Study On Synthesis Of Complexes Of Diphenyl Alkyl Phosphine With Tungsten Hexachloride And Its Catalytic Polymerization Of Dicyclopentadiene

Polydicyclopentadiene?PDCPD?was a new material which was made by dicyclopentadiene?DCPD?through the method of ring opening metathesis polymerization.It had the excellent comprehensive physics properties.There are many varieties of catalysts for polymerization of DCPD,among which the double components catalyst system of tungsten phenolic compound and alkylaluminium was the most common.The main catalyst tungsten phenolic compound was sensitive to oxygen and water vapor,easily became inactivated.In order to improve the environment stability of main catalyst and the solubility in DCPD,in this paper,some sterically hindered organic phosphine ligands were used to coordinate with tungsten hexachloride,and gained a new type coordination catalyst which was environmental stability,and PDCPD was made through DCPD's polymerization.First,a series of diphenyl alkyl phosphine such as diphenyl butyl phosphine?Ph₂PC?4H?9?,diphenyl hexyl phosphine(Ph₂PC₆H₁₃),diphenyl octyl phosphine(Ph₂PC₈H₁₇),diphenyl decyl phosphine(Ph₂PC₁₀H₂₁),diphenyl dodecyl phosphine(Ph₂PC₁₂H₂₅)were synthesized by using triphenylphosphine as raw materials.The structures of the diphenyl alkyl phosphine were characterized by the methods of IR,¹HNMR,13 CNMR and 31 PNMR.Second,five new diphenyl alkyl phosphine/tungsten hexachloride complexes were synthesized by the coordination between five diphenyl alkyl phosphine and tungsten hexachloride,and the structures of the complexes were characterized,and the desired target product was confirmed.Third,the complexes of diphenyl alkyl phosphine/tungsten hexachloride were used as main catalyst?W catalyst for short?,aluminium diethyh monochloride as cocatalyst?Al catalyst for short?to catalyze DCPD's polymerization,the results showed that the complexes were active for polymerization,and possessed good solubility in DCPD and good stability in the air.Forth,the influences of different condition,such as the amount of main catalyst,cocatalyst and the reaction temperature on DCPD's polymerization were all investigated.The optimum reaction condition of every catalyst was explored.And the catalytic activity of five kind catalysts was compared.The results showed that the gel time of DCPD's polymerization decreased with the increase of the amount of primary catalyst,cocatalyst and the reaction temperature.The optimum molar ratio?n?DCPD?:n?W?:n?Al??of five catalytic systems?the carbon chain from short to long?on DCPD's polymerization were 1600:1.2:24,1600:1.2:20,1600:1:20,1200:1:20,1200:1:22.Therefore,the activity order of five new kind catalysts were diphenyl octyl phosphine/tungsten hexachloride>diphenyl hexyl phosphine/tungsten hexachloride>diphenyl butyl phosphine/tungsten hexachloride>diphenyl decyl phosphine/tungsten hexachloride>diphenyl dodecyl phosphine/tungsten hexachloride.Last,PDCPD was made from DCPD by using diphenyl octyl phosphine/tungsten hexachloride as main catalyst and aluminium diethyh monochloride as cocatalyst.The mechanical properties of the material were detected.The results showed that impact strength of the material was 30KJ/m2,and the average tensile strength was 43.75 MPa.