CN108727809A - 一种中空吹塑尼龙微发泡材料及其制备方法 - Google Patents

一种中空吹塑尼龙微发泡材料及其制备方法 Download PDF

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CN108727809A
CN108727809A CN201810251575.9A CN201810251575A CN108727809A CN 108727809 A CN108727809 A CN 108727809A CN 201810251575 A CN201810251575 A CN 201810251575A CN 108727809 A CN108727809 A CN 108727809A
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nylon
blow molding
foaming
hollow blow
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王滨
刘曙阳
蒋顶军
阳明书
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NANJING JULONG TECHNOLOGY Co Ltd
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Abstract

本发明涉及一种尼龙材料及其制备方法，尤其是一种中空吹塑尼龙微发泡材料及其制备方法。本发明的材料包括以下重量份数的组分：尼龙50‑90份,聚酯5‑25份,填充剂0‑30份,聚烃类接枝共聚物1‑15份,枝化剂0.5‑5份,发泡剂0.5‑10份,发泡助剂5‑15份,润滑剂0.2‑1份,抗氧剂0.3‑1份。并公开了其制备方法。本发明的中空吹塑尼龙微发泡材料具有吹塑熔垂性能好、泡孔密度高、泡孔均匀、易加工，好成型、机械性能优良、耐热性好、耐低温性能优良、重量轻、强度高、尺寸稳定性好、表观质量高、成品率高、成型周期短等特点。

Description

一种中空吹塑尼龙微发泡材料及其制备方法
技术领域
本发明涉及一种尼龙材料及其制备方法，尤其是一种中空吹塑微发泡尼龙材料及其制备方法，属于材料技术领域。
背景技术
尼龙材料集优异的力学性能、阻隔性能、高低温性能、电性能、耐化学药品性、耐磨性、耐候性及尺寸稳定性等于一身,成型工艺简单且能耗小,已成为发展最快的工程塑料，经常被用于制造各种汽车、电子电器、电动工具等关键结构零部件。这些其中不乏吹塑成型获得的产品。
随着各行业塑料产品轻量化趋势不断发展，微发泡技术因其独特微孔结构和其带来的轻量化效果得到了众多厂商越来越多的青睐，但是,将通用尼龙材料直接用于吹塑微发泡时还存在一些问题。一是,目前市场上常用的尼龙材料在熔融状态下的熔体强度很低，抗熔垂性能差,不能直接用于吹塑微发泡成型；二是普通气体(二氧化碳、氮气等)在尼龙中的溶解度很低，无法形成足够的溶解量，造成发泡量太低，且发泡不均匀，造成产品性能很差；三是，普通尼龙材料冲击强度并不是很高，特别是低温下的高抗冲击性能仍需要提高才能满足使用要求。因此,若想获得中空吹塑尼龙微发泡材料,则需解决上述几个方面的问题。
发明内容
为解决以上问题，本发明提供一种性能优异且具有明显轻量化特征的中空吹塑尼龙微发泡材料及其制备方法，材料不仅机械强度高，耐热性好，泡孔结构均匀，泡孔密度高，表观质量良好，而且其成型过程中气体溶解度高，抗熔垂性能好，成型周期更短。
