料モノマー及び反応に必要な成分を上記循環系に供給し
循環させ、反応混合物の一部を上記循環系の径路に設け
た混合物抜き出し部から抜き出し、反応混合物の残部を
再循環させる一方、上記第１の循環系から抜き出した上
記反応混合物を背圧弁、気液分離器に導き、該気液分離
器で反応混合物中のガスを抜き、さらに移送用ポンプで
混合部及び循環用ポンプを具備した第２の循環系に供給
して循環させると共に、該第２の循環系に更に必要に応
じ原料モノマー及び反応に必要な成分を供給して循環さ
せ、反応生成物の一部を上記第２の循環系の経路に設け
た生成物抜き出し部から背圧弁、気液分離器を通して抜
き出し、反応生成物の残部を第２の循環系中に再循環さ
せるようにした反応器を用いてスチレン系重合体を製造
する方法であって、 （ｂ）上記反応器として、上記第１及び第２の循環系の
容積比（前者／後者）が1/10〜10/1であるような反応器
を用い、 （ｃ）上記第１の循環系における反応条件を、反応温度
50〜150℃に保持して、重合率が15〜80重量％で重量平
均分子量200,000以上の重合体を上記第１の循環系で
得、 （ｄ）上記第２の循環系における反応条件を、反応温度
100〜220℃に保持して、重合率が80重量％以上で重量平
均分子量100,000以上の分子量と3.0以上の分散指数を有
するスチレン系重合体を上記第２の循環系で得る。(A) When polymerizing or copolymerizing a monomer containing one or more styrene-based monomers as an essential component, a first circulation system having a mixing section and a circulation pump is formed, and raw material monomers and reactions are performed. The components necessary for the above are supplied to the circulation system and circulated, a part of the reaction mixture is withdrawn from the mixture withdrawal section provided in the path of the circulation system, and the rest of the reaction mixture is recirculated, while the first circulation system is used. The reaction mixture extracted from the above is introduced into a back pressure valve and a gas-liquid separator, the gas in the reaction mixture is extracted by the gas-liquid separator, and a second circulation system equipped with a mixing section and a circulation pump by a transfer pump. To the second circulation system, and further, if necessary, the raw material monomer and components necessary for the reaction are further supplied to the second circulation system for circulation, and a part of the reaction product is introduced into the second circulation system path. Extraction of the provided product A method for producing a styrene-based polymer by using a reactor in which the reaction product is withdrawn through a back pressure valve and a gas-liquid separator, and the rest of the reaction product is recirculated into the second circulation system. As the reactor, a reactor in which the volume ratio of the first and second circulation systems (the former / the latter) is 1/10 to 10/1 is used, and (c) the reaction in the first circulation system. Conditions, reaction temperature
While maintaining at 50 to 150 ° C., a polymer having a polymerization rate of 15 to 80% by weight and a weight average molecular weight of 200,000 or more is obtained in the first circulation system, and (d) the reaction conditions in the second circulation system are Reaction temperature
Maintaining at 100 to 220 ° C., a styrene polymer having a polymerization rate of 80% by weight or more, a weight average molecular weight of 100,000 or more and a dispersion index of 3.0 or more is obtained in the second circulation system.

ことを特徴とするスチレン系重合体の製造方法。A method for producing a styrene-based polymer, comprising:

以下、本発明のスチレン系重合体の製造方法について詳
述する。Hereinafter, the method for producing the styrene polymer of the present invention will be described in detail.

本発明のスチレン系重合体の製造方法において、上記反
応器における第１の循環系は、比較的高分子量で分子量
分布のシャープな反応混合物の生成に寄与しており、且
つ第２の循環系は、比較的低分子量の重合体の生成に寄
与しており、その結果、全体として、低分子量域と高分
子量域にそれぞれ分子量分布のピークがある分布のワイ
ドな反応生成物が得られるのである。In the method for producing a styrene-based polymer of the present invention, the first circulation system in the reactor contributes to the formation of a reaction mixture having a relatively high molecular weight and a sharp molecular weight distribution, and the second circulation system is It contributes to the production of a polymer having a relatively low molecular weight, and as a result, a wide reaction product having a distribution of molecular weight peaks in the low molecular weight region and a high molecular weight region is obtained as a whole.

しかし、スチレン系重合体を、電子写真用トナーバイン
ダー樹脂として用いる場合、高分子量成分と低分子量成
分の割合が重要であり、どちらか一方の成分が多すぎた
り少なすぎたり、また高分子量成分と低分子量成分のそ
れぞれの分子量（分子量分布のピークの位置）が適切で
ないと電子写真用トナーバインダー樹脂としての機能を
果たさない。However, when a styrene-based polymer is used as a toner binder resin for electrophotography, the ratio of the high molecular weight component and the low molecular weight component is important, and either one component is too much or too little, and the high molecular weight component is too small. If the molecular weight of each low molecular weight component (the position of the peak of the molecular weight distribution) is not appropriate, it will not function as a toner binder resin for electrophotography.

そこで、本発明の方法は、高分子量成分と低分子量成分
の割合が電子写真用トナーバインダー樹脂として適当な
スチレン系重合体（好ましくは、分子量100,000以上の
高分子量成分の割合が10〜40重量％、分子量10,000以下
の低分子量成分の割合が10〜40重量％で、高分子量成分
の分子量分布のピークが分子量約100,000、低分子量成
分の分子量分布のピークが分子量約10,000のもの）を得
るために、第１及び第２の循環系における反応条件及び
第１及び第２の循環系の容積比等を上述のように規定し
てある。Therefore, the method of the present invention, the ratio of the high molecular weight component and the low molecular weight component is a styrene-based polymer suitable as a toner binder resin for electrophotography (preferably, the ratio of the high molecular weight component having a molecular weight of 100,000 or more is 10 to 40% by weight). , The proportion of low molecular weight components with a molecular weight of 10,000 or less is 10 to 40% by weight, the peak of the molecular weight distribution of the high molecular weight component is about 100,000, and the peak of the molecular weight distribution of the low molecular weight component is about 10,000. The reaction conditions in the first and second circulation systems and the volume ratio of the first and second circulation systems are defined as described above.

すなわち、本発明では、第１の循環系における反応条件
を、反応温度50〜150℃に保持して、重合率が15〜80重
量％で重量平均分子量200,000以上の重合体を第１の循
環系で得る。第１の循環系における重合率が15重量％未
満であると、高分子量成分が少なすぎ、80重量％超では
重合時間が長くなりすぎ、又粘度が高くて（反応温度が
比較的低いので）運転に支障を来す。また、重量平均分
子量が200,000未満では高分子量成分としては分子量が
低すぎる。That is, in the present invention, the reaction conditions in the first circulation system are maintained at a reaction temperature of 50 to 150 ° C., and a polymer having a polymerization rate of 15 to 80% by weight and a weight average molecular weight of 200,000 or more is added to the first circulation system. Get at. If the polymerization rate in the first circulation system is less than 15% by weight, the high molecular weight component is too small, and if it exceeds 80% by weight, the polymerization time becomes too long and the viscosity is high (because the reaction temperature is relatively low). It interferes with driving. When the weight average molecular weight is less than 200,000, the molecular weight is too low as a high molecular weight component.

