Polyacrylonitrile degradation

Secondary bonds are considerably weaker than the primary covalent bonds. When a linear or branched polymer is heated, the dissociation energies of the secondary bonds are exceeded long before the primary covalent bonds are broken, freeing up the individual chains to flow under stress. When the material is cooled, the secondary bonds reform. Thus, linear and branched polymers are generally thermoplastic. On the other hand, cross-links contain primary covalent bonds like those that bond the atoms in the main chains. When a cross-linked polymer is heated sufficiently, these primary covalent bonds fail randomly, and the material degrades. Therefore, cross-linked polymers are thermosets. There are a few exceptions such as cellulose and polyacrylonitrile. Though linear, these polymers are not thermoplastic because the extensive secondary bonds make up for in quantity what they lack in quahty. 

There is much evidence that weak links are present in the chains of most polymer species. These weak points may be at a terminal position and arise from the specific mechanism of chain termination or may be non-terminal and arise from a momentary aberration in the modus operandi of the polymerisation reaction. Because of these weak points it is found that polyethylene, polytetrafluoroethylene and poly(vinyl chloride), to take just three well-known examples, have a much lower resistance to thermal degradation than low molecular weight analogues. For similar reasons polyacrylonitrile and natural rubber may degrade whilst being dissolved in suitable solvents. 

Because the polymer degrades before melting, polyacrylonitrile is commonly formed into fibers via a wet spinning process. The precursor is actually a copolymer of acrylonitrile and other monomer(s) which are added to control the oxidation rate and lower the glass transition temperature of the material. Common copolymers include vinyl acetate, methyl acrylate, methyl methacrylate, acrylic acid, itaconic acid, and methacrylic acid [1,2]. 

There are two pathways for the degradation of nitriles (a) direct formation of carboxylic acids by the activity of a nitrilase, for example, in Bacillus sp. strain OxB-1 and P. syringae B728a (b) hydration to amides followed by hydrolysis, for example, in P. chlororaphis (Oinuma et al. 2003). The monomer acrylonitrile occurs in wastewater from the production of polyacrylonitrile (PAN), and is hydrolyzed by bacteria to acrylate by the combined activity of a nitrilase (hydratase) and an amidase. Acrylate is then degraded by hydration to either lactate or P-hydroxypropionate. The nitrilase or amidase is also capable of hydrolyzing the nitrile group in a number of other nitriles (Robertson et al. 2004) including PAN (Tauber et al. 2000). 

The proposed model for creep rupture based on the condition of maximum shear strain and the Eyring reduced time model explain the observed relations concerning the lifetime of aramid, polyamide 66 and polyacrylonitrile fibres. However, with increasing temperatures, in particular above 300 °C, chemical degradation of PpPTA also determines the lifetime. Furthermore, the model... 

Structural changes in the polymer, which will accompany the formation of small molecule products from the polymer, or may be produced by other reactions, can cause significant changes to the material properties. Development of colour, e.g. in polyacrylonitrile by ladder formation, and in poly(vinyl chloride) through conjugated unsaturation, is a common form of degradation. 

Apart from paints, P.R.224 is also used in polyacrylonitrile spin dyeing. Application in the spin dyeing of polypropylene is compromised by the fact that medium to high pigment concentrations accelerate the degradative action of light on HALS stabilizers (Sec. 3.4.1.4). 

Ability to function long term is an ongoing problem. In general, PUs degrade after about 1.5 years, nylons lose much of their mechanical strength after about 3 years, and polyacrylonitrile loses about 25% strength after 2 years. On the other hand, PTFE loses less than 10% strength after about 1 year and siloxanes retain most of their properties after 1.5 years. 

A series of papers have rqwrted FT-IR studies of the thermal degradation of polyacrylonitrile 22S-226,227 228, 229, 230>. These FT-IR measurements indicate that the nitrile groups play an important role in the degradation process even in the initial stages and show a steady decrease in nitrile with time both in air and under reduced pressure. These results are contrary to previous dispersive infrared measurements... 

Coleman, M. M., Sivy, G. T. Fourier Transform Infrared Studies of the Degration of Polyacrylonitrile) Copolymers I. Introduction and Comparative Rates of the Degradation of Three Copolymers Below 200 °C and Under Reduced Pressure. Preprint submitted to CARBON... 

Polyacrylonitrile has been the subject of investigations by Russian workers, particularly those aspects relating to its thermal degradation. Polyacrylonitrile itself is a semiconductor with an activation energy of 0.32 to 0.84 e. v. (69) or 1.5 to 4.6 e. v. (70) depending upon the method of polymerization, ambient atmosphere and sample history. 

The degradation of the cellulose fraction of the copolymer and subsequent recovery of the polyvinyl polymer have often been used to characterize the polymer. For example, cellulose may be acetylated and acid hydrolyzed to remove it from the copolymer. Then the recovered polymer can be dissolved, in solvent normally used for the polymer, and i the molecular weight of the polymer determined viscometrically (12, 42). As reported previously for polymers, such as polyacrylonitrile, a functional group on the polymer may be altered during the fractionating. These changes have been determined by infrared spectroscopy. For free-... 

Other fibers. The other major class of synthetic fibers, the polyacrylonitriles (orlon, acrilon, etc.) like the cellulosics (rayon, cotton) show no thermal activity up to 300 °C. Above these temperatures degradation of sample accompanies any characteristic transitions or curing exotherms. To minimize this effect, the samples are run in an inert environment such as N2, as seen in figure 16. Under these conditions reproducible characteristic endotherms were obtained for identifying wool, cotton and rayon. In roughly the same temperature region,... 

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. 

Recently the pyrolysis of polymer mixtures has become a focus of interest due to the increasing role of plastics recycling. Many researchers have investigated the thermal decomposition of various polymers in the presence of PVC. Kniimann and Bockhom [25] have studied the decomposition of common polymers and concluded that a separation of plastic mixtures by temperature-controlled pyrolysis in recycling processes is possible. Czegfny et al. [31] observed that the dehydrochlorination of PVC is promoted by the presence of polyamides and polyacrylonitrile however, other vinyl polymers or polyolefins have no effect on the dehydrochlorination. PVC generally affects the decomposition of other polymers due to the catalytic effect of HCI released. Even a few per cent PVC has an effect on the decomposition of polyethylene (PE) [32], HCI appears to promote the initial chain scission of PE. Day et al. [33] reported that PVC can influence the extent of degradation and the pyrolysis product distribution of plastics used in the... 

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