JP3416988B2 - Method for producing copolymer - Google Patents
Method for producing copolymerInfo
- Publication number
- JP3416988B2 JP3416988B2 JP13981393A JP13981393A JP3416988B2 JP 3416988 B2 JP3416988 B2 JP 3416988B2 JP 13981393 A JP13981393 A JP 13981393A JP 13981393 A JP13981393 A JP 13981393A JP 3416988 B2 JP3416988 B2 JP 3416988B2
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- polymerization
- weight
- compound
- copolymer
- styrene
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、連続重合法による、ス
チレン−アクリロニトリル系共重合体の改良された製造
方法に関する。さらに詳細には、アクリロニトリルの結
合含有率が高い、スチレン−アクリロニトリル系共重合
体を製造する際、ゲル状のポリマーの生成を防止し、得
られる共重合体の成形加工時の成形品外観不良となる銀
条（シルバーストリーク）を低減させ、かつ成形加工時
の熱安定性（耐変色性）、耐薬品性、透明性にも優れ、
さらに重合装置へのゲル状ポリマーの付着を低減させ、
長時間の連続重合運転が可能な共重合体の製造方法に関
する。FIELD OF THE INVENTION The present invention relates to an improved method for producing a styrene-acrylonitrile copolymer by a continuous polymerization method. More specifically, a high acrylonitrile bond content, when producing a styrene-acrylonitrile-based copolymer, to prevent the formation of a gel polymer, the appearance of the molded product during molding of the resulting copolymer is poor. It reduces the number of silver streaks, and also has excellent thermal stability (discoloration resistance), chemical resistance, and transparency during molding.
Furthermore, it reduces the adhesion of gel-like polymer to the polymerization equipment,
The present invention relates to a method for producing a copolymer capable of continuous polymerization operation for a long time.
【０００２】[0002]
【従来の技術】スチレンとアクリロニトリルを主成分と
する共重合体、いわゆるＡＳ樹脂は、その優れた透明
性、耐薬品性、剛性、成形性などの諸性質を有すること
から、幅広い分野で使用されている。これらの共重合体
の製造方法としては、従来より、乳化重合、懸濁重合、
塊状−懸濁重合法が採用されており、最近では、省エネ
ルギー、公害対策などのために塊状重合や溶液重合によ
る連続重合法も採用されるようになった。しかしなが
ら、スチレン−アクリロニトリル系共重合体を連続的に
製造する場合、装置の連続運転時間が長くなると、重合
器、配管などにゲル状ポリマーが生成付着し、またアク
リロニトリルの結合含有率が高くなると、さらにゲル状
ポリマーの生成付着が著しく促進され、安定な長時間運
転が不能になる。また、そのゲル状ポリマーの一部は、
製品に混入し、特に成形加工時に成形品の表面に銀条
（シルバーストリーク）が発生し、そして熱安定性、透
明性が低下し、その結果、商品価値を低下させる。この
ため、ゲル状ポリマーは、重合溶液をフィルターでろ別
して分別除去したり、連続運転時間を短縮してゲル状ポ
リマーの洗浄除去を行うなど、多大の時間と労力を要
し、生産性の低下を余儀なくされていた。BACKGROUND OF THE INVENTION Copolymers containing styrene and acrylonitrile as main components, so-called AS resins, are used in a wide range of fields because of their excellent properties such as transparency, chemical resistance, rigidity and moldability. ing. As a method for producing these copolymers, conventionally, emulsion polymerization, suspension polymerization,
A bulk-suspension polymerization method has been adopted, and recently, a continuous polymerization method by bulk polymerization or solution polymerization has also been adopted for energy saving, pollution control, and the like. However, in the case of continuously producing a styrene-acrylonitrile-based copolymer, if the continuous operation time of the apparatus becomes long, a gelled polymer is produced and attached to a polymerization vessel, a pipe, etc., and if the bond content of acrylonitrile becomes high, Furthermore, the formation and adhesion of the gel-like polymer is significantly promoted, and stable long-term operation becomes impossible. In addition, a part of the gel polymer is
It mixes with the product, and silver streaks (silver streaks) are generated on the surface of the molded product, especially during the molding process, and the thermal stability and the transparency are deteriorated, and as a result, the commercial value is decreased. Therefore, the gel polymer requires a great deal of time and labor, such as separating and removing the polymerization solution by filtering with a filter, and washing and removing the gel polymer by shortening the continuous operation time, resulting in a decrease in productivity. Had to be forced.
【０００３】これらを改善する方法としては、例えば原
料中に含まれる水分の量を２００〜５２０ｐｐｍに制御
して連続塊状重合を行う方法（特開昭５７−２５３１０
号公報）や、単量体混合物の反応液１００重量部に対
し、高級脂肪酸アミドを０．１〜３．０重量部添加して
連続的に塊状または溶液重合を行う方法（特開昭６０−
２６０６０５号公報）などが提案されている。しかしな
がら、これらの方法は、単量体中の水分の脱水操作が必
要となったり、高級脂肪酸アミドが得られる共重合体の
透明性を損ねるなど、必ずしも重合操作の簡易化や品質
の改良とはならない。As a method of improving these, for example, a method of carrying out continuous bulk polymerization by controlling the amount of water contained in the raw material to 200 to 520 ppm (JP-A-57-25310).
