JP5683578B2 - ポリエチレン組成物及びそれから構成される最終生成物 - Google Patents
ポリエチレン組成物及びそれから構成される最終生成物 Download PDFInfo
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- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
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Description
1つの好ましい態様においては、ポリエチレン組成物は、1〜17、より好ましくは1.1〜16.5、最も好ましくは2〜16のHI値を有する。この範囲の生成物は、ブローンフィルム及びキャストフィルム製品、最も特にはブローンフィルムを含むフィルム製品に最も良く適している。
本発明によるHIは、次式:
上式中、
Mz及びMwは、多角度レーザー光散乱と組み合わせたゲル透過クロマトグラフィー(GPC−MALLS)によって求められる分子量分布の3次及び2次(又は重量平均)モーメントである。この方法のより詳細な説明は実験セクションにおいて見ることができる。データを記録し、実験で得られた分布曲線からMz及びMwの値を算出するために、市販のGPCソフトウエア(hs GmbH, Hauptstrasse 36, D-55437, Ober-Hilbersheimから)を用いた。
ηE,maxは、一定の伸長の後にプラトーが観察されない場合には、試験片の変形又は伸長L(ln(L(t)/L(0))≧3)の開始の10〜50秒後に測定される最大ポリマー溶融粘度値(「ヘンキー歪み」の定義に基づく)として定義することができる。
分析方法:
a.伸長レオロジー
Sentmanant伸長レオロジー用具(SER)を取り付けたAntonPaar GmbH(Graz,オーストリア)からのPhysica MCR301平行プレート流動計装置上で測定を行った。測定は、測定温度において5分間アニーリングした後に150℃において行った。それぞれの試料の異なる試験片に関して、0.01s−1〜10s−1の間で変化する伸長速度、通常は0.01、0.05、0.1、0.5、1、5、10s−1において測定を繰り返した。それぞれの測定に関して、一軸伸長溶融粘度を時間の関数として記録した。
DIN−55672−1:1995−02(1995年2月発行)に記載されている方法を用いて、高温ゲル透過クロマトグラフィーによって、モル質量Mn、Mw(及び必要に応じてピーク分子量Mp)の測定を行った。言及したDIN標準規格に対する変更は次の通りである。溶媒=1,2,4−トリクロロベンゼン(TCB);装置及び溶液の温度=145℃;及び濃度検出器として、TCBと共に用いることができるPolymerChar(Valencia, Paterna 46980,スペイン)IR-4赤外検出器。直列に接続した次のプリカラム:SHODEX UT-G、並びに分離カラムSHODEX UT806M(3x)及びSHODEX UT807:を取り付けたWATERS Alliance 2000を用いた。溶媒は窒素下で真空蒸留し、0.025重量%の2,6−ジ−tert−ブチル−4−メチルフェノールで安定化した。用いた流速は1mL/分であり、注入量は400μLであり、ポリマー濃度は0.008%<濃度<0.05%w/wの範囲であった。分子量の較正は、580g/モル〜11600000g/モルの範囲のPolymer Laboratories(現在はVarian, Inc., Essex Road, Church Stretton, Shropshire, SY6 6AX,英国)からの単分散ポリスチレン(PS)標準試料、及び更にヘキサデカンを用いることによって行った。次に、汎用較正法(Benoit H., Rempp P., 及びGrubisic Z., J. Polymer Sci., Phys. Ed., 5, 753 (1967))を用いて、較正曲線をポリエチレン(PE)に適合させた。ここで用いたMark-Houwingパラメーターは、TCB中135℃における有効値で、PSに関しては、kPS=0.000121dL/g、αPS=0.706であり、PEに関しては、kPE=0.000406dL/g、αPE=0.725であった。データの記録、較正、及び計算は、それぞれNTGPC-Control-V6.02.03及びNTGPC-V6.4.24(hs GmbH, Hauptstrasse 36, D-55437 Ober-Hilbersheim)を用いて行った。
以下に記載するようにして、多角度レーザー光散乱(MALLS)と組み合わせたゲル透過クロマトグラフィー(GPC)によって、実験的に求められる分岐因子g(これによって分子量Mzにおける長鎖分岐を求めることができる)を測定した。
それぞれのデータの組について個々に注記したように20μm又は10μmのいずれかの厚さを有するフィルムについて、ASTM−D1709:2004方法Aにしたがってダートドロップ衝撃(DDI)試験を行った。
