PET/AlOOH纳米复合材料的制备及性能研究
摘要
采用原位聚合法制备PET/AlOOH纳米复合材料,将纳米AlOOH的乙二醇溶胶加入到制备PET的中间产物对苯二甲酸乙二醇酯(BHET)中,在液态下均匀混合,再经过缩聚反应制得PET/AlOOH纳米复合材料,对制得的复合材料进行了结构表征及性能分析研究。
通过红外测试,发现纳米AlOOH确实存在PET基体中,证实制备出PET/AlOOH纳米复合材料。且通过TEM图像可以看出AlOOH的粒径在二十纳米左右,均匀分散在PET基体中,没有形成团聚。
通过TG测试对PET和PET/AlOOH纳米复合材料的热降解动力学进行的分析研究表明,PET/AlOOH纳米复合材料初始阶段的降解活化能降低,其它阶段的活化能明显提高。这说明,在降解过程中的高温阶段,AlOOH使复合材料降解变得困难。
通过DSC对非等温结晶动力学的研究表明,由于复合材料中AlOOH表面接枝了一定量的PET大分子,引起部分交联结构,严重限制了PET大分子的活动,因此复合材料中的AlOOH对PET的结晶起到阻碍作用。
通过CONE对材料的燃烧性能研究表明,虽然PET/AlOOH纳米复合材料的点燃时间较普通PET缩短,但是AlOOH的加入明显降低了复合材料的热释放速率、热释放速率峰值及峰值出现时间、总热释放量,因此AlOOH可以在一定程度上延缓复合材料的燃烧过程,具有阻燃性能。
通过扫描电镜对残炭进行了研究,可以看出纯PET燃烧产物的炭层比较薄产生的泡比较大;PET/AlOOH纳米复合材料的燃烧产物形成的炭层比较厚,产生的泡很小。通过裂解色谱研究了其阻燃机理,PET/AlOOH纳米复合材料裂解产物比纯PET明显的少,说明阻燃剂的引入是聚酯分解不彻底,减少可燃性物质的生成。
PET/AlOOH nanocomposites were synthesized via the in-situ method.Firstly, terephthalic acid was reacted with excess ethylene glycol to form bis(hydroxyethyl) terephthalate(BHET);Second,the boehmite(AIOOH) was added into the BHET and mixed homogeneously with it,then concurrent with polycondensation of BHET to produce the PET matrix.The characterization and properties of PET/AlOOH nanocomposites prepared by in-situ method were investigated.
The composites examined by FT-IR showed to be boehrnite,which indicated that boehmite had been added into PET matrix.The TEM image showed that the boehrnite particles ranged from about several to tens nanometers in diameter.The nanoparticles were dispersed well in PET matrix.
The kinetics of thermal oxidative degradation of pure PET and PET/AlOOH nanocomposites were investigated by TGA.The results showed that nano AlOOH enhanced the activation energy of different degradation steps except the initial step of degradation,which showed that nano AlOOH made the degradation of PET become difficult at high temperature.
The nonisothermal crystallization kinetics of pure PET and PET/AlOOH nanocomposites were examined by DSC.The results showed that these boehmite particles made the crystallization capability of PET decline.Because the crosslink structure of PET/AlOOH nanocrnpsite dramatically restricted the movement of PET chains so as to cause the decrease of crystallization capability.
The flame retardancy was investigated by CONE.Although the initial ignition time of PET/AlOOH nanocomposite were shorter than that of pure PET,the heating release rate, peak of heating release rate and its time,total heating release of PET/AlOOH nanocomposites were all lower than those of pure PET.So the boehmite could retard the burning processes of PET/AlOOH nanocomposite.
The carbon layers under SEM,the char of pure PET was very thin and the hole was bigger. The char of PET/AlOOH was very thick and the hole was smaller.The flame retardant can make more carbon formation during buming,so the carbon layer formed after addition of AlOOH.The existing of a lot of fine holes may be because of the action of AlOOH.
通过红外测试,发现纳米AlOOH确实存在PET基体中,证实制备出PET/AlOOH纳米复合材料。且通过TEM图像可以看出AlOOH的粒径在二十纳米左右,均匀分散在PET基体中,没有形成团聚。
通过TG测试对PET和PET/AlOOH纳米复合材料的热降解动力学进行的分析研究表明,PET/AlOOH纳米复合材料初始阶段的降解活化能降低,其它阶段的活化能明显提高。这说明,在降解过程中的高温阶段,AlOOH使复合材料降解变得困难。
通过DSC对非等温结晶动力学的研究表明,由于复合材料中AlOOH表面接枝了一定量的PET大分子,引起部分交联结构,严重限制了PET大分子的活动,因此复合材料中的AlOOH对PET的结晶起到阻碍作用。
通过CONE对材料的燃烧性能研究表明,虽然PET/AlOOH纳米复合材料的点燃时间较普通PET缩短,但是AlOOH的加入明显降低了复合材料的热释放速率、热释放速率峰值及峰值出现时间、总热释放量,因此AlOOH可以在一定程度上延缓复合材料的燃烧过程,具有阻燃性能。
通过扫描电镜对残炭进行了研究,可以看出纯PET燃烧产物的炭层比较薄产生的泡比较大;PET/AlOOH纳米复合材料的燃烧产物形成的炭层比较厚,产生的泡很小。通过裂解色谱研究了其阻燃机理,PET/AlOOH纳米复合材料裂解产物比纯PET明显的少,说明阻燃剂的引入是聚酯分解不彻底,减少可燃性物质的生成。
PET/AlOOH nanocomposites were synthesized via the in-situ method.Firstly, terephthalic acid was reacted with excess ethylene glycol to form bis(hydroxyethyl) terephthalate(BHET);Second,the boehmite(AIOOH) was added into the BHET and mixed homogeneously with it,then concurrent with polycondensation of BHET to produce the PET matrix.The characterization and properties of PET/AlOOH nanocomposites prepared by in-situ method were investigated.
