JPH0686497B2 - Styrene-based copolymer - Google Patents
Styrene-based copolymerInfo
- Publication number
- JPH0686497B2 JPH0686497B2 JP58244672A JP24467283A JPH0686497B2 JP H0686497 B2 JPH0686497 B2 JP H0686497B2 JP 58244672 A JP58244672 A JP 58244672A JP 24467283 A JP24467283 A JP 24467283A JP H0686497 B2 JPH0686497 B2 JP H0686497B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- styrene
- copolymer
- parts
- maleic anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 78
- 229920001577 copolymer Polymers 0.000 title claims description 67
- 239000000178 monomer Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 23
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 8
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000000034 method Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920006249 styrenic copolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- -1 β-substituted bromostyrene Chemical class 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 本発明は、耐熱性の改良された透明な新規なスチレン系
共重合体に関する。The present invention relates to a novel transparent styrenic copolymer having improved heat resistance.
従来、ポリスチレンは、透明性に優れた成形加工材料と
して広く使用されているが、耐熱性が低いため高温での
使用については改良の余地が残されていた。Conventionally, polystyrene has been widely used as a molding material having excellent transparency, but since it has low heat resistance, there is room for improvement in use at high temperatures.
かかる問題を解決する手段として、例えば特公昭58-409
70号には、スチレン（St）、無水マレイン（Mahn）及び
メチルメタアクリレート（MMA）を共重合した共重合体
組成物が提案されている。しかしながら、かかる組成物
は一応の透明性はあるものの、その透明度は低いレベル
にあり、外観の重視される成形物、例えば、カセットテ
ープのケースやディジタルオーディオディスク用のディ
スクケース、あるいは光学的用途等においては問題を残
していた。As means for solving such a problem, for example, Japanese Patent Publication No. Sho 58-409.
No. 70 proposes a copolymer composition in which styrene (St), maleic anhydride (Mahn) and methyl methacrylate (MMA) are copolymerized. However, although such a composition is tentatively transparent, its transparency is at a low level, and a molded article whose appearance is important, for example, a case of a cassette tape or a disk case for a digital audio disk, or an optical application, etc. Was left with a problem.
本発明者等は、かかる耐熱性のスチレン系共重合体の透
明度を向上するという問題の重要性に鑑み鋭意検討した
結果、極めて優れた透明性を有するスチレン系共重合体
は、該共重合体を構成する単量体の量的関係が特定され
た範囲内にあり、かつ全く意外なことに、その重量平均
分子量Mwと数平均分子量Mnとの比Mw/Mnが特定の範囲内
にあることにより特定されることが見い出された。そし
て、このような共重合体は、例えば、特定の重合反応装
置を用い、かつ反応に供する無水マレイン酸の量と、生
成共重合体中の共重合された無水マイレン酸の量とを特
定の範囲内となるよう調整して重合を実施する方法によ
り得られることが判明し、本発明に到達した。The present inventors have made extensive studies in view of the importance of the problem of improving the transparency of such heat-resistant styrene-based copolymers, and as a result, the styrene-based copolymers having extremely excellent transparency are The quantitative relationship of the monomers constituting is within the specified range, and, quite surprisingly, the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn is within the specified range. It was found to be specified by. Then, such a copolymer, for example, using a specific polymerization reaction device, and the amount of maleic anhydride to be subjected to the reaction, and the amount of the copolymerized maleic anhydride in the produced copolymer is specified. It was found that it can be obtained by a method in which polymerization is carried out by adjusting the content to fall within the range, and the present invention was achieved.
すなわち、本発明のスチレン系共重合体は、スチレン系
単量体20〜94重量部、メチルメタアクリレート５〜60重
量部、無水マレイン酸１〜30重量部及びその他の上記単
量体と共重合可能な単量体０〜30重量部からなる共重合
体であって、完全混合槽型反応と揮発分分離除去を行う
に際し、重合反応に供給する単量体の総量100重量部中
の無水マレイン酸の量をｘ重量部とし揮発分を分離除去
したスチレン系共重合体100重量部中に於ける共重合さ
れた無水マレイン酸の量をｙ重量部としたとき、ｘとｙ
とが式 1.38＜y/x を満足するように重合し、かつ、該スチレン系共重合体
の重量平均分子量Mwと数平均分子量Mnとの比Mw/Mnを 3.0＞Mw/Mn＞1.8 に調節したこと、を特徴とする。That is, the styrene-based copolymer of the present invention is copolymerized with 20 to 94 parts by weight of a styrene-based monomer, 5 to 60 parts by weight of methyl methacrylate, 1 to 30 parts by weight of maleic anhydride and the above-mentioned other monomers. It is a copolymer consisting of 0 to 30 parts by weight of possible monomers, and maleic anhydride in 100 parts by weight of the total amount of monomers to be supplied to the polymerization reaction when performing a complete mixing tank type reaction and separating and removing volatile components. Assuming that the amount of acid is x parts by weight and the amount of maleic anhydride copolymerized in 100 parts by weight of the styrene-based copolymer from which volatile components have been separated and removed is y parts by weight, x and y
Are polymerized so as to satisfy the formula 1.38 <y / x, and the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn of the styrene-based copolymer is adjusted to 3.0> Mw / Mn> 1.8. What you have done is characterized.
