CN110240739A - 一种反应诱导三维填料网络构筑技术制备轻质高性能聚合物复合材料的方法 - Google Patents
一种反应诱导三维填料网络构筑技术制备轻质高性能聚合物复合材料的方法 Download PDFInfo
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Abstract
本发明公开了一种反应诱导三维填料网络构筑技术制备轻质高性能聚合物复合材料的方法。所述反应诱导三维填料网络构筑技术,即在聚合物和填料混合过程中,加入能够与填料表面修饰基团发生化学反应/物理强相互作用的网络诱导剂,通过反应的发生来驱动三维填料网络的自发形成,最终得到类“隔离结构”纳米复合材料。该技术具有简单、可适用于绝大多数聚合物基体和传统聚合物加工工艺、可制备低填料含量、高性能聚合物复合材料等优点。
Description
技术领域
本发明涉及聚合物复合材料领域,具体涉及一种反应诱导三维填料网络构筑技术制备轻质高性能聚合物复合材料的方法。
背景技术
轻质、高性能聚合物复合材料在航空航天、轨道交通、军事等各个领域具有重要的应用。
在聚合物复合材料制备方面,通过溶液混合法、本体混合法、熔融混合法或原位聚合法等传统方法构建的“随机结构”聚合物复合材料,由于填料在聚合物基体中随机分布,不仅会因所形成的填料网络结构松散而导致复合材料的逾渗阈值较高和极限功能性较差,而且会因填料含量的增加所引起的体系黏度迅速上升而导致填料的分散性和复合体系的加工性急剧下降【Prog.Polym.Sci.,2014,39,1908-1933;Compos.Part A-Appl.S.,2019,119,101-110.】。
相比之下,通过直接模压法、回填法和不相容聚合物共混法等特殊方法构建的“隔离结构”聚合物复合材料,由于填料集中分布在聚合物粒子周围或双连续结构共混物的一相中/两相界面处,填料在极低的含量下就能够形成完整密实的三维网络,所以“隔离结构”聚合物复合材料在发挥功能性方面(导电、导热、电磁屏蔽和阻燃等)要明显优于“随机结构”聚合物复合材料,为低成本、高性能聚合物复合材料的制备提供了一种可选方案【Compos.Sci.Technol.,2018,167,260-267;Chem.Eng.J.,2019,363,300-308.】。
不幸的是,“隔离结构”聚合物复合材料制备方法的局限性却极大地限制了其应用推广。例如,直接模压法是先制备聚合物/填料核壳粒子,然后将其直接模压成型【Carbon,2017,121,267-273;Chem.Eng.J.,2018,344,184-193.】。该方法成功的关键是在成型温度和压力下,聚合物粒子能够保持高模量或高黏度以避免基体的流动对填料网络的破坏。由此,该方法不仅具有很大的基体选择性和成型局限性,而且由于基体的连续性较差还会导致最终复合材料的力学性能较差【Prog.Polym.Sci.,2014,39,1908-1933.】。回填法是先构建三维多孔填料骨架,然后回填聚合物基体成型。低收缩、高强度三维多孔填料骨架的构建是该方法成功的关键。尽管该方法制备的“隔离结构”聚合物复合材料具有最完整均匀的三维填料网络,然而三维多孔填料骨架的构筑不仅需要冷冻干燥水凝胶/分散液法、化学气相沉积法或模板法等复杂低效的制备工艺,而且骨架的多孔性所带来的高收缩和低强度问题难以避免。不相容聚合物共混法是选择合适的聚合物组合和比例,通过精确的调控混合工艺参数、填料表面性质等使填料选择性分布在不相容共混物的一相中/两相界面处【ACSAppl.Mater.Interfaces,2018,10,8411-8416;ACS Appl.Mater.Interfaces,2017,9,14358-14370.】。虽然该方法可适用于常规的聚合物加工工艺(混炼、挤出、注射等),但是由于填料的选择分布受众多动力学和热力学因素的复杂影响,该方法的成功案例也屈指可数。
因此,发展一种简单的、可适用于绝大多数聚合物基体和传统聚合物加工工艺的三维填料网络调控新方法对构建低填料含量、高性能聚合物复合材料具有重要的现实意义。
发明内容
鉴于上述情况,本发明的目的是提供一种简单的、可适用于绝大多数聚合物基体和传统聚合物加工工艺的低填料含量、高性能聚合物复合材料制备方法。
