JPS60206848A - Preparation of expandable thermoplastic copolymer particle - Google Patents
Preparation of expandable thermoplastic copolymer particleInfo
- Publication number
- JPS60206848A JPS60206848A JP6463184A JP6463184A JPS60206848A JP S60206848 A JPS60206848 A JP S60206848A JP 6463184 A JP6463184 A JP 6463184A JP 6463184 A JP6463184 A JP 6463184A JP S60206848 A JPS60206848 A JP S60206848A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- weight
- expandable thermoplastic
- thermoplastic copolymer
- particles
- 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.)
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Abstract
Description
【発明の詳細な説明】
本発明は、耐熱性・耐溶剤性に優れ、かつ発泡性・成形
性の良好な発泡性熱可塑性共重合体粒子の工業的に有利
な製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an industrially advantageous method for producing expandable thermoplastic copolymer particles having excellent heat resistance and solvent resistance, and good foamability and moldability.
発泡性重合体粒子としては、発泡性ポリスチレン樹脂粒
子がよく知られており、該粒子を用いることによって安
価で容易に型発泡成形体を得ることが出来る。しかしな
がら、該発泡成形体は、重合物を構成する単量体がスチ
レンであるため、比較的温度の高い配管の保温材、屋根
用断熱材、自動車部材、ソーラーシステム用保温材等の
耐熱性を要求される用途には使用できない欠点がある。As expandable polymer particles, expandable polystyrene resin particles are well known, and by using these particles, a molded foamed article can be easily obtained at low cost. However, since the monomer constituting the polymer is styrene, the foam molded product has poor heat resistance for use in relatively high-temperature pipe insulation materials, roof insulation materials, automobile parts, solar system insulation materials, etc. There are drawbacks that prevent it from being used for the required purpose.
また、特に自動車部材等において、他素材と貼り合わせ
て用いる場合、耐溶剤性が劣るので、接着材の選択が困
難であるという欠点も有している。In addition, when used in combination with other materials, particularly in automobile parts, etc., it also has the disadvantage that it is difficult to select an adhesive because of its poor solvent resistance.
本発明者らは、実用性に於て、充分な耐熱性と耐溶剤性
を有する発泡性熱可塑性重合体粒子を得るには、重合体
を構成する単量体組成として、アルファメチルスチレン
１０５以上、かつアクリロニトリルを５％以上含有して
なる共重合体粒子を得、この樹脂粒子に易揮発性発泡剤
を含有せしめる必要があると考えた。しかるに、かかる
観点に基づいて、従来アルファメチルスチレンを上記の
如く多量使用し、耐熱性の優れた共重合体を懸濁重合に
より得るには、ｔ−ブチルパーオキシベンゾエート、ジ
−ｔ−ブチルパーオキサイド、ｔ−ブチルパーオキシア
セテート等の有機過酸化物を重合開始剤として用いる方
法があるが、これらの開始剤を用いる方法においては、
重合温度の如何に拘らず、はなはだ多量用いることが必
要であり、従って得られる共重合体は、その重合度が極
度に低くなり、該共重合体粒子に易揮発性発泡剤を含浸
せしめて発泡性熱可塑性樹脂粒子となしたものは、発泡
性が著しく悪く、満足な発泡成形体が得難いのみならず
、その成形体も弱いものになってしまう。更に、これら
の開始剤を用いて重合度を上げる為に、その使用量を少
なくすると、いわゆるｄｅａｄ ｅｎｄ重合となり、工
業的に高転化率は得られず、従って満足な発泡成形体は
得難い。又、ベンゾイルパーオキサイドの如き有機過酸
化物を使用すれば、これに適する重合温度に於ても工業
的に利用し得る高転化率の共重合体は全く得られないの
である。The present inventors have determined that in order to obtain expandable thermoplastic polymer particles having sufficient heat resistance and solvent resistance for practical use, the monomer composition constituting the polymer should be alpha methylstyrene of 105 or more. It was considered necessary to obtain copolymer particles containing 5% or more of acrylonitrile, and to incorporate a readily volatile blowing agent into the resin particles. However, based on this viewpoint, in order to obtain a copolymer with excellent heat resistance by suspension polymerization using a large amount of alpha methylstyrene as described above, t-butyl peroxybenzoate, di-t-butyl peroxybenzoate, di-t-butyl peroxybenzoate, etc. There are methods using organic peroxides such as oxide and t-butyl peroxyacetate as polymerization initiators, but in methods using these initiators,
Regardless of the polymerization temperature, it is necessary to use a very large amount, and the resulting copolymer has an extremely low degree of polymerization. The foaming property of the thermoplastic resin particles is extremely poor, and not only is it difficult to obtain a satisfactory foamed molded product, but the molded product is also weak. Furthermore, if the amount of these initiators used is reduced in order to increase the degree of polymerization, so-called dead end polymerization will occur, making it impossible to obtain a high conversion rate industrially and, therefore, making it difficult to obtain a satisfactory foamed molded product. Furthermore, if an organic peroxide such as benzoyl peroxide is used, it is impossible to obtain a copolymer with a high conversion rate that can be used industrially even at an appropriate polymerization temperature.
