碳纳米管的改性及其复合材料性能的研究
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摘要
在本论文中,通过二乙胺和环氧氯丙烷间的反应合成了聚季铵盐,然后用聚季铵盐修饰酸氧化处理过的碳纳米管(CNTs)。本文采用浓硫酸和浓硝酸对碳纳米管进行混酸氧化,使碳纳米管壁上生成羧基。将羧基化的碳纳米管在二环已基碳二亚胺(DCC)催化下与聚季铵盐进行缩合反应生成酯基。对产品进行水溶性测试,结果表明,与聚季铵盐缩合反应后的碳纳米管水溶性大大提高。
通过用不同混酸处理时间的碳纳米管来制备不同聚乙烯醇高分子基碳纳米管复合材料。应用混酸氧化的方法使碳纳米管表面的缺陷氧化形成羧基,再借助超声波的作用,使CNTs均匀分散于单体中,然后通过溶液混合的方法制备了碳纳米管/聚乙烯醇(CNTs/PVA)复合材料。通过透射电镜和扫描电镜观察了CNTs的分散状况和材料的结构,然后对材料的力学性能及热学性能进行了研究,并探讨了CNTs对复合材料的结构和性能的影响。
实验结果表明,氧化后的CNTs在基体中分散良好,两相间有较好的相容性,材料的力学性能得到提高,氧化时间对材料的力学性能有较大的影响,在CNTs的氧化时间为0.5h左右时达到最好的效果。CNTs/PVA复合材料的耐高温性能远远大于单独聚乙烯醇材料的耐高温性,并且加入的碳纳米管酸化的时间越长耐高温性越好。
In this paper, polyquaternary ammonium salts were synthesized by the reaction of diethylamine with epichlorohydrin, and then oxidation-treated carbon nanotubes (CNTs) with acids were modified using the resulting polyquaternary ammonium salts. Carboxyls in the tube wall of CNTs were produced via oxidizing CNTs under the action of mixed concentrated sulfuric acid and nitric acid, and lastly were converted to ester groups through reacting with polyquaternary ammonium salts using dicyclohexylcarbodiimide (DCC) as a catalyzer. Water solubility of the product was analyzed. Results indicated that the water solubility was greatly improved.
Different polyvinyl alcohol/CNTs composite materials were prepared via altering the treating time of mixed acid, and the surface defect of CNTs was oxidized to carboxyl. Then the CNTs were dispersed in monomer under ultrasonic and polyvinyl alcohol/CNTs composite materials were obtained by mixing the solutions. The dispersed state and the structure of CNTs were characterized by transmission electron microscopy and scanning electron microscopy. Mechanical property and thermal characteristic of the composite materials were studied. In addition, effect of CNTs on the structure and the performance of the composite materials were researched.
Based on our experiment results the oxidized CNTs dispersed well in the matrix, and the mechanical property of materials was improved. The effect of oxidation time on the mechanical property of materials was quite great. The optimal oxidation time was 0.5 h. The high temperature resistant capability of polyvinyl alcohol/CNTs composite materials was far more than polyvinyl alcohol. Besides, the longer of acidifying time for CNTs, the better of the high temperature resistant capability.
通过用不同混酸处理时间的碳纳米管来制备不同聚乙烯醇高分子基碳纳米管复合材料。应用混酸氧化的方法使碳纳米管表面的缺陷氧化形成羧基,再借助超声波的作用,使CNTs均匀分散于单体中,然后通过溶液混合的方法制备了碳纳米管/聚乙烯醇(CNTs/PVA)复合材料。通过透射电镜和扫描电镜观察了CNTs的分散状况和材料的结构,然后对材料的力学性能及热学性能进行了研究,并探讨了CNTs对复合材料的结构和性能的影响。
实验结果表明,氧化后的CNTs在基体中分散良好,两相间有较好的相容性,材料的力学性能得到提高,氧化时间对材料的力学性能有较大的影响,在CNTs的氧化时间为0.5h左右时达到最好的效果。CNTs/PVA复合材料的耐高温性能远远大于单独聚乙烯醇材料的耐高温性,并且加入的碳纳米管酸化的时间越长耐高温性越好。
In this paper, polyquaternary ammonium salts were synthesized by the reaction of diethylamine with epichlorohydrin, and then oxidation-treated carbon nanotubes (CNTs) with acids were modified using the resulting polyquaternary ammonium salts. Carboxyls in the tube wall of CNTs were produced via oxidizing CNTs under the action of mixed concentrated sulfuric acid and nitric acid, and lastly were converted to ester groups through reacting with polyquaternary ammonium salts using dicyclohexylcarbodiimide (DCC) as a catalyzer. Water solubility of the product was analyzed. Results indicated that the water solubility was greatly improved.
