JPH07112699B2 - Method for manufacturing resin molded products - Google Patents
Method for manufacturing resin molded productsInfo
- Publication number
- JPH07112699B2 JPH07112699B2 JP61103195A JP10319586A JPH07112699B2 JP H07112699 B2 JPH07112699 B2 JP H07112699B2 JP 61103195 A JP61103195 A JP 61103195A JP 10319586 A JP10319586 A JP 10319586A JP H07112699 B2 JPH07112699 B2 JP H07112699B2
- Authority
- JP
- Japan
- Prior art keywords
- molding
- styrene
- poly
- resin molded
- present
- 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 - Fee Related
Links
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は樹脂成形品の製造方法に関し、詳しくは特定の
樹脂素材を用いるとともに、急冷操作を行なうことによ
り、樹脂成形品を比較的低い温度で製造することのでき
る方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing a resin molded product, and more specifically, by using a specific resin material and performing a quenching operation, the resin molded product is kept at a relatively low temperature. And a method that can be manufactured in.
一般に、ポリスチレンはラジカル重合によって製造され
たものが用いられている。このラジカル重合によるポリ
スチレンは、立体規則性がアタクチック構造であるた
め、得られる成形品は機械的強度や耐熱性に劣るという
問題があった。Generally, polystyrene produced by radical polymerization is used. Since the stereoregularity of the radical-polymerized polystyrene has an atactic structure, there is a problem that the obtained molded product is inferior in mechanical strength and heat resistance.
そこで、本発明者らは上記従来の欠点を解消したポリス
チレン系樹脂の成形品を開発すべく鋭意研究を重ねたと
ころ、本発明者らのグループが先般開発した立体規則性
が高度のシンジオタクチック構造を有するスチレン系重
合体が、耐熱性や機械的強度にすぐれた性質を有するこ
とを見出した。しかし、この高度のシンジオクタチック
構造を有するスチレン系重合体は、耐熱性が良好である
が故に、成形に際しては高い成形温度を必要とし、分解
劣化を生じやすいなどの問題を有するとともに、成形装
置や成形操作などにおいて様々な問題を有する。Therefore, the inventors of the present invention have conducted intensive studies to develop a molded product of polystyrene resin that eliminates the above-mentioned conventional drawbacks, and as a result, the group of the inventors of the present invention has recently developed a highly stereoregular syndiotactic substance. It was found that the styrenic polymer having a structure has excellent heat resistance and mechanical strength. However, since this styrene-based polymer having a high syndioctatic structure has good heat resistance, it requires a high molding temperature at the time of molding and has a problem that decomposition and deterioration are likely to occur and a molding device There are various problems in molding and molding operations.
本発明者らはこのような問題を解決するために、さらに
研究を続けた結果、シンジオクタチック構造を有するス
チレン系重合体を成形するにあたって、一旦溶融あるい
は溶解したスチレン系重合体を急冷することにより、低
い温度で成形が可能になることを見出した。本発明はか
かる知見に基いて完成したものである。As a result of further research to solve such a problem, the present inventors have found that when molding a styrene-based polymer having a syndioctatic structure, the once melted or dissolved styrene-based polymer is rapidly cooled. It has been found that this enables molding at a low temperature. The present invention has been completed based on such findings.
すなわち本発明は、主としてシンジオタクチック構造を
有するスチレン系重合体を主成分とする樹脂を、加熱溶
融あるいは溶媒中で加熱溶解し、次いで50℃／分以上の
冷却速度で100℃以下にまで急冷した後に成形すること
を特徴とする樹脂成形品の製造方法を提供するものであ
る。That is, the present invention mainly comprises a resin mainly composed of a styrene-based polymer having a syndiotactic structure, which is melted by heating or dissolved in a solvent and then rapidly cooled to 100 ° C or less at a cooling rate of 50 ° C / min or more. The present invention provides a method for producing a resin molded product, which is characterized in that the molding is performed after that.