一方、高重合度で、かつ高転化率のアルファメチルスチ
レン−アクリロニトリル系共重合体を得る方法として乳
化重合法があるが、この方法によって発泡性熱可塑性重
合体粒子を製造するには、特開昭５７−６５７８５に見
られるごとく、乳化重合した後、凝固、ペレット化を行
ない、得られたペレットに発泡剤含浸を行なうという極
めて煩雑なプロセスが必要となり、製造コストが高くな
るのみならず、得られる樹脂には乳化剤、凝固剤等が多
量混入してしまう為、発泡性、強度等の劣ったものしか
得られないという欠点を有する。On the other hand, emulsion polymerization is a method for obtaining alpha-methylstyrene-acrylonitrile copolymers with a high degree of polymerization and a high conversion rate. As seen in Sho 57-65785, an extremely complicated process of emulsion polymerization, coagulation, pelletization, and impregnation of the resulting pellets with a blowing agent is required, which not only increases production costs but also reduces yield. Since the resulting resin contains a large amount of emulsifiers, coagulants, etc., it has the disadvantage that only products with poor foamability, strength, etc. can be obtained.
本発明者等は、かかる欠点に鑑み鋭意研究をした結果、
特定のアゾ系開始剤を用い、アクリロニトリルを併用す
ることによって、多量のアルファメチルスチレンを用い
ても高重合度、かつ高転化率の共重合体が得られる懸濁
重合方法を見出し、得られる共重合体粒子に易揮発性発
泡剤を含浸せしめることによって耐熱性に優れた発泡性
熱可塑性共重合体粒子を得ることに成功し、本発明をな
すに到った。As a result of intensive research in view of these shortcomings, the present inventors found that
We have discovered a suspension polymerization method that uses a specific azo initiator and acrylonitrile to obtain a copolymer with a high degree of polymerization and a high conversion rate even when using a large amount of alpha methylstyrene. By impregnating polymer particles with an easily volatile blowing agent, we succeeded in obtaining expandable thermoplastic copolymer particles with excellent heat resistance, and thus achieved the present invention.
すなわち本発明は、アルファメチルスチレン１０〜８０
重量％、アクリロニトリル５〜５０重量％、更にスチレ
ン、クロルスチレン、パラメチルスチレン、ｔ−ブチル
スチレン、アクリル酸エステル、メタクリル酸エステル
から選ばれた少なくとも１種の化合物０〜７０重量％の
使用割合にある単量体を用い、１０時間半減期温度が５
０〜１３０°Ｃのアゾ系開始剤を使用して、重合温度８
０〜１５０°Ｃで共重合を行なわせ、重合中又は重合後
、易揮発性発泡剤を含浸せしめることを特徴とする発泡
性熱可塑性共重合体粒子製造の方法を要旨とする。That is, the present invention uses alpha methylstyrene 10 to 80
% by weight, 5 to 50% by weight of acrylonitrile, and further 0 to 70% by weight of at least one compound selected from styrene, chlorostyrene, paramethylstyrene, t-butylstyrene, acrylic ester, and methacrylic ester. Using a certain monomer, the 10-hour half-life temperature is 5.
