Search

We demonstrate a scalable continuous feed method for the synthesis of polymer Janus nanoparticles with different composition and with different aspect ratios between lobes, including with one hard cross-linked polystyrene lobe and one soft film-forming poly(methyl methacrylate-co-butyl acrylate) (P(MMA-co-BA)) lobe, through reversible addition-fragmentation chain transfer (RAFT)-mediated emulsion polymerization. Snowman shaped particles of size around 40 nm are synthesized through a continuous monomer feeding method, which enables kilogram-scale synthesis of diverse polymer Janus nanoparticles, with a solids content greater than 30%. The Janus nanoparticles with the soft P(MMA-co-BA) lobes spontaneously self-assemble around solid particles in an aqueous phase, forming a thin (5 -100 nm) polymer film that completely encapsulates the solid particles. The process is achieved at room temperature and under mild conditions. The film-forming Janus nanoparticles show excellent encapsulation ability for a variety of solid particles, such as organic and inorganic pigments, carbon nanotubes and calcite, without requiring polymerization to be conducted in the presence of the solid particles. When the Janus nanoparticles were used to encapsulate calcite particles in low sheen paints, the encapsulation provided superior stain resistance to the formed paint film.

A novel method is demonstrated to encapsulate titanium dioxide pigment using directed polymerization-induced self-assembly (PISA) with reversible addition-fragmentation chain-transfer (RAFT) controlled emulsion polymerization. The polymerization is carried out in a batch process in which both styrene (Sty) and the pigment are emulsified using triblock amphiphilic macro-RAFT copolymers as stabilizers. RAFT-controlled chain growth leads to directed lamellar self-assembly, forming polystyrene (PS) shells' encapsulating pigment particles with 100% efficiency. The pigment resides either at centers of single-void vesicles or within the interior of multivoid vesiculated particles. The presence of complex morphologies such as spherical particles, nanofibers, nanoplatelets, and polymer vesicles confirms the PISA pathway. The process is optimized to preferably produce polymer-vesiculated pigment for use as an enhanced opacifier in water-based paint.

A robust polymerization technique that enables the surfactant-free aqueous synthesis of a high solid content latex containing polymeric hollow particles is presented. Uniquely designed amphiphilic macro-reversible addition fragmentation chain transfer (RAFT) copolymers were used as sole stabilizers for monomer emulsification as well as for free-radical emulsion polymerization. The polymerization was found to be under RAFT control, generating various morphologies from spherical particles, wormlike structures to polymer vesicles. The final particles were dominantly polymeric vesicles which had a substantially uniform and continuous polymer layer around a single aqueous filled void. They produced hollow particles once dried and were successfully used as opacifiers to impart opacity into polymer paint films. This method is simple, can be performed in a controllable and reproducible manner, and may be performed using diverse procedures.

Polymer encapsulation of raw ferrofluids was carried out by free radical emulsion polymerization using macro-RAFT copolymers as stabilizers. The iron oxide cores with positively charged surface at the pH of encapsulation were dispersed in a solution of negatively charged random macro-RAFT copolymer by ultrasonication. Uniform polymer encapsulated super paramagnetic iron oxide nanoparticles (SPIONs) were produced by feeding the mixture of methyl methacrylate (MMA) and n -butyl acrylate (BA) monomers into the dispersion containing water soluble initiator 4,4’-azobis (4-cyanopentanoic acid) (V501). Shell thickness could be controlled by adjusting the amount of coating monomer added. Polymer encapsulation of SPIONs aligned in a magnetic field produced polymer encapsulated SPION rods. Monodispersed sterically stabilized crosslinked polymer encapsulated SPIONs were synthesized using diblock and random macro-RAFT copolymers as stabilizers. Rhodamine labeled SPIONs were found to be non-cytotoxic and suitable for cell labeling.

