阻燃增强聚对苯二甲酸乙二醇酯（PET）工程塑料结晶性能及配方优化研究
|
摘要
论文研究了基础树脂粘度、成核剂和结晶促进剂的种类与含量、阻燃剂及其体系、玻璃纤维对PET结晶行为的影响。选定了13种成核剂和8种结晶促进剂,发现滑石粉的成核效果和聚丁二酸丁二醇酯(PBS)的结晶促进效果较好；确定了阻燃增强PET工程塑料的工艺配方。所得阻燃增强PET工程塑料的阻燃性能达V-0级,拉伸强度为145MPa,弯曲强度为212MPa,冲击强度为8.0kJ／m2,热变形温度为223℃,与国外同类产品性能接近,在国内处于领先地位。
在配方研究的基础上,进行了结晶理论研究：利用差示扫描量热仪(DSC)对结晶PET的升温与降温过程进行测试,详细研究PET在成核剂、结晶促进剂作用下的结晶行为,并通过偏光显微镜(POM)、广角X射线衍射(WAXS)研究结晶PET的微观形态,初步探讨成核剂、结晶促进剂的作用机理。
结果发现,各类成核剂的加入均不同程度地提高了PET的结晶温度(Tc),加快其结晶速率,使PET的晶粒增多,且细化均一。其中以滑石粉的成核效果最优,当添加量为0.5%时可使结晶温度提高12.54℃,且随降温速率的减小结晶完善程度得以提高；利用非等温结晶动力学方程证实了滑石粉对PET结晶行为的影响。此外,结合力学性能和热性能测试对滑石粉、有机蒙脱土、稀土化合物、进口成核剂(P250)、山梨醇类(BQ-88)、受阻酚磷酸酯盐类(MD-NA-28)、苯甲酸钠等成核剂的作用机理进行了分析探讨,其中多以诱导PET降解来加快成核结晶速率。结晶促进剂的加入可不同程度地降低PET的冷结晶温度(Tcc),其中PBS与聚乙二醇(PEG-1500)质量比为1：1的混合物当添加量为3%时,可使PET的Tcc降低17.5℃。PBS的促进机理主要是通过其自身的快速结晶成核诱导PET大分子成核。
研究发现阻燃剂及阻燃协效剂具有成核作用；而玻璃纤维作为增强材料对PET的结晶成核无明显贡献。
在上述研究基础上,进行了阻燃增强PET工程塑料配方优化的探讨。结果发现,阻燃剂、阻燃协效剂在满足材料的阻燃性能的同时还具有成核作用；成核剂、结晶促进剂在不同阻燃增强PET体系中的作用不及其在纯PET中显著；配方优化应考虑助剂兼效,实现一剂多效。
Effects of the viscosity of the resin, the type and content of nucleating agents and the nucleating promoters, the flame retardants, glass fiber on the crystallization behavior of PET have been investigated. Talc and polysuccinate (PBS) were chosen from thirteen nucleating agents and eight nucleating promoters respectively. The process formulation of enhanced flame retardant PET was determined. The fire performance of PET can reach up to V-0 with the tensile strength of 145MPa, flexural strength of 212MPa, the impact strength of 8.0 kJ/m2 and heat distortion temperature of 223℃, which can compete with similar foreign products.
The effect of nucleating agents and nucleating promoters on the crystallization behavior has been studied by using differential scanning calorimetry (DSC), and morphology of PET was observed by polarized light microscopy (POM) and wide-angle X-ray diffraction (WAXS). The mechanisms of both nucleation and nucleating promotion were proposed.
The results show that the crystallization temperature Tc of PET has been increased in varying degrees by the addition of various nucleating agents, the crystallization rate has been speeded up. Among them, talc powder has the best nucleating effect, which can increase the crystallization temperature by 12.54℃with 0.5%addition and the crystallization can be improved with the cooling rate reduction; non-isothermal crystallization kinetics equations also was used to confirm the effect of talc powder on the crystallization of PET. In addition, the function of talc, montmorillonite, rare earth compounds, import product (P250), sorbitol (BQ-88), hindered phenol phosphate salts (MD-NA-28), sodium benzoate, the nucleating mechanism were analyzed and discussed according to the mechanical properties and molecular structure.
The nucleating promoters can reduce cold crystallization temperature Tcc by different degrees, the Tcc of PET which added with 3%of the mixture of PBS and polyethylene glycol (PEG-1500) with the mass ratio of 1:1 can be reduced by 17.5℃. PBS as a better nucleating promoter is due to its faster crystallization rate.
Flame retardants and the synergistic flame retardant can also promote nucleation; however, the effect of glass fibre on the crystallization behavior of PET is minimal.
The principle of enhanced flame retardant PET engineering plastic formulation has been discussed. The results show that the flame retardants can also be used as nucleating agents, the effects of nucleating agents and nucleating promoters on different enhanced flame retardant PET systems are not as significant as that on pure PET; the efficiency of additives in formulation should be considered.
