CN110819074B - 一种石墨烯复合材料的制备方法 - Google Patents
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Abstract
本发明属于材料领域，具体为一种石墨烯复合材料的制备，通过化学氧化技术制备出氧化石墨，将制备出的氧化石墨与含两个异氰酸酯基的化合物反应，得到表面含异氰酸酯基的氧化石墨，除去过量游离的二异氰酸酯后再用封端剂反应封闭异氰酸酯基，通过热还原将氧化石墨还原成石墨烯，得到室温空气中稳定存在的封闭异氰酸酯基改性的石墨烯，将改性后的石墨烯与欲改性的含活泼氢的树脂在高温下反应接枝并复合。
Description
技术领域
本发明专利属于材料技术领域，涉及一种高分子复合材料。
背景技术
石墨烯是单层碳原子紧密堆积而形成的炭质新材料，厚度只有0.335 nm，是目前世界上最薄的二维材料，其C-C键长约为0.142 nm。石墨烯具有优异的力学、热学和电学性能：强度达130GPa，比世界上最好的钢高100倍，是目前强度最高的材料；热导率可达5000W·m－1·k－1，是金刚石的3倍；石墨烯载流子迁移率高达15000cm2·V－1·S－1，是商用硅片的10倍以上。石墨烯还有超大的比表面积（2630m2/g）、室温量子霍尔效应和良好的铁磁性，是目前已知的在常温下导电性能最好的材料，电子在其中的运动速度远超过一般导体，达到了光速的1/300。由于石墨烯具有上述优异的性能，使其有望在微电子、能源、信息、材料和生物医药等领域具有重大的应用前景。
制备石墨烯高分子复合材料的方法主要有两种：先让氧化石墨与其他材料复合，再将其中的氧化石墨还原得到石墨烯纳米复合材料；或者在石墨烯表面进行接枝改性，再用改性过的石墨烯与其他材料复合。这些复合材料广泛地应用在超级电容器、锂电池、电催化和燃料电池等领域。未经改性的石墨烯与高分子材料的相容性较差，仅仅用物理方法很难达到很好的混溶。
聚氨酯是指主链上含有重复氨基甲酸酯基团的一大类聚合物材料。通过改变原料的种类与组成，可以大幅度地改变产品的形态及物理、化学性质。由于石墨烯和氧化石墨表面含有羟基和羧基等活性基团很容易可以和异氰酸酯基反应，从而把聚氨酯接枝到石墨烯表面。文献（氧化石墨烯的表面改性及其复合材料的制备，王莹莹，吉林大学硕士学位论文，2012.4）报道了一种通过用甲苯二异氰酸酯（TDI）对石墨烯表面进行表面功能化的方法。由于异氰酸酯基在空气中不稳定，该方法所要接枝到氧化石墨烯表面的异氰酸酯基团在空气中不稳定，保存和使用都不方便。本发明中得到的石墨烯表面接枝的封端聚氨酯（或异氰酸酯），这种封端的聚氨酯在空气中稳定存放，可在加热后与各种链段上含有羟基、羧基、巯基等活性基团的聚合物接枝反应，这种反应也可以在改性石墨烯与这类树脂的熔融共混的过程中进行。
本发明提出了一种表面接枝聚氨酯链段的石墨烯及其制备方法。
发明内容
本发明的目的是提供一种可在空气中稳定存放，在高温下与熔融的含活泼氢的树 脂或其溶液反应接枝共混同步进行，解决了现有技术中存在的接枝与共混必须分开进行的问题。
本发明所采用的技术方案是，
第一步：通过化学氧化技术制备出氧化石墨；
第二步：将制备出的氧化石墨二异氰酸酯反应，得到表面含异氰酸酯基的氧化石墨，除去过量游离的二异氰酸酯后再苯酚等封端剂反应封闭异氰酸酯基；