(Japanese Patent Laid-Open Publication No. 60-90), or a method in which 0.1 to 3.0 parts by weight of a higher fatty acid amide is added to 100 parts by weight of a reaction solution of a monomer mixture to continuously perform bulk or solution polymerization (JP-A-60-
No. 260605) has been proposed. However, these methods require dehydration operation of water in the monomer, impair the transparency of the copolymer from which the higher fatty acid amide is obtained, and do not necessarily simplify the polymerization operation and improve the quality. I won't.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、前記従来技
術の課題を背景になされたもので、アクリロニトリルの
結合含有率の高いスチレン−アクリロニトリル系共重合
体を連続的に、溶液重合あるいは塊状重合法により製造
する際に、ゲル状ポリマーの生成を防止し、その結果、
長時間の連続重合運転が可能となり、また成形品の表面
外観性、熱安定性および透明性が一段と優れた共重合体
を製造することができる、スチレン−アクリロニトリル
系共重合体の製造方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art. A styrene-acrylonitrile copolymer having a high acrylonitrile bond content is continuously polymerized by solution polymerization or bulk polymerization. Prevents the formation of gel-like polymer during manufacturing by law, resulting in
Provided is a method for producing a styrene-acrylonitrile-based copolymer, which enables continuous polymerization operation for a long time, and can produce a copolymer having excellent surface appearance, thermal stability and transparency of a molded article. The purpose is to do.
【０００５】[0005]
【課題を解決するための手段】本発明は、シアン化ビニ
ル化合物の含有率が３３〜８５重量％、芳香族ビニル化
合物の含有率が１５〜６７重量％およびこれらと共重合
可能な他の単量体の含有率が０〜３０重量％である共重
合体を、溶液重合および／または塊状重合で製造する方
法であって、２基以上の重合器を連結した重合装置を用
い、第１基目の重合器にシアン化ビニル化合物３０〜９
０重量％（この割合を「ａ重量％」とする）、芳香族ビ
ニル化合物１０〜７０重量％およびこれらと共重合可能
な他の単量体０〜３０重量％からなる単量体を連続的に
または回分的に供給し、第１基目の重合器の出口の反応
物の重合転化率が３０〜８０重量％まで重合し、次いで
第２基目以降のいずれかの少なくとも１つの重合器へ供
給する際に、芳香族ビニル化合物を添加して、反応物中
に存在する未反応単量体中のシアン化ビニル化合物の含
有率がａ重量％±２０重量％の範囲になるようにし、第
２基目以降の重合器で重合転化率が５０重量％以上にな
るように重合する、ことを特徴とする共重合体の製造方
法を提供するものである。DISCLOSURE OF THE INVENTION According to the present invention, the content of vinyl cyanide compound is 33 to 85% by weight, the content of aromatic vinyl compound is 15 to 67% by weight, and other copolymerizable with them. A method for producing a copolymer having a content of a monomer of 0 to 30% by weight by solution polymerization and / or bulk polymerization, which comprises using a polymerization device in which two or more polymerization units are connected, Vinyl cyanide compound 30-9 in the eye polymerization vessel
0% by weight (this ratio is referred to as "a% by weight"), 10 to 70% by weight of the aromatic vinyl compound, and 0 to 30% by weight of another monomer copolymerizable therewith are continuously used as monomers. Or batchwise, the reaction product at the outlet of the first polymerization unit is polymerized to a polymerization conversion rate of 30 to 80% by weight, and then fed to at least one of the second and subsequent polymerization units. When supplying, an aromatic vinyl compound is added so that the content of the vinyl cyanide compound in the unreacted monomer present in the reaction product is in the range of a% by weight ± 20% by weight. It is intended to provide a method for producing a copolymer, characterized in that the polymerization is performed so that the polymerization conversion rate becomes 50% by weight or more in the second and subsequent polymerization vessels.
【０００６】本発明で使用するシアン化ビニル化合物と
しては、例えばアクリロニトリル、メタクリロニトリル
などが挙げられ、これらは単独であるいは混合して用い
ることができる。Examples of the vinyl cyanide compound used in the present invention include acrylonitrile and methacrylonitrile, which can be used alone or in combination.
【０００７】また、芳香族ビニル化合物としては、例え
ばスチレン、α−メチルスチレン、ｐ−メチルスチレ
ン、３，５−ジメチルスチレンなどのアルキル基置換ス
チレン、α−ブロムスチレン、ｐ−ブロムスチレンなど
のハロゲン化スチレンなどが挙げられ、これらは単独
で、あるいは混合して用いることができる。芳香族ビニ
ル化合物としては、好ましくはスチレン、α−メチルス
チレン、さらに好ましくはスチレンである。Examples of the aromatic vinyl compound include alkyl group-substituted styrene such as styrene, α-methylstyrene, p-methylstyrene and 3,5-dimethylstyrene, halogen such as α-bromostyrene and p-bromostyrene. Examples thereof include styrene and the like, and these can be used alone or in combination. The aromatic vinyl compound is preferably styrene, α-methylstyrene, and more preferably styrene.
【０００８】さらに、共重合可能な他の単量体として
は、例えばメチルメタクリレート、エチルメタクリレー
ト、メチルアクリレート、エチルアクリレートなどの
（メタ）アクリル酸エステル類、アクリル酸、メタクリ
ル酸などの不飽和酸、無水マレイン酸、無水イタコン酸
などの不飽和酸無水物、Ｎ−メチルマレイミド、Ｎ−フ
ェニルマレイミド、Ｎ−ｏ−クロルフェニルマレイミ
ド、Ｎ−シクロヘキシルマレイミドなどのマレイミド化
合物などが挙げられる。これらは、単独であるいは混合
して用いることができる。Further, other copolymerizable monomers include, for example, (meth) acrylic acid esters such as methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate, unsaturated acids such as acrylic acid and methacrylic acid, Examples thereof include unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride, N-methylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, N-cyclohexylmaleimide and other maleimide compounds. These can be used alone or as a mixture.
