稀土掺杂改性塑料的研究
|
摘要
本论文的研究工作主要分为两大部分：有机阴离子插层镁铝镧水滑石的制备和镁铝镧水滑石/聚合物杂化材料、稀土偶联剂/聚合物杂化材料与不同改性轻质碳酸钙/聚合物杂化材料的制备及测试。
用少量的稀土镧离子(La3+)代替镁铝水滑石层板中的铝离子,并用有机阴离子代替碳酸根阴离子,通过共沉淀法,组装得到有机阴离子插层的镁铝镧水滑石(Mg-Al-La-LDHs),经表征显示,该水滑石的层间距有小幅度地增大,说明有机阴离子部分插入水滑石层间,并且这种水滑石比不含La的有机阴离子插层镁铝水滑石耐热性好。通过原位乳液聚合方法,将一定量的甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)两种单体分散于镁铝镧水滑石层间,于80℃下共沉淀,同时引发单体发生共聚,制备聚-(甲基丙烯酸甲酯-丙烯酸丁酯)/镁铝镧水滑石(PMBA/Mg-Al-La-LDHs)纳米杂化母料,经XRD、TEM与TG测试表明,这种杂化母料中水滑石部分剥离,并且比未加镁铝镧水滑石的试样热稳定性好。
通过熔融共混法,分别用Mg-Al-La-LDHs、PMBA/Mg-Al-La-LDHs、稀土偶联剂、稀土偶联剂改性后的CaCO3掺杂改性PET、ABS、PS,研究结果表明：
Mg-Al-La-LDHs使PET变脆；掺杂0.2%-0.4%G-4或G-40稀土偶联剂能使PET的断裂伸长率提高了24倍多；掺杂0.3%X-10使PET的拉伸强度提高36.2%,使其PET冲击强度提高3.1倍,4%L0-CaCO3(0.5%X-10偶联剂表面改性CaCO3)掺杂到PET使其断裂伸长率提高了12.8倍,10% L0-CaCO3掺杂到PET中能使其弯曲强度提高63.7%,8% L0-CaCO3掺杂到PET中能使其冲击强度提高1.6倍。0.6%G-2稀土偶联剂使PET过冷结晶温度降低了33.4℃,这表明G-2能诱导PET结晶而大大地提高其结晶速度,0.5%G-40/PET的结晶度提高2.03倍；L0-CaCO3(8%)/PET的结晶度提高了2.12倍。0.2%G-1/PET的平衡转矩降低了50%,提高了其加工流变性。
0.3%H-4掺杂ABS使其断裂伸长率提高了33.15%,使其弯曲强度提高了11.6%,使其熔融指数提高了22.36%; L0-CaCO3(4%)/ABS的断裂伸长率提高了12.16%,弯曲强度提高了20.11%,熔融指数提高了7.3%,但是,冲击强度降低了20.8%。
掺杂2%PMBA/Mg-Al-La-LDHs能使PS的拉伸强度提高了约2倍、冲击强度提高了16%、断裂伸长率提高了约27%; 0.6%G-1/PS的拉伸强度提高了2.35倍,0.8%G-40/PS的断裂伸长率提高了1.5倍,其冲击强度提高了43.85%。
This thesis is mainly composed of two sections:the synthesis of new rare earth hydrotalcite-like compounds; the preparation and characterization of hydrotalcite-like compound/polymer composites, rare earth coupling agent/polymer composites, different acitivated CaCO3/polymer composites.
Firstly, the new hydrotalcite containing La (Mg-Al-La-LDHs) is synthesized by coprecipitation method, Organic anions intercalate into the hydrotalcite-like layers in the sample. the sample is characterized by XRD, IR and TG, its structure and thermal stability are determined, The results indicate that the distance of hydrotalcite-like layers increases a little and some organic anions have intercalated into the hydrotalcite-like layers,The thermal stability of the sample is better than the one not containing La. Through in-situ emulsion polymerixation mathod, the new composite masterbatch containing La(PMBA/Mg-Al-La-LDHs) is synthesized and characterized by XRD, TEM and TG The results indicate that some layer double hydroxides have delaminated and the thermal stability of composite masterbatch is better than the one not containing La.
Secondly,Through melt blending method,it dops and modifies PET, ABS, PS with doped Mg-Al-La-LDHs,PMBA/Mg-Al-La-LDHs,rare earth coupling agent and activatied CaCO3 respectively; The properties of composites are investigated by mechanical property test,DSC, TG, Rheological property test and SEM,The results are as follows:
Mg-Al-La-LDHs make PET brittle. The elongation at break of PET with doped 0.2%-0.4% G-4 or G-40 increases by 24 times. The tensile strength and impact strength of PET with doped 0.3% X-10 rare earth agent increases by 36.2% and 3.1 times. The elongation at break of PET with doped 4% Lo-CaCO3 increases by 12.8 times; The bending strength of PET with doped 10% L0-CaCO3 increases by 63.7%. The elongation at break of PET with doped 8% L0-CaCO3 increases by 1.6 times. The super-cooling crystallizing temperature of PET with 0.6%G-2 rare earth agents reduces by 33.4℃,Which shows that G-2 rare earth agent can promoted greatly crystallization of PET,The degree of crystallization of PET with doped 0.5% G-40 rare earth agent increases by 2.03 times, The degree of crystallization of PET with doped 8% L0-CaCO3 increases by 2.12 times.The balance torque of PET with 0.2% G-1 rare earth agent reduces by 50%, Which shows G-2 rare earth agent can improve the processing rheological property of PET.
The elongation at break and impact strength of ABS with 0.3% H-4 rare earth agent increases by 33.15% and 11.6%.The melting index of PET with 0.3% H-4 rare earth agent increases by 22.36%.The elongation at break and bending strength of PET with 4% L0-CaCO3 increase by 12.16% and 20.11%, and its melt index increases by 7.3%, but its impact strength reduces by 20.8%.
