季铵盐与烷基胺插层高岭石结构及其热动力学对比
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摘要
采用X射线衍射、Fourier变换红外光谱及热分析等表征方法对高岭石/十二烷基三甲基氯化铵(Kaol-DTAC)及高岭石/十二胺(Kaol-DA)插层复合物的结构进行对比研究,并进一步研究了插层复合物的热动力学。结果表明:插层作用使高岭石在加热过程中脱羟基温度降低了10℃左右。由于插层分子DTAC与DA的结构差异,致使其在高岭石层间的排列方式存在差异。前者主要以呈90°夹角垂直于高岭石晶层面的方式单层排列,后者则以分子链与高岭石晶面呈39.9°夹角双层倾斜排列为主,且二者在高岭石层间排列方式的不同导致其结构稳定性存在差异。采用KAS法和Ozawa法对Kaol-DTAC和Kaol-DA插层复合物进行热力学分析并且分别计算其活化能。Kaol-DTAC的活化能为102.44 k J/mol,Kaol-DA的活化能为130.80 k J/mol,进一步说明DA比DTAC在高岭石层间更为稳定。
The intercalation complexes of kaolinite/dodecyl trimethyl ammonium chloride(Kaol-DTAC) and kaolinite/dodecylamine(Kaol-DA) were compared and studied by using X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry and differential scanning calorimetry analysis, and the thermodynamic of the intercalation complexes was further studied. The intercalation made the temperature of dehydroxylation of kaolinite reduced by approximately 10 ℃ during the heating process. There is a difference in the arrangement of DTAC and DA in kaolinite interlayer space which is due to the structure difference between DTAC and DA molecules. The former is mainly arranged in a single layer with an angle of 90° perpendicular to the level of kaolinite crystals while the latter is tilted to the kaolinite surface in bilayer and the inclination angle of the chains is 39.9° and the different agreements in kaolinite interlayer space result in differences in their structural stability. The activation energy was calculated by using KAS and Ozawa methods to thermodynamic analysis for the composites of Kaol-DTAC and Kaol-DA. The activation energy E of Kaol-DTAC is 102.44 kJ/mol and the activation energy E of Kaol-DA is 130.80 k J/mol which further shows that DA is more stable than DTAC between kaolinite interlayer space.
The intercalation complexes of kaolinite/dodecyl trimethyl ammonium chloride(Kaol-DTAC) and kaolinite/dodecylamine(Kaol-DA) were compared and studied by using X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry and differential scanning calorimetry analysis, and the thermodynamic of the intercalation complexes was further studied. The intercalation made the temperature of dehydroxylation of kaolinite reduced by approximately 10 ℃ during the heating process. There is a difference in the arrangement of DTAC and DA in kaolinite interlayer space which is due to the structure difference between DTAC and DA molecules. The former is mainly arranged in a single layer with an angle of 90° perpendicular to the level of kaolinite crystals while the latter is tilted to the kaolinite surface in bilayer and the inclination angle of the chains is 39.9° and the different agreements in kaolinite interlayer space result in differences in their structural stability. The activation energy was calculated by using KAS and Ozawa methods to thermodynamic analysis for the composites of Kaol-DTAC and Kaol-DA. The activation energy E of Kaol-DTAC is 102.44 kJ/mol and the activation energy E of Kaol-DA is 130.80 k J/mol which further shows that DA is more stable than DTAC between kaolinite interlayer space.
引文
[1]刘钦甫,程宏飞,张玉德,等.高岭石插层、剥片及其在橡胶中的应用[M].北京,科学出版社,2016.
[2]程宏飞,吉雷波,李阔,等.插层剥片对高岭土/橡胶纳米复合材料阻隔性能影响研究[J].非金属矿,2014(2):12-14.CHENG Hongfei,Leibo J I,LI Kuo,et al.Non-Met Mines(in Chinese),2014(2):12-14.
