Dispersion polymerization of acrylamide. III. Partial isopropyl ester of poly(vinyl methyl ether-alt-maleic anhydride) as a stabilizer

Dispersion polymerization of acrylamide at 40 degrees C in t-butyl alcohol-water media of varying composition (50 to 90 vol% alcohol) using a partial isopropyl ester of poly(vinyl methyl ether-alt-maleic anhydride) as the stabilizer has been studied. The isopropyl ester derivative proves to be a better stabilizer than its precursor polymer. However, the particles were polydisperse in size. The number average diameter of the particles increases linearly with the solubility parameter of the dispersion medium. Dispersions of nanoparticles of polyacrylamide are produced when the t-butyl alcohol content of the dispersion medium is 90% by volume. Comparison of the particle diameter measured by transmission electron microscopy with that measured by dynamic light scattering in acetone reveals a thickness of the hairy stabilizer layer on the dispersion particles of 31 nm.     

Conversion of solid poly(methyl vinyl ether-alt-maleimide) to poly(methyl vinyl ether-alt-maleic anhydride)

Solid poly(methyl vinyl-alt-maleimide), when subjected to heating at 100°C while being vacuum pumped at 0.1 mm Hg pressure, was converted to a copolymer in which a substantial portion of the imide groups were converted to anhydride groups. Similarly, heating at 100°C at atmospheric pressure in a circulating air oven brought about the same reaction but at a faster rate. This confirms the hypothesis that the formation of maleic anhydride comonomer units from poly(methyl vinyl ether-alt-ammonium maleamate) not only proceeds directly by ring closure of amic acid formed by loss of ammonia but probably also includes, as a parallel pathway, hydrolysis by atmospheric moisture of maleimide comonomer units.     

Sterically stabilized polypyrrole–palladium nanocomposite particles synthesized by aqueous chemical oxidative dispersion polymerization

Aqueous chemical oxidative dispersion polymerizations of pyrrole using PdCl₂ oxidant were conducted using water-soluble polymeric colloidal stabilizers in order to synthesize polypyrrole–palladium (PPy–Pd) nanocomposite particles in one step. PPy–Pd nanocomposite particles with number average diameters of approximately 30 nm were successfully obtained as colloidally stable aqueous dispersions, which were stable at least for 7 months, using poly(4-lithium styrene sulfonic acid) colloidal stabilizer. The resulting nanocomposite particles were extensively characterized with respect to particle size, size distribution, colloidal stability, nanomorphology, surface/bulk chemical compositions, and conductivity. X-ray photoelectron spectroscopy indicated the existence of poly(styrene sulfonic acid) colloidal stabilizer on the surface of the nanocomposite particles. Transmission electron microscopy studies confirmed that nanometer-sized Pd nanoparticles were distributed in the PPy matrix.     

Surface Functionalization Methods to Enhance Bioconjugation in Metal-Labeled Polystyrene Particles

Lanthanide-encoded polystyrene particles synthesized by dispersion polymerization are excellent candidates for mass cytometry based immunoassays, however they have previously lacked the ability to conjugate biomolecules to the particle surface. We present here three approaches to post-functionalize these particles, enabling the covalent attachment of proteins. Our first approach used partially hydrolyzed poly(N-vinylpyrrolidone) as a dispersion polymerization stabilizer to synthesize particles with high concentration of -COOH groups on the particle surface. In an alternative strategy to provide -COOH functionality to the lanthanide-encoded particles, we employed seeded emulsion polymerization to graft poly(methacrylic acid) (PMAA) chains onto the surface of these particles. However, these two approaches gave little to no improvement in the extent of bioconjugation. In our third approach, seeded emulsion polymerization was subsequently used as a method to grow a functional polymer shell (in this case, poly(glycidyl methacrylate) (PGMA)) onto the surface of these particles, which proved highly successful. The epoxide-rich PGMA shell permitted extensive surface bioconjugation of NeutrAvidin, as probed by an Lu-labeled biotin reporter (ca. 7 × 10(5) binding events per particle with a very low amount of non-specific binding) and analyzed by mass cytometry. It was shown that coupling agents such as EDC were not needed, such was the reactivity of the particle surface. These particles were stable and the addition of a polymeric shell was shown did not affect the narrow lanthanide ion distribution within the particle interior as analyzed by mass cytometry. These particles represent the most promising candidates for the development of a highly multiplexed bioassay based on lanthanide-labeled particles to date.     