【０００９】本発明の製造方法で得られる共重合体中に
共重合されている、シアン化ビニル化合物の結合含有率
は３３〜８５重量％、好ましくは３５〜８０重量％、さ
らに好ましくは４０〜７８重量％、特に好ましくは４５
〜７５重量％、芳香族ビニル化合物の結合含有率は１５
〜６７重量％、好ましくは２０〜６５重量％、さらに好
ましくは２５〜５５重量％、共重合可能な他の単量体の
結合含有率は０〜３０重量％、好ましくは０〜２０重量
％である。シアン化ビニル化合物の結合含有率が３３重
量％未満では、最近の一段と厳しい耐薬品性の要求に対
して充分に対応することができず、一方８５重量％を超
えると、熱安定性が劣る。The bond content of the vinyl cyanide compound copolymerized in the copolymer obtained by the production method of the present invention is 33 to 85% by weight, preferably 35 to 80% by weight, more preferably 40 to 78% by weight, particularly preferably 45
~ 75% by weight, the bond content of the aromatic vinyl compound is 15
-67% by weight, preferably 20-65% by weight, more preferably 25-55% by weight, the bond content of other copolymerizable monomers is 0-30% by weight, preferably 0-20% by weight. is there. If the bond content of the vinyl cyanide compound is less than 33% by weight, it is not possible to sufficiently meet the recent demands for even more severe chemical resistance, while if it exceeds 85% by weight, the thermal stability becomes poor.
【００１０】本発明の目的とする効果を有する上記組成
の共重合体の製造方法を以下に示す。すなわち、本発明
において、連続重合を行わせる重合装置は、一般的な完
全混合型攪拌重合器を２器以上連結することによって与
えられる。反応系が実質的に均一になるような混合状態
を保持する実施形態については特に限定はしないが、通
常はリボン型攪拌翼、タービン型攪拌翼、スクリュー型
攪拌翼、錨型攪拌翼などによる攪拌混合、あるいは反応
系の外部に設けられたポンプなどによる循環混合などが
使用され、これらの組み合わせも好適である。また、第
２基目以降の重合器には、管型重合器、押出機型重合
器、ニーダー型重合器などを用いることもできる。The method for producing the copolymer having the above composition having the effects aimed at by the present invention will be described below. That is, in the present invention, a polymerization apparatus for carrying out continuous polymerization is provided by connecting two or more common complete mixing type stirring polymerization vessels. The embodiment for maintaining the mixed state such that the reaction system is substantially uniform is not particularly limited, but is usually stirred by a ribbon type stirring blade, a turbine type stirring blade, a screw type stirring blade, an anchor type stirring blade, or the like. Mixing, circulation mixing by a pump provided outside the reaction system, or the like is used, and a combination thereof is also suitable. Further, as the second and subsequent polymerization units, a tube-type polymerization unit, an extruder-type polymerization unit, a kneader-type polymerization unit and the like can be used.
【００１１】重合は、溶液重合または塊状重合、あるい
は溶液重合と塊状重合の併用系重合が挙げられる。この
うち、溶液重合では、溶剤が用いられる。溶剤として
は、通常、ラジカル重合で使用される不活性重合溶剤で
あり、例えばエチルベンゼン、トルエンなどの芳香族炭
化水素、メチルエチルケトン、アセトンなどのケトン
類、ジクロルメチレン、四塩化炭素などのハロゲン化炭
化水素、アセトニトリル、ジメチルホルムアミド、Ｎ−
メチルピロリドンなどが挙げられる。溶剤の使用量は、
全単量体１００重量部に対し、好ましくは１０〜７０重
量部、さらに好ましくは２０〜６０重量部程度である。
溶剤は、任意の重合器に供給することができる。Examples of the polymerization include solution polymerization or bulk polymerization, or combined system polymerization of solution polymerization and bulk polymerization. Of these, a solvent is used in the solution polymerization. The solvent is usually an inert polymerization solvent used in radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene, ketones such as methylethylketone and acetone, halogenated carbonization such as dichloromethylene and carbon tetrachloride. Hydrogen, acetonitrile, dimethylformamide, N-
Examples thereof include methylpyrrolidone. The amount of solvent used is
The amount is preferably 10 to 70 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of all the monomers.
The solvent can be supplied to any polymerization vessel.
【００１２】また、塊状重合は、シアン化ビニル化合物
の含有量が高い系の重合に有用であり、シアン化ビニル
化合物の分布が均一になる利点がある。また、塊状重合
において、重合系の粘度が高くなった場合には、重合途
中で例えば第２基目以降の重合器中へ溶媒を添加するの
が有効である。The bulk polymerization is useful for polymerization of a system having a high vinyl cyanide compound content and has an advantage that the distribution of the vinyl cyanide compound is uniform. Further, in bulk polymerization, when the viscosity of the polymerization system becomes high, it is effective to add a solvent to the second or subsequent polymerization vessel during the polymerization, for example.
【００１３】本発明では、第１基目の重合器に供給され
る単量体は、シアン化ビニル化合物３０〜９０重量％
（このシアン化ビニル化合物の割合を「ａ重量％」とす
る）、好ましくは３５〜８５重量％、さらに好ましくは
４０〜８０重量％、芳香族ビニル化合物１０〜７０重量
％、好ましくは１５〜６５重量％、さらに好ましくは２
０〜６０重量％、これらと共重合可能な他の単量体０〜
３０重量％、好ましくは０〜２０重量％とする。単量体
が、上記の組成範囲外であると、本発明の目的である成
形品の外観および耐薬品性、透明性が達成されない。上
記の単量体は、第１基目の重合器へ連続的あるいは回分
的に供給される。供給された単量体は、第１基目の重合
器の出口の反応物の重合転化率が３０〜８０重量％、好
ましくは３５〜７５重量％、さらに好ましくは３８〜７
０重量％になるように重合反応を行う。この重合転化率
の制御は、重合温度、平均滞留時間、開始剤量、溶剤量
などを適宜組み合わせることで調節することができる。
上記重合転化率が３０重量％未満、あるいは８０重量％
を超えると、ゲル状ポリマーの生成が多くなり、好まし
くない。In the present invention, the monomer supplied to the first polymerization unit is 30 to 90% by weight of a vinyl cyanide compound.
