Cationic copolymerization of 1,1‐diphenylethylene with p‐substituted styrenes

Abstract

Controlled cationic copolymerization of nonpolymerizable 1,1‐diphenylethylene (DPE) with p‐methylstyrene or p‐tert‐butylstyrene was achieved using an EtAlCl2/SnCl4 initiating system at –78 °C. This is the first example of effective cationic copolymerization of DPE with other vinyl monomers.

Cationic Copolymerization of o-Phthalaldehyde and Vinyl Monomers with Various Substituents on the Vinyl Group or in the Pendant: Effects of the Structure and Reactivity of Vinyl Monomers on Copolymerization Behavior

“…Polymers obtained from monomers that have bulky structures around polymerizable groups are expected to exhibit specific properties, such as the rigid main chain and high thermal stability, compared to those obtained from normal monomers. − However, such bulky monomers are generally difficult to polymerize due to steric hindrance and low ceiling temperatures. Consequently, copolymerization is an effective strategy to obtain polymers from such bulky monomers; , however, when the comonomer or the bulky monomer does not have sufficient reactivity to react with the propagating species derived from the bulky monomer or the comonomer, respectively, copolymerization does not proceed . The use of appropriate comonomers, such as monomers with both high reactivity and small steric hindrance, is indispensable for successful copolymerization beyond the limitation of reactivity.…”

“… a Circles: homopolymerizable or copolymerizable alternatingly with benzaldehyde (BzA) derivatives; triangles: oligomer generation; crosses: no homopolymerizability, homopolymers of vinyl monomers (for pMOS, IPVE, and MPE), or no copolymerizability with BzAs (others); bars: not examined. b Reference c Reference . d Reference . e Reference . f Reference . g Reference . h Reference . i Reference . j Reference . k Reference . l Reference . …”

Living and Alternating Cationic Copolymerization of o-Phthalaldehyde and Various Bulky Enol Ethers: Elucidation of the “Limit” of Polymerizable Monomers

“…To form polymers from nonhomopolymerizable monomers with bulky substituents, copolymerization with other monomers has been widely utilized. For example, β-methylstyrene − or 1,1-diphenylethylene derivatives, − which are difficult to homopolymerize, have been copolymerized with styrene derivatives via radical, cationic, or anionic mechanisms. These copolymerizations were feasible due to mitigation of the steric hindrance.…”