CN1822939A - 由气体浸渍聚合物制造热成形制品的方法 - Google Patents
由气体浸渍聚合物制造热成形制品的方法 Download PDFInfo
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- CN1822939A CN1822939A CNA2004800204573A CN200480020457A CN1822939A CN 1822939 A CN1822939 A CN 1822939A CN A2004800204573 A CNA2004800204573 A CN A2004800204573A CN 200480020457 A CN200480020457 A CN 200480020457A CN 1822939 A CN1822939 A CN 1822939A
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- polymer
- gas
- goods
- hot forming
- foaming
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
一种固态方法使用气体浸渍以增强热塑性材料的热成形。如果气体是增塑的,则制品由此被增塑用于热成形。在一些实施方式中,本发明通过在气体暴露期间产生高浓度的溶解气体,在热成形之前或在热成形期间使聚合物发泡。发泡可通过从气体压力一减压而自发进行,或者可通过将聚合物片材(112)加热到接近于或高于聚合物的玻璃化转变温度,而增强发泡,从而生成用于热成形的增塑泡沫聚合物。当期望制成非发泡聚合物的物体时,可通过在气体压力下热成形气体饱和制品而抑制发泡。该工艺可用于增强先前已发泡的制品包括现有方法发泡的制品的热成形性能。在一些实施方式中,聚合物被充分增塑以致没有加热就能发泡。聚合物的增塑是可逆的。
Description
相关申请的交叉引用
本申请要求2003年5月17日申请的名为“THERMOFORMEDFOAMED THERMOPLASTIC PACKING(热成形的泡沫热塑性包装)”的美国临时申请号60/471,477的优先权。
技术领域
本发明涉及一种制造热成形的热塑性聚合物制品的方法。更具体地,本发明涉及通过在热成形前用气体浸渍聚合物而改进的热成形工艺。
背景技术
热成形工艺用于制造现代生活中广泛的成形制品。由热成形的热塑性片材制造的产品包括盘、碗、烧杯、标志、公文包外壳、冰箱门胆和包装。
热成形中使用的热塑性材料包括丙烯酸类聚合物、低密度聚乙烯(LDPE)、高密度聚乙烯(HDPE)、聚丙烯(PP)和聚对苯二甲酸乙二酯(PET),后者既可以是结晶型的结晶聚酯(CPET)也可以是二醇类改性聚酯(PETG)。泡沫材料也是热成形的,特别是聚苯乙烯泡沫。
热成形工艺通常需要以红外辐射的方式将热施加于热塑性片材或薄膜以便把材料升高到使热塑性塑料变软和柔韧的温度,在现有技术中通常在120到180℃之间。其后,取决于具体的热成形工艺,使软化的热塑性材料成形并让其冷却到它能保持期望形状的温度。然后切割和修整模塑的片材以获得模塑的热成形制品。
如本领域的技术人员理解的那样,热成形一般指的是一组用于制造热塑性成形制品的有关工艺。热成形中包括有真空成形、压力辅助热成形、高精度热成形、包模成形、冲压成形和线弯曲。
在真空成形中,通过应用真空将加热的片材吸进阳模或阴模内而成形。这种热成形工艺的主要限制是,物体的边和角不可避免地总使圆到一定程度,并且不可能有显著的倒陷或折返(reentries)。真空成形是能够经济、大量生产的简单技术。
在压力辅助热成形中,与传统的真空成形不同,使用的模具通常是阴模。利用空气压力将塑料片材推入模具。虽然一般不适于非常高速的生产,但是用这种技术制造的制品中可实现卷曲的细节、90度角和复杂的特征。
高精度热成形使用专门合适的成形机。通过使用由例如微孔透气铝复合材料的高级制模材料制成的压力箱和阴模,该工艺给予接近于压力辅助热成形中达到的元件精度,而同时保持与传统真空成形相关的较高生产率和较低的成本。
包模成形在不使用压力的情况下简单地将加热的片材覆盖在阳模上或阴模中。其仅可形成单曲率制品。由于不施加压力并且使用简单曲线,所以片材在成形过程中不变薄。该工艺特别用于冲击强度是必不可少的聚碳酸酯片材的成形。
