CN108570072A - 一种合成膦酸改性石墨烯或膦酸酯改性石墨烯的方法 - Google Patents
一种合成膦酸改性石墨烯或膦酸酯改性石墨烯的方法 Download PDFInfo
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- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
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Abstract
本发明公开了一种膦酸改性石墨烯或膦酸酯改性石墨烯的方法，属无机新材料领域。该方法首先将氨基膦酸酯溶于溶剂中，控制温度，加入亚硝酸钠和酸搅拌均匀，再加入石墨烯反应。经过滤，洗涤，得到膦酸酯改性石墨烯。将膦酸酯改性石墨烯，氢氧化钠和水混合，加热反应，调节酸度，过滤，得到膦酸改性石墨烯。本发明工艺流程简单，条件温和，安全性高，成本低，提高了产物稳定性，实现了大量合成制备膦酸改性石墨烯或膦酸酯改性石墨烯工业化生产可能性。
Description
技术领域
本发明涉及合成膦酸改性石墨烯或膦酸酯改性石墨烯的方法，属无机新材料领域。
背景技术
石墨烯是一种新型碳材料，具有多种优异性能，如非同寻常的导电性能、超出钢铁数十倍的强度和良好的透光性，未来会有广泛应用。石墨烯理论比表面积大，很容易成为良好的吸附剂。近来，在石墨烯片层上引入羧基，胺基，磺酸基等用来提高其吸附性和选择性成为热点。
随着我国科技不断发展，高品质稀土元素需求不断增加。磷酸酯类萃取剂在稀土富集与纯化领域有很好的应用前景。目前很多研究致力于开发新型磷酸酯类萃取剂，比如有相关文献报道将磷酸酯（或膦酸酯）固定到石墨烯片层上，用于提高萃取高分离性和回收性。目前有掺杂改性方法，化学反应性改性法，但石墨烯亲水性不高，膦酸改性石墨烯或膦酸酯改性石墨烯的方法不够成熟，尤其将磷稳定地连接到片层的改性方法很难实现。因此，探索化学反应性改性法，将磷与石墨烯稳定连接，得到膦酸改性石墨烯（或膦酸酯）改性石墨烯十分必要，有利于稀土富集的开发和应用。
发明内容
本发明目的在于提供一种合成膦酸改性石墨烯或膦酸酯改性石墨烯的方法，提高产物稳定性，实现工业化制备膦酸（酯）改性石墨烯。
为实现本发明目的，本发明通过重氮盐与石墨烯反应，形成稳定的化学键，将磷与石墨烯连接，得到膦酸改性石墨烯或膦酸酯改性石墨烯。本发明具体技术方案通过下述步骤实现：
（1）将氨甲基膦酸酯溶于溶剂，控制温度-10~60℃，加入亚硝酸钠和酸，搅拌反应。
（2）加入石墨烯反应，反应结束后，回收溶剂，过滤，得到膦酸酯改性石墨烯。
（3）膦酸酯改性石墨烯在碱性溶液中水解，调节pH=3-4，得到膦酸改性石墨烯。
步骤（1）中，所述氨甲基膦酸酯包括氨甲基膦酸二甲酯、氨甲基膦酸二乙酯、氨甲基膦酸二苯酯、1-氨乙基膦酸二乙酯、O,O-二苯基-2-苯基-氨甲基膦酸酯及其衍生物。
步骤（1）中，所述溶剂为乙腈、四氢呋喃、水或其混合物等。
步骤（1）中，反应时间优选0.1~36小时。
步骤（2）中，所用石墨烯包括石墨剥离法制得石墨烯、沉积法制得石墨烯、氧化还原法制得石墨烯或氧化石墨烯等。石墨烯：氨甲基膦酸酯质量比=1：0.001~1000。
本发明创新点及优点在于：通过重氮盐与石墨烯反应，形成稳定的化学键，将磷与石墨烯连接，从而提高了产物稳定性，从根本上避免改性物‘丢失’的可能性。产物产率高，达 70 %以上，且终产物与原料容易分离。该方法在常温条件下，实现了大量制备膦酸改性石墨烯和膦酸酯改性石墨烯，适宜工业生产。
具体实施方式
以下结合具体的实施例对本发明技术方案作进一步说明：
实施例1