[3]GUGGENHEIM S,ADAMS J M,BAIN D C,et al.Summary of recommendations of nomenclature committees relevant to clay mineralogy:report of the Association Internationale pour l'Etude des Argiles(AIPEA)Nomenclature Committee for 2006[J].Clay Miner,2006,41(4):863-877.
[4]MATUSIK J,KLAPYTA Z.Characterization of kaolinite intercalation compounds with benzylalkylammonium chlorides using XRD,TGA/DTA and CHNS elemental analysis[J].Appl Clay Sci,2013,84:433-440.
[5]BERGAYA F,DETELLIER C,LAMBERT J F,et al.Introduction to clay-polymer nanocomposites(CPN)[J].Dev Clay Sci,2013,5:655-677.
[6]LIU Q,ZHANG Y,XU H.Properties of vulcanized rubber nanocomposites filled with nanokaolin and precipitated silica[J].Appl Clay Sci,2008,42:232-237.
[7]ZHANG Y,LIU Q,ZHANG Q,et al.Gas barrier properties of natural rubber/kaolin composites prepared by melt blending[J].Appl Clay Sci,2010,50(2):255-259.
[8]CHOUDALAKIS G A,GOTSIS A D.Permeability of polymer/clay nanocomposites:A review[J].Eur Polym J,2011,1312(4):967-984.
[9]MOHAN T P,KURIAKOSE J,KANNY K.Effect of nanoclay reinforcement on structure,thermal and mechanical properties of natural rubber-styrene butadine rubber(NR-SBR)[J].J Ind Eng Chem,2011,17(2):264-270.
[10]张印民,刘钦甫,伍泽广,等.高岭石/二甲基亚砜插层复合物的制备及影响因素[J].硅酸盐学报,2011,39(10):1637-1643.ZHANG Yinmin,LIU Qinfu,WU Zeguang,et al.J Chin Ceram Soc,2011,39(10):1637-1643.
[11]冯莉,林喆,刘炯天,等.超声波法制备高岭石插层复合物[J].硅酸盐学报,2006,35(10):1226-1231.FENG Li,LIN Zhe,LIU Jiongtian,et al.J Chin Ceram Soc,2006,35(10):1226-1231.
[12]YUAN P,TAN D,YAN W,et al.From platy kaolinite to aluminosilicate nanoroll via one-step delamination of kaolinite:Effect of the temperature of intercalation[J].Appl Clay Sci,2013,83/84(10):68-76.
[13]周熠,程宏飞,杜贝贝,等.高岭石_二甲基亚砜插层复合物结构模拟[J].人工晶体学报,2017,46(1):26-32.ZHOU Yi,CHENG Hongfei,DU Beibei,et al.J Synth Cryst(in Chinese),2017,46(1):26-32.
[14]KOMORI Y,ENOTO H,TAKENAWA R,et al.Modification of the interlayer surface of kaolinite with methoxy groups[J].Langmuir,2000,16(12):5506-5508.
[15]刘钦甫,王定,郭鹏,等.季铵盐-高岭石系列插层复合物的制备及结构表征[J].硅酸盐学报,2015,43(2):222-230.LIU Qinfu,WANG Ding,GUO Peng,et al.J Chin Ceram Soc,2015,43(2):222-230.
[16]MCNULTY D,BUCKLEY D N,O'DWYER C.Synthesis and electrochemical properties of vanadium oxide materials and structures as Li-ion battery positive electrodes[J].J Power Sources,2014,267(4):831-873.
[17]CHENG H,XU P,WANG D,et al.Thermal decomposition behavior and de-intercalation kinetics of kaolinite/quaternary ammonium salt complexes[J].J Therm Anal Calorim,2016,126(2):421-433.
[18]CHENG H,FROST R L,YANG J,et al.Infrared and infrared emission spectroscopic study of typical Chinese kaolinite and halloysite[J].Spectrochim Acta Part A,2010,77(5):1014-1020.
[19]CHENG H,YANG J,FROST R L,et al.Thermal analysis and Infrared emission spectroscopic study of kaolinite-potassium acetate intercalate complex[J].J Therm Anal Calorim,2011,103(2):507-513.
