Self-assembly of water insoluble polymers into Colloidal Unimolecular Polymer (CUP) particles of 3–9 nm

Colloidal Unimolecular Polymer, CUP, particles were synthesized and characterized as a potential new and useful spheroidal polymer conformation for a variety of applications. Also known as single chain nanoparticles, these nanomaterials are gaining in popularity. The route to CUP particle formation is an innovative approach utilizing a small number of hydrophilic groups along a hydrophobic polymer backbone which transitions from a random coil conformation in organic solvent to a hard sphere in water through a slow gradient with subsequent solvent removal. The CUP particles have diameters which are proportional to their molecular weights and range typically from 3 nm to over 9 nm. These CUP particles were stable in water and free of solvent or surfactants. The sodium or potassium salts of CUP particles are spheroidal and are able to be dried then re-dissolved in water with no aggregation, unlike the original polymer. The diameters of the CUP particles correlate with the absolute number average molecular weight (M_n) and distributions from the GPC. Molecular weights from 28K to 122K are reported here and are based on an acrylic copolymer having a molar ratio of 9:1 MMA:MAA.     

Semi-continuous emulsion copolymerization of vinyl acetate and butyl acrylate in presence of AMPS

The emulsifier-free emulsion polymerization of vinyl acetate (VAc) and butyl acrylate (BA) in the presence of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) was carried out by a semi-continuous process. AMPS was a reactive surfactant in the aqueous emulsion, due to its amphiphilic structure and the unsaturated double bonds. Potassium persulfate (KPS) was used as initiator. The following factors were mainly examined: quantity of AMPS, BA and KPS concentrations, which could significantly affect the particle size and its distribution, conversion, gel content, minimum film-forming temperature, etc. The particle size and its distribution were characterized by dynamic laser particle size analyzer, and morphology of the latex particles was characterized by transmission electron microscopy (TEM). Fourier transform infrared spectroscopy was used to characterize chemical structure of copolymers. The results indicated that AMPS was successfully reacted onto the resulted copolymer of vinyl acetate and butyl acrylate. A hydrophilic sulfonic acid group in the molecular structure of AMPS tended to be distributed in particles surface after polymerization. As a result, an electrostatic repulsion between the particles was produced in order to maintain stability of the system. Thermogravimetric analysis curves suggested that as BA content increased, thermal stability of the polymer increased accordingly. The conversion-time plots with varying AMPS and initiator contents were obtained, which illustrated that the initiator concentration could greatly influence the polymerization rate and the final conversion. The TEM micrographs of the final emulsifier-free latex particles for P(VAc/BA/AMPS) system revealed small particle size in monodisperse polymer latex. The particles of the latex were measured as about 150 nm.     

Preparation and assembly performance of colloidal particles of photonic crystals with controlled photonic band gaps

Monodisperse microspheres with average particle size in the range of 100–600 nm, whose main monomer was styrene, were prepared by soap-free emulsion polymerization. The factors influencing polymer colloidal particle sizes and size distributions were investigated, including initiator concentration, polymerization temperature and hydrophilic monomer amount. Then, six kinds of polymer microspheres with average size from 153 nm to 565 nm were selected to grow colloid photonic crystal by vertical deposition method. Results showed that photonic band gaps could be effectively adjusted by changing the particle size. The obtained photonic crystals were highly ordered face-centered cubic structures. Furthermore, vertical deposition was only suitable for particles with average size less than 300 nm.     

