Introduction to Radical Polymerisation

The polymers are synthesised in ethyl acetate using ■■■■■ as free‐radical polymerisation initiator.

Pulsed-laser-assisted methods have enormously improved the understanding of kinetics and mechanism of the basic steps of radical polymerisation, i.

The use of bacteria as catalysts for radical polymerisations of synthetic monomers has recently been established.

These hyperbranched cores are used as macroinitiators for 'grafting-from' polymerisation using controlled radical polymerisation to achieve amphiphilic copolymers which can subsequently be self-assembled into spherical core-shell micelles.

This contribution summarises the fundamental properties of well-defined molecular cationic bismuth compounds and highlights recent advancements in the understanding of their Lewis acidity, in their utilisation for challenging stoichometric reactions (such as CH activation and small molecule activation), and in catalytic applications (such as Lewis acid catalysis, radical polymerisation, and Bi(iii)/Bi(v) redox catalysis).

Photomediated-reversible-deactivation radical polymerisation (photo-RDRP) has a limited scope of available photocatalysts (PCs) due to multiple stringent requirements for PC properties, limiting options for performing efficient polymerisations under long wavelengths.

The feasibility of single and double emulsion production with wall formation as a secondary step through UV radical polymerisation was explored using a discrete membrane emulsification dispersion cell.

The radical polymerisation of acrylic acid is largely concentration dependent and affected by the type of the surrounding solvent.

Reversible-Deactivation Radical Polymerisation (RDRP) is one of the most exciting developments in chemistry over the past few decades, but it is rarely mentioned when polymerisation mechanisms are introduced in the final years of secondary education or first years of tertiary education.

In this study, free-radical polymerisation inside MCM-41 mesopores was examined to expose a construction route for a temperature-responsive switchable polymer-silica nanohybrid material with well-defined porosity.

RFMi could be synthesised efficiently via a Mitsunobu reaction condition and copolymerised with St by free radical and reversible-deactivation radical polymerisation protocols.

In this study, a nonionic poly(N-acryloyl morpholine)-brush-grafted-poly(vinylidene fluoride) membrane (PVDF-g-PACMO) was fabricated via surface-initiated atom transfer radical polymerisation (ATRP) to separate various surfactant-stabilised emulsions.

Based on this, a polyhydroxylated monomer was synthesised from α-pinene, a sustainable terpene feedstock derived from pine trees, and used to prepare a low molar mass polymer TPA5 through free radical polymerisation.

Previously, we have shown that a range of terpene(meth)acrylate monomers can be synthesised from the most commonly available terpenes (α-pinene, β-pinenene and limonene) and that these readily undergo radical polymerisation.

Potassium persulfate (K2S2O8) was used to initiate the free radical polymerization reaction and tetramethylethylenediamine (TEMED) to accelerate radical polymerisation.

The first example of activators regenerated by electron transfer atom transfer radical polymerisation (ARGET ATRP) under precipitation polymerisation (PP) conditions is reported.

The presence of BCPC resulted in a fast radical polymerisation of HDDA and no cationic ring-opening reaction of the epoxy, which was observed by monitoring the double bond and epoxy group conversion in real time-NIR rheology measurement.

DMA is copolymerised with 2-hydroxyethyl methacrylate (HEMA) and glycidyl methacrylate (GMA) using free radical polymerisation.

Several characterisations of the acrylate/epoxy IPNs final properties, such as the mechanical properties, adhesion properties, shrinkage and swelling, indicated the possibilities to adapt or tune their properties compared to radical polymerisation of TMPTA.

In this study, we used oxygen tolerant, visible light-activated free radical polymerisation to functionalise cotton with a biocompatible, fire retardant, antimicrobial coating that provided good fire retardancy when dry, and quickly absorbed water to provide exceptional fire retardancy and thermal insulation in more extreme fire conditions.

In this study, new molecularly imprinted polymer particles (MIP) were synthesised to extract Cu2+ ions from aqueous solutions using radical polymerisation.

One of the versatile radical polymerisation techniques, the reversible addition fragmentation chain transfer (RAFT) process, was used to synthesize the bifunctional monomer, vinylbenzyl chloride (VBC) into poly(vinylbenzyl chloride) (PVBC).

The thermo-responsive copolymers were synthesised by free radical polymerisation from a monomer with a reactive side chain (3-methacryloxypropyl trimethoxysilane (S)) and water-soluble monomers with different thermo-responsivities (N-isopropyl acrylamide (N) or N-(3-methoxy propyl)acrylamide (M)).

A series of highly ordered morphologies in aqueous solution were obtained by self-assembly of ABC miktoarm terpolymers with mutually immiscible hydrophilic poly(ethylene glycol) monomethyl ether (mPEG), hydrophobic polystyrene (PS) and superhydrophobic poly(1H,1H,5H-octafluoropentyl methacrylate) (POFPMA), which were synthesised by a combination of atom transfer radical polymerisation (ATRP), single electron transfer living radical polymerisation (SET-LRP) and click chemistry.

The use of reversible deactivation radical polymerisation (RDRP) techniques has allowed advances in the synthesis of amphiphilic polymers.

Herein, we report the synthesis of a poly(ethylene glycol)-block-poly(2-dimethylaminoethyl methacrylate-co-(butyl methacrylate-co-methyl methacrylate)) via atom transfer radical polymerisation at a molar ratio of methacrylic monomers of 2:1:1.

The presented approach uses a cost efficient air plasma activation and subsequent radical polymerisation in highly concentrated aqueous monomer solutions to generate efficient antibacterial materials.

