CN115534458A - 一种石墨烯/pen/pet复合阻隔薄膜及其制备方法 - Google Patents
一种石墨烯/pen/pet复合阻隔薄膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种石墨烯/PEN/PET复合阻隔薄膜及其制备方法，复合阻隔薄膜为ABA三层结构，阻隔膜中的A层材料为PET，B层材料为对苯二甲酸、2，6‑萘二甲酸、乙二醇和吸氧型石墨烯进行聚合反应得到的石墨烯/PEN/PET复合材料。本发明将对氨基苯酚引入到石墨烯表面，不仅解决了石墨烯的团聚问题，还能通过酚羟基与微量的氧气反应，进一步增加聚合物基体的阻隔性能，而在PET酯化过程中引入2，6‑萘二甲酸和酚羟基修饰的石墨烯，既实现了PET基体自身阻隔性能的提升，又延长了气体在基体中的扩散路径，且石墨烯表面的酚羟基可将进入PET基体内部的氧气进行有效吸收，显著提升材料的阻隔性能。
Description
技术领域
本发明涉及薄膜技术领域，具体为一种石墨烯/PEN/PET复合阻隔薄膜及其制备方法。
背景技术
PET是一种价格便宜、可回收利用且综合性能优良的聚合物，目前已经广泛地应用于食品、药品包装和饮料瓶等领域，但其气体阻隔性能尚不够好，限制了其作为长期储存包装材料的使用，因此，提高PET薄膜的阻隔性能，以提升PET薄膜的价值，进而推动整个PET薄膜产业向高值化发展具有重要的现实意义。
目前，提高PET阻隔性能的方法主要有：(1)将PET与阻隔性能好的树脂(如PA6、EVOH、PEN等)共混改性，使阻隔树脂在PET基体中形成多层结构，使得气体分子穿透途径变得迂回曲折，增加了扩散途径，因而增加了PET的阻隔性能，但该方法中各种材料的相容性是个很大的问题，往往导致多层复合效果不理想，生产过程中次品、废品较多，且生产工艺复杂，制造成本高；(2)通过对PET分子链结构进行设计，共聚改性制备本身具有高阻隔性能的聚合物，该方法制备的聚合物虽自身阻隔性能优异，但因聚合物中往往含有氢键，因此其阻隔性能受环境的影响比较大，不适用于阻隔性能要求高的材料；(3)在PET基体中引入不可渗透的片状填料(如石墨烯、蒙脱土等)增加气体分子在聚合物中扩散的路径，以提高PET的阻隔性能，但是这种阻隔性能的提高是依赖于增加氧气分子在聚合物中扩散路径而实现的，只是减缓氧气通过包装材料的扩散速度，而无法从根本上解决氧气对被包装材料的氧化作用。
发明内容
本发明的目的在于提供一种石墨烯/PEN/PET复合阻隔薄膜及其制备方法，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：一种石墨烯/PEN/PET复合阻隔薄膜，复合阻隔薄膜为ABA三层结构，阻隔膜中的A层材料为PET，B层材料为对苯二甲酸、2，6-萘二甲酸、乙二醇和吸氧型石墨烯进行聚合反应得到的石墨烯/PETN复合材料，其中，吸氧型石墨烯是由对氨基苯酚和鳞片石墨在球磨过程中通过叠氮反应制备而成。
优选的，所述复合阻隔薄膜厚度为2.5-75um。
一种石墨烯/PEN/PET复合阻隔薄膜的制备方法，按照如下步骤制备：
1)吸氧型石墨烯制备：先将石墨与对氨基苯酚在氮气保护下充分混合均匀，然后再加入亚硝酸异戊酯和乙二醇混合球磨，球磨时间为4-48h，所得产物经洗涤分离后在60℃条件下真空干燥得到吸氧型石墨烯，其中石墨：对氨基苯酚：亚硝酸异戊酯：乙二醇质量比为1：0.1-10：0.1-10：5-50；
2)石墨烯/PEN/PET复合材料的制备：取适量的乙二醇在氮气保护下加入步骤1)制备的吸氧型石墨烯充分混合均匀，然后加入对苯二甲酸、2，6-萘二甲酸和催化剂，在氮气的保护下升温至200-260℃，使对苯二甲酸和2，6-萘二甲酸全部溶解，反应2-4h后再升温至270-290℃，于真空条件下进行缩聚反应，反应2-4h后结束，在氮气保护下出料，固化切粒即得到吸氧型石墨烯/PEN/PET复合材料粒料；
