CN101171294B - 由包含聚乙烯的共混物制备的单层旋转模塑制品 - Google Patents

由包含聚乙烯的共混物制备的单层旋转模塑制品 Download PDF

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CN101171294B
CN101171294B CN2006800159399A CN200680015939A CN101171294B CN 101171294 B CN101171294 B CN 101171294B CN 2006800159399 A CN2006800159399 A CN 2006800159399A CN 200680015939 A CN200680015939 A CN 200680015939A CN 101171294 B CN101171294 B CN 101171294B
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埃里克·梅齐尔斯
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Total Petrochemicals Research Feluy SA
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Abstract

本发明公开了一种由聚乙烯、官能化聚烯烃和一种或多种选自聚醚酯或饱和聚酯或聚碳酸酯或聚酰胺的树脂的共混物制备的单层旋转模塑制品。

Description

由包含聚乙烯的共混物制备的单层旋转模塑制品
本发明涉及由包含混合有一种或多种其它组分的聚乙烯的共混物制备的单层旋转模塑制品领域，所述其它组分选自聚醚酯、饱和聚酯、聚碳酸酯或聚酰胺。 
聚乙烯代表了超过80％的用于旋转模塑领域的聚合物。这是由于聚乙烯在加工期间具有出色的耐热降解性、易于研磨、良好的流动性和低温冲击性。 
旋转模塑法用于简单及复杂的中空塑料产品的制造。其可用于模塑各种材料如聚乙烯、聚丙烯、聚碳酸酯、聚酰胺或聚氯乙烯(PVC)。根据例如由D.Annechini，E.Takacs和J.Vlachopoulos在ANTEC 2001年第一卷中的“Somenew results on rotational moulding of metallocene polyethylenes”中记载的，优选使用线性低密度聚乙烯。 
通常将使用Ziegler-Natta催化剂制备的聚乙烯用于旋转模塑，但由茂金属制备的聚乙烯是期望的，因为其窄分子量分布使得能够拥有更好的冲击性质和更短的加工循环时间。 
现有技术(见ANTEC 2001年第一卷)中的由茂金属制备的聚乙烯存在高收缩和翘曲的问题，以及在某些应用中存在其自然状态下的白度问题。 
例如记载于US-5,457,159中的塑弹性体(plastoelastomeric)组合物也可用于旋转模塑，但其需要复杂的混合及硫化加工步骤。 
US-6,124,400公开了包含半结晶聚烯烃链区(sequence)的聚合物合金的旋转模塑的应用，所述半结晶聚烯烃链区具有由一种单体在一步(one-pot)聚合法中制备的不同受控微结构的链。这些聚合物合金的聚合需要包括有机金属催化剂前体、阳离子形成助催化剂和桥接试剂(cross-over agent)的复杂催化剂体系。 
因而期望生产采用包含聚乙烯与一种或多种相似或不同材料的其它树脂的共混物制备的单层旋转模塑制品，以改进最终产品的最终性质。例如，可以期望将聚醚酯的良好振动吸收性及冲击性质与聚乙烯的可接受的食品接触性和质量进行组合，如低成本和良好的低温冲击性。 
本发明的一个目的在于制备具有良好耐阻隔性的旋转模塑制品。 
本发明的进一步目的在于制备具有良好振动吸收性的旋转模塑制品。 
