Block copolymers of styrene and 4-vinylpyridine: Synthesis and structure

Zaremski, M. Yu.; Chen, Xin; Orlova, A. P.; Blagodatskikh, I. V.; Никонорова, Н. И.

doi:10.1134/s1560090415030112

Cited by 7 publications

(8 citation statements)

References 22 publications

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“…The latter is considered closer to the nature of BCP structure in the large-scale industrial process [12]. Previous reports demonstrated that the morphologies such as disordered microstructure [19][20][21], ordered lamellar or cylinder [17,[19][20][21] were observed depending on the fraction of the individual components. The coexistence of two morphologies [19] and the shift of the phase boundaries [17,18] were assigned to the broad PDI of BCPs.…”

Section: Introductionmentioning

confidence: 91%

“…The coexistence of two morphologies [19] and the shift of the phase boundaries [17,18] were assigned to the broad PDI of BCPs. In addition, the sizes [13,17] and the size distribution [20] of the microdomain increased as the PDI increased. However, there is a disagreement issue on the presence of macrophase domain [13,18,19,22], which is due to the phase separation of low molecular weight homopolymer incorporated to polydisperse BCPs.…”

Section: Introductionmentioning

confidence: 98%

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Preparation of polydisperse polystyrene-block-poly(4-vinyl pyridine) synthesized by TEMPO-mediated radical polymerization and the facile nanostructure formation by self-assembly

2018

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This article reports a successful nanostructure formation from block copolymer having broad distribution of molecular weight. The block copolymer synthesis and the nanosphere formation are facile; therefore, it is promising for fabrication of nanostructure materials in large-scale manufactory. The polydisperse diblock copolymer of polystyrene-block-poly(4-vinyl pyridine) (PSVP) was prepared by the nitroxide-mediated radical polymerization that contains the fraction of poly(4-vinyl pyridine) block of 45 mol% and the overall polydispersity index of 2.08. The phase separation of PSVP was induced by the simple evaporation of co-solvent DMF:THF (70:30 v/v) of the PSVP solution. The SEM images of the self-assembled polydisperse PSVP display the spherical morphology with the diameter of ~ 50 nm, which is larger than that of block copolymer having narrow molecular weight distribution. By simply immersing the self-assembled film into iron chloride solution, the transformation from the spherical structure to the porous structure occurred directly without sacrificing the block copolymer component indicating the advantage of stimuli-response properties of the self-assembled PSVP. The results demonstrated that the polydisperse block copolymer could be used for the nanostructure formation by simple synthesis and evaporation procedures and, therefore, it is suitable for industrial applications. Graphical Abstract

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Section: Introductionmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 98%

Preparation of polydisperse polystyrene-block-poly(4-vinyl pyridine) synthesized by TEMPO-mediated radical polymerization and the facile nanostructure formation by self-assembly

2018

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“…Various methods of controlled/living radical polymerization of 4‐vinylpyridine (4VP) to homopolymer and block copolymers have been reported in a plenty of papers. In particular, many papers are focused on the synthesis of the poly(styrene‐ co ‐4VP) [P(S‐4VP)] block and random copolymers and some of the cited ones on their applications . Radical polymerization requires a compound acting as a source of odd‐electron species; in nitroxide‐mediated radical polymerization (NMRP) one of the most important compounds and most used for P(S‐4VP) synthesis is 2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO).…”

Section: Introductionmentioning

confidence: 99%

“…In the 4VP polymerization and copolymerization, acyclic derivatives have been exploited too. For instance, 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐nitroxide (TIPNO) used as phenyl and p ‐bromophenyl (referred to as TIPNO‐PhBr) or terpyridine functionalized TIPNO . Various solid‐state techniques are used to characterize the copolymers and the resulting composites, for example, scanning electron microscopy and transmission electron microscopy.…”

Section: Introductionmentioning

confidence: 99%

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An innovative approach for the chemical structural characterization of poly(styrene 4‐vinylpyridine) copolymers by matrix‐assisted laser desorption/ionization time of flight mass spectrometry

Montaudo

Puglisi

Battiato

et al. 2018

J of Applied Polymer Sci

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ABSTACT: Poly(styrene-co-4-vinylpyridine) random copolymers with different molar composition were synthesized by nitroxidemediated controlled-radical polymerization using 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) as a mediator. We record the matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) spectra under various conditions, and we find (at last) that they show mostly intact ions [using 2(-4-hydroxyphenylazo-)benzoic acid as MALDI matrix]. Spectra are highly resolved, and thus they allow for the determination of all end-groups, even some less-abundant ones. Spectra are dominated by intact "dormant" copolymer chains terminated with TIPNO at one end and with (4-Bromo-phenyl)ethyl group (starting fragment) at the other one. Applying the mass analysis of copolymers (MACO) statistical model to the spectra, we show that the MACO/MALDI-TOF mass spectrometry (MS) analysis can be successfully applied to copolymers having a difference between the mass of the comonomers as small as 1 g mol −1 (the styrene and 4-vinylpyridine units are 104.15 and 105.15 g/mol, respectively), which results in overlapping isotopic patterns. The results are accurate: chemical composition evaluated by means of MS agrees with that calculated by 1 H-nuclear magnetic resonance, for all copolymers investigated. This analytical method allows to extract detailed information on the composition of the copolymer samples and their structure. Glass transition temperatures of copolymers were also determined by differential scanning calorimetry.In the present work, several P(S-4VP) essentially random copolymers with different molar percentage of 4VP units (5, 10, 20, and 50% mol, on the base of the feed) were synthesized by NMRP using TIPNO mediator, as depicted in Scheme 1. We selected the Additional Supporting Information may be found in the online version of this article.

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Irregular polystyrene peroxides – a promising macroinitiators synthesized by radical polymerization under oxygen inflow

Silant'ev

Perepelitsina

Grachev

et al. 2017

European Polymer Journal

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Block copolymers of styrene and 4-vinylpyridine: Synthesis and structure

Cited by 7 publications

References 22 publications

Preparation of polydisperse polystyrene-block-poly(4-vinyl pyridine) synthesized by TEMPO-mediated radical polymerization and the facile nanostructure formation by self-assembly

Preparation of polydisperse polystyrene-block-poly(4-vinyl pyridine) synthesized by TEMPO-mediated radical polymerization and the facile nanostructure formation by self-assembly

An innovative approach for the chemical structural characterization of poly(styrene 4‐vinylpyridine) copolymers by matrix‐assisted laser desorption/ionization time of flight mass spectrometry

Irregular polystyrene peroxides – a promising macroinitiators synthesized by radical polymerization under oxygen inflow

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