改性氧化石墨烯/聚氨酯复合包覆层的制备与性能测试
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摘要
为提升固体推进剂中聚氨酯包覆层的耐热性能并降低残渣率,对原有包覆层体系进行了改性研究;用异佛尔酮二异氰酸酯(IPDI)改性氧化石墨烯;采用XRD、FT-IR和Raman光谱对改性后的氧化石墨烯(MGO)进行了表征;分析了MGO在3种有机溶剂(正庚烷、乙酸正丁酯和N,N-二甲基甲酰胺)中的分散性;以溶液共混法制备了改性氧化石墨烯(MGO)/聚氨酯复合包覆层材料,并测试了其力学性能、耐烧蚀性能和残渣率。结果表明,经过IPDI改性后,MGO在DMF和乙酸正丁酯中有较好的分散效果;相较于原聚氨酯包覆层材料,MGO质量分数为5%的复合聚氨酯包覆层表现出更好的使用性能,其50%定伸应力提高31. 85%,拉伸强度下降5. 25%,线烧蚀速率和残渣率分别降低34. 10%和17. 71%,表明使用性能有明显提高。
To improve the heat resistance of polyurethane coating layer in solid propellant and decrease the residue rate,the original coating layer system was modified. Graphene oxide was modified by isophorone diisocyanate(IPDI). The modified graphene oxide(MGO) was characterized by XRD,FTIR and Raman spectra. The dispersity of MGO in three kinds of organic solvents(n-heptane,n-butyl acetate and N,N-dimethylformamide(DMF)) was analyzed. MGO/polyurethane composite coating layer were prepared by solution blending method. Its mechanical properties,ablation resistance performance and residue rate were tested. The results show that MGO has good dispersion effect in DMF and n-butyl acetate after modified by IPDI. Polyurethane coating layer composites with the incorporation of 5 % of MGO shows better properties. When compared with the original polyurethane coating layer,its 50 % modulus increase by 31. 85 % and tensile strength decrease by 5. 25 %. The linear ablation rate and residue rate decrease by 34. 10 % and 17. 71 %,respectively,which means that the service performances are significantly improved.
To improve the heat resistance of polyurethane coating layer in solid propellant and decrease the residue rate,the original coating layer system was modified. Graphene oxide was modified by isophorone diisocyanate(IPDI). The modified graphene oxide(MGO) was characterized by XRD,FTIR and Raman spectra. The dispersity of MGO in three kinds of organic solvents(n-heptane,n-butyl acetate and N,N-dimethylformamide(DMF)) was analyzed. MGO/polyurethane composite coating layer were prepared by solution blending method. Its mechanical properties,ablation resistance performance and residue rate were tested. The results show that MGO has good dispersion effect in DMF and n-butyl acetate after modified by IPDI. Polyurethane coating layer composites with the incorporation of 5 % of MGO shows better properties. When compared with the original polyurethane coating layer,its 50 % modulus increase by 31. 85 % and tensile strength decrease by 5. 25 %. The linear ablation rate and residue rate decrease by 34. 10 % and 17. 71 %,respectively,which means that the service performances are significantly improved.
引文
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[23]时艺娟,张艳,仲许灵.降低聚氨酯包覆层修补率措施探讨[J].化工新型材料,2016,44(6):235-236,239.SHI Yi-juan,ZHANG Yan,ZHONG Xu-ling,et al. Discussion on measure to reduce the patching ratio of PU inhibitor[J]. New Chemical Materials,2016,44(6):235-236,239.
[24]刘益军.聚氨酯原料及助剂手册[M].北京:化学工业出版社,2012.
[25]孙哲,何亚洲,范浩军,等.石墨烯/聚氨酯复合涂饰剂的制备及性能研究[J].皮革科学与工程,2016,26(5):10-15.SUN Zhe,HE Ya-zhou,FAN Hao-jun,et al. The preparation and properties of graphene/polyurethane composites for leather finishing[J]. Leather Science and Engineering,2016,26(5):10-15.