本発明にいうスチレン系単量体としては、スチレン及び
その誘導体が挙げられ、例えばスチレン、α−メチレス
チレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ
−メチルスチレン、核−、α−若しくはβ−置換ブロム
スチレン、ｔ−ブチルスチレン、クロスチレン等の一種
以上が用いられ、好ましくは、スチレン、α−メチルス
チレン、ｐ−メチルスチレン、特に好ましくはスチレ
ン、ｐ−メチルスチレンが用いられる。Examples of the styrene-based monomer referred to in the present invention include styrene and derivatives thereof, such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p.
-Methylstyrene, nuclear-, α- or β-substituted bromostyrene, t-butylstyrene, chlorostyrene, and the like are used, and preferably, styrene, α-methylstyrene, p-methylstyrene, and particularly preferably styrene. , P-methylstyrene is used.
本発明にいうその他の上記単量体と共重合可能な単量体
としては、例えばメタクリル酸メチル以外の他の（メ
タ）アクリル酸アルキルエステル類、例えば、アクリル
酸メチル，アクリル酸エチル等が代表的なものとして挙
げられる。Examples of the monomer copolymerizable with the above-mentioned other monomers in the present invention include, for example, other (meth) acrylic acid alkyl esters other than methyl methacrylate, such as methyl acrylate and ethyl acrylate. It can be cited as an example.
本発明の共重合体を構成する各単量体の量的関係として
は、スチレン系単量体20〜70重量部、メチルメタアクリ
レート10〜40重量部、無水マレイン酸１〜15重量部であ
ることが好ましい。スチレン系単量体が20重量部未満で
も94重量部を超えても、得られる共重合体の機械的強度
が弱く、また、メチルメタアクリレートが10重量部未満
では共重合体の製造時に重合液が不均一になりやすく、
60重量部を越えた場合には得られる共重合体の耐熱温度
が低下する。更に、無水マレイン酸の量が１重量部未満
では得られる共重合体の耐熱性改善効果が低く、30重量
部を超えると透明な共重合体は得られない。The quantitative relationship of each monomer constituting the copolymer of the present invention, 20-70 parts by weight of styrene-based monomer, 10-40 parts by weight of methyl methacrylate, 1-15 parts by weight of maleic anhydride. It is preferable. Even if the styrene-based monomer is less than 20 parts by weight or more than 94 parts by weight, the mechanical strength of the obtained copolymer is weak, and if the methyl methacrylate is less than 10 parts by weight, the polymerization liquid at the time of production of the copolymer is Is likely to be uneven,
When it exceeds 60 parts by weight, the heat resistant temperature of the obtained copolymer decreases. Further, when the amount of maleic anhydride is less than 1 part by weight, the heat resistance improving effect of the obtained copolymer is low, and when it exceeds 30 parts by weight, a transparent copolymer cannot be obtained.
本発明に於いては、スチレン系共重合体は、重量平均分
子量Mwと数平均分子量Mnとの比Mw/Mnが、 3.0＞Mw/Mn＞1.8 好ましくは、 2.7＞Mw/Mn＞2.0 に保持されなければならない。In the present invention, the styrene copolymer has a ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of 3.0> Mw / Mn> 1.8, preferably 2.7> Mw / Mn> 2.0. It must be.
これらの分子量は、通常のスチレンホモポリマーと同様
の方法により、ゲルパーミエーションクロマトグラフィ
ー（以下GPCと称す）により測定される。すなわち、溶
媒として、テトラヒドロフランを用い、ウォーターズ社
製の単分散スチレン重合体を用い、GPCにより単分散ス
チレン重合体のピークの分子量とGPCの溶出体積との関
係を用いて、各溶出体積に於ける分子量を求め、測定の
ベースとする。用いる単分散スチレン重合体のピーク分
子量は、230万、65.5万、45.1万、19.6万、11.1万、3.4
5万、２万、0.85万および0.36万である。かかる単分散
スチレン重合体のピークの分子量と溶出体積の検量線を
作成する。共重合体のGPC測定によって、溶出体積分布
曲線を得、かかる過分布曲線を前記検量線に変換し、常
法によりMwとMnとを求める。かかる測定に於いて、GPC
装置の検出部は吸光度法を用いる。なお、分子量を測定
するにあたって、0.1万以下の分子量に相当する共重合
体については、測定精度を維持する上で測定から除外す
る。These molecular weights are measured by gel permeation chromatography (hereinafter referred to as GPC) by the same method as that for ordinary styrene homopolymers. That is, using tetrahydrofuran as a solvent, using a monodisperse styrene polymer manufactured by Waters, using the relationship between the peak molecular weight of the monodisperse styrene polymer by GPC and the elution volume of GPC, in each elution volume Obtain the molecular weight and use it as the basis for measurement. The peak molecular weight of the monodisperse styrene polymer used is 2.3 million, 655,000, 451,000, 196,000, 111,000, 3.4.