在配方研究的基础上,进行了结晶理论研究：利用差示扫描量热仪(DSC)对结晶PET的升温与降温过程进行测试,详细研究PET在成核剂、结晶促进剂作用下的结晶行为,并通过偏光显微镜(POM)、广角X射线衍射(WAXS)研究结晶PET的微观形态,初步探讨成核剂、结晶促进剂的作用机理。
结果发现,各类成核剂的加入均不同程度地提高了PET的结晶温度(Tc),加快其结晶速率,使PET的晶粒增多,且细化均一。其中以滑石粉的成核效果最优,当添加量为0.5%时可使结晶温度提高12.54℃,且随降温速率的减小结晶完善程度得以提高；利用非等温结晶动力学方程证实了滑石粉对PET结晶行为的影响。此外,结合力学性能和热性能测试对滑石粉、有机蒙脱土、稀土化合物、进口成核剂(P250)、山梨醇类(BQ-88)、受阻酚磷酸酯盐类(MD-NA-28)、苯甲酸钠等成核剂的作用机理进行了分析探讨,其中多以诱导PET降解来加快成核结晶速率。结晶促进剂的加入可不同程度地降低PET的冷结晶温度(Tcc),其中PBS与聚乙二醇(PEG-1500)质量比为1：1的混合物当添加量为3%时,可使PET的Tcc降低17.5℃。PBS的促进机理主要是通过其自身的快速结晶成核诱导PET大分子成核。
研究发现阻燃剂及阻燃协效剂具有成核作用；而玻璃纤维作为增强材料对PET的结晶成核无明显贡献。
在上述研究基础上,进行了阻燃增强PET工程塑料配方优化的探讨。结果发现,阻燃剂、阻燃协效剂在满足材料的阻燃性能的同时还具有成核作用；成核剂、结晶促进剂在不同阻燃增强PET体系中的作用不及其在纯PET中显著；配方优化应考虑助剂兼效,实现一剂多效。
Effects of the viscosity of the resin, the type and content of nucleating agents and the nucleating promoters, the flame retardants, glass fiber on the crystallization behavior of PET have been investigated. Talc and polysuccinate (PBS) were chosen from thirteen nucleating agents and eight nucleating promoters respectively. The process formulation of enhanced flame retardant PET was determined. The fire performance of PET can reach up to V-0 with the tensile strength of 145MPa, flexural strength of 212MPa, the impact strength of 8.0 kJ/m2 and heat distortion temperature of 223℃, which can compete with similar foreign products.
The effect of nucleating agents and nucleating promoters on the crystallization behavior has been studied by using differential scanning calorimetry (DSC), and morphology of PET was observed by polarized light microscopy (POM) and wide-angle X-ray diffraction (WAXS). The mechanisms of both nucleation and nucleating promotion were proposed.
The results show that the crystallization temperature Tc of PET has been increased in varying degrees by the addition of various nucleating agents, the crystallization rate has been speeded up. Among them, talc powder has the best nucleating effect, which can increase the crystallization temperature by 12.54℃with 0.5%addition and the crystallization can be improved with the cooling rate reduction; non-isothermal crystallization kinetics equations also was used to confirm the effect of talc powder on the crystallization of PET. In addition, the function of talc, montmorillonite, rare earth compounds, import product (P250), sorbitol (BQ-88), hindered phenol phosphate salts (MD-NA-28), sodium benzoate, the nucleating mechanism were analyzed and discussed according to the mechanical properties and molecular structure.
The nucleating promoters can reduce cold crystallization temperature Tcc by different degrees, the Tcc of PET which added with 3%of the mixture of PBS and polyethylene glycol (PEG-1500) with the mass ratio of 1:1 can be reduced by 17.5℃. PBS as a better nucleating promoter is due to its faster crystallization rate.
Flame retardants and the synergistic flame retardant can also promote nucleation; however, the effect of glass fibre on the crystallization behavior of PET is minimal.
The principle of enhanced flame retardant PET engineering plastic formulation has been discussed. The results show that the flame retardants can also be used as nucleating agents, the effects of nucleating agents and nucleating promoters on different enhanced flame retardant PET systems are not as significant as that on pure PET; the efficiency of additives in formulation should be considered.
引文
[1]K. Parikh, K. Cattanach, R. Rao, ect. Flexible vapour sensors using single walled carbon nanotubes[J]. Sensors and Actuators B,2006,113:55-63.
[2]M. Wu and L.L. Shaw, Int. J. Anovel concept of carbon-filled polymer blends for application-s in PEM fuel cell bipolar plates[J]. Hydrogen Energy,2005,30:373-380.
[3]M. Wu and L.L. Shaw, J. On the improved properties of injection-molded, carbon nanotube-filled PET/PVDF blends[J]. Power Sources,2004,136:37-44.
[4]赵耀明.非纤维用热塑性聚脂工艺与应用,化学工业出版社,2002.
[5]金国珍.工程塑料,化学工业出版社,2001.
[6]张克惠,张广成.塑料材料学,化学工业出版社,2001.
[7]焦剑,雷渭媛.高聚物结构、性能与测试,化学工业出版社,2003.
[8]G.Y.Gao, S.L.An, J.L.Yu. Research on conductive group in carbon black/polyester composite fibers[J]. J Tianjin Polytech Univ,2005,24:12-15.
[9]Y.Huang, Z.F.Li, G.H.Luo. Research on conductive group in carbon black/polyester compo-site fibers[J]. China Syn Fiber Ind,2004,27:1-8.
[10]Xiaolei Chen, Chunzhong Li, Wei Shao. Isothermal crystallization kinetics and melting behaviour of PET/ATO nanocomposites prepared by in situ polymerization[J]. European Polymer Journal,2007,43:3177-3186.
[11]M.T. Run, S.Z. Wu, D.Y. Zhang, ect. Melting behaviors and isothermal crystallization kine-tics of poly(ethylene terephthalate)/mesoporous molecular sieve composite[J]. Polymer, 2005,46:5308-5316.
[12]M.L. Di Lorenzo, C. Silvestre. Non-isothermal crystallization of polymers[J]. Prog Polym Sci,1999,24:917-950.
[13]H.R.Dennis, D.L.Hunter, D.Chang, ect. Preparation and characterization of PBT nanocomp-osites compounded with different montmorillonites[J]. Polymer,2001,42:9513-9522.
[14]裴运同,杨军忠,等.增强阻燃PET工程塑料的研究[J].中国塑料,2003,17(1)：58-62.
[15]陈军,陆宾峰,臧惠蕊等.玻纤、阻燃剂和纳米成核剂对PET性能的影响[J].工程塑料应用,2005,33(3)：9-12.
[16]杨得志,庞纯,赵建青.玻纤增强阻燃PET的研制[J].工程塑料应用,2005,33(4)：8-11.
[17]刘锋,王锡柱,张德善.PET改性工程塑料的发展动态[J].弹性体,2005,15(6)：59-63.