Synthesis and characterization of novel biodegradable water dispersed poly(ether-urethane)s and their MWCNT-AS nanocomposites functionalized with aspartic acid as dispersing agent

New biodegradable poly(ether-urethane)s (PEU)s were synthesized via the reaction of L-leucine anhydride cyclo-peptide, polyethylene glycol-1000 and hexamethylene diisocyanate. Then, they were end-functionalized with aspartic acid (AS) as a dispersing agent and were dispersed in water. MWCNTs were also functionalized by AS under microwave irradiation. Polymer/MWCNT-AS composites and polymer/MWCNT-AS water dispersed composites were prepared through an ultrasound-assisted method. We have designed these PEUs with two different structural architectures (PA1and PA2) which can be readily dispersed in water (PA1-D and PA2-D). The structure and properties of the polymers, MWCNTs-AS and PEUs/MWCNTs-AS composites were investigated by FTIR and NMR spectroscopy methods and FE-SEM, TEM and TGA techniques. The particle sizes of the resulting PA1-D and PA2-D dispersions were in the range of 200–300 nm. The results showed that by increasing MWCNT-AS loading, the degradation rate and particle sizes of the dispersed composites decreased, while thermal stability and dispersion stability of the composite systems increased. The degradation tests of polymers and their composites in PBS at 37 °C after 10 days showed weight losses ranging from 23 to 44 and 17–37%, respectively. The cytotoxicity study of polymers using the direct-contact test on L929 mouse fibroblast cell line showed no toxicity. Other properties such as thermal stability, dispersion’s particle size, degradation rate and morphology of the composites were studied, and the effect of simultaneous dispersion of MWCNTs-AS and PEUs in water on the properties of the resulting mixtures was studied. We suggest that these polymers have tunable properties which may potentially be considered for drug carriers’ studies.     

Synthesis and characterization of poly(styrene‐co‐butyl acrylate)/clay nanocomposite latexes in miniemulsion by AGET ATRP

Polymer/clay nanocomposite latexes in the form of positively charged nanoparticles were synthesized by a newly developed initiating system, activators generated by electron transfer (AGET), which has been employed in atom transfer radical polymerization (ATRP). These clay‐dispersed latexes were synthesized using AGET ATRP of styrene and butyl acrylate in a miniemulsion system in which, ascorbic acid as a reducing agent was added drop wise to reduce termination reactions. Particle size and particle size distribution of resulted nanocomposite latexes were characterized by dynamic light scattering (DLS). These latexes were in the range of 138 to 171 nm in size. Gel permeation chromatography (GPC) was used to characterize the molecular weight and molecular weight distribution of the resultant copolymer nanocomposites. GPC traces showed that polymers of narrow molecular weight distribution and low Polydispersity Index (PDI) have been synthesized; this clearly shows ATRP reaction is conducted successfully. By increasing nanoclay content, molecular weight of the nanocomposites decreases. The presence of the nanofiller increases the thermal stability of the nanocomposites as investigated by thermogravimetric Analysis (TGA). Glass transition temperature of nanocomposites increases compared with the neat copolymer which was studied by differential scanning calorimetry (DSC). scanning electron microscope (SEM) showed sphere morphology of polymer particles synthesized by miniemulsion polymerization. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that mixed intercalated and exfoliated morphology is obtained. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

A novel approach to prepare large-scale and narrow-dispersed latex particles by emulsion polymerization based on particle coagulation mechanism

In order to understand the mechanism of narrow particle size distribution of the final latex during particle coagulation, a series of experiments were performed to investigate the effect of polymer nature on particle coagulation capability. In particular, thermodynamics and kinetics in aqueous phase were considered to illustrate the detail process of particle coagulation. The final particle size decreased with the increasing side chain length of alkyl methacrylate from 181.5 nm in MMA to 131.6 nm in EMA, 119.3 nm in PMA, and 115.1 nm in BMA, indicating that the particle coagulation capability was proportional to the hydrophilicity of polymer. With increasing polymer hydrophilicity, the affinity between surfactant molecules and particle surface decreased, thus enhancing the particle coagulation capability. Moreover, the critical length of oligomer radical also increased with increasing hydrophilicity and the efficiency of radical capture decreased, thus increasing the saturation of monomer concentration in the inner part of particle, promoting particle coagulation. Combining these results and the La Mer Diagram, a novel approach was developed to prepare large-scale, narrow-dispersed, and high solid content polymer latex based on particle coagulation mechanism. Three criteria, namely, rapid nucleation, fast coagulation, and a long growth period, should be met to produce latex with a narrow particle size distribution.     

