阻燃聚左旋乳酸及其纤维的制备与结构性能
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摘要
为提高聚左旋乳酸(PLLA)的阻燃性及其可纺性,设计了环保[(6-氧-6H-二苯并-(c,e)(1,2)-氧磷杂己环-6-酮)-甲基]-丁二酸(DDP)阻燃PLLA体系,通过双螺杆熔融挤出方法制备了PLLA/DDP阻燃复合物,借助锥形量热仪、极限氧指数仪、垂直燃烧仪、扫描电子显微镜、差示扫描量热仪、热失重分析仪对复合物的结构与性能进行表征,研究了阻燃剂质量分数对PLLA阻燃性能的影响及其阻燃机制,并对阻燃剂最优添加量时的纺丝工艺及纤维性能进行分析。结果表明:当DDP质量分数为9%时,复合物的阻燃性能显著提高,其极限氧指数达到29%,垂直燃烧测试达到V-0级;复合物在800℃时的残炭量由10. 7%增加到13. 5%,且在该添加比例下具有优良的可纺性;将初生纤维3倍牵伸热定型后,其断裂强度为1. 77 c N/dtex,断裂伸长率为44. 9%。
In order to study the flame retardancy and spinnability of poly( L-lactic acid)( PLLA),an environmentally [( 6-oxo-6 H-dibenzo-( c,e)( 1,2)-oxaphosphorin-6-one) methyl]butanedioic acid( DDP)flame retardant PLLA system was designed. PLLA/DDP composites were prepared by twin-screw melt extrusion,and the structures and properties thereof were characterized by cone calorimetry,limiting oxygen index, vertical combustion, scanning electron microscopy, differential scanning calorimetry and thermogravimetric analysis. The effect of the flame retardant content on the flame retardant properties of PLLA and the flame retardant mechanism of DDP on PLLA were also investigated. The spinning process and fiber properties at the optimum flame retardant dosage were studied. The results show that when the mass content of DDP is 9%,the LOI of the composite reaches 29% and the UL-94 test reaches grade V-0.The amount of carbon residue of the composite at 800 ℃ increases from 10. 7% to 13. 5%,and the composite has excellent spinnability. After the nascent fiber is stretched and heat set by 3 times,the breaking strength is 1. 77 c N/dtex,and the elongation at break is 44. 9%.
In order to study the flame retardancy and spinnability of poly( L-lactic acid)( PLLA),an environmentally [( 6-oxo-6 H-dibenzo-( c,e)( 1,2)-oxaphosphorin-6-one) methyl]butanedioic acid( DDP)flame retardant PLLA system was designed. PLLA/DDP composites were prepared by twin-screw melt extrusion,and the structures and properties thereof were characterized by cone calorimetry,limiting oxygen index, vertical combustion, scanning electron microscopy, differential scanning calorimetry and thermogravimetric analysis. The effect of the flame retardant content on the flame retardant properties of PLLA and the flame retardant mechanism of DDP on PLLA were also investigated. The spinning process and fiber properties at the optimum flame retardant dosage were studied. The results show that when the mass content of DDP is 9%,the LOI of the composite reaches 29% and the UL-94 test reaches grade V-0.The amount of carbon residue of the composite at 800 ℃ increases from 10. 7% to 13. 5%,and the composite has excellent spinnability. After the nascent fiber is stretched and heat set by 3 times,the breaking strength is 1. 77 c N/dtex,and the elongation at break is 44. 9%.
引文
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[2] LIM L T, AURAS R, RUBINO M. Processing technologies for poly(lactic acid)[J]. Progress in Polymer Science,2008,33(8):820-852.
[3] CHEN L,WANG Y Z. A review on flame retardant technology in China:Part I:development of flame retardants[J]. Polymers for Advanced Technologies,2010,21(1):1-26.
[4] REN J. Biodegradable Poly(lactic acid):Synthesis,Modification, Processing and Applications[M].Beijing:Tsinghua University Press,2011:6-17.
[5] BOURBIGOT S,FONTAINE G. Flame retardancy of polylactide:an overview[J]. Polymer Chemistry,2010,1(9):1413-1422.
[6]徐亚雷,侯连龙,夏鹏.聚乳酸高性能化的研究进展[J].塑料工业,2012,40(10):14-19.XU Yalei,HOU Lianlong,XIA Peng. Study progress on the performance promotion of PLA[J]. China Plastics Industry,2012,40(10):14-19.
