勃姆石改性PET复合材料的阻燃和增强机理研究
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摘要
采用勃姆石(BM)作为阻燃和增强材料,利用熔融共混法制备了BM阻燃和增强改性的聚对苯二甲酸乙二醇酯(PET)/BM复合材料。分别测试了BM用量对于PET复合材料的力学性能、结晶性能、热性能、阻燃性能的影响。结果表明,随着BM用量的增加,PET/BM复合材料的刚性逐渐增加,韧性逐渐降低;PET/BM复合材料的热结晶温度(T_c)和冷结晶温度(T_(cc))分别随着BM用量的增加逐渐升高和降低,且ΔT(T_c-T_(cc))逐渐增加,BM具有异相成核作用,提高了复合材料的结晶速率和相对结晶度(X_c);而复合材料的熔融温度则随着BM用量的增加而逐渐降低;BM对PET具有良好的阻燃作用,BM能够使PET/BM复合材料的残炭量增加,使复合材料的分解温度降低,增加了材料燃烧时的热稳定性。
The PET/boehmite(BM) composites were prepared using BM as a flame-retardant and reinforcement additive, and the effects of BM dosage on the mechanical, crystalline, thermal and flame-retardant properties of the composites were investigated. The experimental results indicated that the rigidity of the composites increased gradually with an increase of BM content, but the toughness tended to decrease gradually. The T_c and T_(cc) of the composites were found to increase and decrease gradually with an increase of BM content, respectively. However, the value of ΔT·(T_c-T_(cc)) shows a gradual increase. BM could act as a nucleation agent to promote the crystallization rate and the relative degree of crystallinity(X_c) of PET domain by heterogeneous nucleation. Nevertheless, the melting temperature of the composites presented a decrease with increasing the content of BM. BM could also generate good flame retardant effect on PET. The incorporation of BM resulted in an increase in char yield and a decrease in decomposition temperature for the composites. As a result, the thermal stability of the composites was improved during combustion. In summary, BM plays an important role in enhancement of mechanical, crystalline and flame-retardant properties for the PET/BM composites.
The PET/boehmite(BM) composites were prepared using BM as a flame-retardant and reinforcement additive, and the effects of BM dosage on the mechanical, crystalline, thermal and flame-retardant properties of the composites were investigated. The experimental results indicated that the rigidity of the composites increased gradually with an increase of BM content, but the toughness tended to decrease gradually. The T_c and T_(cc) of the composites were found to increase and decrease gradually with an increase of BM content, respectively. However, the value of ΔT·(T_c-T_(cc)) shows a gradual increase. BM could act as a nucleation agent to promote the crystallization rate and the relative degree of crystallinity(X_c) of PET domain by heterogeneous nucleation. Nevertheless, the melting temperature of the composites presented a decrease with increasing the content of BM. BM could also generate good flame retardant effect on PET. The incorporation of BM resulted in an increase in char yield and a decrease in decomposition temperature for the composites. As a result, the thermal stability of the composites was improved during combustion. In summary, BM plays an important role in enhancement of mechanical, crystalline and flame-retardant properties for the PET/BM composites.
引文
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[20] CAI Y,ZHAO M,WANG H,et al.Synthesis and Properties of Flame-retardant Poly(Vinyl Alcohol)/Pseudo-boehmite Nanocomposites with High Transparency and Enhanced Refractive Index[J].Polymer Degradation & Stability,2014,99(13):53-60.
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[22] 罗观晃.勃姆石/尼龙66复合材料及勃姆石协同阻燃机理研究[D].广州:华南理工大学,2016.
[2] 蔡远征,郭正虹,方征平.稀土离子改性有机蒙脱土及其在PET阻燃中的应用[J].高分子材料科学与工程,2013,29(01):123-126.CAI Y Z,GUO Z H,FANG Z P.Flame Retardancy of Poly (Ethylene Terephthalate) Nanocomposites Based on Rare Earth Ions Modified Organo-Montmorillonite[J].Polymeric Materials Science and Engineering,2013,29(01):123-126.
[3] 卢攀峰,阎修维,刘敏,等.PET改性研究进展及应用现状[J].中国塑料,2008,22(10):1-6.LU P F YAN X W,LIU M,et al.Research Progress in Modification of PET and Its application[J].China Plastics,2008,22(10):1-6.
[4] 曹民,肖中鹏,张传辉,等.透明尼龙的性能与应用[J].化工新型材料,2014,42(06):213-215+225.CAO MIN,XIAO Z P,ZHANG C H,et al.Characterization and application of transparent nylon[J].New Chemical Materials,2014,42(06):213-215+225.
[5] 郑现国,李馥梅,余卫勋.高韧性尼龙6的研究与应用[J].中国塑料,2002,(09):19-23.ZHENG X G,LI F M,YU W X.Advance and Application of High-Impact Polyamide 6[J].China Plastics,2002,(09):19-23.
