超分子结构聚合物/LDH纳米复合材料的组装及性能研究
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摘要
水滑石(LDH)因其特殊的层状结构、层间距可调性和层间阴离子可交换性,近年来受到人们的广泛关注。经离子交换,向层间引入新的客体阴离子或分子(如有机阴离子、聚合物、药物活性分子等),可使层状结构和组成产生相应的变化,得到不同结构的一大类兼具有机(或聚合物)和LDH优点的特殊性质的功能材料。因此,在吸附、离子交换、药物缓释、阻燃材料、催化等方面具有巨大的应用前景。
本文选用恒定pH液相单滴法,通过单因素实验优化合成工艺条件。并以聚乙二醇为分散剂,正丁醇为置换剂通过溶剂共沸分别合成了层间阴离子为CO32-, Cl-, NO3-的LDH,粒径范围在50～100nm。经XRD分析表明产物衍射峰尖锐,结晶度良好;TG-DTA分析表明产物热稳定性良好。
以离子交换法制备有机酸插层C032--LDH,确定了最佳反应温度,pH,反应时间。对脂肪酸插层LDH的XRD分析表明,层间距随碳链长度先增加,但随着碳链的增长由于层板的作用碳链的旋转弯曲使得层间距不随碳链增长而增大。
以离子交换法制备马来酸插层Cl--LDH,经XRD与FT-IR分析表明马来酸进入LDH层间。通过130℃原位引发聚合,经XRD分析表明,聚合反应后LDH层间距减小；FT-IR谱图特征峰出现；SEM分析得出聚合后粒径为70-200nm,有轻微团聚。结果表明制备得到了聚马来酸插层LDH纳米复合材料。
以离子交换法与共沉淀法制备萘普生插层NO3--LDH,结合XRD、FT-IR、TG-DTA分析表明萘普生进入LDH层间与层板相互作用形成超分子结构,提高了萘普生的热稳定性。对萘普生插层LDH进行缓释研究表明共沉淀法制备所得产物具有良好的缓释性能。
In recent years, LDH is being paid more and more attention for special samdwich, controllability of layers interval and anionic exchanging. New gusts can be inducted to interlayer by ion exchange, consequently alter the layer configuration and constitution. Then, the functional material would be abtained with the characters of organ and LDH. Thus, it show wide application prospects in the fields of absorption, drug retarded release, fire-retardant and catalysis etc.
LDH, the anion of CO32-, Cl-, NO3- and particle size of 50～100nm, were synthesized by means of azeotropic distillatio with dispersant of Polyethylene glycol, replacement of butyl alcohol. The XRD showed that the products had sharply diffraction peak and well crystal. Meantime, TG-DTA indicated they had the good thermal stability.
The optimal reactive temperature, pH and time were ascertained via single factor tests. XRD result beared out layer distance would increase as carbon chain lengthen, and this phenomenon would be disspear as long as overlong carbon chain rotate and bend.
Maleic/LDH was prepared by ion exchange methods in this paper. XRD and FT-IR analysis indicated that Maleic had had entered into LDH interlayer. By 130℃in-situ initiation polymerization, XRD analyse showed the LDH interlayer distance decreased after polymerization; character peak emerge in the chart of FT-IR; it can be seen by the SEM that the particle size is about 70-200nm and slight reunite. Result proved the prepared polymaleic/LDH were nanometer composite materials.
NO3--LDH was made by way of ion exchange and co-deposition methods. Analyses implied the Naproxen had untried into the LDH interlayer and super molecule configuration could be formed by XRD、FT-IR、TG-DTA. This configuration improved the thermal stability of Naproxen. The study of retarded releasing showed the products prepared by co-deposition had well property of retarded releasing.
本文选用恒定pH液相单滴法,通过单因素实验优化合成工艺条件。并以聚乙二醇为分散剂,正丁醇为置换剂通过溶剂共沸分别合成了层间阴离子为CO32-, Cl-, NO3-的LDH,粒径范围在50～100nm。经XRD分析表明产物衍射峰尖锐,结晶度良好;TG-DTA分析表明产物热稳定性良好。
以离子交换法制备有机酸插层C032--LDH,确定了最佳反应温度,pH,反应时间。对脂肪酸插层LDH的XRD分析表明,层间距随碳链长度先增加,但随着碳链的增长由于层板的作用碳链的旋转弯曲使得层间距不随碳链增长而增大。
以离子交换法制备马来酸插层Cl--LDH,经XRD与FT-IR分析表明马来酸进入LDH层间。通过130℃原位引发聚合,经XRD分析表明,聚合反应后LDH层间距减小；FT-IR谱图特征峰出现；SEM分析得出聚合后粒径为70-200nm,有轻微团聚。结果表明制备得到了聚马来酸插层LDH纳米复合材料。
以离子交换法与共沉淀法制备萘普生插层NO3--LDH,结合XRD、FT-IR、TG-DTA分析表明萘普生进入LDH层间与层板相互作用形成超分子结构,提高了萘普生的热稳定性。对萘普生插层LDH进行缓释研究表明共沉淀法制备所得产物具有良好的缓释性能。
In recent years, LDH is being paid more and more attention for special samdwich, controllability of layers interval and anionic exchanging. New gusts can be inducted to interlayer by ion exchange, consequently alter the layer configuration and constitution. Then, the functional material would be abtained with the characters of organ and LDH. Thus, it show wide application prospects in the fields of absorption, drug retarded release, fire-retardant and catalysis etc.