Population balance modeling for a continuous gas phase olefin polymerization reactor

Steady-state population balance models have been developed for a continuous flow gas phase olefin polymerization process with both uniform sized and log-normally size distributed high activity catalyst feeds. For the calculation of polymer properties such as molecular weight averages and weight fraction of comonomers in the copolymer, a multigrain solid core model was used with an assumption that intraparticle monomer mass transfer resistance is negligibly small. The multigrain solid core model was incorporated into the population balance model and the effects of feed catalyst particle size distribution and catalyst deactivation parameters on the polymer production rate, polymer particle size distribution, and polymer properties were investigated. It is observed for deactivating catalyst that the polymer particle size distribution tends to be narrower with a reduced amount of large polymer particles. For the catalyst with nonuniform site deactivation, polymer particles of different sizes exhibit different molecular weight and copolymer composition. © 1994 John Wiley & Sons, Inc.     

Einfluß des stofftransportes bei der polymerisation von äthylen und 1-okten mit Ziegler-Katalysatoren

The polymerization of ethylene and 1-octene with supported Ziegler-catalysts was investigated with regard to the influence of mass transport of monomers on the kinetics, molecular weight and molecular weight distribution. In the case of the polymerization of ethylene, it was found that for certain conditions of reaction the mass transport of ethylene can influence the kinetics of polymerization respectively the catalyst efficiency strongly. The molecular weight and molecular weight distribution of the polyethylene formed are practically not affected by the conversion as well as particle size of catalyst and polymer. The molecular weight distribution however is affected by the concentration of the catalyst. The polymerization process of ethylene in suspension is distinguished by chemical and physical processes. A continuous chain initiation, for example, is based on the continuous reduction of the catalyst particles to small pieces during the course of polymerization. An apparent chain termination respectively catalyst deactivation can occur when catalyst particles are encapsulated within the growing polymer particles. The polymerization of 1 -octene for similar conditions of reaction gave polymers which were solved completely in the system used. The molecular weight distribution of the polymer formed nevertheless was very broad. This indicates that the mass transport of the monomers through the solid phase of polymer cannot be the main reason for the broad molecular weight distribution of the polymers which are produced by heterogeneous Ziegler-catalysts in suspension.     

Effect of Basic Factors of Preparation on Characteristics,Hydrolytic Degradation,and Drug Release From Poly(ester-anhydride) Microspheres

Functional poly(ester-anhydride) microspheres were prepared using emulsion solvent evaporation (ESE) and phase inversion methods (PIM). The poly(ester-anhydride)s were obtained by polycondensation of sebacic acid (SBA) and oligo(3-allyloxy-1,2-propylene succinate) terminated with carboxyl groups (OSAGE). The effects of various parameters, including: polymer and emulsifier concentrations, stirring speed and molecular weight of polyvinyl alcohol (PVA) used as emulsifier on size, size distribution and morphology of microspheres obtained by ESE technique were examined. The size of microspheres obtained was in the range 2–30 µm and depended mainly on the stirring rate in emulsion formulation process, as well as concentration of polymer solution used. Molecular weight of PVA, and its concentration in aqueous phase, significantly influenced tendency to agglomeration of microparticles formed, but only slightly changed the size of microspheres. The present study demonstrated that the ESE method can be useful to formulate, from functional poly(ester-anhydride)s, small (2–3 µm) or large (20–30 µm) microspheres with relatively narrow size distribution. Such microspheres were loaded with three model compounds (rhodamine B, p-nitroaniline, and piroxicam) with different water solubility and their release characteristics were examined. In the present study microparticles were also obtained by alternative phase inversion method to compare mainly stability of polymers during formulation of microspheres by both techniques.     

