Dispersion polymerization of acrylamide with 2‐acrylamido‐2‐methyl‐1‐propane sulfonate in aqueous solution

The copolymer of acrylamide (AM) and 2‐acrylamido‐2‐methyl‐1‐propane sulfonate (AMPS) was synthesized through the free radical dispersion polymerization in an aqueous solution of ammonium sulfate and in the presence of poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonate) as stabilizer. The average particle size of the copolymer ranged from 1 to 4 μm, and the molecular weight was from 2.0 × 10⁶ to 7.0 × 10⁶ g mol^?1. By analyzing apparent viscosity and particle size, the swelling property of the dispersion copolymer was studied. When the dispersion was diluted with salt water in which the ammonium sulfate concentration kept equal with that of the original dispersion, particle size and particle size distribution of the diluted dispersion changed a little, compared with that of the original dispersion. While diluted with deionized water, particle size and particle size distribution could expand several times. The effects of varying concentrations of the stabilizer, the monomer, the salt and the initiator on particle size, and molecular weight of the copolymer were investigated, respectively. The reaction conditions for preparing stable dispersion were concentrations of 20–28% of the salt, 6–14% of monomers, and 1.8–2.7% of the stabilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:2379–2385, 2006     

Dispersion polymerization of acrylamide with quaternary ammonium cationic comonomer in aqueous solution

Copolymer particles consisting of acrylamide (AM) and acryloyloxyethyl dimethylbenzyl ammonium chloride (AODBAC) were prepared by dispersion polymerization in an aqueous solution of ammonium sulfate and in the presence of poly(acryloyloxyethyl trimethyl ammonium chloride) (PAOTAC) as the stabilizer. The average particle size ranged from 4 to 7 μm, and M_w and M_n were 2–6 ×10⁶ g/mol and 1–3 × 10⁶ g/mol, respectively. The effects of the AM/AODBAC ratio, monomer, initiator, salt, and stabilizer concentration on the particle size and molecular weight were studied. Increase of the AODBAC/AM ratio resulted in a decrease in the molecular weight and an increase in particle size. With the increase of the AODABA/AM ratio, the dispersion became less stable during long storage. Due to the presence of the salt, ionization of the quaternary ammonium groups in the dispersed particles is considered significantly suppressed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1101–1108, 2003     

Aqueous dispersion polymerization of acrylamide with quaternary ammonium cationic comonomer

Using aqueous solution of ammonium sulfate as medium, acrylamide (AM) and dimethylaminoethyl methacrylate methyl chloride (DMC) as main raw materials, poly(dimethylaminoethyl methacrylate methyl chloride) (PDMC) as stabilizer and 2,2′‐azobis (2‐amidinopropane) dihydrochloride (V‐50) as initiator, the cationic polyelectrolyte of P(DMC‐AM) was synthesized by aqueous dispersion polymerization. The effects of the major reaction variables on synthesis conditions, product characteristics (particle size and molecular weight), and polymerization rate were investigated. The polymerization was retarded by the presence of the ammonium sulfate. The optimum reaction conditions for obtaining a stable aqueous dispersion were concentrations of 1.8 × 10^?4–7.0 × 10^?4 mol L^?1 for V‐50, 1.5–3.5% for stabilizer, and 23.2–30.0% for salt. The molecular weight of PDMC formed was 1.5 × 10⁵ to 7.0 × 10⁵. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of synthesis variables on the fluorescence properties of CdSe-polystyrene latexes

