.794. 北京科技大学学报 第30卷 表3催化剂H3 PWsMos040/MC一48与其他催化剂的催化性能比较 Table 3 Comparison of the catalytic activities of H3PW6Mo60/MCM-48 with other catalysts 催化剂 n(丁嗣)n(1,2丙二醇) 催化剂用量/% 反应时间/h 带水剂 收率/% FeCls-6H2O 11.5 1.5 1.5 环己烷 47.5 Fe2(S04)3xH20 1:2.0 2.0 4.5 苯 47.0 十二水合硫酸铁铵 11.5 2.6 2.0 环己烷 58.8 分子筛 1:1.5 2.6 1.5 来 58.8 S0/Ti021a203 1:2.5 0.5 2.0 环己烷 68.7 H3P WsMo6040 1:1.4 0.2 1.0 环己烷 56.5 H3PW6Mo6040/MCM-18 1:1.4 0.2 1.0 环己烷 81.0 1,2丙二醇缩酮产物的主要红外光谱数据v(IR, [4]Wang C D.Qian W Y.Study of catalytic synthesis of acetals and KBr)为1250,1218,1194和1157cm-1,1HNMR ketals with molecular sieve.Chem World,1993(1):20 (CDCl3,300MHh)8a为4.11~4.24(m,1H,CH), (王存德,钱文元·分子筛催化合成缩醛(酮)的研究.化学世 界,1993(1):20) 3.83>4.06(m,1H,CH),3.34~3.46(m,1H, [5]Yang S J.Wang M,Chen N Y.Catalytic synthesis of butanone CH,1.60~1.69(dd,2H,CH2),1.34(s,3H, 1.2-propanediol ketal by S/TiO2-La2O3.Chem Reagent. CH),1.26~1.30(d,3H,CH3),0.90~0.96(t, 2004,26(6):373 3H,CH3)·由IR和HNMR数据可确认产物为丁 (杨水金,王敏,陈年友,S0/Ti02一La203催化合成丁酮1, 2-丙二醇缩酮.化学试剂,2004,26(6):373) 酮1,2丙二醇缩酮的结构 [6]Wang E B.Hu C.W.Xu L.Polyhydric Chemist Introduction. 3结论 Beijing:Chemical Industry Press.1998:146 (王恩波,胡长文,许林.多酸化学导论·北京:化学工业出版社, (1)以H3PW6Mo6O4o/MC一48催化合成丁酮 1998.146) 1,2丙二醇缩酮的适宜条件为:n(丁酮)n(1,2丙 [7]Misono M.Heterogeneous catalysis by heteropoly compounds of 二醇)=1:1.4,催化剂用量为反应物料总量的 Molybdenum and Tungsten.Catal Rev.1987.29(2/3):269 [8]Kresge C T.Leonowicz M E.Roth W J.et al.Ordered meso- 0.2%,反应时间1.0h,丁酮1,2-丙二醇缩酮收率 porous molecular sieves synthesized by a liquid -crystal template 可达81.0%. mechanism.Nature,1992.359(10):710 (2)H3PW6Mo604o/MC48对合成丁酮1,2- [9]Beck JS.Vartuli J C.Roth W J,et al.A new family of meso- 丙二醇缩酮产品具有催化活性高、催化剂用量少、反 porous molecular sieves prepared with liquid crystal templates. Am Chem Soc,1992,114(27):10834 应时间短等优点,因此H3PW6Mo6O4o/MCM一48是 [10]Cai Q.Zhang H B.Lin W Y,et al.The synthesis of mesoporous 合成丁酮1,2丙二醇缩酮产品的优良催化剂,具有 molecular sieve MCM-48.Chem J Chin Univ.1999.20(5): 良好的应用前景 675 (蔡强,张慧波,林文勇,等.MCM一48介孔分子筛的合成研 参考文献 究.高等学校化学学报,1999,20(5):675) [1]Yu S X.Peng H Y.Catalytic synthesis of acetals and ketals with [11]Huo QS,Margol Ese DI,Cl Esla U.et al.Generalized synthe- FeCl3-6H2O.Mod Chem Ind.1994(12):29 sis of periodic surfactant/inorganic composite materials.Nature. (俞善信,彭红阳.三氯化铁催化合成缩醛(酮)·现代化工, 1994,368,317 1994(12):29) [12]He J.FengT,Yang J,et al.Insite polymerization of tetrahy [2]Li Y Z.Huang H M.Jin H,et al.Aldol condensation of cyclo- drofuran on HPA/MCM-48.Acta Petrol Sin Petrol Process hexanone and synthesis of acetal or ketals.Acta Sci Nat Univ Sect,2002,18(1):37 filin,1989(2):113 (何静,冯桃,杨佳,等.HPA/MCM一8催化剂上四氢呋喃开 (李叶芝,黄化民,金辉,等.疏酸铁催化环己酮的缩合反应和缩 环聚合.石油学报:石油加工,2002,18(1):37) 醛(酮)反应,吉林大学学报,1989(2):113) [13]Yu Z L,Li S F,Han F R.et al.Investigation on physical and [3]Chen C J.Catalytic synthesis of acetals and ketals with chemical properties of HsP Moz-W040.Sci Bull.1986 NHiFe(SO)2-12H2O.Aging Appl Synth Mater.2001(2):20 (19):1478 (陈翠娟.十二水硫酸铁铵催化合成缩醛和缩酮,合成材料老 (于作龙,李淑芳,韩富荣,等.H3P Mo12-。W.00杂多酸物理 化与应用,2001(2):20) 化学性质的研究.