Benzyl potassium: An efficient one‐pot initiator for the synthesis of block co‐ and terpolymers of ethylenoxide

Ekizoglou, Nikos; Hadjichristidis, Nikos

doi:10.1002/pola.1097

Cited by 30 publications

(25 citation statements)

References 14 publications

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“…Despite a reasonable control over the molecular weight, the dispersity was a little broader than analogous polymers prepared using alkyl lithium initiators (usually Đ < 1.1), in line with what has been previously discussed and reported in literature as regards the DPMK initiator . However, these results, in terms of dispersity, are much better than the results obtained when using (unfunctionalized) DPMK initiator for the polymerization of styrene in benzene (in‐house attempt gave a Đ > 1.3).…”

Section: Resultssupporting

confidence: 85%

“…As reported above, an excess of BuLi results in the production of unfunctionalized chains and an excess of DPE results in chains with more than one functional DPE moiety per chain, since DPE can copolymerize. The proposed solution is to use a functional initiator based on BPF—or a functional derivative of diphenylmethyl potassium, which has been widely used for the anionic ring opening polymerization of ethylene oxide . The advantage of this approach is that the BPF is cheap and readily available, the resulting initiator carries the two required protected phenol groups but is an initiator in its own right, so does not need to be produced in situ, avoiding the issues of stoichiometry (Scheme c).…”

Section: Resultsmentioning

confidence: 99%

“…DPMK has poor solubility in nonpolar solvents resulting in heterogeneous initiation and the polymerization of chains with a broad dispersity. Moreover, it has been reported that DPMK is not effective as an initiator for styrene and diene monomers due to the delocalization of the negative charge in the two phenyl rings also leading to high dispersity chains …”

Section: Introductionmentioning

confidence: 99%

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End‐Functionalized Chains via Anionic Polymerization: Can the Problems with Using Diphenylethylene Derivatives be Solved by using Bisphenol F?

Pagliarulo

2017

Macro Chemistry & Physics

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The controlled functionalization of polymers via anionic polymerization draws great attention not only because of the importance of introducing functionality into otherwise unfunctionalized polymers, but also because of the possibility to use the resulting macromonomers to make a variety of complex architectures. The versatile family of 1,1‐diphenylethylene (DPE) derivatives is widely used to produce many different functionalized (co)polymers. DPE can be added either as an end‐capping agent or be activated by butyllithium to initiate the polymerization. However, each approach faces potential problems in gaining precise control over the number of DPE moieties per chain. In this work, for the first time, the effectiveness of each approach is compared by the characterization of 1,1‐bis(4‐tert‐butyldimethylsiloxyphenyl)ethylene functionalized polystyrene, synthesized via both the procedures. A combination of NMR, size exclusion chromatography, matrix‐assisted laser desorption ionization‐time of flight (MALDI‐ToF) mass spectrometry, and interaction chromatography is used. To overcome the limitations of DPE derivatives, the use of a novel (protected) bisphenol F potassium initiator is proposed.

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Section: Resultssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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End‐Functionalized Chains via Anionic Polymerization: Can the Problems with Using Diphenylethylene Derivatives be Solved by using Bisphenol F?

Pagliarulo

2017

Macro Chemistry & Physics

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“…27,36À41 Furthermore, the synthesis of polyisoprene (PI)-b-P2VP-b-poly(ethylene oxide) (PEO), PI-b-P2VP-b-P t BMA, and even a particular PI-b-P2VP-b-P t BMA-b-PEO was reported by Hadjichristidis et al 42,43 Needless to say, the corresponding triblock and tetrablock polymers having block segments different in sequential order cannot be synthesized by changing the sequential addition order of monomers.…”

Section: ' Introductionmentioning

confidence: 88%

Facile Synthesis of Triblock Co- and Terpolymers of Styrene, 2-Vinylpyridine, and Methyl Methacrylate by a New Methodology Combining Living Anionic Diblock Copolymers with a Specially Designed Linking Reaction

et al. 2011

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Triblock co-and terpolymers with orders of blocks synthetically difficult to be obtained by means of sequential living anionic polymerization were successfully synthesized by developing a new methodology combining living anionic block copolymers with a specially designed linking reaction. The synthesized polymers involve ACB and BAC triblock terpolymers and ABA 0 , ACA 0 , and BCB 0 triblock copolymers, where A, B, and C are polystyrene, poly(2-vinylpyridine), and poly(methyl methacrylate) segments, respectively. The A 0 , A as well as B, B 0 are identical in polymer structure but different in molecular weight. All of them are new type triblock ter-and copolymers with well-defined structures, i.e., predictable molecular weights, compositions, and narrow molecular weight distributions. Transmission electron microscopic studies were performed on bulk morphologies of ACB and BAC triblock terpolymers to exemplarily investigate the influence of changing block sequence and thus changing interfaces. Although both terpolymers showed the tendency to form a lamellaÀlamella morphology, ACB revealed unusually strongly curved lamellae and BAC even undulated lamellae. ' INTRODUCTIONBlock polymers with a high degree of molecular and compositional homogeneity have attracted increasing interest as model polymers to elucidate interesting properties and behavior in combination with morphologies and molecular assemblies. 1À9 Such welldefined block polymers are usually synthesized by means of living anionic polymerization where two or more monomers are sequentially added to appropriate anionic initiators. 10 In fact, well-defined AB diblock copolymers, ABC triblock terpolymers, and (AB) n multiblock copolymers have been successfully synthesized.In order to achieve further design and synthesis of well-defined block polymers by using living anionic polymerization, it is

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“…106 In contrast, benzyl potassium was successfully employed as initiator for the synthesis of block copolymers containing EO. PS-b-PEO block copolymer, PI-b-P2VP-b-PEO triblock terpolymer, PS-b-PI-b-P2VP-b-PEO tetrablock quaterpolymer, and PS-b-PI-b-P2VP-b-PtBuMA-b-PEO pentablock quintopolymer were prepared by sequential addition of monomers 107,108 (Scheme 15).…”

Section: Block Copolymers By Anionic Polymerizationmentioning

confidence: 99%

Ionic Polymerization

Pitsikalis

2013

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

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Benzyl potassium: An efficient one‐pot initiator for the synthesis of block co‐ and terpolymers of ethylenoxide

Abstract: This study shows that benzyl potassium is an efficient initiator for the polymerization of ethylenoxide. Well‐defined diblock copolymers and triblock terpolymer of ethylenoxide have been synthesized using this initiator.

Cited by 30 publications

References 14 publications

End‐Functionalized Chains via Anionic Polymerization: Can the Problems with Using Diphenylethylene Derivatives be Solved by using Bisphenol F?

End‐Functionalized Chains via Anionic Polymerization: Can the Problems with Using Diphenylethylene Derivatives be Solved by using Bisphenol F?

Facile Synthesis of Triblock Co- and Terpolymers of Styrene, 2-Vinylpyridine, and Methyl Methacrylate by a New Methodology Combining Living Anionic Diblock Copolymers with a Specially Designed Linking Reaction

Ionic Polymerization

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