Thermal stability of poly(methyl methacrylate-co-butyl acrylate) and poly(styrene-co-butyl acrylate) polymers

Thermal stability of poly(methyl methacrylate-co-butyl acrylate) and poly(styrene-co-butyl acrylate) modified with a small amount of acrylic acid and/or N-methylolacrylamide as a crosslinking agent was studied in this work. Programmed thermogravimetric analysis has been used to study the effect of copolymer composition on thermal stability, over a temperature range from 50 to 450°C, under a constant flow of nitrogen. Kinetic parameters of thermal degradation, activation energy, pre-exponential factor, and reaction order were obtained by using MacCallum-Tanner's approach. Kinetic data indicate that the thermal degradation of the investigated copolymer systems is the first order reaction, and that the increase of activation energy may be an indication of thermal stability changes in copolymer systems.     

Crosslinked poly(sodium acrylate) hydrogels

Summary Samples of poly(acry1ic acid) (PAA) neutralized to varying degrees with sodium hydroxide were subjected to -irradiation to yield insoluble crosslinked polyacrylate hydrogels. The efficiency of crosslinking was found to be dependent on the degree of neutralization of the sample and the concentration of the irradiated polymer solution. The extent of water uptake of the gel was shown to be related to the degree of neutralization by titration of acid groups within the gel subsequent to cross-linking. Lightly crosslinked gels exhibited a maximum degree of swelling at a particular neutralization level. This was ascribed to a maximum in the long-range forces exerted cooperatively by the polymeric charges. The presence of simple electrolyte ions reduces swelling by screening these forces.     

Viscometric behaviour of hydrophobically modified poly(sodium acrylate)

Summary Hydrophobically associating poly(acrylic acid) was obtained by reaction of a small amount of octadecylamine on the carboxyl groups of the polymer. In pure water, this modified polymer exhibits a very high thickening power. By increasing the ionic strength of the aqueous solution a strong viscosity increase can be obtained instead of the decrease classically observed with polyelectrolytes. For instance, in 1% NaCl the modified poly(sodium acrylate) is of several orders of magnitude more viscous than the precursor polymer.     

聚丙烯酸钠∕高岭土复合高吸水性树脂的制备、结构与性能

以丙烯酸和高岭土为原料,用反相悬浮聚合法合成了聚丙烯酸钠/高岭土复合高吸水性树脂.研究了加入高岭土的聚丙烯酸钠复合高吸水性树脂合成中反应温度、中和度、交联剂用量、引发剂用量、高岭土添加量等影响树脂吸水性能的主要因素.结果表明,用反相悬浮聚合法合成的复合高吸水性树脂后处理容易,树脂的吸水率达到512 g/g,吸盐水率达到81 g/g,吸水速度比不加高岭土提高20%,保水能力提高15%,在250 ℃加热30 min仍能保持原吸水率的95%.用IR和TEM研究了复合高吸水性树脂的表面和结构,TEM显示高岭土的加入对树脂颗粒大小和形状有较大的影响,IR初步表明聚丙烯酸与高岭土产生了交联.     

聚丙烯酸钠/高岭土复合高吸水性树脂的制备、结构与性能

以丙烯酸和高岭土为原料,用反相悬浮聚合法合成了聚丙烯酸钠/高岭土复合高吸水性树脂。研究了加入高岭土的聚丙烯酸钠复合高吸水性树脂合成中反应温度、中和度、交联剂用量、引发剂用量、高岭土添加量等影响树脂吸水性能的主要因素。结果表明,用反相悬浮聚合法合成的复合高吸水性树脂后处理容易,树脂的吸水率达到512g/g,吸盐水率达到81g/g,吸水速度比不加高岭土提高20%,保水能力提高15%,在250℃加热30min仍能保持原吸水率的95%。用IR和TEM研究了复合高吸水性树脂的表面和结构,TEM显示高岭土的加入对树脂颗粒大小和形状有较大的影响,IR初步表明聚丙烯酸与高岭土产生了交联。     

Structural studies of poly(butyl acrylate) - poly(ethylene oxide) miktoarm star polymers

