Coumarone-indene polymers

Initiation by protonic acids is relatively inexpensive. The major applications of such processes are for reactions of simple olefins like propylene or butenes or olefinic derivatives of aromatics such as coumarone (9-15) and indene (9-16). The products of these reactions have very low molecular weights because of transfer reactions which are discussed below (Section 9.4.4). The low polymers of olelins are used as lubricants and fuels while the coumarone-indene polymers are employed in coatings and as softeners for rubbers and bitumens. 

Coumarone-indene polymers are chemically inert and are used as binders in cheaper grades of floor tiles. They are also used as additives in various surface coating formulations. 

Johnston, W.D.J. Separation of magnetic catalysts from polymers such as hydrogenated coumarone-indene resins. US Patent (1941) 2,264,756. 

Till this time, polymer science was largely empirical, instinctive, and intuitive. Several polymers were commercially available prior to World War I celluloid, shellac, Galalith (casein), Bakelite, and cellulose acetate plastics hevea rubber, cotton, wool, and silk rayon fibers Glyptal polyester coatings bitumen or asphalt, and coumarone-indene and petroleum resins. However, as evidenced by the chronological data shown in Table 1.1, there was little... 

Dermal/Ocular Effects. No skin lesions or dermatitis were reported in an early review of the dermatological problems associated with the manufacture of coumarone-indene resin (a polymer made from 2,3-benzofuran and indene) however, the manufacturing process essentially prevented contact with monomers (Schwartz 1936), so the significance of these negative findings is questionable. Workers continuously exposed to wood varnished with coumarone-indene resin developed dermatitis, but the sensitivity was attributed to the sulfuric acids in the varnish (Schwartz 1936). 

The coumarone-indene resins have been important commercial polymers produced in the sulfuric acid-catalyzed polymerization of mixed concentrates of these two compounds from coal tar naphthas. These and other unsaturated cyclics are also produced in the pyrolysis of petroleum oils for the production of manufactured gas, and the use of such petroleum-derived unsaturates is becoming of increasing significance in the production of this type of resin. 

P. 0. Powers, Coumarone-indene resins, Encyclopedia of Polymer Science and Technology (EPST), Wiley-Interscience, New York, 1966, Vol. 4, pp. 272-294. 

The first truly synthetic resin was developed by Baekeland in 1911 (phenol-formaldehyde). This was soon followed by a petroleum-derived product called coumarone-indene, which did indeed have the properties of a resin. The first synthetic elastomer was polychloroprene (1931) originated by Nieuwland and later called neoprene. Since then many new types of synthetic polymers have been synthesized, perhaps the most sophisticated of which are nylon and its congeners (polyamides, by Carothers), and the inorganic silicone group (Kipping). Other important types are alkyds, acrylics, aminoplasts, polyvinyl halides, polyester, epoxies, and polyolefins. 

Coumarone Indene and Petroleum Pol3rmer Resins. The coumarone indene class excludes modification with phenolics. The data on these two classes of resins are usually lumped in with miscellaneous resins and are not disclosed. The coumarone indene figures were disclosed in the annual Tariff Commission figures in 1940 11), Coumarone-indene and petroleum polymer combined are disclosed in the annual Tariff Commission figures in 1950 11) and are disclosed in the monthly figures starting in 1951 ( ). 

Indene Polymers. Since the commercial resins contain a high content of indene, a commercial coumarone indene resin, Piccoumaron 450-L,... 

Uses Coumarone-indene in adhesives, coatings (emulsion, citrus fruit, epoxy, industrial, marine, paper, traffic, wire and cable), rubber (cements, mech. goods, molded goods, tires), and caulking compds. food pkg. adhesives, coatings, paper, polymers, rubber articles Features Exc. resist, to alkalis, dil. acids, and moisture Regulatory FDA 21CFR 172.215,175.105,175.300,176.170,176.180, 177.1210,177.2600... 

The structural element of a coumarone-indene resin is relatively similar to that for aromatic hydrocarbon resins, as they differ only in the proportion of indene-type structures which are present in higher concentration in the coumarone-indene resins. The main monomers in the aromatic resins are styrene and indene. Styrene produces the atactic conformation of the resins, whereas indene introduces rigidity into the polymer chain. A typical structural element of an aromatic resin is given in Fig. 11. 

Miscellaneous Plasticizers. Hydrocarbons and halogenated hydrocarbons belong mainly to the secondary plasticizer type. Aromatic and aliphatic hydrocarbons are used as extenders coumarone-indene resins and coal tar oils are miscible with rubber and slightly miscible with vinyl polymers. Alkylnaphtha-lenes are used as lubricants for vinylic polymers. Chlorinated hydrocarbons are used as secondary plasticizers in PVC, rubber or cellulose acetate-based blends to increase the resistance to inflammation. 

The term hydrocarbon resins refers to hydrocarbon oligomers derived from coke-oven gas, coal-tar fractions, cracked and deeply cracked petroleum stocks, essentially pure hydrocarbon feeds, and turpentines. Typical hydrocarbon resins (HRs) include coumarone—indene resins (ClRs), petroleum resins (PRs), styrene polymers (SPs), cyclopentadiene resins (CPRs), and terpene resins (TRs). 

Ethylene Glycol Monoethyl Ether Acetate n (Cellosolve acetate) C2H5OC2H4OOCCH3. A solvent for cellulose nitrate, ethyl cellulose, vinyl polymers and copolymers, polymethyl methacrylate, polystyrene, epoxy, coumarone-indene, and alkyd resins. 

Indene n C9H8. Colorless liquid with a sp gr of 1.006 (20/ 4°C), mp of 3.5°C, bp of 182°C, refractive index of 1.5726, and a flp of 78.3°C. Insoluble in water, soluble in most organic solvents, rapidly absorbs oxygen from the air, forms polymers by exposure to air and sunlight. Derivation Contained in the fraction of crude coal tar distillates which boils from 176°C to 182°C. Uses Preparation of synthetic resins. See Coumarone-Indene Resins. 

Tackifiers. Although SBRs can be produced with tack, the physical properties of such polymers usually do not fully satisfy the application requirements. For this reason tackifying resins are normally incorporated into adhesives based on SBRs. These resins improve the kinetics of wetting and increase the overall Tg of the adhesive composition. Typical tackifiers for SBR are rosin-based materials, aromatic-containing petroleum hydrocarbon resins, alpha-pinene, coumarone-indene, and some phenolic resins. 

Effects of Additives. The ratio of endblock phase to midblock phase can be varied by adding materials which associate preferentially with one phase or the other. Coumarone-indene resins, for example, associate with the end-block phase in S-B-S and S-I-S polymers. Figure 7 shows how the initial portion of the stress-strain curve of the neat polymer. Curve B, is shifted upward to Curve A when the end-block phase concentration is increased by adding a resin of that type. Curve C shows how the reverse occurs when, for example, a tacki-fying resin or a plasticizing oil which associates with the rubber phase is present instead. 

Tackifiers may be required for building plies of HNBR compounds to other HNBR compounds or to other polymer formulations for composite constructions. Coumarone-Indene resins, Phenol-acetylene resins, Aromatic hydrocarbon resins, and Styrene-vinyl toluene resins work well at levels of up to 15 phr to tackify the resulting HNBR compound. 

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