CN106916358A - 一种高耐候高流动玻纤浸渍聚烯烃配方及其制备方法 - Google Patents
一种高耐候高流动玻纤浸渍聚烯烃配方及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种高耐候高流动玻纤浸渍聚烯烃配方及其制备方法。按质量份计，配方包括：1)聚烯烃100份；2)抗紫外老化助剂0.5‑2份；3）抗氧剂0.5‑2份；4）流动促进剂0.2‑2份；5）增韧剂2‑10份；6）相容剂1‑5份；将以上组份按照一定比例预混好后，通过双/单螺杆挤出机熔融混合挤到模头中进行分流及浸渍，制得高耐候高流动玻纤浸渍聚烯烃。本发明在于：超支化尾端活性官能团与玻纤结合，增强了聚烯烃树脂与玻纤之间的界面结合能力，提高了力学性能。
Description
技术领域
本发明涉及塑料制造技术领域，特别是涉及一种高耐候高流动玻纤浸渍聚烯烃配方及其制备方法。
背景技术
在通用塑料种类里，常规聚烯烃主要指聚乙烯和聚丙烯。聚乙烯（Polyethylene，简称PE）是由乙烯单体聚合而制得的一种热塑性树脂，工业上也包括乙烯与少量α-烯烃的共聚物。聚乙烯无臭，无毒，手感似蜡，具有优良的耐低温性能，化学稳定性好，能耐大多数酸碱的侵蚀，被广泛应用于薄膜、中空制品、电线电缆、管材等领域。聚丙烯（Polypropylene，简称PP）是由丙烯聚合而制得的一种热塑性树脂，也包括丙烯与少量乙烯的共聚物在内，通常为半透明无色固体，无臭无毒；由于结构规整而高度结晶化，故熔点可高达167℃。密度小，是最轻的通用塑料；对水特别稳定，在水中吸水率仅为0.01%左右；耐热、耐腐蚀，制品可用蒸汽消毒是其突出优点。其强度、刚度、硬度耐热性均优于低压聚乙烯，可在100℃左右使用。具有良好的介电性能和高频绝缘性且不受湿度影响。由于其以上优异的性能，广泛应用于包装、管材、服装、汽车、家用电器等领域。但其在-35℃低温时变脆，不耐磨、易老化。
随着生活水平的提高以及节能、减排、环保、可持续发展意识的增强，在汽车、家用电器等许多领域都提出了高性能化、轻量化的要求。例如虽然聚丙烯强度高于聚乙烯，拉伸强度可达30MPa以上，但仍然限制了其在高性能要求领域的应用。纵观聚合物增强塑料的发展，以芳纶纤维、碳纤维、玻璃纤维增强聚合物材料最为突出，性能可以钢材媲美甚至有过之而无不及，密度却远远低于钢材，而其中又以玻璃纤维高强、高模以及成本较低备受市场关注和欢迎。长玻纤增强聚丙烯(Long Glass Fiber Reinforced Polypropylene.简称LGFPP)是倍受人们关注的新品种之一。一般聚丙烯树脂拉伸强度在20-30MPa，弯曲强度在25-50MPa，弯曲模量在800-1500MPa之间，而LGFPP的拉伸强度提高到100-150MPa，是纯树脂的3-5倍，弯曲强度和模量也是原来的3-5倍左右，力学性能大大提高；当制成单向连续玻纤增强片材时，其拉伸强度高达700-1000MPa，复合成多层板材后拉伸强度也可高达300-400MPa。作为汽车模块载体材料，该材料不仅能有效地提高制品的刚性、抗冲击强度、抗蠕变性能和尺寸稳定性，而且可以做出复杂的汽车模块制品。
但是，一方面由于某些特定领域的应用，长期暴露在太阳光下，对抗紫外性能和热氧老化性能提出了更高的要求，比如140℃下1000h热氧老化后拉伸强度性能保留率需达到80%以上；另一方面，现有聚丙烯材料对玻纤浸渍效果较差，直接影响了制品的力学性能；有通过技术改进用过氧化物对聚丙烯进行降解处理来提高其流动性能，或者添加润滑或流动促进剂等小分子添加剂对PP、PE进行改性，虽然提高了聚烯烃的流动性能，改善了其与玻纤的浸渍效果，但同时损害了它们的力学性能。此外，由于聚烯烃材料粘度调控存在不足，使其应用于单向连续玻纤增强片材时，市场上聚丙烯片材厚度只能达到0.2-0.3mm，聚乙烯片材厚度主要在0.25-0.3mm，满足不了轻量化和高性能化发展需求。
发明内容
针对现有技术存在的不足，本发明的目的在于提供一种高耐候高流动玻纤浸渍聚烯烃及其制备方法。
