CN110684282A - 一种3d中空吹塑微发泡聚烯烃材料及其制备方法 - Google Patents

一种3d中空吹塑微发泡聚烯烃材料及其制备方法 Download PDF

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CN110684282A
CN110684282A CN201911050685.XA CN201911050685A CN110684282A CN 110684282 A CN110684282 A CN 110684282A CN 201911050685 A CN201911050685 A CN 201911050685A CN 110684282 A CN110684282 A CN 110684282A
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foaming
polyolefin
blow molding
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王滨
刘曙阳
蒋顶军
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Nanjing Dongju Carbon Fiber Composite Material Research Institute Co Ltd
NANJING JULONG TECHNOLOGY Co Ltd
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Nanjing Dongju Carbon Fiber Composite Material Research Institute Co Ltd
NANJING JULONG TECHNOLOGY Co Ltd
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Abstract

本发明涉及一种吹塑微发泡聚烯烃材料及其制备方法，尤其是一种3D中空吹塑微发泡聚烯烃材料及其制备方法。本发明的材料包括以下重量份数的组分：聚烯烃75‑100份，超支化聚合物1‑10份，填料3‑15份，相容剂1‑5份，粘度调节剂1‑5份，发泡剂1‑5份，发泡助剂1‑7份，抗氧剂0.3‑1份，并公开了其制备方法。本发明中空吹塑微发泡聚烯烃材料具有出口膨胀比小，流动稳定，熔体强度高、泡孔密度高，表观质量好等特点，满足3D中空吹塑微发泡成型要求；本发明在实现吹塑产品轻量化，减少成型过程中边角废料，显著降低产品制造成本的同时，还赋予了产品良好的隔热、保温、降噪等特点。

Description

一种3D中空吹塑微发泡聚烯烃材料及其制备方法
技术领域
本发明涉及一种吹塑微发泡材料及其制备方法，尤其是一种可实现3D中空吹塑的微发泡聚烯烃材料及其制备方法，属于材料技术领域。
背景技术
微发泡技术是一种非常有效的轻量化技术之一，具有非常广泛地应用领域。在吹塑制品行业已经有所应用，例如包装瓶、中空容器、管道等。但，这些应用主要集中在传统的2D吹塑成型应用，对于新兴的3D吹塑成型仍然无法满足成型要求，例如，在吹塑汽车风管等产品时，现有微发泡材料成型时主要面临挑战如下：1)现有微发泡材料吹塑成型时，出口膨胀比太大且不均匀，无法准确覆盖模具形状，导致合模时产品破裂甚至不能合模；2)成型过程中微发泡熔体流动稳定性较差，出口管胚会有忽长忽短现象；3)熔体强度不足。
