JPS59120605A - Production of ultrahigh molecular weight polyethylene resin - Google Patents
Production of ultrahigh molecular weight polyethylene resinInfo
- Publication number
- JPS59120605A JPS59120605A JP22729982A JP22729982A JPS59120605A JP S59120605 A JPS59120605 A JP S59120605A JP 22729982 A JP22729982 A JP 22729982A JP 22729982 A JP22729982 A JP 22729982A JP S59120605 A JPS59120605 A JP S59120605A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- component
- ultra
- high molecular
- weight polyethylene
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は成形加工ｔｔの改善された超高分子量ボリエヂ
レン系４ｎＪ Ｊ指の製造方法に関する。更に詳しくは
、チーブジー型触媒の存在下、２段階以上で重合を行う
、ポリプロピ１／ン又はポリブテン−１成分を含む超高
分子量ポリエチレン系樹脂の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing ultra-high molecular weight polyethylene-based 4nJ J fingers with improved molding process tt. More specifically, the present invention relates to a method for producing an ultra-high molecular weight polyethylene resin containing a polypropylene-1/1 or polybutene-1 component, which is polymerized in two or more stages in the presence of a Chevesey-type catalyst.
超高分子量ポリエチレンはその分子量が１００万〜７０
０万にも達するため劇摩耗性、耐衝撃性、自己潤滑性、
耐溶剤性などの性質に優れ、特殊な高性能樹脂として注
目を集めている。Ultra-high molecular weight polyethylene has a molecular weight of 1 million to 70
0.00000000000000000000000000000000000000000000000000000000,0
It has excellent properties such as solvent resistance, and is attracting attention as a special high-performance resin.
しかし、上述したごとくその分子量があまりにも大きい
ため通常の方法では成形出来ず、特殊な成形加工法を必
要とし、その為成形品は高価格となり利用範囲も限定さ
れている。However, as mentioned above, since its molecular weight is too large, it cannot be molded using normal methods, and a special molding process is required, resulting in high prices for molded products and a limited scope of use.
従来超高分子量ポリエチレンの成形加工性の改善は主と
してその成形加工法についてなされており、例えば超高
分子量ポリエチレンの粉末をベレント化し、射出成形す
る方法（特開昭５７−８２０５１号公報）はその代表的
例である。Conventionally, the molding processability of ultra-high molecular weight polyethylene has been improved mainly by its molding process. For example, the method of turning ultra-high molecular weight polyethylene powder into belent and injection molding (Japanese Patent Application Laid-open No. 82051/1982) is a representative example. This is an example.
−力成形加工性そのものを改善する方法として超高分子
量ポリエチレンに潤滑油、ワックスなどを添加する方法
（特公昭４１−２１７８６５号公報）、アクリル重合体
、ポリプロピレンなどを混合する方法（特開昭５１−２
４６４９号公報、ボーランド特許第８６５５４号）が提
案されている。- Methods for improving the force forming processability include adding lubricating oil, wax, etc. to ultra-high molecular weight polyethylene (Japanese Patent Publication No. 41-217865), mixing acrylic polymer, polypropylene, etc. -2
No. 4649, Borland Patent No. 86554) have been proposed.
しかし超高分子量のポリエチレンにボリプｔ１ピレンを
単に粉末の状態や押し出し機内で添加混練する方法では
、両者は均一には分散せず、全く伸びのない組成物が得
られ、ポリプロピレンの添加により超高分子量ポリエチ
レンの代表的物性の一つである低温での劇＠撃性も大巾
に悪化してしまう。However, if polypropylene is simply added to ultra-high molecular weight polyethylene in powder form or in an extruder and kneaded, the two will not be dispersed uniformly and a composition with no elongation will be obtained. The impact resistance at low temperatures, which is one of the typical physical properties of molecular weight polyethylene, also deteriorates significantly.
本発明者らは謂ゆるチーブシーを触媒を用いて第一段階
で溶融流動性の良いポリプロピレン又はポリブテン−１
を重合し、同−触媒上で第二段階として超高分子量ポリ
エチレンを重合して得られた重合体が、耐摩耗性、耐衝
撃性、低い摩擦係数などの優れた物性を有し℃いるにも
かかわらず、驚くべきことに通常の成形機で成形するに
充分な溶融流動↑゛トを有していることを見い出し、こ
れに基づき更に鋭意検討した結果以下に説明する本発明
に到達した。The present inventors used so-called chivesea as a catalyst to produce polypropylene or polybutene-1, which has good melt flowability, in the first step.
The polymer obtained by polymerizing ultra-high molecular weight polyethylene as a second step on the same catalyst has excellent physical properties such as wear resistance, impact resistance, and low coefficient of friction. Nevertheless, it was surprisingly found that the melt flow rate was sufficient to allow molding with a normal molding machine.Based on this, further intensive studies were carried out, and the present invention as described below was arrived at.
