乙基纤维素微胶囊红磷的制备及性能表征
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摘要
目前微胶囊红磷大多采用原位聚合法制备,工艺较为复杂,使用的囊壳原料可能对环境造成危害。为解决这一问题,本文以可降解材料乙基纤维素(EC)为壁材,无水乙醇为壁材溶剂,蒸馏水为壁材非溶剂,采用相分离法制备微胶囊红磷,并利用FTIR、SEM及XPS表征微胶囊红磷的形态及包覆效果,同时对样品的热稳定性、吸湿性及感度进行测定,以此确定最佳工艺条件。实验结果表明:经EC包覆后的红磷样品表面粗糙,包覆率随乙基纤维素添加量的增多而升高,最高可达94.8%;EC囊壳能有效提高红磷的热稳定性及安定性,降低吸湿率。在保证红磷正常使用不受影响的前提下,取0.6g乙基纤维素、2g红磷为最佳工艺条件,包覆率达93.2%;制备的微胶囊红磷样品热稳定性提高,着火点升高至310℃;10d后吸湿率降低至6.8%,较普通红磷降低约16.8%;微胶囊红磷摩擦感度降至34%,较未处理红磷降低52%。采用相分离法在常温、中性条件下制备EC包覆微胶囊红磷,工艺简便,材料绿色环保,制备的微胶囊红磷样品具有良好的使用性能。
Microencapsulation red phosphorus(MRP) were generally prepared by in-situ method at present. While the preparation process was complex and the shell raw material may do harm to environment. To solve the problem above, biodegradable material ethyl cellulose(EC) was selected as shell material of MRP. Meanwhile, with ethyl alcohol and distilled water serving as solvent and nonsolvent for EC respectively, phase separation method was applied to EC coating MRP preparation. The morphology and encapsulation ratio of MRP were tested by FTIR, SEM and XPS. The thermal stability,water absorption and sensitivity of MRP were also characterized to determine the optimal process conditions. The results indicated that after being encapsulated by EC, MRP exhibited a rougher surface morphology. The encapsulation ratio can reach to 94.8% with the addition of increasing EC. Meanwhile,the introduction of EC shell structure improved the thermal stability and mechanical stability of pristine red phosphorus(RP), while reduced the water absorption. On the premise of the performance of RP being affected least, 0.6 g EC and 2 g RP were selected as the optimal process condition. MRP prepared under such condition got a satisfied encapsulation ratio as 93.2%. Furthermore, the ignition point of the sample increased to 310℃, and the water absorption decreased to 6.8%, reducing by 16.8% compared with RP.The friction sensitivity of MRP decreased to 34%, which was 52% lower than pristine red phosphorus.Phase separation method allowed MRP preparation conducting under a normal temperature and neutral condition, simplifying the technological process. EC was more environmental than traditional organic shell material, and the sample satisfied the needs of practical application.
Microencapsulation red phosphorus(MRP) were generally prepared by in-situ method at present. While the preparation process was complex and the shell raw material may do harm to environment. To solve the problem above, biodegradable material ethyl cellulose(EC) was selected as shell material of MRP. Meanwhile, with ethyl alcohol and distilled water serving as solvent and nonsolvent for EC respectively, phase separation method was applied to EC coating MRP preparation. The morphology and encapsulation ratio of MRP were tested by FTIR, SEM and XPS. The thermal stability,water absorption and sensitivity of MRP were also characterized to determine the optimal process conditions. The results indicated that after being encapsulated by EC, MRP exhibited a rougher surface morphology. The encapsulation ratio can reach to 94.8% with the addition of increasing EC. Meanwhile,the introduction of EC shell structure improved the thermal stability and mechanical stability of pristine red phosphorus(RP), while reduced the water absorption. On the premise of the performance of RP being affected least, 0.6 g EC and 2 g RP were selected as the optimal process condition. MRP prepared under such condition got a satisfied encapsulation ratio as 93.2%. Furthermore, the ignition point of the sample increased to 310℃, and the water absorption decreased to 6.8%, reducing by 16.8% compared with RP.The friction sensitivity of MRP decreased to 34%, which was 52% lower than pristine red phosphorus.Phase separation method allowed MRP preparation conducting under a normal temperature and neutral condition, simplifying the technological process. EC was more environmental than traditional organic shell material, and the sample satisfied the needs of practical application.