本发明一方面提供一种高耐候高流动玻纤浸渍聚烯烃，其特征在于：按质量份计，配方包括：
1)聚烯烃100份；
2)抗紫外老化助剂0.5-2份；
3）抗氧剂0.5-2份；
4）流动促进剂0.2-2份；
5）增韧剂2-10份；
6）相容剂1-5份。
优选为，所述的聚烯烃选自聚乙烯、聚丙烯中的一种。
优选为，所述的抗紫外老化助剂选自聚合型受阻胺光稳定剂HS-944、聚合型受阻胺光稳定剂HS-950中的一种。
优选为，所述的抗氧剂选自抗氧剂1010、抗氧剂1076、抗氧剂168、抗氧剂DSTP、抗氧剂P-EPQ、抗氧剂PEP-36A、抗氧剂300、抗氧剂PAT 218中的一种或几种复配。
优选为，所述的流动促进剂选自超支化聚合物树脂HyperC100T、超支化聚合物树脂CYD-2136PE中的一种。
优选为，所述的增韧剂选自乙烯辛烯共聚物POE、乙烯醋酸乙烯酯共聚物EVA、苯乙烯-丁二烯-苯乙烯共聚物SBS、苯乙烯-异戊二烯-苯乙烯嵌段共聚物SIS、纳米二氧化硅、超支化树脂CYD-6100等中的一种或几种复配。
优选为，所述的相容剂选自以聚烯烃为载体的接枝物，接枝单体为马来酸酐MAH或甲基丙烯酸缩水甘油酯GMA。
本发明有益效果如下几点：
1）针对浸渍玻纤用聚烯烃树脂和玻璃纤维结构特点，采用超支化聚合物对其流动性能和相容性进行改进，从而达到制备性能优异的玻纤增强热塑性材料；其中超支化聚合物微观结构为基体与聚烯烃具有很好相容性，支化末端为与玻纤具有非常好结合力的活性官能团的球状分子；由于这种球状结构对聚烯烃分子链起到润滑效果，大大提高了聚烯烃熔体的流动性能，使其玻纤增强材料应用与片材时可实现超薄化、高性能化；而超支化尾端活性官能团与玻纤结合，增强了聚烯烃树脂与玻纤之间的界面结合能力，提高了力学性能。
2）采用高性能聚合型受阻胺光稳定剂，具有与聚烯烃树脂极佳的相容性和耐抽提性，与传统受阻胺光稳定剂相比分子量分布更窄，有效氮含量更能高；再与多种协效抗氧剂进行复配，制得耐候性优异的长或连续玻纤增强热塑性聚烯烃塑料。
本发明一方面提供高耐候高流动玻纤浸渍聚烯烃的制备方法，其特征在于：包括如下步骤：
将以上组份按照一定比例预混好后，通过双/单螺杆挤出机熔融混合挤到模头中进行分流及浸渍，制得高耐候高流动玻纤浸渍聚烯烃。
优选为，以聚乙烯为基体树脂时螺杆挤出机温度为180-250℃；模头温度220-250℃。
优选为，以聚丙烯为基体树脂时螺杆挤出机温度为：200-250℃；模头温度230-260℃。
本制备方法的有益效果如下：
该制备方法制备出来的长玻纤增强聚烯烃粒子力学性能优良，耐候性优异；制备出来的连续玻纤增强热塑性聚烯烃片材可实现超薄化和高性能化，复合得到的板材机械强度更高，耐候性优异可满足许多特定领域的应用。该专用料可按照常规玻纤浸渍设备加工，具有重要现实应用价值，市场前景广阔。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为本发明各实施例力学性能表。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
聚烯烃：（a）聚乙烯，主要指HDPE、LDPE、LLDPE以及乙烯与少量α-烯烃的共聚物，其熔融指数大于等于15g/10min；（b）聚丙烯主要指丙烯聚合或者丙烯与少量乙烯共聚物，其熔融指数大于等于25g/10min。其中聚烯烃及其组合物主要指PE或者PP，其中PE可以是HDPE、LDPE、LLDPE以及乙烯与少量α-烯烃的共聚物的一种或两种以上复配体系，PP可以是等规聚丙烯或共聚聚丙烯的单品种或复配体系。
具体实施例1
一种高耐候高流动玻纤浸渍聚烯烃，按质量份计，配方包括：HDPE树脂100 kg，抗紫外线助剂HS-944 0.5 kg，抗氧剂1010 0.2kg，抗氧剂168 0.1kg，抗氧剂DSTP 0.2kg，超支化聚合物树脂Hyper C100T 0.2 kg，乙烯辛烯共聚物POE 2kg，聚乙烯接枝甲基丙烯酸缩水甘油酯PE-g-GMA 1kg。