また、第２の循環系では、上記第１の循環系から抜き出
した反応混合物を導入して循環させると共に、更に必要
に応じ原料モノマー及び反応に必要な成分を供給して循
環させ、反応温度100〜220℃に保持して、全体として反
応条件を、重合率が80重量％以上で重量平均分子量100,
000以上の分子量と3.0以上の分散指数を有するスチレン
系重合体を第２の循環系で得る。その際、反応温度を比
較的高温にすることが必要である。第２の循環系におけ
る重合率が80重量％未満では装置効率が悪すぎる。ま
た、重量平均分子量が100,000未満又は分散指数が3.0未
満では電子写真用トナーバインダー樹脂としては不適で
ある。In the second circulation system, the reaction mixture extracted from the first circulation system is introduced and circulated, and further, raw material monomers and components necessary for the reaction are supplied and circulated, if necessary, at a reaction temperature of 100. The reaction conditions are generally maintained at ~ 220 ° C, the polymerization rate is 80% by weight or more, and the weight average molecular weight is 100,
A styrenic polymer having a molecular weight of 000 or more and a dispersion index of 3.0 or more is obtained in the second circulation system. At that time, it is necessary to make the reaction temperature relatively high. If the polymerization rate in the second circulation system is less than 80% by weight, the efficiency of the apparatus is too low. If the weight average molecular weight is less than 100,000 or the dispersion index is less than 3.0, it is not suitable as a toner binder resin for electrophotography.

更に、第１及び第２の循環系の容積比を適切に設定（第
１の循環系／第２の循環系＝1/10〜10/1）する必要があ
る。第１及び第２の循環系の容積比を適切に設定してい
ないと、低分子量成分の割合に、多い少ないが生じた
り、低分子量成分としては分子量が高すぎて高分子量成
分と分布が重なってしまい独立のピークを持たなかった
り、逆に低分子量成分としては分子量が低すぎて好まし
くない（この場合、電子写真用トナーバインダー樹脂と
してはケーキング性が発生する）場合が生じる。このよ
うなことは第１及び第２の循環系に供給する原料モノマ
ーの量が多すぎたり少なすぎたりするときにも生じる場
合があるので、第１の循環系に供給する原料モノマー量
に対する第２の循環系に供給する原料モノマー量の比
（前者／後者）を100/1〜100/1000とすることが好まし
い。第１及び第２の循環系の容積比並びに第１及び第２
の循環系に供給する原料モノマー量比と、得られるスチ
レン系重合体の高分子量成分及び低分子量成分の割合等
との関係を下記表−１に示す。Furthermore, it is necessary to appropriately set the volume ratio of the first and second circulation systems (first circulation system / second circulation system = 1/10 to 10/1). If the volume ratio of the first and second circulatory systems is not set appropriately, the proportion of low molecular weight components will be large or small, or the molecular weight will be too high for low molecular weight components and the distribution will overlap with the high molecular weight components. In some cases, it does not have independent peaks, and conversely, it has a low molecular weight as a low molecular weight component, which is not preferable (in this case, caking properties occur as a toner binder resin for electrophotography). Such a case may occur when the amount of the raw material monomer supplied to the first and second circulation systems is too large or too small. It is preferable that the ratio of the amount of the raw material monomers supplied to the second circulation system (the former / the latter) is 100/1 to 100/1000. Volume ratio of first and second circulation systems and first and second
The following Table 1 shows the relationship between the raw material monomer amount ratio to be supplied to the circulation system and the ratio of the high molecular weight component and the low molecular weight component of the obtained styrene polymer.

次に、本発明のスチレン系重合体の製造方法の実施態様
について図面を参照し乍ら詳述する。 Next, an embodiment of the method for producing a styrene-based polymer of the present invention will be described in detail with reference to the drawings.

本発明で用いられる原料モノマーは、スチレン系モノマ
ー、又はスチレン系モノマー及びこれと重合可能なモノ
マーの混合物であれば良く、本発明は、特に、スチレ
ン、アクリル酸エステル、連鎖移動剤、及び架橋剤をそ
れぞれ１種又は２種以上含有するモノマーの重合又は共
重合に適している。上記スチレン系モノマーとしては、
スチレンの他、α−メチルスチレン、クロロスチレン、
ｔ−ブチルスチレン等の置換スチレンが挙げられる。ま
た、上記のスチレン系モノマーと重合可能なモノマーと
しては、アクリル酸メチル、アクリル酸エチル、アクリ
ル酸ブチル、アクリル酸２エチルヘキシル等のアクリル
酸エステル等が挙げられ、また、上記連鎖移動剤として
は、メルカプタン等が挙げられ、また、上記架橋剤とし
ては、ジビニルベンゼン等が挙げられる。上記のスチレ
ン系モノマーと重合可能なモノマーの使用量は、スチレ
ン系モノマー100重量部に対して15〜50重量部であるの
が好ましい。The raw material monomer used in the present invention may be a styrene-based monomer, or a mixture of a styrene-based monomer and a monomer polymerizable with the styrene-based monomer, and the present invention particularly includes styrene, an acrylate ester, a chain transfer agent, and a crosslinking agent. Are suitable for the polymerization or copolymerization of monomers each containing one or more. As the styrene-based monomer,
In addition to styrene, α-methylstyrene, chlorostyrene,
Substituted styrenes such as t-butyl styrene may be mentioned. In addition, examples of the monomer that can be polymerized with the styrene-based monomer include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, and the chain transfer agent includes Examples of the crosslinking agent include mercaptan and divinylbenzene. The amount of the styrenic monomer and the polymerizable monomer used is preferably 15 to 50 parts by weight based on 100 parts by weight of the styrenic monomer.

また、本発明の重合又は共重合体反応に必要な成分とし
ては、有機過酸化物（例えばラウリルパーオキサイド、
ジクミルパーオキサイド、1,1−ビス（ｔ−ブチルパー
オキシ）3,3,5−トリメチルシクロヘキサン）及びアゾ
系有機化合物（例えば2,2′−アゾビス−2,4ジメチルバ
レロニトリル、2,2′−アゾビスイソブチルニトリル、
1,1′−アゾビスシクロヘキサンカルボニトリル）等の
重合開始剤が挙げられ、これらは１種単独使用しても２
種以上併用しても良い。The components necessary for the polymerization or copolymer reaction of the present invention include organic peroxides (for example, lauryl peroxide,
Dicumyl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane) and azo organic compounds (eg 2,2'-azobis-2,4 dimethylvaleronitrile, 2,2 ′ -Azobisisobutylnitrile,
1,1′-azobiscyclohexanecarbonitrile) and the like. These are 2
You may use together more than one kind.