Structural behavior of miktoarm star polymers comprising poly(butyl acrylate) (PBA) and poly(ethylene oxide) (PEO) arms was studied by means of Differential Scanning Calorimetry (DSC), Wide Angle X-Ray Scattering (WAXS), Polarized Optical Microscopy (POM) and Fourier Transform Infrared Spectroscopy (FTIR) methods. The aim of this study was to correlate changes in the composition of the arms of the PBA/PEO miktoarm star polymers with their structures. As a consequence of increasing PBA content, the decrease in crystallinity of the studied PBA/PEO heteroarm star copolymers was observed. Regardless of the copolymer composition, fraction of oxyethylene units in the crystalline PEO phase was similar in all investigated systems. The POM images showed spherulitic morphology of the materials having low PBA content, while an increase in PBA arms fraction leads to the formation of less ordered structures. The analysis of FTIR vibrational spectrum indicates helical conformation of PEO chains in the crystalline phase. Isothermal crystallization studies carried out using the FTIR technique suggest the existence of isolated domains in the nanoscopic scale of investigated materials.     

Superabsorbent polymeric materials. XII. Effect of montmorillonite on water absorbency for poly(sodium acrylate) and montmorillonite nanocomposite superabsorbents

A series of novel xerogels based on sodium acrylate (NaA), montmorillonite (MMT), and N,N′‐methylene‐bisacrylamide (NMBA) were prepared by inverse suspension polymerization and water solution polymerization. The influences of pure MMT, intercalated MMT, the method of polymerization, and the content of the MMT in the copolymeric gels on the water absorbency and the initial absorption rate in deionized water and various salt solutions were investigated. Results showed that the water absorbency was increased by adding a small amount of the pure MMT into the copolymeric gels, but decreased by adding intercalated MMT into the gels. In addition, the water absorbency of the gels prepared by water solution polymerization was lower than that prepared by inverse suspension polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3422–3429, 2004     

Polyelectrolyte complexes formed by hyperbranched poly(sulfone‐amine) hydrochlorate and poly(sodium acrylate)

A new type of polyelectrolyte complexes formed by hyperbranched poly(sulfone‐amine) hydrochlorate and poly(sodium acrylate) has been reported. It has been found that the stoichiometry between polycation and polyanion is 1.16, which means that hyperbranched polyelectrolyte can also form the compact complexes in spite of the ill‐defined structure. Moreover, the effect of various parameters, such as the architecture of poly(sulfone‐amine), molecular weight of polymer, concentration and low molecular salt, on the complexation is also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2323–2329, 2007     

Heterogeneities during the formation of poly(sodium acrylate) hydrogels

Summary In situ fluorescence and light scattering techniques were used to study the formation of heterogeneities during the free-radical crosslinking polymerization of sodium acrylate (NaAc) in the presence of N,N'-methylene(bisacrylamide) (BAAm) as a crosslinker. Pyranine was used as a fluorescence probe in the experiments. The reactions were carried out at room temperature and at a monomer concentration of 20.6 w/v% in water. It was found that the gel forming system became turbid at the start of the reaction; continuing polymerization and crosslinking reactions turned the opaque gels into slightly opaque and finally transparent gels. Two peaks were observed both in the scattered and emitted light intensities versus the reaction time plots. The first peak corresponds to the formation and growth of the phase separated domains whereas the second peak reflects the macrogelation point in the reaction system. Received: 14 June 1999/Revised version: 10 October 1999/Accepted: 10 October 1999     

Studies with gradient polymers of polystyrene and poly(methyl acrylate)

A series of [net-polystyrene]-ipn-[net-poly(methyl acrylate)] systems with gradients of poly(methyl acrylate) in a polystyrene matrix are prepared and tested mechanically. The results showed no distinct differences from that of corresponding interpenetrating polymer network (IPN) samples with similar compositions, in contrast to the substantially improved fracture strains obtained for [net-poly(methyl methacrylate)]-ipn-[-net poly(methyl acrylate)] gradient systems and their nongradient IPN's in our previous work. Hence, it is concluded that the toughening effect of gradient structure observed is not universally applicable for all gradient systems but it is unique for the acrylic system studied. Moduli-temperature responses and dynamic mechanical spectra of gradients and IPN's prepared in the current study are also presented. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1721–1725, 1999     

