熔体微分电纺PLA/OMMT可降解纳米纤维膜制备及污染处理
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摘要
采用无溶剂的熔体静电纺丝技术制备可降解聚乳酸(PLA)纳米纤维,是一种很有前景和挑战性的绿色制备技术。其制备的纳米纤维膜孔隙率高、吸附能力强,可高效地处理环境污染问题。借助自制的熔体微分电纺装置,在PLA中引入了有机改性蒙脱土(OMMT),在260℃下制备了PLA/OMMT纳米纤维膜。探究了OMMT含量对PLA纤维形貌、吸油性能、空气过滤性能及降解性能的影响,并获得了最佳的OMMT配比含量。研究表明:加入OMMT后PLA热稳定性提高,结晶度大幅降低。OMMT质量分数为2%时制备的纤维,其直径为450nm。该纤维膜吸油倍率为133.5g/g,是市售PP无纺布的4～5倍,保油倍率为84.2g/g,具有良好的重复使用性能。针对粒径≥0.3μm尘埃粒子的空气过滤效率为99.31%,达到欧标H11过滤等级。且相比于纯PLA纤维膜降解性能提高,减少了二次污染,符合工业化绿色环保要求。
Degradable polylactide(PLA) nanofibers can be prepared by solvent free melt electrospinning technology which is promising,challenging and green. The nanofiber membrane prepared by this method have high porosities and strong adsorption capacities,and thus are useful for treating the environmental pollution efficiently. The organic montmorillonite(OMMT) was introduced into PLA, and the PLA/OMMT nanofiber membrane were prepared at 260℃ by using a self-made melt differential electrospinning device. The effect of OMMT content of PLA nanofiber membrane on the morphology,the oil absorption property,the air filtration performance and the degradability was investigated, and the optimum OMMT content was obtained. The research shows that the thermal stability of PLA is increased and the crystallinity of PLA is decreased significantly after adding OMMT. When the OMMT content is 2%,the diameter of the fiber reaches 450 nm. The oil absorption rate of the nanofiber membrane is 133.5 g/g which is 4-5 times higher than that of commercially available PP non-wovens,and the oil holding rate is 84.2 g/g. Moreover,the nanofiber membrane has good reuse performance. The air filtration efficiency of the nanofiber membrane for dust particles(≥0.3μm) is 99.31%,reaching the European standard H11 filtration class. The degradation of PLA/OMMT nanofiber membrane is improved comparing with the pure PLA, which reduces the second pollution and accords with the requirements of industrial green environmental protection.
Degradable polylactide(PLA) nanofibers can be prepared by solvent free melt electrospinning technology which is promising,challenging and green. The nanofiber membrane prepared by this method have high porosities and strong adsorption capacities,and thus are useful for treating the environmental pollution efficiently. The organic montmorillonite(OMMT) was introduced into PLA, and the PLA/OMMT nanofiber membrane were prepared at 260℃ by using a self-made melt differential electrospinning device. The effect of OMMT content of PLA nanofiber membrane on the morphology,the oil absorption property,the air filtration performance and the degradability was investigated, and the optimum OMMT content was obtained. The research shows that the thermal stability of PLA is increased and the crystallinity of PLA is decreased significantly after adding OMMT. When the OMMT content is 2%,the diameter of the fiber reaches 450 nm. The oil absorption rate of the nanofiber membrane is 133.5 g/g which is 4-5 times higher than that of commercially available PP non-wovens,and the oil holding rate is 84.2 g/g. Moreover,the nanofiber membrane has good reuse performance. The air filtration efficiency of the nanofiber membrane for dust particles(≥0.3μm) is 99.31%,reaching the European standard H11 filtration class. The degradation of PLA/OMMT nanofiber membrane is improved comparing with the pure PLA, which reduces the second pollution and accords with the requirements of industrial green environmental protection.
引文
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[2] 李培勋,于波,卫秀成,等.吸油树脂的研究进展[J].材料工程,2002(10):39-42.LI P X,YU B,WEI X C,et al.Progress in oil absorption resin[J].Journal of Materials Engineering,2002(10):39-42.
[3] DUTTA P,GOGOI B,DASS N N,et al.Efficient organic solvent and oil sorbent co-polyesters:poly-9-octadecenylacrylate/metha-crylate with 1-hexene[J].Reactive & Functional Polymers,2013,73(3):457-464.
[4] KORHONEN J T,KETTUNEN M,RAS R H A,et al.Hydro-phobic nanocellulose aerogels as floating,sustainable,reusable,and recyclable oil absorbents[J].Applied Materials & Interfaces,2011,3(6):1813-1816.
