Photoinitiated Cationic Polymerization of Mono and Divinyl Ethers in Aqueous Medium Using Ytterbium Triflate as Lewis Acid

Kahveci, Muhammet U.; Taşdelen, Mehmet Atilla; Cook, Wayne D.; Yaǧcı, Yusuf

doi:10.1002/macp.200800304

Cited by 35 publications

(10 citation statements)

References 24 publications

(50 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Yb(OTf) 3 was the first water‐tolerant Lewis acid successfully used to catalyze the slow (several days) cationic polymerization of p MOS in aqueous suspension3 or emulsion at 30 °C 4. Apart from p MOS, only isobutyl vinyl ether could be polymerized under similar conditions3a, 5 but with limited reproducibility 6. Such lack of reactivity was attributed to the complete dissociation of the Yb(OTf) 3 salt in water with the formation of a hydrated Yb cation,7 which is a weak Lewis acid.…”

Section: Methodsmentioning

confidence: 99%

A Catalyst Platform for Unique Cationic (Co)Polymerization in Aqueous Emulsion

et al. 2015

View full text Add to dashboard Cite

Sodium dodecyl benzene sulfonate (DBSNa) surfactants, with a polydisperse and hyperbranched structure, combined with different rare earth metal salts generate highly water-dispersible Lewis acid surfactant combined catalysts (LASCs). This platform of new complexes promotes fast, efficient cationic polymerization of industrially relevant monomers in direct emulsion at moderate temperature. The process described here does not require high shearing, long polymerization time, or large catalyst content. It allows the reproducible generation of high-molar-mass homopolymers of pMOS, styrene, and isoprene, as well as random or multiblock copolymers of the latter two, in a simple and straightforward one-pot reaction.

show abstract

Section: Methodsmentioning

confidence: 99%

A Catalyst Platform for Unique Cationic (Co)Polymerization in Aqueous Emulsion

et al. 2015

View full text Add to dashboard Cite

show abstract

“…As a result, the cationic polymerization proceeds in a controlled/living manner with suppressed chain-breaking reactions due to the coordination of Lewis acids, leading to polymers with controlled molecular weight properties (Scheme ). Various approaches have been reported in this regard which include direct photolysis of onium salts, − free radical promoted, photosensitization, and other approaches such as the use of substituted vinyl halides , to generate the initiating protonic acid species.…”

Section: Photoinitiation Of Chain Polymerization By Photoinduced Elec...mentioning

confidence: 99%

Photoinduced Electron Transfer Reactions for Macromolecular Syntheses

2016

Self Cite

View full text Add to dashboard Cite

Photochemical reactions, particularly those involving photoinduced electron transfer processes, establish a substantial contribution to the modern synthetic chemistry, and the polymer community has been increasingly interested in exploiting and developing novel photochemical strategies. These reactions are efficiently utilized in almost every aspect of macromolecular architecture synthesis, involving initiation, control of the reaction kinetics and molecular structures, functionalization, and decoration, etc. Merging with polymerization techniques, photochemistry has opened up new intriguing and powerful avenues for macromolecular synthesis. Construction of various polymers with incredibly complex structures and specific control over the chain topology, as well as providing the opportunity to manipulate the reaction course through spatiotemporal control, are one of the unique abilities of such photochemical reactions. This review paper provides a comprehensive account of the fundamentals and applications of photoinduced electron transfer reactions in polymer synthesis. Besides traditional photopolymerization methods, namely free radical and cationic polymerizations, step-growth polymerizations involving electron transfer processes are included. In addition, controlled radical polymerization and "Click Chemistry" methods have significantly evolved over the last few decades allowing access to narrow molecular weight distributions, efficient regulation of the molecular weight and the monomer sequence and incredibly complex architectures, and polymer modifications and surface patterning are covered. Potential applications including synthesis of block and graft copolymers, polymer-metal nanocomposites, various hybrid materials and bioconjugates, and sequence defined polymers through photoinduced electron transfer reactions are also investigated in detail.

show abstract

“…The Fors group reported LCPs controlled by an external stimulus including light , and electricity . The Yagci group developed LCPs starting from a photoinduced radical oxidation process. − Although recent innovations provide PVEs with degradable backbones, , nonmetal contamination, − good mechanical performance, spatiotemporal controlled chain length, and many other outstanding features, − these methods could be difficult in generating PVEs with various terminal groups under general reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

Thienyl Chloride Initiated Living Cationic Polymerization: A General and Efficient Access toward Terminally Functionalized Poly(vinyl ether)s

et al. 2020

View full text Add to dashboard Cite

Poly(vinyl ether)s (PVEs) are useful materials of different applications. In this work, we have developed a versatile and highly efficient initiation approach based on thienyl chloride derivatives with readily available starting materials for the living cationic polymerization of vinyl ethers. The resulting polymers exhibited precise chemical structures, predetermined molecular weights, and narrow molecular weight distributions at complete monomer conversions, allowing in situ chain extension to give diblock copolymers in several minutes. The synthetic advances of this method enable highly efficient connection of aryl, benzyl, and alkyl groups, as well as other functional substituents onto PVEs' terminals, and also facilitate the preparation of di-end-functional polymers. Furthermore, the high chain-end fidelity allows post-synthetic modifications through diverse pathways, such as RAFT polymerization, photocontrolled radical polymerization, Ni-catalyzed Negishi cross-couplings, and Pd-catalyzed Suzuki−Miyaura cross-couplings. While the incorporation of PVEs could bring macromolecules interesting properties, this method provides a new and simple pathway for materials engineering with such segments. Article pubs.acs.org/Macromolecules

show abstract

Photoinitiated Cationic Polymerization of Mono and Divinyl Ethers in Aqueous Medium Using Ytterbium Triflate as Lewis Acid

Cited by 35 publications

References 24 publications

A Catalyst Platform for Unique Cationic (Co)Polymerization in Aqueous Emulsion

A Catalyst Platform for Unique Cationic (Co)Polymerization in Aqueous Emulsion

Photoinduced Electron Transfer Reactions for Macromolecular Syntheses

Thienyl Chloride Initiated Living Cationic Polymerization: A General and Efficient Access toward Terminally Functionalized Poly(vinyl ether)s

Contact Info

Product

Resources

About