[7]宋艳朋,王德义,林玲,等.主链含磷阻燃聚乳酸的制备及其与聚乳酸共混材料的研究[C]//中国阻燃学术年会.北京:中国阻燃学会,2009:156-160.SONG Yanpeng, WANG Deyi, LIN Ling, et al.Preparation of flame retardant polylactic acid containing phosphor in main chain and its application with polylactic acid blends[C]//China Flame Retardant Academic Annual Meeting. Beijing:China Flame Perarlant Society,2009:156-160.
[8]张胜,陈宸,谷晓昱,等.聚乳酸的无卤阻燃研究进展[J].塑料,2015,44(4):6-12.ZHANG Sheng, CHEN Chen, GU Xiaoyu, et al.Research progress on non-halogen flame retardant polylactic acid[J]. Plastic,2015,44(4):6-12.
[9]周旋,武永刚,李娟,等.聚乳酸阻燃改性研究进展[J].工程塑料应用,2012,40(8):98-103.ZHOU Xuan,WU Yonggang,LI Juan,et al. Research progress on flame retardance modication of poly(lactic acid)[J]. Engineering Plastics Application, 2012,40(8):98-103.
[10] PRICE D, PYRAH K, HULL T R, et al. Flame retarding poly(methyl methacrylate)with phosphoruscontaining compounds:comparison of an additive with a reactive approach[J]. Polymer Degradation&Stability,2001,74(3):441-447.
[11] FANG Keyi,LI Juan,KE Chenhao,et al. Synergistic effect between a novel hyperbranched flame retardant and melamine pyrophosphate on the char forming of polyamide 6[J]. Journal of Macromolecular Science:Part D-Reviews in Polymer Processing,2010,49(14):1489-1497.
[12] CHANG S J,CHANG F C. Characterizations for blends of phosphorus-containing copolyesters with poly(ethylene terephthalate)[J]. Polym Eng Sci,1998,38(9):1471-1481.
[13] WANG C S,LIN C H. Synthesis and properties of phosphorus containing advanced epoxy resins[J].Journal of Applied Polymer Science,2015,75(3):429-436.
[14] ZHANG W,LI X,GUO X,et al. Mechanical and thermal properties and flame retardancy of phosphoruscontaining polyhedral oligomeric silsesquioxane(DOPOPOSS)/polycarbonate composites[J]. Polymer Degradation&Stability,2010,95(12):2541-2546.
[15] CHENG X W,GUAN J P,TANG R C,et al. Phytic acid as a bio-based phosphorus flame retardant for poly(lactic acid)nonwoven fabric[J]. Journal of Cleaner Production,2016,124:114-119.
[16]张玉梅.聚酯熔体直纺超细旦长丝POY可纺性研究[D].天津:天津大学,2012:10-19.ZHANG Yumei. Study on spinnability of polyethylene terephthalate microfilaments pre-oriented yarn by direct melt spinning[D]. Tianjin:Tianjin University,2012:10-19.
[17]魏丽菲,朱志国,靳昕怡,等.基于三(2-羟乙基)异氰尿酸酯的膨胀型阻燃剂对聚合物燃烧性能的影响[J].纺织学报,2017,38(9):24-31.WEI Lifei,ZHU Zhiguo,JIN Xinyi,et al. Influence of tris(2-hydroxyethyl)isocyanurate-based intumescent flame retardants on combustion performance of polymers[J]. Journal of Textile Research, 2017,38(9):24-31.
[18]刘淑强,张蕊萍,贾虎生,等.可生物降解聚乳酸长丝的熔融纺丝工艺[J].纺织学报,2012,33(11):11-14.LIU Shuqiang,ZHANG Ruiping,JIA Husheng,et al.Melt spinning process of biodegradable PLA filaments[J]. Journal of Textile Research, 2012,33(11):11-14.
[19]俞建勇,赵恒迎,程隆棣.新型绿色环保纤维:聚乳酸纤维性能及其应用[J].纺织导报,2003(3):63-66.YU Jianyong,ZHAO Hengying,CHENG Longdi. New green environmental fiber:polylactic acid fiber performance and its application[J]. China Textile Leader,2003(3):63-66.
[20]王亚丽,周微伟.熔融纺丝法中聚乳酸切片干燥工艺探讨[J].天津纺织科技,2009(4):11-14.WANG Yali, ZHOU Weiwei. Discussion on drying process of polylactic acid slices in melt spinning[J].Tianjin Textile Science&Technology,2009(4):11-14.