RHEOLOGICAL BEHAVIOR OF POLYMER MELTS (I) UNIFIED MOLECULAR THEORY OF NON-LINEAR ISCOELASTICITY WITH CONSTRAINTS OF GAUSSIAN CHAIN ENTANGLEMENT FOR POLYMER MELTS

An approach with statistical mechanics and a unified molecular theory of non-linearviscoelasticity with constraints of Gaussian chain entanglement for polymer melts were proposed.Amultimode model structure for a single polymer chain with tail segments and N reversibleentanglement sites on the test polymer chain was developed.The probability distribution function ofthe end-to-end vector for a single polymer chain at entangled state and the viscoelastic free energyof deformation for polymer melts were calculated.Four types of stress-strain relationship and mem-ory function were derived from this theory.The above theoretical relationships were verified by experi-mental data of PS(polystyrene)and LDPE(low density polyethylene)melts.     

RHEOLOGICAL BEHAVIOR OF POLYMER MELTS (Ⅰ)UNIFIED MOLECULAR THEORY OF NON-LINEAR ISCOELASTICITY WITH CONSTRAINTS OF GAUSSIAN CHAIN ENTANGLEMENT FOR POLYMER MELTS

An approach with statistical mechanics and a unified molecular theory of non-linearviscoelasticity with constraints of Gaussian chain entanglement for polymer melts were proposed.Amultimode model structure for a single polymer chain with tail segments and N reversibleentanglement sites on the test polymer chain was developed.The probability distribution function ofthe end-to-end vector for a single polymer chain at entangled state and the viscoelastic free energyof deformation for polymer melts were calculated.Four types of stress-strain relationship and mem-ory function were derived from this theory.The above theoretical relationships were verified by experi-mental data of PS(polystyrene)and LDPE(low density polyethylene)melts.     

复合离子液体催化碳酸乙烯酯水解制备乙二醇(英文)

An ionic liquid system of [Bmim]X/[Bmim]OH (X Cl, BF4, and PF6,) was developed for the hydrolysis of ethylene carbonate to ethylene glycol. The important parameters, such as the variety of ionic liquids, molar ratio of [Bmim]X to [Bmim]OH, amount of ionic liquid, molar ratio of water to ethylene carbonate, reaction temperature, pressure and reaction time, were investigated systematically. Excellent yield (>93%) and high selectivity (99.5%) of ethylene glycol were achieved. Under the optimum reaction conditions, the ionic liquid system could be reused at least five times and the selectivity of ethylene glycol remained higher than 99.5%.     

Zwitterionic polymer-coated porous poly(vinyl acetate–divinyl benzene)microsphere: A new support for enhanced performance of immobilized lipase

Enzyme immobilization has attracted great attention for improving the performance of enzymes in industrial applications. This work was designed to create a new support for Candida rugosa lipase(CRL) immobilization.A porous poly(vinyl acetate–divinyl benzene) microsphere coated by a zwitterionic polymer, poly(maleic anhydride-alt-1-octadecene) and N,N-dimethylethylenediamine derivative, was developed for CRL immobilization via hydrophobic binding. The catalytic activity, reaction kinetics, stabilities and reusability of the immobilized CRL were investigated. It demonstrated the success of the zwitterionic polymer coating and subsequent CRL immobilization on the porous microsphere. The immobilized lipase(p2-MS-CRL) reached27.6 mg·g~(-1) dry carrier and displayed a specific activity 1.5 times higher than free CRL. The increase of Vmax and decrease of Kmwere also observed, indicating the improvement of catalytic activity and enzyme-substrate affinity of the immobilized lipase. Besides, p2-MS-CRL exhibited significantly enhanced thermal stability and p H tolerance. The improved performance was considered due to the interfacial activation regulated by the hydrophobic interaction and stabilization effect arisen by the zwitterionic polymer coating. This study has thus proved the advantages of the zwitterionic polymer-coated porous carrier for lipase immobilization and its potential for further development in various enzyme immobilizations.     