[20]刘钦甫,纪阳,杜妍娜,等.高岭石/APTES插层复合物的表征及其脱嵌反应动力学[J].无机化学学报,2015,31(3):501-508.LIU Qinfu,JI Yang,DU Yanna,et al.Chin J Inorg Chem(in Chinese),2015,31(3):501-508.
[21]CHENG H,LI K,LIUQ,et al.Insight into the thermal decomposition of kaolinite intercalated with potassium acetate:an evolved gas analysis[J].J Therm Anal Calorim,2014,117(3):1231-1239.
[22]刘钦甫,李晓光,郭鹏,等.高岭石-烷基胺插层复合物的制备与纳米卷的形成[J].硅酸盐学报,2014,42(8):1064-1069.LIU Qinfu,LI Xiaoguang,GUO Peng,et al.J Chin Ceram Soc,2014,42(8):1064-1069.
[23]CHENG H,LIU Q,LIU J,et al.TG-MS-FTIR(evolved gas analysis)of kaolinite-urea intercalation complex[J].J Therm Anal Calorim,2014,116(1):195-203.
[24]SAHNOUNE F,SAHEB N,KHAMEL B,et al.Thermal analysis of dehydroxylation of Algerian kaolinite[J].J Therm Anal Calorim,2012,107(3):1067-1072.
[25]GABOR M.Thermal behavior and decomposition of intercalated kaolinite[J].Clays Clay Miner,2015,43(2):223-228.
[26]李湘,郭海福,闫鹏.热重分析测定脱附活化能分布研究[J].离子交换与吸附,2011,27(6):555-561.LI Xiang,GUO Haifu,YAN Peng.Ion Exch Adsorpt(in Chinese),2011,27(6):555-561.
[2]程宏飞,吉雷波,李阔,等.插层剥片对高岭土/橡胶纳米复合材料阻隔性能影响研究[J].非金属矿,2014(2):12-14.CHENG Hongfei,Leibo J I,LI Kuo,et al.Non-Met Mines(in Chinese),2014(2):12-14.
[3]GUGGENHEIM S,ADAMS J M,BAIN D C,et al.Summary of recommendations of nomenclature committees relevant to clay mineralogy:report of the Association Internationale pour l'Etude des Argiles(AIPEA)Nomenclature Committee for 2006[J].Clay Miner,2006,41(4):863-877.
[4]MATUSIK J,KLAPYTA Z.Characterization of kaolinite intercalation compounds with benzylalkylammonium chlorides using XRD,TGA/DTA and CHNS elemental analysis[J].Appl Clay Sci,2013,84:433-440.
[5]BERGAYA F,DETELLIER C,LAMBERT J F,et al.Introduction to clay-polymer nanocomposites(CPN)[J].Dev Clay Sci,2013,5:655-677.
[6]LIU Q,ZHANG Y,XU H.Properties of vulcanized rubber nanocomposites filled with nanokaolin and precipitated silica[J].Appl Clay Sci,2008,42:232-237.
[7]ZHANG Y,LIU Q,ZHANG Q,et al.Gas barrier properties of natural rubber/kaolin composites prepared by melt blending[J].Appl Clay Sci,2010,50(2):255-259.
[8]CHOUDALAKIS G A,GOTSIS A D.Permeability of polymer/clay nanocomposites:A review[J].Eur Polym J,2011,1312(4):967-984.
[9]MOHAN T P,KURIAKOSE J,KANNY K.Effect of nanoclay reinforcement on structure,thermal and mechanical properties of natural rubber-styrene butadine rubber(NR-SBR)[J].J Ind Eng Chem,2011,17(2):264-270.
[10]张印民,刘钦甫,伍泽广,等.高岭石/二甲基亚砜插层复合物的制备及影响因素[J].硅酸盐学报,2011,39(10):1637-1643.ZHANG Yinmin,LIU Qinfu,WU Zeguang,et al.J Chin Ceram Soc,2011,39(10):1637-1643.