The tensile strength and impact strength of PS with doped 2% PMBA/Mg-Al-La-LDHs increase by 16% and 2 times, and its elongation at break increases by 27%. The tensile strength of PS with doped 0.6% G-1 rare earth agent increases by 2.35 times.The elongation at break and impact strength of PS with doped 0.8% G-40 rare earth agent increases by 1.5 times and 43.85%.
用少量的稀土镧离子(La3+)代替镁铝水滑石层板中的铝离子,并用有机阴离子代替碳酸根阴离子,通过共沉淀法,组装得到有机阴离子插层的镁铝镧水滑石(Mg-Al-La-LDHs),经表征显示,该水滑石的层间距有小幅度地增大,说明有机阴离子部分插入水滑石层间,并且这种水滑石比不含La的有机阴离子插层镁铝水滑石耐热性好。通过原位乳液聚合方法,将一定量的甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)两种单体分散于镁铝镧水滑石层间,于80℃下共沉淀,同时引发单体发生共聚,制备聚-(甲基丙烯酸甲酯-丙烯酸丁酯)/镁铝镧水滑石(PMBA/Mg-Al-La-LDHs)纳米杂化母料,经XRD、TEM与TG测试表明,这种杂化母料中水滑石部分剥离,并且比未加镁铝镧水滑石的试样热稳定性好。
通过熔融共混法,分别用Mg-Al-La-LDHs、PMBA/Mg-Al-La-LDHs、稀土偶联剂、稀土偶联剂改性后的CaCO3掺杂改性PET、ABS、PS,研究结果表明：
Mg-Al-La-LDHs使PET变脆；掺杂0.2%-0.4%G-4或G-40稀土偶联剂能使PET的断裂伸长率提高了24倍多；掺杂0.3%X-10使PET的拉伸强度提高36.2%,使其PET冲击强度提高3.1倍,4%L0-CaCO3(0.5%X-10偶联剂表面改性CaCO3)掺杂到PET使其断裂伸长率提高了12.8倍,10% L0-CaCO3掺杂到PET中能使其弯曲强度提高63.7%,8% L0-CaCO3掺杂到PET中能使其冲击强度提高1.6倍。0.6%G-2稀土偶联剂使PET过冷结晶温度降低了33.4℃,这表明G-2能诱导PET结晶而大大地提高其结晶速度,0.5%G-40/PET的结晶度提高2.03倍；L0-CaCO3(8%)/PET的结晶度提高了2.12倍。0.2%G-1/PET的平衡转矩降低了50%,提高了其加工流变性。
0.3%H-4掺杂ABS使其断裂伸长率提高了33.15%,使其弯曲强度提高了11.6%,使其熔融指数提高了22.36%; L0-CaCO3(4%)/ABS的断裂伸长率提高了12.16%,弯曲强度提高了20.11%,熔融指数提高了7.3%,但是,冲击强度降低了20.8%。
掺杂2%PMBA/Mg-Al-La-LDHs能使PS的拉伸强度提高了约2倍、冲击强度提高了16%、断裂伸长率提高了约27%; 0.6%G-1/PS的拉伸强度提高了2.35倍,0.8%G-40/PS的断裂伸长率提高了1.5倍,其冲击强度提高了43.85%。
This thesis is mainly composed of two sections:the synthesis of new rare earth hydrotalcite-like compounds; the preparation and characterization of hydrotalcite-like compound/polymer composites, rare earth coupling agent/polymer composites, different acitivated CaCO3/polymer composites.
Firstly, the new hydrotalcite containing La (Mg-Al-La-LDHs) is synthesized by coprecipitation method, Organic anions intercalate into the hydrotalcite-like layers in the sample. the sample is characterized by XRD, IR and TG, its structure and thermal stability are determined, The results indicate that the distance of hydrotalcite-like layers increases a little and some organic anions have intercalated into the hydrotalcite-like layers,The thermal stability of the sample is better than the one not containing La. Through in-situ emulsion polymerixation mathod, the new composite masterbatch containing La(PMBA/Mg-Al-La-LDHs) is synthesized and characterized by XRD, TEM and TG The results indicate that some layer double hydroxides have delaminated and the thermal stability of composite masterbatch is better than the one not containing La.
Secondly,Through melt blending method,it dops and modifies PET, ABS, PS with doped Mg-Al-La-LDHs,PMBA/Mg-Al-La-LDHs,rare earth coupling agent and activatied CaCO3 respectively; The properties of composites are investigated by mechanical property test,DSC, TG, Rheological property test and SEM,The results are as follows:
Mg-Al-La-LDHs make PET brittle. The elongation at break of PET with doped 0.2%-0.4% G-4 or G-40 increases by 24 times. The tensile strength and impact strength of PET with doped 0.3% X-10 rare earth agent increases by 36.2% and 3.1 times. The elongation at break of PET with doped 4% Lo-CaCO3 increases by 12.8 times; The bending strength of PET with doped 10% L0-CaCO3 increases by 63.7%. The elongation at break of PET with doped 8% L0-CaCO3 increases by 1.6 times. The super-cooling crystallizing temperature of PET with 0.6%G-2 rare earth agents reduces by 33.4℃,Which shows that G-2 rare earth agent can promoted greatly crystallization of PET,The degree of crystallization of PET with doped 0.5% G-40 rare earth agent increases by 2.03 times, The degree of crystallization of PET with doped 8% L0-CaCO3 increases by 2.12 times.The balance torque of PET with 0.2% G-1 rare earth agent reduces by 50%, Which shows G-2 rare earth agent can improve the processing rheological property of PET.
