WO2016041310A1 - 一种防水隔氧密封膜及其制备和应用 - Google Patents
一种防水隔氧密封膜及其制备和应用 Download PDFInfo
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Abstract
本发明公开了一种防水隔氧密封膜及其制备方法和应用。首先采用纵向氧化切割多壁碳纳米管法制得氧化石墨烯纳米带(GONRs),改性得到功能化氧化石墨烯纳米带(K-GONRs),然后将K-GONRs与乙烯‐乙酸乙烯共聚物(EVA)在涂膜机上复合成膜。经本发明制备的复合材料薄膜,K-GONRs与EVA基体相容性很好,同时K-GONRs在基体中实现了良好的分散。另外所得薄片状K-GONRs大部分平行分布于EVA复合薄膜中。这种多层、平行分布的特殊结构以及K-GONRs插层与EVA基体间的紧密结合,使得该种薄膜具有优异的阻隔性能、良好的耐酸碱性能并且力学性能得到了进一步提高,同时该种薄膜安全环保,尤其适用于制备贵重精密仪器密封膜、包装冰和冷冻产品的冰袋,以及食品包装膜,具有广阔的实际应用价值。
Description
本发明属于高分子复合薄膜制备技术领域,具体涉及一种防水隔氧密封膜及其制备和应用。
乙烯‐乙酸乙烯共聚物(EVA)是由无极性的乙烯单体与强极性的乙酸乙烯单体共聚而成的热塑性树脂,是一种支化度高的无规共聚物。相比于聚乙烯,EVA由于分子链上引入了乙酸乙烯(VA)单体,结晶度降低,从而使得产品在较宽的温度范围内具有优异的柔软性和良好的低温挠曲性、表面光泽性、化学稳定性、抗老化性和无毒性,广泛应用于高性能/功能材料领域。其中,VA含量低于20%的薄膜级EVA材料,由于具有无毒、质轻、包装美观、成本低廉等特点,应用领域在不断拓展,现已几乎渗透到工农产品和日常生活用品的各个方面。但是对于空气、水蒸汽等小分子物质阻隔性能要求较高的应用领域,如贵重精密仪器密封膜、包装冰和冷冻产品的EVA冰袋等,目前市场上的众多EVA膜产品已经不能满足要求,因此需要对产品的阻隔性能进行改性以便更好地适应市场的需求。目前一般通过在EVA基体中共混有机粘土、累托石、纳米微纤或者与其他高分子熔融共混等方法来提高EVA薄膜的阻隔、耐酸碱以及机械性能。采取上述方法能在一定程度上起到提高EVA薄膜阻隔性能的目的,但是共同的缺点在于添加量大、成型工艺复杂并且影响EVA薄膜材料的其他性能,局限了材料的应用领域并限制了其的发展前景,因此寻找一种行之有效的改性剂/方法来对其进行改性是一项十分有意义的工作。
为了提高薄膜材料的阻隔性能,可以考虑在EVA基体中均匀分散适量的具有高阻隔效率的填料,从而使得气体的扩散渗透通路变得曲折迂回,延长扩散路径。石墨烯(Graphene)是一种由碳原子构成的单层片状结构的新材料,自从2004年Graphene被成功制备以来,Graphene的研究在世界上掀起了巨大的热潮,因为结构的特殊性,使得Graphene对空气、水蒸汽等小分子物质具有一定的不渗透性,从而在阻隔材料应用领域具有较大的发展前景,然而目前通过上述方法难以制得大量的Graphene材料,并且由于所得Graphene表面往往存在多褶皱、高起伏等诸多缺陷,无法满足市场需求,因此有必要寻求其的衍生物来达到高阻隔要求。功能化氧化石墨烯纳米带作为石墨烯的衍生物之一,是一种理想的高阻隔性填料,相比石墨烯与氧化石墨烯,其具有对水等小分子物质稳定、高比表面积、低缺陷、形态可调、在有机溶剂中分散性良好等优点,在提高材料对O2、水蒸气等的
