CN1303327A - 阴离子聚合弹性聚合物的造粒方法 - Google Patents

阴离子聚合弹性聚合物的造粒方法 Download PDF

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CN1303327A
CN1303327A CN99806683A CN99806683A CN1303327A CN 1303327 A CN1303327 A CN 1303327A CN 99806683 A CN99806683 A CN 99806683A CN 99806683 A CN99806683 A CN 99806683A CN 1303327 A CN1303327 A CN 1303327A
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CN1191922C (zh
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E·M·德格鲁特
D·R·斯图尔特
杨斌
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Shell Internationale Research Maatschappij BV
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Abstract

阴离子聚合弹性聚合物的造粒方法,包括使聚合物在长径比为10∶1或更小的单螺杆挤出机中固态挤出,其中挤出机的机筒有纵向沟槽和横向延伸的销钉以增进混合,挤出机中的温度足以使聚合物聚结或塑化但低于聚合物的降解温度,挤出机螺杆的转速为30到100转/分。

Description

阴离子聚合弹性聚合物的造粒方法
发明领域
本发明涉及阴离子聚合弹性聚合物的造粒方法。
发明背景
在有机溶剂中通过阴离子聚合得到苯乙烯和丁二烯或异戊二烯的弹性聚合物。这种聚合物在有机溶剂中通常会氢化。这些聚合物的最终生产步骤需要从聚合物/溶剂混合物/浆液/悬浮液中除去溶剂，通常指的是聚合物胶结剂，以生产可以包装的干物料。这最终的加工步骤通常指的是“整理”聚合物。这些聚合物通常以碎屑形式生产出来，有时难以处理，而且常常具有不期望的粘性。这种粘物料的粘性引起的问题限制了它的可行或有利的生产。
即使实际可能生产这些产品，这些产品通常是以碎屑的形式包装在袋中出售的，产品的形状使最终使用者难以处理并将其用于需要的用途。碎屑的粒度通常很小，它易于在设备上结层，特别是粘性物料，产生脏东西和废料。一些产品在袋中结块，形成13.6-18.1千克(30到40磅)的聚合物“垫”。与其它成分混合前，袋装的聚合物必须用手开封，结块的物料必须加入机械研磨机中。
很多的聚合物，特别是热塑性非弹性的聚合物，很容易以粒状产品生产出来。这种形状易于处理，而且通过把聚合物与抗粘剂弄成粉末，很容易解决结块问题。这些商品热塑性聚合物的颗粒在熔融挤出机、通常是双螺杆挤出机中形成，挤出机使聚合物塑化并将其在模口挤出，在模口处将聚合物切成小颗粒。本发明的许多聚合物为高分子量的材料和高弹性的材料。在双螺杆熔融挤出机中加工这些聚合物时，聚合物会产生足够的剪切热，导致显著的降解。降解使聚合物的性能受损，是个很大的缺点。
因此，把本发明的粘性弹性聚合物整理为可以以粒状形式生产出来显然是非常有利的。在没有显著的聚合物降解下进行这种处理是最有利的。
发明总结
本发明解决上述问题。苯乙烯和丁二烯或异戊二烯的弹性阴离子聚合物、包括聚异戊二烯的星形聚合物在过去是通过阴离子聚合的。如果需要，这一过程还可包括氢化。聚合物以碎屑形式生产出来。
然后通过固态挤出，把干聚合物碎屑转化为颗粒。聚合物碎屑在单螺杆挤出机中挤出，该挤出机有带纵向沟槽的机筒，聚合物流动的横向上有延伸到机筒的销钉。挤出机的长径比(L/D)为10∶1或更小，优选地为8∶1或更小，在30到100转/分的转速下运转，优选地在40到60转/分的转速下运转。挤出机中聚合物的温度必须足够高，以使聚合物聚结或塑化，但温度不应超过聚合物的降解温度。优选地，固态挤出在200℃或更低的温度下进行，最优选地在160℃或更低的温度下进行。发明详述
