Synthesis of cationic poly(methyl methacrylate)-poly(N-isopropyl acrylamide) core-shell latexes via two-stage emulsion copolymerization

Thermally sensitive poly(methyl methacrylate (MMA))-poly(N-isopropylacrylamide (NIPAM)) core-shell particles were prepared via a two-stage emulsion copolymerization process. Methylene bisacrylamide (MBA), 2,2′-azobis (2-amidinopropane) dihydrochloride (V50) and dodecylethyl dimethyl ammonium bromide (DEDAB) were used as crosslinker, cationic initiator and surfactant, respectively. Functional core-shell particles were prepared using aminoethyl methacrylate hydrochloride (AEMH) as cationic co-monomer to increase the surface charge density. The influences of the crosslinker and co-monomer concentrations on the thickness and swelling capacity of the PNIPAM-based shell layer were studied. The latex particle size and particle size distribution were determined both by dynamic light scattering (DLS) and scanning electron microscopy (SEM). Monodisperse particles were produced with diameters between 150-250 nm (at 25 °C) and 140-190 nm (at 50 °C). The surface charge density was determined by chemical titration and higher values (∼10 μmol/g) were obtained for the functional core-shell particles. The electrokinetic properties of the dispersions at several pH and temperature values confirm the presence of the shell layer and cationic surface charges.     

Preparation and properties of polymer lattices polymerised without surfactants

Series of polystyrene and polymethyl methacrylate latex dispersions have been prepared in the absence of any surfactant using potassium persulphate as an initiator. The latex particles are stabilised by the electrical repulsion generated by the sulphate groups which are covalently linked to the polymer molecules and are not removed by dialysis. The effects of polymerisation temperature, monomer concentration and initiator concentration on the ultimate particle size and conversion were investigated for these two series of lattices. The modal diameters of these lattices were found to be in the range of 530 to 1550 nm for polystyrene lattices, and 140 to 270 nm for polymethyl methacrylate lattices. The surface charge densities were calculated from conductometric titration results for polymethyl methacrylate lattices and were found to increase almost linearly with increase of the concentration of potassium persulphate used.     

Octadecyl acrylate based block and random copolymers prepared by ATRP as comb-like stabilizers for colloidal micro-particle one-step synthesis in organic solvents

Three random and three block copolymers of methyl methacrylate (MMA) and octadecyl acrylate (ODA) were synthesised by atom transfer radical polymerisation. These copolymers were assessed for their application as stabilizers in the one-step non-aqueous dispersion polymerisation of MMA in a non-polar solvent mixture of hexane and dodecane. In all cases stable spherical micro-particle colloidal dispersions were formed with particle diameters in the range of 400-2730 nm. Uniform monodisperse particles with standard deviations in size distributions of less than 5% were obtained in two cases demonstrating the utility of ODA:MMA copolymers as replacement preformed stabilizers in the one-step synthesis of MMA micro-spheres.     

Analysis of sequence distribution in methyl methacrylate-methyl acrylate copolymers by C NMR spectroscopy

Methyl methacrylate (MMA)-methyl acrylate (MA) copolymers, prepared in bulk at 50 °C using AIBN as initiator, were characterized by 150 MHz ¹³C NMR spectroscopy, including use of the Distortionless Enhancement by Polarization Transfer (DEPT) experiment to obtain methylene and methine carbon resonances as subspectra. Dyad, triad, tetrad and partial pentad distributions were measured from the α-methyl, methine and methylene carbon resonances. These were in good agreement with distributions calculated for the copolymers based on monomer feed compositions, conversions and reactivity ratios of 2.60 and 0.27 for methyl methacrylate and methyl acrylate, respectively.     

