CN106633287A - 耐磨导热型辐照交联超高分子量聚乙烯的制备方法 - Google Patents

耐磨导热型辐照交联超高分子量聚乙烯的制备方法 Download PDF

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CN106633287A
CN106633287A CN201611071055.7A CN201611071055A CN106633287A CN 106633287 A CN106633287 A CN 106633287A CN 201611071055 A CN201611071055 A CN 201611071055A CN 106633287 A CN106633287 A CN 106633287A
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李建喜
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Zhongguang Nuclear High-tech Nuclear Material Technology (Suzhou) Co., Ltd.
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Abstract

本发明公开一种耐磨导热型辐照交联超高分子量聚乙烯的制备方法，包括以下步骤：将分子量为200万左右的超高分子量聚乙烯的粒料加入8wt%的导热填料、氮化硼、0.5wt%耐磨填料，碳纳米管、1wt%交联促进剂和0.lwt%的抗氧化剂形成混合物；将混合物充分混合后，送入挤出机，加热熔融后，由挤出机挤出，在加热过程中，对原料的温度、压力实行控制，挤出的材料厚度保持在1~10mm；将所得样品在空气中用钴源的γ射线辐照，辐照剂量为50‑180kGy，辐照样品放入真空条件的烘箱中。本发明在保证超了超高分子量聚乙烯材料的固有性能稳定的同时，进一步提高超高分子量聚乙烯材料的耐磨性能、导热性能、耐温性能和力学强度。