Core-shell structured latex particles. III. Structure–properties relationship in toughening of polycarbonate with poly(n-butyl acrylate)/poly(benzyl methacrylate–styrene) structured latex particles

The performance of the designed structured core-shell latex particles in toughening polycarbonate (PC) matrix was examined. Izod impact testing of the PC-core-shell latex blends were used to evaluate the influence of parameters related to the core-shell latex particles on toughening polycarbonate. Among these parameters are the particle size and levels of crosslinking of the core rubber particles, composition and molecular weight of the shell polymer, and weight ratio of shell to core polymers as well as the particle morphology. In this work, core-shell structured latex particles with thinner shells of higher molecular weight polymers were found to improve the impact resistance of polycarbonate. The role of chain entanglements in increased adhesion between the discrete rubbery phase and the continuous glassy matrix and the importance of surface-to-surface interparticle distance for toughening at various temperatures are discussed. © 1995 John Wiley & Sons, Inc.     

Synthesis, characterization and morphology of polyanthranilic acid micro- and nanostructures

Polyanthranilic acid (PANA) nanofibres, nanorods, nanospheres and microspheres were synthesized by polymerization of anthranilic acid using ammonium peroxydisulfate (APS) as oxidant without hard or soft templates. Polymerization of anthranilic acid was carried out in aqueous solutions of strong (hydrochloric) and weak (acetic) acids. The influence of synthetic parameters such as oxidant, initiator, dopant acid and its concentration, redox initiator, and reaction medium on the morphology and particle size of PANA have been investigated. PANA nanofibres and nanorods were obtained via redox polymerization of anthranilic acid initiated by FeSO₄ as redox initiator. PANA nanospheres and nanofibres were also obtained when used aromatic amines as initiators. When polymerization carried out in the solution of weak (acetic) acid the microsphere morphology obtained and the particle size increase with increasing the concentration of weak acid. PANA nanorods were obtained also by polymerization of anthranilic in ethanol-water mixture unlike interfacial polymerization of anthranilic acid (in chloroform-water) that give PANA microspheres. The morphology and particle size of PANA was studied by scanning electron microscope (SEM) and transmission electron microscope (TEM). The average diameter of nanostructures obtained ≤100 nm. The optical bandgap of microspheres and nanofibers polymeric products were determined using UV-vis spectroscopic technique and found to be 2.0 eV and 1.6 eV, respectively. The bandgap decreased with decreasing the particle size. IR spectrum confirmed the structure of PANA nanofibres (synthesized with FeSO₄ as redox initiator) in emeraldine form. The thermal stability of polymer obtained was determined by thermal gravimetric analysis (TGA). The molecular weight was determined also by gel permeation chromatography (GPC).     

Preparation of Raspberry-Like Adsorbed Silica Nanoparticles via Miniemulsion Polymerization Using a Glycerol-Functionalized Silica Sol

A series of polymer/SiO₂ organic-inorganic composite microspheres were successfully prepared through miniemulsion polymerization. A TEM study indicated that the composite microspheres had raspberry-like morphology and silica particles were successfully deposited onto the surfaces of organic polymer microspheres. The average particle size and the silica content of composite microspheres could range from 180 nm to 240 nm and 15 ～ 35 wt%, respectively. The influence of reaction conditions such as the amount of emulsifier, the sonification frequency and sonification time, the amount of silica sol, butyl acrylate (BA) on the particle size, silica content and morphology of composite microspheres have been studied.     

Effect of Supercritical Ethanol Drying on the Properties of Zinc Oxide Nanoparticles

The synthesis, characterization, and application as polymers and anti-wear additives of nanosized zinc oxide particles obtained by conventional and supercritical ethanol drying are reported in this study. The nanaoparticles of ZnO produced by the two different drying techniques were characterized using Fourier Transform Infrared (FT-IR) spectrophotometry, Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD) and Thermogravimetric analysis (TGA) to elucidate the shape, size, composition, and stability of the nanoparticles. ZnO nanoparticles were then applied to poly (vinyl chloride) (PVC) powder and light mineral oil to assess their effectiveness and suitability as additives in diverse areas. XRD analysis revealed ZnO crystalline structure with average particle size of 24.7 nm for zinc oxide nanoparticles prepared by supercritical ethanol drying while SEM showed well-isolated and monodisperse particles with average size of 61.08 nm.     