(The proportion of this vinyl cyanide compound is "a% by weight"), preferably 35 to 85% by weight, more preferably 40 to 80% by weight, aromatic vinyl compound 10 to 70% by weight, preferably 15 to 65%. % By weight, more preferably 2
0 to 60% by weight, other monomers copolymerizable with them 0 to
30% by weight, preferably 0 to 20% by weight. If the monomer is out of the above composition range, the appearance, chemical resistance and transparency of the molded article, which is the object of the present invention, cannot be achieved. The above-mentioned monomer is continuously or batchwise supplied to the first polymerization vessel. The monomer supplied has a polymerization conversion rate of the reaction product at the outlet of the first base polymerization vessel of 30 to 80% by weight, preferably 35 to 75% by weight, and more preferably 38 to 7% by weight.
The polymerization reaction is carried out so that the content becomes 0% by weight. The control of the polymerization conversion rate can be adjusted by appropriately combining the polymerization temperature, the average residence time, the amount of the initiator, the amount of the solvent and the like.
The polymerization conversion rate is less than 30% by weight, or 80% by weight
When it exceeds, the gelled polymer is often produced, which is not preferable.
【００１４】次いで、上記の反応物が、第２基目以降の
いずれか少なくとも１つの重合器に供給される際に、反
応物中に存在する未反応単量体中のシアン化ビニル化合
物の含有率が上記ａ重量％±２０重量％の範囲、好まし
くはａ重量％±１５重量％の範囲になるよう、芳香族ビ
ニル化合物を添加し、調整する。この添加する芳香族ビ
ニル化合物は、上記反応物に直接添加してもよく、また
反応物が供給される重合器に直接添加してもよく、さら
に両者を併用する添加方法でもよい。芳香族ビニル化合
物の添加は、連続的あるいは回分的方法で添加される。
上記の未反応単量体中のシアン化ビニル化合物の含有率
が、上記の範囲未満または範囲を超えても、シアン化ビ
ニル化合物が均一に共重合されず、得られる共重合体の
熱安定性、透明性を低下させることになり、また上記範
囲を超えると、ゲル状ポリマーが多く生成することにな
る。Then, when the above-mentioned reaction product is fed to at least one of the second and subsequent polymerization vessels, the content of the vinyl cyanide compound in the unreacted monomer present in the reaction product is contained. The aromatic vinyl compound is added and adjusted so that the rate is within the range of a% by weight ± 20% by weight, preferably a% by weight ± 15% by weight. The aromatic vinyl compound to be added may be added directly to the above reaction product, may be added directly to the polymerization vessel to which the reaction product is supplied, or may be an addition method in which both are used in combination. The aromatic vinyl compound is added continuously or batchwise.
If the content of the vinyl cyanide compound in the unreacted monomer is less than or more than the above range, the vinyl cyanide compound is not uniformly copolymerized, and the thermal stability of the resulting copolymer is high. However, the transparency is lowered, and when it exceeds the above range, a large amount of gel polymer is produced.
【００１５】第２基目以降の重合器における重合転化率
は、５０重量％以上、好ましくは５５〜９５重量％、さ
らに好ましくは５０〜９０重量％である。重合転化率が
５０重量％未満では、得られる共重合体の重合生産性が
低下する。第２基目以降の重合転化率の制御も、第１基
目と同様の方法で行うことができる。The polymerization conversion rate in the second and subsequent polymerization vessels is 50% by weight or more, preferably 55 to 95% by weight, and more preferably 50 to 90% by weight. If the polymerization conversion rate is less than 50% by weight, the polymerization productivity of the resulting copolymer will decrease. The control of the polymerization conversion rate after the second group can be performed in the same manner as in the first group.
【００１６】なお、共重合体の重合反応中に、下記一般
式（Ｉ）で表される化合物〔以下「化合物（Ｉ）」とい
う〕を添加すると、得られる共重合体の熱安定性が一段
と向上する。When a compound represented by the following general formula (I) [hereinafter referred to as "compound (I)"] is added during the polymerization reaction of the copolymer, the thermal stability of the resulting copolymer is further improved. improves.
【００１７】[0017]
【化２】 [Chemical 2]
【００１８】（式中、Ｒ1 は水素原子またはメチル基、
Ｒ2 はメチル基、ｔ−ブチル基またはｔ−アミル基、Ｒ
3 はｔ−ブチル基またはｔ−アミル基を示す。）化合物
（Ｉ）の使用量は、全単量体１００重量部に対し、好ま
しくは０．０５〜３重量部、さらに好ましくは０．１〜
２．５重量部である。また、化合物（Ｉ）の添加は、溶
剤あるいは重合に用いられる単量体に溶解して添加する
方法が好ましい。(Wherein R 1 is a hydrogen atom or a methyl group,
R 2 is a methyl group, a t-butyl group or a t-amyl group, R 2
3 represents a t-butyl group or a t-amyl group. ) The amount of compound (I) used is preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 100 parts by weight of all the monomers.
2.5 parts by weight. The compound (I) is preferably added by dissolving it in a solvent or a monomer used for polymerization.