本发明的另一个目的在于制备易于在其上粘合其它部件的旋转模塑制品。 
本发明的再一个目的在于制备具有柔软触感的旋转模塑制品。 
本发明的更进一步目的在于制备具有良好亲水性或疏水性的制品。 
因此，本发明公开了一种通过由包含以下物质的共混物进行旋转模塑制备的单层制品： 
a.10-99.9wt％，优选50-99.9wt％的聚乙烯(PE)； 
b.0.1-90wt％，优选0.1-50wt％的一种或多种选自聚醚酯、饱和聚酯、聚碳酸酯、聚酰胺或乙烯醋酸乙烯酯(EVA)的树脂；和 
c.0-20wt％的官能化聚烯烃。 
在本发明的更优选实施方式中，所述共混物包含至少75wt％的由茂金属制备的聚乙烯。 
优选地，所述官能化聚烯烃为官能化聚乙烯，其选自接枝聚乙烯或离聚物或其组合，并以0.5-20wt％的量存在。 
所述共混物作为通过共挤出聚乙烯树脂、一种或多种选自聚醚酯、饱和聚酯、聚碳酸酯、聚酰胺的树脂和官能化聚烯烃而制备的标准颗粒来提供。可将该标准颗粒进一步研磨成粉末或微球。 
所述制品可包含任意数量的其它常规层。 
优选地，聚乙烯(PE)采用Ziegler-Natta或茂金属基催化剂体系制备，或者聚乙烯为由Ziegler-Natta制备的聚乙烯和由茂金属基催化剂体系制备的聚乙烯的组合。 
用于本发明的聚醚酯、饱和聚酯、聚碳酸酯或聚酰胺可包括选自聚醚嵌段共聚酰胺、热塑性聚氨酯和含氟聚合物的较少组分(minor component)。 
所述较少组分是指占不足50重量％的组分。 
聚醚酯是具有聚酯嵌段和聚醚嵌段的共聚物。其典型地由软聚醚嵌段和硬链段(segment)(聚酯嵌段)组成，其中所述软聚醚嵌段为聚醚二醇的残基，和所述硬链段通常由至少一种二羧酸与至少一种扩链(chain-extending)短二醇单元反应形成。聚酯嵌段和聚醚嵌段通常通过由酸的酸官能团与聚醚二醇的OH官能团反应形成的酯键连接。所述短扩链二醇可选自新戊二醇、环己二甲醇和式HO(CH2)nOH的脂肪族二醇，所述式HO(CH2)nOH中n为在2-10 之间变化的整数。有利地，所述二酸为具有8-14个碳原子的芳香族二羧酸。高达50mol％的二羧基芳香酸可使用至少一种其它具有8-14个碳原子的二羧基芳香酸代替，和/或高达20mol％的可使用具有2-12个碳原子的二羧基脂肪酸代替。 
作为二羧基芳香酸的例子，可以提及对苯二甲酸、间苯二甲酸、二苯甲酸、萘二羧酸、4，4’-二亚苯基二羧酸、双(对羧基苯基)甲酸、亚乙基双(对苯甲酸)、1，4-四亚甲基双(对氧化苯甲酸)、亚乙基双(对氧化苯甲酸)和1，3-三亚甲基双(对氧化苯甲酸)。作为二醇的例子，可以提及乙二醇、1，3-三亚甲基二醇、1，4-四亚甲基二醇、1，6-六亚甲基二醇、1，3-丙二醇、1，8-八亚甲基二醇、1，10-十亚甲基二醇和1，4-亚环己基二甲醇。具有聚酯嵌段和聚醚嵌段的共聚物为例如具有衍生自聚醚二醇(如聚乙二醇(PEG)、聚丙二醇(PPG)或聚四亚甲基二醇(PTMG))的聚醚嵌段、二羧酸单元(如对苯二甲酸)、和二醇(乙二醇)或1，4-丁二醇单元的共聚物。所述聚醚与二酸的链连接形成软链段，而乙二醇或丁二醇与二酸的链连接形成共聚醚酯的硬链段。这类共聚醚酯公开于例如EP402883和EP405227中。这些聚醚酯为热塑性弹性体。其可包含增塑剂。 
聚醚酯可通过例如DuPont公司在Hytrel
Figure 2006800159399_0
商标下得到。 
饱和聚酯树脂为二羧酸与二羟基醇的缩聚产物。其是一种特殊的醇酸树脂，通常不使用脂肪酸或干性油改性，当被催化时，其具有在室温中于较低或没有压力下固化或硬化的能力。优选的饱和聚酯为聚对苯二甲酸亚烷基酯，更优选聚对苯二甲酸乙二醇酯(PET)和聚对苯二甲酸丁二醇酯(PBT)。 
饱和聚酯可通过例如Cyclics在Cyclics CBT