The elongation at break and impact strength of ABS with 0.3% H-4 rare earth agent increases by 33.15% and 11.6%.The melting index of PET with 0.3% H-4 rare earth agent increases by 22.36%.The elongation at break and bending strength of PET with 4% L0-CaCO3 increase by 12.16% and 20.11%, and its melt index increases by 7.3%, but its impact strength reduces by 20.8%.
The tensile strength and impact strength of PS with doped 2% PMBA/Mg-Al-La-LDHs increase by 16% and 2 times, and its elongation at break increases by 27%. The tensile strength of PS with doped 0.6% G-1 rare earth agent increases by 2.35 times.The elongation at break and impact strength of PS with doped 0.8% G-40 rare earth agent increases by 1.5 times and 43.85%.
引文
[1]郑德.稀土助剂在塑料中的应用研究进展[J].国外塑料.2004,7(22):45-50
[2]Li D M,Qi Z N.第三十七回高分子讨论会稿集.1988,37:2339
[3]M.Z.B.Hussein, Z.Zainal, C.Y.Ming. Microwave-assisted synthesis of Zn-Al-layered double hydroxide-sodium dodecyl sulfate nanocomposite. J.Mater. Sci. Lett.2000,19,879
[4]易宪武.无机化学丛书.北京：化学出版社,1998:157
[5]K.Strawheeker, E.Manias. Flammability properties of polymer-layered-silicate nanocomposites polypropylene and polystyrene nanocomposites. Chem. Mater.2000,12,2943
[6]J.Bujdak, E.Haekett, E.P.Giannelis. Influence of the layer charge dnsity of smectites on the interaction with methylene blue. Chem.Mater.2000,12,2168
[7]Z.Wang, T.Lan, T.J.Pinnavaia. Analysis of heat and mass transfer for microwave freeze drying of unsaturated porous media. Chem. Mater:1996,8,2200
[8]Yang D.J,Lin Y.H. Brownian dynamics simulatons of the effects of hydrodynamic interactions on the polymer viscoelactic behavior, polymer,2003,44(9):2087-2815
[9]Moujahid M, Inacio J, Besse J.P, ASDSorption of styrenene vs polystyre sulfonatc on layered double hydroxides.Microporous Mesoporous Mater.2003,57,37-46
[10]陈伟,挫保钧,冯莉.原位聚合法制备聚丙烯酸甲酯/ZnAl层状双氢氧化物插层纳米复合材料及其形貌特征[J].高等学校化学学报.2003,24(10)：1920-1922
[11]Bergbretter D.E.,Chen L.B.,et al. Recyclable polymer-bound lanthanide diene polymerization catalysts. Macromolecules,1985,18(6):1055-1057
[12]郑德,庄和宽,肖伟平等.稀土稳定剂对PVC的作用机理及其在型材中的应用[J].新型建筑材料,2001(7)：7-9
[13]郑德,李壮利,黄玉松.无铅化稳定剂应用研究进展[J].国外塑料.2006,24(9):34-36
[14]叶志强,蒋柏泉,农谷珍.硬脂酸镧的制备与动力学研究[J].稀土,2007,28(1):113-116
[15]叶春民,刘景江,唐功本.超微氧化钇填充聚丙烯的结晶行为[J].塑料工业,1994, (5)：45-47
[16]冯嘉春,陈鸣才,黄志镗.硬脂酸镧复合物对聚丙烯β晶的诱导作用[J].高等学校化学学报,2001,22(1)：154-156
[17]冯嘉春,陈鸣才.聚丙烯β晶型成核剂及其应用[P].中国,CN1282750[P].2001-02-07
[18]何阳,黄德花,肖利群等.稀土β成核剂在聚丙烯中的应用[J].中国塑料,2007,21(1)：81-85
[19]朱连超,唐功本,石强,等.稀土化合物在高分子科学中的应用研究进展[J].高分子通报,2007,3:55-60
[20]中日特殊农用地膜研究开发实施委员会.中国合作研究开发特殊农用地膜鉴定资料[G].1992:60
[21]孟继武,任新光,彭连群,等.作用光谱模拟小白菜高产栽培研究[J].发光学报,1997,18(3):265-268
[22]张海霞,陈明辉,张然,朱卫华.浅谈稀土在农业生产中的应用[J].农业装备技术,2007,33(4)：17-19
[23]Liu WM,Wang L H,Wang J F,et al.Study on Synthesisand Polymerization of Mono (isopropylmaleate-oyloxyl)DiisopropoxylDysprosium[J]. JRareEarth,2000,18(2):98
[24]王文,林美娟,章文贡.苯乙烯类聚合物的增韧增强[J].高分子材料科学与工程,2005,21(2):37-41
[25]孙向东,孙旭东,张慧波.MC尼龙改性研究的新进展[J].工程塑料应用,2003,(2):59-63
[26]杜选,吴明丽,杨哲,等.耐热纤维的开发及应用[J].北京纺织,2002,23(3):321
[27]张明,陈晓松,周兰香等.稀土改性PVC膜的制备及性能研究[J].中国稀土学报,2002,20(6):684-687
[28]邱关明,张明,周兰香.稀土掺杂PVC的紫外及微波交联研究[J].中国稀土学报,2001,19(5):463
[29]胡福增.聚合物及其复合材料的表界面[M].北京：中国轻工业出版社,2001
[30]曹珂,于中振.等.界面性能对刚性粒子填充高聚物力学行为的影响(z1).兵工学报,2000：65-66
[31]杨毅,李凤生.超细粒子复合技术进展.材料导报(z1),2001,15(3)：35-37
[32]姚超,俞志敏,张统潮.超细碳酸钙制备的研究.无机盐工业,2001,32(1):3-5.
