CN109988362B - 一种微发泡聚丙烯材料及其制备方法 - Google Patents
一种微发泡聚丙烯材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及高分子领域，尤其涉及一种微发泡聚丙烯材料及其制备方法。本发明提供一种具备低密度，高发泡倍率，泡孔孔径均匀且主要集中在材料内部，表面无留痕具有优异外观的微发泡聚丙烯材料及该种微发泡聚丙烯材料的制备方法。通过基体颗粒与复合发泡剂制备粒径分布D50值在1‑10微米的发泡剂复合粉，使发泡剂均匀负载于基体颗粒上，将发泡剂复合粉与聚丙烯树脂混合挤出造粒、注塑制备得到微发泡聚丙烯材料。与传统微发泡方式相比，本发明成本更低，对特种设备的要求更少，且可最大可能的保留纯聚丙烯本身的优良特性。
Description
技术领域
本发明涉及高分子领域，尤其涉及一种微发泡聚丙烯材料及其制备方法。
背景技术
和普通塑料相比，发泡树脂因为其密度低，良好的聚热性能，高热稳定性，良好的力学性能，如冲击强度、韧性、耐疲劳等优点，在包装材料，汽车零配件，吸附剂，力学支撑装备等地方有着诸多应用。在其中，聚丙烯，由于其成本低，高熔点，高拉伸模量，低密度，良好的化学稳定性，被广泛的应用到发泡树脂行业。根据发泡孔径尺寸的区别，发泡聚丙烯可分为普通发泡PP和微发泡PP。普通发泡聚丙烯通常泡孔肉眼可见，泡孔直径高于100微米，可用于制备包装材料。当泡孔直径低于100微米时，则称为微发泡聚丙烯，可用于车体的部分注塑配件，有效降低车体的重量。但是，制备微发泡聚丙烯有两大难点，第一大难点是发泡尺寸的控制，因为和聚氨酯、聚苯乙烯等材料相比，聚丙烯的熔体强度较低，使得发泡成型非常困难，易出现泡的融合和破裂等问题而产生不规则分布的大泡，第二大难点是发泡尺寸均一性难以控制，除了受聚丙烯本身熔体强度影响以外，聚丙烯发泡尺寸的均一性控制较难主要有2个原因，原因一为聚丙烯本身是一种半结晶高分子，在形成球晶的过程中，整个高分子内部物理结构不再均匀，导致成泡均一性出现问题，原因二则为发泡剂、微泡成核剂和聚丙烯树脂的混合不够均匀导致发泡大小有所差异。而发泡剂、微泡成核剂和聚丙烯树脂的混合也存在两个问题，其一是发泡剂本身的团聚，其二是发泡剂、微泡成核剂等无机颗粒与聚丙烯树脂之间的混合。
当前，针对聚丙烯熔点以上发泡成型困难，发泡尺寸分布均一性不好的问题，主要的技术路线是改进聚丙烯的熔体强度，对聚丙烯的极性进行改性，或采用物理超临界发泡法进行制备。为了提高聚丙烯的熔体强度，第一种常见方式为使用高熔体强度聚丙烯HMSPP，如采用新的催化剂或者反应器引入少量长支链聚丙烯，但是通常制备成本很高；第二种方式为何其他高熔体强度的聚烯烃(如聚乙烯)进行共混，但是加入其他聚烯烃会降低聚丙烯本身的耐热性和良好的力学性能等优势；第三种方式为引入一定的交联结构，如通过辐射交联或者化学交联剂对部分聚丙烯进行交联，但是交联度的控制较为困难，且易存在化学残留，制备工艺比较难控制，甚至可能存在一定的爆炸风险。为了改善聚丙烯和无机填料的混合，常见方式为采用马来酸酐对聚丙烯进行修饰以改进其和无机填料间的相容性，但是马来酸酐成本较高，且对于泡孔大小的控制也并不理想。此外，采用物理超临界发泡法进行制备则是利用以超临界流体形式存在的聚合物-气体均相体系，利用迅速改变温度的方式使得气体在聚合物中的溶解度急剧变化而制备微泡，但是超临界流体发法通常需要特种设备，工艺复杂，产品质量控制困难，且成本较高。