Dispersion polymerization of methyl methacrylate: Mechanism of particle formation

The mechanism for the formation of micron-size polymer particles in the dispersion polymerization of methyl methacrylate was investigated by applying dynamic light scattering to monitor the evolution of the average particle size in the early stages of the polymerization. In addition, the contributions of physically adsorbed stabilizer and graft copolymer were evaluated by measuring the bound, unbound (adsorbed), and free stabilizer, and by determining the amount of added stabilizer required in seeded dispersion polymerizations. Twenty nanometer particles (termed nuclei) were the smallest particles detected and are considered to be formed by aggregation of growing polymer chains precipitating from solution as they exceed their critical chain length. Aggregation of these nuclei with themselves and their aggregates continues until mature and stable particles are formed. This occurs when sufficient stabilizer occupies the particle surface which includes both the polymeric stabilizer [poly(vinylpyrrolidone)] and its graft copolymer which is created in situ. The effects of process variables are discussed based on this mechanistic picture of the dispersion polymerization process. © 1994 John Wiley & Sons, Inc.     

Synthesis of polyaspartate macromonomer having a vinyl end group and application to dispersion copolymerization of styrene

Sodium polyaspartate (PAspNa) macromonomer with an acryloyl end group was synthesized for dispersion polymerization. At first, a poly(succinimide) (PSI) derivative with a hydroxyphthalimide end group was synthesized by polycondensation of l-aspartic acid and 4-hydroxyphthalic acid. Then, the PSI derivative was end-capped with an acryloyl group by a reaction with acrlyloyl chloride. Finally, a PAspNa derivative with a vinyl end group was synthesized by a hydrolysis of succinimide units by sodium hydroxide. The synthesized macromonomer was applied as a polymerizable stabilizer in dispersion copolymerization of styrene in a mixture of ethanol and water. The PAspNa macromonomer acted as an effective stabilizer and gave sub-micron-sized polymeric particles in dispersion polymerization in polar medium.     

硫酸铵水溶液中分散聚合法制备两性共聚物P(AM-co-AA-co-DAC-co-DMC)

利用分散聚合技术,在硫酸铵水溶液中以丙烯酰胺(AM)、丙烯酸(AA)、丙烯酰氧乙基三甲基氯化铵(DAC)、甲基丙烯酰氧乙基三甲基氯化铵(DMC)为单体,合成了两性共聚物P(AM-co-AA-co-DAC-co-DMC).用FTIR,13C-NMR,TEM等方法表征了聚合物的结构和组成.考察了不同分散稳定剂、正负离子单体配比和pH对分散聚合的影响,并对P(AM-co-AA-co-DAC-co-DMC)水基分散聚合条件及稳定性进行了一些探讨.实验表明,在硫酸铵水溶液中制得较稳定的P(AM-co-AA-co-DAC-co-DMC)分散体系,应选用非离子型或阳离子型的分散稳定剂,如聚乙烯吡咯烷酮(PVP)、聚甲基丙烯酰氧乙基三甲基氯化铵(PDMC)、聚丙烯酰氧乙基三甲基氯化铵(PDAC),而其pH应在2到4之间.当选用占总质量1.5%的聚乙烯吡咯烷酮(PVP)为分散稳定剂,引发温度为40℃,正负离子单体物质的量比值大于1,pH=3时,可以制得总离子度超过25%的纳米级两性聚合物.     

