August 1949
INDUSTRIAL AND ENGINEERING CHEMISTRY
there also seein to be values for the liquid space rate and the hydrogen rate beyond which some loss of catalyst activity occurs. If the former is increased above about 1.5 volumes per volume per hour or the latter decreased below 15 moles per mole of feed, the catalyst slowly deteriorates, probably for the reasons postulated above. The optimum caonditions appear to be about those of run 31, Table IV. Although much more extensive testing would be required, it seems likely that a commercial process could be designed t o operate under approximately these conditions. Since nitrobenzene does not explode or resinify seriously in the absence of aniline below about 356" C. ( 5 ) ,its purely thermal decomposition does not complicate the hydrogenation. When nitrovylene is hydrogenated at 400 to 500 pounds gage and hot-spot temperatures below 300' C , the results are similar t o those with nitrobenzene With temperatures above this value, honever, there is still some fouling of the catalyst and even of the preheat section where no hydrogenation takes place. Kitrouylene has been s h w n to explode at 308" C. and to resinify belorn this temperature (6). The thermal instability of nitroxylene would complicate the commercial hydrogenation of this material at 400 to 500 pounds pressure. The preceding article ( 5 ) showed that the minimum decomposition temperature of nitroxylene is not changed by increasing the pressure. The batch runs reported above suggest that nitroxylene might be rapidly reduced around 230' C. if the pressure were raised to 3000 pounds gage The effect of increasing preswre is, therefore, i o spread the rrtngr hetween the tem-
1709
perature a t which rapid hydrogenation takes place and the minimum decomposition temperature. Brown, Smith, and Scharmann ( 2 ) indicated that an extension of the catalyst life may be obtained in the hydrogenation of nitroxyIene by operating at 3000 pounds gage and about 230' C. LITERATURE CITED
Adkins, H., and Shriner, R. L.,in Gilman's "Organic Chemistry," 2nd ed.. p. 815, New York, John Wiley & Sons, 1943. Brown, C. L., Smith, W. M., and Scharmann, W. G., IND.Eiw. CHEM.,
40, 1538 (1948).
Brown, 0. W., et al., J . Phgs. Chem., 26, 161, 273, 715 (1922); 31, 864 (1927); 34,2651 (1930). Ibid., 41, 477 (1937) ; 43, 383 (1939).
Condit, P. C., and Haynor, R. L., IND.ENC.CHEM.,41, 1700 (1949).
Gohr, E. J., Barr, F. T., and Roetheli, B. E., U. S. Patent 2,415,817 (Feb. 18, 1947). Grimm, H. G., Proc. 3rd Intern. Conf. Bituminous Coal, 2, 49 (1931).
Groggins, P. H., "Unit Processes in Organic Synthesis," 2nd ed., pp. 88-92, New York, McGraw-Hill Book Co., 1938. International Critical Tables, Vol. 5, pp. 162-8, Xew York, McGraw-Hill Book Co., 1926. Kling, And&, and Florentin, Daniel, Proc. Srd Intern. Conf. Bztuminous Coal, 2, 28 (1931).
Redcay, A. K., U. S. Patent 2,417,886 (March 25, 1947). Tropsch, H., Proc. 3rd Intern. Conf. Bituminoz~sCoal, 2, 35 (1931).
Tutwiler, C.C., .I. Am. Chem. Soc., 23, 173 (1901). RECEIVKD April 8, 1948.
DRYING OILS AND RESINS Oxygen-Convertible Alkyd Resins from Glycerol
Alpha-Allyl Ether If. DANNENBERG, T. F. BRADLEY, AND T. W. EVANS Shell D e v e l o p m e n t Company, E m e r y v i l l e , Calif.
oxygen-convertible alkyd resins with excellent properties have been synthesized from petroleum as the only required source of organic matter by reaction of glycerol or-allyl ether with phthalic or succinic acids under conditions to form polyesters. Surface coatings made from the polyesters have outstanding properties in applications where elevated temperature can be used for forced drying or baking of the films. Conversion at room temperature is possible but relatively slow. The properties of the coatings can be varied writhin wide limits by the choice of dibasic acid. Toughness and high chemical resistance are introduced by phthalic anhydride, hardness and abrasion resistance by succinic acid, softness and flexibility by adipic acid or alkenylsuccinic acids. If coating materials are prepared asdescribed, naturaldryingoilsare not needed. However, i t is possible to incorporate drying fatty acids into glycerol a-allyl ether esters or to modify conventional alkyd resins by replacing part of the glycerol by glycerol a-allyl ether.