冲压成形是最早的成形技术之一。用来自模具的定向压力把加热的片材精确地压制成形。原先被开发用来成形流延丙烯酸片材,现在用于加工PVC、聚碳酸酯和PET。元件形状的复杂度必须比真空成形的低,但是该工艺产生的变形更少。当在透明或半透明表面光洁度中要求光学透明度时,它是优选的技术。
线弯曲用于通过弯曲和折叠成形热塑性片材。使用电热丝式加热器对部分预切割的塑料片材进行局部加热。这产生“热铰链”(hothinge),从而使片材成形为要求的形状。当它冷却时使用夹具支撑该塑料。
不管使用什么工艺,所有热成形都是基于热成形材料在低温下由于范德华力使热塑性聚合物分子保持固体结构形状而相对刚性的原理。对于给定的热塑性塑料,随着温度升高,聚合物分子的动能也增加,直到在称为玻璃化转变温度Tg的温度时,分子的动能通常克服相对弱的范德华力并且使聚合物材料成为可塑。在可塑状态下,聚合物分子虽然不是处于完全液态,但能彼此滑动,使材料弯曲而不保持固定形状。然后热成形就是简单地加热聚合物直到它被增塑,使其成形,然后使其冷却同时物理上保持其形状,直到聚合物低于玻璃化转变温度并将保持其自身的形状。
增塑是聚集的分子行为的结果,在一定程度上是度的现象。在玻璃化转变温度时,大量聚合物分子从弱的范德华力保持的固态变得松散,并且虽然聚合材料还不是液体,但是其粘度显著下降。重要的是,随着材料的温度升高到高于其玻璃化转变温度,有较大百分比的聚合物分子克服弱的范德华力,并且随着温度增高粘度降得更低。当温度达到聚合物的熔融温度Tm时,基本上所有聚合物分子的动能显著地克服分子间力达到材料可自由流动的程度。
在热成形中,增塑的热塑性塑料的流变行为在成形高质量制品中是至关重要的。如本领域的技术人员完全理解的那样,在许多情况下,期望增塑的材料具有非常低的粘度,从而使软化的聚合物能呈现最大化的细节、尖角以及当制品所要求并使用的工艺能做到时的凸起的特征、凹槽和凹角。因此,在热成形中,一般做法是在成形前通过将热塑性塑料加热到完全高于其玻璃化转变温度但低于其熔点而得到低塑性粘度。
现有热成形技术具有许多缺点。低塑性粘度要求的较高温度需要更大能量输入,并因此增加热成形的费用。不足以实现可由花费更少和/或产率更高的工艺实现的细节的塑性粘度需要使用更贵和/或产率更低的热成形工艺来获得同样的结果。当聚合物材料经受较高的温度时,它们会经受热氧化降解,其中聚合物链断裂并且聚合物变得更难以重复利用从而减小其价值。此外,对一些热成形应用,不管多高的温度,在现有技术中一些聚合物的粘度不能简单地通过加热而充分地降低。
泡沫聚合材料的现有热成形技术存在另外的问题。在现有技术中,泡沫聚合物通过发泡挤出产生,其需要产生或迫使非反应发泡气体进入熔融的聚合物混合物,或可选地用熔融的聚合物内的化学反应产生气体,从而在熔体中形成气泡。使混合物冷却并在气泡周围硬化,气泡在现在的泡沫材料中变成充气的泡孔。
现有技术的泡沫聚合物不适于在发泡挤出后立刻热成形,然而需要一段“固化”的时间,在该段时间内将挤出后的泡沫聚合物暴露于大气中几天。由于以下原因,固化过程一般是必要的。在发泡挤出后进行冷却时,由于发泡气体的热收缩,新冷却的泡沫聚合物中的当前硬的泡孔包含的发泡气体的压力显著地小于大气压,大约为0.5大气压。在这种低绝对压力下成形很可能会导致泡孔壁的弯曲和泡孔的坍陷。由于泡孔壁对于大气气体比对发泡气体中使用的各种气体更容易渗透,所以在固化期间,大气气体渗透性地穿透泡沫聚合物中的泡孔,实际上开始将泡孔内的压力增加到高于大气压,大约为1.5大气压。当现有技术的泡沫聚合物固化到泡孔内压力高于大气压时,主要由于泡沫聚合物中的额外压力导致加热时聚合物的二次膨胀,所以这促进了热成形。增压的泡孔在热成形期间耐坍陷和变形,从而产生出众的热成形的泡沫产品。
然而,当现有技术的泡沫聚合物在热成形前被暴露于空气较长的时间时,捕集的发泡气体逐渐从聚合物泡沫中的泡孔散去,并且泡孔的压力接近大气压。因此,在热成形已经存储超过对于固化的最佳时间的聚合物泡沫时,泡沫中相当大百分比的微孔在热成形期间坍陷或变形,导致材料在成形期间可能会裂开或变形,或者产生劣等的热成形泡沫产品。由于现有技术的泡沫聚合物非常难以重新利用,所以这种废泡沫聚合物的重复发泡挤出和固化过程通常不是经济可行的选择。
现有热成形技术的另一限制是与热的现有技术泡沫材料的流变性相关,这限制了能用这种材料形成的产品的几何形状。在现有技术中,热成形温度下不充足的塑性、强度和延展性不仅限制物体壁的陡度,由此无法制造与垂直方向小于35度角的壁,而且限制物体的相对高度,由此无法达到超过1∶1的深宽比。