Dispersion Stability and Electrorheological Properties of Polyaniline Particle Suspensions Stabilized by Poly(vinyl methyl ether)

In the present article, a novel method of stabilization of a semi conductive polyaniline particle nonaqueous suspension of electrorheological (ER) materials was introduced. Using as the steric stabilizer poly(vinyl methyl ether) (PVME), a dispersion polymerization of aniline was performed and stable aqueous dispersions of the polyaniline were obtained. However, a stable colloidal suspension of polyaniline in silicone oil medium can be obtained only with a low concentration of PVME (0.75%), although the average size of the individual, redispersed particles in oil generally decreased with increasing concentration of PVME. At higher concentrations of PVME, formation of highly packed particle aggregates was investigated, as seen in the scanning electron microscopy images. The polyaniline suspension stabilized by 0.75% PVME content exhibited the best dispersing state and, therefore, showed the highest zero-field viscosity. Such a well-stabilized polyaniline suspension also showed the maximum ER property, namely the largest normalized yield stress in an electric field. Copyright 2001 Academic Press.     

Preparation and properties of poly(acrylic acid) oligomer stabilized superparamagnetic ferrofluid

Ferrofluids, which are stable dispersions of magnetic particles, behave as liquids that have strong magnetic properties. Nanoparticles of magnetite with a mean diameter of 10-15 nm, which are in the range of superparamagnetism, are usually prepared by the traditional method of co-precipitation from ferrous and ferric electrolyte solution. When diluted, the ferrofluid dispersions are not stable if anionic or cationic surfactants are used as the stabilizer. This work presents an efficient way to prepare a stable aqueous nanomagnetite dispersion. A stable ferrofluid containing Fe3O4 nanoparticles was synthesized via co-precipitation in the presence of poly(acrylic acid) oligomer. The mechanism, microstructure, and properties of the ferrofluid were investigated. The results indicate that the PAA oligomers promoted the nucleation and inhibited the growth of the magnetic iron oxide, and the average diameter of each individual Fe3O4 particle was smaller than 10 nm. In addition, the PAA oligomers provided both electrostatic and steric repulsion against particle aggregation, and the stability of dispersions could be controlled by adjusting the pH value of solution. A small amount of Fe2O3 was found in the nanoparticles but the superparamagnetic behavior of the nanoparticles was not affected.     

Synthesis and characterization of fluorescently labelled poly(vinyl acetate) particles

Nonaqueous dispersions of poly(vinyl acetate) particles stabilized with poly(2-ethylhexyl methacrylate) and labelled with fluorescent dyes in the core and stabilizer polymer phases were prepared. The materials were characterized using a broad range of techniques (NMR, UV, and fluorescence spectroscopy. GPC, particle sizing, and DSC). The data show that dispersion polymerization of vinyl acetate in the presence of stabilizers containing certain fluorescent dye derivatives, instead of unlabelled stabilizer, results in changes in the mean particle size, size distribution, composition, and molecular weights of the colloidal polymer particles. It was found that increasing the amounts of fluorescent groups in the stabilizer resulted in smaller mean particle sizes and larger amounts of irreversibly attached stabilizer. When the average number of labels in stabilizer exceeded one per chain, a new ultra-high molecular weight polymer fraction appeared. The fluorescence spectra for several of these materials are reported. We describe how fluorescence decay curves can be used to assess block formation and local phase separation in particles labelled with phenanthrene groups. These materials are intended to be used for more detailed studies by fluorescence spectroscopy. Those results will be published in due course.     

Preparation of stable dispersion of graphene using copolymers: dispersity and aromaticity analysis

In this study, effectiveness of non-ionic block copolymers such as Lugalvan BNO12 and Triton X series (Triton X100 & Triton X405) has been reported for graphene dispersion in aqueous solutions. Stability of the aqueous graphene dispersions is investigated using UV–visible spectroscopy, Rheological, and Conductivity studies. Adsorption isotherms are constructed to determine the amount of polymers adsorbed on the surface of graphene by the spectroscopic analysis. Lugalvan BNO12 has been found to be adsorbed in higher amounts on the graphene surface compared to the Triton X series polymers. Thermogravimetric analysis (TGA) and Fourier Transform Infrared (FTIR) Spectroscopy investigations indicated grafting of polymers chains to the graphene surfaces. The dispersions prepared with optimum concentrations (as determined from adsorption isotherms) of polymers have shown lower viscosity and conductivity values. Lugalvan BNO12 has been found to be a better stabilizer for graphene than the Triton X series dispersants because the former contains two aromatic rings in its structure that acts as an anchoring group and helps in the stabilization of graphene dispersion in comparison to the single aromatic group in the Triton X series. The experimental results reported have shown that the aromaticity of polymeric dispersants plays significant role in the aqueous graphene dispersions. The non-ionic block copolymers that assisted dispersed graphene are potential candidates for the fabrication of various devices such as sensors, batteries, and supercapacitors applications.     

