CN103747940B - 挤出聚对苯二甲酸乙二醇酯型坯、容器，以及方法 - Google Patents

挤出聚对苯二甲酸乙二醇酯型坯、容器，以及方法 Download PDF

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CN103747940B
CN103747940B CN201280041202.XA CN201280041202A CN103747940B CN 103747940 B CN103747940 B CN 103747940B CN 201280041202 A CN201280041202 A CN 201280041202A CN 103747940 B CN103747940 B CN 103747940B
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pet
extruded polymer
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CN103747940A (zh
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W·C·扬
H·S·霍尔特
G·摩斯
M·C·基茨米勒
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Plastipak Packaging Inc
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Abstract

挤出PET型坯包括包含PET的第一挤出聚合物，以及包含PET的第二挤出聚合物。在实施例中，所述第一挤出聚合物和所述第二挤出聚合物为共挤出的，并且所述第一挤出聚合物具有比所述第二挤出聚合物的特性粘度更高的特性粘度。还揭示了一个单层实施例。在实施例中，单层挤出PET容器由瓶级PET树脂组成，所述瓶级PET树脂已经是固态的并且可以具有从约0.96到约1.4的IV。

Description

挤出聚对苯二甲酸乙二醇酯型坯、容器，以及方法
相关申请的交叉参考
本申请主张2011年8月25日提交的美国临时专利申请61/527,443和2012年1月25日提交的美国临时专利申请61/590,652的优先权，其整个揭示内容以引用的方式并入本文中。
技术领域
本发明大体上涉及能够利用注拉吹塑（ISBM）级聚对苯二甲酸乙二醇酯（PET）来生产包括瓶子和容器的物品的挤出吹塑（EBM）方法和系统。
背景技术
聚合物树脂，包括PET，常被用于塑料包装行业。因为其良好的加工特性，并且因为PET被认为是再循环环境友好的，所以PET被广泛用于生产许多类型的瓶子和容器（所述瓶子和容器可以在本文中统一简称为“容器”）。例如，在瓶行业中，瓶级PET通常具有约0.65dL/g到0.87dL/g的树脂特性粘度（IV），并且通常结合ISBM加工而使用。
可挤出PET合成物或制剂（例如，可挤出PET共聚物）在包装行业也是已知的。EBMPET可以是多个应用所需要的，因为它可以允许使用PET以形成通常由HDPE形成的物品，例如具有手柄的较大塑料容器。对于将适合于EBM工艺的PET，可能需要更高分子量PET，也即，具有更高IV（例如，约1.0dL/g或更大）的PET。然而，此类共聚物通常是非晶形的，或缓慢结晶的，这会呈现出某些转换和回收挑战。尽管缓慢结晶的共聚物可以允许在EBM环境中更容易的加工，但所产生的容器会尤其呈现出可循环性挑战。举例来说，当材料还未结晶并且保持非晶形时，它可以在较低温度熔化。此外，当非晶形或缓慢结晶的树脂被添加到PET再循环流体中时，树脂尤其会导致不希望的粘着、热凝聚，以及桥接（或端口堵塞）问题。此类问题会使PET聚合物树脂不适合于常规的再循环程序和工艺。使用伊士曼EB062材料的容器由于其呈现出此类再循环和性能问题而落入此类别中，因为利用添加剂修改了PET树脂以增加熔体强度。
此外，如果瓶级PET和可挤出PET合成物被混合或合并，以便以分支PET共聚物的形式提供，那么所产生的树脂组合可能不显示出足够需要的性能特征。也就是说，通常从再循环立场考虑，挤出级PET的百分比越高，所产生产品的特征越是不合意的。