LDH, the anion of CO32-, Cl-, NO3- and particle size of 50～100nm, were synthesized by means of azeotropic distillatio with dispersant of Polyethylene glycol, replacement of butyl alcohol. The XRD showed that the products had sharply diffraction peak and well crystal. Meantime, TG-DTA indicated they had the good thermal stability.
The optimal reactive temperature, pH and time were ascertained via single factor tests. XRD result beared out layer distance would increase as carbon chain lengthen, and this phenomenon would be disspear as long as overlong carbon chain rotate and bend.
Maleic/LDH was prepared by ion exchange methods in this paper. XRD and FT-IR analysis indicated that Maleic had had entered into LDH interlayer. By 130℃in-situ initiation polymerization, XRD analyse showed the LDH interlayer distance decreased after polymerization; character peak emerge in the chart of FT-IR; it can be seen by the SEM that the particle size is about 70-200nm and slight reunite. Result proved the prepared polymaleic/LDH were nanometer composite materials.
NO3--LDH was made by way of ion exchange and co-deposition methods. Analyses implied the Naproxen had untried into the LDH interlayer and super molecule configuration could be formed by XRD、FT-IR、TG-DTA. This configuration improved the thermal stability of Naproxen. The study of retarded releasing showed the products prepared by co-deposition had well property of retarded releasing.
引文
[1]C.Cavani, E.Trfiro, A. Vaccari. Hydrotalcite-type anionic clays, preparation properties and applications [J]. Catalysts Today,1991,11(2):173～301.
[2]孟锦宏,张慧,王治强.插层组装超分子结构有机物柱撑阴离子层状材料.化学通报,2003(2)：85～94.
[3]Jean Francois Nicod. Toward new mufti-property materials[J]. Science,1994,263(4):636-637.
[4]杜以波,D.G.Evans,段雪等.阴离子型层柱材料研究进展[J].化学通报,2005(5)：20～24.
[5]Khan A I, O'Hare D. Intercalation chemistry of layered double hydroxides:recent developments and applications[J]. Journal of materials Chemistry,2002,12:3191～3198
[6]雷立旭,张卫锋,胡猛.层状复合金属氢氧化物：结构、性质及其应用.无机化学学报[J],2005,21(4)：451～464.
[7]杜芸.层状双金属氢氧化物及氧化物的可控制备和应用研究[D].北京：北京化工大学,2002.
[8]Dubey A, Rives V, Kannan S. Catalytic hydroxylation of phenol over ternaryhydrotalcites containing Cu, Ni and Al[J]. J Mole Catal A:Chemical,2002,181:151.
[9]Rives V, Dubey A, Kannan S. Layered double hydroxides with the hydrotalcite-type structure containing Cu2+, Ni2+ and Al3+[J]. Physical Chemistry Chemical Physics,2001,3:4826～4836.
[10]Auer S M, Gredig S V, Koppel R A, et al. Journal of Molecular Caxalysis a-Chemical,1999, 141:193～203.
[11]Miyata S, Kumura T. Synthesis of new hydrotalcite-like compounds and their physicochemical properties[J]. Chem Letters,1975,8:843～848.
[12]Mascolo G, Marino O. Discrimination between synthetic Mg-Al double hydroxides and related carbonate phases[J]. Thermochim. Acta,1980,35(1):93～98.
[13]陈善云.水滑石及全氟辛酸柱撑水滑石的合成与应用性能研究[D].北京：北京化工大学,2005.
[14]Chibwe K, Jones W. Intercalation of organic and inorganic anions into layered double hydroxides[J]. J Chem Soc Chem Commun.1989:926～928.
[15]Bhattacharyya A, Hall D B. New triborate-pillared hydrotalcite[J]. Inorg. Chem,1992,31(18): 3689～3670.
[16]Bhattacharyya A, Hall DB. Barnes T J Novel oligovanadate-pillared hydrotalcites[J]. Appl Clay Sci. 1995,10:57～67.
[17]孙幼松,矫庆泽,赵芸等.己二酸柱撑水滑石的制备及表征[J].无机化学学报,2001,17(3)：414～418
[18]Sumio Aisawa, Satoshi Takahashi. Wataru Ogasawara etc. Direct Intercalation of Amino Acids into Layered Double Hydroxides by Coprecipitation[J]. Journal of Solid State Chemistry,2001,162: 52～62.
[19]刘红霞,段雪,马润宇.层状材料水滑石固定青霉素酸化酶的研究[J].北京化工大学学报.2002, 29(3)：9-11.
[20]吴祥根,朱建芬,高永良.新型医药用载体-层状双金属氢氧化物[J].中国药学杂志,2006,41(5)：327～330.
[21]彭霞辉,黄可龙,焦飞鹏等.水滑石作为药物载体-萘普生的插层和缓释[J].功能材料,2006,37(3)：415～417.
