Template polymerization of methacrylic acid along poly(N-acetyliminoethylene) in water. Influence of template architecture

The kinetic study of the photochemical polymerization of methacrylic acid (MAA) in aqueous dilute solution in the presence of poly(N-acetyliminoethylene) (PNAI) oligomers evidenced template features. The process proceeded in two stages, depending on [PNAI]/[MAA]₀ ratio and polymerization duration, two different complexes being formed, both by a “zip” chain-growth mechanism. Computing and transmission electron microscopy data revealed that this aspect is due to the replacing of the initial PNAI template by the newly formed poly(methacrylic acid) daughter polymer, as a result of the structural peculiarities of the latter as a component of the primary complex. Its specific mode of packing in a complex aggregate was considered to be the main reason for the reported behavior. © 1996 John Wiley & Sons, Inc.     

Preparation of AgCl-polyacrylamide composite microspheres via combination of a polymer microgel template method and a reverse micelle technique

A new route was created for the preparation of AgCl-polyacrylamide (AgCl-PAM) composite microspheres with patterned surface structures. The route is a combination of a polymer microgel template method and a reverse micelle technique. The size of the AgCl nanoparticles existing on the surfaces of the composite microspheres and the clearness of the surface patterns of the composite microspheres can be altered by simply adjusting the amount of precipitated AgCl and the rate of the deposition reaction. The route can be also used for the preparation of other water-insoluble salt-polymer composite microspheres, such as BaSO(4)-PAM. It is expected that the composite microspheres with patterned surface structures may not only combine the advantages of polymers and those of inorganic compounds, but also combine the advantages of microspheres in the micrometer size range and those in the nanometer size range.     

Swelling-assisted modification of poly(ethylene terephthalate) by methacrylic acid

When a poly(ethylene terephthalate), PET, film is heated in an aqueous solution of methacrylic acid in the presence of hydrogen peroxide as an initiator, it is found that the weight of the film is increased. The amount of methacrylic acid that may be added onto the film is dependent upon the concentration of the monomer, the initiator, and the temperature at which the reaction occurs. Pretreatment of the film with 1,1,2,2,tetrachloroethane causes swelling and the amount of add-on is increased as the swelling level increases. Methacrylic-acid-modified PET films hydrolyze at room temperature in aqueous sodium hydroxide; the rate of hydrolysis is dependent upon the amount of add-on and the concentration of the base. This procedure leads to a chemically induced blend of polymethacrylic acid and poly(ethylene terephthalate), and grafting of the monomer onto the polymer film does not occur. © 1995 John Wiley & Sons, Inc.     

Preparation of multisensitive poly (N-isopropylacrylamide-co-acrylic acid)/TiO2 composites for degradation of methyl orange

Composites of poly (N-isopropylacrylamide-co-acrylic acid)/titanium dioxide (TiO₂) have been prepared via UV-initiated free radical polymerization. Fourier transform infrared spectra (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), environmental scanning electron microscope (ESEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) are used to study the composition, structure, and morphology of the as-prepared composites. TiO₂ is found to be successfully encapsulated in the copolymer in spherical shapes with size of 2.5 μm. The thermo- and pH-responsive properties of the composites are observed using dynamic light scattering (DLS). The photocatalytic property of the composites is studied using UV–vis spectrophotometer on the degradation of methyl orange (MO) solution under various pHs and temperatures. Degradation ratio is higher at low pH and increases with increasing temperature above volume phase transition temperature (VPTT).     

Binding of a surfactant counterion to low-charge-density poly(acrylic acid) and poly(methacrylic acid)

