497232-72-1Relevant academic research and scientific papers
Reaction of vinyl chloride with group 4 metal olefin polymerization catalysts
Stockland Jr., Robert A.,Foley, Stephen R.,Jordan, Richard F.
, p. 796 - 809 (2003)
The reactions of three types of group 4 metal olefin polymerization catalysts, (C5R5)2ZrX2/activator, (C5Me5)TiX3/MAO (MAO = methylalumoxane), and (C5Me4SiMe2NtBu) MX2/activator (M = Ti, Zr), with vinyl chloride (VC) and VC/propylene mixtures have been investigated. Two general pathways are observed: (i) radical polymerization of VC initiated by radicals derived from the catalyst and (ii) net 1,2 VC insertion into LnMR+ species followed by β-Cl elimination, rac-(EBI)ZrMe(μ-Me)B(C6F5)3. (EBI = 1,2-ethylenebis-(indenyl)) reacts with 2 equiv of VC to yield oligopropylene, rac-(EBI)ZrCl2, and B(C6F5)3. This reaction proceeds by net 1,2 VC insertion into rac-(EBI)ZrMe+ followed by fast β-Cl elimination to yield [rac-(EBI)- ZrCl][MeB(C6F5)3] and propylene. Methylation of rac-(EBI)ZrCl+ by MeB(C6F5)3- enables a second VC insertion/β-Cl elimination to occur. The evolved propylene is oligomerized by rac-(EBI)ZrR+ as it is formed. At high Al/Zr ratios, rac-(EBI)ZrMe2/MAO catalytically converts VC to oligopropylene by 1,2 VC insertion into rac-(EBI)ZrMe+, β-Cl elimination, and realkylation of rac-(EBI)ZrCl+ by MAO; this process is stoichiometric in Al-Me groups. The evolved propylene is oligomerized by rac-(EBI)ZrR+. Oligopropylene end group analysis shows that the predominant chain transfer mechanism is VC insertion/β-Cl elimination/realkylation. In the presence of trace levels of O2, rac-(EBI)ZrMe2/MAO polymerizes VC to poly(vinyl chloride) (PVC) by a radical mechanism initiated by radicals generated by autoxidation of Zr-R and/or Al-R species. Cp*TiX3/MAO (Cp* = C5Me5; X = OMe, Cl) initiates radical polymerization of VC in CH2Cl2 solvent at low Al/Ti ratios under anaerobic conditions; in this case, the source of initiating radicals is unknown. Radical VC polymerization can be identified by the presence of terminal and internal allylic chloride units and other radical defects in the PVC which arise from the characteristic chemistry of PCH2CHCl? macroradicals. However, this test must be used with caution, since the defect units can be consumed by postpolymerization reactions with MAO. (C5Me4SiMe2NtBu) MMe2/[Ph3C]][B(C6F5)4] catalysts (M = Ti, Zr) react with VC by net 1,2 insertion/β-Cl elimination, yielding [(C5Me4SiMe2NtBu) MCl][B(C6F5)4] species which can be trapped as (C5Me4SiMe2NtBu)MCI2 by addition of a chloride source. The reaction of rac-(EBI)ZrMe2/MAO or [(C5Me4- SiMe2NtBu)ZrMe][B(C6 F5)4] with propylene/VC mixtures yields polypropylene containing both allylic and vinylidene unsaturated chain ends rather than strictly vinylidene chain ends, as observed in propylene homopolymerization. These results show that the VC insertion of LnM(CH2CHMe)nR+ species is also followed by β-Cl elimination, which terminates chain growth and precludes propylene/VC copolymerization. Termination of chain growth by β-Cl elimination is the most significant obstacle to metal-catalyzed insertion polymerization/copolymerization of VC.