在挤出情况下，标准ISBM级PET的使用可以有助于处理一些前述可循环性问题。然而，出于诸如上文所提到的原因，此类树脂由于多个挑战大体上尚未成功商业化。此类树脂通常具有低IV，也即，通常从约0.65到0.87。因此，它们倾向于不能够承载其自身重量并且/或者树脂可能挤出得太快以致不能形成所需的可捕获型坯。这对于大部分（如果不是所有）EBM工艺呈现出一个问题，所述EBM工艺需要足够的熔体强度以生产可接受型坯（无论它在梭式EBM系统、轮式EBM系统，还是任何其他系统中）。在没有足够熔体强度的情况下，型坯将不能正确地形成并且可能流动得太快（“类似于水”）以致不能被吹塑模具捕获。另外地，在一些物品中，较低的IV可能提供较小的容器强度、更易因对应力断裂或破裂，以及不合意的视觉模糊或条纹。
因此，存在对EBM方法和系统的需要以由挤出级PET合成物或制剂生产商业上可接受的瓶子和/或容器，所述瓶子和/或容器与再循环流相容。
发明内容
本发明揭示了挤出PET型坯、容器，以及生产此类型坯和容器的方法。在实施例中，第一挤出聚合物和第二挤出聚合物为共挤出的，第一挤出聚合物包含PET，第二挤出聚合物包含PET，并且第一挤出聚合物的特性粘度比第二挤出聚合物的特性粘度更高。共挤出的型坯随后可以被吹塑以形成容器。
在实施例中，第一挤出聚合物（也即，较高IV聚合物）可以包含具有从约0.96起或更大的IV的PET。如果需要，第一挤出聚合物可以具有从约1.0到1.4的IV，并且可以（例如）由固态标准瓶级PET产生并且可能缺乏扩链剂。第二挤出聚合物（也即，较低IV聚合物）也可以包含PET，并且可以具有约0.85或更小的IV。如果需要，第二挤出聚合物可以具有从约0.8到0.85的IV。另外地，第二挤出聚合物可以进一步包含消费后回收的（PCR）PET以及再磨研PET，并且/或者可以任选地包括着色剂和/或阻挡层。
附图说明
现将参考附图通过举例描述本发明的实施例，其中：
图1为大体上显示了多层挤出吹塑容器的实施例的部分脱落视图；
图2为大体上显示了模塑容器的壁的部分截面视图；
图3为中间物品的一个实施例的壁的部分截面视图；以及
图4为另一实施例的壁的部分截面视图，所述实施例与单层物品相关联。
具体实施方式
现将详细参考本发明的实施例，所述实施例的实例描述在本文中并且图示在附图中。虽然将结合实施例来描述本发明，但应理解，所述实施例无意使本发明限于这些实施例。相反，本发明意欲涵盖可包括在如所附权利要求书界定的本发明的精神和范围内的替代方案、修改和等效物。
仅作为实例而非限制性地，图1大体上显示出了部分脱落视图，所述视图大体上图示了多层挤出吹塑容器10的一个实施例。图2描绘了大体上显示了容器10的壁（确认为部分A）的一部分的部分截面视图。在所图示的实施例中，最内的三个层12、14、16可以在第一加工阶段形成并且可以提供中间物品20，所述第一加工阶段可以涉及材料的共挤出或多层挤出。在所图示的实施例中，第四/最外层18被包括。如果被包括，那么可任选的最外层18可以由与其他层类似或不同的塑料材料组成，并且如果需要，可以包含涂层。图3中大体上图示了中间物品的壁部分的一个实施例。尽管结合中间物品20揭示了三层，并且结合容器10揭示了四层，但所属领域的技术人员能够认识到，可以提供更多的层（或甚至相对于中间物品20更少的层），并且这些层可以具有不同的配置和厚度（包括关于给定层的不同厚度和相关的层间厚度变化）。图4大体上图示了单层物品或容器的壁部分的一个实施例。物品或容器大体上由单个层（大体上图示为层14）组成。
在本发明的实施例中，提供了一种方法，其中两种或两种以上的聚合物被共挤出以形成型坯，所述型坯随后可以被吹塑成瓶或容器。在一实施例中，可以提供两种不同的聚合物。第一聚合物可以包含PET并且可以具有相对较高的IV，例如，0.96或更大（或，举例来说，从约1.0到约1.4）。第一聚合物可以（例如且不限于）由固态标准瓶级PET产生并且可能缺乏扩链剂。第二聚合物也可以包含PET并且可以具有相对较低的IV，举例来说，小于约0.85（或，例如从约0.8到约0.87）。第二聚合物，也即，具有相对较低IV的聚合物，可以包含消费后回收的（PCR）PET和/或再磨研PET。此外，对于一些实施例，第二聚合物可以另外包括一种或多种着色剂。