Preparation of styrene‐maleic acid copolymers and its application in encapsulated pigment red 122 dispersion

Styrene‐maleic acid copolymers were synthesized by free radical polymerization. Encapsulated pigment red 122 dispersions were prepared by sedimentation with these copolymers. Effects of copolymer structure such as molar content of maleic acid, molecular weight, and the amount of copolymers on stability and particle size of dispersion were investigated. The results showed that encapsulated pigment dispersion with higher stability, smaller particle size, and narrower particle distribution could be achieved when the molar content of maleic acid was at 0.43 and the intrinsic viscosity was at 79.65 ml/g with amount of copolymers 10%. The encapsulated layer was about 5 nm which could be observed by TEM. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Size-Resolved Particle Fluxes and Vertical Gradients over and in a Sparse Pine Forest

Although a number of flux data sets indicate apparent upward fluxes of particles over forests, the causes of such fluxes remain only partially understood. Using data collected during the 2011 BEACHON experiment, it is shown that over one third of fluxes of both sub- and super-30-nm diameter particles over this sparse pine forest are upward. Quadrant analysis, timescale analysis using a particle dynamics model, and frequency power spectra of particle concentrations demonstrate that, in this environment, the morning upward fluxes tend to be associated with downward “sweeps” of particle depleted air during break down of the nocturnal inversion, and it is the most common mechanism resulting in upward fluxes of particle size distributions with diameters above 30 nm. Upward fluxes of particles later in the day are more strongly linked to “ejections” of particle enriched air from the canopy that are attributable to growth of fairly recently nucleated particles by both addition of oxidation products of biogenic volatile organic compounds and coagulation. This mechanism appears to dominate upward fluxes of sub-30-nm particles, although the resulting destabilization of the particle size distribution can result in upward fluxes of larger particles. Vertical gradients of particle size distribution above, through, and below the canopy are also analyzed to investigate the size dependence of canopy uptake of particles and indicate that, in accord with wind tunnel analyses, penetration efficiencies are lower for smaller geometric mean diameters (～15–20 nm) and increase with diameter up to approx. 80 nm (the largest diameter considered here).

Copyright 2013 American Association for Aerosol Research     

Effects of molecular weight distribution on the spinodal temperature of polymer mixtures

The effects of molecular weight distribution on the phase stability of polymer mixtures were explored theoretically and experimentally. Based on the lattice‐fluid theory and volume‐fluctuation thermodynamics, the spinodal conditions for a lattice‐fluid mixture of two polymers with molecular weight distribution were derived. The results indicated that the phase stability of a polymer mixture decreases by increasing the molecular weight distribution of polymers in the blend. To confirm the theoretical results with experiments, the changes in the spinodal temperatures of poly(ethyl methacrylate)/polystyrene (PEMA/PS) blends and tetramethyl polycarbonate/polystyrene (TMPC/PS) blends were examined when each component has a different molecular weight distribution. When the weight‐average molecular weight of each component is the same, a blend composed of polymers having broad molecular weight distribution always exhibited lower phase separation than that composed of polymers having narrow molecular weight distribution at the same blend composition. Copyright © 2004 Society of Chemical Industry     

Particle nucleation and growth mechanisms in miniemulsion polymerization of styrene

Styrene miniemulsion polymerizations stabilized by sodium lauryl sulfate in combination with a reactive costabilizer, lauryl methacrylate (LMA) or stearyl methacrylate (SMA), were studied. A small amount of extremely hydrophobic dye was incorporated into monomer droplets (10² nm in diameter) to investigate particle nucleation and growth mechanisms. In addition to monomer droplet nucleation, particle nuclei generated in the aqueous phase (homogeneous nucleation) also play an important role in both LMA‐ and SMA‐containing polymerization systems. The way that these two nucleation mechanisms compete with each other is closely related to the water solubility of the costabilizer (LMA > SMA). The fraction of latex particles originating from homogeneous nucleation increases with decreasing hydrophobicity of the costabilizer. Zeta potential data of latex particles and the molecular weight and molecular weight distribution of emulsion polymers provide supporting evidence for the proposed competitive particle nucleation and growth mechanisms. © 2002 Society of Chemical Industry     

