JPS6377905A - Styrene polymer molding - Google Patents
Styrene polymer moldingInfo
- Publication number
- JPS6377905A JPS6377905A JP22209286A JP22209286A JPS6377905A JP S6377905 A JPS6377905 A JP S6377905A JP 22209286 A JP22209286 A JP 22209286A JP 22209286 A JP22209286 A JP 22209286A JP S6377905 A JPS6377905 A JP S6377905A
- Authority
- JP
- Japan
- Prior art keywords
- styrenic polymer
- stretching
- styrene polymer
- polymer
- molecular weight
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 55
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title abstract description 42
- 238000000465 moulding Methods 0.000 title abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000005481 NMR spectroscopy Methods 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 abstract 1
- -1 poly(alkyl styrene Chemical compound 0.000 description 19
- 239000004793 Polystyrene Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 125000003011 styrenyl group Polymers [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はスチレン系重合体成形品に関し、詳しくは機械
的強度や耐熱性のすぐれたスチレン系重合体成形品に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a styrenic polymer molded article, and more particularly to a styrenic polymer molded article with excellent mechanical strength and heat resistance.
［従来の技術および発明が解決しようとする問題点］
スチレン系重合体、特にポリスチレンはその立体規則性
がアタクチック構造を有するものが一般に用いられてい
るが、このようなアタクチックポリスチレンは結晶化し
ないため、機械的強度や耐熱性に劣り、また延伸しても
その物性の改善は期待できない、さらに立体規則性がア
イソタクチック構造のポリスチレンも知られており、ま
たこれを延伸した成形品も提案［高分子化学２１，２０
８（１９６４）］されているが、このアイソタクチック
ポリスチレンは結晶化速度が遅く、しかも結晶構造が螺
旋状であるため、延伸してもその効果の発現が充分なも
のではない。[Prior art and problems to be solved by the invention] Styrenic polymers, especially polystyrene, whose stereoregularity has an atactic structure are generally used, but such atactic polystyrene does not crystallize. Therefore, polystyrene has poor mechanical strength and heat resistance, and no improvement in its physical properties can be expected even if it is stretched.Additionally, polystyrene with isotactic stereoregularity is also known, and molded products made by stretching it have also been proposed. [Polymer chemistry 21, 20
8 (1964)], but since this isotactic polystyrene has a slow crystallization rate and has a helical crystal structure, its effect is not sufficiently expressed even when it is stretched.
本発明者らは先般、シンジオタクテイシテイ−の高いス
チレン系重合体を開発することに成功した（特願昭８１
−１０１９２８号明細書）。The present inventors have recently succeeded in developing a styrenic polymer with high syndiotacticity (Patent application No. 81).
-101928 specification).
［問題点を解決するための手段］
本発明らは、この新たなシンジオタクチック構造のスチ
レン系重合体の物性等についてさらに研究をすすめたと
ころ、このスチレン系重合体を延伸処理すると、機械的
強度、特に弾性率が飛躍的に向上することを見出した。[Means for Solving the Problems] The present inventors conducted further research on the physical properties of this new styrenic polymer with a syndiotactic structure, and found that when this styrenic polymer is stretched, mechanical It has been found that the strength, especially the elastic modulus, is dramatically improved.
本発明はかかる知見に基いて完成したものである。The present invention was completed based on this knowledge.
すなわち本発明は、主としてシンジオタクチック構造を
有する重量平均分子量３００，０００以上のスチレン系
重合体を延伸してなるスチレン系重合体成形品を提供す
るものである。That is, the present invention provides a styrenic polymer molded article obtained by stretching a styrenic polymer having a weight average molecular weight of 300,000 or more and mainly having a syndiotactic structure.
本発明の成形品の材料は、主としてシンジオタクチック
構造を有するスチレン系重合体である。The material of the molded article of the present invention is mainly a styrenic polymer having a syndiotactic structure.
