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CN110343336B - 一种高表面质量聚丙烯微发泡复合材料及其制备方法 - Google Patents

一种高表面质量聚丙烯微发泡复合材料及其制备方法 Download PDF

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CN110343336B
CN110343336B CN201910459216.7A CN201910459216A CN110343336B CN 110343336 B CN110343336 B CN 110343336B CN 201910459216 A CN201910459216 A CN 201910459216A CN 110343336 B CN110343336 B CN 110343336B
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polypropylene
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antioxidant
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李胜男
蒋团辉
曾祥补
沈超
朱能贵
王醴均
何力
龚维
张纯
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Kangmingyuan Guizhou Technology Development Co ltd
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Abstract

本发明一种高表面质量聚丙烯微发泡复合材料，按重量份计，包括以下组分：共聚聚丙烯树脂10～60份，均聚聚丙烯树脂10～50份，增韧剂0～30份，填料0～30份，气体吸附剂0.01～10份，气体阻隔剂0.01～10份，发泡剂0.05～5份，成核剂0～4份，其通过气体吸附剂和气体阻隔剂来调控气体在聚合物熔体内的溶解、扩散、迁移，从而减少气体向聚合物表面的迁移和扩散，在保证复合材料物理性能和内部发泡量的同时，解决了聚丙烯发泡制品表面气穴、银纹等表面缺陷问题，进而使得制品表面质量大幅提升，同时，本发明还提供一种专用的制备方法，用以将上述组分制备成具有高表面质量的聚丙烯微发泡制件。