また、本発明の実施に用いられる反応器は、混合部及び
循環用ポンプをそれぞれ具備した第１及び第２の循環系
を形成し、それらを連結した２段式のもので、それぞれ
の循環系の出口のすぐ下流に背圧弁及び気液分離器が設
けてある。Further, the reactor used in the practice of the present invention is a two-stage type reactor in which first and second circulation systems each having a mixing section and a circulation pump are formed and are connected to each other. A back pressure valve and a gas-liquid separator are provided immediately downstream of the outlet of the.

第１の循環系の好ましい具体例としては、第１図に示す
如く、循環経路（管）３内に混合部１及び循環用ポンプ
２を配して形成した循環系Ｉが挙げられ、混合抜き出し
部５を循環系Ｉの上部に設けるのが好ましい。また、背
圧弁６及び気液分離器７は、混合物抜き出し部５のすぐ
下流に背圧弁６、気液分離器７の順序でそれぞれ配する
のが好ましい。A preferable specific example of the first circulation system is a circulation system I formed by arranging a mixing section 1 and a circulation pump 2 in a circulation path (pipe) 3 as shown in FIG. The part 5 is preferably provided above the circulation system I. The back pressure valve 6 and the gas-liquid separator 7 are preferably arranged immediately downstream of the mixture withdrawing section 5 in the order of the back pressure valve 6 and the gas-liquid separator 7.

また、第２の循環系IIは、第１の循環Ｉにおける混合物
抜き出し部５に対応する部位に生成物抜き出し部５′を
設けてあり、第１の循環系Ｉの混合物抜き出し部５から
抜き出した反応混合物を導入するための供給部４を、混
合部１′の直前に設けてある以外は、第１の循環系Ｉと
同様に形成してある。また、背圧弁６′及び気液分離器
７′は、生成物抜き出し部５′のすぐ下流に背圧弁
６′、気液分離器７′の順序でそれぞれ配するのが好ま
しい。Further, the second circulation system II is provided with a product withdrawing section 5 ′ at a site corresponding to the mixture withdrawing section 5 in the first circulation I, and withdrawn from the mixture withdrawing section 5 of the first circulation system I. It is formed in the same manner as the first circulation system I, except that the supply section 4 for introducing the reaction mixture is provided immediately before the mixing section 1 '. Further, the back pressure valve 6'and the gas-liquid separator 7'are preferably arranged immediately downstream of the product withdrawing section 5'in the order of the back pressure valve 6'and the gas-liquid separator 7 '.

そして、第２の循環系IIの供給部４と第１の循環系Ｉの
混合物抜き出し部５とは、背圧弁６、気液分離器７及び
移送用ポンプ８を経て、連通路14により連通させてあ
る。Then, the supply part 4 of the second circulation system II and the mixture withdrawing part 5 of the first circulation system I are made to communicate with each other by the communication passage 14 via the back pressure valve 6, the gas-liquid separator 7 and the transfer pump 8. There is.

また、図中、第１の循環系Ｉにおける９、10は、原料モ
ノマー及び反応に必要な成分の供給口で、原料モノマー
及び反応に必要な成分は、供給口９、10から同時に又は
別々に供給し得る他、必要に応じて、それらの一部又は
全部を第１図における部位Ｐ、Ｑから供給することもで
きる。また、第２の循環系IIにおける９′、10′は、原
料モノマー及び反応に必要な成分の供給口で、第１の循
環系Ｉにおける場合と同時に原料モノマー及び反応に必
要な成分は、供給口９′、10′から同時に又は別々に供
給し得る他、必要に応じて、それらの一部又は全部を第
１図における部位Ｐ′、Ｑ′から供給することもでき
る。また、第２の循環系IIにおける供給部４の位置は変
更可能であり、部位Ｐ′の他に部位Ｑ′に設けることも
できる。In the figure, 9 and 10 in the first circulation system I are feed ports for the raw material monomers and components necessary for the reaction, and the raw material monomers and the components required for the reaction are fed from the feed ports 9, 10 simultaneously or separately. In addition to the supply, some or all of them can be supplied from the parts P and Q in FIG. 1 as required. Further, 9'and 10 'in the second circulation system II are feed ports for the raw material monomers and components necessary for the reaction, and at the same time as in the first circulation system I, the raw material monomers and the components necessary for the reaction are fed. It can be supplied simultaneously or separately from the ports 9'and 10 ', or if necessary, part or all of them can be supplied from the portions P'and Q'in FIG. Further, the position of the supply part 4 in the second circulation system II can be changed, and it can be provided in the part Q'in addition to the part P '.

第１及び第２の循環系における混合物１及び１′として
は、管内混合ミキサー（静止型混合器、ステラック・イ
ン・ライン・ミキサー）等が挙げられるが、第１図に示
す如く循環系内全体にわたって静止型混合器を配するの
が好ましい。そして、第１及び第２の循環系は、所望の
重合率により系内の温度を調整するために、二重熱交換
ジャケット12及び12′によって加熱又は冷却できるよう
になしてある。Examples of the mixtures 1 and 1'in the first and second circulation systems include in-pipe mixing mixers (static mixers, Stellac in-line mixers) and the like, but as shown in FIG. A static mixer is preferably arranged over. Then, the first and second circulation systems can be heated or cooled by the double heat exchange jackets 12 and 12 'in order to adjust the temperature in the system according to a desired polymerization rate.

また、第１及び第２の循環系における循環用ポンプ２及
び２′並びに移送用ポンプ８としては、例えば、ギヤポ
ンプ、遠心力ポンプ、ロープポンプが挙げられるが、高
粘度で安定して運転できるギヤーポンプが好ましい。Further, examples of the circulation pumps 2 and 2'and the transfer pump 8 in the first and second circulation systems include a gear pump, a centrifugal pump, and a rope pump, but a gear pump that can be stably operated with high viscosity. Is preferred.

また、上記気液分離器７及び７′としては、流下膜式気
液分離器が好ましい。尚、気液分離器７及び７′のガス
排出部13及び13′には、第１図に示す如く、同伴ガス中
の蒸気を凝縮するための熱交換器11及び11′を設置する
ことができる。A falling film gas-liquid separator is preferable as the gas-liquid separators 7 and 7 '. As shown in FIG. 1, heat exchangers 11 and 11 'for condensing vapor in the accompanying gas may be installed in the gas discharge parts 13 and 13' of the gas-liquid separators 7 and 7 '. it can.