すなわち、本発明は、遷移金属成分を含む固体触媒成分
と有機金属成分とから成るチー゛グラー型触媒を用い、
モノマー組成及び水素濃度の異なる２段階以上で七ツマ
−を重合して超高分子量ポリエチ１／ン系樹脂を製造す
るに際し、そのいずれかの段階で水素存在下でプロピレ
ン又はプロピレンを主成分とするモノマー又はブテン−
１又はブテン−１を主成分とするモノマーを重合して全
重合体の２〜６０重量％のポリプロピ１／ン又はポリブ
テン−１成分を製造し、残りの一段階以上で実質的に水
素の不存在下でエチレン又はエチレンを主成分とするｔ
ツマ−を重合して全重合体の９８〜４０重景％の超高分
子量ポリエチレン成分を製造することを％徴とする成形
加工性の改善された超高分子量ポリエチレン系樹脂の製
造方法に存する。That is, the present invention uses a Ziegler type catalyst consisting of a solid catalyst component containing a transition metal component and an organometallic component,
When producing an ultra-high molecular weight polyethylene resin by polymerizing 7-mer in two or more stages with different monomer compositions and hydrogen concentrations, propylene or propylene as the main component is added in the presence of hydrogen at any stage. monomer or butene
Polypropylene-1 or polybutene-1 is polymerized to produce a polypropylene-1 or polybutene-1 component of 2 to 60% by weight of the total polymer, and in one or more remaining steps, substantially no hydrogen is produced. In the presence of ethylene or ethylene-based t
The present invention provides a method for producing an ultra-high molecular weight polyethylene resin with improved molding processability, which comprises polymerizing a polyester resin to produce an ultra-high molecular weight polyethylene component of 98 to 40 percent by weight of the total polymer.
本発明で用いる遷移金属成分を含む固体触媒成分と有機
金属成分とから成る謂ゆるチーゲタ−型触媒とは、アイ
ソタクチックポリプロピレン又はポリブテン−１を与え
る公知の触媒系であり、固体触媒成分としてはハロゲン
原子及びＴｉ、ｌ／、Ｚｒ、ａｒ のうち少な（とも
いずれか一つの原子を含むもので好ましい例としては０
６価及び／又は４価のチタニウム化合物を主成分とする
もの■有機化合物及び／又は無機化合物等で変性された
チタニウム化合物複合体、■これら■、■を更に電子供
与性化合物で処理したもの■■、■をＴｉ０ｆ４や有機
アルミニウム成分で処理したもの■■〜■をエチレンや
プロピレンで予重合したものなどを挙げることが出来る
。The so-called Ziegeter-type catalyst, which is composed of a solid catalyst component containing a transition metal component and an organometallic component, used in the present invention is a known catalyst system that provides isotactic polypropylene or polybutene-1, and the solid catalyst component is A halogen atom and a small amount of Ti, l/, Zr, and ar (all of which contain one atom, and a preferable example is 0
Items whose main component is a hexavalent and/or tetravalent titanium compound; ■Titanium compound complexes modified with organic compounds and/or inorganic compounds; ■These items, which are further treated with electron-donating compounds. Examples include those in which (1) and (2) are treated with Ti0f4 or an organic aluminum component, and (2) to (2) which are prepolymerized with ethylene or propylene.
有機金属成分としてはトリエチルアルミニウム、トリイ
ソブチルアルミニウムのごときトリアルキルアルミニウ
ム、ジエチルアルミニウムクロライド、ジイソブチルモ
ノブロマイド、エチルアルミニウムジクロライドのごと
きアルキル゛ｒルミニウム−・ライドな挙げ４）ことが
出来るが、必要に応じて電ｆ・供与性化合物を同時に用
いる。Examples of organometallic components include trialkylaluminum such as triethylaluminum and triisobutylaluminum, alkylaluminum-rides such as diethylaluminium chloride, diisobutyl monobromide, and ethylaluminum dichloride4), but if necessary, An electron f-donating compound is used at the same time.
特にＭｇ＋Ｔｉ、ハロゲン原子及びｄＬ子倶１ｉ−性化
合物を含む固体触媒とトリアルギルアルミニウムなどを
主成分とする有機アルミニウム化合物とを組み合せた触
媒系が好適である。Particularly suitable is a catalyst system in which a solid catalyst containing Mg+Ti, a halogen atom, and a dL-containing compound is combined with an organoaluminum compound whose main component is trialgyl aluminum or the like.
いずれかの段階で重合されるポリプロピレンとは、プロ
ピレンホモポリマー又はプロピレンとα−オレフィンと
の共重合体をいう。α−オレフィンとしては例えばエチ
レン、ブテン−１、ヘギセン−１，４−メチルペンテン
−１、オクテン−１、デセン−１などがあり、これらの
中の１種又は２種以上を共重合する。共重合体中のプロ
ピレン含昂・は８０重量％以上好ましくは９０重量％以
上である。このＭ重合体のＭＦＩ （２５０℃、２．１
６ｋｙ荷重）は好ましくは０．１〜６０００ｙ／１０分
更に好ましくは２〜２０００Ｉ！１１７１０分である。The polypropylene polymerized at any stage refers to a propylene homopolymer or a copolymer of propylene and an α-olefin. Examples of α-olefins include ethylene, butene-1, hegycene-1,4-methylpentene-1, octene-1, and decene-1, and one or more of these are copolymerized. The propylene content in the copolymer is at least 80% by weight, preferably at least 90% by weight. MFI of this M polymer (250°C, 2.1
6ky load) is preferably 0.1 to 6000y/10 minutes, more preferably 2 to 2000I! It is 11,710 minutes.