50,000, 20,000, 0.85 million and 0.36 million. A calibration curve of the molecular weight of the peak and the elution volume of the monodisperse styrene polymer is prepared. An elution volume distribution curve is obtained by GPC measurement of the copolymer, the hyperdistribution curve is converted into the calibration curve, and Mw and Mn are determined by a conventional method. In such measurement, GPC
The absorbance part is used for the detection part of the device. When measuring the molecular weight, a copolymer corresponding to a molecular weight of 10 thousand or less is excluded from the measurement in order to maintain the measurement accuracy.
比Mw/Mnの値を、前記の数値範囲内にすることは、後述
する例示方法により達成することができるが、一般に、
反応容器内での各単量体の混合状態（例えば、使用する
反応容器のタイプ、撹拌条件、反応容器の単量体の供給
位置と重合液の抜き出し位置との関係）の適切化、連続
重合法の採用、重合反応器から揮発分分離除去装置へ至
るまでの間に於ける重合や揮発分分離除去装置での共重
合体の変質（架橋および分離）の抑制等の条件を最適に
選定することによって達成することができる。The value of the ratio Mw / Mn is within the above numerical range, which can be achieved by an exemplary method described later, but in general,
Optimization of the mixed state of each monomer in the reaction vessel (for example, the type of reaction vessel used, stirring conditions, the relationship between the monomer supply position in the reaction vessel and the withdrawal position of the polymerization solution), continuous weight Optimum selection of conditions such as adoption of legal method, suppression of polymerization in the period from the polymerization reactor to the devolatilization / removal device and suppression of alteration (crosslinking and separation) of the copolymer in the devolatilization / removal device Can be achieved by
比Mw/Mnの値が3.0を越える場合には、スチレン系共重合
体の組成が前記の規定を満たすものであっても、得られ
る共重合体の透明性は悪化し、また、Mw/Mnの値を1.8以
下にすることは、これまでの本発明者らの検討では、通
常の工業的製法に於いては達成が困難である。When the value of the ratio Mw / Mn exceeds 3.0, even if the composition of the styrene-based copolymer satisfies the above-mentioned requirements, the transparency of the obtained copolymer deteriorates, and Mw / Mn It has been difficult to achieve the value of 1.8 or less in the usual industrial production method according to the studies conducted by the present inventors.
このような、特定された単量体組成から構成され、かつ
平均分子量Mwと数平均分子量Mnとの比Mw/Mnが特定され
た範囲内にあるスチレン系共重合体の製造方法としては
次の方法が採用される。Such a method for producing a styrene-based copolymer composed of the specified monomer composition, and having a ratio Mw / Mn of the average molecular weight Mw and the number average molecular weight Mn within the specified range is as follows. The method is adopted.
すなわち、スチレン系単量体20〜94重量部、メチルメタ
アクリレート５〜60重量部、無水マレイン酸１〜30重量
部及びその他の上記単量体と共重合可能な単量体０〜30
重量部からなる単量体混合物を、完全混合槽型反応器と
揮発分分離除去装置を直列に接続した重合反応装置に供
給して、連続的にスチレン系共重合体を製造するに際し
て、重合反応に供する上記単量体の総量100重量部中の
無水マレイン酸の量をｘ重量部とし、揮発分分離除去装
置から取り出されるスチレン系共重合体100重量部中に
於ける共重合された無水マレイン酸の量をｙ重量部とし
たとき、ｘとｙとが次式（Ｉ）、 1.38＜y/x （Ｉ） 好ましくは次式（II） 1.5＜y/x （II） を満足するように重合を実施することによって達成され
る。That is, 20 to 94 parts by weight of styrene-based monomer, 5 to 60 parts by weight of methyl methacrylate, 1 to 30 parts by weight of maleic anhydride, and 0 to 30 monomers copolymerizable with the above-mentioned monomers.
The monomer mixture consisting of parts by weight is supplied to a polymerization reaction device in which a complete mixing tank type reactor and a volatile matter separation / removal device are connected in series to continuously produce a styrene-based copolymer. The amount of maleic anhydride in the total amount of 100 parts by weight of the above-mentioned monomers is x parts by weight, and the copolymerized maleic anhydride in 100 parts by weight of the styrene copolymer taken out from the volatile matter separation / removal device is used. When the amount of acid is y parts by weight, x and y should satisfy the following formula (I), 1.38 <y / x (I), preferably the following formula (II) 1.5 <y / x (II). This is achieved by carrying out the polymerization.
ここでいう完全混合槽型反応器とは、特に特定されたタ
イプの反応器に限定されるものではないが、反応槽内の
各部において、重合液の組成及び温度等が実質的に等し
く保持されるものであることが必要とされる。上記の方
法に於いて使用されるかかる完全混合槽型反応器の槽の
数は、特に限定されるものではないが、一基が好ましく
用いられる。The complete mixing tank reactor here is not particularly limited to a reactor of a specified type, but the composition and temperature of the polymerization liquid are kept substantially equal in each part in the reaction tank. It is required to be one. The number of tanks of the complete mixing tank type reactor used in the above method is not particularly limited, but one is preferably used.
