JP6980932B2 - 高いスウェル比、fnct及び衝撃耐性を有するポリエチレン組成物 - Google Patents
高いスウェル比、fnct及び衝撃耐性を有するポリエチレン組成物 Download PDFInfo
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Description
1) 23℃でISO 1183にしたがって測定した、 0.945〜0.958 cm3、好ましくは 0.948〜0.955 g/cm3の密度;
2) 2〜10、特に4〜8のMIF/MI10比、ここでMIFは21.60kgの荷重下の190℃での溶融流れ指数であり、MI10は10kgの荷重下の190℃での溶融流れ指数であり、両方ともISO 1133にしたがって測定する;
3) 200,000〜800,000 Pa.s、好ましくは 200,000〜600,000 Pa.s、より好ましくは 250,000 〜600,000 Pa.s、特に 350,000〜600,000 Pa.sのη0.02;ここでη0.02は190℃の温度でプレート-プレート回転型レオメータでの動的振動剪断(dynamic oscillatory shear)によって測定される、0.02rad/sの角振動数における複合剪断粘度である;
4) 1,000,000 g/molのモル重量において、長鎖分岐指数(LCBI)が、0.80以下、好ましくは0.75未満、特に0.74以下で、好ましい下限が0.63または0.65であり、ここでLCBIは、GPC-MALLSで測定した測定平均二乗回転半径Rg対、同一の分子量を有する線形PEに対する平均二乗回転半径の比である;
5) 1000とLCBIで割ったη0.02である、比(η0.02/1000)/LCBIが、350以上、好ましくは380以上である。
- 1,500,000〜8,000,000 g/mol、好ましくは2,500,000 ~ 4,500,000 g/mol、特に2,500,000 ~ 3,500,000g/molのMz;
- 0.5〜10 g/10分、特に 1〜8 g/10分のMIF;
- 組成物の総重量を基準に2重量%以下のコモノマー含量;
- 1〜15のHMWcopoの指数;
前記HMWcopoの指数は下記の式にしたがって測定される:
HMWcopo = (η0.02 x tmaxDSC)/(10^5)
前記式において、η0.02は0.02rad/sの角周波数の印加による動的振動剪断モード(dynamic oscillatory shear mode)で平行板(またはいわゆるプレート-プレート)レオメータで190℃の温度で測定された溶融物の複合剪断粘度(Pa.s)であり;tmaxDSCは示差走査熱量計(DSC)装置において等温モードで測定した静止状態下で124℃の温度で結晶化の熱流の最大値(mW)に達するのに必要な時間(分)(結晶化のハーフタイム(t1/2)に該当する最大結晶化速度が達成される時間)である;
- 30 超過、好ましくは 40 超過、特に 30 または 40〜500のET;
ETは下記式によって計算する:
tan δ = C3におけるET = C2/G*
式中:
G* = [(G’)2 + (G”)2]1/2;
tan δ = G’/G’;
C2 = 106 dyn/cm2 及び C3 = 1.5
G’ = 貯蔵弾性率;
G’ = 損失弾性率;
G’とG”との両方ともが、190℃の温度でプレート-プレート回転型レオメータでの動的振動剪断によって測定される;
- 10未満のMz/Mw*LCBI。
A) 密度が0.956g/cm3以上であり、ISO 1133-1にしたがって2.16kgの荷重下で190℃で測定した溶融流れ指数MIEが 0.5 g/10分以上、好ましくは 1 g/10分以上である30〜70重量%、好ましくは40〜60重量%のエチレン単独重合体またはコポリマー(単独重合体が好ましい);
B) A)のMIE値よりも低いMIE値、好ましくは0.5g/10分未満のMIE値を有する30〜70重量%、好ましくは40〜60重量%のエチレンコポリマー。