阻隔方面具有广泛的应用前景。
但是,将功能化氧化石墨烯纳米带与EVA混合制成复合膜,有许多问题需要解决。
发明内容
本发明的目的在于针对现有技术中的不足与缺陷,提供一种防水隔氧密封膜及其制备和应用。经本发明方法制得的薄膜材料,因功能化氧化石墨烯纳米带与EVA基体之间的相互作用,具有优异的阻隔性能、良好的耐酸碱性能并且力学性能得到了进一步提高,同时该种薄膜安全环保,尤其适用于制备贵重精密仪器密封膜、包装冰和冷冻产品的冰袋,以及食品包装膜,具有广阔的实际应用价值。
为实现上述目的,本发明采用如下技术方案:
一种防水隔氧密封膜,以多壁碳纳米管、乙烯-乙酸乙烯共聚物为原料,采用纵向氧化切割多壁碳纳米管法制得氧化石墨烯纳米带,然后利用γ-甲基丙烯酰氧丙基三甲氧基硅烷对其进行改性得到功能化氧化石墨烯纳米带;以乙烯‐乙酸乙烯共聚物为基体,与功能化氧化石墨烯纳米带混合制得糊状液体后,经涂覆成膜工艺制得功能化氧化石墨烯纳米带/乙烯-乙酸乙烯共聚物复合薄膜。
所述的多壁碳纳米管管径为40~80nm,优选范围为40~60nm。
所述的乙烯‐乙酸乙烯共聚物中乙酸乙烯含量为10~20wt%,优选范围为12~15wt%,熔融指数值为1.0~3.0g/10min,优选范围为2.5~3.0g/10min。
功能化氧化石墨烯纳米带与乙烯‐乙酸乙烯共聚物的质量比为0.012~0.24:10~15。
一种制备如上所述的防水隔氧密封膜的方法,包括以下步骤:
(1)氧化石墨烯纳米带的制备:称量180~200ml浓H2SO4缓慢加入到圆底烧瓶中,然后将20~25ml 85.5wt%H3PO4逐滴加入到浓硫酸中,搅拌均匀;稳定后,加入1~1.2g多壁碳纳米管搅拌1~2h,当多壁碳纳米管分散均匀后,将6~8g KMnO4缓慢加入到上述混合液中,加入时间为0.5~1h,然后匀速搅拌0.5~1h;然后将上述反应体系移至45~60℃的油浴锅中,搅拌反应1~2d,之后将该混合体系缓慢加入到含有500ml去离子水的大烧杯中,混合搅拌1~2h,当温度降至室温后,加入10~15ml 30wt%H2O2反应2~4h;然后将混合液在100W的超声波清洗器中超声分散0.5~1h后,加入100~120ml 38wt%HCl与去离子水后,在聚四氟乙烯滤膜上过滤洗涤4~6次,最后再冷冻干燥得到氧化石墨烯纳米带粉末;
(2)功能化氧化石墨烯纳米带的制备:取干燥好后的氧化石墨烯纳米带粉末分散于500ml的无水乙醇中,超声分散1~2h后形成均匀分散液,再加入HCl,并调节体系pH至3~4;称取2.5~3gγ-甲基丙烯酰氧丙基三甲氧基硅烷分散于100ml的无水乙醇中,超声分散
20~30min后缓慢加入上述分散液中,搅拌均匀,待上述混合液稳定后,将体系升温至60~70℃下反应1~2d;当体系反应完全后,离心分离,然后用无水乙醇和去离子水在聚四氟乙烯滤膜上过滤洗涤4~6次,完全除去未反应的γ-甲基丙烯酰氧丙基三甲氧基硅烷,并调节体系至中性,最后冷冻干燥得到功能化氧化石墨烯纳米带;
