CN1788043B - 具有提高的再热特性的聚丙烯的模制 - Google Patents

具有提高的再热特性的聚丙烯的模制 Download PDF

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CN1788043B
CN1788043B CN2004800130118A CN200480013011A CN1788043B CN 1788043 B CN1788043 B CN 1788043B CN 2004800130118 A CN2004800130118 A CN 2004800130118A CN 200480013011 A CN200480013011 A CN 200480013011A CN 1788043 B CN1788043 B CN 1788043B
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polypropylene
thermit powder
polypropene composition
antimony
acid
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CN1788043A (zh
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M·A·尼尔
D·A·哈里森
S·D·詹金斯
J·P·达维斯
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Invista Technologies SARL USA
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Invista Technologies SARL USA
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    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

瓶、容器和其它制品，通过聚丙烯组合物形成，该聚丙烯组合物包含再热剂，比如锑，碳黑，石墨，钛，铜，锰，铁，钨，石墨，红外吸收染料或其它红外吸收材料。由于注拉吹成型或热成型缩短了聚丙烯组合物的再热时间，以及具有再热剂的聚丙烯颗粒组合物所具有的L＊值为不添加再热剂的聚丙烯颗粒对照物的L＊值的至少80％，该L＊值通过加德纳颜色试验来测定。该再热剂可以通过金属化合物比如三乙醇酸锑用还原剂比如次磷酸的就地化学还原来引入到聚丙烯组合物中.另外，具有再热剂的聚丙烯组合物可以由具有高浓度的再热剂的聚丙烯母料获得。

Description

具有提高的再热特性的聚丙烯的模制
技术领域
本发明涉及由聚丙烯聚合物组合物制造瓶、容器和其它制品的方法，尤其是采用注拉吹模塑和热成型技术。
背景技术
聚酯组合物，比如聚对苯二甲酸乙二醇酯或其共聚物(下文统称为“PET”)是众所周知的包装材料。例如，在US专利4,340,721中，使用PET组合物通过各种模塑方法来制造饮料瓶和其它容器(下文称之为“瓶”)。
在现行方法中，用于大多数饮料应用的尺寸和形状的PET瓶通常通过注拉吹模塑技术来制备。注拉吹模塑法具有两个主要步骤。第一，颗粒形状的PET在注塑机内熔融，熔体注入到冷却的模具内，形成最终瓶的前体，称为“预成型体”。通常，该预成型体具有螺纹颈与长度大约8-20cm的缩短瓶体形状和3-6mm的材料厚度。第二，将该预成型体转移到其外表面通过红外(IR)灯再热的拉吹成型机中。一旦预成型体达到了所需温度，它被拉吹成型为最终瓶。
再热预成型体所花的时间是整个工艺的速率限制因素。该预成型体在环境温度下起始，不得不被加热到聚酯的玻璃转化温度以上(通常达到约110℃)，使得该预成型体具有充分的柔性，从而使拉吹步骤可有效进行。一般，聚酯聚合物具有低劣的吸收IR辐射的能力。因此，除了延长了总的生产时间以外，预成型体再热步骤还需要大量的能量。为了解决该问题，某些在先专利教导了将黑色材料和/或金属颗粒加入到PET组合物中能够减少再热所需的时间和能量。因此，在先专利教导了添加碳黑(US专利4,476,272)，氧化铁(US专利4,250,078)以及锑和其它金属颗粒(US专利5,419,936和5,529,744)来减少PET预成型体再热时间。锑金属颗粒作为优选材料被指出，因为此类颗粒优先吸收由在大多数拉吹成型机中的IR灯所发出的红外波长处或附近的辐射，例如500nm-2000nm。此外，如在US专利5,419,936和5,529,744中所述，锑化合物通常存在于聚酯组合物本身中(作为熔体聚合的催化剂)，并且可以通过在熔体聚合生产阶段添加还原剂而转化为具有所需IR吸收特性的锑金属颗粒。
虽然PET已经广泛应用于饮料瓶，但生产PET的原料的成本要比某些非PET聚合物高得多。因此，工业上继续寻求由PET向低成本替代物转变。在寻求这些替代物的同时，容器制造商不希望在新资本设备上投资大量资源来加工新型聚合物材料，而是首选使它们的现有PET注吹成型设备适用于该新型材料。