Preparation and Application of Nano-composite Poly(vinyl alcohol) Gel Electrolyte in Electrochemical Capacitor

A nano-composite polymer gel electrolyte was prepared using titanium oxide nanowire, poly(vinyl alcohol) (PVA), lithium salt and organic solvent N-methyl-2-pyrrolidone (NMP). The obtained electrolyte has the potential for application in electrochemical capacitor, the PVA in it is in an amorphous state. The ionic conductivities of electrolytes increased after addition of the nanowire, and the electrolyte with 3%(w) of nanowire exhibited the highest ionic conductivity of 3.2 mS/cm at 20℃, as measured by electrochemical impedance spectroscopy. The temperature dependence of the conductivity was found to be in agreement with the Arrhenius equation. Functioning as separator and electrolyte, this nano-composite PVA gel electrolyte was used to assemble the electrochemical capacitor with active carbon film as electrodes. The compositing of nanowire may extend the life of electrochemical capacitors as they keep more than 90% of their capacitance after 5000 cycles of charging and discharging.     

EQUATIONS OF STATE FOR HARD-SPHERE CHAIN FLUIDS AND SQUARE-WELL CHAIN FLUIDS

Based on the statistical theory for chemical association,equations of state for hard-spherechain fluids(HSCFs)and square-well chain fluids(SWCFs)can be derived through the n-particlecavity correlation function(CCF)of the corresponding reference system,where n is the chain lengthor the number of segments of a chain molecule.The reference system is a fluid composed of only cor-responding monomers.In this work,the n-particle CCF is approximated by a product of effectivetwo-particle CCFs which accounts for correlations in nearest-neighbour and next-to-nearest-neighboursegment pairs.The CCFs for SWCFs may be expressed by a product of the corresponding functionfor HSCFs and a perturbation term originated from the square-well attractive potential.All these ef-fective two-particle CCFs and perturbation terms are density dependent.The dependence is determinedmainly by using computer-simulation results.The obtained equations can excellently describecompressibility factors and second Virial coefficients for HSCFs     

甲烷水合物在纯水和抑制剂体系中的生成动力学

Kinetic data of methane hydrate formation in the presence of pure water,brines with single salt and mixed salts,and aqueous solutions of ethylene glycol(EG) and salt EG were measured.A new kinetic model of hydrate formation for the methane water systems was developed based on a four-step formation mechanism and reaction kinetic approach.The proposed kinetic model predicts the kinetic behavior of methane hydrate formation in pure water with good accuracy.The feasibility of extending the kenetic model of salt(s) and EG containing systems was explored.     

Partial pore blockage and polymer chain rigidification phenomena in PEO/ZIF-8 mixed matrix membranes synthesized by in situ polymerization

Nanostructured zeolitic imidazolate frameworks(ZIF-8) was incorporated into the mixture of poly(ethylene glycol) methyl ether acrylate(PEGMEA) and pentaerythritol triacrylate(PETA) to synthesize mixed matrix membranes(MMMs) by in situ polymerization for CO_2/CH_4 separation. The solvent-free polymerization between PEGMEA and PETA was induced by UV light with 1-hydroxylcyclohexyl phenyl ketone as initiator. The chemical structural characterization was performed by Fourier transform infrared spectroscopy. The morphology was characterized by scanning electron microscope. The average chain-to-chain distance of the polymer chains in MMMs was investigated by X-ray diffraction. The thermal property was evaluated by differential scanning calorimetry. The CH_4 and CO_2 gas transport properties of MMMs are reported. The relationship between gas permeation–separation performances or physical properties and ZIF-8 loading is also discussed. However, the permeation–separation performance was not improved in Robeson upper bound plot compared with original polymer membrane as predicted. The significant partial pore blockage and polymer rigidification effect around the ZIFs confirmed by the increase in glass temperature and the decrease in the d-spacing, were mainly responsible for the failure in performance improvement, which offset the high diffusion induced by porous ZIF-8.     