また、揮発分分離除去装置とは、例えば予熱装置、真空
槽及び排出ポンプをそなえたもの、あるいはまたベント
部を有するスクリュー付押出し機等が代表的なものとし
て挙げられる。このような揮発分分離除去装置として
は、一基の予熱器及び一基の真空槽より構成された装置
が好ましく用いられる。かかる予熱器を用いるにあたっ
ては、予熱器入口部の内圧は低く保持することが好まし
い。圧力が高い場合には、予熱器入口部に於いて反応が
進行しやすく、比Mw/Mnの値の調整が困難になりやす
い。Typical examples of the volatile matter separation / removal device include a preheating device, a device equipped with a vacuum chamber and a discharge pump, and an extruder with a screw having a vent portion. As such a volatile matter separation / removal device, a device composed of one preheater and one vacuum tank is preferably used. When using such a preheater, it is preferable to keep the internal pressure at the inlet of the preheater low. If the pressure is high, the reaction easily proceeds at the inlet of the preheater, and it becomes difficult to adjust the value of the ratio Mw / Mn.
また、前記の式のy/xの数値の意味について説明する
と、一般に、無水マレイン酸の共重合体への転化率を抑
制した条件下及び／又は重合反応に供する単量体の重合
体への総転化率を高くするに従いy/xの値は小さくな
る。しかしながら、上記のような反応装置を使用して重
合を実施しても、y/xが1.38以下の場合には、得られる
共重合体の有する前記比Mw/Mnは3.0以上の値を呈し、し
たがってその透明性は十分なものではなく、透明性の卓
越した共重合体が得られない。また、y/xの値として
は、1.5を超えることが比Mw/Mnのより小さな共重合体を
得る上では好ましい。例えば特公昭58-40970号で開示さ
れている方法による共重合体に於いては、y/xの値は1.0
5〜1.2で、比Mw/Mnの値については記載されていない
が、本発明者らが後述する比較例２の試験に於いて特公
昭58-40970号の実施例１とほぼ同様の共重合体組成物を
得た結果に於いては、Mw/Mn＝3.5であり、本発明の共重
合体と異なる性質を示すものである。Further, explaining the meaning of the numerical value of y / x in the above formula, generally, to the polymer of the monomer to be subjected to the conditions and / or the polymerization reaction of suppressing the conversion of maleic anhydride to the copolymer The value of y / x decreases as the total conversion rate increases. However, even if the polymerization is carried out using the reactor as described above, when y / x is 1.38 or less, the ratio Mw / Mn of the obtained copolymer exhibits a value of 3.0 or more, Therefore, its transparency is not sufficient, and a copolymer having excellent transparency cannot be obtained. Further, the value of y / x is preferably more than 1.5 in order to obtain a copolymer having a smaller ratio Mw / Mn. For example, in the copolymer produced by the method disclosed in Japanese Examined Patent Publication No. 58-40970, the value of y / x is 1.0
5 to 1.2, the value of the ratio Mw / Mn is not described, but in the test of Comparative Example 2 described below by the present inventors, the same weight as that of Example 1 of JP-B-58-40970 is used. In the result obtained by the combined composition, Mw / Mn = 3.5, which shows a property different from that of the copolymer of the present invention.
また、y/xの値は、重合反応に供する無水マレイン酸共
重合体への転化率を向上すること、及び／又は重合反応
に供する単量体の重合体への総転化率を抑制するほど大
きくなり、y/xを４以上とした場合にも比Mw/Mnが3.0未
満の共重合体を製造することは可能ではあるが、この場
合には、総転化率を25％未満とする必要があり、かかる
条件では揮発分分離除去工程での熱負荷及び未反応単量
体の回収の労力が大きくなり、エネルギーロス、装置の
巨大化を伴い好ましくない。また場合によっては、熱負
荷が大きくなることにより、生成ポリマーに異常過熱さ
れる部分が生じやすくなり、その結果得られる共重合体
中に茶色に着色した部分が発生することも生じる。Further, the value of y / x is such that the conversion rate to the maleic anhydride copolymer to be subjected to the polymerization reaction is improved, and / or the total conversion rate of the monomer to be subjected to the polymerization reaction to the polymer is suppressed. It is possible to produce a copolymer having a ratio Mw / Mn of less than 3.0 even if y / x is 4 or more, but in this case, the total conversion rate must be less than 25%. However, under such conditions, the heat load in the step of separating and removing volatile components and the labor of recovering unreacted monomers increase, resulting in energy loss and enormous equipment, which is not preferable. In some cases, the heat load becomes large, so that a part of the produced polymer that is abnormally overheated is likely to occur, and as a result, a part colored in brown is generated in the resulting copolymer.
