Polymerization of styrene in a continuous filled tubular reactor

Free radical solution polymerization of styrene has been studied using a binary mixture of symmetrical bifunctional initiators in a filled tubular reactor packed with static mixers. Owing to intensive radial mixing induced by the static mixers, a near plug flow pattern was obtained in the reactor with some axial dispersion effect. The axial mass dispersion coefficient was determined from the residence time distribution experiment and a dynamic axial dispersion model has been developed and solved to investigate steady state and transient behavior of the filled tubular reactor. With a solvent volume fraction of 0.3, the monomer conversion up to 70% was obtained without fouling problems in the temperature range 90 to 120°C. The experimental filled tubular reactor was operated under various reaction conditions and a reasonably good agreement between the model and the experimental data was obtained without using any adjustable parameters.     

Thermal and thermomechanical properties of poly(ethylene oxide) networks produced with silica and organic crosslinking agents

The thermal and thermomechanical properties of two series of poly(ethylene oxide) networks (NPEOs) were investigated as a function of the chain length between crosslink sites (M_c) and the concentration of LiClO₄ (C_L) in the NPEOs. The two series of networks were produced with silica and organic crosslinking agents and, therefore, had crosslink sites of different natures: one was an inorganic silicate network (silica NPEO), and the other was an organic polar group (organic NPEO). The crosslink sites in both series of networks were commonly covalently bonded to the poly(ethylene oxide) (PEO) phase through a urethane group in the NPEOs. The glass‐transition temperatures (T_g's) of the PEO phases in the NPEOs, according to differential scanning calorimetry, increased with a decrease in M_c and were higher in the silica NPEOs than in the organic NPEOs under the same M_c conditions. The difference in T_g between the two series of networks with the same M_c values increased with decreasing M_c. These results suggested that the interaction of crosslink sites with the PEO phase was stronger in the silica NPEOs than in the organic NPEOs. The addition of LiClO₄ to the NPEOs resulted in T_g of the PEO phase in the NPEOs being elevated and increased according to the increase in C_L. The increase of T_g of the PEO phase according to the increase of C_L in the NPEOs was retarded or saturated at high values of C_L, and this indicated that the limit of solubility of the salt in the polymer was attained. The retardation or saturation of the increase of T_g was also observed in dynamic mechanical analyses. The curves of the loss factor tan δ and temperatures from the dynamic mechanical analyses for the NPEOs with high values of C_L showed shoulders or double peaks indicating the existence of the second phase in the polymer networks. In the curves of tan δ for salt‐complexed NPEOs with high values of C_L, silica NPEOs showed a shoulder of low intensity, but organic NPEOs showed a distinguished second peak becoming stronger with increasing C_L. The results of the T_g behavior and tan δ curves suggested that the salt solubility in the NPEOs was limited and that the salt solubility of PEO in the silica NPEOs was higher than that in the organic NPEOs. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 270–277, 2003     

Synthesis and biological activity of phthalimide‐based polymers containing 5‐fluorouracil

The attachment of anticancer agents to polymers is a promising approach towards reducing the toxic side‐effects and retaining the potent antitumour activity of these agents. A new tetrahydrophthalimido monomer containing 5‐fluorouracil (ETPFU) and its homopolymer and copolymers with acrylic acid (AA) and with vinyl acetate (VAc) have been synthesized and spectroscopically characterized. The ETPFU contents in poly(ETPFU‐co‐AA) and poly(ETPFU‐co‐VAc) obtained by elemental analysis were 21 mol% and 20 mol%, respectively. The average molecular weights of the polymers determined by gel permeation chromatography were as follows: M_n = 8900 g mol^?1, M_w = 13 300 g mol^?1, M_w/M_n = 1.5 for poly(ETPFU); M_n = 13 500 g mol^?1, M_w = 16 600 g mol^?1, M_w/M_n = 1.2 for poly(ETPFU‐co‐AA); M_n = 8300 g mol^?1, M_w = 11 600 g mol^?1, M_w/M_n = 1.4 poly(ETPFU‐co‐VAc). The in vitro cytotoxicity of the compounds against FM3A and U937 cancer cell lines increased in the following order: ETPFU > 5‐FU > poly(ETPFU) > poly(ETPFU‐co‐AA) > poly(ETPFU‐co‐VAc). The in vivo antitumour activities of all the polymers in Balb/C mice bearing the sarcoma 180 tumour cell line were greater than those of 5‐FU and monomer at the highest dose (800 mg kg^?1). © 2002 Society of Chemical Industry     

Gamma‐ray irradiation effect of polyethylene on dimaleimides as a class of new multifunctional monomers

Multifunctional monomers, m‐xylylenedimaleimide, p‐phenylenedimaleimide, m‐phenylenedimaleimide, and p‐phenylenedinadimide, all of which have maleimide groups, were synthesized to increase thermal and radiation stabilities. The synthesized multifunctional monomers showed good compatibility with low‐density polyethylene (LDPE). Mixtures of LDPE and these multifunctional monomers were irradiated with γ‐rays from a Co‐60 source at room temperature in a nitrogen atmosphere. The absorbed dose ranged from 0 to 160 KGy. Among these multifunctional monomers, m‐xylylenedimaleimide was the best in gel fraction enhancement. Crosslinked LDPE with m‐xylylenedimaleimide displayed a higher modulus than that of crosslinked LDPE with triallyl cyanurate. For the elongation property, LDPE with m‐xylylenedimaleimide as a multifunctional monomer showed better results than that with commercial multifunctional monomers such as triallyl cyanurate (TAC) and trimethylol propane triacrylate (TMPTA). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2339–2345, 2003     

Modeling of the drying process in paper plants

In this study a model for the drying process in paper production plants was developed based on the mass and heat balances around drying cycles. Relationships for the heat transfer coefficients between the web and the air as well as between the drying cylinder and the web were extracted from the closed-loop plant operation data. It was found that the heat transfer coefficients could be represented effectively in terms of moisture content, basis weight and reel velocity. The effectiveness of the proposed model was illustrated through numerical simulations. From the comparison with the operation data, the proposed model represents the paper plant being considered with sufficient accuracy.     

