CN100363413C - 用于生产简便油桶的聚乙烯吹塑组合物 - Google Patents
用于生产简便油桶的聚乙烯吹塑组合物 Download PDFInfo
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Abstract
本发明涉及一种具有多峰形分子量分布的聚乙烯组合物，特别适合于吹塑容积在2-20dm3(l)范围内的桶。该组合物具有在23℃为0.950-0.958g/cm3范围内的密度和在0.30-0.50dg/min范围内的MFI190/5。它包含40-50%重量的低分子量乙烯均聚物A，25-35%重量的由乙烯和另一种具有4-8个碳原子的1-烯烃制成的高分子量共聚物B和24-28%重量的超高分子量乙烯共聚物C。
Description
本发明涉及具有多峰形分子量分布的聚乙烯组合物，它特别适合用于吹塑容量在2-20dm3(1)范围的桶(简便油桶，jerry can)，和涉及制备这种聚乙烯组合物的方法，是在由齐格勒催化剂和助催化剂组成的催化剂体系存在下通过由连续的淤浆聚合反应组成的多步反应方法进行的。本发明还涉及由模塑组合物通过吹塑生产的桶。
聚乙烯广泛地用于生产要求材料具有特别高的机械强度、高的耐腐蚀性和绝对可靠的长期稳定性的各种类型的吹塑品。聚乙烯的另一个特殊优点是它也具有良好的耐化学品性和内在地是轻质材料。
EP-A-603,935以前已经描述了一种基于具有双峰形分子量分布的聚乙烯的吹塑组合物，并适合于生产具有良好机械性质的模塑品。
US-A5,338,589描述了一种具有甚至更宽的分子量分布的材料，是通过使用从WO91/18934已知的高耐用性(mileage)催化剂制备的，其中镁醇盐以凝胶状的悬浮体形式使用。令人意外地，已经发现在模塑品中，特别是在管子中使用这种材料允许同时改善通常在半结晶热塑性塑料中反向相关的性质，这些特别是一方面为硬挺度和蠕变和另一方面为耐应力开裂性和韧度。
然而，这种已知的双峰形产品在加工过程中特别地具有相对低的熔体强度。这意味着挤出的型坯经常在熔融状态就会断裂，使得挤出过程对加工不可接收地敏感。此外，特别当生产厚壁的容器时，发现壁厚度由于熔体从上部区域向下部区域流动而是不均匀的。
因此，本发明的目的是开发一种用于吹塑的聚乙烯组合物，它在通过吹塑以生产桶的加工中显示出超过所有已知材料的进一步改善。特别地，模塑组合物的高熔体强度应该允许长时间地操作挤出工艺而没有型坯破坏，和精确调整的组合物溶胀比应该允许壁厚度控制的最优化。
我们已经意外地发现该目的通过开头所述的组合物而实现，该组合物的特征性特征是它包含40-50％重量的低分子量乙烯均聚物A，25-35％重量的由乙烯和另一种具有4-8个碳原子的1-烯烃制成的高分子量共聚物B和24-28％重量的超高分子量乙烯-1-烯烃共聚物C，其中所有的百分数值基于组合物的总重量。
本发明还涉及以级联的淤浆聚合反应制备这种组合物的方法和涉及由此组合物制造容量在2-20dm3(1)范围和具有相当优异的机械强度性质的桶的方法。
本发明的聚乙烯聚合物具有在23℃为0.950-0.958g/cm3范围内的密度和宽的三峰形分子量分布。高分子量共聚物B只含有低比例的具有4-8个碳原子的其它烯烃单体单元，即0.2-0.5％重量。这些共聚单体的例子有1-丁烯，1-戊烯，1-己烯，1-辛烯或4-甲基-1-戊烯。超高分子量的乙烯均聚物或共聚物C也含有1-2％重量范围内的一种或多种上述共聚单体。
本发明的组合物具有的熔流指数ISO1133在0.3-0.5dg/min的范围内，以MFR190/5表示，和粘数VNtot在330-380cm3/g的范围内，特别是在340-370cm3/g范围内，根据ISO/R 1191在萘烷中在135℃测量。
三峰形是三个独立的分子量分布的重心位置的量度，和可以借助于在连续的聚合反应阶段中形成的聚合物的根据ISO/R 1191的粘数VN描述。因此，在反应的每一阶段中形成的聚合物的有关谱带宽度如下：
在第一聚合反应阶段后对聚合物测量的粘数VN1与低分子量聚乙烯A的粘数VNA是一致的，并根据本发明是在60-80cm3/g的范围内。
在第二聚合反应阶段后对聚合物测量的粘数VN2不等于在第二聚合反应阶段中形成的高分子量聚乙烯B的粘数VNB，而是代表聚合物A和聚合物B的混合物的粘数，VNB仅能够通过计算确定。根据本发明，VN2是在160-200cm3/g的范围内。
在第三聚合反应阶段后对聚合物测量的粘数VN3不等于在第三聚合反应阶段中形成的超高分子量共聚物C的粘数VNc，而是代表聚合物A，聚合物B和聚合物C的混合物的粘数，VNc仅能够通过计算确定。根据本发明，VN3是在330-380cm3/g的范围内，特别是在350-370cm3/g的范围内。
聚乙烯通过在淤浆中在70-90℃的范围内，优选80-90℃范围内，在0.15-1MPa的压力下，和在由过渡金属化合物和有机铝化合物如三乙基铝、三异丁基铝、烷基氯化铝和烷基氢化铝构成的高耐用性齐格勒催化剂存在下聚合单体而得到。聚合反应分三阶段进行，即三个系列排列的阶段，每一个分子量借助于氢进料调节。
