Reactive compatibilization of polyamide 6 with isocyanate functionalized ethylene-propylene copolymer

Reactive compatibilization of ethylene-propylene copolymer functionalized with allyl (3-isocyanato-4-tolyl) carbamate (TAI) isocyanate (EPM-g-TAI) and polyamide 6 (PA6) was investigated in this paper, FTIR analysis revealed the evidence of a chemical reaction between the end groups of PA6 and EPM-g-TAI. Thermal, rheological, morphological, and mechanical properties of the resultant system were examined, DSC analysis indicated that the crystallization of PA6 in Pa6/EPM-g-TAI blends was inhibited, due to the chemical reaction that occurs at the interface of PA6 and EPM-g-TAI. Rheological measurement showed that complex viscosity and storage modulus of PA6/EPM-g-TAI were both dramatically enhanced compared to those of PA6/EPM at the same blending composition. After examining the morphology of both blending systems, smaller particile sizes, more homogeneous distribution of domains and improved interfacial adhesion between matrix and domains were observed in the compatibilized system. Mechanical properties such as tensile strength. Young's modulus, flexural strength and modulus, as well as notched and un-notched impact strength of PA6/EPM-g-TAI blends were also found to improve gradually with increasing the content of grafted TAI.

Functionalization of an ethylene-propylene copolymer with allyl (3-isocyanate-4-tolyl) carbamate

An ethylene-propylene copolymer (EPM) was functionalized with an iso cyanate-bearing unsaturated monomer, allyl(3-isocyanate-4-tolyl) carbamate (TAI), with dicumyl peroxide as an initiator in a xylene solution. Fourier transform infrared (FTIR) was used to confirm the formation of EPM-g-TAI. The peak at 2273 cm(-1), characteristic of -NCO groups in EPM-g-TAI, revealed evidence of grafting. The grafting degree was determined with both chemical titration and FTIR. The grafting degree could be adjusted, and the maximum was over 6 wt % without any gelation. The molar mass distribution of EPM-g-TAI was narrower than that of EPM. The rheological behavior of both EPM-g-TAI and EPM was investigated with a rotational rheometer. The apparent viscosity of EPM-g-TAI was higher than that of EPM and increased with an increasing grafting degree of TAI. Surface analysis by contact-angle measurements showed that contact angles of EPM-g-TAI samples to a given polar liquid decreased with an increasing grafting degree of TAI. We also obtained the dispersion component of the surface free energy (gamma(S)(d)), the polar component of the surface free energy (gamma(S)(d)), and the total surface free energy (gamma(S) = gamma(S)(d) + gamma(S)(p)) of the grafted EPM. These parameters increased with the enhancement of the grafting degree, which gave us a quantitative estimation of the polar contribution of the grafted TAI to the total surface free energy of EPM-g-TAI.

Confining conducting polyaniline in a stable inorganic network

Water soluble conducting polyaniline with electrical conductivity of 10(-1)-10(-2) S/cm was prepared employing dopant induced water solubility technology. The water resistance of the conducting film was significantly improved employing,sol-gel hybrids method, especially when the conductive polyaniline loading was below 30 wt%. The reason for the improvement is that the conducting polyaniline chains are confined in a stable inorganic network.

Conductive hybrids from water-borne conductive polyaniline and (3-glycidoxypropyl)trimethoxysilane

Free-standing conductive films of organic-inorganic hybrids were prepared employing the sol-gel process of (3-glycidoxypropyl)trimethoxysilane (GPTMS) and water-borne conductive polyaniline (cPANI) in water/ethanol solution. The hybrids displayed a percolation threshold for electrical conductivity at a volume fraction of 2.1% polyaniline (PANI); the maximum conductivity of the hybrids reached 0.6 S/cm. GPTMS showed good compatibility with water-borne cPANI during the sol-gel process, and freestanding conductive films were obtained at room temperature. Transmission electron microscopy images of the hybrids indicated that the cPANI was dispersed in the inorganic phase in nanoscale. Because of good confinement of cPANI chains in the inorganic network, water resistance of the hybrid films was significantly improved compared with that of pure cPANI; the electrical conductivity of the films kept stable for 6-7 days soaking in water, whereas it decreased sharply for 1 day soaking for the pure cPANI.

What has brought on the effects of number-average molecular weight on the spinodals in polymer mixtures?