[33]普鲁特曼E P,梁发思,谢世杰.硅烷和钛酸酯偶联剂[M].上海科学技术出版社,1987:262,303
[34]贾晓林,谭伟.纳米粉体分散技术发展概况[J].非金属矿,2003,26(24):145-149
[35]章文贡,陈田安,苏光东.铝酸酯偶联剂在碳酸钙表面上的反应及其偶联机理的研究[J].中国塑料,1989,3(4):87-91
[36]朱庆英,莫永才.稀土偶联剂对碳酸钙表面改性的研究[J].塑料科技,2006,22(5):48-51.
[37]冯嘉春,陈鸣才,张秀菊,等.稀土偶联剂对Mg(OH)2的改性作用及其在PP/Mg(OH)2体系中的应用[J].高分子学报,2001,26(2):6-11
[38]冯嘉春,陈鸣才,黄志镗,等.稀土化合物对LLDPE流变性能的影响[J].高分子材料科学与工程,2003,19:161-165
[39]陈鸣才,冯嘉春,张秀菊,等.稀土偶联剂在无机刚性粒子增韧聚丙烯体系中应用[J].塑料,2004,33(2)：23-28
[40]赵芸,李峰,段雪等.镁基高抑烟纳米阻燃剂在高分子材料中的应用研究[J].塑料,2002,31(4)：57-63
[41]钱康,刘斌,王茁,陈寿田.新型无机阻燃剂水滑石表面改性的研究[J].绝缘材料,2003(3)：19-22
[42]郑秀婷,吴大鸣,刘颖,等.纳米双羟基复合金属氧化物(LDHs)对聚氯乙烯(PVC)阻燃抑烟研究[J].塑料,2004,33(3):62-65
[43]李蕾,张春英,段雪.影响纳米锌铝复合氧化物紫外吸收性能的因素[J].北京化工大学学报,2002,29(2):83-87
[44]段雪,矫庆泽,李蕾.均分散超细阴离子层状材料的新合成方法.中国专利：CN99119385.7,1999-09-14
[45]李蕾,孙鹏,段雪.MgAl-CO3水分散液的稳定性及流变性[J].应用化学,2001,18(6):436-439
[46]杨飘萍,吴通好等.水滑石的结构性质与合成及催化应用[J].石化技术及应用,2005,23(1)：61-66
[47]W.T.Reichle, S.Y Kang, D.S.Everhardt. The nature of the thermal decomposition of a catalytically active anionic clay mineral[J].Journal of molecular Catalysis B:Enzymatic,2002(18):8-11
[48]贺鹤鸣,矫庆泽.三元系钨硅锰杂多酸柱水滑石的制备[J].化学通报,1994(7):47-54
[49]Chibwe K., Jones W., Intercalation of organic and inorganic anions into layereddouble hydroxides. J.Chem.Soc.Chem.Commun.,1989:926-927
[50]杜以波,何静,李峰,D G Evans,段雪,王作新.微波技术在制备水滑石和柱撑水滑石中的应用[J].应用科学学报,1989,16(3):349-354
[51]翁腾飞,周志明,冉长荣.镁铝水滑石的制备及表面改性[J].应用化工,2009,38(9):23-29
[52]杨文虎,刘斌,马占峰等.水滑石的表面改性研究[J].化学工业与工程,2004,21(5)：331-333
[53]冯春瑶,矫庆泽,李蕾等.双(基)金属复合氧化物的表面改性[J].应用化学,2001,18(2)：140-142
[54]刘斌,钱康,王茁等.新型无机阻燃剂水滑石表面改性的研究[J].绝缘材料,2004,36(3)：19-22
[55]李爱元,徐国财,邢宏龙.纳米粉体表面改性技术及应用[J].化工新型材料,2002,30(10):25-28
[56]杨巧珍,李峰,段雪.层状双羟基氢氧化物的表面有机化研究[J].塑料,2003,32(6)：11-14
[57]M.Z.B.Hussein,Z.Zainal,C. Y.Ming, J. Effect of low protein amino acid fortified grower and finisher diets on broiler growth performance.Mater.Sci.Lett.2000,19,879
[58]V.Prevot, C.Forano, J.P.Besse et al., Syntheses and thermal and chemical behavior of tartrate and succinate intercalated Zn3Al and Zn2Cr layered double hydroxides. Inorg Chem.1998,37:4293
[59]M.A.Aramendia, V.Borau, C.Jimenez et al., Epoxidation of limonene over hydrotalcite-like compounds with hydrogen peroxide in the presence of nitriles. Appl.Catal.a.Gen.2001,216,257
[60]J.W.Gilman, C.L.Jackson, A.B.Morgan et al., Flammbility properties of polymer-silicate nancomposites:PP and PS nanocomposites. Chem.Mater. 2000,12,1866
[61]E.Manias, A.Touny, L.Wu et al., Nano-technology in asphalt. Chem.Mater. 2001,13,3516
[62]K.Masenelli-Varlot, E.Reynaud, GVigier et al., Mechanical properties of clay-reinforced polymide. J.Polym.Sci.Pol.Phs.2002,40,272
[63]A.Micael, D.Philippe.Neurodegeneration prevented by lentiviral vector delivery of GDNF in primate modeles of pardinson's disease. Mater.Sci.Eng.R.Rep.2000,28,1
[64]L.L.Musselman, C.Misra, D.K.Grubbs et al., Bromide intercalated hydrotalcite for use as a flame retardant smoke suppressant additive. US Patent 5,225,115,1993
[65]华幼卿,秦倩.层状双羟基氢氧化物的结构表征及对PVC的热稳定作用[J].高分子材料科学与工程,2003,19,172
[66]L.C.Du, B.J.Qu, Z.J.Xu. Preparation of LLDPE/MgAl-LDH exfoliation nanoconposites with enhanced thermal properties by melt intercalation Polym. Degrad.Stabil,2006,91,995
[67]L.Z.Qiu, W.Chen, B.J.Qu. Sythesis and properties of soluble polyimides based on isomeric ditrifluoromethyl substituted 1,4-bis(4-aminophenoxy)benxene. Polymer 2006,47,922
[68]Huai-Bin Hsueh, Chuh-Yung Chen. Preparation and properties of LDHs/polyimide nanocomposites. Polymer,2003,44:5275-5283
[69]Huai-Bin Hsueh, Chuh-Yung Chen. Preparation and properties of LDHs/epoxy nanocomposites. Polymer,2003,44:1151-1161
[70]吕海金,宋国君,李培耀,王立,孙良栋,周连仲.尼龙6/水滑石纳米复合材料的制备与表征[J].塑料工业,2007,09:11-14.
