Adsorption of anionic dyes on chitosan grafted poly(alkyl methacrylate)s

Chitosan grafted poly(alkyl methacrylate)s (namely chitosan grafted poly(methyl methacrylate) (ChgPMMA), chitosan grafted poly(ethyl methacrylate)(ChgPEMA), chitosan grafted poly(butyl methacrylate) (ChgPBMA) and chitosan grafted poly(hexyl methacrylate) (ChgPHMA)) were synthesized and characterized by using FT-IR and C-13 NMR techniques. The adsorption batch experiments on these grafted copolymers were conducted by using an anionic sulfonated dye. Orange-G. A pseudo-second-order kinetic model was used to determine the kinetics of adsorption. The effect of grafting, effect of process variables and the effect of different sulfonated anionic dyes (Orange-C, Congo Red, Remazol Brill Blue R and Methyl Blue) on the adsorption kinetics was determined. The Langmuir and Freundlich models were used to fit the adsorption isotherms and from the values of correlation coefficients (R-2), it was observed that the experimental data fits very well to the Langmuir model. The values of the maximum adsorption capacity of the adsorbents follow the order: ChgPMMA > ChgPEMA > ChgPBMA > ChgPHMA > chitosan. (C) 2010 Elsevier B.V. All rights reserved.

Main chain and segmental dynamics of semi interpenetrating based on polyisoprene and poly(methyl methacrylate)

Main chain and segmental dynamics of polyisoprene (PI) and poly(methyl methacrylate)(PMMA) chains in semi IPNs were systematically studied over a wide range of temperatures (above and below T-g of both polymers) as a function of composition, crosslink density, and molecular weight. The immiscible polymers retained most of its characteristic molecular motion; however, the semi IPN synthesis resulted in dramatic changes in the motional behavior of both polymers due to the molecular level interpenetration between two polymer chains. ESR spin probe method was found to be sensitive to the concentration changes of PMMA in semi IPNs. Low temperature spectra showed the characteristics of rigid limit spectra, and in the range of 293-373 K.complex spectra were obtained with the slow component mostly arisingout of the PMMA rich regions and fast component from the PI phase. We found that the rigid PMMA chains closely interpenetrated into thehighly mobile PI network imparts motional restriction in nearby PI chains, and the highly mobile PI chains induce some degree of flexibility in highly rigid PMMA chains. Molecular level interchain mixing was found to be more efficient at a PMMA concentration of 35 wt.%. Moreover, the strong interphase formed in the above mentionedsemi IPN contributed to the large slow component in the ESR spectra at higher temperature. The shape of the spectra along with the data obtained from the simulations of spectra was correlated to the morphology of the semi IPNs. The correlation time measurement detected the motional region associated with the glass transition of PI and PMMA, and these regions were found to follow the same pattern of shifts in a-relaxation of PI and PMMA observed in DMA analysis. Activation energies associated with the T-g regions were also calculated. T-50G was found to correlate with the T-g of PMMA, and the volume of polymer segments undergoing glass transitional motion was calculated to be 1.7 nm(3).C-13 T-1 rho measurements of PMMA carbons indicate that the molecular level interactions were strong in semi IPN irrespective of the immiscible nature of polymers. The motional characteristics of H atoms attached to carbon atoms in both polymers were analyzed using 2D WISE NMR. Main relaxations of both components shifted inward, and both SEM and TEM analysis showed the development of a nanometer sized morphology in the case of highly crosslinked semi IPN. (C) 2010 Elsevier Ltd. All rights reserved.

Ultrasonic degradation of poly (styrene-co-alkyl methacrylate) copolymers

The ultrasonic degradation of poly (styrene-co-methyl methacrylate) (SMMA), poly (styrene-co-ethyl methacrylate) (SEMA) and poly (styrene-co-butyl methacrylate) (SBMA) copolymers of different compositions was studied. The copolymers were synthesized and NMR spectroscopy was used to determine the composition, and the glass transition temperatures were determined by DSC. The reactivity ratios were determined by the Kelen-Tudos method and it indicated that the copolymers were random. The effect of solvent, temperature and copolymer composition on the ultrasonic degradation rate of these copolymers was investigated. A model based on continuous distribution kinetics was employed to study the degradation kinetics. The degradation rate coefficients of the copolymers decreased with an increase in the styrene content in the copolymer. At any particular copolymer composition the rate of degradation follows the order: SBMA >SEMA > SMMA. Thermogravimetric analysis (TGA) of the copolymers was carried in order to assess their thermal stability. The same order of degradation was observed for the thermal degradation of the copolymers as that observed for ultrasonic degradation. (C) 2010 Elsevier B.V. All rights reserved.

