Amphiphilic polythiophene for the formation of gold nanowire networks

Polythiophene containing amphiphilic decyl-tri(oxyethylene) side group was synthesized. Gold nanowire networks having almost uniform wire diameters could be prepared when the amphiphilic polythiophene was mixed with hydrogen tetrachloroaurate (HAuCl₄) in THF followed by the addition of aqueous sodium borohydride solution. The size of nanowire networks and the diameter of the component wires could be controlled by changing the polymer concentration and the gold salt to polymer ratios. When polythiophene derivatives having hydrophobic or hydrophilic side groups were used instead of the amphiphilic polythiophene, disconnected poor networks and coagulated nanoparticle chunks, respectively, were obtained, although the same reduction process was applied.     

Crystallinity and fusion of low molecular weight α,ω-alkoxy-poly (ethylene oxide): octadecoxy to triacontanoxy end-groups

Samples of α, ω-alkoxy-poly(ethylene oxide) with an average oxyethylene chain length of 45 units and with C₁₈, C₂₆, and C₃₀ end-groups have been prepared and characterized. Several experimental methods have been used to investigate the crystalline structure and the melting behaviour of the solids produced by crystallization in the range T_c = 25° to 45°C. The oxyethylene chains crystallize in folded-chain conformation in all samples. The methylene chains also crystallize in samples with C₂₆ (low T_c) and C₃₀ end-groups. The extent of crystallinity is low in the solids in which both types of chain crystallize. The melting points of the oxyethylene lamelae increase markedly as the methylene chain length is increased. This is explained by the high free energy change on mixing oxyethylene and methylene chains when the solid is transformed to a random melt, especially as unlike segments are more effectively segregated in the layer structure of the solid when the methylene chain is long.     

Supramolecular structures of an amphiphilic hairy-rod conjugated copolymer bearing poly(ethylene oxide) side chain

The structures of an amphiphilic conjugated graft copolymer, poly(2,3-diphenyl-5-(trimethylene-heptadeca(oxyethylene)-methoxy-phenylene vinylene) (denoted as PVEO₁₇) composing of a conjugated DP-PPV backbone and PEO side chains, in bulk and solutions with tetrahydrofuran (THF) and water have been investigated by small-angle X-ray scattering (SAXS). In bulk state, the DP-PPV main chains in PVEO₁₇ stacked to form flat disk microdomains dispersed in the PEO side-chain matrix. The corresponding wide angle X-ray scattering pattern revealed the existence of crystallinity of the PEO side chains. The structure of the polymer in solution was affected by the solvent quality and the polymer concentration. PVEO₁₇ chains were relatively well dispersed in THF. In aqueous solutions, however, the amphiphilic PVEO₁₇ chains aggregated significantly over the concentration range of 1–8 wt%, where the polymer was found to self-organize to form cylindrical micelles with the aggregation number increasing with the increase of concentration. The photophysical properties characterized by UV–Vis and photoluminescence spectroscopy were strongly affected by the aggregation state of the polymer.     

Cellulose furoate. III. Properties and applications

Cellulose furoates synthesized by a homogeneous reaction was used to make film and fiber. Either colorless or light yellow, transparent cellulose furoate film can be made by solvent cast. Cellulose furoate film with a DS of 2.56 and 20% PEG-400 as the plasticizer displayed 5441 psi maximum tenacity and 21.5% maximum strain. The film without plasticizer has a water vapor permeability of 0.124 ng · m/m² · s · Pa. DMTA study identified the T_g of cellulose furoate with a DS of 2.77 was 225°C. As the DS decreased, the T_g shifted toward higher temperature. The success of wet-spun fibers from LiCl/DMAc solution of cellulose and cellulose furoate substantiated cellulose furoate is compatible with cellulose. Unfortunately, the wet-spun fibers lost their mechanical and surface properties, and bioresistant property against Myrothecium verrucaria, Cheatomium globosum, and Aspergillus terreus. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 253–257, 2001     

Synthesis and characterization of polyimides from 9,10-dialkyloxy-1,2,3,4,5,6,7,8-octahydro-2,3,6,7-anthracenetetracarboxylic-2,3:6,7-dianhydrides and 4,4'-oxydianiline