现有技术泡沫热成形的又一限制是,在未处理的现有技术的泡沫材料中缺乏连续的平滑表面,导致热成形物体外观差、耐久性低、抗污性缺乏和其它不理想的质量。缺少表皮可导致现有技术泡沫材料在加热和热成形期间产生气泡或裂开,从而限制这种材料对于热成形的适用性。在现有技术中,为了试图解决这些缺点,可将非发泡材料的单独表皮层压于泡沫材料或者附于泡沫材料上,但是在经济和环境费用方面,后者由于附着的表皮会使由它形成的材料和物体对重复利用的适用性更差。为解决现有技术热成形泡沫材料的缺点而作出的努力进一步包括使用封闭的或双边模塑(two sided molding),如本领域的技术人员很好理解的那样,这需要相当高的模具费用并导致生产线效率降低。
因此,对本发明的技术人员来说很清楚的是,现有技术中用于热成形泡沫聚合物的工艺具有几个显著的缺点。第一,由于固化时间是必需的,聚合物发泡和热成形的工艺必定是不连续的,导致工业效率低。第二,已固化了过长时间的泡沫聚合物丧失了热成形的价值,对于这种损失现有技术无法提供满意的补救方法。第三,用现有技术材料的热成形泡沫体的几何形状相当受限制。第四,缺乏完整表皮需要粘附一层非发泡材料和/或使用导致生产线效率下降的昂贵的模具。
所需要的是用于处理用于热成形的热塑性材料的方法,其中热塑性塑料的塑性可以在较低的温度下可逆地被增强。进一步需要的是用于处理热塑性材料的方法,由此使处于材料玻璃化转变温度和熔融温度之间的给定温度下的材料的粘度低于现有技术中材料的粘度。进一步需要的是用于处理热塑性材料的方法,以便可在较低温度下使其热成形,允许更经济的生产以及增强热成形聚合物的可重复利用性。仍进一步需要的是不需要固化时间的用于热成形泡沫聚合物的工艺。还进一步需要的是抑制在热成形时在泡沫表面上形成气泡的方法。仍进一步需要的是用于热成形泡沫聚合物从发泡一直到热成形都是连续的方法。此外,所需要的是用于处理传统的已固化了过长时间的泡沫聚合物的经济、工业规模的方法,以便它能再适于最佳的热成形。还需要的是允许成形的物体具有较宽范围的几何形状的方法,这种物体包括(1)具有陡峭或几乎垂直壁的泡沫体和(2)具有超过1∶1的深宽比的高的泡沫体。仍进一步需要的是适应于连续或半连续工业生产要求的方法。也期望这样的方法具有最小的负面环境影响。
已发现在聚合物中溶解诸如二氧化碳的非反应气体会引起“增塑效应”,其影响聚合物的流变和热性能(例如,参见Effects of CO2 onPolymer Properties,by Surat Areerat et al.,presented at the RegionalMeeting on Polymer Processing,Taipei,2002,available athttp://www.cheme.kyotou.ac.jp/6koza/pdf/H14/ID059.pdf)。令人惊讶的是,具有溶解气的聚合物比没有溶解气的情况要显著低的温度下进行玻璃化转变。例如,当将PET暴露于21℃和5MPa下作为增塑气体的CO2中一段时间以致CO2的浓度为约8-9wt%时,被暴露的材料的玻璃化转变温度足足下降了20℃。而且,在高于正常玻璃化转变温度的给定温度下,具有溶解气的聚合材料比没有溶解气的聚合物具有更低的粘度。还进一步,由于溶解气在大气压下随着时间的过去从聚合物中去溶剂化,所以增塑效应是暂时和可逆的。
基于这些发现,对本领域的技术人员来说将清楚的是,可通过利用在其中溶解有充足的非反应气体以产生增塑效应的热塑性聚合物来实现改进的热成形。然而,为了使这种热成形具有实际价值,需要一种能用连续或半连续工艺以工业规模生产显示增塑效应的气体浸渍聚合物的方法。
Kumar等人的美国专利第5,684,055号公开了用固态的气体浸渍聚合物生产泡沫材料的方法,将其全部内容在此引入作为参考。在这种方法中,聚合物片材辊在聚合物层之间具有气体窜槽装置(gaschanneling means)。将该辊在高压下暴露于非反应气体中使时间足以在聚合物内达到期望的气体浓度。然后将饱和的聚合物片材与气体窜槽装置分离。在‘055中,然后通过加热开始气泡成核和生长来发泡聚合物片材。然而,有利地,在气体压力下,使用气体窜槽装置促进聚合物片材的气体浸渍的技术,可用作为了增塑在聚合物中气体一般浸渍的工业方法,而不管聚合物随后是否被发泡。