第三步：通过热还原将氧化石墨还原成石墨烯，得到室温空气中稳定存在的封闭异氰酸酯基改性的石墨烯；
第四步：将改性后的石墨烯与欲改性的含活泼氢的树脂在高温下反应接枝并共混复合。
所述方法的第一步，将石墨氧化插层制备出氧化石墨，这些方法包括但不限于：hummer法、staudenmair法。
所述方法第二步，将制备出的氧化石墨在DMF溶剂中通过超声、搅拌进行分散，再与二异氰酸酯份反应，得到表面含异氰酸酯基的氧化石墨，离心或加正己烷沉淀除去过量游离的二异氰酸酯后再次加DMF溶剂，通过超声、搅拌进行分散并与苯酚等封端剂反应封闭异氰酸酯基；所述的封端剂可以是含各种取代基的苯酚、伯胺、咪唑。
所述第三步，将制备出的改性氧化石墨在水合肼水溶液中通过超声、搅拌进行分散，在60℃反应5小时，进行热还原将氧化石墨还原成石墨烯。
所述第四步的接枝共混方法包括：1）将改性后的石墨烯与末端或分子链中间含羟基、巯基、氨基、羧基的一种或几种的聚乙二醇、聚乳酸、聚酯、聚氨酯、聚酰胺进行熔融共混改性。2）将改性后的石墨烯与分子链中含有羟基、巯基、氨基、羧基中的一种或几种的不饱和聚酯树脂或环氧乙烯基树脂及其交联剂和引发剂充分混匀，按照一定的固化温度制度进行固化得到石墨烯改性的不饱和聚酯树脂或环氧乙烯基树脂固化物。3）将改性后的石墨烯与分子链中含有羟基的环氧树脂及其固化剂充分混匀，按照一定的固化温度制度进行固化得到石墨烯改性的环氧树脂固化物。
具体实施方式
以下结合实例进一步说明本发明的内容，并非对发明内容的限制。
实施例一：
1、氧化石墨的制备：利用改进的staudcnmair法，在98%的浓硫酸中加入天然鳞片石墨、硝酸和KClO3，控制反应温度在0-10℃之间，搅拌反应5h后，用去离子水将反应液稀释再过滤，离子水充分洗涤直至中性，然后干燥；
2、苯酚封闭异氰酸酯基改性的氧化石墨烯的制备：将氧化石墨250mg加入50 mL的DMF中，加热至60℃，搅拌并超声1h。冷却至室温，加甲苯二异氰酸酯50mg，升温至60 ℃反应2h，静置使所有氧化石墨烯沉淀，除去上层清液并用四氢呋喃50mL分两次洗涤，得到表面是异氰酸酯基的石墨烯。将上述得到的末端是异氰酸酯基的石墨烯加入加入50 mL的DMF中，加热至60℃，搅拌并超声1h，而后加入对叔丁基苯酚50 mg，60 ℃下搅拌反应2h。静置使所有氧化石墨烯沉淀，除去上层清液并用四氢呋喃50mL分两次洗涤，真空干燥，得到表面是对叔丁基苯酚封端的异氰酸酯基的氧化石墨烯。
3、苯酚封闭异氰酸酯基改性的石墨烯的制备：将上述苯酚封闭异氰酸酯基改性的氧化石墨烯放入50mL去离子水中，超声分散1h，加5 g水合肼，80℃反应2h后室温静置1h，除去水清液，THF50mL分两次洗产物，真空干燥得到苯酚封闭异氰酸酯基改性的石墨烯。
4、上述改性后的石墨烯定量分散到丙酮中超声处理1.5h，加入环氧树脂10 g，继续超声1.5h之后将混合液置于70 ℃的真空压力烘箱中处理12h以确保蒸发掉所有溶剂。然后将环氧树脂冷却到室温，按照固化剂质量占树脂质量的5%，加入固化剂双氰胺，搅拌均匀后倒入涂有脱模剂的模具固化。80 ℃下固化2h，120 ℃下固化2h，140 ℃下固化24h，固化后脱模便得到石墨烯/环氧树脂复合材料。按照GB/13525-1992测试样品的拉伸性能，拉伸速率为4mm/min，试样厚度为1 mm。测试后产品拉伸强度为340MPa，模量为40GPa，弯曲强度为400MPa。