Summary New dianhydrides having alkyloxy side chains were synthesized and polymerized with 4,4'-oxydianiline in NMP. Chemically cyclized polyimides were obtained with inherent viscosities of 0.30∼0.84 dL/g range. All the polymers were highly soluble in polar solvent such as NMP at room temperature. TGA pyrograms showed two-step degradation and in DSC thermograms the polymers exhibited T_gs between 124°C and 259°C. Wide-angle X-ray diffractograms revealed very low crystallinity and layered structure, which was better developed in the polymers with longer side chains Received: 16 October 2000/Accepted: 10 November 2000     

Kinetics of sol-to-gel transition for poloxamer polyols

Kinetics of gelation for aqueous solutions of poloxamers 407 and 288 were determined using pulse shearometry. The principle of this method for determining the shear modulus of a semisolid was based on generation of a torsional force that is transmitted through the poloxamer sample at discrete time intervals. Three distinct linear phases were observed for the log dynamic shear modulus (G′) vs. time profiles as poloxamer 407 and 288 solutions of varying concentrations were allowed to passively warm at room temperature to a temperature exceeding the sol-to-gel transition temperature, T_m. The beginning of the second exponential phase coincided with the onset of the gelation process as determined by visual observation. Although gelation appeared visually to be complete at the beginning of the third exponential phase of the log G′ vs. time profiles, this last exponential phase may indicate the rate of formation of the polymer network. A comparison of poloxamer 407 [30% (w/w); T_m = 10.9°C] and poloxamer 288 [37% (w/w); T_m = 11.1°C] would suggest that the concentration of poloxamer required to achieve approximately the same gelation temperature for poloxamers having a similar ratio of poly(oxypropylene):poly(oxyethylene) units decreases with increasing molecular weight of the poly(oxypropylene) hydrophobe contained in the copolymer. Results of these preliminary studies suggest that the gelation process was significantly (p < .05) more rapid for poloxamer 407 at a 30% (w/w) concentration compared to a 30% (w/w) solution of poloxamer 288 when the poloxamer solutions were allowed to passively warm at room temperature. In addition, it appears that the rate of gelation for the poloxamer solutions studied was dependent on the rate of heat transfer through the polymer solution.     

Synthesis and Surface Properties Characterization of Perfluoroalkylated Oligo(oxyethylene)glycols

A series of perfluoroalkylated oligo(oxyethylene) glycols as non-ionic fluorinated surfactants was prepared. The synthesis was performed by adding a molecule of a oligo(oxyethylene)glycol of the general formula HO(CH₂CH₂O)_nOH (n = 1, 2, 4, 6.4, 22.3) to 2-(perfluorooctylmethyl) oxirane in the presence of catalytic amounts of a Lewis acid. This procedure led to the formation of an amphiphilic molecule characterized by an hydrophobic lipophobic perfluorinated tail and hydrophilic non-ionic oligo(oxyethylene)chain. Infra red spectroscopy, mass spectroscopy and multinuclear NMR spectroscopy allowed the chemical characterization of the synthesized compounds to be made. Critical micellar concentration, surface tension, interfacial tension and cloud point measurements carries out on aqueous solutions allowed us to evaluate the surface and interfacial properties of the perfluoroalkylated oligo(oxyethylene)glycols. In addition, surface pressure-area (π, A) diagrams allowed us to determine the principal parameters characterizing the state of their monolayers. The aim of the work was to investigate the effect of the hydrophilic chain length on physical and surface properties.     

Characterization and thermal stability of cellulose‐graft‐polyacryloniytrile prepared by using KMnO4/citric acid redox system

An effective condition of graft polymerization of acrylonitrile onto cellulose fiber in large volume of KMnO₄/citric acid aqueous solution was examined and the produced grafted copolymers were characterized by using SEM, NMR, FTIR, XRD, TGA, and DSC in comparison with component homopolymers. Graft yield, GY, obtained by simple weighting method was close to the value obtained by NMR analysis. Significant change of chemical structure in cellulose fiber, other than graft reaction, was not detected by NMR and FTIR measurements, whereas a decrease in the degree of crystallinity by the reaction was detected by XRD measurement. It was pointed out that thermograms for grafted samples resembles with that of cellulose at T < 370°C and become similar with that for polyacrylonitrile at T > 370°C and the mass of residue at 550°C is proportional to the content of polyacrylonitrile (GY) only. It is concluded that thermal decomposition of both polymers occurs almost independently in grafted polymers and thermal stability of cellulose fiber is not improved. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dielectric investigation of isotropic and anisotropic solutions of cellulose acetate in dioxane