为实现上述目的，本发明采用如下技术方案：
一种中空吹塑尼龙微发泡材料，包括以下重量份数的组分：
尼龙 50-90份
聚酯 5-25份
填充剂 0-30份
聚烃类接枝共聚物 1-15份
枝化剂 0.5-5份
发泡剂 0.5-10份
发泡助剂 5-15份
润滑剂 0.2-1份
抗氧剂 0.3-1份。
进一步的技术方案，所述尼龙为由内酸胺开环聚合制得或者由二元酸和二元胺缩聚制得的聚合物，包括尼龙6、尼龙66、尼龙1010等，优选尼龙6。
进一步的技术方案，所述聚酯为含有的聚合物，包括环己二醇共聚聚酯(PETG)、聚对苯二甲酸丙二醇酯(PTT)、聚碳酸酯(PC)、聚酯弹性体等，优选PETG；
所述枝化剂为环氧树脂、噁嗪类、咪唑啉类、酯化二内酰胺类中的一种，优选环氧树脂。
进一步的技术方案，所述聚烃类接枝共聚物包括聚烯烃类接枝共聚物和聚芳烃类接枝共聚物。
进一步的技术方案，所述聚烯烃类接枝共聚物包括甲基丙烯酸缩水甘油醚(GMA)接枝聚烯烃共聚物、丙烯酸酯接枝聚烯烃共聚物、亚甲基丁二酸接枝聚烯烃共聚物、甲基丙烯酸接枝聚烯烃共聚物，其中聚烯烃包括聚乙烯、聚丙烯、聚丁烯、聚丁二烯、乙烯-丁烯共聚物、乙烯-辛烯共聚物；优选甲基丙烯酸缩水甘油醚(GMA)接枝乙烯-丁烯共聚物。
所述聚芳烃类包括甲基丙烯酸缩水甘油醚(GMA)接枝聚芳烃共聚物、丙烯酸酯接枝聚芳烃共聚物，其中聚芳烃包括聚苯乙烯、苯乙烯-乙烯-丁二烯-苯乙烯共聚物等；优选甲基丙烯酸缩水甘油醚(GMA)接枝苯乙烯-乙烯-丁二烯-苯乙烯共聚物(GMA-g-SEBS)。
进一步的技术方案，所述填充剂为玻璃纤维、碳纤维、滑石粉、碳酸钙、晶须、玻璃微珠、硅灰石、云母中的一种，优选玻璃纤维；
所述润滑剂为硅酮、聚乙烯蜡、硬脂酸钙、乙撑双硬脂酰胺中的一种，优选硅酮；
所述抗氧剂为1010、1098、168、H10、H318中的一种，优选1098。
进一步的技术方案，所述发泡剂为有机发泡剂和无机发泡剂按照1：1-1：9复配而成，有机发泡剂为偶氮类，磺酰肼类中的一种，无机发泡剂为碳酸氢盐、碳酸盐、铵盐中的一种；优选偶氮类发泡剂和碳酸氢盐按照重量比3：2复配的混合发泡剂。
进一步的技术方案，所述发泡助剂包括成核剂、稳泡剂、分散剂以及相容剂；
其中，成核剂为纳米二氧化钛、纳米碳酸钙、纳米蒙脱土中的一种，优选纳米碳酸钙；
稳泡剂为乙烯醋酸乙烯共聚物(其中，VA含量为10％-30％)、有机硅油(包括改性有机硅油)、甘油单脂肪酸酯、聚乙二醇中的一种，优选乙烯-醋酸乙烯共聚物(EVA)；
分散剂为氯化石蜡、氧化聚乙烯、乙撑双脂肪酰胺、硬脂酸、硬脂酸甘油酯中的一种，优选乙撑双脂肪酰胺；
相容剂为丙烯酸酯接枝改性聚烯烃，甲基丙烯酸缩水甘油醚(GMA)接枝改性聚芳烃、聚丙烯酸脂中的一种，优选丙烯酸酯接枝改性乙烯-丁烯共聚物。
所述的中空吹塑尼龙微发泡材料的制备方法，包括以下步骤：
步骤一：将尼龙50-90份，聚酯5-25份，填充剂0-30份，聚烃类接枝共聚物1-15份，枝化剂0.5-5份，润滑剂0.2-1份，抗氧剂0.3-1份放入混合机中混合1-3min，通过料斗加入到双螺杆挤出机中，在240-300℃温度下造粒，螺杆转速400-800r/min，得到适用于吹塑微发泡的尼龙复合材料；
步骤二：将发泡剂0.5-10份预先在高混机中进行充分混合，然后由侧喂料口加入单螺杆吹塑机中；同时，将步骤一获得的尼龙复合材料、发泡助剂5-15份加入到单螺杆吹塑机料筒；在230-280℃温度下，进行吹塑，获得中空微发泡尼龙产品；其中，单螺杆吹塑机的螺杆长径比为18：1-50:1，压缩比为3:1-5:1。