このスチレン系重合体は、主としてシンジオタクチック
構造、即ち炭素−炭素結合から形成される主鎖に対して
側鎖であるフェニル基や置換フェニル基が交互に反対方
向に位はする立体構造を有するものであり、そのタフテ
ィシティ−は同位体炭素による核磁気共鳴法（＋ ３０
−ＮＭＲ法）により定量される。This styrenic polymer mainly has a syndiotactic structure, that is, a steric structure in which phenyl groups or substituted phenyl groups, which are side chains, are alternately positioned in opposite directions with respect to the main chain formed from carbon-carbon bonds. Its toughness is determined by nuclear magnetic resonance method using carbon isotope (+30
-NMR method).
＋ ３０−ＮＭＲ法により測定されるタフティシティ−
は、連続する複数個の構成単位の存在割合、例えば２個
の場合はダイアツド、３個の場合はトリアット、５個の
場合はペンタッドによって示すことができるが、本発明
に言う主としてシンジオタクチック構造を有するスチレ
ン系重合体とは。+ Toughness measured by 30-NMR method
can be expressed by the abundance ratio of a plurality of consecutive structural units, for example, a diad in the case of two, a triat in the case of three, and a pentad in the case of five, but mainly syndiotactic structure as referred to in the present invention. What is a styrenic polymer having
通常はペンタッド（ラセミペンタッド）テ８５％以上、
好ましくは８５％以上のシンジオタクテイシテイ−を有
するポリスチレン、ポリ（アルキルスチレン）、ポリ（
ハロゲン化スチレン）、ポリ（アルコキシスチレン）、
ポリ（安息香醜エステルスチレン）およびこれらの混合
物、あるいはこれらを主成分とする共重合体を指称する
。なお、ここでポリ（アルキルスチレン）としては、ポ
リ（メチルスチレン）、ポリ（エチルスチレン）。Usually pentad (racemic pentad) te 85% or more,
Preferably polystyrene, poly(alkyl styrene), poly(
halogenated styrene), poly(alkoxystyrene),
Refers to poly(benzoic ester styrene), mixtures thereof, or copolymers containing these as main components. Note that poly(alkylstyrene) here includes poly(methylstyrene) and poly(ethylstyrene).
ポリ（イソプロピルスチレン）、ポリ（ターシャリ−ブ
チルスチレン）などがあり、ポリ（ハロゲン化スチレン
）としては、ポリ（クロロスチレン）、ポリ（ブロモス
チレン）などがある。また、ポリ（アルコキシスチレン
）としては、ポリ（メトキシスチレン）、ポリ（エトキ
シスチレン）などがある。Examples of poly(isopropylstyrene) and poly(tert-butylstyrene) include poly(halogenated styrene) such as poly(chlorostyrene) and poly(bromostyrene). Furthermore, examples of poly(alkoxystyrene) include poly(methoxystyrene) and poly(ethoxystyrene).
上述の如く、本発明に用いるスチレン系重合体のラセミ
ペンタッドでのシンジオタクテイシテイ−は、通常８５
％以上であるが、多少低い値であっても延伸処理の条件
を選定すれば充分な引張弾性率を発現することができる
。しかし、シンジオタクテイシテイ−があまり低いスチ
レン系重合体では、延伸処理しても充分な引張弾性率の
向上は期待できない。As mentioned above, the racemic pentad syndiotacticity of the styrenic polymer used in the present invention is usually 85
% or more, but even if the value is somewhat low, a sufficient tensile modulus can be achieved if the stretching conditions are selected. However, if the styrenic polymer has very low syndiotacticity, a sufficient improvement in tensile modulus cannot be expected even if the stretching treatment is performed.