用于饮料瓶的注拉吹成型的PET的一种可行替代物是聚丙烯。US专利6,258,313教导，如果预成型体从外部和从内部同时被加热，那么聚丙烯预成型体的注拉吹成型是可能的。虽然如此，到目前为止，通过该方法由聚丙烯更难以制造令人满意的饮料瓶。首先，聚丙烯具有比PET更低的密度和比热，因此显示了明显更窄的加工范围。第二，聚丙烯就其低劣的吸收IR辐射的能力而言遭受了与PET相同的限制。此外，聚丙烯一般比PET具有更高的不透明度，这减损了它的样式美观。工业上因此继续寻求改进聚丙烯的IR吸收性能的方法，使得它能够用于在与PET相同的注拉吹成型设备上制造饮料瓶和/或用来制造其它热成型制品。
本发明的概述
在第一个方面，本发明是由包括含有再热剂的聚丙烯组合物的预成型体注拉吹成型聚丙烯瓶的方法。该再热剂可以是锑、钛、铜、锰、铁和钨的一种或多种金属颗粒，其中锑是最优选的。该再热剂还可以是碳黑、石墨、红外吸收染料或其它红外吸收材料的颗粒。
该预成型体通常通过用一个或多个加热灯加热来再热到所需再热温度。再热该预成型体的时间短于再热由没有再热剂的聚丙烯组合物形成的相等尺寸的对照预成型体的时间。用来制备该预成型体的聚合物颗粒具有的L＊值为用于制备对照预成型体的聚合物颗粒的L＊值的至少大约80％。L＊值通过加德纳颜色试验来测定。例如，如果对照聚丙烯组合物颗粒具有大约75的L＊值，那么用于制造根据本发明的预成型体的颗粒具有约60或以上的L＊值。该L＊值与对照物的L＊值越接近，最终的瓶就越类似于由对照聚丙烯制备的瓶的颜色/美观。
优选地，该再热剂以具有大约10纳米(nm)到大约100微米，更优选10nm到10微米的粒度的颗粒的形式引入到聚丙烯中。优选，该再热剂颗粒以大约2ppm到1000ppm，更优选2ppm到350ppm，最优选2ppm到50ppm的量引入到聚丙烯中。该再热剂颗粒还可以以具有10hm到100微米的粒度的颗粒的形式以50ppm到25,000ppm的量引入到聚丙烯组合物中，形成聚丙烯母料。该母料然后可以与其它聚丙烯组合物(可能不含再热剂或含有不同再热剂或不同比例的相同再热剂)共混，形成具有所需比例的再热剂的聚丙烯组合物。
另外，该再热剂可以通过金属化合物与还原剂的就地化学还原而在聚丙烯组合物内产生。
因此，该金属化合物可以含有锑、钛、铜、锰、铁和钨中的一种或多种，以及该还原剂可以是一种或多种有机含磷酸(phosphorousacid)或无机含磷酸(phosphorous acid)，或者鞣酸，没食子酸，焦性没食子酸，或肼，或亚硫酸盐，或锡II盐，氢氧化镍或具有足以将金属化合物还原为金属态的电化学电位的任何有机或无机化合物。优选地，该金属化合物是三乙醇酸锑，该还原剂是次磷酸。
由该聚丙烯组合物与再热剂制备的预成型体、聚丙烯瓶以及其它聚丙烯制品也被要求保护。其它聚丙烯制品的实例包括三维制品，比如杯子或招待托盘或食品容器，以及二维制品，比如片材。取决于所需最终制品的美观，用于形成这些其它聚丙烯制品的具有再热剂的聚丙烯颗粒的L＊值可以是在用于形成注拉吹成型为瓶的瓶预成型体的组合物的L＊的优选范围之外。
附图简述
在以下详细说明中参考附图描述了本发明：
图1A-1D是在用于制造瓶的注拉吹成型方法中的典型步骤的示意图；
图2是显示了具有单一IR灯的用于加热聚合物板的装置的示意图，该装置可以用来测定聚合物的穿透加热时间；
图3是用不同聚丙烯组合物形成的板进行的板表面再热实验的再热时间-板温度数据的图；
图4是数据图，它显示了相对于在形成板的聚丙烯组合物中的再热剂的量，将聚丙烯板穿透加热到目标温度(即80℃)所需的时间的变化；
图5是比较再热时间(到80℃的秒数)与加入到形成板的聚丙烯组合物中的再热剂的量的数据图；和
图6是比较L＊(色度)与加入到形成板的聚丙烯组合物中的再热剂的量的数据图。
优选实施方案的详细说明
本发明涉及可用于制造具有良好颜色质量和透明性的拉吹成型容器，尤其瓶的聚丙烯组合物。此类组合物还可以用来采用其它两步技术比如热成型法制造其它聚丙烯容器和聚丙烯制品。该聚丙烯组合物含有作为再热剂的某些金属颗粒，这些金属颗粒固有地吸收500-2000nm波长范围内的辐射，所述波长是在PET注拉吹成型中在IR加热中使用的红外灯的辐射的典型波长。在注拉吹成型或热成型过程中，这些金属颗粒足量存在以减少再热时间，否则需要再热时间以使聚丙烯组合物的预成型体再热到期望温度。具有再热剂的此类聚丙烯组合物仍然具有对于期望终端用途应用而言的可接受的颜色和透明度。
首先参考图1A-1D，已知的注拉吹成型方法包括某些步骤。首先，如图1A所示的注塑预成型体10具有螺纹颈部分12和瓶体部分14。该预成型体10由含有再热剂的聚丙烯组合物注塑而成，或者由与没有再热剂的聚合物颗粒混合的再热剂浓缩物母料颗粒注塑而成。最通常，各聚丙烯颗粒长2.5-4.0mm和直径2.0-3.0mm。该聚丙烯组合物或聚丙烯颗粒的混合物被加热到熔融该组合物/颗粒，从而形成可流动的聚合物熔体，其通过注射引入到模具内。该注塑模具具有模腔和配合模塞，用于将该预成型体成型为期望的外形。从模具内取出预成型体10，冷却和储存，直到准备将它形成瓶。