We present the preparation of 11 nm polyacrylamide-stabilized polystyrene latex particles for conjugation to a microRNA model by surfactant-free RAFT emulsion polymerization. Our synthetic strategy involved the preparation of amphiphilic polyacrylamide-block-polystyrene copolymers, which were able to self-assemble into polymeric micelles and "grow" into polystyrene latex particles. The surface of these sterically stabilized particles was postmodified with a disulfide-bearing linker for the attachment of the microRNA model, which can be released from the latex particles under reducing conditions. These nanoparticles offer the advantage of ease of preparation via a scaleable process, and the versatility of their synthesis makes them adaptable to a range of applications.

This work describes a versatile method to encapsulate graphene oxide (GO) with polymers using reversible addition-fragmentation chain transfer (RAFT) mediated emulsion polymerization. A living low molecular weight anionic macro-RAFT statistical copolymer of sodium styrene sulfonate, acrylic acid, and butyl acrylate (BA) was synthesized using 2-{[(butylsulfanyl)carbonothioyl] sulfanyl} propanoic acid as the chain transfer agent. GO was dispersed in water by pretreating the surface with poly(allylamine hydrochloride) (PAH), before being stabilized by the addition of the anionic macro-RAFT copolymer. PAH was used to facilitate the adsorption of the macro-RAFT copolymer to the GO surface via electrostatic attraction between opposite charges. The dispersed GO sheets were encapsulated with polymer by the free radical emulsion polymerization of methyl methacrylate and BA under starved fed conditions. The polymer shells encapsulating the GO sheets were formed by the chain extension of the adsorbed living macro-RAFT copolymer. TEM, SEM, FTIR, and AFM were used to confirm the presence of the polymer layer on the surface of the GO. The thickness of the polymer coating can be adjusted by controlling the amount of monomer fed into the system. Partial polymer coatings of the GO could be achieved by varying the amount of PAH. The encapsulated GO was found to be easily dispersed in both aqueous and organic solvents over a range of polarities. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1413–1421

In this work, we present a novel platform to synthesize polymeric “raspberry” particles and explore their use to fabricate surfaces with low wettability and high water adhesion, resembling the properties of naturally occurring surfaces such as the rose petal. The raspberry particles were obtained by layer-by-layer self-assembly of 850 nm core polystyrene particles bearing surface carboxylate groups and corona nanoparticles of different sizes and polymers (polystyrene, poly(para-fluorostyrene) or poly(2,3,4,5,6- penta-fluorostyrene), also bearing surface carboxylates), interleaved with positively charged poly(ally amine) hydrochloride.The raspberry particles were then bound together by covalent coupling of the carboxylate groups with the amine groups of the polymeric interlayer. The films produced by drop-casting the raspberry particles exhibited static water contact angles between ∼135° and ∼146°, depending on the nature of the corona, hysteresis of ∼135° and high adhesion of water droplets. Since all particles were synthesized from scratch by surfactant free emulsion polymerization in air and every step of the protocol was performed in water, this platform is up-scalable and environmentally friendly.

In this study, we propose an alternative method to produce high solids, micrometer-sized polystyrene (PS) latexes with narrow size distribution, based on the use of large amounts of polymerization initiator and allowing the presence of oxygen in the reaction vessel. We have demonstrated that the deoxygenation of the reaction mixture in surfactant-free emulsion polymerization becomes redundant if enough radical initiator is employed, and that particles with narrow size distribution can be obtained in the presence or absence of oxygen. The significance of this method lies in its simplicity and robustness: the method requires only a single-neck flask sealed with a rubber septum, a magnetic stirrer, and an oil bath. We also show that the use of large amounts of radical initiator allows the preparation of latexes with particularly high solid contents (up to 20 wt %), which is uncommon in systems with no added stabilizing agent.