而して、本発明は、上述の原料モノマー及び上述の反応
に必要な成分を上述の第１及び第２の循環系を形成した
２段式の反応器に供給して実施されるもので、この実施
態様を第１図に示す反応器を使用する場合に基づいて次
に説明する。Thus, the present invention is carried out by supplying the above-mentioned raw material monomers and the components necessary for the above-mentioned reaction to the two-stage reactor in which the above-mentioned first and second circulation systems are formed, This embodiment will be described below based on the case of using the reactor shown in FIG.

先ず、第１及び第２の循環系における循環経路（管）3,
3′それぞれに、反応溶媒として反応に不活性な溶媒で
沸点の高いもの例えばフタル酸エステルを満たし、該フ
タル酸エステルをそれぞれ循環用ポンプ２及び２′によ
り循環させながら二重熱交換ジャケット12及び12′で加
熱する。次いで第１の循環系Ｉにおける循環経路３内の
フタル酸エステルの液温が90〜100℃、第２の循環系II
における循環経路３′内のフタル酸エステルの液温が17
0〜180℃に達した後、上述の原料モノマー及び上述の反
応に必要な成分を第１の循環系Ｉに供給する。First, the circulation paths (pipes) 3 in the first and second circulation systems,
Each of the 3'is filled with a reaction-inert solvent having a high boiling point, for example, a phthalate ester as a reaction solvent, and the double heat exchange jacket 12 and the phthalate ester are circulated by the circulation pumps 2 and 2 ', respectively. Heat at 12 '. Next, the liquid temperature of the phthalate ester in the circulation path 3 in the first circulation system I is 90 to 100 ° C., and the second circulation system II.
The liquid temperature of the phthalate ester in the circulation route 3'at 17 is 17
After reaching 0 to 180 ° C., the above raw material monomers and the components necessary for the above reaction are fed to the first circulation system I.

原料モノマー及び反応に必要な成分の第１の循環系Ｉへ
の供給方法及び供給位置は、前述した如く特に制限され
ないが、第１図に示す反応器による場合、混合物抜き出
し部５のすぐ下流で、静止型混合器（混合部）１の直前
に、それぞれ別個の供給口９、10又は同じ供給口から同
時に且つ任意の順序で供給するのが好ましい。The feed method and feed position of the raw material monomers and the components necessary for the reaction to the first circulation system I are not particularly limited as described above, but in the case of the reactor shown in FIG. 1, just downstream of the mixture withdrawing section 5. Immediately before the static mixer (mixing section) 1, it is preferable to supply the same simultaneously and in any order from separate supply ports 9 and 10 or the same supply port.

原料モノマー及び反応に必要な成分の供給により直ちに
反応が開始され、反応混合物は溶媒と共に循環経路３内
を第１図矢標方向に循環される。第１の循環系Ｉにおけ
る反応は極めて発熱性で、生成した熱は二重熱交換ジャ
ケット12で反応混合物が冷却されることによって除かれ
る。The reaction is immediately started by supplying the raw material monomers and components necessary for the reaction, and the reaction mixture is circulated in the circulation path 3 along with the solvent in the direction of the arrow in FIG. The reaction in the first circulation system I is extremely exothermic and the heat generated is removed by cooling the reaction mixture in the double heat exchange jacket 12.

そして、反応に必要な成分として、重合開始剤の有機過
酸化物やアゾ系有機化合物を使用した場合には、循環系
中での反応により窒素や低沸点分解ガスが発生し、これ
らのガスは、反応混合物中に混入するが、循環系の上部
に設けられた混合物抜き出し部５から反応混合物と共に
順次抜き出され、気液分離器７を通過する際に反応混合
物から選択的に分離され、熱交換器１で凝縮されてガス
排出部13から系外に排出される。そのため、本発明で
は、反応中にガスが発生しても、循環系内にガスが一定
量以上滞留しないため、何等循環系における反応に支障
を来さない。また、循環系の混合物抜き出し部５のすぐ
下流で、気液分離器７の直前に背圧弁６が設けられて循
環系内が加圧されているため、モノマー等の蒸気の発生
が極力抑えられる。When an organic peroxide or an azo organic compound as a polymerization initiator is used as a component necessary for the reaction, nitrogen or a low boiling point decomposition gas is generated by the reaction in the circulation system, and these gases are , Which is mixed in the reaction mixture, is sequentially extracted together with the reaction mixture from the mixture withdrawing section 5 provided at the upper part of the circulation system, and selectively separated from the reaction mixture when passing through the gas-liquid separator 7, It is condensed in the exchanger 1 and discharged from the gas discharge part 13 to the outside of the system. Therefore, in the present invention, even if a gas is generated during the reaction, the gas does not stay in the circulation system at a certain amount or more, so that the reaction in the circulation system is not hindered. Further, immediately behind the mixture withdrawing section 5 of the circulation system, immediately before the gas-liquid separator 7, a back pressure valve 6 is provided to pressurize the inside of the circulation system, so that the generation of vapor such as monomers is suppressed as much as possible. .

次いで、第１の循環系Ｉの混合物抜き出し部５から反応
混合物の一部が連続的に抜き出され、抜き出された反応
混合物は、連通路14を介して背圧弁６、気液分離器７を
経て、移送用ポンプ８により供給部４から第２の循環系
IIに供給される。第１の循環系Ｉにおける反応混合物の
残部は、新たな原料モノマー及び反応に必要な成分と混
合するために循環経路３に再循環される。この際、再循
環される反応混合物：抜き出される反応混合物の比は、
好ましくは10:1〜1000:1、更に好ましくは20:1〜200:1
である。Next, a part of the reaction mixture is continuously withdrawn from the mixture withdrawing section 5 of the first circulation system I, and the withdrawn reaction mixture is passed through the communication passage 14 to the back pressure valve 6 and the gas-liquid separator 7 After that, the transfer pump 8 causes the second circulation system from the supply unit 4 to pass.
Supplied to II. The rest of the reaction mixture in the first circulation system I is recycled to the circulation line 3 for mixing with new raw material monomer and components necessary for the reaction. At this time, the ratio of the recycled reaction mixture to the withdrawn reaction mixture is
Preferably 10: 1 to 1000: 1, more preferably 20: 1 to 200: 1
Is.

次いで、第２の循環系IIに供給された反応混合物は、第
２の循環系IIの循環経路３′内を第１の循環系Ｉにおけ
る場合と同様に第１図矢標方向に循環させる。そして、
第２の循環系IIにおいても、第１の循環系Ｉにおける場
合と同様に新たに原料モノマー及び反応に必要な成分を
供給し第１の循環系Ｉから供給された反応混合物と共に
循環させることが好ましい。第２の循環系IIに新たに供
給される原料モノマー及び反応に必要な成分の供給方法
及び供給位置等は、第１の循環系Ｉにおける場合と全く
同様に行うことができる。Then, the reaction mixture supplied to the second circulation system II is circulated in the circulation path 3'of the second circulation system II in the arrow direction of FIG. 1 as in the case of the first circulation system I. And
Also in the second circulation system II, as in the case of the first circulation system I, the raw material monomer and the components necessary for the reaction can be newly supplied and circulated together with the reaction mixture supplied from the first circulation system I. preferable. The raw material monomer newly supplied to the second circulation system II and the supply method and position of the components necessary for the reaction can be exactly the same as those in the first circulation system I.