在一个实施例中，第一聚合物可以具有（例如）约0.97的IV，而第二聚合物可以具有（例如）0.76的IV。具有相对较高IV的层可以用于应付较高的熔体温度并且提供强度，并且可以另外有助于防止迁移。
在方法和系统的实施例中，第一（较高IV）和第二（较低IV）聚合物可以被挤出并且合并（例如，通过挤出头）以形成具有多（例如，二）层的型坯。在一个实施例中，较高IV层的横截面厚度（沿着侧壁并且垂直于型坯的中心线）可以为总型坯厚度的约20%（0.20），并且较低IV层的厚度可以为总型坯厚度的约80%（0.80）。此外，根据所产生的瓶或容器所需承装的内容物，较高IV层和较低IV层可以对于哪层为内部共挤出层和哪层为外部共挤出层进行互换。
根据本发明生产的瓶子和容器的实施例可以包含结晶状PET、可以显示出商业上可接受的清晰度，并且可以在标准PET再循环流中完全可再循环（也即，标记为“1号”）。
在实施例中，非固态的可挤出PET可以具有约0.96或更小的“复合材料”IV，以便能够向下挤出。然而，本发明并不限于在重力方向上挤出的设备，并且其他已知技术也可以被采用。
此外，所揭示的方法和系统可以应用于在一个共挤出层、或在具有两个或两个以上挤出层的多层实施例中形成的型坯。此外，在实施例中，一个层可以充当载体层，而其他层可以给予一个或多个其他结构或特征。此类其他结构或特征可以包括PCR的使用、着色（例如，外部颜色），或成本优化（例如，包括相对较不昂贵（“废料”）的中间层）。非限制性地，在一个实施例中，相对较高IV聚合物可以充当骨架，而另一层可以包括28%或更多的PCR。此外，非限制性地，所产生的瓶子或容器的一些实施例可以包含按重量计在约10%到50%之间的PCR含量。在其他实施例中，PCR含量可以具有按重量计约20%到30%的性质。此外，如果需要，可以另外包括80%或更多（甚至多达100%）PCR的废料层。本发明的实施例并不依靠扩链剂，并且不是非晶形和固态树脂的组合。也就是说，可挤出聚合物可以在固态条件下提供，并且不是非晶形的。
两层的潜在益处是可以利用载体树脂的能力。还可能对一个或两个层着色以提供不同的视觉效果，不论该层或这些层是单独还是以各种组合着色。此外，如果渗透为潜在的问题，那么一个或多个阻挡层可以用来与型坯/物品的一个或多个层结合。
与所揭示的概念相关联的型坯可以利用已知加工技术的各种形式和设备来加工。对于一些实施例，可以使用“梭”式系统。利用梭式设备，具有多个出口的头可以在共同的点处提供型坯，并且一个或多个模具可以在型坯下适当的位置处移动或穿梭。如果空间为一个问题和/或如果生产将变得更加“按需求”而较少关注高容量和速度，那么此系统可以较好地起作用。可替代地，当需要具有可能的较高速度和输出的更加“连续”的过程时，可以采用各种已知的旋转或“轮式”挤出技术。在实施例中，轮式挤出装置和设备可以如所需经配置以在各个方向上挤出，例如，朝上，或对于一些应用可能更加合乎需要地，朝下。
本发明的另一实施例包含由已经为固态的标准瓶级PET树脂制成的单层挤出PET容器。标准瓶级PET树脂可以具有从约0.65到约0.87的IV。在本发明的实施例的情况下，此类PET树脂可以为固态的以将其IV增加至从约0.96到约1.4，并且对于一些实施例，约1.1。此类树脂可能缺乏扩链剂或其他类似添加剂或改性剂。（例如）结合朝下挤出轮式工艺的此类树脂的挤出吹塑可以生产具有良好的清晰度和材料分配（所述材料分配可以导致改进的容器强度和性能）的可再循环（例如，标记为#1）PET容器。如本文所引用的“良好清晰度”可以描述大体上不含条纹和/或模糊的容器。根据本发明的教示所生产的容器可以产生非常适合于经受跌落试验的容器，包括常规的三英尺跌落试验（所述试验可以为“冷却的”或“未冷却的”试验）。也就是说，在限制试验的情况下，相当大数目（例如，超过50%）的测试容器经过了三英尺跌落试验。在实施例中，结合此类树脂的EBM加工，可能需要维持大体上一致的模具温度。
已经出于说明和描述的目的呈现出对本发明的具体实施例的前述描述。这些描述并不意在覆盖所有范畴或将本发明限于所揭示的精确形式，且依照以上教示，各种修改和变化都是可能的。实施例经挑选和描述以便说明本发明的原理及其实际应用，以由此使得所属领域的技术人员能够利用本发明及具有适合于所预期的特定用途的各种修改的各种实施例。本发明的范围既定由所附权利要求书及其等效物界定。