The development of photoluminescent materials based on the incorporation of quantum dots (QDs) into polymeric latexes has gained importance due to the multiple potential applications. Through the process of miniemulsion polymerization it is possible to encapsulate quantum particles into polymer matrix to provide both chemical stability and to maintain emission properties. The polymerization process was achieved with continuous magnetic stirring and nitrogen atmosphere. Cetyl trimethylammonium bromide (CTAB) was used as surfactant at concentration levels of 1.3 × 10^-3, 3.2 × 10^-3 and 5.4 × 10^-3 M. The initiator 2,2-azobisisobutyronitrile (AIBN) was used at 0.50 and 0.75 wt% and CdSe QDS were used at 0.075, 0.15 and 0.225 wt%, both in relation to monomer content. A STEM study on the composite latexes and later a statistical study on the measurement of polymer particle diameter let us corroborate that the increment in surfactant concentration produces a decrement in polymer particle size. The obtained composite latexes were stable and showed fluorescence by excitation with UV light. The spectrofluorometry studies indicated that in composite latexes fluorescent emission was a function of polymer particle size, showing higher intensity those formulations with smaller surfactant concentrations and bigger polymer particle size.     

Preparation of monodisperse PMMA particles by dispersion polymerization of MMA using poly(styrene-co-methacrylic acid) copolymer as a steric stabilizer

Dispersion polymerization of MMA was conducted using poly(styrene-co-methacrylic acid) copolymer as a steric stabilizer in an aqueous methanol medium. Various composition copolymers were easily prepared with a conventional radical polymerization by changing the monomer ratios of styrene to methacrylic acid, and were employed as a steric stabilizer for dispersion polymerization. The copolymers prepared with monomer ratios of 1.25–1.50 were found to be suitable steric stabilizers for dispersion polymerization. A very small amount of copolymer (0.6 wt% based on MMA) could act as a steric stabilizer effectively to obtain monodisperse PMMA particles. The particle size decreased with increasing the solvent polarity from 4 to 0.14 μm.     

A study of aggregation behavior of a sulfobetaine copolymer in dilute solution

A copolymer poly(acrylamide-co-3-[N-(2-methacroyloylethyl)-N, N-dimethylammonio]-propane sulfonate) (P(AM/DMAPS)) was synthesized via conventional free-radical polymerization in aqueous media. Its aggregation and disaggregation in aqueous solution were studied as a function of copolymer concentration, ionic strength and ageing time at different temperature by gel permeation chromatography combined with laser light scattering (GPC-MALLS) technique, static and dynamic laser light scattering. GPC-MALLS analysis shows that at low copolymer concentrations (below 0.4 g.L⁻¹), a decrease of both apparent weight-average molecular weight and radius of gyration is observed due to the dissociation of the interchain association. With increasing copolymer concentration, the interchain association is enhanced and both apparent weight-average molecular weight and radius of gyration increase. Correspondingly, the exponent ρ of the radius of gyration/molecular weight (R_g−M_w) relationship shows an increase from 0.29 to 0.6 with increasing copolymer concentration (below 0.4 g.L⁻¹), and then decreases continuously to 0.33 with further increasing copolymer concentration. Dynamic laser light scattering studies reveal that the addition of a small amount of salts (below 0.1 mol.L⁻¹) leads to the disaggregation of the intra- and interchain aggregation. Further addition of salts results in the enhancement of interchain aggregation. The influence of various anions on the aggregation behavior increases in the order Cl ⁻ < Br ⁻ < I ⁻. The prolonging of the ageing time at 25 °C and 70 °C leads to the disaggregation of the interchain association of P(AM/DMAPS) copolymer in both deionzied water and 0.15 mol.L⁻¹ NaCl solution.     

Segregation behavior of polyethylene with broad molecular weight distribution by annealing procedure in temperature gradient

An annealing treatment in a molten state, in which temperature of the top plate is different from that of the bottom one in a compression-molding, leads to molecular weight segregation of high-density polyethylene (HDPE) prepared by mixture of two types of HDPE with different molecular weights (Mw = 1.8 × 10⁵ and 2.9 × 10⁴). Low molecular weight fraction tends to localize at the surface attached to the higher temperature and vice versa. The segregation behavior is obvious at a large temperature gradient. Although the accuracy and mechanism of the phenomenon have not been clarified yet, this could be applied as a new fractionation method, which does not use a solvent.     

