CN1324383A - 具有高质量共混的双峰型聚乙烯共混物 - Google Patents

具有高质量共混的双峰型聚乙烯共混物 Download PDF

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CN1324383A
CN1324383A CN99812720A CN99812720A CN1324383A CN 1324383 A CN1324383 A CN 1324383A CN 99812720 A CN99812720 A CN 99812720A CN 99812720 A CN99812720 A CN 99812720A CN 1324383 A CN1324383 A CN 1324383A
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P·德兰格
A·德克尔斯
T·凯斯勒
W·罗德
T·布吕梅尔
M·卢克斯
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Abstract

从高分子量乙烯共聚物和低分子量乙烯均或共聚物制备双峰型聚乙烯共混物,它们具有6－14g/10min的熔体流速MFR190/21.6,0.94－0.97g/cm3的密度,>150h的抗环境应力开裂性ESCR和当在共混物中的共混质量根据ISO13949测量时低于3的值。本发明涉及通过在混合装置中熔融和均化及由齿轮泵排出来的方法可制备这类聚乙烯共混物的方法。本发明还涉及该共混物在生产模制品,尤其是中空制品和压力管的应用。

Description

具有高质量共混的双峰型聚乙烯共混物
本发明涉及从高分子量乙烯共聚物和低分子量乙烯均聚或共聚物制成的双峰型聚乙烯共混物，它具有6-14g/10min的熔体流速MFR190/21.6,0.94-0.97g/cm3的密度，＞150h的抗环境应力开裂性ESCR和在共混物中的共混质量当根据ISO13949测量时低于3的值。本发明进一步涉及通过在混合装置中熔融和均化及由齿轮泵排料来制备这类聚乙烯共混物的方法，和涉及它们用于生产模制品，尤其中空制品和压力管的用途。
对聚乙烯模制品的机械承载能力不断提出了更高的要求。尤其，对于高抗环境应力开裂性、抗冲击性和刚性的产品有需求，该产品尤其适合于生产中空制品以及压力管。对于同时具有良好的抗环境应力开裂性和刚度的需求不容易满足，因为这些是对立的性能。当刚度随聚乙烯的密度增加而增加时，抗环境应力开裂性因为密度的增加而降低。
对于中空制品和压力管而言，例如通过L.L.Bhm等，Adv.Mater.4,234-238(1992)的叙述，因此已经证实，理想的是使用从高分子量、低密度乙烯共聚物和低分子量、高密度乙烯均聚物制成的共混物。在EP-A 100 843,EP-A 533 154,EP-A 533 155,EP-A 533 156,EP-A 533160和US 5,350,807中公开了类似的聚乙烯共混物。
然而，双峰型聚乙烯共混物的性能不单独依赖于组分的性能。尤其对于共混物的机械性能，决定性的作用是高分子量和低分子量组分以及任选的其它添加剂，如颜料或加工助剂的共混的质量。差的共混质量尤其导致了低的抗环境应力开裂性和减弱了由聚乙烯共混物制成的压力管的蠕变性能。
聚合物共混物的共混质量能够通过使用光学显微镜检查样品的薄切片(超薄切片机切片)来检测。不均匀性作为斑点或所谓的白点见到。斑点或白点主要是在低粘度基质中的高分子量、高粘度颗粒(例如参见，U.Burkhardt等，在“具有新颖特性聚合物的制备”(“Aufbereitenvon Polymeren mit neuartigen Eigenschaften”)，VDI-出版社，Düsseldorf 1995,71页)。这类包含物的大小是至多300um。它们能引起组分的环境应力开裂和脆断。当在共混物中的共混质量更好时，这些包含物的数目会更少和它们的尺寸会更小。如果定量，在共混物中的共混质量根据ISO13949测定。按测量规定要求从共混物的样品制备超薄切片机切片，计算这些包含物的数量和尺寸，并根据已固定的评价体系确定本发明共混合物的等级。
双峰型聚乙烯共混物的重要应用是生产输送气体、饮用水和废水的压力管。由聚乙烯制成的压力管逐渐代替了金属管。这类应用的重要因素是管的尽可能长期的使用寿命，而不用担心老化和脆断。甚至在压力管中的小缺陷或压痕能够即使在低压下变大，和引起脆断，该过程能够通过温度增加和/或侵蚀性化学品得到加速。因此极其重要的是尽可能减少在管子中的缺陷的数目和尺寸，如斑点或白点。
对于输送饮用水，其它重要因素是共混物具有很低的气味，和味道是中性的。