第２の循環系IIには新たに原料モノマー等を添加しなく
ても良いが、得られるスチレン系重合体の高分子量成分
と低分子量成分の割合を適切にするために、第１の循環
系Ｉに供給する原料モノマー量と第２の循環系IIに供給
する原料モノマー量の比（前者／後者）を100/1〜100/1
000とすることが好ましい。It is not necessary to newly add a raw material monomer to the second circulation system II, but in order to make the ratio of the high molecular weight component and the low molecular weight component of the obtained styrene polymer appropriate, the first circulation system II The ratio of the amount of the raw material monomer supplied to I and the amount of the raw material monomer supplied to the second circulation system II (the former / the latter) is 100/1 to 100/1.
It is preferably 000.

第２の循環系IIにおける生成物抜き出し部５′からの反
応生成物の抜き出しは、第１の循環系Ｉにおける反応混
合物の抜き出しと同様な態様で行われ、その抜き出し量
の割合も同様にするのが好ましい。The withdrawal of the reaction product from the product withdrawal section 5'in the second circulation system II is performed in the same manner as the withdrawal of the reaction mixture in the first circulation system I, and the ratio of the withdrawal amount is also the same. Is preferred.

また、本発明の実施において、定常状態となった後の第
１及び第２の循環系中における反応混合物及び反応生成
物の平均滞留時間及び循環速度、第１の循環系と第２の
循環系の容積比、原料モノマー及び反応に必要な成分の
供給量は、第１の循環系の重合率が15〜80重量％、例え
ば40〜70重量％で重量平均分子量が200000以上、第２の
循環系の重合率が80重量％以上、例えば90重量％以上で
重量平均分子量が100000以上、且つ分散指数が3.0以
上、例えば5.0〜50のスチレン系重合体が得られるよう
に選定すれば良い。Further, in the practice of the present invention, the average residence time and circulation rate of the reaction mixture and the reaction product in the first and second circulation systems after the steady state, the first circulation system and the second circulation system, The volume ratio, the raw material monomers and the amount of components necessary for the reaction are 15 to 80% by weight of the first circulation system, for example 40 to 70% by weight, and the weight average molecular weight of 200,000 or more, the second circulation. It may be selected so as to obtain a styrene polymer having a polymerization rate of 80% by weight or more, for example 90% by weight or more, a weight average molecular weight of 100,000 or more, and a dispersion index of 3.0 or more, for example, 5.0 to 50.

この場合、通常、第１の循環系と第２の循環系の容積比
（前者／後者）は1/10〜10/1、例えば1/3〜3/1で、平均
滞留時間は１分〜360分、例えば10分〜240分であり、第
２の循環系における平均滞留時間は、好ましくは第１の
循環系における平均滞留時間の0.2〜３倍とする。滞留
時間が長くなると、通常重合率が高くなり分子量は大き
くなる。In this case, the volume ratio of the first circulation system and the second circulation system (the former / the latter) is usually 1/10 to 10/1, for example, 1/3 to 3/1, and the average residence time is 1 minute to It is 360 minutes, for example 10 minutes to 240 minutes, and the average residence time in the second circulation system is preferably 0.2 to 3 times the average residence time in the first circulation system. A longer residence time usually leads to a higher polymerization rate and a higher molecular weight.

また、平均反応温度は、第１の循環系で50〜150℃、例
えば90〜110℃で、第２の循環系で100〜220℃、例えば1
50〜180℃である。また、混合物抜き出し部５及び生成
物抜き出し部５′からの反応混合物及び反応生成物の抜
き出し量は、それぞれ、第１及び第２の循環系における
原料モノマーを含む全供給量と等しい量である。The average reaction temperature is 50 to 150 ° C. in the first circulation system, for example 90 to 110 ° C., and 100 to 220 ° C. in the second circulation system, for example 1
50 to 180 ° C. Further, the amounts of the reaction mixture and the reaction product extracted from the mixture withdrawing section 5 and the product withdrawing section 5'are equal to the total supply amounts including the raw material monomers in the first and second circulation systems, respectively.

第２の循環系の生成物抜き出し部５′から抜き出された
反応生成物は、通常、重合体（若しくは共重合体）と未
反応モノマーとの混合物からなり、再循環される反応生
成物の分析値（組成）と同じ分析値（組成）をもつ。し
かし、反応生成物を抜き出す時には、反応は通常完全に
完了していないから、この場合には反応生成物中の未反
応モノマーを従来法で除去するか、あるいは有利には更
に反応に必要な成分を添加することなく100〜220℃例え
ば150〜200℃で0.01〜５時間、例えば0.5〜２時間、２
〜60分熟成が行われる。The reaction product withdrawn from the product withdrawing section 5'of the second circulation system usually comprises a mixture of a polymer (or copolymer) and unreacted monomer, and the reaction product to be recycled is recycled. It has the same analytical value (composition) as the analytical value (composition). However, when the reaction product is withdrawn, the reaction is usually not completely completed, in which case the unreacted monomers in the reaction product are removed in a conventional manner or, advantageously, the components necessary for further reaction are added. Without addition of 100-220 ° C, for example 150-200 ° C, for 0.01-5 hours, for example 0.5-2 hours, 2
Aged for ~ 60 minutes.

〔実施例〕〔Example〕

以下に実施例及び比較例を挙げ、本発明を更に詳細に説
明する。Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