In this work, successful polymer coating of COOH-functionalized multiwalled carbon nanotubes (MWCNTs) via reversible addition fragmentation chain transfer (RAFT) mediated emulsion polymerization is reported. The method used amphiphilic macro-RAFT copolymers as stabilizers for MWCNT dispersions, followed by their subsequent coating with poly(methyl methacrylate-co-butyl acrylate). Poly(allylamine hydrochloride) was initially used to change the charge on the surface of the MWCNTs to facilitate adsorption of negatively charged macro-RAFT copolymer onto their surface via electrostatic interactions. After polymerization, the resultant latex was found to contain uniform polymer-coated MWCNTs where polymer layer thickness could be controlled by the amount of monomer fed into the reaction. The polymer-coated MWCNTs were demonstrated to be dispersible in both polar and nonpolar solvents. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

In this work, successful synthesis of polymer nanorattles containing titanium dioxide pigment particles in the centers of air voids is reported. The method used amphiphilic macro-RAFT copolymers as stabilizers for pigment dispersion and the subsequent encapsulation of the pigment with polymer. The particles were first encapsulated by a water swellable hydrophilic layer, followed by a hard hydrophobic layer. Nanorattles were formed by swelling of hydrophilic polymer layers on the surface of the encapsulated pigment particles in a basic solution at elevated temperature. After swelling, the outer hard polymer shell was crosslinked to improve its strength. Air void sizes of the nanorattles were found to be controlled by swelling time, temperature, and the hydrophilic polymer layer thickness. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Two model polystyrene seed-latexes were studied by γ-irradiation dilatometry, with one latex stabilized by short chain poly(acrylic acid) the other stabilized by short chain poly(methacrylic acid),...

RAFT-mediated free-radical emulsion polymerization is successfully used to synthesize polystyrene nanofibers using triblock amphiphilic macro-RAFT copolymers as stabilizers. The polymerization is under RAFT control, producing various morphologies from spherical particles, nanofibers, nanoplatelets, and polymer vesicles. Optimum conditions are established for the synthesis of predominantly negatively charged polymer nanofibers. Superparamagnetic iron oxide nanoparticles (SPION)-decorated nanofibers are formed by simple mixing of the SPIONs with the fibers at an appropriate pH. The composite material has been found to be superparamagnetic and could be aligned under a magnetic field.

We describe a method and conditions for the preparation of monodisperse latex particle dispersions using low molecular-weight, amphiphilic styrene-b-acrylic acid macro-RAFT diblock copolymers as sole stabilizers. The macro-RAFT copolymers are soluble in styrene monomer droplets when the acrylic acid is in its neutral, protonated form, but adsorb irreversibly at the interface between the monomer droplets and the aqueous phase to form an insoluble monolayer when conditions favor deprotonation. Droplets thus stabilized exhibited no coarsening by Ostwald ripening over at least several days. Polymerization yielded a one-to-one correspondence between the size of the initial droplets and the resultant latex particles, consistent with ideal miniemulsion polymerization, when the least labile macro-RAFT stabilizer was used. GPC analysis of molecular weights showed that in all cases the polymerization remained under RAFT control. The approach described enables true miniemulsion polymerization to proceed in the absen...

A new method is described, based on living amphipathic random macro-RAFT copolymers, which enables the efficient polymeric encapsulation of both inorganic and organic particulate materials via free-radical polymerization. The mechanism for this new approach is examined in the context of the polymer coating of zirconia- and alumina-coated titanium dioxide particles and its breadth of application demonstrated by the coating of organic phthalocyanine blue pigment particles. The particulate materials were first dispersed in water using a macro-RAFT copolymer as a stabilizer. Monomer and water-soluble initiator were then added to the system, and the monomer polymerized to form the coating. If nucleation of new polymer particles in the aqueous phase was to be avoided, it was found necessary to use a macro-RAFT copolymer that did not form micelles; within this constraint, a broad range of RAFT agents could be used. The macro-RAFT agents used in this work were found not to transfer competitively in the aqueous phase and therefore did not support growth of aqueous-phase polymer. Successful encapsulation of particles was demonstrated by TEM. The process described enables 100% of the particles to be encapsulated with greater than 95% of the polymer finishing up in the polymeric shells around the particles. Moreover, the coating reaction can be carried out at greater than 50% solids in many cases and avoids the agglomeration of particles during the coating step.