[11]冯莉,林喆,刘炯天,等.超声波法制备高岭石插层复合物[J].硅酸盐学报,2006,35(10):1226-1231.FENG Li,LIN Zhe,LIU Jiongtian,et al.J Chin Ceram Soc,2006,35(10):1226-1231.
[12]YUAN P,TAN D,YAN W,et al.From platy kaolinite to aluminosilicate nanoroll via one-step delamination of kaolinite:Effect of the temperature of intercalation[J].Appl Clay Sci,2013,83/84(10):68-76.
[13]周熠,程宏飞,杜贝贝,等.高岭石_二甲基亚砜插层复合物结构模拟[J].人工晶体学报,2017,46(1):26-32.ZHOU Yi,CHENG Hongfei,DU Beibei,et al.J Synth Cryst(in Chinese),2017,46(1):26-32.
[14]KOMORI Y,ENOTO H,TAKENAWA R,et al.Modification of the interlayer surface of kaolinite with methoxy groups[J].Langmuir,2000,16(12):5506-5508.
[15]刘钦甫,王定,郭鹏,等.季铵盐-高岭石系列插层复合物的制备及结构表征[J].硅酸盐学报,2015,43(2):222-230.LIU Qinfu,WANG Ding,GUO Peng,et al.J Chin Ceram Soc,2015,43(2):222-230.
[16]MCNULTY D,BUCKLEY D N,O'DWYER C.Synthesis and electrochemical properties of vanadium oxide materials and structures as Li-ion battery positive electrodes[J].J Power Sources,2014,267(4):831-873.
[17]CHENG H,XU P,WANG D,et al.Thermal decomposition behavior and de-intercalation kinetics of kaolinite/quaternary ammonium salt complexes[J].J Therm Anal Calorim,2016,126(2):421-433.
[18]CHENG H,FROST R L,YANG J,et al.Infrared and infrared emission spectroscopic study of typical Chinese kaolinite and halloysite[J].Spectrochim Acta Part A,2010,77(5):1014-1020.
[19]CHENG H,YANG J,FROST R L,et al.Thermal analysis and Infrared emission spectroscopic study of kaolinite-potassium acetate intercalate complex[J].J Therm Anal Calorim,2011,103(2):507-513.
[20]刘钦甫,纪阳,杜妍娜,等.高岭石/APTES插层复合物的表征及其脱嵌反应动力学[J].无机化学学报,2015,31(3):501-508.LIU Qinfu,JI Yang,DU Yanna,et al.Chin J Inorg Chem(in Chinese),2015,31(3):501-508.
[21]CHENG H,LI K,LIUQ,et al.Insight into the thermal decomposition of kaolinite intercalated with potassium acetate:an evolved gas analysis[J].J Therm Anal Calorim,2014,117(3):1231-1239.
[22]刘钦甫,李晓光,郭鹏,等.高岭石-烷基胺插层复合物的制备与纳米卷的形成[J].硅酸盐学报,2014,42(8):1064-1069.LIU Qinfu,LI Xiaoguang,GUO Peng,et al.J Chin Ceram Soc,2014,42(8):1064-1069.
[23]CHENG H,LIU Q,LIU J,et al.TG-MS-FTIR(evolved gas analysis)of kaolinite-urea intercalation complex[J].J Therm Anal Calorim,2014,116(1):195-203.
[24]SAHNOUNE F,SAHEB N,KHAMEL B,et al.Thermal analysis of dehydroxylation of Algerian kaolinite[J].J Therm Anal Calorim,2012,107(3):1067-1072.
[25]GABOR M.Thermal behavior and decomposition of intercalated kaolinite[J].Clays Clay Miner,2015,43(2):223-228.
[26]李湘,郭海福,闫鹏.热重分析测定脱附活化能分布研究[J].离子交换与吸附,2011,27(6):555-561.LI Xiang,GUO Haifu,YAN Peng.Ion Exch Adsorpt(in Chinese),2011,27(6):555-561.