如图1B所示，然后将该预成型体10安装在固定装置18上，并保持在再热或预热腔20内。加热灯22可以是一个灯或系列的灯，发出红外辐射，加热预成型体10的外表面，同时预成型体10在固定装置18上旋转。再热可以如图1B所示从预成型体的外部进行，从预成型体的内部进行，或者从预成型体的外部和内部进行，不过当成型PET瓶时，从外部加热是最常见的技术。
当预成型体10达到所需温度时，再热过的预成型体10然后准备进行拉吹成型。接下来参考图1C和1D，固定装置18与再热过的预成型体10保持在具有可将聚合物材料模塑为瓶的外形的模腔30内。通过固定装置18中的喷嘴将气体，比如空气或氮气注入到预成型体10的内体积中，同时推杆32推动聚合物材料向外膨胀，使之遵照模具的内部形状。一旦注拉吹成型完成，从模具中取出成品瓶(未示出)。在一个方面，本发明涉及采用工业上目前常用于PET的注拉吹成型的设备来注拉吹成型聚丙烯组合物。
根据本发明的、加入到聚丙烯组合物中以便减少再热时间的再热剂包括锑(Sb)，锰(Mn)，铁(Fe)，碳黑，石墨，红外染料，钛(Ti)，钨(W)和铜(Cu)。锑和碳黑是优选的再热剂，以及锑是特别优选的。这些再热剂优选以大约2ppm到大约1000ppm，更优选大约2ppm到350ppm，最优选大约2到50ppm的量加入到聚丙烯组合物中，并且粒度为大约10nm到大约100微米，最优选10nm到10微米。
再热剂可以以许多方式引入到聚丙烯组合物中。作为一个选择的方案，再热剂可以直接与聚丙烯颗粒混合，之后才将该混合物引入到注塑模具内，用于形成预成型体。作为另一个更优选的选择方案，再热剂可以直接与聚丙烯颗粒混合，通过双螺杆配混挤出机或类似设备中，形成充分分散和分布的聚丙烯配混料，之后引入到注塑机内。作为替代的更优选的选择方案，可以通过金属化合物用还原剂的就地化学还原在聚丙烯组合物内产生再热剂。作为第四个并且还更优选的选择方案，再热剂能够通过以上选择方案之一引入到聚丙烯组合物中，但以高浓度形成母料颗粒。然后，这种母料颗粒可以与具有不同浓度的再热剂或无再热剂或一定浓度的不同再热剂的聚丙烯颗粒共混，形成含有所需浓度的一种或多种再热剂的期望聚丙烯组合物。例如，聚丙烯母料可以引入50-25,000ppm，优选小于1250ppm的量的具有10nm到100微米，优选小于10微米的粒度的颗粒形式的再热剂。
在聚丙烯组合物中的再热剂分布和分散度影响了再热效力。也就是说，再热剂在聚合物中分布越均匀和分散更广泛，再热效力就越好。同样，再热剂在聚合物中的更佳分布和分散改进了聚合物的美观。
在一种更优选的实施方案中，通过金属化合物用还原剂的就地化学还原来形成再热剂。该金属化合物优选含有锑、钛、铜、锰、铁和钨中的一种或多种，以及该还原剂优先选自有机含磷酸，无机含磷酸，鞣酸，没食子酸，焦性没食子酸，肼，亚硫酸盐，锡II盐和氢氧化镍中的一种或多种，或具有足以将金属化合物还原为金属态的电化学电位的任何有机或无机化合物。
作为再热剂的锑优选通过锑化合物用还原剂比如次磷酸或其它有机含磷酸或无机含磷酸的就地化学还原来形成。优选的锑化合物包括三乙醇酸锑(ATG)，三醋酸锑(ATA)或三氧化二锑(ATO)。次磷酸将锑化合物还原为锑，其分散于聚丙烯组合物中。当以这种方式引入到聚丙烯组合物中时，锑颗粒似乎更均匀地分散。尤其，我们发现，通过ATA、ATO或ATG与次磷酸和/或含磷酸的反应所沉积的锑颗粒具有特别有利的粒度，并且尤其充分地分散于聚丙烯中。
本发明提供了制备具有接近没有再热剂的聚丙烯组合物的美学特性的聚丙烯容器(比如瓶)和其它聚丙烯制品的方法。同时，与没有再热剂的聚丙烯组合物相比，该方法还减少了用于再热的能量需求。一个直接的优点是由于周期时间减少所带来的成本节约或能量节约。本发明的另一个优点是在后续加工比如巴氏消毒或清洗中聚丙烯能够在比PET更高的温度下使用。另外，聚丙烯可以与PET相同的程度再循环。
以下实施例进一步举例说明本发明。所有份和百分率按重量表示，除非另有规定。
实施例
采用测量再热温度的两种方法来评定含有不同再热剂的聚丙烯组合物的再热时间。首先，由聚丙烯组合物形成注塑板，再根据下述工序来测定这种板的穿透加热时间。其次，由聚丙烯组合物模塑板，根据下述工序测量这种板的表面再热时间。
制备聚丙烯母料组合物
按照以下步骤，将具有长度大约2.5-4.0mm和直径2.0-3.0mm的大小的聚丙烯聚合物颗粒与再热剂混合。首先，在塑料袋中，将大约5-7kg聚丙烯聚合物与液体石蜡(大约20ml)混合。将袋内的聚合物翻滚，以便用油的薄膜涂布聚合物颗粒。接下来，将再热剂加入到袋内，再次翻滚该混合物。然后，该涂布的聚丙烯聚合物颗粒用APV MP2030双螺杆挤出机配混，随后用配备了4段空腔转移混合机的BostonMathews单螺杆挤出机配混。然后将所得配混料注塑形成为板，以便进一步测试。
测量板的穿透加热温度的工序
聚丙烯板穿透加热温度测量如下进行：