実施例１ 第１図に示す如く構成した、全容積0.3の第１の循環
系Ｉと全容積1.0の第２の循環系IIに、それぞれフタ
ル酸ジオクチル（DOP）を満たし、それぞれ循環用ポン
プ2,2′により循環させながら、二重熱交換ジャケット1
2,12′で第１の循環系Ｉ内が95℃、第２の循環系II内が
145℃に達するまで加熱した。次いで、スチレンモノマ
ー、アクリル酸２エチルヘキシル、１−１′−アゾビス
シクロヘキサンカルボニトリルを重量基準で84:16:1の
比率で合計量0.135kg/hrで連続的に供給口９より第１の
循環系Ｉに供給した。また、この際、第１の循環系Ｉの
反応温度が95〜100℃に保持されるように二重熱交換ジ
ャケット12で冷却した。循環用ポンプ２の能力は、循環
流量／供給量＝150/1にした。第１の循環系Ｉにおける
スチレン系重合体の重合率は60％で、重量平均分子量は
180,000であった。Example 1 A first circulation system I having a total volume of 0.3 and a second circulation system II having a total volume of 1.0, each of which is configured as shown in FIG. 1, is filled with dioctyl phthalate (DOP), respectively, and a circulation pump 2 is used. Double heat exchange jacket 1 while circulating by 2 '
2,12 '95 ° C in the first circulation system I, and in the second circulation system II
Heated to reach 145 ° C. Then, the styrene monomer, 2-ethylhexyl acrylate, and 1-1′-azobiscyclohexanecarbonitrile were continuously circulated from the supply port 9 at a ratio of 84: 16: 1 on a weight basis at a total amount of 0.135 kg / hr. Feeded to system I. In addition, at this time, cooling was carried out by the double heat exchange jacket 12 so that the reaction temperature of the first circulation system I was maintained at 95 to 100 ° C. The capacity of the circulation pump 2 was set to circulation flow rate / supply amount = 150/1. The polymerization rate of the styrene polymer in the first circulation system I is 60%, and the weight average molecular weight is
It was 180,000.

次いで、第１の循環系Ｉにおける反応混合物の一部（第
１の循環系における原料モノマーの供給量と同一量）
を、混合物抜き出し部５から連続的に抜き出し、背圧弁
６（設定値1kg/cm2G）、気液分離器７、移送ポンプ８を
経て供給部４から第２の循環系IIに導入し、また、第２
の循環系IIに、新たにスチレンモノマー、アクリル酸２
エチルヘキシル、１−１′−アゾビスシクロヘキサンカ
ルボニトリルを重量基準で84:16:0.5の比率で合計量0.0
45kg/hrで連続的に供給口９′から供給した。また、こ
の際、第２の循環系IIの反応温度が145〜150℃に保持さ
れるように二重熱交換ジャケット12′で調整した。循環
用ポンプ２′の能力は、循環流量／供給量＝90/1にし
た。反応生成物の一部（第２の循環系IIにおける反応混
合物及び原料モノマーの供給量と同一量）を、生成物抜
き出し部５′から背圧弁６′（設定値2kg/cm2G）、気液
分離器７′を通して連続的に取り出した。定常状態に達
していると思われるスチレン系重合体の重合率は98％、
重量平均分子量は110000で分散指数は5.5であった。Next, a part of the reaction mixture in the first circulation system I (the same amount as the feed amount of the raw material monomer in the first circulation system)
Is continuously withdrawn from the mixture withdrawing section 5 and introduced into the second circulation system II from the supply section 4 via the back pressure valve 6 (setting value 1 kg / cm 2 G), the gas-liquid separator 7 and the transfer pump 8. Also, the second
New styrene monomer, acrylic acid 2
Ethylhexyl, 1-1'-azobiscyclohexanecarbonitrile was added to a total amount of 0.0 at a ratio of 84: 16: 0.5 by weight.
It was continuously supplied at 45 kg / hr from the supply port 9 '. At this time, the double heat exchange jacket 12 'was adjusted so that the reaction temperature of the second circulation system II was maintained at 145 to 150 ° C. The capacity of the circulation pump 2'is set to the circulation flow rate / supply rate = 90/1. A part of the reaction product (the same amount as the supply amount of the reaction mixture and the raw material monomer in the second circulation system II) is fed from the product withdrawal section 5'to the back pressure valve 6 '(set value 2 kg / cm 2 G) and the gas. It was continuously taken out through the liquid separator 7 '. The polymerization rate of the styrene-based polymer that seems to have reached a steady state is 98%,
The weight average molecular weight was 110,000 and the dispersion index was 5.5.

実施例２ 第１図に示す如く構成した、全容量１の第１の循環系
Ｉと全容量の0.3の第２の循環系IIに、それぞれフタ
ル酸ジオクチル（DOP）を満たし、それぞれ循環用ポン
プ2,2′により循環させながら、二重熱交換ジャケット1
2,12′で第１の循環系Ｉ内が95℃、第２の循環系II内が
175℃に達するまで加熱した。次いで、スチレンモノマ
ー、アクリル酸２エチルヘキシル、1,1−ビス（ｔ−ブ
チルパーオキシ）3,3,5−トリメチルシクロヘキサンを
重量基準で84:16:0.5の比率で合計量0.30kg/hrで連続的
に供給口９から供給した。また、この際、第１の循環系
Ｉの反応温度が95〜100℃に保持されるように二重熱交
換ジャケット12で冷却した。循環用ポンプ２の能力は、
循環流量／供給量＝150/1にした。第１の循環系Ｉにお
けるスチレン系重合体の重合率は70％で、重量平均分子
量は290,000であった。Example 2 A first circulation system I having a total capacity of 1 and a second circulation system II having a total capacity of 0.3, each of which is configured as shown in FIG. 1, is filled with dioctyl phthalate (DOP), and a circulation pump is used. Double heat exchange jacket 1 while circulating by 2, 2 '
2,12 '95 ° C in the first circulation system I, and in the second circulation system II
Heated to reach 175 ° C. Next, styrene monomer, 2-ethylhexyl acrylate, and 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane were added continuously at a ratio of 84: 16: 0.5 on a weight basis in a total amount of 0.30 kg / hr. It was supplied from the supply port 9. In addition, at this time, cooling was carried out by the double heat exchange jacket 12 so that the reaction temperature of the first circulation system I was maintained at 95 to 100 ° C. The capacity of the circulation pump 2 is
Circulation flow rate / supply rate = 150/1. The polymerization rate of the styrene polymer in the first circulation system I was 70%, and the weight average molecular weight was 290,000.