また１本発明に用いるスチレン系重合体は、重量平均分
子量が３００，０００以上のものであることが望ましく
、特に１，０００，０００以上のものが好適である。こ
こで、重量平均分子量が３００．０００未満のものでは
、充分な強度や弾性率を得ることができない。また、分
子量分布については広くても狭くても制約を受けること
なく用いることができる。The styrenic polymer used in the present invention preferably has a weight average molecular weight of 300,000 or more, particularly preferably 1,000,000 or more. Here, if the weight average molecular weight is less than 300,000, sufficient strength and elastic modulus cannot be obtained. Moreover, the molecular weight distribution can be used without being restricted, whether it is wide or narrow.
本発明によれば、上述のスチレン系重合体を延伸するこ
とにより、すぐれた物性の成形品が得られるが、ここで
延伸は一軸延伸、二軸延伸のどちらによってもよく、ま
た延伸倍率は特に制約はないが３倍以上が好ましく、５
〜１０倍が最適である。さらに延伸方法としても溶融延
伸、湿潤延伸、ゲル延伸などをあげることができる。こ
こで湿潤延伸またはゲル延伸を行なう場合には、溶媒と
してベンゼン、トルエン、キシレン、エチルベンゼン、
シクロヘキサン、デカリン、Ｎ−メチルピロリドン、テ
トラヒドロフラン、四塩化炭素。According to the present invention, a molded article with excellent physical properties can be obtained by stretching the above-mentioned styrenic polymer, but the stretching may be carried out by either uniaxial stretching or biaxial stretching, and the stretching ratio is particularly There is no restriction, but 3 times or more is preferable, and 5
~10 times is optimal. Furthermore, examples of stretching methods include melt stretching, wet stretching, and gel stretching. When performing wet stretching or gel stretching, benzene, toluene, xylene, ethylbenzene,
Cyclohexane, decalin, N-methylpyrrolidone, tetrahydrofuran, carbon tetrachloride.
クロロホルム、ジクロロメタン、モノクロロベンゼン、
ジクロロベンゼン、トリクロロベンゼン。Chloroform, dichloromethane, monochlorobenzene,
Dichlorobenzene, trichlorobenzene.
トリクレンなどを用いればよい、また、このシンジオタ
クチック構造のスチレン系重合体に、アタクチック構造
のスチレン系重合体、アイソタクチック構造のスチレン
系重合体あるいは低分子量のシンジオタクチック構造の
スチレン系重合体を配合したものを用いて延伸処理を行
なうこともできる。In addition, in addition to this styrene polymer with a syndiotactic structure, a styrene polymer with an atactic structure, a styrene polymer with an isotactic structure, or a styrene polymer with a low molecular weight syndiotactic structure may be used. Stretching treatment can also be carried out using a blended material.
［実施例］
次に、本発明を実施例および比較例によりさらに詳しく
説明する。[Examples] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例１
（１）スチレン系重合体の製造
反応容器に、溶媒としてトルエン２０ｍ！！と触媒成分
としてテトラエトキシチタニウム０．０５ミリモルおよ
びメチルアルミノキサンをアルミニウム原子として５ミ
リモル加え、４０℃においてこれにスチレン１５ｈρを
加え、４時間重合反応を行なった。Example 1 (1) Production of styrenic polymer 20ml of toluene was added as a solvent to a reaction vessel! ! 0.05 mmol of tetraethoxytitanium and 5 mmol of methylaluminoxane as aluminum atoms were added as catalyst components, and 15 hρ of styrene was added thereto at 40° C., and a polymerization reaction was carried out for 4 hours.
