JPH0348202B2 - - Google Patents
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- JPH0348202B2 JPH0348202B2 JP56067537A JP6753781A JPH0348202B2 JP H0348202 B2 JPH0348202 B2 JP H0348202B2 JP 56067537 A JP56067537 A JP 56067537A JP 6753781 A JP6753781 A JP 6753781A JP H0348202 B2 JPH0348202 B2 JP H0348202B2
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Description
本発明は未反応単量体を著しく抑え、かつ、加
熱時の熱分解性の少ない耐熱性共重合体の製造方
法に関する。
現在、α−メチルスチレン−アクリロニトリル
共重合体とスチレン−アクリロニトリル−ブタジ
エングラフト重合体とを混合したいわゆる耐熱性
ABS樹脂が広く用いられているが、これらの耐
熱性ABS樹脂であつても使用分野においては充
分とは言えず、より優れた耐熱性を有する熱可塑
性樹脂が望まれている。
この耐熱性ABS樹脂の耐熱性温度は主として
マトリツクスを形成するα−メチルスチレン−ア
クリロニトリル共重合体の耐熱温度に依存するも
のであり、また、共重合体の耐熱温度はα−メチ
ルスチレン含有量に左右される。
より多くのα−メチルスチレンを含有すること
により、さらに優れた耐熱性が得られるが、α−
メチルスチレンはラジカル重合では反応性が悪
く、アクリロニトリル等を共重合させないと単独
では重合を行い難い性質がある。
したがつて、α−メチルスチレン含有量の高い
α−メチルスチレン−不飽和ニトリル共重合体の
製造において、重合終了時の未反応単量体を１重
量％未満（全仕込量あたり）に抑えようとすると
おのずからα−メチルスチレンの使用量には制限
がある。
現在用いられているα−メチルスチレン−アク
リロニトリル共重合体のα−メチルスチレン含有
量は最高70重量％程度であり、これを用いた耐熱
性ABS樹脂の耐熱温度は最高105℃位である。
しかも、従来の製造法ではα−メチルスチレン
含有量が70重量％のものを作るには１重量％以上
の未反応単量体が残り、１重量％未満に抑えよう
とすればα−メチルスチレン量を減少させなけれ
ばならず、共重合体の耐熱性のみならずABS樹
脂の耐熱性の低下をまねくといつた致命的な欠点
を有している。
さらに、α−メチルスチレン−アクリロニトリ
ル共重合体はα−メチルスチレン量が多くなるに
従つて、成形加工時等で加熱される事により熱分
解を起こしやすい欠点を有している。
本発明者らは、前記従来技術の欠点を改良すべ
く鋭意研究した結果、単量体添加終了時における
重合系内の未反応不飽和ニトリル濃度をある一定
濃度以上になるように単量体を調整しながら添加
し、かつ、共重合体ラテツクス粒子の90重量％以
上の粒子径が0.10μ以下となるように重合させる
ことによりα−アルキルスチレンを70−80重量％
含む共重合体を重合体ラテツクス中の凝固物の生
成と未反応単量体を著しく抑え、かつ生成共重合
体の加熱時の熱分解性の少ない重合体を製造でき
る方法を見い出し本発明に到達した。
すなわち、本発明は、α−アルキルスチレン70
−80重量％と不飽和ニトリル30−20重量％とをラ
ジカル性開始剤を用いて乳化重合する際、単量体
添加終了時における重合系内の全未反応単量体に
対する未反応不飽和ニトリルの濃度が31重量％以
上になるように調整して単量体を添加し、かつ、
共重合体ラテツクス粒子の90重量％以上の粒子径
が0.10μ以下となるように重合する事を特徴とす
る共重合体の製造方法を提供するものである。
本発明の方法にしたがえば、高α−アルキルス
チレン含有の共重合体を、重合体ラテツクス中の
凝固物の生成と未反応単量体を著しく抑えかつ、
生成共重合体の加熱時の熱分解性の少ない重合体
を容易に製造することができる。
また、それゆえ従来のようなストリツピング処
理を行う必要がなくなり生産性に優れ、工業生産
上有利である。
本発明をさらに詳しく説明すると、α−アルキ
ルスチレンとは、下記一般式で示される化合物で
ある。