Nanoparticle formation by highly diffusion-controlled emulsion polymerisation

Emulsion polymerisations of several monomers with different water solubilities including styrene, butyl acrylate, methyl methacrylate, vinyl acetate, and methyl acrylate were carried out under highly diffusion-controlled conditions. The monomer was placed on top of an aqueous solution of an emulsifier and an initiator, while being gently stirred. Polymerisation occurred by diffusion of monomer from the monomer phase via the interface to the micellar solution. Nanoparticles as small as 25 nm were produced as a result of reduced particle growth and delayed depletion of emulsifier micelles. Nanolatexes with relatively high solids content (20%) but with a low surfactant/monomer ratio (1/50) were obtained. The monomers with the highest solubility, with the exception of methyl acrylate, produced the smallest particles. The rate of diffusion-controlled polymerisation was found to be almost proportional to the saturation monomer concentration in the water phase . The results were compared with those obtained with a high rate of agitation which allowed kinetics of polymerisation to become the rate determinant. While particles obtained by kinetics-controlled emulsion polymerisation of the monomers were large, as well as similar in size, particles obtained from diffusion-controlled runs were small, but different in size. On the other hand, particles made by kinetics-controlled emulsion polymerisation had increasing surface coverage (by emulsifier) with monomer solubility in water. Whereas, nanoparticles made by diffusion-controlled emulsion polymerisation reached almost a constant surfactant coverage independent of the monomer type (except for methyl acrylate), a surface coverage as low as 0.20 was found to be sufficient for stabilisation of nanoparticles.     

Dispersion of polymer-grafted magnetic nanoparticles in homopolymers and block copolymers

The dispersion of magnetic nanoparticles (NPs) in homopolymer poly(methyl methacrylate) (PMMA) and block copolymer poly(styrene-b-methyl methacrylate) (PS-b-PMMA) films is investigated by TEM and AFM. The magnetite (Fe₃O₄) NPs are grafted with PMMA brushes with molecular weights from M = 2.7 to 35.7 kg/mol. Whereas a uniform dispersion of NPs with the longest brush is obtained in a PMMA matrix (P = 37 and 77 kg/mol), NPs with shorter brushes are found to aggregate. This behavior is attributed to wet and dry brush theory, respectively. Upon mixing NPs with the shortest brush in PS-b-PMMA, as-cast and annealed films show a uniform dispersion at 1 wt%. However, at 10 wt%, PS-b-PMMA remains disordered upon annealing and the NPs aggregate into 22 nm domains, which is greater than the domain size of the PMMA lamellae, 18 nm. For the longest brush length, the NPs aggregate into domains that are much larger than the lamellae and are encapsulated by PS-b-PMMA which form an onion-ring morphology. Using a multi-component Flory-Huggins theory, the concentrations at which the NPs are expected to phase separate in solution are calculated and found to be in good agreement with experimental observations of aggregation.     

Multi-site phase transfer catalyst assisted radical polymerisation of glycidyl methacrylate using potassium peroxydisulphate as initiator – a kinetic study

In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate (PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has been proposed to account for the experimental observations and its significance discussed.     

The transformation of acetylene black into onion-like hollow carbon nanoparticles at 1000 °C using an iron catalyst

Acetylene carbon blacks were heat treated at 1000 °C in the presence of ferric nitrate. The morphologies and structural features of original carbon blacks and the carbonized product were investigated using TEM, HRTEM, XRD and nitrogen sorption measurements. It was found that, with the increase of ferric nitrate loading from 4:1, 8:1, 12:1 to 16:1 (the weight ratio of ferric nitrate to acetylene carbon black), the yield of carbonized product decreased from 64.6%, 61.8%, 46.2% to 28.6%. Onion-like hollow carbon nanoparticles with diameter of 40 to 100 nm were generated, implying that the discontinuous short fragments of carbon black were reconstructed and transformed into turbostratic concentric graphitic layers by the iron-based catalytic graphitization. The mechanism was discussed briefly.     