Description

耐磨导热型辐照交联超高分子量聚乙烯的制备方法
技术领域
本发明涉及工程塑料材料技术领域，尤其涉及一种耐磨导热型辐照交联超高分子量聚乙烯的制备方法。
背景技术
根据美国菲利普石油公司的划分方法，分子量在150万以上的聚乙烯称为"UHMWPE"即Ultra-high molecular weight PE ，中文称超高分子量聚乙烯。德国赫斯特（Hoechst）公司、美国赫尔克乐斯（Hercules）公司和日本三井石油化学公司是世界上生产UHMWPE的三大公司，中国主要生产厂家是北京助剂二厂、上海高桥石化公司化工厂，中国石化齐鲁石化分公司。
UHMWPE极高的分子量（HDPE的分子量通常只有2-30万）赋予其优异的使用性能，而且属于价格适中、性能优良的热塑性工程塑料，它几乎集中了各种塑料的优点，具有普通聚乙烯和其它工程塑料无可比拟的耐磨、耐冲击、自润滑、耐腐蚀、吸收冲击能、耐低温、卫生无毒、不易粘附、不易吸水、密度较小等综合性能。事实上，目前还没有一种单纯的高分子材料兼有如此众多的优异性能。
超高分子量聚乙烯（UHMWPE）作为工程塑料具有许多优异性能，在众多场合中得到广泛应用。如人工关节、高速铁路的桥梁支座、机车、航空航天等，都是基于其良好的耐磨性、尺寸稳定性以及良好的耐候性能而制备的。但由于其超长的线性分子结构，使得其耐热性能、硬度以及抗磨粒磨损和抗疲劳磨损性能与其它工程塑料相比尚有一定差距，尤其是在注塑过程中，UHMWPE由于导热性太差导致其脱模后形状发生变化，严重影响了产品的质量和生产的效率。基于UHMWPE的难加工性、较差的表面硬度、耐热性、抗磨粒磨损和高温下的塑性形变UHMWPE的改性主要分为三部分：一是改善UHMWPE加工流动性能；二是改善UHMWPE的摩擦磨损性能；三是改善UHMWPE的高温塑性形变。显然UHMWPE加工流动性能可能通过提高加工温度来改善，而UHMWPE自身的化学或辐照交联以及与填料配合交联可以适度地改善表面硬度、耐热性、抗磨粒磨损和高温下的塑性形变这些性能。
发明内容
本发明的目的是提供一种耐磨导热型辐照交联超高分子量聚乙烯的制备方法，该制备方法获得的辐照交联超高分子量聚乙烯不仅保证了超高分子量聚乙烯充分交联，而且克服了高辐射剂量对UHMWPE造成的降解、破坏材料表面的缺点，得到高凝胶含量、高力学强度和耐磨导热型辐照交联超高分子量聚乙烯材料。
为达到上述发明目的，本发明采用的技术方案是：一种耐磨导热型辐照交联超高分子量聚乙烯的制备方法，其特征在于：包括以下步骤：
步骤一、将分子量为200万左右的超高分子量聚乙烯的粒料加入8wt%的导热填料、氮化硼、0.5wt%耐磨填料，碳纳米管（CNT）、1wt%交联促进剂和0.lwt%的抗氧化剂形成混合物；
步骤二、将步骤一的混合物充分混合后，送入挤出机，加热熔融后，由挤出机挤出，在加热过程中，对原料的温度、压力实行控制，挤出的材料厚度保持在1~10mm；
步骤三、将所得样品在空气中用钴源的γ射线辐照，辐照剂量为50-180kGy，辐照样品放入真空条件的烘箱中，在65-120℃下退火1~5小时。
上述技术方案进一步改进的技术方案如下：
1. 上述方案中，所述交联促进剂为三烯丙基异氰脲酸酯（TAIC）或者三烯丙基氰尿酸酯（TAC）。
2. 上述方案中，所述抗氧化剂为受阻酚、受阻胺、4，4′-硫代双（6-叔丁基-3-甲基苯酚）中的至少一种。
3. 上述方案中，所述导热剂为纳米级氧化铝、氧化镁、氧化锌、氮化铝、碳化硅中的至少一种。
4. 上述方案中，所述耐磨填料为微纳米碳酸钙晶须、微纳米四氧化三铁中至少一种。
由于上述技术方案的运用，本发明与现有技术相比具有下列优点：
本发明耐磨导热型辐照交联超高分子量聚乙烯的制备方法，其在导热剂和耐磨填料的共同作用下，超高分子量聚乙烯的导热和耐磨性能得到了提高；经过交联促进剂和抗氧化剂的共同作用，使熔融挤出UHMWPE材料能够在较低的剂量下辐照发生交联，降低了材料表面辐射降解的产生，实现了高效率的交联；而高温退火进一步保证了辐射交联材料的稳定性，保证了UHMWPE基本性能的同时，提高了其耐热性能和力学强度，通过上述技术控制，辐射交联UHMWPE的达到相同交联程度，所需辐射剂量明显降低。
具体实施方式
下面结合实施例对本发明作进一步描述：
实施例：一种耐磨导热型辐照交联超高分子量聚乙烯的制备方法，包括以下步骤：
步骤一、将分子量为200万左右的超高分子量聚乙烯的粒料加入8wt%的导热填料、氮化硼、0.5wt%耐磨填料，碳纳米管（CNT）、1wt%交联促进剂和0.lwt%的抗氧化剂形成混合物；
步骤二、将步骤一的混合物充分混合后，送入挤出机，加热熔融后，由挤出机挤出，在加热过程中，对原料的温度、压力实行控制，挤出的材料厚度保持在1~10mm；
步骤三、将所得样品在空气中用钴源的γ射线辐照，辐照剂量为50-180kGy，辐照样品放入真空条件的烘箱中，在65-120℃下退火1~5小时。
上述交联促进剂为三烯丙基异氰脲酸酯（TAIC）或者三烯丙基氰尿酸酯（TAC）。
上述抗氧化剂为受阻酚、受阻胺、4，4′-硫代双（6-叔丁基-3-甲基苯酚）中的至少一种。
上述导热剂为纳米级氧化铝、氧化镁、氧化锌、氮化铝、碳化硅中的至少一种。
上述耐磨填料为微纳米碳酸钙晶须、微纳米四氧化三铁中至少一种。
实施例1：
本发明所述的耐磨导热型辐照交联超高分子量聚乙烯材料，其制备步骤为：将分子量为200万左右的超高分子量聚乙烯的粒料作为原料，加入8wt%的导热填料、氮化硼（BN）、0.5wt%耐磨填料，碳纳米管（CNT）、1wt%多官能团交联促进剂三烯丙基异氰脲酸酯(TAIC)、和0.lwt%的抗氧化剂4，4′-硫代双（6-叔丁基-3-甲基苯酚），充分混合后，送入挤出机，加热熔融后，由挤出机挤出。在加热过程中，对原料的温度、压力实行控制，挤出的材料厚度保持在1-10mm。将所得样品在空气中用钴源的γ射线辐照，辐照剂量为100kGy，剂量率为5kGy/h。辐照样品放入烘箱中80℃退火2小时；上述耐磨填料为微纳米碳酸钙晶须。
根据ASTM标准，测定辐照后样条的物理性能，其结果见表1。
表1辐照改性前后UHMWPE物理性能对比：
实施例2：
本发明所述的耐磨导热型辐照交联超高分子量聚乙烯材料，其制备步骤为：将分子量为300万左右的超高分子量聚乙烯的粒料作为原料，加入6wt%的导热填料、氮化硼（BN）、1wt%耐磨填料，碳纳米管（CNT）、1.5wt%多官能团交联促进剂三烯丙基氰尿酸酯(TAC)、和0.3wt%的抗氧化剂4，4′-硫代双（6-叔丁基-3-甲基苯酚），充分混合后，送入挤出机，加热熔融后，由挤出机挤出。在加热过程中，对原料的温度、压力实行控制，挤出的材料厚度保持在1-10mm。将所得样品在空气中用高能电子束射线辐照，辐照剂量为100kGy，剂量率为440000kGy/h。辐照样品放入恒温热水中80℃退火4小时。上述耐磨填料微纳米四氧化三铁。
根据ASTM标准，测定辐照后样条的物理性能，其结果列于表2。
表2辐照改性前后UHMWPE物理性能对比：
从对比数据看出，本发明耐磨导热型辐照交联超高分子量聚乙烯材料，在相对较低剂量的高能射线（电子束或钴源）辐照后，其蠕变性能、力学强度、耐温性能、耐磨性能和导热性能均有所提升。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (5)