有益效果
与现有技术相比，本发明具有如下显著优点：
1、本发明采用聚酯与枝化剂协同作用，通过枝化反应，增加了尼龙分子量，抑制了其结晶过程中的运动速度，聚酯的存在进一步消弱了尼龙分子的规则排列，进而抑制了其在吹塑微发泡成型过程中的早结晶，同时，改善微发泡成型过程中尼龙材料的抗熔垂性能，实现优化产品壁厚分布，保证尼龙吹塑微发泡过程的顺利进行，同时也在一定程度上改善了泡孔生长稳定性和均匀性，保证产品轻量化特征，提升了制品表观质量。
2、本发明中使用的发泡剂为复配型发泡剂，保证了吹塑成型过程中气体连续性，产生气体主要为二氧化碳和氮气，无毒无害，绿色环保，使吹塑发泡成型过程中稳定性好，同时，二氧化碳为不可燃性气体，增加了生产安全，应用更加广泛。
3、本发明中聚烃类接枝共聚物可以有效增加二氧化碳、氮气等气体在尼龙复合材料中的溶解度，提高气体在吹塑过程中的保留率，获得更多气泡，保证产品重量减轻，同时发泡助剂中的成核剂和分散剂以及相容剂的使用具有微细化泡孔作用，能够在发泡过程中调控泡孔成核和生长过程，增加泡孔密度，消除制品表观气痕等缺陷，利于改善中空微发泡制品外观质量。
4、本发明材料的制备方法中，将发泡剂通过侧喂料引入，这有利于避免发泡剂在螺杆中的提前分解，气体的逃逸损失，提高发泡剂效率。
5、本发明提供该材料的制备方法，生产周期短，工艺稳定可控，生产成本低，效率高、易于实现工业化。
6、本发明的中空吹塑尼龙微发泡材料具有吹塑熔垂性能好、泡孔密度高、泡孔均匀、易加工，好成型、机械性能优良、耐热性好、耐低温性能优良、重量轻、强度高、尺寸稳定性好、表观质量高、成品率高、成型周期短等特点，不但能够解决零部件轻量化问题，还解决了产品的尺寸稳定性、隔音、抗撕裂、抗震问题。
附图说明
图1为本发明的中空吹塑微发泡尼龙材料的内部微孔结构示意图。
具体实施方式
下面结合附图和实施例对本发明作进一步详细的说明。
实施例1
一种中空吹塑尼龙微发泡材料的制备方法，包括以下步骤：
步骤一：将尼龙6 50份，PETG 25份，玻璃纤维20份，GMA-g-POE 5份，二噁唑啉0.5份，硅酮1份，抗氧剂1098 0.3份放入混合机中混合1-3min，通过料斗加入到双螺杆挤出机中，在240-300℃温度下造粒，螺杆转速400-800r/min，得到适用于吹塑微发泡的尼龙复合材料；
步骤二：将偶氮二甲酰胺6份、碳酸氢钠4份预先在高混机中进行充分混合，然后由侧喂料口加入单螺杆吹塑机中；同时，将步骤一获得的尼龙复合材料、纳米二氧化钛1份、乙烯-醋酸乙烯共聚物1份、氧化聚乙烯1份、丙烯酸酯接枝改性聚乙烯-丁烯共聚物2份加入到单螺杆吹塑机料筒；在230-280℃温度下，进行吹塑，获得中空微发泡尼龙产品；其中，单螺杆吹塑机的螺杆长径比为18：1-50:1，压缩比为3:1-5:1。
实施例2
一种中空吹塑尼龙微发泡材料的制备方法，包括以下步骤：
步骤一：将尼龙66 90份，PC 15份，GMA-g-SEBS 15份，环氧树脂5份，乙撑双硬脂酰胺0.2份，抗氧剂168 0.5份放入混合机中混合1-3min，通过料斗加入到双螺杆挤出机中，在240-300℃温度下造粒，螺杆转速400-800r/min，得到适用于吹塑微发泡的尼龙复合材料；
步骤二：将4,4-二磺酰肼二苯醚4份、碳酸钠4份预先在高混机中进行充分混合，然后由侧喂料口加入单螺杆吹塑机中；同时，将步骤一获得的尼龙复合材料、纳米碳酸钙3份、聚乙二醇5份、乙撑双脂肪酰胺2份、聚丙烯酸脂5份加入到单螺杆吹塑机料筒；在230-280℃温度下，进行吹塑，获得中空微发泡尼龙产品；其中，单螺杆吹塑机的螺杆长径比为18：1-50:1，压缩比为3:1-5:1。