The dielectric and optical characteristics of a sample of cellulose acetate (DS = 2.45) in dioxane solutions were studied at 10–50°C of concentration 10–50 wt% to include both isotropic and anisotropic phases. The study showed that the loss maximum, ε_max″, magnitude of polarization, (ε₀ ? ε_∞), static dielectric constant, ε₀, time of relation, (2πf_m)^?1, and refractive index, n_D, steadily increase with concentration up to the critical concentration (41 wt%) and then decrease. The mean-square dipole moment, 〈gμ²〉, decreases steadily up to the critical concentration then remains nearly constant, indicating that the isotropic solution changes to anisotropic, with smaller mean-square dipole moment. Comparison between the results of cellulose acetate (CA) and those of hydroxypropyl cellulose (HPC) reveals that, at the critical concentration in dioxane, the cholesteric structure of HPC possesses a greater mean-square dipole moment with higher temperature coefficient than does CA. The activation energy of the relaxation process for hydroxypropyl cellulose is higher, indicating a greater intrachain interaction compared with cellulose acetate.     

Wetting properties of nonionic surfactants of homogeneous structure C12H25(OC2H4)xOH1

The wetting of cotton skeins by aqueous solutions of individual surfactants of structure C₁₂H₂₅(OC₂H₄ )_XOH, where x = 4-8, with homogeneous head groups, and of a Poisson distribution mixture containing an average of 5.5 oxyethylene groups, has been measured at various temperatures using the Draves technique. An individual compound with a homogeneous polyoxyethylene head group is a more effective wetting agent than a Poisson distribution mixture with the same average number of oxyethylene units. Loglog plots of wetting time vs surfactant concentration are linear in the concentration range of 0.25 to 1 g/L. The best wetting agents at any temperature have slopes in the -1.5 to -1.6 range and Y-intercepts from +0.6 to +0.7. Wetting in these systems appears to be diffusion-controlled. The wetting time at 1 g/L concentration is a measure of the wetting effectiveness of the surfactant, because it is roughly inversely proportional to the diffusion constant of the surfactant at that concentration. For materials 30 C or more below their cloud point, temperature increase causes an increase in wetting effectiveness. As the cloud point of the surfactant solution is approached, however, both the slope and the Y-intercept of the log-log plot of wetting time vs surfactant concentration change sharply. The absolute value of the negative slope decreases and the positive value of the Y-intercept increases, resulting in greatly reduced wetting effectiveness.     

Rheological studies of cellulose derivatives solutions

The rheological behavior of solutions of cellulose derivatives, acetate, and hydroxypropyl was studied as a function of different parameters; molecular weight, concentration,…, at T = 25°C in the vicinity of the liquid crystal phase transition. A variation of the strain rate sensitivity parameter with concentration is found. A degradation of the solution in trifluoroacetic acid is demonstrated.     

Hydrogel of biodegradable cellulose derivatives. I. Radiation‐induced crosslinking of CMC

Radiation crosslinking of carboxymethylcellulose (CMC) with a degree of substitution (DS) from 0.7 to 2.2 was the subject of the current investigation. CMC was irradiated in solid‐state and aqueous solutions at various irradiation doses. The DS and the concentration of the aqueous solution had a remarkable affect on the crosslinking of CMC. Irradiation of CMC, even with a high DS, 2.2 in solid state, and a low DS, 0.7 in 10% aqueous solution, resulted in degradation. However, it was found that irradiation of CMC with a relatively high DS, 1.32, led to crosslinking in a 5% aqueous solution, and 20% CMC gave the highest gel fraction. CMC with a DS of 2.2 induced higher crosslinking than that with a DS of 1.32 at lower doses with the same concentration. Hence, it was apparent that a high DS and a high concentration in an aqueous solution were favorable for high crosslinking of CMC. It is assumed that high radiation crosslinking of CMC was induced by the increased mobility of its molecules in water and by the formation of CMC radicals from the abstraction of H atoms from macromolecules in the intermediate products of water radiolysis. A preliminary biodegradation study confirmed that crosslinked CMC hydrogel can be digested by a cellulase enzyme. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 278–283, 2000     

