4,4′-二氨基二苯甲烷与碳酸二甲酯甲氧基羰基化制备4,4′-二苯甲烷二氨基甲酸甲酯
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摘要
研究了4,4′-二氨基二苯甲烷(MDA)与碳酸二甲酯(DMC)甲氧基羰基化合成4,4′-二苯甲烷二氨基甲酸甲酯(MDC)的反应,研究了反应的影响因素,并采用FTIR、1 H NMR等测试方法对合成产物的结构进行了表征。结果表明,合成MDC的最佳反应工艺为反应温度160℃,用醋酸铅催化,且m(醋酸铅)∶m(MDA)=6%,反应物配比n(DMC)∶n(MDA)=20∶1,反应时间3h。在上述反应条件下,MDA的转化率达到100%,MDC的收率达到96.6%。
The reaction of 4,4′-diaminodiphenylmethane(MDA)and dimethyl carbonate(DMC)methoxycarbonylation to 4,4′-diphenylmethanedicarbamate(MDC)was studied.The influencing factors of the reaction were characterized by FTIR,1 H-NMR and other methods.The results show that the optimal reaction process for synthesizing MDC is:reaction temperature is 160℃,and m(lead acetate)∶m(MDA)is 6%,and the ratio of reactants is n(DMC)∶n(MDA)=20∶1.The reaction time is 3 h.Under the above reaction conditions,the conversion of MDA reached 100%,and the yield of MDC reached 96.6%.
The reaction of 4,4′-diaminodiphenylmethane(MDA)and dimethyl carbonate(DMC)methoxycarbonylation to 4,4′-diphenylmethanedicarbamate(MDC)was studied.The influencing factors of the reaction were characterized by FTIR,1 H-NMR and other methods.The results show that the optimal reaction process for synthesizing MDC is:reaction temperature is 160℃,and m(lead acetate)∶m(MDA)is 6%,and the ratio of reactants is n(DMC)∶n(MDA)=20∶1.The reaction time is 3 h.Under the above reaction conditions,the conversion of MDA reached 100%,and the yield of MDC reached 96.6%.
引文
[1]ECEIZA A,DE LA CABA K,KORTABERRIA G,et al.Influence of molecular weight and chemical structure of soft segment in reaction kinetics of polycarbonate diols with4,4′-diphenylmethane diisocyanate[J].Eur Polym,2005,41(12):3051-3059.
[2]李绍雄,刘益军.聚氨酯树脂及其应用[M].北京:化学工业出版社,2002:52-53,56-57.
[3]汪多仁.异氰酸酯MDI制造及市场概况[J].弹性体,1997,7(1):55-59.
[4]汪多仁.非光气法生产4,4′-二苯甲烷二异氰酸酯及产品应用[J].化工生产与技术,1996(2):38-41.
[5]PORTA F,CENINI S,et al.Reaction of dimethyl cabonate with amines catalyzed by metal centers[J].Gazz Chim Ital,1985,115(5):275-277.
[6]陈冠荣,时钧.化工百科全书[M].北京:化学工业出版社,1998:209-220.
[7]BRAVERMAN S,CHERKINSKY M.ChemInform abstract:Anovel synthesis of isocyanates and ureas visβ-elimination of haloform[J].Tetrahedron Letters,1990,40(18):3235-3238.
[8]Production of 4,4′-alkylidene diphenyldiisocyanate:US4163019[P].1979-07-31.
[9]KATADA N,FUJINAGA H,NAKAMURA Y,et al.Catalytic activity of mesoporous silica for synthesis of methyl N-phenyl carbamate from dimethyl carbonate and aniline[J].Catalysis Letters,2002,80(1/2):47-51.
[10]SELVA M,TUNDO P,PEROSA A.Reaction of functionalized anilines with dimethyl carbonate over Na Y FaujaSite.3.chemoselectivity toward mono-N-methylation[J].J Org Chem,2003,68(19):7374-7378.
[11]PEI Y X,LI H Q,LIU H T,et al.Kinetic study of methoxycarbonylation of methylene dianiline with dimethyl carbonate using lead acetate catalyst[J].Eng Chem Res,2011,50:1955-1961.
[12]BABA T,KOBAYASHI A,YAMAUCHI T,et al.Catalytic methoxycarbonylation of aromatic diamines with dimethyl carbonate to their dicarbamates using zinc acetate[J].Catalysis Letters,2002,82(3/4):193-197.
[13]BABA T,KOBAYASHI A,KAWANAMI Y,et al.Characteristics of methoxycarbonylation of aromatic diamine with dimethyl carbonate to dicarbamate using a zinc acetate catalyst[J].Green Chem,2005,7(3):159-165.
[14]TONTO P,MEKASUWANDUMRONG O,PHATANASRIS,et al.Preparation of ZnO nanorod by solvothermal reaction of zinc acetate in various alcohols[J].Ceram Int,2008,34(1):57-62.
[2]李绍雄,刘益军.聚氨酯树脂及其应用[M].北京:化学工业出版社,2002:52-53,56-57.
[3]汪多仁.异氰酸酯MDI制造及市场概况[J].弹性体,1997,7(1):55-59.
[4]汪多仁.非光气法生产4,4′-二苯甲烷二异氰酸酯及产品应用[J].化工生产与技术,1996(2):38-41.
[5]PORTA F,CENINI S,et al.Reaction of dimethyl cabonate with amines catalyzed by metal centers[J].Gazz Chim Ital,1985,115(5):275-277.
[6]陈冠荣,时钧.化工百科全书[M].北京:化学工业出版社,1998:209-220.
[7]BRAVERMAN S,CHERKINSKY M.ChemInform abstract:Anovel synthesis of isocyanates and ureas visβ-elimination of haloform[J].Tetrahedron Letters,1990,40(18):3235-3238.
[8]Production of 4,4′-alkylidene diphenyldiisocyanate:US4163019[P].1979-07-31.
[9]KATADA N,FUJINAGA H,NAKAMURA Y,et al.Catalytic activity of mesoporous silica for synthesis of methyl N-phenyl carbamate from dimethyl carbonate and aniline[J].Catalysis Letters,2002,80(1/2):47-51.
[10]SELVA M,TUNDO P,PEROSA A.Reaction of functionalized anilines with dimethyl carbonate over Na Y FaujaSite.3.chemoselectivity toward mono-N-methylation[J].J Org Chem,2003,68(19):7374-7378.
[11]PEI Y X,LI H Q,LIU H T,et al.Kinetic study of methoxycarbonylation of methylene dianiline with dimethyl carbonate using lead acetate catalyst[J].Eng Chem Res,2011,50:1955-1961.
[12]BABA T,KOBAYASHI A,YAMAUCHI T,et al.Catalytic methoxycarbonylation of aromatic diamines with dimethyl carbonate to their dicarbamates using zinc acetate[J].Catalysis Letters,2002,82(3/4):193-197.
[13]BABA T,KOBAYASHI A,KAWANAMI Y,et al.Characteristics of methoxycarbonylation of aromatic diamine with dimethyl carbonate to dicarbamate using a zinc acetate catalyst[J].Green Chem,2005,7(3):159-165.
[14]TONTO P,MEKASUWANDUMRONG O,PHATANASRIS,et al.Preparation of ZnO nanorod by solvothermal reaction of zinc acetate in various alcohols[J].Ceram Int,2008,34(1):57-62.