y/xを1.38より大きな値に保持する方法としては、単に
混合が良好な重合反応容器を用いるだけでは不十分な場
合があり、完全混合槽型反応器槽の原料の入口部と重合
液の出口部の位置関係の適切化、すなわち、入口部と出
口部とをできるだけ遠い位置関係に設置すること、また
完全混合槽出口から揮発分分離除去の装置での処理終了
までの重合の進行を抑制すること、原料モノマーの供給
量に応じて、完全混合槽内の混合時間を調整すること等
により実施され得る。例えば原料モノマーの供給量を増
大させた場合には、それに従い混合時間を短くすること
が必要となる。As a method of holding y / x at a value larger than 1.38, it may be insufficient to simply use a polymerization reaction container with good mixing. Optimized the positional relationship of the outlet, that is, install the inlet and the outlet as far apart as possible, and suppress the progress of polymerization from the complete mixing tank outlet to the end of processing in the device for volatile separation removal. By adjusting the mixing time in the complete mixing tank according to the supply amount of the raw material monomer, it can be carried out. For example, when the supply amount of the raw material monomer is increased, it is necessary to shorten the mixing time accordingly.
ここでいう完全混合槽内の混合時間は、反応器内に１ポ
イズ程度の溶液を導入し撹拌を行い、撹拌を継続しつつ
溶剤に溶解した一定量の可溶性の標識物質（染料、別種
の溶剤）を瞬間的に注入し、それ以後継続的に反応槽内
の液体を少量づつ抜き取り、この抜き取りサンプル中の
標識物質の濃度と理論混合濃度との差異が５％以内にな
るのに要する時間Tmで測定される。かかる混合時間Tmと
反応流体の完全混合槽内の平均滞留時間θとの関係につ
いて更に詳しく述べると、通常のポリスチレンの製造に
於いては、θはTmの10倍以上であれば、供給原料と反応
槽内の反応混合物の混合は十分に行われるが、本発明の
スチレン系共重合体の製造を実施する上では、θがTmの
20倍以上、特に好ましくは30倍以上とすることが望まし
い。また、混合時間をかかる条件に調整する他に、上述
した原料の供給方法、反応混合物の抜き出し方法等を組
み合わせて実施することが好ましい。As for the mixing time in the complete mixing tank, a solution of about 1 poise is introduced into the reactor and stirred, and a certain amount of a soluble labeling substance (dye, another kind of solvent) dissolved in the solvent while continuing stirring. ) Is momentarily injected, and thereafter, the liquid in the reaction tank is continuously withdrawn little by little, and the time Tm required for the difference between the concentration of the labeled substance and the theoretical mixed concentration in this withdrawn sample to be within 5% Tm Measured at. More detailed description of the relationship between the mixing time Tm and the average residence time θ of the reaction fluid in the complete mixing tank, in the production of ordinary polystyrene, if θ is 10 times or more of Tm, Although the mixing of the reaction mixture in the reaction tank is sufficiently performed, in carrying out the production of the styrene-based copolymer of the present invention, θ is Tm
It is desired to be 20 times or more, particularly preferably 30 times or more. Further, in addition to adjusting the mixing time to such a condition, it is preferable to combine the above-mentioned raw material supply method, reaction mixture withdrawal method and the like.
上記の重合方法に於いては、必要ならば単量体混合物の
供給液を反応器中に分割供給、または追添してもよい。
場合によっては、各成分単量体を別々にリアクターに供
給してもよいし、また追添してもよい。スチレン系単量
体とは別個に無水マレイン酸とメチルメタアクリレート
及び必要な場合には溶剤を加えた原料液をつくり、スチ
レン系単量体とは互いに独立の貯槽から、これらの単量
体を供給することは好ましい方法である。In the above-mentioned polymerization method, the feed liquid of the monomer mixture may be dividedly fed into the reactor or added additionally if necessary.
Depending on the case, each component monomer may be separately supplied to the reactor or may be added additionally. Separately from the styrenic monomer, prepare a raw material liquid by adding maleic anhydride and methyl methacrylate and, if necessary, a solvent, and store these monomers from a storage tank independent of the styrenic monomer. Feeding is the preferred method.
本発明のスチレン系共重合体を製造する場合には、ラジ
カル重合法が採用されるが、好ましくは、ラジカル重合
開始剤が用いられる。When producing the styrene-based copolymer of the present invention, a radical polymerization method is adopted, but a radical polymerization initiator is preferably used.
また、重合反応をを実施するに際して、公知の分子量調
節剤、溶剤等を重合反応の段階で添加しても良く、また
必要に応じて、公知の可塑剤、熱、光等に対する安定
剤、離型剤を任意の段階において添加しても良い。In carrying out the polymerization reaction, known molecular weight regulators, solvents and the like may be added at the stage of the polymerization reaction, and if necessary, known plasticizers, stabilizers against heat, light, etc. The mold agent may be added at any stage.