基于此，发明一种可用于常见熔体强度聚丙烯树脂，无需采用特殊的超临界流体设备即可实现聚丙烯微发泡，发泡均一性好、发泡剂无团聚、且可有效控制成本的材料工艺变得非常重要。
发明内容
本发明的目的在于提供一种具备低密度，高发泡倍率，泡孔孔径均匀且主要集中在材料内部，表面无留痕具有优异外观的微发泡聚丙烯材料及该种微发泡聚丙烯材料的制备方法。
本发明通过基体颗粒与复合发泡剂制备粒径分布D50值在1-10微米的发泡剂复合粉，使发泡剂均匀负载于基体颗粒上，将发泡剂复合粉与聚丙烯树脂混合挤出造粒、注塑制备得到微发泡聚丙烯材料。制备得到的微发泡聚丙烯表面平整无留痕，内部存在孔径均匀、平均尺寸为50-250微米的微泡以及孔径小于10微米的微小泡共同组成的复合微泡结构，或孔径小于20微米的微小泡的超微泡结构。材料密度为0.8-0.95g/cm3，熔体流动速度为2.5-50g/10min，拉伸强度>8Mpa，断裂伸长率高于500％，悬臂梁缺口冲击强度>5kJ/m2。本发明与传统微发泡聚丙烯的制备工艺相比，通过制备新型复合发泡粉，无需采用特殊的超临界流体设备，用常见熔体强度聚丙烯树脂，即可实现聚丙烯微发泡的孔径大小和均一性的控制，并同时解决了发泡剂团聚的问题。
本发明提供一种微发泡聚丙烯材料，包括50-99.5wt％的聚丙烯树脂和0.5-50wt％的粒径分布D50值在1-10微米的发泡剂复合粉，其中发泡剂复合粉包括以下质量百分含量的组分：基体颗粒10-95％，复合发泡剂5-90％，发泡剂助剂0-10％。
其中，基体颗粒包括但不限于：木粉、硅藻土、粉煤灰、白云石、碳酸钙、硅酸钙、玻璃微珠、二氧化钛钛白粉、海泡石、凹凸棒、沸石、石英、高岭土、二氧化硅、膨润土或珍珠岩中的一种或多种。
复合发泡剂包括50-100wt％的第一相发泡剂和0-50wt％的第二相发泡剂，其中第一相发泡剂为对甲苯磺酰氨基脲、偶氮二甲酰胺、偶氮二甲酸钡或5-苯基四氮唑中的一种或多种，第二相发泡剂为碳酸氢盐、如碳酸氢钠、碳酸氢钙或碳酸氢钙中的一种或多种。
发泡剂助剂为碳酸氢钠，柠檬酸钠，尿素，乳酸，苹果酸中的一种或多种。
本发明提供一种微发泡聚丙烯材料的制备方法，首先制备发泡剂复合粉，将10-95wt％基体颗粒，5-90wt％复合发泡剂，0-10wt％发泡剂助剂混合；再将50-99.5wt％的聚丙烯树脂和质0.5-50wt％的发泡剂复合粉混合并进行挤出造粒得到改性聚丙烯粒料；最后将改性聚丙烯粒料送入注塑机中，在注塑温度为210-250℃的条件下注塑成型，制备得到聚丙烯微发泡材料。
其中原料聚丙烯树脂为熔体流动速度为2-45g/10min的聚丙烯树脂颗粒。
其中造粒是通过双螺杆挤出机进行熔融挤出造粒，挤出温度为140-180℃，得到改性聚丙烯粒料。
其中，基体颗粒包括但不限于：木粉、硅藻土、粉煤灰、白云石、碳酸钙、硅酸钙、玻璃微珠、二氧化钛钛白粉、海泡石、凹凸棒、沸石、石英、高岭土、二氧化硅、膨润土或珍珠岩中的一种或多种。
