溶胶凝胶法改性乙基纤维素微胶囊红磷
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摘要
目的开发一种绿色环保、简便高效的微胶囊红磷制备及改性工艺。方法以无水乙醇为溶剂,水为非溶剂,乙基纤维素为囊壳材料,采用相分离法制备乙基纤维素微胶囊红磷(ECRP)。在此基础上,以正硅酸乙酯(TEOS)作为改性剂,采用溶胶凝胶法制备Si O2/EC复合囊壳微胶囊红磷(Si-ECRP)。通过改变TEOS的添加量制备多组Si-ECRP样品,对样品进行形态表征及性能测试,探究最佳工艺条件。结果采用相分离法制备了ECRP,样品包覆效果良好,包覆率为86.5%。10 d后,ECRP的吸湿率降至6.8%,相对于红磷24%的吸湿率,具有明显改善。ECRP的热稳定性和安定性提高,着火点上升至300℃,摩擦感度降至34%。随着TEOS添加量的增加,三组Si-ECRP囊壳结构由Si O2/EC复合结构向SiO_2-EC双层包覆结构过渡。选取1m LTEOS添加量作为最佳工艺条件,此时囊壳呈复合结构,样品包覆率达94.2%,着火点较ECRP样品提高100℃,摩擦感度较ECRP下降14%,低至20%,具有更优异的使用性能。结论采用相分离法制备ECRP样品,整个工艺流程在常温、中性条件下进行,原料绿色环保,工艺简便高效。利用乙基纤维素的成壳机理,简化了溶胶凝胶法改性工艺,制备了SiO_2/EC复合囊壳结构,微胶囊红磷的安定性能得到进一步提升。
The work aims to develop an eco-environment and efficient microencapsulated red phosphorus preparation and modification method. Ethyl alcohol and distilled water were used as solvent and non-solvent respectively and ethyl cellulose was selected as shell material to prepare microencapsulated red phosphorus(ECRP) by phase separation method. Then, tetraethoxysilane(TEOS) was introduced as the modifier to prepare SiO_2/EC composite shell microencapsulated red phosphorus(Si-ECRP) by sol-gel method. Several groups of Si-ECRP samples were prepared by changing the addition of TEOS and the morphology and performance of the samples were characterized to determine the optimal process condition. ECRP prepared by phase separation method had good coating effects and possessed a coating ratio of 86.5%. The moisture ratio after 10 days decreased to 6.8% and improved obviously when compared with the ratio of pristine red phosphorus of 24%. The thermal and mechanical stability of ECRP increased, the ignition point reached 300 ℃ and the friction sensitivity decreased to 34%. As the addition of TEOS increased, the shell structure of three groups of Si-ECRP transferred from composite to double-layer. When 1 m L TEOS was used as the optimal condition, Si-ECRP got a composite shell material and the coating ratio was 94.2%. The ignition point of Si-ECRP was 100 ℃ higher than that of ECRP. The friction sensitivity of Si-ECRP decreased by 14% and reached 20%. Therefore, Si-ECRP had more excellent properties. ECRP can be prepared by phase separation method under normal temperature and neutral environment. In addition, the raw materials are all environmental materials and the method is simple and efficient. On the basis of ethyl cellulose shell forming mechanism, the Si-ECRP preparation process is simplified and SiO_2/EC composite shell structure is prepared, so the performance of pristine has been improved further.
The work aims to develop an eco-environment and efficient microencapsulated red phosphorus preparation and modification method. Ethyl alcohol and distilled water were used as solvent and non-solvent respectively and ethyl cellulose was selected as shell material to prepare microencapsulated red phosphorus(ECRP) by phase separation method. Then, tetraethoxysilane(TEOS) was introduced as the modifier to prepare SiO_2/EC composite shell microencapsulated red phosphorus(Si-ECRP) by sol-gel method. Several groups of Si-ECRP samples were prepared by changing the addition of TEOS and the morphology and performance of the samples were characterized to determine the optimal process condition. ECRP prepared by phase separation method had good coating effects and possessed a coating ratio of 86.5%. The moisture ratio after 10 days decreased to 6.8% and improved obviously when compared with the ratio of pristine red phosphorus of 24%. The thermal and mechanical stability of ECRP increased, the ignition point reached 300 ℃ and the friction sensitivity decreased to 34%. As the addition of TEOS increased, the shell structure of three groups of Si-ECRP transferred from composite to double-layer. When 1 m L TEOS was used as the optimal condition, Si-ECRP got a composite shell material and the coating ratio was 94.2%. The ignition point of Si-ECRP was 100 ℃ higher than that of ECRP. The friction sensitivity of Si-ECRP decreased by 14% and reached 20%. Therefore, Si-ECRP had more excellent properties. ECRP can be prepared by phase separation method under normal temperature and neutral environment. In addition, the raw materials are all environmental materials and the method is simple and efficient. On the basis of ethyl cellulose shell forming mechanism, the Si-ECRP preparation process is simplified and SiO_2/EC composite shell structure is prepared, so the performance of pristine has been improved further.
引文
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[17]许伟,刘军利,缪存标,等.乙基纤维素包覆成型活性炭的制备及其性能研究[J].林产化学与工业,2017,37(2):49-56.XU Wei,LIU Jun-li,MIU Cun-biao,et al.Preparation and properties of formed activated carbon coated by ethyl cellulose[J].Chemistry and industry of forest products,2017,37(2):49-56.