3)多层挤出双向拉伸成膜：采用三层挤出工艺，以A层材料为PET，B层材料为步骤2)制备的石墨烯/PEN/PET复合材料进行ABA三层熔融共挤，熔体通过泵直接输送至模头挤出成片状熔流，经急冷辊冷却成复合厚片，然后通过纵向拉伸和横向拉伸形成双向拉伸形成复合阻隔薄膜。
优选的，所述石墨烯/PEN/PET复合材料中的吸氧型石墨烯的质量分数为0.05wt％-2wt％。
优选的，所述乙二醇：对苯二甲酸的摩尔比为1-2.5：1。
优选的，所述2，6-萘二甲酸：对苯二甲酸摩尔比为0.03-0.4：1。
优选的，所述催化剂为Sb(OAc)3、Co(OAc)2、Sb2O3、H3PO4中的一种或两种。
与现有技术相比，本发明的有益效果如下：
1、本发明将对氨基苯酚引入到石墨烯表面，不仅解决了石墨烯的团聚问题，还能通过酚羟基与微量的氧气反应，进一步增加聚合物基体的阻隔性能；2、B层用的共聚聚酯树脂是在PET酯化过程中引入2，6-萘二甲酸和酚羟基修饰的石墨烯，形成了部分阻隔性能优异的聚2，6-萘二甲酸二乙酯(PEN)并原位有机结合上片层的石墨烯，这样既实现了PET基体自身阻隔性能的提升，又延长了气体在基体中的扩散路径，且石墨烯表面的酚羟基可将进入PET基体内部的氧气进行有效吸收，显著提升材料的阻隔性能。
具体实施方式
下面将结合本发明的实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1：一种石墨烯/PEN/PET复合阻隔薄膜的制备方法，按照如下方法制备得到：
1)吸氧型石墨烯制备：在球磨罐中加入2.5g石墨鳞片和5g对氨基苯酚充分混合均匀，然后再加入6.44g亚硝酸异戊酯和12.5g乙二醇，在氮气保护下以500转/min的转速混合球磨24h，所得产物经洗涤分离后在60℃条件下真空干燥便得到吸氧型石墨烯；
2)石墨烯/PEN/PET复合材料粒料的制备：取77.34g乙二醇在氮气保护下加入步骤1)制备的吸氧型石墨烯2.28g充分混合均匀，然后加入166.13g对苯二甲酸、8.31g 2，6-萘二甲酸和0.17g Sb(OAc)3，在氮气的保护下升温至250-260℃，使对苯二甲酸和2，6-萘二甲酸全部溶解，反应3h后再升温至280-290℃，于真空条件下进行缩聚反应，反应4h后结束，在氮气保护下出料，固化切粒即得到吸氧型石墨烯/PEN/PET复合材料粒料；
3)多层挤出双向拉伸成膜：采用三层挤出工艺，A层材料为PET，B层材料为步骤2)制备的吸氧型石墨烯/PEN/PET复合材料，进行ABA三层熔融共挤，熔体通过泵直接输送至模头挤出成片状熔流，经急冷辊冷却成复合厚片，然后通过纵向拉伸和横向拉伸形成双向拉伸形成复合阻隔薄膜，膜厚度为75um，其中A层和B层的厚度均为25um。
实施例2制备方法同实施例1，不同之处在于步骤2)中乙二醇为80.21g，2，6-萘二甲酸为16.62g。
实施例3制备方法同实施例1，不同之处在于步骤2)中乙二醇为83.06g，2，6-萘二甲酸为24.92g。
实施例4和实施例5与实施例2相同，不同之处在于步骤2)中吸氧型石墨烯分别为1.14g和2.53g。
实施例6与实施例2制备方法相同，不同之处在于步骤1)中石墨鳞片为5g，对氨基苯酚为2.5g，亚硝酸异戊酯为3.2g，乙二醇为25g。
实施例7与实施例1制备方法相同，不同之处在于所制备的膜的厚度为45um，其中A层和B层的厚度均为15um。
对比例1与实施例1相同，不同之处在于步骤1)中只加入2.5g石墨鳞片和12.5g乙二醇进行球磨。
对比例2：取77.34g乙二醇，166.13g对苯二甲酸、8.31g 2，6-萘二甲酸和0.17g Sb(OAc)3，在氮气的保护下升温至250-260℃，使对苯二甲酸和2，6-萘二甲酸全部溶解，反应3h后再升温至280-290℃，于真空条件下进行缩聚反应，反应4h后结束，在氮气保护下出料，固化切粒即得到PETN材料粒料，然后采用三层挤出工艺，A层材料为PET，B层材料为制备的PEN/PET材料，进行ABA三层熔融共挤，熔体通过泵直接输送至模头挤出成片状熔流，经急冷辊冷却成复合厚片，然后通过纵向拉伸和横向拉伸形成双向拉伸形成三层共挤复合/PEN/PET阻隔薄膜，膜厚度为75um。