其中，复合发泡剂包括50-100wt％的第一相发泡剂和0-50wt％的第二相发泡剂，其中第一相发泡剂为对甲苯磺酰氨基脲，偶氮二甲酰胺，偶氮二甲酸钡，5-苯基四氮唑中的一种或多种，第二相发泡剂为碳酸氢盐，如碳酸氢钠，碳酸氢钙，碳酸氢钙中的一种或多种。
其中，发泡剂助剂为碳酸氢钠，柠檬酸钠，尿素，乳酸，苹果酸中的一种或多种。
其中，发泡剂复合粉制备时混合方式使用高速混合搅拌机、振动磨、砂磨机、气流磨、搅拌磨、蜂巢磨、雷蒙磨、环辊磨、万能冲击磨、高速冲击式气流粉碎机、湿法或干法球磨机的一种或多种，制备得到的发泡剂复合粉由复合发泡剂包覆于基体颗粒上，粒径分布D50值在1-10微米。
制备得到的微发泡聚丙烯表面平整无留痕，内部存在孔径均匀、平均尺寸为50-250微米的微泡以及孔径小于10微米的微小泡共同组成的复合微泡结构，示例图如附图1，或孔径小于20微米的微小泡的超微泡结构，示例图如附图2。
通过预先将复合发泡剂负载在基体颗粒上，可以有效避免传统发泡剂粉团聚的问题，并同时能够实现发泡剂在聚丙烯中的有效分散性和发泡尺寸均一性的控制，避免出现由于泡的融合、破裂引起的不规则分布大泡。进一步，材料的孔径可通过调整发泡剂复合粉的成分、组分质量分数、粒径分布等参数进行调整。制得材料的密度为0.8-0.95g/cm3，熔体流动速度为2.5-50g/10min，且有着良好的力学特性，拉伸强度>8Mpa，断裂伸长率高于500％，悬臂梁缺口冲击强度>5kJ/m2。与传统微发泡方式相比，本发明成本更低，对特种设备的要求更少，且可最大可能的保留纯聚丙烯本身的优良特性。
附图说明
附图1是本发明制备得到的复合微泡结构断口扫描电镜图；
附图2是本发明制备得到的超微泡结构断口扫描电镜图；
附图3是对比例的扫描电镜图。
具体实施方式
对比例
将熔体流动速率为38g/min的聚丙烯树脂与纯偶氮二甲酰胺按照质量比10:1在最高温180℃的温度下进行挤出造粒，并在最高温度230℃的温度下进行注塑成型，制得产品密度为0.88g/cm3，部分地方出现孔径在500微米以上的宏观大泡，部分地方无泡，未出现泡孔孔径在10微米以下的超微泡，严重影响材料的力学性能，悬臂梁缺口冲击强度<4kJ/m2，泡孔微观结构如附图3所示。
实施例1
使用高速冲击式气流粉碎机将质量百分比为95％的滑石粉和质量百分比为5％的复合发泡剂复合制得发泡剂复合粉，其中，复合发泡剂选择第一相发泡剂偶氮二甲酰胺、第二相发泡剂碳酸氢钠，所制发泡剂复合粉粒径分布D50值为8.5微米。将熔体流动速率为2.5的聚丙烯树脂与改性发泡剂复合粉按照质量比10:1在最高温180℃的温度下进行挤出造粒，并在最高温度230℃的温度下进行注塑成型，制得产品密度为0.88g/cm3。所制样品表面平整无留痕，内部存在孔径均匀，平均尺寸为150微米的微泡以及孔径小于10微米的微小泡共同组成的复合微泡结构，材料熔体流动速度为2.5-50g/10min，拉伸强度8.1Mpa，断裂伸长率高于500％，悬臂梁缺口冲击强度6kJ/m2。泡孔微观结构如附图1所示，材料的泡孔结构主要在材料内部，在100微米量级上存在气泡孔径均匀分布的平均孔径为150-200微米的微孔结构，并在1微米量级上存在孔径均匀分布，平均孔径为2微米的微小孔。
实施例2
