Controlled, Copper-Catalyzed Functionalization of Polyolefins

Copper, silver and gold-based catalysts for carbene addition or insertion reactions

“…However, the synthesis of those materials is quite difficult, since most of the common olefin polymerization catalysts are somewhat incompatible with many polar groups of the co-monomers. Because of this, we decided to investigate the potential of the carbene insertion methodology to the field of polyolefin modification [19], with the idea of inserting polar groups in the chains a posteriori, that is, after the polymer has been prepared. We started with a sample of polybutene [20], a very stereoregular polymer (one methyl branch every four carbons), and Tp Br3 Cu(NCMe) as the catalyst.…”

Catalytic cyclopropanation of polybutadienes

“…The oxyfunctionalization of polyethylenes and polypropylenes by metal‐based catalysts can afford hydroxyl groups 7. We have recently reported8 the functionalization of saturated polybutene and poly(ethylene‐1 octene) by insertion of :CHCO 2 Et into CH bonds employing commercially available ethyl diazoacetate (EDA) as the carbene source, using [Tp Br3 Cu(NCMe)] as a catalyst precursor (Tp Br3 = hydrotris(3,4,5‐tribromo‐1‐pyrazolyl)borate). Degrees of functionalization, which occurred on tertiary and secondary sites, were 4–10%.…”

C−H Functionalization of Commodity Polymers

“…PØrez and co-workers reported the copper-catalyzed generation of carbenes from ethyl diazoacetate (EDA) to achieve the addition of up to 13 mol %e ster groups onto various polyolefins ( Figure 7C). [91] Ther eaction was conducted at room temperature and resulted in tertiary regioselectivity for poly(2-butene) and secondary regioselectivity for poly(ethylene-1-octene). This switch in selectivity was attributed to the substantial increase in the number of methylene sites in poly(ethylene-1-octene) compared to poly(2-butene).…”