Polyacrylonitrile solution

To understand the mechanism of polyblending, experiments have been carried out with polymeric solution. W. Borchard and G. Rehage mixed two partially miscible polymer solutions, measured the temperature dependence of the viscosity, and determined the critical point of precipitation. When two incompatible polymers, dissolved in a common solvent, are intimately mixed, a polymeric oil-in-oil emulsion is formed. Droplet size of the dispersed phase and its surface chemistry, along with viscosity of the continuous phase, determine the stability of the emulsion. Droplet deformation arising from agitation has been measured on a dispersion of a polyurethane solution with a polyacrylonitrile solution by H. L. Doppert and W. S. Overdiep, who calculated the relationship between viscosity and composition. 

B 13 Bisschofs, J. Viscosity, diffusion and sedimentation of polyacrylonitrile solution. Polymer Sci. 17, 81 (1954). 

Lee, J. W. et al.. Heterogeneous adsorption of activated carbon nanofibers synthesized by electro spinning polyacrylonitrile solution. J. Nanosci. Nanotechnoi 2006, 6(11), 3577-3582. 

Houtz RC, Orlan acrylic fibre Chemistry and Properties, J Text Res, 20, 786 01, 1950. Mackenzie HD, Reeder F, Courtaulds Ltd., Improvements in and relating to polyacrylonitrile solutions, Brit.Pat. 944,217, 1963. 

Grobe V, Mann G, Structure formation of polyacrylonitrile solutions into aqueous spinning baths, Faserforsch Textiltech, 19, 49-55, 1968. 

Ch. Wang, et al. (2007). Electrospinning of Polyacrylonitrile Solutions at Elevated Temperatures. Macmmohcules. 40, 7973-7983. 

A polyacrylonitrile solution that was electrospun into ultrafine fibers. The obtained nanocomposite fibrils were characterized by the structure, composition, and physical properties of the resulting nanocomposite fibrils (Ko et al. 2002). 

Resin and Polymer Solvent. Dimethylacetamide is an exceUent solvent for synthetic and natural resins. It readily dissolves vinyl polymers, acrylates, ceUulose derivatives, styrene polymers, and linear polyesters. Because of its high polarity, DMAC has been found particularly useful as a solvent for polyacrylonitrile, its copolymers, and interpolymers. Copolymers containing at least 85% acrylonitrile dissolve ia DMAC to form solutions suitable for the production of films and yams (9). DMAC is reportedly an exceUent solvent for the copolymers of acrylonitrile and vinyl formate (10), vinylpyridine (11), or aUyl glycidyl ether (12). 

The first reported synthesis of acrylonitrile [107-13-1] (qv) and polyacrylonitrile [25014-41-9] (PAN) was in 1894. The polymer received Htde attention for a number of years, until shortly before World War II, because there were no known solvents and the polymer decomposes before reaching its melting point. The first breakthrough in developing solvents for PAN occurred at I. G. Farbenindustrie where fibers made from the polymer were dissolved in aqueous solutions of quaternary ammonium compounds, such as ben2ylpyridinium chloride, or of metal salts, such as lithium bromide, sodium thiocyanate, and aluminum perchlorate. Early interest in acrylonitrile polymers (qv), however, was based primarily on its use in synthetic mbber (see Elastomers, synthetic). 

In the case of solvent spinning, ie, secondary acetate, polyacrylonitrile, and poly(vinyl chloride), the FWA is added to the polymer solution. An exception is gel-whitening of polyacrylonitrile, where the wet tow is treated after spinning in a washbath containing FWA. 

Polymer Solvent. Sulfolane is a solvent for a variety of polymers, including polyacrylonitrile (PAN), poly(vinyhdene cyanide), poly(vinyl chloride) (PVC), poly(vinyl fluoride), and polysulfones (124—129). Sulfolane solutions of PAN, poly(vinyhdene cyanide), and PVC have been patented for fiber-spinning processes, in which the relatively low solution viscosity, good thermal stabiUty, and comparatively low solvent toxicity of sulfolane are advantageous. Powdered perfluorocarbon copolymers bearing sulfo or carboxy groups have been prepared by precipitation from sulfolane solution with toluene at temperatures below 300°C. Particle sizes of 0.5—100 p.m result. 

Fig. 13. Scanning election micrograph of polyacrylonitrile fibrils formed by spraying a 0.05 wt % polyacrylonitrile in dimetbylform amide solution into CO2 through a 50-//m inner diameter, 18-cm-long no22le at a temperature of 40°C, density of 0.66 g/mL, and solution flow rate of 0.36 ml,/min (118).

Bead Polymerization Bulk reaction proceeds in independent droplets of 10 to 1,000 [Lm diameter suspended in water or other medium and insulated from each other by some colloid. A typical suspending agent is polyvinyl alcohol dissolved in water. The polymerization can be done to high conversion. Temperature control is easy because of the moderating thermal effect of the water and its low viscosity. The suspensions sometimes are unstable and agitation may be critical. Only batch reaciors appear to be in industrial use polyvinyl acetate in methanol, copolymers of acrylates and methacrylates, polyacrylonitrile in aqueous ZnCh solution, and others. Bead polymerization of styrene takes 8 to 12 h. 

