Coal tar resin

The first resins to be produced on a commercial scale were the coumarone—indene or coal-tar resins (1) production in the United States was started before 1920. These resins were dominant until the development of petroleum resins, which were estabHshed as important raw materials by the mid-1940s. Continued development of petroleum-based resins has led to a wide variety of aHphatic, cyclodiene, and aromatic hydrocarbon-based resins. The principal components of petroleum resins are based on piperylenes, dicyclopentadiene (DCPD), styrene, indene, and their respective alkylated derivatives. 

Coumarone—indene or coal-tar resins, as the name denotes, are by-products of the coal carbonization process (coking). Although named after two particular components of these resins, coumarone (1) and indene (2), these resins are actually produced by the cationic polymerization of predominantly aromatic feedstreams. These feedstreams are typically composed of compounds such as indene, styrene, and their alkylated analogues. In actuaUty, there is very tittle coumarone in this type of feedstock. The fractions used for resin synthesis typically boil in the range of 150—250°C and are characterized by gas chromatography. 

These products, called by-products of coal, include coal gas, coal oil, coal tar, coal tar pitch, coal tar resins and coke Coal gas is obtd by destructive distillation of bituminous coal heated to high temps in fire-clay or silica retorts, or in special by-product ovens. The gas is used in domestic industrial heating lighting and as a source of coal-tar, ammonia, benzene, toluene, xyline and related items (Refs 1,2,8,10 11)... 

Paradene [Neville], TM for low-priced, dark, thermoplastic, coal tar resins (coumarone-in-dene) available in low to high softening-point ranges. 

Alcohol resins, polyvinyl Alkyd resins Allyl resins Butadiene copolymers, containing less than 50 percent butadione Carbohydrate plastics Casein plastics Cellulose nitrate resins Cellulose propionate (plastics) Coal tar resins Condensation plastics Coumarone-iodene resins Cresol resins Cresol-furfural resins Dicyandiamine resins Diisocyanate resins Elastomers, nonvulcanizable (plastics)... 

Nitrile rubbers are compatible with phenol-formaldehyde resins, resorcinol-formaldehyde resins, vinyl chloride resins, alkyd resins, cou-marone-indene resins, chlorinated rubber, hydrogenated rosins, coal-tar resins, epoxies, and other resins, forming compositions which can be cured and which can provide excellent adhesives of high strength, high oil resistance, and good resilience. Nitrile rubber cements are... 

The first development of antioxidants was for natural rubber. As early as 1861 August Hofinann [ 2 ] found that deterioration of natural rubber was associated with the absorption of oxygen. In 1870 Murphy [3 ] filed a patent to use phenol and cresol as antioxidants. For the next 40 years, the materials used as antioxidants were natural products including coal tar resins, coumarone resins, paraffins, and cresol. There was little or no understanding of their mechanisms. The stability of the natural rubber products was not very much improved. 

Phenol was first isolated m the early nineteenth century from coal tar and a small por tion of the more than 4 billion lb of phenol produced m the United States each year comes from this source Although significant quantities of phenol are used to prepare aspirin and dyes most of it is converted to phenolic resins used m adhesives and plastics... 

Naphthalene, anthracene, carbazole [86-74-8] phenol [108-95-2] and cresyUc acids are found in the tar. Phenol and cresyUc acids are useful as chemical and resin intermediates. The aromatic chemicals are useful in the manufacture of pharmaceuticals, dyes, fragrances, and pesticides. Various grades of pitch are made from residues of tar refining. Coal-tar pitch is used for roofing and road tar, and as a binder mixed with petroleum coke to produce anodes for the aluminum industry. 

Hydrocarbon resin is a broad term that is usually used to describe a low molecular weight thermoplastic polymer synthesized via the thermal or catalytic polymerization of coal-tar fractions, cracked petroleum distillates, terpenes, or pure olefinic monomers. These resins are used extensively as modifiers in the hot melt and pressure sensitive adhesive industries. They are also used in numerous other appHcations such as sealants, printing inks, paints, plastics, road marking, carpet backing, flooring, and oil field appHcations. They are rarely used alone. 

