JPH03705A - Transparent and heat-resistant styrenic resin - Google Patents
Transparent and heat-resistant styrenic resinInfo
- Publication number
- JPH03705A JPH03705A JP13456989A JP13456989A JPH03705A JP H03705 A JPH03705 A JP H03705A JP 13456989 A JP13456989 A JP 13456989A JP 13456989 A JP13456989 A JP 13456989A JP H03705 A JPH03705 A JP H03705A
- Authority
- JP
- Japan
- Prior art keywords
- units
- weight
- resin
- heat
- mechanical strength
- 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.)
- Pending
Links
- 229920001890 Novodur Polymers 0.000 title claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000008064 anhydrides Chemical group 0.000 claims abstract description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000005395 methacrylic acid group Chemical group 0.000 claims abstract description 9
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 6
- 229920005604 random copolymer Polymers 0.000 claims abstract description 4
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical group CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 21
- 239000011347 resin Substances 0.000 abstract description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 16
- 229920001577 copolymer Polymers 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 aromatic vinyl compound Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003440 styrenes Chemical class 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
- 238000012546 transfer Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分計
本発明は新規な透明耐熱スチレン系樹脂に関するもので
ある。さらに詳しくいえば、本発明は、耐熱変形性、熱
安定性、加工性に優れ、特に機械的強度の高い発泡シー
トや発泡成形品を与えうる、透明性の良好な耐熱スチレ
ン系樹脂に関するものである。DETAILED DESCRIPTION OF THE INVENTION Industrial Application The present invention relates to a novel transparent heat-resistant styrenic resin. More specifically, the present invention relates to a heat-resistant styrene resin with excellent heat deformation resistance, thermal stability, processability, and good transparency, which can provide foamed sheets and foamed molded products with particularly high mechanical strength. be.
従来の技術
従来、耐熱性に優れ、かつ機械的強度が高い上、良好な
透明性を有する樹脂としては、例えばポリカーボネート
が知られているが、このポリカーボネートは汎用樹脂と
しては高価であり、かつ成形加工性に劣るという欠点を
有している。Conventional technology For example, polycarbonate has been known as a resin that has excellent heat resistance, high mechanical strength, and good transparency, but this polycarbonate is expensive as a general-purpose resin and difficult to mold. It has the disadvantage of poor workability.
一方、透明性及び加工性がかつ良好で、かつ安価な樹脂
としては例えばポリスチレンが知られている。しかしな
がら、このポリスチレンは耐熱性及び機械的強度が十分
ではないという欠点を有している。On the other hand, polystyrene, for example, is known as an inexpensive resin that has good transparency and processability. However, this polystyrene has the drawback of insufficient heat resistance and mechanical strength.
また、ポリスチレンの耐熱性を改良するために、例えば
、スチレンとメタクリル酸との共重合体（ＳＭＡＡ）、
スチレンと無水マレイン酸との共重合体（ＳＭＡ）など
が開発されているが、これらの共重合体においては、耐
熱性は向上しているものの機械的強度が低く、ポリスチ
レンとほぼ同等であって、成形品は成形歪によりクラッ
クが発生しやすいという欠点があり、用途が制限される
のを免れない。In order to improve the heat resistance of polystyrene, for example, a copolymer of styrene and methacrylic acid (SMAA),
Copolymers of styrene and maleic anhydride (SMA) have been developed, but although these copolymers have improved heat resistance, their mechanical strength is low and is almost equivalent to polystyrene. Molded products have the disadvantage of being susceptible to cracks due to molding distortion, which inevitably limits their uses.
このようなポリスチレンや、スチレン系共重合体の欠点
を改良するために、例えば、メタクリル酸メチル単位を
ポリマー主鎖中に導入したスチレン、メタクリル酸及び
メタクリン酸メチルの三元共重合体、あるいはスチレン
、α−メチルスチレン、メタクリル酸及びメタクリル酸
メチルの四元共重合体が開発され上布されている。In order to improve the disadvantages of polystyrene and styrenic copolymers, for example, styrene with methyl methacrylate units introduced into the polymer main chain, terpolymer of methacrylic acid and methyl methacrylate, or styrene Quaternary copolymers of α-methylstyrene, methacrylic acid and methyl methacrylate have been developed and applied.