[18]刘学习,庄辉,程勇峰,等.长玻纤增强PET工程塑料的性能研究[J].塑料工业,2006,34(12)：26-28.
[19]董纪震,赵耀明等.合成纤维工艺学(下册),第二版,1994.
[20]王显楼.涤纶生产基本知识,北京,’纺织工业出版社,1993.
[21]国家标准局纤维检验局.化学纤维检验技术(上册),北京,1983.
[22]殷敬华,莫志深.现代高分子物理学(上册),科学出版社,2001.
[23]殷敬华,莫志深.现代高分子物理学(下册),科学出版社,2001.
[24]张光华,杨玉芹,林瑛等.聚对苯二甲酸乙二酯球晶的形态结构[J].高分子材料科学与工程,1992,(3)：114-117.
[25]杨始堃.聚酯树脂质量指标述评(5)[J].聚酯工业,2002,15(1)：58-61.
[26]杨始堃.聚酯(PET)树脂切片的干燥和结晶[J].聚酯工业,2005,18(6)：55-57.
[27]周达飞,唐颂超.高分子材料成型加工,北京,轻工业出版社,2000.
[28]Feng Wang, Xiangfu Meng, Xinfeng Xu, ect. Inhibited transesterification of PET/PBT blends filled with silica nanoparticles during melt processing[J]. Polymer Degradation and Stability,2008,93:1397-1404.
[29]Geun Hyung Kim, Woo Jun Kim, Seung Mo Kim, ect. Analysis of thermo-physical and optical properties of a diffuser using PET/PC/PBT copolymer in LCD backlight units[J]. Displays,2005,26:37-43.
[30]Vladimir N. Ignatov, Claudio Carraro, Vittorio Tartari t. PET/PC blends and copolymers by one-step extrusion:1. Chemical structure and physical properties of 50/50 blends[J]. Polymer,1997,38 (1):195-200.
[31]Vladimir N. Ignatov, Claudio Carraro, Vittorio Tartari t. PET/PC blends and copolymers by one-step extrusion:2. Influence of the initial polymer composition and type of catalyst[J]. Polymer,1997,38 (1):201-205. [32] Paola Marchese, Annamaria Celli, Maurizio Fiorini, ect. Effects of annealing on crystallinity and phase behaviour of PET/PC block copolymers[J]. European Polymer Journal 2003, 39:1081-1089.
[33]于中振,欧玉春,冯宇鹏.界面粘结对PET／尼龙66共混物结晶行为和力学性能的影响[J].高分子材料科学与工程,1997,13(3)：57-61.
[34]华东理工大学.PA／PET高分子合金材料[P].CN1749314,2006-03-22.
[35]Hiroshi Shimizu, Takeshi Kitano, Kazuo Nakayama. Morphological control of LCP/PET blends using a melt mixer equipped with a milling part[J]. Materials Letters,2004,58: 1277-1281.
[36]Hung-Chih Chin, Feng-Chih Chang. Reactive cornpatibilization of PET/LCP blends by a multifunctional epoxy coupler[J]. Polymer,1997,38 (12):2947-2956.
[37]Nadka Avramova. Amorphous poly(ethylene terephthalate)/poly(butylene terephthalate) blends:miscibility and properties[J]. Polymer,1995,36 (4):801-808.
[38]I. Puente Orench a, N. Stribeck b, F. Ania a, ect. SAXS study on the crystallization of PET under physical confinement in PET/PC multilayered films[J]. Polymer,2009,50:2680-2687.
[39]Zhang Z, Xie Y, M a D. Relationship between miscibility and chemical structures in reactive blending of poly(bisphenol A carbonate) and poly(ethylene terephthalate)[J]. Eur Polym J, 2001,37:1961-1966.
[40]吕军,黄锐,魏刚.PET／PC共混体系结晶行为研究进展[J].功能高分子学报,2005,18(1)：161-166.
[41]李建勋,彭少贤,郦华兴.反应性增韧和增容技术在PET回收料及其共混物PET／PC中的应用[J].塑料,1998,27(2)：33-36.
[42]Xanthos M., BaltzisB.C., Hsu.PP. Effects of Carbonate. Salts on Crystallization Kinetics and Properties of Recycled polyethylene terephthalate[J]. Polym Sci,1997,64:1433-1435.
[43]周理水.PET塑料的改性及应用.塑料加工,2000,29(3)：32-36.
[44]陈玉君,何国山,侯巩.聚烯烃接枝MAH对PET／PA6性能的影响.中国塑料,2002,16(5)：44-46.
[45]宗立明,范奎城,刘德山.PET与液晶高分子注射模塑原位复合材料的研究[J].高分子材料科学与工程,1998,14(3)：87-90.
[46]Shu-cai Li, Li-nong Lu. Melt Rheological Properties of Reactive Compatibilized HDPE/PET blends[J]. Journal of Applied polymer science,2008,108:3559-3564.
[47]Mustapha Kaci, Aida Benhamida, Sossio Cimmino, ect. Waste and virgin LDPE/PET blends compatibilized with an ethylene-butyl acrylate-glycidyl methacrylate (EBAGMA) terpoly-mer, morphology and mechanical properties[J]. Macromolecular materials and engineering, 2005,290:987-995.
[48]Hongsheng Zhang, Weihong Guo, Yingbo Yu. Structure and properties of compatibilized recycled poly(ethylene terephthalate)/linear low density polyethylene blends[J]. European polymer journal,2007,43:3662-3670.
[49]S. Iyer, D.A. Schiraldi. Role of ionic interactions in the compatibility of polyester ionomers with poly(ethylene terephthalate) and nylon 6[J]. J Polym Sci Part B Polym Phys,2006,44: 2091-2103.
[50]C. Guerrero, T. Lozano, V. Gonzalez, E. Arroyo. Properties and morphology of poly (ethyle-ne terephthalate) and high-density polyethylene blends[J]. J Appl Polym Sci,2001,82: 1382-1390.