The composites examined by FT-IR showed to be boehrnite,which indicated that boehmite had been added into PET matrix.The TEM image showed that the boehrnite particles ranged from about several to tens nanometers in diameter.The nanoparticles were dispersed well in PET matrix.
The kinetics of thermal oxidative degradation of pure PET and PET/AlOOH nanocomposites were investigated by TGA.The results showed that nano AlOOH enhanced the activation energy of different degradation steps except the initial step of degradation,which showed that nano AlOOH made the degradation of PET become difficult at high temperature.
The nonisothermal crystallization kinetics of pure PET and PET/AlOOH nanocomposites were examined by DSC.The results showed that these boehmite particles made the crystallization capability of PET decline.Because the crosslink structure of PET/AlOOH nanocrnpsite dramatically restricted the movement of PET chains so as to cause the decrease of crystallization capability.
The flame retardancy was investigated by CONE.Although the initial ignition time of PET/AlOOH nanocomposite were shorter than that of pure PET,the heating release rate, peak of heating release rate and its time,total heating release of PET/AlOOH nanocomposites were all lower than those of pure PET.So the boehmite could retard the burning processes of PET/AlOOH nanocomposite.
The carbon layers under SEM,the char of pure PET was very thin and the hole was bigger. The char of PET/AlOOH was very thick and the hole was smaller.The flame retardant can make more carbon formation during buming,so the carbon layer formed after addition of AlOOH.The existing of a lot of fine holes may be because of the action of AlOOH.
引文
1 郭大生,王文科.聚酯纤维科学与工程.中国纺织出版社,2001.6
2 吴剑南,我国聚酯工业的现状和前景展望.当代石油化工,2004,12(6):16-19
3 李玲,向航.功能材料与纳米技术.化学工业出版社,2002.1
4 李凤生.超细粉体技术.国防工业出版社,2000
5 高其标,申屠宝卿,翁志学.纳米改性聚合物材料研究进展.化工生产与技术,2001,8(6):22-26
6 R Roy,S Komarneni,D M Roy.Multi-phase ceramic composites made by Sol-Gol technique.Mater.Res.Symp.Proc,1984,32:347-359
7 潘飞.PET/TiO_2纳米复合材料性能研究及其纺丝模拟:[学位论文]上海:东华大学.,2006
8 黄锐,王旭,李忠明.纳米塑料.中国轻工业出版社,2002.4
9 杨玉芬,陈清如.纳米材料的基本特征与纳米科技的发展.中国粉体技术,2002,8(3):22-27
10 杨鼎宜,孙伟.纳米材料的结构特征与特殊性能.材料导报,2003,17(10):7-10
11 Kubo,R.Electronic Properties of Metallic Fine Particles.Ⅰ.Journal of the Physical Society of Japan,17(6):975-986
12 张立德.纳米材料.化学工业出版社,2000:40-41
13 S.C.Tjong.Structural and mechanical properties of polymer nanocomposites.Materials Science and Engineering,2006,Article in Press
14 周卫平,朱光中,翟泽军.纳米技术在高聚物中的应用及其进展.现代化工,2002,22(6):19-23
15 卢春生,米耀荣.化整为零:聚合物粘土纳米复合材料的微观结构和阻隔性能.研究快讯,2006,35(7):550-552
16 丁运生,张志成,史铁钧.阻隔性高分子材料研究进展.功能高分子学报,2001,14:360-364
17 葛建华,王迎军,郑裕东,龚克诚,溶胶凝胶法在聚合物/无机纳米复合材料中的应用.材料科学与工程学报,2004,22(3):442-445
18 李曦,孙江勤,张超灿.溶胶-凝胶法制备有机-无机杂化纳米级功能材料.湖北化工,2000,3:5-7
19 任杰,刘艳.聚合物基有机-无机纳米复合材料研究及应用前景.材料导报,2003,17(2):58-62
20 张军丽,叶文玉.溶胶凝胶法聚合物/无机复合材料的研究与应用.云南化工,2005,32(3):43-46
21 Suzuki F.GrecoR J Appl Polymer Sci.1990,39:371
22 刘晓蕾,何毅,李赛,刘孝波.聚ε-己内酯/SiO_2杂化材料的制备.四川大学学报(工程科学版),2003,35(1):59-62
23 Q.Hu,E.Marand.In situ formation of nanosized TiO_2 domains within poly(amide-imide) by a sol-gel process.Polymer,1999,40:4833-4843
24 Rajatendu Senguptaa,Abhijit Bandyopadhyaya,Sunil Sabharwalb,Tapan K.Chakia,Anti K.Bhowmick.Polyamide-6,6/in situ silica hybrid nanocomposites by sol-gel technique:synthesis,characterization and properties.Polymer,2005,46:3343-3354
25 C.J.Wung,Y.Yang,P.N.Prasad and F.E.Karasz.Poly(p-phenylene vinylene)-silica composite:a novel sol-gel processed non-linear opticalmaterial for optical waveguides.Polymer,1991,32:604-608
26 Q.Hu,E.Marand.In situ formation of nanosized TiO_2 domains within poly(amide-imide) by a sol-gel process.Polymer,1999,40:4833-4843
27 D.Khastgir,H.S.Maiti,P.C.Bandyopadhyay.Polystyrene-titania composite as a dielectric material.Material Science Engineering,1988,100:245-253
28 S.Wang,J.E.Mark.Generation of finely divided nickel particles in a protective medium and their use as high-activity catalysts.Polymer Bulletin,1992,29:343-348