本发明的基本原理是:在聚合物和填料混合过程中,加入能够与填料表面修饰基团发生化学反应/物理强相互作用的网络诱导剂,通过反应的发生来驱动三维填料网络的自发形成,最终得到类“隔离结构”纳米复合材料。
本发明具体的技术方案如下:
1)填料的表面修饰:根据聚合物基体和填料的性质,选用合适的表面改性剂,在一定的条件下对填料进行表面修饰;
2)填料在聚合物基体中的分散:将步骤1)中经过表面修饰的填料与聚合物基体混合,得到聚合物-填料预混料;
3)三维填料网络的诱导构筑:选用在聚合物混合/成型条件下能够与改性填料表面基团发生化学/强物理相互作用的网络诱导剂,与步骤(2)制备的聚合物-填料预混料混合,在混合/成型条件下反应诱导三维填料网络在聚合物基体中的形成,得到聚合物复合材料。
所述表面改性剂能够通过与填料之间发生化学或物理作用,将既能够提高填料在聚合物基体中分散又能够与网络诱导剂发生化学/强物理相互作用的基团修饰到填料表面。
所述表面改性剂-网络诱导剂组合具体地可以是多酚化合物-多价金属盐、多酚化合物-多元胺、多酚化合物-多元硫醇、多酚化合物-蛋白质、多酚化合物-聚乙烯吡咯烷酮、含环氧基硅烷偶联剂-多元胺、含胺基硅烷偶联剂-多元异氰酸酯、含双键硅烷偶联剂-过氧化物等。
与传统工艺技术相比,本发明具有以下有益效果:不仅克服了传统“随机结构”聚合物复合材料填料含量高、性能和加工性差的缺点,而且克服了传统“隔离结构”聚合物复合材料制备方法的局限性,具有简单、可适用于绝大多数聚合物基体和传统聚合物加工工艺、可制备低填料含量、高性能聚合物复合材料等优点。
附图说明
图1是对比例1中的“随机结构”丁腈橡胶/石墨烯复合材料的扫描电镜照片。
图2是实施例1中的“隔离结构”丁腈橡胶/石墨烯复合材料的扫描电镜照片。
图3是对比例1和实施例1中不同结构的丁腈橡胶/石墨烯复合材料的电导率-石墨烯关系图,其中石墨烯含量为石墨烯在聚合物复合材料中的含量。
具体实施方式
下面结合附图并通过具体实施例来进一步详细说明本发明。应理解,下述实施例是用于说明本发明而不是限制其保护范围的。
对比例1:
非反应诱导三维填料网络构筑技术制备丁腈橡胶/石墨烯复合材料,制备步骤如下:
1)单宁酸物理修饰石墨烯的制备:在500mL烧杯中,依次加入100ml超纯水、1g石墨烯和0.1g单宁酸,采用高速匀质器4500r/min高速搅拌30min使石墨烯分散到水中,同时单宁酸物理吸附到石墨烯表面实现石墨烯的物理修饰;
2)石墨烯在丁腈橡胶中的分散:按照一定的石墨烯的质量分数,将步骤(1)所制备的单宁酸改性石墨烯与丁腈胶乳混合均匀,得到丁腈橡胶-石墨烯预混料;
3)丁腈橡胶/石墨烯复合材料的制备:按照盐酸/单宁酸摩尔比1:1,向步骤(2)制备的丁腈橡胶-石墨烯预混料中加入盐酸,搅拌混合均匀后、过滤、洗涤、干燥;然后,在开炼机上混入其它橡胶助剂:硫磺2.8质量份,氧化锌5质量份,硬脂酸3质量份,促进剂CZ 1.4质量份,促进剂DM 0.1质量份,防老剂4010NA 3质量份;最后,在平板硫化机上150℃,10MPa下硫化20min,测试硫化橡胶片的微观结构(如图1所示)和电导率(如图3所示)。
实施例1:
反应诱导三维填料网络构筑技术制备丁腈橡胶/石墨烯复合材料,制备步骤如下:
1)单宁酸物理修饰石墨烯的制备:在500mL烧杯中,依次加入100ml超纯水、1g石墨烯和0.1g单宁酸,采用高速匀质器4500r/min高速搅拌30min使石墨烯分散到水中,同时单宁酸物理吸附到石墨烯表面实现石墨烯的物理修饰;
2)石墨烯在丁腈橡胶中的分散:按照一定的石墨烯的质量分数,将步骤(1)所制备的单宁酸改性石墨烯与丁腈胶乳混合均匀,得到丁腈橡胶-石墨烯预混料;
3)三维石墨烯网络的诱导构筑:按照三氯化铁/单宁酸摩尔比1:1,向步骤(2)制备的丁腈橡胶-石墨烯预混料中加入三氯化铁,搅拌混合均匀后、过滤、洗涤、干燥;然后,在开炼机上混入其它橡胶助剂:硫磺2.8质量份,氧化锌5质量份,硬脂酸3质量份,促进剂CZ 1.4质量份,促进剂DM 0.1质量份,防老剂4010NA 3质量份;最后,在平板硫化机上150℃,10MPa下硫化20min,测试硫化橡胶片的微观结构(如图2所示)和电导率(如图3所示)。