Microscopic polymer cups by electrospinning

Polymer solution above a critical concentration is generally required for making a uniform diameter nano fiber by electrospinning. Below this critical concentration, nanofibers are accompanied with bead formation and, therefore, this concentration region has not received much attention. A systematic investigation reveals that unique particle shapes can be obtained by electroprocessing within this lower concentration range. Several micrometer diameter poly(methyl methacrylate) PMMA cups with wall thickness in the 200-800 nm range and 50-300 nm size pores have been obtained by electroprocessing in high dielectric constant solvents.     

Fabrication and characterisation of polymer thin-films derived from cineole using radio frequency plasma polymerisation

The development of organic polymer thin-films is critical for the progress of many fields including organic electronics and biomedical coatings. This paper describes the fabrication of an organic polymer thin film produced from 1,8-cineole via radio frequency plasma polymerisation. A deposition rate of 55 nm/min was obtained under the polymerisation conditions employed. Infrared spectroscopic analysis demonstrated that some functional groups observed in the monomer were retained after the polymerisation process, while new functional groups were introduced. The refractive index and extinction coefficient were estimated to be 1.543 (at 500 nm) and 0.001 (at 500 nm) respectively. The polymers were shown to be optically transparent. AFM images of the polymer established a very smooth and uniform surface with average roughness of 0.39 nm. Water contact angle data demonstrated that the surface was stable while in contact with water.     

Single-monomer acrylate-based resin for three-dimensional photonic crystal fabrication

A single-monomer acrylate resin (SR348, Sartomer) with an aromatic ketone photoinitiator (Irgacure 369, Ciba) has been developed to produce photonic crystal structures by two-photon photopolymerisation. Compared with more complex acrylate-based resins, this one-component resin is easily prepared. The material is homogeneous before and after photocuring and has a high photosensitivity. SR348 (ethoxylated (2) bisphenol A dimethacrylate) is a difunctional monomer, which generates an insoluble crosslinked network by free radical polymerisation. The polymerised material is thermally stable up to 300 °C. Its refractive index jumps from 1.54 to 1.59 upon polymerisation. Scanning electron microscopy images of photonic crystal structures reveal a minimum structural element size of approximately 300 nm. The photonic crystals were fabricated in a 40 layer woodpile structure at a layer-spacing of 500 nm and an in-plane rod spacing of 1.5 μm. Fundamental stop gaps were observed in the stacking direction at wavelengths of 1.9-2.3 μm dependent on the rod size. Suppression of infrared light transmission of as much as 40% in the stop gap region and gap/midgap ratios of up to 0.15 demonstrate the high degree of correlation of structural elements in three dimensions.     

Dispersion polymerization of 2-hydroxyethyl methacrylate stabilized by a hydrophilic/CO2-philic poly(ethylene oxide)-b-poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) (PEO-b-PFDA) diblock copolymer in supercritical carbon dioxide

Dispersion polymerization of 2-hydroxyethyl methacrylate (HEMA) has been successfully performed in supercritical carbon dioxide at P=370 bar and T=65 °C with azobis(isobutyronitrile) as initiator and a hydrophilic/CO₂-philic poly(ethylene oxide)-b-poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) (PEO-b-PFDA) block copolymer as steric stabilizer. The PEO-b-PFDA (2K/21K) block copolymer was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Spherical particles of poly(HEMA) were obtained in the range of 200-400 nm diameter size with a narrow particle size distribution (D_w/D_n<1.1). The effect of the stabilizer concentration on the dispersion polymerization was investigated from 20 w/w% down to 3.5 w/w% versus HEMA. Precipitation polymerization in the absence of stabilizer lead to the formation of large aggregates of partially coalesced particles whereas discrete spherical particles of poly(HEMA) were obtained by dispersion polymerization even at low concentration of PEO-b-PFDA (3.5 w/w% versus HEMA).     