引文
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[18]徐华,林粤顺,周红军,等.毒死蜱/乙基纤维素微胶囊的制备及其缓释性能[J].化工进展, 2017, 36(12):4622-4627.XU H, LIN Y S, ZHOU H J, et al. Preparation and sustained release of chlorpyrifos/ethyl cellulose microcapsules[J]. Chemical Industry and Engineering Progress, 2017, 36(12):4622-4627.
[19] YU Z P, WANG X, ZHANG X M, et al. Preparation of melamine formaldehyde resin coated red phosphorus by inverse suspension polymerization[J]. Journal of Natural Science of Hunan Normal University, 2015, 38(5):59-63.
[20]王玄玉,潘功配.红磷烟幕对10.6μm激光的消光系数测试研究[J].红外与激光工程, 2005, 34(6):636-640.WANG X Y, PAN G P. Study and test of extinction coefficient of red phosphorus smoke to 10.6μm laser emission[J]. Infrared and Laser Engineering, 2005, 34(6):636-640.
[21]鲁涛,赵雁,欧阳的华.含能材料表面分形维数计算及其对摩擦感度影响[J].计算机与应用化学, 2014, 31(2):226-230.LU T, ZHAO Y, OUYANG D H. Estimation of surface fractal dimension of energetic materials and influence on friction sensitivity[J]. Computer and Applied Chemistry, 2014, 31(2):226-230.
[2] LI J, CHEN X, WANG Y L, et al. Burning and radiance properties of red phosphorus in magnesium/PTFE/Viton(MTV)-based compositions[J]. Infrared Physics and Technology, 2017, 85:109-113.
[3]马千,刘增杰,梁轶,等.二元醇改性密胺甲醛树脂包覆红磷[J].应用化学, 2015, 32(10):1153-1158.MA Q, LIU Z J, LIANG Y, et al. Encapsulated red phosphorus in dihydric alcohol modified melamine formaldehyde resin[J]. Chinese Journal of Applied Chemistry, 2015, 32(10):1153-1158.
[4] LIU J C, PENG S G, ZHANG Y B, et al. Influence of microencapsulated red phosphorus on the flame retardancy of high impact polystyrene/magnesium hydroxide composite and its mode of action[J]. Polymer Degradation&Stability, 2015, 121:208-221.
[5] CAO Z J, DONG X, FU T, et al. Coated vs. naked red phosphorus:a comparative study on their fire retardancy and smoke suppression for rigid polyurethane foams[J]. Polymer Degradation and Stability, 2017,136:103-111.
[6] LIU J, GUAN H. Preparation, characterization and performance of microencapsulated red phosphorus[J]. Propellants, Explosives,Pyrotechnics, 2017, 42:1-9.
[7] JIAN R K, CHEN L, HU Z, et al. Flame-retardant polycarbonate/acrylonitrile-butadiene-styrene based on red phosphorus encapsulated by polysiloxane:flame retardance, thermal stability, and water resistance[J]. Journal of Applied Polymer Science, 2012, 123(5):2867-2874.
[8] LONG Y, SONG K, YORK D, et al. Composite microcapsules with enhanced mechanical stability and reduced active ingredient leakage[J]. Particuology, 2016, 26(3):40-46.
[9]陈海群,卑凤利,王志成,等.微胶囊化超细红磷的制备及其安定性研究[J].无机材料学报, 2004, 20(8):905-909.CHEN H Q, BEI F L, WANG Z C, et al. Preparation and stability of microencapsulated ultrafine red phosphorus[J]. Chinese Journal of Inorganic Chemistry, 2004, 20(8):905-909.