[71]M.Zammarano, S.Bellayer,J.W.Gilman,M.Francesehi,F.L.Beyer,R.H.Harris, S.Meriani,Polymer 2006,47,652
[72]W.D.Lee, S.S.Im, H.M.Lim, K. J.Kim. Preparation and properties of layered double hydroxide/poly(ethylene terephthalate) nanocomposites by direct melt compounding. Polymer,2006,47,1364
[73]L.C.Du,B.J.Qu,J.Mater,Structural characterization and thermal behavior of LLDPE/MgAl-LDH exfoliated nanocomposites prepared by part organic modification and melt intercalation Chem.2006,16,1549
[74]F.Leroux, J.P.Besse. Delamination and restacking of layered double hydroxides. Chem.Mater.2001,13,3507
[75]G.T.D. Shouldice, P.Y.Choi, B.E.Koene, L.F Nazar et al., A novel way to study the initial stages of soap-free emulsion polymerization:the intercalation of polystyrene oligomers into hydrotalcite. J.Polym.Sci.1995,33,1409
[76]W.Chen,B.J.Qu.Chinese,J.Prepapration of nanocomposites by exfoliation of ZnAl-LDH in nonpoplar LLDPE solutionChem.2003,21,998
[77]W.Chen, L.Feng, B.J.Qu. In situ synthesis of poly(methyl methacrylate)/MgAl layered double hydroxide nanocomposite with high transparency and enhanced thermal properties. Solid.State.Commun.2004,130,259
[78]O.C.Wilson, T.Olorunyolemi, A.Jaworski et al., Surface and interfacial properties of polymer-intercalated layered double hydroxide nanocomposites. Appl. Clay. Sci. 1999,15,265
[79]王辉,包永忠,黄志明,翁志学.聚氯乙烯/纳米水滑石复合材料的形态与力学性能[J].高分子学报,2005,5:691-697
[80]Chapleau N,Ajji A.Micromechanical Behavior of Impact Modifled Poly(Ethylene Terephthalate)[J].Polym Eng Sci,2003,43(6):1197.
[81]李桂娟,李栉,于宝杰,等.成核剂1,3或2,4-(亚苄基)-D山梨醇对PET/PEN共混体系结构和结晶形态影响[J].中国塑料.2004.18(3):20.
[82]Chen W Feng, L Qu BJ. Preparation of nanocomposites by exfoliation of ZnAl layered double hydroxides in nonpolar LLDPE solution,Chem. Mater.,2004,16: 368-370
[83]郭冰之,矫庆泽.聚对苯二甲酞对苯二胺/水滑石纳米复合材料的制备与表征[J].高等学校化学学报,2005,26(7)：1372-1374.
[84]王岩,包永忠等.聚氯乙烯/水滑石纳米复合材料的热稳定性和抑烟性[M].浙江大学.2007,5
[85]Chen H Y, Cronin J A, Archer R D. Synthesis and characterization of linear cerium(Ⅳ) Schiff-base coordination polymers. Macromolecules,1994,27:2180.
[86]刘景江,唐功本,周华荣,等.超微氧化镧填充聚丙烯恒温结晶动力学[J].应用化学,1991,8(3):1.
[87]李连生,惠建斌,等.稀土水滑石的合成与表征(Ⅰ)[J].高等学校化学学报.1993(8)：1048-1050.
[88]Mohd Z.H.,Tan K.H. Synmesis and properties of layed organic-inorganic hybrid material:Zn-Al layered double hydroxide-dioctyl sulfosuccinate.nanocomposite. J. of Nanopart Rese,2000,2:293-298.
[89]Velu S,RamkumV,Narayanan A,Effect of interlayer anions on the physicochemical properties of zinc-aluminum hydrotalcite-like compounSDS.J.Mater Sci,1997,32: 957-964.
[90]刘伯元,陈宇,郑德,等.新型稀土偶联剂在塑料制品中的应用研究[J],2004,12(8):9
[91]郭涛,王炼石.镧化合物改性超碳酸钙对玻纤增加PET结晶性和力学性能的影响[J].中国稀土学报,2004(8):454-457.
[92]Beck H N, Ledbetter H D.DTA study of heterogenous nucleation of crystallization in Polypropylene[J]. Appl.Polym.Sci.1965,9:21-31
[93]Ruan LM, Wang H, Hao YY, Zhou H, Liu X, Xu B. Intramolecular energy transfer models and energy band characteristic of rare-earth complexes with o-phthalic acid.J.Lumin.2007,122:467-470.
[94]章文贡,王文,汪联辉.烷氧基钦掺杂聚苯乙烯及其性质研究[J].福建师范大学学报(自然科学版),1996,12(4):70-74
[95]王朝晖,陈宇.新型稀土表面处理剂在塑料改性中的应用[J].塑料工业,2004,9(32):237-241.
[96]胡圣飞.纳米级CaCO3粒子对PVC增韧增强研究[J].中国塑料.1999,13(6):25-28.
[97]胡圣飞,徐声钧,李纯清.纳米级无机粒子对塑料增韧增强研究进展[J].塑料,1998(4)：13.
