Relaxation behavior of polymer blends with complex morphologies: Palierne emulsion model for uncompatibilized and compatibilized PP/PA6 blends

This paper deals with the dynamic rheological behavior of polypropylene/polyamide6 (PP/PA6) uncompatibilized blends and those compatibilized with a maleic anhydride grafted PP (PP/PP-g-MAH/PA6). The terminal relaxation times of the blends predicted by the Palierne emulsion model were compared with those obtained from experimental relaxation time spectra. The Palierne model succeeded well in describing PP/PA6 uncompatibilized blends with relatively low dispersed phase contents (10 wt%) and failed doing so for those of which the dispersed contents were high (30 wt%). It also failed for the compatibilized ones, irrespective of the dispersed phase content (10 or 30 wt%) and whether or not interface relaxation was taken into consideration. In the case of the uncompatibilized blend with high dispersed-phase content, interconnections among inclusions of the dispersed phase were responsible for the failure of the Palierne model. As for the compatiblized blends, in addition to particle interconnections, the existence of emulsion-in-emulsion (EE) structures was another factor responsible for the failure of Palieme model.

Effect of different VOPO4 phase catalysts on oxidative dehydrogenation of cyclohexane to cyclohexene in acetic acid

alpha(1)-VOPO4, alpha(II)-VOPO4 and beta-VOPO4 have been investigated as catalysts for the gas phase oxidative dehydrogenation (ODH) of cyclohexane to cyclohexene with the addition of acetic acid (HOAc) in the feeds in a fixed bed reactor. Different VOPO4 phases showed different acidity and reducibility. beta-VOPO4 phase is more active than alpha(I)-VOPO4 and alpha(II)-VOPO4 in the ODH without acetic acid addition. In the presence of acetic acid, the acidity of the catalyst may play an important role in the ODH process. Due to higher acidity, alpha(I)-VOPO4 phase catalyst gives better catalytic performances than alpha(I)-VOPO4 and beta-VOPO4 for the ODH of cyclohexane by adding of acetic acid in the reactants.

Kinetics study on melt grafting copolymerization of LLDPE with acid monomers using reactive extrusion method

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetics studies on reactive extrusion were carried out for the difficulties as expected. In this work, the macromolecular peroxide-induced grafting of acrylic acid and methyl methacrylate onto linear low density polyethylene by reactive extrusion was chosen as the model system for the kinetics study; the samples were taken out from the barrel at five ports along screw axis and analyzed by FTIR, H-1 NMR, and ESR. For the first time, the time-evolution of reaction rate, the reaction order, and the activation energy of graft copolymerization and homopolymerization in the twin screw extruder were directly obtained. On the basis of these results, the general reaction mechanism was tentatively proposed. It was demonstrated that an amount of chain propagation free radicals could keep alive for several minutes even the peroxides completely decomposed and the addition of monomer to polymeric radicals was the rate-controlled step for the graft copolymerization.

Influence of the degree of grafting on the morphology and mechanical properties of blends of poly(butylene terephthalate) and glycidyl methacrylate grafted poly(ethylene-co-propylene) (EPR)

Poly(ethylene-co-propylene) (EPR) was functionalized to varying degrees with glycidyl methacrylate (GMA) by melt grafting processes. The EPR-graft-GMA elastomers were used to toughen poly(butylene terephthalate) (PBT). Results showed that the grafting degree strongly influenced the morphology and mechanical properties of PBT/EPR-graft-GMA blends. Compatibilization reactions between the carboxyl and/or hydroxyl of PBT and epoxy groups of EPR-graft-GMA induced smaller dispersed phase sizes and uniform dispersed phase distributions. However, higher degrees of grafting (>1.3) and dispersed phase contents (>10 wt%) led to higher viscosities and severe crosslinking reactions in PBT/EPR-graft-GMA blends, resulting in larger dispersed domains of PBT blends. Consistent with the change in morphology, the impact strength of the PBT blends increased with the increase in EPR-graft-GMA degrees of grafting for the same dispersion phase content when the degree of grafting was below 1.8. However, PBT/EPR-graft-GMA1.8 displayed much lower impact strength in the ductile region than a comparable PBT/EPR-graft-GMA1.3 blend (1.3 indicates degree of grafting).