Poly(phenylenediamine) Dispersions

The formation and properties of poly(phenylenediamine) colloidal dispersions were investigated. Oxidative dispersion polymerization of 1,3-phenylenediamine dihydrochloride stabilized with poly(N-vinylpyrrolidone) was taken as a reference experiment. Conductivity, temperature, and acidity of the reaction mixture were recorded during the polymerization. Oxidations of all three phenylenediamine bases, of corresponding dihydrochlorides, and of dihydrochlorides in excess acid are compared. The effect of the nature of steric stabilizer on the course of polymerization was found to be marginal. Dispersion polymerization was observed to proceed faster than the precipitation one. Dynamic light scattering was used to assess particle sizes in poly(phenylenediamine) dispersions. The results are discussed in relation to an analogous polymerization of aniline leading to polyaniline dispersions. Copyright 2001 Academic Press.     

Photoinitiated dispersion polymerization of methyl methacrylate: A quick approach to prepare polymer microspheres with narrow size distribution

Photoinitiated dispersion polymerization of methyl methacrylate was carried out in a mixture of ethanol and water as dispersion medium in the presence of poly(N‐vinylpyrrolidone) (PVP) as the steric stabilizer and Darocur 1173 as photoinitiator. 93.7% of conversion was achieved within 30 min of UV irradiation at room temperature, and microspheres with 0.94 μm number–average diameter and 1.04 polydispersity index (PDI) were obtained. X‐ray photoelectron spectroscope (XPS) analysis revealed that only parts of surface of the microspheres were covered by PVP. The particle size decreased from 2.34 to 0.98 μm as the concentration of PVP stabilizer increased from 2 to 15%. Extra stabilizer (higher than 15%) has no effect on the particle size and distribution. Increasing medium polarity or decreasing monomer and photoinitiator concentration resulted in a decrease in the particle size. Solvency of reaction medium toward stabilizer, which affects the adsorption of stabilizer on the particle surface, was shown to be crucial for controlling particle size and uniformity because of the high reaction rate in photoinitiated dispersion polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1329–1338, 2008     

Poly(aniline-2-sulfonic acid) modified multiwalled carbon nanotubes with good aqueous dispersibility

Poly(aniline-2-sulfonic acid) (PASA)-modified multiwalled carbon nanotubes (MWNTs) were prepared by in situ oxidative polymerization. HRTEM images show that the PASA-modified MWNTs (PASANTs) are core (MWNT)-shell (PASA) tubular structures with a shell thickness of several nanometers. The strong interaction between the surface of the MWNTs and the conjugated structure of the PASA shell layer was proven by FTIR spectra. It was found that the aqueous dispersibility and dispersion stability of PASANTs were significantly improved compared to those of the raw MWNTs. Furthermore, when the PASA content is greater than 30 wt%, no precipitation is found for the dispersions of modified MWNTs after sedimentation for 500 h, exhibiting an excellent stability. The electrical conductivity of these modified MWNTs is 2-5 times higher than that of raw MWNTs and is 10(3) times higher than that of PASA.     