Different polyvinyl alcohol/CNTs composite materials were prepared via altering the treating time of mixed acid, and the surface defect of CNTs was oxidized to carboxyl. Then the CNTs were dispersed in monomer under ultrasonic and polyvinyl alcohol/CNTs composite materials were obtained by mixing the solutions. The dispersed state and the structure of CNTs were characterized by transmission electron microscopy and scanning electron microscopy. Mechanical property and thermal characteristic of the composite materials were studied. In addition, effect of CNTs on the structure and the performance of the composite materials were researched.
Based on our experiment results the oxidized CNTs dispersed well in the matrix, and the mechanical property of materials was improved. The effect of oxidation time on the mechanical property of materials was quite great. The optimal oxidation time was 0.5 h. The high temperature resistant capability of polyvinyl alcohol/CNTs composite materials was far more than polyvinyl alcohol. Besides, the longer of acidifying time for CNTs, the better of the high temperature resistant capability.
引文
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[2]聂海瑜.碳纳米管的制备[J],塑料工业,2004,10(32):11-4.
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[14]李文治,解思深,钱露茜等.纳米碳管催化热解方法的制备及其微观结构的研究,电子显微学报,1998,17(3):243-247.
[15] Bahr J L, Mickelson E T, Bronikowski M J. Dissolution of small diameter single-wall carbon nanotubes in organic solvents [J], Chem Common, 2001: 193-194.
[16]龚晓钟,汤皎宁,古坤明.碳纳米管分散性的研究[J],深圳大学,2005,4:1-3.
[17] Arefmanesh A, Advani S G. Nonisothermal Bubble Growth in Poly-meric Foams[J], Poly, Eng Sci, 1995, 35 (3) : 252-260.
[18] O’Connell M J, Boul P, Ericson L M. Reversible water-solubilization of single-walledcarbon nanotubes by polymer wrapping[J], Chem Phys Lett, 2001, 342: 265-271.
[19] O’Connell M J, Bachilo S M, Huffmann C B. Band gap fluorescence from individual single walled carbon nanotubes[J], Science, 2002, 297: 597.
[20] Dalton A B, Stephan C, Coleman J N. Selective interaction of asemiconjugated organic polymer with single-wall nanotubes[J], Phys Chem B, 2000, 104: 10012-10 016.
[21] Star A, Steuerman D W, Heath J R. Starched carbon nanotubes[J], Angew Chem Int Ed Engl, 2002, 41: 2508-2 512.
[22] Chambers G, Carroll C, Farrell G F. Characterization of the interaction of gamma cyclodextrin with single-walled carbon nanotubes[J], Nano Lett, 2003(3): 843-846.
[23] Chen Jian, Liu Haiying, Weimer W A. Functional conjugated polymers [J], J Am Chem Soc, 2002, 124: 9034-9035.
[24]杨杰,沈曾民,熊涛.聚苯胺原位包裹碳纳米管材料的制备及性能[J],新型炭材料,2003,18(2):95-100.
[23]余荣清,程大典,詹梦熊.液相化学腐蚀法用于碳纳米管的纯化及顶端开口研究[J],化学通报,1996(4):25-26.
[24]杨占红,李新海,王红强.碳纳米管的提纯-重铬酸钾氧化法[J],化学世界,1999 (12):627-630.
[25] Ausman K D, Piner R, Lourie O. Organic solvent dispersions of single-walled carbon nanotubes, toward solutions of nanotubes[J], J Phy Chem B, 2000, 104:8911-8915.
[26]曹春华,李家麟,贾志杰.用二胺在碳纳米管上引入胺基团的研究[J],新型碳材料,2004,19(2): 137-140.
[27] Wang Y. Photophysical properties of fullereenes and fullerene/N,Ndiethylaniline charge-transfer complexs[J], J Phys Chem, 1992, 96: 764-767.
[28] Ajayan P M, Ebbesen T W, Ichihashi T. Opening carbon nanotubes with oxygen and implications for filling[J], Nature, 1993, 362:522-525.
[29]郭玲香,郝晓红.聚季铵盐与丙烯酰胺的接枝聚合[J],高分子材料科学与工程,2003,6(19):70-75.
[30]王哲,黄玉东,岳姗姗.水溶性聚季铵盐修饰多壁碳纳米管的制备[J],黑龙江大学自然科学学报,2007,6(24):787-790.
[31]刘爱红,孙康宁,王菲.壳聚糖对碳纳米管的表面修饰[J],硅酸盐学报,2008,2(36):28-31.
[2]聂海瑜.碳纳米管的制备[J],塑料工业,2004,10(32):11-4.
[3]成会明.纳米碳管制备、结构、物性及应用[M],化学工业出版社,北京,2002.
[4] Krishnan A, Dujardin E, Ebbesen T W, Yianilos P N and Treacy M J. Young’s modulus of single-walled nanootubes, Physical Review B, 1998, 58: 14013-14019.