Solution Polymerization These processes may retain the polymer in solution or precipitate it. Polyethylene is made in a tubular flow reactor at supercritical conditions so the polymer stays in solution. In the Phillips process, however, after about 22 percent conversion when the desirable properties have been attained, the polymer is recovered and the monomer is flashed off and recyled (Fig. 23-23 ). In another process, a solution of ethylene in a saturated hydrocarbon is passed over a chromia-alumina catalyst, then the solvent is separated and recyled. Another example of precipitation polymerization is the copolymerization of styrene and acrylonitrile in methanol. Also, an aqueous solution of acrylonitrile makes a precipitate of polyacrylonitrile on heating to 80°C (176°F). 

Aqueous solutions of polyacrylamide may be used as plugging solutions for high-permeability formations. Partially hydrolyzed polyacrylamide polymer also has been used [1211] and completely hydrolyzed polyacrylonitrile has been proposed [1427]. 

A. A. Perejma and L. V. Pertseva. Complex reagent for treating plugging solutions—comprises hydrolysed polyacrylonitrile, ferrochro-moUgnosulphonate Cr-containing additive, waste from lanolin production treated with triethanolamine and water. Patent RU 2013524-C, 1994. 

Polyacrylonitrile is soluble in TV, V-dimethylformamide (DMF) => the solution can be used to spin fibers. 

The high purity carbon nanotubes (CNTs) used in this study were obtained by decomposition of acetylene over a powdered CoxMgi xO solid solution catalyst [19]. Different proportions of CNTs from 15 to 70% and polyacrylonitrile (PAN, Aldrich) have been mixed in an excess of acetone to obtain a slurry. After evaporation of acetone, precursor electrodes were formed by pressing the CNTs/PAN mixture at 1-2 tons/cm2. The C/C composites were formed by carbonisation of the pellets at 700-900°C for 30-420 min under nitrogen flow [20], The optimal capacitance properties of the composite were obtained for a mixture CNTs/PAN (30/70 wt%) treated at 700°C. Such C/C composite remains still quite rich in nitrogen (9 at% of N) demonstrating that PAN is an efficient nitrogen carrier. On the other hand,... 

Oxide-water interfaces, in silica polymer-metal ion solutions, 22 460—461 Oxidimetric method, 25 145 Oxidization devices, 10 77-96 catalytic oxidization, 10 78—96 thermal oxidation, 20 77-78 Oxidized mercury, 23 181 Oxidized polyacrylonitrile fiber (OPF), 23 384... 

In practical application, it was reported that the platinum particles dispersed in highly porous carbonized polyacrylonitrile (PAN) microcellular foam used as fuel-cell electrocatalyst160 have the partially active property. The fractal dimension of the platinum particles was determined to be smaller than 2.0 by using the potentiostatic current transient technique in oxygen-saturated solutions, and it was considered to be a reaction dimension, indicating that not all of the platinum particle surface sites are accessible to the incoming oxygen molecules. 

However, DMF is a solvent for polyacrylonitrile and the polymerization occurs in a homogeneous medium for solutions containing 30 per cent monomer or less. This reduces the value of these experiments as an argument to show the influence of a matrix effect. Indeed the fact that auto-acceleration disappears when DMF is added to acrylonitrile was considered as a proof for the fact that precipitation of the polymer was the cause of autoacceleration. 

The most important commercial processes for polyacrylonitrile (XLIII) are solution and suspension polymerizations. Almost all the products containing acrylonitrile are copolymers. Styrene-acrylonitrile (SAN) copolymers are useful as plastics (Sec. 6-8a). 

Surprising effects can also be observed when solvent mixtures are used to dissolve a polymer. There are examples where mixtures of two non-solvents act as a solvent vice versa, a mixture of two solvents may behave like a non-solvent. For example, polyacrylonitrile is insoluble in both, nitromethane and water, but it dissolves in a mixture of the two solvents. Similar behavior can be observed for polystyrene/acetone/hexane and poly(vinyl chloride)/acetone/carbon disulfide. Examples of systems where the polymer dissolves in two pure solvents but not in their mixture are polyacrylonitrile/malonodinitrile/dimethylforma-mide and poly(vinyl acetate)/formamide/acetophenone. These peculiarities are especially to be taken into account if one wants to adjust certain solution properties (e.g., for fractionation) by adding one solvent to another. 

Martin and coworkers tried to prepare carbon tubes from the carbonization of polyacrylonitrile (PAN) in the channels of anodic oxide film (10). A commercially available film with a pore diameter of 260 nm was immersed in an aqueous acrylonitrile solution. After adding initiators, the polymerization was carried out at acidic conditions under N2 flow at 40°C. The PAN formed during the reaction was deposited both on the pore walls and on both sides of the film. Then the Film was taken from the polymerization bath, followed by polishing both faces of the film to remove the PAN deposited on the faces. The resultant PAN/alumina composite film was heat-treated at 250°C in air, and then it was heat-treated at 600°C under Ar flow for 30 min to carbonize the PAN. Finally, this sample was repeatedly rinsed in I M NaOH solution for the dissolution of the alumina film. The SEM observation of this sample indicated the formation of carbon tubes with about 50 xm long, which corresponds to the thickness of the template film. The inner structure of these tubes was not clear because TEM observation was not done. The authors claim that it is possible to control the wall thickness of the tubes with varying the polymerization period. 

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