为制备双峰型聚乙烯共混物，使用级联反应器，即两个或多个串联的聚合物反应器。低分子量组分在一个反应器中聚合，和高分子量组分在下一个中聚合(例如参见，M.Rtzsch,W.Neiβl在“具有新颖特性聚合物的制备”3-25页中的“基于PP和PE的双峰型聚合物材料”VDI-出版社，Düsseldorf 1995)。聚乙烯的不同分子量分布和化学组成的混合已经在聚合物颗粒内部发生。然而，该方法的缺点是在级联的各反应器中不得不使用相同的催化剂。需要高的设备成本以确保在一个反应器中加入的共聚单体或作为调节剂加入的氢不进入下一个反应器。另外，很难调节各反应器的聚合速度以得到所需的共混物的组成。
制备聚合物共混物的最熟悉的方法一般是例如通过在挤出机或捏合机中熔融挤出紧密混合各个组分(例如参见，在Ullmann’sEncyclopedia of Industrial Chemistry,6th Edition,1998中的“Polymer Blends”,Electronic Release)。与用于制备所述这类双峰型聚乙烯共混物的级联反应器反应相比，该方法的优点是它的适应性更高，因此共混物的组分因此也可从各种方法得到。然而，在另一方面，该方法具有特别的困难。
双峰型聚乙烯共混物的高和低分子量组分的熔体粘度是极不相同的。而在制备共混物的通常温度下，即大约190-210℃，低分子量组分已经几乎成为了低粘度液体，高分子量组分仅被软化(“扁豆汤”)。因此很难均匀混合两种组分。另外，已知高分子量组分容易通过在挤出机中的热应力或通过剪切力被破坏，损坏共混物的性能。为避免这些缺陷，提议使用帮助排料的齿轮泵(例如参见，W.Gerber“Optimierung des Compoundierprozesses durch Rezeptur-undVerfahrensverstandnis”VDI-出版社，Düsseldorf,1997,S.253-280)。
本发明的目的是提供具有改进质量的共混和适合生产压力管的双峰型聚乙烯共混物。本发明的另一个目的是提供从高分子量和低分子量组分在温和的条件下制备这种共混物的低成本和适应性强的方法。
因此发现了从高分子量乙烯共聚物和低分子量乙烯均或共聚物制备的且具有6-14g/10min的熔体流速MFR190/21.6,0.94-0.97g/cm3的密度，＞150h的抗环境应力开裂性ESCR和在共混物中的共混质量根据ISO13949测量时低于3的值的双峰型聚乙烯共混物。也已经发现通过在混合装置中熔融和均化及经齿轮泵排出来制备这种聚乙烯共混物的方法，也发现了该共混物用于中空制品和压力管的用途。
本发明的双峰型聚乙烯共混物的密度是0.94-0.98g/cm3，优选0.95-0.97g/cm3和更尤其优选0.95-0.96g/cm3。熔体流速MFR190/21.6是6-14g/10min。如果熔体流速高于14g/10min，抗环境应力开裂性对于压力管不再是足够充分的，而如果熔体流速低于6，很难加工共混物以得到管子。熔体流速优选是8-12g/10min，和更尤其优选9-11g/10min。共混物的抗环境应力开裂性是至少150h，优选至少200h。当在双峰型聚乙烯共混物中共混的质量根据ISO13949测量时获得的值低于3，优选低于2.5。
本发明的聚乙烯共混物包括两种组分。
低分子量组分由重均分子量为8000-80,000g/mol，优选20,000-70,000g/mol和更尤其优选30,000-60,000g/mol的乙烯均聚物或乙烯共聚物组成。它的多分散性Mw/Mn是2.5-12，优选3-10且更尤其优选5-8。
低分子量组分可包括除了乙烯还有其他共聚单体。共聚单体的选择取决于所需的性能。然而，优选使用1-烯烃作为共聚单体，尤其优选丙烯，1-丁烯，1-戊烯，1-己烯，1-辛烯或4-甲基戊烯。所用共聚单体的量的选择也取决于所需的性能，但优选不高于1mol％，以所使用的全部单体的量为基础计算。
低分子量乙烯均聚物或乙烯共聚物的熔体流速MFR190/2.16优选是20-100g/10min和尤其优选25-40g/10min。它的密度优选是在0.95g/cm3以上。它可以通过本技术领域的技术人员所已知的方法中的任何一种来制备。然而，低分子量组分优选在二茂铬(Chromocen)催化剂/氧化物载体的存在下制备。与用齐格勒(Ziegler)催化剂的制备方法相比，该制备方法的优点是不需使用低分子量有机铝化合物作为辅助催化剂。高挥发性、低分子量有机铝化合物或它们的分解产物能够不利地影响所得到的聚乙烯的气味，并因此影响共混物的气味。
高分子量组分由重均分子量≥300,000g/mol，优选350,000-700,000g/mol和更尤其优选400,000-600,000g/mol的乙烯共聚物组成。除了乙烯还使用的共聚单体的选择取决于所需的性能。然而，优选使用1-烯烃作为共聚单体，尤其优选丙烯，1-丁烯，1-戊烯，1-己烯，1-辛烯或4-甲基戊烯。所用的共聚单体的量的选择同样取决于所需的性能。然而，优选0.2-4.0mol％的量，以所使用的全部共聚单体的量为基础计算。多分散性Mw/Mn是1-10，优选3-9和更尤其优选5-9。