反応終了後、生成物を塩酸−メタノール混合液で洗浄し
、触媒成分を分解除去した。ついで乾燥し、スチレン系
重合体（ポリスチレン）２５ｇを得た。つぎに、この重
合体をメチルエチルケトンを溶媒としてソックスレー抽
出し、抽出残分（以下ＭＩＰという−） ９５ｗｔ％を
得た。このものの重量平均分子量は１，３５０，０００
、数平均分子量は４８０，０００であり、融点は２７
０℃であった。また、１３０−ＮＭＨによる分析から、
シンジオタクチック構造に基因する１４５．３５ｐｐｍ
に吸収が認められ、そのピーク面積から算出したラセミ
ペンタッドでのシンジオタクテイシテイ−は９６％であ
った。After the reaction was completed, the product was washed with a hydrochloric acid-methanol mixture to decompose and remove the catalyst component. It was then dried to obtain 25 g of a styrene polymer (polystyrene). Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue (hereinafter referred to as MIP) of 95 wt%. The weight average molecular weight of this product is 1,350,000
, the number average molecular weight is 480,000 and the melting point is 27
It was 0°C. Also, from analysis by 130-NMH,
145.35ppm due to syndiotactic structure
Absorption was observed, and the syndiotacticity for racemic pentad calculated from the peak area was 96%.
（２）成形品の製造
上記（１）で得られたシンジオタクチック構造のスチレ
ン系重合体を、押出機により押出してストランドを得た
。このストランドを１３０℃に保持されたオイルバス中
において、延伸倍率を３倍として延伸し、緊張下に室温
まで冷却した。このようにして得られた延伸ストランド
の機械的性質を測定した。結果を表に示す。(2) Production of molded product The styrenic polymer having a syndiotactic structure obtained in the above (1) was extruded using an extruder to obtain a strand. This strand was stretched at a stretching ratio of 3 times in an oil bath maintained at 130° C., and cooled to room temperature under tension. The mechanical properties of the drawn strand thus obtained were measured. The results are shown in the table.
実施例２
（１）スチレン系重合体の製造
実施例１の（１）と全く同様にしてスチレン系重合体を
得た。Example 2 (1) Production of styrenic polymer A styrenic polymer was obtained in exactly the same manner as in Example 1 (1).
（２）成形品の製造
上記（１）で得たスチレン系重合体を、溶媒のエチルベ
ンゼン中に入れて加熱溶解し、２重量％の濃度のスチレ
ン系重合体溶液を得た。この溶液を充分に冷却したアル
ミニウム製の箱に流し込み、寒天状のゲルを得た。この
ゲルをクツチェ上でプレスしつつ吸引乾燥し、室温にお
いて減圧下、２４時間乾燥してゲル板を得た。つぎに、
このゲル板を短冊状に切断し、この短冊を空気中、１３
０℃において延伸倍率８倍に延伸した。得られた延伸物
につき、機械的強度を測定した。結果を表に示す。(2) Production of molded article The styrenic polymer obtained in the above (1) was placed in ethylbenzene as a solvent and dissolved by heating to obtain a styrene polymer solution having a concentration of 2% by weight. This solution was poured into a sufficiently cooled aluminum box to obtain an agar-like gel. This gel was dried by suction while being pressed on a Kutsche, and dried at room temperature under reduced pressure for 24 hours to obtain a gel plate. next,
This gel plate was cut into strips, and the strips were placed in the air for 13 minutes.
The film was stretched at a stretching ratio of 8 times at 0°C. The mechanical strength of the drawn product was measured. The results are shown in the table.
実施例３
（１）スチレン系重合体の製造
重合温度を５０℃としたほかは、実施例１の（１）と同
様の操作を行ない、スチレン系重合体（ポリスチレンつ
２．８ｇを得た。このものの旧Ｐは９４ｗｔ％であった
。また得られたスチレン系重合体（ＮＩＰ）は、重量平
均分子量５００，０００ 、数平均分子量１８０，００
０． シンジオタクテイシテイ−９５％であった。Example 3 (1) Production of styrenic polymer 2.8 g of a styrenic polymer (polystyrene) was obtained by carrying out the same operation as in Example 1 (1) except that the polymerization temperature was changed to 50°C. The old P of this product was 94 wt%.The obtained styrenic polymer (NIP) had a weight average molecular weight of 500,000 and a number average molecular weight of 180,000.