On the basis of the thermodynamics of Gibbs, the spinodal for the quasibinary system was derived in the framework of the Sanchez-Lacombe lattice fluid theory. All of the spinodals were calculated based on a model polydisperse polymer mixture, where each polymer contains three different molecular weight subcomponents. According to our calculations, the spinodal depends on both weight-average ((M) over bar (w)) and number-average ((M) over bar (n)) molecular weights, whereas that of the z-average molecular weight is invisible. Moreover, the extreme of the spinodal decreases when the polydispersity index (eta = (M) over bar (w)/(M) over bar (n)) of the polymer increases. The effect of polydispersity on the spinodal decreases when the molecular weight gets larger and can be negligible at a certain large molecular weight. It is well-known that the influence of polydispersity on the phase equilibrium (coexisting curve, cloud point curves) is much more pronounced than on the spinodal. The effect of M, on the spinodal is discussed as it results from the infuluence of composition temperatures, molecular weight, and the latter's distribution on free volume. An approximate expression, which is in the assumptions of v* v(1)* = v(2)* and 1/r --> 0 for both of the polymers, was also derived for simplification. It can be used in high molecular weight, although it failed to make visible the effect of number-average molecular weight on the spinodal.

Preparation of polymer/silica nanoscale hybrids through sol-gel method involving emulsion polymers. II. Poly(ethyl acrylate)/SiO2

Poly(ethyl acrylate) (PEA)/SiO2 hybrids with different compositions were prepared under different casting temperatures and pH values. Their morphology as investigated by transmission electron microscopy (TEM) shows that samples with different compositions have different morphologies. When the SiO2 content is lower, PEA is the continuous phase and SiO2 is the dispersed phase. At higher SiO2 content, the change in phase morphology takes place, nd PEA gradually dispersing in the form of latex particles in SiO2 matrix. Change in phase morphology depends mainly on the time the sol-gel transition occurs. At suitable casting temperature and pH value, PEA/SiO2 in 95/5 and 50/50 hybrids with even dispersion was obtained.

Morphology and thermal properties of conductive polyaniline/polyamide composite films

Polyaniline (PANI) in an emeraldine-base form, synthesized by chemical oxidation polymerization, was doped with camphor sulfonic acid (CSA). The conducting complex (PANI-CSA) and a matrix, polyamide-66, polyamide-11, or polyamide-1010, were dissolved in a mixed solvent, and the blend solution was dropped onto glass and dried for the preparation of PANI/polyamide composite films. The conductivity of the films ranged from 10(-7) to 10(0) S/cm when the weight fraction of PANI-CSA in the matrices changed from 0.01 to 0.09, and the percolation threshold was about 2 wt %. The morphology of the composite films before and after etching was studied with scanning electron microscopy, and the thermal properties of the composite films were monitored with differential scanning calorimetry. The results indicated that the morphology of the blend systems was in a globular form. The addition of PANI-CSA to the films resulted in a decrease in the melting temperature of the composite films and also affected the crystallinity of the blend systems.

Synthesis and characterization of poly(beta-hydroxybutyrate) and poly(epsilon-caprolactone) copolyester by transesterification

To synthesize the copolyester of poly(beta-hydroxybutyrate) (PHB) and poly(epsilon-caprolactone) (PCL), the transesterification of PHB and PCL was carried out in the liquid phase with stannous octoate as the catalyzer. The effects of reaction conditions on the transesterification, including catalyzer concentration, reaction temperature, and reaction time, were investigated. The results showed that both rising reaction temperature and increasing reaction time were advantageous to the transesterification. The sequence distribution, thermal behavior, and thermal stability of the copolyesters were investigated by C-13 NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry, wide-angle X-ray diffraction, optical microscopy, and thermogravimetric analysis. The transesterification of PHB and PCL was confirmed to produce the block copolymers. With an increasing PCL content in the copolyesters, the thermal behavior of the copolyesters changed evidently. However, the introduction of PCL segments into PHB chains did not affect its crystalline structure. Moreover, thermal stability of the copolyesters was little improved in air as compared with that of pure PHB.

Theoretical estimation of thermodynamic properties of the system PS/PPO on the basis of modified combining rule of Sanchez-Lacombe lattice fluid model

The three scaling parameters described in Sanchez-Lacombe lattice fluid theory (SLLFT), T*, P* and rho* of pure polystyrene (PS), pure poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and their mixtures are obtained by fitting corresponding experimental pressure volume-temperature data with equation-of-state of SLLFT. A modified combining rule in SLLFT used to match the volume per mer, v* of the PS/PPO mixtures was advanced and the enthalpy of mixing and Flory-Huggins (FH) interaction parameter were calculated using the new rule. It is found that the difference between the new rule and the old one presented by Sanchez and Lacombe is quite small in the calculation of the enthalpy of mixing and FH interaction parameter and the effect of volume-combining rule on the calculation of thermodynamic properties is much smaller than that of energy-combining rule. But the relative value of interaction parameter changes much due to the new volume-based combining rule. This effect can affect the position of phase diagram very much, which is reported elsewhere [Macromolecules 34 (2001) 6291]

