CN102216050B - 用于制备聚乙烯容器、型坯和瓶子的注坯拉伸吹塑成型方法 - Google Patents
用于制备聚乙烯容器、型坯和瓶子的注坯拉伸吹塑成型方法 Download PDFInfo
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Abstract
用于制备聚乙烯容器的注坯拉伸吹塑成型方法，其中使用具有等于或者大于0.945g/cm3的密度和等于或者大于60的F/E比值的乙烯(共聚)聚合物作为聚乙烯材料。
Description
本申请涉及用于制备聚乙烯容器，特别是瓶子的注坯拉伸吹塑成型方法。
在本领域中通常使用一步法和二步法注坯拉伸吹塑成型方法生产由热塑性聚合物材料，尤其是聚对苯二甲酸乙二醇酯(PET)制成的容器。事实证明，PET尤其适用于上述提到的方法，因为其允许在宽的温度范围内(加工性能窗口)操作，且获得具有优异机械性能和高透明度的模制产品。
然而，由于技术缺陷，例如耐热性和耐化学性，存在使用可替代的热塑性材料代替PET的强烈需求。尤其是，已知结晶聚烯烃聚合物或者共聚物(特别是聚丙烯和聚乙烯)与PET相比具有优异的机械和热性能。
因此，在本领域已经提出很多通过注坯拉伸吹塑成型烯烃聚合物以获得聚合物容器，尤其是瓶子的技术方案。
然而，如EP-A-0654 340所述，聚乙烯的注坯拉伸吹塑成型涉及很多技术难题。根据该文件，所述难题可以通过从注射模具释放气体之前向芯模和型坯之间的边界引入气体来克服。然而其实施例也显示，光学性能仍旧非常差，仅获得乳白色瓶子。
目前已经发现，通过使用具有特定熔体流动速率(如下文定义的)和密度值的聚乙烯，获得了具有宝贵的机械和光学性能的拉伸吹塑模制容器，不需要修改传统注坯拉伸吹塑成型方法技术，尤其无需在从注射模具释放型坯之前的所述引入气体。因而本发明提供用于制备聚乙烯容器的注坯拉伸吹塑成型方法，其中使用具有等于或者大于0.945g/cm3的密度(根据ISO 1183测得)和等于或者大于60的F/E比值(根据ISO 1133测得)的乙烯(共聚)聚合物作为聚乙烯材料。
具体地，本发明的方法包括拉伸吹塑成型由上文所述乙烯(共聚)聚合物制成或者包含上文所述乙烯(共聚)聚合物的型坯。
因而所述方法包括以下步骤：
1)将聚乙烯材料注射成型为型坯；
2)将所述型坯拉伸吹塑成型；
其中，所述聚乙烯材料包括具有等于或者大于0.945g/cm3，尤其是0.945g/cm3至0.960g/cm3的密度(根据ISO 1183测量)和等于或者大于60，尤其是60至100的F/E比值(根据ISO 1133测量)的所述乙烯(共聚)聚合物。
根据本发明，“乙烯共聚物”的定义包括选自乙烯均聚物、包含具有4-8个碳原子(优选数量高达10wt％)的α-烯烃单体单元的乙烯共聚物及它们的混合物的聚合物材料。所述具有4-8个碳原子的α-烯烃单体单元的例子为1-丁烯、1-戊烯、1-己烯、1-辛烯和4-甲基1-戊烯。1-丁烯是优选的。
F/E比值是在190℃、21.6kg负荷(也称为条件F)下测得的熔体流动速率与在190℃、2.16kg负荷(也称为条件E)下测得的熔体流动速率的比值。
所述乙烯(共聚)聚合物的优选特征为：
-密度等于或者大于0.950g/cm3，尤其等于或大于0.952g/cm3，上限值最优选0.960g/cm3；
-F/E比值等于或大于70，更优选等于或大于75，尤其等于或大于80，上限值最优选100；
-熔体流动速率E为0.1g/10min或者更大，更优选0.5g/10min或者更大，尤其为0.1或0.5至10g/10min。
当乙烯(共聚)聚合物的密度等于或小于0.955g/cm3时，尤其优选熔体流动速率E值为0.5g/10min或者更高，尤其为1g/10min或者更高(优选上限值为10g/10min)。
所述乙烯(共聚)聚合物在市场上有售。在实施例中描述了具有所述性能的特种商业聚合物。它们属于可以在配位催化剂存在下通过聚合方法获得的(共聚)聚合物家族。本领域大量描述了所述方法和由它们得到的(共聚)聚合物。
特别地，能够在齐格勒-纳塔(Ziegler-Natta)催化剂存在下施行该聚合方法。
众所周知，齐格勒-纳塔聚合催化剂包括元素周期表中I-III族金属的有机化合物(例如烷基铝)和元素周期表中IV-VIII族过渡金属的无机化合物(例如卤化钛)的反应产物，优选负载在卤化镁上。采用此类催化剂所使用的聚合条件通常也是众所周知的。
所述乙烯(共聚)聚合物也可以包含传统的添加剂。
这些添加剂的例子为热稳定剂、抗氧化剂、UV吸收剂、光稳定剂、金属钝化剂、破坏过氧化物的化合物和基础助稳定剂，典型地含量为0.01至10wt％，优选为0.1至5wt％。
