CN109971096A - 一种高韧性pvc复合材料膜的制备方法 - Google Patents

一种高韧性pvc复合材料膜的制备方法 Download PDF

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CN109971096A
CN109971096A CN201910280891.3A CN201910280891A CN109971096A CN 109971096 A CN109971096 A CN 109971096A CN 201910280891 A CN201910280891 A CN 201910280891A CN 109971096 A CN109971096 A CN 109971096A
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孙昌梅
董聪聪
曲荣君
张盈
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Abstract

本发明公开了一种高韧性PVC复合材料膜的制备方法，包括制备芳纶纳米纤维ANFs、乙基化改性ANFs和制备PVC复合材料膜等步骤。本发明将芳纶纳米纤维通过烷基化改性后，作为增强材料添加到PVC基体中，线性的芳纶纳米纤维对PVC基体增韧的同时会和PVC大分子相互缠结，增强体系的强度，与纯PVC膜力学性能相比，本发明所得PVC复合材料的杨氏模量、屈服强度和断裂韧性均得到大幅提高，与颗粒状的无机纳米粒子相比，芳纶纳米纤维呈线性，与PVC基体相容性好，不存在界面力学性能下降的情况。

Description

一种高韧性PVC复合材料膜的制备方法
技术领域
本发明涉及复合材料领域，尤其涉及一种高韧性PVC复合材料膜的制备方法。
背景技术
聚氯乙烯(PVC)是一种综合性能优良的通用塑料，其产量和用量仅次于聚乙烯，位居世界树脂产量的第二位。PVC具有良好的耐化学腐蚀性和阻燃性，价格低廉，原料来源广泛，在工业制品、日用品、管材、包装膜等方面均有广泛应用。但PVC也存在一定的缺点，如冲击强度低、热稳定性差、抗蠕变性差以及低温脆性等，这些缺点降低了PVC的使用范围和使用价值。
国内外自20世纪70年代起开始大规模开展PVC增韧改性的研究，采用弹性体共混、纳米粒子填充、纤维增强、弹性体/纳米粒子复合材料增韧等方法对其进行改性，进一步拓宽了其应用领域。目前共混改性PVC是改性与提高PVC冲击强度等性能的常用方法。人们在研究PVC/热塑性聚氨酯弹性体(TPU)共混材料力学性能时发现，TPU可显著提高PVC的韧性和冲击强度。但TPU改性PVC虽然能够显著提高共混体系的韧性，却会使材料的刚度和强度有一定程度的损失。相比之下，刚性粒子尤其是纳米颗粒增韧改性PVC具有一定优势，例如有研究通过基于碾磨的固态剪切复合技术(S3C)制备了PVC/高岭土纳米复合材料。研究发现，无机纳米粒子的加入能同时实现PVC的增强和增韧，但同时也发现了纳米粒子与PVC间界面相容性较差的问题。
发明内容
本发明针对现有PVC增韧改性方法会降低PVC强度以及改性物质与PVC界面相容性差的问题，提供一种高韧性PVC复合材料膜的制备方法。
本发明解决上述技术问题的技术方案如下：一种高韧性PVC复合材料膜的制备方法，其特征在于，包括以下步骤：
1)制备芳纶纳米纤维ANFs：将KOH加入DMSO中，70℃机械搅拌2h后降至室温，加入对位芳纶纤维，室温下保持搅拌反应一周，制得ANFs溶液；
2)乙基化改性ANFs：向步骤1)所得ANFs溶液中加入溴乙烷，30℃下反应17h后过滤，干燥后制得乙基化改性ANFs；
3)制备PVC复合材料膜：将步骤2)所得乙基化改性ANFs溶解到DMSO中，超声1.5h后制得乙基化改性ANFs溶液，将PVC粉末置入DMF中，400r/min搅拌1h后制得PVC溶液，将所得PVC溶液与乙基化改性ANFs溶液混合，70℃下400r/min搅拌15min，再超声震荡15min，制得混合溶液，将混合溶液导入聚四氟乙烯浅平板中，放入真空干燥箱60℃干燥48h，制得PVC复合材料膜。
其中，步骤1)中所述KOH与所述对位芳纶的质量比为(1-1.5):1；所述ANFs溶液的浓度为2-2.5mg/mL。步骤2)中所述ANFs溶液与所述溴乙烷的用量为1L:(1-1.5)mL。步骤3)中，所述混合溶液中乙基化改性ANFs与PVC的重量比为(0.5-1.5):1000。
