Phenolic resin, pyrolysis

T.A. Centeno, J.L. Vilas, A.B. Fuertes, Effects of phenolic resin pyrolysis conditions on carbon membrane performance for gas separation, /. Membrane Sci., 2004,228,45-54. 

Ammonia is used in the fibers and plastic industry as the source of nitrogen for the production of caprolactam, the monomer for nylon 6. Oxidation of propylene with ammonia gives acrylonitrile (qv), used for the manufacture of acryHc fibers, resins, and elastomers. Hexamethylenetetramine (HMTA), produced from ammonia and formaldehyde, is used in the manufacture of phenoHc thermosetting resins (see Phenolic resins). Toluene 2,4-cHisocyanate (TDI), employed in the production of polyurethane foam, indirectly consumes ammonia because nitric acid is a raw material in the TDI manufacturing process (see Amines Isocyanates). Urea, which is produced from ammonia, is used in the manufacture of urea—formaldehyde synthetic resins (see Amino resins). Melamine is produced by polymerization of dicyanodiamine and high pressure, high temperature pyrolysis of urea, both in the presence of ammonia (see Cyanamides). 

A hard carbon with high capacity can be made from epoxy novolac resin [12]. The epoxy resins used cost about US 2.50 per pound and give pyrolysis yields between 20 and 30%. However, it is well known that phenolic (or phenol-formaldehyde) resins can be pyrolyzed to give hard carbons with a yield of over 50% [42]. In addition, these resins cost about USSl.OO per pound. Phenolic resins therefore offer significant cost advantages over epoxy resins, so we... 

Modification of porous inorganic materials by carbon makes it possible to obtain porous carboniferous composites with high thermal and chemical stability and strength. To introduce carbon into pores, both gas phase pyrolysis and carbonization through thermochemical solid-phase reactions are employed. The formation of carbon structures depends on carbonization conditions process rate, precursor concentration, presence of catalyst, etc. [1-3]. Phenolic resins, polyimides, carbohydrates, condensed aromatic compounds are most widely used as polymeric and organic precursors[4-6]. 

The Influence of the Matrix Precursor. The first requirement for a suitable matrix precursor is high carbon yield, which must be achievable under simple pyrolysis conditions. Figure 14 (left-hand side) shows weight loss as a function of pyrolysis temperature for several matrix precursors practical precursors that are commercially available include coal-tar and petroleum pitches, phenolic resins, polyimides, and the para-polyphenyleneacetylene resin Hercules HA 43 (35,36) The structural formulas of some polymer binders are shown in Figure 15. 

It was first produced in the early 1960s by The General Electric Company, UK, by using cellulose as a substrate. Present techniques of preparation of glassy carbon utilize such organic substrates as phenolic resins and involve controlled pyrolysis in inert atmosphere at temperatures ranging between 1000 and 3000 °C. 

Figure 11.7 Fourier transform infrared spectra of the oils/waxes derived from the pyrolysis of polyester resin (a), phenolic resin (b) and epoxy resin (c)...

Electrical and electronic devices are made utilizing several various types of plastic materials, thus when discarded their waste is difficult to recycle. The plastics employed in housing and other appliances are more or less homogeneous materials (among others PP, PVC, PS, HIPS, ABS, SAN, Nylon 6,6, the pyrolysis liquids of which have been discussed above). However, metals are embedded in printed circuit boards, switches, junctions and insulated wires, moreover these parts contain fire retardants in addition to support and filler materials. Pyrolysis is a suitable way to remove plastics smoothly from embedded metals in electrical and electronic waste (EEW), in addition the thermal decomposition products of the plastics may serve as feedstock or fuel. PVC, PBT, Nylon 6,6, polycarbonate (PC), polyphenylene ether (PPO), epoxy and phenolic resins occur in these metal-containing parts of EEW. 

A detailed study on scavenging HCl by calcium-based sorbents (Ca-C sorbent, consisting of 90 wt% of CaCOs and 10 wt% of phenol resin) during or after pyrolysis has been completed recently by Bhaskar et al. [36] and is planned for technical application at a municipal plastic waste pyrolysis plant at Mizushima, Japan. Calcium-based scavenging is a strategy already followed in industry and studied deeply for fluidized-bed pyrolysis of thermoplastics by Sinn and Kaminsky [37-39]. 

The principle of the carbon synthesis is shown in Fig. 1. Suitable carbon sources such as sucrose, furfuryl alcohol, phenol-resin monomers and acetylene gas are converted to carbon frameworks inside mesoporous silica template by pyrolysis. An effective method for the restriction of carbonization to inside the template is to incorporate a suitable catalyst such as Al, Sn and Fe onto the silica pore walls prior to the use as template. The template after the carbonization is removed using ethanol-water solution of HF or NaOH. 

Carbon molecular sieve membranes. Molecular sieve carbons can be produced by controlled pyrolysis of selected polymers as mentioned in 3.2.7 Pyrolysis. Carbon molecular sieves with a mean pore diameter from 025 to 1 nm are known to have high separation selectivities for molecules differing by as little as 0.02 nm in critical dimensions. Besides the separation properties, these amorphous materials with more or less regular pore structures may also provide catalytic properties. Carbon molecular sieve membranes in sheet and hollow fiber (with a fiber outer diameter of 5 pm to 1 mm) forms can be derived from cellulose and its derivatives, certain acrylics, peach-tar mesophase or certain thermosetting polymers such as phenolic resins and oxidized polyacrylonitrile by pyrolysis in an inert atmosphere [Koresh and Soffer, 1983 Soffer et al., 1987 Murphy, 1988]. 

Phenol-formaldehyde (PF) resins have been used as model compounds for the study of pyrolysis and combustion reactions that occur in solid fuels [10]. Utilising these resins it is possible to incorporate a wide range of heteroatomic and hydrocarbon moieties to simulate compounds that arise naturally in the solid fuels. A series of phenol resins crosslinked with thiophene, dibenzo-thiophene, diphenylsulfide, benzyl phenyl sulfide, thioanisole, 8-hydroxyquin-oline and 2-hydroxycarbazole were synthesised. These samples were then cured at 200°C (Fig. 15.2.1) and the resulting resins examined by solid-state NMR spectroscopy. The C CP/MAS spectra of a standard PF resin is shown... 

Organic precursors can be used both polycarbosilane and a small amount of phenolic resin, giving CSi and carbon by in situ pyrolysis the resulting boron-carbide ceramies have high density (> 92 %) and contain no free carbon and a small amount of SiC( 5wt%) . 

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