しかしながら、これらの三元共重合体や四元共重合体に
おいては、射出成形した場合に成形品の表面にシルバー
ストリークスが発生しやすいという問題がある。これは
、加熱により分子内のメタクリル酸メチル単位の間で脱
水反応や脱メタノールが起こり、その際生成した水やメ
タノールがガスとなるｔ；めである。However, these terpolymers and quaternary copolymers have a problem in that silver streaks are likely to occur on the surface of the molded product when injection molded. This is because dehydration and methanol removal occur between the methyl methacrylate units within the molecule upon heating, and the water and methanol produced at that time turn into gas.
このような欠点を改良するために、例えば芳香族ビニル
化合物、メタクリル酸及びメタクリル酸メチルの三元共
重合体を加熱処理して、式で示される六員環無水物単位
を分子中に成形させた耐熱共重合体が提案されている（
特公昭６１−４９３２５号公報）。In order to improve these drawbacks, for example, a terpolymer of an aromatic vinyl compound, methacrylic acid, and methyl methacrylate is heat-treated to form a six-membered anhydride unit represented by the formula into the molecule. Heat-resistant copolymers have been proposed (
(Special Publication No. 61-49325).
しかしながら、この耐熱共重合体においては、芳香族ビ
ニル化合物単位の含有量を６７重量％以下にすることが
必要なため、溶融流動性が低くなるのを免れず、このた
め、易加工性が要求される発泡シート、二軸延伸シート
、シート成形品などの用途には不適当である。However, in this heat-resistant copolymer, it is necessary to keep the content of aromatic vinyl compound units to 67% by weight or less, so the melt flowability is inevitably low, and therefore easy processability is required. It is unsuitable for applications such as foamed sheets, biaxially oriented sheets, and sheet molded products.
また、メタクリル酸アルキル単位又はスチレン単位のい
ずれかの単量体単位を主体とし、かつメタクリル酸単位
とその酸無水物単位を含む共重合体も提案されているが
（特開昭４９−８５１８４号公報）、この共重合体は、
耐熱性、機械的強度、成形加工性、吸水性などの物性の
すべてを必ずしも十分に満たしているとはいえない。In addition, a copolymer mainly composed of either an alkyl methacrylate unit or a styrene unit and also containing a methacrylic acid unit and its acid anhydride unit has been proposed (Japanese Patent Laid-Open No. 49-85184). Publication), this copolymer is
It cannot be said that all physical properties such as heat resistance, mechanical strength, moldability, and water absorption are fully satisfied.
さらに、メタクリル酸単位を主体とする重合体であって
、それから誘導される六員環無水物単位５０重量％以上
を含有する重合体も提案されている（特開昭５８−７１
９２８号公報）。しかしながら、この重合体においては
、熱変性の点では改良されているものの、溶融流動性が
低く、成形加工性に劣る上、特に発泡シートを成形し、
深絞り成形品を作成しようとしても、成形品の強度が低
く、その表面にクラックが発生して実用に耐えないなど
の欠点がある。Furthermore, a polymer mainly composed of methacrylic acid units and containing 50% by weight or more of six-membered ring anhydride units derived therefrom has also been proposed (Japanese Patent Application Laid-Open No. 58-71
Publication No. 928). However, although this polymer has been improved in terms of thermal denaturation, it has low melt flowability and poor moldability, and is especially difficult to mold into foam sheets.
Even if an attempt is made to produce a deep-drawn molded product, the strength of the molded product is low and cracks occur on the surface, making it unsuitable for practical use.
発明が解決しようとする課題
本発明は、このような事情のもとで、耐熱変形性や熱安
定性に優れ、かつ高い機械的強度を有する上、加工性が
良好で、特に機械的強度が高くて、クラックの発生のな
い発泡シートや発泡成形品を与えうる透明耐熱スチレン
系樹脂を提供することを目的としてなされＩこものであ
る。Problems to be Solved by the Invention Under these circumstances, the present invention has excellent heat deformation resistance and thermal stability, high mechanical strength, good workability, and particularly low mechanical strength. The purpose of this work is to provide a transparent heat-resistant styrenic resin that can be used to produce foamed sheets and foamed molded products that are expensive and free from cracks.
