CN103756134A - 利用发泡技术的长玻璃纤维增强聚丙烯材料及其制备方法 - Google Patents

利用发泡技术的长玻璃纤维增强聚丙烯材料及其制备方法 Download PDF

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CN103756134A
CN103756134A CN201310738669.6A CN201310738669A CN103756134A CN 103756134 A CN103756134 A CN 103756134A CN 201310738669 A CN201310738669 A CN 201310738669A CN 103756134 A CN103756134 A CN 103756134A
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long glass
glass fiber
fiber reinforced
reinforced polypropylene
polypropylene material
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吴建国
李兰军
王飞
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NANJING JULONG TECHNOLOGY Co Ltd
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Abstract

本发明涉及一种材料及其制备方法，尤其涉及利用发泡技术的长玻璃纤维增强聚丙烯材料及其制备方法，属于材料技术领域。本发明包括以下质量百分比的原料组分：聚丙烯30-75wt%，长玻璃纤维20-60wt%，化学发泡剂0.5-5wt%，相容剂1-5wt%。本发明采用微发泡技术，进一步降低树脂的粘度，同时减少玻璃纤维强力分散装置因降低避免玻璃纤维束直接与辊或突出的部分接触几率，减少了对玻纤的损伤，降低料条牵引阻力，其有益效果是：保证聚丙烯树脂对玻璃纤维浸渍效果的同时，提高了产品性能、质量稳定性和生产效率。

