[ONSO]型金属铝配合物催化环氧环己烷与酸酐共聚制备聚醚
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摘要
设计合成了3种[ONSO]型金属铝配合物,通过核磁共振氢谱(1H-NMR)、傅里叶变换红外光谱仪(FT-IR)、紫外可见分光光度计(UV-vis)和液质联用仪(HPLC-MS)对金属铝配合物进行了表征。将其作为催化剂考察在环氧环己烷(CHO)和邻苯二甲酸酐(PA)聚合反应中的催化行为。使用配合物1详细考察了聚合时间、反应温度等条件对聚合反应活性的影响,所得聚合物采用1H-NMR、FT-IR和凝胶渗透色谱(GPC)进行表征。结果显示,所得聚合物聚醚含量为98%,单位时间内每摩尔催化剂转化的单体数(TOF)最高可达2475 h-1,Mw最高可达3. 2×105,相对分子质量分布最低为2. 0,聚合反应动力学研究结果表明,该聚合反应对单体呈一级反应,活化能为13. 91 k J/mol。
Three kinds of aluminum complexes bearing [ONSO]-type ligands were synthesized. They were characterized by1H-NMR,FT-IR,UV-vis and HPLC-MS. The complex was used in the polymerization of cyclohexene oxide and phthalic anhydride as catalysts. The reaction parameters,such as different polymerization temperature,mole ratio and polymerization time were employed in order to study the influences on the polymerization activity. The polymers obtained were characterized by1H-NMR,FT-IR,and GPC. The results show that polyether linkage of obtained polymer is98%,the turnover frequency of epoxide to products( TOF) is highly up to 2475 h-1,weight average molecular weight( Mw) could reach 3. 2 × 105 and polydispersity is around 2. 0. The kinetic behavior of complex 1 was investigated and the results show that the polymerization reaction for monomer is first-order reaction and the activation energy is 13. 91kJ/mol.
Three kinds of aluminum complexes bearing [ONSO]-type ligands were synthesized. They were characterized by1H-NMR,FT-IR,UV-vis and HPLC-MS. The complex was used in the polymerization of cyclohexene oxide and phthalic anhydride as catalysts. The reaction parameters,such as different polymerization temperature,mole ratio and polymerization time were employed in order to study the influences on the polymerization activity. The polymers obtained were characterized by1H-NMR,FT-IR,and GPC. The results show that polyether linkage of obtained polymer is98%,the turnover frequency of epoxide to products( TOF) is highly up to 2475 h-1,weight average molecular weight( Mw) could reach 3. 2 × 105 and polydispersity is around 2. 0. The kinetic behavior of complex 1 was investigated and the results show that the polymerization reaction for monomer is first-order reaction and the activation energy is 13. 91kJ/mol.
引文
[1]Baker R J,Walshe A.New reactivity of the uranyl ion:ring opening polymerisation of epoxides[J].Chem.Commun.,2012,48:985-987.
[2]Cui D M,Nishiura M,Hou Z M.Alternating copolymerization of cyclohexene oxide and carbon dioxide catalyzed by organo rare earth metal complexes[J].Macromolecules,2005,38:4089-4095.
[3]Thiam M,Spassky N.Polymerization of cyclohexene oxide using yttrium isopropoxide and a bimetallic yttrium-aluminium isopropoxide as initiators[J].Macromol.Chem.Phys.,1999,200:2107-2110.
[4]房江华,胡富陶.Fe-Al-α,α'-联吡啶体系催化邻苯二甲酸酐与环氧环己烷开环共聚反应[J].催化学报,2002,23(1):88-90.Fang J H,Hu F T.Ring-opening copolymerization of phthalic anhydride with cyclohexene oxide catalyzed by Fe-Al-α,α'-dipyridine catalyst[J].Chinese Journal of Catalysis,2002,23(1):88-90.
[5]Ikpo N,Barbon S M,Drover M W,et al.Aluminum methyl and chloro complexes bearing monoanionic aminephenolate ligands:synthesis,characterization,and use in polymerizations[J].Organometallics,2012,31:8145-8158.
[6]Doherty S,Errington R J,Housley N,et al.Dimeric aluminum chloride complexes of N-alkoxyalkyl-β-ketoimines:activation with propylene oxide to form efficient lactide polymerization catalysts[J].Organometallics,2004,23:2382-2388.
[7]Zevaco T A,Sypien J K,Janssen A.Synthesis,structural characterisation of new oligomeric alkyl aluminium(2,2'-methylenep-chloro-bisphenoxides)and application as catalysts in polymerisation reactions involving cyclohexene oxide[J].J.Organomet.Chem.,2007,692:1963-1973.
[8]Sarbu T,Beckman E J.Homopolymerization and copolymerization of cyclohexene oxide with carbon dioxide using zinc and aluminum catalysts[J].Macromolecules,1999,32:6904-6912.
[9]Wasserman E P,Annis I,Chopin L J,et al.Ethylene oxide polymerization catalyzed by aluminum complexes of sulfur-bridged polyphenols[J].Macromolecules,2005,38:322-333.
[10]Han B,Zhang L,Kyran S J,et al.Copolymerization of carbon dioxide and cyclohexene oxide catalyzed by chromium complexes bearing semirigid[ONSO]-type ligands[J].J.Polym.Sci.:Polm.Chem.,2016,54:1938-1944.
[11]Aouissi A,Al-Othman Z A,Salhabi A.Keggin-type heteropolyacid for ring-opening polymerization of cyclohexene oxide:molecular weight control[J].Int.J.Polym.Sci.,2015,2015:826512.