29 H.Schmidt,H.Wolter.Organically modified ceramics and their applications.Journal of Non-Crystallization Solids,1990,121:428-435
30 B.Wang,G.L.Wilkes.Novel hybrid inorganic-organic abrasion-resistant coatings prepared by a sol-gel process.Journal of Macromolecular Science Pure Application Chemistry,1994,31:249-258
31 徐钿,王立.原位聚合制备高分子功能纳米复合材料的研究.武汉理工大学学报,2002,24(9):25-27
32 生瑜,朱德钦,陈建定.聚合物基无机纳米复合材料的制备方法Ⅰ.原位生成法.高分子通报,2001,4:9-14
33 I.J.Kim,O.S.Kwon,J.B.Park,H.Jo.Synthesis and characterization of ABS/silica hybrid nanocomposites.Current Applied Physics,2006,6:43-47
34 Hongyan Li,Gang Liu,Bin Liu,Wei Chen,Shoutian Chen.Dielectric properties of polyimide/Al_2O_3 hybrids synthesized by in-situ polymerizationv Materials Letters,ARTICLE IN PRESS,2006
35 Minsung Kang,Seung Jun Myung,Hyoung-Joon Jin.Nylon 6,10 and carbon nanotube composite by in situ interfacial polymerization.Polymer,2006,47:3961-3966
36 熊传溪,闻获江,皮正杰.高分子材料科学与工程,1995,6:49
37 Benedicte Lepoittevin,Nadege Pantoustier,Myriam Devalckenaere,Michael Alexandre,Cedric Calberg,Robert Jerome,Catherine Henrist,Andre Rulmont and Philippe Dubois.Polymer/layered silicate nanocomposites by combined intercalative polymerzation and melt intercalation:a masterbatch process.Polymer,2003,44(7):2033-2040
38 Zhiqi Shen,George P.Simon and Yi-Bing Cheng,Comparison of solution intercalation and melt intercalation of polymer-clay nanocomposites.Polymer,2002,43(15):4251-4260
39 Michael Alexandre,Philippe Dubois.Polymer-layered silicate nanocomposites:preparation,properties and uses of a new class of materials.Materials Science and Engineering,2000,28:1-63
40 Peter C.LeBaron,Zhen Wang,Thomas J.Pinnavaia.Polymer-layered silicate nanocomposites:an overvie.Applied Clay Science,1999,15:11-29
41 王华林,史铁钧,杨善中,翟林峰.聚合物/层状硅酸盐有机无机纳米复合材料制备与性能研究进展.高分子材料科学与工程,2005,21(6):36-40
42 舒中俊,刘晓辉,漆宗能.聚合物/粘土纳米复合材料研究.中国塑料,2000,14(3):12-18
43 赵海超,杨凤,张学全,陈斌,李刚,蔡洪光,冯之榴,黄葆同.原位聚合制备聚丙烯/蒙脱土纳米复合材料及其结构性能表征.高分子材料科学与工程,2004,20(2):185-187
44 Wei Chen,Baojun Qu.Enhanced thermal and mechanical properties of poly(methyl acrylate)/ZnAl layered double hydroxide nanocomposites formed by in situ polymerization.Polymer Degradation and Stability,2005,90(1):162-66
45 Masami Okamoto,Satoshi Morita,Hideyuki Taguchi,Yong Hoon Kim,Tadao Kotaka,Hiroshi Tateyama.Synthesis and structure of smectic clay/poly(methyl methacrylate) and clay/polystyrene nanocomposites via in situ intercalative polymerization.Polymer,2000,41:3887-3890
46 Kada Boukerma,Jean-Yves Piquemal,Mohamed M.Chehimi,Miroslava Mravcakova,Maria Omastova,Patricia Beaunier.Synthesis and interfacial properties of montmorillonite/polypyrrole nanocomposites.Polymer,2006,47(2):569-576
47 Douglas R.Dillon,Kishore K.Tenneti,Christopher Y.Li,Frank K.Ko,Igors Sics,Benjamin S.Hsiao.On the structure and morphology of polyvinylidene fluoride-nanoclay nanocomposites.Polymer,2006,47:1678-1688
48 彭人勇,张英杰.聚乙烯醇/蒙脱石纳米复合材料的制备工艺研究.塑料科技,2005,5:5-8
49 马建中,高党鸽,陈新江,储芸.溶液剥离-吸附法制备高分子纳米复合材料.高分子材料科学与工程,2006,22(3):219-222
50 慕波,王齐华,王宏刚,简令奇.熔融插层法制备聚合物复合材料的研究进展.塑料工业,2006,34(2):4-7
51 Jun-Chao Huang,Zi-kang Zhu,Jie Yin,Xue-feng Qian and Yang-Yang Sun.Poly(etherimide)/montmorillonite nanocomposites prepared by melt intercalation:morphology,solvent resistance properties and thermal properties.Polymer,42(3):873-877
52 Benedicte Lepoittevin,Myriam Devalckenaere,Nadege Pantoustier,Michael Alexandre,Dana Kubies,Cedric Calberg,Robert Jerome,Philippe Dubois.Poly(ε-caprolactone)/clay nanocomposites prepared by melt intercalation:mechanical,thermal and rheological properties.Polymer,43(14):4017-4023
53 J.Xu,R.K.Li,Y.Xu,L.Li,Y.Z.Meng.Preparation of poly(propylene carbonate)/organo-vermiculite nanocomposites via direct melt intercalation.European Polymer Journal,2005,41(4):881-888
54 刘立柱,张文龙,朱兴松,邓涛,方兰.熔融插层制备聚乙烯/蒙脱土纳米复合材料及其性能研究.中国塑料,2005,19(10):35-38
55 袁绍彦,余木火.纳米粒子在聚合物熔体中分散方法的研究.现代化工,2005,25:290-292
56 黄锐.熔融共混法制备聚烯烃/无机纳米粒子复合材料.塑料,2001,6(30):19-22
57 陈利,瞿美臻,王贵欣,尤玉静,张伯兰,于作龙.溶液共混法制备碳纳米管/双酚A型聚碳酸酯复合物的研究.功能材料,2005,36(1):139-141