Reactive blending of modified polypropylene and polyamide 12: Effects of compatibilizer content on crystallization and blend morphology

The crystallization behavior and morphology of nonreactive and reactive melt-mixed blends of polypropylene (PP) and polyamide (PA12; as the dispersed phase) were investigated. It Was found that the crystallization behavior and the size of the PA12 particles were dependent on the content of the compatibilizer (maleic anhydride-modified polypropylene) because an in situ reaction occurred between the maleic anhydride groups of the compatibilizer and the amide end groups of PA12. When the amount of compatibilizer was more than 4%, the PA12 did not crystallize at temperatures typical for bulk crystallization. These finely dispersed PA12 particles crystallized co-incidently with the 1313 phase. The changes in domain size with compatibilizer content were consistent with Wu's theory. These investigations showed that crystallization of the dispersed phase Could not be explained solely by the size of the dispersion. The interfacial tension between the polymeric components in the blends may yield information on the fractionation of crystallization.

Thermotropic liquid crystallinity, thermal decomposition behavior, and aggregated structure of poly(propylene carbonate)/ethyl cellulose blends

Maleic anhydride end capped poly(propylene carbonate) (PPC-MA) was blended with ethyl cellulose (EC) by casting from dichloromethane solutions. The thermotropic liquid crystallinity, thermal decomposition behavior, and aggregated structure were investigated by differential scanning calorimetry (DSC), thermogravimetry (TGA), and wide angle X-ray diffraction (WAXD). DSC exhibits thermotropic liquid crystallinity in the rich EC composition range. TGA shows that thermal decomposition temperatures were elevated upon interfusing EC into PPC-MA. WAXD corroborates that EC and PPC-MA/EC blend films cast from dilute dichloromethane solution possessed cholesteric liquid crystalline structure in the rich EC composition range, and that dilution of PPC-MA with EC increased the dimension of noncrystalline region, leading to a more ordered packed structure.

Structure-properties relationship in toughening of poly(butylene terephthalate) with core-shell modifier

The performance of acrylonitrile-butadiene-styrene (ABS) core-shell modifier with different grafting degree, acrylonitrile (AN) content, and core-shell ratio in toughening of poly(butylene terephthalate) (PBT) matrix was investigated. Results show PBT/ABS blends fracture in ductile mode when the grafting degree is high, and with the decrease of grafting degree PBT/ABS blends fracture in a brittle way. The surface of rubber particles cannot be covered perfectly for ABS with low grafting degree and agglomeration will take place; on the other hand, the entanglement density between SAN and PBT matrix decreases because of the low grafting degree, inducing poor interfacial adhesion. The compatibility between PBT and ABS results from the strong inter-action between PBT and SAN copolymer and the interaction is influenced by AN content. Results show ABS cannot disperse in PBT matrix uniformly when AN content is zero and PBT/ABS fractures in a brittle way. With the addition of AN in ABS, PBT/ABS blends fracture in ductile mode. The core-shell ratio of ABS copolymers has important effect on PBT/ABS blends.

Properties of compatibilized nylon 6/ABS polymer blends

Nylon 6/poly(acrylonitrile-butadiene-styrene)(ABS) blends were prepared in the molten state by a twin-screw extruder. Maleic anhydride-grafted polypropylene (MAP) and solid epoxy resin (bisphenol type-A) were used as compatibilizers for these blends. The effects of compatibilizer addition to the blends were studied via tensile, torque, impact properties and morphology tests. The results showed that the additions of epoxy and MA copolymer to nylon 6/ABS blends enhanced the compatibility between nylon 6 and ABS, and this lead to improvement of mechanical properties of their blends and in a size decrease of the ABS domains.