Polymerization temperature 8 using an azo initiator between 0 and 130°C
The gist of the present invention is a method for producing expandable thermoplastic copolymer particles characterized by carrying out copolymerization at 0 to 150°C and impregnating an easily volatile blowing agent during or after the polymerization.
本発明に使用されるアルファメチルスチレンの量は１０
〜８０重量％の範囲で、所望する耐熱性と発泡倍率によ
って決められるが、１０重量％未満であると耐熱性向上
の効果が見られなくなり、８０重量％をこえると重合転
化率が低下し、樹脂中に多量の単量体が残って耐熱性が
悪化する。The amount of alpha methylstyrene used in the present invention is 10
It is determined in the range of ~80% by weight depending on the desired heat resistance and expansion ratio, but if it is less than 10% by weight, the effect of improving heat resistance will not be seen, and if it exceeds 80% by weight, the polymerization conversion rate will decrease. A large amount of monomer remains in the resin, resulting in poor heat resistance.
５０倍発発泡形体で１００°Ｃの耐熱性を得る為には、
アルファメチルスチレン２０〜５０重量％を用いる必要
があり、５〜１５倍発泡成形体で１１０°Ｃの耐熱性を
得る為には５０〜８０重量％のアルファメチルスチレン
を用いる必要がある。In order to obtain heat resistance of 100°C with a 50 times expanded foam,
It is necessary to use 20 to 50% by weight of alpha methylstyrene, and in order to obtain a heat resistance of 110°C with a 5 to 15 times foamed product, it is necessary to use 50 to 80% by weight of alpha methylstyrene.
又、本発明に使用されるアクリロニｌ−ＩＪルは、組成
物の重合転化率を向上させる為、及び耐油性を発揮させ
る為に必要である。その量が５重量％未満では、組成物
の重合転化率が低くなり、かつ耐油性において効果が発
揮できなくなり好ましくない。又、５０重量％をこえて
用いても重合転化率は変らず、樹脂が黄褐色に着色する
ので好ましくない。Further, acrylonyl-IJ used in the present invention is necessary to improve the polymerization conversion rate of the composition and to exhibit oil resistance. If the amount is less than 5% by weight, the polymerization conversion rate of the composition will be low and the oil resistance will not be effective, which is not preferable. Further, even if it is used in an amount exceeding 50% by weight, the polymerization conversion rate does not change and the resin is colored yellowish brown, which is not preferable.
アルファメチルスチレン、アクリロニトリル以外の単量
体としては、スチレン、クロルスチレン、パラメチルス
チレン、ｔ−ブチルスチレン等の各種置換スチレン、メ
チルアクリレートエチルアクリレート、ブチルアクリレ
ート等のアクリル酸エステル、メチルメタクリレート、
エチルメタクリレートブチルメタクリレート等のメタク
リル酸エステルの中の１種又は２種以上を適宜用いるこ
とができる。Monomers other than alpha methylstyrene and acrylonitrile include styrene, various substituted styrenes such as chlorostyrene, paramethylstyrene, and t-butylstyrene, acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, methyl methacrylate,
One or more methacrylic esters such as ethyl methacrylate butyl methacrylate can be used as appropriate.