Blends of chlorinated isotactic polypropylene with poly(ethylene-co-vinyl acetate) I. Effect of component polymers composition on the blend miscibility

Chlorinated isotactic polypropylenes (CPP) having various chlorine contents were blended with poly(ethylene-co-vinyl acetate)s (EVA) having various vinyl acetate (VA) contents. The blends were made by casting films from dilute THF solutions and miscibility of the blends was identified by single glass transition temperature, which was confirmed by DSC and dynamic mechanical measurements. Based on the miscibility data from a large number of CPP/EVA combinations, a miscibility map was depicted where CO equivalent weight (CO-EQW) of EVA was plotted against chlorine equivalent weight (Cl-EQW) of CPP. Though an attractive interaction between CPP and EVA could be detected in all the miscible and immiscible blend pairs, miscibility of the CPP/EVA blends could solely be observed in a relatively narrow range of Cl-EQW ca. 65–100 and CO-EQW ca. 170–230.     

Improved mechanical properties of shape‐memory polyurethane block copolymers through the control of the soft‐segment arrangement

High‐performance shape‐memory polyurethane block copolymers, prepared with two types of poly(tetramethylene glycol) (PTMG) used as soft segments, were investigated for their mechanical properties. Copolymers with a random or block soft‐segment arrangement had higher stresses at break and elongations at break than those with only one kind of PTMG. Random copolymers with fewer interchain interactions showed higher elongation than block copolymers. All the copolymers had shape‐recovery ratios higher than 80%. In dynamic mechanical testing, the glass‐transition behavior clearly depended on the soft‐segment arrangement: random copolymers had only one glass‐transition peak, whereas block copolymers showed two separate glass‐transition peaks. Overall, the control of the soft‐segment arrangement plays a vital role in the development of high‐performance shape‐memory polyurethane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2410–2415, 2004     

Kinetics of cellobiose decomposition under subcritical and supercritical water in continuous flow system

The effects of reaction temperature, pressure and residence time were investigated with a flow apparatus. Cellobiose decomposition kinetics and products in suband supercritical water were examined at temperatures from 320 to 420 °C at pressures from 25 to 40 MPa, and at residence times within 3 sec. Cellobiose was found to decompose via hydrolysis and pyrolysis. The yield of desired hydrolysis product, glucose, was the maximum value of 36.8% at 320 °C, 35 MPa, but the amount of 5-(hydroxymethyl)furfural (HMF), fermentation inhibitor increased too because residence time increased in the subcritical region owing to decrease of reaction rate. Meanwhile, though the yield of glucose is low in the supercritical region, the yield of HMF decreased compared with the subcritical region; and at the minimum yield of HMF (380 °C, 25 MPa), the yield of glucose was 21.4%. The decomposition of cellobiose followed first-order kinetics and the activation energy for the decomposition of cellobiose was 51.05 kJ/mol at 40MPa.     

Mobile phase composition for resolving whey proteins in reversed-phase high performance liquid chromatography

Reversed-phase high-performance liquid chromatography was successfully developed for the simultaneous and rapid separation for the main whey proteins, α-Lactalbumin and β-Lactoglobulin. This method consisted of a linear gradient of the two mobile phases of 0.1% trifluoroacetic acid in water and 0.1% trifluoroacetic acid in acetonitrile. The total run time for this separation was approximately 30 min, and α-Lactalbumin was eluted followed byβ- Lactoglobulin. The injection volume was fixed at 20 μl and the flow rate was 1 ml 1/min. The optimum mobile phase composition and gradient conditions to separate α-Lactalbumin and β-Lactoglobulin (A+B) were experimentally obtained at the 15 μm particle with a pore size of 300 Å on the linear-gradient mode.     

Effects of Acetic Acid on the Crystallization Temperature of Sol–Gel-Derived MgO Nano-Powders and Thin Films

The influences of acetic acid addition to Mg-methoxide on the stability of the precursor and the crystallization behavior of sol–gel-derived MgO nano-powders and thin films were investigated using X-ray powder diffraction, transmission electron microscopy, Fourier-transformed infrared spectroscopy, and thermogravimetry. The addition of acetic acid enhanced the stability of the alkoxide against precipitation. Moreover, during postheat treatment of the gel powders treated with acetic acid, a significantly lowered crystallization temperature (250°C) was observed as compared to the untreated counterpart (350°C). The low-temperature crystallization of MgO, induced by the modification of Mg-methoxide with acetic acid, was related to the decomposition of organics at a lower temperature. These results could be explained in terms of the decrease of the O–R bond strength depending on the increase in the alkyl group size. MgO thin films having a high degree of crystallinity were successfully obtained from the Mg-methoxide treated with acetic acid at 300°C. The low-temperature crystallization of sol–gel-derived MgO thin films showed the feasibility for their application as a protective layer in alternative current plasma display panel cells.