Effect of graft chain length of the stabilizer on dispersion polymerization of methyl methacrylate in petrol

To carry out dispersion polymerization of methyl methacrylate (MMA) in petrol, we have used a poly(MMA) grafted-poly(12-hydroxystearic acid) copolymer as the stabilizer. This special copolymer was prepared as a solution in a mixture of ethyl acetate and butyl acetate solvents. We investigated the effect of graft chain length of the stabilizer on the dispersion polymerization in petrol. We synthesized the stabilizer copolymer with n = 1–4 and determined the rate and the molecular weight of the PMMA formed. There is no dispersion polymerization for n = 1. However, for any other n, for a given stabilizer concentration, as the chain length of the graft is increased, the molecular weight as well as the rate of PMMA formation increases. As opposed to this for a given graft length as the concentration of the stabilizer increases, the molecular weight of PMMA first rises, but for a larger concentration, it begins to fall after undergoing a maximum. In this work, we modeled the heterogeneity of the reaction mass and proposed a mathematical model for dispersion polymerization of MMA in petrol. The computer results are found to conform to the experimentally observed molecular weight of the PMMA. © 1993 John Wiley & Sons, Inc.     

Adsorption of methyl ethyl ketone onto poly(vinyl alcohol)(PVA)/peat/organoclay composite beads in aqueous solution

A new type of poly(vinyl alcohol)(PVA)/peat/organoclay composite beads was prepared. This composite bead was a porous spherical particle with a diameter of 3.0–5.0 mm and a porosity of about 50%. The oragnoclay is prepared by hexadecyl trimethyl ammonium bromide (HDTMA) exchanged clay. The dynamic adsorption behavior between methyl ethyl ketone (MEK) and this composite bead was investigated. The adsorption process occurs in two stages with external mass transport occurring in the early stage and intraparticle diffusion occurring in the later stage. The rate of MEK diffusion in the external mass transport process and the intraparticle diffusion process in the adsorption temperature 20–35 °C was 3.28–76.98 × 10⁻⁸ cm²/s and 1.62–3.17 × 10⁻⁷ cm²/s, respectively. The rate of MEK diffusion in both processes was concentration independent, and it increased with increasing the adsorption temperature. Langmuir isotherm adsorption model was more suitable for describing the adsorption equilibrium of MEK. The calculated Q values in the adsorption temperature 20–35 °C were 5.90–22.78 mg/g composite bead. The adsorption capacity of this composite bead increased with increasing the adsorption temperature. The adsorption process was physical adsorption, endothermic and non-spontaneous process.     

Aqueous dispersion polymerization of amphoteric polyacrylamide

The terpolymer of acrylamide (AM), dimethylaminoethyl methacrylate methyl chloride (DMC), and acrylic acid (AA) was synthesized with their molar ratio of 70 : 15 : 15 through dispersion polymerization in aqueous solution of ammonium sulfate (AS), using poly(dimethylaminoethyl methacrylate methyl chloride) (PDMC) as stabilizer and 2,2′‐azobis(2‐amidinopropane) dihydrochloride (V‐50) as initiator. The particle size of the terpolymer ranged from 5 to 8 μm and the intrinsic viscosity was from 5.5 to 11.6 dL g^?1. The terpolymer had anti‐ polyelectrolyte effect under low AS concentration, but polyelectrolyte effect with the concentration beyond 10%. Polymerization dispersion with low apparent viscosity, uniform particles, good stability, and high molecular weight terpolymer was obtained in single stage. The effects of varying concentrations of salt, stabilizer, and monomers on particle morphology and intrinsic viscosity were investigated. With increasing concentration of AS and PDMC, the intrinsic viscosity of terpolymer increased, then decreased afterward. However, it increased gradually with increase in monomer concentration. The particle size was enlarged with increasing of AS and monomer concentration and decreasing of PDMC concentration. The optimum condition was the concentrations of salt, stabilizer, and monomers 28%, 3.0%, and 8% to 15%, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Copolymerization of 4-cyanophenyl acrylate with methyl methacrylate: synthesis, characterization and determination of monomer reactivity ratios