-FNCT 4MPa/80℃で測定した5時間以上、特に5〜50時間の環境応力亀裂抵抗;
-180%超過、特に190%超過、好ましい上限が220%であるスウェル比;
--30℃において150kJ/m2以上、特に200kJ/m2以上のノッチ引張衝撃Atn;
-700μm超過のゲル直径を有するゲルが実質的に存在しない。
A) Ti,Mg,塩素及び1つ以上の内部電子供与体化合物EDを含む固体触媒成分;
B) 有機Al化合物;及び任意選択的に
C) 外部電子供与体化合物EDext。
a) 水素の存在下で気相反応器においてエチレンを任意選択的に1種以上のコモノマーとともに重合するステップ;
b) ステップa)より少ない量の水素の存在下で、別の気相反応器においてエチレンを1種以上のコモノマーと共重合するステップ;
ここで、前記気相反応器のうち少なくとも1つにおいて、成長中のポリマー粒子が高速流動化または輸送条件下で、第1重合ゾーン(上昇管(riser))を通って上方に流れ、前記上昇管を離れた後、第2重合ゾーン(下降管(downdomer))に入り、前記第2重合ゾーンを通ってそれらは重力の作用下で下方に流れ、前記下降管を離れた後、前記上昇管内に再び投入されることによって前記2つの重合ゾーンの間にポリマーの循環を確立する。
実施例
下記のように0.02rad/sの角周波数及び190℃で測定した。
検体を200℃及び200バール下で4分間1mm厚のプレートに溶融圧縮した。直径25mmのディスク標本がスタンピングされ、190℃で予熱したレオメータに挿入した。市販されている任意の回転型レオメータを用いて測定を行うことができる。ここでプレート-プレートジオメトリが備えられたAnton Paar MCR 300を用いた。いわゆる振動数掃引(frequency−sweep)を5%の一定する歪み振幅下でT=190℃で行い(測定温度で検体を4分間アニーリングした後)、628〜0.02rad/sの励起振動数ωの範囲で物質の応力反応の測定及び分析を行った。標準化された基本ソフトウェアを用いて流動学的特性、すなわち貯蔵弾性率G′、損失弾性率G″、位相遅れδ(=arctan(G″/G′))及び複素粘度η*を、適用された振動数の関数として計算し、すなわち、η*(ω)=[G′(ω)2+G″(ω)2]1/2/ωである。0.02rad/sの適用された振動数ωでの後者の値はη0.02である。
tan δ = C3におけるET = C2/G*
式中:
G* = [(G’)2 + (G”)2]1/2;
tan δ = G’VG’;
C2 = 106 dyn/cm2 及び C3 = 1.5。
HMWcopo = (η0.02 x tmaxDSC)/(10^5)
g′(M)=<Rg2>サンプル、M/<Rg2>線形参照、M
ここで、<Rg2>、Mは分子量Mの画分に対する平均二乗根回転半径である。
Zimm BH, Stockmayer WH (1949) The dimensions of chain molecules containing branches and rings. J Chem Phys 17
Rubinstein M., Colby RH. (2003), Polymer Physics, Oxford University Press
SR=(Dextrudate-Ddie)100%/Ddie
Claims (10)
- 下記の特徴を有する、エチレンホモポリマーと1種以上のエチレンコポリマーとを含むポリエチレン組成物:
1) 23℃でISO 1183にしたがって測定した、0.945〜0.958cm 3 の密度;
2) 2〜10のMIF/MI10比、ここでMIFは21.60kgの荷重下の190℃での溶融流れ指数であり、MI10は10kgの荷重下の190℃での溶融流れ指数であり、両方ともISO 1133にしたがって測定する;
3) 200,000〜800,000Pa.sのη0.02;ここでη0.02は190℃の温度でプレート-プレート回転型レオメータでの動的振動剪断(dynamic oscillatory shear)によって測定される、0.02rad/sの角振動数における複合剪断粘度である;