科学通报,1986(19):1478)表3 催化剂 H3PW6Mo6O40/MCM-48与其他催化剂的催化性能比较 Table3 Comparison of the catalytic activities of H3PW6Mo6O40/MCM-48with other catalysts 催化剂 n(丁酮)∶n(12-丙二醇) 催化剂用量/% 反应时间/h 带水剂 收率/% FeCl3·6H2O 1∶1∙5 1∙5 1∙5 环己烷 47∙5 Fe2(SO4)3·xH2O 1∶2∙0 2∙0 4∙5 苯 47∙0 十二水合硫酸铁铵 1∶1∙5 2∙6 2∙0 环己烷 58∙8 分子筛 1∶1∙5 2∙6 1∙5 苯 58∙8 SO 2- 4 /TiO2-La2O3 1∶2∙5 0∙5 2∙0 环己烷 68∙7 H3PW6Mo6O40 1∶1∙4 0∙2 1∙0 环己烷 56∙5 H3PW6Mo6O40/MCM-48 1∶1∙4 0∙2 1∙0 环己烷 81∙0 12-丙二醇缩酮产物的主要红外光谱数据 υ(IR KBr)为125012181194和1157cm -11H NMR (CDCl3300MHz)δH 为4∙11~4∙24(m1HCH) 3∙83~4∙06(m1HCH)3∙34~3∙46(m1H CH)1∙60~1∙69(dd2HCH2)1∙34(s3H CH3)1∙26~1∙30(d3HCH3)0∙90~0∙96(t 3HCH3).由 IR 和1H NMR 数据可确认产物为丁 酮12-丙二醇缩酮的结构. 3 结论 (1) 以 H3PW6Mo6O40/MCM-48催化合成丁酮 12-丙二醇缩酮的适宜条件为:n(丁酮)∶n(12-丙 二醇) =1∶1∙4催化剂用量为反应物料总量的 0∙2%反应时间1∙0h丁酮12-丙二醇缩酮收率 可达81∙0%. (2) H3PW6Mo6O40/MCM-48对合成丁酮12- 丙二醇缩酮产品具有催化活性高、催化剂用量少、反 应时间短等优点因此 H3PW6Mo6O40/MCM-48是 合成丁酮12-丙二醇缩酮产品的优良催化剂具有 良好的应用前景. 参 考 文 献 [1] Yu S XPeng H Y.Catalytic synthesis of acetals and ketals with FeCl3·6H2O.Mod Chem Ind1994(12):29 (俞善信彭红阳.三氯化铁催化合成缩醛(酮).现代化工 1994(12):29) [2] Li Y ZHuang H MJin Het al.Aldol condensation of cyclohexanone and synthesis of acetal or ketals.Acta Sci Nat Univ Jilin1989(2):113 (李叶芝黄化民金辉等.硫酸铁催化环己酮的缩合反应和缩 醛(酮)反应.吉林大学学报1989(2):113) [3] Chen C J. Catalytic synthesis of acetals and ketals with NH4Fe(SO4)2·12H2O.Aging Appl Synth Mater2001(2):20 (陈翠娟.十二水硫酸铁铵催化合成缩醛和缩酮.合成材料老 化与应用2001(2):20) [4] Wang C DQian W Y.Study of catalytic synthesis of acetals and ketals with molecular sieve.Chem World1993(1):20 (王存德钱文元.分子筛催化合成缩醛(酮)的研究.化学世 界1993(1):20) [5] Yang S JWang MChen N Y.Catalytic synthesis of butanone 12-propanediol ketal by SO 2- 4 /TiO2-La2O3.Chem Reagent 200426(6) :373 (杨水金王敏陈年友.SO 2- 4 /TiO2-La2O3 催化合成丁酮1 2-丙二醇缩酮.化学试剂200426(6):373) [6] Wang E BHu C WXu L.Polyhydric Chemist Introduction. Beijing:Chemical Industry Press1998:146 (王恩波胡长文许林.多酸化学导论.北京:化学工业出版社 1998:146) [7] Misono M.Heterogeneous catalysis by heteropoly compounds of Molybdenum and Tungsten.Catal Rev198729(2/3):269 [8] Kresge C TLeonowicz M ERoth W Jet al.Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism.Nature1992359(10):710 [9] Beck J SVartuli J CRoth W Jet al.A new family of mesoporous molecular sieves prepared with liquid crystal templates.J A m Chem Soc1992114(27):10834 [10] Cai QZhang H BLin W Yet al.The synthesis of mesoporous molecular sieve MCM-48.Chem J Chin Univ199920(5): 675 (蔡强张慧波林文勇等.MCM-48介孔分子筛的合成研 究.高等学校化学学报199920(5):675) [11] Huo Q SMargol Ese D ICl Esla Uet al.Generalized synthesis of periodic surfactant/inorganic composite materials.Nature 1994368:317 [12] He JFeng TYang Jet al.In-site polymerization of tetrahydrofuran on HPA/MCM-48. Acta Petrol Sin Petrol Process Sect200218(1):37 (何静冯桃杨佳等.HPA/MCM-48催化剂上四氢呋喃开 环聚合.石油学报:石油加工200218(1):37) [13] Yu Z LLi S FHan F Ret al.Investigation on physical and chemical properties of H3PMo12- n W nO40. Sci Bull1986 (19):1478 (于作龙李淑芳韩富荣等.H3PMo12- nW nO40杂多酸物理 化学性质的研究.科学通报1986(19):1478) ·794· 北 京 科 技 大 学 学 报 第30卷