使用直径100毫米(100mm)和断面厚度4毫米(4mm)的聚丙烯板来评价各种聚丙烯组合物的再热时间。使用购自Negri Bossi ofMilan Italy的NB 90 Negri Bossi 90te注塑设备，通过标准注塑方法来制备含有再热剂的聚合物组合物的各聚丙烯板和相应对照组合物的各板。所有样品和对照板被制备成刚好相同的尺寸-直径100mm和横断面厚度4mm。板是清洁的，无表面污染物，并且具有平整的上下表面。
如图2所示，定位单个IR辐射灯22a，它是由Phillips制造的300瓦灯泡，用于加热板26的一个面。系列平坦的热电偶定位在板26的对侧，用于测定辐射和传导温度。温度测量设备是出自The MillHouse，Cambridge Street，St.Neots，PE 19 1QB的Pico TechnologyLimited的TC-08 8槽形热电偶数据记录器，以及温度测量软件是为该TC-08装置提供的Pico Technology Limited专利程序。板是在红外灯底部以下165mm。该试验方法反映了从加热侧通过板传递的热量。温度以对来自各试验样品和标准对照板的五件不同板的五个测量值的平均值来记录。我们认为由该板穿透加热方法获得的数据更实际地代表了在通过典型注拉吹成型方法加工的制品比如预成型体中或者通过再热方法随后物理成型，比如热成型来加工的制品中的热传递和分布。
该测量装置通过使用具有规定组成的对照板来校准。这些对照板反复测试，显示了一致的再热测量结果。然后，为了对比而测试的板的再热时间参考对照物来表示。使用两种测量：(1)将板加热到80℃所用的时间(秒)；和(2)在300秒的加热时间之后的板的温度。我们已经发现，为了正确的对比，在本方法中采用的板应该具有相同的起始环境温度。在试验之前，新板应该被冷却到室温并保持足够的时间。在我们的试验中，在进行再热试验之前，将新板冷却到室温并保持至少30分钟。
参考图4、5和6，评价由聚丙烯对照物和含有不同量的锑或碳黑的聚丙烯组合物形成的板的再热分布情况。
对于在图4中的再热试验，所测试的组合物是：Sb1：25ppm通过相等重量份的三乙醇酸锑和次磷酸的还原反应所形成的锑；Sb2：25ppm粒度范围600nm-2微米的锑金属(研磨)；CB1：25ppm的40nm碳黑；和CB2：25ppm的较大粒度6-30微米碳黑。再热剂全部以相同的量25ppm使用，按聚丙烯的重量计。如图4所示，引入了再热剂的聚丙烯板全部比没有再热剂的对照聚丙烯更快地再热。引入了再热剂的板全部在300-360秒内达到所需80℃再热温度，而对照物要花480秒以上才达到该再热温度，这代表再热时间减少了30-35％或更多。
图5和6比较了对照物和含有不同量的锑或碳黑的聚丙烯达到80℃所需的再热时间。在图5和6中，再热剂是：Sb1：10ppm使用相等重量份的三乙醇酸锑和次磷酸形成的Sb；Sb2：25ppm锑金属(研磨)；CB1：40nm碳黑；和CB2：较大粒度600nm-2微米碳黑。虽然锑和碳黑均能有效地减少再热时间(图5)，但低水平的碳黑可以导致显著更深的着色(L＊明显低于60，而对照物L＊是75)(图6)，这能够在美学上减损其作为聚丙烯组合物的再热剂的应用。在聚丙烯中提供2-350ppm，最优选10-30ppm的锑含量的三乙醇酸锑和次磷酸的结合是特别有效的。
在聚丙烯组合物中引入再热剂能够导致最终容器、制品或瓶产品的不希望有的着色。由再热剂诱发的着色度根据所使用的再热剂的类型和量而改变。对于既定再热剂，使用再热剂越少，最终产品的着色就越小。如果再热剂的用量低得足以使不希望有的着色最小化至可接受水平，对于减少再热时间来说该量可能不是充分的。因此，挑战是寻找能够有效减少再热时间，还产生了具有最小着色的最终容器、制品或瓶的再热剂。
我们使用得自加德纳色度计的颜色测量值(L＊)来评价由不同再热剂引起的聚丙烯组合物的着色。该颜色测量值(L＊)反映了光被测试材料的吸收和散射。Gardner BYK Color-View分光光度计No.9000型可从BYK Gardner Inc.，Columbia，Maryland USA购得。测定由含有不同量的不同再热剂的聚丙烯组合物制备的聚丙烯板的L＊值。
图6所示的L＊测量说明了在聚丙烯板的着色和在制备板的聚丙烯组合物中的再热剂的量之间的相互关系。对照板是没有添加再热剂的聚丙烯。对照板具有大约75的L＊值。聚丙烯组合物的着色越浅，它的L＊值就越接近对照物的L＊值。如图6所示，具有10ppm锑的聚丙烯组合物(组合物Sb1)具有最接近没有任何再热剂的聚丙烯的(对照物)的美学特性。在这些实施例中，与聚丙烯对照物的大约75的L＊比较，具有约60及以上的L＊值的样品具有为对照物的L＊值的至少80％的颜色美感性。
以下表1总结了由于再热时间减少获得的能量节约和这些测试聚丙烯组合物的相对颜色美观性。
表1、在吹塑试验中的能量节约和再热剂美观性
吹塑试验1
 再热剂水平(ppm)   能量节约(％)  美观性(L<sup>＊</sup>)(颗粒)