Magnetically loaded poly(methyl methacrylate-co-acrylic acid) nano particles

Magnetically loaded polymeric nano-particles carrying functional groups on their surface were prepared by a two-stage process. In the first stage, super-paramagnetic magnetite (Fe₃O₄) nano-particles were produced by a co-precipitation method from the aqueous solutions of FeCl₂·4H₂O and FeCl₃·6H₂O using a NaOH solution. The smallest size obtained was 40.9 nm with poly-dispersity index of 0.194 obtained by using a Zeta Sizer. The effects of Fe²⁺/Fe³⁺ molar ratio, stirring rate, temperature, base concentration, and pH on the particle size/size distribution and stability of the dispersions were examined. Increasing the relative concentration of Fe²⁺ ion and decreasing the stirring rate and pH increased the particle size, while the concentration of NaOH and temperature did not change the particle size significantly. Polymer coating was achieved by emulsion polymerization at high surfactant to monomer ratio of methyl methacrylate (MMA) and acrylic acid which were used as comonomers (comonomer ratio: 90/10 weight) with high surfactant to monomer ratio. The surfactant and initiator were SDS and KPS, respectively. Nano-particles in the range of 115 and 300 nm in diameter were produced depending on recipe. Increasing the Fe₃O₄/monomer and surfactant/monomer ratios, the KPS concentration caused a decrease in the average diameter. Magnetic properties of the nano-particles were obtained by electron spin resonance and vibrating-sample magnetometer. Most of the polymer-coated nano-particles exhibited super paramagnetic behavior.An erratum to this article can be found at     

Structure and rheology of aqueous poly(vinyl acetate) dispersions modified with montmorillonite

It has been shown that the rheological properties and resistance to sedimentation of aqueous poly(vinyl acetate) (PVA) latexes, which are used for the preparation of coatings and adhesives, can be controlled by adding sodium montmorillonite (MMT). The adding of MMT initiates gelation of the PVA dispersions, which manifests itself as the appearance of the yield stress, thixotropy, and viscoelasticity. X-ray diffraction analysis of the complex dispersions and films based on them has shown a transition from exfoliated to intercalated clay tactoids with an increase in their content. In view of the complex composition of the PVA latexes, which contain a stabilizer (poly(vinyl alcohol)) and a plasticizer (dibutyl phthalate), the components that are predominantly intercalated into the MMT interplanar space, have been identified. The highest yield stress and rigidity of the structural network, which arises in a sample as a result of the joint coagulation of PVA and MMT particles, are observed upon the incorporation of 1.2 wt % MMT into the latex.     

On the origin of colloidal particles in the dispersion polymerization of aniline

When aniline is oxidized in an aqueous medium in the presence of a steric stabilizer, colloidal polyaniline (PANI) dispersions are obtained. The generally accepted model of the stabilization assumes that the macromolecules of the water-soluble steric stabilizer are adsorbed at the polymer, precipitating during the dispersion polymerization, and provide steric protection against further aggregation. An alternative mechanism of conducting-polymer particle formation is proposed in the present study. We suggest that the steric stabilizer provides a site for adsorption of oligoaniline initiation centers; subsequent polymerization from anchored centers yields particle nuclei that grow to produce colloidal PANI particles. This hypothesis is based on the observation that the colloidal particles are obtained only in the case where the steric stabilizer is introduced in the early stages of polymerization when aniline oligomers are present in the reaction mixture. If the stabilizer had been added during the growth of PANI chains, colloidal dispersions would not have been produced. The process of particle growth is completely analogous to the formation of conducting PANI films on the surface of microparticles and various materials. There, the polymerization of aniline at the surfaces is preferred to the same process proceeding in the bulk of the reaction mixture. While the films grow at the interfaces with the reaction mixture, the dispersion particles similarly emanate from the stabilizer chains. The particle size, the formation of nonspherical morphologies, the importance of the chemical nature of the stabilizer chains, and the general relation between the conducting-polymer film and particle growth are discussed in the light of the proposed model.     

Control of particle size in dispersion polymerization of methyl methacrylate

Poly(methyl methacrylate) (PMMA) particles ranging in diameter from 2 to 10 μm were prepared by dispersion polymerization. The effects of various polymerization parameters on the size and monodispersity were systematically investigated. The particle size was found to increase with increasing polymerization temperature, concentration and decomposition rate of the initiator, and solvency of the dispersion medium. It also increased with increasing concentration and molecular weight of the polymeric stabilizer, poly(vinyl pyrrolidone) (PVP). As the monomer concentration was increased from 5 to 20 wt %, a minimum was found in the particle size at a monomer concentration of 10 wt %. A costabilizer was found to be necessary for preparing monodisperse particles at stabilizer concentrations below 2 wt %. A recycling experiment showed that the consumption of PVP was quite small in each cycle and the residual materials in this system could be reused readily. © 1993 John Wiley & Sons, Inc.     