将熔体流动速率为20的聚丙烯树脂与上述实施例1中的发泡剂复合粉按照质量比10:1在最高温180℃的温度下进行挤出造粒，并在最高温度230℃的温度下进行注塑成型，制得产品密度为0.91g/cm3。
实施例3
将熔体流动速率为20的聚丙烯树脂与上述实施例1中的发泡剂复合粉按照质量比10:1在最高温180℃的温度下进行挤出造粒，并在最高温度230℃的温度下进行注塑成型，制得产品密度为0.92g/cm3。
实施例4
将熔体流动速率为38的聚丙烯树脂与上述实施例1中的发泡剂复合粉按照质量比10:1在最高温180℃的温度下进行挤出造粒，并在最高温度230℃的温度下进行注塑成型，制得产品密度为0.94g/cm3。
实施例5
使用高速冲击式气流粉碎机将质量百分比为95％的滑石粉和质量百分比为5％的复合发泡剂复合制得发泡剂复合粉，其中，复合发泡剂选择第一相发泡剂甲苯磺酰氨基脲、第二相发泡剂碳酸氢钠，所制发泡剂复合粉粒径分布D50值为8.5微米。将熔体流动速率为2.5的聚丙烯树脂与发泡剂复合粉按照质量比10:1在最高温180℃的温度下进行挤出造粒，并在最高温度230℃的温度下进行注塑成型，制得产品密度为0.92g/cm3。泡孔微观结构如附图2所示。
实施例6
将熔体流动速率为20的聚丙烯树脂与上述实施例5中的发泡剂复合粉按照质量比10:1在最高温180℃的温度下进行挤出造粒，并在最高温度230℃的温度下进行注塑成型，制得产品密度为0.94g/cm3。
实施例7
使用高速冲击式气流粉碎机将质量百分比为95％的滑石粉和质量百分比为5％的复合发泡剂复合制得发泡剂复合粉，其中，复合发泡剂选择第一相发泡剂偶氮二甲酸钡、第二相发泡剂碳酸氢钠，所制发泡剂复合粉粒径分布D50值为8.5微米。将熔体流动速率为2.5的聚丙烯树脂与发泡剂复合粉按照质量比10:1在最高温180℃的温度下进行挤出造粒，并在最高温度230℃的温度下进行注塑成型，制得产品密度为0.85g/cm3。
实施例8
将熔体流动速率为20的聚丙烯树脂与上述实施例7中的发泡剂复合粉按照质量比10:1在最高温180℃的温度下进行挤出造粒，并在最高温度230℃的温度下进行注塑成型，制得产品密度为0.92g/cm3。
实施例9
使用高速冲击式气流粉碎机将质量百分比为95％的滑石粉和质量百分比为5％的复合发泡剂复合制得发泡剂复合粉，其中，复合发泡剂选择第一相发泡剂为5-苯基四氮唑、第二相发泡剂碳酸氢钠，所制发泡剂复合粉粒径分布D50值为8.5微米。将熔体流动速率为2.5的聚丙烯树脂与发泡剂复合粉按照质量比10:1在最高温180℃的温度下进行挤出造粒，并在最高温度230℃的温度下进行注塑成型，制得产品密度为0.84g/cm3。
实施例10
将熔体流动速率为20的聚丙烯树脂与上述实施例9中的发泡剂复合粉按照质量比10:1在最高温180℃的温度下进行挤出造粒，并在最高温度230℃的温度下进行注塑成型，制得产品密度为0.90g/cm3。
以上所述仅为本发明的较佳实施方式，本发明的保护范围并不以上述实施方式为限，但凡本领域普通技术人员根据本发明所揭示内容所作的等效修饰或变化，皆应纳入权利要求书中记载的保护范围内。
Claims (11)