高分子量乙烯共聚物的熔体流速MFR190/21.6优选不高于1.5g/10min和尤其优选0.5-1.5g/10min。它的密度优选不高于0.93g/cm3。高分子量乙烯共聚物优选通过单体在齐格勒(Ziegler)催化剂的存在下的聚合来制备。
本发明的共混物包括40～80wt％的高分子量组分和20-60wt％的低分子量组分。它们优选包括40-60wt％的高分子量组分和60-40wt％的低分子量组分。它们也可以此外包括至多10wt％的其它组分，如本身已知的抗氧化剂，UV稳定剂，染料或颜料或由这些制成的制剂，抗静电剂或加工助剂。
本发明的共混物可以在装有作为排料系统的齿轮泵的混合装置中制备。这种混合装置的实例是单或双螺杆挤出机或捏合机，Ko-捏合机或连续捏合机。本技术领域的技术人员可以根据所需的共混性能选择这些装置的螺杆构型。然而，应注意共混物的机械负荷不能太大以致于导致高分子量组分降解和因此损坏共混物机械性能。共混物的两种组分分别经两个进给装置给入。在聚乙烯中的其它组分，如颜料或颜料的制剂(如果需要的话)可以由第三进给装置给入。本发明方法的决定性因素是使用齿轮泵作为排料系统。令人惊奇的是，齿轮泵的使用不仅抑制了共混物的高分子量组分的热力学降解，明显的熔体流速的增加，而且对本技术领域的技术人员来说意外地显著改进了在共混物中的共混质量。
由于它们高质量的共混，良好的抗环境应力开裂性和高冲击强度，本发明的共混物高度适合于生产膜和模制品，尤其中空制品和压力管。
下面的实施例更详细地描述本发明，但不限制它的范围。
给出的值如下测定：
密度  ISO 1183
熔体流速MFR 190/21.6或MFR 190/2.16  ISO 1133
重均分子量Mw，和多分散性Mw/Mn 基于DIN 55672，用聚乙烯标准
抗环境应力开裂性ESCR 盘形测试样品(直径40mm，厚度2mm，一面具有深0.1mm和长20mm的切迹)浸没在80℃下的1％Nekanil溶液中和经受3巴的压力。测量环境应力开裂出现所经历的时间(以h给出)
表(续)
在共混物中的共混质量 根据ISO 139496件超薄切片机切片(厚度＞60μm，直径3-5mm)从共混物样品的6个不同部位制备。切片在放大100倍的显微镜下检测以测定在0.7mm2的面积中包含物(“白点”，团块，颗粒)的数目和尺寸。忽略尺寸低于5μm的包含物，如在ISO13949中那样。使用在ISO13949中的分类表取决于包含物的数目和尺寸来给出等级0,1.5,1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5或7。从全部6件样品得到的算术平均值计算总的等级。等级值越小表明在共混物中存在越少的包含物，因此在共混物中有更高质量的共混。
 对于下面的实施例使用下列起始原料：
高分子量聚乙烯组分 熔体流速MFR190/21.6 0.8g/10min
Mw 537,000g/mol
Mw/Mn 6.8
密度 0.924g/cm3
低分子量聚乙烯组分 熔体流速MFR190/2.16 30g/10min
Mw 57,000g/mol
Mw/Mn 6.5
密度 0.967g/cm3
颜料制剂     40％碳黑，非晶态，分散在聚乙烯中(等级：RKK40/P 0.1 IRG-5032 L,Degussa)
使用齐格勒(Ziegler)催化剂制备高分子量组分，和使用担载在载体上的二茂铬催化剂制备低分子量组分。
各实验使用50wt％的高分子量组分，45wt％的低分子量组分和5％的颜料制剂。在实验中的加工在200℃下进行。
结果在表1和2中列举。
实施例和对比实施例表明，齿轮泵的使用能够提高在聚乙烯共混物中的共混质量，和它们的抗环境应力开裂性。虽然在双螺杆挤出机的排料区域使用筛子得到了在双峰型聚乙烯共混物中改进质量的共混，但发生了高分子量组分的降解。熔体流速因此显著增加和抗环境应力开裂性显著降低，以及所获得的共混物对于压力管不再具有足够的机械性能。
表1：在具有齿轮泵的设备中共混实验的结果
机器类型 生产率[kg/h] 单位能量供    应[kWh/kg] 熔体流速MFR190/21.6[g/10min] 密度[g/cm3] 抗环境应力开裂性ESCR[h] 根据IS013949的共混质量
实施例1 双螺杆捏合机*+齿轮泵 50  0.224  9.3  0.955 ＞200+ 2.8
实施例2 连续混合机**+齿轮泵 200  0.250  10  0.956 ＞200+ 2.4
实施例3 连续混合机**+齿轮泵 175  0.316  11.5  0.954 ＞200+ 2.0
*ZSK 40(Werner & Pfleiderer)，**4”UMSD(Farrel)，+实验在200h之后终止。
表2：在没有齿轮泵的设备中的共混实验的结果
机器类型 生产率[kg/h] 单位能量供    应[kWh/kg] 熔体流速MFR190/21.6[g/10min] 密度[g/cm3] 抗环境应力开裂性ESCR[h] 根    据ISO13949的共混质量
对比实施例4 双螺杆捏合机* 80  0.315  16.7  0.955  22  3.7