(3)混合糊状液体的制备:将0.012~0.24g功能化氧化石墨烯纳米带溶解在甲苯溶液中,在100W的超声波清洗器中超声分散1~2h;然后将分散液缓慢倒入圆底烧瓶中,搅拌均匀;加入10~15g预先烘干的乙烯‐乙酸乙烯共聚物颗粒,升温至65~75℃下反应24~30h后得到混合糊状液体;
(4)涂膜:将玻璃片放置在涂膜机上,然后将所得糊状液体涂敷在玻璃片上,控制涂膜厚度0.06~0.08mm;当涂敷完成后,将玻璃片在室温下晾置2~4d以充分挥发溶剂,得到功能化氧化石墨烯纳米带/乙烯‐乙酸乙烯共聚物复合材料薄膜。
步骤(3)中甲苯的体积与乙烯‐乙酸乙烯共聚物的质量比为10~15:1。
一种如上所述的防水隔氧密封膜的应用,能用于制备贵重精密仪器密封膜、包装冰和冷冻产品的冰袋,以及食品包装膜。
本发明的有益效果在于:
1、经本发明制备的复合材料薄膜,K-GONRs与EVA基体相容性很好,同时K-GONRs在EVA基体中实现了良好的分散;另外所得薄片状K-GONRs大部分垂直分散于复合薄膜断面,即其大部分平行分布于EVA复合薄膜中;这种多层、平行分布的特殊结构以及K-GONRs插层与EVA基体间的紧密结合,使得该种薄膜具有优异的阻隔性能、良好的耐酸碱性能并且力学性能得到了进一步提高;
2、本发明制备的复合材料安全环保,尤其适用于制备贵重精密仪器密封膜,包装冰和冷冻产品的冰袋、或食品包装膜,具有广阔的实际应用价值。本发明适应当今市场的需求,制备方法科学合理、工序简单、操作性强,提高了产品的附加值,极大地扩展了EVA包装膜的应用范围,具有广泛的市场前景和显著的社会经济效益。
图1为GONRs制备过程示意图;
图2为MWNTs、K-GONRs以及二者在EVA复合薄膜中分散状态的FE-SEM;(a)MWNTs;(b)K-GONRs;(c)掺入1.0wt%MWNTs的EVA复合薄膜;(d)掺入1.0wt%K-GONRs的EVA复合薄膜
下面以具体实施例来对本发明做进一步说明,但本发明的保护范围不限于此。
实施例1
本实施例说明本发明提供的复合材料薄膜组合物、复合材料薄膜及其制备方法。
将12g预先烘干的EVA颗粒缓慢倒入含有120ml甲苯溶液(mEVA:V甲苯=1:10)并带有磁性转子的圆底烧瓶中,待稳定后将体系升温至70℃下反应24h得到混合糊状液体。将玻璃片放置在涂膜机上,然后将所得糊状液体涂敷在玻璃片上,控制涂膜厚度0.07±0.01mm。当涂敷完成后,将玻璃片在室温下晾置24h以充分挥发溶剂,得到纯EVA材料薄膜。
实施例2
(1)氧化石墨烯纳米带的制备:称量180ml浓H2SO4缓慢加入到圆底烧瓶中,然后将20ml 85.5wt%H3PO4逐滴加入到浓硫酸中,搅拌均匀;稳定后,加入1g多壁碳纳米管搅拌1h,当多壁碳纳米管分散均匀后,将6g KMnO4缓慢加入到上述混合液中,加入时间为0.5h,然后匀速搅拌0.5h;然后将上述反应体系移至45℃的油浴锅中,搅拌反应1d,之后将该混合体系缓慢加入到含有500ml去离子水的大烧杯中,混合搅拌1h,当温度降至室温后,加入10ml 30wt%H2O2反应2h;然后将混合液在100W的超声波清洗器中超声分散0.5h后,加入100ml 38wt%HCl与去离子水后,在聚四氟乙烯滤膜上过滤洗涤4次,最后再冷冻干燥得到氧化石墨烯纳米带粉末;