本発明に用いられる開始剤の選択は、重合度が高く、か
つ高い重合転化率の重合体を効率よく得る為に重要であ
る。重合転化率が低く単量体が５％以上樹脂中に残存し
ている場合、満足な発泡成形体を得ることが困難であり
、かろうじて発泡成形体を得ることが出来ても著しく耐
熱性の悪いものになってしまう。かかる観点から、使用
されるべき開始剤としては、１０時間半減期温度が５０
〜１３０°Ｃのアゾ系開始剤を用いることが必要である
。かかる開始剤としては各種あるが、１．１−アゾビス
シクロヘキサン−１−カルボニトリル、２−ｔ−ブチル
アゾ−２−シアノプロパン、２−ｔ−ブチルアゾ−２−
シアノブタン、１−ｔ−ブチルアゾ−１−シアノシクロ
ヘキサンが好適である。これらの開始剤の使用量は、用
いる単量体に対して０．０５〜３．０重量％が好ましい
。０．０５重量％以下では工業的に実用性のある重合転
化率が全く得られないか、もしくは長時間を要し、著し
く生産性の悪いものとなってしまい、また３、０重量％
以上では分子量が著しく低下し、満足な発泡成形が行な
えないか、もしくはかろうじて発泡成形が行なえても強
度が大巾に劣った発泡成形体しか得られない。Selection of the initiator used in the present invention is important in order to efficiently obtain a polymer with a high degree of polymerization and a high polymerization conversion rate. If the polymerization conversion rate is low and 5% or more of the monomer remains in the resin, it is difficult to obtain a satisfactory foam molded product, and even if a foam molded product can be obtained, the heat resistance is extremely poor. It becomes something. From this point of view, the initiator to be used should have a 10-hour half-life temperature of 50
It is necessary to use an azo initiator at ~130°C. There are various types of such initiators, including 1,1-azobiscyclohexane-1-carbonitrile, 2-t-butylazo-2-cyanopropane, and 2-t-butylazo-2-
Cyanobutane, 1-t-butylazo-1-cyanocyclohexane are preferred. The amount of these initiators used is preferably 0.05 to 3.0% by weight based on the monomers used. If it is less than 0.05% by weight, an industrially practical polymerization conversion rate will not be obtained at all, or it will take a long time, resulting in extremely poor productivity;
If the molecular weight is above that, the molecular weight is significantly lowered, and satisfactory foam molding cannot be carried out, or even if foam molding can be carried out, only a foam molded product with significantly inferior strength can be obtained.
本発明における開始剤を用いる場合の重合温度は８０〜
１５０°Ｃが好ましい。８０°Ｃ未満では重合転化率が
極めて低くなり、また１５０’Ｃをこえると分子量が低
下して満足な発泡成形体が得難い。The polymerization temperature when using an initiator in the present invention is 80~
150°C is preferred. If it is less than 80°C, the polymerization conversion rate will be extremely low, and if it exceeds 150'C, the molecular weight will decrease and it will be difficult to obtain a satisfactory foam molded product.
本発明に於て、かかる発泡性熱可塑性共重合体粒子を得
る方法としては懸濁重合法が採用される。In the present invention, a suspension polymerization method is employed as a method for obtaining such expandable thermoplastic copolymer particles.
乳化重合法に於ては、先に述べたごとくプロセスの煩雑
さによるコストアップと、乳化剤、凝固剤の混入による
品質の低下があり、塊状重合法に於ては、重合後ペレッ
ト化を行なった後、発泡剤含浸を行なわなければならな
いというプロセスの煩雑さの点で懸濁重合法に劣ってい
る。As mentioned earlier, in the emulsion polymerization method, there is an increase in cost due to the complexity of the process and a decrease in quality due to the contamination of emulsifiers and coagulants.In the bulk polymerization method, pelletization is performed after polymerization. It is inferior to the suspension polymerization method in terms of the complexity of the process, which requires subsequent impregnation with a blowing agent.
