Manufacturing and foaming of high melt viscosity of polypropylene by using electron beam radiation technology

The high melt viscosity of polypropylene was studied by grafting bifunctional monomers, 1,6‐hexanediol diacrylate (HDDA) and tripropylene glycol diacrylate (TPGDA), onto homopolypropylene (HPP) and random ter‐polypropylene (RTPP) under electron‐beam irradiation. Creation of the high‐melt‐viscosity polypropylene was possible at low radiation dosage and low monomer content, under a prohibition of both radiation degradation and homopolymerization. TPGDA monomer was more effective in increasing the melt viscosity of HPP compared with RTPP, whereas HDDA monomer was more effective for enhancing the melt viscosity of RTPP. Such different effects of monomers on melt viscosity may arise from different monomer structures, namely, TPGDA has additional three methyl groups, but HDDA has no methyl groups. Electron‐beam radiation technology, on an increase of the melt viscosity, was much more effective in HPP than RTPP, when compared with virgin polymers. Modified RTPP and HPP with high melt viscosity were capable of foaming with numerous fine cells, of which the modified HPP with 1.5 mmol TPGDA and 0.5 kGy could create more spherical foam cells and its bending strength was 1.5 times more than that of the foamed RTPP. POLYM. ENG. SCI., 46:431–437, 2006. © 2006 Society of Plastics Engineers.     

Numerical simulation of fixed-bed catalytic reactor for isopropyl alcohol synthesis

The mathematical model and the method of its numerical analysis for fixed-bed catalytic reactors were developed and were applied to the pilot reactor of isopropyl alcohol (IPA). The experimental results from pilot test runs were used to test and verify the simulation results. The numerical simulation gives the IPA concentration and temperature profiles in the reactor. The production of IPA from a commercialized ethanol rector was examined. The operation conditions of IPA synthesis were established.     

Diamond growth by carbon ion implantation of diamond

Medium energy (5–25 keV) ¹³C⁺ ion implantation into diamond (100) to a fluence ranging from 10¹⁶ cm⁻² to 10¹⁸ cm⁻² was performed for the study of diamond growth via the approach of ion beam implantation. The samples were characterized with Rutherford backscattering/channelling spectroscopy, Raman spectroscopy, X-ray photoemission spectroscopy and Auger electron spectroscopy. Extended defects are formed in the cascade collision volume during bombardment at high temperatures. Carbon incorporation indeed induces a volume growth but the diamond (100) samples receiving a fluence of 4 × 10¹⁷ to 2 × 10¹⁸ at. cm⁻² (with a dose rate of 5 × 10¹⁵ at. cm⁻² s⁻¹ at 5 to 25 keV and 800 °C) showed no He-ion channelling. Common to these samples is that the top surface layer of a few nanometers has a substantial amount of graphite which can be removed by chemical etching. The rest of the grown layer is polycrystalline diamond with a very high density of extended defects.     

Characteristics of selective adsorption using D-phenylalanine imprinted terpolymer beads

A D-Phenylalanine (Phe) imprinted terpolymer, Polyacrylonitrile-Poly(acrylic acid)-Poly(acryl amide) (Poly(AN-AA-AAm)) bead was prepared by the wet-phase inversion method. Acrylamide (AAm) and acrylic acid (AA) were used as the functional monomer and acrylonitrile (AN) was used as a physical cross linker. The characteristics of selective adsorption by the D-Phe imprinted terpolymer beads were investigated at high concentrations of Phe racemate solution, 1 g Phe/L, and 10 g Phe/L. The adsorption selectivity of the D-Phe imprinted terpolymer beads prepared by anin-situ implanting method reached 0.82 and 0.8 at 1.0 g and 10 g Phe/L racemate solution, respectively, and almost all of the adsorbed D-Phe and about 43% of the adsorbed L-Phe were desorbed by 4% acetic acid. The uptake capacities of the terpolymer beads were maintained for several repeated batches.     

Design and control of reactive distillation for ethyl and isopropyl acetates production with azeotropic feeds

Reactive distillations for the production of ethyl acetate (EtAc) and isopropyl acetate (IPAc) are classified as the type-II process where the first column consists of a reactive zone and a rectifying section followed by a stripper [Tang et al., 2005. Design of reactive distillations for acetic acid esterification with different alcohols. A.I.Ch.E. Journal 51, 1683-1699]. Instead of using pure alcohols and acetic acid as reactants, this paper studies the effects of reactant purity on the design and control of reactive distillation. This offers significant economical incentives (by reducing raw materials costs), because ethanol forms an azeotrope with water at 90 mol% and isopropanol/water has an azeotrope at 68%. The purities of the acid is set to 95% for acetic acid (industrial grade), 87% for ethanol, and 65% for isopropanol. The results show that the total annual costs (TAC) increase by a factor of 5% for EtAc and 8% for IPAc production using reactive distillation. Next, the operability of the reactive distillations with azeotrope feeds is explored. Three disturbances, feed flow, acid feed purity, and alcohol feed composition, are introduced to assess control performance using dual-temperature control and one-temperature-one-composition control. Simulation results indicate good control performance can be achieved for reactive distillation with azeotropic feeds.     

