相关论文
2003
Radiation-Induced Polymerization Monitored with Fluorogenic Molecular Probes

Each year over one billion pounds of acrylic-based polymeric products are produced world wide. Such products include windows in aircraft, lenses in eyeglasses and CD players, coatings on parquet flooring and various architectural structures such as skylights and domes. Often these products are made by injecting monomer or monomer solutions into molds in which it is polymerized, i.e. cured, by the application of heat. Alternatively, acrylic-based products are produced as coatings by exposing the polymerizable medium to UV light or high-energy radiation. Obviously, it is of importance to such processes that the curing stage is optimized. Insufficient curing will lead to the production of materials with inferior properties. Alternatively, excessive heating or exposure can lead to both slow rates and high costs of production. In this thesis a novel method is introduced by which the polymerization process may be monitored. This non-invasive manner of monitoring the polymerization process involves the use of trace concentrations of molecular probes in the polymerizing media. Unique to the molecular probes discussed in this thesis is their fluorogenic character. These probe molecules which are initially non-fluorescent chemically react with growing polymer chains and thereby become fluorescent. The fluorescence from the polymerizing system is therefore a direct measure of the overall extent of polymerization. Because of the associated chemical change to the probe molecule, this is a highly sensitive technique for monitoring the polymerization process. This is especially true for the early stage of polymerization, a stage in which the physical properties (viscosity, dielectric constant) of the polymerizing media do not change significantly (see chapter seven). Furthermore, because of the high sensitivity of fluorescence techniques, only a very small (millimolar or less) probe concentration is required. The polymerization of methyl methacrylate, MMA, was chosen as the system to study for two reasons; the ready availability of scientific data on this system and the associated Trommsdorff effect observed as a rapid autoacceleration of polymerization when the monomer conversion reaches a certain extent. Obviously, the bulk of scientific data present in the literature enabled rapid comparisons between the experimental results obtained with those from research institutes throughout the world.

2003
Monte Carlo Simulations for the Very Beginning of RAFT Seeded Emulsion Polymerization

Monte Carlo simulation technique was used to simulate the scenarios of the very beginning of a particle in RAFT seeded emulsion polymerization. It was first found that by introducing a high reactive RAFT agent, a large number of free radical need to be captured by the particle before polymerization starts up. The phenomenon was ascribed to the high reactivity of RAFT agent and fast exit of fragmented group of the original RAFT agent. The simulations could be successfully used to explain an unexpected long induction period and polymerization retardation reported. The results of this study will be of particular use in understanding and design of RAFT emulsion polymerization.

2014
From cationic ring-opening polymerization to atom transfer radical polymerization

Roots of controlled radical polymerization, including atom transfer radical polymerization (ATRP), origi- nate in living ionic polymerizations accompanied by reversible deactivation, such as cationic ring-opening polymeri- zation of tetrahydrofuran and other heterocyclics. Recent developments in ATRP, including mechanistic understan- ding, synthesis of polymers with precisely controlled architecture and some applications of polymers prepared by ATRP are presented.

2002 - Journal of the American Chemical Society
Control of polymer topology through transition-metal catalysis: synthesis of hyperbranched polymers by cobalt-mediated free radical polymerization.

A novel approach was demonstrated for the synthesis of hyperbranched polymers by direct free radical polymerization of divinyl monomers controlled by a cobalt chain transfer catalyst (1). By controlling the competition between propagation and chain transfer with 1, the free radical polymerization of ethylene glycol dimethacrylate (3) afforded soluble hyperbranched polymers in one pot. The structure of the hyperbranched polymers was confirmed by (1)H and (13)C NMR. The molecular weight and intrinsic viscosity of the hyperbranched polymers were measured by matrix-assisted laser desorption ionization (MALDI) mass spectrometry and size exclusion chromatography (SEC) equipped with triple detectors. The intrinsic viscosities of the hyperbranched polymers are much lower than those of their linear analogues and do not show molecular weight dependence. The unique structure and properties of these hyperbranched polymers combined with the commercial availability of many divinyl monomers and the robustness of free radical polymerization make this new approach attractive for the preparation of new functional materials.