[51]A. Retolaza, J.I. Eguiazabal, J. Nazabal. Poly(ethylene-co-methacrylic acid)-lithium ionomer as a compatibilizer for poly(ethylene terephthalate)/linear low-density polyethylene blends [J]. J Appl Polym Sci,2003,87:1322-1328.
[52]A. Retolaza, J.I. Eguiazabal, J. Nazabal. A lithium ionomer of poly(ethylene-co-methacrylic acid) copolymer as compatibilizer for blends of poly(ethylene terephthalate) and high density polyethylene[J]. Polym Eng Sci,2002,42:2072-2083.
[53]吴玉萍,罗红林.聚酯聚醚嵌段共聚酯的合成及性能研究[J].江西教育学院学报,2001,22(6)：30-32.
[54]ZhiYong Qian, Sai Li, Yi He, XiaoBo Liu. Synthesis and in vitro degradation study of poly (ethylene terephthalate)/poly (ethylene glycol) (PET/PEG) multiblock copolymer[J]. Polymer Degradation and Stability,2004,83:93-100.
[55]刘亚利,余木火,韩克清.PET-季戊四醇共聚酯的固相聚合及其结晶性能[J].合成纤维,2007,(3)：13-17.
[56]戴均明.PET-PBT共聚酯的结晶性能[J].合成技术及应用,2002,17(1)：1-4.
[57]Ahmed I. Abou-Kandil, Alan H. Windle The morphology of 50%PET/PEN random copoly-mer as revealed by high resolution scanning electron microscopy and X-ray diffraction[J]. Polymer 48 (2007) 48244836.
[58]G.E. Welsh, A.H. Windle. Levels of structural order in crystals of PET/PEN random copoly-mers[J]. Polymer,2001,42:5727-5735.
[59]贾宏涛,赵蕴慧,盛京.PET-PTMG聚醚酯熔融与结晶行为的研究[J].化学工业与工程,2003,20(6)：319-323.
[60]张广成,史学涛,项士新,等.成核剂对聚对苯二甲酸乙二醇酯的结晶行为影响[J].机械科学与技术,2006(6),25(6)：641-646.
[61]郭涛,王炼石,蔡彤旻,等.稀土氧化镧对PET结晶行为和力学性能的影响[J].工程塑料应用,2003,31(12)：6-8.
[62]陈汉周,刘钦甫,赵庆章,等.改性黏土对PET纳米复合材料结晶性能的影响[J].中国矿业大学学报,2007(9),36(5)：701-706.
[63]Thallada Bhaskar. Effect of poly(ethylene terephthalate) on the pyrolysis of brominated flame retardant containing high impact polystyrene and catalytic debromination of the liquid products[J] J. Anal Appl Pyrolysis,2004,71:765-769.
[64]刘治国.溴代聚苯乙烯阻燃剂制备方法研究进展[J].河南化工,2004(1)：5-7.
[65]孔令杰.国内外塑料阻燃剂的发展现状与展望[J].河北化工,2003,(3)：11-14.
[66]贡长生.磷系阻燃剂的合成和应用[J].化工技术经济,2002,(2)：9-15.
[67]欧荣庆.二溴新戊二醇不饱和聚酯树脂及其阻燃玻璃钢性能[J].阻燃材料与技术,2004,(1)：31-34.
[68]郭增山,王栋,刘克忠,等.用于PET阻燃的聚季戊四醇磷酸酯的合成、表征[J].第七届全国磷化学化工暨第四届海峡化学生物学、生物技术与医药发展讨论会,2006,(4)：6-10.
[69]李杰.高性能增强阻燃聚酯(PET)工程塑料,中国CN1789329,2006.
[70]彭治汉.一种双环膦酸酯阻燃剂及其合成方法,中国CN1888013,2007.
[71]陈涛,牛艳华,吴智华.GF处理工艺及熔体流动场对PET／GF复合材料微观结构的影响[J].工程塑料应用,2006,34(4)：29-33.
[72]安军,刘佑习.玻璃纤维增强PET工程塑料性能及界面研究[J].高分子材料科学与工程,1996(9),12(5)：83-87.
[73]杨得志,庞纯,等.玻纤增强阻燃PET的研制[J].工程塑料应用,2005,33(4)：8-11.
[74]廖明义,陈平.高分子合成材料.化学工业出版社,2005.
[75]赵均.PET工程塑料研究进展[J].河南化工,2002,5：1-4.
[76]周晓沧.PET工程塑料现在及展望[J].合成技术及应用,2006(3),21(1)：34-38.
[77]刘学习,庄辉,张大陆.纳米硫酸钡增强PET复合材料性能研究[J].塑料工业,2007,35(4)：21-23.
[78]石峰,陶杰,董祥.纳米ZnO对PET的力学性能影响[J].云南大学学报(自然科学版),2005,27(3A)：228-230
[79]戴长华.纳米复合材料的制备方法和进展[J].精细石油化工进展,2001,2(1)：35-39.
[80]Woo Jin Choi, Sung Chul Kim. Effects of talc orientation and non-isothermal crystallization rate on crystal orientation of polypropylene in injection-molded polypropylene/ethylene-propylene rubber/talc blends[J]. Polymer,2005,45:2393-2401.
[81]Yimin Wang, Junpeng Gao, Yunqian Ma, ect. Study on mechanical properties, thermal stability and crystallization behavior of PET/MMT nanocomposites[J]. Composites:Part B 2006.37:399-407.
[82]Yang-Chuan Ke, Tian-Bin Wu, Yan-Feng Xia. The nucleation, crystallization and dispersion behavior of PET emonodisperse SiO2composites[J]. Polymer,2007,48:3324-3336.
[83]唐仕东,辛忠,张黎.有机羧酸钠盐对PET结晶和熔融行为的影响[J].中国塑料,2006,20(11)：21-25.
[84]Y. Ma, U.S.Agarwal. Solvent assisted post-polymerization of PET[J]. Polymer,2005,46: 5447-5455.