Kinetics of sono-photooxidative degradation of poly(alkyl methacrylate)s

The mechano-chemical degradation of poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA) and poly(n-butyl methacrylate) (PBMA) using ultrasound (US), ultraviolet (UV) radiation and a photoinitiator (benzoin) has been investigated. The degradation of the polymers was monitored using the reduction in number average molecular weight (M-n) and polydispersity (PDI). A degradation mechanism that included the decomposition of the initiator, generation of polymer radicals by the hydrogen abstraction of initiator radicals, reversible chain transfer between stable polymer and polymer radicals was proposed. The mechanism assumed mid-point chain scission due to US and random scission due to UV radiation. A series of experiments with different initial M-n of the polymers were performed and the results indicated that, irrespective of the initial PDI, the PDI during the sono-photooxidative degradation evolved to a steady state value of 1.6 +/- 0.05 for all the polymers. This steady state evolution of PDI was successfully predicted by the continuous distribution kinetics model. The rate coefficients of polymer scission due to US and UV exhibited a linear increase and decrease with the size of the alkyl group of the poly(alkyl methacrylate)s, respectively. (C) 2010 Elsevier B.V. All rights reserved.

Oxidative copolymerization: microstructure analysis of the terpolymer of styrene, methyl methacrylate, and oxygen

This paper reports the first study of the microstructure of a copolyperoxide by nuclear magnetic resonance spectroscopy. The copolyperoxides of styrene and methyl methacrylate (MMA) of various compositions have been synthesized. An analysis of the resonance signal of the backbone methylene protons gave the diad sequence probabilities which led to the calculation of the oxidative copolymerization reactivity ratios for styrene and MMA and the microstructural parameters like average chain length of the repeat unit sequences, run number, etc. The results point to the tendency of the SO1 and MO:! units to alternate in the chain. Compared to poly(styrene peroxide), the aromatic C1 seems to be stereosensitive in the terpolymers.

Second harmonic generation in poled molecularly doped polymer films : Push-pull butadienes in poly(methyl methacrylate) and polystyrene

We report second harmonic generation in a new class of organic materials, namely donor-acceptor substituted all-trans butadienes doped in poly(methyl methacrylate) or polystyrene and oriented by corona poling at elevated temperatures. Second harmonic measurements were made at room temperature. The observed d33 coefficients are greater than those of potassium dihydrogen phosphate or 4-dimethylamino-4'-nitrostilbene doped in similar polymer matrices. Rotational diffusion coefficients estimated from the decay characteristics of the second harmonic intensity in the polymer films indicate that the polymer matrix plays a major role in stabilizing the dopants in a nonlinear optics conducive environment.

Carbon-13 relaxation study of chain segmental motion and side-chain internal rotations of poly(isobutyl methacrylate) in solution

The dynamics of poly(isobutyl methacrylate) in toluene solution has been examined by C-13 spin-lattice relaxation time and NOE measurements as a function of temperature. The experiments were performed at 50.3 and 100.6 MHz. The backbone carbon relaxation data have been analyzed using the Dejean-Laupretre-Monnerie (DLM) model, which describes the dynamical processes in the backbone in terms of conformational transitions and bond librations. The relaxation data of the side chain nuclei have been analyzed by assuming different motional models, namely, unrestricted rotational diffusion, three site jumps, and restricted rotational diffusion. The different models have been compared for their ability to reproduce the experimental spin-lattice relaxation times and also to predict the behavior of NOE as a function of temperature. Conformational energy calculations have been carried out on a model compound by using the semiempirical quantum chemical method, AM1, and the results confirm the validity of the motional models used to describe the side-chain motion.

Comparison of the miscibility strategies in poly(benzyl methacrylate)-polystyrene blends

Exothermic interactions like hydrogen bonding, ionic and charge transfer, etc., and ''copolymer effect'' are commonly used to induce miscibility in immiscible blends. The efficacy of these methods in promoting miscibility in poly(benzyl methacrylate) (PBMA)-polystyrene (PS) immiscible blends has been studied by suitably modifying the structure of the component polymers. It has been found that hydrogen bonding approach is most advantageous among these approaches as it involves the need for minimum interacting sites. It has also been shown that these results can be extended to the blends of poly(acrylate)s or poly(methacrylate)s with PS. (C) 1996 John Wiley & Sons, Inc.

Influence of poling methods on the orientational dynamics of 2-methyl-4-nitro-aniline in poly(methyl methacrylate) studied by second harmonic generation

The magnitude and stability of the induced dipolar orientation of 2-methyl-4-nitroaniline (MNA)/poly(methyl methacrylate) (PMMA) guest/host system is investigated. The chromophores are aligned using both the corona discharge and contact electrode poling techniques. The magnitude of order parameter (also an indicator for the second order nonlinear susceptibility) is measured by recording absorbances of the poled (by the two different techniques) and unpoled PMMA films at different concentrations of MNA. Under the same conditions the corona poling technique creates a higher alignment of molecules along the field direction. The time dependence of the second harmonic intensity of the MNA/PMMA film prepared by the two techniques can be described by a Kohlrausch-Williams-Watts stretched exponential. The temperature dependence of the decay time constant is found to generally follow a modified Williams-Landel-Ferry (WLF) or Vogel-Tamann-Fulcher (VTF) equation. The glass transition temperature seems to be the single most important parameter for determining the relaxation time tau(T).