Amphiphilic, RAFT-capped, (acrylic acid)x(styrene)y diblock copolymers (x = 10, y ) 10, 5, 0) were synthesized and used as stabilizers in emulsion polymerization. Above the critical micelle concentration (cmc) of the diblocks and under appropriate reaction conditions micelles of the more hydrophobic diblocks were sufficiently nonlabile to be nucleated and act as seed particles for latex particle formation. The key parameters which allow control over the system are diblock hydrophobicity and initiator concentration. A homogeneous nucleation mechanism is most likely to operate below the cmc of the diblocks.

Controlled radical polymerization using RAFT has the potential to make polymers with virtually any desired molecular architecture. For this to be implemented on an industrial scale, it must be performed by polymerization in disperse media. However, simply adding a RAFT agent to a conventional emulsion polymerization recipe leads to a loss of molecular weight control and formation of coagulum, probably because of nucleation in droplets, which is normally an unlikely phenomenon in emulsion polymerizations. Recently, a method has been devised for implementing RAFT in ab initio emulsion polymerization that avoids droplets in the particle formation stage. The molecular weight distribution of the polymer thus formed shows that molecular weight control is maintained throughout the polymerization. A model is developed to predict the particle size formed in this new type of emulsion polymerization. The new methodology enables synthesis of novel dispersions where molecular architecture can be precisely controlled, such as structured core-shell particles.

A method is developed to enable emulsion polymerization to be performed under RAFT control to give living character without the problems that often affect such systems: formation of an oily layer, loss of colloidal stability, or loss of molecular weight control. Trithiocarbonate RAFT agents are used to form short stabilizing blocks from a water-soluble monomer, from which diblocks can be created by the subsequent polymerization of a hydrophobic monomer. These diblocks are designed to self-assemble to form micelles. Polymerization is initially performed under conditions that avoid the presence of monomer droplets during the particle formation stage and until the hydrophobic ends of the diblocks have become sufficiently long to prevent them from desorbing from the newly formed particles. Polymerization is then continued at any desired feed rate and composition of monomer. The polymer forming in the reaction remains under RAFT control throughout the polymerization; molecular weight polydispersities are generally low. The number of RAFT-ended chains within a particle is much larger than the aggregation number at which the original micelles would have self-assembled, implying that in the early stages of the polymerization, there is aggregation of the micelles and/or migration of the diblocks. The latexes resulting from this approach are stabilized by anchored blocks of the hydrophilic monomer, e.g., acrylic acid, with no labile surfactant present. Sequential polymerization of two hydrophobic monomers gives completely novel core-shell particles where most chains extend from the core of the particles through the shell layer to the surface.

A detailed dynamic model was developed for a styrene emulsion polymerisation semi-batch reactor to predict the evolution of the product particle size distribution (PSD) and molecular weight distribution (MWD) over the entire range of monomer conversion. A system exhibiting zero-one kinetics was employed, with the model comprising a set of rigorously developed population balance equations to predict monomer conversion, PSD and MWD. The modelling equations included diffusion-controlled kinetics at high monomer conversion where the transition from the zero-one regime to a pseudo-bulk regime occurs. The model predictions were found to be in good agreement with experimental results. Both particle growth and the PSD were found to be strongly affected by the monomer feedrate. Reactor temperature had a major influence on the MWD which was, however, insensitive to changes in the monomer feedrate. These findings were confirmed experimentally. As a result, it seems reasonable to propose that the use of the monomer feedrate to control the PSD and the reactor temperature to control the MWD are appropriate in practical situations. Consequently, an optimal monomer feed trajectory was developed off-line (using the validated reactor simulation) and verified experimentally by producing a polymer with specific PSD characteristics.