[6] 吴三清.汽车用改性聚丙烯(PP)材料的开发与应用[J].汽车工艺与材料,2004,(02):26-28.WU S Q.Development and Application of Automobile used and Modified Polyproplene(PP)[J].Automobile Technology & Material,2004,(02):26-28.
[7] 井蒙蒙,刘继纯,刘翠云,等.高分子材料的阻燃方法[J].中国塑料,2012,26(02):13-19.JING M M,LIU J C,LIU C Y,et al.Flame Retardant Methods for Polymer Materials[J].China Plastics,2012,26(02):13-19.
[8] 黄辉,曹家胜.高分子材料无卤阻燃剂的研究现状[J].塑料科技,2011,39(06):75-79.HUANG H,CAO J S.Research Status on Non-halogen Flame Retardants of Polymers[J].Plastics Science and Technology,2011,39(06):75-79.
[9] LAOUTID F,BONNAUD L,ALEXANDRE M,et al.New Prospects in Flame Retardant Polymer Materials:From Fundamentals to Nanocomposites[J].Materials Science & Engineering R Reports,2009,63(3):100-125.
[10] DENG Y,WANG Y Z,BAN D M,et al.Burning Behavior and Pyrolysis Products of Flame-retardant PET Containing Sulfur-containing Aryl Polyphosphonate[J].Journal of Analytical & Applied Pyrolysis,2006,76(1/2):198-202.
[11] HAN S K,BILSKI P,KARRIKER B,et al.Oxidation of Flame Retardant Tetrabromobisphenol A by Singlet Oxygen[J].Environmental Science & Technology,2008,42(1):166.
[12] DIDANE N,GIRAUD S,DEVAUX E,et al.Thermal and Fire Resistance of Fibrous Materials Made by PET Containing Flame Retardant Agents[J].Polymer Degradation & Stability,2012,97(12):2 545-2 551.
[13] 曲德智.无卤阻燃PET的制备及性能研究[D].哈尔滨:哈尔滨工业大学,2015.
[14] 司明明,郝建薇,徐利时,等.纳米三氧化二锑阻燃应用分析[J].中国塑料,2013,27(08):1-7.SI M M,HAO J W XU L S,et al.Analysis of Nano-Sb2O3 in Flame Retardancy Applications[J].China Plastics,2013,27(08):1-7.
[15] 冯霞,刘有智,申红艳,等.超细氢氧化镁阻燃剂的研究现状[J].塑料工业,2013,41(02):7-10+69.FENG X,LIU Y Z,SHEN H Y,et al.Research Progress of Superfine Magnesium Hydroxide Flame Retardant[J].China Plastics Industry,2013,41(02):7-10+69.
[16] 徐晓楠.溴化环氧树脂协同三氧化二锑阻燃PBT的性能研究[J].塑料科技,2009,37(07):33-36.XU X N.Study on Properties of PBT Flame Retarded by Brominated Epoxy Resin Synchronized withAntimony Trixide[J].Plastics Science and Technology,2009,37(07):33-36.
[17] 李征征,李三喜,张爱玲,等.氢氧化镁阻燃剂研究进展[J].塑料科技,2009,37(04):83-87.LI Z Z,LI S X,ZHANG A L,et al.Research Progress on Flame Retarding Polystyrene[J].Plastics Science and Technology,2009,37(04):83-87.
[18] 蔡挺松,郭奋,陈建峰.纳米改性氢氧化铝与包覆红磷协效阻燃PBT的研究[J].高分子材料科学与工程,2006,(06):205-208.CAI T S,GUO F,CHEN J F.Synergetic Fire Retardant Effect of Nano CGATH and Red Phosphorus for PBT[J].Polymer Materials Science & Engineering,2006,(06):205-208.
[19] 刘丽君,郭奋,陈建峰.纳米氢氧化铝阻燃剂表面改性及其在聚丙烯中的应用[J].中国塑料,2004,(02):76-79.LIU L J,GUO F,CHEN J F.Modification of Nano Aluminum Trihydrate Flame Retardant and Its Application in PP[J].China Plastics,2004,(02):76-79.
[20] CAI Y,ZHAO M,WANG H,et al.Synthesis and Properties of Flame-retardant Poly(Vinyl Alcohol)/Pseudo-boehmite Nanocomposites with High Transparency and Enhanced Refractive Index[J].Polymer Degradation & Stability,2014,99(13):53-60.
[21] HUANG P H,CHANG S J,LI C C,et al.Boehmite-based Microcapsules as Flame-retardants for Lithium-ion Batteries[J].Electrochimica Acta,2017,228:597-603.
[22] 罗观晃.勃姆石/尼龙66复合材料及勃姆石协同阻燃机理研究[D].广州:华南理工大学,2016.