58 S.C.Tjong.Structural and mechanical properties of polymer nanocomposites.Materials Scieace and Engineering,2006,53:73-197
59 周卫平,朱光中,翟泽军.纳米技术在高聚物中的应用及其进展.现代化工,2002,22(6):19-23
60 Xiao-Lin Xie,Qing-Xi Li,Robert Kwok-Yiu Li,Xing-Ping Zhou,Qing-Xin Zhang,Zhong-Zhen Yu,Yiu-Wing Mai.Rheological and mechanical properties of PVC/CaCO_3nanocomposites prepared by in situ polymerization.Polymer,2004,45:6665-6673
61 Koji Nakane,Takeharu Kurita,Takashi Ogihara,Nobuo Ogata.Properties of poly(vinyl butyral)/TiO_2 nanocomposites formed by sol-gel process.Composites,2004,35:219-222
62 Donghai Sun,Rui Zhang,Zhimin Liu,Ying Huang,Yong Wang,Jun He,Buxing Han,Guanying Yang.Polypropylene/Silica Nanocomposites Prepared by in-Situ Sol-Gel Reaction with the Aid of CO_2.Macromolecules,2005,38:5617-5624
63 Jiawen Xiong,Zhen Zheng,Xiumin Qin,Ming Li,Huiqing Li,Xinling Wang.The thermal and mechanical properties of a polyurethane/multi-walled carbon nanotube composite.Carbon,2006,44(13):2701-2707
64 Shaoxu Wang,Zhicheng Tan,Yansheng Li,Lixian Sun,Tao Zhang:Synthesis,characterization and thermal analysis of polyaniline/ZrO_2 composites.Thermochimica Acta,2006,441(2):191-194
65 舒中俊,陈光明,漆宗能.聚合物/粘土纳米复合材料及其特殊阻燃性能.2001,28(3):24-26
66 胡源,汪少锋,宋磊,陈祖耀,范维澄.聚合物/层状粘土纳米复合材料阻燃性能研究进展.高分子材料科学与工程,2003,19(4):13-17
67 卢春生,米耀荣.化整为零:聚合物粘土纳米复合材料的微观结构和阻隔性能.研究快讯,2006,35(7):550-552
68 丁运生,张志成,史铁钧.阻隔性高分子材料研究进展.功能高分子学报,2001,14:360-364
69 Maged A.Osman,Jorg E.P.Rupp,Ulrich W.Suter.Effect of non-ionic surfactants on the exfoliation and properties of polyethylene-layered silicate nanocomposites.Polymer,2005,46:8202-8209
70 Zeng Ke,Bai Yongping.Improve the gas barrier property of PET film with montmorillonite by in situ interlayer polymerization.Materials Letters,2005,59:3348-3351
71 Tao Jiang,Yu-hua Wang,Jen-taot Yeh,Zhi-qiang Fan.Study on solvent permeation resistance properties of nylon6/clay nanocomposite.European Polymer Journal,2005,41:459-466
72 Benaissa M,Gonsaives K E,Rangarajan S P.Applied Polymer Letters.1997,71(25):3685-3687
73 Haitao Wang,Peng Xu,Sheng Meng,Wei Zhong,Weichuan Du,Qiangguo Du.Poly(methyl methacrylate)/silica/titania ternary nanocomposites with greatly improved thermal and ultraviolet-shielding properties.Polymer Degradation and Stability,2006,91:1455-1461
74 Hongyan Li,Gang Liu,Bin Liu,Wei Chen,Shoutian Chen.Dielectric properties of polyimide/Al_2O_3 hybrids synthesized by in-situ polymerization.Materials Letters,2007,61(7):1507-1511
75 Susumu Kuwabata,Naoya Takahashi,Shigeki Hirao,Hiroshi Yoneyama.Light Image Formations on Deprotonated Polyaniline Films Containing TiO_2 Particles.Chemical Materials,1993,5(4):437-441
76 Zaitsev V S,Filimonov D S,Presnyankov I A.Physical and chemical properties of mannetite and mannetite-polymer nanoparticles and their colloidal dispersions.Journal of Colloid Interface Science,1999,212(1):49-57
77 钱家盛,何平笙.功能性聚合物基纳米复合材料.功能材料,2003,34(4):371-374
78 Maycumber,S.G.Daily News Record.1999,29(9):10
79 Segnov,I.S.M.Schultz and S.Farikov.Journal of Applied Polymer
80 Science 1986,Vol.32,No.2,3371.R.A.Weiss and J.A.Lefelar,Polymer,1986,7:3000
81 K.Kishore,P.Kannan,J.Polym.Sci,Part A:Polym.Chem,1990,23,3481
82 Amold J.Rosenthal,Whippany,Ales S.Forsechirm,Lake Hiawatha;Bruce P.Barnes,US Pat4035542,1977,06,12
83 ail H.Birum,kirkwood,Jansen,Us Patent4081463,1978
84 黄象安,合成纤维,1991,(1):29-33
85 王利生,黄金印,朱庆松,李前树.化学通报,1994,4,48-50
86 Ashok Reddy.T,Srinivasan.M,J.Polym.Sci,Polym.Chem.Edn,1987,25,2327
87 Lewin M.Flame Retardant Polyeric Materials.New York:Plenum Press,1975:193-196
88 Herlinger H.合成纤维发展趋势,合成纤维工业,1981,(1):55-60
89 欧育湘,有机阻燃剂最新进展,现代化工,1997,(4):9-12
90 Kidder R C,Fire safety issue in the United States in 1990.In:The British Plastics
91 王元宏.阻燃剂化学及其应用,上海:上海科学技术文献出版社,1988,1-20
92 Shinn Jenchang,Feng Chihchang,Polymer Engineering and Science,1998,38(9),1471-1481
93 SRI International,Flame Retardant,in Specialty Chemicals-A Multiclient Report,1993
94 S.R.Sandler and W.Karo,Polymer Synthesis Academic,New York,1974(1):367
95 Qu Y X.Fire Retardant Technology and Marketing.New York:Wiley Inter-science,1990.25-31