懸濁重合に用いられる分散剤としては、ポリビニルアル
コール、ポリビニルピロリドン、メチルセルロース等の
有機分散剤；第三リン酸カルシウム、ピロリン酸カルシ
ウム、ケイ酸ソーダ、酸化亜鉛、炭酸マグネシウム等の
無機分散剤等を用いることが出来るが、無機分散剤を用
いる場合には、アルキルベンゼンスルフオン酸ソータ、
α−オレフィンスルフオン酸ソーダ等のアニオン界面活
性剤を用いることにより分散剤の効果は著しく良好とな
る。分散剤を用いて上記組成の共重合体粒子を懸濁重合
にて得ようとする場合、粒子径が非常に小さくなってし
まう傾向にあり、比較的大粒子を得ようとして分散剤を
減少すれば、重合後半に懸濁異常を起こして、所望する
比較的大粒子径の粒子を得ることが困難である。従って
、所望する粒子径の粒子を得ようとする場合には、重合
初期に少量の分散剤を用いて重合を行ない、重合後半に
分散剤を追加することが好ましい。As dispersants used in suspension polymerization, organic dispersants such as polyvinyl alcohol, polyvinylpyrrolidone, and methylcellulose; inorganic dispersants such as tricalcium phosphate, calcium pyrophosphate, sodium silicate, zinc oxide, and magnesium carbonate can be used. However, when using an inorganic dispersant, alkylbenzenesulfonic acid sorter,
By using an anionic surfactant such as sodium α-olefin sulfonate, the effect of the dispersant becomes significantly better. When trying to obtain copolymer particles with the above composition by suspension polymerization using a dispersant, the particle size tends to become very small, and it is difficult to reduce the amount of the dispersant in order to obtain relatively large particles. For example, suspension abnormalities occur in the latter half of polymerization, making it difficult to obtain particles with a relatively large particle size as desired. Therefore, in order to obtain particles with a desired particle size, it is preferable to carry out the polymerization using a small amount of dispersant at the beginning of the polymerization, and to add the dispersant at the latter half of the polymerization.
本発明に用いられる易揮発性発泡剤としては、プロパン
、ブタン、ペンタン等の脂肪族炭化水素るシクロブタン
、シクロペンタン、シクロヘキサン等の環式脂肪族炭化
水素、及びトリクロルフルオルメタン、ジクロルフルオ
ルメタン、シクロルジフルオルメタン、メチルクロライ
ド、ジクロルテトラフルオルメタン、エチルクロライド
等のハロゲン化炭化水素があげられる。これら発泡剤の
用いられるべき量は、所望する発泡成形体の発泡倍率に
よって異なるが、２重量％から１５重量％を含有させる
ことにより２倍から１００倍の発泡成形体を得ることが
可能である。しかして、これらの発泡剤を添加する時期
は、重合中あるいは重合後のいずれの時期でもよい。Easily volatile blowing agents used in the present invention include aliphatic hydrocarbons such as propane, butane, and pentane, cycloaliphatic hydrocarbons such as cyclobutane, cyclopentane, and cyclohexane, and trichlorofluoromethane and dichlorofluorocarbons. Examples include halogenated hydrocarbons such as methane, cyclodifluoromethane, methyl chloride, dichlorotetrafluoromethane, and ethyl chloride. The amount of these blowing agents to be used varies depending on the desired expansion ratio of the foamed molded product, but by containing 2 to 15% by weight, it is possible to obtain a foamed molded product that is 2 to 100 times larger. . These blowing agents may be added either during or after polymerization.
一方、本発明において、高度に発泡した成形体を目的と
する場合には、トルエン、キシレン、エチルベンゼン、
ヘプタン、オクタン等の溶剤逼スチレン、アルファメチ
ルスチレン、アクリロニトリル等の単量体；又はフタル
酸エステル、アジピン酸エステル等の可塑剤を、該発泡
性熱可塑性共重合体粒子中に含有せしめることが好まし
い。これらの溶剤、単量体、可塑剤を含有せしめる方法
としては、あらかじめ単量体に混合して、重合せしめる
方法、発泡剤含浸と同時に含浸せしめる方法等がある。On the other hand, in the present invention, when the purpose is a highly foamed molded article, toluene, xylene, ethylbenzene,
It is preferable that the expandable thermoplastic copolymer particles contain a solvent such as heptane or octane, a monomer such as styrene, alpha methylstyrene, or acrylonitrile; or a plasticizer such as phthalate or adipate. . Methods for incorporating these solvents, monomers, and plasticizers include a method in which they are mixed with the monomers in advance and polymerized, a method in which they are impregnated simultaneously with the impregnation with the blowing agent, and the like.
又、単量体を含有せしめる方法としては、重合後、未反
応の単量体を残こすことになるが、その残存量のコント
ロールが難かしい。Furthermore, the method of containing monomers leaves unreacted monomers after polymerization, but it is difficult to control the remaining amount.
これら溶剤、可塑剤の使用量は３重量％以下であること
が好ましい。The amount of these solvents and plasticizers used is preferably 3% by weight or less.