发明内容
为解决以上问题，本发明提供3D中空吹塑微发泡聚烯烃材料及其制备方法。本发明的中空吹塑微发泡聚烯烃材料具有出口膨胀比小，流动稳定，熔体强度高、泡孔密度高，表观质量好等特点，完全满足3D中空吹塑微发泡成型要求；本发明在实现吹塑产品轻量化，能够有效减少成型过程中边角废料，显著降低产品制造成本，还赋予了产品良好的隔热、保温、降噪等特点。
为实现上述目的，本发明采用如下技术方案：
一种3D中空吹塑微发泡聚烯烃材料，包括以下重量份数的组分：
聚烯烃75-100份，
超支化聚合物1-10份，
填料3-15份，
相容剂1-5份
粘度调节剂1-5份，
发泡剂1-5份，
发泡助剂1-7份，
抗氧剂0.3-1份。
进一步方案，所述聚烯烃为聚乙烯、聚丙烯、聚丁烯、聚苯乙烯中的一种或几种组合物，优选聚乙烯与聚丙烯的组合物。
进一步方案，所述超支化聚合物为超支化聚苯乙烯、超支化聚对氯甲基苯乙烯、超支化聚醚醚酮、超支化聚醚、超支化聚硅氧烷、超支化聚酯、超支化聚酰胺中的一种，优选超支化聚酯。
进一步方案，所述填料为具有超高长径比的填料，具体为玻璃纤维、碳纤维、天然纤维、玄武岩纤维中的一种，优选玻璃纤维；所述相容剂为功能基团接枝聚烯烃，例如马来酸酐接枝聚乙烯、马来酸酐接枝聚丙烯、马来酸酐接枝聚苯乙烯、硅烷接枝聚乙烯、丙烯酸酯接枝聚丙烯等，优选马来酸酐接枝聚丙烯。
进一步方案，所述粘度调节剂为氧化聚乙烯蜡、聚氧化乙烯、核壳型聚丙烯酸酯类聚合物、聚丙烯蜡、丙烯-苯乙烯共聚物中的一种，优选丙烯-苯乙烯共聚物。
进一步方案，所述发泡剂为成核型吸热发泡剂，例如纳米碱金属氧化物改性碳酸盐类发泡剂、纳米碱金属氧化物改性碳酸氢盐类发泡剂、纳米金属氧化物改性柠檬酸及其衍生物、纳米二氧化硅或纳米二氧化钛改性的碳酸氢盐发泡剂中的一种或几种组合物。优选纳米碱金属氧化物改性碳酸氢盐发泡剂，例如纳米氧化钙改性碳酸氢钠。
进一步方案，所述发泡助剂为硬脂酸锌、氧化锌、硫酸氢盐、磷酸二氢盐、硼酸、葡萄糖酸盐中的一种，优选葡萄糖酸盐；所述抗氧剂为1010、1098、168中的一种，优选抗氧剂1010。
进一步方案，任一项所述的3D中空吹塑微发泡聚烯烃材料的制备方法，其特征在于：包括以下步骤：
步骤一：将聚烯烃75-100份，超支化聚合物1-10份，填料3-15份，粘度调节剂1-5份，发泡助剂1-7份，抗氧剂0.3-1份按照重量份数在混合机中混合1-3min，通过料斗加入到双螺杆挤出机中，在150-250℃温度下造粒，螺杆转速200-800r/min，得到聚烯烃复合材料；
步骤二：将发泡剂与步骤一得到的聚烯烃复合材料按照重量份数预先在高混机中进行充分混合，然后加入到吹塑机料筒；在150-240℃温度下，通过3D中空吹塑成型方式制备微发泡吹塑产品。
有益效果
与现有技术相比，本发明具有如下显著优点：
1、本发明中空吹塑微发泡聚烯烃材料具有出口膨胀比小，流动稳定，熔体强度高、泡孔密度高，表观质量好等特点，完全满足3D中空吹塑微发泡成型要求；
2、本发明在实现吹塑产品轻量化，能够有效减少成型过程中边角废料，显著降低产品制造成本，同时本产品良好的隔热、保温、降噪等特点。
3、本发明通过超枝化聚合物与成核型吸热发泡剂的协同使用，显著提高了其在发泡过程中的材料熔体强度和泡孔生长的稳定性，有利于消除制品表面缺陷。另外通过粘度调节剂优化成型粘度，能够缩短成型周期，提高产品生产效率。
4、本发明提供该材料的制备方法，工艺可控，生产成本低，效率高、易于实现工业化。
附图说明
图1为本发明制得材料外观图。
具体实施方式
实施例1