96 “我国阻燃技术的现状与相关政策的研究”课题研究组研究报告,阻燃材料与技术,1995,3-5
97 Cooney,J.D,Day,M.,Wiles,D.M.J.Thermal Degradation of Poly(ethylene Terephthalate).Appl.Polym.Sci.1983,28:2887-2901
98 Kissinger H.E.Reaction kinetics in differential thermal analysis.Anal.Chem,1975,29:1702-1706
99 Nelson MI,Brindley J,Mc Intosh AC.Ignition of thermally thin thermoplastics-The effectiveness of inert additives in reducing flammability.Polym Degrad Stab,1996,54:255-266
100 Vijayakumar CT,Thermal and pyrolysis studies of copolyester.J Polym Sci:Polym Chem,1982,20:2715-2725
101 Friedman H.L.Kinetics of thermal degradation of char-forming plastics from thermogravimetry.Application to a phenolic plastic.J.Polym.Sci.Part C,1964,6(1):183- 195
102 Flynn J.H,Wall,L.A.A quick direct method for the determination of activation energy from thermogravimetric data Polym.Lett.1966,4:323-328
103 Ozawa.T.A new method of analyzing thermogravimatric data.Bull.Chem.Soc.Jpn.1965,38(11):1881-1886
104 Doyle C.D.Kinetic analysis of thermogravimetric data.J.Appl.Polym.Sci.1961,5:285-292
105 Groeninckx G,Berghmans H,Overbergh NC.Polym Phys,1974.12:303-316
106 Gupta A K,Purwar S N.Crystallization of PP in PP/SEBS blends and its correlation with tensile properties.J Appl Polym Sci,1984,29(5):1595-1609
107 Ozawa T.Kinetics of non-isothermal crystallization.Polymer,1971,12:150-158
108 Jeziomy A.Parameters characterizing the non-isothemal crystallization of poly(ethylene terephthalate) determined by DSC.Polymer,1978,19:1142-1148
109 Liu T,Mo Z,Zhang H.Nonisothermal crystallization behavior ofa novel poly(aryl etherketone):PEDEKmK.J.Appl.Polym.Sci.1998,67:815-821
110 Augis JA,Bennett JE.Calculation of avrami parameters for heterogeneous solid-state reactions using a modification of Kissinger method.J Thermal Anal,1978,13(2):283-292
111 Kissingcr,H.E.Reaction kinetics in differential thermal analysis.1957,29:1702-1706
112 Takhor RL.Advances in nucleation and crystallization of glasses.American Ceramics Society:Columbus,1971,166-172
113 Weibing Xu,Mingliang Ge,Pingsheng He.Nonisothermal crystallization kinetics of polypropylene/montmorillonite nanocomposites.Journal of Polymer Science:Part B:Polymer Physics,2002,40:408-414
114 Wang ZG,Hsiaoa BS,Sauerb BB,Kampert WG.The natural of secondary crystallization in poly(ethylene terephthalate).Polymer,1999,40:4615-4627
115 Kissinger H.E.Variation of peak temperature with heating rate in different thermal analysis,J.Res.Natl.Bur.Stand,1956,57(4):217-221
116 Hirschler MM.,Babrauskas Vm Grayson SJ.Heat release in fires.London:Elsevier Applied Science,1992
117 Weil ED.,Hirschler MM.,Patel NG.,Said MM.,Shakir S.Fire& Mater.1992,16,159
118 舒中俊,漆中能.聚合物及其复合材料火灾危险与对策.工程塑料与应用,1999,27(11):37-39
119 胡小平.聚乙烯用新型膨胀型阻燃剂的合成与应用及阻燃机理的研究:[学位论文]:四川,四川大学,2005
120 BourbigotS,LeBrasM,DelobelRJ.FireSci,1995,13:3-8
121 SnikovichAL,Levechick SV.J Therm Anal,1983,27,89-93
2 吴剑南,我国聚酯工业的现状和前景展望.当代石油化工,2004,12(6):16-19
3 李玲,向航.功能材料与纳米技术.化学工业出版社,2002.1
4 李凤生.超细粉体技术.国防工业出版社,2000
5 高其标,申屠宝卿,翁志学.纳米改性聚合物材料研究进展.化工生产与技术,2001,8(6):22-26
6 R Roy,S Komarneni,D M Roy.Multi-phase ceramic composites made by Sol-Gol technique.Mater.Res.Symp.Proc,1984,32:347-359
7 潘飞.PET/TiO_2纳米复合材料性能研究及其纺丝模拟:[学位论文]上海:东华大学.,2006
8 黄锐,王旭,李忠明.纳米塑料.中国轻工业出版社,2002.4
9 杨玉芬,陈清如.纳米材料的基本特征与纳米科技的发展.中国粉体技术,2002,8(3):22-27
10 杨鼎宜,孙伟.纳米材料的结构特征与特殊性能.材料导报,2003,17(10):7-10
11 Kubo,R.Electronic Properties of Metallic Fine Particles.Ⅰ.Journal of the Physical Society of Japan,17(6):975-986
12 张立德.纳米材料.化学工业出版社,2000:40-41
13 S.C.Tjong.Structural and mechanical properties of polymer nanocomposites.Materials Science and Engineering,2006,Article in Press
14 周卫平,朱光中,翟泽军.纳米技术在高聚物中的应用及其进展.现代化工,2002,22(6):19-23
15 卢春生,米耀荣.化整为零:聚合物粘土纳米复合材料的微观结构和阻隔性能.研究快讯,2006,35(7):550-552
16 丁运生,张志成,史铁钧.阻隔性高分子材料研究进展.功能高分子学报,2001,14:360-364
17 葛建华,王迎军,郑裕东,龚克诚,溶胶凝胶法在聚合物/无机纳米复合材料中的应用.材料科学与工程学报,2004,22(3):442-445
18 李曦,孙江勤,张超灿.溶胶-凝胶法制备有机-无机杂化纳米级功能材料.湖北化工,2000,3:5-7
19 任杰,刘艳.聚合物基有机-无机纳米复合材料研究及应用前景.材料导报,2003,17(2):58-62
20 张军丽,叶文玉.溶胶凝胶法聚合物/无机复合材料的研究与应用.云南化工,2005,32(3):43-46