[98]宋继瑞,沈志刚,陈建峰.等.ABS/改性纳米CaCO3复合材料微观结构和力学性能[J].高分子材料科学与工程,2004,20(3)：127
[99]杨晋涛,范宏,卜志扬,等.ABS/蒙脱土纳米复合材料的制备、结构及性能[J].塑料工业,2006,34(4):26-28.
[2]Li D M,Qi Z N.第三十七回高分子讨论会稿集.1988,37:2339
[3]M.Z.B.Hussein, Z.Zainal, C.Y.Ming. Microwave-assisted synthesis of Zn-Al-layered double hydroxide-sodium dodecyl sulfate nanocomposite. J.Mater. Sci. Lett.2000,19,879
[4]易宪武.无机化学丛书.北京：化学出版社,1998:157
[5]K.Strawheeker, E.Manias. Flammability properties of polymer-layered-silicate nanocomposites polypropylene and polystyrene nanocomposites. Chem. Mater.2000,12,2943
[6]J.Bujdak, E.Haekett, E.P.Giannelis. Influence of the layer charge dnsity of smectites on the interaction with methylene blue. Chem.Mater.2000,12,2168
[7]Z.Wang, T.Lan, T.J.Pinnavaia. Analysis of heat and mass transfer for microwave freeze drying of unsaturated porous media. Chem. Mater:1996,8,2200
[8]Yang D.J,Lin Y.H. Brownian dynamics simulatons of the effects of hydrodynamic interactions on the polymer viscoelactic behavior, polymer,2003,44(9):2087-2815
[9]Moujahid M, Inacio J, Besse J.P, ASDSorption of styrenene vs polystyre sulfonatc on layered double hydroxides.Microporous Mesoporous Mater.2003,57,37-46
[10]陈伟,挫保钧,冯莉.原位聚合法制备聚丙烯酸甲酯/ZnAl层状双氢氧化物插层纳米复合材料及其形貌特征[J].高等学校化学学报.2003,24(10)：1920-1922
[11]Bergbretter D.E.,Chen L.B.,et al. Recyclable polymer-bound lanthanide diene polymerization catalysts. Macromolecules,1985,18(6):1055-1057
[12]郑德,庄和宽,肖伟平等.稀土稳定剂对PVC的作用机理及其在型材中的应用[J].新型建筑材料,2001(7)：7-9
[13]郑德,李壮利,黄玉松.无铅化稳定剂应用研究进展[J].国外塑料.2006,24(9):34-36
[14]叶志强,蒋柏泉,农谷珍.硬脂酸镧的制备与动力学研究[J].稀土,2007,28(1):113-116
[15]叶春民,刘景江,唐功本.超微氧化钇填充聚丙烯的结晶行为[J].塑料工业,1994, (5)：45-47
[16]冯嘉春,陈鸣才,黄志镗.硬脂酸镧复合物对聚丙烯β晶的诱导作用[J].高等学校化学学报,2001,22(1)：154-156
[17]冯嘉春,陈鸣才.聚丙烯β晶型成核剂及其应用[P].中国,CN1282750[P].2001-02-07
[18]何阳,黄德花,肖利群等.稀土β成核剂在聚丙烯中的应用[J].中国塑料,2007,21(1)：81-85
[19]朱连超,唐功本,石强,等.稀土化合物在高分子科学中的应用研究进展[J].高分子通报,2007,3:55-60
[20]中日特殊农用地膜研究开发实施委员会.中国合作研究开发特殊农用地膜鉴定资料[G].1992:60
[21]孟继武,任新光,彭连群,等.作用光谱模拟小白菜高产栽培研究[J].发光学报,1997,18(3):265-268
[22]张海霞,陈明辉,张然,朱卫华.浅谈稀土在农业生产中的应用[J].农业装备技术,2007,33(4)：17-19
[23]Liu WM,Wang L H,Wang J F,et al.Study on Synthesisand Polymerization of Mono (isopropylmaleate-oyloxyl)DiisopropoxylDysprosium[J]. JRareEarth,2000,18(2):98
[24]王文,林美娟,章文贡.苯乙烯类聚合物的增韧增强[J].高分子材料科学与工程,2005,21(2):37-41
[25]孙向东,孙旭东,张慧波.MC尼龙改性研究的新进展[J].工程塑料应用,2003,(2):59-63
[26]杜选,吴明丽,杨哲,等.耐热纤维的开发及应用[J].北京纺织,2002,23(3):321
[27]张明,陈晓松,周兰香等.稀土改性PVC膜的制备及性能研究[J].中国稀土学报,2002,20(6):684-687
[28]邱关明,张明,周兰香.稀土掺杂PVC的紫外及微波交联研究[J].中国稀土学报,2001,19(5):463
[29]胡福增.聚合物及其复合材料的表界面[M].北京：中国轻工业出版社,2001
[30]曹珂,于中振.等.界面性能对刚性粒子填充高聚物力学行为的影响(z1).兵工学报,2000：65-66
[31]杨毅,李凤生.超细粒子复合技术进展.材料导报(z1),2001,15(3)：35-37
[32]姚超,俞志敏,张统潮.超细碳酸钙制备的研究.无机盐工业,2001,32(1):3-5.
[33]普鲁特曼E P,梁发思,谢世杰.硅烷和钛酸酯偶联剂[M].上海科学技术出版社,1987:262,303
[34]贾晓林,谭伟.纳米粉体分散技术发展概况[J].非金属矿,2003,26(24):145-149
[35]章文贡,陈田安,苏光东.铝酸酯偶联剂在碳酸钙表面上的反应及其偶联机理的研究[J].中国塑料,1989,3(4):87-91
[36]朱庆英,莫永才.稀土偶联剂对碳酸钙表面改性的研究[J].塑料科技,2006,22(5):48-51.