Phase transition of 2,3-O-methylcellulose

Summary In this work, a series of 2,3-O-methylcellulose (MC) with different DS value were prepared. Its phase transition behavior in aqueous solution was studied in terms of DS value, concentration and molecular weight. The the following conclusions were obtained. (1) All the 2,3-O-MC samples show no sol-gel transition in aqueous solution despite the molecular weight. (2) No phase separation was observed for the 2,3-O-MCs with a DS value lower than 1.0, even when the temperature was raised to 95°C. (3) The precipitation temperature is surprisingly different between 2,3-O-MCs. and other MCs possessing comparable total DS value. (4) The precipitation temperature of 2,3-O-MCs depends on the molecular weight rather than on the concentration. Received: 3 February 1998/Revised version: 30 March 1998/Accepted: 11 April 1998     

Vinylic graft copolymers of cellulose. I. Effects of monomer concentrations and crystallinity index of cellulosic substrate on grafting vinyl acetate onto cotton

Graft copolymerization of vinyl acetate (VA) and methyl acrylate (MA) on cotton cellulose was initiated by the Ce (IV) ion, and ungrafted vinylic polymer was separated from the graft copolymer by acetone extraction. The influence of the ratio aqueous initiator solution volume/monomeric volume (V_aq/V_mon), vinyl acetate volume/methyl acrylate volume (V_VA/V_MA), and the cellulose crystallinity index (CI) on the grafting reaction were studied. To modify the crystallinity of cellulose, native cotton was treated with NaOH in the concentrations 10, 15, and 20% (mercerized). The viscosimetric average molecular weight (M_v), the polymerization degree (PD), and the crystallinity index proposed by Nelson and O'Connor (CI) were determined for native and NaOH-treated cotton. The polymeric side chains grafted were separated from the cellulose backbone by acid hydrolysis in 72% H₂SO₄. The viscosimetric average molecular weight (M_v) was determined, and the number of vinylic chains per cellulosic chain (graft frequency, GF) were calculated. The grafting percentage, %G, was higher for most amorphous cellulose and for a higher methyl acrylate percentage (%MA) in monomeric reaction mixtures (VA-MA). The V_aq/V_mon ratio that yields the highest %G was 70/30. The increase of the %G with the %MA in the VA–MA monomeric mixture seems to be due to both an increase in the length of vinylic grafted chains (as shown by its M_v) and the number of grafted chains (GF). The increase in the %G when the crystallinity index (CI) of the cellulosic substrate decreases seems to be due to an increase in the length of the vinylic grafted chains, but not to an increase in the number of grafted chains, since the M_v increases and GF decreases when the CI of cellulose decreases.     

Flow birefringence and viscosity of cellulose solutions in semi-dilute regime

An attempt was made to study the flow birefringence and the viscosity of the systems of cellulose in aqueous sodium hydroxide and cadoxen solutions. For this purpose alkali-soluble cellulose samples with crystal form I (simply denoted as cellulose I sample), prepared from conifer wood pulp by the steam-explosion method, and alkali-soluble cellulose samples with crystal form of cellulose II (cellulose II sample), regenerated from cuprammonium cellulose solution under specific conditions, were used. The extinction angle χ of aqueous alkali solutions of the cellulose I sample is significantly less shear rate (γ) dependent as compared with that of the cellulose II sample. In the latter system the χ versus γ relations for a given cellulose sample shifted to the higher γ side with decrease in the average molecular weight. The viscosity of the cellulose II sample in aqueous sodium hydroxide solutions is approximately twice that of the cellulose I sample in the same solvent if compared at the same molecular weight, same concentration, and same temperature. The latter solution showed a non-Newtonian property at relatively smaller γ than the former solution did. Spin-lattice relaxation time T₁ (by ¹³C-NMR) of cellulose in cadoxen solution was smaller in cellulose I, suggesting the existence of intra- and intermolecular hydrogen bondings at the C₆ position of cellulose molecules in cellulose I solution. A dynamic light scattering study on cellulose in cadoxen showed that in a 5 wt % solution of cellulose I cellulose particles are dispersed with time into smaller particles and the larger particles could be excluded by ultracentrifuge and in cellulose II solutions the cellulose particles had almost the same size during storage. The above findings indicate that in 5 wt% cellulose I solutions in aqueous alkali or in cadoxen, cellulose I is not dissolved molecularly, but a supra-molecular structure of the solid is at least partly reserved in the above solutions.     