【００１９】また、共重合体の重合反応において使用さ
れる開始剤としては、例えば有機過酸化物、アゾ化合物
などの重合開始剤を用いることができる。また、開始剤
を用いないで、熱重合することもできる。連鎖移動剤と
しては、例えばメルカプタン類、α−メチルスチレンダ
イマーなどを用いることができる。As the initiator used in the polymerization reaction of the copolymer, for example, a polymerization initiator such as an organic peroxide or an azo compound can be used. Moreover, it is also possible to carry out thermal polymerization without using an initiator. As the chain transfer agent, for example, mercaptans, α-methylstyrene dimer and the like can be used.
【００２０】重合反応における重合温度は、開始剤を用
いない熱重合方法では、好ましくは１２０〜２００℃、
重合開始剤を用いる場合には、開始剤種類によって重合
温度は異なるが、通常、５０〜１８０℃である。また、
重合器内の反応物の平均滞留時間は、好ましくは１〜５
時間、さらに好ましくは１．５〜４時間である。The polymerization temperature in the polymerization reaction is preferably 120 to 200 ° C. in the thermal polymerization method using no initiator.
When a polymerization initiator is used, the polymerization temperature varies depending on the type of the initiator, but is usually 50 to 180 ° C. Also,
The average residence time of the reactants in the polymerization vessel is preferably 1 to 5
Time, more preferably 1.5 to 4 hours.
【００２１】重合反応により得られる反応物から、溶
剤、未反応単量体などを脱溶し、共重合体を回収する方
法としては、水中へ懸濁分散させてスチームストリッピ
ングする方法、共重合体溶液を予熱し、減圧下フラッシ
ングする方法、あるいは直接ベント付き押し出し機で脱
溶する方法など、一般的な方法を選ぶことができる。Solvents, unreacted monomers, and the like are dissolved from the reaction product obtained by the polymerization reaction, and the copolymer is recovered by suspending and dispersing in water and steam stripping, copolymerization. A general method such as a method of preheating the combined solution and flushing under reduced pressure, or a method of desolving directly with an extruder with a vent can be selected.
【００２２】なお、 本発明により得られる共重合体の
固有粘度（メチルエチルケトンを溶媒として３０℃で測
定）は、０．４〜０．７５ｄｌ／ｇが好ましい。この固
有粘度が０．４ｄｌ／ｇ未満では耐衝撃性が劣り、一方
０．７５ｄｌ／ｇを超えると流動性劣る。この固有粘度
は、連鎖移動剤、重合時間、重合温度などによって制御
することができる。The intrinsic viscosity of the copolymer obtained by the present invention (measured at 30 ° C. with methyl ethyl ketone as a solvent) is preferably 0.4 to 0.75 dl / g. When the intrinsic viscosity is less than 0.4 dl / g, the impact resistance is poor, and when it exceeds 0.75 dl / g, the fluidity is poor. This intrinsic viscosity can be controlled by a chain transfer agent, polymerization time, polymerization temperature and the like.
【００２３】本発明の方法により得られる共重合体は、
シアン化ビニル化合物の結合含有率が高く、かつ優れた
品質を有することから、耐薬品性の要求の厳しい電気冷
蔵庫、冷凍庫の成形材料として、単独あるいはＡＢＳ樹
脂などの他の樹脂とのブレンド物として好適に使用され
る。The copolymer obtained by the method of the present invention is
As it has a high bond content of vinyl cyanide compound and excellent quality, it can be used alone or as a blend with other resins such as ABS resin as a molding material for electric refrigerators and freezers with severe chemical resistance requirements. It is preferably used.
【００２４】[0024]
【実施例】以下、実施例を挙げて本発明をさらに具体的
に説明する。なお、実施例中、部および％は、特に断ら
ない限り重量基準である。また、実施例中の各種評価
は、次のようにして測定した値である。EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, parts and% are based on weight unless otherwise specified. Further, various evaluations in the examples are values measured as follows.
【００２５】ゲル状ポリマー量
ポリマー溶液約２０ｇを精秤（Ａｇ）し、これをアセト
ン５００ｍｌを用い溶解させ、この溶液を０．４μｍメ
ンブランフィルター（Ｂｇ）を通してろ過を行い、１１
０℃で１時間乾燥させて、乾燥後の重量を精秤（Ｃｇ）
し、下記式より求めた。
ゲル状ポリマー量（ｐｐｍ）＝｛（Ｃ−Ｂ）／〔Ａ×固
形分濃度（％）〕｝×１０6 ＹＩ、曇値
熱安定性、透明性の指標として、射出成形機内で２５０
℃×１０分滞留し、成形して得られた試験片を、スガ試
験機（株）製、分光測色計にてＹＩ値と曇価を測定し
た。耐薬品性（フロン膨潤度）
日本合成ゴム（株）製のＡＢＳ樹脂（ＡＢＳ＃１０）と
ペレット化された共重合体を重量比で５０／５０にブレ
ンドして、射出成形で得られた試験片を、フロンガス中
に２６℃で２４時間放置し、膨潤度を測定した。 Amount of gelled polymer About 20 g of polymer solution was precisely weighed (Ag), dissolved with 500 ml of acetone, and filtered through a 0.4 μm membrane filter (Bg).
Dry at 0 ° C for 1 hour, and weigh accurately after drying (Cg)
Then, it was calculated from the following formula. Gel polymer amount (ppm) = {(C−B) / [A × solid content concentration (%)] × 10 6 YI, haze value 250 in an injection molding machine as an index of thermal stability and transparency.
The YI value and the haze value of the test piece obtained by staying at 10 ° C for 10 minutes and molding were measured with a spectrophotometer manufactured by Suga Test Instruments Co., Ltd. Chemical resistance (CFC swelling ratio) ABS resin (ABS # 10) manufactured by Japan Synthetic Rubber Co., Ltd. and pelletized copolymer were blended at a weight ratio of 50/50, and the test was obtained by injection molding. The pieces were allowed to stand in CFC gas at 26 ° C. for 24 hours, and the swelling degree was measured.