かくして得られた発泡性熱可塑性樹脂粒子は、水蒸気、
熱風等の加熱媒体により所望する倍率まで予備発泡せし
めた後、閉塞し得るが密閉し得ない型中に充填され、水
蒸気等の加熱媒体によって再び加熱することによって、
所望の形状を有する耐熱性発泡体となし得る。The expandable thermoplastic resin particles obtained in this way are exposed to water vapor,
After pre-foaming to a desired magnification with a heating medium such as hot air, the foam is filled into a mold that can be closed but cannot be sealed, and heated again with a heating medium such as water vapor.
It can be made into a heat-resistant foam having a desired shape.
以下、本発明を実施例にて説明する。The present invention will be explained below with reference to Examples.
実施例１
撹拌機付きオートクレーブに水１１０重量部、第三リン
酸カルシウム０．０８重量部、ドデシルベンゼンスルフ
オン酸ソーダ０００３重量部、塩化す） ＩＪウム０．
２重量部を入れ、次いで撹拌状態で１．１−アゾビスシ
クロヘキサン−１−カルボニトリル０．５重量部と、ト
ルエン１．０重量部を溶解したアルファメチルスチレン
３０重量部、アクリロニトリル２０重量部、スチレン５
０重量部の混合系単量体を該系に導入し、懸濁状態とし
、直ちに１００°Ｃに昇温し、３時間後に第三リン酸カ
ルシウム０．３重量部を追加した。その後、更に４時間
の重合を行なった後、更に１１５°Ｃに昇温して３時間
の後重合を行なった。得られた樹脂の重合転化率は９９
．４％であった。次いで、１００’Ｃに温度を下げ、ブ
タン１０重量部を加え、１００°Ｃで８時間の発泡剤含
浸を行なった。得られた発泡性熱可塑性共重合体を水蒸
気で加熱して見掛倍率５０倍に予備発泡した後、閉塞し
得るが密閉し得ない金型に充填し、水蒸気で加熱するこ
とにより４５０×３０αＸ２Ｇの板状発泡成形体を得た
。Example 1 In an autoclave equipped with a stirrer, 110 parts by weight of water, 0.08 parts by weight of tribasic calcium phosphate, 0.03 parts by weight of sodium dodecylbenzenesulfonate, and 0.00 parts by weight of sodium chloride) were added.
2 parts by weight of alpha methylstyrene, 20 parts by weight of acrylonitrile, and 0.5 parts by weight of 1.1-azobiscyclohexane-1-carbonitrile and 1.0 parts by weight of toluene were dissolved under stirring. Styrene 5
0 parts by weight of mixed monomers were introduced into the system to form a suspension, the temperature was immediately raised to 100°C, and 3 hours later, 0.3 parts by weight of tribasic calcium phosphate was added. After that, polymerization was carried out for an additional 4 hours, and then the temperature was further raised to 115°C, and post-polymerization was carried out for 3 hours. The polymerization conversion rate of the obtained resin was 99
．． It was 4%. Next, the temperature was lowered to 100'C, 10 parts by weight of butane was added, and blowing agent impregnation was carried out at 100C for 8 hours. The obtained expandable thermoplastic copolymer is heated with steam to pre-foam to an apparent magnification of 50 times, then filled into a mold that can be closed but cannot be sealed, and heated with steam to form a mold of 450×30α×2G. A plate-shaped foam molded product was obtained.
この成形体を１００°Ｃの熱風式均熱乾燥機内に１週間
放置した後の、初期寸法に対する寸法変化率は、−１，
５％であった。After this molded body was left in a hot air soaking dryer at 100°C for one week, the dimensional change rate with respect to the initial dimension was -1,
It was 5%.
実施例２〜４
実施例１において、ｌ、１−アゾビスシクロヘキサン−
１−カルボニトリルを、夫々、表−１に示す物質と重合
温度に変えた以外は実施例１と同様に実施した。結果を
表−１に示す。Examples 2 to 4 In Example 1, l,1-azobiscyclohexane-
The same procedure as in Example 1 was carried out except that 1-carbonitrile was changed to the substance and polymerization temperature shown in Table 1, respectively. The results are shown in Table-1.