然而,当聚合物的气体浸渍用于将被热成形的泡沫聚合物时,它有附加的优势。不管浸渍的气体是否增塑,刚进行发泡后的固态泡沫聚合物在室温下具有含有高于大气压的气体的微孔。因此已发现这样的聚合物不需要固化期就具有现有技术中经过固化的泡沫聚合物的出众热成形质量。
进一步发现,当把现有技术的已固化了过长时间的泡沫聚合物暴露于非反应气体以便其泡孔用高压气体饱和时,这种材料的热成形性被极大地改进。
本发明的目的是提供用于处理用于热成形的热塑性材料的方法,其中热塑性塑料的塑性在较低的温度下可逆地被增强。本发明进一步的目的是提供用于降低在给定温度下用于热成形的热塑性塑料的粘度的方法。如果在现有技术中材料的热成形确实是可能的话,本发明进一步的目的是能在比现有技术的可能温度更低的温度下热成形热塑性材料,包括使热成形工艺能够不需要加热热塑性材料使物体成形。本发明进一步的目的包括:提供用于在不需要固化期热成形泡沫聚合物的方法;提供用于从发泡一直到热成形都是连续的热成形泡沫聚合物的方法;提供用于处理传统的已经固化了过长时间的泡沫聚合物的经济、工业规模的方法,以便它再适于最佳的热成形;以及提供用于改进用于热成形的材料的方法,其是适应于工业规模的连续或半连续的工艺并且是环境可接受的。
发明内容
本发明利用气体浸渍的固态工艺来增强热成形中使用的热塑性材料的性能。聚合物片材辊在聚合物层之间交错(interleaved)有气体窜槽装置。将该辊聚合物在高压下暴露于非反应气体中的时间足以在聚合物内达到增高的高压气体浓度。如果该气体是增塑气体,则暴露以带来聚合物的增塑效果所要求的时间。然后将饱和的聚合物片材与气体窜槽装置分离并减压随后热成形。在使用增塑气体的实施方式中,降低了暴露的聚合物的玻璃化转变温度,并因此使热成形可在比用于未暴露的聚合物更低的温度下进行。
在一些应用中,本发明通过在气体暴露期间产生高浓度的溶解气体,提供在热成形之前发泡聚合物。在一些实施发泡的实施方式中,一减压,气泡成核与生长就自发地进行,而在其它发泡的实施方式中,气泡成核与生长是通过将聚合物加热到接近或高于聚合物的玻璃化转变温度而开始和增强,从而生成准备用于紧接着热成形的泡沫聚合物。在实施发泡的实施方式中,发泡和热成形过程可以是连续的。在进行连续发泡和热成形的优选实施方式中,发泡是通过仅在成形之前加热而进行的。此外,应当注意,传统的泡沫聚合物的热成形可由固态气体浸渍而增强。
在一些不期望发泡的其它实施方式中,本发明使饱和的聚合物在压力下热成形,将聚合物冷却到对于饱和的聚合物的玻璃化转变温度之下,并且然后减压聚合物以产生未发泡聚合物的热成形制品。
附图说明
通过考虑以下说明和权利要求并参考附图,本发明的其它目的、优点、特征和特性以及相关结构元件的方法、操作和功能,以及各部分的结合和配置的经济性将很清楚,所有这些内容构成本说明书的一部分,其中:
图1是根据本发明用于增塑聚合物并由此热成形制品的工艺流程图;和
图2是说明从固态工艺发泡的聚合物的发泡开始的CO2气体浓度随时间变化的图。
具体实施方式
本发明涉及用于可逆地增强用于热成形的热塑性塑料的塑性的工艺。它一般适用于玻璃态的无定形类、非玻璃态的弹性类或半结晶的热塑性聚合物或共聚体。虽然本文中的许多描述以PET为例,但应理解,除了PET外,或代替PET,可使用其它聚合物或聚合物的混合物。适合的气体-聚合物体系包括CO2和聚丙烯,如在CO2-AssistedCrystallization of Polypropylene for Increased Melting Temperature andCrystallinity by Mitsuko Takada et al,Proceedings of Polymer ProcessingSociety meeting,Hertogenbosh,Netherland,May 3l,1999中所公开的。可使用其它气体和压力(例如,CO2可与聚乙烯、聚氯乙稀、丙烯腈-丁二烯-苯乙烯、聚碳酸酯、聚对苯二甲酸乙二醇酯、和聚丙烯使用;N2可与聚苯乙烯使用)。意图是这些教导应包括为任何和所有这些聚合物的热成形可逆地增强塑性。
现在转到图1,其描绘的是用于可逆地增强然后被热成形的聚合材料的塑性的一般方法。在该方法中,聚合物片材102用气体窜槽装置104交错以形成交错的辊,片材迭层,或聚合物的花彩108和气体窜槽。气体窜槽装置104优选地由柔性透气材料构成。虽然多孔纸片是优选的材料,但其它透气材料,例如颗粒材料、丝网、网格和机织或非机织织物也可成功地用于本发明。