Description

利用发泡技术的长玻璃纤维增强聚丙烯材料及其制备方法
技术领域
本发明涉及一种材料及其制备方法，尤其涉及利用发泡技术的长玻璃纤维增强聚丙烯材料及其制备方法，属于材料技术领域。
背景技术
长玻璃纤维增强聚丙烯是一种聚丙烯中的玻璃纤维长度较长，而且纤维长度分布更好的材料，其优点是可以提高制品的力学性能，特别是冲击强度提高显著，刚性增加，尺寸稳定性蠕变性能更好，有利于在结构件上的应用。现在已有一些生产长玻璃纤维增强聚丙烯树脂材料和浸渍结构的方法和装置，例如公开号为CN1810870A的专利，配方中直接使用了不饱和羧酸或其酸酐，主要目的是使聚丙烯树脂降解，提高流动性，同时对聚丙烯树脂进行接枝，改善玻璃纤维与聚丙烯树脂熔体的界面结合力，然而在材料生产过程中，这类物质有难闻的刺激性气味，不仅危害对人体健康、污染环境，而且腐蚀加工设备，降低设备的使用寿命；再如公开号为CN101338051A的专利，配方中加入流动改性剂，目的是提高聚丙烯树脂的流动性，便于浸渍，然而流动改性剂为PP降温母粒，主要成分为过氧化物，不仅带入有害物质，而且对聚丙烯流动性提高的稳定性很差、产品质量控制十分困难。公开号为CN101152767A的专利中，提出了一种浸渍方法，在浸渍模具内采用一组或多组张力辊，玻纤通过与张力辊表面接触，沿着一个折线使纤维束松散，从而与熔融树脂浸渍，但其摩擦阻力大，纤维易断损、生产效率低；公开号为CN101337402A的专利中，将纤维通过与一系列导向辊和压辊接触，从而达到纤维松散，与熔融树脂浸渍，同样摩擦阻力大，纤维易断损、生产效率低。上述现有技术存在的问题是：由于增强纤维束在张力的作用下通过围绕张力辊或突出的部分时，要与这些辊或突出部分强制接触，因此纤维不仅将受到严重的破坏，而且摩擦阻力大、生产效率低。这些方法存在一个无法避免的难题，即由于纤维受破坏形成断裂，断裂的形成损害了所要的树脂浸渍结构的稳定性，最终导致浸渍装置的运行中断，同时，严重影响生产的稳定性和生产效率。
发明内容
本发明针对现有技术存在的缺陷，提出一种利用发泡技术的长玻璃纤维增强聚丙烯材料及其制备方法，降低树脂粘度，减少对玻璃纤维的损伤，保证生产的稳定性和质量。
本发明通过以下技术方案解决技术问题：利用发泡技术的长玻璃纤维增强聚丙烯材料，包括以下质量百分比的原料组分：聚丙烯30-75wt%，长玻璃纤维20-60wt%，化学发泡剂0.5-5wt%，相容剂1-5wt%。
以上配比中较为优选的配方包括以下质量百分比的原料组分，聚丙烯45wt%，长玻璃纤维50wt%，相容剂3wt%，化学发泡剂2.0wt%。
其中，所述聚丙烯为高流动性聚丙烯，熔体流动速率在30-100g/10min。
所述长玻璃纤维为连续无捻粗纱，纤维类型为E玻璃，纤维单丝直径为2400Tex17μm，1200Tex16μm。
所述化学发泡剂为偶氮二甲酰胺、偶氮二甲酸钡、高温膨胀型微胶囊发泡剂中的至少一种。
所述化学发泡剂为偶氮二甲酰胺。
所述相容剂为马来酸酐接枝聚丙烯型相容剂。
本发明进一步提供在可快速牵引速度下，同时又可保持高水平产品质量的、生产稳定生产率的利用发泡技术的长玻璃纤维增强聚丙烯材料的制备方法，包括以下步骤：
步骤一、将聚丙烯、相容剂、化学发泡剂按所述比例加入混合机中混合均匀，得到混合物；
步骤二、将步骤一所得的混合物加入双螺杆挤出机，在压力为5-20MPa的条件下,经过挤出机熔融、混合，得到化学发泡剂处于将要分解的临界状态的PP熔体，并用计量泵计量，继续送入温度为220-280℃、压力为0.1-3MPa、已引入长玻璃纤维的浸渍模具中，在快速压力下降过程中，化学发泡剂分解气化，形成多微孔状的PP熔体；
步骤三、将PP熔体与长玻璃纤维混合，使长玻璃纤维被多微孔PP熔体浸渍，最后将均匀浸渍的长玻璃纤维增强PP材料牵引出浸渍模具，通过冷却、切粒，即得到微发泡长玻璃纤维增强聚丙烯粒料。
上述方法的所述步骤二中，双螺杆挤出机温度共设8段，第一段和第二段挤出温度在160-200℃，其它段数的挤出温度在200-220℃。
本发明采用微发泡技术，在降低树脂的粘度的同时，减少玻璃纤维与玻璃纤维强力分散装置（辊或凸出部分）直接接触几率，降低对玻纤的损伤和料条牵引阻力，同时泡孔中的气体有力地将PP熔体推压入长玻璃纤维丝束中，使长玻璃纤维被多微孔PP熔体快速、高效、充分浸渍；与现有技术相比，本发明将按比例混合的聚丙烯、相容剂、化学发泡剂等，经双螺杆挤出机，在压力为5-20MPa的条件下,熔融、混合，得到化学发泡剂待分解的PP熔体，经计量泵稳定计量高压聚丙烯熔体供入低压浸渍模具中，通过化学发泡剂产生的气体压力作用，形成多微孔结构。该结构的引入，一方面将会极大地进一步降低树脂的粘度，令树脂的流动性提高，有利于浸渍，另一方面气体压力将PP熔体推压入长玻璃纤维丝束中，使长玻璃纤维被多微孔PP熔体快速、高效、充分浸渍且环保。另外，浸渍模具中存在的多微孔PP熔体于浸渍模具内部形成气相-熔体相-固相三相共存，随着固相纤维的向前牵引，伴随着沿纤维束的移动方向在其表面附近的熔融树脂的流动。同时，产生的熔体树脂流与微孔结构熔体树脂的气相流相冲撞，引起流动方向的变化并离开纤维束，而产生一个漩流，其中纤维束水平轴线作为它的中心。以浸渍模具中一束纤维的某一小段为例，在纤维束的上方，树脂流产生一个向上指向的逆时针漩流并返回到上游侧，然后下降并且几乎垂直地与纤维束上表面冲撞，而在纤维束下方，树脂流的行为则正好相反，更具体地说，树脂流产生一个顺时针漩流，返回到上游侧然后上升且向上地与纤维束下表面冲撞。这样纤维束上下表面产生的漩流同时作用于纤维表面，从而使得纤维束松散展开，在浸渍模具中与树脂浸渍。这样，避免了纤维束直接与辊或凸出的部分接触，既减少了对玻纤的损伤，又降低了纤维与辊或凸出部分的摩擦力，其有益效果是：在保证浸渍效果的同时，提高了产品性能和质量稳定性，减少料条牵引阻力，提高了生产效率。
具体实施方式
实施例一
本实施例按以下质量百分比组成进行配比：市售高流动性聚丙烯（熔指30g/10min）为35wt%，市售环保型相容剂（低气味马来酸酐接枝PP）为4wt%，市售化学发泡剂偶氮二甲酰胺1wt%。
将上述原料组分按以下方法制备，
步骤一、首先将上述物料加入到高速搅拌机中搅拌均匀；
步骤二、将第一步得到的混合物加入到双螺杆挤出机内，双螺杆挤出机温度共设8段，第一段和第二段挤出温度在160-200℃，其它几段挤出温度在200-220℃；压力为12MPa,通过挤出机熔融、混合，以计量泵稳定计量，连续送入温度为220-280℃、模具压力为1MPa的浸渍模具中；
步骤三、再将总量占60wt%长玻璃纤维（LFT长纤专用玻纤,市售）通过浸渍模具，使长玻璃纤维被多微孔PP熔体充分浸渍，最后牵引、冷却、牵引、切粒，即得到长玻璃纤维增强聚丙烯粒料。所得长玻璃纤维增强聚丙烯粒料长度为12mm。
实施例二
本实施例按以下质量百分比组成进行配比：市售高流动性聚丙烯（熔指50g/10min）为70wt%，市售环保型相容剂（低气味马来酸酐接枝PP）为2wt%，市售化学发泡剂偶氮二甲酰胺3wt%。
将上述原料组分按以下方法制备，
步骤一、首先将上述物料加入到高速搅拌机中搅拌均匀；
步骤二、将第一步得到的混合物加入到双螺杆挤出机内，双螺杆挤出机温度共设8段，第一段和第二段挤出温度在160-200℃，其它几段挤出温度在200-220℃；压力为18MPa,通过挤出机熔融、混合，以计量泵稳定计量，连续送入温度为220-280℃、模具压力为2MPa的浸渍模具中；
步骤三、再将总量占25wt%长玻璃纤维（LFT长纤专用玻纤,市售）通过浸渍模具，使长玻璃纤维被多微孔PP熔体充分浸渍，最后牵引、冷却、牵引、切粒，即得到长玻璃纤维增强聚丙烯粒料。所得长玻璃纤维增强聚丙烯粒料长度为12mm。
实施例三
本实施例按以下质量百分比组成进行配比：市售高流动性聚丙烯（熔指100g/10min）为53wt%，市售环保型相容剂（低气味马来酸酐接枝PP）为5wt%，市售化学发泡剂偶氮二甲酰胺2wt%。
将上述原料组分按以下方法制备，
步骤一、首先将上述物料加入到高速搅拌机中搅拌均匀；
步骤二、将第一步得到的混合物加入到双螺杆挤出机内，双螺杆挤出机温度共设8段，第一段和第二段挤出温度在160-200℃，其它几段挤出温度在200-220℃；压力为16MPa,通过挤出机熔融、混合，以计量泵稳定计量，连续送入温度为220-280℃、模具压力为0.8MPa的浸渍模具中；
步骤三、再将总量占40wt%长玻璃纤维（LFT长纤专用玻纤,市售）通过浸渍模具，使长玻璃纤维被多微孔PP熔体充分浸渍，最后牵引、冷却、牵引、切粒，即得到长玻璃纤维增强聚丙烯粒料。所得长玻璃纤维增强聚丙烯粒料长度为12mm。
上述实施例所得产物的性能检测结果见表1：
由表1可知，本发明产品性能优异、质量稳定，可减少料条牵引阻力，提高生产效率。
除上述实施外，本发明还可以有其他实施方式。凡采用等同替换或等效变换形成的技术方案，均落在本发明要求的保护范围。