[22]Sumio Aisawa, Hiroko Kudo, Tomomi Hoshi etc. Intercalation behavior of amino acids into Zn-Al-layered double hydroxide by calcination-rehydration reaction[J]. Journal of Solid State Chemistry,2004,177:3987～3994.
[23]徐光年,蒋惠亮.表面活性剂在聚合物／蒙脱石纳米复合材料制备中的应用[J].日用化学工业.2003,33(2)：102～104.
[24]Huai-Bin Hsueh, Chuh-Yung Chen. Preparation and properties of LDHs/Polyimide nanocomposites[J]. Polymer,2003,44:1151～1161.
[25]Huai-Bin Hsueh, Chuh-Yung Chen. Preparation and properties of LDHs/epoxy nanocomposites[J]. Polymer.2004,44:5275-5283.
[26]杨亲正,张春光,孙德军.聚合物层状双氢氧化物纳米复合材料[J].化学通报,2002,65：1～6.
[27]Chr. Bender Koch, Structures and properties of anionic clay minerals[J]. Hyperfine Interactions,, 1998,171:131.
[28]赵芸,层状双金属氢氧化物及氧化物的可控制备和应用研究[D].北京：北京化工大学,2002.
[29]任玲玲,何静,段雪.阴离子型层柱材料的插层组装.科学通报[J],2001(11)：686～691.
[30]吴正,卫敏,沈军,段雪.酒石酸插层水滑石层间距的可控性研究[J].北京化工大学学报,2004,31(4)：74～77.
[31]陈天虎,庆承松,谌香秀等.物理化学条件对合成Mg/A1_LDH结晶度和结构的影响[J].岩石矿物学杂志,2005,24(4)：324～328.
[32]冯桃,李殿卿,段雪.层状双金属氢氧化物晶粒尺寸的控制[J].应用化学,2003,20(2)：117～120.
[33]Reichle WT. Catalytic reactions by thermally activated, synthetic anionic clayminerals[J]. Catal, 1985,94:547～557
[34]Rocha J, Arco M.del, Rives V. Ulibarri MA.Reconstruction of layered double hydroxides from calcined precursors:a power XRD and Al MAS NMR study[J]. Mater Chem,1999,9(28):2499～2503.
[35]Toshiyuki Hibino, Arsumu Tsunashima. Characterization of repeatedly reconstructured Mg-Al hydrotalcite-like compounds:gradual segregation of aluminium from the structure[J]. Chem. Mater, 1998,10(23):4055～4061.
[36]郭军,贺深阳,葛科.不同方法制备水杨酸根插层水滑石[J].湖南人文科技学院学报,2005(5)：20～23.
[37]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,申请号CN99119 385.7,1999
[38]T. Lopez, P. Bosch, M. Asomoza et al. DTA-TGA and FT-IR spectroscopies of sol-gel hydrotalcites:
aluminum sorce effect on physicochemical properties. Mater. Lett,1997,31:311.
[39]王军峰.纳米Mg/Al-LDH的制备工艺研究及结构表征[D].西安：西安理工大学,2006：41
[40]杨飘萍,宿美平,杨青微等.尿素法合成高结晶度类水滑石[J].无机化学学报,2003,19(5)：485～489.
[41]吕亮,吾国强,段雪等.水滑石的制备、表征及其在醋交换反应中的应用[J].精细石油化工,2001,1(1)：9-12.
[42]Prevot V, Casal B, Hitzky E.R. Intracrystalline alkylation of benzoate ions into layered double hydroxides[J]. Mater. Chem,2001,11:554～560.
[43]吕亮,吾国强,段雪等.阴离子型层柱材料催化醋交换反应的研究进展[J].浙江化工,2002：24～25.
[44]张慧,徐彦红,EVANS.David.G等,磁性纳米固体碱催化剂MgAl2(OH)2LDH/NiFe204的合成表征与性能研究[J].化学学报,2004,62(8)：750～756.
[45]刘云,孙广东,翟龙霞等.Zn-Mg-Al类水滑石催化制备生物柴油的研究[J].中国粮油学报,2009,24(1)：75～79.
[46]邢颖.超分子结构紫外阻隔材料的插层组装及结构与性能研究[D].北京：北京化工大学,2003.
[47]刘建才,廉世勋,朱爱玲等.铕掺杂类水滑石的发光性质及其选择性红外吸收[J].发光学报,2007,28(1)：67～73
[48]王良玉,崔海龙,焦红文.水滑石对农膜性能影响的红外光谱研究[J].光谱学与光谱分析,2007,27(2)：259～261
[49]杨巧珍,李峰,段雪.镁铝碳酸根型LDH与聚氯乙烯的复合性能研究[J].复合材料学报,2003,20(5)：82～87.
[50]李贤慧,钱学仁.镁铝水滑石用作造纸阻燃填料的研究.中国造纸,2008,27(12)：16～19.
[51]Mohd Zobir bin Hussein, Ismail Yaziz, Teoh Chi Beng. The use of Mg/Al layered double hydroxide for color removal of textile wastewater[J]. J. ENVIRON. SCI. HEALTH,2001. A36(4): 565～573.
[52]臧运波,侯万国,王文兴.Cr(Ⅵ)在Mg-Al型类水滑石上的吸附-脱附性研究[J].化学学报,2007,65(9)：773～778.