Microstructure of copolyperoxides of alpha-methylstyrene with styrene and methyl methacrylate

This paper reports a study on the microstructure of two series of copolyperoxides of alpha-methylstyrene, with styrene and with methylmethacrylate. The copolyperoxides were synthesized by the free radical-initiated oxidative copolymerization of the vinyl monomer pairs. The copolyperoxide compositions obtained from the H-1 and C-13 NMR spectra led to the determination of the reactivity ratios. The product of the reactivity ratios indicates that alpha-methylstyrene forms a block copolyperoxide with styrene and a random copolyperoxide with methylmethacrylate. Microstructural parameters like average sequence length, run number, etc. have been determined for the latter copolyperoxide from analysis of its C-13 NMR spectrum. The aromatic quaternary and carbonyl carbons were found to be sensitive to triad sequences. The end groups of the copolyperoxides have been identified by H-1 NMR as well as FTIR spectroscopic techniques. The thermal degradation of the copolyperoxides has been studied by differential scanning calorimetry, which confirms the alternating peroxide units in the copolyperoxide chain.

Synthesis and characterization of tetrapolymers of styrene, methyl methacrylate, alpha-methylstyrene, and oxygen

This paper presents the first report on a terpolyperoxide (TPPE) synthesized by the oxidative terpolymerization of styrene, methyl methacrylate, and a-methylstyrene. TPPEs of different compositions were synthesized by varying the vinyl monomers feed, and they were then characterized by spectroscopic and thermal studies. The conventional terpolymer equation has been used to predict the composition of TPPEs. The H-1 NMR chemical shift values of TPPEs were found to vary with the composition. The shape of the backbone methylene protons (4.00-4.50 ppm) was found to be sensitive to the sequence distribution of vinyl monomers in the polymer chain. Formaldehyde, benzaldehyde, acetophenone, and methyl pyruvate were identified as the primary degradation products. The overall thermal stability and the average enthalpy of degradation (Delta H-d), as obtained by thermogravimetric analysis and differential scanning calorimetry, respectively, do not vary much with the composition of TPPEs.

Stabilization of thermal degradation of poly(methyl methacrylate) by polysulfide polymers

The thermal degradation of poly(methyl methacrylate) (PMMA) in the presence of polysulfide polymers, namely, poly( styrene disulfide) (PSD) and poly(styrene tetrasulfide) (PST) was studied using thermogravimetry (TG) and direct pyrolysis-mass spectrometric (DP-MS) analysis. Both PSD and PST were found to stabilizethe PMMA degradation, which was explained by both radical recombination and a chain-transfer mechanism. (C) 1997 John Wiley & Sons, Inc.

Reactivity ratios for the oxidative copolymerizations of indene with methyl methacrylate and methacrylonitrile

The copolyperoxides of indene with methyl methacrylate and methacrylonitrile have been synthesized by the free-radical-initiated oxidative copolymerization of indene and the monomers. The compositions of copolyperoxides, obtained from H-1 and C-13 NMR spectra, have been utilized to determine the reactivity ratios. The reactivity ratios indicate that the copolyperoxides contain a large proportion of the indene units in random placement. Thermal degradation studies of the copolyperoxides by differential scanning calorimetry and electron-impact mass spectroscopy support alternating peroxide units in the copolyperoxide chain. The energy of activation for thermal degradation suggests that the degradation is controlled by the dissociation of the peroxide (-O-O-) bonds in the copolyperoxide chain. The flexibility of copolyperoxide in terms of glass transition temperature (T-g) has also been examined. (C) 2002 Elsevier Science Ltd. All rights reserved.

Continuous distribution kinetics for ultrasonic degradation of poly(methyl methacrylate)

Ultrasonic degradation of poly(methyl methacrylate) (PMMA) was carried out in several solvents and some mixtures of solvents. The time evolution of molecular weight distribution (MWD), determined by gel permeation chromatography, is analysed by continuous distribution kinetics. The rate coefficients for polymer degradation are determined for each solvent. The variation of rate coefficients is correlated with the vapour pressure of the solvent, kinematic viscosity of the solution and solvent-polymer interaction parameters. The vapour pressure and the kinematic viscosity of the solution are found to be more critical than other parameters (such as the Huggins and Flory-Huggins constants) in determining the degradation rates. (C) 2001 Society of Chemical Industry.