(2)功能化氧化石墨烯纳米带的制备:取干燥好后的氧化石墨烯纳米带粉末分散于500ml的无水乙醇中,超声分散1h后形成均匀分散液,再加入HCl,并调节体系pH至3;称取2.5gγ-甲基丙烯酰氧丙基三甲氧基硅烷分散于100ml的无水乙醇中,超声分散20min后缓慢加入上述分散液中,搅拌均匀,待上述混合液稳定后,将体系升温至60℃下反应1d;当体系反应完全后,离心分离,然后用无水乙醇和去离子水为在聚四氟乙烯滤膜上过滤洗涤4次,完全除去未反应的γ-甲基丙烯酰氧丙基三甲氧基硅烷,并调节体系至中性,最后冷冻干燥得到功能化氧化石墨烯纳米带;
(3)混合糊状液体的制备:将0.012g功能化氧化石墨烯纳米带溶解在甲苯溶液中,在100W的超声波清洗器中超声分散1h;然后将分散液缓慢倒入圆底烧瓶中,搅拌均匀;加入12g预先烘干的乙烯‐乙酸乙烯共聚物颗粒,升温至70℃下反应24h后得到混合糊状液体;V甲苯:mEVA为10:1;
(4)涂膜:将玻璃片放置在涂膜机上,然后将所得糊状液体涂敷在玻璃片上,控制涂膜厚度0.06mm;当涂敷完成后,将玻璃片在室温下晾置2d以充分挥发溶剂,得到功能化氧化
石墨烯纳米带/乙烯‐乙酸乙烯共聚物复合材料薄膜。
所制得的功能化氧化石墨烯纳米带/乙烯‐乙酸乙烯共聚物复合材料薄膜中含0.1wt%K-GONRs。
实施例3
其他条件参数与实施例2相同,所不同的是步骤(3)中加入0.024g功能化氧化石墨烯纳米带、乙烯‐乙酸乙烯共聚物颗粒12g,制得的功能化氧化石墨烯纳米带/乙烯‐乙酸乙烯共聚物复合材料薄膜中含0.2wt%K-GONRs。
实施例4
其他条件参数与实施例2相同,所不同的是步骤(3)中加入0.06g功能化氧化石墨烯纳米带、乙烯‐乙酸乙烯共聚物颗粒12g,制得的功能化氧化石墨烯纳米带/乙烯‐乙酸乙烯共聚物复合材料薄膜中含0.5wt%K-GONRs。
实施例5
其他条件参数与实施例2相同,所不同的是步骤(3)中加入0.12g功能化氧化石墨烯纳米带、乙烯‐乙酸乙烯共聚物颗粒12g,制得的功能化氧化石墨烯纳米带/乙烯‐乙酸乙烯共聚物复合材料薄膜中含1.0wt%K-GONRs。
实施例6
其他条件参数与实施例2相同,所不同的是步骤(3)中加入0.24g功能化氧化石墨烯纳米带、乙烯‐乙酸乙烯共聚物颗粒12g,制得的功能化氧化石墨烯纳米带/乙烯‐乙酸乙烯共聚物复合材料薄膜中含2.0wt%K-GONRs。
表1 实施例所制得的EVA复合材料薄膜的各项物理性能检测结果见下表所示:
3、通过表1的数据可以看出,实施例1制得的纯EVA薄膜,氧气透过率为2436.64cm3/m2.d.Pa,明显大于实施例2-6添加有功能化氧化石墨烯纳米带的复合EVA薄膜,说明
其隔氧性能没有本发明的复合膜好;拉伸强度、耐酸性、耐碱性相比,本发明制得的复合膜也明显优于纯EVA薄膜,说明功能化氧化石墨烯纳米带/乙烯-乙酸乙烯共聚物复合材料薄膜具有优异的阻隔性能,良好的耐酸碱性能,并且力学性能得到了进一步提高。
这些复合薄膜因其优异的阻隔性能、耐酸碱性,适用于制备贵重精密仪器的密封膜,包装冰和冷冻产品的冰袋,以及食品包装膜。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (8)
