Polyacrylonitrile, pyrolysis

Source Reprinted with permission from Peebles LH Jr., Peyser P, Snow AW, Peters WC, On the exotherm of polyacrylonitrile pyrolysis of the homopolymer under inert conditions. Carbon, 28, 707, 1990. Copyright 1990, Elsevier. 

Combination techniques such as microscopy—ftir and pyrolysis—ir have helped solve some particularly difficult separations and complex identifications. Microscopy—ftir has been used to determine the composition of copolymer fibers (22) polyacrylonitrile, methyl acrylate, and a dye-receptive organic sulfonate trimer have been identified in acryHc fiber. Both normal and grazing angle modes can be used to identify components (23). Pyrolysis—ir has been used to study polymer decomposition (24) and to determine the degree of cross-linking of sulfonated divinylbenzene—styrene copolymer (25) and ethylene or propylene levels and ratios in ethylene—propylene copolymers (26). 

The production of carbon fibres is based on the pyrolysis of organic fibres or precursors. The main starting materials are polyacrylonitrile (PAN) and pitch (coal tar or petroleum asphalt). They can be classified according to their mechanical performances ... 

In principle, molecular sieve carbons (MSC) can be achieved by the pyrolysis of thermosetting polymers such as polyvinylidene chloride, polyfurfuryl alcohol, cellulose, cellulose triacetate, polyacrylonitrile and phenol formaldehyde (Koresh 1980). An example is given by Trimm and Cooper (1970,1973) for the preparation of MSC (mixed with metallic compounds) for catalyst systems. A mixture of furfuryl alcohol, platinum oxide and formaldehyde was heated to 40°C and additional formaldehyde was added to ensure the... 

Figure 1.77 Pyrolysis of polyacrylonitrile (PAN) to form carbon fibers.

Polyaniline has been formed in the pores of Cu- or Fe-exchanged MCM-41 by adsorption of aniline vapour and subsequent oxidative polymerization (Figure 7.23), and these molecular wires demonstrate significant electronic conduction, although less than that of bulk polyaniline. Pyrolysis of polyacrylonitrile in the pores produces a graphitelike carbon chain, which exhibits microwave conductivity ten times that of bulk carbonized polyacrylonitrile. Such materials have potential for use in information processing as storage capacitors. 

A growing specialty application for acrylonitrile is in the manufacture of carbon fibres. These are produced by pyrolysis of oriented polyacrylonitrile fibres and are used to reinforce composites for high-performance applications in the aircraft, defence and aerospace industries. Other minor specialty applications of acrylonitrile are in the production of fatty amines, ion exchange resins and fatty amine amides used in cosmetics, adhesives, corrosion inhibitors and water-treatment resins (Brazdil, 1991). 

Perhaps one of the best known syntheses of a heterocyclic polymer via the modification method is the generation of nitrogen-containing ladder polymers by pyrolysis of polyacrylonitrile) (77MI11109). The thermolysis is known to take place in discrete steps. The first step in the sequence, which can take place with explosive violence if the heating rate is not sufficiently slow, occurs at about 150 °C and can be detected by the onset of intense color formation. The product of this reaction (Scheme 101) is the cyclic tetrahydropyridine ladder structure (209). The next step, which is conducted in the presence of air at ca. 250 °C, involves the thermooxidation of polymer (209) to form what is best described as terpolymer (210) containing dihydropyridine, pyridone and pyridine units. 

A manufactured fiber made by pyrolysis of sin organic precursor— rayon, polyacrylonitrile, or pitch in an inert atmosphere. 

It is also possible to prepare all-carbon polymers of closely related structure. For example, pyrolysis of polyacrylonitrile, (-CH2CHCN-)X, first results in cyclization of some of the -CN side chains.61 Prolonged pyrolysis yields very pure graphitic material. It is very strong and has high thermal stability. In the form of fibers, it can be used for reinforcement in high-performance composites. Additional information on pyrolysis is given in Chapter 9. 

Carbon fiber is produced from several different organic polymers, but polyacrylonitrile has many advantages as a starting material. It is easily spun into fibers, and the chemistry of its pyrolysis reactions favors aromatization as a pathway to graphite-like structures. The process is outlined in reaction sequence (5). 

Carbon fibers are the most rigid and strongest of commonly used reinforcements. They are produced by the pyrolysis (high-temperature decomposition) of natural and synthetic materials, such as rayon, polyacrylonitrile (PAN), and pitch (the tacky residue left from the distillation of petroleum or coal tar). Carbon fibers are commercially available in a variety of formats, including single strands and bundles (known as tows). They are midway in density between glass and polymer fibers and are the most expensive of commonly used reinforcements. 

Machnikowski, J., Grzyb, B., Weber, J.V., Frackowiak, E., Rouzaud, J.N., and Beguin, F. Structural and electrochemical characterization of nitrogen enriched carbons produced by the co-pyrolysis of coal-tar pitch with polyacrylonitrile. Electrochim. Acta 49, 2004 423-432. 

Keywords polyacrylonitrile, IR pyrolysis, graphite, carbon nanotubes, nanostructured carbon, transmission electron microscopy... 

Usami, T., Itih, T., Ohtani, H., Tsuge, S. (1990) Structural study of polyacrylonitrile libers during oxidative thermal degradation by pyrolysis-gas chromatography, solid state 13C Nuclear magnetic resonance and Fourier transform infrared spectroscopy, Macromolecules 23, 2460-2465. 

Molecular weight characterization of modacrylic fibers is difficult because of the limited number of solvents available and inhomogeneties in composition between individual polymer chains that affect solution properties, particularly if the comonomers are ionic in character. Di-methylformamide and dimethylacetamide are suitable for measurement of molecular weight of polyacrylonitrile, but errors are introduced when copolymers are analyzed (126). Bortniak et al. (127) have analyzed modacrylic fibers quantitatively in microgram quantities by using pyrolysis gas chromatography. 

An alternative to using commercially available carbon for electrocatalyst carbon substrates is to build a specific carbon structure having controlled properties. Thus, carbons have been prepared by the controlled pyrolysis of polyacrylonitrile (PAN) and contain surface nitrogen groups that act as peroxide decomposing agents.62... 

Strong graphite fibers are made by pyrolysis, at 1500°C or above, of oriented organic polymer fibers (e.g., those of polyacrylonitrile, polyacrylate esters, or cellulose). When incorporated into plastics the reinforced materials are light and very strong. Other forms of graphite such as foams, foils, or whiskers can also be made. 

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