对比实施例5 双螺杆捏合机** 70  0.393  11  0.953  148  4.5
对比实施例6 具有63μm筛子的双螺杆捏合机料 60  0.467  32  0.956  3  2.8
对比实施例7 双螺杆捏合机*** 40  0.235  14.3  0.958  47  4.8
对比实施例8 双螺杆捏合机*** 60  0.228  15.6  0.954  10  5.2
*ZSK 53(Werner & Pfleiderer)(长)**ZSK 53(短)***FTX80(Farrel)

Claims (8)

1、熔体流速MFR190/21.6为6-14g/10min的，密度为0.94-0.97g/cm3和抗环境应力开裂性ESCR＞150h的双峰型聚乙烯共混物，它包括：
40-80wt％的重均分子量≥300,000g/mol和多分散性Mw/Mn是1-12的高分子量乙烯共聚物，和
20-60wt％的重均分子量为8000～80,000g/mol和多分散性Mw/Mn是2.5-12的低分子量乙烯均或共聚物，
其中在共混物中的共混质量根据ISO13949的测量得到了低于3的值。
2、在权利要求1中所要求的双峰型聚乙烯共混物，其特征是高分子量乙烯共聚物包含比例为0.2-4.0mol％的共聚单体，和低分子量乙烯均或共聚物包含比例为0-1mol％的共聚单体，在各种情况下以所使用的全部单体的量为基准，和其中共聚单体是选自丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯和4-甲基戊烯中的至少一种共聚单体。
3、在权利要求2中所要求的双峰型聚乙烯共混物，其特征是高分子量乙烯共聚物通过在齐格勒催化剂的存在下的聚合获得和低分子量乙烯均或共聚物通过在氧化载体上的二茂铬催化剂的存在下的聚合获得。
4、在权利要求3中所要求的双峰型聚乙烯共混物，其特征是高分子量乙烯共聚物具有≤1.5g/10min的熔体流速MFR190/21.6和低分子量乙烯均或共聚物具有20-100g/10min的熔体流速MFR190/2.16。
5、在权利要求3中所要求的双峰型聚乙烯共混物，其特征是高分子量乙烯共聚物具有≤0.93g/cm3的密度，和低分子量乙烯均或共聚物具有≥0.95g/cm3的密度。
6、制备权利要求1-5中任一项所要求的双峰型聚乙烯共混物的方法，其特征是分别将高分子量乙烯共聚物和低分子量乙烯均或共聚物给入到混合装置中，熔融两种组分，均化它们，和利用齿轮泵从用于造粒的混合装置中排出它们。
7、权利要求1-5中任一项所要求的双峰型聚乙烯共混物用于生产膜或模制品，尤其中空制品和压力管的用途。
8、由权利要求1-5中任一项所要求的聚乙烯生产的膜或模制品，尤其是中空制品或压力管。
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Families Citing this family (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2285723C (en) * 1999-10-07 2009-09-15 Nova Chemicals Corporation Multimodal polyolefin pipe
FI111954B (fi) * 2000-02-21 2003-10-15 Borealis Tech Oy Menetelmä polyeteenipäällysteen valmistamiseksi substraatille
DE60043574D1 (de) * 2000-04-13 2010-02-04 Borealis Tech Oy Polymerzusammensetzung für Rohre
DE60025551T2 (de) * 2000-04-13 2006-08-24 Borealis Technology Oy Polymerzusammensetzung für Rohre
US7829646B2 (en) * 2000-08-18 2010-11-09 Chevron Phillips Chemical Company Lp Olefin polymers, method of making, and use thereof
ATE303236T1 (de) * 2001-06-14 2005-09-15 Solvay Verfahren zum compoundieren einer multimodalen polyethylenzusammensetzung
MXPA04001496A (es) 2001-08-17 2004-05-14 Dow Global Technologies Inc Composicion de polietileno bimodal y articulos elaborados a partir de la misma.