このときの七ツマー組成及び水素一度は用いる触媒系、
共重合するコモノマー、目的とするＭＦＩ及び重合温度
などにより異なるので、あらかじめ、この段階の・人の
重合を行ない決定１゛る。At this time, the seven-mer composition and hydrogen catalyst system used,
Since it differs depending on the comonomer to be copolymerized, the target MFI, the polymerization temperature, etc., it is determined in advance by carrying out human polymerization at this stage.
又いずれかの段階で重合されるポリブテン−１とは、ブ
テン−１ホモポリマー又はブテン−１とα−オレフィン
との共重合体をいう。α−オレンインとしては例えばエ
チレン、プロピレン、ヘギ七ン−１，４−メチルペンテ
ン−１、オクテン−１、デセン−１などがあり、これら
の中の１種又は２種以上を共工【（合する。共重合体中
のブテン−１含量は８０重λ％以上々ｆま１−くは９０
重量％以上である。この重合体のＭ Ｉ（１９０”’Ｇ
、 ２．１６ｋｌ荷車）は好ましくは０．１〜５０００
．！ｉ’７１０分更に好ましくは２〜２０００ｙ／１０
分である。このときのモノーｒ−組成及び水素濃度は用
いる触媒系、共重合するコモノマー、目的とするＭＦＩ
及び重合温度などにより異なるので、あらかじめ、この
段階のみの′ｊ１【合を行ない決定する。Moreover, the polybutene-1 polymerized at any stage refers to a butene-1 homopolymer or a copolymer of butene-1 and an α-olefin. Examples of α-olenin include ethylene, propylene, hegynane-1,4-methylpentene-1, octene-1, decene-1, etc., and one or more of these can be co-processed. The butene-1 content in the copolymer is 80% by weight or more or 90% by weight.
% by weight or more. The M I of this polymer (190"'G
, 2.16kl cart) is preferably 0.1~5000
．． ! i'710 minutes, more preferably 2-2000y/10
It's a minute. The monor-composition and hydrogen concentration at this time are determined by the catalyst system used, the comonomer to be copolymerized, and the target MFI.
Since it differs depending on the polymerization temperature, etc., 'j1' is determined in advance by carrying out the polymerization at this stage only.
残りの少なくとも＝一段階で重合する超高分子量ポリエ
チレンとは、実質的に水素の不存在下で重合されるもの
でエチレンのホモポリマ′−又はエチレンとα−オレン
インとの共重合体である。α−オレンインとしては例え
ばプロピレン、ブグンー１、−＼キセノ−１，４−メチ
ルペンテン−１、オクテン−１、デセン−１などで１厖
又は２ｆｌｌｉ以上を共重合する３、共１Ｆ合体中のエ
チレンａ童は６０２Ｊｉ、址％以上好ましくは８０Ｍ！
、量％以上である。この際６％以下のジエン化合物が共
Ｗ−合されていても良い。The remaining ultra-high molecular weight polyethylene that is polymerized in at least one step is one that is polymerized substantially in the absence of hydrogen and is a homopolymer of ethylene or a copolymer of ethylene and α-olenein. As α-olein, for example, propylene, Bugun-1, -\xeno-1,4-methylpentene-1, octene-1, decene-1, etc. are used to copolymerize 1 or 2 or more 3, ethylene in the co-1F polymer. A child is 602Ji, preferably 80M or more!
, amount% or more. At this time, 6% or less of the diene compound may be co-W-combined.
超高分子量ポリエチレンの分子量は５０力以上好ましく
は１００万以上であるが、この段階の重合温度、コモノ
マー含量、微量の水素によりλ化するので、あらかじめ
、この段階のみの重合を別に行ない所望の分子量となる
よう条件を設定する。The molecular weight of ultra-high molecular weight polyethylene is 50% or more, preferably 1,000,000 or more, but because it becomes λ due to the polymerization temperature, comonomer content, and trace amount of hydrogen at this stage, the polymerization at this stage is carried out separately in advance to obtain the desired molecular weight. Set the conditions so that
ポリプロピレン又はポリブテン−１部分と超高分子Ｊｍ
ポリエチレン部分とから成る全重合体中の超高分子量ポ
リエチレン部分の含量は４０〜９８重量％好ましくは５
０〜９７重ｋｊ％更に好ましくは６０〜９５ｍｍ％であ
る。Polypropylene or polybutene-1 part and super high polymer Jm
The content of the ultra-high molecular weight polyethylene part in the total polymer consisting of the polyethylene part is 40 to 98% by weight, preferably 5
It is 0 to 97% by weight kj, more preferably 60 to 95mm%.