課題を解決するだめの手段
本発明者らはポリスチレンのもつ好ましい物性に加えて
、耐熱性に優れ、かつ機械的強度の高いスチレン系樹脂
を開発すべく鋭意研究を重ねた結果、スチレン単位、σ
−メチルスチレン単位、メタクリル酸メチル単位、メタ
クリル酸単位及び六員環無水物単位を、それぞれ所定の
割合で含有し、かつ還元粘度が特定の範囲にあるランダ
ム共重合体により、その目的を達成しうろことを見い出
し、この知見に基づいて本発明を完成するに至った。Means to Solve the Problem The inventors of the present invention have conducted intensive research to develop a styrenic resin that has excellent heat resistance and high mechanical strength in addition to the favorable physical properties of polystyrene.
- A random copolymer containing methyl styrene units, methyl methacrylate units, methacrylic acid units, and six-membered ring anhydride units in predetermined proportions and having a reduced viscosity within a specific range achieves the purpose. They discovered scales and completed the present invention based on this knowledge.
すなわち、本発明は、（Ａ）スチレン単位７０〜９２重
量％、（Ｂ）α−メチルスチレン単位５〜２０重量％、
（Ｃ）メタクリル酸単位１〜５重量％、（Ｄ）メタクリ
ル酸メチル単位１〜２５重量％及び（Ｅ）式
で表わされる六員環無水物単位０．５〜１．５重量％か
ら成るランダム共重合体であって、濃度０．３ｇ／ｄＱ
のクロロホルム溶液の温度２５°Ｃにおける還元粘度か
帆１５〜２．ＯｄＱ／ｇである透明耐熱スチレン系樹脂
を提供するものでる。That is, the present invention comprises (A) 70 to 92% by weight of styrene units, (B) 5 to 20% by weight of α-methylstyrene units,
Random consisting of (C) 1 to 5% by weight of methacrylic acid units, (D) 1 to 25% by weight of methyl methacrylate units, and (E) 0.5 to 1.5% by weight of six-membered anhydride units represented by the formula Copolymer, concentration 0.3g/dQ
The reduced viscosity of a chloroform solution at a temperature of 25°C is 15-2. The present invention provides a transparent heat-resistant styrenic resin having a value of OdQ/g.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明樹脂は、前記（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）及
び（Ｅ）の各単位がランダムに配列された分子構造を有
するものであって、これらの中で（Ａ）単位、すなわち
スチレン単位は該樹脂の溶融流動性を向上させて成形加
工性を良好にするとともに、発泡シート成形時に発泡ミ
セルをコントロールするなどの役割を有している。The resin of the present invention has a molecular structure in which the units (A), (B), (C), (D), and (E) are randomly arranged, and among these, (A) The unit, that is, the styrene unit, improves the melt flowability of the resin and improves the molding processability, and also has the role of controlling foamed micelles during foamed sheet molding.
このスチレン単位の含有量は７０〜９０重量％の範囲に
あることが必要である。この量が７０重量％未満では溶
融流動性が低く、発泡シート成形時における成形性に劣
るし、９２重量％を超えると耐熱性が低下する。The content of this styrene unit needs to be in the range of 70 to 90% by weight. If this amount is less than 70% by weight, melt flowability will be low and moldability during foam sheet molding will be poor, and if this amount exceeds 92% by weight, heat resistance will decrease.
前記（Ｂ）単位、すなわちσ−メチルスチレン単位の含
有量５〜２０重量％の範囲にあることが必要であって、
この量が５重量％未満では耐熱性の向上効果が十分に発
揮されないし、２０重量％を超えると熱成形時における
熱安定性が不十分となる。It is necessary that the content of the unit (B), that is, the σ-methylstyrene unit, be in the range of 5 to 20% by weight,
If this amount is less than 5% by weight, the effect of improving heat resistance will not be sufficiently exhibited, and if it exceeds 20% by weight, thermal stability during thermoforming will be insufficient.
前記（Ｃ）単位、すなわちメタクリル酸単位は１〜５重
量％の割合で含有することが必要である。The (C) unit, that is, the methacrylic acid unit, needs to be contained in a proportion of 1 to 5% by weight.
この含有量が１重量％未満では耐熱性の向上効果が十分
に発揮されないし、５重量％を超えると発泡シートに成
形したときのシート強度が不足するようになる。If the content is less than 1% by weight, the effect of improving heat resistance will not be sufficiently exhibited, and if it exceeds 5% by weight, the sheet strength will be insufficient when formed into a foamed sheet.