（R1はC1〜C3のアルキル基であり、R2は水素、
C1〜C3のアルキル基またはハロゲン化アルキル
基である。）
例えば、α−メチルスチレン、α−エチルスチ
レン、メチル−α−メチルスチレン等が例示され
るが、好ましくはα−メチルスチレンである。
不飽和ニトリルとしては、アクリロニトリル、
メタクリロニトリル、エタクリロニトリル等が例
示されるが、好ましくはアクリロニトリルであ
る。
ラジカル性開始剤としては、過硫酸カリウム、
過硫酸ナトリウム、過硫酸アンモニウムやキユメ
ンハイドロパーオキサイド、ジイソプロピルベン
ゼンハイドロパーオキサイドのレドツクス等が例
示されるが、好ましくは過硫酸カリウム、過硫酸
ナトリウムである。
乳化重合に用いられる乳化剤としては常用の乳
化剤が使用できるが、好ましくはアニオン系乳化
剤であり、ラウリル硫酸ナトリウム、オレイン酸
カリウム、オレイン酸ナトリウム、脂肪酸のカリ
ウムまたはナトリウム塩、ロジン酸のカリウムま
たはナトリウム塩、およびアルキルベンゼンスル
ホン酸ナトリウム等が例示される。
本発明においては、α−アルキルスチレン70−
80重量％および不飽和ニトリル30−20重量％が用
いられる。
α−アルキルスチレンが70重量％未満であると
得られた共重合体の耐熱性は著しく劣り好ましく
ない。また80重量％を超えると重合終了時の未反
応単量体を１重量％以下に抑えることが困難とな
る。
また、本発明においては、単量体添加終了時に
おける重合系内の未反応不飽和ニトリル濃度（単
量体添加終了時の重合系内の全未反応単量体に基
づく）が31重量％以上となるように調整して単量
体を添加し、かつ、共重合体ラテツクス粒子の90
重量％以上の粒子径が0.10μ以下となるように重
合を進める必要がある。粒子径は重合終了時にお
ける共重合体ラテツクス粒子径を意味する。
単量体添加終了時における重合系内の未反応不
飽和ニトリル濃度が31重量％未満であると、重合
終了時の未反応単量体を１重量％以下に抑えるこ
とが困難となる。また、生産性が低下する。
重合系内の未反応不飽和ニトリル濃度が31重量
％以上となるように単量体を添加する具定的な調
整方法としては、重合系内のかかる濃度を測定し
ながらα−アルキルスチレンと不飽和ニトリルの
それぞれの添加速度を調整する方法、添加される
α−アルキルスチレンと不飽和ニトリル混合単量
体の混合比率を調整する方法、さらには、α−ア
ルキルスチレンを全量仕込み、かかる濃度が31重
量％以上となるよう不飽和ニトリルの添加速度と
調節する方法が例示される。
又、本発明では、重合終了時の共重合体ラテツ
クス粒子の90重量％以上の粒子径を0.10μ以下に
する必要がある。
0.10μを超えると生成共重合体を成形加工等で
加熱した時、熱分解性が激しくなつてくる。
更に重合時の重合速度が遅くなり生成ラテツク
ス中に凝固物を生成し、かつ、未反応単量体が多
くなる。
共重合体ラテツクス粒子の90重量％以上の粒子
径を0.10μ以下にする具体的方法は、重合時使用
する脱イオン水量を多く使用したり、乳化剤量を
多く使用する等である。
α−アルキルスチレンと不飽和ニトリルの重合
系への添加方法には特に制限はなく、連続的、分
割的に添加してもよい。
さらに必要に応じて重合度調節剤等を加えても
よい。
本発明による共重合体は、従来のスチレン−ア
クリロニトリル−ブタジエングラフト共重合体と
混合することができ、得られた樹脂組成物は従来
法によるα−メチルスチレン−アクリロニトリル
共重合体を含有する耐熱性ABS樹脂より優れた
耐熱性を有する。
以下に実施例を用いて本発明を具体的に説明す
るが、これらによつて本発明が何ら制限されるも
のではない。
実施例及び比較例に記載されている、ガラス転
移点及び50％重量減少時の熱分解温度の測定に供
される共重合体は３％硫酸マグネシウム水溶液に
共重合体ラテツクスを添加して、共重合体を塩析
し、これを乾燥して用いた。
実施例 １
窒素置換した反応器に脱イオン水180重量部、
ラウリル硫酸ナトリウム３重量部、過硫酸カリウ
ム0.7重量部およびｎ−ドデシルメルカプタン0.1
重量部を加え、70℃に加熱した後、α−メチルス
チレン75重量部とアクリロニトリル10重量部から
なる単量体混合物の50％を添加し２時間に亘り重
合を行い更に残りの50％を３時間に亘り連続添加
した。
次に重合系内の未反応アクリロニトリル濃度を