Claims (9)

1.利用发泡技术的长玻璃纤维增强聚丙烯材料，包括以下质量百分比的原料组分：聚丙烯30-75wt%，长玻璃纤维20-60wt%，化学发泡剂0.5-5wt%，相容剂1-5wt%。
2.根据权利要求1所述利用发泡技术的长玻璃纤维增强聚丙烯材料，其特征在于：包括以下质量百分比的原料组分，聚丙烯45wt%，长玻璃纤维50wt%，相容剂3wt%，化学发泡剂2.0wt%。
3.根据权利要求1所述利用发泡技术的长玻璃纤维增强聚丙烯材料，其特征在于:所述聚丙烯的熔体流动速率在30-100g/10min。
4.根据权利要求1所述利用发泡技术的长玻璃纤维增强聚丙烯材料，其特征在于：所述长玻璃纤维为连续无捻粗纱，纤维类型为E玻璃，纤维单丝直径为2400Tex17μm，1200Tex16μm。
5.根据权利要求1所述利用发泡技术的长玻璃纤维增强聚丙烯材料，其特征在于：所述化学发泡剂为偶氮二甲酰胺、偶氮二甲酸钡、高温膨胀型微胶囊发泡剂中的至少一种。
6.根据权利要求5所述利用发泡技术的长玻璃纤维增强聚丙烯材料，其特征在于：所述化学发泡剂为偶氮二甲酰胺。
7.根据权利要求1所述利用发泡技术的长玻璃纤维增强聚丙烯材料，其特征在于：所述相容剂为马来酸酐接枝聚丙烯型相容剂。
8.根据权利要求1所述利用发泡技术的长玻璃纤维增强聚丙烯材料的制备方法，包括以下步骤：
步骤一、将聚丙烯、相容剂、化学发泡剂按所述比例加入混合机中混合均匀，得到混合物；
步骤二、将步骤一所得的混合物加入双螺杆挤出机，在压力为5-20MPa的条件下,经过挤出机熔融、混合，得到化学发泡剂待分解的PP熔体，然后用计量泵计量，将上述熔体送入温度为220-280℃、压力为0.1-3MPa、已引入长玻璃纤维的浸渍模具中，在压力从5-20MPa下降到0.1-3MPa过程中，化学发泡剂分解气化，形成多微孔状的PP熔体；
步骤三、将PP熔体与长玻璃纤维混合，使长玻璃纤维被多微孔PP熔体浸渍，最后将均匀浸渍的长玻璃纤维增强PP材料料条牵引出浸渍模具，通过冷却、切粒，即得到长玻璃纤维增强聚丙烯粒料。
9.根据权利要求8所述利用发泡技术的长玻璃纤维增强聚丙烯材料的制备方法，其特征在于：所述步骤二中，双螺杆挤出机温度共设8段，第一段和第二段挤出温度在160-200℃，其它段数的挤出温度在200-220℃。
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