本发明的有益效果是：本发明将芳纶纳米纤维通过烷基化改性后，作为增强材料添加到PVC基体中，线性的芳纶纳米纤维对PVC基体增韧的同时会和PVC大分子相互缠结，增强体系的强度，与纯PVC膜力学性能相比，本发明所得PVC复合材料的杨氏模量、屈服强度和断裂韧性均得到大幅提高；与颗粒状的无机纳米粒子相比，芳纶纳米纤维呈线性，与PVC基体相容性好，不存在界面力学性能下降的情况。本发明工艺简单，反应条件温和，时间短，易控制，合成效率高。
附图说明
图1为本发明所得乙基化改性ANFs的透射电镜图；图2是本发明所得PVC复合材料膜的透射电镜图。
具体实施方式
以下结合实例对本发明进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1
一种高韧性PVC复合材料膜的制备方法，包括以下步骤：
1)制备芳纶纳米纤维ANFs：将干燥的500mL三口瓶用氮气吹扫5min向其内部加入0.9g KOH和300mLDMSO，70℃机械搅拌2h后降至室温，加入0.6g对位芳纶纤维，室温下保持搅拌反应一周，制得ANFs溶液；
2)乙基化改性ANFs：在氮气保护下，量取步骤1)所得ANFs溶液50mL于三口烧瓶中，加入溴乙烷0.06mL，在30℃下机械搅拌17h后过滤，干燥后制得乙基化改性ANFs；
3)制备PVC复合材料膜：将0.001g步骤2)所得乙基化改性ANFs溶解到5mL DMSO中，超声1.5h后制得乙基化改性ANFs溶液，将2g PVC粉末置入15mL DMF中，400r/min搅拌1h后制得PVC溶液，将所得PVC溶液与乙基化改性ANFs溶液混合，70℃下400r/min搅拌15min，再超声震荡15min，制得混合溶液，将混合溶液导入聚四氟乙烯浅平板中，放入真空干燥箱60℃干燥48h，制得PVC复合材料膜。
实施例2
一种高韧性PVC复合材料膜的制备方法，包括以下步骤：
1)制备芳纶纳米纤维ANFs：将干燥的500mL三口瓶用氮气吹扫5min向其内部加入0.75g KOH和240mL DMSO，70℃机械搅拌2h后降至室温，加入0.6g对位芳纶纤维，室温下保持搅拌反应一周，制得ANFs溶液；
2)乙基化改性ANFs：在氮气保护下，量取步骤1)所得ANFs溶液50mL于三口烧瓶中，加入溴乙烷0.05mL，在30℃下机械搅拌17h后过滤，干燥后制得乙基化改性ANFs；
3)制备PVC复合材料膜：将0.002g步骤2)所得乙基化改性ANFs溶解到5mL DMSO中，超声1.5h后制得乙基化改性ANFs溶液，将2g PVC粉末置入15mL DMF中，400r/min搅拌1h后制得PVC溶液，将所得PVC溶液与乙基化改性ANFs溶液混合，70℃下400r/min搅拌15min，再超声震荡15min，制得混合溶液，将混合溶液导入聚四氟乙烯浅平板中，放入真空干燥箱60℃干燥48h，制得PVC复合材料膜。
实施例3
一种高韧性PVC复合材料膜的制备方法，包括以下步骤：
1)制备芳纶纳米纤维ANFs：将干燥的500mL三口瓶用氮气吹扫5min向其内部加入0.6g KOH和270mL DMSO，70℃机械搅拌2h后降至室温，加入0.6g对位芳纶纤维，室温下保持搅拌反应一周，制得ANFs溶液；
2)乙基化改性ANFs：在氮气保护下，量取步骤1)所得ANFs溶液50mL于三口烧瓶中，加入溴乙烷0.075mL，在30℃下机械搅拌17h后过滤，干燥后制得乙基化改性ANFs；
3)制备PVC复合材料膜：将0.003g步骤2)所得乙基化改性ANFs溶解到5mL DMSO中，超声1.5h后制得乙基化改性ANFs溶液，将2g PVC粉末置入15mL DMF中，400r/min搅拌1h后制得PVC溶液，将所得PVC溶液与乙基化改性ANFs溶液混合，70℃下400r/min搅拌15min，再超声震荡15min，制得混合溶液，将混合溶液导入聚四氟乙烯浅平板中，放入真空干燥箱60℃干燥48h，制得PVC复合材料膜。
将实施例1-3所得PVC复合材料膜和纯PVC膜进行相关力学性能分析，如表1和表2所示，PVC复合材料膜的杨氏模量、拉伸强度及韧性与纯PVC膜相比都得到了很大提高，拉伸强度增率为51.02％，杨氏模量增率为28.29％，其中韧性增强效果最为显著，增率可达到86.40％。
表1.纯PVC膜与实施例1-3所得PVC复合材料膜力学性能对比
表2.实施例1-3所得PVC复合材料膜相较纯PVC膜力学性能增率
图1为本发明所得乙基化改性ANFs的透射电镜图，改性后的对位芳纶仍保持了原有的线性结构；图2是本发明所得PVC复合材料膜的透射电镜图，从图中可以看出制得的PVC复合材料膜表面光滑、密度均匀，乙基化改性ANFs在PVC基体中分布均匀，没有明显的界面痕迹。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (5)

