Kinetic Analysis of “Living” Polymerization Processes Exhibiting Slow Equilibria. 6. Cationic Polymerization Involving Covalent Species, Ion Pairs, and Free Cations†

1996 ◽  
Vol 29 (25) ◽  
pp. 8057-8063 ◽  
Author(s):  
Deyue Yan ◽  
Hai Dong ◽  
Peng Ye ◽  
Axel H. E. Müller
Polymers ◽  
2018 ◽  
Vol 10 (12) ◽  
pp. 1404 ◽  
Author(s):  
Hisaaki Takeshima ◽  
Kotaro Satoh ◽  
Masami Kamigaito

In this study, we investigated direct-controlled/living cationic polymerization and copolymerization of 4-vinylguaiacol (4VG), i.e., 4-hydroxy-3-methoxystyrene, which can be derived from naturally-occurring ferulic acid, to develop novel bio-based amphiphilic polystyrenes with phenol functions. The controlled/living cationic polymerization of 4VG was achieved using the R–OH/BF3·OEt2 initiating system, which is effective for the controlled/living polymerization of petroleum-derived 4-vinylphenol in the presence of a large amount of water via reversible activation of terminal C–OH bond catalyzed by BF3·OEt2, to result in the polymers with controlled molecular weights and narrow molecular weight distributions. The random or block copolymerization of 4VG was also examined using p-methoxystyrene (pMOS) as a comonomer with an aqueous initiating system to tune the amphiphilic nature of the 4VG-derived phenolic polymers. The obtained polymer can be expected not only to be used as a novel styrenic bio-based polymer but also as a material with amphiphilic nature for some applications.


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