Spontaneous termination in living polymers

Glasse, M. D.

doi:10.1016/0079-6700(83)90002-3

Cited by 44 publications

(33 citation statements)

References 131 publications

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“…540 nm). [36] A possible mechanism for formation of poly(styryl)cesium (2) and 1,3-diphenylallylcesium (3) chromophores is shown in Scheme 4. This mechanism is supported by the fact that similar spectral changes were observed upon reaction of polystyrene with cesium metal in THF [34] and by the extensive studies of polystyryl anion decomposition.…”

Section: Preparation Of Ps-b-ppo By Initiation Of Propylene Oxide Polmentioning

confidence: 99%

“…This mechanism is supported by the fact that similar spectral changes were observed upon reaction of polystyrene with cesium metal in THF [34] and by the extensive studies of polystyryl anion decomposition. [36] In order to investigate the effect of counterion on poly-(propylene oxide) block formation using polystyrene alkali metal alkoxides as initiators, polymerizations were effected in THF/DMSO (2/1, vol/vol) mixtures at room temperature in the presence of crown ethers ([crown ether]/[PSOMt] = 2.5). For potassium and rubidium counterions, the crown ether used was 18-crown-6 ether; for cesium, the crown ether used was dicyclohexano-24-crown-8.…”

Section: Preparation Of Ps-b-ppo By Initiation Of Propylene Oxide Polmentioning

confidence: 99%

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Anionic synthesis of well-defined, poly[(styrene)-block-(propylene oxide)] block copolymers

Quirk

Lizarraga

2000

Macromol. Chem. Phys.

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Section: Preparation Of Ps-b-ppo By Initiation Of Propylene Oxide Polmentioning

confidence: 99%

Section: Preparation Of Ps-b-ppo By Initiation Of Propylene Oxide Polmentioning

confidence: 99%

Anionic synthesis of well-defined, poly[(styrene)-block-(propylene oxide)] block copolymers

Quirk

Lizarraga

2000

Macromol. Chem. Phys.

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“…Whilst it has been reported that no significant termination of PSLi by THF occurs over the lifetime of the experiment when 20% (v/v) THF is used in cyclohexane, 16 a general problem with the use of THF in organolithium synthesis is metallation of the solvent 17,18 -even PSLi itself is unstable in pure THF. 19,20 It could thus be anticipated that in some cases functionalization of polymers with 4-VBC would be accompanied by a significant amount of side reaction with THF. A method was thus sought that would avoid the design and use of new and complicated equipment, and which would not require extensive optimization in order to generate macromonomers from different anionic polymerizations.…”

Section: Resultsmentioning

confidence: 99%

Block Copolymers by the Conversion of Living Lithium Initiated Anionic Polymerization into Living Ruthenium ROMP

Castle

Khosravi

2006

Macromolecules

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. (2006) 'Block copolymers by the conversion of living lithium initiated anionic polymerization into living ruthenium ROMP. ', Macromolecules., 39 (17). pp. 5639-5645.Further information on publisher's website: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. ABSTRACT: This paper describes a method for the synthesis of well-defined AB block copolymers, where one block is synthesized via anionic polymerization initiated with alkyllithium compounds, and one by ring opening metathesis polymerization (ROMP) using well-defined ruthenium macroinitiators.This methodology was demonstrated by copolymerizing styrene with norbornene derivatives.Polystyrene was synthesized via living anionic polymerization initiated by sec-butyllithium, and functionalized to form macromonomers. These were used as precursors to well-defined ruthenium 2 macroinitiators, the macromonomers being converted by an alkylidene exchange reaction with ruthenium propylidene initiator RuCl 2 (=CHEt)(PCy 3 ) 2 . These macroinitiators were used to initiate the ROMP of various norbornene derivatives in order to synthesize well-defined block copolymers with narrow molecular weight distributions.

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“…Gleiches Styren-AZ beim Ubergang von I P zu F I erwahnen [65], was deren Verhalten mit dem der kationischen Styren-AZ vergleichbar macht.…”

Section: Zusammenstellung Der Wachsenden Ketten Von Verschiedener Naturunclassified

Besonderheiten des Verhaltens unterschiedlicher aktiver Zentren bei nichtradikalischen Polymerisationsprozessen. Fortschrittsbericht

Erussalimsky

1986

Acta Polymerica

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Die Besonderheiten des Verhaltens der wachsenden Ketten in anionischen, kationischen und ZIEGLER-NATTA-P01y-merisationsprozessen ungesattigter Monomere werden diskutiert. An konkreten Beispielen von Monomeren, die nach allen drei Mechanismen polymerisiert werden konnen, wird versucht, Gemeinsamkeiten der entsprechenden aktiven Zentren hinsichtlich ihrer Stabilitat, Stereospezifitat und Reaktionsfahigkeit herauszuarbeiten. Oco6ennocmu noeeaenus atcmuermx yenmpos paanoii npupoaa, e npoyeccax nepackccucawoii noauaepuaayuu. 0630p 0 6 c y m~a m~c~ OCO6eHHOCTH IIOBegeHHH PaCTYqHX qeIIeP HeHaCHqeHHHX MOHOMePOB B PHHOHHbIX, KaTHOHHbIX H qHrJIep0BCKHX IIpO~eCCaX IIOJIHMepH3aqHH. H a IIpHMepe MOHOMePOB, CIIOCO~HHX K lIOJIHMepH3aqHH B KamAOM H 3 BTHX CJIyWeB CAeJIaHa IIOnbITKa COIIOCTaBJIeHHFI OTJIWIHTeJIbHbIX OCO6eHHOCTefi COOTBeTCTByIoQHX aKTHBHhIX qeHTPOB, XapaRTepH3yIoQHX HX CTa6HJIbHOCT6, CTepeOCIIeqH@iWIOCTb H PeaKqHOHHyIO CIIOCO6HOCTb. Peculiarities of the behaviour of different active centres in non-radical polymerization processes. ReviewThe specific behaviour of the growing chains in anionic, cationic and ZIEGLER-NATTA polymerization processes of unsaturated monomers is discussed. With examples of monomers which can be polymerized by all of these processes, it is attempted t o compare the characteristic features of the corresponding active sites in respect to their stability, stereospecifity and reactivity.

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Spontaneous termination in living polymers

Cited by 44 publications

References 131 publications

Anionic synthesis of well-defined, poly[(styrene)-block-(propylene oxide)] block copolymers

Anionic synthesis of well-defined, poly[(styrene)-block-(propylene oxide)] block copolymers

Block Copolymers by the Conversion of Living Lithium Initiated Anionic Polymerization into Living Ruthenium ROMP

Besonderheiten des Verhaltens unterschiedlicher aktiver Zentren bei nichtradikalischen Polymerisationsprozessen. Fortschrittsbericht

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