[5] Safadi B, Andrews R, Grulke E A. Multiwalled carbon nanotube polymer composites, Synthesls and characterization of thin films [J], J Appl Polym Sci, 2002, 84:2660-669.
[6] Naedeli M B, Brabec C, Maiti A, Roland C, Bernholc J. Lip-lip interactions and the growth of multiwalled carbon nanotubes, Physical review leters, 1998, 80(2): 313-316.
[7] Huang J Y, Chen S, Wang Z Q, Kempa K. Superplastic carbon nanotubes, Nature, 439:281.
[8] Saito Y. Field emission from multi-walled carbon nanotubes and its application to electron tubes, Appl Phys A67, 1998: 95-100.
[9] Long Y, Chen Z, Zhang X. et al. Electrieal properties of MWNT/Polyrrole nanoeables, Percolation-dominated conductivity[J], J PhysD: ApplPhys, 2004, 34:1965-1969.
[10] Heer W A, Chatelain A, Ugrate D A. Carbon nanotube field-emission electron source[J], Science, 1995, 270: 1179-1180.
[11] Brenner D W, Empirical potential for hydrocarbons for use in simulating the chemical vapor deposition of diamond films. Physical Review B, 1990, 42: 9458-9471.
[12]曹肇基,解思深.碳纳米管研究的最新进展,物理,1998,27(12):707-709.
[13]吕德义,陈万喜,徐铸德.碳纳米管的制备[J],化学通报,2000,63(10):15-21.
[14]李文治,解思深,钱露茜等.纳米碳管催化热解方法的制备及其微观结构的研究,电子显微学报,1998,17(3):243-247.
[15] Bahr J L, Mickelson E T, Bronikowski M J. Dissolution of small diameter single-wall carbon nanotubes in organic solvents [J], Chem Common, 2001: 193-194.
[16]龚晓钟,汤皎宁,古坤明.碳纳米管分散性的研究[J],深圳大学,2005,4:1-3.
[17] Arefmanesh A, Advani S G. Nonisothermal Bubble Growth in Poly-meric Foams[J], Poly, Eng Sci, 1995, 35 (3) : 252-260.
[18] O’Connell M J, Boul P, Ericson L M. Reversible water-solubilization of single-walledcarbon nanotubes by polymer wrapping[J], Chem Phys Lett, 2001, 342: 265-271.
[19] O’Connell M J, Bachilo S M, Huffmann C B. Band gap fluorescence from individual single walled carbon nanotubes[J], Science, 2002, 297: 597.
[20] Dalton A B, Stephan C, Coleman J N. Selective interaction of asemiconjugated organic polymer with single-wall nanotubes[J], Phys Chem B, 2000, 104: 10012-10 016.
[21] Star A, Steuerman D W, Heath J R. Starched carbon nanotubes[J], Angew Chem Int Ed Engl, 2002, 41: 2508-2 512.
[22] Chambers G, Carroll C, Farrell G F. Characterization of the interaction of gamma cyclodextrin with single-walled carbon nanotubes[J], Nano Lett, 2003(3): 843-846.
[23] Chen Jian, Liu Haiying, Weimer W A. Functional conjugated polymers [J], J Am Chem Soc, 2002, 124: 9034-9035.
[24]杨杰,沈曾民,熊涛.聚苯胺原位包裹碳纳米管材料的制备及性能[J],新型炭材料,2003,18(2):95-100.
[23]余荣清,程大典,詹梦熊.液相化学腐蚀法用于碳纳米管的纯化及顶端开口研究[J],化学通报,1996(4):25-26.
[24]杨占红,李新海,王红强.碳纳米管的提纯-重铬酸钾氧化法[J],化学世界,1999 (12):627-630.
[25] Ausman K D, Piner R, Lourie O. Organic solvent dispersions of single-walled carbon nanotubes, toward solutions of nanotubes[J], J Phy Chem B, 2000, 104:8911-8915.
[26]曹春华,李家麟,贾志杰.用二胺在碳纳米管上引入胺基团的研究[J],新型碳材料,2004,19(2): 137-140.
[27] Wang Y. Photophysical properties of fullereenes and fullerene/N,Ndiethylaniline charge-transfer complexs[J], J Phys Chem, 1992, 96: 764-767.
[28] Ajayan P M, Ebbesen T W, Ichihashi T. Opening carbon nanotubes with oxygen and implications for filling[J], Nature, 1993, 362:522-525.
[29]郭玲香,郝晓红.聚季铵盐与丙烯酰胺的接枝聚合[J],高分子材料科学与工程,2003,6(19):70-75.
[30]王哲,黄玉东,岳姗姗.水溶性聚季铵盐修饰多壁碳纳米管的制备[J],黑龙江大学自然科学学报,2007,6(24):787-790.
[31]刘爱红,孙康宁,王菲.壳聚糖对碳纳米管的表面修饰[J],硅酸盐学报,2008,2(36):28-31.