次いで、第１の循環系Ｉにおける反応混合物の一部を、
混合物抜き出し部５から連続的に抜き出し、背圧弁６
（設定値1kg/cm2G）、気液分離器７、移送ポンプ８を経
て供給部４から第２の循環系IIに導入し、また、第２の
循環系IIに、新たにスチレンモノマー、アクリル酸２エ
チルヘキシル、1,1−ビス（ｔ−ブチルパーオキシ）3,
3,5−トリメチルシクロヘキサンを重量基準で84:16:1.0
の比率で合計量0.15kg/hrで連続的に供給口９から供給
した。また、この際、第２の循環系IIの反応温度が175
〜180℃に保持されるように二重熱交換ジャケット12′
で調整した。循環用ポンプ２′の能力は、循環流量／供
給量＝60/1にした。反応生成物の一部を、生成物抜き出
し部５′から背圧弁６′（設定値2kg/cm2G）、気液分離
器７′を通して連続的に取り出した。定常状態に達して
いると思われるスチレン系重合体の重合率は95％、重量
平均分子量165000で、分散指数は12.8であった。Then, a part of the reaction mixture in the first circulation system I is
The back pressure valve 6 is continuously withdrawn from the mixture withdrawing section 5.
(Set value 1 kg / cm 2 G), introduced into the second circulation system II from the supply section 4 via the gas-liquid separator 7 and the transfer pump 8, and newly added styrene monomer to the second circulation system II. 2-ethylhexyl acrylate, 1,1-bis (t-butylperoxy) 3,
84: 16: 1.0 by weight of 3,5-trimethylcyclohexane
The total amount of 0.15 kg / hr was continuously supplied from the supply port 9 at the ratio of. At this time, the reaction temperature of the second circulation system II is 175
Double heat exchange jacket 12 'so as to be kept at ~ 180 ℃
I adjusted it with. The capacity of the circulation pump 2'is set to circulation flow rate / supply rate = 60/1. A part of the reaction product was continuously taken out from the product withdrawing section 5'through a back pressure valve 6 '(set value 2 kg / cm 2 G) and a gas-liquid separator 7'. The polymerization rate of the styrenic polymer that seems to have reached a steady state was 95%, the weight average molecular weight was 165,000, and the dispersion index was 12.8.

比較例１ 背圧弁6,6′、気液分離器7,7′、及び移送ポンプ８を設
置しない以外は第１図に示した反応器と同じタイプの反
応器を用い、実施例１と同一条件で操作（運転）したと
ころ、供給開始後、約10時間頃から第１の循環系内の圧
力が上昇し始め、約12時間頃には20kg/cm2に達し運転の
続行が不可能となった。第１の循環系内及び第２の循環
系内の液をサンプリングしてみるとガスがかなり多く含
まれていた。Comparative Example 1 Same as Example 1 except that the back pressure valves 6, 6 ', gas-liquid separators 7, 7', and transfer pump 8 were not installed, and the same type of reactor as that shown in FIG. 1 was used. When operated (operating) under the conditions, the pressure in the first circulation system began to rise from about 10 hours after the start of supply, and reached about 20 kg / cm 2 in about 12 hours, making it impossible to continue operation. became. When the liquids in the first circulation system and the second circulation system were sampled, a considerable amount of gas was contained.

比較例２ 第１図に示した反応器で第２の循環系を設置せず、第１
の循環系のみの反応器を用いた以外は実施例２と同一条
件で操作（運転）した。定常状態に達していると思われ
るスチレン系重合体の重合率は70％、重量平均分子量29
0000で分散指数2.1と分子量分布のシャープなものであ
った。Comparative Example 2 In the reactor shown in FIG. 1, the second circulation system was not installed, and the first
The operation (operation) was carried out under the same conditions as in Example 2 except that the reactor having the circulation system was used. The styrene polymer that seems to have reached a steady state has a polymerization rate of 70% and a weight average molecular weight of 29.
At 0000, the dispersion index was 2.1 and the molecular weight distribution was sharp.

〔発明の効果〕〔The invention's effect〕

本発明のスチレン系重合体の製造方法によれば、反応に
必要な成分として有機過酸化物やアゾ系有機化合物を用
いることにより分解ガスが発生し、循環する反応混合物
中に多量の気泡が混入しても、これらのガスは気液分離
器で分離できるため、循環系内にガスが一定量以上滞留
せず、且つ背圧弁でモノマー蒸気の発生を抑えているの
で、ループ内の圧力の上昇といった支障を来すことがな
く、また、反応を２段式で行いその際第１と第２の循環
系の容積比や反応条件を適切に設定しているため、高分
子量成分と低分子量成分が適当に存在し合う分子量分布
がワイドなスチレン系重合体を製造できる。According to the method for producing a styrene-based polymer of the present invention, a decomposition gas is generated by using an organic peroxide or an azo-based organic compound as a component necessary for the reaction, and a large amount of bubbles are mixed in the circulating reaction mixture. Even so, since these gases can be separated by the gas-liquid separator, the gas does not stay in the circulation system more than a certain amount, and the back pressure valve suppresses the generation of monomer vapor, so the pressure in the loop rises. In addition, since the reaction is carried out in a two-stage system and the volume ratio of the first and second circulation systems and the reaction conditions are appropriately set, the high molecular weight component and the low molecular weight component are It is possible to produce a styrene-based polymer having a wide molecular weight distribution in which the above are appropriately present.

【図面の簡単な説明】[Brief description of drawings]

第１図は本発明の実施に用いられる反応器の一例を示す
フローシートである。 Ｉ……第１の循環系、II……第２の循環系 1,1′……混合部（静止型混合器） 2,2′……循環用ポンプ 3,3′……循環経路、４……供給部、 ５……混合物抜き出し部 ５′……生成物抜き出し部、6,6′……背圧弁 7,7′……気液分離器、８……移送用ポンプ 9,10,9′,10′……供給口 11,11′……熱交換器 12,12′……二重熱交換ジャケット 13,13′……ガス排出部、14……連通路FIG. 1 is a flow sheet showing an example of a reactor used for carrying out the present invention. I ... First circulation system, II ... Second circulation system 1,1 '... Mixing section (static mixer) 2,2' ... Circulation pump 3,3 '... Circulation path, 4 …… Supply part, 5 …… Mixture withdrawal part 5 ′ …… Product withdrawal part, 6,6 ′ …… Back pressure valve 7,7 ′ …… Gas-liquid separator, 8 …… Transfer pump 9,10,9 ′, 10 ′ …… Supply port 11,11 ′ …… Heat exchanger 12,12 ′ …… Double heat exchange jacket 13,13 ′ …… Gas discharge part, 14 …… Communication passage

Claims (10)