Molecular characterization of sodium poly(acrylate) by an aqueous g.p.c./LS method

The molecular characterization of a commercial sample of sodium poly(acrylate) (NaPA) has been carried out by a g.p.c./LS method in 0.3 N NaCl at 25°C. The sample is fractionated into eight fractions. The agreements between the weight-average molecular weights of the NaPA fractions determined by light scattering and those measured directly by the g.p.c./LS method are excellent. Universal calibration is established for both the standard poly(ethylene oxide) and the NaPA fractions. The degree of branching for the fractions with high molecular weights are estimated using the experimental results obtained by the g.p.c./LS method.     

Superabsorbent polymeric materials. XIII. Effect of oxyethylene chain length on water absorbency for the sodium acrylate and poly(ethylene glycol) methyl ether acrylate (PEGMEAn) copolymeric gels

In a previous study, we prepared a series of xerogels based on sodium acrylate (NaA) and 2‐hydroxyethyl methacrylate (HEMA, OE = 1) or poly(ethylene glycol) methacrylate (PEGMA, OE = 6) with different oxyethylene (OE) units. The effect of the contents of HEMA and PEGMA in the copolymeric gel on the swelling behavior in deionized water and various saline solutions was studied. Their results showed that the water absorbencies for these two series gels were effectively improved by adding a small amount of HEMA or PEGMA. In this article, a series of novel xerogels based on NaA and hydrophilic monomer poly(ethylene glycol) methyl ether acrylate (PEGMEA_n), which was synthesized from acryloyl chloride and poly(ethylene glycol) monomethyl ether with three oxyethylene (OE = 9, 16, 45) chain lengths, were prepared by inverse suspension polymerization. The effects of OE chain length in the copolymeric gel on the water absorption behavior and initial absorption rate for the present xerogels were investigated. Results showed that adding a small amount of PEGMEA_n could effectively increase the water absorbency of the gels. In addition, the water absorbency decreased with an increase of the OE chain length in PEGMEA_n. The initial absorption rate for the present copolymeric gels increased with increasing OE chain length in PEGMEA_n and the content of PEGMEA_n in the copolymeric gels. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 927–934, 2006     

Dispersion of calcite by poly(sodium acrylate) prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization

Calcite is dispersed into nanoparticles with the use of polysodium acrylate, PAANa. The molecular weight distribution of PAANa greatly influences the characteristics of the dispersion. Near-monodisperse PAANa adsorbs irreversibly and totally onto the CaCO₃ surface, but for polydisperse PAANa, a mass segregation occurs, where only chains with a selected molecular weight are adsorbed. With polydisperse samples, small spherical CaCO₃ particles are generated in addition to calcite crystals. This bimodal dispersion is less viscous than the dispersion containing only calcite crystals.     

Superabsorbent polymeric materials X: Effect of degree of neutralization on swelling behavior of crosslinked poly(sodium acrylate) in aqueous salt solutions

A series of xerogels based on different degrees of neutralizations (DN) of acrylic acid (AA) and N,N-methylene-bis-acrylamide (NMBA) were prepared by inverse suspension polymerization. The influence of the DN values of AA on water absorbency and swelling behavior for these highly absorbent polymers in deionized water and various saline solutions were investigated. Results indicate that the equilibrium-water absorbency (Q_eq) increases with an increase in the DN of AA until the DN value reaches 95% and then decreases at 100% of the DN value. However, the initial absorption rate for these gels decreases with an increase in the DN value of AA in both deionized water and 0.9 wt% NaCl solution. The adsorption of copper ions by these gels was also investigated.     

Synthesis and properties of a poly(sodium acrylate) bioadhesive nanocomposite

Poly(sodium acrylate) (PNaA) based nanocomposites were synthesized using different nanosilver loadings via redox solution polymerization at room temperature and under full exposure to the atmosphere. The nanocomposites exhibited increasing antibacterial activity with increased nanosilver content. Biocompatibility was determined using an MTT assay; no significant cytotoxicity was observed at the examined nanosilver loadings. Adhesion was measured using a tensile test and the stress versus strain curve showed an acceptable stress development in the model tissue using bioadhesive containing 2 wt% nanosilver. Introducing a second, more degradable polymer to the system as an interpenetrating polymer network enabled tuning the bioadhesive degradation rate.     