0. Syndiotacticity was -95%.
（２）成形品の製造
上記（１）で得たスチレン系重合体を用いたほかは、実
施例２の（２）と同様の操作を行なった。結果を表に示
す。(2) Production of molded article The same operation as in Example 2 (2) was performed except that the styrene polymer obtained in (1) above was used. The results are shown in the table.
実施例４
（１）スチレン系重合体の製造
重合温度を３０℃としたほかは、実施例１の（１）と同
様の操作を行ない、スチレン系重合体（ポリスチレン）
９．０ｇを得た。このもののＮＩＰは９９ｗｔ％で
あった。また得られたスチレン系重合体（ＮＩＰ）は、
重量平均分子１ ｔ、ａｏｏ、ｏｏｏ、 数平均分子
量６５０．０００ 、 シンジオタクテイシテイ−８
８％であった。Example 4 (1) Production of styrenic polymer A styrene polymer (polystyrene) was produced by carrying out the same operation as in Example 1 (1), except that the polymerization temperature was 30°C.
9.0g was obtained. The NIP of this product was 99 wt%. The obtained styrenic polymer (NIP) is
Weight average molecular weight 1t, aoo, ooo, number average molecular weight 650.000, syndiotacticity -8
It was 8%.
（２）成形品の製造
上記（１）で得たスチレン系重合体を用い、延伸倍率を
７倍としたほかは、実施例２の（２）と同様の操作を行
なった。結果を表に示す。(2) Production of molded article The same operation as in Example 2 (2) was carried out, except that the styrene polymer obtained in (1) above was used and the stretching ratio was increased to 7 times. The results are shown in the table.
実施例５
（１）スチレン系重合体の製造
重合温度を２０℃としたほかは、実施例１の（１）と同
様の操作を行ない、スチレン系重合体（ポリスチレン）
４．０ｇを得た。このもののＭＩＰは９２ｗｔ％であっ
た。また得られたスチレン系重合体（旧Ｐ）は、重量平
均分子量２，４００，０００ 、数平均分子ｌ ８６０
．０００ 、 シンジオタクテイシテイ−１００％で
あったφ
（２）成形品の製造
上記（１）で得たスチレン系重合体を用い、延伸倍率を
６倍としたほかは、実施例２の（２）と同様の操作を行
なった。結果を表に示す。Example 5 (1) Production of styrenic polymer A styrene polymer (polystyrene) was produced by carrying out the same operation as in Example 1 (1), except that the polymerization temperature was 20°C.
4.0g was obtained. The MIP of this product was 92 wt%. The obtained styrene polymer (old P) had a weight average molecular weight of 2,400,000 and a number average molecular weight of 860
．． 000, syndiotacticity - φ of 100% (2) Production of molded product The styrene polymer obtained in (1) above was used and the stretching ratio was 6 times, but the same procedure as in Example 2 (2) was carried out. ) was performed. The results are shown in the table.
実施例６
（１）スチレン系重合体の製造
重合温度を０℃とし、かつ重合時間を８時間としたほか
は、実施例１の（１）と同様の操作を行ない、スチレン
系重合体（ポリスチレン） １．５ｇｅ得た。このも
ののＭＩＰは７０ｖｔ％であった。また得られたスチレ
ン系重合体（ＮＩＰ）は、重量平均分子量４，５００，
０００ 、数平均分子量１，８００，０００． シン
ジオタクテイシテイ−１００％であった。Example 6 (1) Production of styrenic polymer A styrene polymer (polystyrene ) 1.5ge was obtained. The MIP of this product was 70vt%. The obtained styrenic polymer (NIP) had a weight average molecular weight of 4,500,
000, number average molecular weight 1,800,000. Syndiotacticity was 100%.