調整しながらα−メチルスチレン３重量部および
アクリロニトリル12重量部を２時間に亘り添加し
た。
単良体添加終了時の重合系内の未反応アクリロ
ニトリル濃度は35重量％であつた。
単量体添加終了後、さらに２時間重合を継続し
た。
重合終了後の結果は以下のとおりであつた。
未反応α−メチルスチレン*1：0.59重量％
未反応アクリロニトリル*1：0.19重量％
共重合体ラテツクス中の凝集物量：0.002重量％
共重合体ラテツクスの平均粒子径*2：0.08μ
共重合体ラテツクスの粒子径が0.10μであつた割
合*2：93重量％
共重合体の軟化点*3：135℃
50％重量減少時の熱分解温度*3：379℃
実施例 ２
窒素置換した反応器に脱イオン水200重量部、
ラウリル硫酸ナトリウム３重量部、過硫酸カリウ
ム0.7重量部およびｎ−ドデシルメルカプタン0.1
重量部を加えた後、さらに、α−メチルスチレン
71重量部とアクリロニトリル20重量部からなる単
量体混合物の20重量％を加え、70℃に加熱し１時
間重合した後、かかる単量体混合物の残部（80重
量％）を４時間に亘り連続的に添加した。
次に重合系内の未反応アクリロニトリル濃度を
調整しながらα−メチルスチレン２重量部および
アクリロニトリル７重量部を２時間に亘り添加し
た。
単量体添加終了時の重合系内の未反応アクリロ
ニトリル濃度は43重量％であつた。
単量体添加終了後、さらに２時間重合を継続し
た。
重合終了後の結果は以下のとおりであつた。
未反応α−メチルスチレン：0.29重量％
未反応アクリロニトリル：0.16重量％
共重合体ラテツクス中の凝集物量：0.002重量
％
共重合体ラテツクスの平均粒子径：0.050μ
共重合体ラテツクスの粒子径が0.10μ以下であ
つた割合：95重量％
共重合体の軟化点：129℃
50％重量減少時の熱分解温度：392℃
実施例 ３
窒素置換した反応器に脱イオン水200重量部、
ラウリル硫酸ナトリウム４重量部、過硫酸カリウ
ム0.7重量部およびｎ−ドデシルメルカプタン0.1
重量部を加えた後さらに、α−メチルスチレン74
重量部とアクリロニトリル８重量部からなる単量
体混合物全量を加え70℃に昇温し３時間重合を行
う。
次に重合系内の未反応アクリロニトリル濃度を
調整しながらアクリロニトリル18重量部を４時間
にわたつて連続添加した。アクリロニトリル添加
終了時の未反応アクリロニトリル濃度は49重量％
であつた。
添加終了後さらに２時間重合を継続した。重合
終了後の結果は以下のとおりであつた。
未反応α−メチルスチレン：0.26重量％
未反応アクリロニトリル：0.22重量％
共重合体ラテツクス中の凝集物量：0.009重量
％
共重合体ラテツクスの平均粒子径：0.045μ
共重合体ラテツクスの粒子径が0.10μ以下であ
つた割合：98重量％
共重合体の軟化点：130℃
50％重量減少時の熱分解温度：392℃
比較例 １
窒素置換した反応器に脱イオン水200重量部、
ラウリル硫酸ナトリウム３重量部、過硫酸カリウ
ム0.7重量部およびｎ−ドデシルメルカプタン0.1
重量部を加え、70℃に加熱した後、α−メチルス
チレン78重量部とアクリロニトリル22重量部から
なる単量体混合物の20％を添加し、１時間重合し
た後、残りの80％を４時間にわたつて連続的に添
加した。
単量体添加終了時の重合系内の未反応アクリロ
ニトリル濃度は18重量％であつた。
単量体添加終了後、さらに２時間重合を継続し
た。
重合終了後の結果は以下のとおりであつた。
未反応α−メチルスチレン：7.8重量％
未反応アクリロニトリル：0.06重量％
共重合体ラテツクス中の凝集物量：0.09重量％
共重合体ラテツクスの平均粒子径：0.08μ
共重合体ラテツクスの粒子径が0.10μ以下であ
つた割合：93重量％
共重合体の軟化点：102℃
50％重量減少時の熱分解温度：360℃
比較例 ２
窒素置換した反応器に脱イオン水200重量部、
ラウリル硫酸ナトリウム３重量部、過硫酸カリウ
ム0.7重量部およびｎ−ドデシルメルカプタン0.1
重量部を加えた後、さらに、α−メチルスチレン
70重量部とアクリロニトリル15重量部とからなる
単量体混合物の20重量％を加え、70℃に加熱し１
時間重合した後、かかる単量体混合物の残部（80
重量％）を４時間に亘り連続的に添加した。
次に重合系内の未反応アクリロニトリル濃度を
調整することなくα−メチルスチレン８重量部お