Cationic polymerization of coal-tar fractions has been commercially achieved through the use of strong protic acids, as well as various Lewis acids. Sulfuric acid was the first polymerization catalyst (11). More recent technology has focused on the Friedel-Crafts polymerization of coal fractions to yield resins with higher softening points and better color. Typical Lewis acid catalysts used in these processes are aluminum chloride, boron trifluoride, and various boron trifluoride complexes (12). Cmde feedstocks typically contain 25—75% reactive components and may be refined prior to polymerization (eg, acid or alkali treatment) to remove sulfur and other undesired components. Table 1 illustrates the typical components found in coal-tar fractions and their corresponding properties. 

G-9 Aromatic Petroleum Resins. Feedstocks typically used for aromatic petroleum resin synthesis boil in the approximate range of 100—300°C at atmospheric pressure, with most boiling in the 130—200°C range. The C-9 designation actually includes styrene (C-8) through C-10 hydrocarbons (eg, methylindene). Many of the polymerizable monomers identified in Table 1 for coumarone—indene type cmdes from coal tar are also present in aromatic fractions from cracked petroleum distillates. Therefore, the technology developed for the polymerization of coal-tar cmdes is also appHcable to petroleum-derived aromatic feedstocks. In addition to availabiHty, aromatic petroleum resins offer several advantages over coumarone—indene resins. These include improved color and odor, as weU as uv and thermal stabiHty (46). 

Until the mid-1950s the main raw material source for the European plastics industry was coal. On destructive distillation coal yields four products coal tar, coke, coal gas and ammonia. Coal tar was an important source of aromatic chemicals such as benzene, toluene, phenol, naphthalene and related products. From these materials other chemicals such as adipic acid, hexamethylenedia-mine, caprolactam and phthalic anhydride could be produced, leading to such important plastics as the phenolic resins, polystyrene and the nylons. 

A number of other phenols obtained from coal tar distillates are used in the manufacture of phenolic resins. Of these the cresols are the most important... 

The cresols occur in cresylic acid, a mixture of the three cresols together with some xylenols and neutral oils, obtained from coal tar distillates. Only the /n-cresol has the three reactive positions necessary to give cross-linked resins and so this is normally the desired material. The o-isomer is easily removed by distillation but separation of the close-boiling m- and p-isomers is difficult and so mixtures of these two isomers are used in practice. 

Xylenols, also obtained from coal tar, are sometimes used in oil-soluble resins. Of the six isomers (Figure 23.7) only 3,5-xylenol has the three reactive positions... 

Other higher boiling phenolic bodies obtainable from coal tar distillates are sometimes used in the manufacture of oil-soluble resins. Mention may also be made of cashew nut shell liquid which contains phenolic bodies and which is used in certain specialised applications. 

The polymerization process of coal tar and petroleum fraction (from which aromatic hydrocarbon resins are obtained) are similar. The process is extensively described in the book by Mildenberg et al. [25]. There are three basic steps in the polymerization of coumarone-indene and hydrocarbon resins. 

A further source of C9 material is coal tar. Structures of the two resins precursors are roughly similar, except the presence of small quantities of coumarone in coal tar feedstream. There is a significant difference in the concentrations of individual monomers coal-tar-based raw material is richer in indene (styrene/indene ratio =1 7) than the petroleum-based feedstream (styrene/indene ratio =1 1). 

Aromatic hydrocarbon resins. The polymerization procedure and variables in the reactions of the aromatic hydrocarbon resins are similar to those for the coumarone-indene resins. However, the Cg feedstreams used in the polymerization of the aromatic hydrocarbon resins do not contain significant amounts of phenols or pyridine bases, so they are submitted directly to fractional distillation. Distillation produced more byproducts than light coal-tar oils. The aromatic hydrocarbon resins obtained have softening points between liquid and 125°C and Gardner colour of 6 to 11. By changing distillation conditions, aromatic hydrocarbon resins with softening points between 65 and 170°C and Gardner colour of 5 to 10 can also be obtained. 

Benzene An aromatic hydrocarbon which is a colorless, volatile, flammable liquid. Benzene is obtained chiefly from coal tar and is used as a solvent for resins and fats in dye manufacture. 

Vinyl tars These are a combination of vinyl resins and selected coal tars. They are claimed to be similar to the two-pack coal tar epoxies but with the advantages that they are a single pack, not dependent on temperature for curing, and are easy to re-coat at any stage. 

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