Development of portable aerosol mobility spectrometer for personal and mobile aerosol measurement

We describe development of a portable aerosol mobility spectrometer (PAMS) for size distribution measurement of submicrometer aerosol. The spectrometer is designed for use in personal or mobile aerosol characterization studies and measures approximately 22.5×22.5×15 cm and weighs about 4.5 kg including the battery. PAMS uses electrical mobility technique to measure number-weighted particle size distribution of aerosol in the 10–855 nm range. Aerosol particles are electrically charged using a dual-corona bipolar corona charger, followed by classification in a cylindrical miniature differential mobility analyzer. A condensation particle counter is used to detect and count particles. The mobility classifier was operated at an aerosol flow rate of 0.05 L/min, and at two different user-selectable sheath flows of 0.2 L/min (for wider size range 15–855 nm) and 0.4 L/min (for higher size resolution over the size range of 10.6–436 nm). The instrument was operated in voltage stepping mode to retrieve the size distribution in approximately 1–2 min. Sizing accuracy and resolution were probed and found to be within the 25% limit of NIOSH criterion for direct-reading instruments. Comparison of size distribution measurements from PAMS and other commercial mobility spectrometers showed good agreement. The instrument offers unique measurement capability for on-person or mobile size distribution measurement of ultrafine and nanoparticle aerosol.     

Semibatch styrene suspension polymerization processes

Emulsion and suspension polymerization processes have widely been studied for more than 40 years. Although both polymerization processes are performed in heterogeneous media, each one presents its own typical characteristics, such as the particle size distribution, molecular weight distribution, polymer particle nucleation rate, and polymerization rate. In this study, semibatch styrene suspension polymerizations were carried out with feed compositions typical of emulsion processes. The initial reactor charge resembled the recipe of standard styrene suspension polymerizations, and the emulsion polymerization constituents were added during the batch. The influence of the moment at which the emulsion feed was started on the course of the polymerization and the effects of the feed on the polymer properties were analyzed. The polymer particle morphology and the average molecular weights changed very significantly with the emulsion feed time, and the changes could lead to the production of broad molecular weight distributions. Core–shell polymer particles could also be obtained, with the core being formed of polymer particles originating from the suspension polymerization process and the shell being formed of polymer particles originating from the emulsion polymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3021–3038, 2003     

Effects of operational mode on particle size and number emissions from a biomass gasifier cookstove

Interest in the size distribution of particles emitted from biomass cookstoves stems from the hypothesis that exposure to ultrafine particles is more detrimental to human health than exposure to accumulation mode or other size regimes. Previous studies have reported that gasifier cookstoves emit smaller particles than other cookstove designs under steady operating conditions. In the present study, the number size distribution of particles emitted from a forced-air gasifier cookstove was measured at 1 Hz as the stove transitioned between several steady and transient operating modes. During normal operation, when the stove functioned as a top-lit updraft gasifier, the distribution was bimodal, with peaks at 10 nm and 40 nm, when a pot of water was on the stove. The distribution became unimodal with a peak at 10 nm when the pot was removed. Once the fuel bed had completely gasified and the secondary flame extinguished, the concentration of particles increased and the peak in number concentration shifted to approximately 80 nm. After refueling, when the stove operated as a conventional updraft gasifier, the peak in number concentration decreased to 10 nm. When the secondary flame extinguished a second time, the peak in number concentration increased to approximately 100 nm before decreasing to 20 nm during the char burn-out phase. These results demonstrate that changes in operational mode influence the combustion process and produce distinct changes in the size distribution and rate of particle emissions.

Copyright © 2018 American Association for Aerosol Research