Figure 2006800159399_1
商标下得到。 
聚碳酸酯(PC)为一种由二羟基化合物与羧酸衍生物或碳酸二酯得到的热塑性树脂。优选的聚碳酸酯为双酚A和碳酰氯的缩合产物。 
聚酰胺为以下物质的缩聚产物： 
-一种或多种内酰胺(如己内酰胺、庚内酰胺和十二烷基内酰胺)的一种或多种氨基酸(例如氨基己酸、7-氨基庚酸、11-氨基十一酸和12-氨基十二酸)；和 
-二胺与二酸的一种或多种盐或其混合物，所述二胺例如为六亚甲基二胺、十二亚甲基二胺、间亚二甲苯基二胺、双(对氨基环己基)甲烷和三甲基六亚甲基二胺，所述二酸例如为间苯二甲酸、对苯二甲酸、己二酸、壬二酸、 辛二酸、癸二酸和十四烷双酸。 
作为聚酰胺的例子，可以提及PA6和PA6-6。 
还可有利地使用共聚酰胺。可提及由至少两种α，ω-氨基羧酸或两种内酰胺或一种内酰胺与一种α，ω-氨基羧酸缩合形成的共聚酰胺。还可提及由至少一种α，ω-氨基羧酸(或内酰胺)、至少一种二胺与至少一种二羧酸缩合形成的共聚酰胺。 
有利地，所述共聚酰胺选自PA6/12和PA6/6-6。 
更通常地，在本发明的共混物中还可使用胺终止材料，其优选选自聚酰胺二胺(PAdiNH2)。根据其制造方法和/或使用的链抑制剂(limiter)，聚酰胺可具有过量的酸或胺端基，或甚至具有一定比例的烷基或衍生自选用的抑制剂结构的其它端基，例如芳基或任何其它官能团。过量的酸端基衍生自二酸链抑制剂。过量的胺端基衍生自二胺链抑制剂。伯胺链抑制剂导致具有烷端基和胺端基的聚酰胺链。 
可在本发明共混物中使用的聚酰胺还可以是冲击改性聚酰胺。柔性改性剂可由例如官能化聚烯烃、接枝脂肪族聚酯、任选地含聚醚嵌段和聚酰胺嵌段的接枝共聚物、和乙烯与(甲基)丙烯酸烷基酯和/或饱和乙烯基羧酸酯的共聚物制备。所述改性剂还可以是具有聚酰胺接枝或聚酰胺低聚物的聚烯烃链，从而与聚酰胺和聚烯烃具有亲合力。该柔性改性剂还可以是嵌段共聚物。 
还可使用发泡聚酰胺。 
所述聚酰胺共混物可进一步有利地包括聚氨酯或包含聚酰胺和乙烯/乙烯醇共聚物(EVOH)的组合物，和更通常地，任何包含聚酰胺和阻挡层的组合物。 
聚醚嵌段共聚酰胺由以下通式表示 
HO-[C(O)-PA-C(O)-O-PEth-O]n-H  (I) 
其中PA表示聚酰胺链段，和PEth表示聚醚链段。例如聚酰胺链段可以是PA6、PA66、PA11或PA12。聚醚链段可以例如是聚乙二醇(PEG)或聚丙二醇(PPG)或聚四亚甲基二醇(PTMG)。聚酰胺链区的分子量Mn通常为300-15,000。聚醚链区的分子量Mn通常为100-6000。这类材料可例如通过Arkema在Pebax
Figure 2006800159399_2
商标下商购获得。 
具有聚酰胺嵌段和聚醚嵌段的共聚物通常可由具有活性端基的聚酰胺嵌段与具有活性端基的聚醚嵌段缩聚得到，例如其中： 
1)具有二胺链端的聚酰胺嵌段与具有二羧基链端的聚氧化亚烷基嵌段； 
2)具有二羧基链端的聚酰胺嵌段与具有二胺链端的聚氧化亚烷基嵌段，通过称作聚醚二醇的脂肪族二羟基化的α，ω-聚氧化亚烷基嵌段的氰乙基化和氢化得到；和 
3)具有二羧基链端的聚酰胺嵌段与聚醚二醇，该得到的产物在该特定情况下为聚醚酯酰胺。 
具有二羧基链端的聚酰胺嵌段例如来自于在链终止羧基二酸(carboxylicdiacid)存在下的聚酰胺前体的缩合。 
具有二胺链端的聚酰胺嵌段例如来自于在链终止二胺存在下的聚酰胺前体的缩合。 
具有聚酰胺嵌段和聚醚嵌段的聚合物还可包括无规分布的单元。这些聚合物可通过同时发生的聚醚反应和聚酰胺嵌段前体的反应制备。 
例如，可使聚醚二醇、聚酰胺前体和链终止二酸共同反应。得到了一种聚合物，其基本上具有非常可变长度的聚醚嵌段和聚酰胺嵌段，而且还另外具有已发生无规反应的各种反应物，其以无规方式沿聚合物链分布。 