1.一种高韧性PVC复合材料膜的制备方法，其特征在于，包括以下步骤：
1)制备芳纶纳米纤维ANFs：将KOH加入DMSO中，70℃机械搅拌2h后降至室温，加入对位芳纶纤维，室温下保持搅拌反应一周，制得ANFs溶液；
2)乙基化改性ANFs：向步骤1)所得ANFs溶液中加入溴乙烷，30℃下反应17h后过滤，干燥后制得乙基化改性ANFs；
3)制备PVC复合材料膜：将步骤2)所得乙基化改性ANFs溶解到DMSO中，超声1.5h后制得乙基化改性ANFs溶液，将PVC粉末置入DMF中，400r/min搅拌1h后制得PVC溶液，将所得PVC溶液与乙基化改性ANFs溶液混合，70℃下400r/min搅拌15min，再超声震荡15min，制得混合溶液，将混合溶液导入聚四氟乙烯浅平板中，放入真空干燥箱60℃干燥48h，制得PVC复合材料膜。
2.根据权利要求1所述的高韧性PVC复合材料膜的制备方法，其特征在于，步骤1)中所述KOH与所述对位芳纶的质量比为(1-1.5):1。
3.根据权利要求1所述的高韧性PVC复合材料膜的制备方法，其特征在于，步骤1)中所述ANFs溶液的浓度为2-2.5mg/mL。
4.根据权利要求1所述的高韧性PVC复合材料膜的制备方法，其特征在于，步骤2)中所述ANFs溶液与所述溴乙烷的用量为1L:(1-1.5)mL。
5.根据权利要求1所述的高韧性PVC复合材料膜的制备方法，其特征在于，步骤3)中，所述混合溶液中乙基化改性ANFs与PVC的重量比为(0.5-1.5):1000。
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CN112999893A (zh) * 2021-03-17 2021-06-22 鲁东大学 一种基于芳纶纳米微球的高效pvc复合超滤膜的制备方法
CN112999893B (zh) * 2021-03-17 2022-06-14 鲁东大学 一种基于芳纶纳米微球的高效pvc复合超滤膜的制备方法

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