The limits of precision monomer placement in chain growth polymerization

Precise control over the location of monomers in a polymer chain has been described as the ‘Holy Grail’ of polymer synthesis. Controlled chain growth polymerization techniques have brought this goal closer, allowing the preparation of multiblock copolymers with ordered sequences of functional monomers. Such structures have promising applications ranging from medicine to materials engineering. Here we show, however, that the statistical nature of chain growth polymerization places strong limits on the control that can be obtained. We demonstrate that monomer locations are distributed according to surprisingly simple laws related to the Poisson or beta distributions. The degree of control is quantified in terms of the yield of the desired structure and the standard deviation of the appropriate distribution, allowing comparison between different synthetic techniques. This analysis establishes experimental requirements for the design of polymeric chains with controlled sequence of functionalities, which balance precise control of structure with simplicity of synthesis

Block copolymer synthesis by controlled/living radical polymerisation in heterogeneous systems

Nanostructured soft materials open up new opportunities in material design and application, and block copolymer self-assembly is one particularly powerful phenomenon that can be exploited for their synthesis. The advent of controlled/living radical polymerisation (CLRP) has greatly simplified block copolymer synthesis, and versatility towards monomer types and polymer architectures across the different forms of CLRP has vastly expanded the range of functional materials accessible. CLRP-controlled synthesis of block copolymers has been applied in heterogeneous systems, motivated by the numerous process advantages and the position of emulsion polymerisation at the forefront of industrial latex synthesis. In addition to the inherent environmental advantages of heterogeneous routes, the incidence of block copolymer self-assembly within dispersed particles during polymerisation leads to novel nanostructured materials that offer enticing prospects for entirely new applications of block copolymers. Here, we review the range of block copolymers prepared by heterogeneous CLRP techniques, evaluate the methods applied to maximise purity of the products, and summarise the unique nanoscale morphologies resulting from in situ self-assembly, before discussing future opportunities within the field

Polymerization induced self-assembly : tuning of morphology using ionic strength and pH

Investigations of RAFT dispersion polymerization-induced self-assembly (PISA) of 2-hydroxypropyl methacrylate (HPMA) in water/methanol at 60 °C using a cationically charged macroRAFT agent as the stabilizer block, namely P(N,N-diethylaminoethyl methacrylate)-stat-poly((ethylene glycol) methyl ether methacrylate) (PDEAEMA-stat-PEGMA), have been conducted with a view to tune particle morphologies by manipulation of the pH and the ionic strength. Above the LCST (45 °C) of (PDEAEMA-stat-PEGMA), the system can only be conducted as a dispersion polymerization at sufficiently low pH such that the stabilizer block is sufficiently protonated to ensure solubility in the continuous phase. It is demonstrated (reported in the form of an extensive morphology diagram) that a range of morphologies including spherical particles, rods and vesicles can be accessed by adjustment of the pH (via addition of HCl) and the ionic strength (via the concentration of NaCl). A decrease in the charge density of the coronal stabilizer layer via an increase in the pH (less protonation) shifts the system towards higher order morphologies. At a given pH, an increase in ionic strength leads to more extensive charge screening, thus allowing formation of higher order morphologies

Exploitation of compartmentalization in RAFT miniemulsion polymerization to increase the degree of livingness

It is demonstrated that the degree of livingness (chain-end fidelity) in RAFT polymerization for a given degree of polymerization can be markedly increased in miniemulsion polymerization relative to the corresponding homogeneous bulk system. Polymerization of styrene was conducted using a poly(methyl methacrylate) benzodithioate as macroRAFT agent in both miniemulsion and bulk. The substantially higher polymerization rate in miniemulsion, which is attributed to the segregation effect (compartmentalization) causing a reduction in the rate of bimolecular termination, makes it possible to reach a given degree of polymerization in a significantly shorter time than in the corresponding bulk system. As a consequence, fewer initiating radicals are required throughout the polymerization, leading to higher livingness in the more rapid miniemulsion system. It is demonstrated how this approach facilitates synthesis of high molecular weight block copolymers comprising slowly propagating monomers such as styrene and methacrylates