1999
Reactivity in Radical Polymerization of Poly(2-oxazoline) Macromonomers

Reactivity in radical homopolymerization of vinylbenzyl-ended poly(2-alkyl-2-oxazoline) macromonomers (VB-PROZO-n; n (degree of polymerization) = 3—34) and methacryloyl-ended macromonomers (MA-PROZO-n; n=4—34) was examined at 60°C in CD3CN, CDCl3, or D2O using 2,2′-azobis(isobutyronitrile) (in organic solvents) or 2,2′-azobis(2-amidinopropane) dihydrochloride (in D2O) as initiator. R was Me, Bu, or n-octyl (Oc) group. In CD3CN (R = Me, Bu), macromonomers were polymerized faster with increase in n. Higher Rp was observed for Bu group and MA end group than Me group or VB end group, respectively. In CDCl3, polymerization of VB-ended POcOZO macromonomers showed higher Rp than PBuOZO macromonomers. The rate increased with in n, whereas, polymerization of MA-ended POcOZO macromonomers showed lower Rp than PBuOZO macromonomers of similar n, and rate decreased with increase in n. In D2O, PMeOZO macromonomers were polymerized 9 to 14 times faster than CD3CN. Kinetic orders of monomer concentration were 1.55 to 1.73 in organic solvents, while nearly 1.0 in water, and those of initiator concentration were close to 0.5 in CD3CN. Rp is thus affected by carbon number of acyl side chains in PROZO and by n, and D2O increases enormously Rp of PMeOZO macromonomers by micelle formation.

2007 - Journal of Polymer Science: Polymer Symposia
Mechanism of emulsion polymerization

Both conventional and inverse emulsion polymerization comprise the emulsification of an immiscible monomer in a continuous medium followed by polymerization with a free radical initiator to give a colloidal sol of polymer particles. Both processes give “emulsion polymerization kinetics,” i.e., a proportionality of both the polymerization rate and polymer molecular weight to the number of particles instead of the inverse relationship between rate and molecular weight observed for mass, solution, and suspension polymerization. The emulsion polymerization process can be divided into particle nucleation and particle growth stages and can be carried out using batch, semicontinuous, or continuous processes. Seeded emulsion polymerization can be used to avoid the particle nucleation stage in all three processes. The many mechanisms proposed for the initiation of emulsion polymerization can be divided into four categories according to the locus of particle initiation: (i) monomer-swollen micelles; (ii) adsorbed emulsifier layer; (iii) aqueous phase; (iv) monomer droplets. These general principles are applied to: (i) the preparation of monodisperse latexes by seeded emulsion polymerization; (ii) the locus of particle initiation for various monomers and initiators; (iii) emulsion copolymerization; (iv) core-shell emulsion copolymerization; (v) polymerization in fine monomer droplets; (vi) inverse emulsion polymerization.

2007 - Chemical Communications
Ultra-fast microwave enhanced reversible addition-fragmentation chain transfer (RAFT) polymerization: monomers to polymers in minutes.

Microwave mediated RAFT polymerization leads to ultra-fast polymerizations, whilst keeping excellent control over molecular weights and molecular weight distributions; this is the first example of such a dramatic effect of microwaves on living radical polymerization kinetics, and it shows the potential for chemists to produce very well controlled polymers in a matter of minutes.

2010 - ChemBioChem
Interaction of hIAPP with Model Raft Membranes and Pancreatic β‐Cells: Cytotoxicity of hIAPP Oligomers

Type II diabetes mellitus (T2DM) is associated with β‐cell failure, which correlates with the formation of pancreatic islet amyloid deposits. The human islet amyloid polypeptide (hIAPP) is the major component of islet amyloid and undergoes structural changes followed by self‐association and pathological tissue deposition during aggregation in T2DM. There is clear evidence that the aggregation process is accelerated in the presence of particular lipid membranes. Whereas hIAPP aggregation has been extensively studied in homogeneous model membrane systems, especially negatively charged lipid bilayers, information on the interaction of hIAPP with heterogeneous model raft membranes has been missing until now. In the present study, we focus on the principles of aggregation and amyloid formation of hIAPP in the presence of model raft membranes. Time‐lapse tapping mode AFM and confocal fluorescence microscopy experiments followed membrane permeabilization and localization of hIAPP in the raft membrane. Together with the ThT and WST‐1 assay, the data revealed elevated cytotoxicity of hIAPP oligomers on INS‐1E cells.

2001 - Biomaterials
Conversion and temperature profiles during the photoinitiated polymerization of thick orthopaedic biomaterials.