[37]冯嘉春,陈鸣才,张秀菊,等.稀土偶联剂对Mg(OH)2的改性作用及其在PP/Mg(OH)2体系中的应用[J].高分子学报,2001,26(2):6-11
[38]冯嘉春,陈鸣才,黄志镗,等.稀土化合物对LLDPE流变性能的影响[J].高分子材料科学与工程,2003,19:161-165
[39]陈鸣才,冯嘉春,张秀菊,等.稀土偶联剂在无机刚性粒子增韧聚丙烯体系中应用[J].塑料,2004,33(2)：23-28
[40]赵芸,李峰,段雪等.镁基高抑烟纳米阻燃剂在高分子材料中的应用研究[J].塑料,2002,31(4)：57-63
[41]钱康,刘斌,王茁,陈寿田.新型无机阻燃剂水滑石表面改性的研究[J].绝缘材料,2003(3)：19-22
[42]郑秀婷,吴大鸣,刘颖,等.纳米双羟基复合金属氧化物(LDHs)对聚氯乙烯(PVC)阻燃抑烟研究[J].塑料,2004,33(3):62-65
[43]李蕾,张春英,段雪.影响纳米锌铝复合氧化物紫外吸收性能的因素[J].北京化工大学学报,2002,29(2):83-87
[44]段雪,矫庆泽,李蕾.均分散超细阴离子层状材料的新合成方法.中国专利：CN99119385.7,1999-09-14
[45]李蕾,孙鹏,段雪.MgAl-CO3水分散液的稳定性及流变性[J].应用化学,2001,18(6):436-439
[46]杨飘萍,吴通好等.水滑石的结构性质与合成及催化应用[J].石化技术及应用,2005,23(1)：61-66
[47]W.T.Reichle, S.Y Kang, D.S.Everhardt. The nature of the thermal decomposition of a catalytically active anionic clay mineral[J].Journal of molecular Catalysis B:Enzymatic,2002(18):8-11
[48]贺鹤鸣,矫庆泽.三元系钨硅锰杂多酸柱水滑石的制备[J].化学通报,1994(7):47-54
[49]Chibwe K., Jones W., Intercalation of organic and inorganic anions into layereddouble hydroxides. J.Chem.Soc.Chem.Commun.,1989:926-927
[50]杜以波,何静,李峰,D G Evans,段雪,王作新.微波技术在制备水滑石和柱撑水滑石中的应用[J].应用科学学报,1989,16(3):349-354
[51]翁腾飞,周志明,冉长荣.镁铝水滑石的制备及表面改性[J].应用化工,2009,38(9):23-29
[52]杨文虎,刘斌,马占峰等.水滑石的表面改性研究[J].化学工业与工程,2004,21(5)：331-333
[53]冯春瑶,矫庆泽,李蕾等.双(基)金属复合氧化物的表面改性[J].应用化学,2001,18(2)：140-142
[54]刘斌,钱康,王茁等.新型无机阻燃剂水滑石表面改性的研究[J].绝缘材料,2004,36(3)：19-22
[55]李爱元,徐国财,邢宏龙.纳米粉体表面改性技术及应用[J].化工新型材料,2002,30(10):25-28
[56]杨巧珍,李峰,段雪.层状双羟基氢氧化物的表面有机化研究[J].塑料,2003,32(6)：11-14
[57]M.Z.B.Hussein,Z.Zainal,C. Y.Ming, J. Effect of low protein amino acid fortified grower and finisher diets on broiler growth performance.Mater.Sci.Lett.2000,19,879
[58]V.Prevot, C.Forano, J.P.Besse et al., Syntheses and thermal and chemical behavior of tartrate and succinate intercalated Zn3Al and Zn2Cr layered double hydroxides. Inorg Chem.1998,37:4293
[59]M.A.Aramendia, V.Borau, C.Jimenez et al., Epoxidation of limonene over hydrotalcite-like compounds with hydrogen peroxide in the presence of nitriles. Appl.Catal.a.Gen.2001,216,257
[60]J.W.Gilman, C.L.Jackson, A.B.Morgan et al., Flammbility properties of polymer-silicate nancomposites:PP and PS nanocomposites. Chem.Mater. 2000,12,1866
[61]E.Manias, A.Touny, L.Wu et al., Nano-technology in asphalt. Chem.Mater. 2001,13,3516
[62]K.Masenelli-Varlot, E.Reynaud, GVigier et al., Mechanical properties of clay-reinforced polymide. J.Polym.Sci.Pol.Phs.2002,40,272
[63]A.Micael, D.Philippe.Neurodegeneration prevented by lentiviral vector delivery of GDNF in primate modeles of pardinson's disease. Mater.Sci.Eng.R.Rep.2000,28,1
[64]L.L.Musselman, C.Misra, D.K.Grubbs et al., Bromide intercalated hydrotalcite for use as a flame retardant smoke suppressant additive. US Patent 5,225,115,1993
[65]华幼卿,秦倩.层状双羟基氢氧化物的结构表征及对PVC的热稳定作用[J].高分子材料科学与工程,2003,19,172
[66]L.C.Du, B.J.Qu, Z.J.Xu. Preparation of LLDPE/MgAl-LDH exfoliation nanoconposites with enhanced thermal properties by melt intercalation Polym. Degrad.Stabil,2006,91,995
[67]L.Z.Qiu, W.Chen, B.J.Qu. Sythesis and properties of soluble polyimides based on isomeric ditrifluoromethyl substituted 1,4-bis(4-aminophenoxy)benxene. Polymer 2006,47,922
[68]Huai-Bin Hsueh, Chuh-Yung Chen. Preparation and properties of LDHs/polyimide nanocomposites. Polymer,2003,44:5275-5283
[69]Huai-Bin Hsueh, Chuh-Yung Chen. Preparation and properties of LDHs/epoxy nanocomposites. Polymer,2003,44:1151-1161
[70]吕海金,宋国君,李培耀,王立,孙良栋,周连仲.尼龙6/水滑石纳米复合材料的制备与表征[J].塑料工业,2007,09:11-14.