前記（Ｄ）単位、すなわちメタクリル酸メチル単位の含
有量は１〜２５重量％の範囲にあることが必要であって
、この量が１重量％未満ではその発泡成形品は機械的強
度が低く、かつ耐油性に劣り、使用に耐えないし、２５
重量％を超えると成形加工性が著しく低下する。The content of the (D) unit, that is, the methyl methacrylate unit, must be in the range of 1 to 25% by weight, and if this amount is less than 1% by weight, the foam molded product will have low mechanical strength. Moreover, it has poor oil resistance and cannot withstand use.
If it exceeds % by weight, moldability will be significantly reduced.
前記（Ｅ）単位、すなわち式
で表わされる六員環無水物単位は０．５〜１．５重量％
の割合で含有することが必要である。この含有量が０．
５重量％未満では耐熱性の向上性効果が十分に発揮され
ないし、１．５重量％を超えると発泡シートに成形した
ときのシート強度が不足するようになる。The above (E) unit, that is, the six-membered ring anhydride unit represented by the formula, is 0.5 to 1.5% by weight.
It is necessary to contain it in a proportion of . This content is 0.
If it is less than 5% by weight, the effect of improving heat resistance will not be sufficiently exhibited, and if it exceeds 1.5% by weight, the sheet strength will be insufficient when formed into a foamed sheet.
本発明樹脂における各単位の定量は、次のようにして実
施することができる。すなわち、（Ａ）スチレン単位と
（Ｂ）α−メチルスチレン単位はｕｌ−ＮＭＲの測定に
より行うことができ、（Ｅ）六員環無水物単位は該樹脂
をジメチルホルムアミドに溶解し、アンモニア水と反応
させて、定量的に六員環イミド単位に変換させたのち、
窒素分析により定量するか、あるいはＣ”−ＮＭＲを測
定して、六員環無水物単位中のカルボニル炭素を定量す
ることにより行うことができる。さらに、（Ｃ）のメタ
クリル酸単位は、該樹脂をアセトンに溶解し、迅速なア
ルカリ滴定により定量するか、あるいは該樹脂を１２０
℃の温度の加圧水の中で１０時間加熱し、樹脂中に含ま
れる六員環無水物単位をすべてメタクリル酸単位に変換
したのち、アルカリ滴定を行い、これから、元素分析に
より定量した六員環無水物単位の量を差引くことにより
定量することができる。このようにして、（Ａ）、（Ｂ
）、（Ｃ）及び（Ｅ）単位を定量することにより、（Ｄ
）メタクリル酸メチル単位の量を算出することができる
。Quantification of each unit in the resin of the present invention can be carried out as follows. That is, (A) styrene units and (B) α-methylstyrene units can be determined by ul-NMR measurement, and (E) six-membered ring anhydride units can be determined by dissolving the resin in dimethylformamide and adding aqueous ammonia. After reacting and quantitatively converting it into a six-membered ring imide unit,
It can be determined by nitrogen analysis or by measuring C''-NMR to determine the carbonyl carbon in the six-membered anhydride unit.Furthermore, the methacrylic acid unit in (C) can be determined by dissolved in acetone and determined by rapid alkaline titration, or the resin
After heating in pressurized water at a temperature of ℃ for 10 hours to convert all six-membered ring anhydride units contained in the resin into methacrylic acid units, alkaline titration was performed, and from this six-membered ring anhydride was determined by elemental analysis. It can be quantified by subtracting the amount of physical units. In this way, (A), (B
), (C) and (E) units, (D
) The amount of methyl methacrylate units can be calculated.
本発明樹脂を射出成形や押出成形などの成形加工用に供
するためには、該樹脂は適当な分子量を有することが必
要である。すなわち、本発明樹脂は、濃度０．３ｇ／ｄ
Ｑのクロロホルム溶液の温度２５°Ｃにおける還元粘度
〔ηｓｐ／ｃ）が０．１５〜２．（ＪｄＱ／９、好まし
くは０．２〜１．０ｄＱｈｔの範囲にあることが必要で
ある。この還元粘度が０．１５ｄＣ／ｇ未満では樹脂の
機械的強度が十分でないし、２．ＯｄＱ／ｇを超えると
溶融粘度が大きくなり、成形加工性が低下する。In order to use the resin of the present invention for molding processes such as injection molding and extrusion molding, it is necessary that the resin has an appropriate molecular weight. That is, the resin of the present invention has a concentration of 0.3 g/d.