本発明のスチレン系共重合体は、耐熱性に優れるのみな
らず、透明性が従来の組成物に比して一段と優れたもの
であり、工業的利用価値は極めて大きい。また、このよ
うなスチレン系共重合体を製造することのできる前記例
示方法によれば、揮発分分離除去装置で回収される未反
応単量体中の無水マレイン酸の濃度は極めて低く保持さ
れ、したがって、回収単量体の保存時の重合等の反応が
抑制され、回収単量体の取り扱いが簡便であり好まし
い。The styrene-based copolymer of the present invention is excellent not only in heat resistance but also in transparency as compared with the conventional composition, and has an extremely great industrial utility value. Further, according to the above-mentioned exemplary method capable of producing such a styrene-based copolymer, the concentration of maleic anhydride in the unreacted monomer recovered by the volatile matter separation / removal device is kept extremely low, Therefore, the reaction such as polymerization during storage of the recovered monomer is suppressed, and the recovered monomer is easy to handle, which is preferable.
以下、本発明を実施例により具体的に説明するが、本発
明はこれらに限定されるものではない。Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
実施例１ 〔共重合体の製造〕 （ａ）１時間当りスチレン75重量部と、（ｂ）無水マレ
イン酸５重量部をメチルメタアクリレート20重量部とエ
チルベンゼン10重量部に溶解した混合液を１時間当り35
重量部とを、別個の供給ポンプにより一基の完全混合槽
型反応器に連続的に供給した。該完全混合槽は、ドラフ
ト付スクリュー型攪拌翼を内装し、さらに、供給原料入
口部にタービン型攪拌翼を設けたものであり、両攪拌翼
の回転数は150rpmに保持した。原料入口部は槽の下部に
設け、槽の上部より重合反応液を抜き出した。この液抜
き出し速度は、単量体の供給速度と同じく１時間当り11
0重量部である。完全混合槽内の平均滞留時間を２時間
とし、反応温度は145℃に保持した。槽出口より抜き出
した重合反応液は、ジャケット温度100℃の二重管を通
して、入口部に圧力コントロールバルブを備えた予熱器
と真空槽より成る揮発分分離除去装置に連続的に導入し
た。予熱器の入口部の真空度は400〜600Torrに保持し、
真空槽の真空度は10Torrに保持した。真空槽下部より生
成共重合体を連続的に抜き出しペレット状の共重合体を
得た。また、真空槽の上部より、重合反応液中に残存す
る単量体及びエチルベンゼンを抜き出し、全量を温度−
５℃に保持した貯槽に回収した。回収した液（回収液）
の量は単位時間当り60重量部であった。Example 1 [Production of Copolymer] (a) 75 parts by weight of styrene per hour, and (b) 5 parts by weight of maleic anhydride were dissolved in 20 parts by weight of methyl methacrylate and 10 parts by weight of ethylbenzene to prepare a mixed solution. 35 per hour
And parts by weight were continuously fed to one complete mixing tank reactor by separate feed pumps. The complete mixing tank was equipped with a screw type stirring blade equipped with a draft and was further provided with a turbine type stirring blade at the inlet of the raw material, and the rotation speed of both stirring blades was maintained at 150 rpm. The raw material inlet was provided at the bottom of the tank, and the polymerization reaction liquid was extracted from the top of the tank. The liquid withdrawal rate is the same as the monomer supply rate, which is 11 per hour.
0 parts by weight. The average residence time in the complete mixing tank was 2 hours, and the reaction temperature was maintained at 145 ° C. The polymerization reaction liquid extracted from the outlet of the tank was continuously introduced through a double tube having a jacket temperature of 100 ° C. into a volatile matter separation / removal device consisting of a preheater equipped with a pressure control valve at the inlet and a vacuum tank. The degree of vacuum at the inlet of the preheater is maintained at 400 to 600 Torr,
The vacuum degree of the vacuum chamber was maintained at 10 Torr. The produced copolymer was continuously extracted from the lower portion of the vacuum chamber to obtain a pellet-shaped copolymer. Further, the monomer and ethylbenzene remaining in the polymerization reaction solution were extracted from the upper part of the vacuum chamber, and the whole amount was kept at the temperature
It was collected in a storage tank kept at 5 ° C. Collected liquid (collected liquid)
Was 60 parts by weight per unit time.
また、共重合体の重量平均分子量Mwと数平均分子量Mnと
の比Mw/Mnの値については前述の方法に基づき測定し
た。The value of the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the copolymer was measured according to the method described above.
