侧基含磷阻燃共聚酯的制备及其固相增黏反应  

Synthesis and solid-state polymerization of flame retardant copolyester containing phosphorus side groups

作　　者：尚小愉 朱坚 王滢 张先明[1] 陈文兴[1] SHANG Xiaoyu;ZHU Jian;WANG Ying;ZHANG Xianming;CHEN Wenxing(National Engineering Laboratory for Textile Fiber Materials&Processing Technology,Zhejiang Sci-Tech University,Hangzhou,Zhejiang 310018,China)

机构地区：[1]浙江理工大学纺织纤维材料与加工技术国家地方联合工程实验室,浙江杭州310018

出　　处：《纺织学报》2023年第7期1-9,共9页Journal of Textile Research

基　　金：浙江省重点研发计划资助项目(2020C01143,2021C01020)。

摘　　要：为制得高特性黏度的侧基含磷阻燃共聚酯,研究不同反应条件对固相增黏效果的影响及其反应动力学。将侧基含磷阻燃剂共聚到聚酯分子链中制得侧基含磷阻燃共聚酯,并对其进行固相增黏,分析了阻燃剂质量分数、增黏反应温度、时间3个因素对增黏效果的影响。结果表明:成功将阻燃剂共聚到聚酯分子链中制得侧基含磷阻燃共聚酯,当阻燃剂质量分数为5%时,共聚酯的极限氧指数为31.8%,热分解后的残炭量达到13.6%,结晶度为15%;与纯聚酯相比,阻燃共聚酯增黏反应过程的特性黏度变化趋势差异不明显,故阻燃共聚酯的固相增黏反应可以参照纯聚酯的增黏工艺,其特性黏度均随着增黏反应温度的升高、反应时间的延长而增加;对阻燃共聚酯的固相增黏反应动力学分析发现,其反应温度的上升、阻燃剂质量分数的减少与反应速率常数的增加呈正相关,其阻燃剂质量分数的增加与反应活化能的降低呈负相关。Objective Poly(ethylene terephthalate)(PET),as the major polyester material,has excellent performance but is flammable,and hence it is important to improve the flame retardant properties of PET to satisfy the requirement for various applications.Introducing phosphorus-based flame retardants into PET molecular chains by copolymerization is one of the effective flame retardant modification methods at present.The flame retardant copolyester produced by melt polymerization has a intrinsic low viscosity of 0.6-0.7 dL/g,which cannot meet the flame retardant specifications of copolyester in fields such as engineering plastics,bottles,and industrial filament.This research represents an effort to increase the intrinsic viscosity of copolyester by polycondensation so as to expand the applications.Method The side group phosphorus-containing flame retardant 9,10-dihydro-10-[2,3-di(hydroxycarbonyl)propyl]10-phosphorus-phenanthrene-10-oxide(DDP)was copolymerized into PET molecular chain to obtain copolyester(PETD).Nuclear magnetic resonance hydrogen spectroscopy(1H NMR)and Fourier transform infrared spectrometer characterization methods were adopted to measure the success of copolyester synthesis.The intrinsic viscosity of copolyesters was determined by using viscosity test.The thermal stability,crystallinity,carbon formation capacity,flame retardant properties,actual phosphorus content and carboxyl endgroup content of copolyesters were characterized by differential scanning calorimetry,thermogravimetric analysis,limiting oxygen index(LOI)test,inductively coupled plasma-optical emission spectrometer test and carboxyl endgroup concentrations test.In order to investigate the intrinsic viscosity changes of flame retardant copolyester containing phosphorus side group after solid-state polycondensation reaction under different reaction conditions,different amount of side group phosphate-containing flame retardant were used for optimisation.Reaction rate constants and activation energy were calculated by analyzing the viscosity incr

关 键 词：侧基含磷阻燃剂 共聚 含磷阻燃聚酯 固相增黏反应 反应动力学 

分 类 号：TQ342.92[化学工程—化纤工业]