よびアクリロニトリル７重量部の混合物を２時間
にわたつて連続的に添加した。
添加終了後の重合系内の未反応アクリロニトリ
ル濃度は23重量％であつた。単量体添加終了後、
さらに４時間重合を継続した。
重合終了後の結果は以下のとおりであつた。
未反応α−メチルスチレン：4.0重量％
未反応アクリロニトリル：0.08重量％
共重合体ラテツクス中の凝集物量：0.07重量％
共重合体ラテツクスの平均粒子径：0.09μ
共重合体ラテツクスの粒子径が0.10μ以下であ
つた割合：93重量％
共重合体の軟化点：108℃
50％重量減少時の熱分解温度：363℃
比較例 ３
窒素置換した反応器に脱イオン水120重量部、
ラウリル硫酸ナトリウム2.0重量部、過硫酸カリ
ウム0.7重量部およびｎ−ドデシルメルカプタン
0.1重量部を加えた後、さらに、α−メチルスチ
レン75重量部とアクリロニトリル10重量部とから
なる単量体混合物の20重量％を加え、70℃に加熱
し１時間重合した後、かかる単量体混合物の残部
（80重量％）を４時間に亘り連続的に添加した。
次に重合系内の未反応アクリロニトリル濃度を
調整しながらα−メチルスチレン３重量部および
アクリロニトリル12重量部を２時間にわたつて連
続的に添加した。
添加後の重合系内の未反応アクリロニトリル濃
度は32重量％であつた。単量体添加終了後、さら
に２時間重合を継続した。
重合終了後の結果は以下のとおりであつた。
未反応α−メチルスチレン：0.77重量％
未反応アクリロニトリル：0.23重量％
共重合体ラテツクス中の凝集物量：0.42重量％
共重合体ラテツクス中の平均粒子径：0.13μ
共重合体ラテツクスの粒子径が0.10μ以下であ
つた割合：30重量％
共重合体の軟化点：134℃
50％重量減少時の熱分解温度：345℃
比較例 ４
窒素置換した反応器に脱イオン水120重量部、
ラウリル硫酸ナトリウム２重量部、過硫酸カリウ
ム0.7重量部およびｎ−ドデシルメルカプタン0.1
重量部を加えた後、さらに、α−メチルスチレン
71重量部とアクリロニトリル20重量部とからなる
単量体混合物の20重量％を加え、70℃に加熱し１
時間重合した後、かかる単量体混合物の残部（80
重量％）を４時間に亘り連続的に添加した。
次に重合系内の未反応アクリロニトリル濃度を
調整しながらα−メチルスチレン２重量部および
アクリロニトリル７重量部を２時間にわたつて連
続的に添加した。
添加後の重合系内の未反応アクリロニトリル濃
度は39重量％であつた。単量体添加終了後、さら
に２時間重合を継続した。
重量終了時の未反応単量体（仕込み単量体に対
する）は以下のとおりであつた。
未反応α−メチルスチレン：0.68重量％
未反応アクリロニトリル：0.31重量％
共重合体ラテツクス中の凝集物量：0.28重量％
共重合体ラテツクスの平均粒子径：0.12μ
共重合体ラテツクスの粒子径が0.10μ以下であ
つた割合：40重量％
共重合体の軟化点：127℃
50％重量減少時の熱分解温度：369℃
比較例 ５〜９
窒素置換した３反応器に、表−１に示される
前段用混合単量体の30重量％を入れ反応槽内を70
℃に加熱し、撹拌しながら１時間反応を行いその
後残りの前段用混合単量体を３時間で連続添加し
前段重合を行う。
重合熱がなくなつた後、１時間にわたつて後段
添加用のアクリロニトリルを添加し、さらに70℃
で３時間後段重合を行う。
添加後の重合系内の未反応アクリロニトリル濃
度、重合終了時の未反応単量体、ラテツクスの平
均粒子径ならびに得られた共重合体の熱分解温度
を表−１に示す。
The present invention relates to a method for producing a heat-resistant copolymer that significantly suppresses the amount of unreacted monomer and exhibits less thermal decomposition during heating. Currently, so-called heat-resistant products are made by mixing α-methylstyrene-acrylonitrile copolymer and styrene-acrylonitrile-butadiene graft polymer.