Synthesis of carbon nanocapsules and carbon nanotubes by an acetylene flame method

The fabrication of carbon nanocapsules and carbon nanotubes (CNTs) using an acetylene flame method was investigated. Carbon nanocapsules, a graphitic structure of nanoparticles with a hollow core, were synthesized using catalyst-free acetylene flames while CNTs were formed with the presence of cobalt-based catalysts in addition to acetylene flames. When the synthesis of these materials was carried out, the results showed that a massive amount of high-purity carbon nanocapsules with a particle size in the range of 15-30 nm can be produced with the acetylene flame method. The CNTs produced were multi-walled carbon nanotubes measuring a few micrometers in length and 20-30 nm in diameter. The acetylene flame method holds great potential for the cost-effective production of CNTs as well as carbon nanocapsules.     

Gadolinium and europium catalyzed growth of single-walled carbon nanotubes

The inner transition metals, gadolinium (Gd) and europium (Eu) have been shown to catalyze the growth of single-walled carbon nanotubes (SWCNTs) using chemical vapor deposition. The Gd and Eu nanocatalysts, prepared using a diblock copolymer templating method and characterized by atomic force microscopy, were uniformly spaced over a large deposition area with an average diameter of 1.9 nm and narrow size distribution. Characterization by transmission electron microscopy and Raman spectroscopy confirms the presence of SWCNTs catalyzed by Gd and Eu with an average diameter of 2.05 nm.     

Electroreduction of oxygen on Pt nanoparticle/carbon nanotube nanocomposites in acid and alkaline solutions

The kinetics of O₂ reduction on novel electrocatalyst materials deposited on carbon substrates were studied in 0.5 M H₂SO₄ and in 0.1 M NaOH solutions using the rotating disk electrode (RDE) technique. Pt nanoparticles (PtNP) supported on single-walled (PtNP/SWCNT) and multi-walled carbon nanotubes (PtNP/MWCNT) were prepared using two different synthetic routes. Before use, the CNTs were cleaned to minimize the presence of metal impurities coming from the catalyst used in the synthesis of this material, which can interfere in the electrochemical response of the supported Pt nanoparticles. The composite catalyst samples were characterised by transmission electron microscopy (TEM) showing a good dispersion of the particles at the surface of the carbon support and an average Pt particle size of 2.4 ± 0.7 nm in the case of Pt/CNTs prepared in the presence of citrate and of 3.8 ± 1.1 nm for Pt/CNTs prepared in microemulsion. The values of specific activity (SA) and other kinetic parameters were determined from the Tafel plots taking into account the real electroactive area of each electrode. The electrodes exhibited a relatively high electrocatalytic activity for the four-electron oxygen reduction reaction to water.     

稳定的阳离子型聚合物纳米粒子胶乳的研制

以甲基丙烯酸甲酯 ( MMA)和丙烯酸乙酯 ( EA)为主单体 ,甲基丙烯酰氧乙基三甲基氯化铵( DMC)为功能单体 ,分别采用 4种阳离子乳化剂和阴离子引发剂过硫酸铵 ( A PS)进行自由基乳液共聚合。探讨了乳化剂种类和用量、聚合温度及加料方式对乳胶粒大小、胶乳稳定性和胶膜耐水性的影响。研究发现 ,当采用十六烷基三甲基氯化铵 ( 16 31)作乳化剂 ,用量为 1.75%～ 2 .0 % ,聚合温度为 70℃ ,采用种子半连续法可以成功研制出粒径为 57.5nm、稳定的耐水性较好的阳离子型聚合物纳米粒子胶乳     

Synthesis and characterization of new polymethacrylates bearing perfluorocyclobutyl and sulfonyl units

