Preparation and characterization of poly(ethylene terephthalate) copolyesters modified with sodium‐5‐sulfo‐bis‐(hydroxyethyl)‐isophthalate and poly(ethylene glycol)

Two types of poly(ethylene terephthalate) (PET) copolyesters were successfully prepared with sodium‐5‐sulfo‐bis‐(hydroxyethyl)‐isophthalate (SIPE) and poly(ethylene glycol) (PEG) units with different molecular weights named as cationic dyeable polyester and easy cationic dyeable polyester. Their chemical and crystalline structures were characterized by the nuclear magnetic resonance (NMR), wide angle X‐ray diffraction (WAXD), and small angle X‐ray scattering measurement, and their thermal properties were tested by differential scanning calorimetry and thermogravimetric analysis, respectively. NMR experimental results showed that the actual molar ratio of comonomers was basically consistent with the correlative feed ratio. WAXD results indicated that the crystalline structures of prepared copolyesters were similar to that of PET. Moreover, the glass transition temperature, melting temperature, and thermal degradation temperature were found to decrease with the reduction of the of PEG units as the incorporation of lower of PEG units brought more ether bonds into molecular chains, which increased the irregularity of molecular chain arrangement and led to lower crystallinity. In addition, because the incorporation of PEG units with lower molecular weight led to more ether bonds and hydroxyl end‐groups in molecular chains, the value of contact angle of PET copolyesters dropped, manifesting PET copolyesters had better hydrophilicity with the decreasing molecular weight of PEG units.© 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39823.     

Influences of van der waals volume of substitute groups on CO2 permselectivity of polyimide‐A molecular simulation study

Polyimide (PI) as a typical glassy polymer material was investigated by molecular simulation to reveal the relationship between polymer molecular structure and its gas separation properties. The influences of van der waals volume (V_w) on CO₂ permselectivity of PI polymers (with four kinds of backbone substitute groups and a series of side substitute groups from small to large volume) and V_w was proposed as an intermediate to establish the relationship between the substitute group and permselectivity. The results show that the CO₂ permeability (P) simply increases and CO₂/N₂ selectivity (S) decreases with the increasing V_w of side substitute groups. The linear fitline of P‐V_w is much suitable to describe and predict the effect of the increasing V_w of side substitute group on improving permeability by analyzing the experimental and calculated CO₂ permeability. The increasing V_w of backbone substitute group can slow down the increasing of CO₂ permeability, but result in the decreasing first and then recovering to the original level. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41082.     

Calendered linear low‐density polyethylene consolidated meat and bone meal composites

Bioplastics produced from meat and bone meal (MBM) suffer from rapid and drastic mechanical property deterioration because of their hydrophilic nature. This study investigates mechanical and water stability of composites produced from introduction of a minor component of a synthetic polyethylene as a binder phase to consolidate MBM. The milled and sieved MBM was compounded with 5–60 wt % linear low‐density polyethylene (LLDPE) and formed into composite sheets by calendering, which is an industrially relevant process. Results indicated that a minimum of 15 wt % LLDPE content was required to form a nominally continuous binder phase that allowed for good processability and environment stability of the composites. As expected, the water vapor permeability (WVP) and water absorption characteristics of the composites were intermediate between those of MBM and LLDPE. Sheets containing 15 wt % LLDPE absorbed up to 35 wt % water. Composites tested after being soaked in water showed an initial decrease in TS of about 30% for the first hour but then remained fairly unchanged in the next 72 hours, confirming their moderate environment stability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41145.     

Structure and mechanical properties of crosslinked glycidyl azide polymers via click chemistry as potential binder of solid propellant

Depending upon the advantages of high efficiency, insensitivity to humidity and so on, the reaction of azide groups in glycidyl azide polymers (GAP) with alkynyl compounds has been used as a substitute of the urethane curing strategy to develop GAP‐based binder for solid propellant. In this work, an alkynyl compound of dimethyl 2,2‐di(prop‐2‐ynyl)malonate (DDPM) reacted with GAP to produce new crosslinked materials under the catalysis of Cu(I)Cl at ambient temperature, and showed great potential as a binder in composite propellant. As the feeding molar ratio of DDPM vs. GAP increased from 1 : 1 to 5 : 1, the crosslinking densities of as‐prepared materials gradually increased, together with simultaneous enhancement of Young's modulus and tensile strength. The breaking elongation showed the maximum value of ca. 82% when the feeding molar ratio of DDPM vs. GAP was 3 : 1. In addition, with an increase of the crosslinking densities, the glass transition temperatures of as‐prepared materials significantly increased from ?43.9°C to ?5.1°C while the mechanical loss peaks also gradually broadened and shifted up to high temperature, and even presented two peaks at the feeding molar ratio of DDPM vs. GAP higher than 4 : 1. It indicated that the formation of triazole‐based network resulted in structural heterogeneity in the as‐prepared materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40636.     