The binding of a cationic surfactant, dodecylpyridinium (C12Py) chloride, with a low-charge-density poly (methacrylic acid) (PMA) was investigated in buffer solutions under the condition of constant pH. The binding isotherms with PMA consisted of two and three steps at a pH lower and higher than 3.2, respectively. Bindings in the first step were independent of pH and this step was considered to correspond to the solubilization of the hydrocarbon chains of C12Py into the nonpolar region of the compact form of PMA. This is the indication of the compact form from the binding isotherm. At pH higher than 3.2, the second step was discriminated and it depended on the pH. In the third step, a sharp rise in the degree of binding (β) was observed accompanying the solubilization of the precipitates of the PMA–C12Py complex. The binding with poly(acrylic acid) (PAA) and PMA in conventional unbuffered NaCl solutions was also examined and the pH profile of the solution during the binding process was determined. In the case of unbuffered NaCl solutions, the binding with PAA took place cooperatively at the critical association concentration (cac). The binding isotherm consisted of two steps and the pH decreased with the increase in β. The binding isotherm of PMA, on the other hand, consisted of three steps: the pH decreased slightly in the first step and considerably in the second step with the increase in β but it increased with β in the third step, exhibiting a pH minimum around 3.2. The binding in the first step coincided with that obtained in the buffered solutions. Linear relationships between β and the pH were found for both polymers. In the case of PMA, no cac was observed in both buffered and unbuffered NaCl solutions. Received: 24 January 2001 Accepted: 23 May 2001     

Preparation and rheological characterization of poly(n-butyl methacrylate)/montmorillonite composites

Intercalated nanocomposites constituted of poly(butyl methacrylate) (PBMA) as the matrix and an organically modified montmorillonite as the nanosize filler were prepared and rheologically characterized in detail. The rheological behavior of the composites showed dependence on both temperature and clay content. For composites of low clay contents, the steady shear viscosity showed a Newtonian plateau in the low shear rate region at low temperatures and the plateau was replaced by a shear-thinning curve when the temperature was raised. For composites of higher clay contents, strong shear-thinning behavior were observed at all shear rates and all temperatures. The viscoelastic data of the composites showed unusual terminal behavior of a decreasing terminal slope at low frequencies with increasing temperature and clay loading. X-ray diffraction spectra showed that annealing process at higher temperatures shifted the Bragg reflection peaks to a lower angle and broadened the peaks, which provided the evidence for the existence of a temperature-induced solid-like structure that was responsible for the shear thinning and the unusual terminal viscoelastic behavior.     

Synthesis of monodisperse poly(methacrylic acid) microspheres by distillation-precipitation polymerization

Monodisperse poly(methacrylic acid) (PMAA) microspheres were prepared by distillation-precipitation polymerization in acetonitrile with 2,2′-azobisisobutyronitrile (AIBN) as initiator. The polymeric microspheres were formed simultaneously via a precipitation polymerization manner during the distillation of the solvent out of the reaction system in the absence of any surfactant and crosslinker. Monodisperse PMAA microspheres with spherical shape and smooth surface were synthesized with diameters ranging from 60 to 290 nm below the glass transition temperature of PMAA without any stabilizer. The particle size increased with increasing monomer concentration, which may be resulted from the higher molecular weight for the polymerization. To investigate the growth procedure of PMAA microspheres, the morphology of microspheres over the distillated acetonitrile volume was conducted by monitoring the morphologies with TEM. GPC and FTIR provide key insights into the particle growth mechanism. The PMAA microspheres may be formed by an internal contraction due to the marginal solvency of the continuous phase with the aid of the hydrogen-bonding interaction between the carboxylic acid unit, in which the particles were stabilized by the steric effect of the pendent chains and surface gel as well as the electrostatic repulsion from the carboxylic acid group.     

Water absorption and enzymatic degradation of poly(lactic acid)/rice starch composites

Poly(lactic acid) (PLA) composites consisting of PLA, rice starch (RS) (0–50 wt%) and epoxidised natural rubber (ENR50) were compounded by a twin-screw extruder and compression moulded into dumbbell specimens. Tensile tests were performed to characterize the mechanical properties of the PLA/RS composites. Morphological studies were done on the tensile fractured surface of the specimens by using scanning electron microscopy (SEM). Twenty weight percent of RS achieved a good balance of strength and stiffness. Beyond 20 wt% loading of RS, the tensile strength and elongation at break of PLA decreased drastically. This may be attributed to the agglomeration of RS, which could then act as stress concentrator. The incorporation of ENR50 increased the tensile strength and elongation at break of the PLA/RS composites remarkably, owing to the elastomeric behaviour and compatibilisation effects of ENR50. Interestingly, the morphology of PLA/RS composites transformed to a more ductile one with the addition of ENR. The kinetics of water absorption of the PLA/RS composites conforms to Fick's law. The M_m and D values are dependent on the RS and ENR concentrations. The tensile properties of the PLA/RS composites deteriorated after water absorption. The retention-ability and recoverability of the PLA/RS composites are relatively low, attributed to the hydrolysis of PLA, degradation of the PLA–RS interface and leaching of the RS particles. In addition, the tensile properties of PLA/RS composites decreased drastically upon exposure to enzymatic degradation. Extensive pinhole and surface erosion on the PLA/RS composites indicate high degree of hydrolysis. Whilst the addition of ENR leads to some improvements in tensile properties, nevertheless, it enhanced the biodegradability of the PLA/RS composites when exposed to water and -amylase enzymatic treatments.     