所述的3D中空吹塑微发泡聚烯烃材料的制备方法：包括以下步骤：
步骤一：将聚烯烃100份分别为聚丙烯50份，聚乙烯50份；超支化聚合物为超支化聚苯乙烯1份，填料为天然麻纤维15份，相容剂为马来酸酐接枝聚丙烯5份，粘度调节剂为氧化聚乙烯蜡5份，发泡助剂为氧化锌5份，抗氧剂1010为0.3份按照重量份数在混合机中混合3min，通过料斗加入到双螺杆挤出机中，在150-250℃温度下造粒，螺杆转速200r/min，得到聚烯烃复合材料；
步骤二：将发泡剂为纳米氧化钙改性碳酸钠3份与步骤一得到的聚烯烃复合材料按照重量份数预先在高混机中进行充分混合，然后加入到吹塑机料筒；在150-240℃温度下，通过3D中空吹塑成型方式制备微发泡吹塑产品。
实施例2
所述的3D中空吹塑微发泡聚烯烃材料的制备方法，：包括以下步骤：
步骤一：将聚烯烃为聚丁烯75份，超支化聚合物为超支化聚醚7份，填料为天然麻纤维10份，相容剂为丙烯酸酯接枝聚乙烯3份，粘度调节剂为聚氧化乙烯4份，发泡助剂磷酸二氢钙7份，抗氧剂168为1份，按照重量份数在混合机中混合2min，通过料斗加入到双螺杆挤出机中，在150-250℃温度下造粒，螺杆转速500r/min，得到聚烯烃复合材料；
步骤二：将发泡剂为纳米氧化镁改性碳酸氢铵5份与步骤一得到的聚烯烃复合材料按照重量份数预先在高混机中进行充分混合，然后加入到吹塑机料筒；在150-240℃温度下，通过3D中空吹塑成型方式制备微发泡吹塑产品。
实施例3
所述的3D中空吹塑微发泡聚烯烃材料的制备方法，：包括以下步骤：
步骤一：将聚烯烃80份，分别为聚丙烯20份，聚乙烯60份；超支化聚合物为超支化聚酯5份；料为玻璃纤维6份；相容剂为马来酸酐接枝聚丙烯2份；粘度调节剂为丙烯-苯乙烯共聚物3份，发泡助剂为葡萄糖酸钠2份，抗氧剂1010为0.3份，按照重量份数在混合机中混合1min，通过料斗加入到双螺杆挤出机中，在150-250℃温度下造粒，螺杆转速800r/min，得到聚烯烃复合材料；
步骤二：将发泡剂纳米氧化钙改性碳酸钠为4份与步骤一得到的聚烯烃复合材料按照重量份数预先在高混机中进行充分混合，然后加入到吹塑机料筒；在150-240℃温度下，通过3D中空吹塑成型方式制备微发泡吹塑产品。
实施例4
所述的3D中空吹塑微发泡聚烯烃材料的制备方法，：包括以下步骤：
步骤一：将聚烯烃为聚丙烯90份，超支化聚合物为超支化聚硅氧烷4份，填料为碳纤维3份，相容剂为马来酸酐接枝聚乙烯1份，粘度调节剂为聚丙烯蜡1份，发泡助剂为硼酸1份，抗氧剂1010为0.4份按照重量份数在混合机中混合3min，通过料斗加入到双螺杆挤出机中，在150-250℃温度下造粒，螺杆转速200-800r/min，得到聚烯烃复合材料；
步骤二：将发泡剂为纳米二氧化钛改性柠檬钠1份与步骤一得到的聚烯烃复合材料按照重量份数预先在高混机中进行充分混合，然后加入到吹塑机料筒；在150-240℃温度下，通过3D中空吹塑成型方式制备微发泡吹塑产品。
根据上述制备方法，对比例1、实施例1、实施例2、实施例3、实施例4，具体配方如下表所示：
对上表中的对比例和实施例进行检测，性能结果如下表所示：
本发明产品对比例和实施例性能表
Figure BDA0002254076590000062
从以上结果含图1可以看出，与对比例1比较，本发明实施例1、实施例2、实施例3、实施例4重量更轻，同时，本发明材料的出口膨胀比明显降低，这保证了3D吹塑微发泡成型产品的尺寸以及成型过程的可行性；更高的熔体流长说明了本发明具有更短成型周期，更高的生产效率。通过图1可见本材料制得产品表面质量好。