本发明的聚乙烯组合物可以包含其它添加剂与聚乙烯并排。这些添加剂的例子有热稳定剂，抗氧化剂，UV吸收剂，光稳定剂，金属减活剂，破坏过氧化物的化合物，和用量在0-10％重量，优选在0-5％重量的碱性助稳定剂，以及填料，增强剂，增塑剂，润滑剂，乳化剂，颜料，光学增亮剂，阻燃剂，抗静电剂，发泡剂，或它们的组合，总量为0-50％重量，基于混合物的总重。
本发明的组合物特别适合于吹塑工艺以生产桶，通过首先在挤出机中在200-250℃范围内塑化聚乙烯组合物，和接着通过模头挤出到模具中，在此被冷却并固化。
本发明的组合物在用于生产桶的吹塑工艺中产生特别良好的加工性能，因为它具有在130-145％范围内的溶胀比，和由此生产的桶具有特别高的机械强度，因为本发明的模塑组合物具有在14-17KJ/m2范围内的缺口冲击强度(ISO)。其耐应力开裂性(FNCT)在150-220h的范围。
缺口冲击强度(ISO)根据ISO 179-1/1eA/DIN 53453在23℃测定。试样尺寸为10×4×80mm，和V缺口使用45°角插入，深度为2mm和缺口基础半径为O.25mm。
本发明的模塑组合物的耐应力开裂性通过内部实验方法确定并以小时(h)给出。该实验室方法被M.Fleissner在Kunststoffe 77(1987)，第45及随后页所描述，和对应于ISO/FDIS 16770，后者已经生效。在乙二醇作为促进应力开裂的介质并在80℃下使用3.5MPa的拉伸应力时，由于应力引发时间被缺口(1.6mm/刀片)缩短而断裂时间缩短。试样通过从10mm厚的压制板锯下三个尺寸为10×10mm×90mm的试样而生产。这些试样在为此目的而特制的冲切装置上用刀片而制出一个中心缺口(见公开文本中图5)。缺口深度为1.6mm。
实施例1
在串连排列的的三个反应器中乙烯用连续法聚合。如WO 91/18934，实施例2所述制备的相对于钛化合物为1.3mol/h量的齐格勒催化剂，在WO中可操作数为2.2，与2.7mol/h三乙基铝及足量的稀释剂(己烷)、乙烯和氢一起加到第一个反应器中。调整乙烯的量(＝6.75t/h)和氢的量(7.3kg/h)以便在第一个反应器的气相中测定的乙烯和氢的百分比例分别为18％体积和70％体积，剩余的为氮和蒸发的稀释剂的混合物。
第一个反应器中的聚合反应在84℃进行。
然后将第一个反应器中的淤浆转移到第二个反应器中，其中气相中氢的百分比已降至10-12％体积，16.6kg/h的1-丁烯与4.35t/h的乙烯一起加入到此反应器中。氢的量通过中间的H2减压作用而降低。在第二个反应器的气相中测定到70％体积乙烯、10.5％体积氢和1.1％体积1-丁烯，剩余的是氮和蒸发的稀释剂的混合物。
第二个反应器中的聚合反应在82℃进行。
将第二个反应器中的淤浆转移到第三个反应器中，用进一步的中间H2减压作用调整第三个反应器的气相中氢的量到0.5％体积。
67kg/h的1-丁烯和3.90t/h的乙烯一起加到第三个反应器中。在第三个反应器的气相中测定到85％体积乙烯、0.5％体积氢和2.2％体积1-丁烯的百分比，剩余是氮和蒸发的稀释剂的混合物。
第三个反应器中的聚合反应在80℃进行。
上述级联方法所要求的长期聚合反应催化剂活性通过WO中开始所述的特定开发的齐格勒催化剂来提供。此催化剂有用性的量度是它特别高的氢敏感性和1-8小时长时间的均匀高活性。
从离开第三个反应器的聚合物淤浆中除去稀释剂，将材料干燥然后造粒。
下面所示表1给出了实施例1制备的聚乙烯模塑组合物中聚合物A、B和C的粘数和定量比例wA，wB，和wc。
表1
| 实施例号 | 1 |
| 密度[g/cm<sup>3</sup>] | 0.954 |
| MFR<sub>190/5</sub>[dg/min] | 0.40 |
| W<sub>A</sub>[％重量] | 45 |
| W<sub>B</sub>[％重量] | 29 |
| W<sub>C</sub>[％重量] | 26 |
| VN<sub>1</sub>[cm<sup>3</sup>/g] | 70 |
| VN<sub>2</sub>[cm<sup>3</sup>/g] | 180 |
| VN<sub>tot</sub>[cm<sup>3</sup>/g] | 360 |
| SR[％] | 135 |
| FNCT[h] | 170 |
| NIS<sub>ISO</sub>[kJ/m<sup>2</sup>] | 16 |
表1中物理性质缩写具有以下意义：
-SR(＝溶胀比)以[％]表示，在190℃和剪切速率1440S-1下，在带有锥形入口(角度＝15°)的2/2圆形截面模头的高压毛细管流变仪中测定。
-FNCT＝用M.Fleissner的内部测试方法测试的耐应力开裂性(全缺口蠕变测试)，以[h]表示.