还可使聚醚二胺、聚酰胺前体和链终止二酸共同反应。得到一种聚合物，其基本上具有非常可变长度的聚醚嵌段和聚酰胺嵌段，而且还具有已发生无规反应的各种反应物，其以无规方式沿聚合物链分布。 
在这些具有聚酰胺嵌段和聚醚嵌段的共聚物中，聚醚嵌段的量有利地为共聚物重量的10-70％，优选为35-60％。 
聚醚二醇嵌段可同样使用，并与具有羧基端基的聚酰胺嵌段共缩聚，或可将其胺化以转化为聚醚二胺，并与具有羧基端基的聚酰胺嵌段缩合。其还可与聚酰胺前体和二酸链终止剂共混，以制备具有聚酰胺嵌段和具有无规分布单元的聚醚嵌段的聚合物。 
除在第二种类型聚酰胺嵌段的情况下以外，聚酰胺嵌段的数均摩尔质量Mn通常为300-15,000。聚醚嵌段的质量Mn通常为100-6000。 
如果存在，聚氨酯典型地由软聚醚嵌段和硬嵌段(聚氨酯)组成，其中软聚醚嵌段通常为聚醚二醇的残基，和硬嵌段可由至少一种二异氰酸酯与至少一种短二醇反应制备。所述短扩链二醇可选自在上述聚醚酯中提及的二醇。 聚氨酯嵌段和聚醚嵌段通过由异氰酸酯官能团与聚醚二醇中的OH官能团反应形成的键合而连接。 
热塑性聚氨酯可例如由Elastogran GmbH在Elastollan
Figure 2006800159399_3
商标下获得，或由Dow Chemical公司在Pellethane
Figure 2006800159399_4
商标下获得。 
在本发明中适于用作加工助剂的含氟聚合物为例如偏二氟乙烯(H2C＝CF2)聚合物和/或偏二氟乙烯与六氟丙烯(F2C＝CF-CF3)的共聚物。虽然偏二氟乙烯和六氟丙烯的共聚物不具有弹性，但其通常被称作“含氟弹性体”。在含氟弹性体中六氟丙烯共聚单体的含量通常在30重量％-40重量％范围内。在本发明中适于用作加工助剂的含氟聚合物为例如可由Dyneon、DuPont-Dow Elastomers或Arkema在Dynamar、Viton
Figure 2006800159399_6
和Kynar
Figure 2006800159399_7
商标下商购得到。 
采用Ziegler-Natta或茂金属催化剂或最近的过渡金属催化剂体系制备的聚乙烯典型地用于旋转模塑应用中。根据例如由D.Annechini，E.Takacs和J.Vlachopoulos在ANTEC 2001年第一卷中的“Some new results on rotationalmoulding of metallocene polyethylenes”中记载的，优选使用线性低密度聚乙烯。 
根据本发明优选的聚乙烯为使用包含在二氧化硅/铝氧烷载体上的茂金属的催化剂生产的乙烯均聚物或共聚物。更优选，所述茂金属组分为亚乙基-双-四氢茚基二氯化锆或双-(正丁基环戊二烯基)二氯化锆或二甲基亚甲硅基-双(2-甲基-4-苯基茚基)二氯化锆。最优选的茂金属组分为亚乙基-双-四氢茚基二氯化锆。 
在本说明书中，术语共聚物是指一种单体与一种或多种共聚单体的聚合产物。 
优选本发明中使用的聚乙烯树脂的熔融指数典型地落在0.1-25dg/min范围内，优选在0.2-15dg/min范围内，最优选在0.5-10dg/min范围内。所述熔体流动指数MI2根据ASTM D 1283标准测试方法在190℃、2.16kg负载下测量。 
可用于本发明的乙烯均聚物和共聚物优选具有在0.910-0.975g/ml范围内，更优选0.915-0.955g/ml范围内的密度。所述密度根据ASTM D 1505标准测试方法在23℃下测量。 
本发明的聚乙烯还可具有双峰或多峰分子量分布，即其可以是两种或多 种具有不同分子量分布的聚烯烃的共混物，该共混物既可以物理共混也可以化学共混，即在两个或多个反应器中连续制备。 
适用于本发明的聚乙烯的多分散性D在2-20范围内，优选2-8，更优选小于或等于5，和最优选小于或等于4，后一范围典型地与所述优选的由茂金属制备的聚乙烯树脂相关。该多分散指数D定义为重均分子量Mw与数均分子量Mn的比Mw/Mn。 