[851 C.I.W.Calcagno, C.M.Mariani, S.R.Teixeira, ect. The effect of organic modifier of the clay on morphology and crystallization properties of PET nanocomposites[J]. Polymer,2007,48: 966-974.
[86]U.S.Agarwal, G.de Wit, P.J.Lemstra. A new solid-state process for chemical modification of PETfor crystallization rate enhancement[J]. Polymer,2002,43:5709-5712.
[87]姜润喜,梁伯润,戴承渠,等.PET／离聚物共混体系的相容性及形态结构[J].中国纺织大学学报.1995,21(3)：46-56.
[88]姜润喜,刘春生,汪进玉,等.PET离聚物共混体系的结晶与熔融行为研究[J].合成技术及应用,1995,10(3)：1-6.
[89]姜润喜.离子聚合物及其应用[J].合成技术及应用,1994,9(2)：22-26.
[90]田东,卜海山.离子聚合物surlyn的成核效应(Ⅰ)-surlyn与聚对苯二甲酸乙二酯的反应[J].复旦学报(自然科学版),1992,31(2)：21-220.
[91]田东,卜海山,胡家伦.离子聚合物Surlyn的成核效应(Ⅱ)-surlyn对聚对苯二甲酸乙二酯的结晶行为和形态的影响[J].复旦学报(自然科学版),1992,31(4)：441-449.
[92]刘森林,马敬红,梁伯润.PET结晶成核剂及促进剂活性的表征[J].合成技术及应用,1999,14(2)：6-9.
[93]卜海山,虎燎婉,胡文兵.聚对苯二甲酸乙二酯结晶的成核促进剂[J].复旦学报(自然科学版),1991,30(1)：1-7.
[94]陈彦,徐成核剂和促进剂对聚对苯二甲酸乙二酯结晶的影响.1999,(1)：7-14.
[95]郭仁义,危大福,卢红.结晶促进剂和成核剂对PET结晶性能的影响[J].高分子材料科学与工程,2003,19(4)：121-124.
[96]Lifang Liu, Jianyong Yu, Longdi Cheng, ect. Biodegradability of poly (butylene succinate) (PBS) composite reinforced with jute fibre[J]. Polymer degradation and stability,2009,94: 90-94.
[97]顾军渭,张广成,等.PET阻燃技术的研究进展[J].工程塑料应用,2005,33(2)：67-70.
[98]储九荣.环氧树脂的精细化[J].化工进展,1999(1)：49-51.
[99]李林,陆建锋.增强、阻燃PET的研究与应用[J].工程塑料应用,2001,29(1)：3-5.
[100]YOKOSHIMA. Reifforced flame-retarded polyester resin composition[P]. EP0549118,1993.
[101]卢攀峰,阎修维,等.PET改性研究进展及应用现状[J].中国塑料,2008,22(10)：1-6.
[102]Deyrup, E.J.Toughened thermoplastic polyester compositions:US,4753980[P].1988-06-28
[103]Akkapeddi M.K., Van Buskirk. Polyester molding compositions and articles exhibiting good impact, heat and solvent resistance:US,5723520[P].1998-03-03.
[104]Nelsen S., Golder. Method and compositions for toughening polyester resins:US,6020414 [P].2000-02-01.
[105]Tong Wan, Ling Chen, Yang Choo Chua, ect. Crystalline morphology and isothermal crystal-lization kinetics of poly (ethylene terephthalate)/clay nanocomposites[J]. Journal of applied polymer science,2004,94:1381-1388.
[106]Jae Woo Chung, Be-bum Son, Sang-wook Chun, ect. Nonisothermal crystallization behavior of exfoliated poly (ethylene terephthalate)-layered silicate nanocomposites in the presence and absence of organic modifier[J]. Journal of Polymer Science:Part B:Polymer Physics, 2008,46:989-999.
[107]Avrami M.J. Chem.Phys.,1939.
[108]Tomoko Yoshii, Hirohisa Yoshida, Tadashi Kawai. Effect of structural relaxation of glassy PET on crystallization process observed by the simultaneous DSC-XRD and DSC-FTIR[J]. Thermo-chimicaacta,2005,431:177-181.
[109]B. Lee, T.J.Shin, S.W.Lee. Time-resolved X-ray scattering and calorimetric studies on the crystallization behaviors of poly (ethylene terephthalate) (PET) and its copolymers contain-ing isophthalate units[J]. Polymer,2003,44:2509-2518.
[110]H.GHaubruge, R.Daussin, A.M.Jonas, ect. Epitaxial nucleation of poly (ethylene terephthal-ate) by talc:structure at the lattice and lamellar scales[J]. Macromolecules,2003,36:4452-4456.
[2]M. Wu and L.L. Shaw, Int. J. Anovel concept of carbon-filled polymer blends for application-s in PEM fuel cell bipolar plates[J]. Hydrogen Energy,2005,30:373-380.
[3]M. Wu and L.L. Shaw, J. On the improved properties of injection-molded, carbon nanotube-filled PET/PVDF blends[J]. Power Sources,2004,136:37-44.
[4]赵耀明.非纤维用热塑性聚脂工艺与应用,化学工业出版社,2002.
[5]金国珍.工程塑料,化学工业出版社,2001.
[6]张克惠,张广成.塑料材料学,化学工业出版社,2001.
[7]焦剑,雷渭媛.高聚物结构、性能与测试,化学工业出版社,2003.
[8]G.Y.Gao, S.L.An, J.L.Yu. Research on conductive group in carbon black/polyester composite fibers[J]. J Tianjin Polytech Univ,2005,24:12-15.
[9]Y.Huang, Z.F.Li, G.H.Luo. Research on conductive group in carbon black/polyester compo-site fibers[J]. China Syn Fiber Ind,2004,27:1-8.
[10]Xiaolei Chen, Chunzhong Li, Wei Shao. Isothermal crystallization kinetics and melting behaviour of PET/ATO nanocomposites prepared by in situ polymerization[J]. European Polymer Journal,2007,43:3177-3186.
