Facile syntheses of cylindrical molecular brushes by a sequential RAFT and ROMP “grafting‐through” methodology

Zhou, Li; Zhang, Ke; Ma, Jun; Cheng, Chong; Wooley, Karen L.

doi:10.1002/pola.23626

Cited by 141 publications

(151 citation statements)

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“…In grafting through method, modification process is performed by introducing a suitable organic modifier (containing a vinyl moiety) on the surface of the nanoparticles and then these vinyl moieties can participate in the polymerization reaction [36,37]. Therefore, the hydrophilic silica aerogel nanoparticles are functionalized with double bond containing modifier (MPS) that this process is illustrated in Fig.…”

Section: Resultsmentioning

confidence: 99%

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SR&NI atom transfer radical random copolymerization of styrene and butyl acrylate in the presence of MPS-functionalized silica aerogel nanoparticles

Sarsabili

Kalantari

Khezri

2016

J Therm Anal Calorim

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Hydrophilic silica aerogel nanoparticles' surface was functionalized with 3-(trimethoxysilyl)propyl methacrylate (MPS). Then, the resultant functionalized nanoparticles were used in grafting through copolymerization of styrene and butyl acrylate by simultaneous reverse and normal initiation technique for atom transfer radical copolymerization (SR&NI ATRP) to synthesize tailor-made random poly (styrene-co-butyl acrylate) nanocomposites with twofold chains. Successful surface modification of hydrophilic silica aerogel nanoparticles with MPS is demonstrated by Fourier transform infrared spectroscopy and thermogravimetric analysis (TG). Nitrogen adsorption/desorption isotherm is applied to examine surface area and structural characteristics of the synthesized silica aerogel nanoparticles. Evaluation of size distribution and morphological studies were also performed by scanning and transmission electron microscopy. Conversion and molecular weight determinations were carried out using gas and size exclusion chromatography, respectively. Addition of MPS-functionalized nanoparticles by 3 mass% results in a decrease in conversion from 71 to 46 %. Molecular weight (M n ) of the free poly (styrene-cobutyl acrylate) chains decreases by adding 3 mass% MPSfunctionalized silica aerogel nanoparticles; however, polydispersity index (PDI) value increases from 1.17 to 1.48. Although PDI values of the attached poly (styrene-cobutyl acrylate) chains are increased from 1.54 to 1.76, M n values reveal an increment by adding silica aerogel nanoparticles. 1 H NMR spectroscopy results indicate that the molar ration of each monomer in the copolymer chains is approximately similar to the initial selected mole ratio of the monomers. Increasing thermal stability of the nanocomposites is demonstrated by TG. Differential scanning calorimetry also shows a decrease in glass transition temperature by increasing modified silica aerogel nanoparticles.

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Section: Resultsmentioning

confidence: 99%

“…Surface modification via grafting method is classified into three main groups: grafting from, grafting to, and grafting through [36]. In grafting through technique, the surface modifier contains a double bond moiety that this double bond can participate in the polymerization reaction as a vinyl monomer [37].…”

Section: Introductionmentioning

confidence: 99%

SR&NI atom transfer radical random copolymerization of styrene and butyl acrylate in the presence of MPS-functionalized silica aerogel nanoparticles

Sarsabili

Kalantari

Khezri

2016

J Therm Anal Calorim

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“…21,22 Besides ATRP, other controlled radical polymerization (CRP) methods were used, such as reversible addition fragmentation transfer polymerization (RAFT) and nitroxide-mediated polymerization. 23,24 Macromolecular engineering was performed by combination of PEG macromonomers polymerization with ''click chemistry'' . 25 A critical review of polymerization procedures of PEG-based macromonomers has been recently published by Neugebauer.…”

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confidence: 99%

Hierarchically organized micellization of thermoresponsive rod‐coil copolymers based on poly[oligo(ethylene glycol) methacrylate] and poly(ε‐caprolactone)

Luzon

Corrales

Catalina

et al. 2010

J. Polym. Sci. A Polym. Chem.

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A series of amphiphilic triblock copolymers, poly [oligo(ethylene glycol) methacrylate] x -block-poly(e-caprolactone)-block-poly[oligo(ethylene glycol) methacrylate] x , POEGMA Co (x), were synthesized. Formation of hydrophobic domains as cores of the micelles was studied by fluorescence spectroscopy. The critical micelle concentrations in aqueous solution were found to be in the range of circa 10 À6 M. A novel methodology by modulated temperature differential scanning calorimetry was developed to determine critical micelle temperature. A significant concentration dependence of cmt was found. Dynamic light scattering measurements showed a bidispersed size distribution.The micelles showed reversible dispersion/aggregation in response to temperature cycles with lower critical solution temperature between 75 and 85 C. The interplay of the two hydrophobic and one thermoresponsive macromolecular chains offers the chance to more complex morphologies. V C 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: [4909][4910][4911][4912][4913][4914][4915][4916][4917][4918][4919][4920][4921] 2010

