The polymerization of alkyl isocyanates catalyzed by rare earth chloride salen complexes/triisobutyl aluminum(Ln(H2salen)2Cl3·2C2H7OH/Al(i-Bu)3) at room temperature was investigated.The influences of ligand structure,catalyst composition,polymerization temperature,polymerization time,the concentration of catalyst and monomer,and the polymerization solvent on the polymerization of isocyanates were studied.It was found that under the polymerization conditions,examined La(H2salenA)2Cl3·2C2-H7OH/Al(i-Bu)3(H2salenA= N,N’-disalicylideneethylene diamine) is a fairly high efficient catalyst for the polymerization of n-hexyl isocyanate(n-HexNCO) to prepare high molecular weight poly(n-hexyl isocyanate)(PHNCO) with narrower molecular weight distribution at room temperature.PHNCO could be prepared with yield of 74.0%,number-average molecular weight(Mn) of 40.20×104 and MWD of 1.79 under the following optimum conditions:[Al]/[La]=30(molar ratio),[n-HexNCO]/[La]=100(molar ratio),[n-HexNCO]=3.43 mol/L polymerization at 20℃ for 12 h in toluene.In the same polymerization conditions,poly(n-octyl isocyanate)(PONCO) with yield of 67.3%,and poly(n-butyl isocyanate)(PBNCO) with yield of 45.5%,could be prepared respectively.The kinetics of the polymerization of n-HexNCO was also investigated and found to be first-order with respect to both monomer and catalyst concentrations. The polymerization of alkyl isocyanates catalyzed by rare earth chloride salen complexes / triisobutyl aluminum (Ln (H2salen) 2Cl3.2C2H7OH / Al (i-Bu) 3) at room temperature was investigated.The influences of ligand structure, catalyst composition, polymerization time, the concentration of catalyst and monomer, and the polymerization solvent on the polymerization of isocyanates were studied. It was found that under the polymerization conditions, examined La (H2salenA) 2Cl3.2C2-H7OH / Al (i- Bu) 3 H2salenA = N, N’-disalicylideneethylene diamine is a fairly high efficient catalyst for the polymerization of n-hexyl isocyanate (n-HexNCO) to prepare high molecular weight poly (n-hexyl isocyanate) (PHNCO) with narrower molecular weight distribution at The room temperature. PHNCO could be prepared with yield of 74.0%, number-average molecular weight (Mn) of 40.20x104 and MWD of 1.79 under the following optimum conditions: [Al] / [La] = 30 (molar ratio) n-HexNCO] / [La] = 100 (molar ratio), [n-HexNCO] = 3.43 mol / L polymerization at 20 ° C for 12 h in toluene. In the same polymerization conditions, poly (n-octyl isocyanate) (PONCO) with yield of 67.3%, and poly %, could be prepared. The kinetics of the polymerization of n-HexNCO was also investigated and found to be first-order with respect to both monomer and catalyst concentrations.