Polymerization of a tetrafunctional monomer was investigated under a variety of photoinitiation conditions to assess the ability to form thick materials in situ for orthopaedic applications. The major biological concerns include local cell and tissue necrosis due to the polymerization exotherm and low conversions at greater depths due to light attenuation through thick samples. Experimental results indicate that depth of cure and temperature rises are controllable by altering the photoinitiator concentration, initiating light intensity, and type of photoinitiator. For example, no measurable conversion was detected at a 1.0 cm depth when polymerization was initiated with 1.0 wt% DMPA and 100 mW/cm2 ultraviolet light, whereas approximately 40% conversion was obtained when the initiator concentration was lowered to 0.1 wt%. This conversion was further increased to approximately 55% when a photobleaching initiator system was employed. At the highest rate of initiation studied (i.e., 1.0 wt% DMPA irradiated with 100 mW/cm2 ultraviolet light), a maximum temperature of approximately 49 degrees C was reached at the sample surface; however, this temperature dramatically decreased to approximately 33 degrees C when the light intensity was decreased to 25 mW/cm2. Finally, dual initiating systems that synergistically combine the advantages of photoinitiation and thermal initiation were investigated.

2015 - Langmuir : the ACS journal of surfaces and colloids
Fabrication of Two-Component, Brush-on-Brush Topographical Microstructures by Combination of Atom-Transfer Radical Polymerization with Polymer End-Functionalization and Photopatterning.

Poly(oligoethylene glycol methyl ether methacrylate) (POEGMEMA) brushes, grown from silicon oxide surfaces by surface-initiated atom transfer radical polymerization (SI-ATRP), were end-capped by reaction with sodium azide leading to effective termination of polymerization. Reduction of the terminal azide to an amine, followed by derivatization with the reagent of choice, enabled end-functionalization of the polymers. Reaction with bromoisobutryl bromide yielded a terminal bromine atom that could be used as an initiator for ATRP with a second, contrasting monomer (methacrylic acid). Attachment of a nitrophenyl protecting group to the amine facilitated photopatterning: when the sample was exposed to UV light through a mask, the amine was deprotected in exposed regions, enabling selective bromination and the growth of a patterned brush by ATRP. Using this approach, micropatterned pH-responsive poly(methacrylic acid) (PMAA) brushes were grown on a protein resistant planar poly(oligoethylene glycol methyl ether methacrylate) (POEGMEMA) brush. Atomic force microscopy analysis by tapping mode and PeakForce quantitative nanomechanical mapping (QNM) mode allowed topographical verification of the spatially specific secondary brush growth and its stimulus responsiveness. Chemical confirmation of selective polymer growth was achieved by secondary ion mass spectrometry (SIMS).

2002 - Polymer
Modeling of the bulk free radical polymerization up to high conversion—three stage polymerization model I. Model examination and apparent reaction rate constants

In this paper, a simple and useful model, the three stage polymerization model (TSPM) is proposed on the basis of recent experimental evidence and our preliminary treatment of the experimental kinetic results found in the literature. The model accounts for gel effect and glass effect in bulk free-radical polymerization. Equations for calculating the conversion of the polymerization reaction are derived based on TSPM. Using experimental kinetic data available in the literature, general expressions for apparent reaction rate constants in three stages for methylmethacrylate (MMA) and styrene (St) are obtained. In general, the experimental kinetic data can be treated very well with the TSPM from the low conversion stage to high conversion, except for some experimental data near the transition points. However, the deviation for this data may be reasonably explained by the non-isothermal effects that occur in this regime of experiments. This deviation is smaller for a smaller ampoule reactor used in polymerization experiments because of its better heat transfer ability. In order to establish that there is no glass effect stage when the reaction temperature is greater than the glass transition temperature for a polymerization process, some experimental data for ethylmethacrylate (EMA) bulk polymerization at a reaction temperature higher than its glass transition temperature were checked with TSPM. The plots show that the model is also suitable for EMA bulk polymerization.