Although ABS resins are widely used, even these heat-resistant ABS resins are not sufficient in the field of use, and thermoplastic resins with better heat resistance are desired. The heat-resistant temperature of this heat-resistant ABS resin mainly depends on the heat-resistant temperature of the α-methylstyrene-acrylonitrile copolymer that forms the matrix, and the heat-resistant temperature of the copolymer also depends on the α-methylstyrene content. Depends on it. Even better heat resistance can be obtained by containing more α-methylstyrene;
Methylstyrene has poor reactivity in radical polymerization and is difficult to polymerize alone unless copolymerized with acrylonitrile or the like. Therefore, when producing an α-methylstyrene-unsaturated nitrile copolymer with a high α-methylstyrene content, it is recommended to keep the amount of unreacted monomer at the end of polymerization to less than 1% by weight (per total amount charged). Therefore, there is naturally a limit to the amount of α-methylstyrene used. The α-methylstyrene content of currently used α-methylstyrene-acrylonitrile copolymers is about 70% by weight at most, and the heat-resistant ABS resin using this copolymer has a maximum temperature resistance of about 105°C. Moreover, in the conventional manufacturing method, in order to make a product with an α-methylstyrene content of 70% by weight, more than 1% by weight of unreacted monomer remains; This has a fatal drawback in that the amount must be reduced, leading to a decrease in not only the heat resistance of the copolymer but also the heat resistance of the ABS resin. Furthermore, the α-methylstyrene-acrylonitrile copolymer has the disadvantage that as the amount of α-methylstyrene increases, it is more likely to undergo thermal decomposition due to heating during molding. As a result of intensive research in order to improve the drawbacks of the prior art, the present inventors have determined that the monomer is added so that the concentration of unreacted unsaturated nitrile in the polymerization system at the end of monomer addition is at a certain level or higher. 70-80% by weight of α-alkylstyrene is added by adjusting the amount and polymerizing so that the particle size of 90% by weight or more of the copolymer latex particles is 0.10μ or less.
The present invention has been achieved by discovering a method for producing a copolymer containing a copolymer that significantly suppresses the formation of coagulated products and unreacted monomers in a polymer latex, and that produces a copolymer that is less thermally decomposable when heated. did. That is, the present invention provides α-alkylstyrene 70
When emulsion polymerizing -80% by weight and 30-20% by weight of unsaturated nitrile using a radical initiator, the unreacted unsaturated nitrile is based on the total unreacted monomer in the polymerization system at the end of monomer addition. The monomer is added so that the concentration of the monomer is adjusted to be 31% by weight or more, and
The present invention provides a method for producing a copolymer, characterized in that the copolymer latex particles are polymerized so that 90% by weight or more of the copolymer latex particles have a particle diameter of 0.10 μm or less. According to the method of the present invention, the copolymer containing high α-alkylstyrene can be significantly suppressed from forming coagulum and unreacted monomer in the polymer latex, and
A copolymer that is less thermally decomposable when heated can be easily produced. Furthermore, it is not necessary to carry out stripping treatment as in the past, resulting in excellent productivity and advantages in industrial production. To explain the present invention in more detail, α-alkylstyrene is a compound represented by the following general formula. (R 1 is a C 1 to C 3 alkyl group, R 2 is hydrogen,
It is a C1 - C3 alkyl group or a halogenated alkyl group. ) Examples include α-methylstyrene, α-ethylstyrene, methyl-α-methylstyrene, and α-methylstyrene is preferred. Examples of unsaturated nitriles include acrylonitrile,
Examples include methacrylonitrile and ethacrylonitrile, with acrylonitrile being preferred. As a radical initiator, potassium persulfate,
Examples include redoxes such as sodium persulfate, ammonium persulfate, cumene hydroperoxide, and diisopropylbenzene hydroperoxide, but potassium persulfate and sodium persulfate are preferred. As the emulsifier used in emulsion polymerization, commonly used emulsifiers can be used, but anionic emulsifiers are preferred, such as sodium lauryl sulfate, potassium oleate, sodium oleate, potassium or sodium salts of fatty acids, potassium or sodium salts of rosin acid. , and sodium alkylbenzenesulfonate. In the present invention, α-alkylstyrene 70-
80% by weight and 30-20% by weight of unsaturated nitriles are used. If the α-alkylstyrene content is less than 70% by weight, the resulting copolymer will have significantly poor heat resistance, which is not preferred. Moreover, if it exceeds 80% by weight, it becomes difficult to suppress the amount of unreacted monomer at the end of polymerization to 1% by weight or less. In addition, in the present invention, the concentration of unreacted unsaturated nitrile in the polymerization system at the end of monomer addition (based on the total unreacted monomer in the polymerization system at the end of monomer addition) is 31% by weight or more. Add the monomer so that it becomes 90% of the copolymer latex particles.
