CN106003973B - 一种纳米粒子改性聚丙烯复合片材的制备方法 - Google Patents

一种纳米粒子改性聚丙烯复合片材的制备方法 Download PDF

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CN106003973B
CN106003973B CN201610365941.4A CN201610365941A CN106003973B CN 106003973 B CN106003973 B CN 106003973B CN 201610365941 A CN201610365941 A CN 201610365941A CN 106003973 B CN106003973 B CN 106003973B
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李明华
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Jin Baoli Technology (suzhou) Co Ltd
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Abstract

本发明公开了一种纳米粒子改性聚丙烯复合片材的制备方法,步骤如下：改性组合物加入第一挤出机中，于90℃‑100℃挤出得到改性薄膜；聚丙烯组合物加入第二挤出机中，于220℃‑240℃挤出得到聚丙烯发泡片材；复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；改性组合物由氰基丙烯酸乙酯、苯甲酸苯酯、十二烷基磺酸钠、纳米多孔氧化镍以及磷酸三丁酯组成；所述聚丙烯组合物由均聚聚丙烯、烷基葡萄糖酰胺、表面偶联三乙胺的纳米二氧化硅、发泡剂组成。本发明采用简单挤出机熔炼组合物，挤出得到本体以及改性体材料，再利用多层复合制造方法，制备出复合塑料片材，操作简便，所生产的复合片材，具有耐热、力学好等特点。