2007 - Microfluidics and Nanofluidics
Free radical polymerization in multilaminated microreactors: 2D and 3D multiphysics CFD modeling

This paper investigates the modeling of styrene free radical polymerization in two different types of microreactor. A multiphysics model which simultaneously takes into account the hydrodynamics, thermal and mass transfer (convection, diffusion and chemical reaction) is proposed. The set of partial differential equations resulting from the model is solved with the help of the finite elements method either in a 2D or a 3D approach. The different modeled microreactors are on one hand an interdigital multilamination microreactor with a large focusing section, and on the other hand a simple T-junction followed by a straight tube with three different radii. The results are expressed in terms of reactor temperature, polydispersity index, number-average degree of polymerization and monomer conversion for different values of the chemical species diffusion coefficient. It was found that the 2D approach gives the same results as the 3D approach but allows to dramatically reduce the computing time. Despite the heat released by the polymerization reaction, it was found that the thermal transfer in such microfluidic devices is high enough to ensure isothermal conditions. Concerning the polydispersity index, the range of diffusion coefficients over which the polydispersity index can be maintained close to the theoretical value for ideal conditions increases as the tube reactor radius decreases. The interdigital multilamination microreactor was found to act as a tubular reactor of 0.78 mm ID but with a shorter length. This underlines that the use of microfluidic devices can lead to a better control of polymerization reactions.

2009
Determination of the Mode of Termination in Radical Polymerization via Mass Spectrometry

We comprehensively explore the use of mass spectrometry (MS) for quantitative determination of the mode of termination, i.e., the extent of disproportionation versus combination, in radical polymerization. Development of the underlying kinetic theory forms a major portion of our endeavors. What emerges from this theory is that the ratio of polymer from disproportionation to combination is a function of chain length and of fundamental kinetic parameters such as the rate of initiation and the rate coefficients for propagation and termination. Therefore, all this information must be at hand in order to determine λ, the fraction of termination by disproportionation. We implement our findings using electrospray−ionization MS results for poly(methyl methacrylate) that we synthesized at 85 °C in benzene employing bis(3,5,5-trimethylhexanoyl) peroxide as initiator, chosen because it has the advantage of yielding only one primary radical species. Our results are well fitted by theory and are found to vary with cha...

1996 - Macromolecular Chemistry and Physics
Polyelectrolyte complexes obtained by radical polymerization in the presence of chitosan

The radical polymerization of acrylic acid and sodium 4-styrenesulfonate in the presence of chitosan as a template gives insoluble products, identified as the polyelectrolyte complexes chitosan-poly(acrylic acid) and chitosan-poly(4-styrenesulfonate). Kinetic results do not permit to propose any mechanism in the first case, while suggest a “pick-up” one in the second. The polyelectrolyte complexes have been characterized by FT-IR spectroscopy, X-ray diffractometry, optical and scanning electron microscopies, differential scanning calorimetry and thermogravimetric analysis. The results obtained indicate an ordered structure for the first complex, while the second one appears similar to that obtained by reacting the parent polymers. Therefore, the template polymerization technique appears advantageous only for the synthesis of the chitosan-poly(acrylic acid) complex. The thermal analysis shows that the complexes undergo two successive modifications on heating. FT-IR analysis demonstrates that the first process is an esterification between the hydroxyls of chitosan and the acidic groups of both daughter polymers; the second one appears to be an amidation of the chitosan ammonium groups only with the sulfonate groups.

2009
RAFT Miniemulsion Polymerization Kinetics, 2 – Molecular Weight Distribution†

The molecular weight distribution formed in a RAFT polymerization conducted inside submicron particles (D p < 300 nm) is considered. For small particles, the MWD at low to middle conversion might be rather broad because of the large differences in MWDs formed in different polymer particles. Such a broad MWD can be made narrower by increasing the radical entry frequency. On the other hand, larger frequencies of radical entry result in a broader MWD at the final conversion levels. The number of dead polymer chains increases with time, and the dead polymer peak could be observed in the MWD at a prolonged aging time. According to this theoretical investigation, smaller particles are advantageous in implementing a faster polymerization rate, a narrower MWD, and a smaller number of dead polymer molecules.

2006
Cobalt-mediated radical polymerization (CMRP) of vinyl acetate initiated by redox systems : Toward the scale-up of CMRP

A redox initiating system was developed in order to bypass 2,2‘-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V70) as the initiator of the cobalt-mediated radical polymerization (CMRP) of vinyl acetate (VAc) in the presence of cobalt(II) acetylacetonate (Co(acac)2). It is indeed a problem to stock up with V70 because of needed storage at −20 °C during transportation. This paper reports on the controlled CMRP of VAc initiated by ascorbic acid combined with either lauroyl peroxide or benzoyl peroxide at 30 °C. Substitution of citric acid for ascorbic acid results in faster polymerization whereas the polymerization control is maintained. All these improvements facilitate the implementation of the vinyl acetate CMRP and open the door to the scale-up of the process.