21 Suzuki F.GrecoR J Appl Polymer Sci.1990,39:371
22 刘晓蕾,何毅,李赛,刘孝波.聚ε-己内酯/SiO_2杂化材料的制备.四川大学学报(工程科学版),2003,35(1):59-62
23 Q.Hu,E.Marand.In situ formation of nanosized TiO_2 domains within poly(amide-imide) by a sol-gel process.Polymer,1999,40:4833-4843
24 Rajatendu Senguptaa,Abhijit Bandyopadhyaya,Sunil Sabharwalb,Tapan K.Chakia,Anti K.Bhowmick.Polyamide-6,6/in situ silica hybrid nanocomposites by sol-gel technique:synthesis,characterization and properties.Polymer,2005,46:3343-3354
25 C.J.Wung,Y.Yang,P.N.Prasad and F.E.Karasz.Poly(p-phenylene vinylene)-silica composite:a novel sol-gel processed non-linear opticalmaterial for optical waveguides.Polymer,1991,32:604-608
26 Q.Hu,E.Marand.In situ formation of nanosized TiO_2 domains within poly(amide-imide) by a sol-gel process.Polymer,1999,40:4833-4843
27 D.Khastgir,H.S.Maiti,P.C.Bandyopadhyay.Polystyrene-titania composite as a dielectric material.Material Science Engineering,1988,100:245-253
28 S.Wang,J.E.Mark.Generation of finely divided nickel particles in a protective medium and their use as high-activity catalysts.Polymer Bulletin,1992,29:343-348
29 H.Schmidt,H.Wolter.Organically modified ceramics and their applications.Journal of Non-Crystallization Solids,1990,121:428-435
30 B.Wang,G.L.Wilkes.Novel hybrid inorganic-organic abrasion-resistant coatings prepared by a sol-gel process.Journal of Macromolecular Science Pure Application Chemistry,1994,31:249-258
31 徐钿,王立.原位聚合制备高分子功能纳米复合材料的研究.武汉理工大学学报,2002,24(9):25-27
32 生瑜,朱德钦,陈建定.聚合物基无机纳米复合材料的制备方法Ⅰ.原位生成法.高分子通报,2001,4:9-14
33 I.J.Kim,O.S.Kwon,J.B.Park,H.Jo.Synthesis and characterization of ABS/silica hybrid nanocomposites.Current Applied Physics,2006,6:43-47
34 Hongyan Li,Gang Liu,Bin Liu,Wei Chen,Shoutian Chen.Dielectric properties of polyimide/Al_2O_3 hybrids synthesized by in-situ polymerizationv Materials Letters,ARTICLE IN PRESS,2006
35 Minsung Kang,Seung Jun Myung,Hyoung-Joon Jin.Nylon 6,10 and carbon nanotube composite by in situ interfacial polymerization.Polymer,2006,47:3961-3966
36 熊传溪,闻获江,皮正杰.高分子材料科学与工程,1995,6:49
37 Benedicte Lepoittevin,Nadege Pantoustier,Myriam Devalckenaere,Michael Alexandre,Cedric Calberg,Robert Jerome,Catherine Henrist,Andre Rulmont and Philippe Dubois.Polymer/layered silicate nanocomposites by combined intercalative polymerzation and melt intercalation:a masterbatch process.Polymer,2003,44(7):2033-2040
38 Zhiqi Shen,George P.Simon and Yi-Bing Cheng,Comparison of solution intercalation and melt intercalation of polymer-clay nanocomposites.Polymer,2002,43(15):4251-4260
39 Michael Alexandre,Philippe Dubois.Polymer-layered silicate nanocomposites:preparation,properties and uses of a new class of materials.Materials Science and Engineering,2000,28:1-63
40 Peter C.LeBaron,Zhen Wang,Thomas J.Pinnavaia.Polymer-layered silicate nanocomposites:an overvie.Applied Clay Science,1999,15:11-29
41 王华林,史铁钧,杨善中,翟林峰.聚合物/层状硅酸盐有机无机纳米复合材料制备与性能研究进展.高分子材料科学与工程,2005,21(6):36-40
42 舒中俊,刘晓辉,漆宗能.聚合物/粘土纳米复合材料研究.中国塑料,2000,14(3):12-18
43 赵海超,杨凤,张学全,陈斌,李刚,蔡洪光,冯之榴,黄葆同.原位聚合制备聚丙烯/蒙脱土纳米复合材料及其结构性能表征.高分子材料科学与工程,2004,20(2):185-187
44 Wei Chen,Baojun Qu.Enhanced thermal and mechanical properties of poly(methyl acrylate)/ZnAl layered double hydroxide nanocomposites formed by in situ polymerization.Polymer Degradation and Stability,2005,90(1):162-66
45 Masami Okamoto,Satoshi Morita,Hideyuki Taguchi,Yong Hoon Kim,Tadao Kotaka,Hiroshi Tateyama.Synthesis and structure of smectic clay/poly(methyl methacrylate) and clay/polystyrene nanocomposites via in situ intercalative polymerization.Polymer,2000,41:3887-3890
46 Kada Boukerma,Jean-Yves Piquemal,Mohamed M.Chehimi,Miroslava Mravcakova,Maria Omastova,Patricia Beaunier.Synthesis and interfacial properties of montmorillonite/polypyrrole nanocomposites.Polymer,2006,47(2):569-576
47 Douglas R.Dillon,Kishore K.Tenneti,Christopher Y.Li,Frank K.Ko,Igors Sics,Benjamin S.Hsiao.On the structure and morphology of polyvinylidene fluoride-nanoclay nanocomposites.Polymer,2006,47:1678-1688
48 彭人勇,张英杰.聚乙烯醇/蒙脱石纳米复合材料的制备工艺研究.塑料科技,2005,5:5-8