A novel acrylic monomer, 4-cyanophenyl acrylate (CPA) was synthesized by reacting 4-cyanophenol dissolved in methyl ethyl ketone with acryloyl chloride in the presence of triethylamine as a catalyst. Copolymers of CPA with methyl methacrylate (MMA) at different composition was prepared by free radical solution polymerization at 70 ± 1 °C using benzoyl peroxide as an initiator. The copolymers were characterized by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The solubility tests were checked in various polar and non polar solvents. The molecular weight and polydispersity indices of the copolymers were estimated by using gel permeation chromatography. The glass transition temperature of the copolymers increases with increases MMA content. The thermal stability of the copolymer increases with increases in mole fraction of CPA content in the copolymer. The copolymer composition was determined by using ¹H-NMR spectra. The monomer reactivity ratios determined by the application of linearization methods such Fineman–Ross (r ₁ = 0.535, r ₂ = 0. 0.632), Kelen–Tudos (r ₁ = 0.422, r ₂ = 0.665) and extended Kelen–Tudos methods (r ₁ = 0.506, r ₂ = 0. 0.695).     

Emulsion polymerization of methyl methacrylate using poly(methyl methacrylate-co-2-hydroxypropyl methacrylate)-graft-polyoxyethylene as the stabilizer

This study involved the use of an amphipathic graft copolymer, poly(methyl methacrylate-co-2-hydroxypropyl methacrylate)–graft–polyoxyethylene, as a stabilizer in the emulsion polymerization of methyl methacrylate. The stabilizing effectiveness of this graft copolymer was studied as a function of its chemical structure. It was found that the stabilizing effectiveness of the graft copolymer was independent of the molecular weight of the backbone within the investigated range of 4 × 10³ g/mol to 2 × 10⁴ g/mol. In all cases, stable emulsion polymerizations of methyl methacrylate were observed. Effective stabilization also occurred when the graft moieties possessed a molecular weight of either 2 × 10³ g/mol or 5 × 10³ g/mol. However, the stabilizing effectiveness was found to be dependent on the amount of polyoxyethylene (POE) contained in the graft copolymer. In this case, graft copolymers possessing 67% by weight POE were poor stabilizers, but ones with 85% POE were very good stabilizers. Moreover, the graft copolymers were found to be superior stabilizers as compared to POE homopolymers.     

Synthesis,characterization, and flocculation performance of anionic polyacrylamide P (AM‐AA‐AMPS)

In this study, a kind of anionic polyacrylamide (P(AM‐AA‐AMPS)) was synthesized using acrylamide (AM), acrylic acid (AA), and 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS) under ultraviolet (UV) irradiation. The conditions of the polymerization reaction such as monomer mass ratio, solution pH value, EDTA concentration and urea concentration were investigated by using the single factor approach and an L₁₆ (4⁵) orthogonal array. The structure and morphologies of the copolymer were determined by nuclear magnetic resonance spectrometer (NMR), infrared spectrometer (IR) and scanning electron microscope (SEM). The results show P(AM‐AA‐AMPS) with the intrinsic viscosity of 1.5 × 10³ mL g^?1 was synthesized at optimal conditions: mass ratio, m(AM) : m(AA) : m(AMPS) of 70 : 10 : 10, pH value of 9.0, EDTA concentration of 0.10% and urea concentration of 0.20%. In addition, P(AM‐AA‐AMPS) had better flocculation efficiency than commercial PAM in sludge dewatering experiment; the minimum filter cake moisture content could be reduced to 65.1%. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Surface structure of stimuli-responsive polystyrene particles prepared by dispersion polymerization with a polystyrene/poly(l-lysine) block copolymer as a stabilizer