1.一种耐磨导热型辐照交联超高分子量聚乙烯的制备方法，其特征在于：包括以下步骤：
步骤一、将分子量为200万左右的超高分子量聚乙烯的粒料加入8wt%的导热填料、氮化硼、0.5wt%耐磨填料，碳纳米管（CNT）、1wt%交联促进剂和0.lwt%的抗氧化剂形成混合物；
步骤二、将步骤一的混合物充分混合后，送入挤出机，加热熔融后，由挤出机挤出，在加热过程中，对原料的温度、压力实行控制，挤出的材料厚度保持在1~10mm；
步骤三、将所得样品在空气中用钴源的γ射线辐照，辐照剂量为50-180kGy，辐照样品放入真空条件的烘箱中，在65-120℃下退火1~5小时。
2.根据权利要求1所述的耐磨导热型辐照交联超高分子量聚乙烯的制备方法，其特征在于：所述交联促进剂为三烯丙基异氰脲酸酯（TAIC）或者三烯丙基氰尿酸酯（TAC）。
3.根据权利要求1所述的耐磨导热型辐照交联超高分子量聚乙烯的制备方法，其特征在于：所述抗氧化剂为受阻酚、受阻胺、4，4′-硫代双（6-叔丁基-3-甲基苯酚）中的至少一种。
4.根据权利要求1所述的耐磨导热型辐照交联超高分子量聚乙烯的制备方法，其特征在于：所述导热剂为纳米级氧化铝、氧化镁、氧化锌、氮化铝、碳化硅中的至少一种。
5.根据权利要求1所述的耐磨导热型辐照交联超高分子量聚乙烯的制备方法，其特征在于：所述耐磨填料为微纳米碳酸钙晶须、微纳米四氧化三铁中至少一种。
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