The reduced viscosity [ηsp/c) of the chloroform solution of Q at a temperature of 25°C is 0.15 to 2. (JdQ/9, preferably in the range of 0.2 to 1.0 dQht. If this reduced viscosity is less than 0.15 dC/g, the mechanical strength of the resin will not be sufficient; If it exceeds , the melt viscosity will increase and moldability will decrease.
本発明樹脂は、通常ビカット軟化点が１１０℃以上であ
り、一般のポリスチレンよりも１０℃以上も高く、かつ
熱重量天秤（ＴＧＡ）による１重量％減量温度が３００
’Ｃ！以上であって、各種の熱成形加工に十分に耐えう
る耐熱分解性を有し、発泡成形品の強度も高いなどの特
徴を有し、広範囲の用途に使用が可能である。The resin of the present invention usually has a Vicat softening point of 110°C or more, which is 10°C or more higher than that of general polystyrene, and a 1% weight loss temperature of 300°C on a thermogravimetric balance (TGA).
'C! As described above, it has characteristics such as heat decomposition resistance that can sufficiently withstand various thermoforming processes, and high strength of foamed molded products, and can be used in a wide range of applications.
本発明樹脂を製造するには、連続塊状重合法、連続溶液
重合法、懸濁重合法などのラジカル重合法を用いること
ができるが、乳化重合法は透明性に優れた樹脂を得る方
法としては適当でない。また、懸濁重合法も光学レンズ
類などの分野において、色調を良好にし、かつゴミなど
の混濁を極めて少なくする必要がある用途には好ましく
ない。Radical polymerization methods such as continuous bulk polymerization method, continuous solution polymerization method, and suspension polymerization method can be used to produce the resin of the present invention, but emulsion polymerization method is a method for obtaining resin with excellent transparency. It's not appropriate. Further, the suspension polymerization method is also unfavorable for applications in the field of optical lenses, where it is necessary to improve the color tone and extremely reduce turbidity due to dust and the like.
溶液重合の際に使用する溶媒としては、例えばトルエン
、エチルベンゼン、キシレンなトノ炭化水素系溶媒か好
ましいが、メチルエチルケトン、ブチルアルコール、テ
トラヒドロフランなどの極性溶媒の使用も可能である。The solvent used in solution polymerization is preferably a hydrocarbon solvent such as toluene, ethylbenzene, or xylene, but polar solvents such as methyl ethyl ketone, butyl alcohol, or tetrahydrofuran can also be used.
次に、本発明樹脂を連続溶液重合法によって製造する好
適な１例について説明すると、まずスチレン、α−メチ
ルスチレン、メタクリル酸、メタクリル酸メチル及び必
要に応じて用いられる溶媒をそれぞれ所定の割合で混合
し、これに、必要に応じて用いられる有機過酸化物や有
醗アゾ化合物などのラジカル重合開始剤、アルキルメル
カプタンやσ−メチルスチレンダイマーなどの連鎖移動
剤及びヒンダードアミン類やベンゾトリアゾール系など
の耐候剤を添加して成る溶液を、連続して重合器に仕込
み、次いで連続的に重合体溶液を取り出して、高温減圧
容器に導入し、未反応単量体及び溶媒を除去するととも
に、分子内反応により、脱水、脱メタノールを行い六員
環無水物単位を成形させ、その後溶融状態の重合体を押
出し、冷却、固化、細断することにより、本発明樹脂を
製造することができる。Next, a preferred example of producing the resin of the present invention by a continuous solution polymerization method will be explained. First, styrene, α-methylstyrene, methacrylic acid, methyl methacrylate, and a solvent used as necessary are added in predetermined proportions. This is then mixed with radical polymerization initiators such as organic peroxides and azo compounds, chain transfer agents such as alkyl mercaptans and σ-methylstyrene dimers, and hindered amines and benzotriazole compounds, as needed. A solution containing a weathering agent is continuously charged into a polymerization vessel, and then the polymer solution is continuously taken out and introduced into a high-temperature vacuum vessel to remove unreacted monomers and solvent, and to remove intramolecular The resin of the present invention can be produced by dehydrating and removing methanol to form six-membered ring anhydride units through reaction, and then extruding the molten polymer, cooling, solidifying, and shredding.