  对照物   0   0   75.71
  Sb1   10   10   68.31
  CB1   10   20   51.58
Sb1：锑(如上所述)；CB1：40nm碳黑(如上所述)。
吹塑试验2
 再热剂水平(ppm)   周期时间节约(％)  美观性(L<sup>＊</sup>)(颗粒)
  对照物   0   0   73.94
  Sb1   10   24   65.26
  Sb2   10   24   63.79
  CB1   5   24   59.96
  CB1   10   31   47.74
Sb1：锑(如上所述)；Sb2：锑(如上所述)；CB1：40nm碳黑(如上所述)。
吹塑试验细节
用实验室规模的联合注塑和吹塑机制备用于吹塑试验的预成型体。该预成型体用典型的聚丙烯加工条件注塑——熔体温度是220℃，模具温度是15℃，以及周期时间是27秒。我们然后使用已经特地为聚丙烯设计的独立实验室吹塑机。该吹塑机有两个加热炉，各自具有10,000瓦加热能力和各自配备了强制通风设备。使用几个旋转预成型体固定器来将预成型体在由气隙分隔的两个炉内转位(index)。各预成型体在大约60-80秒内转位通过第一个炉。然后该预成型体转位到气隙中，以便使加热的预成型体平衡大约60-80秒。接下来，该预成型体转位到第二个炉达大约60-80秒，然后，在空气中进一步10秒钟的转位之后，它被输送到吹塑台。
对于能量节约实验，机器转位速度设定在恒定的750个瓶/小时的产量，以及对于各样品调节(减小)烘箱参数，以提供最佳的注塑瓶。然后基于再热由含有再热剂的聚丙烯组合物形成的瓶所需的更少加热能量与再热对照瓶所需的加热能量，计算能量节约。在表1中，能量节约按百分率来表示。
对于周期时间节约实验，两个炉设定于恒定的8900瓦输出(17,800瓦总输出)。然后增加周期时间，直到预成型体被充分加热，以便最佳地吹塑瓶。计算相对于对照周期时间的各样品的增加周期时间，并按百分率表示。
表1中的结果指示，使用由三乙醇酸锑与次磷酸形成的10ppm Sb将预成型体再热能量和周期时间减低到与5ppm碳黑相同的水平，但含有锑的聚丙烯颗粒的颜色和视觉美感性比含有碳黑的颗粒要好得多。因此，由具有锑的聚丙烯组合物形成的所得瓶比由含有5ppm或10ppm碳黑的聚丙烯组合物形成的瓶具有更好的颜色和视觉美感性。
与对照预成型体相比，具有再热剂的预成型体获得了大约10-30％，优选15-20％的能量节约，以及大约25到35％的周期时间节约(参见表1)。因此，具有再热剂的聚丙烯组合物缩短了再热时间和仍然生产出了具有可接受的颜色和视觉美感性的瓶。
我们进一步探索了不同类型的锑试剂的再热和美学特性。更具体地说，我们测试了不同浓度的三乙醇酸锑，三氧化二锑和三乙酸锑。我们另外探索了其它再热剂的再热和美学特性。我们还测试了用于混合再热剂与聚丙烯的不同方法，即，通过直接施加于聚丙烯颗粒，和通过混合聚丙烯颗粒与含有高浓度的再热剂的母料颗粒。对于还原剂，还测试了不同剂量的不同含磷酸。对于这些结果的总结，参见以下表2和3。
我们发现，鉴于美感性，添加锑作为再热剂比碳黑优选。我们进一步发现，添加锑化合物与磷酸，优选次磷酸，更彻底地将金属颗粒分散在聚丙烯组合物中。最后，致使在聚丙烯组合物中形成2-350ppm锑金属颗粒的三乙醇酸锑、三氧化二锑或三乙酸锑与次磷酸结合物获得了就再热性能和颜色美感性而言的最佳结果。
测量板表面再热温度的工序
旋转由如在表1、2和3中规定的聚丙烯组合物注塑的板，同时通过由IR加热灯发出的辐射来加热(175瓦灯，IR-175C-PAR型，出自Phillips，2400°K)(参见例如图2A)。将红外高温计(型号Cyclops300AF，出自Minolta Land)(图2未示出)定位在相对于IR灯的板的对侧。监控板的表面温度，并在再热过程中记录。
所测试的板含有各种量的各种再热剂，比如锑(Sb)，锰(Mn)，铁(Fe)，钛(Ti)，钨(W)，铜(Cu)，石墨，红外染料和碳黑。在以下表2和3中报告了结果。对于在表2和3中所述的组合物，对照物是由不含再热添加剂的聚丙烯制备的板。与对照聚丙烯相比，测试的所有再热剂改进了板表面再热时间。然而，当引入到聚丙烯颗粒(和板)中时，某些再热剂具有比目标L＊(对照物的80％)低得多的L＊值，因此可能不适合用于瓶的注拉吹成型。当用热成型技术制备其它聚丙烯制品时，仍然可以应用这些组合物。
在图3中示出了与对照物C1相比的包含再热剂的某些聚丙烯组合物的表面再热时间的数据。
表2、L＊和再热特性的比较
  样品No.   目标配制料   对照聚合物   颗粒L<sup>＊</sup>   板L<sup>＊</sup>   穿透加热到80℃(秒)   300秒穿透加热(℃)
  C1   Eltex PPC KV 276对照物A   73.99   75.17   500   69.2
  C2   Eltex PPC KV 276对照物A   70.25   75.11   458   69.2
