Synthesis and Morphological Study of Thick Benzyl Methacrylate–Styrene Diblock Copolymer Brushes

Munirasu, Selvaraj; Karunakaran, Raghuraman G.; Rühe, Jürgen; Dhamodharan, R.

doi:10.1021/la202855u

Cited by 16 publications

(10 citation statements)

References 35 publications

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“…The second factor is that the polymerization rate is fast in comparison to conformational relaxation of the growing chains. The rate of polymerization may have a direct influence of the grafting density of the polymer brush as previously reported in literature …”

Section: Resultsmentioning

confidence: 71%

Hydrophilic PET surfaces by aminolysis and glycopolymer brushes chemistry

Lepoittevin

Costa

Pardoue

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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Poly(ethylene terephthalate) (PET) is a semiaromatic thermoplastic polyester used in many fields. For specific applications, controlled of the surface wettability (hydrophily/hydrophoby) could be a great challenge. Aminolysis of PET surfaces with branched polyethylenimine gives amino functional groups on the surface with high grafting density. Then, in a second step, atom transfer radical polymerization (ATRP) initiator was grafted by reaction with 2-bromoisobutyryl bromide. Surface initiated ATRP of 2-lactobionamidoethyl methacrylate (LAMA) was performed in solution in the presence of a sacrificial initiator or an appropriate amount of Cu(II) species that act as deactivator. The efficiency of all reactions was confirmed by X-ray photoelectron spectroscopy. Wetting properties and surface energy were found to vary systematically depending to the type of functionalization and grafting. The quantity of grafted carbohydrate was determined by phenol/sulfuric acid colorimetric titration. The sugar graft density was observed to vary according to the ratio (monomer)/(free initiator). High graft density could be obtained yielding to superhydrophilic polymer brushes.

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Section: Resultsmentioning

confidence: 71%

Hydrophilic PET surfaces by aminolysis and glycopolymer brushes chemistry

Lepoittevin

Costa

Pardoue

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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“…Unlike the morphologies of nanoparticles with heavy contrast in the core region and faint contour in the corona region captured in Figures a–f and a–e, the morphologies of nanoparticles in Figure a′–c′ were always taken with light contrast in the core region and clear contour in the corona region with target DP PB n MA = 100. We envisioned that the core‐forming block PB n MA can be solvated by ethanol solvent at high temperature 65 °C, which was slightly higher than the reported glass transition temperature ( T g ) of homopolymer PB n MA (54 °C) . Once the dispersion at high temperature was directly diluted into room temperature ethanol, the corona region of the nanoparticle was rapidly frozen and the ethanol encapsulated in the core region cannot be sufficiently squeezed out.…”

Section: Methodsmentioning

confidence: 99%

ICAR ATRP Polymerization‐Induced Self‐Assembly Using a Mixture of Macroinitiator/Stabilizer with Different Molecular Weights

Cao

Zhang

Wang

et al. 2019

Macromol. Rapid Commun.

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polymer bearing dual functions of macroinitiator and stabilizer, PISA can be realized by simultaneous polymerization and self-assembly procedures. [7][8][9] In a typical PISA procedure, the core-forming block is gradually extended and becomes insoluble with the conversion of monomer, and the formed block copolymer tends to be aggregated as various morphologies, such as spheres, worms, lamellae, vesicles, and so on. [10,11] Superior to the traditional postpolymerization self-assembly technique performed with highly diluted concentration (<1% w/w) and complicated operation procedures, the PISA technique features higher solid content (up to 50%) and simpler operation procedure. [5,6] The PISA technique has essentially accelerated the theoretical study and practical applications of self-assembled nanoparticles, and thus, is attracting more and more attention from researchers.On the one hand, most of the current PISA works are still based on the reversible addition-fragmentation chain transfer (RAFT) polymerization mechanism. [12][13][14][15][16][17][18][19][20][21][22][23][24] Relatively, nitroxide mediated polymerization (NMP), [25][26][27][28] atom transfer radical polymerization (ATRP), [29][30][31] living anionic polymerization, [32] and ring-opening metathesis polymerization (ROMP) [33] mechanisms are rarely involved in the PISA system. The reason can be attributed to some unavoidable drawbacks of each polymerization mechanism. For example, due to the intrinsic color question brought by copper catalyst, the normal ATRP PISA was originally attempted and later stagnated. [29][30][31]34,35] Fortunately, with the continuous optimization and improvement of the ATRP mechanism, the ATRP PISA was revived and greatly developed in recent years. For example, in our previous work, [36] the ppm copper catalyst system of initiators for continuous activator regeneration (ICAR) ATRP was successfully introduced into PISA using poly[oligo(ethylene oxide) methyl ether methacrylate] (POEOMA) (labeled as POEOMA 50 , 50 representing the degree of polymerization [DP]) as macroinitiator/stabilizer, poly(benzyl methacrylate) (PBnMA) as core-forming block, and ethanol as solvent. This work confirms the practical feasibility of ATRP PISA and presents an alternative way to enrich the PISA system. [37][38][39][40][41][42] On the other hand, most of the current RAFT PISA works are still focused on the morphology diagram by modulating Polymerization-Induced Self-Assembly The poly[oligo(ethylene oxide) methyl ether methacrylate]s, POEOMA 24 and POEOMA 78 with average degree of polymerization (DP) of 24 and 78, respectively, are separately achieved by initiators for continuous activator regeneration (ICAR) atom transfer radical polymerization (ATRP) of OEOMA 300 monomer. The mixtures of [POEOMA 24 ] 0 /[POEOMA 78 ] 0 = 1/1, 2/1, or 4/1 are employed as macroinitiator/stabilizer to practice the ICAR ATRP polymerization-induced self-assembly (PISA) of benzyl methacrylate (BnMA) at 65 °C. When the obtained dispersions are sequentially cooled to roo...

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“…Munirasu et al synthesised benzylmethacrylate polymer brushes as well as diblock copolymers with styrene on silicon wafer. 259 Benzylmethacrylate polymer brushes followed a linear trend with time showing that brush length can be controlled with precision due to the additional EBIB. Their GPC results from the free polymer showed very low polydispersity indicating that the surface attached polymer grew at a uniform rate.…”

Section: Polymer Brushes Synthesismentioning

confidence: 97%

“…17A shows an ATRP initiator except it has no silane head group meaning that it will not form a monolayer and stay in solution. 242,255,259 Polymers formed in solution can be analysed by gel permeation chromatography (GPC), or size exclusion chromatography 124,246,255,260,261 to calculate the degree of polymerisation. The polymers formed via free initiators are shown to correlate well with surface attached initiators.…”

Section: Sacricial Initiatorsmentioning

confidence: 99%

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Challenges and developments of self-assembled monolayers and polymer brushes as a green lubrication solution for tribological applications

et al. 2015

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ab Self-assembled monolayers (SAMs), after originally being investigated due to their functions in changing surface wettability, have been significantly developed over the years. Many types of SAMs have been developed on a variety of substrates. However their formation mechanism, rate and quality are found to be influenced by many factors. A range of SAMs including single-and multi-component are included in this review with focus on the nano and macro tribological properties. More recently, surface initiated polymer brushes, i.e. macromolecular assemblies attached to a substrate, have emerged to be an alternative and promising method for surface modification. The ability to tether these macromolecules to tribological contacts is key to their resistance to shear under loaded contacts. This review also covers atom transfer radical polymerisation (ATRP) and the role of this technique in developing new lubrication solutions. Particular care has been taken to include the development of lubrication solutions for silicon nitride due to the importance of this material as an engineering ceramic. This paper reviews the stateof-the-art development of SAMs and polymer brushes especially the potential opportunities and challenges in applying them in tribological contacts as a lubrication solution.

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Synthesis and Morphological Study of Thick Benzyl Methacrylate–Styrene Diblock Copolymer Brushes

Cited by 16 publications

References 35 publications

Hydrophilic PET surfaces by aminolysis and glycopolymer brushes chemistry

Hydrophilic PET surfaces by aminolysis and glycopolymer brushes chemistry

ICAR ATRP Polymerization‐Induced Self‐Assembly Using a Mixture of Macroinitiator/Stabilizer with Different Molecular Weights

Challenges and developments of self-assembled monolayers and polymer brushes as a green lubrication solution for tribological applications

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