この際の重合温度は通常１００〜１６０°Ｃの範囲で選
ばれ、また、該高温減圧容器における反応条件としては
、通常温度は２００〜２７０℃、真空度は０．１〜５０
トール及び滞留時間は５〜１６０分の範囲で選ばれる。The polymerization temperature at this time is usually selected in the range of 100 to 160°C, and the reaction conditions in the high-temperature vacuum vessel are usually 200 to 270°C and a degree of vacuum of 0.1 to 50°C.
Torr and residence time are selected in the range of 5 to 160 minutes.
発明の効果
本発明の透明耐熱スチレン系樹脂は新規なものであって
、耐熱変形性、熱安定性、加工性に優れ、高い機械的強
度を有し、かつ透明性に優れており、例えば二軸延伸シ
ートや発泡シート成形品として、電子レンジで加熱する
食品包装容器類に好適に用いることができ、さらに自動
車部品やレンズ類の素材としても有用である。Effects of the Invention The transparent heat-resistant styrenic resin of the present invention is novel and has excellent heat deformation resistance, thermal stability, processability, high mechanical strength, and excellent transparency. It can be suitably used as an axially stretched sheet or foamed sheet molded product in food packaging containers heated in a microwave oven, and is also useful as a material for automobile parts and lenses.
実施例
次に、実施例により本発明をさらに詳細に説明するが、
本発明はこれらの例によってなんら限定されるものでは
ない。Examples Next, the present invention will be explained in more detail with reference to examples.
The present invention is not limited in any way by these examples.
なお、例中の各物性は次に示す方法により求めＩ；。In addition, each physical property in the example was determined by the method shown below.
（１） ビカット軟化点
ＡＳＴＭ−Ｄ １５２５に準じて、圧縮成形された３ｍ
ｍ厚みの試験片を用いてｆｕｌｌ定した。(1) Vicat softening point 3m compression molded according to ASTM-D 1525
A full determination was made using a test piece with a thickness of m.
（２）引張り強さ ＡＳＴ）Ｊ−→６３８に準じて測定した。(2) Tensile strength AST) J-→638.
（３） １％減量温度〔熱重量天秤（ＴＧＡ）による〕
島洋装作所製熱重量測定装置（ＴＧＡ、−４０）を用い
て、１０°Ｃ／分の昇温速度、窒素気流下において測定
した。(3) 1% weight loss temperature [according to thermogravimetric balance (TGA)]
Measurement was carried out using a thermogravimetric analyzer (TGA, -40) manufactured by Shimayoso Seisakusho at a heating rate of 10°C/min under a nitrogen stream.
（４） メルトフローインデックス
ＪＩＳに７２１０に準じ、２３０°Ｃ，３，８ｋｇ荷重
条件下で測定しｔ；。(4) Melt flow index Measured at 230°C and under a load of 3.8 kg according to JIS 7210.
（５）還元粘度Ｃｖ ｓｐ／ｃ）
試料０．１５９を、りｏｏホルム５０ｍＱに溶解し、２
５０Ｃでキャノン７工ンスケ粘度計５０＃を用いて流下
秒数を測定し、次式により算出した。(5) Reduced viscosity Cv sp/c) Sample 0.159 was dissolved in 50 mQ of Rioo form,
The number of seconds of flow was measured at 50C using a 50# Canon 7K Suke viscometer, and calculated using the following formula.
Ｕ、ｌコ
（１： 試料溶液の流下秒数
ｔｏ： クロロホルムの流下秒数
実施例１
スチレン８０重量部、α−メチルスチレン１５重量部、
メタクリル酸２．５重量部及びメタクリル酸から成る単
量体混合物９５重量％と、エチルベンゼン５重量部及び
１．１−ジーし一ブチルパーオキシシクロヘキサノン帆
０２重量部から成る混合液５重量％との減量溶液を、Ｉ
Ｑ／ｈｒの速度で連続的に反応容積２Ｑの完全混合反応
器に仕込み、重合を行った。U, l (1: Number of seconds for sample solution flow to: Number of seconds for chloroform flow Example 1 80 parts by weight of styrene, 15 parts by weight of α-methylstyrene,
2.5 parts by weight of methacrylic acid and 95% by weight of a monomer mixture consisting of methacrylic acid, and 5% by weight of a liquid mixture consisting of 5 parts by weight of ethylbenzene and 02 parts by weight of 1,1-butylperoxycyclohexanone. The weight loss solution is
The mixture was continuously charged into a complete mixing reactor having a reaction volume of 2Q at a rate of Q/hr, and polymerization was carried out.