A block copolymer composed of polystyrene and poly(α-l-lysine hydrobromide) (PLL) segments was used as a stabilizer for dispersion polymerization of styrene in water–methanol medium to give narrowly-distributed polystyrene particles in the size range from 0.36 to 1.09 μm, on which the PLL segment was grafted with a surface density of 0.2–3.4 l-lysine residue/nm². We investigated effects of polymerization time, stabilizer concentration, segmental composition of the block copolymer, and composition of the medium on surface structure and particle size of the affording particles. Interestingly, we obtained an experimental evidence that the surface density of the PLL clearly depends on structural parameters of the stabilizer and various polymerization conditions. Based on the dependence, it was possible to control the surface density of the narrowly-distributed particles within the range between the minimum and the maximum density limits of the graft chain by changing the structure of the stabilizer and polymerization conditions. Conformation of the PLL, which underwent a helix–coil transformation with an increase in water composition of the medium, had a strong effect on the surface structure, the size, and property of the resulting particles. Further modification of the particle surface was possible by utilizing the amino groups in the PLL graft.     

Influence of anionic stabilization of alumina particles in 2-propanol medium on the electrophoretic deposition and mechanical properties of deposits

The ceramic dispersions were prepared using 0.85, 1.70, 4.25, 12.75 or 21.25 wt.% of monochloroacetic, dichloroacetic or trichoroacetic acid, 15 wt.% alumina and 2-propanol. The mechanism of anionic stabilization in 2-propanolic media was described. Alumina green bodies were prepared from the stable dispersion via electrophoretic deposition (EPD). It was found that increasing dispersion conductivity significantly influenced the EPD yields. The most effective electrophoretic depositions were performed from dispersions with conductivity in range 4.0–5.3 × 10⁻⁴ S m⁻¹. Deposits with the highest green density were prepared from the dispersion stabilized by trichloroacetic acid. This behavior was explained by low voltage drop during deposition. The surface roughness was high at low dispersion conductivity and with increasing acid concentration in dispersion the surface of deposits was smoother. The mechanism of particle arrangement in deposit was discussed. Influence of stabilizer amount in the dispersion on the hardness and fracture toughness was described.     

Study of macroinitiator efficiency and microstructure–thermal properties in the atom transfer radical polymerization of methyl methacrylate

The atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) with poly vinylacetate macroinitiator (PVAc-CCl₃) and CuCl/PMDETA as catalyst was successfully carried out in bulk and solution. The apparent propagation rate constant () and concentration of active species ([P°]) were higher in the bulk. In solution they increased with polarity of solvent. Two different molecular weights of macroinitiators were used in ATRP of MMA. The linear relation of Ln[M]₀/[M] versus time was only confirmed for the low molecular weight macroinitiator. The ratio of was calculated in the bulk reaction with the low molecular weight macroinitiator, this ratio was 1.77 × 10¹⁴ M⁻¹ s⁻¹ for larger macroinitiator in solution. The MWD of block copolymers were sharper with lower molecular weight macroinitiator in the solution, but it appeared broader in the bulk polymerization. Our results indicated that smaller molecular weight macroinitiator was more efficient and formed a block copolymer with lower PDI. Thermal analysis and microstructure of the block copolymers are investigated by ¹H NMR, FT-IR, TGA and DSC. The chain tacticity of the MMA units is found not to be sensitive to the kinetic of the reactions with two different molecular weights of macroinitiator. DSC measurement shows two different transitions at 39 and 108 °C assigned to PVAc and PMMA blocks. The TGA profile shows a three-step degradation. The initial small weight loss that occurs around 220 °C and two large weight loss around 238 and 310 °C are attributed to dechlorination step and decomposition of the PMMA and PVAc blocks.     