Description

一种高表面质量聚丙烯微发泡复合材料及其制备方法
技术领域
本发明涉及聚丙烯微发泡技术领域，具体涉及一种高表面质量聚丙烯微发泡复合材料及其制备方法。
背景技术
聚丙烯发泡材料以丙烯为主要原料，采用物理发泡技术制成发泡珠粒，主要用来进行模具发泡成型为各种各样的形状和尺寸，以供在不同场合使用；聚丙烯发泡材料具有质量轻、绿色环保、尺寸稳定性好、隔热隔音、力学性能优异等特点，因此被广泛应用于汽车、航空航天、家电及包装等领域。
目前，现有的聚丙烯发泡材料在充模过程中气体易迁移和扩散到聚合物表面，使聚丙烯发泡材料的发泡质量及制品表面质量不好，经常出现气穴和银纹等表面缺陷，从而限制了聚丙烯发泡材料的拓展应用。
发明内容
针对上述现有的聚丙烯发泡材料在充模过程中气体易迁移和扩散到聚合物表面，使聚丙烯发泡材料的发泡质量及制品表面质量不好，经常出现气穴和银纹等表面缺陷，从而限制了聚丙烯发泡材料的拓展应用的问题，本发明提供一种高表面质量聚丙烯微发泡复合材料及其制备方法
本发明采用的技术方案如下：
一种高表面质量聚丙烯微发泡复合材料，按重量份计，包括以下组分：
共聚聚丙烯树脂10～60份，均聚聚丙烯树脂10～50份，增韧剂0～30份，填料0～30份，气体吸附剂0.01～10份，气体阻隔剂0.01～10份，发泡剂0.05～5份，成核剂0～4份。
进一步的，按重量份计，还包括主抗氧剂0.01～3份，辅助抗氧剂0.01～3份；所述主抗氧剂和辅助抗氧剂均为抗氧剂1010、抗氧剂168、抗氧剂1076、抗氧剂TPL、抗氧剂DSTP中的任一种或多种。
进一步的，按重量份计，还包括耐擦刮剂0.1～4份；所述耐擦刮剂为芥酸酰胺、聚硅氧烷、油酸或硬脂酸中的任一种或多种。
进一步的，按重量份计，还包括光稳定剂0.1～3份；所述光稳定剂为光稳定剂622、光稳定剂1084、光稳定剂770、光稳定剂901或光稳定剂GW-540中的任一种或多种。
进一步的，所述共聚聚丙烯树脂，在温度230℃、压重2.16Kg的测试条件下，熔融指数为1～150g/10min；所述均聚聚丙烯树脂，在温度230℃、压重2.16Kg的测试条件下，熔融指数为0.5～70g/10min。
进一步的，所述增韧剂为橡胶和热塑性弹性体中的一种或两种。
进一步的，所述气体吸附剂为硅油、聚乙酸乙烯酯、密胺基微孔有机聚合物中的任一种或多种。
进一步的，所述气体阻隔剂为乙烯-乙烯醇共聚物、纳米水滑石、聚对苯二甲酸类塑料、聚偏二氯乙烯、尼龙中的任一种或多种。
进一步的，所述发泡剂为偶氮化合物、亚硝基化合物、磺酰肼类化合物、碳酸盐、碳酸氢盐、亚硝酸盐、柠檬酸或氢化物中的任一种或多种；所述发泡剂的剂型通常选用颗粒剂。
进一步的，所述成核剂为蒙脱土、二氧化硅、山梨醇类、有机磷酸盐、苯甲酸钠或松香类成核剂中的任一种或多种。
进一步的，所述填料为滑石粉、碳酸钙、纤维、白炭黑、硅灰石粉或磷石膏中的任一种或多种。
基于上述聚丙烯微发泡复合材料配方，本技术方案还提供一种用于制备所述高表面质量聚丙烯微发泡复合材料的方法。
该制备方法具体包括以下步骤：
(1)按配方比例称取各原料组分，并将称好的除发泡剂外的其余原料组分混合均匀，得混合料；
(2)将混合料在挤出温度为160～210℃的条件下，挤出造粒，得改性聚丙烯复合材料；
(3)按重量份计，将95～99.95份改性聚丙烯复合材料与0.05～5份发泡剂混合均匀(两者合计重量份数为100份)，得发泡混合料；
(4)将发泡混合料在注塑温度为170～210℃的条件下，注塑成型，得聚丙烯微发泡复合材料。
综上所述，本发明相较于现有技术的有益效果是：
(1)本发明中，通过气体吸附剂和气体阻隔剂来调控气体在聚合物熔体内的溶解、扩散、迁移；其中，气体吸附剂可增加气体在聚合物中的溶解度和扩散系数，并减缓气体的解吸速度，从而使聚合物保留较高的气体含量，同时，气体阻隔剂可在聚合物基体中产生迷宫，使气体透过基体的路径更加曲折，从而一定程度上阻碍气体分子通过的进程；两者之间的协同作用，可减少气体向聚合物表面的迁移和扩散，在保证复合材料内部发泡量的同时，解决了聚丙烯发泡制品的表面气穴、银纹等表面缺陷问题，进而使得制品表面质量大幅提升；
(2)本发明中，所提供的复合材料配方体系，在保证获得较现有技术更优的表面质量的同时，仍然能够保证良好的物理性能，能够满足实际应用需求；
(3)本发明中，微发泡复合材料中还可以通过增加抗氧剂、耐擦刮剂、光稳定剂来提高所得复合材料的综合耐受性能；而上述添加，在本体系下，对所得制品表面质量不造成影响，从而在保证复合材料表面质量的同时，进一步提高了复合材料的性能品质，扩大了其可应用范围，延长了其使用寿命；
(4)本发明中，针对所述聚丙烯微发泡复合材料配方所提供的制备方法，选用了适应各组分功能发挥的工艺参数条件，从而进一步提升了所制得复合材料的成型表面质量。
附图说明
图1为对比例样品与实施例2样品的表面对比图；
图2为对比例样品与实施例2样品的断面对比图。
其中，图1和图2中，示意对比例样品的图片均在左，示意实施例2样品的图片均在右；所有图片均为放大图像，放大倍数均为15倍；所有图片的比例尺均为1000:1。
具体实施方式
为了使本领域的技术人员更好地理解本发明的技术方案，下面结合具体的实施例对本发明作进一步的详细说明。同时，本发明所示的实施例仅在于举例说明，不对本发明的范围作出界定。
首先需要说明的是，在实施例和对比例的复合材料配方中，所用共聚聚丙烯由燕山石化提供，商品牌号为K7100。均聚聚丙烯由扬子石化提供，商品牌号为F401。增韧剂POE由韩国SK化学提供，商品牌号为Solumer8730。无机填料选取粒径为1250目的滑石粉，由旭丰粉体提供。气体吸附剂选取聚乙酸乙烯酯。气体阻隔剂选取乙烯-乙烯醇共聚物。成核剂为山梨醇类成核剂。主抗氧剂1010、辅助抗氧剂168和光稳定剂622由BASF提供。耐刮擦剂选取芥酸酰胺。应当理解的是，各组分对应的所选品牌及型号并不限于上述，其它的具有等同或相似性质的材料亦可成为所示实施例中的各组分的用料选择。