KR100895729B1 (ko) 2001-08-31 2009-04-30 다우 글로벌 테크놀로지스 인크. 다봉 분자량 분포를 갖는 폴리에틸렌 물질
SE0103425D0 (sv) * 2001-10-16 2001-10-16 Borealis Tech Oy Pipe for hot fluids
US7196138B2 (en) * 2001-12-14 2007-03-27 Corrugatedd Polyethylene Pipe Ltd. Melt blended high density polyethylene compositions with enhanced properties and method for producing the same
US7317054B2 (en) 2001-12-14 2008-01-08 Corrugated Polyethleyne Pipe, Ltd. Melt blended high density polyethylene compositions with enhanced properties and method for producing the same
JP2003246899A (ja) * 2001-12-17 2003-09-05 Asahi Kasei Corp ポリエチレン樹脂組成物
BR0311703B1 (pt) * 2002-06-04 2013-11-19 Composição polimérica, método para fabricar tubos, processo de polimerização e tubo
BE1015053A3 (fr) * 2002-07-25 2004-09-07 Solvay Capsule a visser comprenant une composition a base de polymere de l'ethylene multimodal.
EP1460105B1 (en) 2003-03-20 2012-05-23 Borealis Technology Oy Polymer composition
US6878454B1 (en) * 2003-12-05 2005-04-12 Univation Technologies, Llc Polyethylene films
EP1555292B1 (en) * 2004-01-13 2015-12-23 Borealis Technology Oy Extrusion coating polyethylene
US7193017B2 (en) * 2004-08-13 2007-03-20 Univation Technologies, Llc High strength biomodal polyethylene compositions
US7868092B2 (en) * 2005-06-14 2011-01-11 Univation Technologies, Llc Bimodal polyethylene compositions for blow molding applications
US8202940B2 (en) * 2004-08-19 2012-06-19 Univation Technologies, Llc Bimodal polyethylene compositions for blow molding applications
US7432328B2 (en) * 2005-06-14 2008-10-07 Univation Technologies, Llc Enhanced ESCR bimodal HDPE for blow molding applications
EP1978040B1 (en) * 2004-09-10 2015-06-17 Borealis Technology Oy Semiconductive polymer composition
ATE383400T1 (de) * 2004-11-03 2008-01-15 Borealis Tech Oy Multimodale polyethylenzusammensetzung mit verbesserter homogenität
WO2006074693A1 (en) * 2005-01-12 2006-07-20 Borealis Technology Oy Extrusion coating polyethylene
US7312279B2 (en) * 2005-02-07 2007-12-25 Univation Technologies, Llc Polyethylene blend compositions
US20060275571A1 (en) * 2005-06-02 2006-12-07 Mure Cliff R Polyethylene pipes
US7858702B2 (en) * 2005-06-14 2010-12-28 Univation Technologies, Llc Enhanced ESCR bimodal HDPE for blow molding applications
KR100702492B1 (ko) * 2005-08-11 2007-04-02 삼성토탈 주식회사 광택성 및 강도가 우수한 중공성형용 고밀도 폴리에틸렌수지 및 그를 포함하는 수지 조성물
US7595364B2 (en) 2005-12-07 2009-09-29 Univation Technologies, Llc High density polyethylene
CA2568454C (en) * 2006-11-17 2014-01-28 Nova Chemicals Corporation Barrier film for food packaging
DE602007009964D1 (de) * 2007-07-18 2010-12-02 Borealis Tech Oy Formartikel mit Polyethylen-Copolymer von hoher Dichte
EP2130859A1 (en) 2008-06-02 2009-12-09 Borealis AG Polymer compositions having improved homogeneity and odour, a method for making them and pipes made thereof
EP2130863A1 (en) 2008-06-02 2009-12-09 Borealis AG High density polymer compositions, a method for their preparation and pressure-resistant pipes made therefrom
EP2130862A1 (en) 2008-06-02 2009-12-09 Borealis AG Polymer compositions and pressure-resistant pipes made thereof