本发明的聚烯烃还可包含其它添加剂，例如抗氧剂、酸清除剂、抗静电添加剂、填料、滑爽添加剂或防粘添加剂。 
如果存在，官能化聚烯烃为接枝有提供极性和/或反应性的材料的聚烯烃，且因此其取决于邻近层的性质。在本发明中优选聚烯烃使用酸酐接枝，和优选聚烯烃为聚乙烯或聚丙烯，更优选为聚乙烯。可选地，所述官能化聚烯烃为离聚物。接枝聚乙烯提供优异的粘附性，而离聚物增强了机械性能。在本发明的更优选的实施方式中，所述官能化聚烯烃为离聚物与接枝聚乙烯的混合物。 
包含于共混物中的树脂的选择根据期望的最终性质决定，所述最终性质例如： 
-优异的振动吸收； 
-优异的冲击性质； 
-柔软触感； 
-与聚酰胺同样优良的阻隔性，但成本更低； 
-干燥时防滑和潮湿时易滑 
-宽范围的操作温度 
-优良的硬度 
-亲水或疏水性 
-耐刮擦性。 
最终制品的壁厚由最终产品的尺寸、期望的性质和成本决定，其可在1mm-数厘米间变化。 
旋转模塑制品的尺寸可在0.1L-70m3范围内变化。由于其优异的冲击和振动吸收性质，根据本发明制备的旋转模塑制品可以很大，例如鼓状物、缓冲器或大容器。 
本发明还公开了一种制备单层旋转模塑制品的方法。 
旋转模塑制品可通过在模塑周期中手动引入材料或使用落箱(drop-box)来制备。 
手动添加涉及由炉中移动模具，移开通风管或塞子，从而在该部分形成开口，并使用fennel或杆添加材料。对于每个额外的层必须重复该操作。 
落箱典型地包含单材料层，其是一种隔离的容器，该容器保持原料直至在该周期中适宜的时间被释放。该原料的释放信号通常由通过机器臂的空气管路以压力脉冲的形式传递。所述隔离必须保持冷却以避免箱中的原料熔融。 
附图说明
图1表示由77wt％聚乙烯、3wt％接枝聚乙烯和20wt％Pebax
Figure 2006800159399_8
3533的共混物制备的旋转模塑制品的显微结构。 
图2表示由仅使用与图1的共混物中使用的相同的聚乙烯制备的旋转模塑制品的显微结构。 
图3表示以牛顿表示的冲击强度对以ms表示的时间的函数，其中使用P表示峰值能量。制品的变形作为时间的函数同样在该图中表明。 
实施例 
如下制备了几种旋转模塑制品。 
不同共混物通过共挤出制备。 
其由以下物质组成： 
-77wt％的聚乙烯，其采用基于乙烯-双-四氢茚基二氯化锆的茂金属催化剂体系制备，具有4dg/min的熔体流动指数MI2和0.940g/cm3的密度。 
-3wt％的由以下结构式表征的接枝聚乙烯 
并具有25dg/min的熔体流动指数MI2和0.940g/cm3的密度；和 
-20wt％的具有疏水性的 
Figure DEST_PATH_G200680015939920080114D000011
3533，或具有亲水性的 
Figure DEST_PATH_G200680015939920080114D000012
MH1657。 
在另一个共混物中，使用下述离聚物代替所述3wt％的接枝聚乙烯 
Figure DEST_PATH_G200680015939920080114D000013
所述共混物作为通过研磨标准颗粒得到的微球或粉末制备。 
用于共混物的 
Figure DEST_PATH_G200680015939920080114D000014
为一种增塑剂，具有远低于聚乙烯的杨氏模量。 
所有试验模塑品在ROTOSPEED旋转模塑机中制备。其为具有偏移臂、具有523Kw/hr燃烧能力的LPG燃烧臂、冷却风扇和1.5m最大盘径的回转(carrousel)型机。 
使用铝盒模具生产所述试验模塑品。该模具以倾角安装以促进脱膜，和所述双层制品使用落箱(drop box)制备。该落箱中装有第一层需要的原料，然后将其连在所述模具的盖子上。落箱中的气锤使原料保持在原位，直至达到要求的温度，然后该锤被激发，所述原料落下(drop in)。对于每一层在下述条件下重复该操作。 