本発明の製造方法においては、成形素材として、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を
主成分とする樹脂が用いられる。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置する新規な立
体構造を有するものであり、そのタクティシティーは核
磁気共鳴法（NMR法）により定量される。In the production method of the present invention, a resin mainly containing a styrene polymer having a syndiotactic structure is used as a molding material. This styrene polymer mainly has a syndiotactic structure, that is, a novel three-dimensional structure in which a phenyl group or a substituted phenyl group, which is a side chain, is alternately located in the opposite direction with respect to the main chain formed from carbon-carbon bonds. The tacticity is determined by the nuclear magnetic resonance method (NMR method).
NMRにより測定されるタクティシティーは、連続する複
数個の構造単位の存在割合、例えば２個の場合はダイア
ッド,3個の場合はトリアッド,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、総
じてダイアッドで85％以上若しくはペンタッドで35％以
上のシンジオタクチック構造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（安息香酸エ
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，樹脂組成物を指称する。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），ポリ
（イソプロピルスチレン），ポリ（ターシャリーブチル
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。The tacticity measured by NMR can be represented by the abundance ratio of a plurality of continuous structural units, for example, diad in the case of 2, triad in the case of 3, and pentad in the case of the present invention. The styrene-based polymer mainly having a syndiotactic structure means polystyrene, poly (alkylstyrene), poly (halogenated styrene), which has a syndiotactic structure of 85% or more in diads or 35% or more in pentads in general. It refers to poly (alkoxystyrene), poly (benzoic acid ester styrene) and mixtures thereof, or copolymers and resin compositions containing these as the main components. Here, as the poly (alkylstyrene), there are poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiarybutylstyrene), etc., and as the poly (halogenated styrene), Examples include poly (chlorostyrene) and poly (bromostyrene). Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).
本発明の製造方法の成形素材は、上述のスチレン系重合
体を主成分とする樹脂であるが、さらに酸化防止剤，紫
外線吸収剤，滑剤，強化剤，充填剤など様々な添加剤を
加えることもできる。The molding material of the production method of the present invention is a resin containing the above-mentioned styrene-based polymer as a main component, but various additives such as an antioxidant, an ultraviolet absorber, a lubricant, a reinforcing agent and a filler may be added. You can also
本発明の方法では、まず上記成形素材を加熱溶融あるい
は溶媒中で加熱溶解する。加熱溶融の温度は、通常は26
0〜350℃、好ましくは280〜330℃である。また溶媒中で
加熱溶解する場合には、溶媒としては一般にトルエン，
キシレン，ベンゼン，エチルベンゼンなどの芳香族炭化
水素が好適に用いられる。In the method of the present invention, first, the above molding material is melted by heating or melted by heating in a solvent. The temperature for heating and melting is usually 26
The temperature is 0 to 350 ° C, preferably 280 to 330 ° C. In the case of dissolving by heating in a solvent, the solvent is generally toluene,
Aromatic hydrocarbons such as xylene, benzene and ethylbenzene are preferably used.
本発明の方法では、成形素材を上述のようにして充分に
溶融あるいは溶解した後、急冷することが必要である。
この急冷操作により、成形素材であるシンジオタクチッ
ク構造を有するスチレン系重合体が非晶質のものとな
り、そのため後続する成形操作を低温下で進行させるこ
とが可能となるのである。In the method of the present invention, it is necessary to melt or melt the molding material sufficiently as described above and then quench it.
By this quenching operation, the styrenic polymer having a syndiotactic structure, which is a molding material, becomes amorphous, so that the subsequent molding operation can proceed at a low temperature.
したがって、この急冷は上記スチレン系重合体が非晶質
のものとなるような条件で行なえばよく、その条件は特
に制限されないが、可能な限り速やかに冷却すべきであ
り、具体的には50℃／分以上、好ましくは100℃／分以
上の冷却速度で100℃以下にまで冷却すればよい。Therefore, this rapid cooling may be carried out under conditions such that the styrene-based polymer becomes amorphous, the conditions are not particularly limited, it should be cooled as quickly as possible, specifically 50 It may be cooled to 100 ° C or lower at a cooling rate of 100 ° C / min or higher, preferably 100 ° C / min or higher.