Effect of solid‐state shear milling on structure and properties of HDPE/UHMWPE blends

The structure and properties of HDPE/UHMWPE blends prepared through a pan‐milling reactor in solid state at ambient temperature were compared with the blends made by melt mixing. The changes of structure and properties of the blends were investigated by FTIR, melt flow index, mechanical properties, dynamic rheological measurement, DSC, and WAXD. DSC measurement illustrated that after pan‐milling treatment, the half‐width of the melting temperature became smaller. The more content of UHMWPE added in the blend, the more evident change was observed. Combined with the dynamic rheological analysis, it was proved that, the pan‐milling treatment can improve the compatibility of the HDPE/UHMWPE blends. X‐ray diffraction analysis showed that after pan‐milling treatment some ordered structure could be induced, but after heat treatment, the induced crystalline structure disappeared. The tensile properties of pan‐milled HDPE/UHMWPE blends also achieved improvement after pan milling treatment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39916.     

EDTA and pH‐sensitive crosslinking polymerization of acrylic acid, 2‐acrylamidoglycolic acid,and 2‐acrylamide‐2‐methyl‐1‐propanesulfonic acid

Network formation was monitored by shear storage modulus (G′) during free radical crosslinking polymerization to investigate the effects of pH and ethylenediaminetetraacetic acid (EDTA; a complex agent). Three types of acrylic monomers, acrylic acid (AAc), 2‐acrylamidoglycolic acid (AmGc), and 2‐acrylamido‐2‐methyl propanesulfonic acid (AmPS), were polymerized in the presence of a crosslinking agent. The ratio of crosslinking agent (methylene bis‐acrylamide; MBAAm) to monomer was varied as: 0.583 × 10^?3, 1.169 × 10^?3, 1.753 × 10^?3, and 2.338 × 10^?3. G′ of the hydrogel in crosslinking polymerizations of AAc and AmPS was effectively increased by addition of EDTA, which was not the case for the crosslinking polymerization of AmGc. The order of magnitude of G′ differed based on the acidity of monomer. The maximum values of G′ in crosslinking polymerizations of AAc, AmGc, and AmPS were ～20,000 Pa, 6000 Pa, and 400 Pa, respectively. G′ varied linearly with the molecular weight between crosslinks (M_wc). pH and EDTA‐complex affected the rate of intramolecular propagation during crosslinking polymerization. Our results indicated that G′ was primarily affected by the following factors in the order: (1) acidity of monomer, (2) M_wc, and (3) physical interactions induced by pH and EDTA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41026.     

Influence of change in ether structure on the low temperature dielectric relaxation of some poly(ether imide)

Broad band dielectric relaxation spectra are reported on a range of polymers created by varying the ether segment in a series of poly(ether imide)s. Changes in the structure allow the effects of steric constraints on the local conformational dynamics of the polymer chain to be explored. These changes have a significant effect on the glass transition temperatures of these polymers which range from 245 to over 420°C. In contrast, the low temperature dielectric relaxation behavior of these polymers is very similar and is attributed to cooperative local oscillatory—librational motions. Changes in the stereochemistry effect the amplitude, activation energy for the relaxation process, the packing chain density, and values of the high frequency limiting permittivity, ε_∞′. This latter parameter is sensitive to the extent of dipole induced dipole and π‐π electron interactions and is influenced by the packing density. The magnitude of ε_∞′ is a very important parameter in determining the suitability of poly(imide)s for electrical applications. The magnitude of ε_∞′ increases with the density; however, deviations from this general trend are observed when large nonpolar groups inhibit the interaction of neighboring chains. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41191.     

