RAFT copolymerization of methacrylic acid and poly(ethylene glycol) methyl ether methacrylate in the presence of a hydrophobic chain transfer agent in organic solution and in water

Rinaldi, David; Hamaide, Thierry; Graillat, C.; D’Agosto, Franck; Spitz, Roger; Georges, Sébastien; Mosquet, Martin; Maitrasse, Philippe

doi:10.1002/pola.23374

Cited by 64 publications

(59 citation statements)

References 51 publications

(53 reference statements)

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“…17,25 However, copolymerization leads to a high degree of polydispersity regarding the statistical distribution of the side chains as well as the length of the backbone. This shortcoming can be overcome using RAFT copolymerization, 71 but this does not seem to be used on a large scale in industry for PCE production. Independently of this, both free radical and RAFT copolymerization lead to polymers for which determining the final molar mass can be problematic.…”

Section: Sidebar 1 Pce Structure and Chemistrymentioning

confidence: 99%

Molecular and submolecular scale effects of comb‐copolymers on tri‐calcium silicate reactivity: Toward molecular design

Marchon

Juilland²,

Gallucci³

et al. 2017

J Am Ceram Soc

124

110

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The impact of organic compounds on the processing and reactivity of inorganic materials has been a source of inspiration for materials scientists for decades and continues to trigger novel and innovative applications in a broad range of disciplines. However, molecular design of such compounds to reach targeted properties remains challenging, particularly for reactive and multicomponent systems. This outstanding challenge is met here by combining a model cement, hosting different coupled reactions of dissolution, nucleation and growth, together with combcopolymers that offer large and well-controlled variations of their molecular architecture. We show that silicate reactivity is affected by a combination of molecular and submolecular scale effects of these polymers. The first can be described by scaling laws from polymer physics, whereas the second involves specific chemical interactions. In particular, the ability of these polymers to hinder dissolution appears to be crucial, something for which strong experimental evidence is provided. K E Y W O R D Scalcium silicate,

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Section: Sidebar 1 Pce Structure and Chemistrymentioning

confidence: 99%

Molecular and submolecular scale effects of comb‐copolymers on tri‐calcium silicate reactivity: Toward molecular design

Marchon

Juilland²,

Gallucci³

et al. 2017

J Am Ceram Soc

124

110

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“…The co-polymers were synthesized by radical polymerization in water according to [39,40]. Their specifications, obtained from aqueous gel permeation chromatography (GPC) are (backbone size in kDa, number of carboxylic acids per side chain and side chain size in kDa): Polymer A: PMAA(4.…”

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confidence: 99%

Microscopic Mechanism for Shear Thickening of Non-Brownian Suspensions

et al. 2013

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We propose a simple model, supported by contact-dynamics simulations as well as rheology and friction measurements, that links the transition from continuous to discontinuous shear-thickening in dense granular pastes to distinct lubrication regimes in the particle contacts. We identify a local Sommerfeld number that determines the transition from Newtonian to shear-thickening flows, and then show that the suspension's volume fraction and the boundary lubrication friction coefficient control the nature of the shear-thickening transition, both in simulations and experiments.Flow non-linearities attract fundamental interest and have major consequences in a host of practical applications [1,2]. In particular, shear-thickening (ST), a viscosity increase from a constant value (Newtonian flow-Nw) upon increasing shear stress (or rate) at high volume fraction φ, can lead to large-scale processing problems of dense pastes, including cement slurries [3]. Several approaches have been proposed to describe the microscopic origin of shear-thickening [4][5][6][7]. The most common explanation invokes the formation of "hydroclusters", which are responsible for the observed continuous viscosity increase [6,8,9] and which have been observed for Brownian suspensions of moderate volume fractions [10,11]. However, this description no longer holds for bigger particles and denser pastes, where contact networks can develop and transmit positive normal stresses [12]. Moreover, the link between hydroclusters and CST for non-Brownian suspensions is still a matter of debate [13]. Additionally, dense, non-Brownian suspensions can also show sudden viscosity divergence under flow [14][15][16][17] with catastrophic effects, such as pumping failures. In contrast to a continuous viscosity increase at any applied rate, defined as continuous shear-thickening (CST), the appearance of an upper limit of the shear rate defines discontinuous shear-thickening (DST). This CST to DST transition is observed when the volume fraction of the flowing suspension is increased above a critical value, which depends on the system properties, e.g. polydispersity or shape, and on the flow geometry [3,18]. An explanation for its microscopic origin is still lacking [19]. Moreover, experiments have demonstrated that the features of the viscosity increase (slope, critical stress) can be controlled by tuning particle surface properties such as roughness [20] and/or by adsorbing polymers [21,22]. These findings suggest that inter-particle contacts play a crucial role in the macroscopic flow at high volume fractions. A more precise description of these contacts is therefore essential to interpret the rheological behavior.In this paper, we present a unified theoretical framework, supported by both numerical simulations and experimental data, which describes the three flow regimes of rough, frictional, non-Brownian particle suspensions (Nw,CST,DST) and links the Nw-ST (in terms of shear) and the CST-DST transitions (in terms of volume fraction) to the local friction. Our micro...

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“…S S * BzMA [161] MMA [162] PEGMA [163] 302 [164] 301 [165] 312 [166] 396 [167] MA [168] PFPVB [169] PVS [169] St [132,162] 359 [170] St [171] BA [122] MMA/BDSMA [172] (MAA/TPMMA) [173] (MAA/293) [173] DEGMA/PEGMA [174] tBMA/DMAEMA/290 [175] MMA/LMA [163] 396-b-PEGMA [167] St/AcS [176] 4VP/EGDMA [177] (St-b-DMAEMA) [171] BzMA-b-HPMAm [161] DEGMA/PEGMA-b-DMAPMAm [174] PEGMA-b-MMA [163] LMA/MMA-b-PEGMA [163] 12 S S CN D* [178] MMA [178][179][180][181][182][183][184] PEGMA [111,185] GMA [186] 289 [186,187] 297 [188] 324 [189] 453 [190] iPOx [191] St [132,…”

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confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(¼S)SR) by a mechanism of reversible addition-fragmentation chain transfer ( Chem. 2009Chem. , 62, 1402. This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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RAFT copolymerization of methacrylic acid and poly(ethylene glycol) methyl ether methacrylate in the presence of a hydrophobic chain transfer agent in organic solution and in water

Cited by 64 publications

References 51 publications

Molecular and submolecular scale effects of comb‐copolymers on tri‐calcium silicate reactivity: Toward molecular design

Molecular and submolecular scale effects of comb‐copolymers on tri‐calcium silicate reactivity: Toward molecular design

Microscopic Mechanism for Shear Thickening of Non-Brownian Suspensions

Living Radical Polymerization by the RAFT Process – A Third Update

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