It is necessary to proceed with the polymerization so that the particle size in weight percent or more is 0.10μ or less. The particle size means the copolymer latex particle size at the end of polymerization. If the concentration of unreacted unsaturated nitrile in the polymerization system at the end of monomer addition is less than 31% by weight, it will be difficult to suppress the unreacted monomer to 1% by weight or less at the end of polymerization. Also, productivity decreases. A specific adjustment method for adding a monomer so that the concentration of unreacted unsaturated nitrile in the polymerization system is 31% by weight or more is to add α-alkylstyrene and unsaturated nitrile while measuring the concentration in the polymerization system. A method of adjusting the addition rate of each saturated nitrile, a method of adjusting the mixing ratio of the added α-alkylstyrene and the unsaturated nitrile mixed monomer, and a method of adjusting the mixing ratio of the α-alkylstyrene to be added and the unsaturated nitrile mixed monomer, and furthermore, a method of adjusting the addition rate of each of the saturated nitrile, and a method of adjusting the mixing ratio of the α-alkylstyrene to be added and the unsaturated nitrile mixed monomer. An example is a method of adjusting the addition rate of unsaturated nitrile so that the amount is at least % by weight. Further, in the present invention, it is necessary that the particle diameter of 90% by weight or more of the copolymer latex particles at the end of polymerization is 0.10 μm or less. If it exceeds 0.10μ, the resulting copolymer becomes more thermally decomposable when heated during molding or the like. Furthermore, the polymerization rate during polymerization becomes slow, coagulates are formed in the produced latex, and unreacted monomers increase. Specific methods for reducing the particle diameter of 90% by weight or more of the copolymer latex particles to 0.10 μm or less include using a large amount of deionized water or using a large amount of an emulsifier during polymerization. There is no particular restriction on the method of adding α-alkylstyrene and unsaturated nitrile to the polymerization system, and they may be added continuously or in portions. Furthermore, a degree of polymerization regulator or the like may be added if necessary. The copolymer according to the present invention can be mixed with a conventional styrene-acrylonitrile-butadiene graft copolymer, and the resulting resin composition is a heat-resistant one containing a conventional α-methylstyrene-acrylonitrile copolymer. Has better heat resistance than ABS resin. EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these in any way. The copolymers used for measuring the glass transition point and thermal decomposition temperature at 50% weight loss described in Examples and Comparative Examples were prepared by adding the copolymer latex to a 3% aqueous magnesium sulfate solution. The polymer was salted out, dried and used. Example 1 180 parts by weight of deionized water was added to a reactor purged with nitrogen.
3 parts by weight of sodium lauryl sulfate, 0.7 parts by weight of potassium persulfate, and 0.1 part by weight of n-dodecylmercaptan.
After adding parts by weight and heating to 70°C, 50% of a monomer mixture consisting of 75 parts by weight of α-methylstyrene and 10 parts by weight of acrylonitrile was added and polymerized for 2 hours. Continuous addition was made over time. Next, 3 parts by weight of α-methylstyrene and 12 parts by weight of acrylonitrile were added over 2 hours while adjusting the concentration of unreacted acrylonitrile in the polymerization system. The concentration of unreacted acrylonitrile in the polymerization system at the end of addition of the monomer was 35% by weight. After the monomer addition was completed, polymerization was continued for an additional 2 hours. The results after completion of polymerization were as follows. Unreacted α-methylstyrene *1 : 0.59% by weight Unreacted acrylonitrile *1 : 0.19% by weight Amount of aggregates in copolymer latex: 0.002% by weight Average particle diameter of copolymer latex *2 : 0.08μ Copolymer latex Percentage of particles with a particle size of 0.10μ *2 : 93% by weight Copolymer softening point *3 : 135°C Thermal decomposition temperature at 50% weight reduction *3 : 379°C Example 2 In a reactor purged with nitrogen 200 parts by weight of deionized water,
3 parts by weight of sodium lauryl sulfate, 0.7 parts by weight of potassium persulfate, and 0.1 part by weight of n-dodecylmercaptan.
After adding parts by weight, further add α-methylstyrene.
Add 20% by weight of a monomer mixture consisting of 71 parts by weight and 20 parts by weight of acrylonitrile, heat to 70°C and polymerize for 1 hour, then add the remainder of the monomer mixture (80% by weight) continuously for 4 hours. added. Next, 2 parts by weight of α-methylstyrene and 7 parts by weight of acrylonitrile were added over 2 hours while adjusting the concentration of unreacted acrylonitrile in the polymerization system. The concentration of unreacted acrylonitrile in the polymerization system at the end of monomer addition was 43% by weight. After the monomer addition was completed, polymerization was continued for an additional 2 hours. The results after completion of polymerization were as follows. Unreacted α-methylstyrene: 0.29% by weight Unreacted acrylonitrile: 0.16% by weight Amount of aggregates in copolymer latex: 0.002% by weight Average particle size of copolymer latex: 0.050μ Particle size of copolymer latex is 0.10μ Proportion below: 95% by weight Softening point of copolymer: 129°C Thermal decomposition temperature at 50% weight loss: 392°C Example 3 200 parts by weight of deionized water was added to a reactor purged with nitrogen.
4 parts by weight of sodium lauryl sulfate, 0.7 parts by weight of potassium persulfate, and 0.1 part by weight of n-dodecylmercaptan.