所述的一种高耐候高流动玻纤浸渍聚烯烃的制备方法，包括如下步骤：将以上组份按照一定比例预混好后，通过单螺杆机组熔融混合挤到“衣架”型模头中进行分流，最后进入“S”型模头对玻纤进行充分浸渍，牵条经过冷却水冷却造粒，制得长玻纤增强热塑性粒子LFRT，玻纤含量50%。
具体实施例2
一种高耐候高流动玻纤浸渍聚烯烃，按质量份计，配方包括：： HDPE树脂80 kg，LLDPE20kg，抗紫外线助剂HS-944 2 kg，抗氧剂1010 0.4kg，抗氧剂168 0.2kg，抗氧剂DSTP0.4kg，超支化聚合物树脂Hyper C100T 2 kg，乙烯醋酸乙烯酯共聚物EVA 5kg，聚乙烯接枝马来酸酐PE-g-MAH 3kg。
所述的一种高耐候高流动玻纤浸渍聚烯烃的制备方法，包括如下步骤：将以上组份按照一定比例预混好后，通过单螺杆机组熔融混合挤到“衣架”型模头中进行分流，最后进入“S”型模头对玻纤进行充分浸渍，牵条经过冷却水冷却造粒，制得长玻纤增强热塑性粒子LFRT，玻纤含量控制在50%左右。
具体实施例3
一种高耐候高流动玻纤浸渍聚烯烃，按质量份计，配方包括： 均聚PP树脂100 kg，抗紫外线助剂HS-950 2 kg，抗氧剂1010 0.4kg，抗氧剂168 0.1kg，抗氧剂PAT218 0.8kg，超支化聚合物树脂CYD-2136PE 1.2 kg，乙烯辛烯共聚物POE 6kg，聚丙烯接枝马来酸酐PP-g-MAH 5kg。
所述的一种高耐候高流动玻纤浸渍聚烯烃的制备方法，包括如下步骤：将以上组份按照一定比例预混好后，通过单螺杆机组熔融混合挤到“衣架”型模头中进行分流，最后进入“S”型模头对玻纤进行充分浸渍，牵条经过冷却水冷却造粒，制得长玻纤增强热塑性粒子LFRT，玻纤含量50%。
具体实施例4
一种高耐候高流动玻纤浸渍聚烯烃，按质量份计，配方包括： 均聚PP树脂70 kg，共聚PP树脂30kg；抗紫外线助剂HS-950 2 kg，抗氧剂1010 0.4kg，抗氧剂168 0.1kg，抗氧剂PAT218 1.5kg，超支化聚合物树脂Hyper C100T 1.0 kg，乙烯辛烯共聚物POE 5kg，聚丙烯接枝马来酸酐PP-g-MAH 2kg。
所述的一种高耐候高流动玻纤浸渍聚烯烃的制备方法，包括如下步骤：将以上组份按照一定比例预混好后，通过双螺杆机组熔融混合挤到“衣架”型模头中进行分流，最后进入“S”型模头对玻纤进行充分浸渍，牵条经过冷却水冷却造粒，制得长玻纤增强热塑性粒子LFRT，玻纤含量50%。
具体实施例5
一种高耐候高流动玻纤浸渍聚烯烃，按质量份计，配方包括： HDPE树脂80 kg，LLDPE20kg，抗紫外线助剂HS-944 2 kg，抗氧剂1010 0.4kg，抗氧剂168 0.2kg，抗氧剂DSTP0.4kg，超支化聚合物树脂CYD-2136PE 2 kg，超支化树脂CYD-6100 5kg， 聚乙烯接枝甲基丙烯酸缩水甘油酯PE-g-GMA 4kg。
所述的一种高耐候高流动玻纤浸渍聚烯烃的制备方法，包括如下步骤：将以上组份按照一定比例预混好后，通过单螺杆机组熔融混合挤到“衣架”型模头中进行分流，最后进入“S”型模头对玻纤进行充分浸渍，成片后经过钢辊进行压制冷却定型、收卷，制得连续玻纤增强热塑性带材CFRT，玻纤含量控制在60%左右，带材厚度0.22mm。
具体实施例6
一种高耐候高流动玻纤浸渍聚烯烃，按质量份计，配方包括： 均聚PP树脂100 kg，抗紫外线助剂HS-950 2 kg，抗氧剂1010 0.4kg，抗氧剂168 0.1kg，抗氧剂PAT218 0.8kg，超支化聚合物树脂Hyper C100T 1.2 kg，乙烯辛烯共聚物POE 6kg， 聚丙烯接枝马来酸酐PP-g-MAH 3kg。
