CN108570072B - 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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- 229910021389 graphene Inorganic materials 0.000 claims abstract description 27
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
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- UIBCDEFKKLRXHR-UHFFFAOYSA-N diethoxyphosphorylmethanamine Chemical compound CCOP(=O)(CN)OCC UIBCDEFKKLRXHR-UHFFFAOYSA-N 0.000 claims description 3
- RLRLWECTYYJXST-UHFFFAOYSA-N diphenoxyphosphorylmethanamine Chemical compound C=1C=CC=CC=1OP(=O)(CN)OC1=CC=CC=C1 RLRLWECTYYJXST-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
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- 238000010438 heat treatment Methods 0.000 abstract description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
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- 238000005406 washing Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
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- 239000007864 aqueous solution Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
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- 239000010452 phosphate Substances 0.000 description 3
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- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 2
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- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- 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)]
- C07F9/40—Esters thereof
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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，0.11 moL）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，0.11 moL）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-10~0℃，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、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。
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、四氢呋喃或其混合物。
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| KR20200104708A (ko) * | 2019-02-27 | 2020-09-04 | 현대자동차주식회사 | 기계적 강성 및 수소 이온 전도성이 향상된 연료전지용 막-전극 접합체 및 그 제조방법 |
| CN110643068B (zh) * | 2019-09-02 | 2020-12-22 | 厦门大学 | 形貌可调控的金属苯基膦酸酯阻燃材料、制备方法及其应用 |
| CN110903505B (zh) * | 2019-11-22 | 2022-05-06 | 桂林电器科学研究院有限公司 | 石墨烯增强的聚酰亚胺复合薄膜及其制备方法和人工石墨膜 |
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