长碳链耐高温聚酰胺10T/66热降解机理
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摘要
采用癸二胺、对苯二甲酸、己二胺和己二酸合成了耐高温聚酰胺(PA)10T/66。通过热重(TG)分析法研究了PA10T/66的热降解动力学。结果显示,随着升温速率的增大,热降解外推起始温度,最大失重速率温度和热降解外推结束温度均逐渐升高。不同升温速率下的TG曲线结果显示PA10T/66的降解过程都为一步降解。用Kissinger-Akahira-Sunose (KAS),Flynn-Wall-Ozawa (FWO)和Tang等方法确定了PA10T/66的热降解动力学参数和热降解活化能,并通过Coats–Redfern积分法确定了其热降解机理函数类型为[相边界反应(球形)](R3型)。
Heat resistant copolyamide PA10 T/66 was synthesized from sebacediamine,terephthalic acid,hexanediamine and adipic acid. The thermal degradation kinetics of PA10 T/66 was studied by thermogravimetric analysis(TGA). The results show that the initial temperature(T1), the maximum weight loss rate temperature(Tp) and the end temperature(T2) of thermal degradation increase with the increasing of heating rate. The results of TG curves at different heating rates showes that the degradation process of PA10 T/66 is one-step degradation. The Kissinger-Akahira-Sunose(KAS),Flynn-Wall-Ozawa(FWO) and Tang methods were used to determine the thermal decomposition kinetic parameters and thermal decomposition activation energy of PA10 T/66. The CoatsRedfern integral method is used to determine the type of thermal decomposition mechanism function of PA10 T/66 as [phase boundary reaction(spherical)](R3).
Heat resistant copolyamide PA10 T/66 was synthesized from sebacediamine,terephthalic acid,hexanediamine and adipic acid. The thermal degradation kinetics of PA10 T/66 was studied by thermogravimetric analysis(TGA). The results show that the initial temperature(T1), the maximum weight loss rate temperature(Tp) and the end temperature(T2) of thermal degradation increase with the increasing of heating rate. The results of TG curves at different heating rates showes that the degradation process of PA10 T/66 is one-step degradation. The Kissinger-Akahira-Sunose(KAS),Flynn-Wall-Ozawa(FWO) and Tang methods were used to determine the thermal decomposition kinetic parameters and thermal decomposition activation energy of PA10 T/66. The CoatsRedfern integral method is used to determine the type of thermal decomposition mechanism function of PA10 T/66 as [phase boundary reaction(spherical)](R3).
引文
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[3]Zhang Gang,Yan Guangmin,Yu Ting,et al.Semiaromatic polyamides containing carboxyl unit:Synthesis and properties[J].I n d u s t r i a l&E n g i n e e r i n g C h e m i s t r y R e s e a r c h,2 0 1 7,56(33):9 275-9 284.
[4]Cao Min,Zhang Chuanhui,He Bo,et al.Synthesis of 2,5-furandicarboxylic acid-based heat-resistant polyamides under existing industrialization process[J].Macromolecular Research,2017(7):1-8.
[5]Feng Wutong,Wang Pingli,Zou Guangji,et al.Synthesis and characterization of semiaromatic copolyamide 10T/1014 with high performance and flexibility[J].Designed Monomers&Polymers,2018,21(1):33-42.
[6]Zhang Cailiang,Wan Li,Gu Xueping,et al.A study on a prepolymerization process of aromatic-contained polyamide copolymers PA(66-co-6T)via one-step polycondensation[J].Macromolecular Reaction Engineering,2015,9(5):512-521.
[7]Alsalem S M,Sharma B K,Khan A R,et al.Thermal degradation kinetics of virgin polypropylene(PP)and PP with starch blends exposed to natural weathering[J].Industrial&Engineering Chemistry Research,2017,56(18):5 210-5 220.
[8]Vyazovkin S,Chrissafis K,Lorenzo M L D,et al.ICTAC kinetics committee recommendations for collecting experimental thermal analysis data for kinetic computations[J].Thermochimica Acta,2014,590(19):1-23.
[9]Flynn J H,Wall L A,Quick A.Direct method for the determination of activation energy from thermogravimetric data[J].Journal of Polymer Science Part C Polymer Letters,1966,4(5):323-328.
[10]Manafi P,Ghasemi I,Karrabi M,et al.Thermal stability and thermal degradation kinetics(model-free kinetics)of nanocomposites based on poly(lactic acid)/graphene:The influence of functionalization[J].Polymer Bulletin,2015,72(5):1 095-1 112.
[11]Maiti S C,Ghoroi C.Thermo-kinetic analysis of Ni-Al intermetallic phase formation in powder system[J].Journal of Thermal Analysis&Calorimetry,2016,124(2):1-13.
[12]王咪咪.PET解聚过中间产物的热降解动力学程研究[D].温州:温州大学,2016.Wang Mimi.Thermal degradation kinetics of depolymerized intermediate products of PET[D].Wenzhou:Wenzhou University,2016.
[13]Sharp J H,Wentworth S A.Kinetic analysis of thermogravimetric data[J].Analytical Chemistry,1969,41(14):2 060-2 062.
[14]Byczyński?,Dutkiewicz M,Maciejewski H.Thermal degradation kinetics of semi-interpenetrating polymer network based on polyurethane and siloxane[J].Thermochimica Acta,2013,560(15):55-62.
[15]Do?an F,Kaya?,Bilici A.Azomethine-based phenol polymer:Synthesis,characterization and thermal study[J].Synthetic Metals,2011,161(1-2):79-86.
[16]Pitchaimari G,Vijayakumar C T.Studies on thermal degradation kinetics of thermal and UV cured N-(4-hydroxy phenyl)maleimide derivatives[J].Thermochimica Acta,2014,575(1):70-80.
[17]袁慧萍,张腾,索红莉,等.热致液晶聚酰胺的热分解动力学及寿命[J].高分子材料科学与工程,2011,27(4):32-36.Yuan Huiping,Zhang Teng,Suo Hongli,et al.Thermotropic liquid crystal polyamide thermal decomposition kinetics and life[J].Polymer Materials Science and Engineering,2011,27(4):32-36.
[18]Erceg M,Kova?i?T,Klari?I.Dynamic thermogravimetric degradation of poly(3-hydroxybutyrate)/aliphatic-aromatic copolyester blends[J].Polymer Degradation&Stability,2005,90(1):86-94.
[19]Metzger J D.Role of endogenous plant growth regulators in seed dormancy of avena fatua:II.Gibberellins[J].Plant Physiology,1983,73(3):791-795.
[20]Naqvi S R,Uemura Y,Osman N,et al.Kinetic study of the catalytic pyrolysis of paddy husk by use of thermogravimetric data and the coats-redfern model[J].Research on Chemical Intermediates,2015,41(12):1-13.
[21]Yang Shaohui,Fu Peng,Liu Minying,et al.Synthesis,characterization of polytridecamethylene 2,6-naphthalamide as semiaromatic polyamide containing naphthalene-ring[J].Journal of Applied Polymer Science,2010,118(2):1 094-1 099.