Alternating-like Cationic Copolymerization of Styrene Derivatives and Benzaldehyde: Precise Synthesis of Selectively Degradable Copoly(styrenes)

Abstract

Cationic copolymerizations of styrene derivatives and benzaldehyde (BzA) were systematically investigated for the purpose of both achieving living alternating copolymerization and creating "degradable polystyrene derivatives". As a result of the optimization of reaction conditions, the copolymerization of pmethylstyrene (pMeSt) and BzA was demonstrated to proceed in a living manner with GaCl 3 as a catalyst in the presence of tetrahydropyran, yielding a copolymer with a nearly alternating sequence and a controllable molecular weight. sec-Benzylic ether structures were generated in the main chain of the copolymer due to the crossover reactions between the monomers; hence, the copolymer was degraded into low-molecular-weight compounds under acidic conditions. In addition, the copolymer exhibited a glass transition temperature and degradation temperature that were comparable to those of the pMeSt homopolymer.

Synthesis and characterization of zwitter ion functionalized Poly(styrene) based random co-polymer: One pot method

“…Copolymer between styrene and benzaldehyde was reported in the literature [24] . Similarly, copolymers of styrene with 1,3-butadiene [25] , styrenesulfonicacid [26] and poly(glycidol) [27] were reported in the year 2022.…”

Umpolung Isomerization in Radical Copolymerization of Benzyl Vinyl Ether with Pentafluorophenylacrylate Leading to Degradable AAB Periodic Copolymers

“…In most cases, the resultant (co)polymers are made of the repetitive carbon–carbon bond, and the robust backbone causes difficulty in the decomposition into low molecular weight compounds, i.e., monomers or other valuable chemicals. Recently, some efforts have been made to introduce the cleavable bond in the repetitive carbon‐carbon bonded backbone [35–58] or the trigger in the pendant [59–66] /terminal [67–72] for the promotion of backbone decomposition. For example, the use of a cyclic ketene acetal as a co‐monomer in radical polymerization of commodity olefin monomer allows the introduction of ester bonds in the backbone, and thus the resultant copolymer becomes degradable under basic conditions (Figure 1B).…”

Synthesis and Degradation of Vinyl Polymers with Evenly Distributed Thioacetal Bonds in Main Chains: Cationic DT Copolymerization of Vinyl Ethers and Cyclic Thioacetals

“…To overcome this issue, various strategies for providing or triggering degradation to vinyl polymers have been proposed. [ 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ] Among them, copolymerization of heteroatom‐containing cyclic monomers with common vinyl monomers, by which labile carbon‐heteroatom bonds can be introduced via ring opening of the cyclic structures, is one of the most efficient methods. [ 23 , 24 , 25 , 26 ] Various cyclic compounds, which are copolymerizable via ring‐opening reactions, have been developed to date and include cyclic ketene acetals,[ 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 ] thionolactones,[ 41 , 42 , 43 , 44 , 45 , 46 , 47 ] and cyclic allylic sulfur compounds[ 48 , 49 , 50 , 51 , …”