The authors report the preparation of a novel range of functional polyacrylamide stabilized polystyrene nanoparticles, obtained by surfactant-free reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization, their fluorescent tagging, cellular uptake, and biodistribution. The authors show the versatility of the RAFT emulsion process for the design of functional nanoparticles of well-defined size that can be used as drug delivery vectors. Functionalization with a fluorescent tag offers a useful visualization tool for tracing, localization, and clearance studies of these carriers in biological models. The studies are carried out by labeling the sterically stabilized latex particles chemically with rhodamine B. The fluorescent particles are incubated in a healthy human renal proximal tubular cell line model, and intravenously injected into a mouse model. Cellular localization and biodistribution of these particles on the biological models are explored.

The extended retardation of the free-radical seeded emulsion polymerisation of vinyl acetate by oxygen has been modelled and fitted to experimental data. It is argued that the unusually long retardation observed in this system is due to the high entry efficiency of the aqueous-phase oligomeric radicals which allows latex particles to compete with dissolved oxygen for these initiating radicals. This, in the case of VAc, is due to the high value of the product of the propagation rate coefficient and the water solubility. As oxygen is consumed the competition increasingly favours entry of initiating radicals into particles and the polymerisation rate gradually increases. The model also qualitatively predicts the much shorter retardation behaviour of styrene and MMA which is due to the lower values of the product of the propagation rate coefficient and the water solubility for these monomers.

Emulsion polymerization offers consider-able advantages for such industrial synthesis. Hitherto,attempts to implement RAFT in ab initio (unseeded)emulsion have met with problems such as loss ofmolecular weight control, loss of colloidal stability, and/or formation of an intractable oily layer (e.g., ref 2).Various reasons for these problems have been suggested(e.g., refs 2 and 3), including hydrolysis of the RAFTagent, poor transport of RAFT agent through the waterphase, and formation of oligomers in droplets (i.e.,droplet polymerization) arising from the presence ofRAFT agent therein. On the other hand, it has provedpossible to eliminate all these problems by performingRAFT in a seeded emulsion polymerization using a (78nm diameter) seed and a highly hydrophobic RAFTagent which was transported to the seed particles usingacetone, the acetone being subsequently removed byrotary evaporation prior to polymerization.

Anisotropic polymer-inorganic composite latex particles were synthesized by using a RAFT-based encapsulation approach on cationic gibbsite platelets. By using the RAFT agent dibenzyl trithiocarbonate, a series of amphipatic living random RAFT copolymers with different combinations of acrylic acid and butyl acrylate units were synthesized. These RAFT copolymers were used as living stabilizers for the gibbsite platelets and chain extended to form a polymeric shell by starved feed emulsion polymerization. Cryo-TEM characterization of the resulting composite latexes demonstrates the formation of anisotropic composite latex particles with mostly one platelet per particle. Monomer feed composition, chain length, and hydrophilic-lipophilic balance of the RAFT copolymer were found to be important factors for the overall efficiency of the encapsulation. Good control over platelet orientation and high encapsulation efficiency were achieved via this route. © 2009 American Chemical Society.

Anisotropic polystyrene nanoparticles of diameters below 0.5 microm were prepared by coating the surface of cross-linked polystyrene latex particles with a thin hydrophilic polymer layer prior to swelling the particles with styrene and then initiating second-stage free-radical polymerization. Conditions were found so that all particles had uniform asymmetry. The effect of surface chemistry on the development of particle anisotropy during seeded emulsion polymerization of sub-0.5 microm diameter particles was studied. The extent and uniformity of the anisotropy of the final particles depended strongly on the presence of the hydrophilic surface coating. Systematic variation of the degree of hydrophilicity of the surface coating provided qualitative insight into the mechanism responsible for anisotropy. Conditions were chosen so that the surface free energy favored the extrusion of a hydrophobic bulge of monomer on the hydrophilic surface of the particle during the swelling phase: the presence of a hydrophilic layer on the particle surface causes this asymmetry to be favored above uniform wetting of the particle surface by the monomer. Kinetic effects, arising from the finite time required for the seed to swell with the monomer, also play a role.

