The anionic block copolymerization of ethylene oxide with tert-butyl methacrylate. Diblock and multiblock copolymers

Reuter, H.; Berlinova, Iliyana V.; Höring, S.; Ulbricht, Joachim

doi:10.1016/0014-3057(91)90156-i

Cited by 20 publications

(10 citation statements)

References 15 publications

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“…No more transesterification reactions could be detected, but polymerization with cumylpotassium at 25 8C resulted in a tailing of the molar mass distribution towards low molar masses indicative of some side reactions. [27] This situation could be significantly improved in two subsequent studies. [28,29] In contrast to the earlier ones, TBMA was polymerized at -78 8C in THF.…”

Section: Hydrophobic Precursor Blocksmentioning

confidence: 91%

“…The influence of the PEO block length on the tacticity of the poly(alkyl methacrylate) block was investigated applying a modified synthesis. [26] In further studies, TBMA was initiated with living PEO in analogy to the literature, [26] and also living PTBMA was used to initiate EO polymerization at 25 or 40 8C [27] in THF. No more transesterification reactions could be detected, but polymerization with cumylpotassium at 25 8C resulted in a tailing of the molar mass distribution towards low molar masses indicative of some side reactions.…”

Section: Hydrophobic Precursor Blocksmentioning

confidence: 99%

“…EO was allowed to react for 20 h. [28,30] The resulting block copolymers revealed narrower molar mass distribution (M -w /M -n = 1.05-1.09) [28] compared to those obtained before (M -w /M -n = 1.16-1.81). [27] A very low polydispersity was recently reported for PEO block copolymers with polyisoprene or poly(butadiene) (PB), which are novel precursor polymers of DHBCs due to their reactive double bonds. [31,32] They can be prepared in a one-step synthesis based on a phosphazene base as the complex agent for lithium.…”

Section: Hydrophobic Precursor Blocksmentioning

confidence: 99%

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Double-Hydrophilic Block Copolymers: Synthesis and Application as Novel Surfactants and Crystal Growth Modifiers

Cölfen¹

2001

Macromol. Rapid Commun.

601

536

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Section: Hydrophobic Precursor Blocksmentioning

confidence: 91%

Section: Hydrophobic Precursor Blocksmentioning

confidence: 99%

Section: Hydrophobic Precursor Blocksmentioning

confidence: 99%

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Double-Hydrophilic Block Copolymers: Synthesis and Application as Novel Surfactants and Crystal Growth Modifiers

Cölfen¹

2001

Macromol. Rapid Commun.

601

536

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“…For a block copolymer involving PEO and an alkyl methacrylate sequential anionic polymerization is not possible as the addition of ethylene oxide to living poly(alkyl methacrylate) anions bears potential complications. [15] Side reactions between living poly(ethylene oxide) and the alkyl ester group of the poly(alkyl methacrylate) block cause the formation of inhomogeneous block copolymers. [16] The synthesis of block copolymers through addition of alkyl methacrylate to living PEO involves difficulties, too.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Amphiphilic Poly(ethylene oxide)‐block‐poly(hexyl methacrylate) Copolymers

Mahajan

Renker

Simon

et al. 2003

Macro Chemistry & Physics

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We describe the preparation of amphiphilic diblock copolymers made of poly(ethylene oxide) (PEO) and poly(hexyl methacrylate) (PHMA) synthesized by anionic polymerization of ethylene oxide and subsequent atom transfer radical polymerization (ATRP) of hexyl methacrylate (HMA). The first block, PEO, is prepared by anionic polymerization of ethylene oxide in tetrahydrofuran. End capping is achieved by treatment of living PEO chain ends with 2‐bromoisobutyryl bromide to yield a macroinitiator for ATRP. The second block is added by polymerization of HMA, using the PEO macroinitiator in the presence of dibromobis(triphenylphosphine) nickel(II), NiBr2(PPh3)2, as the catalyst. Kinetics studies reveal absence of termination consistent with controlled polymerization of HMA. GPC data show low polydispersities of the corresponding diblock copolymers. The microdomain structure of selected PEO‐block‐PHMA block copolymers is investigated by small angle X‐ray scattering experiments, revealing behavior expected from known diblock copolymer phase diagrams.SAXS diffractograms of PEO‐block‐PHMA diblock copolymers with 16, 44, 68 wt.‐% PEO showing spherical (A), cylindrical (B), and lamellae (C) morphologies, respectively.magnified imageSAXS diffractograms of PEO‐block‐PHMA diblock copolymers with 16, 44, 68 wt.‐% PEO showing spherical (A), cylindrical (B), and lamellae (C) morphologies, respectively.

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“…The main approaches to synthesizing PEO–vinyl monomer block copolymers are as follows: (i) sequential anionic polymerization of certain monomers, such as styrene,6–10 methacrylates,11, 12 dienes13, 14 and ethylene oxide; (ii) radical polymerization of vinyl monomers starting from PEO oligomers possessing appropriate ‘end‐functionalities’,15–19 or from ‘macroinitiators’ containing alternating sequences of PEO chains and radical‐initiator moieties,20, 21 (iii) coupling of PEO oligomers with other oligomers through the reaction between the end groups of the two species 22. Among these, the anionic method requires the smallest number of steps and offers the best results in terms of control of molecular weight, polydispersity and composition of the resulting block copolymers.…”

Section: Introductionmentioning

confidence: 99%

Poly(ethylene oxide)‐block‐polystyrene copolymers obtained by radical polymerization involving chain‐transfer processes

Teodorescu

Dimonie

Drăghici³

et al. 2004

Polymer International

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Poly(ethylene oxide)‐block‐polystyrene (PEO–PSt) block copolymers were prepared by radical polymerization of styrene in the presence of iodoacetate—terminated PEO (PEO‐I) as a macromolecular chain‐transfer agent. PEO‐I was synthesized by successively converting the OH end‐group of α‐methoxy ω‐hydroxy PEO to chloroacetate and then to the iodoacetate. The chain‐transfer constant of PEO‐I was estimated from the rate of consumption of the transfer agent versus the rate of consumption of the monomer (Ctr, PEO‐I = 0.23). Due to the involvement of degenerative transfer, styrene polymerization in the presence of PEO‐I displayed some of the characteristics of a controlled/‘living’ process, namely an increase in the molecular weight and decrease of polydispersity with monomer conversion. However, because of the slow consumption of PEO‐I due to its low chain‐transfer constant, this process was not a fully controlled one, as indicated by the polydispersity being higher than in a controlled polymerization process (1.65 versus < 1.5). The formation of PEO–PSt block copolymers was confirmed by the use of size‐exclusion chromatography and 1H NMR spectroscopy. Copyright © 2004 Society of Chemical Industry

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The anionic block copolymerization of ethylene oxide with tert-butyl methacrylate. Diblock and multiblock copolymers

Cited by 20 publications

References 15 publications

Double-Hydrophilic Block Copolymers: Synthesis and Application as Novel Surfactants and Crystal Growth Modifiers

Double-Hydrophilic Block Copolymers: Synthesis and Application as Novel Surfactants and Crystal Growth Modifiers

Synthesis and Characterization of Amphiphilic Poly(ethylene oxide)‐block‐poly(hexyl methacrylate) Copolymers

Poly(ethylene oxide)‐block‐polystyrene copolymers obtained by radical polymerization involving chain‐transfer processes

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