以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本领域的技术人员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 (9)

1.一种3D中空吹塑微发泡聚烯烃材料，其特征在于，包括以下重量份数的组分：
聚烯烃 75-100份，
超支化聚合物 1-10份，
填料 3-15份，
相容剂 1-5份
粘度调节剂 1-5份，
发泡剂 1-5份，
发泡助剂 1-7份，
抗氧剂 0.3-1份。
2.根据权利要求1所述3D中空吹塑微发泡聚烯烃材料，其特征在于：所述聚烯烃为聚乙烯、聚丙烯、聚丁烯、聚苯乙烯中的一种；所述填料为具有超高长径比的填料，为玻璃纤维、碳纤维、天然纤维、玄武岩纤维中的一种；所述相容剂为功能基团接枝聚烯烃；所述粘度调节剂为氧化聚乙烯蜡、聚氧化乙烯、核壳型聚丙烯酸酯类聚合物、聚丙烯蜡、丙烯-苯乙烯共聚物中的一种；所述发泡助剂为硬脂酸锌、氧化锌、硫酸氢盐、磷酸二氢盐、硼酸、葡萄糖酸盐中的一种，所述的抗氧剂为1010,1098,168中的一种。
3.根据权利要求2所述3D中空吹塑微发泡聚烯烃材料，其特征在于：所述聚烯烃为聚乙烯与聚丙烯混合物；所述的填料为玻璃纤维；功能基团接枝聚烯烃为马来酸酐接枝聚乙烯、马来酸酐接枝聚丙烯、马来酸酐接枝聚苯乙烯、硅烷接枝聚乙烯、丙烯酸酯接枝聚丙烯；所述的粘度调节剂为丙烯-苯乙烯共聚物；所述的发泡助剂为葡萄糖酸盐，所述的抗氧剂为1010。
4.根据权利要求1所述3D中空吹塑微发泡聚烯烃材料，其特征在于：所述超支化聚合物为超支化聚苯乙烯、超支化聚对氯甲基苯乙烯、超支化聚醚醚酮、超支化聚醚、超支化聚硅氧烷、超支化聚酯、超支化聚酰胺中的一种。
5.根据权利要求4所述3D中空吹塑微发泡聚烯烃材料，其特征在于：所述超支化聚合物为超支化聚酯。
6.根据权利要求1所述3D中空吹塑微发泡聚烯烃材料，其特征在于：所述发泡剂为成核型吸热发泡剂，所述的成核型吸热发泡剂为纳米碱金属氧化物改性碳酸盐类发泡剂、纳米碱金属氧化物改性碳酸氢盐类发泡剂、纳米金属氧化物改性柠檬酸及其衍生物、纳米二氧化硅或纳米二氧化钛改性的碳酸氢盐发泡剂中的一种或几种组合物。
7.根据权利要求6所述3D中空吹塑微发泡聚烯烃材料，其特征在于：所述的发泡剂为纳米碱金属氧化物改性碳酸氢盐类发泡剂。
8.根据权利要求1所述3D中空吹塑微发泡聚烯烃材料，其特征在于：含有如下成分，聚烯烃80份，分别为聚丙烯20份，聚乙烯60份；超支化聚合物为超支化聚酯5份；填料为玻璃纤维6份；相容剂为马来酸酐接枝聚丙烯2份；粘度调节剂为丙烯-苯乙烯共聚物3份；发泡剂为纳米氧化钙改性碳酸钠4份；发泡助剂为葡萄糖酸钠2份，抗氧剂1010为0.3份。
9.根据权利要求1-8任一项所述的3D中空吹塑微发泡聚烯烃材料的制备方法，其特征在于：包括以下步骤：
步骤一：将聚烯烃75-100份，超支化聚合物1-10份，填料3-15份，相容剂1-5份、粘度调节剂1-5份，发泡助剂1-7份，抗氧剂0.3-1份按照重量份数在混合机中混合1-3min，通过料斗加入到双螺杆挤出机中，在150-250℃温度下造粒，螺杆转速200-800r/min，得到聚烯烃复合材料；
步骤二：将发泡剂与步骤一得到的聚烯烃复合材料按照重量份数预先在高混机中进行充分混合，然后加入到吹塑机料筒；在150-240℃温度下，通过3D中空吹塑成型方式制备微发泡吹塑产品。
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