4) 1,000,000g/molのモル重量において、長鎖分岐指数(LCBI)が、0.80以下であり、ここでLCBIは、GPC-MALLSで測定した測定平均二乗回転半径Rg対、同一の分子量を有する線形PEに対する平均二乗回転半径の比である;
5) 1000とLCBIで割ったη0.02である、比(η0.02/1000)/LCBIが、350以上であり;
前記エチレンコポリマーに存在するコモノマーまたはコモノマーらは、プロピレン、ブテン-1、ペンテン-1、ヘキセン-1およびオクテン-1から選択される。 - チーグラー-ナッタ重合触媒を使用して得られる、請求項1に記載のポリエチレン組成物。
- 前記チーグラー-ナッタ重合触媒が下記のA)〜C)の反応生成物を含む、請求項2に記載のポリエチレン組成物:
A) Ti、Mg、塩素及び脂肪族モノカルボン酸(EAA)のエステルから選択された1つの内部電子供与体ED及び環状エーテル(CE)から選択された別の内部供与体EDIを、EAA/CEモル比が0.02〜20未満の範囲となる量で含む、固体触媒成分;
B) 有機Al化合物;及び任意選択的に
C) 外部電子供与体化合物。 - 下記の追加的な特徴のうち少なくとも1つを有する、請求項1に記載のポリエチレン組成物:
- 1,500,000〜8,000,000g/molのMz;
- 0.5〜10g/10分のMIF;
- 組成物の総重量を基準に2重量%以下のコモノマー含量;
- 1〜15のHMWcopoの指数;
前記HMWcopoの指数は下記の式にしたがって測定される:
HMWcopo=(η0.02xtmaxDSC)/(10^5)
前記式において、tmaxDSCは示差走査熱量計(DSC)装置において等温モードで測定した静止状態下で124℃の温度で結晶化の熱流の最大値(mW)に達するのに必要な時間(分)(結晶化のハーフタイム(t1/2)に該当する最大結晶化速度が達成される時間)である;
- 30超過のET;
ETは下記式によって計算する:
tanδ=C3におけるET=C2/G*
式中:
G*=[(G’)2+(G”)2]1/2;
tanδ=G”/G’;
C2=106dyn/cm2及びC3=1.5
G’=貯蔵弾性率;
G”=損失弾性率;
G’とG”との両方ともが、190℃の温度でプレート-プレート回転型レオメータでの動的振動剪断によって測定される;
- 10未満のMz/Mw*LCBI。 - 下記のA)及びB)を含む、請求項1に記載のポリエチレン組成物:
A) 密度が0.956g/cm3以上であり、ISO 1133にしたがって2.16kgの荷重下で190℃で測定した溶融流れ指数MIEが0.5g/10分以上である30〜70重量%のエチレン単独重合体;
B) A)のMIE値よりも低いMIE値を有する30〜70重量%のエチレンコポリマー。 - 請求項1に記載のポリエチレン組成物を含む製造品。
- ブロー成形中空物品の形態の請求項6に記載の製造品。
- Lリングドラム(L-RingDrum)またはオープントップドラム(OpenTopDrum)の形態である、請求項7に記載の製造品。
- すべての重合ステップをMgCl2上に担持されたチーグラー-ナッタ重合触媒の存在下で行う、請求項1に記載のポリエチレン組成物の製造方法。
- 下記のステップを任意の相互順序で含む、請求項9に記載の方法:
a) 水素の存在下で気相反応器においてエチレンを任意選択的に1種以上のコモノマーとともに重合するステップ;
b) ステップa)より少ない量の水素の存在下で、別の気相反応器においてエチレンを1種以上のコモノマーと共重合するステップ;
ここで、前記気相反応器のうち少なくとも1つにおいて、成長中のポリマー粒子は高速流動化または輸送条件下で、第1重合ゾーンを通って上方に流れ、前記第1重合ゾーンを離れた後、第2重合ゾーンに入り、第2重合ゾーンを通ってそれらは重力の作用下で下方に流れ、前記第2重合ゾーンを離れた後、前記第1重合ゾーンに再び投入されることによって前記2つの重合ゾーンの間にポリマーの循環を確立する。
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