高性能CNA的制备及其在HMX基混合炸药中的应用
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摘要
为改善纤维素硝酸酯(NC)的力学性能,通过对纤维素进行硝酸与醋酸酯化的化学改性,制备了含有硝酸酯基、醋酸酯基双基团修饰的纤维素混合酯?纤维素硝酸醋酸混合酯(CNA)黏合剂。采用元素分析(EA)、动态热机械分析(DMTA)、热重法(TG)、差示扫描量热法(DSC)等表征了CNA的元素含量、在丙酮、乙酸乙酯、二氯甲烷等中的溶解性、热性能及相容性。测定了CNA粘结炸药的爆速、爆热和板痕。结果表明,制备的两种CNA的含氮量分别为4.27%、8.16%;醋酸酯基团的引入,提高了纤维素混合酯的溶解性,改善了分子链的柔顺性,较高醋酸酯基含量(1.28)的CNA的热稳定性较NC提高了6～13℃;CNA与大部分含能材料间具有较好的相容性;CNA可用作压装混合炸药的粘合剂。CNA粘结炸药比氟橡胶粘结炸药具有更高的能量性能。
To improve the mechanical properties of nitrocellulose(NC),a cellulose mixed ester modified with double groups of nitrate and acetate groups?cellulose nitrate?acetate mixed ester(CNA)adhesive was prepared through the chemical modification of esterifying cellulose using nitric acid and acetic acid. The elemental content,solubility in acetone,ethyl acetate,dichloromethane,etc.,thermal properties,and compatibility of CNA were characterized by elemental analyses(EA),dynamic mechanical thermal analysis(DMTA),thermogravimetry(TG),differential scanning calorimetry(DSC),etc.. The detonation velocity,heat of detonation and plate mark of CNA?bonded explosives were measured. Results show that the nitrogen contents of two kinds of CNAs prepared are 4.27% and 8.16%,respectively. The introduction of acetate groups increases the solubility of cellulose mixed esters and improves the flexibility of molecular chains. The thermal stability of CNA with larger acetate?group?content(1.28)is increased by 6 ℃ to 13 ℃ compared with that of NC. The compatibility between CNA and most energetic materials is good. CNA is used as a binder for press?packed mixed explosives. CNA?bonded explosives have higher energy performance than fluororubber?bonded explosives.
To improve the mechanical properties of nitrocellulose(NC),a cellulose mixed ester modified with double groups of nitrate and acetate groups?cellulose nitrate?acetate mixed ester(CNA)adhesive was prepared through the chemical modification of esterifying cellulose using nitric acid and acetic acid. The elemental content,solubility in acetone,ethyl acetate,dichloromethane,etc.,thermal properties,and compatibility of CNA were characterized by elemental analyses(EA),dynamic mechanical thermal analysis(DMTA),thermogravimetry(TG),differential scanning calorimetry(DSC),etc.. The detonation velocity,heat of detonation and plate mark of CNA?bonded explosives were measured. Results show that the nitrogen contents of two kinds of CNAs prepared are 4.27% and 8.16%,respectively. The introduction of acetate groups increases the solubility of cellulose mixed esters and improves the flexibility of molecular chains. The thermal stability of CNA with larger acetate?group?content(1.28)is increased by 6 ℃ to 13 ℃ compared with that of NC. The compatibility between CNA and most energetic materials is good. CNA is used as a binder for press?packed mixed explosives. CNA?bonded explosives have higher energy performance than fluororubber?bonded explosives.
引文
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[2]邵自强.硝化纤维素生产工艺及设备[M].北京:北京理工大学出版社,2002:1-3.SHAO Zi?qiang.Processing and equipment of nitrocellulose[M].Beijing:Beijing Institute of Technology Press,2002:1-3.
[3]李宁.基于含能热塑性弹性体的高能发射药研究[D].南京:南京理工大学,2013.LI Ning.Study on high energy propellant based on energetic thermoplastic elastomers[D].Nangjing:Nanjing University of Science and Technology,2010.
[4]Lili Li,Margaret Frey.Preparation and characterization of cellulose nitrate?acetate mixed ester fibers[J].Polymer,2010,51:3774-3783.
[5]Bell F H.Igniter for low vulnerability ammunition propellant ordnance?comprises potassium or sodium nitrate and cellulose acetate:US 4570540?A[P].1986,2.
[6]Thelma Manning,Jeffrey Wyckoff,Carlton Adam,et al.Formulation development and characterization of cellulose acetate nitratebased propellants for improved insensitive muni?tions properties[J].Defence Technology,2014,10:92-100.
[7]刘栓虎,程根旺,骆广梁.高能推进剂钝感含能材料研究现状[J].化学推进剂与高分子材料,2010,8(2):5-10.LIU Shuang?hu,CHENG Gen?wang,LUO Guang?liang.Re?search status of insensitive energetic materials used in high?en?ergy propellant[J].Chemical Propellants&Polymeric Materials,2010,8(2):5-10.
[8]石小兵,庞维强,蔚红建.钝感推进剂研究进展及发展趋势[J].化学推进剂与高分子材料,2007,5(2):24-28.SHI Xiao?bing,PANG Wei?qiang,WEI Hong?jian.Research progress and development trends of insensitive propellant[J].Chemical Propellants&Polymeric Materials,2007,5(2):24-28.
[9]赵超.高能钝感混合炸药的研究进展及发展趋势[J].兵工自动化,2013,32(1):67-70.ZHAO Chao.Research progress and trend of insensitive high mixture explosives[J].Ordnance Industry Automation,2013,32(1):67-70.
[10]毛润生,黄继才,伍风莲.氰乙基醋酸纤维素乙酰基含量分析[J].广州化学,1990,1:50-56.MAO Run?sheng,HUANG Ji?cai,WU Feng?lian.Acetyl con?tent analysis of cyanoethyl cellulose acetate[J].Guangzhou Chemistry,1990,1:50-56.
[11]王瑞,孟子晖,薛敏,等.DSC法研究高能炸药TEX与推进剂组分的相容性[J].火炸药学报,2015,2(38):66-69.WANG Rui,MENG Zi?hui,XUE Min,et al.Compatibility of high energetic explosive TEX with components of propellants by DSC method[J].Chinese Journal of Explosives and Propellants,2015,2(38):66-69.
[12]毕福强,葛忠学,孙序东,等.1,1'?二羟基?5,5'?联四唑二羟胺盐和CMDB推进剂组份的相容性[J].含能材料,2014,22(5):716-718.BI Fu?qiang,GE Zhong?xue,SUN Xu?dong,et al.Compatibili?ty of dihydroxylammonium 5,5'?bistetrazole?1,1'?diolate with components of CMDB propellant[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2014,22(5):716-718.
[13]刘子如.含能材料热分析[M].北京:国防工业出版社,2008:22-23.LIU Zi?ru.Thermal analyses for energetic materials[M].Bei?jing:National Defence Industry and Technology,2001.
[14]Gogulya M F,Makhov M N,Brazhnikov M A,et al.Explosive Characteristics of Aluminized HMX?Based Nanocomposites[J].Combustion Explosion and Shock Waves,2008,2(44):198-212.
[15]夏建才.火工品制造[M].北京:北京理工大学出版社,2009:78.XIA Jian?cai.Pyrotechnics manufacturing[M].Beijing:Beijing Institute of Technology Press,2009:78.