【００２６】実施例１
内容積３０リットルのリボン翼を備えた重合器２基を連
結し、表１に示す成分を第１基目の重合器に供給した。
第１基目の重合器（以下「第１重合器」あるいは「第１
基」という）の反応物は、第１重合器の外部に設けられ
たポンプにより、供給量と同量連続的に取り出して、第
２基目の重合器（以下「第２重合器」あるいは「第２
基」という）に供給した。Example 1 Two polymerization units equipped with a ribbon blade having an internal volume of 30 liters were connected, and the components shown in Table 1 were supplied to the first polymerization unit.
The first polymerization vessel (hereinafter referred to as “first polymerization vessel” or “first polymerization vessel”)
The reaction product of the "group") is continuously taken out by a pump provided outside the first polymerization unit in the same amount as the supply amount, and the second polymerization unit (hereinafter referred to as "second polymerization unit" or "second polymerization unit"). Second
Supplied as "Moto".
【００２７】[0027]
【表１】 [Table 1]
【００２８】＊）平均滞留時間は、液比重０．８８ｇ／
分としての概算値である。
なお、第１重合器におけるｔ−ドデシルメルカプタン
０．２部は、トルエン５０部のうち１０部を用い、０．
２％溶液として連続的に供給した。また、第２重合器に
おける化合物（Ｉ）０．５部は、第２重合器に供給され
るスチレン２０部のうち５部を用い、０．５％溶液とし
て連続的に供給した。*) The average residence time is a liquid specific gravity of 0.88 g /
It is an approximate value as minutes. In addition, 0.2 part of t-dodecyl mercaptan in the first polymerizer was 10 parts of 50 parts of toluene,
It was fed continuously as a 2% solution. Further, 0.5 part of compound (I) in the second polymerization vessel was continuously supplied as a 0.5% solution using 5 parts of 20 parts of styrene fed to the second polymerization vessel.
【００２９】得られた共重合体溶液は、２軸３段ベント
付き押出機に、直接、供給し、未反応単量体と溶剤を脱
揮回収して再使用するとともに、共重合体はペレットと
して回収した。連続運転開始後、３６０時間目の第２重
合器のポリマー溶液中のゲル状ポリマーの量の測定を行
った。他の物性とともに、表２に示す。The obtained copolymer solution was directly supplied to an extruder with a twin-screw three-stage vent, and the unreacted monomer and the solvent were volatilized and recovered for reuse, and the copolymer was pelletized. Was collected as. The amount of the gelled polymer in the polymer solution in the second polymerization vessel was measured 360 hours after the continuous operation was started. Table 2 shows the other physical properties.
【００３０】実施例２
第１重合器へのアクリロニトリル／スチレンの組成を、
５２／４８（部）、第２重合器へのスチレン供給量を２
５部とした以外は、実施例１と同様にして重合を行っ
た。結果を表２に示す。
実施例３
第１重合器へのアクリロニトリル／スチレンの組成を、
７０／３０（部）、第２重合器へのスチレン供給量を１
５部とし、重合溶剤としてアセトニトリル４０部、化合
物（Ｉ）２．５部を用いた以外は、実施例１と同様にし
て重合を行った。結果を表２に示す。Example 2 The composition of acrylonitrile / styrene in the first polymerization vessel was changed to
52/48 (part), 2 styrene supply to the second polymerization reactor
Polymerization was performed in the same manner as in Example 1 except that the amount was 5 parts. The results are shown in Table 2. Example 3 The composition of acrylonitrile / styrene in the first polymerization vessel was changed to
70/30 (part), the amount of styrene supplied to the second polymerization vessel is 1
Polymerization was carried out in the same manner as in Example 1 except that 5 parts were used, and 40 parts of acetonitrile and 2.5 parts of compound (I) were used as a polymerization solvent. The results are shown in Table 2.
【００３１】実施例４
重合溶剤として、メチルエチルケトン３５部を用いる以
外は、実施例１と同様にして重合を行った。結果を表２
に示す。
実施例５
開始剤として、ジクミルパーオキサイド０．０３部を用
い、重合温度を１４０℃として、各重合器での重合転化
率を所定の範囲に入るようにした以外は、実施例１と同
様にして重合を行った。結果を表２に示す。Example 4 Polymerization was carried out in the same manner as in Example 1 except that 35 parts of methyl ethyl ketone was used as the polymerization solvent. The results are shown in Table 2.
Shown in. Example 5 Same as Example 1 except that 0.03 part of dicumyl peroxide was used as an initiator, the polymerization temperature was 140 ° C., and the polymerization conversion rate in each polymerization vessel was within a predetermined range. The polymerization was carried out. The results are shown in Table 2.
【００３２】実施例６
第１重合器へのアクリロニトリル／スチレン／メチルメ
タクリレートの組成を、５６／２９／１５（部）、第２
重合器へのスチレン供給量を１５部とした以外は、実施
例１と同様にして重合を行った。結果を表２に示す。
実施例７
第１重合器へのアクリロニトリル／スチレンの組成を、
５２／４８（部）、第２重合器へのスチレン供給量を２
５部とし、化合物（Ｉ）の添加を０とした以外は、実施
例１と同様にして重合を行った。結果を表２に示す。Example 6 The composition of acrylonitrile / styrene / methylmethacrylate to the first polymerization vessel was 56/29/15 (part), second
Polymerization was performed in the same manner as in Example 1 except that the amount of styrene supplied to the polymerization vessel was 15 parts. The results are shown in Table 2. Example 7 The composition of acrylonitrile / styrene in the first polymerization vessel was changed to
52/48 (part), 2 styrene supply to the second polymerization reactor
Polymerization was carried out in the same manner as in Example 1 except that the amount of compound (I) was 5 parts. The results are shown in Table 2.