在固态挤出过程中必需用单螺杆挤出机，以将聚合物的剪切减到最小。过度的剪切会导致聚合物温度不理想的升高，如上所述，这会导致显著的降解。双螺杆挤出机会增大聚合物的剪切，因而本发明中不使用双螺杆挤出机。
本方法中，在没有设备辅助加热或碎屑的预热下，聚合物挤出必需产生足够的机械热。必需产生足够的热以使聚合物充分聚结或塑化，这样可将聚合物挤出，随后切成颗粒。聚结的意思是，聚合物足够软足够粘，彼此粘在一起，但没有超过聚合物熔化的玻璃化转变温度。
已知这里所述类型的聚合物在300℃及更高的温度下会降解，因此单螺杆挤出机中的温度应低于这一温度是很重要的。但是，挤出机中可能会出现局部温度过高，因而挤出机中的温度为200℃或更低是极为优选的。最优选的温度为160℃或更低，以使在局部可导致聚合物降解的局部温峰减到最小。
必需用单螺杆(与双螺杆相对)挤出机，以在不太高的温度下使聚合物聚结，聚合物达到充分的混合也是很重要的。为确定聚合物达到充分混合，单螺杆挤出机的机筒有纵向的沟槽，聚合物流动的横向上有延伸到机筒的销钉。这些特点在不显著增大聚合物剪切下，增进了聚合物的混合。
聚合物在挤出机中加工的时间越长，聚合物发生降解的可能性就越大。因此，优选不用长挤出机。优选的长径比(L/D)为10∶1或更小，优选地为8∶1或更小，最优选地为4∶1或更小。
为达到充分的混合，长径比L/D为2∶1到10∶1的挤出机螺杆的转速应为30到100转/分。如果L/D更小，螺杆的转速可以低一些。目的也是为了在不把聚合物加热到其降解温度下，提供充分的混合。
适于通过本发明的方法整理的聚合物包括含有4到12个碳原子的二烯烃的氢化均聚物和共聚物，一种或多种共轭二烯和一种或多种含有8到16个碳原子的单烯基芳烃的氢化共聚物。基础聚合物可为星形或线形结构。氢化聚合物可为选择性氢化、完全氢化或部分氢化。共轭二烯的氢化聚合物及共轭二烯和单烯基芳烃的共聚物优选地为氢化的，以使大于90％的起始烯不饱和键通过氢化除去。优选地，氢化聚合物大体上没有烯不饱和键。
选择性氢化是指使大部分烯不饱和键氢化，而大部分起始芳烃不饱和键未氢化的过程。此处所用的大体上没有烯不饱和键的烃聚合物为平均每个聚合物链上含有低于10个碳-碳烯双键的烃聚合物。超过这一烯不饱和键量的聚合物，在一定条件下，在可提供高机械剪切的混合设备中进行的官能化反应中，会过度交联。
可用的烃聚合物包括在本体聚合、悬浮聚合、溶液聚合或乳液聚合中制备的聚合物。众所周知，可用自由基、阳离子和阴离子引发剂或聚合催化剂实现单体的聚合，产生烃聚合物。
大范围分子量的聚合物都可以如此处所述被加工。一般地，聚合物的分子量越大，在常规熔融加工中聚合物降解的可能性就越大。因而，本发明对于高分子量聚合物特别有利。一般地，重均分子量在100,000到1,200,000之间的聚合物都可以由本方法加工。
此处所用的重均分子量，对线形阴离子聚合物是指通过以聚苯乙烯为标准的凝胶渗透色谱法测定的重均分子量。对于星形聚合物，重均分子量通过光散射法测定。
实施例比较实施例1
为更好了解熔融挤出机的性能，进行了几项典型的实验室规模的流变试验。首先，尝试在270℃的温度下，测定聚合物A的熔体流动指数(MFI)，聚合物A为含有6％重量聚苯乙烯的氢化聚异戊二烯的星形聚合物。即使在这样的高温和高达9.9千克的重荷下，物料极难通过O.2毫米(0.008英寸的模口)的熔体流动模孔压出。在同样的高温下用毛细管流变仪所做的另外的试验得到了很差的结果。尝试用加热到200℃到220℃的19毫米(0.75英寸)的布拉本达单螺杆熔融挤出机挤出聚合物B，含有6％重量聚苯乙烯的另一种氢化聚异戊二烯星形聚合物，的确发生了一些降解反应。具有高剪切混合能力的双螺杆挤出机可能会产生更多的降解。实施例2
在57毫米(2.25英寸)、带有装有刀片的Bodine马达的单螺杆挤出机中，使不同等级的聚合物聚结并造粒。挤出机在机筒上有6条9.5毫米(3/8英寸)宽、1.6毫米(1/16英寸)深的纵向沟槽，流动的横向上有10个延伸的销钉。