  C3   Eltex PPC KV 276对照物A   71.24   75.71   419   70.4
  C4   Boreslis PP RE420M0对照物B   70.96   78.84   466   67.3
  C5   Borealis PP RE420M0对照物B   68.73   79.4   401   72.1
  1   5ppm Cu   A   66.11   75.28   439   67
  2   50ppm Cu   A   53.90   61.18   386   72
  3   5ppm粗粒碳黑   A   56.73   75.85   366   74.3
  4   10ppm粗粒碳黑   A   48.5   72.64   334   76.7
  5   20ppm粗粒碳黑   A   37.83   37.30   331   76.7
  6   10ppm Elftex 254 CB   B   46.85   53.73   325   77.2
  样品No.   目标配制料   对照聚合物   颗粒L<sup>＊</sup>   板L<sup>＊</sup>   穿透加热到80℃(秒)   300秒穿透加热(℃)
  7   2ppm 20nm细粒CB N   B   61.51   73.11   443   69.1
  8   5ppm 20nm细粒CB N   B   53.96   61.32   442   69.2
  9   10ppm细粒碳黑   B   45.82   53.93   336   76.4
  10   25ppm细粒碳黑   B   39.10   31.95   336   76.7
  11   50ppm细粒碳黑   B   26.32   15.53   292   80.4
  12   红外染料-10ppmAvecia pro-jet 830 NP   B   63.54   75.07   407   71.6
  13   10ppm Fe   A   64.80   72.88   412   71
  14   100ppm 100nm Fe N   A   47.48   49.49   341   75.4
  15   200ppm M Fe N   A   70.21   78.94   498   66.9
  16   10ppm氧化铁(III)   B   58.36   71.54   413   71.6
  17   10ppm石墨EP 1020   B   64.15   72.16   389   72.9
  18   10ppm1-2微米石墨   B   63.89   72.94   366   73.8
  19   200ppm M Mn N   A   62.44   71.00   417   70.6
  20   2.5ppm Sb，经由ATG/H<sub>3</sub>PO<sub>2</sub>   A   67.22   76.15   436   70
  21   5ppm Sb，经由ATG/H<sub>3</sub>PO<sub>2</sub>+10ppm Ti   A   59.84   67.64   418   70.4
  22   5ppm细粒Sb   B   68.00   75.65   405   71.6
  23   10ppm Sb，经由ATG/H<sub>3</sub>PO<sub>2</sub>   A   59.91   69.20   388   72.7
  24   10ppm细粒Sb   B   63.37   72.32   380   73.6
  样品No.   目标配制料   对照聚合物   颗粒L<sup>＊</sup>   板L<sup>＊</sup>   穿透加热到80℃(秒)   300秒穿透加热(℃)
  25   20ppm Sb，经由ATG/H<sub>3</sub>PO<sub>2</sub>   B   57.74   69.44   349   75
  26   30ppm Sb，经由ATG/H<sub>3</sub>PO<sub>4</sub>   B   54.27   65.01   337   76.2
  27   50ppm Sb，经由ATG/H<sub>3</sub>PO<sub>3</sub>N   A   64.48   71.17   327   77.3
  28   50ppm Sb，经由ATG/TNPP低N   A   73.62   78.27   457   68.8
  29   50ppm Sb，经由ATG/TNPP/H<sub>3</sub>PO<sub>2</sub>   A   70.19   77.89   457   68.8
  30   50ppm细粒Sb   B   46.58   51.69   315   78.8