Template polymerization of N-vinylimidazole along poly(methacrylic acid) in water. VI. Crosslinked PMAA as template

The effect of crosslinked poly(methacrylic acid) (c-PMAA) on the polymerization of N-vinylimidazole in aqueous solution was studied using UV, calorimetry, SEM, and TEM. It was established that synthetic lightly crosslinked PMAA samples behaved intermediate between rigid crosslinked PMAA particles functioning as microreactors, and linear conventional PMAA, where template and conventional polymerization in the surrounding solution are integrated. A modified calorimetric technique was used to measure monomer conversion, and to correct for the rapid adsorption process. Rate enhancements up to a factor of 4 were obtained for the c-PMAA's, which were lower than those obtained for linear conventional PMAA, and which slightly decreased with increasing crosslink density of the samples. Template complexes possessed a platelet-like morphology similar to template complexes obtained for linear PMAA.     

Preparation and characterization of poly (N-isopropylacrylamide-co-dimethylaminoethyl methacrylate) microgel latexes

Monodisperse cationic thermosensitive latex microgels have been prepared by radical-initiated precipitation polymerization of N-isopropylacrylamide, methylene bisacrylamide using 2,2′-azobis(2-amidinopropane hydrochloride) as an initiator and dimethylaminoethyl methacrylate (DMAEMA) as a cationic monomer. The final microgel latexes were characterized with respect to water-soluble polymer formation, particle size and size distribution. Adding cationic monomer (DMAEMA) was found to drastically affect the particle size, but not the size distribution as observed both by transmission electron microscopy and quasielastic light scattering (QELS). However, too high a DMAEMA concentration in the feed composition led to enhanced formation of water-soluble polymer. The volume phase-transition temperature of cleaned microgels examined by QELS (particle size versus temperature) was found to be around 32 °C and was slightly dependent on the concentration of the cationic monomer. The volume phase-transition temperature range becomes broader with increasing cationic monomer concentration. In addition, the pH of the polymerization medium was found to affect the final particle size and amount of water-soluble polymer formed. Received: 29 March 2001 Accepted: 2 July 2001     

Reparation of silica/poly(methacrylic acid)/poly(divinylbenzene-co-methacrylic acid) tri-layer microspheres and the corresponding hollow polymer microspheres with movable silica core

 Hollow poly(divinylbenzene-co-methacrylic acid) (P(DVB-co-MAA)) microspheres were prepared by the selective dissolution of the non-crosslinked poly(methacrylic acid) (PMAA) mid-layer in ethanol from the corresponding silica/PMAA/P(DVB-co-MAA) tri-layer hybrid microspheres, which were afforded by a three-stage reaction. Silica/PMAA core-shell hybrid microspheres were prepared by the second-stage distillation polymerization of methacrylic acid (MAA) via the capture of the oligomers and monomers with the aid of the vinyl groups on the surface of 3-(methacryloxy)propyl trimethoxysilane (MPS)-modified silica core, which was prepared by the Stöber hydrolysis as the first stage reaction. The tri-layer hybrid microspheres were synthesized by the third-stage distillation precipitation copolymerization of functional MAA monomer and divinylbenzene (DVB) crosslinker in presence of silica/PMAA particles as seeds, in which the efficient hydrogen-bonding interaction between the carboxylic acid groups played as a driving force for the construction of monodisperse hybrid microspheres with tri-layer structure. The morphology and the structure of silica core, silica/PMAA core-shell particles, the tri-layer hybrid microspheres and the corresponding hollow polymer microspheres with movable silica cores were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy (XPS).     

