Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases

Ντέτσικας, Κωνσταντίνος; Alzahrany, Yahya; Polymeropoulos, George; Bilalis, Panayiotis; Gnanou, Yves; Hadjichristidis, N.

doi:10.3390/polym9100538

Cited by 18 publications

(14 citation statements)

References 57 publications

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“…It has been shown that the rate of polymerization of styrene, initiated by carbanions, is accelerated in the presence of Lewis bases, such us ethers and amines . In our previous report, the anionic polymerization of styrene, in benzene at room temperature (23 °C), with sec ‐BuLi in the presence of superbases ( t ‐BuP 4 , t ‐BuP 2 , and t ‐BuP 1 ) with phosphazene /sec ‐BuLi: 0.5 (t ‐BuP 2 and t ‐BuP 1 ) and 1 ( t ‐BuP 4 , t ‐BuP 2 , and t ‐BuP 1 ) ratios, was studied . In the case of t ‐BuP 2 and t ‐BuP 1 , the results were comparable to the ones already published for Lewis bases .…”

Section: Resultsmentioning

confidence: 99%

Ultrafast phosphazene‐promoted controlled anionic polymerization of styrenic monomers

Ντέτσικας

Polymeropoulos

Ζάψας

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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This manuscript is dedicated to Professor Mitsuo Sawamoto's outstanding achievements in polymer chemistry and recognizes his recent retirement from 40 years of exceptional service to Kyoto University.ABSTRACT: The anionic polymerization of styrenic monomers with phosphazene bases as promoters, utilizing "seeding" technique in a nonpolar solvent and at room temperature was studied. In all experiments, the phosphazene base (t-BuP 4 , t-BuP 2 , and t-BuP 1 ) was added in an equimolar amount to the organolithium initiator after the formation of oligomers (2 min) by conventional anionic polymerization. When t-BuP 4 was used, the polymerization of styrene and 4-methylstyrene was extremely fast (100 % conversion within 5 min) and the final homopolymers exhibited narrow molecular weight distribution and controlled molecular characteristics.Likewise, when weaker bases were employed, the polymerization was also controlled but showing slower reaction rate. To examine the "livingness" of this system, block copolymers were synthesized by sequential monomer addition. Further studies were conducted in order to extend this novel method to the anionic polymerization of dienes.

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Section: Resultsmentioning

confidence: 99%

Ultrafast phosphazene‐promoted controlled anionic polymerization of styrenic monomers

Ντέτσικας

Polymeropoulos

Ζάψας

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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“…PS- b -PEO number-average molecular weight ( M n ) = 80- b -30 (110 kDa) and PS- b -PEO M n = 58- b -22 (80 kDa) were synthesized by anionic polymerization via high-vacuum living anionic polymerization of styrene in benzene using sec -BuLi as the initiator at RT for 6 h followed by polymerization of ethylene oxide in the presence of t- BuP 4 at 45 °C for 48 h. , All other polymers used in this study, PS- b -PEO M n = 102- b -34 (136 kDa), PS- b -PEO M n = 480- b -227 (707 kDa), polystyrene- block -poly(2-vinylpyridine) (PS- b -P2VP) M n = 79- b -36 (115 kDa), PS M n = 35 kDa, PS M n = 113 kDa, and PS M n = 173 kDa, were purchased from Polymer Source Inc. and used as received. All solvents and additives were purchased from Sigma-Aldrich and used as received.…”

Section: Methodsmentioning

confidence: 99%

“…Materials. PS-b-PEO number-average molecular weight (M n ) = 80-b-30 (110 kDa) and PS-b-PEO M n = 58-b-22 (80 kDa) were synthesized by anionic polymerization via high-vacuum living anionic polymerization of styrene in benzene using sec-BuLi as the initiator at RT for 6 h followed by polymerization of ethylene oxide in the presence of t-BuP 4 at 45 °C for 48 h. 30,31 and used as received. All solvents and additives were purchased from Sigma-Aldrich and used as received.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Strain-Induced Nanocavitation in Block Copolymer Thin Films for High Performance Filtration Membranes

Weller

Galuska

et al. 2021

ACS Appl. Polym. Mater.

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A new pore formation process was investigated for the manufacture of composite ultrafiltration membranes. Phase-separated block copolymer (BCP) thin films supported on a compliant macroporous poly(ether sulfone) (PES) support craze under tensile strain, leaving behind pores of predictable size based on the self-assembled nanoscopic domains. The high aspect ratio pores formed in this process were used to create membranes that were highly permeable (959 L/ (m 2 h bar) with near complete rejection of 40 nm diameter gold nanoparticles (AuNP). By use of BCP's inherent ability to cavitate under strain, tedious block removal steps are avoided. Membranes can thus be prepared in a simple, roll-toroll ready, one-step process. In this initial study, BCP craze formation and filtration performance were characterized for various polymer types, molecular weights, and thicknesses. All these factors influenced the BCP's thin film morphology, mechanical performance, deformation mechanism, and ultimately filtration performance. This work demonstrates a possible new path toward achieving scalable, BCP-based ultrafiltration membranes.

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“…In this method, the anionic active chain ends are actively maintained to permit the polymerization. There is a wide variety of monomers such as cyclic siloxanes, dienes, epoxides, styrenes, episulfides, and styrenes that can be polymerized anionically [Quirk, 2002;Ntetsikas et al, 2017]. Polystyrene and polydienes are typical examples of controlled block copolymer, that are synthesized by anionic polymerization.…”

Section: Ionic Polymerizationmentioning

confidence: 99%

Role of Block Copolymers in Tissue Engineering Applications

Malik

Sundarrajan

Hussain

et al. 2021

Cells Tissues Organs

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Research on synthesis, characterization, and understanding of novel properties of nanomaterials has led researchers to exploit their potential applications. When compared to other nanotechnologies described in the literature, electrospinning has received significant interest due to its ability to synthesize novel nanostructures (such as nanofibers, nanorods, nanotubes, etc.) with distinctive properties such as high surface-to-volume ratio, porosity, various morphologies such as fibers, tubes, ribbons, mesoporous and coated structures, and so on. Various materials such as polymers, ceramics, and composites have been fabricated using the electrospinning technique. Among them, polymers, especially block copolymers, are one of the useful and niche systems studied recently owing to their unique and fascinating properties in both solution and solid state due to thermodynamic incompatibility of the blocks, that results in microphase separation. Morphology and mechanical properties of electrospun block copolymers are intensely influenced by quantity and length of soft and hard segments. They are one of the best studied systems to fit numerous applications due to a broad variety of properties they display upon varying the composition ratio and molecular weight of blocks. In this review, the synthesis, fundamentals, electrospinning, and tissue engineering application of block copolymers are highlighted.

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Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases

Cited by 18 publications

References 57 publications

Ultrafast phosphazene‐promoted controlled anionic polymerization of styrenic monomers

Ultrafast phosphazene‐promoted controlled anionic polymerization of styrenic monomers

Strain-Induced Nanocavitation in Block Copolymer Thin Films for High Performance Filtration Membranes

Role of Block Copolymers in Tissue Engineering Applications

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