STUDIES ON SYNTHESIS OF SILICA SOL-ORGANIC POLYMER COMPOSITE EMULSION

An emulsion of polystyrene/poly (butylacrylate-methyl methacrylate acrylic acid) core/shell latex particles (PS/P (BA-MMA-AA)) has been prepared by use of three synthetic methods. The effects of synthetic methods on the distribution of carboxyl groups in latex particles were studied. The results show that the seed emulsion polymerization in which the pre-emulsified monomers were added by dropping method to the second stage is the best technique for obtaining the optimum distribution of carboxyl groups on the surface of the latex particles. Furthermore, by using PS/P (BA-MMA-AA), a type of novel composite emulsion of silica sol-PS/P (BA-MMA-AA) was synthesized with the above method. By observation through transmission EM, the morphology of the latex particles obtained shows that a composite structure has been formed between silica sol particles and organic polymer particles.     

甲基丙烯酸-N, N-2-甲基乙胺酯原子转移自由基聚合动力学研究

A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2-(N,N-dimethylamino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the atom transfer equilibrium for primary radical, the propagation of growing polymer radical, and the atom transfer equilibrium for the growing polymer radical. An experiment was carried out to measure the conversion of monomer, the number-average molecular weight of polymer and molecular weight distribution for the ATRP process of DMAEMA. The experimental data were used to correlate the kinetic model and rate constants were obtained. The rate constants of activation and deactivation in the atom transfer equilibrium for primary radical are 1.0 × 104 L·mol-1·s-1 and 0.04L·mol-1·s-1, respectively. The rate constant of the propagation of growing polymer radical is 8.50L·mol-1·s-1, and the rate constants of activation and deactivation in the atom transfer equilibrium for growing polymer radica     

Volumetric properties of polymer blends from Tao–Mason equation of state

The present study is an improvement of previous work (Yousefi and Karimi, Ionics 18:135–142, 17) concern to the assessment of the ability of the Tao–Mason equation of state to predict pressure–volume–temperature (PVT) of melting polymers. The present paper, focus on the modeling of volumetric properties of polymer blends based on melting temperature (T _m) and melting point density (ρ _m), as scaling constants. The calculation of second Virial coefficients (B ₂), effective van der Waals co-volume (b) and correction factor (α) are required for judgment about applicability of this model. The new correlations were used to predict the PVT behavior of polymer blends containing poly(propylene glycol) + poly(ethylene glycol) (PEG-200), poly(ethylene glycol) methyl ether(PEGME-350) + PEG-200, PEGME-350 + PEG-600, poly(2,6-dimethyl-1,4-phenylene oxide) + poly styrene(PS), and PS + poly(vinylmethylether) in different temperatures, pressures, and mole fractions. A collection of 5,397 data points has been examined for the aforementioned polymers in the temperature in the range of 298.15–605.05 K and pressures up to 200 MPa. The average absolute deviation between the calculated and experimental densities is of the order of 0.78 %.     

Pressure-volume-temperature properties for binary and ternary polymer solutions of poly(ethylene glycol), poly(propylene glycol), and poly(ethylene glycol methyl ether) with anisole

Pressure-volume-temperature properties were measured for polymer solutions of poly(propylene glycol) (PPG)+anisole, polymer blends of PPG+poly(ethylene glycol methyl ether) (PEGME), and the blends of PPG+PEGME and poly(ethylene glycol) (PEG)+PPG with anisole at temperatures from 298.15 to 348.15 K and pressures up to 50 MPa. The Tait equation represents accurately the pressure effect on the liquid densities over the entire pressure range. The excess volumes change from positive to negative as increasing the mole fraction of PPG in the binary systems of PPG+anisole and PPG+PEGME. The volumetric data of the related binary systems were correlated with the Flory-Orwoll-Vrij and the Schotte equations of state to determine the binary parameters. By using these determined binary parameters, both equations predicted the specific volumes of the polymer blends with anisole to average absolute deviations of better than 0.13%.     