Influence of stereoregularity on binding of counterions by poly(methacrylic acid)

The activity coefficient γ, of sodium ion, in aqueous solutions of both isotactic and conventional poly(methacrylic acid) (PMA) has been studies throughout the whole range of degree of neutralization α with a Beckman Na electrode and membrane electrodes. The results show that the fraction of sodium ions bound to isotactic PMA is higher than that bound to conventional (or syndiotactic) PMA over the entire range of α. The binding of divalent counterions (Mg⁺², Cu⁺², Co⁺², and Ni⁺²) by the two forms of PMA (at α = 0.95) has been evaluated from the release of Na⁺ ions with the Beckman Na electrode. Turbidimetric determinations of the critical amount of various divalent cation chlorides necessary to bring about precipitation of both isotactic and conventional PMA (at α = 0.95) have also been carried out.     

Diffusion of dextran within poly(methacrylic acid) hydrogels

We describe an investigation of fluorescence correlation spectroscopy into the diffusion of fluorescein‐tagged dextran (FDEX) in a poly(methacrylic acid) (PMAA) hydrogel. The temperature dependence of FDEX diffusion is shown to follow Zimm behavior in pure water, and the decrease in the diffusion coefficient when in the PMAA hydrogel has been modeled. The addition of acid and alkali (HCl and NaOH, respectively) not only control the swelling and collapse of the hydrogel but also reveal a strong pH dependence of the dextran diffusion coefficient, which shows a (nonmonatonic) increase with pH. The addition of NaCl and CaCl₂ salts similarly showed evidence of network swelling, most notably at low salt concentration, but also that the diffusion coefficient within the gel at these low concentrations is larger than that in the equivalent solution without the hydrogel, indicating that the combination of hydrogel and salt works to increase the diffusion coefficient above that in pure water. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Preparation and phenol-recognizing ability of a poly(methacrylic acid) molecular imprint on the surface of a silica gel

Molecularly imprinted solid phase extraction is an excellent tool for the preconcentration of trace analytes. We report on the preparation of such a material by firstly graft-polymerizing methacrylic acid onto the surface of silica gel particles, and then imprinting it by using phenol as a template and ethylene glycol diglycidyl ether as a crosslinker. The binding and recognition of phenol were examined by static methods. The binding capacity at saturation is 160?mg·g^?1 in 9?h at pH 6. The selectivity coefficients relative to o-cresol and chlorophenol are 22 and 23, respectively. The pH value has a large effect. Adsorbed phenol can be eluted easily from the imprint with diluted sodium hydroxide solution, and the material is reusable.

The synthesis and characterization of monodisperse poly(acrylic acid) and poly(methacrylic acid)

A number of polyacrylic (PAA) and polymethacrylic (PMAA) acids have been synthesized by living anionic polymerization of the monomeric tert-butyl esters followed by subsequent hydrolysis of the corresponding polyesters. The necessary precautions were taken in order to assure good molecular weight control, as well as high yields in the polymerization reactions. The intermediate and final polymers were characterized by gel permeation chromatography and NMR-H¹ spectrometry.     

Effect of urea on poly(methacrylic acid) and poly(acrylic acid) aqueous solutions

The effects of urea on aqueous solutions of both poly(methacrylic acid (PMA) and poly(acrylic acid) (PAA) have been investigated by using potentiometry, viscometry and study of the fluorescence of Auramine O, a cationic dye. The viscosity behaviour of unionized PMA obtained from direct dissolution of solid powder shows that the unneutralized macromolecules can be associated in water. The stability of such “aggregates” seems weak as indicated by their disappearance as soon as the charge density is very low. For PMA salt solution percolated through a cation (H⁺) exchange resin column, no association is observed. The pH-dependent conformational behaviour of PMA which, contrary to PAA, presents compact conformations in water at low charge density is discussed in terms of solvophobic/solvophilic interactions. It is shown that, even for urea concentration up to 8 M, the compact conformations of PMA are not completely destroyed. The formation of H⁺/urea complex is taken into account.