Ethyl α-bromophenylacetate (EBrPA) is able to initiate the bulk radical polymerisation of methyl methacrylate (MMA) under thermal conditions (90 °C) in the presence of a variety of simple alkali or alkaline-earth metal or nBu4N salts (Mt+X− with X− = chloride, bromide, iodide, carbonate, bicarbonate, sulfate, bisulfate, nitrate, hydroxide and hexafluorophosphate).

Surface-initiated Atom Transfer Radical Polymerisation (ATRP) was applied to obtain a dense hydrophilic (protein repellent) PGMMA layer of tunable size, under conditions which are compatible with the nanoencapsulation of horseradish peroxidase.

In this way, the development of novel techniques for conjugation, especially living radical polymerisation (LRP) has greatly enhanced the potential to broaden the scope of therapeutic conjugates.

The reactions – a urethane reaction and a radical polymerisation – are modelled based on atom distances and probabilities calculated by an Arrhenius law, without the need for intermediate minimisation steps.

Cu-Catalysed reversible-deactivation radical polymerisation of hydrophobic methacrylate monomers in anhydrous alcohols has been expanded to explore the scope of this unusual choice of solvent.

Tailor-made photoinitiators play an important role for efficient radical polymerisations in aqueous media, especially in hydrogel manufacturing.

Here, we demonstrate a highly efficient one-pot synthesis of such materials by combining copper-mediated reversible-deactivation radical polymerisation (Cu-RDRP) with thiol-bromo post-polymerisation modification.

In this work, free-radical polymerisation of poly (ethylene glycol)-dimethacrylate (PEGDMA) in UV light was assessed.

This report details the synthesis of lipidated 2-vinyl-4,4-dimethyl-5-oxazolone (VDM) oligomers via an optimised Cu(0)-mediated reversible-deactivation radical polymerisation approach, and the use of these oligomers as a versatile functional platform for the rapid generation of antimicrobial materials.

We show that glycoside hydrolases can catalyse the synthesis of glycosyl acrylate monomers using renewable hemicellulose as glycosyl donor, and we also demonstrate the preparation of novel glycopolymers by radical polymerisation of these monomers.

Recent experimental observations of the role played by copper polyamine catalysts in atom transfer radical polymerisation (ATRP) have indicated that important side reactions in competition with conventional radical activation by halogen atom transfer may occur and that these can potentially affect reaction control.

Polymerisation of dialkylaminoethyl methacrylates by reversible deactivation radical polymerisation (RDRP) provides a route for the synthesis of block polymers or macro-initiators/macro-chain transfer agents for subsequent grafting onto various substrates.

: The continuous amalgamation of photocatalysis into existing reversible deactivation radical polymerisation processes has initiated a rapidly propagating area of polymer research in recent years.

The terpolymers were synthesised via atom transfer radical polymerisation (ATRP), single electron transfer living radical polymerisation (SET-LRP) and azide-alkyne Huisgen cycloaddition (click reaction).

Atom Transfer Radical Polymerisation (ATRP) is one of the most important techniques to synthesize well-defined polymers with predetermined molecular weight, designed microstructure and tailor-made functionalities.

Furthermore, the recovered MMA with methanol was polymerised to poly-MMA using a benzoyl peroxide induced free radical polymerisation process.

Diffusion of chiral compound filled in the silica aerogel resulted in the non-uniform pitch distribution, which can be anchored by UV-radical polymerisation.

Herein, a handy and efficient chemical modification process is proposed to modify extreme surface of poly(ethylene terephthalate) (PET) films towards the final purpose of grafting PFPMA polymer from PET surface via surface-initiated Cu(0)-mediated radical polymerisation.

However, knowledge of their polymerisation behaviour in metal mediated radical polymerisation is limited, although the thioester functionality allows efficient post modifications.

In this study, a polymerization initiator is covalently grafted on the alkali-activated Ti substrates by using a phosphonic acid as coupling agent and the resulting surfaces are used as scaffolds to drive the growth of tethered poly(methyl methacrylate) (PMMA) chains via a surface initiated atom transfer radical polymerisation (SI-ATRP).

The continuous amalgamation of photocatalysis into existing reversible deactivation radical polymerisation (RDRP) processes has initiated a rapidly propagating area of polymer research in recent years.

A “Benchtop” NMR spectrometer is used for detailed monitoring of controlled and free radical polymerisations performed in batch and continuous reactors both offline and in real-time.

The mechanism of the reactions involves classical free radical polymerisation, controlled and living polymerisation and can be realized as for example bulk, suspension, emulsion and precipitation polymerisation.

Unlike non-reversible deactivation radical polymerisation (RDRP) synthetic routes this generates accurately controlled KHI candidates with target molecular weight, narrow molecular weight distributions and controlled architecture, so that the effect on hydrate inhibition can be more accurately assessed.

It was found that the process of peroxide-vulcanised PAAP was a free-radical polymerisation mechanism.

The control approach is developed on the basis of feedback passivation and then applied to stabilise globally exponentially a class of free-radical polymerisation reactors.

We report, for the first time, the metal-free green synthesis of linear poly(vinyl pyrrolidone) (PVP) homopolymers of molecular weight higher than 100 kg mol-1 and narrow dispersities via thermal and photo-induced free radical polymerisation carried out within alumina nanoporous membranes acting as "nanoreactors".

Synthesis of the star-comb (also referred to as star-graft) copolymer architecture of a polycarboxylate ether or poly(acrylic acid)-co-poly(isoprenyl oxy poly(ethylene glycol) ether) (PCE) using a star chain transfer agent (CTA) with multiple mercapto groups by free radical polymerisation and its properties in cement pastes are discussed.