Effect of PMR-POI on the melt behavior and isothermal crystallization of poly(phenylene sulfide)

The crystallization behavior of neat PPS and PPS in blends with PMR-POI prepared by melt mixing were investigated by differential scanning calorimetry (DSC). It was found that POI was an effective nucleation agent of the crystallization for PPS. The enthalpy of crystallization of PPS in the blends increased compared with that of neat PPS. During isothermal crystallization from melt, the dependence of relative degree of crystallinity on time was described by the Avrami equation. It has been shown that the addition of POI causes an increase in the overall crystallization rate of PPS; it also changed the mechanism of nucleation of the PHB crystals from homogeneous nucleation to heterogeneous nucleation. The equilibrium melting temperature of PPS and PPS/POI blends were determined. The analysis of kinetic data according to nucleation theories shows that the increase in crystallization rate of PPS in the composite is due to the decrease in surface energy of the extremity surface.

A novel preparation method of maleic anhydride grafted syndiotactic polystyrene and its blend performance with nylon6

This work is intended to provide a method for the preparation of maleic anhydride grafted syndiotactic polystyrene (sPS-g-MA). In particular, a novel solid reaction method by a radical grafting approach is investigated. The grafting reaction is performed at a solid state, where the syndiotactic polystyrene (sPS) is swollen in solvent at relatively low temperature compared to the conventional melt modification method. The formation of sPS-g-MA is directly confirmed by Fourier transform infrared spectroscopy and by the morphology observation of sPS/polyamide-6 (Nylon6) blends, when sPS-g-MA is used as a reactive compatibilizer.

Non-isothermal crystallization behavior and kinetics of metallocene short chain branched polyethylene

The non-isothermal crystallization behavior and kinetics of metallocene short chain branched polyethylene were investigated via DSC at cooling rates from 2.5 to 20 degreesC/min, and subsequent heating at rate of 10 degreesC/min. To verify the effect of molecular weight and branching content on crystallization, three group samples were chosen: (1) linear polyethylene with low molecular weight and high molecular weight; (2) low molecular weight polyethylene with low branching content and high branching content; (3) high molecular weight polyethylene with low branching content and high branching content. The results show that crystallization temperature, crystallinity, melting temperature and crystallization rate are highly branching content-dependent. Molecular weight effect is less important, compared to branching content. A dramatic decrease of crystallization temperature, crystallinity, crystallization rate and melting temperature was observed for branched samples. The non-isothermal kinetics was analyzed via the methods, developed by Gupta and Mo Zhi-shen, and good agreement was obtained.

Theoretical representation of shear and pressure influence on the phase separation behavior of PVME/PS mixture

In the framework of lattice fluid model, the Gibbs energy and equation of state are derived by introducing the energy (E-s) stored during flow for polymer blends under shear. From the calculation of the spinodal of poly(vinyl methyl ether) (PVME) and polystyrene (PS) mixtures, we have found the influence of E., an equation of state in pure component is inappreciable, but it is appreciable in the mixture. However, the effect of E, on phase separation behavior is extremely striking. In the calculation of spinodal for the PVME/PS system, a thin, long and banana miscibility gap generated by shear is seen beside the miscibility gap with lower critical solution temperature. Meanwhile, a binodal coalescence of upper and lower miscibility gaps is occurred. The three points of the three-phase equilibrium are forecasted. The shear rate dependence of cloud point temperature at a certain composition is discussed. The calculated results are acceptable compared with the experiment values obtained by Higgins et at. However, the maximum positive shift and the minimum negative shift of cloud point temperature guessed by Higgins are not obtained, Furthermore, the combining effects of pressure and shear on spinodal shift are predicted.

Nonisothermal crystallization and melting behavior of poly(3-hydroxybutyrate) and maleated poly(3-hydroxybutyrate)

Nonisothermal crystallization and melting behavior of poly(3-hydroxybutyrate) (PHB) and maleated PHB were investigated by differential scanning calorimetry using various cooling rates. The results show that the crystallization behavior of maleated PHB from the melt greatly depends on cooling rates and its degree of grafting. With the increase in cooling rate, the crystallization process for PHB and maleated PHB begins at lower temperature. For maleated PHB, the introduction of maleic anhydride group hinders its crystallization, causing crystallization and nucleation rates to decrease, and crystallite size distribution becomes wider. The Avrami analysis, modified by Jeziorny, was used to describe the nonisothermal crystallization of PHB and maleated PHB. Double melting peaks for maleated PHB were observed, which was caused by recrystallization during the heating process.