B
ECAUSEof world-wide shortages of rnaterialssuitable for the production of coating compositions, particularly of fats and oils, considerable interest has developed in petroleum as a source of organic chemicals. During a search for chemicals which could help both to alleviate the shortage of drying oils and to enable the production of improved coating compositions, this laboratory synthesined the a-monoallyl ether of glycerol and certain of its polyesters. The latter yield promising new oxygen-convertible
alkyd resins in which the conventional inclusion of the fatty acids of drying oils may be omitted ( 1 ) . These syntheses involve the reaction of dibasic acids such as phthalic anhydride or succinic acid, which may be obtained by oxidizing aromatic petroleum hydrocarbons, with the a-allyl ether of glycerol which is likewise synthesized froin petroleum. The resulting polyesters can be polymerized to form insoluble, infusible resins, apparently because of their degree of functionality and the presence of reactive double bonds associated with the allyloxy radical. GLYCEROL a-ALLYL ETHER
The structural formula of glycerol or-allyl ether ( C O H I ~ Ois~ ) HL!=CH-CH2-O-CH2-CHOH-CHpOH; its molecular weight is 132.16. It boils at 84.5" C. (1 mm.; and melts between -90" and -100" C.; its flash point (Tag opencup) is >175" F. (79.4 O C.). Specific gravity (vacuum) data for the ether are as follows: d! = 1.0841, di0 = 1.0760, dfO = 1.0679, di0 = 1.0597, d:' = 1.0515. Refractive index figures are: ng = 1.4627, ,io = 1.4600, mio = 1.4692, &5 = 1.4589. The refractive dispersion, ( n -~ no) X is 91.7. Viscosity is 41.4 centipoises at 20" C., and 24.3 a t 30" C. Sa= face tension is 33.3 dynes per cm. at 20 C. The solubility of the ether in octane at 20" C. is 0.6Oi, by weight; solubility of octane in the ether is 2.4%. The ether is completely miscible with water, acetone, and toluene a t 20" C.
Vol. 41, No. E:
INDUSTRIAL AND ENGINEERING CHEMISTRY
1710
TABLE I. EVALUATION OF UXPIGVENTED Test Hardness Sward rocker Falling sand Scratch test (Bierbaum) Abrasion (Taber)
Sample on Glass Step1 Steel Steel
Flexibility Conical mandrel Steel Cold check Wood Exposure-twin-arc WeatherSteel o!neter Outdoor exDosure Kood Chemical rcsistancc Cold water Steel 5% K O H Steel Steel Toluene Boiling soap s o h . , 5 7 , Steel Boiling w-ater Wood Citric acid, 5 % Wood Vinegar Wood Alcohol, 100-proof Wood For 10% loss of gloss. b Using CS-10 wheel a t 1000 grams. C Temperature for last 25 cycles f r om 60' t o -38'
Testing Method a n d Unit Glass = 100 Carhorunrlu in
10h!/2)2 lIg./100 rerolationsb
C O kTINGY PROM
Glycerol a-Allyl E t h e r Phthalate 40
140 32.7
GLYCEROL a - A L L Y L ETHER Glycerol a-Allyl E t h e r Succinate 12
2900
10.1
43.3 1.7
Alkyd Resin (Medium-Oil)
Kitrocellulose (.Ukyd-Modified)
12 1040
27.7 12.7
40 161
28. 10. >
Elongat,ion, % .ifter 100 cyclric Hi.. t o beginning of failure After 106 days
30 Passes >2000
