Preparation and Aromatization of Poly-1,3-cyclohexadiene¹

How well can renewable resources mimic commodity monomers and polymers?

“…Anionic, free-radical, and transition metal catalyzed polymerizations are common methods for polymerizing 1,3-CHD. [90][91][92][93][94][95] Anionic polymerization methods result in microstructures with 1,2 and 1,4-linkages whereas certain metal-based catalysts can produce predominately 1,4-linkages. The presence of 1,4-sequences in the polymer can serve as a precursor to polyparaphenylene.…”

“…90,96 Recently, a renewable method for the synthesis and polymerization of 1,3-CHD was reported. 97 As shown in Figure 9, plant oils, such as soybean, corn, and canola oils, contain polyunsaturated triglycerides which will react with metathesis catalysts to produce 1,4-CHD.…”

Synthesis and Polymerization of Renewable 1,3‐Cyclohexadiene Using Metathesis, Isomerization, and Cascade Reactions with Late‐metal Catalysts

“…As a result, a polymerization was examined with transition metal catalyst systems rather than alkyllithium initiated anionic polymerizations which are known to undergo chain transfer with 1,4-CHD. [38] Early transition metal catalysts, such as Et(Ind) 2 2 ] will polymerize styrene, 1,3-butadiene, and 1,3-CHD. [39,40] In Table 1, the polymerization of renewable 1,3-CHD (4) was successful even in the presence of 1,4-CHD (1) and dodecene isomers (2-3).…”

“…Strategies for polymerizing 1,3-CHD involve anionic, cationic, and freeradical mechanisms, as well as polymerizations conducted with rare-earth and transition metal catalysts. [1][2][3][4][5][6] Much of the interest in polycyclohexadiene (polyCHD) stems from the excellent physical properties that cyclic monomers impart to polymers and the ability to transform polyCHD into conducting polymers and proton conductors. [7,8] Numerous synthetic methods have been reported for the synthesis of 1,3-CHD that utilize dehydrohalogenation, dehydration, and oxidation reactions.…”

Poly(1,3-cyclohexadiene-alt-alpha-fluoroacrylonitrile): Synthesis and Structural Analysis of a New Alternating Copolymer

“…12,13 The resultant cyclohexene ring on the main chain provides a unit which, under severe conditions, may be convened to a phenylene ring. 14 As such, it is of importance to obtain a detailed understanding of the structure of 1,3-CHD/acceptor olefin alternating polymers. We have been interested in examining the effect of localized dipoles on the dielectric properties of polymer films.…”