本発明の方法においては、このように急冷して得た成形
素材のペレット、シート、フィルム、ストランド、フィ
ラメント、中空体等を適宜手段で成形することにより、
目的とする樹脂成形品を製造することができる。この際
の成形は圧縮成形，押出成形，射出成形，一軸延伸成
形，二軸延伸成形，真空成形，圧空成形，吹込成形，圧
縮成形など様々な熱成形手段によればよいが、このとき
の成形温度は急冷操作をしない場合に比べて大幅に低下
させることができる。In the method of the present invention, the pellets, sheets, films, strands, filaments, hollow bodies and the like of the molding material thus obtained by rapid cooling are molded by an appropriate means,
A desired resin molded product can be manufactured. The molding at this time may be performed by various thermoforming means such as compression molding, extrusion molding, injection molding, uniaxial stretch molding, biaxial stretch molding, vacuum molding, pressure molding, blow molding, and compression molding. The temperature can be lowered significantly as compared to the case where the quenching operation is not performed.
叙上の如く、本発明の方法によれば、その過程で比較的
低温下に成形することができる成形素材が得られるとと
もに、この成形素材から低温下の成形で樹脂成形品が製
造される。そのため、本発明の方法で得られる樹脂成形
品は、分解劣化などがほとんどなく高品質のものであ
る。As described above, according to the method of the present invention, a molding material that can be molded at a relatively low temperature is obtained in the process, and a resin molded product is manufactured from this molding material by molding at a low temperature. Therefore, the resin molded product obtained by the method of the present invention is of high quality with almost no decomposition and deterioration.
したがって、本発明の方法によって製造されるフィル
ム，シート，繊維，ヤーン，容器，パイプ，その他三次
元成形体などの樹脂成形品は、耐熱性，耐溶剤性に優
れ、各種日用品をはじめ、様々な機械部品や産業用の資
材として有効かつ幅広く利用することができる。Therefore, resin molded products such as films, sheets, fibers, yarns, containers, pipes, and other three-dimensional molded products produced by the method of the present invention have excellent heat resistance and solvent resistance, and can be used for various daily necessities and various It can be effectively and widely used as a machine part or industrial material.
次に本発明を実施例によりさらに詳しく説明する。 Next, the present invention will be described in more detail with reference to Examples.
参考例１ 反応容器に溶媒としてトルエン１と、触媒成分である
シクロペンタジエニルチタニウムトリクロライド10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0.4モル加え、20℃においてスチレン1.8を加え
て１時間重合反応を行なった。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。ついで乾燥して重合体165g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95重量％を得た。この重合体は重合平均
分子量が280000,数平均分子量57000であり、融点は270
℃であった。また、この重合体は同位体炭素の核磁気共
鳴（13C−NMR）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
積から算出したペンタッドでのシンジオクタティシティ
ーは96％のポリスチレンであった。Reference Example 1 Toluene 1 as a solvent, 10 mmol of cyclopentadienyl titanium trichloride as a catalyst component, and 0.4 mol of methylaluminoxane as an aluminum atom were added to a reaction vessel, and styrene 1.8 was added at 20 ° C. to carry out a polymerization reaction for 1 hour. I did. After the reaction was completed, the product was washed with a hydrochloric acid-methanol mixed solution to decompose and remove the catalyst component. Then, it was dried to obtain 165 g of a polymer. Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue of 95% by weight. This polymer has a polymerization average molecular weight of 280000, a number average molecular weight of 57,000 and a melting point of 270.
It was ℃. This polymer was also found to have an absorption at 145.35 ppm due to the syndiotactic structure from the analysis of isotopic carbon nuclear magnetic resonance ( 13 C-NMR), and the syndioctaticity in the pentad calculated from the peak area. Was 96% polystyrene.