实施例1
将共聚聚丙烯树脂45.3份，均聚聚丙烯树脂20份，增韧剂12份，填料20份，气体吸附剂0.1份，气体阻隔剂0.1份，成核剂0.05份，主抗氧剂1010 0.7份，辅助抗氧剂168 0.7份，耐刮擦剂0.55份，光稳定剂0.5份投入高速混合机中混合3-5min，待混合均匀后，将混合物加入到双螺杆挤出机中熔融共混，挤出造粒。挤出机料筒温度设置为160-210℃。
将制得的改性聚丙烯复合材料96份与4份化学发泡剂母粒混合均匀后加入到注塑机中，采用注塑成型工艺，得到聚丙烯微发泡复合材料，注塑机注塑温度设置为170-210℃。所得聚丙烯微发泡复合材料性能测试结果对比如下表1。
实施例2
将共聚聚丙烯树脂45份，均聚聚丙烯树脂20份，增韧剂12份，填料20份，气体吸附剂0.2份，气体阻隔剂0.3份，成核剂0.05份，主抗氧剂1010 0.7份，辅助抗氧剂168 0.7份，耐刮擦剂0.55份，光稳定剂0.5份投入高速混合机中混合3-5min，待混合均匀后，将混合物加入到双螺杆挤出机中熔融共混，挤出造粒。挤出机料筒温度设置为160-210℃。
将制得的改性聚丙烯复合材料96份与4份化学发泡剂母粒混合均匀后加入到注塑机中，采用注塑成型工艺，得到聚丙烯微发泡复合材料。注塑机注塑温度设置为170-210℃。所得聚丙烯微发泡复合材料性能测试结果对比如下表1。
实施例3
将共聚聚丙烯树脂44.5份，均聚聚丙烯树脂20份，增韧剂12份，填料20份，气体吸附剂0.4份，气体阻隔剂0.6份，成核剂0.05份，主抗氧剂1010 0.7份，辅助抗氧剂168 0.7份，耐刮擦剂0.55份，光稳定剂0.5份投入高速混合机中混合3-5min，待混合均匀后，将混合物加入到双螺杆挤出机中熔融共混，挤出造粒。挤出机料筒温度设置为160-210℃。
将制得的改性聚丙烯复合材料96份与4份化学发泡剂母粒混合均匀后加入到注塑机中，采用注塑成型工艺，得到聚丙烯微发泡复合材料，注塑机注塑温度设置为170-210℃。所得聚丙烯微发泡复合材料性能测试结果对比如下表1。
实施例4
将共聚聚丙烯树脂44份，均聚聚丙烯树脂20份，增韧剂12份，填料20份，气体吸附剂0.5份，气体阻隔剂1份，成核剂0.05份，主抗氧剂1010 0.7份，辅助抗氧剂168 0.7份，耐刮擦剂0.55份，光稳定剂0.5份投入高速混合机中混合3-5min，待混合均匀后，将混合物加入到双螺杆挤出机中熔融共混，挤出造粒。挤出机料筒温度设置为160-210℃。
将制得的改性聚丙烯复合材料96份与4份化学发泡剂母粒混合均匀后加入到注塑机中，采用注塑成型工艺，得到聚丙烯微发泡复合材料，注塑机注塑温度设置为170-210℃。所得聚丙烯微发泡复合材料性能测试结果对比如下表1。
实施例5
将共聚聚丙烯树脂43.5份，均聚聚丙烯树脂20份，增韧剂12份，填料20份，气体吸附剂0.8份，气体阻隔剂1.2份，成核剂0.05份，主抗氧剂1010 0.7份，辅助抗氧剂168 0.7份，耐刮擦剂0.55份，光稳定剂0.5份投入高速混合机中混合3-5min，待混合均匀后，将混合物加入到双螺杆挤出机中熔融共混，挤出造粒。挤出机料筒温度设置为160-210℃。
将制得的改性聚丙烯复合材料96份与4份化学发泡剂母粒混合均匀后加入到注塑机中，采用注塑成型工艺，得到聚丙烯微发泡复合材料，注塑机注塑温度设置为170-210℃。所得聚丙烯微发泡复合材料性能测试结果对比如下表1。
对比例
将共聚聚丙烯树脂45.5份，均聚聚丙烯树脂20份，增韧剂12份，填料20份，成核剂0.05份，抗氧剂1010 0.7份，抗氧剂168 0.7份，耐刮擦剂0.55份，光稳定剂0.5份投入高速混合机中混合3-5min，待混合均匀后，将混合物加入到双螺杆挤出机中熔融共混，挤出造粒。挤出机料筒温度设置为160-210℃。
将制得的改性聚丙烯复合材料96份与4份化学发泡剂母粒混合均匀后加入到注塑机中，采用注塑成型工艺，得到聚丙烯微发泡复合材料，注塑机注塑温度设置为170-210℃。所得聚丙烯微发泡复合材料性能测试结果对比如下表1。
实施例1-5和对比例所得产品各项物理性能的测试结果列于表1中。
表1实施例1～5与对比例制得的聚丙烯微发泡复合材料性能测试结果
Figure GDA0003068532020000051
将实施例1～5和对比例进行比较可知，加入气体吸附剂和气体阻隔剂后，聚丙烯微发泡复合材料的拉伸强度和弯曲强度变化不大，而缺口冲击韧性有所提高。泡孔与表面质量随着气体吸附剂和气体阻隔剂的加入，表面气痕、银纹等缺陷越来越少(见图1)，泡孔越来越均匀致密(见图2)。进而说明气体吸附剂和气体阻隔剂的加入可调控气体在聚合物熔体内的溶解、扩散和迁移，减少迁移和扩散到聚合物表面的气体，从而达到改善发泡制品表面质量的目的。此外，从图2中还可以看出，相较于对比例，实施例中所得聚丙烯微发泡复合材料，其内泡孔更加均匀，且泡孔数量增多，因此，在本技术方案的配方体系下，还能够进一步提高复合材料的发泡均匀程度(缺口冲击韧性提高的原因)和发泡率(进一步提高复合材料的轻质化以及其他发泡相关性能)。
以上所述实施例仅表达了本申请的具体实施方式，其描述较为具体和详细，但并不能因此而理解为对本申请保护范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请技术方案构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。