- 一种防水隔氧密封膜,其特征在于:以多壁碳纳米管、乙烯-乙酸乙烯共聚物为原料,采用纵向氧化切割多壁碳纳米管法制得氧化石墨烯纳米带,然后利用γ-甲基丙烯酰氧丙基三甲氧基硅烷对其进行改性得到功能化氧化石墨烯纳米带;以乙烯-乙酸乙烯共聚物为基体,与功能化氧化石墨烯纳米带混合制得糊状液体后,经涂覆成膜工艺制得的功能化氧化石墨烯纳米带/乙烯-乙酸乙烯共聚物复合薄膜。
- 根据权利要求1所述的防水隔氧密封膜,其特征在于:所述的多壁碳纳米管管径为40~80nm。
- 根据权利要求1所述的防水隔氧密封膜,其特征在于:所述的乙烯-乙酸乙烯共聚物中乙酸乙烯含量为10~20wt%,熔融指数值为1.0~3.0g/10min。
- 根据权利要求1所述的防水隔氧密封膜,其特征在于:功能化氧化石墨烯纳米带与乙烯-乙酸乙烯共聚物的质量比为0.012~0.24:10~15。
- 一种制备如权利要求1所述的防水隔氧密封膜的方法,其特征在于:包括以下步骤:(1)氧化石墨烯纳米带的制备:称量180~200ml浓H2SO4缓慢加入到圆底烧瓶中,然后将20~25ml 85.5wt%H3PO4逐滴加入到浓硫酸中,搅拌均匀;稳定后,加入1~1.2g多壁碳纳米管搅拌1~2h,当多壁碳纳米管分散均匀后,将6~8g KMnO4缓慢加入到上述混合液中,加入时间为0.5~1h,然后匀速搅拌0.5~1h;然后将上述反应体系移至45~60℃的油浴锅中,搅拌反应1~2d,之后将该混合体系缓慢加入到含有500ml去离子水的大烧杯中,混合搅拌1~2h,当温度降至室温后,加入10~15ml 30wt%H2O2反应2~4h;然后将混合液在100W的超声波清洗器中超声分散0.5~1h后,加入100~120ml 38wt%HCl水溶液后,在聚四氟乙烯滤膜上过滤洗涤4~6次,最后再冷冻干燥得到氧化石墨烯纳米带粉末;(2)功能化氧化石墨烯纳米带的制备:取干燥好后的氧化石墨烯纳米带粉末分散于500ml的无水乙醇中,超声分散1~2h后形成均匀分散液,再加入HCl,并调节体系pH至3~4;称取2.5~3gγ-甲基丙烯酰氧丙基三甲氧基硅烷分散于100ml的无水乙醇中,超声分散20~30min后缓慢加入上述分散液中,搅拌均匀,待上述混合液稳定后,将体系升温至60~70℃下反应1~2d;当体系反应完全后,离心分离,然后用无水乙醇和去离子水在聚四氟乙烯滤膜上过滤洗涤4~6次,除去未反应的γ-甲基丙烯酰氧丙基三甲氧基硅烷,并调节体系至中性,最后冷冻干燥得到功能化氧化石墨烯纳米带;(3)混合糊状液体的制备:将功能化氧化石墨烯纳米带溶解在甲苯溶液中,在100W的超声波清洗器中超声分散1~2h;然后将分散液缓慢倒入圆底烧瓶中,搅拌均匀;加入预先烘干的乙烯‐乙酸乙烯共聚物颗粒,升温至65~75℃下反应24~30h后得到混合糊状液体;(4)涂膜制得功能化氧化石墨烯纳米带/乙烯‐乙酸乙烯共聚物复合材料薄膜。
- 根据权利要求5所述的防水隔氧密封膜的制备方法,其特征在于:步骤(4)所制得的功能化氧化石墨烯纳米带/乙烯‐乙酸乙烯共聚物复合材料薄膜厚度为0.06~0.08mm。
- 根据权利要求5所述的防水隔氧密封膜的制备方法,其特征在于:步骤(3)加入甲苯的体积与乙烯-乙酸乙烯共聚物的质量比值为10~15:1。
- 一种如权利要求1所述的防水隔氧密封膜的应用,其特征在于:用于制备贵重精密仪器密封膜、包装冰和冷冻产品的冰袋,以及食品包装膜。
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