试验的模塑条件如下： 
·炉温：300℃ 
.峰值内部空气温度(PIAT)：200℃ 
·冷却介质：强迫通风 
·预热臂和模具 
·周期时间：20分钟 
·旋转模塑部件的壁厚：1.5mm。 
所述旋转模塑制品具有优异的均匀性，和如图1所示 
Figure DEST_PATH_G200680015939920080114D000015
完全分散在最终制品中：对于公知的难于分散的 
Figure DEST_PATH_G200680015939920080114D000016
该结果是非常出乎预料的。此外，同样如图1所示，其显微结构非常精细，远精细于图2中所示的典型聚 乙烯的显微结构。这赋予最终制品以优异的机械性能。 
所述旋转模塑制品的冲击性质使用ISO 6602-3标准试验在-40℃下，采用26.024kg落体以4.43m/s的落体速度和255J冲击能测量。所有试验均表现了图3所示的延展性。 

Claims (7)

1.一种由通过共挤出生产的共混物制备的单层旋转模塑制品，所述共混物包含下列组分：
a.10-99.9wt％的聚乙烯；
b.0.1-90wt％的一种或多种任选地混合有较少组分的选自聚醚酯、饱和聚酯、聚碳酸酯、聚酰胺或乙烯醋酸乙烯酯的树脂，其中，所述较少组分的量低于该组分b重量的50wt％且所述较少组分选自聚醚嵌段共聚酰胺、热塑性聚氨酯和含氟聚合物；和
c.0.5-20wt％的官能化聚烯烃，其中所述官能化聚烯烃为接枝的聚乙烯或离聚物或其混合物，
其中，所有组分的总和为100wt％。
2.权利要求1的单层旋转模塑制品，其中所述共混物包含下列组分：
a.50-99.9wt％的聚乙烯；
b.0.1-50wt％的选自聚醚酯、饱和聚酯、聚碳酸酯或聚酰胺的一种或多种树脂；和
c.0.5-20wt％的官能化聚烯烃，
其中，所有组分的总和为100wt％。
3.权利要求1的单层旋转模塑制品，其中所述聚乙烯采用Ziegler-Natta或茂金属基催化剂体系制备，或者所述聚乙烯为由Ziegler-Natta制备的聚乙烯和由茂金属基催化剂体系制备的聚乙烯的组合。
4.权利要求1的单层旋转模塑制品，其中所述共混物包含至少75wt％的由茂金属制备的聚乙烯。
5.权利要求3或4的单层旋转模塑制品，其中所述茂金属催化剂为亚乙基-双-四氢茚基二氯化锆、双-(正丁基环戊二烯基)二氯化锆、或二甲基亚甲硅基-双(2-甲基-4-苯基茚基)二氯化锆。
6.一种通过在模塑周期中手动引入原料或采用落箱来生产权利要求1的单层旋转模塑制品的方法。
7.由权利要求1的旋转模塑制品制备的鼓状物。
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US8715796B2 (en) 2014-05-06
EA200702183A1 (ru) 2008-04-28
JP5230408B2 (ja) 2013-07-10
EP1879960A1 (en) 2008-01-23
KR101288699B1 (ko) 2013-07-23
EP1721931A1 (en) 2006-11-15
ATE556116T1 (de) 2012-05-15
US20140170356A1 (en) 2014-06-19
JP2008540757A (ja) 2008-11-20
WO2006120191A1 (en) 2006-11-16
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US9987810B2 (en) 2018-06-05

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