After adding parts by weight, α-methylstyrene 74
A total amount of a monomer mixture consisting of parts by weight and 8 parts by weight of acrylonitrile was added, the temperature was raised to 70°C, and polymerization was carried out for 3 hours. Next, 18 parts by weight of acrylonitrile was continuously added over 4 hours while adjusting the concentration of unreacted acrylonitrile in the polymerization system. Unreacted acrylonitrile concentration at the end of acrylonitrile addition was 49% by weight
It was hot. After the addition was completed, polymerization was continued for another 2 hours. The results after completion of polymerization were as follows. Unreacted α-methylstyrene: 0.26% by weight Unreacted acrylonitrile: 0.22% by weight Amount of aggregates in copolymer latex: 0.009% by weight Average particle size of copolymer latex: 0.045μ Particle size of copolymer latex is 0.10μ Proportion below: 98% by weight Softening point of copolymer: 130°C Thermal decomposition temperature at 50% weight loss: 392°C Comparative Example 1 200 parts by weight of deionized water in a reactor purged with nitrogen,
3 parts by weight of sodium lauryl sulfate, 0.7 parts by weight of potassium persulfate, and 0.1 part by weight of n-dodecylmercaptan.
After adding parts by weight and heating to 70°C, 20% of a monomer mixture consisting of 78 parts by weight of α-methylstyrene and 22 parts by weight of acrylonitrile was added, and after polymerizing for 1 hour, the remaining 80% was polymerized for 4 hours. It was added continuously over the period of time. The concentration of unreacted acrylonitrile in the polymerization system at the end of monomer addition was 18% by weight. After the monomer addition was completed, polymerization was continued for an additional 2 hours. The results after completion of polymerization were as follows. Unreacted α-methylstyrene: 7.8% by weight Unreacted acrylonitrile: 0.06% by weight Amount of aggregates in copolymer latex: 0.09% by weight Average particle size of copolymer latex: 0.08μ Particle size of copolymer latex is 0.10μ Proportion below: 93% by weight Softening point of copolymer: 102°C Thermal decomposition temperature at 50% weight loss: 360°C Comparative Example 2 200 parts by weight of deionized water was added to a reactor purged with nitrogen.
3 parts by weight of sodium lauryl sulfate, 0.7 parts by weight of potassium persulfate, and 0.1 part by weight of n-dodecylmercaptan.
After adding parts by weight, further add α-methylstyrene.
Add 20% by weight of a monomer mixture consisting of 70 parts by weight and 15 parts by weight of acrylonitrile, and heat to 70°C.
After polymerization for an hour, the remainder of such monomer mixture (80
% by weight) was added continuously over a period of 4 hours. Next, a mixture of 8 parts by weight of α-methylstyrene and 7 parts by weight of acrylonitrile was continuously added over 2 hours without adjusting the concentration of unreacted acrylonitrile in the polymerization system. After the addition was completed, the concentration of unreacted acrylonitrile in the polymerization system was 23% by weight. After monomer addition is complete,
Polymerization was continued for an additional 4 hours. The results after completion of polymerization were as follows. Unreacted α-methylstyrene: 4.0% by weight Unreacted acrylonitrile: 0.08% by weight Amount of aggregates in copolymer latex: 0.07% by weight Average particle size of copolymer latex: 0.09μ Particle size of copolymer latex is 0.10μ Proportion below: 93% by weight Softening point of copolymer: 108°C Thermal decomposition temperature at 50% weight loss: 363°C Comparative Example 3 120 parts by weight of deionized water was added to a reactor purged with nitrogen.
2.0 parts by weight of sodium lauryl sulfate, 0.7 parts by weight of potassium persulfate, and n-dodecyl mercaptan
After adding 0.1 part by weight, 20% by weight of a monomer mixture consisting of 75 parts by weight of α-methylstyrene and 10 parts by weight of acrylonitrile was added, and after polymerizing for 1 hour by heating to 70°C, such monomers were added. The remainder of the mixture (80% by weight) was added continuously over a period of 4 hours. Next, 3 parts by weight of α-methylstyrene and 12 parts by weight of acrylonitrile were continuously added over 2 hours while adjusting the concentration of unreacted acrylonitrile in the polymerization system. The concentration of unreacted acrylonitrile in the polymerization system after addition was 32% by weight. After the monomer addition was completed, polymerization was continued for an additional 2 hours. The results after completion of polymerization were as follows. Unreacted α-methylstyrene: 0.77% by weight Unreacted acrylonitrile: 0.23% by weight Amount of aggregates in copolymer latex: 0.42% by weight Average particle size in copolymer latex: 0.13μ Particle size of copolymer latex is 0.10 Proportion below μ: 30% by weight Softening point of copolymer: 134°C Thermal decomposition temperature at 50% weight loss: 345°C Comparative Example 4 120 parts by weight of deionized water was added to a reactor purged with nitrogen.
2 parts by weight of sodium lauryl sulfate, 0.7 parts by weight of potassium persulfate, and 0.1 part by weight of n-dodecyl mercaptan.
After adding parts by weight, further add α-methylstyrene.