一般地，在本发明方法中，通过使用本领域众所周知的方法和设备在适合的模具中注射熔融聚合物获得所述型坯。
注射聚合物材料以获得型坯的温度应由本领域技术人员根据所采用的特定聚合物组合物进行选择。
优选注射温度为210至260℃。
典型地注射压力为32至78MPa(320至780巴)。
在此工艺步骤中使用的模具可以是在注坯拉伸吹塑成型设备中用于制备型坯的任何传统模具。
在所谓的一步法中，该方法的步骤1)和2)都在同一机械中进行。在这种情况下，运行时无需冷却型坯到室温。
二者择一地，并且优选地，在所谓的两步法中，步骤1)可以在第一设备(第一工艺阶段)中进行，并且随后在第二工艺阶段中，所得到的型坯按照路线传送到第二设备用于拉伸吹塑成型2)。在这种情况下，可以允许型坯在拉伸吹塑成型前冷却到室温(约25℃)。
典型地，一步法的拉伸吹塑成型温度为115至130℃。
对于两步法，型坯还被再加热到115至130℃的典型温度。
更优选，一步法和/或两步法的温度为122至128℃，这是最大温度，远远低于本发明方法中使用的标准聚乙烯的熔点。
典型地使用红外线加热装置，但是本领域技术人员会认识到，可以使用任何与该聚合物组合物的性能相一致的加热源。型坯典型地沿着一组加热装置传送，同时旋转以均匀分配热量。型坯也可以在加热过程中和加热后与冷却空气接触，以使型坯表面过热最小化。一旦预热的型坯离开加热炉，该型坯被传递到吹塑模具。
一般地，为了进行工艺步骤2)，将拉伸棒插入到型坯中，用以在轴向上中心拉伸和引导该型坯。引入0.1至4MPa(1至40巴)，优选0.4至2MPa(4至20巴)的压缩气体(优选空气)，用以完成最终容器或者瓶子的吹塑成型。任选地，可在两个步骤中引入压缩气体，其中通过引入0.1至2MPa(1至20巴)，优选0.4至1.2MPa(4至12巴)的压缩气体进行预吹塑，接下来在上文描述的较高压力下完成最后的吹塑成型。
拉伸比优选为2至4。
如之前所述，本发明的方法允许获得具有高物理-机械性能的聚合物容器。
尤其是，其允许获得具有高抗冲击性和相当低雾度值，优选50％或者更少的容器，特别是瓶子。
提供以下关于注坯拉伸吹塑成型瓶子制备的实施例用于举例说明的目的而非限制的目的。
制备两种类型的500ml瓶子。
使用密度(ISO 1183)为0.959g/cm3、熔体流动速率E为0.25g/10min且F/E比值为84的乙烯聚合物制备类型1，其为Lyondellbasell出售的商标Hostalen ACP5831D。
使用密度(ISO 1183)为0.954g/cm3、熔体流动速率E为1.45g/10min且F/E比值为87.5的乙烯聚合物制备类型2，其为Lyondellbasell出售的商标HostalenACP 6541AUV。
工艺条件显示在表1中，所获得瓶子的特性显示在表2中。
表1
表2
1根据ASTM D1003测量；
2和3根据“Voluntary Standard Test Methods For PET Bottles”测量，其发表于2004年，International Society of Beverage Technologists，8110 South Suncoats Boulevard，Homossa，FL34446-5006，USA。
Claims (7)
1.用于制备聚乙烯容器的注坯拉伸吹塑成型方法，包括以下步骤：
1) 将聚乙烯材料注射成型为型坯；
2) 将所述型坯拉伸吹塑成型；
其中所述聚乙烯材料包括具有等于或者大于0.945 g/cm3的密度和等于或者大于60的F/E比值的乙烯(共聚)聚合物，且所述乙烯(共聚)聚合物具有0.5 g/10 min或者更大的熔体流动速率E。
2.权利要求1所述的方法，其中所述乙烯(共聚)聚合物选自乙烯均聚物、包含具有4-8个碳原子的α-烯烃单体单元的乙烯共聚物及它们的混合物。
3.权利要求1所述的方法，其中在第一阶段制备并且冷却所述型坯到达室温，然后在第二阶段进行再加热和拉伸吹塑成型。
4.权利要求1所述的方法，其中制备所述型坯并且将其拉伸吹塑成型而无需冷却到室温。
5.用于拉伸吹塑成型的型坯，包括具有大于0.945 g/cm3的密度和大于60的F/E比值的乙烯(共聚)聚合物，且所述乙烯(共聚)聚合物具有0.5 g/10 min或者更大的熔体流动速率E。
6.注坯拉伸吹塑成型的容器，包括具有等于或者大于0.945 g/cm3的密度和等于或者大于60的F/E比值的乙烯(共聚)聚合物，且所述乙烯(共聚)聚合物具有0.5 g/10 min或者更大的熔体流动速率E。