EP2539123A1 (en) * 2010-02-22 2013-01-02 Ineos Commercial Services UK Limited Improved polyolefin manufacturing process
CA2752407C (en) 2011-09-19 2018-12-04 Nova Chemicals Corporation Polyethylene compositions and closures for bottles
US9371442B2 (en) 2011-09-19 2016-06-21 Nova Chemicals (International) S.A. Polyethylene compositions and closures made from them
EP2583998B1 (en) 2011-10-21 2018-02-28 Borealis AG Polyethylene composition with high rapid crack propagation resistance and pressure resistance
BR112015008956B1 (pt) * 2012-10-22 2021-07-06 Basell Polyolefine Gmbh composição de polietileno, seu processo de preparação e artigos manufaturados compreendendo a mesma
US9475927B2 (en) 2012-12-14 2016-10-25 Nova Chemicals (International) S.A. Polyethylene compositions having high dimensional stability and excellent processability for caps and closures
CA2798854C (en) 2012-12-14 2020-02-18 Nova Chemicals Corporation Polyethylene compositions having high dimensional stability and excellent processability for caps and closures
US9783663B2 (en) 2012-12-14 2017-10-10 Nova Chemicals (International) S.A. Polyethylene compositions having high dimensional stability and excellent processability for caps and closures
US9758653B2 (en) 2015-08-19 2017-09-12 Nova Chemicals (International) S.A. Polyethylene compositions, process and closures
US9783664B1 (en) 2016-06-01 2017-10-10 Nova Chemicals (International) S.A. Hinged component comprising polyethylene composition
WO2019067055A1 (en) 2017-09-28 2019-04-04 Exxonmobil Chemical Patents Inc. PROCESS FOR THE PRODUCTION OF POLYMER COMPOSITIONS HAVING MULTIMODAL MOLECULAR WEIGHT DISTRIBUTION
US11952480B2 (en) 2018-02-05 2024-04-09 Exxonmobil Chemical Patents Inc. Enhanced processability of LLDPE by addition of ultra-high molecular weight density polyethylene
CA3028148A1 (en) 2018-12-20 2020-06-20 Nova Chemicals Corporation Polyethylene copolymer compositions and articles with barrier properties
CA3221443A1 (en) * 2021-05-31 2022-12-08 Borealis Ag Polyethylene blend

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4438238A (en) 1981-01-30 1984-03-20 Sumitomo Chemical Company, Limited Low density copolymer composition of two ethylene-α-olefin copolymers
US4461873A (en) 1982-06-22 1984-07-24 Phillips Petroleum Company Ethylene polymer blends
US6194520B1 (en) * 1991-03-06 2001-02-27 Mobil Oil Corporation Ethylene polymer resins for blow molding applications
CA2078366A1 (en) 1991-09-18 1993-03-19 Joel L. Martin Polyethylene blends
KR930006091A (ko) 1991-09-18 1993-04-20 제이 이이 휘립프스 폴리에틸렌 블렌드 및 그로부터 제조된 필름, 병 또는 파이프
KR930006090A (ko) 1991-09-18 1993-04-20 제이 이이 휘립프스 에틸렌 중합체 조성물
KR930006089A (ko) 1991-09-18 1993-04-20 제이 이이 휘립프스 폴리에틸렌 블렌드
US5350807A (en) 1993-06-25 1994-09-27 Phillips Petroleum Company Ethylene polymers
CA2200448A1 (en) * 1994-11-02 1996-05-17 Herbert Bongartz Molding composition, method of preparation, method of molding, and molded articles
US6485662B1 (en) * 1996-12-03 2002-11-26 Union Carbide Chemicals & Plastics Technology Corporation Process for preparing a simulated in situ polyethylene blend

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