[26] Chen W,Liu P,Min L,et al. Non-covalently functionalized graphene oxide-based coating to enhance thermal stability and flame retardancy of PVA film[J]. Nano-micro Letters,2018,10(3):39.
[27] Wang X,Hu Y,Song L,et al. Insitu polymerization of graphene nanosheets and polyurethane with enhanced mechanical and thermal properties[J]. Journal of materials Chemistry,2011,21(12):4222-4227.
[28]傅晓莉.组分对发射药燃烧残渣形成的影响研究[D].南京:南京理工大学,2010.FU Xiao-li. Study on the effect of components on the formation of propellant combustion residue[D]. Nanjing:Nanjing University of Science and Technology,2010.
[2]史爱娟,覃光明,王吉贵.聚氨酯包覆层的现状及展望[J].火炸药学报,2002,25(3):58-60,65.SHI Ai-juan,QIN Guang-ming,WANG Ji-gui. Current status of polyurethane inhibitors and prospect[J]. Chinese Journal of Explosives&Propellants(Huozhayao Xuebao),2002,25(3):58-60,65.
[3]史爱娟,李冬,曹继平,等.异氰酸酯指数对聚氨酯包覆层性能的影响[J].化工新型材料,2015,43(8):198-200.SHI Ai-juan,LI Dong,CAO Ji-ping,et al. Influence of isocyanate index on the property of polyurethane inhibitor[J]. New Chemical Materials,2015,43(8):198-200.
[4]常海,张腊莹,刘子如,等.磷酸盐阻燃剂对聚氨酯包覆层动态力学性能的影响[J].火炸药学报,2009,32(2):60-63.CHANG Hai,ZHANG La-ying,LIU Zi-ru,et al. Influence of phosphate deterrent on dynamic mechanical properties of polyurethane coating[J]. Chinese Journal of Explosives&Propellants(Huozhayao Xuebao),2009,32(2):60-63.
[5]张晨,冯圣玉.填料对聚氨酯性能的影响[J].化工进展,2004,23(4):418-420.ZHANG Chen,FENG Sheng-yu. Effect of fillers on properties of polyurethane[J]. Chemical Industry and Engineering Progress,2004,23(4):418-420.
[6] Lee J W,Hall A S,Kim J D,et al. A facile and template-free hydrothermal synthesis of Mn3O4nanorods on graphene sheets for supercapacitor electrodes with long cycle stability[J]. Chemistry of Materials,2012,24(6):1158-1164.
[7] Jiang R,Zhou X,Liu Z. Electroless ni-plated graphene for tensile strength enhancement of copper[J].Materials Science and Engineering:A,2017,679:323-328.
[8] Hou Y,Duan L,Gui Z,et al. An infiltration method to synthesize thermoplastic polyurethane composites based on size-controlled graphene foams[J]. Composites Part A:Applied Science and Manufacturing, 2017, 97:67-75.
[9] Liang J Z,Wang J Z,Tsui G C P,et al. Thermal properties and thermal stability of polypropylene composites filled with graphene nanoplatelets[J]. Journal of Thermoplastic Composite Materials,2017,31(2):246-264.
[10] Zhang S, Liu P, Zhao X, et al. Enhanced tensile strength and initial modulus of poly(vinyl alcohol)/graphene oxide composite fibers via blending poly(vinyl alcohol)with poly(vinyl alcohol)-grafted graphene oxide[J]. Journal of Polymer Research,2018,25(3):65.
[11] Tao C,Zhang H,Huang J,et al. Reduction versus cross-linking:how to improve the tensile strength of graphene oxide/polyvinyl alcohol composite film[J]. Materials Research Express,2017,4(8):085601.
[12] Bhattacharyya A,Chen S,Zhu M. Graphene reinforced ultra high molecular weight polyethylene with improved tensile strength and creep resistance properties[J]. Express Polymer Letters,2014,8(2):74-84.