超高分子量ポリエチレン部分の含−清／い少ないと、成
形加工性は向上するが耐摩耗性や１ｌｌｉ１％撃ｔ！Ｌ
が低下してしまう。この含１）（が多ずきると上記物性
は優れるが、成形加工性の改停効果に乏しくなる。If the content of ultra-high molecular weight polyethylene is low, the moldability will improve, but the wear resistance will decrease. L
will decrease. If this (1) is too large, the above-mentioned physical properties will be excellent, but the effect of changing the molding processability will be poor.
一方ポリプロピレン又はポリブテン−１部分の含量は２
〜６０重量％好ましくは６〜５０重黛％更に好ましくは
５〜４０重量％である。On the other hand, the content of polypropylene or polybutene-1 part is 2
The content is preferably 60% to 60% by weight, preferably 6% to 50% by weight, and more preferably 5% to 40% by weight.
重合は２段階以上で行われるが、そのいずれかの段階で
ポリプロピレン又はポリブテン−１を製造し、残りの少
なくとも一段Ｖ４！１で超高分子量ポリエチレンを製造
する。各々の段階でも前述した組成及び分子量範囲であ
れば２槽以上で重合しても良い。またこハ、らの段階の
他に上述した２段階の中間的分子量又は中間的Ａ１１成
重合体を３０服景％以下重合しても良い。Polymerization is carried out in two or more stages, one of which produces polypropylene or polybutene-1, and the remaining at least one stage V4!1 produces ultra-high molecular weight polyethylene. At each stage, polymerization may be carried out in two or more tanks as long as the composition and molecular weight are within the above-mentioned ranges. In addition to the above steps, an intermediate molecular weight or intermediate A11 polymer in the above two steps may be polymerized in an amount of 30% or less.
必須成分であるポリプロピレン又はポリブテン−１製造
段階と超高分子ｈｔポリエチレン製造段階の順序はいず
れが先でも良いが、最終重合体の分散の均質性という点
からは、ポリプロピレン又はポリブテン−１成分を重合
した後に超高分子量ポリエチレン成分を重合することが
好ましい。The step of producing polypropylene or polybutene-1, which is an essential component, and the step of producing ultra-high molecular weight HT polyethylene can be carried out in any order, but from the viewpoint of homogeneity of dispersion of the final polymer, it is preferable to polymerize the polypropylene or polybutene-1 component. It is preferable to polymerize the ultra-high molecular weight polyethylene component after this step.
最終重合体のメルトフローインデックス（１９０℃、２
．１６ｋｙ荷重）は０．２．９７１０分以下であり好ま
しくは０．１．？／１０分更に好ましくは０゜０５．９
７１０分以下である。メルトフローインデックスが高く
なると成形性は更に改吟されるが超高分子量ポリエチレ
ンの！特徴である耐摩耗性や耐寒衝撃性が低下してしま
う。Melt flow index of the final polymer (190°C, 2
．． 16ky load) is 0.2.9710 minutes or less, preferably 0.1. ? /10 minutes, more preferably 0°05.9
It is 710 minutes or less. As the melt flow index increases, the moldability is further improved, but ultra-high molecular weight polyethylene! Characteristic characteristics such as abrasion resistance and cold impact resistance deteriorate.
本発明の特徴の一つは重合体の溶融時の流動性の荷重依
存性及び剪断速度値イ１性が１０倍以」二にも改善され
ていることであり、１９０℃、２１．６ｋｙ荷重での値
（ｊｉＬｌｉ［Ｉ） と２．１６ｋｙ荷重での値（Ｍ
Ｉ）の比（旧；ｕｒ／Ｍ工）は６００以上通常６００以
上になる。通常のポリエチレンでは３０〜１００である
。２．１６ｋｙ荷重のメルトインデックス（ＭＩ）が測
定出来ない程小さい場合には１ｏｋｙ荷重での値（ＭＬ
ＭＩ） との比旧、ＭＩ／ＭＬＭ Ｉ で評価出来
るが、この値は１０以上であリ、通常のポリエチレ／で
は６〜６であり、荷重依存性（すなわち剪断速度依存性
）の大巾な改良が認められる。従って更に剪断速度の大
きい射出成形、ブ１コー成形、シート成形ンよどの通常
成形機においＣは、この剪断速度依存性の、萌異的な大
きさは更に有利に鋤（。トリえば笑成形の代表的な剪断
速度であるＩ Ｘ Ｉ Ｄ”５ｅｃ−１での溶融粘度は
本発明のＭＩｏ、００２Ｆ７１０分の重合体とＭ Ｉ
Ｏ，６、Ｆ／１０分の汎用ポリエチレンとがはソ同じ値
を示す。One of the features of the present invention is that the load dependence of the fluidity during melting of the polymer and the shear rate value are improved by more than 10 times. The value at (jiLli[I) and the value at 2.16ky load (M
The ratio of I) (old; ur/M engineering) is 600 or more, usually 600 or more. In normal polyethylene, it is 30 to 100. 2. If the melt index (MI) at 16ky load is too small to be measured, the value at 1ky load (ML
It can be evaluated by MI/MLMI (MI), but this value is 10 or more, and for ordinary polyethylene, it is 6 to 6, and the load dependence (i.e., shear rate dependence) is large. Improvements are recognized. Therefore, in conventional molding machines such as injection molding, sheet molding, and sheet molding, which have even higher shear rates, C is more advantageous because of the unique size of this shear rate dependence. The melt viscosity at a typical shear rate of I
General-purpose polyethylene of O, 6, F/10 minutes shows the same value.
