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.

Anisotropic electrical transport properties of poly(methyl methacrylate) infiltrated aligned carbon nanotube mats

We report the electrical anisotropic transport properties of poly(methyl methacrylate) infiltrated aligned carbon nanotube mats. The anisotropy in the resistivity increases with decreasing temperature and the conduction mechanism in the parallel and perpendicular direction is different. Magnetoresistance (MR) studies also suggest anisotropic behavior of the infiltrated mats. Though MR is negative, an upturn is observed when the magnetic field is increased. This is due to the interplay of electron weak localization and electron-electron interactions mechanisms. Overall, infiltrated carbon nanotube mat is a good candidate for anisotropically conductive polymer composite and a simple fabrication method has been reported. (C) 2012 American Institute of Physics. [doi: 10.1063/1.3675873]

Synthesis, characterization and thermal degradation of dual temperature- and pH-sensitive RAFT-made copolymers of N,N-(dimethylamino)ethyl methacrylate and methyl methacrylate

Poly{(N,N-(dimethylamino)ethyl methacrylate]-co-(methyl methacrylate)} copolymers of various compositions were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization at 70 degrees C in N,N-dimethylformamide. The polymer molecular weights and molecular weight distributions were obtained from size exclusion chromatography, and they indicated the controlled nature of the RAFT polymerizations; the polydispersity indices are in the range 1.11.3. The reactivity ratios of N,N-(dimethylamino)ethyl methacrylate (DMAEMA) and methyl methacrylate (MMA) (rDMAEMA = 0.925 and rMMA = 0.854) were computed by the extended KelenTudos method at high conversions, using compositions obtained from 1H NMR. The pH- and temperature-sensitive behaviour were studied in aqueous solution to confirm dual responsiveness of these copolymers. The thermal properties of the copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The kinetics of thermal degradation were determined by Friedmann and Chang techniques to evaluate various parameters such as the activation energy, the order and the frequency factor. (c) 2012 Society of Chemical Industry

Size dependent structural relaxations and dielectric properties induced by surface functionalized MWNTs in poly(vinylidene fluoride)/poly(methyl methacrylate) blends

Structural dynamics, dielectric permittivity and ferroelectric properties in poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) (PVDF/PMMA) blends with respect to crystalline morphology was systematically investigated in presence of amine functionalized MWNTs (NH2-MWNTs) using dielectric spectroscopy. The crystalline morphology and the crystallization driven demixing in the blends was assessed by light microscopy (LM), wide angle X-ray diffraction (WXRD) and, in situ, by shear rheology. The crystal nucleation activity of PVDF was greatly induced by NH2-MWNTs, which also showed two distinct structural relaxations in dielectric loss owing to mobility confinement of PVDF chains and smaller cooperative lengths. The presence of crystal-amorphous interphase was supported by the presence of interfacial polarization at lower frequencies in the dielectric loss spectra. On contrary, the control blends showed a single broad relaxation at higher frequency due to defective crystal nuclei. This was further supported by monitoring the dielectric relaxations during isothermal crystallization of PVDF in the blends. These observations were addressed with respect to the spherulite sizes which were observed to be larger in case of blends with NH2-MWNTs. Higher dielectric permittivity with minimal losses was also observed in blends with NH2-MWNTs as compared to neat PVDF. Polarization obtained using P-E (polarization-electric field) hysteresis loops was higher in case of blends with NH2-MWNTs in contrast to control blends and PVDF. These observations were corroborated with the charge trapped at the crystal-amorphous interphase and larger crystal sizes in the blends with NH2-MWNTs. The microstructure and localization of MWNTs were assessed using SEM.

Thermal and Sonochemical Degradation Kinetics of Poly(n-butyl methacrylate-co-alkyl acrylates): Variation of Chain Strength and Stability with Copolymer Composition

The thermal degradation of poly(n-butyl methacrylate-co-alkyl acrylate) was compared with ultrasonic degradation. For this purpose, different compositions of poly (n-butyl methacrylate-co-methyl acrylate) (PBMAMA) and a particular composition of poly(n-butyl methacrylate-co-ethyl acrylate) (PBMAEA) and poly(n-butyl methacrylate-co-butyl acrylate) (PBMABA) were synthesized and characterized. The thermal degradation of polymers shows that the poly(alkyl acrylates) degrade in a single stage by random chain scission and poly(n-butyl methacrylate) degrades in two stages. The number of stages of thermal degradation of copolymers was same as the majority component of the copolymer. The activation energy corresponding to random chain scission increased and then decreased with an increase of n-butyl methacrylate fraction in copolymer. The effect of methyl acrylate content, alkyl acrylate substituent, and solvents on the ultrasonic degradation of these copolymers was investigated. A continuous distribution kinetics model was used to determine the degradation rate coefficients. The degradation rate coefficient of PBMAMA varied nonlinearly with n-butyl methacrylate content. The degradation of poly (n-butyl methacrylate-co-alkyl acrylate) followed the order: PBMAMA < PBMAEA < PBMABA. The variation in the degradation rate constant with composition of the copolymer was discussed in relation to the competing effects of the stretching of the polymer in solution and the electron displacement in the main chain. (C) 2012 Society of Plastics Engineers