[13]吴淑新,姚逸伦,史爱娟,等.聚氨酯在固体推进剂包覆层中的应用[J].化学推进剂与高分子材料,2010,8(6):14-16,21.WU Shu-xin,YAO Yi-lun,SHI Ai-juan,et al. Application of polyurethane in solid propellant coating layer[J].Chemical Propellants and Polymeric Materials,2010,8(6):14-16,21.
[14] Reid D L,Draper R,Richardson D,et al. Insitu synthesis of polyurethane-TiO2nanocomposite and performance in solid propellants[J]. Journal of Materials Chemistry A,2014,2(7):2313-2322.
[15] Lemos M F,Bohn M A. DMA of polyester-based polyurethane elastomers for composite rocket propellants containing different energetic plasticizers[J]. Journal of Thermal Analysis and Calorimetry,2018,131(1):595-600.
[16]吴淑新,史爱娟,姚逸伦,等.异氰脲酸酯改性聚氨酯弹性体包覆层研究[J].化学推进剂与高分子材料,2011,9(2):53-55.WU Shu-xin,SHI Ai-juan,YAO Yi-lun,et al. Study on isocyanurate-modified polyurethane elastomer coating layer[J]. Chemical Propellants and Polymeric Materials,2011,9(2):53-55.
[17] Dreyer D R,Ruoff R S,Bielawski C W. From conception to realization:an historial account of graphene and some perspectives for its future[J]. Angewandte Chemie International Edition,2010,49(49):9336-9344.
[18] Dreyer D R,Park S,Bielawski C W,et al. The chemistry of graphene oxide[J]. Chemical Society Reviews,2010,39(1):228-240.
[19]李晓萱,于涛,伍胜利.甲苯二异氰酸酯插层改性氧化石墨烯[J].化工新型材料,2014,42(4):81-83.LI Xiao-xuan,YU Tao,WU Sheng-li. Intercalation and modification of graphene oxide with toluene diisocyanate[J]. New Chemical Materials,2014,42(4):81-83.
[20]于涛.石墨烯/水性聚氨酯纳米复合材料的制备与性能研究[D].合肥:合肥工业大学,2013.YU Tao. Preparations and properties of waterborne polyure-thane/graphene nanocomposites[D]. Hefei:Hefei University of Technology,2013.
[21]朱明华,胡坪.仪器分析[M].北京:高等教育出版社,2008.
[22]吴力.石墨烯功能化改性及其聚氨酯纳米复合材料的制备[D].广州:华南理工大学,2014.WU Li. Preparation of graphene functional modification and its polyurethane nanocomposites[D]. Guangzhou:South China University of Technology,2014.
[23]时艺娟,张艳,仲许灵.降低聚氨酯包覆层修补率措施探讨[J].化工新型材料,2016,44(6):235-236,239.SHI Yi-juan,ZHANG Yan,ZHONG Xu-ling,et al. Discussion on measure to reduce the patching ratio of PU inhibitor[J]. New Chemical Materials,2016,44(6):235-236,239.
[24]刘益军.聚氨酯原料及助剂手册[M].北京:化学工业出版社,2012.
[25]孙哲,何亚洲,范浩军,等.石墨烯/聚氨酯复合涂饰剂的制备及性能研究[J].皮革科学与工程,2016,26(5):10-15.SUN Zhe,HE Ya-zhou,FAN Hao-jun,et al. The preparation and properties of graphene/polyurethane composites for leather finishing[J]. Leather Science and Engineering,2016,26(5):10-15.
[26] Chen W,Liu P,Min L,et al. Non-covalently functionalized graphene oxide-based coating to enhance thermal stability and flame retardancy of PVA film[J]. Nano-micro Letters,2018,10(3):39.
[27] Wang X,Hu Y,Song L,et al. Insitu polymerization of graphene nanosheets and polyurethane with enhanced mechanical and thermal properties[J]. Journal of materials Chemistry,2011,21(12):4222-4227.
[28]傅晓莉.组分对发射药燃烧残渣形成的影响研究[D].南京:南京理工大学,2010.FU Xiao-li. Study on the effect of components on the formation of propellant combustion residue[D]. Nanjing:Nanjing University of Science and Technology,2010.