A new methacrylate monomer containing perfluorocyclobutyl and sulfonyl units, p-(2-(p-(benzenesulfonyl)phenoxy)perfluorocyclobutoxy)phenyl methacrylate, was synthesized from commercially available reagents in good yield and this kind of methacrylate can be homopolymerized by free radical polymerization using 2,2′-azobis(isobutyronitrile) as initiator or atom transfer radical polymerization using methyl 2-bromopropionate as initiator and CuBr/PMDETA as catalytic system. The reactivity ratios for BSPPFCBPMA and MMA were found to be r₁ = 1.2436 and r₂ = 0.8171 determined by Fineman-Ross method, and r₁ = 1.2279 and r₂ = 0.8023 by Kelen-Tudos method respectively. The resultant polymethacrylates bearing perfluorocyclobutyl and sulfonyl functionalities exhibit excellent thermal stability as evidenced from thermogravimetric analysis and the decomposition temperature rose dramatically with the increasing of molecular weights. Random copolymers of BSPPFCBPMA and methyl methacrylate were obtained by free radical copolymerization and their thermo-stabilities increase while raising the contents of BSPPFCBPMA.     

Preparation of magnetic poly(glycidyl methacrylate) microspheres by emulsion polymerization in the presence of sterically stabilized iron oxide nanoparticles

With the aim to synthesize water‐dispersible superparamagnetic nanoparticles, iron oxide was precipitated in aqueous solution of dextran, (carboxymethyl) dextran (CM‐dextran), (DEAE‐dextran), or D ‐mannose. Glycidyl methacrylate (GMA) was emulsion‐polymerized in the presence of the nanoparticles and the effect of iron oxide modification on the product properties was investigated. The main factors affecting the morphology, size, and size distribution of the latex particles are the type and concentration of emulsifier (Disponil AES 60, Tween 20, Triton X‐100) and initiator [ammonium persulfate (APS) and 4,4′‐azobis(4‐cyanovaleric acid) (ACVA)]. Disponil AES 60 and ACVA are the preferred emulsifier and initiator, respectively, because oxirane groups hydrolyzed during the APS‐initiated polymerization. Up to some 5 wt % of iron was found in poly(glycidyl methacrylate) (PGMA) microspheres obtained by emulsion polymerization in the presence of dextran‐coated iron oxide and emulsified with Disponil AES 60. The size of magnetic PGMA microspheres could be controlled in the range ? 70–400 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4348–4357, 2006     

Polyaniline-carbon composite films as supports of Pt and PtRu particles for methanol electrooxidation

Vulcan XC-72 carbon black particles (average size: ca. 50 nm) was incorporated into polyaniline (PANI) matrix by an electrochemical codeposition technique during the electropolymerization process. The doping by carbon particles leads to a higher polymeric degree and a lower defect density in the PANI structure. Furthermore, the incorporation of carbon particles not only increases the electrochemical accessible surface areas (S_a) and electron conductivity of the PANI film, but also decreases charge transfer resistance at PANI/electrolyte interfaces. Therefore, as expected, a fabricated PANI + C composite film with dispersed Pt and PtRu particles exhibited excellent electrocatalytic activity for methanol oxidation due to better Pt dispersion and utilization. The PANI + C composite film is more promising as a support material in electrocatalysis than a PANI film. Meanwhile, a new application for regular carbon black as a doping material into conducting polymer for electrocatalysis was thus demonstrated.     

Ultraviolet-initiated photografting of glycidyl methacrylate onto styrene–butadiene rubber

Photografting reaction onto styrene–butadiene rubber (SBR) as a function of monomer concentration, grafting method, irradiation time, and the carbon black content has been studied using ultraviolet (UV). Glycidyl methacrylate and benzophenone are used as monomer and initiator, respectively. The occurrence of graft reaction onto SBR surface is identified by infrared attenuated total reflection (IR-ATR) analysis. The degree of monomer graft increases with monomer concentration and tends to level off at high monomer concentration (>8.3M/L). Graft ratio also increases with UV irradiation time. Carbon black content is found as one of important factors that determine the monomer graft efficiency. The amount of monomer graft onto SBR decreases with increasing carbon black content and it is attributed to the reduction of irradiation absorbance due to the presence of carbon black. The occurrence of reaction between glycidyl methacrylate grafted SBR and nylon-6 via melt phase reaction is also identified using IR-ATR analysis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1733–1739, 1999