上記回収液をガスクロマトグラフィー法で分析し、回収
したスチレン、無水マレイン酸、メチルメタアクリレー
ト、エチルベンゼンの量比を求めた。無水マレイン酸の
量は、JIS K1359の指示薬滴定法に準じて測定した。ま
た、ペレット状の共重合体中の共重合していない未反応
の無水マレイン酸の量については、該ペレットをスチレ
ン、メチルメタアクリレートの80対20の混合液に溶解
し、JIS K1359の指示薬滴定法に準じて測定した。測定
の結果、ペレット状の共重合体中の未反応の無水マレイ
ン酸は、実質的に零であった。原料の供給量、回収液の
収量及び上記回収液組成の分析結果より、共重合体中の
無水マレイン酸及びその他の単量体の組成を求めた。ま
た、共重合体の重量平均分子量Mwと数平均分子量Mnとの
比Mw/Mnの値については前述の方法に基づき測定した。The recovered liquid was analyzed by a gas chromatography method to determine the amount ratio of the recovered styrene, maleic anhydride, methyl methacrylate and ethylbenzene. The amount of maleic anhydride was measured according to the indicator titration method of JIS K1359. Further, regarding the amount of unreacted maleic anhydride that has not been copolymerized in the pellet-shaped copolymer, the pellet is dissolved in a mixed solution of 80:20 of styrene and methyl methacrylate, and the indicator titration of JIS K1359 is carried out. It measured according to the method. As a result of the measurement, the unreacted maleic anhydride in the pellet-shaped copolymer was substantially zero. The compositions of maleic anhydride and other monomers in the copolymer were determined from the feed amount of the raw materials, the yield of the recovered liquid and the analysis result of the recovered liquid composition. The value of the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the copolymer was measured according to the method described above.
得られた共重合体を、シリンダー温度230℃にて射出成
形して、共重合体の物性を評価した。物性評価は、次の
方法に従って行った。The obtained copolymer was injection molded at a cylinder temperature of 230 ° C. to evaluate the physical properties of the copolymer. The physical properties were evaluated according to the following methods.
（ａ）耐熱性:ASTM D−1525によるビカット軟化点。(A) Heat resistance: Vicat softening point according to ASTM D-1525.
（ｂ）機械的強度:JIS K6871に準じたアイゾット衝撃強
度、引っ張り強度。(B) Mechanical strength: Izod impact strength and tensile strength according to JIS K6871.
（ｃ）色調:JIS K7105による黄色度。(C) Color tone: Yellowness degree according to JIS K7105.
（ｄ）透明性:JIS K7105による曇価及び全光線透過率。
曇価が低い程、また全光線透過率が高い程透明性が高い
と評価される。(D) Transparency: Haze value and total light transmittance according to JIS K7105.
The lower the haze value and the higher the total light transmittance, the higher the transparency.
反応条件、共重合体組成の解析および物性評価結果を表
１に示す。Table 1 shows the reaction conditions, the analysis of the copolymer composition, and the evaluation results of the physical properties.
実施例2,3,4 共重合体製造時の原料組成、反応温度を表１に示したよ
うに変化させ、また完全混合槽型反応器内の平均滞留時
間を、実施例２では1.1時間とした他は実施例１と全く
同様にして共重合体の製造を実施した。反応条件、共重
合体組成の解析および物性評価結果を表１に示した。Examples 2, 3 and 4 The raw material composition and reaction temperature at the time of copolymer production were changed as shown in Table 1, and the average residence time in the complete mixing tank reactor was 1.1 hours in Example 2. A copolymer was produced in the same manner as in Example 1 except that the above was carried out. Table 1 shows the reaction conditions, the analysis of the copolymer composition, and the evaluation results of the physical properties.
比較例１ 完全混合反応槽出口より抜き出した重合液を通す二重管
の温度を、反応槽と同じ温度として操作した他は、実施
例４と全く同様にして共重合体の製造を実施した。反応
条件、共重合体組成の解析および物性評価結果を表１に
示した。Comparative Example 1 A copolymer was produced in exactly the same manner as in Example 4 except that the temperature of the double tube through which the polymerization liquid extracted from the outlet of the complete mixing reaction tank was passed was the same as that of the reaction tank. Table 1 shows the reaction conditions, the analysis of the copolymer composition, and the evaluation results of the physical properties.
比較例２ 原料入口部と重合液出口部をいずれも反応槽の上部に設
けた完全混合反応槽を使用した他は、実施例１と全く同
様にして共重合体の製造を実施した。生成した共重合体
ペレットには、ときどきにごりが生じていた。安定した
定常状態のサンプルは得られなかった。不安定状態では
あったが、短時間（約10分）回収液と共重合体ペレット
をサンプリングし、共重合体組成の解析および物性評価
を行った。この結果を表１に示した。Comparative Example 2 A copolymer was produced in exactly the same manner as in Example 1 except that a completely mixed reaction tank was used in which both the raw material inlet and the polymerization solution outlet were provided above the reaction tank. Occurrence of dust was occasionally observed in the produced copolymer pellets. No stable steady state sample was obtained. Although it was in an unstable state, the collected liquid and copolymer pellets were sampled for a short time (about 10 minutes), and the copolymer composition was analyzed and the physical properties were evaluated. The results are shown in Table 1.
比較例３ 揮発分分離除去装置の予熱器の入口部の圧力を0.5〜1.5
Kg/cm2Ｇの圧力に保持したことを除いては、実施例１と
全く同様にして共重合体の製造を実施した。反応条件、
共重合体組成の解析および物性評価結果を表１に示し
た。Comparative Example 3 The pressure at the inlet of the preheater of the volatile matter separation / removal device was 0.5 to 1.5.