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“…Such 'brush-like' polymers [45][46][47][48] have been studied in detail by various research groups, including Sheiko and Matyjaszewski, [49][50][51][52][53][54][55][56][57][58][59][60][61][62][63] and by the groups of Grubbs, [64][65][66][67][68][69][70][71][72][73][74][75][76][77][78][79][80] Bowden, [81][82][83][84][85] Wooley, [86][87][88][89][90][91] and others. [92][93][94][95]…”

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confidence: 99%

Synthesis of block polymer miktobrushes

et al. 2013

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Well defined m-A(BC) n 'miktobrush' terpolymers were synthesized utilizing the alternating radical copolymerization of two hydrophobic and incompatible macromonomer (MM) building blocks; a maleimide (MI) end functionalized poly(methyl-caprolactone) block (MI-PMCL) or 'C' and a styrene (Sty) end functionalized poly(perfluoro propylene oxide) block (Sty-PFPO) or 'F'. Polymerizations were mediated by a poly(ethylene oxide) (PEO) functionalized reversible addition-fragmentation chain transfer (RAFT) agent (PEO-CTA) or 'O' to control the chain growth of the MMs from the O block to form O(CF) n ''miktobrush'' terpolymers. The synthesis of a range of well defined m-O(CF) n terpolymers with various compositions was achieved by changing the feed of MMs. All building blocks and brush polymers were characterized by nuclear magnetic resonance (NMR) spectroscopy, size exclusion chromatography (SEC) and elemental analyses. This new strategy offers a powerful route towards a block polymer architecture that can enable the formation of multi-domain hierarchical nanostructures with features on multiple length scales due to the incompatibility and unique connectivity of the building blocks incorporated.Block polymers can spontaneously self-assemble into welldefined nanostructures in block selective solvents and in the bulk, offering a powerful 'bottom up' approach towards precisely engineered materials for many diverse applications including; microelectronics, 1 tissue engineering, 2 drug delivery and water purification. 3 The increased understanding of self-assembled block polymers with varied architectures is of both fundamental and technological importance. 4 Towards this goal, AB diblock copolymers have been studied in depth. 5-7 Adding more blocks and functional groups to AB diblock copolymers increases architectural and functional complexity and can lead to more exotic self-assembled morphologies. 8,9 For instance, in a solvent selective for the A block, an ABC triblock terpolymer will form 'multicompartment micelles' whereby the two solvophobic (and incompatible) B and C blocks will produce two separate nanoscopic core domains. 10,11 If the chemistry of the microphase separated domains (B and C) is sufficiently different, multicompartment micelles can facilitate the storage of distinct small molecules within their separate core domains, thus enabling simultaneous storage and delivery of multiple incompatible payloads. 12 Linear ABC terpolymers, 13-19 linear BAC or ACB terpolymers, 20 side chain grafted ABC terpolymers or 'polysoaps', 21-23 miktoarm star m-ABC terpolymers, 24-30 and blends of block polymers 31-36 have been pursued as multicompartment micelle systems by various research groups. In each case, the connection point of the solvophobic B and C chains relative to the solvophilic corona forming block, A influences the micelle morphology to a great extent, although factors such as the solvophobicity and overall terpolymer composition play important roles. 5,11 In m-ABC terpolymers, three mutually immiscible blocks are...

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Facile syntheses of cylindrical molecular brushes by a sequential RAFT and ROMP “grafting‐through” methodology

Cited by 141 publications

References 30 publications

SR&NI atom transfer radical random copolymerization of styrene and butyl acrylate in the presence of MPS-functionalized silica aerogel nanoparticles

SR&NI atom transfer radical random copolymerization of styrene and butyl acrylate in the presence of MPS-functionalized silica aerogel nanoparticles

Hierarchically organized micellization of thermoresponsive rod‐coil copolymers based on poly[oligo(ethylene glycol) methacrylate] and poly(ε‐caprolactone)

Synthesis of block polymer miktobrushes

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