挤出机设计的细节列于表1中。用这种挤出机来确定是否可能使不同弹性聚合物碎屑物料聚结。多少有些出人意外的是，这种挤出机很容易造出很多不同的这样的物料的颗粒。所有试验中，这种类型的挤出中没有发现聚合物的降解。
表1：单螺杆挤出机
 实施例   螺杆直径       螺距   压缩比  L/D 给料器     功率(千焦/秒)
   2    57毫米(2.25英寸)      42.9毫米(1.69英寸)   无压缩    6  单闸板填塞器      2.2
   3   102毫米(4英寸)    102-76.2毫米(4英寸到3英寸)  1.38∶1    4  双闸板填塞器     11.2
与典型的塑料挤出机(熔融)不同，不需要另外加热挤出机部件以达到聚结。与典型的熔融挤出机15-30的L/D比相比，这种挤出机的L/D比一般较低。另外，这些单螺杆挤出机在低转速下可提供高转矩，因此可把由剪切热引起的降解减到最小。高转矩的性能使这些挤出机可以很容易地加工这些高弹性的材料。经试验的挤出机有带沟槽的机筒和销钉。这两个特点确保物料可得到均匀的剪切并因此加热聚结。没有沟槽和销钉的挤出机所做的另外的试验并不如此成功。
在57毫米(2.25英寸)的挤出机上装变速刀具，以把挤出束切粒。在35转/分的转速下进行挤出。没有外部加热或冷却装置。聚合物由于摩擦生热而具有的温度为150℃。所有试验的物料都没有降解，成功地被挤出。更难以得到聚合物C的均匀的束，聚合物C为苯乙烯和异戊二烯的线形氢化嵌段共聚物。一些束在外边缘上有碎屑的“尘埃”，表明有可能沿机筒腔有滑移以及不充分的混合。挤出机温度升高后，这一现象消失了。
用57毫米(2.25英寸)的设备还挤出了几种KRATON材料(KRATON为商标)。研究用聚合物KRATON GRP-6919和GRP-6912以及商品材料SHELLVIS 50,90,260,300的试验进行得很好(SHELLVIS为商标)。商品聚合物KRATON G1651,G1650,G1652以及研究级GRP-6917经不同设计模口试验后，被成功地造粒。所有这些聚合物由壳牌化学公司生产，为苯乙烯和/或氢化异戊二烯和/或丁二烯的嵌段共聚物。实施例3
57毫米(2.25英寸)的挤出机试验成功后，用更大的102毫米(4英寸)的挤出机进行试验。该挤出机的设计细节见表1。这种挤出机机筒上也有销钉和沟槽。结果证明同样成功。成功地进行了大型造粒试验，造出了大约1361千克(3000磅)的聚合物A颗粒。典型的运转条件为35转/分、11.5安培，生产率为1.36千克/分(3磅/分)。在3.18毫米(1/8英寸)孔径、254孔的模口上装上两刃的造粒机，以在挤出时切削物料。然后把颗粒注入小型流化床冷却器中。冷却器中装有通风机，通风机以71米3/分(2500立方英尺/分)的速度送入室温下的空气。在大约机筒的中部装有温度探针。测得机筒温度为150℃时，过程达到稳态。这一温度是由物料的剪切热引起的。没有外部加热或冷却装置。离开冷却器的颗粒的温度大约为80℃。整个运行的取样中没有发现聚合物降解。
碎屑和从两个挤出机挤出的聚合物A和B的凝胶渗透色谱分析表明没有降解。对聚合物A和聚合物B作为马达油添加剂的给定应用，也进行了试验。使用了碎屑和颗粒形状的物料。含碎屑和颗粒的油浓缩物的流变测量比较表明，挤出聚合物的基本性质没有改变。

Claims (4)

1．阴离子聚合弹性聚合物的造粒方法，包括将聚合物在长径比为10∶1或更小的单螺杆挤出机中固态挤出，其中挤出机的机筒有纵向沟槽和横向延伸的销钉以增进混合，挤出机中的温度足以使聚合物聚结或塑化但低于聚合物的降解温度，挤出机螺杆的转速为30到100转/分。
2．权利要求1的方法，其中挤出机的温度为200℃或更低。
3．权利要求2的方法，其中挤出机的温度为160℃或更低。
4．权利要求1的方法，其中挤出机的长径比为8∶1或更小，挤出机螺杆的转速为40到60转/分。
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