In situ biaxial stretching for the platelet formation of an ethylene–vinyl alcohol copolymer through multistage stretching extrusion and its effect on the gas‐barrier properties of polyethylene

The morphological evolution of ethylene–vinyl alcohol copolymer (EVOH) and its effect on the gas‐barrier properties of high‐density polyethylene (HDPE) were investigated. HDPE/EVOH blends were prepared through a multistage stretching extrusion, which combined an assembly of force‐assembling elements (FAEs) with an extruder. Scanning electron microscopy confirmed that with an increasing number of FAEs, the biaxial‐stretching field existing in each FAE transformed the dispersed EVOH phase into well‐defined platelets along the flowing plane. Dynamic rheological results further revealed that the formation of the platelets enlarged the interfaces between the dispersed barrier phase and the matrix; this not only led to the decline of the complex viscosity but also created more tortuous paths for the diffusion of gas molecules. Compared with that of the non‐FAE specimen blended with 25 wt % EVOH, the oxygen permeability coefficient decreased more than one order of magnitude when one FAE was applied. The structural model for permeability indicated that the enhanced barrier resulted from the increased tortuosity of the diffusion pathway, which was provided by the aligned high‐aspect‐ratio platelets. Compared with the previous biaxial‐stretching method, multistage stretching extrusion provided a simple and economical way to generate a laminar structure of the dispersed phase in the matrix phase without the application of an external stretching force. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40221.     

Investigation on the morphology and tensile behavior of β‐nucleated isotactic polypropylene with different stereo‐defect distribution

Large amount of work has been published on the tacticity‐properties relationship of isotactic polypropylene (iPP). However, the stereo‐defect distribution dependence of morphology and mechanical properties of β‐nucleated iPP (β‐iPP) is still not clear. In this study, two different iPP resins (PP‐A and PP‐B) with similar average isotacticity but different uniformities of stereo‐defect distribution were selected, their β‐iPP injection molding specimens were prepared, and the morphology evolution and tensile behaviors were studied by means of differential scanning calorimetry (DSC), 2D wide‐angle X‐ray diffraction (2D‐WAXD) and scanning electron microscope (SEM). DSC results showed that with the same concentration of β‐nucleating agent (0.3 wt % WBG‐II), PP‐B with more uniform stereo‐defect distribution exhibited more amount of β‐phase than that of PP‐A with less uniform stereo‐defect distribution, indicating that PP‐B is more favorable for the formation of β‐phase. SEM results showed that PP‐B formed more amount of β‐crystals with relatively high structural perfection, while in PP‐A a mixed morphology of α‐ and β‐phase with obviously higher amount of structural imperfection emerges. The results of room‐temperature tensile test indicated that the yield peak width of PP‐B was obviously wider, and the elongation at break of PP‐B was higher than that of PP‐A, showing a better ductile of PP‐B. The morphology evolution results of SEM, 2D‐WAXD and DSC suggest that, a combination of lamellar deformation and amorphous deformation occurred in PP‐A, while only amorphous deformation mainly took place in PP‐B, which was thought to be the reason for the different tensile behaviors of the samples. In the production of β‐PP products via injection molding, the uniformity of stereo‐defect distribution was found to be an important factor. PP with more uniform distribution of stereo‐defect favors the formation of large amount of β‐phase with high perfection, which exhibit superior ductile property. The related mechanism was discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40027.     

Preparation,structure, and properties of end‐functionalized miktoarms star‐shaped polybutadiene–sn–poly(styrene–butadiene) rubber

Two miktoarm star‐shaped rubbers with large‐volume functional groups of 1,1‐diphenylhexyl at the ends of arms (DMS–PB–SBR) and one miktoarm star‐shaped rubber with n‐butyl groups at the ends of arms (BMS–PB–SBR) were prepared by 1,1‐diphenylhexyllithium (DPHLi) and n‐butyl lithium as initiators, respectively. The molecular structures and morphological properties of the three rubbers (MS–PB–SBR) were studied and compared with those acquired from the blend consisting of star‐shaped solution‐polymerized butadiene styrene rubber (S‐SSBR) and butadiene rubber (PBR) prepared by ourselves. The results showed that MS–PB–SBR exhibited a more uniform distribution of PBR phase and a smaller phase size of PBR than that of S‐SSBR/PBR blend. It is found that MS–PB–SBR composites filled with CB showed the lower Payne effect than that of S‐SSBR/PBR/CB composite, suggesting that the MS–PB–SBR/CB composite (particularly the DMS–PB–SBR/CB composites) would possess excellent mechanical properties, high wet‐skid resistance, and low rolling resistance. For the studied MS–PB–SBR systems, the contribution of large‐volume functional groups at the end of PBR molecular chains to decrease the rolling resistance was larger than that of Sn coupling effect. It is envisioned that the miktoarm star‐shaped rubbers with 1,1‐diphenylhexyl groups at the molecular ends would be useful for making treads of green tires. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40002.