（２）成形品の製造
上記（１）で得たスチレン系重合体を用い、延伸倍率を
５倍としたほかは、実施例２の（２）と同様の操作を行
なった。結果を表に示す。(2) Production of molded article The same operation as in Example 2 (2) was performed except that the styrene polymer obtained in (1) above was used and the stretching ratio was increased to 5 times. The results are shown in the table.
比較例１
延伸処理をしなかったほかは、実施例２の（２）と同様
の操作を行なった。結果を表に示す。Comparative Example 1 The same operation as in Example 2 (2) was performed except that the stretching treatment was not performed. The results are shown in the table.
比較例２
触媒として、マグネシウムジェトキシド１０．０ｇに四
塩化チタン５ｈβを反応させ、チタン化合物を担持した
チタン触媒成分１．０ ミリモルと、トリエチルアルミ
ニウム１０ミリモルを組合せたものを用い、ヘプタン溶
媒中、７０℃において、スチレン１００ｍＡ’の重合反
応を２時間行ない、重量平均分子量ｉ、ｏｏｏ、ｏｏｏ
、 数平均分子量２８０，０００のアイソタクチック
構造のスチレン系重合体（ポリスチレン） ４８．７ｇ
を得た。このスチレン系重合体は実施例１と同様にメチ
ルエチルケトンで抽出した残分は９８ｖｔ％であった。Comparative Example 2 As a catalyst, 10.0 g of magnesium jetoxide was reacted with titanium tetrachloride 5hβ, and a combination of 1.0 mmol of a titanium catalyst component supporting a titanium compound and 10 mmol of triethylaluminum was used in a heptane solvent. A polymerization reaction of 100 mA' of styrene was carried out at 70°C for 2 hours, and the weight average molecular weight was i, ooo, ooo.
, 48.7g of isotactic styrenic polymer (polystyrene) with a number average molecular weight of 280,000
I got it. This styrene polymer was extracted with methyl ethyl ketone in the same manner as in Example 1, and the residue was 98 vt%.
このアイソタクチック構造のスチレン系重合体について
、実施例１の（２）と同様に延伸した（但し、延伸倍率
６倍）。得られた延伸物について機械的強度を測定した
。結果を表に示す。This styrene polymer having an isotactic structure was stretched in the same manner as in (2) of Example 1 (however, the stretching ratio was 6 times). The mechanical strength of the drawn product was measured. The results are shown in the table.
比較例３
延伸処理をしなかったほかは、比較例２と同様の操作を
行なった。結果を表に示す。Comparative Example 3 The same operation as Comparative Example 2 was performed except that the stretching treatment was not performed. The results are shown in the table.
［発明の効果］
本発明の成形品、特にせんい、フｉルム、テープなどの
成形品は、シンジオタクチック構造のスチレン系重合体
の属性である耐熱性を維持しつつ、延伸処理によって機
械的強度、特に弾性率の著しく改善されたものである。[Effects of the Invention] The molded products of the present invention, particularly molded products such as fibers, films, and tapes, can be mechanically improved by stretching treatment while maintaining the heat resistance that is an attribute of styrenic polymers with a syndiotactic structure. The strength, especially the modulus of elasticity, is significantly improved.
したがって、本発明のスチレン系重合体成形品は、ロー
プ、ケーブル、複合強化材をはじめとして、各種用途に
幅広く、かつ有効に利用される。Therefore, the styrenic polymer molded article of the present invention can be widely and effectively used in various applications including ropes, cables, and composite reinforcement materials.
Claims (2)
均分子量３００，０００以上のスチレン系重合体を延伸
してなるスチレン系重合体成形品。(1) A styrenic polymer molded article obtained by stretching a styrenic polymer having a weight average molecular weight of 300,000 or more and mainly having a syndiotactic structure.
よる核磁気共鳴スペクトル分析のラセミペンタッドでの
シンジオクタティシティー８５％以上のものである特許
請求の範囲第１項記載の成形品。(2) The molded article according to claim 1, wherein the stereoregularity of the styrenic polymer is 85% or more in syndioctality in racemic pentads in nuclear magnetic resonance spectroscopy using carbon isotopes. .
