PLASTICS AND RESINS FROM HYDROCARBONS1 INTRODUCTION PER K. FROLICH Esso Laboratories of the Standard Oil Development Company, Elizabeth, N. J.
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1. Natural petroleum resins by light hydrocarbon precipitation. 2. Cracking-coil tar resins by condensation of highly condensed petroleum hydrocarbons, such as those which are present in the tar bottoms from the cracking operation, with formaldehyde or ethylene chloride. 3. “Santoresin” by reaction of olefins and diolefins in the presence of aluminum chloride. 4. Polystyrene by polymerization of styrene, which may be produced from ethylbenzene made by alkylation of benzene with ethylene. 5. Polybutene by polymerization of unsaturated gaseous hydrocarbons to give substantially linear polymers ranging in consistency from that of a viscous oil to rubbery materials with molecular weights as high as 300,000. 6. “Buna” rubber and similar products by polymerization of butadiene made from acetylene or from n-butylenes. 7 . Neoprene rubber by polymerization of chloroprene derived from acetylene. 8. “Thiokol” by condensation of sodium polysulfide with ethylene dichloride or other chlorine-containing derivatives. 9. Polysulfones by reaction of olefins with sulfur dioxide. 10. Vinyl resins by polymerization of vinyl chloride and vinyl acetate derived from acetylene or ethylene. 11. P h e n o 1- form a1dehyde resins by condensation of formaldehyde with phenols. 12. Alkyd resins by reaction of dibasic acids with polyhydric alcohols-. g., ethylene glycol and diethylene glycol from ethylene, a n d glycerol which may be prepared from propylene. 13. E t h y 1cellulose by reaction of cellulose with ethyl chloride o r d i e t h y l sulfate Droduced from ethvlene. 14. Cellulose acetate by 1 I I I 1932 1933 1934 1935 1936 I! reaction of cellulose with acetic anhydride, which may be derived from ketene obtained by thermal decomposition of acetone produced by dehydrogenation of isopropyl alcohol. 15. Acrylate and methacrylate resins derived in various ways from olefinic compounds.
’N THIS age of new synthetic products the field of resin6
and plastics has a particular appeal to chemists because of the possibilities it offers with respect to both variety of products and potential volume of business. As for the variety of products, me have in the last decade witnessed the ready customer acceptance of one new type of resin or plastic after the other. And when it comes to volume, figures will be given here to illustrate the tremendous growth in production of materials of this type, a growth which gives promise of a potential expansion that can hardly be equaled by any other branch of the chemical industry. Simultaneousljwith this develop1 5 0 7 y 8 2 1 ment there has been FIGURE I COAL TAR an equally rapid inRESIN PRODUCTION IN crease in our knowlTHE UNITE0 STATES, 1932 - 1937 1 edge of hydrocarbon chemistry: In part i c u l a r we h a v e learned that the lower aliphatic hydrocarbons are far more reactive and far more susceptible to chemical m a n i p u l a t i o n 2 5 - u ’ than was reajized only 1932 1933 1934 1935 1936 1937 afewvearsaao. And what “is equally important, we have learned how to make a variety of such compounds available a t low cost from petroleum. Because of its general setup, however, the petroleum industry is, as a rule, dependent upon a relatively large scale of operation to obtain the full advantage of its low potential manufacturing costs. It is therefore not surprising that the petroleum industry should have become interested in the expanding field of resins and plastics as an outlet for its primary and secondary products. The following is a list of products falling under this general classification which are either now being manufactured wholly or in part from petroleum products, or for which the petroleum industry would be able to supply raw materials: 1 The group of papers on pages 293 to 323 was presented before a joint session of the Divisions of Petroleum Chemistry, of Paint and Varnish Chemistry, and of Rubber Ghemistry a t the 98th Meeting of the .4merioan Chemical Society, Boston, Mass.