【特許請求の範囲】[Claims] 【請求項１】（ａ）スチレン系モノマーの１種又は２種
以上を必須成分とするモノマーを重合又は共重合させる
際に、混合部及び循環用ポンプを具備した第１の循環系
を形成し、原料モノマー及び反応に必要な成分を上記循
環系に供給し循環させ、反応混合物の一部を上記循環系
の径路に設けた混合物抜き出し部から抜き出し、反応混
合物の残部を再循環させる一方、上記第１の循環系から
抜き出した上記反応混合物を背圧弁、気液分離器に導
き、該気液分離器で反応混合物中のガスを抜き、さらに
移送用ポンプで混合部及び循環用ポンプを具備した第２
の循環系に供給して循環させると共に、該第２の循環系
に更に必要に応じ原料モノマー及び反応に必要な成分を
供給して循環させ、反応生成物の一部を上記第２の循環
系の経路に設けた生成物抜き出し部から背圧弁、気液分
離器を通して抜き出し、反応生成物の残部を第２の循環
系中に再循環させるようにした反応器を用いてスチレン
系重合体を製造する方法であって、 （ｂ）上記反応器として、上記第１及び第２の循環系の
容積比（前者／後者）が1/10〜10/1であるような反応器
を用い、 （ｃ）上記第１の循環系における反応条件を、反応温度
50〜150℃に保持して、重合率が15〜80重量％で重量平
均分子量200,000以上の重合体を上記第１の循環系で
得、 （ｄ）上記第２の循環系における反応条件を、反応温度
100〜220℃に保持して、重合率が80重量％以上で重量平
均分子量100,000以上の分子量と3.0以上の分散指数を有
するスチレン系重合体を上記第２の循環系で得る ことを特徴とするスチレン系重合体の製造方法。1. When (a) polymerizing or copolymerizing a monomer containing one or more styrene-based monomers as essential components, a first circulation system having a mixing section and a circulation pump is formed. The raw material monomer and the components necessary for the reaction are supplied to the circulation system and circulated, a part of the reaction mixture is withdrawn from the mixture withdrawal section provided in the path of the circulation system, and the rest of the reaction mixture is recycled, while The reaction mixture extracted from the first circulation system was introduced into a back pressure valve and a gas-liquid separator, the gas in the reaction mixture was extracted by the gas-liquid separator, and the transfer pump was equipped with a mixing section and a circulation pump. Second
To the second circulation system, and at the same time, the raw material monomer and components necessary for the reaction are further supplied to the second circulation system for circulation, and a part of the reaction product is added to the second circulation system. A styrene-based polymer is produced by using a reactor in which the product withdrawal section provided in the above-mentioned path is withdrawn through a back pressure valve and a gas-liquid separator, and the rest of the reaction product is recirculated into the second circulation system. (B) As the reactor, a reactor in which the volume ratio (former / latter) of the first and second circulation systems is 1/10 to 10/1 is used. ) The reaction conditions in the first circulation system are set as follows:
While maintaining at 50 to 150 ° C., a polymer having a polymerization rate of 15 to 80% by weight and a weight average molecular weight of 200,000 or more is obtained in the first circulation system, and (d) the reaction conditions in the second circulation system are Reaction temperature
A styrene-based polymer having a polymerization rate of 80% by weight or more, a weight average molecular weight of 100,000 or more, and a dispersion index of 3.0 or more is obtained in the second circulation system while being maintained at 100 to 220 ° C. Method for producing styrene-based polymer. 【請求項２】混合部が静止型混合器である、特許請求の
範囲第（１）項記載のスチレン系重合体の製造方法。2. The method for producing a styrene polymer according to claim 1, wherein the mixing section is a static mixer. 【請求項３】原料モノマー及び反応に必要な成分を第１
及び第２の循環系の混合部の直前にそれぞれ供給する、
特許請求の範囲第（１）項記載のスチレン系重合体の製
造方法。3. A raw material monomer and a component necessary for the reaction are first
And immediately before the mixing section of the second circulation system,
A method for producing a styrene-based polymer according to claim (1). 【請求項４】混合物抜き出し部が、第１の循環系の上部
に設けてある、特許請求の範囲第（１）項記載のスチレ
ン系重合体の製造方法。4. The method for producing a styrene-based polymer according to claim 1, wherein the mixture withdrawing portion is provided above the first circulation system. 【請求項５】生成物抜き出し部が、第２の循環系の上部
に設けてある、特許請求の範囲第（１）項記載のスチレ
ン系重合体の製造方法。5. The method for producing a styrene polymer according to claim 1, wherein the product withdrawal section is provided above the second circulation system. 【請求項６】背圧弁及び気液分離器が、第１の循環系の
混合物抜き出し部及び第２の循環系の生成物抜き出し部
それぞれのすぐ下流に背圧弁、気液分離器の順序でそれ
ぞれ設けてある、特許請求の範囲第（１）項記載のスチ
レン系重合体の製造方法。6. A back pressure valve and a gas-liquid separator are arranged in the order of a back pressure valve and a gas-liquid separator immediately downstream of the mixture withdrawing section of the first circulation system and the product withdrawing section of the second circulation system, respectively. The method for producing a styrene polymer according to claim (1), which is provided. 【請求項７】原料モノマーが、スチレン、スチレンとア
クリル酸エステルの混合物、又はスチレンとアクリル酸
エステルとジビニルベンゼンの混合物である、特許請求
の範囲第（１）項記載のスチレン系重合体の製造方法。7. A method for producing a styrene polymer according to claim 1, wherein the raw material monomer is styrene, a mixture of styrene and an acrylic ester, or a mixture of styrene, an acrylic ester and divinylbenzene. Method. 【請求項８】反応に必要な成分が、有機過酸化物、アゾ
系有機化合物を含んでいる、特許請求の範囲第（１）項
記載のスチレン系重合体の製造方法。8. The method for producing a styrene polymer according to claim 1, wherein the components required for the reaction include an organic peroxide and an azo organic compound. 【請求項９】第１の循環系における、再循環される反応
混合物：抜き出される反応混合物の比が、10:1〜1000:1
である、特許請求の範囲第（１）項記載のスチレン系重
合体の製造方法。9. The ratio of the reaction mixture recycled to the reaction mixture withdrawn in the first circulation system is from 10: 1 to 1000: 1.
The method for producing a styrene-based polymer according to claim 1, which is 【請求項１０】第２の循環系における、再循環される反
応生成物：抜き出される反応生成物の比が、10:1〜100
0:1である、特許請求の範囲第（１）項記載のスチレン
系重合体の製造方法。10. The ratio of the recycled reaction product to the withdrawn reaction product in the second circulation system is 10: 1 to 100.
The method for producing a styrene-based polymer according to claim (1), wherein the ratio is 0: 1.
JP62121745A 1987-05-19 1987-05-19 Method for producing styrene polymer Expired - Lifetime JPH07116257B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP62121745A JPH07116257B2 (en) 1987-05-19 1987-05-19 Method for producing styrene polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62121745A JPH07116257B2 (en) 1987-05-19 1987-05-19 Method for producing styrene polymer

Publications (2)

Publication Number Publication Date
JPS63286406A JPS63286406A (en) 1988-11-24
JPH07116257B2 true JPH07116257B2 (en) 1995-12-13

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JP62121745A Expired - Lifetime JPH07116257B2 (en) 1987-05-19 1987-05-19 Method for producing styrene polymer

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1290871C (en) * 2002-05-10 2006-12-20 Ps日本株式会社 Styrene polymer resin and composition thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH649230A5 (en) * 1982-06-03 1985-05-15 Sulzer Ag REACTOR FOR THE CONTINUOUS IMPLEMENTATION OF POLYMERISATIONS IN HIGH VISCOSITY MEDIA.
JPS6291506A (en) * 1985-10-17 1987-04-27 Kao Corp Production of carboxylic acid polymer

Also Published As

Publication number Publication date
JPS63286406A (en) 1988-11-24

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