7.权利要求6所述的容器，其为瓶子形式。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08167437.6 | 2008-10-23 | ||
| EP08167437 | 2008-10-23 | ||
| PCT/EP2009/062809 WO2010046223A1 (en) | 2008-10-23 | 2009-10-02 | Injection stretch blow-molding process for the preparation of polyethylene containers, preform and bottle |
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| Publication Number | Publication Date |
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| CN102216050A CN102216050A (zh) | 2011-10-12 |
| CN102216050B true CN102216050B (zh) | 2015-09-16 |
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| CN200980142340.5A Active CN102216050B (zh) | 2008-10-23 | 2009-10-02 | 用于制备聚乙烯容器、型坯和瓶子的注坯拉伸吹塑成型方法 |
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| Country | Link |
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| US (1) | US20110217500A1 (zh) |
| EP (1) | EP2337665B2 (zh) |
| JP (2) | JP2012506329A (zh) |
| CN (1) | CN102216050B (zh) |
| WO (1) | WO2010046223A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2632689B2 (en) † | 2010-10-26 | 2022-03-23 | Basell Poliolefine Italia S.r.l. | Process for producing injection stretch blow molded polyolefin containers |
| EP2956503B1 (en) * | 2013-02-18 | 2019-05-15 | Ineos Europe AG | Composition for injection stretch blow-moulding |
| JP6494984B2 (ja) * | 2014-11-28 | 2019-04-03 | 株式会社吉野工業所 | 二軸延伸ブロー成形用のプリフォーム及び容器 |
| EP3954528A4 (en) * | 2019-04-09 | 2023-04-12 | Nissei Asb Machine Co., Ltd. | PROCESS FOR MANUFACTURING A RESIN CONTAINER |
| JP7375359B2 (ja) * | 2019-08-01 | 2023-11-08 | 日本ポリエチレン株式会社 | 射出延伸ブロー容器の製造方法 |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2337665A1 (en) | 2011-06-29 |
| JP2012506329A (ja) | 2012-03-15 |
| JP2015178276A (ja) | 2015-10-08 |
| US20110217500A1 (en) | 2011-09-08 |
| EP2337665B1 (en) | 2014-05-28 |
| CN102216050A (zh) | 2011-10-12 |
| EP2337665B2 (en) | 2022-12-14 |
| WO2010046223A1 (en) | 2010-04-29 |
| JP6072128B2 (ja) | 2017-02-01 |
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