Preparation of well‐controlled porous carbon nanofiber materials by varying the compatibility of polymer blends

The relationships between the compatibility in binary polymer blends and the pore sizes of carbon nanofibers (CNFs) prepared from the blends were investigated. Compatibility was determined by the difference between the solubility parameters of each polymer in the polymer blends. Porous CNFs were prepared by an electrospinning and carbonization process using binary polymer blends, consisting of polyacrylonitrile (PAN) as the carbonizing polymer and poly(acrylic acid) (PAA), poly(ethylene glycol), poly(methyl methacrylate) or polystyrene (PS) as the pyrolyzing polymer. The pore size of the CNFs increased with increasing difference in solubility parameter. The CNFs prepared using the PAN/PAA blend, which had the smallest solubility parameter difference, exhibited a pore size of 1.66 nm compared to 18.24 nm for the CNFs prepared using the PAN/PS blend. The prepared CNF webs with controlled meso‐sized pores showed a stable cycle performance in cyclic voltammetry measurements and improved impedance characteristics. This method focusing on the compatibility in polymer blends was simple to apply and effective for controlling the pore sizes and surface area of CNFs for application as electrode materials in energy storage systems. © 2013 Society of Chemical Industry     

Thermal analysis of poly(acrylic acid)/poly(oxyethylene) blends

Blends between poly(acrylic acid) and two different poly(oxyethylenes), (1) polyethylene glycol (PEG-1000) and (2) poly(oxyethylene) (20) sorbitan monooleate (Tween-80), were studied by differential scanning calorimetry. The glass transition temperatures, T_g, of the various compositions of these blends were found to follow Fox's equation. At room temperature, blends containing no more than 60% PEG-1000 were amorphous and exhibited only a single glass transition. For these blends with PEG-1000, the glass transition temperatures for the annealed samples were higher than for the quenched samples due to the formation of a PEG crystalline phase. It was also found that addition of an amorphous polymer such as poly(acrylic acid) significantly reduced the degree of crystallinity of a semicrystalline polymer such as poly(oxyethylene). The Tween-80 systems did not show phase separation at room temperature. The compatibility between this poly(acrylic acid) and this poly(oxyethylene) was attributed to hydrogen bonding and to the lower crystalline lattice energy of this poly(oxyethylene) through its effect on its ideal solution solubility. © 1993 John Wiley & Sons, Inc.     

PMMA/PEG共混物形态和热性质的研究

在聚乙二醇存在的情况下,自由基聚合得到的聚甲基丙烯酸甲酯/聚乙二醇(PMMA/PEG)共混物,是一种半结晶聚合物;有相分离发生,一部分PEG晶体依然保持其晶体的特征,另一部分PEG晶体转变成非晶态,与PMMA网络复合,形成完全均一的非晶相。     

Study on morphology of ternary polymer blends. I. Effects of melt viscosity and interfacial interaction

The morphology of some ternary blends was investigated. In all of the blends polypropylene, as the major phase, was blended with two different minor phases, ethylene–propylene–diene terpolymer (EPDM) or ethylene–propylene–rubber (EPR) as the first minor phase and high‐density polyethylene (HDPE) or polystyrene (PS) as the second minor phase. All the blends were investigated in a constant composition of 70/15/15 wt %. Theoretical models predict that the dispersed phase of a multiphase polymer blend will either form an encapsulation‐type phase morphology or phases will remain separately dispersed, depending on which morphology has the lower free energy or positive spreading coefficient. Interfacial interaction between phases was found to play a significant role in determining the type of morphology of these blend systems. A core–shell‐type morphology for HDPE encapsulated by rubber was obtained for PP/rubber/PE ternary blends, whereas PP/rubber/PS blends showed a separately dispersed type of morphology. These results were found to be in good agreement with the theoretical predictions. Steady‐state torque for each component was used to study the effect of melt viscosity ratio on the morphology of the blends. It was found that the torque ratios affect only the size of the dispersed phases and have no appreciable influence on the type of morphology. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1129–1137, 2001     

Thermodynamic miscibility of polymer-liquid crystal blends

The thermodynamic phase behavior of two polymer-liquid crystal blends was investigated in both the solid and molten states. One of the blends (p-hexyloxybenzoic acid and poly[ethylene glycol]) contains a semi-crystalline polymer. The second example (p-pentyloxycinnamic acid and bisphenol-A polycarbonate) contains a high-impact-resistant amorphous thermoplastic. Whereas, the former system is almost completely immiscible at ambient temperature, yet advantageous for applications in the microelectronics industry, the latter blend exhibits partial (concentration-dependent) miscibility. Our multi-technique assessment of miscibility/phase separation includes high-resolution carbon-13 solid state NMR spectroscopy, differential scanning calorimetry (DSC), and group-contribution thermodynamics (Universal Quasi-Chemical Functional-Group Activity Coefficient formalism including a Free Volume correction for the small molecule activity, UNIFAC-FV). Approximate temperature-composition (equilibrium) phase diagrams are constructed for both blends in light of the results from NMR, DSC, and UNIFAC-FV.     