Photopolymerization in dispersed systems

Zero-VOC technologies combining ecological and economic efficiency are destined to occupy a growing place in the polymer economy. Today, Polymerization in dispersed systems and Photopolymerization are the two major key players. The hybrid technology based on photopolymerization in dispersed systems has emerged as the next technological frontier, not only to make processes even more efficient and eco-friendly, but also to expand the range of polymer products and properties. This review summarizes the current knowledge in research relevant to this field in an exhaustive way. Firstly, fundamentals of photoinitiated polymerization in dispersed systems are given to show the favourable context for developing this emerging technology, its specific features as well as the distinctive equipment and materials necessary for its implementation. Secondly, a state-of-the-art and critical review is provided according to the seven main processing methods in dispersed systems: emulsion, microemulsion, miniemulsion, dispersion, precipitation, suspension, and aerosol

How increasingly powerful PRE modeling tools allow to unlock the full potential of FRP and RDRP in aqueous emulsion

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Chain transfer to solvent in the radical polymerization of structurally diverse acrylamide monomers using straight-chain and branched alcohols as solvents

Chain transfer to solvent in conventional radical polymerizations of N-tert-butylacrylamide (TBAM) and N-(2-morpholin-4-ylethyl) acrylamide (MEA) in a range of alcohol solvents is investigated. Mayo analysis of polymerization of TBAM in linear alcohols (C-3-C-9) resulted in an approximately linear increase in chain transfer to solvent constant (C-tr,(S)) with the number of methylene (CH2) units in the solvent. The branched alcohol 3-methyl-3-pentanol gave the smallest C-tr,C-S (using Mayo analysis), and thus allowed attainment of higher molecular weights (MWs) in the nitroxide-mediated polymerizations (NMP) of TBAM. Overall, the data show that MEA is more prone to chain transfer to solvent than TBAM (higher C-tr,C-S), and further analysis of the conventional radical polymerization of MEA in 3-methyl-3-pentanol indicate chain transfer to monomer may also be occurring. The first controlled/ living polymerizations of MEA are detailed with chain transfer having a greater impact on maximum achievable MWs in NMP in comparison to TBAM

Low-dispersity polymers in ab initio emulsion polymerization : improved macroRAFT agent performance in heterogeneous media

We demonstrate that the in-built monomer-feeding mechanism in an emulsion polymerization can be used to dramatically increase control (providing low molar mass dispersity (Đ) ≤1.15) over polymerizations mediated by reversible addition–fragmentation chain transfer (RAFT) agents with relatively low transfer constants (Ctr). An amphiphilic RAFT agent [RSC(═S)Z], based on a hydrophilic methacrylic R-group [Ċ(CH3)2CO2-PEG] and a hydrophobic Z group with Ctr ≈ 2, was used to mediate the polymerization of a range of methacrylate monomers under both heterogeneous and homogeneous conditions. Consistent with the low Ctr, batch miniemulsion or solution polymerizations did not provide polymers with low Đ. The issue of a low Ctr is overcome in an emulsion polymerization when the [monomer]/[RAFT agent] ratio at the locus of polymerization is substantially lower than the overall ratio, due to the presence of a discrete monomer droplet phase. The proposed mechanism is supported by a theoretical model. As a demonstration of the increased level of control achievable, the system has been exploited to generate methacrylate multiblock copolymers

Copper(0)-mediated radical polymerisation in a self-generating biphasic system

Herein, we demonstrate the synthesis of well-defined poly(n-alkyl acrylate)s via copper(0)-mediated radical polymerisation in a self-generating biphasic system. During the polymerisation of n-butyl acrylate in DMSO, the polymer phase separates to yield a polymer-rich layer with very low copper content (ICP-MS analysis: 0.016 wt%). The poly(n-butyl acrylate) has been characterized by a range of techniques, including GPC, NMR and MALDI-TOF, to confirm both the controlled character of the polymerisation and the end group fidelity. Moreover, we have successfully chain extended poly(n-butyl acrylate) in this biphasic system several times with n-butyl acrylate to high conversion without intermediate purification steps. A range of other alkyl acrylates have been investigated and the control over the polymerisation is lost as the hydrophobicity of the polymer increases due to the increase in alkyl chain length indicating that it is important for the monomer to be soluble in the polar solvent