作为选择,气体窜槽装置可机械地提供,而不是以透气材料的方式。这样的机械气体窜槽装置可包括凸起部分,例如附属的或与聚合物材料成一整体的凸起或山脊。这样,材料可以是用它自身进行交错,凸起部分充当材料的隔离层用于气体透过。
无论如何,交错的材料106接着在高压下暴露108于可溶于聚合物的非反应气体中,暴露时间足以在聚合物中达到期望的气体浓度,典型地,对于PET-CO2体系,至少为0.5wt%。溶剂化(solvated)的气体浓度至少是在聚合物中带来增塑效果所需要的量,但不需要高到使气体浸渍聚合物成为初生泡沫。
暴露于压力108一般在室温(大约21℃)下进行。可采用更高的温度以加速聚合物内气体的扩散速率,而较低的温度可随时间引起较高程度的气体饱和度。可用增压泵使压力变得高于罐的供给压力。例如,使用CO2时,优选的罐压范围大约为0.345至5.2MPa。可用适当的增压泵将其增加到8.27MPa以上。高达17.2MPa或更高(超临界CO2)的压力是可用的。
优选的气体可取决于被处理的聚合物。例如,对于用于发泡PET、PVC和聚碳酸酯,二氧化碳是优选的气体,而用于发泡聚苯乙烯,氮是优选气体。通过在压力下反渗透已把大气中氧的百分比降到1%至20%的“改良空气”以及纯大气可以作为选择用在一些实施方式中。
聚合物辊暴露于气体过程中的时间量随固态聚合物片材的厚度,具体的聚合物-气体体系,饱和压力以及扩散到聚合物中的速率而变化,并且一般通过实验确定。然而,3和100小时之间的时间典型地用于厚度为0.25mm至2mm的片材。例如,当用CO2饱和0.5mm厚的PET片材时,约15至30小时之间的饱和时间是优选的。
在聚合物-透气材料片材的饱和之后,使片材返回到常压并去除气体窜槽装置110,产生具有增塑效应的气体浸渍的聚合物片材112,其随着气体从浸渍聚合物112消散而逐渐返回原状态。
在一些实施方式中,浸渍的增塑聚合物112可在热成形122之前发泡114,而在其它实施方式中未发泡的增塑聚合物112被直接热成形。在其它实施方式中,可取决于气体饱和压、吸收的气体浓度水平和热成形温度,增塑聚合物在热成形的加热阶段可以发泡或可以不发泡。
对于在一些实施方式中可选的热成形114,在从气体窜槽110退绕时,通过在拉力下拉过加热站116,将聚合物片材112片材加热到其玻璃化转变温度以上。从而以连续方式使聚合物片材发泡。在通过加热站116之后,可将聚合物片材拉过冷却站118,例如冷水浴、一组冷却的辊或简单的空气,以冷却聚合物并停止气泡成核与生长。在这样的实施方式中,加热站116的温度以及聚合物片材拉过加热站116和冷却站118的速率可以变化,以提供具有不同气泡尺寸和密度的片材。在发泡后,修整120聚合物片材,获得然后可被热成形122的最终的泡沫聚合物材料。
虽然实施方式可在成形的同时实现发泡,但这些实施方式需要额外的成形时间来使材料发泡,因此可能对高生产量要求的适用性较差。对于高生产量要求的优选实施方式使用加热站116以将饱和的聚合物加热到既适于发泡又适于热成形的温度,然后在不需要冷却站118立刻使材料热成形122。
令人惊讶的是,已发现,虽然使用的气体是非反应的并且不从化学上改变聚合物,但由于气体的饱和可逆地增塑聚合物,所以有效地降低了它的玻璃化转变温度,从而使一些发泡能在低于聚合物的正常玻璃化转变温度的温度下进行。实际上,如果暴露于气体压力在充分低的温度下或充分高的压力下进行,则聚合物中溶剂化的气体压力是足以在减压到大气压,在室温下气体的去溶剂化作用可以克服聚合物的屈服强度,引起气泡成核与形成,从而使聚合物发泡。在这种情况下,取决于期望的发泡程度,完全不需要材料的加热116和随后的冷却118就能产生泡沫聚合材料。
根据上述方法发泡气体浸渍聚合物的令人惊讶和重要的结果是得到的聚合物泡沫中的微孔包含压力高于大气压的气体。在热成形温度下,微孔中收集的加压气体的作用是产生微孔的二次膨胀,从而防止泡孔弯曲或坍陷。另外,当气体增塑时,在孔壁的聚合物被高度增塑,又进一步增强了聚合物的有效增塑,从而产生在给定温度下比预期更低的泡沫聚合物的粘度。
当已用现有技术的方法发泡的聚合物然后用气体浸渍时得到类似的结果。发泡聚合物中的微孔在压力下聚集气体,在暴露后保留加压气体。如果这样进行气体浸渍,然后热成形现有技术的泡沫聚合物,则孔壁类似地耐弯曲和坍陷,如果气体是增塑的,则聚合物在热成形温度下的粘度低于未处理的现有技术发泡聚合物的粘度。