Claims (15)

1.一种挤出PET型坯，其包含：
包含PET的第一挤出聚合物；以及
包含PET的第二挤出聚合物；
其中所述第一挤出聚合物和所述第二挤出聚合物为共挤出的，所述第一挤出聚合物和所述第二挤出聚合物处于固态，并且所述第一挤出聚合物具有比所述第二挤出聚合物的特性粘度更高的特性粘度，其中所述第一挤出聚合物具有至少0.96的特性粘度。
2.根据权利要求1所述的型坯，其中所述第一挤出聚合物具有从1.0到1.4的特性粘度。
3.根据权利要求1所述的型坯，其中所述第二挤出聚合物具有小于0.85的特性粘度。
4.根据权利要求1所述的型坯，其中所述第二挤出聚合物具有从0.80到0.87的特性粘度。
5.根据权利要求1所述的型坯，其中所述第二挤出聚合物包含消费后回收(PCR)PET或再磨研PET。
6.根据权利要求1所述的型坯，其中所述第二挤出聚合物包括着色剂。
7.根据权利要求1所述的型坯，其中所述第一挤出聚合物的横截面厚度至少为总型坯厚度的0.20。
8.根据权利要求1所述的型坯，其中所述第二挤出聚合物的横截面厚度小于总型坯厚度的0.80。
9.根据权利要求1所述的型坯，其包括一个或多个额外挤出聚合物层。
10.根据权利要求9所述的型坯，其中所述一个或多个额外挤出聚合物层包含再循环或再磨研材料。
11.一种由根据权利要求1所述的型坯形成的容器。
12.一种用于形成经挤出吹塑的容器的挤出PET型坯，其包含：
包含PET的挤出PET单层聚合物；
其中所述挤出PET单层聚合物处于固态，并且所述挤出PET单层聚合物具有从0.96到1.4的特性粘度；所述挤出PET单层聚合物缺乏扩链剂；和所述挤出PET单层聚合物不是经注拉吹塑成型的。
13.根据权利要求12所述的型坯，其中所述特性粘度为1.1。
14.一种由根据权利要求12所述的型坯形成的容器。
15.根据权利要求14所述的容器，其中所述容器大体上不含条纹和模糊。
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