实施例3
一种中空吹塑尼龙微发泡材料的制备方法，包括以下步骤：
步骤一：将尼龙1010 60份，聚酯弹性体10份，玻璃微珠30份，丙烯酸酯接枝聚乙烯10份，酯化二内酰胺2份，硅酮0.5份，抗氧剂1098 0.6份放入混合机中混合1-3min，通过料斗加入到双螺杆挤出机中，在240-300℃温度下造粒，螺杆转速400-800r/min，得到适用于吹塑微发泡的尼龙复合材料；
步骤二：将偶氮二甲酰胺0.4份、碳酸钠0.1份预先在高混机中进行充分混合，然后由侧喂料口加入单螺杆吹塑机中；同时，将步骤一获得的尼龙复合材料、纳米碳酸钙3份、乙烯-醋酸乙烯共聚物2份、氧化聚乙烯2份、丙烯酸酯接枝改性聚乙烯-丁烯共聚物3份加入到单螺杆吹塑机料筒；在230-280℃温度下，进行吹塑，获得中空微发泡尼龙产品；其中，单螺杆吹塑机的螺杆长径比为18：1-50:1，压缩比为3:1-5:1。
实施例4
一种中空吹塑尼龙微发泡材料的制备方法，包括以下步骤：
步骤一：将尼龙6 70份，PETG 15份，玻璃纤维10份，GMA-g-POE 1份，环氧树脂1份，乙撑双硬脂酰胺0.3份，抗氧剂168 1份放入混合机中混合1-3min，通过料斗加入到双螺杆挤出机中，在240-300℃温度下造粒，螺杆转速400-800r/min，得到适用于吹塑微发泡的尼龙复合材料；
步骤二：将4,4-二磺酰肼二苯醚3份、碳酸氢钠2份预先在高混机中进行充分混合，然后由侧喂料口加入单螺杆吹塑机中；同时，将步骤一获得的尼龙复合材料、纳米二氧化钛4份、聚乙二醇1份、乙撑双脂肪酰胺2份、聚丙烯酸脂1份加入到单螺杆吹塑机料筒；在230-280℃温度下，进行吹塑，获得中空微发泡尼龙产品；其中，单螺杆吹塑机的螺杆长径比为18：1-50:1，压缩比为3:1-5:1。
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，其中对比例1仅是配方与实施例不同，制备方法与对比例相同。
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
本发明实施例与对比例主要性能表
注：熔垂性能测试条件为250℃，测试时间为30min，测试样条下垂长度，越短证明材料抗熔垂性越好。
从以上结果可以看出，与对比例1相比，实施例1、实施例2、实施例3、实施例4抗熔垂性能大幅提高，保证了尼龙材料吹塑发泡过程的稳定性及产品壁厚可调控，另外，本发明具有全封闭泡孔结构，如图1所示，泡孔密度高，机械强度好，伸长率长的特点，改善了中空吹塑产品的缓冲和抗撕裂能力，实现了保证使用性能前提下的产品轻量化。
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 (10)

1.一种中空吹塑尼龙微发泡材料，其特征在于，包括以下重量份数的组分：
尼龙50-90份
聚酯5-25份
填充剂0-30份
聚烃类接枝共聚物1-15份
枝化剂0.5-5份
发泡剂0.5-10份
发泡助剂5-15份
润滑剂0.2-1份
抗氧剂0.3-1份。
2.根据权利要求1所述中空吹塑尼龙微发泡材料，其特征在于：所述尼龙为由内酸胺开环聚合制得或者由二元酸和二元胺缩聚制得的聚合物，包括尼龙6、尼龙66、尼龙1010。
3.根据权利要求1所述中空吹塑尼龙微发泡材料，其特征在于：所述聚酯包括环己二醇共聚聚酯、聚对苯二甲酸丙二醇酯、聚碳酸酯、聚酯弹性体；