总之,未发泡的浸渍聚合物112或气体浸渍的发泡聚合物114都可被热成形122。如先前描述的那样,热成形来自增塑气体浸渍材料的制品所需的温度一般低于并常常显著低于对于没有增塑效应的相同材料的温度。令人惊奇的是,对于一些聚合物高度饱和有增塑气体的气体/聚合物体系,聚合物可被充分地增塑以致材料可在室温下“热成形”。而且,由于增塑效应降低了聚合物的粘度,所以对于给定的热成形工艺,和没有被增塑的材料可能实现的相比,在增塑材料的热成形时可实现更大的细节和更深的“拉伸”。在一些情况下,例如使用PET泡沫的真空成形,制品可以被成形,用未增塑的聚合物不能热成形。
当期望制造非发泡制品,但是将使用的饱和聚合物在大气压下热成形时反而会发泡时,热成形可在压力下进行。参考图1,对于这种非发泡制品,当用压力下气体饱和后,去除气体窜槽装置110并热成形122饱和的聚合物112,同时保持在压力下。如本领域的技术人员将理解的那样,然后使热成形品冷却到低于其玻璃化转变温度或低于它在大气压下会发泡的温度,然后对其减压以产生热成形的非发泡制品。
无论如何,在热成形122之后,根据本领域的技术人员非常熟知的方法,按需要将制品切割和修整124以形成最终的制品126。重要的是,由于所涉及的这些方法对聚合物的化学性质有很小的或没有不可逆的影响,并且因为由于加热要求的降低使热氧化变质最小化,该工艺的废料更可重复利用,并因此比用于热成形制品的现有技术方法的废料更有价值。而且,由于在该方法中仅使用非反应气体,所以对环境安全。
实施例
实施例1试验。在以下每个实例中,0.762mm厚的新鲜PET在21℃下用4MPa压力的CO2饱和67.25小时。在减压后10分钟内,将饱和的材料在100℃下发泡,产生具有很少或没有显著表皮和粗糙表面结构的泡沫聚合物。热成形炉保持在恒定温度(大约550℃)下。因此被热成形的塑料的温度随加热的持续而增高。使用单面阳模,其具有2.4的面积拉伸比,11.11cm的高度,8.636cm的顶口,1.29的高宽比,5.842cm的底径,与垂直方向成6.5度的平均侧壁角。发泡后脱气时间可以变化以观察脱气对没有显著表皮的泡沫物体在不同温度下热成形的影响。随着热成形前随着发泡后逝去的脱气时间增加,聚合物中的气体浓度降低,如图2所示。
1.发泡后脱气时间为10-19分钟的试验
成形压力:0.31MPa。所有试验中都观察到热成形中的二次膨胀。
试验1:0.7秒加热时间:泡沫裂开,无杯子,
试验2:10秒加热时间:形成杯子,一些折皱,良好的成型细节精度,
试验3:15秒加热时间:产生气泡并起泡—没有足够的表皮来维持容纳气泡的二次膨胀。
2.发泡后脱气时间为2.5小时的试验
成形压力:0.31MPa。所有试验中都观察到热成形中的二次膨胀。
试验1:8秒加热时间:泡沫裂开,无杯子,显示出没有足够的延展性,
试验2:12秒加热时间:形成杯子,良好的成型细节精度,一些折皱。
3.发泡后脱气时间为23小时的试验
成形压力:0.31MPa。在任何试验中没有注意到在热成形机中的二次膨胀。
试验1:4秒加热时间:形成杯子,精度差,无折皱
试验2:8秒加热时间:形成杯子,精度差,无折皱
试验3:10秒加热时间:形成杯子,成型细节精度差,无折皱
4.发泡后脱气时间为51小时的试验
对于成形需要0.758MPa的成形压力。在任何试验中没有注意到在热成形机中的二次膨胀。
试验1:4秒加热时间:当物体达到大约5cm的深度时,塑料被拉出夹钳。
试验2:8秒加热时间:塑料的全部深度被拉出夹钳,部分杯子
试验3:14秒加热时间:杯子部分形成,塑料夹钳不影响塑料片材拉伸
实施例1结论:当使没有厚表层或显著表层的泡沫热成形时:
a.发泡后的短脱气时间将加热时间(发泡温度)限制到太低的热成形温度—较长的时间导致气泡产生;
b.气体浓度对可成形性(延展性)的最佳折衷是几小时的脱附时间;
c.较长的脱气时间降低可成形性。在51小时的情况下,甚至在110psi的成形压力下,由于低延展性,用14秒的加热时间不能形成杯子,在23小时的脱气时间情况下,可在45psi压力下用4秒的加热时间制成杯子;
d.热成形机中的二次膨胀增加细节。