在该体系中,石墨烯表面单宁酸的酚羟基与多价金属离子Fe3+能够发生多配位络合,使石墨烯通过配位键相互联结形成三维网络(如图2所示);而在对比例1中,石墨烯间仅存在弱的范德华力,在混炼过程中很容易被破坏,导致石墨烯随机分布在基体中(如图1所示),因此,实施例1复合材料的电导率要明显高于对比例1中复合材料的电导率。
实施例2:
反应诱导三维填料网络构筑技术制备氯丁橡胶/单壁碳纳米管复合材料,制备步骤如下:
1)聚多巴胺化学修饰单壁碳纳米管的制备:在500mL烧杯中,依次加入50ml PH=8.5Tris-HCl缓冲溶液、0.5g单壁碳纳米管和0.1g多巴胺;然后在冰水浴下超声1h使单壁碳纳米管分散开;最后将体系升温到室温,300r/min搅拌反应4h,实现聚多巴胺对单壁碳纳米管的包覆改性,在单壁碳纳米管表面修饰上邻苯二酚基团;
2)单壁碳纳米管在氯丁橡胶中的分散:按照单壁碳纳米管的质量分数1wt%,将步骤(1)所制备的改性单壁碳纳米管与氯丁胶乳混合均匀,得到氯丁橡胶-单壁碳纳米管预混料;
3)三维单壁碳纳米管网络的诱导构筑:按照明胶/多巴胺质量比0.1:1,向步骤(2)制备的氯丁橡胶-单壁碳纳米管预混料中加入明胶,搅拌混合均匀后、过滤、洗涤、干燥;然后,在开炼机上混入其它橡胶助剂:硫磺2.8质量份,氧化锌5质量份,硬脂酸3质量份,促进剂CZ 1.4质量份,促进剂DM 0.1质量份,防老剂4010NA 3质量份;最后,在平板硫化机上150℃,10MPa下硫化20min。测试氯丁橡胶/单壁碳纳米管复合材料的电导率为5.3×10-3S/m,电磁屏蔽效能为31dB;而在相同条件下,不添加网络诱导剂明胶得到氯丁橡胶/单壁碳纳米管复合材料的电导率仅为4.1×10-12S/m,电磁屏蔽效能仅为20dB。
实施例3:
反应诱导三维填料网络构筑技术制备聚苯乙烯/蒙脱土复合材料,制备步骤如下:
1)硅烷偶联剂化学修饰蒙脱土的制备:在500mL烧杯中,依次加入100ml乙醇、2ml超纯水、10g蒙脱土和1gγ-甲基丙烯酰氧基丙基三甲氧基硅烷;然后在500r/min下室温搅拌反应4h,实现硅烷偶联剂对蒙脱土的包覆改性,在蒙脱土表面修饰上双键基团;
2)蒙脱土在聚苯乙烯中的分散:按照蒙脱土的质量分数3wt%,在100r/min下室温搅拌10min,将步骤(1)所制备的改性蒙脱土与聚苯乙烯粉料混合均匀,得到聚苯乙烯-蒙脱土预混料;
3)三维蒙脱土网络的诱导构筑:首先将步骤(2)制备的聚苯乙烯-蒙脱土预混料在120℃的开炼机上混炼包辊;然后按照质量分数0.1wt%加入2,5-二甲基-2,5-双(过氧化叔丁基)己烷,混炼3min;最后,在150℃平板硫化机上,15MPa模压20min。测试聚苯乙烯/蒙脱土复合材料的氧指数为26;而在相同条件下,不添加网络诱导剂2,5-二甲基-2,5-双(过氧化叔丁基)己烷得到的聚苯乙烯/蒙脱土复合材料的氧指数仅为19。
上述实施例只为说明本发明的技术构思及特点,并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰,都应涵盖在本发明的保护范围内。
Claims (2)
1.一种反应诱导三维填料网络构筑技术制备轻质高性能聚合物复合材料的方法,其特征在于,包括如下步骤:
1)填料的表面修饰:根据聚合物基体和填料的性质,选用合适的表面改性剂,在一定的条件下对填料进行表面修饰;
2)填料在聚合物基体中的分散:将步骤(1)制备的改性填料与聚合物基体混合均匀,得到聚合物-填料预混料;
3)三维填料网络的诱导构筑:选用在聚合物混合/成型条件下能够与改性填料表面基团发生化学/强物理相互作用的网络诱导剂,与步骤(2)制备的聚合物-填料预混料混合,在混合/成型条件下反应诱导三维填料网络在聚合物基体中的形成,得到聚合物复合材料。
2.根据权利要求1所述的一种反应诱导三维填料网络构筑技术制备轻质高性能聚合物复合材料的方法,其特征在于,所述表面改性剂能够通过与填料之间发生化学或物理作用,将既能够提高填料在聚合物基体中分散又能够与网络诱导剂发生化学/强物理相互作用的基团修饰到填料表面。
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