2003
Copolymerization of N,N-Dimethylacrylamide with n-Butyl Acrylate via Atom Transfer Radical Polymerization

The (co)polymerization of N,N-dimethylacrylamide (DMAA) was performed by atom transfer radical polymerization (ATRP). Using methyl 2-chloropropionate/CuCl/Me6TREN as the initiating/catalyst system in toluene solution, at room temperature, high molecular weight homopolymers (Mn up to 50 000) with narrow molecular weight distribution (Mw/Mn = 1.05−1.13) were prepared. The controlled polymerization of DMAA has been extended to simultaneous copolymerization with n-butyl acrylate (nBA), which resulted in a comparable rate of conversion for each monomer, indicating formation of a nearly random copolymer. The reactivity ratios of DMAA and nBA in ATRP are similar:  rDMAA = 1.16 and rnBA = 1.01. Block copolymers of nBA and DMAA, with two different polymerization degrees of the second block (DPDMAA = 65 and 100), were synthesized using a well-defined PnBA-Br (DPnBA = 140) macroinitiator. The other approach to block copolymer formation using extension of PDMAA-Cl (DPDMAA = 160) with nBA was used, and block copolymer...

2010 - Progress in Polymer Science
Transition metal catalysts for controlled radical polymerization

Abstract The discovery, in the mid 1990s, that certain cobalt, ruthenium and copper complexes could effectively control the radical polymerization of a number of polar olefins, allowing for the facile synthesis of complex macromolecular architectures, fostered an intense search for increasingly better performing catalysts. As a consequence, several metal complexes were designed and tested. This article presents an organized and detailed overview of the most significant developments in the use of transition metal compounds to initiate, mediate and control radical polymerization, i.e. , atom transfer radical polymerization or organometallic mediated radical polymerization. The catalysts have been classified according to the group of the periodic table to which the relative metal centers belong. Their catalytic performance, the mechanism with which they are supposed to operate, the structure–reactivity correlations as well as the type of monomers and experimental conditions employed are described. The use and the role of non-transition metal complexes in controlled radical polymerization are also discussed.

1995
Controlled Living Radical Polymerization - Halogen Atom-Transfer Radical Polymerization Promoted by a Cu(I)Cu(II) Redox Process

An extension of atom transfer radical addition, ATRA, to atom transfer radical polymerization, ATRP, provided a new and efficient way to conduct controlled/living radical polymerization. By using a simple alkyl halide, R-X (X = Cl and Br), as an initiator and a transition metal species complexed by suitable ligand(s), M t n /L x , e.g., CuX/2,2'-bipyridine, as a catalyst, ATRP of vinyl monomers such as styrenes and (meth)acrylates proceeded in a living fashion, yielding polymers with degrees of polymerization predetermined by Δ[M]/[I] 0 up to M n ≃ 10 5 and low polydispersities, 1.1 < M w /M n < 1.5. The participation of free radical intermediates was supported by analysis of the end groups and the stereochemistry of the polymerization. The general principle and the mechanism of ATRP are elucidated. Various factors affecting the ATRP process are discussed.