所述枝化剂为环氧树脂、噁嗪类、咪唑啉类、酯化二内酰胺类中的一种。
4.根据权利要求1所述中空吹塑尼龙微发泡材料，其特征在于：所述聚烃类接枝共聚物包括聚烯烃类接枝共聚物和聚芳烃类接枝共聚物。
5.根据权利要求4所述中空吹塑尼龙微发泡材料，其特征在于： 所述聚烯烃类接枝共聚物包括甲基丙烯酸缩水甘油醚接枝聚烯烃共聚物、丙烯酸酯接枝聚烯烃共聚物、亚甲基丁二酸接枝聚烯烃共聚物、甲基丙烯酸接枝聚烯烃共聚物，其中聚烯烃包括聚乙烯、聚丙烯、聚丁烯、聚丁二烯、乙烯-丁烯共聚物、乙烯-辛烯共聚物；
所述聚芳烃类包括甲基丙烯酸缩水甘油醚接枝聚芳烃共聚物、丙烯酸酯接枝聚芳烃共聚物，其中聚芳烃包括聚苯乙烯、苯乙烯-乙烯-丁二烯-苯乙烯共聚物等。
6.根据权利要求1所述中空吹塑尼龙微发泡材料，其特征在于：
所述填充剂为玻璃纤维、碳纤维、滑石粉、碳酸钙、晶须、玻璃微珠、硅灰石、云母中的一种；
所述润滑剂为硅酮、聚乙烯蜡、硬脂酸钙、乙撑双硬脂酰胺中的一种；
所述抗氧剂为1010、1098、168、H10、H318中的一种。
7.根据权利要求1所述中空吹塑尼龙微发泡材料，其特征在于：所述发泡剂为有机发泡剂和无机发泡剂按照重量比为1：1-1：9复配而成，有机发泡剂为偶氮类，磺酰肼类中的一种，无机发泡剂为碳酸氢盐、碳酸盐、铵盐中的一种。
8.根据权利要求7所述中空吹塑尼龙微发泡材料，其特征在于：所述发泡剂为偶氮类发泡剂和碳酸氢盐按照重量比3：2复配的混合发泡剂。
9.根据权利要求1所述中空吹塑尼龙微发泡材料，其特征在于：所述发泡助剂包括成核剂、稳泡剂、分散剂以及相容剂；
其中，成核剂为纳米二氧化钛、纳米碳酸钙、纳米蒙脱土中的一种；
稳泡剂为乙烯醋酸乙烯共聚物、有机硅油、甘油单脂肪酸酯、聚乙二醇中的一种；
分散剂为氯化石蜡、氧化聚乙烯、乙撑双脂肪酰胺、硬脂酸、硬脂酸甘油酯中的一种；
相容剂为丙烯酸酯接枝改性聚烯烃，甲基丙烯酸缩水甘油醚接枝改性聚芳烃、聚丙烯酸脂中的一种。
10.根据权利要求1-9任一项所述的中空吹塑尼龙微发泡材料的制备方法，其特征在于：包括以下步骤：
步骤一：将尼龙50-90份，聚酯5-25份，填充剂0-30份，聚烃类接枝共聚物1-15份，枝化剂0.5-5份，润滑剂0.2-1份，抗氧剂0.3-1份放入混合机中混合1-3min，通过料斗加入到双螺杆挤出机中，在240-300℃温度下造粒，螺杆转速400-800r/min，得到适用于吹塑微发泡的尼龙复合材料；
步骤二：将发泡剂0.5-10份预先在高混机中进行充分混合，然后由侧喂料口加入单螺杆吹塑机中；同时，将步骤一获得的尼龙复合材料、发泡助剂5-15份加入到单螺杆吹塑机料筒；在230-280℃温度下，进行吹塑，获得中空微发泡尼龙产品；其中，单螺杆吹塑机的螺杆长径比为18：1-50:1，压缩比为3:1-5:1。
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CN110256840A (zh) * 2019-05-14 2019-09-20 广东星联科技有限公司 一种发泡尼龙板材的制备方法
CN110256840B (zh) * 2019-05-14 2022-04-19 广东星联科技有限公司 一种发泡尼龙板材的制备方法
CN110684282A (zh) * 2019-10-30 2020-01-14 南京聚隆科技股份有限公司 一种3d中空吹塑微发泡聚烯烃材料及其制备方法

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