Optical Purity as a Programmable Variable for Controlling Polyolefin Tacticity in Living Coordinative Chain Transfer Polymerization: Application to the Stereomodulated LCCTP of α,ω-Nonconjugated Dienes

Abstract

Two-state, stereomodulated living coordinative chain transfer polymerization (LCCTP) of 1,6-heptadiene has been achieved to produce a series of cis-poly(methylene-1,3-cyclohexane) (cis-PMCH) with stereochemical microstructures that vary between two limiting forms as a function of the optical purity of the chiral C1-symmetric hafnium preinitiator 1 when activated by the borate co-initiator B1 in the presence of a fixed excess amount of ZnEt2. Optical purity as a programmable variable was demonstrated by premixing the pure homochiral (SC,SHf) and (RC,RHf) enantiomers of 1 in different ratios prior to activation. In contrast, the LCCTP of 1,5-hexadiene using a “racemic” mixture of 1 to produce cis/trans-poly(methylene-1,3-cyclopentane) (cis/trans-PMCP) was less successful due to the loss of stereocontrol for insertion under chain transfer conditions that arises with site epimerization at the transition metal center. A correlation is proposed between the diastereoselectivity and efficiency for the cyclization step in propagation and the magnitude of site epimerization due to reversible chain transfer. These results serve to validate the strategy of using the optical purity of an initiator as a programmable parameter for controlling polyolefin tacticity as well as to better establish the criteria that are required for achieving successful stereomodulated LCCTP for the production of next generation polyolefin materials.