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INDUSTRIAL AND ENGINEERING CHEMISTRY 592.528
FIGURE 3 UNITED STATES CRUDE RUBBER IMPORTS.
u) z
1
/I
c? 510,000
sd I I
u LT
IL
0
I
I925
I
I
1930
1935
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This symposium on resins and plastics from hydrocarbons is sponsored jointly by petroleum, paint and varnish, and rubber chemists. Kothing could be more fitting than for these three groups to meet together for a discussion of problems of mutual interest, representing as they do a large present and potential supplier of both raw materials and finished products, and the two largest consumers. I n my opening remarks I used the adjective “tremendous” to describe the growth of synthetic resin production during the last decade or so. That this is fully justified is illustrated in Figure 1. This curve shows the output of such products manufactured from coal tar chemicals in recent years ( 2 ) ; the production reached 141,000,000 pounds in 1937.
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The production of resins from noncoal tar chemicals is of a much lower order of magnitude, as shown (Figure 2) by a volume of 21,000,000 pounds in 1937 (2). However, in a new and coming field we are perhaps more concerned with the rate of growth than with the actual volume reached in the early stages of the development. This rate of growth is much greater in the case of the resins of noncoal tar origin. It is this capacity for growth that has its special appeal here. Turning now to rubber as the true representative of what are commonly termed “plastics”, Figure 3 shows a steady increase in imports of crude rubber to the United States, amounting to some 1,300,000,000pounds in 1937 (1). Until the problem of manufacturing rubber synthetically from domestically available raw materials has been solved, this high import of the crude product will remain a challenge to our profession. Much has been said on this subject and I need only add that a successful start has been made. We have seen, again within the last decade, several synthetics enter the field and replace rubber for specific uses where it has been possible t o effect actual improvements over nature’s product. Although highly significant both chemically and economically, the progress made so far is small when considered on a volume basis. To develop a synthetic hydrocarbon product capable of competing with natural rubber for general use on a combined basis of quality and cost is a problem that should have special appeal for those engaged in the field of hydrocarbon chemistry.
Literature Cited U.S.D e p t . Commerce, Bur. of the Census, Statistical Abstract of U. S., 1938. (2) U. S. Tariff Commission, R e p t . 131, 2nd series, 1938. (1)
PROPANE PRECIPITATION OF PETROLEUM RESINS P. T. GRAFF AND H. 0. FORREST HE residuum obtained from the distillation of crude
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petroleum may be separated into asphalt, resin, and lubricating oil fractions by the use of the precipitating effect of liquid propane. The behavior of propane in varying ratios and a t various temperatures upon the precipitation of asphalt and resins from propane-oil solutions has been described at length in the literature (1, 6, 6). The information previously published disclosed the improvement or refining effected in the lubricating oil base by the propane precipitation of asphalt and resins. Some data concerning the characteristics of the precipitated asphalts and resins have been given. The purpose of this paper is to disclose more fully the properties of the so-called resins that may be obtained by the precipitating action of propane. The term “resins” is used widely and broadly to describe many different materials occurring naturally or produced synthetically. These range from the gums or hard resinous lacquerlike substances found in trees and plants, to synthetic substances, and to the color bodies adsorbed by decolorizing clays from petroleum fractions or other oils. This paper is confined strictly to a consideration of propane-precipitated petroleum resins.
The M. W. Kellogg Company, 225 Broadway, New York, X. Y.
Propane-precipitated petroleum resins contain those hydrocarbons or color bodies which are adsorbed on clays or earths in the treatment and refining of petroleum lubricating oils and which may be dissolved or washed from the clay by solvents such as benzene. These hydrocarbon substances are similar to asphaltenes except that they are not oxidized or combined with sulfur and are therefore soluble in petroleum ether. I n addition to containing hydrocarbons conforming to the usual definition of petroleum resins, propaneprecipitated petroleum resins contain paraffinic and naphthenic hydrocarbons of high molecular weight and also asphaltenes, in quantities or proportions depending upon the precipitating conditions and the previous treatment of the oil. Propane fractionating technique provides a comparatively simple process method of producing a “resin” fraction from petroleum and this fraction may represent a portion of the crude petroleum not readily isolated by other industrial process methods available to refiners.
Examples of Resin Precipitation The essential operations of precipitating resins by the use of liquid propane are indicated in Figure 1, which shows the