[53]Lv Liang, He Jing, Wei Min, et al. Factors influencing the removal of fluoride from aqueous solution by calcined Mg-Al-CO3 layered double hydroxides[J]. J Hazardous Mater B,2006,133(3):119
[54]Lv Liang, He Jing, Wei Min, et al. Uptake of chlorideion from aqueous solution by calcined layered double hydroxides:Equilibrium and kinetic studies[J]. Water Res,2006,40(4):735.
[55]Sumio Aisawa, S.T. Direct Intercalation of Amino Acids into Layered Double Hydroxides by Coprecipitation Journal of Solid State[J]. Chemistry,2001,162(5):52～62.
[56]Gordijo C R, Barbosa C A S, Ferreira A. Immobilization of Ibuprofen and Copper-Ibuprofen Drugs on Layered Double Hydroxides[J]. Journal of pharmaceutical sciences,2005.94(5):1135～1148.
[57]倪哲明,夏盛杰,王力耕等.诺氟沙星插层镁铝水滑石新型药物-无机复合材料的超分子结构、热稳定性和缓释性能[J],高等学校化学学报,2007,28(7)：1214～1219.
[58]张娴,张慧,草甘膦插层镁铝水滑石MgAl-LDH-gly的释放性能研究[J].高等学校化学学报,2004,25(10)：1869～1874.
[59]许家友,余晓峰,李光照.水滑石填充PVC形态结构的研究[J].塑料工业,2005,33(6)：45.
[60]于湘,王君,杨黎晖等.Zn-Al-[V10O28]6水滑石在镁合金防腐中的机理研究[J].材料工程,2008,(12)：30～33.
[61]刘西文,杨中文,罗承友.纳米LDH在PE热封膜中的应用研究[J].材料与相关产品,2008,34(8)：21～25
[62]杜娜,侯万国,宋淑娥.类水滑石诱导囊泡的自发形成[J].化学学报,2007,65(11)：1003～1006
[63]计剑.超分子科学成为材料科学和生命科学的桥梁[J].国际学术动态,2006(1)：51-52
[64]韩国胜,张宇虹,武现丽.超分子化合物及其在色谱分离中的应用[J].河南化工,2008.25(8)：6～10
[65]李文卓.层嵌主客体功能复合化合物研究[D].长春：吉林大学,2004.
[66]Desiraju, Gautam R. The supramolecular concept as a bridge between organic, inorganic and organometallic crystal chemistry[J]. Journal of Molecular Structure,1996,374:191～198.
[67]武汉大学,分析化学实验[M].北京,高等教育出版社,2001：234～238
[68]周昭明.紫外分光光度法测定水杨酸钠注射液含量[J].中国兽药杂志,2000,34(4)：35～36.
[69]王军峰.纳米Mg/Al-LDH的制备工艺研究及结构表征[D].西安：西安理工大学,2006：18
[70]赵保军.几种阴离子对羟基铝溶液及交联蒙脱石性能的研究[D].北京：北京大学,2002.
[71]Steven P, Newman, William Jones. Synthsis characterization and applications of layered double hydroxides containing organic guests[J]. New.Chem,1998:105～115.
[72]任庆利,陈维,罗强.液相法合成针状镁铝水滑石纳米晶的研究[J].无机材料学报,2004,19(5)：979～984.
[73]许国志,郭灿雄,段雪等.PE膜中层状双羟基复合氢氧化物的红外吸收性能[J].应用化学,1999,16(5)：45～47
[74]许珂敬,许煜汾.表面活性剂在Zr02微粉中的作用[J].无机研究学报,1999,13(4)：434～436.
[75]余钟民,邱建明.溶胶-凝胶法制备纳米级Zr02粉体的团聚及其控制[J].广州化工,2000,28(4)：159～162.
[76]Bao he Wang, Wen bo Zhang, Wei Zhang, et al. Progress in drylngtechnology for nanomaterials[J]. Drying Technology,2005,23(2):7-3.
[77]隋振英,邹东雷.共沸蒸馏中共沸剂的选择[J].化学工程师,1996,(3)：27.
[78]戴焰林,洪玲,施利毅.沉淀—共沸蒸馏法制备纳米Mg(OH)2的研究[J].上海大学学报(自然科学版),2003,9(5)：402.
[79]王宝和,张伟.纳米材料干燥技术进展(一)[J].干燥技术与设备,2003(1)：15～16.
[80]张伟,王宝和.纳米氧化镁粉体制备技术的研究进展[J].中国粉体技术,2004,10(2)：40～44.
[81]O. C. Wilson, Jr T. Olorunyolemi, A. Jaworski, et al. Surface Properties of Layered Double Hydroxide Nanocomposites[M]. Materials and Application Ⅲ, Ceramic Transactions,1999,15: 265-279
[82]Qiu L Z, Chen W, QuBJ. Exfoliation of layered double hydroxide in polystyrene by in-situ atom transfer radical polymerization using initiator-modified precursor[J]. Polymer Degradation and Stability,2005,87:433.
[83]陈伟,瞿保钧,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,(10)：259～263.
[84]H B Hsueh, C Y Chen. Preparation and Properties of LDHs/Epoxy Nanocomposites[J]. Polymer Science Category,2003,44:5275～5283.