Controlling the melting of kinetically frozen poly(butyl acrylate-b-acrylic acid) micelles via addition of surfactant

We have studied the melting of polymeric amphiphilic micelles induced by small-molecule surfactant and explained the results by experimental determination of the interfacial tension between the core of the micelles and the surfactant solutions. Poly(n-butyl acrylate-b-acrylic acid) (PBA-b-PAA) amphiphilic diblock copolymers form kinetically frozen micelles in aqueous solutions. Strong interactions with surfactants, either neutral or anionic [C12E6, C6E4, sodium dodecyl sulfate (SDS)], were revealed by critical micelle concentration (cmc) shifts in specific electrode and surface tension measurements. Since both polymer and surfactant are either neutral or bear negative charges, the attractive interactions are not due to electrostatic interactions. Light scattering, neutron scattering, and capillary electrophoresis experiments showed important structural changes in mixed PBA-b-PAA/surfactant systems. Kinetically frozen micelles of PBA-b-PAA, that are hardly perturbed by concentration, ionization, ionic strength, and temperature stresses, can be disintegrated by addition of small-molecule surfactants. The interfacial energy of the PBA in surfactant solutions was measured by drop shape analysis with h-PBA homopolymer drops immersed in small-molecule surfactant solutions. The PBA/water interfacial energy gammaPBA/H2O of 20 mN/m induces a high energy cost for the extraction of unimers from micelles so that PBA-b-PAA micelles are kinetically frozen. Small-molecule surfactants can reduce the interfacial energy gammaPBA/solution to 5 mN/m. This induces a shift of the micelle-unimer equilibrium toward unimers and leads, in some cases, to the apparent disintegration of PBA-b-PAA micelles. Before total disintegration, polymer/surfactant mixtures are dispersions of polydisperse mixed micelles. Based on core interfacial energy arguments, the disintegration of kinetically frozen polymeric micelles was interpreted by gradual fractionation of objects (polydisperse dispersion mechanism), whereas the disintegration of polymeric micelles in a thermodynamically stable state was interpreted by an exchange between a population of large polymer-rich micelles and a population of small surfactant-rich micelles (bidisperse dispersion mechanism). Finally, in our system and other systems from the literature, interfacial energy arguments could explain why the disintegration of polymer micelles is either partial or total as a function of the surfactant type and concentration and the hydrophobic block molar mass of the polymer.     

Cosolvent gel-like materials from partially hydrolyzed poly(vinyl acetate)s and borax

A gel-like, high-viscosity polymeric dispersion (HVPD) based on cross-linked borate, partially hydrolyzed poly(vinyl acetate) (xPVAc, where x is the percent hydrolysis) is described. Unlike hydro-HVPDs prepared from poly(vinyl alcohol) (PVA) and borate, the liquid portion of these materials can be composed of up to 75% of an organic cosolvent because of the influence of residual acetate groups on the polymer backbone. The effects of the degree of hydrolysis, molecular weight, polymer and cross-linker concentrations, and type and amount of organic cosolvent on the rheological and structural properties of the materials are investigated. The stability of the systems is explored through rheological and melting-range studies. (11)B NMR and small-angle neutron scattering (SANS) are used to probe the structure of the dispersions. The addition of an organic liquid to the xPVAc-borate HVPDs results in a drastic increase in the number of cross-linked borate species as well as the agglomeration of the polymer into bundles. These effects result in an increase in the relaxation time and thermal stability of the networks. The ability to make xPVAc-borate HVPDs with very large amounts of and rather different organic liquids, with very different rheological properties that can be controlled easily, opens new possibilities for applications of PVAc-based dispersions.