本発明の効果は、このように実用的な成形加工性を大巾
に改俯しても超高分子量ポリエチレンの特徴的物性であ
る耐摩耗性及び耐寒衝撃を土等をほとんど悪化させない
点にある。The effect of the present invention is that even if practical moldability is greatly improved in this way, the characteristic physical properties of ultra-high molecular weight polyethylene, such as abrasion resistance and cold impact resistance, are hardly deteriorated by soil, etc. .
同一条件での摩耗量について言えば、上で述べたＭ１１
１００２．９／１０分の本発明の重合体では約０．６％
であるのに対し、剪断速度１×１０３ｓｅｃ−’で同じ
溶融粘度を示すＭＩｏ、６．９７１０分の市販ポリエチ
レンでは約６．５％である。Regarding the amount of wear under the same conditions, the M11 mentioned above
Approximately 0.6% for the polymer of the present invention at 1002.9/10 min.
In contrast, commercially available polyethylene having the same melt viscosity at a shear rate of 1 x 103 sec-' and an MIo of 6.9710 minutes is about 6.5%.
同じ条件で通常の超高分子量ポリエチレンでは約０．５
％であった。−４０℃という極低温におけるＩｚｏｄ
＠撃強度（ノツチ・［ツ）の上記二つの重合体のｎ道
は超高分子量ポリエチレン及び本発明重合体では割れず
、であるのに対し市販ポリエチレンでは３ ｋｙ−ａｎ
／ ｃｔｎであり、前２者に実用的な差はない。重合
は連続式でも回分式でも良く、重合反応器の形態にも特
に制限はない。Under the same conditions, ordinary ultra-high molecular weight polyethylene is approximately 0.5
%Met. Izod at extremely low temperatures of -40℃
The n-way of the above two polymers in terms of impact strength (notchi) is 3 ky-an for ultra-high molecular weight polyethylene and the polymer of the present invention, whereas it is 3 ky-an for commercially available polyethylene.
/ ctn, and there is no practical difference between the former two. Polymerization may be carried out either continuously or batchwise, and there are no particular limitations on the form of the polymerization reactor.
重合温度についても特に制限はなくプロピレン又はブテ
ン−１及びエチレンが重合出来る温度であれば良いが％
超高分子−縫ポリエチレン部分の分子量は重合温度の増
加とともｅこ減少し耐摩耗ｒ土が悪化するため５０〜１
２０℃が好ましい。更に詳しくはボリプＤピレン成分の
製造は４０〜９０℃で炭化水素溶媒中又はモノマー溶媒
中で実施し、超高分子量ポリエチレン成分の製造は炭化
水素中５０〜１００℃で実施するのが特に好ましい。There is no particular restriction on the polymerization temperature, as long as it is a temperature at which propylene or butene-1 and ethylene can be polymerized.
The molecular weight of the super-polymer-sewn polyethylene portion decreases with increasing polymerization temperature and the wear resistance deteriorates, so it is 50 to 1.
20°C is preferred. More specifically, it is particularly preferred that the production of the polyp D pyrene component is carried out at 40-90°C in a hydrocarbon solvent or in a monomer solvent, and the production of the ultra-high molecular weight polyethylene component is carried out in a hydrocarbon at 50-100°C.
本発明の重合体には公知の抗酸化剤、紫外線吸収剤、滑
剤、帯電防止剤、顔料などを任意に添加することが出来
る。Known antioxidants, ultraviolet absorbers, lubricants, antistatic agents, pigments, etc. can be optionally added to the polymer of the present invention.
本発明の重合体はＭｉＪ述したごとく耐り皇−えＵｔ、
而」塵性、自己潤滑性、耐溶剤性、耐薬１５７１↑’ｂ
７１よとの優れた物性を有している０）で、自ホｂ−東
名ト醒１、家電部品などの射出成形品やフ゛ロー成ｊ’
ｊ’ ａｉ′Ｉ、 ／＜イブやシートなどの押出し成形
ｉ漬などＪｌ（範囲に利用することが出来る。The polymer of the present invention is resistant to MiJ as described above,
Dust resistance, self-lubricating property, solvent resistance, chemical resistance 1571↑'b
0), which has excellent physical properties of 71, is suitable for injection molded products such as self-produced materials, home appliance parts, etc.
j'ai'I, /<It can be used for extrusion molding such as eve and sheet Jl (range).
以下に本発明を実施例及び比較例を以って説明するが、
例中の各種物性の測定法（′ｊ：、次の通りである。The present invention will be explained below with reference to Examples and Comparative Examples.
Measurement methods for various physical properties in the examples ('j:, are as follows.