[11]M.T. Run, S.Z. Wu, D.Y. Zhang, ect. Melting behaviors and isothermal crystallization kine-tics of poly(ethylene terephthalate)/mesoporous molecular sieve composite[J]. Polymer, 2005,46:5308-5316.
[12]M.L. Di Lorenzo, C. Silvestre. Non-isothermal crystallization of polymers[J]. Prog Polym Sci,1999,24:917-950.
[13]H.R.Dennis, D.L.Hunter, D.Chang, ect. Preparation and characterization of PBT nanocomp-osites compounded with different montmorillonites[J]. Polymer,2001,42:9513-9522.
[14]裴运同,杨军忠,等.增强阻燃PET工程塑料的研究[J].中国塑料,2003,17(1)：58-62.
[15]陈军,陆宾峰,臧惠蕊等.玻纤、阻燃剂和纳米成核剂对PET性能的影响[J].工程塑料应用,2005,33(3)：9-12.
[16]杨得志,庞纯,赵建青.玻纤增强阻燃PET的研制[J].工程塑料应用,2005,33(4)：8-11.
[17]刘锋,王锡柱,张德善.PET改性工程塑料的发展动态[J].弹性体,2005,15(6)：59-63.
[18]刘学习,庄辉,程勇峰,等.长玻纤增强PET工程塑料的性能研究[J].塑料工业,2006,34(12)：26-28.
[19]董纪震,赵耀明等.合成纤维工艺学(下册),第二版,1994.
[20]王显楼.涤纶生产基本知识,北京,’纺织工业出版社,1993.
[21]国家标准局纤维检验局.化学纤维检验技术(上册),北京,1983.
[22]殷敬华,莫志深.现代高分子物理学(上册),科学出版社,2001.
[23]殷敬华,莫志深.现代高分子物理学(下册),科学出版社,2001.
[24]张光华,杨玉芹,林瑛等.聚对苯二甲酸乙二酯球晶的形态结构[J].高分子材料科学与工程,1992,(3)：114-117.
[25]杨始堃.聚酯树脂质量指标述评(5)[J].聚酯工业,2002,15(1)：58-61.
[26]杨始堃.聚酯(PET)树脂切片的干燥和结晶[J].聚酯工业,2005,18(6)：55-57.
[27]周达飞,唐颂超.高分子材料成型加工,北京,轻工业出版社,2000.
[28]Feng Wang, Xiangfu Meng, Xinfeng Xu, ect. Inhibited transesterification of PET/PBT blends filled with silica nanoparticles during melt processing[J]. Polymer Degradation and Stability,2008,93:1397-1404.
[29]Geun Hyung Kim, Woo Jun Kim, Seung Mo Kim, ect. Analysis of thermo-physical and optical properties of a diffuser using PET/PC/PBT copolymer in LCD backlight units[J]. Displays,2005,26:37-43.
[30]Vladimir N. Ignatov, Claudio Carraro, Vittorio Tartari t. PET/PC blends and copolymers by one-step extrusion:1. Chemical structure and physical properties of 50/50 blends[J]. Polymer,1997,38 (1):195-200.
[31]Vladimir N. Ignatov, Claudio Carraro, Vittorio Tartari t. PET/PC blends and copolymers by one-step extrusion:2. Influence of the initial polymer composition and type of catalyst[J]. Polymer,1997,38 (1):201-205. [32] Paola Marchese, Annamaria Celli, Maurizio Fiorini, ect. Effects of annealing on crystallinity and phase behaviour of PET/PC block copolymers[J]. European Polymer Journal 2003, 39:1081-1089.
[33]于中振,欧玉春,冯宇鹏.界面粘结对PET／尼龙66共混物结晶行为和力学性能的影响[J].高分子材料科学与工程,1997,13(3)：57-61.
[34]华东理工大学.PA／PET高分子合金材料[P].CN1749314,2006-03-22.
[35]Hiroshi Shimizu, Takeshi Kitano, Kazuo Nakayama. Morphological control of LCP/PET blends using a melt mixer equipped with a milling part[J]. Materials Letters,2004,58: 1277-1281.
[36]Hung-Chih Chin, Feng-Chih Chang. Reactive cornpatibilization of PET/LCP blends by a multifunctional epoxy coupler[J]. Polymer,1997,38 (12):2947-2956.
[37]Nadka Avramova. Amorphous poly(ethylene terephthalate)/poly(butylene terephthalate) blends:miscibility and properties[J]. Polymer,1995,36 (4):801-808.
[38]I. Puente Orench a, N. Stribeck b, F. Ania a, ect. SAXS study on the crystallization of PET under physical confinement in PET/PC multilayered films[J]. Polymer,2009,50:2680-2687.
[39]Zhang Z, Xie Y, M a D. Relationship between miscibility and chemical structures in reactive blending of poly(bisphenol A carbonate) and poly(ethylene terephthalate)[J]. Eur Polym J, 2001,37:1961-1966.
[40]吕军,黄锐,魏刚.PET／PC共混体系结晶行为研究进展[J].功能高分子学报,2005,18(1)：161-166.
[41]李建勋,彭少贤,郦华兴.反应性增韧和增容技术在PET回收料及其共混物PET／PC中的应用[J].塑料,1998,27(2)：33-36.
[42]Xanthos M., BaltzisB.C., Hsu.PP. Effects of Carbonate. Salts on Crystallization Kinetics and Properties of Recycled polyethylene terephthalate[J]. Polym Sci,1997,64:1433-1435.
[43]周理水.PET塑料的改性及应用.塑料加工,2000,29(3)：32-36.
[44]陈玉君,何国山,侯巩.聚烯烃接枝MAH对PET／PA6性能的影响.中国塑料,2002,16(5)：44-46.
[45]宗立明,范奎城,刘德山.PET与液晶高分子注射模塑原位复合材料的研究[J].高分子材料科学与工程,1998,14(3)：87-90.