1.一种微发泡聚丙烯材料，其特征在于：表面平整无留痕，内部存在孔径均匀、平均尺寸为50-250微米的微泡及孔径小于10微米的微小泡共同组成的复合微泡结构，或者孔径均匀、平均尺寸小于20微米的微小泡的超微泡结构；材料密度为0.8-0.95g/cm3，熔体流动速度为2.5-50g/10min，拉伸强度>8MPa ，断裂伸长率高于500％，悬臂梁缺口冲击强度>5kJ/m2；
微发泡聚丙烯材料，包括50-99.5wt％的聚丙烯树脂和0.5-50wt％的粒径分布D50值在1-10微米的发泡剂复合粉，其中发泡剂复合粉包括以下质量百分含量的组分：基体颗粒10-95％，复合发泡剂5-90％，发泡剂助剂0-10％；
基体颗粒为木粉、硅藻土、粉煤灰、白云石、碳酸钙、硅酸钙、玻璃微珠、钛白粉、海泡石、凹凸棒、沸石、石英、高岭土、二氧化硅、膨润土或珍珠岩中的一种或多种。
2.如权利要求1所述的一种微发泡聚丙烯材料，其特征在于：复合发泡剂包括50-100wt％的第一相发泡剂和0-50wt％的第二相发泡剂，其中第一相发泡剂为对甲苯磺酰氨基脲、偶氮二甲酰胺、偶氮二甲酸钡或5-苯基四氮唑中的一种或多种，第二相发泡剂为碳酸氢盐。
3.如权利要求2所述的一种微发泡聚丙烯材料，其特征在于：所述碳酸氢盐为碳酸氢钠或碳酸氢钙中的一种或两种。
4.如权利要求1所述的一种微发泡聚丙烯材料，其特征在于：发泡剂助剂为碳酸氢钠、柠檬酸钠、尿素、乳酸或苹果酸中的一种或多种。
5.如权利要求1所述的一种微发泡聚丙烯材料的制备方法，其特征在于：首先制备发泡剂复合粉，将10-95wt％基体颗粒、5-90wt％复合发泡剂、0-10wt％发泡剂助剂混合；再将50-99.5wt％的聚丙烯树脂和0.5-50wt％的发泡剂复合粉混合并进行挤出造粒得到改性聚丙烯粒料；最后将改性聚丙烯粒料送入注塑机中，在注塑温度为210-250℃的条件下注塑成型，制备得到聚丙烯微发泡材料。
6.如权利要求5所述的一种微发泡聚丙烯材料的制备方法，其特征在于：原料聚丙烯树脂为熔体流动速度为2-45g/10min的聚丙烯树脂颗粒。
7.如权利要求5所述的一种微发泡聚丙烯材料的制备方法，其特征在于：造粒是通过双螺杆挤出机进行熔融挤出造粒，挤出温度为140-180℃，得到改性聚丙烯粒料。
8.如权利要求5所述的一种微发泡聚丙烯材料的制备方法，其特征在于：复合发泡剂包括50-100wt％的第一相发泡剂和0-50wt％的第二相发泡剂，其中第一相发泡剂为对甲苯磺酰氨基脲、偶氮二甲酰胺、偶氮二甲酸钡或5-苯基四氮唑中的一种或多种，第二相发泡剂为碳酸氢盐。
9.如权利要求5所述的一种微发泡聚丙烯材料的制备方法，其特征在于：发泡剂助剂为碳酸氢钠、柠檬酸钠、尿素、乳酸或苹果酸中的一种或多种。
10.如权利要求8所述的一种微发泡聚丙烯材料的制备方法，其特征在于：所述碳酸氢盐为碳酸氢钠或碳酸氢钙中的一种或两种。
11.如权利要求5所述的一种微发泡聚丙烯材料的制备方法，其特征在于：发泡剂复合粉制备时混合方式使用高速混合搅拌机、振动磨、砂磨机、气流磨、搅拌磨、蜂巢磨、雷蒙磨、环辊磨、万能冲击磨、高速冲击式气流粉碎机、湿法或干法球磨机的一种或多种，制备得到的发泡剂复合粉由复合发泡剂包覆于基体颗粒上，粒径分布D50值在1-10微米。
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