Description

一种纳米粒子改性聚丙烯复合片材的制备方法
技术领域
本发明涉及复合材料制造方法，特别是涉及一种纳米粒子改性聚丙烯复合片材的制备方法,可以得到性能优异的聚丙烯片材。
背景技术
聚丙烯具有机械性能好、无毒、相对密度低、耐化学药品、容易加工成型等优点，还具有透明性、光泽度，能广泛地应用于医用注射器、食品容器、微波炉炊具等场合。聚丙烯抗冲击强度差，低温脆性尤为突出，现有采用三元乙丙橡胶（EPDM）和乙烯-辛烯共聚物（POE）改性，提高聚丙烯的抗缺口冲击强度，但改性材料的拉伸强度损失较大。由于聚丙烯熔融时粘度急剧下降，熔体强度很低，导致发泡成型非常困难，可以采用交联工艺来提高体系的熔融粘度，制备发泡聚丙烯，但由于聚丙烯易降解，在交联过程中降解和交联会同时发生，这对发泡材料的最终耐热性和力学性能等都会产生影响。
发明内容
本发明的目的是提供一种纳米粒子改性聚丙烯复合片材的制备方法，可以得到耐热性良好、力学性优异的聚丙烯片材，并且成本不高。
本发明的目的所采用技术方案是，一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：改性组合物加入第一挤出机中，于90℃-100℃挤出得到改性薄膜；聚丙烯组合物加入第二挤出机中，于220℃-240℃挤出得到聚丙烯发泡片材；复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；改性组合物由氰基丙烯酸乙酯、苯甲酸苯酯、十二烷基磺酸钠、纳米多孔氧化镍以及磷酸三丁酯组成；所述聚丙烯组合物由均聚聚丙烯、烷基葡萄糖酰胺、表面偶联三乙胺的纳米二氧化硅、发泡剂组成。
本发明中，氰基丙烯酸乙酯、苯甲酸苯酯、十二烷基磺酸钠、纳米多孔氧化镍以及磷酸三丁酯的质量比为1∶（0.8～0.9）∶（0.01～0.02）∶（0.08～0.12）∶（0.3～0.35）。
本发明中，均聚聚丙烯、烷基葡萄糖酰胺、表面偶联三乙胺的纳米二氧化硅、发泡剂的质量比为1∶（0.3～0.4）∶（0.11～0.12）∶（0.28～0.32）。
本发明中，纳米多孔氧化镍是将氧化镍和硝酸钇混合后，机械压片法制备生坯，生坯经烧结、急冷、粉碎后得到。硝酸钇能够增加氧化镍陶瓷的致密性，一般用量为氧化镍的2%，可以提高纳米多孔氧化镍的表面活性，粉碎后过筛可以挑选复合粒径要求的纳米多孔氧化镍，一般100～200纳米较好，可以分散均匀，提高塑料性能。
本发明中，发泡剂为AC发泡剂。
本发明中，挤出机为双螺杆挤出机，可以最大程度的使用现有普通设备，而制备出综合性能良好的产品。
对于组合物体系，特别是有机无机组合物体系，尤其是用于发生聚合反应的有机无机组合物体系，各组分的质量分配很重要，其关系到各组分的相容性以及直接的反应性。本发明公开的组分之间配比合理，得到的产品能够发挥良好的综合性能。
本发明的优点：
（1）本发明在聚丙烯中加入表面偶联三乙胺的纳米二氧化硅，通过其表面的有机胺化合物可以与其他有机组分发生反应，从而减少有机无机界面缺陷；通过在改性组分加入多孔纳米氧化镍，进一步通过纳米粒子改善塑料的力学性能以及耐热性；
（2）本发明通过常规制备方法，利用相容性好、性能互补的各化合物的相互配合，增加聚合物的交联密度，提高最终性能；尤其是利用改性组分增加了聚丙烯本体的表面活性，为聚丙烯的丰富应用打下良好基础。
（3）本发明是采用简单挤出机熔炼组合物，挤出得到本体以及改性体材料，再利用多层复合制造方法，制备出复合塑料片材，操作简便，所生产的复合片材，具有耐热、力学好等特点。
具体实施方式
下面结合实施例进一步说明本发明。
将氧化镍和硝酸钇(2%)混合后，机械压片法制备生坯，生坯经850～950℃烧结、急冷、粉碎后得到100～200纳米的纳米多孔氧化镍。
实施例一
一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：1Kg氰基丙烯酸乙酯、800g苯甲酸苯酯、10g十二烷基磺酸钠、80g纳米多孔氧化镍以及300g磷酸三丁酯加入第一挤出机中，于90℃挤出得到改性薄膜；5Kg均聚聚丙烯、1.5Kg烷基葡萄糖酰胺、550g表面偶联三乙胺的纳米二氧化硅、1.5KgAC发泡剂加入第二挤出机中，于220℃挤出得到聚丙烯发泡片材；热压复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；热变形温度为158℃，拉伸强度38.8Mpa，弯曲强度52.6MPa。
实施例二
一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：1Kg氰基丙烯酸乙酯、800g苯甲酸苯酯、10g十二烷基磺酸钠、80g纳米多孔氧化镍以及300g磷酸三丁酯加入第一挤出机中，于90℃挤出得到改性薄膜；5Kg均聚聚丙烯、1.5Kg烷基葡萄糖酰胺、550g表面偶联三乙胺的纳米二氧化硅、1.5KgAC发泡剂加入第二挤出机中，于240℃挤出得到聚丙烯发泡片材；热压复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；热变形温度为154℃，拉伸强度38.1Mpa，弯曲强度52.1MPa。
实施例三
一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：1Kg氰基丙烯酸乙酯、800g苯甲酸苯酯、10g十二烷基磺酸钠、80g纳米多孔氧化镍以及300g磷酸三丁酯加入第一挤出机中，于100℃挤出得到改性薄膜；5Kg均聚聚丙烯、1.5Kg烷基葡萄糖酰胺、550g表面偶联三乙胺的纳米二氧化硅、1.5KgAC发泡剂加入第二挤出机中，于220℃挤出得到聚丙烯发泡片材；热压复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；热变形温度为155℃，拉伸强度38.1Mpa，弯曲强度52.4MPa。
实施例四
一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：1Kg氰基丙烯酸乙酯、800g苯甲酸苯酯、10g十二烷基磺酸钠、80g纳米多孔氧化镍以及300g磷酸三丁酯加入第一挤出机中，于100℃挤出得到改性薄膜；5Kg均聚聚丙烯、1.5Kg烷基葡萄糖酰胺、550g表面偶联三乙胺的纳米二氧化硅、1.5KgAC发泡剂加入第二挤出机中，于240℃挤出得到聚丙烯发泡片材；热压复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；热变形温度为154℃，拉伸强度38.9Mpa，弯曲强度52.3MPa。
实施例五
一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：1Kg氰基丙烯酸乙酯、900g苯甲酸苯酯、20g十二烷基磺酸钠、120g纳米多孔氧化镍以及350g磷酸三丁酯加入第一挤出机中，于90℃挤出得到改性薄膜；5Kg均聚聚丙烯、2Kg烷基葡萄糖酰胺、600g表面偶联三乙胺的纳米二氧化硅、1.6KgAC发泡剂加入第二挤出机中，于220℃挤出得到聚丙烯发泡片材；热压复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；热变形温度为153℃，拉伸强度38.4Mpa，弯曲强度52.2MPa。
实施例六
一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：1Kg氰基丙烯酸乙酯、900g苯甲酸苯酯、20g十二烷基磺酸钠、120g纳米多孔氧化镍以及350g磷酸三丁酯加入第一挤出机中，于90℃挤出得到改性薄膜；5Kg均聚聚丙烯、2Kg烷基葡萄糖酰胺、600g表面偶联三乙胺的纳米二氧化硅、1.6KgAC发泡剂加入第二挤出机中，于240℃挤出得到聚丙烯发泡片材；热压复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；热变形温度为156℃，拉伸强度38.9Mpa，弯曲强度51.9MPa。
实施例七
一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：1Kg氰基丙烯酸乙酯、900g苯甲酸苯酯、20g十二烷基磺酸钠、120g纳米多孔氧化镍以及350g磷酸三丁酯加入第一挤出机中，于100℃挤出得到改性薄膜；5Kg均聚聚丙烯、2Kg烷基葡萄糖酰胺、600g表面偶联三乙胺的纳米二氧化硅、1.6KgAC发泡剂加入第二挤出机中，于220℃挤出得到聚丙烯发泡片材；热压复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；热变形温度为155℃，拉伸强度37.9Mpa，弯曲强度52.1MPa。
实施例八
一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：1Kg氰基丙烯酸乙酯、900g苯甲酸苯酯、20g十二烷基磺酸钠、120g纳米多孔氧化镍以及350g磷酸三丁酯加入第一挤出机中，于100℃挤出得到改性薄膜；5Kg均聚聚丙烯、2Kg烷基葡萄糖酰胺、600g表面偶联三乙胺的纳米二氧化硅、1.6KgAC发泡剂加入第二挤出机中，于240℃挤出得到聚丙烯发泡片材；热压复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；热变形温度为153℃，拉伸强度38.1Mpa，弯曲强度52.1MPa。
实施例九
一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：1Kg氰基丙烯酸乙酯、900g苯甲酸苯酯、20g十二烷基磺酸钠、120g纳米多孔氧化镍以及350g磷酸三丁酯加入第一挤出机中，于100℃挤出得到改性薄膜；5Kg均聚聚丙烯、1.5Kg烷基葡萄糖酰胺、550g表面偶联三乙胺的纳米二氧化硅、1.5KgAC发泡剂加入第二挤出机中，于220℃挤出得到聚丙烯发泡片材；热压复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；热变形温度为155℃，拉伸强度38.4Mpa，弯曲强度52.7MPa。
实施例十
一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：1Kg氰基丙烯酸乙酯、800g苯甲酸苯酯、10g十二烷基磺酸钠、80g纳米多孔氧化镍以及300g磷酸三丁酯加入第一挤出机中，于90℃挤出得到改性薄膜；5Kg均聚聚丙烯、2Kg烷基葡萄糖酰胺、600g表面偶联三乙胺的纳米二氧化硅、1.6KgAC发泡剂加入第二挤出机中，于240℃挤出得到聚丙烯发泡片材；热压复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；热变形温度为154℃，拉伸强度38.9Mpa，弯曲强度52.4MPa。
实施例十一
一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：1Kg氰基丙烯酸乙酯、850g苯甲酸苯酯、15g十二烷基磺酸钠、100g纳米多孔氧化镍以及320g磷酸三丁酯加入第一挤出机中，于90℃挤出得到改性薄膜；5Kg均聚聚丙烯、1.8Kg烷基葡萄糖酰胺、580g表面偶联三乙胺的纳米二氧化硅、1.6KgAC发泡剂加入第二挤出机中，于240℃挤出得到聚丙烯发泡片材；热压复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；热变形温度为159℃，拉伸强度39.4Mpa，弯曲强度52.8MPa。
实施例十二
一种纳米粒子改性聚丙烯复合片材的制备方法，步骤如下：1Kg氰基丙烯酸乙酯、850g苯甲酸苯酯、15g十二烷基磺酸钠、100g纳米多孔氧化镍以及320g磷酸三丁酯加入第一挤出机中，于100℃挤出得到改性薄膜；5Kg均聚聚丙烯、1.8Kg烷基葡萄糖酰胺、580g表面偶联三乙胺的纳米二氧化硅、1.6KgAC发泡剂加入第二挤出机中，于220℃挤出得到聚丙烯发泡片材；热压复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；热变形温度为161℃，拉伸强度39.8Mpa，弯曲强度52.9MPa。