[46]Shu-cai Li, Li-nong Lu. Melt Rheological Properties of Reactive Compatibilized HDPE/PET blends[J]. Journal of Applied polymer science,2008,108:3559-3564.
[47]Mustapha Kaci, Aida Benhamida, Sossio Cimmino, ect. Waste and virgin LDPE/PET blends compatibilized with an ethylene-butyl acrylate-glycidyl methacrylate (EBAGMA) terpoly-mer, morphology and mechanical properties[J]. Macromolecular materials and engineering, 2005,290:987-995.
[48]Hongsheng Zhang, Weihong Guo, Yingbo Yu. Structure and properties of compatibilized recycled poly(ethylene terephthalate)/linear low density polyethylene blends[J]. European polymer journal,2007,43:3662-3670.
[49]S. Iyer, D.A. Schiraldi. Role of ionic interactions in the compatibility of polyester ionomers with poly(ethylene terephthalate) and nylon 6[J]. J Polym Sci Part B Polym Phys,2006,44: 2091-2103.
[50]C. Guerrero, T. Lozano, V. Gonzalez, E. Arroyo. Properties and morphology of poly (ethyle-ne terephthalate) and high-density polyethylene blends[J]. J Appl Polym Sci,2001,82: 1382-1390.
[51]A. Retolaza, J.I. Eguiazabal, J. Nazabal. Poly(ethylene-co-methacrylic acid)-lithium ionomer as a compatibilizer for poly(ethylene terephthalate)/linear low-density polyethylene blends [J]. J Appl Polym Sci,2003,87:1322-1328.
[52]A. Retolaza, J.I. Eguiazabal, J. Nazabal. A lithium ionomer of poly(ethylene-co-methacrylic acid) copolymer as compatibilizer for blends of poly(ethylene terephthalate) and high density polyethylene[J]. Polym Eng Sci,2002,42:2072-2083.
[53]吴玉萍,罗红林.聚酯聚醚嵌段共聚酯的合成及性能研究[J].江西教育学院学报,2001,22(6)：30-32.
[54]ZhiYong Qian, Sai Li, Yi He, XiaoBo Liu. Synthesis and in vitro degradation study of poly (ethylene terephthalate)/poly (ethylene glycol) (PET/PEG) multiblock copolymer[J]. Polymer Degradation and Stability,2004,83:93-100.
[55]刘亚利,余木火,韩克清.PET-季戊四醇共聚酯的固相聚合及其结晶性能[J].合成纤维,2007,(3)：13-17.
[56]戴均明.PET-PBT共聚酯的结晶性能[J].合成技术及应用,2002,17(1)：1-4.
[57]Ahmed I. Abou-Kandil, Alan H. Windle The morphology of 50%PET/PEN random copoly-mer as revealed by high resolution scanning electron microscopy and X-ray diffraction[J]. Polymer 48 (2007) 48244836.
[58]G.E. Welsh, A.H. Windle. Levels of structural order in crystals of PET/PEN random copoly-mers[J]. Polymer,2001,42:5727-5735.
[59]贾宏涛,赵蕴慧,盛京.PET-PTMG聚醚酯熔融与结晶行为的研究[J].化学工业与工程,2003,20(6)：319-323.
[60]张广成,史学涛,项士新,等.成核剂对聚对苯二甲酸乙二醇酯的结晶行为影响[J].机械科学与技术,2006(6),25(6)：641-646.
[61]郭涛,王炼石,蔡彤旻,等.稀土氧化镧对PET结晶行为和力学性能的影响[J].工程塑料应用,2003,31(12)：6-8.
[62]陈汉周,刘钦甫,赵庆章,等.改性黏土对PET纳米复合材料结晶性能的影响[J].中国矿业大学学报,2007(9),36(5)：701-706.
[63]Thallada Bhaskar. Effect of poly(ethylene terephthalate) on the pyrolysis of brominated flame retardant containing high impact polystyrene and catalytic debromination of the liquid products[J] J. Anal Appl Pyrolysis,2004,71:765-769.
[64]刘治国.溴代聚苯乙烯阻燃剂制备方法研究进展[J].河南化工,2004(1)：5-7.
[65]孔令杰.国内外塑料阻燃剂的发展现状与展望[J].河北化工,2003,(3)：11-14.
[66]贡长生.磷系阻燃剂的合成和应用[J].化工技术经济,2002,(2)：9-15.
[67]欧荣庆.二溴新戊二醇不饱和聚酯树脂及其阻燃玻璃钢性能[J].阻燃材料与技术,2004,(1)：31-34.
[68]郭增山,王栋,刘克忠,等.用于PET阻燃的聚季戊四醇磷酸酯的合成、表征[J].第七届全国磷化学化工暨第四届海峡化学生物学、生物技术与医药发展讨论会,2006,(4)：6-10.
[69]李杰.高性能增强阻燃聚酯(PET)工程塑料,中国CN1789329,2006.
[70]彭治汉.一种双环膦酸酯阻燃剂及其合成方法,中国CN1888013,2007.
[71]陈涛,牛艳华,吴智华.GF处理工艺及熔体流动场对PET／GF复合材料微观结构的影响[J].工程塑料应用,2006,34(4)：29-33.
[72]安军,刘佑习.玻璃纤维增强PET工程塑料性能及界面研究[J].高分子材料科学与工程,1996(9),12(5)：83-87.
[73]杨得志,庞纯,等.玻纤增强阻燃PET的研制[J].工程塑料应用,2005,33(4)：8-11.
[74]廖明义,陈平.高分子合成材料.化学工业出版社,2005.
[75]赵均.PET工程塑料研究进展[J].河南化工,2002,5：1-4.
[76]周晓沧.PET工程塑料现在及展望[J].合成技术及应用,2006(3),21(1)：34-38.
[77]刘学习,庄辉,张大陆.纳米硫酸钡增强PET复合材料性能研究[J].塑料工业,2007,35(4)：21-23.