1981
Principles of polymerization

Preface. 1. Introduction. 1.1 Types of Polymers and Polymerizations. 1.2 Nomenclature of Polymers. 1.3 Linear, Branched, and Crosslinked Polymers. 1.4 Molecular Weight. 1.5 Physical State. 1.6 Applications of Polymers. 2. Step Polymerization. 2.1 Reactivity of Functional Groups. 2.2 Kinetics of Step Polymerization. 2.3 Accessibility of Functional Groups. 2.4 Equilibrium Considerations. 2.5 Cyclization versus Linear Polymerization. 2.6 Molecular Weight Control in Linear Polymerization. 2.7 Molecular Weight Distribution in Linear Polymerization. 2.8 Process Condition. 2.9 Multichain Polymerization. 2.10 Crosslinking. 2.11 Molecular Weight Distributions in Nonlinear Polymerizations. 2.12 Crosslinking Technology. 2.13 Step Copolymerization. 2.14 High-Performance Polymers. 2.15 Inorganic and Organometallic Polymers. 2.16 Dendric (Highly Branched) Polymers. 3. Radical Chain Polymerization. 3.1 Nature and Radical Chain Polymerization. 3.2 Structural Arrangement of Monomer Units. 3.3 Rate of Radical Chain Polymerization. 3.4 Initiation. 3.5 Molecular Weight. 3.6 Chain Transfer. 3.7 Inhibition and Retardation. 3.8 Determination of Absolute Rate Constants. 3.9 Energetic Characteristics. 3.10 Autoacceleration. 3.11 Molecular Weight Distribution. 3.12 Effect of Pressure. 3.13 Process Conditions. 3.14 Specific Commercial Polymers. 3.15 Living Radical Polymerization. 3.16 Other Polymerizations. 4. Emulsion Polymerization. 4.1 Description of Process. 4.2 Quantitative Aspects. 4.3 Other Characteristics of Emulsion Polymerization. 5. Ionic Chain Polymerization. 5.1 Comparison of Radical and Ionic Polymerization. 5.2 Cationic Polymerization of the Carbon-Carbon Double Bond. 5.3 Anionic Polymerization of the Carbon-Carbon Double. 5.4 Block and Other Polymer Architecture. 5.5 Distinguishing Between Radical, Cationic, and Anionic Polymerizations. 5.6 Carbonyl Polymerization. 5.7 Miscellaneous Polymerizations. 6. Chain Copolymerization. 6.1 General Considerations. 6.2 Copolymer Composition. 6.3 Radical Copolymerization. 6.4 Ionic Copolymerization. 6.5 Deviations from Terminal Copolymerization Model. 6.6 Copolymerizations Involving Dienes. 6.7 Other Copolymerizations. 6.8 Applications of Copolymerizations. 7. Ring-Opening Polymerization. 7.1 General Characteristics. 7.2 Cyclic Ethers. 7.3 Lactams. 7.4 N-Carboxy-alphaAmino Acid Anhydrides. 7.5 Lactones. 7.6 Nitrogen Heterocyclics. 7.7 Sulfur Heterocyclics. 7.8 Cycloalkenes. 7.9 Miscellaneous Oxygen Heterocyclics. 7.10 Other Ring-Opening Polymerizations. 7.11 Inorganic and Partially Inorganic Polymers. 7.12 Copolymerization. 8. Stereochemistry of Polymerizaton. 8.1 Types of Stereoisomerism in Polymers. 8.2 Properties of Stereoregular Polymers. 8.3 Forces of Stereoregulation in Alkene Polymerization. 8.4 Traditional Ziegler-Natta Polymerization of Nonpolar Alkene Monomers. 8.5 Metallocene Polymerization of Nonpolar Alkene Monomers. 8.6 Other Hydrocarbon Monomers. 8.7 Copolymerization. 8.8 Postmetallocene: Chelate Initiators. 8.9 Living Polymerization. 8.10 Polymerization of 1,3-Dienes. 8.11 Commercial Applications. 8.12 Polymerization of Polar Vinyl Monomers. 8.13 Alehydes. 8.14 Optical Activity in Polymers. 8.15 Ring-Opening Polymerization. 8.16 Statistical Models of Propagation. 9. Reactions of Polymers. 9.1 Principles of Polymers Reactivity. 9.2 Crosslinking. 9.3 Reactions of Cellulose. 9.4 Reactions of Poly(vinyl) acetate). 9.5 Halogenation. 9.6 Aromatic Substitution. 9.7 Cyclization. 9.8 Other Reactions. 9.9 Graft Copolymers. 9.10 Block Copolymers. 9.11 Polymers as Carriers or Supports. 9.12 Polymer Reagents. 9.13 Polymer Catalysts. 9.14 Polymer Substrates. Index.

Living radical polymerization by the RAFT process

Graeme Moad
|
G. Moad
|
E. Rizzardo
|
S. Thang
|
San H. Thang
|
Ezio Rizzardo

Abstract:This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC(=S)SR] by a mechanism of reversible addition–fragmentation chain transfer (RAFT). Since we first introduced the technique in 1998, the number of papers and patents on the RAFT process has increased exponentially as the technique has proved to be one of the most versatile for the provision of polymers of well defined architecture. The factors influencing the effectiveness of RAFT agents and outcome of RAFT polymerization are detailed. With this insight, guidelines are presented on how to conduct RAFT and choose RAFT agents to achieve particular structures. A survey is provided of the current scope and applications of the RAFT process in the synthesis of well defined homo-, gradient, diblock, triblock, and star polymers, as well as more complex architectures including microgels and polymer brushes.

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2021
Dendritic and Hyperbranched Polymers from Macromolecular Units: Elegant Approaches to the Synthesis of Functional Polymers
2011