[85]Partenheimer W. Catalysis of Organic Reactions[M]. New York:Marcel Dekker,1990. Chapter20.
[86]Rudolf G, Peter G, Volker M, et al. Application of Nanoparticles in Polymers for Electronics and Electrical Engineering[J]. Part Part Syst Charact,2002,62:3442.
[87]N. T. Whilton, P. J. Vickers, S.J.Mann. Bioinorganic clays:synthesis and characterization of amino-and polyamino acid intercalated layered double hydroxides[J]. Mater Chem,1997,7: 1623～1629
[88]F. Leroux, J.P. Besse. Polymer interleaved layered double hydroxide:a new emerging class of nanocomposites[J]. Chem.Mater,2001,13:3507～3515.
[89]高翠英,孟俊亮,李彦威.紫外分光光度法测定马来酸含量[J].太原理工大学学报,2008,9(3)：230～231.
[90]Tyner, Schiffman S, Glannells E. Nanobiohybrids as delivery vehicles for camptothecin [J]. JControlled Release,2004,95(3):501～514.
[91]吴祥根,朱建芬,高永良.新型医药用载体—层状双金属氢氧化物[J].中国药学杂志,2006,41(5)：326～329.
[92]朱兴年.药物缓释、控释制剂的研究进展[J].药学实践杂志,2002,20(3)：155～157.
[93]Aamir K, Lei L, Alexander J, et al. Intercalation and controlled release of pharmaceutically active, compounds from a layered double hydroxidet[J]. Chem Commun,2001,22:2342～2343.
[94]Khan, A.I.Lei, L.X., O'Hare,D. Intercalation andcontrolled release of pHarmaceutically active compounds from a layered doublehydroxide[M]. Chem.Commun,2001:2342～2343.
[95]O'Hare, D. Controlled-release oral drug delivery system containing anintercalation of layered double hydroxide[M]. PCT Int.Appl.WO,2002,4:7729.
[96]Hussein, Zainal Z, Yahaya, A.H.Foo, D.W.V.. Controlled release of aplant growth regulator, α-napHthaleneacetate from the lamella of Zn-Al-layered double hydroxide nanocomposite [J]. Control.Release,2003,82:417～427.
[97]Ambrogi V, Fardella G.,Grandolini G. Intercalation compounds ofhydrotalcite-like anionic clays with antiinflammatory agents—I.Intercalation andin vitro release of ibuprofen.Int[J]. PHarm,2001, 220:23～32.
[98]平其能.《现代药剂学》[M].北京：中国医药科技出版社,1998：321～330.
[99]张宇星,董秀兰,候疏影.药物释放系统的发展[M].重庆：儿科药学杂志,2001,7(3)：1-3.
[100]管清香,张恒弼,林天慕.口服缓／控释制剂的研究进展.2002,20(3),159-162
[101]孙锡维,周芝芳.结肠靶向给药制剂[J].中国现代应用药学杂志,2002,19(3)：196～198.
[102]常翠,杨宏图,毛世瑞,毕殿洲.口服缓释、控释制剂的体外释放度测定方法和体内外相关性的研究发展[J].中国药学杂志,1999,34(3)：796-799.
[103]Hearan Suh, H. W. Jun. Physicochemical and release studies of naproxen in poloxamer gels [J]. International Journal of Pharmaceutics,1996,129:13～20.
[104]陈颖,刘锡钧,黄旭慧等.萘普生缓释片的释放度研究[J].中国医药工业杂志,1998,29(9)：396～398.
[2]孟锦宏,张慧,王治强.插层组装超分子结构有机物柱撑阴离子层状材料.化学通报,2003(2)：85～94.
[3]Jean Francois Nicod. Toward new mufti-property materials[J]. Science,1994,263(4):636-637.
[4]杜以波,D.G.Evans,段雪等.阴离子型层柱材料研究进展[J].化学通报,2005(5)：20～24.
[5]Khan A I, O'Hare D. Intercalation chemistry of layered double hydroxides:recent developments and applications[J]. Journal of materials Chemistry,2002,12:3191～3198
[6]雷立旭,张卫锋,胡猛.层状复合金属氢氧化物：结构、性质及其应用.无机化学学报[J],2005,21(4)：451～464.
[7]杜芸.层状双金属氢氧化物及氧化物的可控制备和应用研究[D].北京：北京化工大学,2002.
[8]Dubey A, Rives V, Kannan S. Catalytic hydroxylation of phenol over ternaryhydrotalcites containing Cu, Ni and Al[J]. J Mole Catal A:Chemical,2002,181:151.
[9]Rives V, Dubey A, Kannan S. Layered double hydroxides with the hydrotalcite-type structure containing Cu2+, Ni2+ and Al3+[J]. Physical Chemistry Chemical Physics,2001,3:4826～4836.
[10]Auer S M, Gredig S V, Koppel R A, et al. Journal of Molecular Caxalysis a-Chemical,1999, 141:193～203.
[11]Miyata S, Kumura T. Synthesis of new hydrotalcite-like compounds and their physicochemical properties[J]. Chem Letters,1975,8:843～848.
[12]Mascolo G, Marino O. Discrimination between synthetic Mg-Al double hydroxides and related carbonate phases[J]. Thermochim. Acta,1980,35(1):93～98.