Water absorbency of poly(sodium acrylate) superabsorbents crosslinked with modified poly(ethylene glycol)s

A series of novel crosslinkers, polyethylene glycol diacrylate (PEGDA) with different molecular weights, were prepared, consisting of acryloyl end groups and the PEG backbones. The corresponding poly(sodium acrylate) superabsorbents of 60 mol % neutralization degree were synthesized by using ammonium persulfate and dimethylaminoethyl methacrylate as redox initiators in aqueous solution. PEGDA was characterized by FTIR and ¹H‐NMR. The maximum of water absorbency (Q) of superabsorbents occurred at a specific mole fraction of crosslinker; Q‐values increased with increasing molecular weight of PEGDA at the same mole fraction, whereas the water absorption rate was the opposite, in which Q‐values decreased gradually with time (>24 h). Compared with superabsorbents containing methylene bisacrylamide crosslinker with PEGDA, the Q‐value of the former was significantly less than that of the latter, although levels of the residual monomer and the soluble polymer were opposite. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1851–1856, 2003     

Superabsorbent poly(acrylic acid) complex

Acrylic acid and crosslinking agent [poly(ethylene glycol)-diacrylate or divinylbenzene] were copolymerized in benzene in the presence of layered sodium silicate (δ-Na₂Si₂O₅) powder. The resultant poly(acrylic acid) complex shows large water absorbability, for which dependency on crosslinking degree was investigated. © 1996 John Wiley & Sons, Inc.     

Dielectric relaxations in poly(methyl acrylate), poly(ethyl acrylate), and poly(butyl acrylate)

A comparative study is undertaken of the dielectric relaxation spectra of poly(methyl acrylate), poly(ethyl acrylate), and poly(butyl acrylate), taking into consideration the spectra of the corresponding polymers in the series of the polymethacrylates. The three polymers, PMA, PEA, and PBA, present an α relaxation zone clearly separated from the secondary relaxations. Its shape is not altered with temperature, and it is possible to construct a master curve. With increasing length of the side chain, its distribution of relaxation times broadens and the temperature of the maximum of the relaxation decreases. A β relaxation with decreasing intensity as the length of the side chain increases is clearly perceptible in PMA and PEA, but almost not perceptible at all in PBA. In PEA this relaxation appears split into two peaks. Computer simulation of restricted motions of the side chain discard an origin similar to that of the γ relaxation in PPA or PBA for the lowest temperature component of the relaxation, and suggests the conjunction of two rotation mechanisms in this relaxation for the polyacrylates. For the experimental temperatures of our tests a γ relaxation shows up only in PBA. Its apparent activation energy, higher than in related polymers of the polymethacrylate series, suggests that the tighter packing of monomeric units in polyacrylates leads to a significant increase in the intermolecular contribution to the potential energy barrier responsible for the relaxation.     

Hydroxyethyl chitosan‐g‐poly(acrylic acid‐co‐sodium acrylate) superabsorbent polymers

A novel hydroxyethyl chitosan‐g‐poly(acrylic acid‐co‐Sodium Acrylate) (HECTS‐g‐(PAA‐co‐PSA)) superabsorbent polymer was prepared through graft copolymerization of acrylic acid and sodium acrylate onto the chain of hydroxyethyl chitosan. The structure of the polymer was characterized by FTIR. By studying the water absorption of the polymer synthesized under different conditions, the optimal conditions for synthesizing the polymer with the highest swelling ratio was defined. This superabsorbent polymer was further treated by the solvent precipitation method and by the freeze‐drying method. We found that the water absorption rate of the treated polymer was greatly increased and the microstructure of the treated polymer was changed from small pores to loose macro pores. The swelling processes of the polymers before and after modification fit first‐order dynamic processes. The amount of the residual acrylic acid was greatly decreased after treatments. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010