摩耗量・・・試験すべき成形材料の試料をｊが１″′に
固定させて７時間１９００ ｒｐｍで１畳拌容器内の砂
／水混合物内で回転さ−ぜ、その後の損失重量（％）を
測定
ＭＦＩ・・弓ＩＳ Ｋ ６７６０に準拠ＭＩ、ＨＬＭＩ
・・・ＪＩＳ Ｋ ６７５８に準拠降伏点応力（σ２片
・・ＡＳＴＭＤ ６５ Ｂに準拠破断点伸び（ＩＣ）・
・・ＡＳＴＭＤ ６３８に準拠アイゾント衝撃強さくノ
ンチ付）パ・ＡＳＴＭＤ ２５０に準拠ポリエチレンの
平均分子量（粘度法）・・・ＡＳＴＭＤ１５０５に準拠
溶融粘度・・・１９０虎、Ｄ二０．７６９６ φ、Ｌ
／ Ｄ＝３３．０８９で測定
実施例１
塩化マグネシウム１００重Ｍ１部と６０重量（ζ［くの
塩化ベンゾイルを共Ｖ〕砕しｚ、 ｈ、をＺｕに１ｉＪ
１％ ”ＡしたＴ１Ｃ！！４／ジメチルジメトキ・ンン
ラン＠に体（モル比２：１）のトルエン溶液に〃ｎえ６
！５’Ｃ２１ｉひ間混合後トルエンで洗浄、乾燥して１
拝た１＾１ルル兄分１．４４．９、） ’）エチルアル
ミニウム２３〃、安ｒＡ 香ｈ’：エチル４．５ｇを１
ｏＯ−ｅのステンレス製オートク１／−ブに入れ、ひき
つづ（・て）゛［ＪビＶ７モ／ −ｑ−５０ｋｙ−、水
素圧５ ｋｇ ／ ｃＷｉ２．６５℃で２０分爪台した
。ここで７°ロビし°ノー及びＨ２を完全にパージし、
新たにインブタン６０．１３を加えエチレンを導入して
超高分子量パｆリニ［チレン成分をエチレン圧５ ｋｆ
／ ｃｔＪ、 ５ ｏ℃で２１１、デｌｊＪ重合しエチ
レン及びインブタンを系外（℃〕（−ジし重合を停止し
た。Amount of wear: A sample of the molding material to be tested was rotated at 1900 rpm for 7 hours in a sand/water mixture in a 1 tatami stirring vessel with j fixed at 1'', and then the weight loss (%) was measured. ) Measures MFI...bow MI, HLMI according to IS K 6760
... Stress at yield point (σ2 piece) in accordance with JIS K 6758 Elongation at break (IC) in accordance with ASTM D 65 B
・・Based on ASTM D 638 Izont impact strength (with non-touch) ・Based on ASTM D 250 Average molecular weight of polyethylene (viscosity method) ・・Based on ASTM D 1505 Melt viscosity... 190 Tiger, D2 0.7696 φ, L
/ Measured at D=33.089 Example 1 1 part of 100 weight M of magnesium chloride and 60 weight (zeta) of benzoyl chloride are crushed and z, h, and 1 iJ are added to Zu.
1% "A T1C!! 4/dimethyldimethoxene in toluene solution (molar ratio 2:1)" 6
! 5'C21i After mixing for a while, wash with toluene and dry.
1 ^ 1 Lulu brother 1.44.9,) ') Ethyl aluminum 23〃, AnrA incense h': 4.5 g of ethyl 1
The sample was placed in an O-e stainless steel autoclave and kept on a stand for 20 minutes at a hydrogen pressure of 5 kg/cWi at 2.65°C. Now 7° lobby and completely purge the NO and H2,
Add 60.13 kg of new inbutane and introduce ethylene to convert the ethylene component into ultra high molecular weight
Polymerization was carried out at 211°C/ctJ, 5°C, and ethylene and inbutane were removed from the system (°C) to stop the polymerization.
第一段階の終了後採取した少量のン％ １ノプロピレン
粉末を測定したところ４ミリグロビレンノＪ見分のＭＦ
Ｉ （２ｓ ０℃２．１＋Ｓｋ〕荷示）Ｑま７６ｇ／１
０分でヘプタン抽出残のフラクションは９６４％であっ
た。A small amount of 1% propylene powder taken after the first stage was measured to have a MF of 4 milliglobin.
I (2s 0℃2.1+Sk) Packing information) Q 76g/1
At 0 minutes, the fraction of heptane extraction residue was 964%.
得らハた重合体は１４．３にノで赤外吸収スペクトルに
よる定−■によりプロピ１／ン含；１１は２６．５ｗｔ
％であった。The obtained polymer was determined by infrared absorption spectrum at 14.3 to contain propylene 1/2; 11 was 26.5 wt.
%Met.
この重合体にＢＩＴ （２，６−ジ第三ブチル−ｐ−フ
レソール） ｏ、１％、カルシウムステアレー） （ａ
ａｓＴ） ０．１ ｗｔ％を添加し５．２３０℃で４０
咽φの抽出し機でペレタイズしたところ、ベレット（１
） ＨＩ、ＭＩ （１９Ｄ ”Ｃ２１，６Ｉｃｙ荷珀
）は６゜６Ｓ／１０分、ＭＬＭＩ（１９０℃１０ｋｌ荷
１１【）は０．０７ ｙでＨＬ Ｍ Ｉ／Ｍ Ｌ Ｍ
Ｉは５１．４であった。このベレットをプレス成形し、
物性ワ１ｊｊ定Ｋ 洪した。This polymer was added with BIT (2,6-di-tert-butyl-p-fresol), 1%, calcium stearate) (a
asT) 0.1 wt% added and 40 at 5.230°C.