A study of global vs. local properties for maleic anhydride modified polypropylene nanocomposites

Nanoindentation of organomodified clay filled maleated polypropylene (MAPP) was investigated. The study aims to identify the relative increase in local stiffness in comparison to the increase in mechanical properties of the bulk in polypropylene-based nanocomposites. Such a study allows one to assess confined material property in addition to increased filler volume at the local scale. A mixture of highly intercalated and well exfoliated clay structures, when dispersed in MAPP matrix, was observed under transmission electron microscopy. The degree of exfoliation was found to increase with clay loading, which was attributed to the higher viscosity and mechanical shear forces during melt compounding. Instrumented indentation was performed on (1) clay aggregate supported by MAPP matrix, (2) clay-matrix boundary, and (3) the MAPP matrix. The clay aggregated region generally showed higher stiffness as compared to the matrix. And, the relative increase in indentation stiffness is substantially higher than the relative increase in tensile and compressive stiffnesses for clay reinforced systems. Polymer chain confinement and topological constraint appeared to be operative to enhance local stiffness in the clay aggregated region. Good correlation was, however, obtained between the change in macroscopic stiffness and the change in highly local indentation stiffness as a result of clay reinforcement.     

Preparation and properties of polyimide/silica hybrid composites based on polymer‐modified colloidal silica

A new type of polyimide/silica (PI/SiO₂) hybrid composite films was prepared by blending polymer‐modified colloidal silica with the semiflexible polyimide. Polyimide was solution‐imidized at higher temperature than the glass transition temperature (T_g) using 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐diaminodiphenyl ether (ODA). The morphological observation on the prepared hybrid films by scanning electron microscopy (SEM) pointed to the existence of miscible organic–inorganic phase, which resulted in improved mechanical properties compared with pure PI. The incorporation of the silica structures in the PI matrix also increased both T_g and thermal stability of the resulting films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2053–2061, 2006     

Separation of Triacylglycerol Species from Interesterified Oils by High-Performance Liquid Chromatography

Using a 1,3-regioselective lipase as a catalyst, soybean oil and olive oil were interesterified with the short-chain triacylglycerol tributyrin (1,2,3-tributyrylglycerol) to produce mixtures of structured triacylglycerols (SL-TAG). The SL-TAG were purified by column chromatography and analyzed by both normal-phase (silica column; NP_SIL) and reversed-phase [octadecyl silane (ODS) column] high-performance liquid chromatography (HPLC). Individual SL-TAG molecular species were detected by evaporative light-scattering detection, and characterized by mass spectrometry. NP_SIL HPLC successfully separated the newly synthesized SL-TAG into two groups of TAG: one composed of one butyryl group and two long-chain fatty acyl groups (from soybean or olive oil); the second was composed of two butyryl groups and one long-chain fatty acyl group. The SL-TAG species were further analyzed by reversed-phase HPLC which gave a more detailed separation of the TAG species present in the two SL-TAG.     

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     

Surface properties for poly(perfluoroalkylethyl methacrylate)/poly(n-alkyl methacrylate)s mixtures

A poly(perfluoroalkylethyl methacrylate) and a series of poly(n-alkyl methacrylate)s such as poly(methyl methacrylate), poly(ethyl methacrylate), and poly(n-butyl methacrylate) were prepared and used to investigate the surface properties of polymer mixtures containing a fluorinated homopolymer and a nonfluorinated homopolymer and the effect of the side-chain length of poly(n-alkyl methacrylate) on the surface free energy for the polymer mixtures. Contact angles were measured for the surfaces of polymer mixtures by varying the concentration of poly(perfluoroalkylethyl methacrylate). From the contact angle data, it can be inferred that most of the poly(perfluoroalkylethyl methacrylate) added to poly(n-alkyl methacrylate)s is located in the outermost layer of polymer-mixture surface. Surface free energies for the outermost surfaces of polymer mixtures were calculated from the contact angle data using Owen and Wendt's equation. The decrease in the surface free energy for the polymer mixture with the poly(perfluoroalkylethyl methacrylate) addition is more pronounced as the side-chain length of poly(n-alkyl methacrylate) decreases. Due to the steric effect of the side chain of poly(n-alkyl methacrylate), the arrangement of the perfluoroalkylethyl group of poly(perfluoroalkylethyl methacrylate) to the air side is considerably hindered. The ESCA analysis of atomic compositions of the surface for the polymer mixture verified that poly(perfluoroalkylethyl methacrylate) is preferentially arranged and concentrates at the polymer mixture–air interface. The results of functional group compositions obtained by ESCA showed that the functional group composition of  CF₃ for the outermost layer has a more important effect on the surface free energy than that of  CF₂ and confirmed the hindrance of the arrangement of perfluoroalkylethyl group to the air side by the side chain of poly(n-alkyl methacrylate). © 1994 John Wiley & Sons, Inc.