A copolymer was produced in exactly the same manner as in Example 1 except that the pressure was kept at Kg / cm 2 G. Reaction conditions,
Table 1 shows the results of the analysis of the copolymer composition and the evaluation of the physical properties.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 (Ｃ０８Ｆ 220/14 212:04 222:08） (72)発明者 安藤 敏彦 神奈川県横浜市戸塚区飯島町2070 (56)参考文献 特公 昭58−40970（ＪＰ，Ｂ２)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Reference number in the agency FI technical display location (C08F 220/14 212: 04 222: 08) (72) Inventor Toshihiko Ando Totsuka Ward, Yokohama City, Kanagawa Prefecture Iijima-cho 2070 (56) References Japanese Patent Publication Sho 58-40970 (JP, B2)
Claims (2)
タアクリレート５〜60重量部、無水マレイン酸１〜30重
量部及びその他の上記単量体と共重合可能な単量体０〜
30重量部からなるスチレン系共重合体であって、 完全混合槽型反応と揮発分分離除去を行うに際し、重合
反応に供給する単量体の総量100重量部中の無水マレイ
ン酸の量をｘ重量部とし揮発分を分離除去したスチレン
系共重合体100重量部中に於ける共重合された無水マレ
イン酸の量をｙ重量部としたとき、ｘとｙとが式 1.38＜y/x を満足するように重合し、かつ、該スチレン系共重合体
の重量平均分子量Mwと数平均分子量Mnとの比Mw/Mnを 3.0＞Mw/Mn＞1.8 に調節したこと、を特徴とするスチレン系共重合体。1. A styrene-based monomer 20 to 94 parts by weight, methylmethacrylate 5 to 60 parts by weight, maleic anhydride 1 to 30 parts by weight, and other monomers 0 to 100 which are copolymerizable with the above monomers.
A styrene-based copolymer consisting of 30 parts by weight, the amount of maleic anhydride in 100 parts by weight of the total amount of monomers to be supplied to the polymerization reaction in the complete mixing tank type reaction and the separation and removal of volatile components is x When the amount of the maleic anhydride copolymerized in 100 parts by weight of the styrene-based copolymer in which the volatile components are separated and removed is defined as y parts by weight, x and y are expressed by the formula 1.38 <y / x. A styrene-based polymer, which is polymerized to satisfy the requirement, and the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of the styrene-based copolymer is adjusted to 3.0> Mw / Mn> 1.8. Copolymer.
メチルスチレン及びパラメチルスチレンからなる群から
選ばれた１種または２種以上である特許請求の範囲１項
記載のスチレン系共重合体。2. The styrene-based monomer is styrene or α-
The styrene-based copolymer according to claim 1, which is one or more selected from the group consisting of methylstyrene and paramethylstyrene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58244672A JPH0686497B2 (en) | 1983-12-27 | 1983-12-27 | Styrene-based copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58244672A JPH0686497B2 (en) | 1983-12-27 | 1983-12-27 | Styrene-based copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60137915A JPS60137915A (en) | 1985-07-22 |
| JPH0686497B2 true JPH0686497B2 (en) | 1994-11-02 |
Family
ID=17122228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58244672A Expired - Lifetime JPH0686497B2 (en) | 1983-12-27 | 1983-12-27 | Styrene-based copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0686497B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4386645B2 (en) * | 2003-01-09 | 2009-12-16 | 電気化学工業株式会社 | Aromatic vinyl resin and method for producing the same |
| CN104350102B (en) * | 2012-06-13 | 2017-02-22 | 株式会社可乐丽 | Ethylene-vinyl alcohol resin composition, multilayer structure, multilayer sheet, container, and packaging material |
| CN104540860B (en) * | 2012-07-30 | 2017-03-08 | 电化株式会社 | For improving the copolymer of methacrylic resin thermostability |
| WO2014021265A1 (en) * | 2012-07-30 | 2014-02-06 | 電気化学工業株式会社 | Copolymer for optical compensation film |
| JP6228126B2 (en) * | 2012-10-22 | 2017-11-08 | デンカ株式会社 | Aromatic vinyl-vinyl cyanide resin Copolymer for improving heat resistance |
| JP6166058B2 (en) * | 2013-02-20 | 2017-07-19 | デンカ株式会社 | Light guide plate |
| JP6058420B2 (en) * | 2013-02-20 | 2017-01-11 | デンカ株式会社 | Light guide plate |
| WO2015178437A1 (en) * | 2014-05-22 | 2015-11-26 | 電気化学工業株式会社 | Copolymer for transparent, scratch-resistant plate, and laminate for transparent, scratch-resistant plate |
| JP2016037522A (en) * | 2014-08-06 | 2016-03-22 | デンカ株式会社 | Styrene-based copolymer for foam molded article |
| EP3181600B1 (en) * | 2014-08-11 | 2018-06-13 | Denka Company Limited | Copolymer suitable for improving heat resistance of methacrylic resin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5840970A (en) * | 1981-09-03 | 1983-03-10 | Canon Inc | fax machine |
-
1983
- 1983-12-27 JP JP58244672A patent/JPH0686497B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60137915A (en) | 1985-07-22 |
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