Study On New Non-Metallocene Catalyst For Ternary Copolymerization Of Ethelene Propylene With Polar Monomer

Functional polyolefin had attracted much attention in the scientific research and industrial production due to its unique properties, and the most critical problem we encountered was the choice of catalysts when prepared by direct copolymerization method. In this paper, we designed and synthesized two novel non-metallocene ligands, reacting with metal elements (Ti, Zr, Pd, Nd) chloride to get eight five-numbered heterocyclic ring catalysts, and these non-metallocene catalysts were used to catalyze ternary copolymerization of ethylene, propylene with polar monomers after activated by MAO. Polar monomers were chose from chlorinated olefins (7-chloro-1-heptene, 9-chloro-1-nonene and 11-chloro-1-undecylene) and hydroxy-substituted olefins(4-penten-1-ol,5-hexen-1-ol and 9-decen-1-ol). The structure and composition of ligand and catalyst were characterized by NMR, EA and MS, and the structure and property of the copolymer were identified by NMR, FT-IR, GPC, DSC, and so on. The effects of ligand structure, metal element (M= Ti, Zr, Pd, Nd), and polymerization conditions (copolymerization temperature, Al/M ratio in mole, length of carbon chain and concentration of polar monomer) on the polymerization behaviors were investigated in detail.New non-metallocene catalyst showed good catalytic activity when catalyzing binary copolymerization of ethylene with propylene and ternary copolymerization of ethylene, propylene with polar monomer, wherein the highest activity of ethylene-propylene copolymerization reached 2.24×105g P /mol·Nd·h. when talking about the ternary copolymerization, with the increase of methylene carbon atoms between carbon double bond and the polar group in polar monomers, the catalytic activity increases. The late transition metal catalyst L2-Pd had the highest activities when catalyzing ternary copolymerization of ethylene, propylene with 11-chloro-1-undecene and ethylene, propylene with 9-decene-1-ol under the optimum reaction conditions (polymerization temperature,50?; nAl/nM,500;catalyst concentration,2×10-4mol/L; the concentration of pretreatment polar monomer, 0.3 mol/L), which were 4.53×104 g P/mol·Pd·h and 4.21×104g P/mol·Pd·h. DSC results showed that the two terpolymers melting points were 102.9? and 101.3 ? respectively. The results confirmed that the highest insert amount of two polar monomers in terpolymers were up to 5.35 and 4.72 mol% in turn. Melting temperature of the terpolymer depended on the content of polar monomer incorporation within the copolymer chain.