[13]陈善云.水滑石及全氟辛酸柱撑水滑石的合成与应用性能研究[D].北京：北京化工大学,2005.
[14]Chibwe K, Jones W. Intercalation of organic and inorganic anions into layered double hydroxides[J]. J Chem Soc Chem Commun.1989:926～928.
[15]Bhattacharyya A, Hall D B. New triborate-pillared hydrotalcite[J]. Inorg. Chem,1992,31(18): 3689～3670.
[16]Bhattacharyya A, Hall DB. Barnes T J Novel oligovanadate-pillared hydrotalcites[J]. Appl Clay Sci. 1995,10:57～67.
[17]孙幼松,矫庆泽,赵芸等.己二酸柱撑水滑石的制备及表征[J].无机化学学报,2001,17(3)：414～418
[18]Sumio Aisawa, Satoshi Takahashi. Wataru Ogasawara etc. Direct Intercalation of Amino Acids into Layered Double Hydroxides by Coprecipitation[J]. Journal of Solid State Chemistry,2001,162: 52～62.
[19]刘红霞,段雪,马润宇.层状材料水滑石固定青霉素酸化酶的研究[J].北京化工大学学报.2002, 29(3)：9-11.
[20]吴祥根,朱建芬,高永良.新型医药用载体-层状双金属氢氧化物[J].中国药学杂志,2006,41(5)：327～330.
[21]彭霞辉,黄可龙,焦飞鹏等.水滑石作为药物载体-萘普生的插层和缓释[J].功能材料,2006,37(3)：415～417.
[22]Sumio Aisawa, Hiroko Kudo, Tomomi Hoshi etc. Intercalation behavior of amino acids into Zn-Al-layered double hydroxide by calcination-rehydration reaction[J]. Journal of Solid State Chemistry,2004,177:3987～3994.
[23]徐光年,蒋惠亮.表面活性剂在聚合物／蒙脱石纳米复合材料制备中的应用[J].日用化学工业.2003,33(2)：102～104.
[24]Huai-Bin Hsueh, Chuh-Yung Chen. Preparation and properties of LDHs/Polyimide nanocomposites[J]. Polymer,2003,44:1151～1161.
[25]Huai-Bin Hsueh, Chuh-Yung Chen. Preparation and properties of LDHs/epoxy nanocomposites[J]. Polymer.2004,44:5275-5283.
[26]杨亲正,张春光,孙德军.聚合物层状双氢氧化物纳米复合材料[J].化学通报,2002,65：1～6.
[27]Chr. Bender Koch, Structures and properties of anionic clay minerals[J]. Hyperfine Interactions,, 1998,171:131.
[28]赵芸,层状双金属氢氧化物及氧化物的可控制备和应用研究[D].北京：北京化工大学,2002.
[29]任玲玲,何静,段雪.阴离子型层柱材料的插层组装.科学通报[J],2001(11)：686～691.
[30]吴正,卫敏,沈军,段雪.酒石酸插层水滑石层间距的可控性研究[J].北京化工大学学报,2004,31(4)：74～77.
[31]陈天虎,庆承松,谌香秀等.物理化学条件对合成Mg/A1_LDH结晶度和结构的影响[J].岩石矿物学杂志,2005,24(4)：324～328.
[32]冯桃,李殿卿,段雪.层状双金属氢氧化物晶粒尺寸的控制[J].应用化学,2003,20(2)：117～120.
[33]Reichle WT. Catalytic reactions by thermally activated, synthetic anionic clayminerals[J]. Catal, 1985,94:547～557
[34]Rocha J, Arco M.del, Rives V. Ulibarri MA.Reconstruction of layered double hydroxides from calcined precursors:a power XRD and Al MAS NMR study[J]. Mater Chem,1999,9(28):2499～2503.
[35]Toshiyuki Hibino, Arsumu Tsunashima. Characterization of repeatedly reconstructured Mg-Al hydrotalcite-like compounds:gradual segregation of aluminium from the structure[J]. Chem. Mater, 1998,10(23):4055～4061.
[36]郭军,贺深阳,葛科.不同方法制备水杨酸根插层水滑石[J].湖南人文科技学院学报,2005(5)：20～23.
[37]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,申请号CN99119 385.7,1999
[38]T. Lopez, P. Bosch, M. Asomoza et al. DTA-TGA and FT-IR spectroscopies of sol-gel hydrotalcites:
aluminum sorce effect on physicochemical properties. Mater. Lett,1997,31:311.
[39]王军峰.纳米Mg/Al-LDH的制备工艺研究及结构表征[D].西安：西安理工大学,2006：41
[40]杨飘萍,宿美平,杨青微等.尿素法合成高结晶度类水滑石[J].无机化学学报,2003,19(5)：485～489.
[41]吕亮,吾国强,段雪等.水滑石的制备、表征及其在醋交换反应中的应用[J].精细石油化工,2001,1(1)：9-12.
[42]Prevot V, Casal B, Hitzky E.R. Intracrystalline alkylation of benzoate ions into layered double hydroxides[J]. Mater. Chem,2001,11:554～560.
