Polyphosphonates obtained by vapor-liquid interfacial polycondensation

Summary A series of polyphosphonates were synthesized by base promoted liquid-vapor interfacial polycondensation of various alkyl (aryl) phosphonic dichlorides (methylphosphonic dichloride (MPD), cyclohexylphosphonic dichloride (CPD) and phenylphosphonic dichloride (PPD)) with different bisphenols (hydroquinone (HQ), bisphenol A (BA), 4,4′ - biphenol (BP), 1,5-naphtalenediol (ND) and 4,4′ - sulfonyldiphenol (SD)). The polyphosphonates were characterized by infrared (IR) and proton magnetic resonance (¹H-NMR) spectroscopy. Yields in the range of 20–80% and Mn of ∼ 8500–35000 were obtained. DSC measurements show Tg in the range 95°–148°C. These polymers are soluble in solvents such as N,N-dimethylformamide, tetrahydrofuran and chloroform. Polyphosphonates were stable up 240°–300°C in air atmosphere. Received: 11 March 2002 / Revised version: 29 May 2002 / Accepted: 12 June 2002     

Unperturbed molecular dimensions and the theta temperature of dextran in dimethylsulfoxide (DMSO) solutions

Summary The unperturbed molecular dimensions of dextran samples have been determined in dimethylsulfoxide (DMSO) solutions from intrinsic viscosity measurements at different temperatures. The unperturbed dimension parameter, K_o, has been calculated from extrapolation methods.The unperturbed root-mean-square end-to-end distance, <r²>_o ^1/2, found for the polymer samples in DMSO solutions, indicate that the polymer coils are contracted. This distance varies from 3.25 × 10⁻⁷ cm to 2.94 × 10⁻⁷ cm for the sample T 40 and from 8.28 × 10⁻⁷ cm to 7.48 × 10⁻⁷ cm for the sample T 500, in the chosen solvent as the temperature is raised from 25°C to 45°C. In the system of dextran/DMSO, the long-range interaction parameter, B, was also determined and a significant decrease is observed between 25°–45°C. The theta temperatures, Θ, were obtained as Θ= 327.25 K, Θ= 327.41 K and Θ= 323.38 K from the temperature dependence of the interaction parameter in Kurata-Stockmayer-Fixman, Berry and Inagaki-Suzuki-Kurata equations, respectively. Received: 19 January 1998/Revised version: 9 June 1998/Accepted: 10 June 1998     

Cationic polymerizations at elevated temperatures by novel initiating systems having weakly coordinating counteranions 2. Isobutylene/isoprene copolymerizations

As a sequel to our studies on isobutylene (IB) homopolymerizations, we have investigated the copolymerization of IB/isoprene (IP) mixtures containing up to ∼20 mole% IP in the feed by the use of the in situ (CH₃)₃Si[B(C₆F₅)₄] initiating system in close-to-neat monomers in the temperature range from −35 to −8 (reflux)°C. The effects of temperature and IB/IP feed ratio on copolymer molecular weights were determined and compared with those produced by AlCl₃. The molecular weights of butyl rubbers obtained by the novel initiating system under a variety of conditions are invariably and significantly higher than those made with AlCl₃. High molecular weight gel-free rubbers containing up to ∼5 mol% unsaturation can be obtained at relatively high temperatures. Copolymer compositions can be controlled by the IB/IP ratio in the feed. Product molecular weights decrease with increasing IP content. To gain insight into the copolymerization mechanism, the activation enthalpy of molecular weights (ΔH^‡=−5.9 kcal/mol, −24.7 kJ/mol) and the reactivity ratios (r_IB= 1.8, r_IP= 1.5) have been determined. Received: 8 July 1998/Revised version: 16 October 1998/Accepted: 16 October 1998     

Effect of temperature on linolenic acid loss and 18:3 Δ9-cis, Δ12-cis, Δ15-trans formation in soybean oil

Oil was extracted from soybeans, degummed, alkalirefined and bleached. The oil was heated at 160, 180, 200, 220 and 240°C for up to 156 h. Fatty acid methyl esters were prepared by boron trifluoride-catalyzed transesterification. Gas-liquid chromatography with a cyanopropyl CPSil88 column was used to separate and quantitate fatty acid methyl esters. Fatty acids were identified by comparison of retention times with standards and were calculated as area % and mg/g oil based on 17:0 internal standard. The rates of 18:3ω3 loss and 18:3 Δ9-cis, Δ12-cis, Δ15-trans (18:3c,c,t) formation were determined, and the activation energies were calculated from Arrhenius plots. Freshly prepared soy oil had 10.1% 18:3ω3 and no detectable 18:3c,c,t. Loss of 18:3ω3 followed apparent first-order kinetics. The first-order rate constants ranged from .0018±.00014 min⁻¹ at 160°C to .083±.0033 min⁻¹ at 240°C. The formation of 18:3c,c,t did not follow simple kinetics, and initial rates were estimated. The initial rates (mg per g oil per h) of 18:3c,c,t formation ranged from 0.0031±0.0006 at 160°C to 2.4±.24 at 240°C. The Arrhenius activation energy for 18:3ω3 loss was 82.1±7.2 kJ mol⁻¹. The apparent Arrhenius activation energy for 18:3c,c,t formation was 146.0±13.0 kJ mol⁻¹. The results indicate that small differences in heating temperature can have a profound affect on 18:3c,c,t formation. Selection of appropriate deodorization conditions could limit the amount of 18:3c,c,t produced.     

Synthesis, characterization and thermal behavior of Poly(methyl-n-octadecyl itaconate) a comb-like polymer with crystallizable side chain

The radical polymerization of methyl n-octadecyl itaconate initiated with AIBN, produces poly(methyl n-octadecyl itaconate) with a yield of 47% and a molecular weight of about 10⁵ g/mol. ¹³C-NMR studies point out that this polymer is mainly syndiotactic. The combined studies of DSC and solid state ¹³C CP/MAS NMR indicate that the polymer side chains are able to crystallize in a paraffinic phase, presumably in an hexagonal form which melts at 44°C with a ΔH of 4.8Kcal/mol. Received: 12 September 2001/Revised version: 3 January 2002/Accepted: 10 January 2002     

Optical waveguiding in novel phosphazene polymer films

Summary Planar optical waveguides of some novel phosphazene inorganic polymers with high glass transition temperatures, T _g≥ 150°C, have been prepared by spin-coating on glass and quartz substrates. Thicknesses between 0.5 and 2 μm and index steps of about Δn∼0.2 (for quartz) and Δn∼0.1 (for glass) at λ= 0.633 μm have been achieved. From one to five modes have been observed at wavelengths ranging from the green to the near infrared. Refractive indices have been well fitted to a Sellmeier dispersion equation. Waveguide losses are estimated to be around 10 dB/cm. Received: 6 December 1999/Revised version: 20 May 2000/Accepted: 15 July 2000     

Crowned polyacetylene. 4. Solid state NMR studies on molecular motions and cis-trans isomerization of poly(4'-ethynylbenzo-15-crown-5)

Summary Chain conformations and molecular motions of poly(4'-ethynylbenzo-15-crown-5) (PEB15C5) and its annealed sample (AN-PEB15C5) in the solid state were investigated by ¹H NMR and CP-MAS ¹³C NMR measurements. The chain conformation was determined to be cis-transoidal for PEB15C5 and 70°-deflected trans-transoidal for AN-PEB15C5. The exothermic peak at 180°C observed in the DSC thermogram was due to the cis-trans isomerization. Motional modes of each chain were observed in the three temperature regions of γ, β and α with an increase of temperature, which are attributed to the sterically hindered oscillation of the side chains and the vibrational and free rotations of the main chain with the oscillating side chain. The free rotation of the trans chain in the α-region occured in a lower temperature region by 15°C, comparing with that of cis chain. Received: 1 December 1997/Revised version: 5 January 1998/Accepted: 12 January 1998     

Dispersed phase destabilization in table spreads

Commercially available butter, regular-fat margarine, and a fat-reduced margarine (38% fat w/w) were stored between 10 and 35°C for up to 4 d to elaborate on the relationship between droplet size and solid fat content (SFC) that exists in these spreads. At 10°C, the mean volume-weighted droplet size for butter was 4.22±0.40 μm followed by margarine (6.22±0.10 μm) and fat-reduced margarine (12.62±0.28 μm). At higher temperatures, as a result of decreasing SFC, the mean droplet size increased as did the droplet size distribution, leading to eventual coalescence and destabilization in all spreads. In butter, the critical SFC was ∼9%, whereas in margarine notable coalescence occurred at ∼5% SFC. The fat-reduced margarine destabilized at lower temperatures than the other spreads (∼20°C vs. ∼30°C), at an SFC of ∼6.5%. In these spreads, two different mechanisms influenced dispersed phase stability: (i) steric stabilization against coalescence via fat crystals located at the droplet interface, known as Pickering stabilization, and (ii) stabilization against droplet sedimentation (and droplet encounters) due to the presence of the fat crystal network.     

Synthesis of poly {4-[bis(trimethylstannyl)methyl]styrene} and its properties for electron-beam resist

Summary To create high performance resist materials, synthesis of novel organostannun-containing polymer was investigated. 4-[Bis(trimethylstannyl)methyl]styrene (BSnMS) was synthesized by a reaction between trimethylstannyl chloride and 4-vinylbenzyllithium that was prepared through a metalation reaction of 4-methylstyrene by lithium diisopropylamide. Radical polymerization of BSnMS proceeded smoothly to give a polymer. Glass transition temperature of poly(BSnMS) (Tg=140°C) was fairly high among polystyrene homologues. Poly(BSnMS) thus obtained showed naga-working properties toward EB exposure. Sensitivity of the poly(BSnMS) was 9.0∼9.6 mC cm^-2, keeping high γ-value (3.2∼4.9).     

The synthesis and thermotropic liquid crystalline behavior of the novel poly(aryl ether ketone)s containing chloro-side group

The novel poly(aryl ether ketone)s containing chloro-side group were synthesized by nucleophilic substitution reactions of 4,4′-biphenol and chlorohydroquinone with either 4,4′-difluorobenzophenone (BP/CH/DF) or 1,4-bis(p-fluorobenzoyl)benzene (BP/CH/BF) and their thermotropic liquid crystalline properties were characterized by a variety of experimental techniques. The thermotropic liquid crystalline behavior was observed in the copolymers containing 50 and 70% biphenol. Melting transition (Tm) and isotropization transition (Ti) both appeared in the DSC thermograms. A banded texture was formed after shearing the sample in the liquid crystalline state. The novel poly(aryl ether ketone)s had relatively higher glass transition temperature (Tg) in the range of 168 ∼ 200 °C and lower melting temperature (Tm) in the range of 290 ∼ 340 °C. The thermal stability (Td) was in the range of 430 ∼ 490 °C. Received: 7 February 1997/Revised: 31 March 1997/Accepted: 2 April 1997     

A colorimetric assay for measuring cell-free and cell-bound cholesterol oxidase

Cholesterol oxidase (cholesterol:oxygen oxidoreductase, EC 1.1.3.6) catalyzes the conversion of sterol Δ⁵-3β-alcohol to the corresponding Δ⁴-3-ketone with the reduction of oxygen to hydrogen peroxide.Rhodococcus species GK 1, a soil isolated microbe, produces an extracellular and a membrane-bound cholesterol oxidase; the latter is bound to the outer surface of the microbial cell membrane. A simple and sensitive assay is described to measure the two enzyme types; no enzyme extraction is needed for measuring the membrane-bound cholesterol oxidase. In this assay, hydrogen peroxide is reduced by the chromogen 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) in the presence of horseradish peroxidase, and the increased absorbance is followed continuously at 600 nm (ε_m = 1.82×10⁴ M⁻¹·cm⁻¹ at pH 7.0 and 30°C). The standardized assay medium contained 46.9 mM sodium-potassium phosphate buffer pH 7.0, 0.16% Triton X-100, 312.5 μM ABTS, 50 μg peroxidase (12.5 units at 25°C), 6.25% isopropanol, 306.3 μM cholesterol or other sterols (kept in solution with isopropanol), and cholesterol oxidase. Oxidation of one molecule of cholesterol by cholesterol oxidase gives one molecule of hydrogen peroxide which reacts with two molecules of ABTS. The method is reproducible and the results correlate well with those obtained by measuring the absorbance of Δ⁴-cholest-3-one at 240 nm (ε_m = 1.40×10⁴ M⁻¹·cm⁻¹ at pH 7.0 and 30°C) and by the method of Allainet al. (Clin. Chem. 20, 470–475, 1974). In terms of efficiency, simplicity, and time saved, this coupled assay is expected to be a useful method for monitoring microbial production of cholesterol oxidase on an industrial scale, and for determining cholesterol or other sterols in biological fluids.     

A spectroscopic study of the interaction of nigerloxin,a fungal metabolite,with serum albumin

Nigerloxin [2-amido-3-hydroxy-6-methoxy-5-methyl-4-(prop-1′-enyl) benzoic acid], a fungal metabolite, is an inhibitor of lipoxygenase and aldose reductase with free radical-scavenging properties. The interaction of nigerloxin with bovine serum albumin (BSA) was investigated using fluorescence spectroscopy and circular dichroic measurements. The fluorescence of BSA was quenched following interaction with nigerloxin, and this property was used to generate a binding constant. The estimated association constant was 1.01±0.2×10⁶ M⁻¹. Job's method of continuous variation indicated that nigerloxin formed a 1∶1±0.1 complex with BSA. To understand the nature of the interaction, the variance in the association constant as a function of temperature in the range of 14–45°C was used to calculate the thermodynamic parameters. The thermodynamic parameters at 27°C derived from the mass action plot and van't Hoff's plot were as follows: ΔG=−8.2±0.1 kcal/mol, ΔH≈0 kcal/mol, and ΔS=27.5±0.4 cal/mol/K (where ΔG is free energy, ΔH is enthalpy, and ΔS is entropy). Increasing ionic strength did not favor interaction. Circular dichroic measurements revealed that the interaction of nigerloxin with BSA did not lead to changes in the secondary structure of the protein. The reversibility of the interaction verified by the dilution method was found to be reversible. These measurements suggest that partial hydrophobic and partial ionic bonding play a role in the interaction of nigerloxin with BSA.     

Ultrasonic attenuation of edible oils

The frequency dependence (1–60 MHz) of the ultrasonic attenuation coefficient of canola oil, corn oil, olive oil, peanut oil, safflower oil, soybean oil, and sunflower oil was measured at 25°C. The attenuation coefficient of all the oils could be described by the relation: α ∼ Af ⁿ(with A between 6 and 40 × 10⁻¹², and n between 1.74 and 1.86).     

Synthesis and thermal properties of new polyester based on indane-1,3-diol and terephtaloyl chloride

SUMMARY New aromatic polyester was synthetized by polycondensation of indane-1,3-diol and terephthaloyl chloride. The indane-1,3-diol was synthesised by metal hydride reduction and characterized by IR, ¹H and ¹³C NMR. Two polycondensation methods was used : solution and interfacial polycondensation in presence of various quaternary ammonium salts. The obtained polymers were characterized by differential scanning calorimetry (DSC) and viscosities measurements. All polymers had glass transition temperature (Tg) in the range of 72–77°C and melting temperature (Tm) in the range of 152–184°C. Received: 19 July 2000/Revised version: 10 December 2000/Accepted: 3 January 2001     

Synthesis and polymerization of 3-(t-butoxycarbonyl)-1-vinylcaprolactam and application as deep UV resists

Poly(3-(t-butoxycarbonyl)-1-vinylcaprolactam) (PBCVC) was synthesized and evaluated as a potential deep UV photoresist. The synthesized polymer has excellent transmittance at 248 nm (absorbance = 0.018 μm⁻¹). In addition, PBCVC possesses good thermal stability up to 220 °C and a high glass transition temperature (174 ∼ 190 °C). The thermal deprotection of side chain ester groups of PBCVC occurs at 220 °C, whereas in the presence of acid the cleavage of the t-butyl ester groups of PBCVC begins at about 80 °C, and followed by evolution of carbon dioxide at about 150 °C. Deprotection of PBCVC gave the corresponding polymer, poly(1-vinylcaprolactam-3-carboxylic acid). The contrast of the PBCVC resist system was not deteriorated with the post-exposure delay (PED) time. Received: 2 September 1996/Revised: 18 December 1996/Accepted: 20 December 1996     

Free radical crosslinking of unsaturated bacterial polyesters obtained from soybean oily acids

Summary Poly(-3-hydroxy alkanoate) containing unsaturated side chains, PHA-soybean, were produced by feeding Pseudomonas oleovorans with soybean oily acids obtained from soybean oil. Unsaturation of PHA-soybean were found to be 10 mol-% of unsaturated side chains. Main saturated part of the biopolymer was Poly(3-hydroxy octanoate) with minor hexanoate and decanoate units. PHA films were crosslinked via free radical mechanism by means of thermally or under UV irradiation in the presence of benzoyl peroxide, benzophenon, and /or ethylene glycol dimethacrylate (EGDM). Crosslinking yield of the PHA films were found to be from 81 to 93 wt.-% from the sol-gel analysis. Swelling properties of the crosslinked PHA films in chloroform and toluene were also studied. Mc values of crosslinked PHAs were also calculated using Flory-Rehner equation. The crosslinked biopolyester obtained by thermally at 60 °C with benzoyl peroxide indicated the highest crosslinking density. Glass transition temperatures (Tg) of crosslinked biopolyester samples were changed from −33 to −45 °C while that of PHA-soybean was −60 °C. Received: 16 June 2000/Revised version: 22 January 2001/Accepted: 20 May 2001     

Barley Protein Isolate: Thermal, Functional, Rheological, and Surface Properties

Barley protein isolate (BPI) was extracted in 0.015 N NaOH in a 10:1 ratio solvent:flour and was precipitated by adjusting the pH to 4.5 and freeze-dried. The thermal properties of BPI were determined using modulated differential scanning calorimetry (MDSC). BPI with 4% moisture content exhibited a glass transition (T _g) with 140 °C onset, 153 °C middle, and 165 °C end temperatures and a ΔC _p of 0.454 J/g per °C. The high moisture content sample (50%) showed a T _g at 89, 91, or 94 °C and 0.067 ΔC _p. Acetylation had no apparent effect on the foaming and emulsifying properties of protein from barley flour but exhibited the least-stable foam among BPI samples. Foaming capacities of both barley protein isolates were ∼12% less than that of acid-precipitated soy protein isolate reported in the literature. Acetylated BPI showed the highest surface hydrophobicity compared to the other samples. The surface-tension test confirmed that unmodified and modified BPI possessed surface activity. BPI phosphorous oxycloride-crosslinked was the most effective in lowering the surface tension of aqueous NaCl, while the crosslinked BPI was the least effective. The G′ value of BPI suspension was greater than G″ at all frequencies from 0.1 to 100 rad/s. The strain value at which linear behavior ceased and nonlinear behavior began ranged from 3 to 10%. Names are necessary to report factually on available data; however, the United States Department of Agriculture (USDA) neither guarantees nor warrants the standard of the product, and the use of the name by the USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Viscosity behavior and chain conformation of a (1→3)-α-glucan from Ganoderma lucidum

Summary Seven fractions of a (1→3)-α-D-glucan from Ganoderma lucidum have been studied by light scattering, sedimentation equilibrium, and viscometry in dimethylsulfoxide (DMSO) containing 0.25 M lithium chloride at 25°C. The intrinsic viscosity [η] - molecular weight relation for this glucan in the mixed solvent is found to be represented approximately by [η] = 0.071 M _w ^0.60 cm³ g⁻¹ in the range of weight-average molecular weight M _w studied, i.e., from 8 × 10³ to 4.4 × 10⁵. Its analysis based on current theories for wormlike chains shows that, without excluded volume effect, the (1→3)-α-D-glucan chain is characterized by a linear mass density of 380 nm⁻¹, a Kuhn segment length of about 3 nm, and a diameter of 1.2 nm and is somewhat more extended but more flexible than amylose, a (1→4)-α-glucan, in DMSO. Received: 28 July 1998/Accepted: 18 August 1998     

Preparation of polynorbornene with β-diketonate titanium / MAO catalysts

Summary Polynorbornene was synthesized by β -diketonate titanium / MAO (methylaluminoxane) catalysts. The polymerization activity was up to 8 × 10³ g polymer/(mol Ti h). FT-IR, ¹H NMR, ¹³C NMR and WAXD analyses showed that the polynorbornenes contained both ring-opening metathesis (trans and cis) and addition polymer chain structures and they are amorphous. The portions of trans- and cis- double bonds decreased when the polymerization temperature and Al/Ti molar ratio decreased. In addition, using 1,2-dichlorobenzene, instead of toluene, as the polymerization solvent increased the activity and produced the polymer containing more cis-double bonds. The glass transition temperature of the elastic polymers ranged from 330°C ∼ 400°C. Received: 10 September 2001/Revised version: 15 October 2001/Accepted: 10 December 2001