比較例１
実施例１において、１．１−アゾビスシクロヘキサン−
１−カルボニトリルをベンゾイル／ Ｘ６−オキサイド
に変え、９０°Ｃで７時間の重合を行なったが、重合転
化率は７８％までしか上がらず、発泡成形体を得るに到
らなかった。Comparative Example 1 In Example 1, 1.1-azobiscyclohexane-
Although 1-carbonitrile was changed to benzoyl/X6-oxide and polymerization was carried out at 90°C for 7 hours, the polymerization conversion rate increased only to 78%, and a foamed molded product could not be obtained.
実施例５
単量体組成をアルファメチルスチレン５０重量部、アク
リロニトリル２５重量部、スチレン２５重量部とした以
外は実施例１と同様にして発泡成形体を得た。この成形
体を１００°Ｃの熱風式均熱乾燥機内に１週間放置した
後の、初期寸法に対する寸法変化率は、−１，８％であ
った。Example 5 A foam molded product was obtained in the same manner as in Example 1 except that the monomer composition was 50 parts by weight of alpha methylstyrene, 25 parts by weight of acrylonitrile, and 25 parts by weight of styrene. After this molded body was left in a hot air soaking dryer at 100°C for one week, the dimensional change rate with respect to the initial size was -1.8%.
表−１
×重合転化率が低くかった為、発泡剤含浸を行なわなか
った。従って、成形体は得られず、耐熱試験も行なわな
かった。Table 1 × Since the polymerization conversion rate was low, impregnation with a blowing agent was not performed. Therefore, no molded body was obtained and no heat resistance test was conducted.
Claims (3)
リロニトリル５〜５０重量％、更にスチレン、クロルス
チレン、パラメチルスチレン、ｔ−ブチルスチレン、ア
クリル酸エステル、メタクリル酸エステルから選ばれた
少なくとも１種以上の化合物０〜７０重量％の使用割合
にある単量体を用い、１０時間半減期温度が５０〜１３
０’Ｃのアゾ系開始剤を使用して、重合温度８０−１５
０°Ｃで共重合を行なわせ、重合中又は重合後、易揮発
性発泡剤を含浸せしめることを特徴とする発泡性熱可塑
性共重合体粒子製造の方法。(1) 10 to 80% by weight of alpha methyl methyleph, 5 to 50% by weight of acrylonitrile, and at least one member selected from styrene, chlorostyrene, paramethylstyrene, t-butylstyrene, acrylic ester, and methacrylic ester Using monomers at a usage rate of 0 to 70% by weight, the compound has a 10-hour half-life temperature of 50 to 13%.
Polymerization temperature 80-15 using 0'C azo initiator
A method for producing expandable thermoplastic copolymer particles, which comprises copolymerizing at 0°C and impregnating the particles with an easily volatile blowing agent during or after the polymerization.
ン−１−カルボニトリルである特許請求の範囲第１項記
載の発泡性熱可塑性共重合体粒子製造の方法。(2) The method for producing expandable thermoplastic copolymer particles according to claim 1, wherein the azo initiator is 1,1-azobiscyclohexane-1-carbonitrile.