[10] LIU J, SONG D M, GUAN H. Preparation and characterization of microcapsule red phosphorus and its multi-step thermal oxidation processes based on kinetic approach[J]. Russian Journal of Applied Chemistry, 2016, 89(6):1009-1018.
[11]李娜,鲍远志,翁世兵,等.微胶囊红磷在木塑复合材料中的阻燃研究[J].林产工业, 2016, 43(7):28-31.LI N, BAO Y Z, WENG S B, et al. Study on flame resistance of inorganic encapsulated red phosphorus application in wood-plastic composite[J]. China Forest Products Industry, 2016, 43(7):28-31.
[12]朱超,李惠萍,陈世军,等.白度化微胶囊红磷阻燃剂的研究与制备[J].现代化工, 2015, 35(4):138-140.ZHU C, LI H P, CHEN S J, et al. Preparation of whitening red phosphorus microcapsule flame retardant[J]. Modern Chemistry Industry, 2015, 35(4):138-140.
[13]裴婷.乙基纤维素-无机变色材料微胶囊制备原理及制备技术研究[J].印染助剂, 2009, 26(5):36-42.PEI T. Study on the preparation mechanism and technology of ethyl cellulose-inorganic thermochromism material microcapsule[J]. Textile Auxiliaries, 2009, 26(5):36-42.
[14] LUIZILDO P, VANJA K, BOJANA V. Synthesis and characterization of ethyl cellulose microcapsules containing model active ingredients[J].Macromolecular Symposia, 2013, 328(1):45-55.
[15]中国国家标准化管理委员会.粉尘物性试验方法:GB/T 16913—2008[S].北京:中国标准出版社, 2008.Standardization Administration of the People’s Republic of China.Methods of dust character test:GB/T 16913—2008[S]. Beijing:Standards Press of China, 2008.
[16]国防科学技术工业委员会.炸药试验方法:GJB 772A—97[S].北京:中国标准出版社, 1997.National Defense Science and Technology Committee. Explosive test method:GJB 772A—97[S]. Beijing:Standards Press of China, 1997.
[17]杨辉,高红芳.反溶剂法制备肉桂醛/乙基纤维素微胶囊及其表征[J].高分子材料科学与工程, 2017, 33(7):121-124.YANG H, GAO H F. Characterization of cinnamaldehyde/ethyl cellulose microcapsule prepared by anti-solvent method[J]. Polymer Materials Science and Engineering, 2017, 33(7):121-124.
[18]徐华,林粤顺,周红军,等.毒死蜱/乙基纤维素微胶囊的制备及其缓释性能[J].化工进展, 2017, 36(12):4622-4627.XU H, LIN Y S, ZHOU H J, et al. Preparation and sustained release of chlorpyrifos/ethyl cellulose microcapsules[J]. Chemical Industry and Engineering Progress, 2017, 36(12):4622-4627.
[19] YU Z P, WANG X, ZHANG X M, et al. Preparation of melamine formaldehyde resin coated red phosphorus by inverse suspension polymerization[J]. Journal of Natural Science of Hunan Normal University, 2015, 38(5):59-63.
[20]王玄玉,潘功配.红磷烟幕对10.6μm激光的消光系数测试研究[J].红外与激光工程, 2005, 34(6):636-640.WANG X Y, PAN G P. Study and test of extinction coefficient of red phosphorus smoke to 10.6μm laser emission[J]. Infrared and Laser Engineering, 2005, 34(6):636-640.
[21]鲁涛,赵雁,欧阳的华.含能材料表面分形维数计算及其对摩擦感度影响[J].计算机与应用化学, 2014, 31(2):226-230.LU T, ZHAO Y, OUYANG D H. Estimation of surface fractal dimension of energetic materials and influence on friction sensitivity[J]. Computer and Applied Chemistry, 2014, 31(2):226-230.