Synthesis and characterization of ion conducting cellulose esters with PEO side chains

Cellulose esters with poly(oxyethylene) (PEO) side chains, denoted COE-1 and HPCOE-1A, were prepared through the homogeneous reactions between cellulose or hydroxypropylcellulose and a PEO monocarboxylic acid in the presence of N,N′-dicyclohexylcarbodiimide and 4-N,N′-dimethylamino-pyridine. The LiCF₃SO₃ complexes of the two polymers were prepared, and the effects of salt concentration on the liquid crystallinity, ionic conductivity and morphology were investigated. It has been found that the two kinds of complexes are both thermotropic liquid crystalline materials and exhibit clearing temperatures, T_c, that increase with increasing salt concentration. The increase in T_c for each system is compensated approximately by a rise in T_g, leaving the liquid crystalline temperature ranges fairly constant. A non-Arrhenius temperature dependence of ionic conductivity is predominant in both systems with the maximum conductivities occurring at [Li]/[O]≈0.07. The environmental scanning electron microscopy reveals a very rough, array-like internal structure for the COE-1 complex at this salt concentration.     

Homogenous carboxymethylation of cellulose in the NaOH/urea aqueous solution

In this work, the carboxymethylation of cellulose in the alkaline cellulose solvent, 7 wt% NaOH/12 wt% urea aqueous solution, was investigated. Carboxymethyl cellulose (CMC) samples were characterized with FT-IR, NMR, HPLC, and viscosity measurements. Water-soluble CMC with DS = 0.20–0.62 was prepared from both Avicel cellulose and cotton linters. Thus, carboxymethylation of cellulose in NaOH/urea leads to a polymer with the lowest DS value for water solubility (0.20) of CMC known. The total DS of CMC could be controlled by varying the molar ratio of reagents and NaOH to AGU and the reaction temperature. Structure analysis by means of HPLC after complete depolymerization showed that the mole fractions of the different carboxymethylated repeating units as well as those of unmodified glucose follow the simple statistic pattern. A distribution of the carboxymethyl groups at the level of the AGU in the order O-6 > O-2 > O-3 was determined. The results were similar with findings for CMC obtained by totally homogeneous reaction of cellulose in aqueous solvents such as Ni[tris(2-aminoethyl)amine](OH)₂.     

羧酸盐表面活性剂与两亲聚合物相互作用研究

根据黏度和表面张力的测定数据研究了羧酸盐表面活性剂(HF-E)与两亲聚合物的相互作用,结果表明,HF-E/两亲聚合物混合溶液的表观黏度随HF-E质量浓度的增加先升高后下降;两亲聚合物的质量浓度越大,HF-E/两亲聚合物混合溶液表面张力越高;随着水的矿化度的升高,HF-E/两亲聚合物混合溶液的表观黏度先略有增加,到一定值后反而降低,而表面张力则随矿化度的增加而降低;温度升高,HF-E/两亲聚合物混合溶液的表观黏度随之降低而其与大庆模拟油间的界面张力则升高。优化后的高黏度低界面张力二元体系配方为HF-E和两亲聚合物的质量浓度分别为3和1.5 g·L-1;此外,还加入质量浓度为1 g·L-1的烷基醇酰胺(NS)。     

The use of DTA to study spontanceous ignition of cellulose

The use of differential thermal analysis has enabled spontaneous ignition behaviour of cotton cellulose to be investigate. The temperature. T_i, at which the onset of spontaneous ignition occurs is recorded as a function of the oxygen concentration of the flowing oxygen-nitrogen atmosphere to which the cellulose sample is exposed in the DTA furnace, when heated at a defined heating rate. The dependence of T_i, on heating rate has enabled the activation energy, E_p, of the rate-determining flammable pyrolysis product reaction to the determined using both a previously derived simple kinetic model and the technique of Ozawa. E_p, increases from a lower limiting value of 112 kJ mol^?1 at zero oxygen concentration to an asymptote value of 169 kJ mol^?1 at oxygen volume concentrations above 30%. This effect is described in terms of oxygen catalysis of competing pyrolysis routes. At a given heating rate, increased oxygen concentration reduces T_i. A plot of 1/T_i versus In [O₂] gives two liner regions which intersect at an oxygen concentration of about 20%, suggesting that two combustion mechanisms exist, one above and the other below this value. Below this concentration, which is similar to the conventional limiting oxygen for cellulose, significant char remains, suggesting that ignition of gaseous products only occurs. If the difference in slopes is sttributed to the variations in E_p with oxygen concentration, then a value for the activation energy of gaseous product oxidation, E_ox = 215 kJ mol^?1 is derived.