所述的一种高耐候高流动玻纤浸渍聚烯烃的制备方法，包括如下步骤：将以上组份按照一定比例预混好后，通过双螺杆机组熔融混合挤到“衣架”型模头中进行分流，最后进入“S”型模头对玻纤进行充分浸渍，成片后经过钢辊进行压制冷却定型、收卷，制得连续玻纤增强热塑性带材CFRT，玻纤含量控制在60%左右，带材厚度0.18mm；然后将其带材按照纤维方向0°和90°交叉铺层，经过层压设备制得厚度为3mm左右的板材。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种高耐候高流动玻纤浸渍聚烯烃，其特征在于：按质量份计，配方包括：
1)聚烯烃100份；
2)抗紫外老化助剂0.5-2份；
3）抗氧剂0.5-2份；
4）流动促进剂0.2-2份；
5）增韧剂2-10份；
6）相容剂1-5份。
2.根据权利要求1所述的高耐候高流动玻纤浸渍聚烯烃，其特征在于：所述的聚烯烃选自聚乙烯、聚丙烯中的一种。
3.根据权利要求1所述的高耐候高流动玻纤浸渍聚烯烃，其特征在于：所述的抗紫外老化助剂选自聚合型受阻胺光稳定剂HS-944、聚合型受阻胺光稳定剂HS-950中的一种。
4.根据权利要求1所述的高耐候高流动玻纤浸渍聚烯烃，其特征在于：所述的抗氧剂选自抗氧剂1010、抗氧剂1076、抗氧剂168、抗氧剂DSTP、抗氧剂P-EPQ、抗氧剂PEP-36A、抗氧剂300、抗氧剂PAT 218中的一种或几种复配。
5.根据权利要求1所述的高耐候高流动玻纤浸渍聚烯烃，其特征在于：所述的流动促进剂选自超支化聚合物树脂Hyper C100T、超支化聚合物树脂CYD-2136PE中的一种。
6.根据权利要求1所述的一种高耐候高流动玻纤浸渍聚烯烃，其特征在于：所述的增韧剂选自乙烯辛烯共聚物POE、乙烯醋酸乙烯酯共聚物EVA、苯乙烯-丁二烯-苯乙烯共聚物SBS、苯乙烯-异戊二烯-苯乙烯嵌段共聚物SIS、纳米二氧化硅、超支化树脂CYD-6100等中的一种或几种复配。
7.根据权利要求1所述的一种高耐候高流动玻纤浸渍聚烯烃，其特征在于：所述的相容剂选自以聚烯烃为载体的接枝物，接枝单体为马来酸酐MAH或甲基丙烯酸缩水甘油酯GMA。
8.一种根据权利要求1至6任意一项所述的高耐候高流动玻纤浸渍聚烯烃的制备方法，其特征在于：包括如下步骤：
将以上组份按照一定比例预混好后，通过双/单螺杆挤出机熔融混合挤到模头中进行分流及浸渍，制得高耐候高流动玻纤浸渍聚烯烃。
9.根据权利要求7所述的高耐候高流动玻纤浸渍聚烯烃的制备方法，其特征在于：以聚乙烯为基体树脂时螺杆挤出机温度为180-250℃；模头温度220-250℃。
10.根据权利要求7所述的高耐候高流动玻纤浸渍聚烯烃的制备方法，其特征在于：以聚丙烯为基体树脂时螺杆挤出机温度为：200-250℃；模头温度230-260℃。
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| CN111087691A (zh) * | 2019-12-23 | 2020-05-01 | 上海普利特复合材料股份有限公司 | 一种高性能、高表面附着力适于喷漆和胶粘用途聚丙烯材料及其制备方法 |
| CN111849064A (zh) * | 2019-04-25 | 2020-10-30 | 振石集团华美新材料有限公司 | 一种连续玻璃纤维增强聚丙烯预浸带及其制备方法 |
| CN112745576A (zh) * | 2020-12-30 | 2021-05-04 | 上海聚威新材料股份有限公司 | 一种高耐热、高耐候的长玻纤增强聚丙烯材料及其制备方法 |
| CN113136061A (zh) * | 2021-03-26 | 2021-07-20 | 广东聚石化学股份有限公司 | 一种阻燃聚乙烯材料及其制备方法和应用 |
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| CN113136061A (zh) * | 2021-03-26 | 2021-07-20 | 广东聚石化学股份有限公司 | 一种阻燃聚乙烯材料及其制备方法和应用 |
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