Recent advances in the use of reversible addition–fragmentation chain transfer (RAFT) polymerization in dispersed phase systems have paved the way for the fine control of the morphology of latex particles that was not possible by conventional free radical polymerization techniques. With this approach, living amphiphilic block copolymers are synthesized that self-assemble to form micelles. The hydrophilic segment is formed from a water-soluble monomer which stabilizes the latex particles as polymerization proceeds and the latex particles grow. The hydrophobic ends of the RAFT diblocks ultimately grow into the polymer that forms the body of the particles. This paper presents examples of ways in which these advances can be used to engineer latex particles with unique morphologies that exhibit specific application properties.

A theoretical procedure is developed that allows the importance of bimolecular termination in the aqueous phase of an emulsion polymerization to be determined. This shows that with sparingly-soluble and slowly propagating monomers like styrene, significant termination occurs in the aqueous phase at high initiator concentrations, as found experimentally. With more water soluble monomers, aqueous phase termination is likely to be small.

Data are presented on the time evolution of particle-size distributions (PSDs) in seeded and ab initio styrene emulsion polymerization systems. Initiation was by chemical reagent (potassium persulfate) or γ-radiation. The unswollen PSDs at various times during interval II of the polymerization were obtained by direct measurement of calibrated electron micrographs. Experimental results were fitted with the equations that describe the time evolution of an initial PSD. Analytic solutions to these equations that allow for entry, exit, and propagation of free radicals were obtained. The values of the rate coefficients for these processes used to fit the experimental data were in excellent agreement with those obtained from dilatometric kinetics experiments.

Matrix methods are used to obtain general solutions for the Smith-Ewart case II mechanism for emulsion polymerizations; this relates to systems for which bimolecular termination is considered to be more important than free radical exit from the particles. These solutions are compared with simplified forms of the general solutions derived from case I, wherein exit is assumed to be more significant than termination. In neither case is resort made to the steady state approximation. There appears to be general agreement between theory and the results for the seeded emulsion polymerization of vinyl acetate, although discrepancies were apparent when very stringent comparisons were made.

Using matrix methods, complete time-dependent solutions are derived for the Smith–Ewart equations describing polymerization in emulsion systems with a constant number of polymerizing loci, where the mechanisms of free radical entry, exit and termination all operate simultaneously. The results, which are valid for any system where the average number of free radicals per particle is < ∼ 0.6, reduce to previous, more restricted, solutions under the appropriate limits.

The kinetics of the seeded emulsion polymerization of styrene, with the swollen radii of the seed ranging from 44 to 79 nm, have been measured dilatometrically. The conversion against time curves displayed an increase in the instantaneous rate of polymerization, followed by an apparent steady state domain. These measurements permitted for the first time the direct evaluation of the kinetic parameters that govern both the entry of free radicals into the latex particles and the first-order loss of free radicals from the particles. The latter rate coefficient was found to vary with the inverse square of the swollen particle radius, as expected for the diffusion controlled exit of free radicals from the particles. The magnitudes of the observed entry rate coefficients, when coupled with their dependence upon the initiator concentration, suggest that free radical capture by the seed particles was relatively inefficient. The capture efficiency increased significantly, however, with decreasing initiator concentration if the number of seed latex particles was held constant. The results obtained show clearly that the average number of free radicals per particle can be < 1/2 for styrene emulsion polymerizations under suitable conditions (e.g., low initiator concentrations and/or small particle sizes). Thus styrene can follow Smith—Ewart case 1 kinetics.The validity of the interpretation of the data is strongly supported by the excellent agreement with literature values obtained for various kinetic parameters.A background initiation process that causes the emulsion polymerization of styrene to proceed in the absence of added initiator was detected. This appears to be the emulsion polymerization analogue of the thermally induced bulk polymerization of styrene.