  31   100ppm Sb/P   A   58.39   68.8   390   72.2
  32   50ppm Sb，经由ATA/H<sub>3</sub>PO<sub>2</sub>N   A   56.30   65.67   394   72.2
  33   50ppm Sb，经由H<sub>3</sub>PO<sub>3</sub>N   A   58.86   69.92   415   70.6
  34   5ppm粗粒Sb   A   66.39   75.85   391   72.7
  35   10ppm粗粒Sb   A   64.3   72.64   365   74.4
  36   25ppm粗粒Sb   A   57.31   64.25   329   77.2
  37   100ppm粗粒Sb   A   42.19   39.68   287   81.8
  38   200ppm M Sb N   A   40.43   39.29   301   79.6
  39   10ppm Sb，经由Sb<sub>2</sub>O<sub>3</sub>/H<sub>3</sub>PO<sub>2</sub>   B   66.3   76.81   417   71
  40   200ppm TiN   A   29.35   20.87   352   74.5
  41   100ppm 100nm WN   A   58.98   68.73   415   70.8
M/b：母料。N：成核.M：研磨.ATG：三乙醇酸锑.
ATA：三乙酸锑。TNPP：亚磷酸三壬基苯基酯。H3PO3＝亚磷酸，
H2PO3＝次磷酸
表3、母料组合物的L＊和再热特性的比较
  样品No.   M/b目标配制料   对照聚合物  M/b颗粒L<sup>＊</sup>   M/b减低比  最终颗粒L<sup>＊</sup>   穿透加热到80℃(秒)  300秒穿透加热(℃)
  42   250ppm细粒20nm CB   B   17.57   12.5∶1   47.74   -   -
  43   250ppm氧化亚铜(I)   B   61.21   -   61.21   412   71.1
  44   250ppm氧化铜(II)   B   60.32   -   60.32   427   70.6
  45   125ppm Avecia projet 803NP(染料)   B   39.7   12.5∶1   63.54   -   -
  46   1000ppm Fe   A   23.09   -   23.09   301   79.8
  47   250ppm草酸亚铁(II)+H<sub>3</sub>PO<sub>2</sub>   B   62.67   -   62.67   398   71.9
  48   250ppm草酸铁(III)+H<sub>3</sub>PO<sub>2</sub>   B   66.5   -   66.5   415   70.5
  49   250ppm氧化铁(II+III)   B   52.15   -   52.15   327   77.7
  50   250ppm Aldrich 1-2微米石墨   B   30.87   25.0∶1   63.89   -   -
  51   1000ppm M Mn   A   47.47   -   47.47   -   -
  52   250ppm ATG+H<sub>3</sub>PO<sub>2</sub>   B   28.83   25.0∶1   63.37   -   -
  53   250ppm Aldrich细粒Sb<sub>2</sub>O<sub>3</sub>   B   65.92   -   65.92   374   73.5
  54   250ppm Aldrich细粒Sb<sub>2</sub>O<sub>3</sub>+H<sub>3</sub>PO<sub>2</sub>   B   37.25   25.0∶1   66.3   -   -
  55   1000ppm Sb/P   A   32.97   -   32.97   421   70.4
  56   266ppm研磨Sb   B   34.19   25.0∶1   63.79   -   -
  57   1000ppm 100nm Ti   A   24.06   -   24.06   329   773
  58   1000ppm 100nm W   A   31.45   -   31.45   -   -
与对照组合物的再热时间相比，根据本发明的具有再热剂的聚丙烯组合物优选获得了至少10％再热时间减少，更优选至少25％再热时间减少，最优选至少35％再热时间减少。因此，从表2和3可以看出，具有达到80℃其再热时间为≤375秒和尤其≤300秒的再热剂的聚丙烯组合物是最有利的。