[5] 李小飞,张明军,王圣杰,等.中国空气污染指数变化特征及影响因素分析[J].环境科学,2012,33(6):1936-1943.LI X F,ZHANG M J,WANG S J,et al.Variation characteristics and influencing factors of air pollution index in China[J].Environmental Science,2012,33(6):1936-1943.
[6] 杨荆泉,田涛.驻极体过滤材料及其在空气净化领域的应用[J].环境与健康杂志,2009,26(8):743-745.YANG J Q,TIAN T.Application of electret filtration material in air purification[J].Journal of Environment and Health,2009,26(8):743-745.
[7] 丁彬,斯阳,俞建勇.静电纺纳米纤维材料在环境领域中的应用研究[J].中国材料进展,2013,32(8):492-502.DING B,SI Y,YU J Y.Progress in the research of electrospun nanofibers for environmental applications[J].Materials China,2013,32(8):492-502.
[8] LI H Y,LI Y,YANG W M,et al.Needleless melt-electrospinning of biodegradable poly(lactic acid) ultrafine fibers for the removal of oil from water[J].Polymers,2017,9(2):3.
[9] 汪策.纳米纤维多孔膜的制备机器在空气过滤中的应用[D].上海:东华大学,2015.WANG C.Preparation and characterization of composite porous nanofibrous membranes for air filtration[D].Shanghai:Donghua University,2015.
[10] 区炜锋,严玉蓉.静电纺多级孔材料制备研究进展[J].化工进展,2009,28(10):1766-1770.QU W F,YAN Y R.Progress of preparation of electrospun hierar-chical porous materials[J].Chemical Industry and Engineering Progress,2009,28(10):1766-1770.
[11] LI H Y,WU W F,MAHMOUD M B,et al.Polypropylene fibers fabricated via a needleless melt-electrospinning device for marine oil-spill cleanup[J].Journal of Applied Polymer Science,2014,131(7):2540-2540.
[12] LIU B W,ZHANG S C,WANG X L,et al.Efficient and reusable polyamide-56 nanofiber/nets membrane with bimodal structures for air filtration[J].Journal of Colloid and Interface Science,2015,457:203-211.
[13] LIN J Y,SHANG Y W,DING B,et al.Nanoporous polystyrene fibers for oil spill cleanup[J].Marine Pollution Bulletin,2012,64(2):347-352.
[14] 汪策,李雄,程诚,等.空气过滤用静电纺聚苯乙烯/碳纳米管复合纤维膜的制备[J].材料科学与工程学报,2016,34(6):960-966.WANG C,LI X,CHENG C,et al.Preparation of ultrafine fibrous membranes of Polystyrene/MWCNTs composites as air filter by electrospinning[J].Journal of Materials Science & Engineering,2016,34(6):960-966.
[15] 杨卫民,李好义,吴卫逢,等.熔体静电纺丝技术研究进展[J].北京化工大学学报(自然科学学报),2014,41(4):1-13.YANG W M,LI H Y,WU W F,et al.Research progress of melt electrospinning technology[J].Journal of Beijing University of Chemical Technology (Natural Science),2014,41(4):1-13.
[16] 唐丹琦,王娟,郑天龙,等.聚乳酸/淀粉固体缓释碳源生物反硝化研究[J].环境科学,2014,35(6):2236-2240.TANG D Q,WANG J,ZHENG T L,et al.Effect of PLA/starch slow-release carbon source on biological denitrification[J].Environmental Science,2014,35(6):2236-2240.
[17] SUPRAKAS S R,PRALAY M,MASAMI O,et al.New polyl-actide/layered silicate nanocomposites 1:preparation,characte-rization,and properties[J].Macromolecules,2002,35(8):3104-3110.
[18] 车晶,秦凡,杨荣杰.聚乳酸/蒙脱土纳米复合材料的原位聚合及表征[J].材料工程,2011(1):28-32.CHE J,QIN F,YANG R J.Polylactide/montmorillonite nanoc-omposites in-situ polymerization and characterization[J].Journal of Materials Engineering,2011(1):28-32.
[19] 崔玲娜,刘跃军.PLA/I.34TCN纳米复合材料的制备及其性能研究[J].包装学报,2017,9(3):36-42.CUI L N,LIU Y J.Preparation and properties of PLA/I.34TCN nanocomposites[J].Packaging Journal,2017,9(3):36-42.
[20] 赵姗姗,李媛,曹海雷,等.聚乳酸/蒙脱土纳米复合材料的微博辅助制备及性能研究[J].材料工程,2012(2):5-8.ZHAO S S,LI Y,CAO H L,et al.Preparation and characterization of PLA/MMT nanocomposites with microwave irradiation[J].Journal of Materials Engineering,2012(2):5-8.
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