Add 20% by weight of a monomer mixture consisting of 71 parts by weight and 20 parts by weight of acrylonitrile, and heat to 70°C.
After polymerization for an hour, the remainder of such monomer mixture (80
% by weight) was added continuously over a period of 4 hours. Next, 2 parts by weight of α-methylstyrene and 7 parts by weight of acrylonitrile were continuously added over 2 hours while adjusting the concentration of unreacted acrylonitrile in the polymerization system. The concentration of unreacted acrylonitrile in the polymerization system after addition was 39% by weight. After the monomer addition was completed, polymerization was continued for an additional 2 hours. The unreacted monomers (relative to the charged monomers) at the end of the weight were as follows. Unreacted α-methylstyrene: 0.68% by weight Unreacted acrylonitrile: 0.31% by weight Amount of aggregates in copolymer latex: 0.28% by weight Average particle size of copolymer latex: 0.12μ Particle size of copolymer latex is 0.10μ Proportion below: 40% by weight Softening point of copolymer: 127°C Thermal decomposition temperature at 50% weight loss: 369°C Comparative Examples 5 to 9 The first stage shown in Table 1 was added to three reactors purged with nitrogen. Add 30% by weight of the mixed monomer for 70% in the reaction tank.
C. and reacted for 1 hour with stirring, and then the remaining mixed monomers for the first stage were continuously added over a period of 3 hours to perform the first stage polymerization. After the heat of polymerization disappeared, acrylonitrile for later addition was added for 1 hour, and the temperature was further increased to 70°C.
Post-polymerization is carried out for 3 hours. Table 1 shows the concentration of unreacted acrylonitrile in the polymerization system after addition, the unreacted monomer at the end of polymerization, the average particle diameter of the latex, and the thermal decomposition temperature of the obtained copolymer.
【表】【table】
Claims (1)
ニトリル30−20重量％とをラジカル性開始剤を用
いて乳化重合する際、単量体添加終了時における
重合系内の全未反応単量体に対する未反応不飽和
ニトリルの濃度が31重量％以上になるように調整
して単量体を添加し、かつ、供重合体ラテツクス
粒子の90重量％以上の粒子径が0.10μ以下となる
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. When emulsion polymerizing 70-80% by weight of α-alkylstyrene and 30-20% by weight of unsaturated nitrile using a radical initiator, all unreacted monomers in the polymerization system at the end of monomer addition. The monomer is added so that the concentration of unreacted unsaturated nitrile is 31% by weight or more, and the particle size of 90% by weight or more of the donor polymer latex particles is 0.10μ or less. A method for producing a copolymer characterized by polymerization.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6753781A JPS57182308A (en) | 1981-05-02 | 1981-05-02 | Production of copolymer |
| DE8181104321T DE3170382D1 (en) | 1980-06-05 | 1981-06-04 | Process for preparing copolymers |
| CA000379018A CA1157999A (en) | 1980-06-05 | 1981-06-04 | Process for preparing copolymers |
| EP81104321A EP0041703B1 (en) | 1980-06-05 | 1981-06-04 | Process for preparing copolymers |
| KR1019810002018A KR840001740B1 (en) | 1980-06-05 | 1981-06-05 | Method of Preparation of Copolymer |
| US06/270,879 US4361684A (en) | 1980-06-05 | 1981-06-05 | Process for preparing copolymers comprising α-alkyl styrene and unsaturated nitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6753781A JPS57182308A (en) | 1981-05-02 | 1981-05-02 | Production of copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57182308A JPS57182308A (en) | 1982-11-10 |
| JPH0348202B2 true JPH0348202B2 (en) | 1991-07-23 |
Family
ID=13347821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6753781A Granted JPS57182308A (en) | 1980-06-05 | 1981-05-02 | Production of copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57182308A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3431194A1 (en) * | 1984-08-24 | 1986-03-06 | Bayer Ag, 5090 Leverkusen | COPOLYMERISATE MADE OF (DELTA) METHYL STYRENE AND ACRYLNITRILE |
| KR100791206B1 (en) | 2006-08-14 | 2008-01-02 | 주식회사 엘지화학 | Method for producing AAS-based graft copolymer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2388591A1 (en) * | 1977-04-29 | 1978-11-24 | Commissariat Energie Atomique | CONTACTOR-SEPARATOR ASSEMBLY IN AN EXTRACTION PLANT |
| JPS5578007A (en) * | 1978-12-06 | 1980-06-12 | Sumitomo Naugatuck Co Ltd | Preparation of thermoplastic resin |
| JPS5667316A (en) * | 1979-11-06 | 1981-06-06 | Japan Synthetic Rubber Co Ltd | Production of vinyl aromatic compound/acrylonitrile copolymer |
-
1981
- 1981-05-02 JP JP6753781A patent/JPS57182308A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57182308A (en) | 1982-11-10 |
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