49 马建中,高党鸽,陈新江,储芸.溶液剥离-吸附法制备高分子纳米复合材料.高分子材料科学与工程,2006,22(3):219-222
50 慕波,王齐华,王宏刚,简令奇.熔融插层法制备聚合物复合材料的研究进展.塑料工业,2006,34(2):4-7
51 Jun-Chao Huang,Zi-kang Zhu,Jie Yin,Xue-feng Qian and Yang-Yang Sun.Poly(etherimide)/montmorillonite nanocomposites prepared by melt intercalation:morphology,solvent resistance properties and thermal properties.Polymer,42(3):873-877
52 Benedicte Lepoittevin,Myriam Devalckenaere,Nadege Pantoustier,Michael Alexandre,Dana Kubies,Cedric Calberg,Robert Jerome,Philippe Dubois.Poly(ε-caprolactone)/clay nanocomposites prepared by melt intercalation:mechanical,thermal and rheological properties.Polymer,43(14):4017-4023
53 J.Xu,R.K.Li,Y.Xu,L.Li,Y.Z.Meng.Preparation of poly(propylene carbonate)/organo-vermiculite nanocomposites via direct melt intercalation.European Polymer Journal,2005,41(4):881-888
54 刘立柱,张文龙,朱兴松,邓涛,方兰.熔融插层制备聚乙烯/蒙脱土纳米复合材料及其性能研究.中国塑料,2005,19(10):35-38
55 袁绍彦,余木火.纳米粒子在聚合物熔体中分散方法的研究.现代化工,2005,25:290-292
56 黄锐.熔融共混法制备聚烯烃/无机纳米粒子复合材料.塑料,2001,6(30):19-22
57 陈利,瞿美臻,王贵欣,尤玉静,张伯兰,于作龙.溶液共混法制备碳纳米管/双酚A型聚碳酸酯复合物的研究.功能材料,2005,36(1):139-141
58 S.C.Tjong.Structural and mechanical properties of polymer nanocomposites.Materials Scieace and Engineering,2006,53:73-197
59 周卫平,朱光中,翟泽军.纳米技术在高聚物中的应用及其进展.现代化工,2002,22(6):19-23
60 Xiao-Lin Xie,Qing-Xi Li,Robert Kwok-Yiu Li,Xing-Ping Zhou,Qing-Xin Zhang,Zhong-Zhen Yu,Yiu-Wing Mai.Rheological and mechanical properties of PVC/CaCO_3nanocomposites prepared by in situ polymerization.Polymer,2004,45:6665-6673
61 Koji Nakane,Takeharu Kurita,Takashi Ogihara,Nobuo Ogata.Properties of poly(vinyl butyral)/TiO_2 nanocomposites formed by sol-gel process.Composites,2004,35:219-222
62 Donghai Sun,Rui Zhang,Zhimin Liu,Ying Huang,Yong Wang,Jun He,Buxing Han,Guanying Yang.Polypropylene/Silica Nanocomposites Prepared by in-Situ Sol-Gel Reaction with the Aid of CO_2.Macromolecules,2005,38:5617-5624
63 Jiawen Xiong,Zhen Zheng,Xiumin Qin,Ming Li,Huiqing Li,Xinling Wang.The thermal and mechanical properties of a polyurethane/multi-walled carbon nanotube composite.Carbon,2006,44(13):2701-2707
64 Shaoxu Wang,Zhicheng Tan,Yansheng Li,Lixian Sun,Tao Zhang:Synthesis,characterization and thermal analysis of polyaniline/ZrO_2 composites.Thermochimica Acta,2006,441(2):191-194
65 舒中俊,陈光明,漆宗能.聚合物/粘土纳米复合材料及其特殊阻燃性能.2001,28(3):24-26
66 胡源,汪少锋,宋磊,陈祖耀,范维澄.聚合物/层状粘土纳米复合材料阻燃性能研究进展.高分子材料科学与工程,2003,19(4):13-17
67 卢春生,米耀荣.化整为零:聚合物粘土纳米复合材料的微观结构和阻隔性能.研究快讯,2006,35(7):550-552
68 丁运生,张志成,史铁钧.阻隔性高分子材料研究进展.功能高分子学报,2001,14:360-364
69 Maged A.Osman,Jorg E.P.Rupp,Ulrich W.Suter.Effect of non-ionic surfactants on the exfoliation and properties of polyethylene-layered silicate nanocomposites.Polymer,2005,46:8202-8209
70 Zeng Ke,Bai Yongping.Improve the gas barrier property of PET film with montmorillonite by in situ interlayer polymerization.Materials Letters,2005,59:3348-3351
71 Tao Jiang,Yu-hua Wang,Jen-taot Yeh,Zhi-qiang Fan.Study on solvent permeation resistance properties of nylon6/clay nanocomposite.European Polymer Journal,2005,41:459-466
72 Benaissa M,Gonsaives K E,Rangarajan S P.Applied Polymer Letters.1997,71(25):3685-3687
73 Haitao Wang,Peng Xu,Sheng Meng,Wei Zhong,Weichuan Du,Qiangguo Du.Poly(methyl methacrylate)/silica/titania ternary nanocomposites with greatly improved thermal and ultraviolet-shielding properties.Polymer Degradation and Stability,2006,91:1455-1461
74 Hongyan Li,Gang Liu,Bin Liu,Wei Chen,Shoutian Chen.Dielectric properties of polyimide/Al_2O_3 hybrids synthesized by in-situ polymerization.Materials Letters,2007,61(7):1507-1511
75 Susumu Kuwabata,Naoya Takahashi,Shigeki Hirao,Hiroshi Yoneyama.Light Image Formations on Deprotonated Polyaniline Films Containing TiO_2 Particles.Chemical Materials,1993,5(4):437-441
76 Zaitsev V S,Filimonov D S,Presnyankov I A.Physical and chemical properties of mannetite and mannetite-polymer nanoparticles and their colloidal dispersions.Journal of Colloid Interface Science,1999,212(1):49-57
77 钱家盛,何平笙.功能性聚合物基纳米复合材料.功能材料,2003,34(4):371-374
78 Maycumber,S.G.Daily News Record.1999,29(9):10