[43]吕亮,吾国强,段雪等.阴离子型层柱材料催化醋交换反应的研究进展[J].浙江化工,2002：24～25.
[44]张慧,徐彦红,EVANS.David.G等,磁性纳米固体碱催化剂MgAl2(OH)2LDH/NiFe204的合成表征与性能研究[J].化学学报,2004,62(8)：750～756.
[45]刘云,孙广东,翟龙霞等.Zn-Mg-Al类水滑石催化制备生物柴油的研究[J].中国粮油学报,2009,24(1)：75～79.
[46]邢颖.超分子结构紫外阻隔材料的插层组装及结构与性能研究[D].北京：北京化工大学,2003.
[47]刘建才,廉世勋,朱爱玲等.铕掺杂类水滑石的发光性质及其选择性红外吸收[J].发光学报,2007,28(1)：67～73
[48]王良玉,崔海龙,焦红文.水滑石对农膜性能影响的红外光谱研究[J].光谱学与光谱分析,2007,27(2)：259～261
[49]杨巧珍,李峰,段雪.镁铝碳酸根型LDH与聚氯乙烯的复合性能研究[J].复合材料学报,2003,20(5)：82～87.
[50]李贤慧,钱学仁.镁铝水滑石用作造纸阻燃填料的研究.中国造纸,2008,27(12)：16～19.
[51]Mohd Zobir bin Hussein, Ismail Yaziz, Teoh Chi Beng. The use of Mg/Al layered double hydroxide for color removal of textile wastewater[J]. J. ENVIRON. SCI. HEALTH,2001. A36(4): 565～573.
[52]臧运波,侯万国,王文兴.Cr(Ⅵ)在Mg-Al型类水滑石上的吸附-脱附性研究[J].化学学报,2007,65(9)：773～778.
[53]Lv Liang, He Jing, Wei Min, et al. Factors influencing the removal of fluoride from aqueous solution by calcined Mg-Al-CO3 layered double hydroxides[J]. J Hazardous Mater B,2006,133(3):119
[54]Lv Liang, He Jing, Wei Min, et al. Uptake of chlorideion from aqueous solution by calcined layered double hydroxides:Equilibrium and kinetic studies[J]. Water Res,2006,40(4):735.
[55]Sumio Aisawa, S.T. Direct Intercalation of Amino Acids into Layered Double Hydroxides by Coprecipitation Journal of Solid State[J]. Chemistry,2001,162(5):52～62.
[56]Gordijo C R, Barbosa C A S, Ferreira A. Immobilization of Ibuprofen and Copper-Ibuprofen Drugs on Layered Double Hydroxides[J]. Journal of pharmaceutical sciences,2005.94(5):1135～1148.
[57]倪哲明,夏盛杰,王力耕等.诺氟沙星插层镁铝水滑石新型药物-无机复合材料的超分子结构、热稳定性和缓释性能[J],高等学校化学学报,2007,28(7)：1214～1219.
[58]张娴,张慧,草甘膦插层镁铝水滑石MgAl-LDH-gly的释放性能研究[J].高等学校化学学报,2004,25(10)：1869～1874.
[59]许家友,余晓峰,李光照.水滑石填充PVC形态结构的研究[J].塑料工业,2005,33(6)：45.
[60]于湘,王君,杨黎晖等.Zn-Al-[V10O28]6水滑石在镁合金防腐中的机理研究[J].材料工程,2008,(12)：30～33.
[61]刘西文,杨中文,罗承友.纳米LDH在PE热封膜中的应用研究[J].材料与相关产品,2008,34(8)：21～25
[62]杜娜,侯万国,宋淑娥.类水滑石诱导囊泡的自发形成[J].化学学报,2007,65(11)：1003～1006
[63]计剑.超分子科学成为材料科学和生命科学的桥梁[J].国际学术动态,2006(1)：51-52
[64]韩国胜,张宇虹,武现丽.超分子化合物及其在色谱分离中的应用[J].河南化工,2008.25(8)：6～10
[65]李文卓.层嵌主客体功能复合化合物研究[D].长春：吉林大学,2004.
[66]Desiraju, Gautam R. The supramolecular concept as a bridge between organic, inorganic and organometallic crystal chemistry[J]. Journal of Molecular Structure,1996,374:191～198.
[67]武汉大学,分析化学实验[M].北京,高等教育出版社,2001：234～238
[68]周昭明.紫外分光光度法测定水杨酸钠注射液含量[J].中国兽药杂志,2000,34(4)：35～36.
[69]王军峰.纳米Mg/Al-LDH的制备工艺研究及结构表征[D].西安：西安理工大学,2006：18
[70]赵保军.几种阴离子对羟基铝溶液及交联蒙脱石性能的研究[D].北京：北京大学,2002.
[71]Steven P, Newman, William Jones. Synthsis characterization and applications of layered double hydroxides containing organic guests[J]. New.Chem,1998:105～115.
[72]任庆利,陈维,罗强.液相法合成针状镁铝水滑石纳米晶的研究[J].无机材料学报,2004,19(5)：979～984.
[73]许国志,郭灿雄,段雪等.PE膜中层状双羟基复合氢氧化物的红外吸收性能[J].应用化学,1999,16(5)：45～47
[74]许珂敬,许煜汾.表面活性剂在Zr02微粉中的作用[J].无机研究学报,1999,13(4)：434～436.