Crystallization and melting behavior of blends comprising poly(3‐hydroxy butyrate‐co‐3‐hydroxy valerate) and poly(ethylene oxide)

Blends of poly(3‐hydroxy butyrate‐co‐3‐hydroxy valerate) (PHBV) and poly(ethylene oxide) (PEO) were prepared by casting from chloroform solutions. Crystallization kinetics and melting behavior of blends have been studied by differential scanning calorimetry and optical polarizing microscopy. Experimental results reveal that the constituents are miscible in the amorphous state. They form separated crystal structures in the solid state. Crystallization behavior of the blends was studied under isothermal and nonisothermal conditions. Owing to the large difference in melting temperatures, the constituents crystallize consecutively in blends; however, the process is affected by the respective second component. PHBV crystallizes from the amorphous mixture of the constituents, at temperatures where the PEO remains in the molten state. PEO, on the other hand, is surrounded during its crystallization process by crystalline PHBV regions. The degree of crystallinity in the blends stays constant for PHBV and decreases slightly for PEO, with ascending PHBV content. The rate of crystallization of PHBV decreases in blends as compared to the neat polymer. The opposite behavior is observed for PEO. Nonisothermal crystallization is discussed in terms of a quasi‐isothermal approach. Qualitatively, the results show the same tendencies as under isothermal conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2776–2783, 2006     

Recycling of high density polyethylene/poly(vinyl chloride)/polystyrene ternary mixture with the aid of high energy radiation and compatibilizers

Ternary mixtures of waste plastics of high density polyethylene (HDPE), poly(vinyl chloride) (PVC), and polystyrene (PS) was recycled using a single‐screw extruder. Poly(ethylene‐co‐vinyl acetate) and poly(styrene‐b‐ethylene/butylenes‐b‐styrene) were introduced as compatibilizers for HDPE/PVC and HDPE/PS, respectively. After the polymer blends was prepared via extrusion, they were subjected to high energy irradiation. The morphology and the mechanical properties of the hybrid blends were examined. Scanning electron micrographs and transmission electron micrographs showed that both compatibilizers and irradiation improved the uniformity and dispersion of the system. The heterogeneous crosslinking generated by irradiation resulted in an optimum impact strength. High elongation at break was achieved by using compatibilizers. The improvement of tensile strength was moderate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 2756–2762, 2003     

Compatibilizers for recycling of the plastic mixture wastes. II. The effect of a compatibilizer for binary blends on the properties of ternary blends

In this article, we discuss the effect of a compatibilizer for binary blends on the properties of ternary blends composed of high‐density polyethylene (HDPE), polypropylene (PP), or polystyrene (PS) and poly(vinyl chloride) (PVC) virgin polymers with a simulated waste plastics fraction. Chlorinated polyethylene (CPE), ethylene–propylene rubber (EPR), and their 1/1 (w/w) mixture were tested as compatibilizers for the HDPE/PP/PVC ternary blend. CPE, styrene‐ethylene‐propylene block copolymer (SEP), or their 1/1 (w/w) mixture were tested as compatibilizers for the HDPE/PS/PVC ternary blend. The composition of the ternary blends were fixed at 8/1/1 by weight ratio. The amount of the compatibilizer was 3 phr. Rheological, mechanical, and thermal properties were measured. For the 8/1/1 HDPE/PP/PVC ternary blends, the tensile strength was slightly decreased, but the impact strength was significantly increased by adding EPR, CPE, or their mixture. EPR exhibited the most significant impact modification effect for the ternary blends. In a similar way, for 8/1/1 HDPE/PS/PVC ternary blends, on adding SEP, CPE, or their mixture, the tensile strength was slightly decreased, but the impact strength was noticeably increased. It was found that the SEP worked much better as an impact modifier for the ternary blends than CPE or the SEP/CPE mixture did. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1048–1053, 2000