实施例2试验。在以下每个实例中,0.762mm厚的新鲜PET在21℃下用5MPa的CO2饱和26小时。通过在发泡前改变减压后的脱附时间而产生不同厚度的表层。饱和的并且部分脱附的材料在105℃下发泡2分钟,从而获得相对于未发泡聚合物密度为21%的泡沫聚合物。热成形炉保持恒定温度(大约550℃)。因此热成形的塑料的温度与加热的持续时间成比例。使用单面阳模,其具有1.7的面积拉伸比,8.73cm的高度,7.62cm的顶口,1.31的高宽比,5.08cm的底径,与垂直方向成6.5度的平均侧壁角。
试验设置1:在减压的10-20分钟内发泡:热成形试图在发泡的10分钟内进行。用10-15秒的加热时间不能充分形成杯子。增加加热时间导致杯子弯曲和起泡。这些杯子在试图成形期间由于塑料的裂开而失败。用肉眼观察,明显地没有形成表皮。
试验设置2:在1.5小时的发泡之前脱附。在泡沫材料上观察到光滑的有光泽的表层。所有杯子具有2.1的面积拉伸比。
a.发泡后脱气38分钟。9秒热成形加热时间:杯子具有良好的表面细节。夹钳夹住塑料。
b.发泡后脱气19小时50分钟,10秒热成形加热时间:杯子定形差;塑料滑出夹钳。
c.发泡后脱气99小时30分钟,经过30秒热成形加热时间:杯子定形差。夹钳不能影响更高硬度的塑料。
d.发泡后脱气135小时,经过30秒热成形加热时间:杯子定形非常差。夹钳不能影响更高硬度的塑料。
e.发泡后脱气135小时,40秒热成形加热时间:杯子泡沫壁通过产生蜘蛛网效应而熔融。无有用结果。
实施例2结论:
a.较长的脱气时间要求较高的用于使物体成形的温度。
b.在大于6.0-7.0%的气体浓度的情况下,注意到可成形性的显著增加,这允许更深的拉伸。
c.在约0.5wt%的气体浓度的情况下,赋予PET很小的延展性。
实施例3试验。许多试验是用0.889mm厚的在21℃下用5MPa的CO2饱和40小时的回收PET进行的。为了形成显著的表皮,对聚合物减压并使其脱附CO2大约390分钟。然后在红外加热器中在550℃下发泡10至30秒的各种时间并在其后立刻热成形。使用具有助压模塞的单面阴模,其具有1.97的面积拉伸比,11.11cm的高度,8.26cm的顶口,1.31的高宽比,5.72cm的底径,与垂直方向成7.0度的平均侧壁角。生成的泡沫体相对于未发泡聚合物的相对密度平均为20%。
实施例3结论:使用气体浸渍聚合物可实现从发泡到热成形的连续加工,生成相对密度低,具有陡壁和高宽比超过1∶1的物体。
将实施例1与实施例2和3比较,很明显,固态完整表皮增加了强度,从而允许更深的拉伸,并包含二次膨胀,从而甚至在较高的气体浓度下也能抑制气泡形成。完整表皮允许使用一边开口的模具,而不是现有技术泡沫热成形中一般使用的闭式模具。
尽管上述详细描述包含许多细节,但是这些细节不应解释为限制本发明的范围,而仅是提供本发明一些目前优选的实施方式的说明。在本发明的范围内可有各种其它实施方式和分支,其中有许多在上文中已做了一般讨论。
虽然用某种程度的特性对本发明进行了描述,但应理解的是,其元素可在不脱离本发明的精神和范围的情况下由本领域的技术人员改变。因此,本发明不打算被限制于本文所述的具体形式,相反,打算覆盖能够合理地包括在本发明范围内的可选方式、修改和等同物。本发明仅由所附的权利要求及其等同物限制。
Claims (20)
1.一种可逆地增强用于热成形的聚合材料的塑性的方法,其包括:
(a)用气体窜槽装置交错原料聚合材料的制品;
(b)在高压下将所述被交错的制品暴露于可溶于所述聚合物的增塑气体充分的时间以在聚合物内达到期望的气体浓度,从而形成至少部分气体-饱和并被增塑的暴露聚合物制品;和
(c)减压所述的暴露聚合物制品并将该制品与所述气体窜槽装置分离。
2.一种高精度地热成形聚合物体的方法,其包括:
(a)用气体窜槽装置交错原料聚合物材料的制品;
(b)在高压下将所述被交错的制品暴露于可溶于所述聚合物的增塑气体充分的时间以在聚合物内达到期望的气体浓度,从而形成至少部分气体-饱和的暴露聚合物制品;
(c)减压所述的暴露聚合物制品并将该制品与所述气体窜槽装置分离;和
(d)从所述至少部分气体-饱和的聚合物制品热成形物体。
3.根据权利要求2所述的方法,其进一步包括在热成形之前使所述制品发泡。
4.根据权利要求3所述的方法,其中通过在暴露所述制品时在聚合物内达到适合的气体浓度和通过在将其减压后将所述制品加热到等于或高于所述暴露制品的玻璃化转变温度,而使所述制品发泡。
5.根据权利要求4所述的方法,其中所述制品在减压后将其加热到的温度低于未暴露的聚合物的玻璃化转变温度。
6.根据权利要求4所述的方法,其中所述制品被加热到的温度等于或高于所述玻璃化转变温度并低于所述暴露制品的熔融温度。