Claims (1)

1.一种纳米粒子改性聚丙烯复合片材的制备方法，其特征是，步骤如下：改性组合物加入第一挤出机中，于90℃-100℃挤出得到改性薄膜；聚丙烯组合物加入第二挤出机中，于220℃-240℃挤出得到聚丙烯发泡片材；复合改性薄膜与聚丙烯发泡片材，得到纳米粒子改性聚丙烯复合片材；改性组合物由氰基丙烯酸乙酯、苯甲酸苯酯、十二烷基磺酸钠、纳米多孔氧化镍以及磷酸三丁酯组成；所述聚丙烯组合物由均聚聚丙烯、烷基葡萄糖酰胺、表面偶联三乙胺的纳米二氧化硅、发泡剂组成；
氰基丙烯酸乙酯、苯甲酸苯酯、十二烷基磺酸钠、纳米多孔氧化镍以及磷酸三丁酯的质量比为1∶（0 .8～0 .9）∶（0 .01～0 .02）∶（0 .08～0 .12）∶（0 .3～0 .35）；
均聚聚丙烯、烷基葡萄糖酰胺、表面偶联三乙胺的纳米二氧化硅、发泡剂的质量比为1∶（0 .3～0 .4）∶（0 .11～0 .12）∶（0 .28～0 .32）；
纳米多孔氧化镍是将氧化镍和硝酸钇混合后，机械压片法制备生坯，生坯经烧结、急冷、粉碎后得到；
发泡剂为AC发泡剂；
挤出机为双螺杆挤出机。
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