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61222092A JPH0788430B2 (en) | 1986-09-22 | 1986-09-22 | Film or tape |
| EP87907535A EP0342234B1 (en) | 1986-09-22 | 1987-11-17 | Styrenic polymer moldings |
| DE3789900T DE3789900T2 (en) | 1986-09-22 | 1987-11-17 | STYRENE POLYMER MOLDED PARTS. |
| PCT/JP1987/000891 WO1989004846A1 (en) | 1986-09-22 | 1987-11-17 | Styrenic polymer moldings |
| US07/524,372 US5166238A (en) | 1986-09-22 | 1990-05-15 | Styrene-based resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61222092A JPH0788430B2 (en) | 1986-09-22 | 1986-09-22 | Film or tape |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7078470A Division JP2538845B2 (en) | 1995-03-10 | 1995-03-10 | Fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6377905A true JPS6377905A (en) | 1988-04-08 |
| JPH0788430B2 JPH0788430B2 (en) | 1995-09-27 |
Family
ID=16777002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61222092A Expired - Fee Related JPH0788430B2 (en) | 1986-09-22 | 1986-09-22 | Film or tape |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788430B2 (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01168709A (en) * | 1987-12-25 | 1989-07-04 | Asahi Chem Ind Co Ltd | Syndiotactic polystyrene film |
| JPH0214055A (en) * | 1988-06-30 | 1990-01-18 | Idemitsu Kosan Co Ltd | Nonwoven fabric |
| JPH0267328A (en) * | 1988-08-31 | 1990-03-07 | Idemitsu Kosan Co Ltd | Raw material for food packaging |
| JPH02194044A (en) * | 1989-01-24 | 1990-07-31 | Idemitsu Kosan Co Ltd | Extrusion molding material and production of molded article thereof |
| EP0387608A2 (en) * | 1989-02-28 | 1990-09-19 | Himont Incorporated | Articles of a new crystalline form of syndiotactic styrene polymer |
| US5089353A (en) * | 1988-10-14 | 1992-02-18 | Kuraray Co., Ltd. | Multi-layer material having gas barrier properties |
| US5145950A (en) * | 1988-08-31 | 1992-09-08 | Idemitsu Kosan Co., Ltd. | Method of storing food or plant materials by wrapping with a stretched syndiotactic polystyrene film |
| US5166238A (en) * | 1986-09-22 | 1992-11-24 | Idemitsu Kosan Co., Ltd. | Styrene-based resin composition |
| JPH0691750A (en) * | 1992-09-11 | 1994-04-05 | Toyobo Co Ltd | Syndiotactic polystyrene biaxially drawn film |
| JPH0699485A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially stretched film |
| JPH06100711A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially oriented film |
| JPH06107813A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH06107812A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH06106616A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Syndiotactic polystyrenr biaxially oriented film |
| JPH0724911A (en) * | 1993-07-08 | 1995-01-27 | Toyobo Co Ltd | Syndyotactic polystyrene film |
| US5446117A (en) * | 1993-08-19 | 1995-08-29 | Queen's University At Kingston | Process for producing amorphous syndiotactic polystyrene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61101926A (en) * | 1984-10-25 | 1986-05-20 | 株式会社東芝 | Refiring surge test for gas-insulated switch gear |
-
1986
- 1986-09-22 JP JP61222092A patent/JPH0788430B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61101926A (en) * | 1984-10-25 | 1986-05-20 | 株式会社東芝 | Refiring surge test for gas-insulated switch gear |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166238A (en) * | 1986-09-22 | 1992-11-24 | Idemitsu Kosan Co., Ltd. | Styrene-based resin composition |
| JPH01168709A (en) * | 1987-12-25 | 1989-07-04 | Asahi Chem Ind Co Ltd | Syndiotactic polystyrene film |
| JPH0214055A (en) * | 1988-06-30 | 1990-01-18 | Idemitsu Kosan Co Ltd | Nonwoven fabric |