アノプロパン、２−ｔ−ブチルアゾ−２−シアノブタン
、１−（−ブチルアゾ−１−シアノシクロヘキサンの中
から選ばれる１抽以上である特許請求の範囲第１項記載
の発泡性熱可塑性共重合体粒子製造の方法。(3) The azo initiator is one or more selected from 2-t-butylamne-2-cyanopropane, 2-t-butylazo-2-cyanobutane, and 1-(-butylazo-1-cyanocyclohexane). A method for producing expandable thermoplastic copolymer particles according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6463184A JPS60206848A (en) | 1984-03-30 | 1984-03-30 | Preparation of expandable thermoplastic copolymer particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6463184A JPS60206848A (en) | 1984-03-30 | 1984-03-30 | Preparation of expandable thermoplastic copolymer particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60206848A true JPS60206848A (en) | 1985-10-18 |
| JPH0510375B2 JPH0510375B2 (en) | 1993-02-09 |
Family
ID=13263804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6463184A Granted JPS60206848A (en) | 1984-03-30 | 1984-03-30 | Preparation of expandable thermoplastic copolymer particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60206848A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6337200A (en) * | 1986-07-30 | 1988-02-17 | ユニリ−バ−・ナ−ムロ−ゼ・ベンノ−トシヤ−プ | Detergent composition |
| JPH01272642A (en) * | 1988-04-26 | 1989-10-31 | Sekisui Plastics Co Ltd | Production of foamable acrylonitrile-styrene copolymer resin particle |
| CN1104445C (en) * | 1996-07-04 | 2003-04-02 | 国际壳牌研究有限公司 | Process for preparation of polymer particles |
| KR100837549B1 (en) * | 2006-01-20 | 2008-06-12 | 주식회사 엘지화학 | Colored expandable polystyrene resin and method for preparing thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52142764A (en) * | 1976-05-24 | 1977-11-28 | Arco Polymers Inc | Antioxidant for |
| JPS55725A (en) * | 1978-06-19 | 1980-01-07 | Denki Kagaku Kogyo Kk | Copolymerization |
| JPS55112240A (en) * | 1979-02-19 | 1980-08-29 | Huels Chemische Werke Ag | Selffextinguishing fineegrain foamed styrol polymer |
| JPS5611930A (en) * | 1979-07-12 | 1981-02-05 | Hitachi Chem Co Ltd | Foaming styrene resin particle |
| JPS5765735A (en) * | 1980-09-13 | 1982-04-21 | Kanegafuchi Chem Ind Co Ltd | Heat-resistant expandable synthetic resin particle and molded article thereof |
| JPS57185328A (en) * | 1982-04-07 | 1982-11-15 | Dow Chemical Co | Foam-linked body with foamable synthetic resin particles |
| JPS58122932A (en) * | 1982-01-14 | 1983-07-21 | Hitachi Chem Co Ltd | Foamable styrene resin particle |
-
1984
- 1984-03-30 JP JP6463184A patent/JPS60206848A/en active Granted
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52142764A (en) * | 1976-05-24 | 1977-11-28 | Arco Polymers Inc | Antioxidant for |
| JPS55725A (en) * | 1978-06-19 | 1980-01-07 | Denki Kagaku Kogyo Kk | Copolymerization |
| JPS55112240A (en) * | 1979-02-19 | 1980-08-29 | Huels Chemische Werke Ag | Selffextinguishing fineegrain foamed styrol polymer |
| JPS5611930A (en) * | 1979-07-12 | 1981-02-05 | Hitachi Chem Co Ltd | Foaming styrene resin particle |
| JPS5765735A (en) * | 1980-09-13 | 1982-04-21 | Kanegafuchi Chem Ind Co Ltd | Heat-resistant expandable synthetic resin particle and molded article thereof |
| JPS58122932A (en) * | 1982-01-14 | 1983-07-21 | Hitachi Chem Co Ltd | Foamable styrene resin particle |
| JPS57185328A (en) * | 1982-04-07 | 1982-11-15 | Dow Chemical Co | Foam-linked body with foamable synthetic resin particles |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6337200A (en) * | 1986-07-30 | 1988-02-17 | ユニリ−バ−・ナ−ムロ−ゼ・ベンノ−トシヤ−プ | Detergent composition |
| JPH06920B2 (en) * | 1986-07-30 | 1994-01-05 | ユニリ−バ−・ナ−ムロ−ゼ・ベンノ−トシヤ−プ | Detergent composition |
| JPH01272642A (en) * | 1988-04-26 | 1989-10-31 | Sekisui Plastics Co Ltd | Production of foamable acrylonitrile-styrene copolymer resin particle |
| CN1104445C (en) * | 1996-07-04 | 2003-04-02 | 国际壳牌研究有限公司 | Process for preparation of polymer particles |
| KR100837549B1 (en) * | 2006-01-20 | 2008-06-12 | 주식회사 엘지화학 | Colored expandable polystyrene resin and method for preparing thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0510375B2 (en) | 1993-02-09 |
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