已经通过详细说明和优选实施方案的实施例举例说明了本发明。各种形式和细节的改变是在本领域技术人员的技能范围内。因此，本发明必须通过权利要求书而不是实施例或优选实施方案的说明来衡量。

Claims (27)

1.注拉成型聚丙烯瓶的方法，该方法包括：
(a)由含有再热剂的聚丙烯组合物形成预成型体；
(b)将该预成型体再热到所需温度，其中该预成型体达到所需温度的时间少于将由不含再热剂的聚丙烯组合物形成的同等尺寸的对照预成型体再热到所需温度所用的时间；和
(c)将该再热过的预成型体注拉吹成型为瓶；
其中当在形成预成型体之前以颗粒形式存在时，含有再热剂的聚丙烯组合物所具有的L＊值为不存在再热剂的颗粒形式的聚丙烯组合物的L＊值的至少80％，该L＊值通过加德纳颜色试验来测定，
其中再热剂包括一种或多种金属颗粒，和其中所述金属颗粒选自锑、钛、铜、锰、铁和钨的一种或多种；或者
其中再热剂包括碳黑、石墨或红外染料。
2.权利要求1的方法，其中再热剂以具有10nm到100微米的粒度的颗粒的形式以2-1000ppm的量引入到聚丙烯组合物中。
3.权利要求1的方法，其中该再热剂以具有10nm到10微米的粒度的颗粒的形式以2-50ppm的量引入到聚丙烯组合物中。
4.权利要求1的方法，其中该再热剂通过金属化合物用还原剂的就地化学还原而在聚丙烯组合物内产生。
5.权利要求4的方法，其中该金属化合物含有锑、钛、铜、锰、铁和钨的一种或多种，以及该还原剂选自有机含磷酸、无机含磷酸、鞣酸、没食子酸和焦性没食子酸、肼、亚硫酸盐、锡II盐和氢氧化镍的一种或多种。
6.权利要求4的方法，其中该金属化合物是三乙醇酸锑和还原剂是次磷酸。
7.权利要求1的方法，其中该再热剂以具有10nm到100微米的粒度的颗粒的形式以50ppm到25,000ppm的量引入到聚丙烯组合物中，形成聚丙烯母料。
8.根据权利要求1的方法制备的聚丙烯瓶。
9.制备含有再热剂的聚丙烯组合物的方法，包括：
将再热剂反应性挤出配混到聚丙烯中，形成聚丙烯组合物，其中该再热剂通过金属化合物用还原剂就地化学还原为金属态而在这种反应性挤出配混过程中产生，其中这样产生的再热剂为具有10nm到100微米的粒度的颗粒，并且这些颗粒均匀分布在整个聚丙烯中，
其中该再热剂包括一种或多种金属颗粒，和其中所述金属颗粒选自锑、钛、铜、锰、铁和钨的一种或多种。
10.权利要求9的方法，其中该再热剂以2-1000ppm的量引入到聚丙烯中。
11.权利要求9的方法，其中再热剂以具有10nm到10微米的粒度的颗粒的形式和以2-350ppm的量引入到聚丙烯中。
12.权利要求9的方法，其中该再热剂以具有10nm到100微米的粒度的颗粒的形式和以50-25,000ppm的量引入到聚丙烯中，用于形成聚丙烯母料。
13.权利要求9的方法，其中该金属化合物含有锑、钛、铜、锰、铁和钨的一种或多种，以及该还原剂选自有机含磷酸、无机含磷酸、鞣酸、没食子酸和焦性没食子酸、肼、亚硫酸盐、锡II盐和氢氧化镍的一种或多种。
14.权利要求9的方法，其中该金属化合物是三乙醇酸锑和还原剂是次磷酸。
15.根据权利要求9的方法制备的聚丙烯组合物。
16.由根据权利要求9的方法制备的聚丙烯组合物形成的聚丙烯瓶。
17.根据权利要求12的方法制备的聚丙烯母料。
18.形成聚丙烯制品的方法，包括：
(a)由含有再热剂的聚丙烯组合物形成片材；
(b)将该片材再热到所需温度，其中该片材达到所需温度的时间少于将由不含再热剂的聚丙烯组合物形成的同等尺寸的对照片材再热到所需温度所用的时间；和
(c)将该再热片材成型为聚丙烯制品，
其中该再热剂包含一种或多种金属颗粒，和其中所述金属颗粒选自锑、钛、铜、锰、铁和钨的一种或多种；或者
其中该再热剂包括碳黑、石墨或红外染料。
19.权利要求18的方法，其中该再热剂以具有10nm到100微米的粒度的颗粒的形式以2-1000ppm的量引入到聚丙烯组合物中。
20.权利要求18的方法，其中该再热剂以具有10nm到10微米的粒度的颗粒的形式以2-50ppm的量引入到聚丙烯组合物中。
21.权利要求18的方法，其中该再热剂通过金属化合物用还原剂的就地化学还原而在聚丙烯组合物内产生。
22.权利要求21的方法，其中该金属化合物含有锑、钛、铜、锰、铁和钨的一种或多种，以及该还原剂选自有机含磷酸、无机含磷酸、鞣酸、没食子酸和焦性没食子酸、肼、亚硫酸盐、锡II盐和氢氧化镍的一种或多种。
23.权利要求21的方法，其中该金属化合物是三乙醇酸锑和还原剂是次磷酸。
24.权利要求18的方法，其中该再热剂以具有10nm到100微米的粒度的颗粒的形式以50ppm到25,000ppm的量引入到聚丙烯组合物中，从而形成聚丙烯母料。
25.根据权利要求18的方法制备的三维聚丙烯制品。
26.根据权利要求18的方法制备的二维聚丙烯制品。
27.权利要求9的方法，其中这种反应挤出配混在双螺杆配混挤出机内进行。
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