Claims (5)

1.一种高表面质量聚丙烯微发泡复合材料，其特征在于，按重量份计，包括以下组分：
共聚聚丙烯树脂43.5～60份，均聚聚丙烯树脂20～50份，增韧剂12～30份，填料20～30份，聚乙酸乙烯酯0.1～10份，乙烯-乙烯醇共聚物0.1～10份，发泡剂4～5份，成核剂0.05～4份，主抗氧剂0.7～3份，辅助抗氧剂0.7～3份、耐擦刮剂0.1～0.55份、光稳定剂0.5～3份，所述主抗氧剂和辅助抗氧剂均为抗氧剂1010、抗氧剂168、抗氧剂1076、抗氧剂TPL、抗氧剂DSTP中的任一种或多种，所述耐擦刮剂为芥酸酰胺、聚硅氧烷、油酸或硬脂酸中的任一种或多种，所述光稳定剂为光稳定剂622、光稳定剂1084、光稳定剂770、光稳定剂901或光稳定剂GW-540中的任一种或多种。
2.根据权利要求1所述的一种高表面质量聚丙烯微发泡复合材料，其特征在于：所述共聚聚丙烯树脂，在温度230℃、压重2.16Kg的测试条件下，熔融指数为1～150g/10min；所述均聚聚丙烯树脂，在温度230℃、压重2.16Kg的测试条件下，熔融指数为0.5～70g/10min。
3.根据权利要求1所述的一种高表面质量聚丙烯微发泡复合材料，其特征在于：所述发泡剂为偶氮化合物、亚硝基化合物、磺酰肼类化合物、碳酸盐、碳酸氢盐、亚硝酸盐、柠檬酸或氢化物中的任一种或多种。
4.根据权利要求1所述的一种高表面质量聚丙烯微发泡复合材料，其特征在于：所述成核剂为蒙脱土、二氧化硅、山梨醇类、有机磷酸盐、苯甲酸钠或松香类成核剂中的任一种或多种。
5.一种用于制备如权利要求1～4任一项所述高表面质量聚丙烯微发泡复合材料的方法，其特征在于，包括以下步骤：
（1）按配方比例称取各原料组分，并将称好的除发泡剂外的其余原料组分混合均匀，得混合料；
（2）将混合料在挤出温度为160～210℃的条件下，挤出造粒，得改性聚丙烯复合材料；
（3）按重量份计，将95～96份改性聚丙烯复合材料与4～5份发泡剂混合均匀，得发泡混合料；
（4）将发泡混合料在注塑温度为170～210℃的条件下，注塑成型，得聚丙烯微发泡复合材料。
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