[75]余钟民,邱建明.溶胶-凝胶法制备纳米级Zr02粉体的团聚及其控制[J].广州化工,2000,28(4)：159～162.
[76]Bao he Wang, Wen bo Zhang, Wei Zhang, et al. Progress in drylngtechnology for nanomaterials[J]. Drying Technology,2005,23(2):7-3.
[77]隋振英,邹东雷.共沸蒸馏中共沸剂的选择[J].化学工程师,1996,(3)：27.
[78]戴焰林,洪玲,施利毅.沉淀—共沸蒸馏法制备纳米Mg(OH)2的研究[J].上海大学学报(自然科学版),2003,9(5)：402.
[79]王宝和,张伟.纳米材料干燥技术进展(一)[J].干燥技术与设备,2003(1)：15～16.
[80]张伟,王宝和.纳米氧化镁粉体制备技术的研究进展[J].中国粉体技术,2004,10(2)：40～44.
[81]O. C. Wilson, Jr T. Olorunyolemi, A. Jaworski, et al. Surface Properties of Layered Double Hydroxide Nanocomposites[M]. Materials and Application Ⅲ, Ceramic Transactions,1999,15: 265-279
[82]Qiu L Z, Chen W, QuBJ. Exfoliation of layered double hydroxide in polystyrene by in-situ atom transfer radical polymerization using initiator-modified precursor[J]. Polymer Degradation and Stability,2005,87:433.
[83]陈伟,瞿保钧,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,(10)：259～263.
[84]H B Hsueh, C Y Chen. Preparation and Properties of LDHs/Epoxy Nanocomposites[J]. Polymer Science Category,2003,44:5275～5283.
[85]Partenheimer W. Catalysis of Organic Reactions[M]. New York:Marcel Dekker,1990. Chapter20.
[86]Rudolf G, Peter G, Volker M, et al. Application of Nanoparticles in Polymers for Electronics and Electrical Engineering[J]. Part Part Syst Charact,2002,62:3442.
[87]N. T. Whilton, P. J. Vickers, S.J.Mann. Bioinorganic clays:synthesis and characterization of amino-and polyamino acid intercalated layered double hydroxides[J]. Mater Chem,1997,7: 1623～1629
[88]F. Leroux, J.P. Besse. Polymer interleaved layered double hydroxide:a new emerging class of nanocomposites[J]. Chem.Mater,2001,13:3507～3515.
[89]高翠英,孟俊亮,李彦威.紫外分光光度法测定马来酸含量[J].太原理工大学学报,2008,9(3)：230～231.
[90]Tyner, Schiffman S, Glannells E. Nanobiohybrids as delivery vehicles for camptothecin [J]. JControlled Release,2004,95(3):501～514.
[91]吴祥根,朱建芬,高永良.新型医药用载体—层状双金属氢氧化物[J].中国药学杂志,2006,41(5)：326～329.
[92]朱兴年.药物缓释、控释制剂的研究进展[J].药学实践杂志,2002,20(3)：155～157.
[93]Aamir K, Lei L, Alexander J, et al. Intercalation and controlled release of pharmaceutically active, compounds from a layered double hydroxidet[J]. Chem Commun,2001,22:2342～2343.
[94]Khan, A.I.Lei, L.X., O'Hare,D. Intercalation andcontrolled release of pHarmaceutically active compounds from a layered doublehydroxide[M]. Chem.Commun,2001:2342～2343.
[95]O'Hare, D. Controlled-release oral drug delivery system containing anintercalation of layered double hydroxide[M]. PCT Int.Appl.WO,2002,4:7729.
[96]Hussein, Zainal Z, Yahaya, A.H.Foo, D.W.V.. Controlled release of aplant growth regulator, α-napHthaleneacetate from the lamella of Zn-Al-layered double hydroxide nanocomposite [J]. Control.Release,2003,82:417～427.
[97]Ambrogi V, Fardella G.,Grandolini G. Intercalation compounds ofhydrotalcite-like anionic clays with antiinflammatory agents—I.Intercalation andin vitro release of ibuprofen.Int[J]. PHarm,2001, 220:23～32.
[98]平其能.《现代药剂学》[M].北京：中国医药科技出版社,1998：321～330.
[99]张宇星,董秀兰,候疏影.药物释放系统的发展[M].重庆：儿科药学杂志,2001,7(3)：1-3.
[100]管清香,张恒弼,林天慕.口服缓／控释制剂的研究进展.2002,20(3),159-162
[101]孙锡维,周芝芳.结肠靶向给药制剂[J].中国现代应用药学杂志,2002,19(3)：196～198.
[102]常翠,杨宏图,毛世瑞,毕殿洲.口服缓释、控释制剂的体外释放度测定方法和体内外相关性的研究发展[J].中国药学杂志,1999,34(3)：796-799.
[103]Hearan Suh, H. W. Jun. Physicochemical and release studies of naproxen in poloxamer gels [J]. International Journal of Pharmaceutics,1996,129:13～20.
[104]陈颖,刘锡钧,黄旭慧等.萘普生缓释片的释放度研究[J].中国医药工业杂志,1998,29(9)：396～398.