-NISISO＝缺口冲击强度，根据ISO 179-1/1eA/DIN 53453中所述在23℃测定，以[kJ/m2]表示。
Claims (10)
1.一种具有多峰形分子量分布的聚乙烯模塑组合物，具有在23℃为0.950-0.958g/cm3范围内的密度和在0.30-0.50dg/min范围内的MFR190/5，它包含40-50％重量的低分子量乙烯均聚物A，25-35％重量的由乙烯和另一种具有4-8个碳原子的1-烯烃制成的高分子量共聚物B和24-28％重量的由乙烯和另一种具有4-8个碳原子的1-烯烃制成的超高分子量共聚物C，其中所有的百分数值基于模塑组合物的总重量。
2.如权利要求1的聚乙烯模塑组合物，其中高分子量共聚物B含有基于共聚物B的重量计0.2-0.5％重量的低比例的具有4-8个碳原子的共聚单体，和其中超高分子量的乙烯共聚物C含有基于共聚物C的重量计1-2％重量范围内的共聚单体。
3.如权利要求1或2的聚乙烯模塑组合物，作为共聚单体它含有1-丁烯，1-戊烯，1-己烯，1-辛烯，4-甲基-1-戊烯，或这些共聚单体的混合物。
4.如权利要求1或2的聚乙烯模塑组合物，具有的粘数VNtot为330-380cm3/g，根据ISO/R 1191在萘烷中在135℃测量。
5.如权利要求1或2的聚乙烯模塑组合物，它具有在130-145％范围内的溶胀比，在14-17KJ/m2范围内的缺口冲击强度，和在150-220h范围内的耐应力开裂性。
6.生产如权利要求1-5中任一项的聚乙烯模塑组合物的方法，其中单体在淤浆中在20-120℃的温度范围内，在0.15-1MPa范围的压力下，和在由过渡金属化合物和有机铝化合物构成的高耐用性齐格勒催化剂存在下聚合，该方法包括分三阶段进行聚合反应，其中每一个阶段中制备的聚乙烯的分子量借助于氢进行调节。
7.如权利要求6的方法，其中调节第一聚合阶段中氢的浓度以便低分子量聚乙烯A的粘数VN1在60-80cm3/g范围内。
8.如权利要求6或7的方法，其中调节第二聚合阶段中氢的浓度以便聚合物A和聚合物B的混合物的粘数VN2在160-200cm3/g范围内。
9.如权利要求6或7的方法，其中调节第三聚合阶段中氢的浓度以便聚合物A、聚合物B和聚合物C的混合物的粘数VN3在330-380cm3/g范围内。
10.如权利要求1-5中任一项的聚乙烯模塑组合物用于生产容量在2-20dm3范围内的桶的用途，其中首先在挤出机中在200-250℃范围内塑化聚乙烯组合物，和接着通过模头挤出到模具中，在此首先吹制然后被冷却和固化。
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| DE10261066.5 | 2002-12-24 | ||
| DE10261066A DE10261066A1 (de) | 2002-12-24 | 2002-12-24 | Polyethylen Formmasse zum Herstellen von Behältern durch Blasformen und damit hergestellte Kanister |
| US60/445,163 | 2003-02-05 |
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| WO2011060954A1 (en) * | 2009-11-20 | 2011-05-26 | Basell Polyolefine Gmbh | Novel trimodal polyethylene for use in blow moulding |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4336352A (en) * | 1979-08-24 | 1982-06-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Blend of three ethylene polymers |
| US4536550A (en) * | 1983-04-21 | 1985-08-20 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyethylene composition |
| CN1376170A (zh) * | 1999-09-24 | 2002-10-23 | 巴塞尔聚烯烃有限公司 | 具有改进的escr/劲度关系和改进的膨胀率的聚乙烯模塑料,生产它的方法和它的用途 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4336352A (en) * | 1979-08-24 | 1982-06-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Blend of three ethylene polymers |
| US4536550A (en) * | 1983-04-21 | 1985-08-20 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyethylene composition |
| CN1376170A (zh) * | 1999-09-24 | 2002-10-23 | 巴塞尔聚烯烃有限公司 | 具有改进的escr/劲度关系和改进的膨胀率的聚乙烯模塑料,生产它的方法和它的用途 |
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| DE60306814T2 (de) | 2007-02-22 |
| DE10261066A1 (de) | 2004-07-08 |
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