Synthesis and characterization of maleated poly(3-hydroxybutyrate)

Graft copolymerization of maleic anhydride (MA) onto poly(3-hydroxybutyrate) (PHB) was carried out by use of benzoyl peroxide as initiator. The effects of various polymerization conditions on graft degree were investigated, including solvents, monomer and initiator concentrations, reaction temperature, and time. The monomer and initiator concentrations played an important role in graft copolymerization, and graft degree could be controlled in the range from 0.2 to 0.85% by changing the reaction conditions. The crystallization behavior and the thermal stability of PHB and maleated PHB were studied by DSC, WAXD, optical microscopy, and TGA. The results showed that, after grafting MA, the crystallization behavior of PHB was obviously changed. The cold crystallization temperature from the glass state increased, the crystallization temperature from the melted state decreased, and the growth rate of spherulite decreased. With the increase in graft degree, the banding texture of spherulites became more distinct and orderly. Moreover, the thermal stability of maleated PHB was obviously improved, compared with that of pure PHB.

Compatibilization of polyamide-6/syndiotactic polystyrene blends using styrene/glycidyl methacrylate copolymers

Blends of polyamide-6 (PA6) with syndiotactic polystyrene (sPS) were prepared using a series of styrene/glycidyl methacrylate (SG) copolymers as compatibilizers. These copolymers are miscible with sPS, and the epoxide units in SG are capable of reacting with PA6 end groups. These copolymers thus have the potential to form SG-g-PA6 graft copolymers at the PA6/sPS interface during melt processing. This study focuses on the effects of functionality and concentration of the compatibilizer on the morphological, mechanical and crystallization behaviors of the blends.. In general, SG copolymers are effective in reducing the sPS domain size and improving the interfacial adhesion. About 5 wt% glycidyl methacrylate (GMA) is the optimum content in SG copolymer that produces the best compatibilization. Both the strength and modulus of the blend have been improved on addition of the SG copolymers, accompanying a loss in toughness when higher concentration copolymer is added. Incorporation of SG compatibilizers to PA6/sPS blend has little influence on the crystallization behavior of PA6 component but resulted in a steady reduction in intensity of crystallinity peak of sPS and simultaneous crystallization of sPS with PA6 is observed.

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.

Rheology and morphology of reactively compatibilized PP/PA6 blends

This work aims to use the Palierne emulsion type model to describe the relationship between the rheological response to small amplitude oscillatory deformation and morphology of polypropylene/polyamide 6 (PP/PA6) blends compatibilized with maleic anhydride grafted polypropylene (PP-g-MAH). It was found that the Palierne emulsion type model could describe very well the linear viscoelastic responses of binary uncompatibilized PP/PA6 blends and failed to describe the ternary compatibilized PP/PP-g-MAH/PA6 blends. These features could be attributed to the fact that the morphology of the ternary blends was not of the emulsion type with the PA6 particles dispersed in the PP matrix but of an emulsion-in-emulsion type, i.e., PA6 particles dispersed in the PP matrix themselves contained PP or PP-g-MAH inclusions. By consideration of PP-in-PA6 particles as pure PA6 particles, where the volume fraction of the PA6 phase was increased accordingly, the Palierne emulsion type model could work very well for a ternary blending system. Preshear at low frequencies modified the morphology of both binary and ternary blends. The particles of the dispersed phase (PA6) became more uniform. These results suggested that the Palierne emulsion type model could be used to extract information on rheological properties and interfacial tension of polymer blends from known morphology and vice versa.

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.

Isothermal crystallization kinetics and melting behavior of poly (beta-hydroxybutyrate) and maleated poly (beta-hydroxybutyrate)

The overall isothermal crystallization kinetics and melting behavior of poly(beta-hydroxybutyrate) (PHB) and maleated PHB with different graft degree were studied by using differential scanning calorimetry (DSC). The Avrami analysis indicates that the introduction of maleic anhydride results in the decrease in the overall crystallization rate of PHB, but does not affect its nucleation mechanism and geometry of crystal growth. The activation energy of the overall crystallization process increases with the increase in graft degree. The phenomenon of multiple melting endotherms is observed, which results from melting and recrystallization during the DSC heating run.