Cationic copolymerization behavior of a bicyclic orthoester having hydroxy group with glycidyl phenyl ether and volume change on their copolymerization

This article describes cationic ring‐opening copolymerization of a bicyclic orthoester having hydroxy group (BOE‐OH) and glycidyl phenyl ether (GPE), and the volume shrinkage behavior during the copolymerization. THF soluble polyethers [poly(BOE‐OH‐co‐GPE)] were obtained by the copolymerizations at 80–180°C, while crosslinked poly(BOE‐OH‐co‐GPE) was obtained by the copolymerizations at 220–250°C. This crosslinking reaction may originate from the dehydration of methylol groups in the side chain of poly(BOE‐OH‐co‐GPE). The volume shrinkage during the cationic copolymerization reduced as the increase of the BOE‐OH feed ratio. By contrast, the volume shrinkage on the crosslinking polymerization was almost independent on the BOE‐OH feed ratio. Poly(BOE‐OH‐co‐GPE)s with higher BOE‐OH composition showed lower thermal weight loss temperature owing to the release of H₂O by dehydration of methylol groups. The BOE‐OH component in the THF soluble poly(BOE‐OH‐co‐GPE)s lowered the glass transition temperature (T_g), while that in the crosslinked poly(BOE‐OH‐co‐GPE) increased the T_g probably because of the higher crosslinking density. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1356–1361, 2006     

Synthesis of poly(tetrahydrofuran-b-ε-caprolactone) macromonomer via the Sml2-induced transformation

Summary A novel well-defined macromonomer consisting of different types of monomers in polymerization mechanisms was synthesized for the first time through the SmI₂-induced transformation. The macromonomer, -methacryloylpoly-(tetrahydrofuran-b--caprolactone), was prepared by the reaction of methacryloyl chloride with living poly(tetrahydrofuran-b--caprolactone) [poly(THF-b-CL)] which was obtained by the two-electron reduction of the cationic growing center of poly(THF) by samarium iodide (SmI₂) followed by the polymerization of CL. ¹H NMR analysis indicated the quantitative introduction of the methacryloyl group onto the polymer end. The molecular weight distribution of the macromonomer was relatively narrow, and the unit ratio of THF to CL could be controlled by both polymerization time of THF and the amount of CL, resulting from the living nature of both CL- and THF-polymerizations. Radical copolymerization of the produced macromonomers with methyl methacrylate in the presence of AIBN resulted in a polymethacrylate backbone grafted with poly(THF-b-CL) block copolymers.     

Rearrangement of the main chain of the organocobalt polymers

The polymers 3 having pyridine moieties in the main chain were synthesized by the reaction of the organocobalt polymers 1 having cobaltacyclopentadiene moieties in the main chain with various nitriles 2. When brown colored 1 and excess 2 were heated in tetrahydrofuran at 80 °C for 24 h and then at 150 °C for 12 h in a sealed tube, the polymers 3 were obtained by the precipitation with methanol in good yields. From the spectroscopic measurements, the resulting polymers 3 were found to contain 35 – 90% of the pyridine moieties depending on the structures of 1. Received: 7 July 1997/Revised: 14 August 1997/Accepted: 25 August 1997     

Synthesis of cationic flocculant by radiation-induced copolymerization of methyl chloride salt of N,N-dimethylaminoethyl methacrylate with acrylamide in aqueous solution

The radiation-induced copolymerization of the methyl chloride salt of N,N-dimethylaminoethyl methacrylate (DMAEM·MC) with acrylamide (AAm) was used to prepare a cationic polymer flocculant. The polymerization rate increased with increasing dose rate, polymerization temperature, monomer concentration and mole fraction of AAm in the monomer mixture. The molecular weight of the copolymer was also found to increase with monomer concentration and mole fraction of AAm, but at high concentration and fraction of AAm, intermolecular crosslinking tends to occur during the polymerization to form water-insoluble copolymer. A water-soluble copolymer having various molecular weights and cationic strengths can be synthesized by selecting suitable reaction conditions; i.e., this radiation process can provide a much higher molecular weight copolymer with a wide range of cationic strength. The flocculation effect was evaluated using sludge from wastewater of sugar manufacture. It was found that the radiation-polymerized copolymer DMAEM·MC–AAm has an excellent flocculation effect.     

Reverse osmosis separation of phenols in aqueous solutions using porous cellulose acetate membranes

Reverse osmosis separations of phenol (9.4 to 108 ppm), p-cresol (108 ppm), and p-chlorophenol (129 ppm) were studied using Loeb-Sourirajan-type porous cellulose acetate membranes, and single-solute aqueous feed solutions at 500 psig and the indicated solute concentrations. It was found that, by dissociating the solute by changing the pH of the feed solution, all the above phenols could be separated by reverse osmosis. Solute separation increased with increase in the degree of dissociation of the solute in the feed solution; and, by the appropriate choice of pore size on the membrane surface, separations of phenol approaching the degree of dissociation of phenol in the feed solution could be obtained under the operating conditions used. Similar experiments using aniline (93 ppm) as the solute showed that dissociation of solute molecules in the feed solution could be a technique generally applicable for the reverse osmosis separation of nonionic solutes in aqueous solution. The effects of operating pressure in the range 250 to 1500 psig and pore size on the membrane surface on the separation of un-ionized phenol and p-chlorophenol showed that, with respect to single-solute aqueous feed solutions of phenols, the component whose relative acidity was greater was preferentially sorbed at the cellulose acetate membrane—aqueous solution interface, and the solute concentration in the membrane-permeated product solution was a function of the extent and mobility of each of the sorbed species.     

Hydrophobic effects on protein/nucleic acid interaction: enhancement of substrate binding by mutating tyrosine 45 to tryptophan in ribonuclease Tl

Hydrophobic effects on binding of ribonuclease Tl to guaninebases of several ribonucleotides have been proved by mutatinga hydrophobic residue at the recognition site and by measuringthe effect on binding. Mutation of a hydrophobic surface residueto a more hydrophobic residue (Tyr45 – Trp) enhances thebinding to ribonucleotides, including mononucleotide inhibitorand product, and a synthetic substrate-analog trinudeotide aswell as the binding to dinucleotide substrates and RNA. Enhancementson binding to non-substrate ribonucleotides by the mutationhave been observed with free energy changes ranging from –2.2 to – 3 .9 kJ/mol. These changes are in good agreementwith that of substrate binding, –2.3 kJ/mol, which iscalculated from Michaelis constants obtained from kinetic studies.It is shown, by comparing the observed and calculated changesin binding free energy with differences in the observed transferfree energy changes of the amino acid side chains from organicsolvents to water, that the enhancement observed on guaninebinding comes from the difference in the hydrophobic effectsof the side chains of tyrosine and tryptophan. Furthermore,a linear relationship between nucleolytic activities and hydrophobicityof the residues (Ala, Phe, Tyr, Trp) at position 45 is observed.The mutation could not change substantially the base specificityof RNase Tl, which exhibits a prime requirement for guaninebases of substrates.     

High thermal stable thermoplastic-thermosetting polyimide film by use of asymmetric dianhydride (a-BPDA)

In order to obtain thermoplastic (before curing) and thermosetting (after curing) polyimides with high T_g for adhesive film, we prepared novel polyimides having phenylethynyl group in the side chain (44% of concentration of curing group) from asymmetric 2,3,3′,4′-biphenyltetracarboxylic dianhydride (a-BPDA), 3,4′-oxydianiline (3,4′-ODA) or 1,3-bis(4-aminophenoxy)benzene (1,3,4-APB) or 1,3-bis(3-aminophenoxy)benzene (1,3,3-APB), and 2,4-diamino-1-(4-phenylethynylphenoxy)benzene (mPDAp). Among three kinds of polymer, uncured polyimide of a-BPDA/1,3,4-APB; mPDAp had rather high T_g (265 °C, DMA) and thermoplasticity (E′ drop>10³ at T_g). After curing reaction of phenylethynyl group, the T_g of the polyimide was increased dramatically (364 °C, DMA). The polyimide derived from 1,3,4-APB having less concentration of curing group (20%) was also prepared to improve further film flexibility and toughness.     

Pervaporation study of water and tert‐butanol mixtures

The permeation behavior of water/tert‐butanol mixture through Sulzer Pervap2510 hydrophilic poly(vinyl alcohol) membranes was investigated and the effects of feed composition and temperature on separation efficiency of the membranes were studied. The pervaporation experiments were carried out with feed water content varying from 0 to 20 wt % according to the existing industrial needs and with the feed temperature from 60 to 100°C. Over this range, both water flux and separation factor increased with increasing water content and feed temperature. These phenomena may be attributed to (1) the strong interaction between water and the membrane, (2) the decoupling effect of the permeants and the membrane at elevated temperatures, and (3) the steric hindrance effect of branch chain alcohol. The permeability ratio (the ideal separation factor) of water to tert‐butanol across the membrane was calculated and found to follow the same relationship with increasing temperature and water content. Both flux and separation factor obtained from the Pervap2510 membrane in this study were much higher than previous reported values, possible causes for which were analyzed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4082–4090, 2004     

Hydrothermal Formation of Hydroxyapatite Layers on the Surface of Type-A Zeolite

Type-A zeolite evenly covered with hydroxyapatite thin layers was prepared using hydrothermal treatment at 120°C for 8 h under autogenous pressure. The hydroxyapatite needlelike nanocrystals, 100–200 nm in diameter and 30 nm in thickness, were grown under the reaction between discharged Ca²⁺ ions from type-A zeolite and PO₄³⁻ ions in (NH₄)₃PO₄ solution. The preferential orientations of the c -axis of hydroxyapatite crystals perpendicular to a zeolite surface were observed using transmission electron microscopy. The crystal structure of type-A zeolite was not destroyed under the reaction, but the surface morphology was changed only with complete covering of scaly hydroxyapatite particles.     

Radiation-induced polymerization of ethylene in pilot plant. III. Heavy-phase recycling process

Radiation-induced polymerization of ethylene using aqueous tert-butyl alcohol as medium was carried out in a large-scale pilot plant with a 50-liter central source-type reactor at a pressure of 105 to 395 kg/cm², temperature of 30° to 80°C, mean dose rate of 4.5 × 10⁴ to 1.9 × 10⁵ rads/hr, ethylene feed rate of 5.5 to 23.5 kg/hr, and medium feed rate of 21 to 102 l./hr. The space–time yield and molecular weight of the polymer were in the range of 4.7 to 16.8 g/l.-hr and 1.3 × 10⁴ to 8.9 × 10⁴, respectively. The space–time yield and molecular weight increased with mean residence time at 30°C, whereas at 80°C they became almost independent of the time. The space–time yield increased with pressure and dose rate, slightly decreased with temperature, and was maximum at ethylene molar fraction of 0.5. The polymer molecular weight increased with pressure and ethylene molar fraction, and decreased with dose rate and temperature. The total amount of deposited polymer on the reactor wall, source case wall, and scraping blades was usually less than 1 kg, which was negligibly small for the analysis of polymerization. Continuous discharge of the polymer slurry and production of fine-powder polyethylene were successfully carried out. In the central source-type reactor, a dose rate of 1.9 × 10⁵ rads/hr was obtained with a ⁶⁰Co source of ca. 12 kCi.