在500mL圆底瓶中，加入氨甲基膦酸二乙酯（16.7g，0.10 moL），亚硝酸钠（7.25g，0.11moL）和硫酸（32.3g，0.33 moL）。冰盐浴，控制在0摄氏度以下搅拌反应，大约60分钟。加入石墨烯（30 g），控温反应30分钟，自然恢复至室温。过滤，得到膦酸二乙酯改性石墨烯A1，收率80% 。氨甲基膦酸二乙酯改性石墨烯在氢氧化钠水溶液中反应，加热到80摄氏度，反应300分钟，用盐酸调节酸度，达到pH=3，过滤，得到膦酸改性石墨烯B1，收率70% 。
实施例2
在500mL圆底瓶中，加入氨甲基膦酸二苯酯（26.3g，0.10 moL），亚硝酸钠（7.25g，0.11moL）和硫酸（32.3g，0.33 moL）。冰盐浴，控制在0摄氏度以下搅拌反应，大约60分钟。加入石墨烯（8 g），控温反应240分钟，自然恢复至室温。过滤，得到膦酸二苯酯改性石墨烯A2，收率82% 。膦酸二苯酯改性石墨烯在氢氧化钠水溶液中反应，加热到80摄氏度，反应300分钟，用盐酸调节酸度，达到pH=3，过滤，得到膦酸改性石墨烯B2，收率71% 。
实施例3
在500mL圆底瓶中，加入O,O-二苯基-2-苯基-氨甲基膦酸酯（NH2CH(Ph)PO(OPh)2）（33.9g，0.10 moL）和四氢呋喃（20mL），亚硝酸钠（7.25g，0.11 moL）和硫酸（32.3g，0.33moL）。冰盐浴，控制在0摄氏度以下搅拌反应，大约60分钟。加入氧化石墨烯（4 g），控温反应240分钟，自然恢复至室温。过滤，得到膦酸二苯酯改性石墨烯A3，收率78%。膦酸二苯酯改性石墨烯，在氢氧化钠水溶液中反应，加热到80摄氏度，反应300分钟，用盐酸调节酸度，达到pH=4，过滤，得到膦酸改性石墨烯B3，收率76% 。
应用例
将本发明产品应用于亚甲基蓝回收和锂离子回收，在采用吸附法回收亚甲基蓝和锂离子过程中检测本发明产品的稳定性 ，百分数以首次吸附量为基准，情况如下：
表一 吸附法回收亚甲基蓝
| 样品 | 使用次数3 | 使用次数5 | 使用次数7 | 使用次数9 |
| A1 | 99% | 98% | 98% | 96% |
| A2 | 99% | 98*% | 95% | 94% |
| A3 | 99% | 97% | 95% | 94% |
| 焦磷酸改性石墨烯 | 91% | 88% | 81% | 71% |
表二 吸附法回收锂离子
| 样品 | 使用次数3 | 使用次数5 | 使用次数7 | 使用次数9 |
| B1 | 98% | 96% | 95% | 95% |
| B2 | 98% | 97*% | 97% | 96*% |
| B3 | 99% | 97% | 96% | 96% |
| 焦磷酸改性石墨烯 | 90% | 84% | 80% | 68% |
Claims (3)
1.膦酸改性石墨烯或膦酸酯改性石墨烯的制备方法，其特征在于：通过下述步骤实现：
（1）将氨甲基膦酸酯溶于溶剂，控制温度-10~60℃，加入亚硝酸钠和酸，搅拌反应；
（2）加入石墨烯反应，反应结束后，回收溶剂，过滤，得到膦酸酯改性石墨烯；
（3）膦酸酯改性石墨烯在碱性溶液中水解，调节pH=3-4，得到膦酸改性石墨烯；
步骤（1）中，所述氨甲基膦酸酯选氨甲基膦酸二甲酯、氨甲基膦酸二乙酯、氨甲基膦酸二苯酯、1-氨乙基基膦酸二乙酯、O,O-二苯基-2-苯基-氨甲基膦酸酯。
2.如权利要求1所述的膦酸改性石墨烯或膦酸酯改性石墨烯的制备方法，其特征在于：
步骤（2）中，所用石墨烯选石墨剥离法制得石墨烯、沉积法制得石墨烯、氧化还原法制得石墨烯或氧化石墨烯。
3.如权利要求1或2所述的膦酸改性石墨烯或膦酸酯改性石墨烯的制备方法，其特征在于：步骤（1）中，所述溶剂为乙腈、四氢呋喃、水或其混合物。
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