实施例二：
改性后的石墨烯和乙二醇加入100 mL超声处理1.5h，然后加入一定量的对苯二甲酸和有机锡催化剂，在200℃下反应4.5h，控制分馏柱顶温度不超过105℃。待分流出的水的质量为理论质量的90%时，降温至160℃加入一定量的反丁烯二酸，通氮气保护，降温至160℃加入一定量的反丁烯二酸，通氮气保护，当温度升至180℃时加入阻聚剂对苯二酚，物料温度控制在210-220℃。当酸值降至一定值后，减压蒸馏脱水，至出水量接近理论值后停止反应，出料冷却，粉碎备用。
将普通不饱和聚酯树脂和上述复合树脂混合与交联剂苯乙烯、玻璃纤维增强材料、氢氧化铝、碳酸钙和引发剂混合，模压成型。模压工艺：温度175℃，压力7 MPa, 时间为4min。冷却后，在140 ℃下后固化2h。
测试后产品拉伸强度为115MPa，模量为15GPa，弯曲强度为230MPa。
实施例三：
改性后的石墨烯和乙二醇加入100 mL超声处理1.5h，然后加入一定量的对苯二甲酸和有机锡催化剂，在190℃下反应5h，控制分馏柱顶温度不超过105℃。待分流出的水的质量为理论质量的90%时，降温至160℃加入一定量的反丁烯二酸，通氮气保护，降温至160℃加入一定量的反丁烯二酸，通氮气保护，当温度升至180℃时加入阻聚剂对苯二酚，物料温度控制在220℃。当酸值降至一定值后，减压蒸馏脱水，至出水量接近理论值后停止反应，出料冷却，粉碎备用。
将普通不饱和聚酯树脂和上述复合树脂混合与交联剂苯乙烯、玻璃纤维增强材料、碳酸钙和引发剂混合，模压成型。模压工艺：温度145℃，压力7 MPa, 时间为6min。冷却后，在140 ℃下后固化2h。
测试后产品拉伸强度为108MPa，模量为14GPa，弯曲强度为220MPa。
Claims (3)
1.一种石墨烯复合材料的制备方法，其特征在于通过化学氧化技术制备出氧化石墨，将制备出的氧化石墨与含两个异氰酸酯基的化合物反应，得到表面含异氰酸酯基的氧化石墨，除去过量游离的二异氰酸酯后再用封端剂反应封闭异氰酸酯基，通过热还原将氧化石墨还原成石墨烯，得到室温空气中稳定存在的封闭异氰酸酯基改性的石墨烯，将改性后的石墨烯与欲改性的含活泼氢的树脂在高温下反应接枝并复合；
其中，所述的封端剂包括苯酚，2,4-二叔丁基苯酚，2,4,6-三叔丁基苯酚，2,6-二叔丁基-4-甲基苯酚；
所述的与含活泼氢的树脂在高温下反应接枝并复合包括与不饱和聚酯树脂混合后在不饱和聚酯树脂的后固化阶段将固化温度升至≥140℃使不饱和聚酯树脂与封闭异氰酸酯基改性的石墨烯接枝反应。
2.根据权利要求1的方法，其特征在于所述含两个异氰酸酯基的化合物包括，2,4-甲苯二异氰酸酯、1,6-正己基二异氰酸酯、4,4'-二异氰酸酯基苯基甲烷，异佛尔酮二异氰酸酯以及由以上二异氰酸酯与乙二醇或聚乙二醇反应生成的末端含异氰酸酯基的聚氨酯预聚物。
3.根据权利要求1的方法，其特征在于所述的含活泼氢的树脂在高温下反应接枝并复合包括与环氧树脂混合后，使环氧树脂在固化过程中固化温度高于140℃的时间保持在1小时以上。
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