对比例3：取166g对苯二甲酸、71.3g乙二醇和0.083g Sb2O3，在氮气的保护下升温至200℃，待对苯二甲酸全部溶解后升温至260℃，反应3h，随后再升温至280-290℃，于真空条件下进行缩聚反应，反应4h后结束，在氮气保护下出料，固化切粒得到PET粒料，然后采用三层挤出工艺，A、B层材料均为PET，进行ABA三层熔融共挤，熔体通过泵直接输送至模头挤出成片状熔流，经急冷辊冷却成复合厚片，然后通过纵向拉伸和横向拉伸形成双向拉伸形成三层共挤PET薄膜，膜厚度为75um。
本发明氧气透过系数和水蒸气透过系数分别按GB/T1038和GB/T1037进行测试计算，且表1为实施例1至6、对比例1-3阻隔性能参数表
以上表格数据说明，采用本方法所制备的石墨烯/PEN/PET复合阻隔薄膜可大幅度提高PET薄膜材料的阻隔性能。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。
Claims (7)
1.一种石墨烯/PEN/PET复合阻隔薄膜，其特征在于：复合阻隔薄膜为ABA三层结构，阻隔膜中的A层材料为PET，B层材料为对苯二甲酸、2，6-萘二甲酸、乙二醇和吸氧型石墨烯进行聚合反应得到的石墨烯/PEN/PET复合材料，其中，吸氧型石墨烯是由对氨基苯酚和鳞片石墨在球磨过程中通过叠氮反应制备而成。
2.根据权利要求1所述的一种石墨烯/PEN/PET复合阻隔薄膜，其特征在于：所述复合阻隔薄膜厚度为2.5-75um。
3.一种石墨烯/PEN/PET复合阻隔薄膜的制备方法，其特征在于：按照如下步骤制备：
1)吸氧型石墨烯制备：先将石墨与对氨基苯酚在氮气保护下充分混合均匀，然后再加入亚硝酸异戊酯和乙二醇混合球磨，球磨时间为4-48h，所得产物经洗涤分离后在60℃条件下真空干燥得到吸氧型石墨烯，其中石墨：对氨基苯酚：亚硝酸异戊酯：乙二醇质量比为1：0.1-10：0.1-10：5-50；
2)石墨烯/PEN/PET复合材料的制备：取适量的乙二醇在氮气保护下加入步骤1)制备的吸氧型石墨烯充分混合均匀，然后加入对苯二甲酸、2，6-萘二甲酸和催化剂，在氮气的保护下升温至200-260℃，使对苯二甲酸和2，6-萘二甲酸全部溶解，反应2-4h后再升温至270-290℃，于真空条件下进行缩聚反应，反应2-4h后结束，在氮气保护下出料，固化切粒即得到吸氧型石墨烯/PEN/PET复合材料粒料；
3)多层挤出双向拉伸成膜：采用三层挤出工艺，以A层材料为PET，B层材料为步骤2)制备的石墨烯/PEN/PET复合材料进行ABA三层熔融共挤，熔体通过泵直接输送至模头挤出成片状熔流，经急冷辊冷却成复合厚片，然后通过纵向拉伸和横向拉伸形成双向拉伸形成复合阻隔薄膜。
4.根据权利要求3所述的一种石墨烯/PEN/PET复合阻隔薄膜的制备方法，其特征在于：所述石墨烯/PEN/PET复合材料中的吸氧型石墨烯的质量分数为0.05wt％-2wt％。
5.根据权利要求3所述的一种石墨烯/PEN/PET复合阻隔薄膜的制备方法，其特征在于：所述乙二醇：对苯二甲酸的摩尔比为1-2.5：1。
6.根据权利要求3所述的一种石墨烯/PEN/PET复合阻隔薄膜的制备方法，其特征在于：所述2，6-萘二甲酸：对苯二甲酸摩尔比为0.03-0.4：1。
7.根据权利要求3所述的一种石墨烯/PEN/PET复合阻隔薄膜的制备方法，其特征在于：所述催化剂为Sb(OAc)3、Co(OAc)2、Sb2O3、H3PO4中的一种或两种。
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