[78]石峰,陶杰,董祥.纳米ZnO对PET的力学性能影响[J].云南大学学报(自然科学版),2005,27(3A)：228-230
[79]戴长华.纳米复合材料的制备方法和进展[J].精细石油化工进展,2001,2(1)：35-39.
[80]Woo Jin Choi, Sung Chul Kim. Effects of talc orientation and non-isothermal crystallization rate on crystal orientation of polypropylene in injection-molded polypropylene/ethylene-propylene rubber/talc blends[J]. Polymer,2005,45:2393-2401.
[81]Yimin Wang, Junpeng Gao, Yunqian Ma, ect. Study on mechanical properties, thermal stability and crystallization behavior of PET/MMT nanocomposites[J]. Composites:Part B 2006.37:399-407.
[82]Yang-Chuan Ke, Tian-Bin Wu, Yan-Feng Xia. The nucleation, crystallization and dispersion behavior of PET emonodisperse SiO2composites[J]. Polymer,2007,48:3324-3336.
[83]唐仕东,辛忠,张黎.有机羧酸钠盐对PET结晶和熔融行为的影响[J].中国塑料,2006,20(11)：21-25.
[84]Y. Ma, U.S.Agarwal. Solvent assisted post-polymerization of PET[J]. Polymer,2005,46: 5447-5455.
[851 C.I.W.Calcagno, C.M.Mariani, S.R.Teixeira, ect. The effect of organic modifier of the clay on morphology and crystallization properties of PET nanocomposites[J]. Polymer,2007,48: 966-974.
[86]U.S.Agarwal, G.de Wit, P.J.Lemstra. A new solid-state process for chemical modification of PETfor crystallization rate enhancement[J]. Polymer,2002,43:5709-5712.
[87]姜润喜,梁伯润,戴承渠,等.PET／离聚物共混体系的相容性及形态结构[J].中国纺织大学学报.1995,21(3)：46-56.
[88]姜润喜,刘春生,汪进玉,等.PET离聚物共混体系的结晶与熔融行为研究[J].合成技术及应用,1995,10(3)：1-6.
[89]姜润喜.离子聚合物及其应用[J].合成技术及应用,1994,9(2)：22-26.
[90]田东,卜海山.离子聚合物surlyn的成核效应(Ⅰ)-surlyn与聚对苯二甲酸乙二酯的反应[J].复旦学报(自然科学版),1992,31(2)：21-220.
[91]田东,卜海山,胡家伦.离子聚合物Surlyn的成核效应(Ⅱ)-surlyn对聚对苯二甲酸乙二酯的结晶行为和形态的影响[J].复旦学报(自然科学版),1992,31(4)：441-449.
[92]刘森林,马敬红,梁伯润.PET结晶成核剂及促进剂活性的表征[J].合成技术及应用,1999,14(2)：6-9.
[93]卜海山,虎燎婉,胡文兵.聚对苯二甲酸乙二酯结晶的成核促进剂[J].复旦学报(自然科学版),1991,30(1)：1-7.
[94]陈彦,徐成核剂和促进剂对聚对苯二甲酸乙二酯结晶的影响.1999,(1)：7-14.
[95]郭仁义,危大福,卢红.结晶促进剂和成核剂对PET结晶性能的影响[J].高分子材料科学与工程,2003,19(4)：121-124.
[96]Lifang Liu, Jianyong Yu, Longdi Cheng, ect. Biodegradability of poly (butylene succinate) (PBS) composite reinforced with jute fibre[J]. Polymer degradation and stability,2009,94: 90-94.
[97]顾军渭,张广成,等.PET阻燃技术的研究进展[J].工程塑料应用,2005,33(2)：67-70.
[98]储九荣.环氧树脂的精细化[J].化工进展,1999(1)：49-51.
[99]李林,陆建锋.增强、阻燃PET的研究与应用[J].工程塑料应用,2001,29(1)：3-5.
[100]YOKOSHIMA. Reifforced flame-retarded polyester resin composition[P]. EP0549118,1993.
[101]卢攀峰,阎修维,等.PET改性研究进展及应用现状[J].中国塑料,2008,22(10)：1-6.
[102]Deyrup, E.J.Toughened thermoplastic polyester compositions:US,4753980[P].1988-06-28
[103]Akkapeddi M.K., Van Buskirk. Polyester molding compositions and articles exhibiting good impact, heat and solvent resistance:US,5723520[P].1998-03-03.
[104]Nelsen S., Golder. Method and compositions for toughening polyester resins:US,6020414 [P].2000-02-01.
[105]Tong Wan, Ling Chen, Yang Choo Chua, ect. Crystalline morphology and isothermal crystal-lization kinetics of poly (ethylene terephthalate)/clay nanocomposites[J]. Journal of applied polymer science,2004,94:1381-1388.
[106]Jae Woo Chung, Be-bum Son, Sang-wook Chun, ect. Nonisothermal crystallization behavior of exfoliated poly (ethylene terephthalate)-layered silicate nanocomposites in the presence and absence of organic modifier[J]. Journal of Polymer Science:Part B:Polymer Physics, 2008,46:989-999.
[107]Avrami M.J. Chem.Phys.,1939.
[108]Tomoko Yoshii, Hirohisa Yoshida, Tadashi Kawai. Effect of structural relaxation of glassy PET on crystallization process observed by the simultaneous DSC-XRD and DSC-FTIR[J]. Thermo-chimicaacta,2005,431:177-181.
[109]B. Lee, T.J.Shin, S.W.Lee. Time-resolved X-ray scattering and calorimetric studies on the crystallization behaviors of poly (ethylene terephthalate) (PET) and its copolymers contain-ing isophthalate units[J]. Polymer,2003,44:2509-2518.
[110]H.GHaubruge, R.Daussin, A.M.Jonas, ect. Epitaxial nucleation of poly (ethylene terephthal-ate) by talc:structure at the lattice and lamellar scales[J]. Macromolecules,2003,36:4452-4456.