【００３３】比較例１
重合温度を１３０℃として、第１基、第２基、それぞれ
の重合転化率を２８％、４５％とした以外は、実施例１
と同様にして重合を行った。結果を表２に示す。
比較例２
第１重合器へのアクリロニトリル／スチレンの組成を、
５０／５０（部）、第２重合器へのスチレン供給量を０
部とした以外は、実施例１と同様にして重合を行った。
結果を表２に示す。Comparative Example 1 Example 1 was repeated except that the polymerization temperature was 130 ° C. and the conversion rates of the first group and the second group were 28% and 45%, respectively.
Polymerization was carried out in the same manner as in. The results are shown in Table 2. Comparative Example 2 The composition of acrylonitrile / styrene in the first polymerization vessel was changed to
50/50 (part), styrene supply to the second polymerization vessel is 0
Polymerization was performed in the same manner as in Example 1 except that the parts were used.
The results are shown in Table 2.
【００３４】比較例３
実施例１の組成で、第２重合器のスチレン供給量を６５
部とした以外は、実施例１と同様にして重合を行った。
結果を表２に示す。
比較例４
第１重合器へのアクリロニトリル／スチレンの組成を、
２０／８０（部）、第２重合器へのスチレン供給量を０
部とした以外は、実施例１と同様にして重合を行った。
結果を表２に示す。Comparative Example 3 The composition of Example 1 was used, and the amount of styrene fed to the second polymerization vessel was 65.
Polymerization was performed in the same manner as in Example 1 except that the parts were used.
The results are shown in Table 2. Comparative Example 4 The composition of acrylonitrile / styrene in the first polymerization vessel was changed to
20/80 (part), styrene supply to the second polymerization vessel is 0
Polymerization was performed in the same manner as in Example 1 except that the parts were used.
The results are shown in Table 2.
【００３５】比較例５
第１重合器へのアクリロニトリル／スチレンの組成を、
９３／７（部）、溶剤をアセトニトリルとした以外は、
実施例１と同様ににして重合を行った。結果を表２に示
す。
比較例６
第１重合器の重合温度を１６５℃として、第１重合器の
重合転化率を８５％とした以外は、実施例１と同様にし
て重合を行った。結果を表２に示す。Comparative Example 5 The composition of acrylonitrile / styrene in the first polymerization vessel was changed to
93/7 (part), except that the solvent was acetonitrile,
Polymerization was carried out in the same manner as in Example 1. The results are shown in Table 2. Comparative Example 6 Polymerization was performed in the same manner as in Example 1 except that the polymerization temperature of the first polymerization vessel was 165 ° C. and the polymerization conversion rate of the first polymerization vessel was 85%. The results are shown in Table 2.
【００３６】[0036]
【表２】 [Table 2]
【００３７】＊１）ＡＮ＝アクリロニトリル ＊２）ＳＴ＝スチレン ＊３）ＴＤＭ＝ｔ−ドデシルメルカプタン ＊４）ＤＣＰ＝ジクミルパーオキサイド ＊５）ＡＣＮ＝アセトニトリル ＊６）ＭＥＫ＝メチルエチルケトン ＊７）ＭＭＡ＝メチルメタクリレート* 1) AN = acrylonitrile * 2) ST = styrene * 3) TDM = t-dodecyl mercaptan * 4) DCP = dicumyl peroxide * 5) ACN = acetonitrile * 6) MEK = methyl ethyl ketone * 7) MMA = methyl methacrylate
【００３８】表２から明らかなように、実施例１〜６に
おいては、スチレン−アクリロニトリル系共重合体で２
基以上の重合器を用い、第２基目以降の重合器へスチレ
ン、さらに必要に応じて化合物（Ｉ）を添加することに
より、銀条（シルバーストリーク）、色調、透明性、耐
薬品性の優れた共重合体が得られることが分かる。As is apparent from Table 2, in Examples 1 to 6, the styrene-acrylonitrile copolymer was used as
By using styrene or more polymerizers and adding styrene, and if necessary, compound (I) to the second and subsequent polymerizers, silver strip (silver streak), color tone, transparency, chemical resistance It can be seen that an excellent copolymer can be obtained.
【００３９】これに対し、比較例１は、重合温度を１３
０℃として、第１基、第２基それぞれの重合転化率が本
発明の範囲未満の例であり、得られる共重合体を射出成
形した試験片では、銀条（シルバーストリーク）の発生
が著しく、透明性に劣る。また、比較例２は、第２基目
に供給される反応物中の未反応アクリロニトリル含有率
が本発明の範囲を超えており、ゲル状ポリマーは低下せ
ず、色調に劣る。On the other hand, in Comparative Example 1, the polymerization temperature was 13
This is an example in which the polymerization conversion rate of each of the first group and the second group at 0 ° C. is less than the range of the present invention, and in the test piece obtained by injection molding of the obtained copolymer, silver streaks (silver streaks) are remarkably generated. , Inferior in transparency. In Comparative Example 2, the content of unreacted acrylonitrile in the reaction product supplied to the second group exceeds the range of the present invention, the gelled polymer does not deteriorate, and the color tone is poor.
【００４０】比較例３は、第２基目以降の未反応単量体
中のアクリロニトリル含有率が本発明の範囲外のもので
あり、ゲル状ポリマーは低下せず、透明性に劣る。比較
例４は、第１重合器へのアクリロニトリル／スチレンの
供給量が本発明の範囲外のものであるため、耐薬品性に
劣る。In Comparative Example 3, the acrylonitrile content in the unreacted monomers after the second group is out of the range of the present invention, the gelled polymer does not decrease, and the transparency is poor. Comparative Example 4 is inferior in chemical resistance because the supply amount of acrylonitrile / styrene to the first polymerization vessel is outside the range of the present invention.