| CN1035121C (en) * | 1988-06-30 | 1997-06-11 | 出光興产株式会社 | Nonwoven fabrics |
| JPH0267328A (en) * | 1988-08-31 | 1990-03-07 | Idemitsu Kosan Co Ltd | Raw material for food packaging |
| US5145950A (en) * | 1988-08-31 | 1992-09-08 | Idemitsu Kosan Co., Ltd. | Method of storing food or plant materials by wrapping with a stretched syndiotactic polystyrene film |
| US5346950A (en) * | 1988-10-14 | 1994-09-13 | Kuraray Co., Ltd. | Resin composition |
| US5089353A (en) * | 1988-10-14 | 1992-02-18 | Kuraray Co., Ltd. | Multi-layer material having gas barrier properties |
| JPH02194044A (en) * | 1989-01-24 | 1990-07-31 | Idemitsu Kosan Co Ltd | Extrusion molding material and production of molded article thereof |
| EP0387608A2 (en) * | 1989-02-28 | 1990-09-19 | Himont Incorporated | Articles of a new crystalline form of syndiotactic styrene polymer |
| JPH0691750A (en) * | 1992-09-11 | 1994-04-05 | Toyobo Co Ltd | Syndiotactic polystyrene biaxially drawn film |
| JPH06100711A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially oriented film |
| JPH0699485A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially stretched film |
| JPH06107813A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH06107812A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH06106616A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Syndiotactic polystyrenr biaxially oriented film |
| JPH0724911A (en) * | 1993-07-08 | 1995-01-27 | Toyobo Co Ltd | Syndyotactic polystyrene film |
| US5446117A (en) * | 1993-08-19 | 1995-08-29 | Queen's University At Kingston | Process for producing amorphous syndiotactic polystyrene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0788430B2 (en) | 1995-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6377905A (en) | Styrene polymer molding | |
| JP2505001B2 (en) | Method for producing syndiotactic polystyrene film | |
| KR960006161B1 (en) | Styrene polymer molding material and process for preparing the same | |
| JPH06104337B2 (en) | Stretched styrene resin film and method for producing the same | |
| EP0291915B1 (en) | Styrene-based resin composition and moldings produced from said composition | |
| JP2826350B2 (en) | Method for producing styrenic polymer film | |
| JP2888856B2 (en) | Syndiotactic polystyrene transparent film | |
| JP2748935B2 (en) | Syndiotactic polystyrene film | |
| JP2672589B2 (en) | Styrene-based polymer molded article and method for producing the same | |
| JP2790636B2 (en) | Stretched film for food packaging | |
| EP0342234B1 (en) | Styrenic polymer moldings | |
| JPH07112699B2 (en) | Method for manufacturing resin molded products | |
| JPH03114728A (en) | Manufacture of rolled article | |
| JP2710324B2 (en) | Styrene-based polymer molded article and method for producing the same | |
| JP2538845B2 (en) | Fiber | |
| JP3734892B2 (en) | Styrene resin stretched sheet | |
| JP3649257B2 (en) | Styrenic resin sheet / film manufacturing method | |
| KR930001482B1 (en) | Stereoregular acrylonitrile polymer and composition comprising same | |
| JP2636900B2 (en) | Stretched styrene resin molded article and method for producing the same | |
| JPH02175228A (en) | Polyarylene sulfide oriented molding | |
| JPH0253909A (en) | High-strength fiber of a stereoregular polystyrene | |
| JP2818284B2 (en) | Molded product of polypropylene and method for producing the same | |
| JP3574694B2 (en) | Polystyrene resin and molded product thereof | |
| JPH02105840A (en) | Stereoregular polystyrene-containing mixture | |
| JPH09263650A (en) | Styrenic resin foamed product and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |