Effect of different ligands on the controlled polymerization of monodisperse polystyrene nanospheres by atom transfer radical polymerization in an aqueous emulsion

Tian, B. Y.; Hu, Ping; Miao, Yuan; Tang, Erjun; Liu, S. J.; Zhao, Xiaoning; Zhao, Di

doi:10.3144/expresspolymlett.2012.89

Cited by 10 publications

(9 citation statements)

References 37 publications

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“…Although ATRP is a versatile and robust technique which can be used in different systems, it is still challenging to carry out ATRP in water. [32][33][34][35][36] Two critical factors that should be taken into account are the choice of an appropriate ligand to maintain the high solubility of the Cu + and Cu 2+ complexes at the locus of polymerisation, 37,38 and a surfactant that does not interfere with the catalyst system. 39 From preliminary experiments it was noticed that addition of a copper catalyst to ATRP macroinitiator adsorbed on Gibbsite platelets led to a dramatic increase in the Z-average diameter.…”

Section: Preparation and Characterisation Of Polymer-gibbsite Latex P...mentioning

confidence: 99%

An ATRP-based approach towards water-borne anisotropic polymer–Gibbsite nanocomposites

et al. 2016

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Section: Preparation and Characterisation Of Polymer-gibbsite Latex P...mentioning

confidence: 99%

An ATRP-based approach towards water-borne anisotropic polymer–Gibbsite nanocomposites

et al. 2016

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“…However, the broadness of the polydispersity indicates poor controlled systems when PPh3 or Vitamin (D) were used. There are many reasons that may explain why a poorly controlled system was obtained such as the steric hindrance of the ligand [6], the ligand compatibility with surfactant [15,16] and the ligand hydrophobicity/ hydrophilicity characteristics. Figure 3 shows GPC traces of PMMA product for the system using Phenol.…”

Section: Resultsmentioning

confidence: 99%

“…However, it is well known that even with a high hydrophobic ligand, not all of the catalyst complex can be prevented from partitioning into the aqueous phase. In another words, it can control the concentrations of the deactivator and activator in the reaction medium [6].…”

Section: Introductionmentioning

confidence: 99%

Effect of Ligands in MMA AGET ATRP in 2L Stirred Tank Emulsion Reactor

Awad¹,

Duever²,

Dhib³

2019

Proceedings of the 5th World Congress on Mechanical, Chemical, and Material Engineering

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Atom Transfer Radical Polymerization (ATRP) in a 2L emulsion batch reactor system was initiated by using the Activator Generated by Electron Transfer (AGET) technique to produce Poly (Methyl Methacrylate) (PMMA). The reactants were composed of Ethyl-2-bromoisobutyrate (EBiB) as the initiator, polyoxyethylene (20) oleyl ether (Brij98) as nonionic surfactant and ascorbic acid as the reducing agent. In addition, the catalyst complex consists of copper bromide (CuBr2) and different ligands such as Triphenylphosphine (PPh3), 1, 10-Phenanthroline (Phenol), and Vitamin D. The effect of using PPh3, Phenol and Vitamin D as novel ligands was investigated to produce PMMA polymers having the features obtained through controlled polymerization. The reaction follows a two-step experimental procedure, during which a transition from microemulsion to emulsion takes place. The mixing process between the organic phase and the aqueous phase was carried out under sufficient amount of air for simplification purposes. However, the reaction is usually sensitive to air and therefore a particular precaution was taken when purging the system inside the reactor. Gravimetric method was used to measure the monomer conversion. Characterization of PMMA samples was done by means of GPC to measure the molecular weight and the polydispersity of the product. FTIR analysis was performed to characterize the polymer product. After 5h of reaction, high monomer conversion was obtained using Phenol and gradually increasing up to 93% with low number average molecular weight of 10,158 g/mol and a relatively narrow PDI of 1.58. A narrower PDi was obtained with Phenol compared with PPh3 and Vitamin D.

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“…It is postulated that the ligand reduces the catalyst partitioning into the aqueous phase by improving the catalyst retention in the particle phase during the polymerization. However, it is a well-known that even with a hydrophobic ligand, not all of the catalyst complex can be prevented from partitioning into the aqueous phase (Tian et al, 2012). It is important to mention that the well-known ligands reported in literature to study ATRP in emulsion media are either expensive, such as 4,4'-Dinonyl-2,2'-dipyridyl (dNbpy), or not commercially available such as N,N-bis(2-pyridylmethyl)octadecylamine (BPMODA).…”

Section: Introductionmentioning

confidence: 99%

Experimental Study of AGET ATRP of MMA and BMA Homopolymerizations in Emulsion Batch Reactor

Awad

2024

Preprint

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Controlled radical polymerization (CRP) is a fast-growing technique for the creation of nano-sized polymer particles. In particular, atom transfer radical polymerization (ATRP) is a promising catalytic CRP method that has been extensively studied in academia and industry. Due to the limited studies of ATRP in emulsion systems, the focus of this research project is to investigate an ATRP procedure initiated by an activator generated by an electron transfer (AGET) scheme in a 2L stirred tank emulsion reactor. The current research incorporates the environmental and sustainable aspects of benign technology. This thesis consists of four parts. The first investigation dealt with the compatibility of the surfactant-ligand design. For instance, hydrophobic ligands, which are very efficient in emulsion ATRP, are expensive and commercially not easily available. Therefore, a successful controlled polymerization system using an eco-friendly and low-cost hydrophilic like HMTA ligand and an anionic surfactant is examined in this research. In addition, the solubilities of the Triphenylphosphine (PPh3), 1, 10-Phenanthroline (Phenol), and Vitamin D ligands in the organic phase were evaluated to confirm the possibility of producing PMMA with controlled characteristics in an emulsion AGET ATRP technique. The second part of this thesis involves a detailed experimental study, which examined the effects of temperature, surfactant concentration, monomer water (M/W) ratio, and agitation speed on the characteristics of poly(methyl methacrylate) (PMMA). The results revealed that it is possible to achieve high monomer conversion at a mild temperature with a limited occurrence of coagulation. The third part of the thesis involves a kinetic study of emulsion ATRP. Literature reveals no detailed reports on chemical kinetics of emulsion ATRP. Thus, an empirical model was using experimental data collected in this study developed to describe the rate of polymerization in emulsion AGET ATRP. The results demonstrate that the behavior of ATRP in emulsion is significantly different from FRP in emulsion media. Lastly, a statistical analysis of poly(butyl methacrylate) PBMA was done using screening design of experiments approach. The results revealed that temperature, surfactant, stirring speed and temperature-surfactant interaction have significant effects on the conversion and the temperature and ligand have a more pronounced impact on the molecular weight distribution (MWD) of the final PBMA product.

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Effect of different ligands on the controlled polymerization of monodisperse polystyrene nanospheres by atom transfer radical polymerization in an aqueous emulsion

Cited by 10 publications

References 37 publications

An ATRP-based approach towards water-borne anisotropic polymer–Gibbsite nanocomposites

An ATRP-based approach towards water-borne anisotropic polymer–Gibbsite nanocomposites

Effect of Ligands in MMA AGET ATRP in 2L Stirred Tank Emulsion Reactor

Experimental Study of AGET ATRP of MMA and BMA Homopolymerizations in Emulsion Batch Reactor

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