When pelletized using a throat extractor, pellets (1
) HI, MI (19D "C21,6Icy cargo) is 6°6S/10 minutes, MLMI (190℃ 10kl cargo 11 [) is 0.07y, HL M I/M L M
I was 51.4. This pellet is press-molded,
The physical properties were constant.
結果を第１表に示す。The results are shown in Table 1.
比較例１
実施例１と全（同様（（但しポリプロピレン成分を製造
せず、Ｈ２なＩ−で超高分子、１１トポリエチレンを重
合した。Comparative Example 1 Same as Example 1 ((However, the polypropylene component was not produced, and an ultrahigh polymer, 11 polyethylene, was polymerized with H2 I-.
得られた重合体は押し出し機ではペレタイズ出来ず、粉
末でプレス成形し、物性測定に供した。結果を第１表に
示す。The obtained polymer could not be pelletized using an extruder, so it was press-molded as a powder and subjected to physical property measurements. The results are shown in Table 1.
比較例２
実施例１のプロピレン成分のＪｋＯ−と超高分子量ポリ
エチレン成分の重合とを別々に行ない、得ら第１、た粉
末を￥施ｆＪ １と同じ比率にブレンドしペレタイズし
た。押し出しく表よりのストランドは不均質で次々に切
断し充分ベレット化出来なかった。混合粉末を同様にプ
レス成形し、物性測定に供した。結果を第１表に示す。Comparative Example 2 The propylene component JkO- of Example 1 and the ultra-high molecular weight polyethylene component were polymerized separately, and the resulting first and second powders were blended in the same ratio as Jk1 and pelletized. The extruded strands from the front were non-uniform and were broken one after another, making it impossible to form them into pellets. The mixed powder was similarly press-molded and subjected to physical property measurements. The results are shown in Table 1.
実施例
第一段で製造するポリプロピレン成分の組成及びＭＦＩ
及び含量を変えて実施例１を繰り返した。結果を第１表
に示す。Composition and MFI of the polypropylene component produced in the first stage of Examples
and Example 1 was repeated with different contents. The results are shown in Table 1.
実施例１０〜１６
第二段で製造する超高分子量ポリエチレンの組成及び分
子針なんえて実施例１を繰り返１−だ。Examples 10 to 16 Example 1 was repeated for the composition and molecular needle of the ultra-high molecular weight polyethylene produced in the second stage.
結果を第１表に示１０
実施例１４
！一段でグロビレンモノマーの変りにブテン−１モノマ
一５０ｋｇ、水素圧１０ｋｙ／イ、２０℃で５０分重合
した以外実施例１を繰り返した。The results are shown in Table 110 Example 14! Example 1 was repeated except that in the first stage, 50 kg of butene-1 monomer was used instead of globylene monomer, and the polymerization was carried out at 20° C. for 50 minutes at a hydrogen pressure of 10 ky/I.
結果を表ＩＫ示す。The results are shown in Table IK.
実施例１５
第一段で超高分子量ポリエチレン成分を第二段でポリプ
ロピレン成分を重合した以外実施例１と同様とした。結
果を表２に示す。Example 15 The procedure was the same as in Example 1 except that the ultra-high molecular weight polyethylene component was polymerized in the first stage and the polypropylene component was polymerized in the second stage. The results are shown in Table 2.
第２表Table 2
Claims (1)
成るチーグラー壓触媒を用い、モノマー組成及び水素濃
度の異なる２段階以」二でモノマーを重合して超高分子
量ポリエチレン系樹脂を製造するに際し、そのいずれか
の段階で水素存在下でプロピレン又はプロピレンを主成
分とするモノマー又はブテン−１又はブテン−１を主成
分とするモノマーを重合して全ｊＡ ａ体の２〜６０重
足％のポリプロビレ又はポリブテン−１成分を製造し、
残りの一段階以上で実質的に水素の不存在ドでエチレン
又はエチレンを主成分とするモノマーを重合して全重合
体の９８〜４０重量％の超高分子量ポリエチレン成分を
製造することを特徴とする成形加工性の改善された超高
分子１寸ポリエチレン系樹脂の製造方法。When producing an ultra-high molecular weight polyethylene resin by polymerizing monomers in two stages with different monomer compositions and hydrogen concentrations using a Ziegler catalyst consisting of a solid catalyst component containing a transition metal component and an organic metal component, In any of the steps, propylene or a monomer containing propylene as a main component, or a butene-1 or a monomer containing butene-1 as a main component is polymerized in the presence of hydrogen to produce polypropylene containing 2 to 60% by weight of the total jA a form. or producing polybutene-1 component,
In the remaining one or more steps, ethylene or an ethylene-based monomer is polymerized in substantially the absence of hydrogen to produce an ultra-high molecular weight polyethylene component of 98 to 40% by weight of the total polymer. A method for producing an ultra-high molecular weight one-dimensional polyethylene resin with improved moldability.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22729982A JPS59120605A (en) | 1982-12-28 | 1982-12-28 | Production of ultrahigh molecular weight polyethylene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22729982A JPS59120605A (en) | 1982-12-28 | 1982-12-28 | Production of ultrahigh molecular weight polyethylene resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59120605A true JPS59120605A (en) | 1984-07-12 |
| JPH0315645B2 JPH0315645B2 (en) | 1991-03-01 |
Family