[12]Isnard F,Lamberti M,Lettieri L.Bimetallic salen aluminum complexes:cooperation between reactive centers in the ring-opening polymerization of lactides and epoxides[J].Dalton Trans.,2016,45:16001-16010.
[13]Sarazin Y,Schormann M,Bochmann M.Novel zinc and magnesium alkyl and amido cations for ring-opening polymerization reactions[J].Organometallics,2004,23:3296-3302.
[14]Farrow E,Sarazin Y,Hughes D L.Synthesis and structure of[Cp2Zr(OPr i)(HOPr i)]+and its activity in the polymerisation of propene oxide[J].J.Organomet.Chem.,2004,689:4624-4629.
[15]Kuran W.Coordination polymerization of heterocyclic and heterounsaturated monomers[J].Prog.Polym.Sci.,1998,23:919-992.
[16]Thiam M,Spassky N.Polymerization of cyclohexene oxide using yttrium isopropoxide and a bimetallic yttrium-aluminium isopropoxide as initiators[J].Macromol.Chem.Phys.,1999,200:2107-2110.
[17]Cui D,Nishiura M,Hou Z.Alternating copolymerization of cyclohexene oxide and carbon dioxide catalyzed by organo rare earth metal complexes[J].Macromolecules,2005,38:4089-4095.
[18]Munoz-Hernandez M A,Mc Kee M L.Six-coordinate aluminium cations:characterization,catalysis,and theory[J].J.Chem.Soc.,Dalton Trans.,2002,3:410-414.
[2]Cui D M,Nishiura M,Hou Z M.Alternating copolymerization of cyclohexene oxide and carbon dioxide catalyzed by organo rare earth metal complexes[J].Macromolecules,2005,38:4089-4095.
[3]Thiam M,Spassky N.Polymerization of cyclohexene oxide using yttrium isopropoxide and a bimetallic yttrium-aluminium isopropoxide as initiators[J].Macromol.Chem.Phys.,1999,200:2107-2110.
[4]房江华,胡富陶.Fe-Al-α,α'-联吡啶体系催化邻苯二甲酸酐与环氧环己烷开环共聚反应[J].催化学报,2002,23(1):88-90.Fang J H,Hu F T.Ring-opening copolymerization of phthalic anhydride with cyclohexene oxide catalyzed by Fe-Al-α,α'-dipyridine catalyst[J].Chinese Journal of Catalysis,2002,23(1):88-90.
[5]Ikpo N,Barbon S M,Drover M W,et al.Aluminum methyl and chloro complexes bearing monoanionic aminephenolate ligands:synthesis,characterization,and use in polymerizations[J].Organometallics,2012,31:8145-8158.
[6]Doherty S,Errington R J,Housley N,et al.Dimeric aluminum chloride complexes of N-alkoxyalkyl-β-ketoimines:activation with propylene oxide to form efficient lactide polymerization catalysts[J].Organometallics,2004,23:2382-2388.
[7]Zevaco T A,Sypien J K,Janssen A.Synthesis,structural characterisation of new oligomeric alkyl aluminium(2,2'-methylenep-chloro-bisphenoxides)and application as catalysts in polymerisation reactions involving cyclohexene oxide[J].J.Organomet.Chem.,2007,692:1963-1973.
[8]Sarbu T,Beckman E J.Homopolymerization and copolymerization of cyclohexene oxide with carbon dioxide using zinc and aluminum catalysts[J].Macromolecules,1999,32:6904-6912.
[9]Wasserman E P,Annis I,Chopin L J,et al.Ethylene oxide polymerization catalyzed by aluminum complexes of sulfur-bridged polyphenols[J].Macromolecules,2005,38:322-333.
[10]Han B,Zhang L,Kyran S J,et al.Copolymerization of carbon dioxide and cyclohexene oxide catalyzed by chromium complexes bearing semirigid[ONSO]-type ligands[J].J.Polym.Sci.:Polm.Chem.,2016,54:1938-1944.
[11]Aouissi A,Al-Othman Z A,Salhabi A.Keggin-type heteropolyacid for ring-opening polymerization of cyclohexene oxide:molecular weight control[J].Int.J.Polym.Sci.,2015,2015:826512.
[12]Isnard F,Lamberti M,Lettieri L.Bimetallic salen aluminum complexes:cooperation between reactive centers in the ring-opening polymerization of lactides and epoxides[J].Dalton Trans.,2016,45:16001-16010.
[13]Sarazin Y,Schormann M,Bochmann M.Novel zinc and magnesium alkyl and amido cations for ring-opening polymerization reactions[J].Organometallics,2004,23:3296-3302.
[14]Farrow E,Sarazin Y,Hughes D L.Synthesis and structure of[Cp2Zr(OPr i)(HOPr i)]+and its activity in the polymerisation of propene oxide[J].J.Organomet.Chem.,2004,689:4624-4629.
[15]Kuran W.Coordination polymerization of heterocyclic and heterounsaturated monomers[J].Prog.Polym.Sci.,1998,23:919-992.
[16]Thiam M,Spassky N.Polymerization of cyclohexene oxide using yttrium isopropoxide and a bimetallic yttrium-aluminium isopropoxide as initiators[J].Macromol.Chem.Phys.,1999,200:2107-2110.
[17]Cui D,Nishiura M,Hou Z.Alternating copolymerization of cyclohexene oxide and carbon dioxide catalyzed by organo rare earth metal complexes[J].Macromolecules,2005,38:4089-4095.
[18]Munoz-Hernandez M A,Mc Kee M L.Six-coordinate aluminium cations:characterization,catalysis,and theory[J].J.Chem.Soc.,Dalton Trans.,2002,3:410-414.