次いで、固形分５０重量％の重合体溶液を２３５００に
加熱するとともに、２０トールの減圧室に導き、脱揮、
環化反応を行ったのち、溶融重合体を取り出して、冷却
固化した。第１表に共重合体組成を、第２表に共重合体
の特性値を示す。Next, a polymer solution with a solid content of 50% by weight was heated to 23,500 ℃ and introduced into a 20 Torr vacuum chamber to devolatilize and
After the cyclization reaction, the molten polymer was taken out and solidified by cooling. Table 1 shows the composition of the copolymer, and Table 2 shows the characteristic values of the copolymer.
実施例２〜４、比較例１〜３
第１表に示す組成の単量体混合を実施例１と同様にして
重合、脱揮、環化旭理を行った。第１表に得られた共重
合体の組成を、第２表に共重合体の特性値を示す。Examples 2 to 4, Comparative Examples 1 to 3 Polymerization, devolatilization, and cyclization were performed in the same manner as in Example 1 using the monomer mixtures having the compositions shown in Table 1. Table 1 shows the composition of the obtained copolymer, and Table 2 shows the characteristic values of the copolymer.
得られｔ；共重合体はすべて無色透明であったか、第２
表から分かるように、本発明共重合体のみが、耐熱性、
機械的強度、溶融流動性のすべてに優れている。All of the copolymers were colorless and transparent, or the second
As can be seen from the table, only the copolymer of the present invention has heat resistance,
Excellent mechanical strength and melt fluidity.
Claims (1)
メチルスチレン単位５〜２０重量％、（Ｃ）メタクリル
酸単位１〜５重量％、（Ｄ）メタクリル酸メチル単位１
〜２５重量％及び（Ｅ）式 ▲数式、化学式、表等があります▼ で表わされる六員環無水物単位０．５〜１．５重量％か
ら成るランダム共重合体であって、濃度０．３ｇ／ｄｌ
のクロロホルム溶液の温度２５℃における還元粘度が０
．１５〜２．０ｄｌ／ｇである透明耐熱スチレン系樹脂
。[Claims] 1 (A) 70 to 92% by weight of styrene units, (B) α-
5-20% by weight of methylstyrene units, (C) 1-5% by weight of methacrylic acid units, (D) 1 methyl methacrylate unit
~25% by weight and a random copolymer consisting of 0.5 to 1.5% by weight of six-membered anhydride units represented by formula (E) ▲ Numerical formula, chemical formula, table, etc. ▼, with a concentration of 0. 3g/dl
The reduced viscosity of the chloroform solution at 25°C is 0.
．． A transparent heat-resistant styrenic resin having a weight of 15 to 2.0 dl/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13456989A JPH03705A (en) | 1989-05-30 | 1989-05-30 | Transparent and heat-resistant styrenic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13456989A JPH03705A (en) | 1989-05-30 | 1989-05-30 | Transparent and heat-resistant styrenic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03705A true JPH03705A (en) | 1991-01-07 |
Family
ID=15131408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13456989A Pending JPH03705A (en) | 1989-05-30 | 1989-05-30 | Transparent and heat-resistant styrenic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03705A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5284925A (en) * | 1991-12-02 | 1994-02-08 | Sumitomo Chemical Company, Limited | Method of polymerizing vinyl monomers with use of a deposit suppressant composition for the internal surfaces of a polymerization reactor |
-
1989
- 1989-05-30 JP JP13456989A patent/JPH03705A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5284925A (en) * | 1991-12-02 | 1994-02-08 | Sumitomo Chemical Company, Limited | Method of polymerizing vinyl monomers with use of a deposit suppressant composition for the internal surfaces of a polymerization reactor |
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