ID=16858632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22729982A Granted JPS59120605A (en) | 1982-12-28 | 1982-12-28 | Production of ultrahigh molecular weight polyethylene resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59120605A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987000184A1 (en) * | 1985-06-27 | 1987-01-15 | Mitsui Petrochemical Industries, Ltd. | Polyethylene composition |
| US4760120A (en) * | 1985-12-17 | 1988-07-26 | Nippon Oil Company, Limited | Easily soluble polyethylene powder for the preparation of fibers or films having high strength and high elastic modulus |
| JPS63241050A (en) * | 1987-03-30 | 1988-10-06 | Mitsui Petrochem Ind Ltd | Ultra-high mw ethylene polymer composition and its production |
| JPH01156349A (en) * | 1987-12-15 | 1989-06-19 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| JPH01156351A (en) * | 1987-12-15 | 1989-06-19 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| JPH01156346A (en) * | 1987-12-15 | 1989-06-19 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| JPH01156350A (en) * | 1987-12-15 | 1989-06-19 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| JPH0593024A (en) * | 1990-10-25 | 1993-04-16 | Tokuyama Soda Co Ltd | Propylene-ethylene/butenic block copolymer and its production |
| JP2007023171A (en) * | 2005-07-19 | 2007-02-01 | Mitsui Chemicals Inc | Ultra-high-molecular-weight polyethylene particulate excellent in heat resistance and method for producing the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105696828B (en) * | 2016-01-18 | 2019-02-12 | 朱力山 | Body turning style parking stall |
-
1982
- 1982-12-28 JP JP22729982A patent/JPS59120605A/en active Granted
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987000184A1 (en) * | 1985-06-27 | 1987-01-15 | Mitsui Petrochemical Industries, Ltd. | Polyethylene composition |
| US4760120A (en) * | 1985-12-17 | 1988-07-26 | Nippon Oil Company, Limited | Easily soluble polyethylene powder for the preparation of fibers or films having high strength and high elastic modulus |
| JPS63241050A (en) * | 1987-03-30 | 1988-10-06 | Mitsui Petrochem Ind Ltd | Ultra-high mw ethylene polymer composition and its production |
| JPH01156349A (en) * | 1987-12-15 | 1989-06-19 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| JPH01156351A (en) * | 1987-12-15 | 1989-06-19 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| JPH01156346A (en) * | 1987-12-15 | 1989-06-19 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| JPH01156350A (en) * | 1987-12-15 | 1989-06-19 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| JPH0593024A (en) * | 1990-10-25 | 1993-04-16 | Tokuyama Soda Co Ltd | Propylene-ethylene/butenic block copolymer and its production |
| JP2007023171A (en) * | 2005-07-19 | 2007-02-01 | Mitsui Chemicals Inc | Ultra-high-molecular-weight polyethylene particulate excellent in heat resistance and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0315645B2 (en) | 1991-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2659375B2 (en) | Polyolefin composition | |
| AU2017322271B2 (en) | High performances multimodal ultra high molecular weight polyethylene | |
| CA2752407C (en) | Polyethylene compositions and closures for bottles | |
| KR910005579B1 (en) | Polyolefin composition for injection molding | |
| JP4216185B2 (en) | Ethylene polymer composition | |
| JP2505752B2 (en) | Molding polyolefin composition | |
| JPS60212443A (en) | Polypropylene composition | |
| JP2006501351A (en) | Polyethylene composition for rotational molding | |
| PL174588B1 (en) | Method of obtaining a mixture of ethylene polymers, mixture of ethylene polymers as such and application of such mixture | |
| CA2993502A1 (en) | Polyethylene compositions, process and closures | |
| WO1999020663A2 (en) | High impact, flexural moduli polymeric materials formed using sequential donors | |
| JPS61275313A (en) | Ultrahigh molecular weight polyethylene composition of improved injection moldability | |
| JPS59120605A (en) | Production of ultrahigh molecular weight polyethylene resin | |
| JPS62179545A (en) | High-modulus, impact-resistant polyolelfin resin composition | |
| CN109415448B (en) | Polymer composition and method for producing a polymer composition | |
| JP3375168B2 (en) | Polyethylene composition | |
| JPH0141178B2 (en) | ||
| JP2674807B2 (en) | Sliding material | |
| JPS61243842A (en) | Polypropylene composition | |
| JPH0832805B2 (en) | Polyolefin composition | |
| JPH0344092B2 (en) | ||
| JPH0819283B2 (en) | Polyolefin composition | |
| JPH0518863B2 (en) | ||
| JPS6231739B2 (en) | ||
| JPH0819282B2 (en) | Polyolefin composition |