Synthesis of amphiphilic magnetic microspheres by dispersion copolymerization of styrene and poly(ethylene oxide) macromonomer

Amphiphilic magnetic microspheres ranging in diameter from 5 to 100 µm were prepared by dispersion copolymerization of styrene and poly(ethylene oxide) vinylbenzyl (PEO‐VB) macromonomer (MPEO) in the presence of Fe₃O₄ magnetic fluid. The effects of various polymerization parameters on the average particle size were systematically investigated. The average particle size was found to increase with increasing styrene concentration and initiator concentration. It also increased with decreasing stabilizer concentration and molecular weight of MPEO. The content of the hydroxyl groups localized in the microspheres ranged from 0.01 to 0.2 mmol g^?1. © 2003 Society of Chemical Industry     

A kinetic study on autoxidation of α-naphthol-formaldehyde polymer in aqueous alkaline solutions

α-naphthol-formaldehyde polymer having active methylene groups and low average molecular weight of 1,000–2,000 was synthesized and characterized by FT-IR and gel permeation chromatography(GPC). Macroscopic kinetics of autoxidation of the polymer was investigated in an aqueous alkaline solution using UV/Vis spectrophotometry. Autoxidation processes in the presence of oxygen (or air) and hydrogen peroxide were associated with a color change of the solution to blue, which was monitored at 650 nm. The overall reaction rate law, order of the reaction, kinetic rate constants, and a proposed mechanism for the autoxidation reaction were obtained and reported. Infrared spectrophotometry shows that autoxidation takes place via conversion of methylene groups into carbonyls. Furthermore, kinetic data confirms the proposed mechanism for this autoxidation reaction which is of pseudo zero-order with respect to the polymer and first-order to the oxidant. The obtained kinetic rate constants of the autoxidation reaction by air and hydrogen peroxide are 0.0052 ± 7.1 × 10⁻⁴ min⁻¹ and 0.0044 ± 9.7 × 10⁻⁴ min⁻¹ at 25°C, respectively.     

Surface‐active amphiphilic poly[(2‐acrylamido‐2‐methylpropanesulfonic acid)‐co‐(N‐isopropylacrylamide)] nanoparticles as stabilizer in aqueous emulsion polymerization

This work reports the effect of nanogel solid particles on the surface and interfacial tension of water/air and water/styrene interfaces. Moreover, the work aimed to use nanogels as a stabilizer for miniemulsion aqueous polymerization. A series of amphiphilic crosslinked N‐isopropylacrylamide (NIPAm) and 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) copolymer nanogels were synthesized based on an aqueous copolymerization batch method. Divinylbenzene and N,N‐methylene bisacrylamide were used as crosslinkers. The morphologies of the prepared nanogels were investigated using transmission and scanning electron microscopies. The lower critical transition temperatures were determined using differential scanning calorimetry. The surface tension of colloidal NIPAm/AMPS dispersions was measured as functions of surface age, temperature and the morphology of the NIPAm/AMPS nanogels. The NIPAm/AMPS nanogels reduced the surface tension of water to about 30.1 mN m^?1 at 298 K with a small increase at 313 K. Surface activities of these nanogels in water were determined by surface tension measurements. The NIPAm/AMPS dispersions had high surface activity and were used as a stabilizer to prepare a crosslinked poly(styrene‐co‐AMPS) microgel based on emulsion crosslinking polymerization. © 2013 Society of Chemical Industry     

Dispersion polymerization of L-lactide in supercritical carbon dioxide

Triblock (A-B-A) oligomers of ε-caprolactone (ε-CL) (A) and poly(ethylene glycol) with an average molecular weight of 400 (PEG400) (B) were synthesized with three different molecular weight in the range of 2–6 kDa by changing the ratio of PEG400/ε-CL. These oligomers were then used in dispersion polymerization of L-lactide in supercritical carbon dioxide (scCO₂) as stabilizers. 5% stabilizer in the polymerization recipe allowed synthesis of poly(L-lactide) (PLLA) in scCO₂ in the powder form with a weight average molecular weight of around 60 kDa with polymerization yields around 80%. Interestingly, there was almost no effect of stabilizer molecular weight on polymerization. L-lactide polymerization in scCO₂ without any stabilizer was also possible but both the PLLA molecular weight and polymerization yield were lower, and the product was as aggregates instead of powders. A stabilizer concentration of 5% in the polymerization recipe was found adequate. Further increases in the stabilizer load resulted lower molecular weights and lower yields.