Table V. Comparative Compounding Test Performance of ACB and Standard Blacksa ACB
GPF black
SRF
FEF
black
black
Modulus a t 300y0 eloiigation, psi Ball rebound
-1025 -350 -425 +lo0 Actual 1225 +13 $10 $11 +9 % Actual 62 a The blacks were mixed with rubber mixes using ASTM test formula which is: Parts by wt 100.0 Natural rubber grade RSS 1 llercaptobenxothiazol disulfide 0.6 2.5 Sulfur Zinc oxide 5.0 Stearic acid 3.0 Carbon black 50.0 __ Total 161.1 The test results are expressed in the customary way which is different from industry Reference Black No. 1.
process of flash pyrolysis of the coal in a high-temperature transport reactor, using air as the medium. The quality of carbon black produced directly from coal compares well with commercially available products. The chemical and compounding tests in rubber mixes reveal that the carbon black produced here has a low structure so t h a t large quantities
can be used in a rubber mix to lower the cost of rubber products. Acknowledgment
Grateful acknowledgment is made t o J. Samson of Firestone Tyre & Rubber Co., Ltd., Bombay, without whose help i t would have been difficult t o perform the compounding tests of the carbon black in rubber mixes. The authors also thank A . K. Singh, J. L. Ghose, and K. S . Goswami for helpful cooperation. References
Johnson, G. E., Decker, W. A., Forney, A. J., Field, J. H., Rubber World, 156 (3), 63-8 (1967a). Johnson. G. E.. Decker. W. A , . Fornev. A. J.. Field. J. H.. U.S. Bur. $lines, Report of Investigation“6994 (Aug. 1967b). Kirk, R. E., Othmer, D. F., Eds., “Encyclopedia of Chemical Technology,” Vol. 3, 53, Interscience Encyclopedia Inc., Sew York, N.Y., 1949. Kirk, R . E., Othmer, D. F., Eds, “Encyclopedia of Chemical Technology,” Vol. 4, 243-82, Interscience Publishers, New York, X.Y., 1964. llischenko, AI. L., Kham. Tverd. Topl., No. 2, 139-41 (hIarchApril 1969). Newman, J. 0. H., Coldrick, A. J. T., Evans, P. L., Kempton, T. J., O’Brien, D. G., Woods, B., Proc., Seventh International Conference on Coal Science, Prague, Sect. 4, Paper No. 26, 1968. Ray, S. K., Long, R., Combust. Flame, 8 , 139 (1964). Smith, E . C. W., Proc. Roy. SOC.,174A, 110 (1940). Smith, R. It.,Thornhill, F. S., Bray, 11. I., Ind. Eny. Cheni., 33, 1303 (1941). Street, J . C., Thomas, A., Fuel, 34, 4 (1935). Warren, B. E., Biscoe, J., J . A p p l . Phys., 13,364 (1942). Wolfhard, H. G., Parker, U’.G., J . Chem. Soc., 1950, p 2038. RECCIT ED for review November 17, 1970 ACCEPTED June 16, 1971
Ortho Esters as Hydrogen Chloride Scavengers George Kesslinl and Olaf Nifontoff Research Department, Kay-Fries Chemicals, Inc.,2 West Haverstraw, N . Y . 10993
Ortho esters react rapidly and essentially quantitively with trace amounts of anhydrous hydrogen chloride in several organic solvents. The speed of reaction i s a function of ortho ester structure and of solvent medium and can be complete in less than 1 min at room temperature. The stoichiometry of the reaction is established, and the products of reaction are demonstrated to be the alcohol, normal ester, and alkyl chloride derived from the ortho ester used.
E t h y l chloride and ethyl formate were previously identified as products of the reaction of anhydrous hydrogen chloride with triethyl orthoformate (Arnhold, 1887). Although quantitative data were lacking, and the presence of alcohol was not demonstrated, Arnhold postulated the reaction as
R’C(0R)s I
+ RC1+ R
1
=
R’C02R
C,H,; R’
=
+ ROH + RC1 H
To whom correspondence should be addressed. Present address, Stony Point, N.Y. 10980.
(1)
As recently as 1943, stoichiometry and mechanism were still uncertain; it was even suggested that if ethyl chloride were formed, it might be assumed to have resulted from the action of hydrochloric acid on ethyl alcohol (Post, 1943). Because of our interest in the frequently unique chemistry of ortho esters (Kesslin and Bradshaw, 1966), it seemed warranted to resolve the uncertainty of the stoichiometry and products from their reaction with hydrogen halides. I n addition, further study to accumulate data for the design of structural features of ortho esters most suited for hydrogen chloride scavenging appeared worthwhile because of the reported stabilization of chlorinated hydrocarbons by a n Ind. Eng. Chem. Prod. Res. Develop., Vol. 10, No. 4, 1971
425
Table 1. Summary of Rates of Hydrogen Chloride Scavenging by Ortho Esters SolventQ
Ortho erteP
Wt
%
HCI, wt %
Half-lives, at 25OC,C min
tlil
Additives
TEOF TEOF TEOF TEOF TEOF TEOF TEOF TEOF TEOF TEOF TEOF TMOF TBOF IDOF IDOF TSOF TAOF BZOF SBEOF IPOF TEOA TEOP TMOB TEOF TMOF TEOF TEOF TEOF TEOF
1.40 24 0.33 1.30 21 0.31 1.30 23 0.31 2.62 12.5 0.32 6.30 10 0.31 1.32 0.62 5d 1.42 8640 0.32 SDBAC, 2 x lo-* mole, 3.7%m 1.29 0.31 24 MA, 2 X mole, 0.87%~ 1.26 DBTDL, 4.4 X mole, 0.13%. 25 0.31 0.72 59 0.17 8 6 0.31 1.30 84 1.00 0.33 2.12 0.32 19 4.30 30 0.31 118 4.65 0.33 5.53 0.19 90,000f 1.80 5 0.33 4a 3.07 0.30 1.65 3h 0.33 1.92 0.35