[71]M.Zammarano, S.Bellayer,J.W.Gilman,M.Francesehi,F.L.Beyer,R.H.Harris, S.Meriani,Polymer 2006,47,652
[72]W.D.Lee, S.S.Im, H.M.Lim, K. J.Kim. Preparation and properties of layered double hydroxide/poly(ethylene terephthalate) nanocomposites by direct melt compounding. Polymer,2006,47,1364
[73]L.C.Du,B.J.Qu,J.Mater,Structural characterization and thermal behavior of LLDPE/MgAl-LDH exfoliated nanocomposites prepared by part organic modification and melt intercalation Chem.2006,16,1549
[74]F.Leroux, J.P.Besse. Delamination and restacking of layered double hydroxides. Chem.Mater.2001,13,3507
[75]G.T.D. Shouldice, P.Y.Choi, B.E.Koene, L.F Nazar et al., A novel way to study the initial stages of soap-free emulsion polymerization:the intercalation of polystyrene oligomers into hydrotalcite. J.Polym.Sci.1995,33,1409
[76]W.Chen,B.J.Qu.Chinese,J.Prepapration of nanocomposites by exfoliation of ZnAl-LDH in nonpoplar LLDPE solutionChem.2003,21,998
[77]W.Chen, L.Feng, B.J.Qu. In situ synthesis of poly(methyl methacrylate)/MgAl layered double hydroxide nanocomposite with high transparency and enhanced thermal properties. Solid.State.Commun.2004,130,259
[78]O.C.Wilson, T.Olorunyolemi, A.Jaworski et al., Surface and interfacial properties of polymer-intercalated layered double hydroxide nanocomposites. Appl. Clay. Sci. 1999,15,265
[79]王辉,包永忠,黄志明,翁志学.聚氯乙烯/纳米水滑石复合材料的形态与力学性能[J].高分子学报,2005,5:691-697
[80]Chapleau N,Ajji A.Micromechanical Behavior of Impact Modifled Poly(Ethylene Terephthalate)[J].Polym Eng Sci,2003,43(6):1197.
[81]李桂娟,李栉,于宝杰,等.成核剂1,3或2,4-(亚苄基)-D山梨醇对PET/PEN共混体系结构和结晶形态影响[J].中国塑料.2004.18(3):20.
[82]Chen W Feng, L Qu BJ. Preparation of nanocomposites by exfoliation of ZnAl layered double hydroxides in nonpolar LLDPE solution,Chem. Mater.,2004,16: 368-370
[83]郭冰之,矫庆泽.聚对苯二甲酞对苯二胺/水滑石纳米复合材料的制备与表征[J].高等学校化学学报,2005,26(7)：1372-1374.
[84]王岩,包永忠等.聚氯乙烯/水滑石纳米复合材料的热稳定性和抑烟性[M].浙江大学.2007,5
[85]Chen H Y, Cronin J A, Archer R D. Synthesis and characterization of linear cerium(Ⅳ) Schiff-base coordination polymers. Macromolecules,1994,27:2180.
[86]刘景江,唐功本,周华荣,等.超微氧化镧填充聚丙烯恒温结晶动力学[J].应用化学,1991,8(3):1.
[87]李连生,惠建斌,等.稀土水滑石的合成与表征(Ⅰ)[J].高等学校化学学报.1993(8)：1048-1050.
[88]Mohd Z.H.,Tan K.H. Synmesis and properties of layed organic-inorganic hybrid material:Zn-Al layered double hydroxide-dioctyl sulfosuccinate.nanocomposite. J. of Nanopart Rese,2000,2:293-298.
[89]Velu S,RamkumV,Narayanan A,Effect of interlayer anions on the physicochemical properties of zinc-aluminum hydrotalcite-like compounSDS.J.Mater Sci,1997,32: 957-964.
[90]刘伯元,陈宇,郑德,等.新型稀土偶联剂在塑料制品中的应用研究[J],2004,12(8):9
[91]郭涛,王炼石.镧化合物改性超碳酸钙对玻纤增加PET结晶性和力学性能的影响[J].中国稀土学报,2004(8):454-457.
[92]Beck H N, Ledbetter H D.DTA study of heterogenous nucleation of crystallization in Polypropylene[J]. Appl.Polym.Sci.1965,9:21-31
[93]Ruan LM, Wang H, Hao YY, Zhou H, Liu X, Xu B. Intramolecular energy transfer models and energy band characteristic of rare-earth complexes with o-phthalic acid.J.Lumin.2007,122:467-470.
[94]章文贡,王文,汪联辉.烷氧基钦掺杂聚苯乙烯及其性质研究[J].福建师范大学学报(自然科学版),1996,12(4):70-74
[95]王朝晖,陈宇.新型稀土表面处理剂在塑料改性中的应用[J].塑料工业,2004,9(32):237-241.
[96]胡圣飞.纳米级CaCO3粒子对PVC增韧增强研究[J].中国塑料.1999,13(6):25-28.
[97]胡圣飞,徐声钧,李纯清.纳米级无机粒子对塑料增韧增强研究进展[J].塑料,1998(4)：13.
[98]宋继瑞,沈志刚,陈建峰.等.ABS/改性纳米CaCO3复合材料微观结构和力学性能[J].高分子材料科学与工程,2004,20(3)：127
[99]杨晋涛,范宏,卜志扬,等.ABS/蒙脱土纳米复合材料的制备、结构及性能[J].塑料工业,2006,34(4):26-28.