実施例１ 参考例１で得られたポリスチレンを押出機に供給し、30
0℃において溶融混練したのち、細孔から押出し、直ち
に氷水中に導入して急冷した。得られた細線状の樹脂を
切断してペレットを得た。ここで得られたペレットは非
晶質であり、200℃において圧縮（プレス）成形するこ
とができた。Example 1 The polystyrene obtained in Reference Example 1 was fed to an extruder,
After melt-kneading at 0 ° C., the mixture was extruded through pores, immediately introduced into ice water, and rapidly cooled. The obtained fine line-shaped resin was cut to obtain pellets. The pellets obtained here were amorphous and could be compression molded at 200 ° C.
比較例１ 参考例１で得られたポリスチレンを押出機に供給し、30
0℃において溶融混練したのち、細孔から押出し、空気
中で徐冷した。得られた細線状の樹脂を切断してペレッ
トを得た。このペレット圧縮（プレス）成形のために30
0℃まで加熱昇温することが必要であった。Comparative Example 1 The polystyrene obtained in Reference Example 1 was fed to an extruder,
After melt-kneading at 0 ° C., the mixture was extruded through pores and gradually cooled in air. The obtained fine line-shaped resin was cut to obtain pellets. 30 for this pellet compression (press) molding
It was necessary to heat up to 0 ° C.
Claims (1)
スチレン系重合体を主成分とする樹脂を、加熱溶融ある
いは溶融中で加熱溶解し、次いで50℃／分以上の冷却速
度で100℃以下に急冷した後に成形することを特徴とす
る樹脂成形品の製造方法。1. A resin mainly comprising a styrene-based polymer having a syndiotactic structure as a main component is melted by heating or is melted during melting, and then rapidly cooled to 100 ° C. or less at a cooling rate of 50 ° C./min or more. A method for producing a resin-molded product, which comprises molding afterwards.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61103195A JPH07112699B2 (en) | 1986-05-07 | 1986-05-07 | Method for manufacturing resin molded products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61103195A JPH07112699B2 (en) | 1986-05-07 | 1986-05-07 | Method for manufacturing resin molded products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62259809A JPS62259809A (en) | 1987-11-12 |
| JPH07112699B2 true JPH07112699B2 (en) | 1995-12-06 |
Family
ID=14347734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61103195A Expired - Fee Related JPH07112699B2 (en) | 1986-05-07 | 1986-05-07 | Method for manufacturing resin molded products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07112699B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2612304B2 (en) * | 1988-04-26 | 1997-05-21 | 旭化成工業株式会社 | Method for producing syndiotactic polystyrene structure |
| JP2612303B2 (en) * | 1988-04-26 | 1997-05-21 | 旭化成工業株式会社 | Method for producing syndiotactic polystyrene crystal structure |
| US5169893A (en) * | 1988-09-01 | 1992-12-08 | The Dow Chemical Company | Mixtures containing stereoregular polystyrene |
| JP2819209B2 (en) * | 1992-07-14 | 1998-10-30 | 基嗣 須加 | Improved recycling method for plastic waste made of styrenic synthetic resin |
| US5760172A (en) * | 1995-05-26 | 1998-06-02 | Idemitsu Petrochemical Co., Ltd. | Process for preparing styrenic resin |
| JPH08318529A (en) * | 1995-05-26 | 1996-12-03 | Idemitsu Petrochem Co Ltd | Manufacture of styrenic resin |
| US6605242B2 (en) * | 2001-03-06 | 2003-08-12 | Idemitsu Petrochemical Co., Ltd. | Method of producing styrenic resin granulate and shaped article |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3974250A (en) * | 1973-09-04 | 1976-08-10 | The Carborundum Company | Method for reducing crystalline orientation of para-oxybenzoyl polyesters |
-
1986
- 1986-05-07 JP JP61103195A patent/JPH07112699B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62259809A (en) | 1987-11-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |