Study of solution properties of poly(α-methyl styrene) in various solvents by dilute-solution viscometry

The values of Mark–Houwink–Sakurada constants were determined for poly(α-methyl styrene) (PαMs) of high and low molecular weights in a variety of solvents by a new approach, which requires only polydisperse samples. The results are in accord with those reported in the literature. In addition, the present work reports the values of the Flory interaction parameter for PαMs in 13 solvents of distinct solvent power at various temperatures. Three refined methods pertaining to both polar and nonpolar solvents were applied to estimate the solubility parameter (δ₂) of PαMs resulting in δ₂ = 18.75 ± 0.15 (J/mL)^1/2 at 30°C. Finally, the scatter data of the Huggins coefficient over a range of expansion factors varying from 0.7 to 2.6 seem to conform better to a newly proposed empirical equation than to the contemporary model after Imai. © 1993 John Wiley & Sons, Inc.     

Rheological properties of the liquid crystalline poly(γ-benzyl α, L-glutamate) gels in benzyl alcohol

We have determined the degree of stiffness of a poly(γ-benzyl α, L-glutamate) (PBLG) chain in benzyl alcohol by measuring the intrinsic viscosities of dilute Solutions with differing molecular weights. Viscoelastic properties in oscillatory shear flow have been studied and the dependence of the loss and storage moduli on temperature, composition, and frequency are reported. We have also studied the transient shear stress relaxation behavior of the PBLG gel at different temperatures and concentrations. A comparison has been made between these gels and a classical poly(dimethyl siloxane) (PDMS) network, as well as, typical glassy polymers. Shear creep and recovery measurements have been made for this system. Some extensional step strain experiments using lubricated squeezing have been investigated. Tensile experiments have been made to determine stress-strain relationship during elongation. Preliminary experiments using the impulse approach to viscoelasticity further indicate the high elastic contribution in the gel.     

Rheological properties of aqueous α A12O3 suspensions: Influence of dispersant concentration

The effects of concentration of polyacrylic acid as a dispersant on rheological properties of aqueous alumina suspensions have been investigated under steady and oscillatory shear conditions. At solid volume fractions between 0.45 and 0.6, a high degree of particle stabilization is achieved when 0.2 wt% of polyacrylic acid is added. At lower dispersant concentrations, suspensions exhibit pronounced irreversible thixotropic behaviour, whereas at higher dispersant concentrations, time dependent effects on the flow properties are not detectable. When the saturation adsorption limit of the polyelectrolyte on Al₂O₃ is reached, further addition of the dispersant appreciably changes the flow behaviour, as well as the viscoelastic response of investigated suspensions. The data under steady shear are described by application of the generalized Casson model, and for the analysis of viscoelastic data the generalized Maxwell model is used.     

Studies of linear polymer dimensions of poly(4-chlorostyrene) in various solvents around the θ temperatures by intrinsic viscosity

Intrinsic viscosities of poly(4-chlorostyrene) solutions in isopropyl-benzene and n-propylbenzene at temperatures above and below the theta (θ) temperatures of these solvents were measured using a capillary viscometer. The viscosity measurements were performed on three poly(4-chlorostyrene) samples having molecular weights (M?;_v) 1.75 × 10⁶, 6.5 × 10⁵ and 2.7 × 10⁵. A smooth and continuous contraction below the θ temperatures was observed for both solvents. The temperature dependence of [/eta] can be represented by a master curve in a plot of α³/eta|/tau|M^1/2 (g^1/2 mol^?1/2) versus |/tau|M^1/2 (g^1/2 mol^?1/2), where α/eta = [/eta(T)]/[/eta(θ)]^1/3 is the expansion factor and /tau = (T - θ)/T is the reduced temperature. A universal plot of reduced viscosity size (α/eta) versus reduced blob parameter (N/N_c) shows the achievement of collapsed state for T<θ. The prediction of thermal blob theory is also verified for T > θ. The temperature dependence of intrinsic viscosity, both below and above the θ temperature, exhibits similar behaviour to the temperature dependence of dipole moments for both of these solvents.     

Rheological characterization of concentrated cellulose solutions in 1‐allyl‐3‐methylimidazolium chloride

The rheological properties of high concentrated wood pulp cellulose 1‐allyl‐3‐methy‐limidazolium Chloride ([Amim]Cl) solutions were investigated by using steady shear and dynamic viscoelastic measurement in a large range of concentrations (10–25 wt %). The measurement reveals that cellulose may slightly degrade at 110°C in [Amim]Cl and the Cox–Merz rule is valid for 10 wt % cellulose solution. All of the cellulose solutions showed a shear thinning behavior over the shear rate at temperature from 80 to 120°C. The zero shear viscosity (η_o) was obtained by using the simplified Cross model to fit experimental data. The η_o values were used for detailed viscosity‐concentration and activation energy analysis. The exponent in the viscosity‐concentration power law was found to be 3.63 at 80°C, which is comparable with cellulose dissolved in other solvents, and to be 5.14 at 120°C. The activation energy of the cellulose solution dropped from 70.41 to 30.54 kJ/mol with an increase of concentration from 10 to 25 wt %. The effects of temperature and concentration on the storage modulus (G′), the loss modulus (G″) and the first normal stress difference (N₁) were also analyzed in this study. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

γ-Ray assisted synthesis of silver nanoparticles in chitosan solution and the antibacterial properties

In the present study, chitosan had been utilized as a “green” stabilizing agent for the synthesis of spherical silver nanoparticles in the range of 5–30 nm depending on the percentage of chitosan used (0.1, 0.5, 1.0 and 2.0 wt%) under γ-irradiation. X-ray diffractometer identified the nanoparticles as pure silver having face-centered cubic phase. Ultraviolet–visible spectra exhibited the influence of γ-irradiation total absorbed dose and chitosan concentration on the yield of silver nanoparticles. The antibacterial properties of the silver nanoparticles were tested against Methicillin-resistant Staphylococcus aureus (MRSA) (gram-positive) and Aeromonas hydrophila (gram-negative) bacteria. This work provides a simple and “green” method for the synthesis of highly stable silver nanoparticles in aqueous solution with good antibacterial property.     

X-ray analysis of α-, β-, and γ-phase Ag–Hg alloy films produced on polymer substrates by casting polyacrylamide–AgNO3 aqueous solution in Hg atmosphere

It is reported that, by dropping Hg metal on the wet α-phase Ag–Hg alloy film formed on the cast polyacrylamide–AgNO₃ aqueous solution, the α phase of fcc structure can be converted into other phases that contain more Hg. The X-ray analysis of these phases reveals that they are the β phase of hexagonal structure and the γ phase of bcc structure. It is also shown that the lattice constant of the α phase can be controlled to some extent by pH of the aqueous solution of PAAm from which the alloy film is formed.     

Rheological properties of concentrated cellulose solutions in N-methylmorpholine-N-oxide

Conclusions -- Rheological properties of concentrated solutions of cellulose in N-mcthylmorpholine-N-oxide on varying the concentration of cellulose in the solution from 10 to 28% by wt. have been studied.-- It has been found that on increasing the cellulose content of the solution, the viscoelastic properties of the solution qualitatively change.-- In spinning highly concentrated solutions (cellulose content greater than 20%) an abrupt impairment takes place in stability of jet formation; this is connected with a change in supermolecular structure and elastic properties of the solution.Translated from Khimicheskie Volokna, No. 6, pp. 32–34, November–December, 1990.     

Solid‐supported synthesis of hyperbranched polymer with β,β‐diethynylstyryl units

Two novel aromatic polyamide supports bearing aromatic bromine and iodine functionality have been synthesised and tested for the solid‐supported polymerization of AB₂ type monomer 4‐(5‐hexynyloxy)‐β,β‐dibromostyrene via Pd‐catalysed cross‐coupling of vinyl halides and terminal acetylenes. It was found that the solid‐supported polymerization leads to a decrease in molecular weight and increase in the degree of branching from 17 000–18 000 g mol⁻¹ to 8000–4000 g mol⁻¹ and from 30–35 % to 50–65 %, respectively, compared to solution polymerization. All other things being equal, the decrease in molecular weight of hyperbranched polymer on solid‐supported polymerization is a function of the distance between adjacent active sites of the polymer support. © 2001 Society of Chemical Industry     

Practical evaluation of the [η]–M relationship. II. Estimation of Kθ values of polymer solutions

A method is proposed for the prediction of the intrinsic viscosity of θ solutions, based upon the constitution of the dissolved polymer. The method makes use of additive values for constitutional groups to calculate a quantity that represents the specific chain stiffness per main chain atom.     

Thermal analysis of polyethylene prepared by γ-ray-induced polymerization in various solvents

Thermal properties of polyethylenes prepared by γ-ray-induced polymerization in various solvents were examined by differential scanning calorimetry. The solvents used were ethyl and n-butyl alcohols, tert-butyl alcohol containing 25 vol% of water, 2,2,4-trimethylpentane, 2,2,5-trimethylhexane, and cyclohexane. The dependence of the profiles of the heating curves for the produced polymers on polymerization temperature varies with the solvent type. This difference was discussed in terms of the degree of undercooling in various solvents during polymerization. In all solvent systems, the melting point and heat of fusion of the polymers decrease continuously with polymerization temperature. This decrease is caused by an increase in branches with reaction temperature. The melting point and heat of fusion are 100–124°C and 30–44 cal/g, respectively, and no superheating is observed. These facts suggest that folded chain crystals are commonly formed in these systems.     

The properties of polymer blends of the β-modification of polypropylene and an elastomer

Blends of β-polypropylene with elastomers have been prepared under laboratory and processing technological conditions. As a result of the elastomer addition the temperature interval favourable for the formation of the β-modification became narrower. Blends have spherulitic structure like pure β-PP. The elastomer has negligible effects on the size of spherulites and on the rate of crystallization. Optical microscopy and DMA measurements revealed that the blends were two-phase systems in the solid state. The mechanical properties of the blends are close to those of β-PP in the investigated composition range. Increasing elastomer content reduced the strength characteristics but considerably improved cold impact resistance, the most beneficial combination containing about 8–12% of elastomer. A mathematical relationship has been proposed describing the relationship between impact strength and elastomer content. The dependence of the structural characteristics and macroscopic properties of elastomer-modified β-PP blends on the composition and on the temperature is similar to that of the identical β-PP blends.     

Immobilization of β‐amylase using polyacrylamide polymer derivatives

Barley β‐amlyase was immobilized on two polymeric materials; poly(acrylamide–acrylic acid) resin [P(AM‐AAc)] and poly(acrylamide–acrylic acid–diallylamine–HCl) resin [P(P(AM‐AAc‐DAA‐HCl) using two different methods: covalent and cross‐linking immobilization. Thionyl chloride, used to activate the polymers for covalent immobilization, has the advantage that it is able to react with a number of surface groups of protein under very mild conditions. Cross‐linking with glutaraldehyde gave a higher coupling yield (approximately 70%) than covalent immobilization (approximately 20%). The activity and stability of the resulting biopolymers have been compared with those of free β‐amylase. The specific activity of the immobilized enzyme was significantly influenced by the amount of enzyme loaded onto the polymers, the optimal level being 3.5 mg g^?1 polymer. It was found that the immobilized β‐amylase stored at 4°C retained approximately 90% of its original activity after 30 days, whereas free β‐amylase stored in solution at 4°C retained only 47% of its activity after same period. The difference in long term stability was more significant when the enzyme was stored at room temperature; the immobilized enzyme maintained 40% of its activity after 30 days, whereas the residual activity of free enzyme was only 10%. Copyright © 2003 Society of Chemical Industry     

An efficient Synthesis of Acetylenic γ- and δ-Hydroxy Ketones, γ- and δ-keto acids,and γ- diketones via addition of 1-alkinyllithium compounds to γ- and δ-lactones

2-Hydroxy-6-alkyn-5-ones 3 , 1-hydroxy-5-alkyn-4-ones 4 , and 1-hydroxy-6-alkyn-5-ones 5 are conveniently obtained in excellent yields through a highly selective monoaddition of an 1-alkynyllithium compound 2 to γ-valerolactone (1a) , γ-butyrolactone (1b) or δ-valerolactone (1c) . They are oxidized by pyridinium dichromate or Jones reagent to the corresponding acetylenic 1,4-diketones 6 , 4-oxo carboxylic acids 7 , and 5-oxo carboxylic acids 8 , respectively.     

Studies on β-alkoxypropionitriles as solvents for extractive distillation

Five solvents of the β-alkoxypropionitrile series have been studied by gas-chromatography in order to examine their potential usefulness as solvents for extractive distillation. Four isomers of C₄-olefin and a diene were used as solutes for the determination of activity coefficients at infinite dilution at 30°C. Relative volatilities were calculated for these solvents and compared with those for other commercial solvents used currently. Relative volatilities of seven C₄-hydrocarbons in two solvents were also studied and compared with the existing literature data for β-methoxypropionitrile containing 5% antisolvent. The present g.c. studies show that besides the well-studied β-methoxypropionitrile, the second member of the series, β-ethoxypropionitrile, also has the potential for use as a selective solvent.     

Studies on β-alkoxypropionitriles as solvents for extractive distillation

Five solvents of the β-alkoxypropionitrile series have been studied by gas-chromatographyin order to examine their potential usefulness as solvents for extractive distillation. Four isomers of C₄-olefin and a diene were used as solutes for the determination of activity coefficients at infinite dilution at 30°C. Relative volatilities were calculated for these solvents and compared with those for other commercial solvents used currently. Relative volatilities of seven C₄-hydrocarbons in two solvents were also studied and compared with the existing literature data for β-methoxypropionitrile containing 5% antisolvent. The present g.c. studies show that besides the well-studied β-methoxypropionitrile, the second member of the series, β-ethoxypropionitrile, also has the potential for use as a selective solvent.     

Chelation properties of poly(β‐diketone) polymer and its oxime toward heavy metal ions

The chelation behavior of poly(β‐diketone), polymer I, and poly(β‐diketone) oxime, polymer II, toward the divalent metal ions, Cu²⁺, Zn²⁺, Ni²⁺, and Cd²⁺, and the trivalent lanthanide metal ions, La³⁺, Nd³⁺, Sm³⁺, Gd³⁺, and Tb³⁺ was investigated by a batch equilibration technique as a function of contact time, pH, and counter ion. Polymer II exhibited improved chelation characteristics toward lanthanide metal ions in comparison with polymer I and the metal‐ion uptake follows the order Tb³⁺ ≈ Gd³⁺ ≈ Sm³⁺ > Nd³⁺ ≈ La³⁺. On the other hand, polymer I showed relatively higher capacity than polymer II, toward the investigated divalent metal ions, where the metal‐ion uptake follows the order Cu²⁺ > Cd²⁺ ≈ Zn²⁺ > Ni²⁺. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008