剪断レオロジーの測定、即ち所定の周波数ωにおける複素粘度η*の測定のために、動的振動剪断変形及びそれに対する応答を、Anton-Paar MCR300(Anton Paar GmbH, Graz/オーストリア)からの平行プレート流動計内のポリマーに適用した。まず、測定のために次のようにして試料(粒状形態又は粉末形態)を製造する。2.2gの材料を秤量し、これを用いて70×40×1mmの成形プレートに充填する。プレートをプレス内に配置し、20〜30barの圧力下において1分間で200℃に加熱する。200℃の温度に到達した後、試料を100barにおいて4分間プレスする。圧縮時間の終了後、材料を室温に冷却し、プレートを型から取り出す。プレスしたプレートにおいて、可能性のある亀裂、不純物、又は異質物に関して視認品質管理試験を行う。プレスした成形体から直径25mm、厚さ0.8〜1mmのポリマーディスクを切り出し、動的機械分析(又は周波数スイープ)測定のために流動計内に導入する。
e.その他の方法
密度(g/cm3)はDIN−EN−ISO−1183−1方法A(浸漬)にしたがって測定した。測定のために、所定の熱履歴を有する圧縮成形プラーク(厚さ2mm)を製造した。プレス条件=温度、圧力、及び時間:180℃、200bar、8時間。沸騰水中での結晶化を30分間。
粘度数は、ISO−1191::1975にしたがって、Ubelohe毛細管粘度計を用いて、デカリン中、135℃の温度において直接測定した。第1、第2、又は第3の重合段階の終了時に得られた反応混合物の試料について測定を行った。
チーグラー触媒として、EP−401776の実施例1にしたがって触媒を製造した。重合は、直列の3つのカスケードスラリー反応器内において連続プロセスで行った。チーグラー触媒は第1の反応器に一回だけ加えた。チーグラー触媒(示されているようにヘキサン中に懸濁)は、以下により詳細に示すように約1:10のモル比の更なる量のトリエチルアルミニウム共触媒と共に用いた。複数の反応器段階の間のフラッシュタンクによって、それぞれの反応器段階に関する水素、エチレン、及びコモノマーの投与量を個々に調節することが可能であった。
触媒:4.4(ミリモル/L);
触媒投与量:4.2(ミリモル/L);
共触媒:TEA、22.8(ミリモル/L)で供給;
活性Al:1(ミリモル/L);
TEA投与量:61(ミリモル/時);
R1、R2等=スラリー反応器No.1、2等。
実施例2
触媒:8.5(ミリモル/L);
触媒投与量:3.6(ミリモル/時);
共触媒:TEA、22.8(ミリモル/L)で供給;
活性Al:1.1(ミリモル/L);
共触媒投与量:61(ミリモル/時);
R1、R2等=スラリー反応器No.1、2等。
実施例3
実施例1、2のポリマー生成物に関する分子量分布(引かれた線)、及びGPC−MALLSによる回転半径から求めた長鎖分岐分布(LCB/1000CH2、分子量の関数として)を図1に示す。フィルム試験の結果を下表3に示す。
実施例1及び2の重合プロセスと同様に、プロセス条件を僅かに変化させ、異なるMw、Mz、HI等の生成物を得ることによって、本発明にしたがって更なるポリマー試料4〜8を製造した。
・重合条件:
・第3反応器における水素/エチレンの比:0.3<H2/C2<0.4;
・第2反応器における水素/エチレンの比:H2/C2=0.08;
・第3反応器におけるコモノマー:0.8<C4<1.3体積%;
・第2反応器におけるコモノマー:0.5<C4<0.8体積%;
・アルキル濃度(トリエチルアルミニウム):0.96<CAl<1.2ミリモル/L;
・エチレン分圧,PC2:第2反応器に関しては<0.65bar、第3反応器に関しては<1.25bar。
・MFI5kg=0.35〜0.44g/10分;
・密度,ρ=0.955〜0.957g/cm3;
・10μmのフィルムに関するDDI:常に>300g。
Claims (8)
- 0.25〜3g/10分のISO−1133:2005にしたがって5kg/190℃で測定したメルトフローレート(MI5kg)、
2,000,000g/モルを超え3,700,000g/モル未満のMz、及び
0.18〜18のホスタレン指数(HI)値を有し、但しMI5kgが>1.9g/10分である場合には、HI値は>1であり、
当該HIが、
Mzはz平均分子量であり;
Mwは重量平均分子量であり;
gMzは分子量M=Mzにおける分岐因子であり;
ehは、0.1s−1の一軸伸長速度及びT=150℃の試験温度におけるポリマーの延伸硬化であり、
として定義される、
ポリエチレン。 - MI5kgが0.3〜2g/10分であり、及び/又はHI値が0.2〜10であり、但しMI5kgが>1.9g/10分である場合には、HI値は>1である、請求項1に記載のポリエチレン。
- 少なくともチーグラー触媒を用いる触媒反応によって得られる、請求項1または2に記載のポリエチレン。
- 多峰分子量分布を有する、請求項1〜3のいずれかに記載のポリエチレン。
- (A)第1の低分子量、(B)第2の高分子量、及び(C)第3の超高分子量フラクションを含む三峰性であり、かかる第1、第2、及び第3の分子量フラクションのピーク分子量Mpx(xはA、B、又はCである)がMpA<MpB<MpCである、
請求項4に記載のポリエチレン。 - 少なくとも1種類のチーグラー触媒を用いる3つの連続反応器段階でエチレンを重合することによって得られる、請求項5に記載のポリエチレン。
- 0.25〜1g/10分のISOにしたがって5kg/190℃で測定したメルトフローレート(MI5kg)、及び/又は1.5〜18のホスタレン指数(HI)値を有する厚さ<1mmの押出しフィルムを製造するための、請求項1に記載のポリエチレン。
- 請求項1〜7のいずれかに記載のポリエチレンから構成されるフィルム。
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