【００４１】比較例５は、第１重合器へのアクリロニト
リル／スチレンの供給量が本発明の範囲外のものであ
り、ゲル状ポリマーは低下せず、透明性が劣る。比較例
６は、第１重合器の重合転化率が本発明の範囲外のもの
であり、ゲル状ポリマーは低下せず、透明性が劣る。In Comparative Example 5, the amount of acrylonitrile / styrene supplied to the first polymerization vessel was out of the range of the present invention, the gel polymer did not deteriorate, and the transparency was poor. In Comparative Example 6, the polymerization conversion rate of the first polymerization vessel is out of the range of the present invention, the gelled polymer does not decrease, and the transparency is poor.
【００４２】[0042]
【発明の効果】本発明のスチレン−アクリロニトリル系
共重合体の製造方法によれば、長期間連続的に安定して
重合が可能であり、これによって得られる高アクリロニ
トリル含有率の共重合体は、成形品の成形材料として使
用した場合、銀条（シルバーストリーク）、色調（熱安
定性）、加工性、透明性、耐薬品性に優れており、その
工業的意義は極めて大きいものである。EFFECT OF THE INVENTION According to the method for producing a styrene-acrylonitrile-based copolymer of the present invention, it is possible to continuously and stably polymerize for a long period of time. When used as a molding material for a molded product, it has excellent silver strip (silver streak), color tone (heat stability), processability, transparency, and chemical resistance, and its industrial significance is extremely large.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭47−42986（ＪＰ，Ａ) 特開 昭48−31285（ＪＰ，Ａ) 特開 昭63−178114（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 2/00 - 2/60 C08F 20/30 C08F 212/10 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-47-42986 (JP, A) JP-A-48-31285 (JP, A) JP-A-63-178114 (JP, A) (58) Field (Int.Cl. 7 , DB name) C08F 2/00-2/60 C08F 20/30 C08F 212/10
Claims (2)
８５重量％、芳香族ビニル化合物の含有率が１５〜６７
重量％およびこれらと共重合可能な他の単量体の含有率
が０〜３０重量％である共重合体を、溶液重合および／
または塊状重合で製造する方法であって、２基以上の重
合器を連結した重合装置を用い、第１基目の重合器にシ
アン化ビニル化合物３０〜９０重量％（この割合を「ａ
重量％」とする）、芳香族ビニル化合物１０〜７０重量
％およびこれらと共重合可能な他の単量体０〜３０重量
％からなる単量体を連続的にまたは回分的に供給し、第
１基目の重合器の出口の反応物の重合転化率が３０〜８
０重量％まで重合し、次いで第２基目以降のいずれかの
少なくとも１つの重合器へ供給する際に、芳香族ビニル
化合物を添加して、反応物中に存在する未反応単量体中
のシアン化ビニル化合物の含有率がａ重量％±２０重量
％の範囲になるようにし、第２基目以降の重合器で重合
転化率が５０重量％以上になるように重合する、ことを
特徴とする共重合体の製造方法。1. The content of vinyl cyanide compound is 33-.
85 wt%, aromatic vinyl compound content 15-67
A copolymer having a content of 0% to 30% by weight and other monomers copolymerizable therewith is solution polymerized and / or
Alternatively, it is a method for producing by bulk polymerization, wherein a polymerization device in which two or more polymerization units are connected is used, and 30 to 90% by weight of the vinyl cyanide compound is contained in the first polymerization unit (this ratio is defined as "a").
%)), 10 to 70% by weight of an aromatic vinyl compound, and 0 to 30% by weight of another monomer copolymerizable therewith, continuously or batchwise, The polymerization conversion rate of the reaction product at the outlet of the first polymerization vessel is 30 to 8
When polymerized to 0% by weight and then fed to at least one of the second and subsequent polymerizers, an aromatic vinyl compound was added so that the unreacted monomer in the reaction product was The content of the vinyl cyanide compound is set within the range of a% by weight ± 20% by weight, and the polymerization is performed so that the polymerization conversion rate becomes 50% by weight or more in the second and subsequent polymerization vessels. A method for producing a copolymer.
れる化合物を、全単量体１００重量部に対し、０．０５
〜３重量部添加する請求項１記載の共重合体の製造方
法。 【化１】 （式中、Ｒ1 は水素原子またはメチル基、Ｒ2 はメチル
基、ｔ−ブチル基またはｔ−アミル基、Ｒ3 はｔ−ブチ
ル基またはｔ−アミル基を示す。）2. In the polymerization step, the compound represented by the general formula (I) is added in an amount of 0.05 based on 100 parts by weight of all the monomers.
The method for producing the copolymer according to claim 1, wherein the amount is 3 to 3 parts by weight. [Chemical 1] (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a methyl group, a t-butyl group or a t-amyl group, and R 3 represents a t-butyl group or a t-amyl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13981393A JP3416988B2 (en) | 1993-05-20 | 1993-05-20 | Method for producing copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13981393A JP3416988B2 (en) | 1993-05-20 | 1993-05-20 | Method for producing copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06329703A JPH06329703A (en) | 1994-11-29 |
| JP3416988B2 true JP3416988B2 (en) | 2003-06-16 |
Family
ID=15254051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13981393A Expired - Fee Related JP3416988B2 (en) | 1993-05-20 | 1993-05-20 | Method for producing copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3416988B2 (en) |
-
1993
- 1993-05-20 JP JP13981393A patent/JP3416988B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06329703A (en) | 1994-11-29 |
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