7.根据权利要求1或2所述的方法,其中所述材料或物体包括先前发泡过的聚合物。
8.根据权利要求2所述的方法,其中热成形包括将所述制品加热到其玻璃化转变温度和其熔融温度之间的温度。
9.根据权利要求8所述的方法,其中所述热成形温度相比对所述原料聚合材料的熔融温度更接近于所述的玻璃化转变温度。
10.根据权利要求2所述的方法,其中当使所述制品热成形时,使所述制品发泡。
11.根据权利要求2所述的方法,其中所述制品通过不加热成形所述制品而热成形。
12.一种能高精度和深度拉伸成形未发泡聚合物体的方法,其包括:
(a)用气体窜槽装置交错原料聚合材料的制品;
(b)在高压下将所述被交错的制品暴露于可溶于所述聚合物的增塑气体充分的时间以在聚合物内达到期望的气体浓度,从而形成至少部分气体-饱和的暴露聚合物制品;
(c)将所述制品与所述气体窜槽装置分离;
(d)在压力下从所述至少部分气体-饱和的聚合物制品热成形物体;和
(e)减压形成的物体并让其脱附增塑气体。
13.根据权利要求12所述的方法,其中不向所述气体-饱和的聚合物制品施加另外的热而进行所述成形物体的步骤。
14.根据权利要求13所述的方法,其中所述物体具有两边并且所述物体通过使用所述制品两边之间的压力差而成形。
15.根据权利要求13所述的方法,其中所述物体通过使用机械装置成形。
16.根据权利要求13所述的方法,其中所述物体通过使用压力而成形。
17.根据权利要求13所述的方法,其中所述物体通过使用机械装置将所述制品推进物体的期望形状而成形。
18.根据权利要求12所述的方法,其中所述制品包括先前发泡过的聚合物。
19.一种制造具有与垂直方向成小于35度的侧壁角的热成形泡沫体的方法。
20.一种制造深宽比超过1∶1的热成形泡沫体的方法。
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CA2526214A1 (en) | 2004-12-02 |
EA200501797A1 (ru) | 2006-12-29 |
CN1822940A (zh) | 2006-08-23 |
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WO2004103675A1 (en) | 2004-12-02 |
BRPI0411154A (pt) | 2006-07-11 |
WO2004104072A3 (en) | 2005-02-24 |
MXPA05012436A (es) | 2006-05-25 |
AU2004241252A1 (en) | 2004-12-02 |
EP1636008A2 (en) | 2006-03-22 |
CA2526295A1 (en) | 2004-12-02 |
JP2011126278A (ja) | 2011-06-30 |
WO2004104072A2 (en) | 2004-12-02 |
WO2004103828A8 (en) | 2005-04-28 |
JP2007516108A (ja) | 2007-06-21 |
WO2004103828A3 (en) | 2005-03-10 |
EP1636008A4 (en) | 2010-12-29 |
EP1644249A2 (en) | 2006-04-12 |
US7501175B2 (en) | 2009-03-10 |
EP2730386A2 (en) | 2014-05-14 |
EP1636009A1 (en) | 2006-03-22 |
US20060257606A1 (en) | 2006-11-16 |
ZA200510141B (en) | 2008-05-28 |
KR20060090163A (ko) | 2006-08-10 |
EA200501796A1 (ru) | 2006-12-29 |
KR20060081655A (ko) | 2006-07-13 |
JP2007516107A (ja) | 2007-06-21 |
AU2004241444B2 (en) | 2010-05-27 |
WO2004103828A2 (en) | 2004-12-02 |
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