[18]NI J X,CHEN L J,ZHAO K M,et al.Preparation of gel-silica ammonium polyphosphate core-shell flame retardant and properties of polyurethane composites[J].Polymers for advanced technologies,2009,22:1824-1831.
[19]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 Hua,LIN Yue-shun,ZHOU Hong-jun,et al.Preparation and sustained release of chlorpyrifos/ethyl cellulose microcapsules[J].Chemical industry and engineering progress,2017,36(12):4622-4627.
[20]于智鹏.一种绿色环保工艺制备微胶囊红磷及应用[D].湖南:湖南师范大学,2015.YU Zhi-peng.A green process for preparation of microencapsulated red phosphorus and its application[D].Hunan:Hunan Normal University,2015.
[2]WANG H T,MENG X F,WEN B,et al.A simple route for the preparation of red phosphorus microcapsule with fine particle distribution[J].Materials letters,2008,62:3745-3747.
[3]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 Xuan-yu,PAN Gong-pei.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.
[4]蒋文俊,李哲曌,张春祥,等.微胶囊红磷的制备及在PP中的阻燃应用[J].光谱学与光谱分析,2010,30(5):1329-1335.JIANG Wen-jun,LI Zhe-hao,ZHANG Chun-xiang,et al.Preparation of microencapsulated red phosphorus and its flame-retardant application in PP composites[J].Spectroscopy and spectral analysis,2010,30(5):1329-1335.
[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]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.
[7]常怀春,吕通建,许秋菊,等.酚醛树脂为囊壁的超细微胶囊红磷的制备及其表征[J].中国塑料,2010,24(6):72-75.CHAGN Huai-chun,LYU Tong-jian,XU Qiu-ju,et al.Preparation and characterization of microencapsulated red phosphorus with phenol-formaldehyde resin as shell material[J].China plastic,2010,24(6):72-75.
[8]LIU J,GUAN H.Preparation,characterization and performance of microencapsulated red phosphorus[J].Propellants,explosives,pyrotechnics,2017,42:1-9.
[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].无机化学学报,2004(8):905-909.CHEN Hai-qun,BEI Feng-li,WANG Zhi-cheng,et al.Preparation and stability of microencapsulated ultrafine red phosphorus[J].Chinese journal of inorganic chemistry,2004,20(8):905-909.
[10]CHANG S K,ZENG C,YUAN W Z,et al.Preparation and characterization of double-layered microencapsulated red phosphorus and its flame retardance in poly(lactic acid)[J].Journal of applied polymer science,2012,125:3014-3022.
[11]方立翠,赵均乐,张雅丽,等.Mg(OH)2/Al(OH)3/包覆红磷阻燃SEBS/PS共混物[J].现代塑料加工应用,2011,23(2):25-28.FANG Li-cui,ZHAO Jun-le,ZHANG Ya-li,et al.SEBS/PS filled with Mg(OH)2/Al(OH)3/clad red phosphorus[J].Modern plastics processing and application,2011,23(2):25-28.
[12]YIN H Q,YUAN D D,CAI X F.Red phosphorus acts as second acid source to form a novel in tumescent-contractive flame-retardant system on ABS[J].Journal of thermal analysis and calorimetry,2013,111(1):12-15.
[13]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):116-118.ZHU Chao,LI Hui-ping,CHEN Shi-jun,et al.Preparation of whitening red phosphorus microcapsule flame retardant[J].Modern chemistry industry,2015,35(4):116-118.
[14]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 Na,BAO Yuan-zhi,WENG Shi-bing,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.
[15]程晨,杜仕国,鲁彦玲,等.溶胶凝胶法改性密胺甲醛树脂微胶囊红磷[J].表面技术,2018,47(9):74-80.CHENG Chen,DU Shi-guo,LU Yan-ling,et al.Melamine-formaldehyde resin microencapsulated red phosphorus modified in sol-gel method[J].Surface technology,2018,47(9):74-80.
[16]ZHAO B B,ZHANG Y,TANG T,et al.Preparation of high-purity monodisperse silica microspheres by the sol-gel method coupled with polymerization-induced colloid aggregation[J].Particuology,2015,22:177-184.
[17]许伟,刘军利,缪存标,等.乙基纤维素包覆成型活性炭的制备及其性能研究[J].林产化学与工业,2017,37(2):49-56.XU Wei,LIU Jun-li,MIU Cun-biao,et al.Preparation and properties of formed activated carbon coated by ethyl cellulose[J].Chemistry and industry of forest products,2017,37(2):49-56.
[18]NI J X,CHEN L J,ZHAO K M,et al.Preparation of gel-silica ammonium polyphosphate core-shell flame retardant and properties of polyurethane composites[J].Polymers for advanced technologies,2009,22:1824-1831.
[19]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 Hua,LIN Yue-shun,ZHOU Hong-jun,et al.Preparation and sustained release of chlorpyrifos/ethyl cellulose microcapsules[J].Chemical industry and engineering progress,2017,36(12):4622-4627.
[20]于智鹏.一种绿色环保工艺制备微胶囊红磷及应用[D].湖南:湖南师范大学,2015.YU Zhi-peng.A green process for preparation of microencapsulated red phosphorus and its application[D].Hunan:Hunan Normal University,2015.