Polyesterification and isomerization of maleic anhydride and 1,6-hexane diol as studied by 1H and 13C n.m.r.

The polyesterification and isomerization reaction of 1,6-hexane diol and maleic anydride in a melt without catalyst was studied by ¹³C and ¹H n.m.r. spectroscopy. The structure and concentration of oligoester species during the polyesterification and isomerization were determined depending on the reaction temperature and time. According to the number and configuration of repeating units determined from ¹H n.m.r. spectra kinetics of both reactions were also considered. The degree of isomerization is continuously increasing in the investigated reaction range.     

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     

磷对饮用水中细菌再生长影响的研究

根据不同成分的水样中细菌再生长情况,研究了水中磷对生物稳定性的限制因子作用。结果显示,在测试水样中添加1 mg/L的NaAc后,细菌总数增加了100%-187%;在水样中添加15μg/L的NaH2PO4后,细菌总数增加了180%-203%。随水样中PO43-P含量的增加,细菌数目也在逐渐增加,但当水中PO43-P的含量大于等于5μg/L时,细菌已无明显增长趋势。试验结果表明磷和碳一样也是水中微生物生长的限制因素之一,并且对于该水样当PO43-P的含量为2μg/L—5μg/L之间的某个值时,磷的限制作用将会表现出来。     

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.     

CaCO3/natural rubber latex nanometer composite and its properties

Calcium carbonate/natural rubber (NR) latex nanometer composites were prepared by adding nanometer CaCO₃ whose surface had been treated to natural rubber latex (NRL) before sulfuration. The physical, thermooxidative aging, and thermal degradation properties and the ultra‐microstructure were analyzed with a multipurpose material testing meter, a thermal analysis meter and a Philips XL‐30 SEM, respectively. The results showed that the structures and properties of nanometer composites could be clearly improved by NRL mixed with surface‐treated nanometer CaCO₃. The physical properties of the nanometer composites were best when the content of surface treatment agent was 2.5% (to nanometer CaCO₃), the nanometer CaCO₃/NRL content was 3:100, and the stirring time for treating the surface of the nanometer CaCO₃ was 20 min. Simultaneously, the thermooxidative aging resistance of the nanometer composites also was significantly improved. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3442–3447, 2006     

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.