79 Segnov,I.S.M.Schultz and S.Farikov.Journal of Applied Polymer
80 Science 1986,Vol.32,No.2,3371.R.A.Weiss and J.A.Lefelar,Polymer,1986,7:3000
81 K.Kishore,P.Kannan,J.Polym.Sci,Part A:Polym.Chem,1990,23,3481
82 Amold J.Rosenthal,Whippany,Ales S.Forsechirm,Lake Hiawatha;Bruce P.Barnes,US Pat4035542,1977,06,12
83 ail H.Birum,kirkwood,Jansen,Us Patent4081463,1978
84 黄象安,合成纤维,1991,(1):29-33
85 王利生,黄金印,朱庆松,李前树.化学通报,1994,4,48-50
86 Ashok Reddy.T,Srinivasan.M,J.Polym.Sci,Polym.Chem.Edn,1987,25,2327
87 Lewin M.Flame Retardant Polyeric Materials.New York:Plenum Press,1975:193-196
88 Herlinger H.合成纤维发展趋势,合成纤维工业,1981,(1):55-60
89 欧育湘,有机阻燃剂最新进展,现代化工,1997,(4):9-12
90 Kidder R C,Fire safety issue in the United States in 1990.In:The British Plastics
91 王元宏.阻燃剂化学及其应用,上海:上海科学技术文献出版社,1988,1-20
92 Shinn Jenchang,Feng Chihchang,Polymer Engineering and Science,1998,38(9),1471-1481
93 SRI International,Flame Retardant,in Specialty Chemicals-A Multiclient Report,1993
94 S.R.Sandler and W.Karo,Polymer Synthesis Academic,New York,1974(1):367
95 Qu Y X.Fire Retardant Technology and Marketing.New York:Wiley Inter-science,1990.25-31
96 “我国阻燃技术的现状与相关政策的研究”课题研究组研究报告,阻燃材料与技术,1995,3-5
97 Cooney,J.D,Day,M.,Wiles,D.M.J.Thermal Degradation of Poly(ethylene Terephthalate).Appl.Polym.Sci.1983,28:2887-2901
98 Kissinger H.E.Reaction kinetics in differential thermal analysis.Anal.Chem,1975,29:1702-1706
99 Nelson MI,Brindley J,Mc Intosh AC.Ignition of thermally thin thermoplastics-The effectiveness of inert additives in reducing flammability.Polym Degrad Stab,1996,54:255-266
100 Vijayakumar CT,Thermal and pyrolysis studies of copolyester.J Polym Sci:Polym Chem,1982,20:2715-2725
101 Friedman H.L.Kinetics of thermal degradation of char-forming plastics from thermogravimetry.Application to a phenolic plastic.J.Polym.Sci.Part C,1964,6(1):183- 195
102 Flynn J.H,Wall,L.A.A quick direct method for the determination of activation energy from thermogravimetric data Polym.Lett.1966,4:323-328
103 Ozawa.T.A new method of analyzing thermogravimatric data.Bull.Chem.Soc.Jpn.1965,38(11):1881-1886
104 Doyle C.D.Kinetic analysis of thermogravimetric data.J.Appl.Polym.Sci.1961,5:285-292
105 Groeninckx G,Berghmans H,Overbergh NC.Polym Phys,1974.12:303-316
106 Gupta A K,Purwar S N.Crystallization of PP in PP/SEBS blends and its correlation with tensile properties.J Appl Polym Sci,1984,29(5):1595-1609
107 Ozawa T.Kinetics of non-isothermal crystallization.Polymer,1971,12:150-158
108 Jeziomy A.Parameters characterizing the non-isothemal crystallization of poly(ethylene terephthalate) determined by DSC.Polymer,1978,19:1142-1148
109 Liu T,Mo Z,Zhang H.Nonisothermal crystallization behavior ofa novel poly(aryl etherketone):PEDEKmK.J.Appl.Polym.Sci.1998,67:815-821
110 Augis JA,Bennett JE.Calculation of avrami parameters for heterogeneous solid-state reactions using a modification of Kissinger method.J Thermal Anal,1978,13(2):283-292
111 Kissingcr,H.E.Reaction kinetics in differential thermal analysis.1957,29:1702-1706
112 Takhor RL.Advances in nucleation and crystallization of glasses.American Ceramics Society:Columbus,1971,166-172
113 Weibing Xu,Mingliang Ge,Pingsheng He.Nonisothermal crystallization kinetics of polypropylene/montmorillonite nanocomposites.Journal of Polymer Science:Part B:Polymer Physics,2002,40:408-414
114 Wang ZG,Hsiaoa BS,Sauerb BB,Kampert WG.The natural of secondary crystallization in poly(ethylene terephthalate).Polymer,1999,40:4615-4627
115 Kissinger H.E.Variation of peak temperature with heating rate in different thermal analysis,J.Res.Natl.Bur.Stand,1956,57(4):217-221
116 Hirschler MM.,Babrauskas Vm Grayson SJ.Heat release in fires.London:Elsevier Applied Science,1992
117 Weil ED.,Hirschler MM.,Patel NG.,Said MM.,Shakir S.Fire& Mater.1992,16,159
118 舒中俊,漆中能.聚合物及其复合材料火灾危险与对策.工程塑料与应用,1999,27(11):37-39
119 胡小平.聚乙烯用新型膨胀型阻燃剂的合成与应用及阻燃机理的研究:[学位论文]:四川,四川大学,2005
120 BourbigotS,LeBrasM,DelobelRJ.FireSci,1995,13:3-8
121 SnikovichAL,Levechick SV.J Therm Anal,1983,27,89-93