35
J
P
B 10
1
I
I
0.5
I .o
1.5
INITIATOR, MOLE
yo OF
Figure 4. Initiator efficiency varied inversely with initiator charge, but isopropyl alcohol conversion was nearly linearly dependent
ALC CHARGE
having higher boiling points than ethylene were handled in the liquid state. Addition of liquid olefin a t the same rate as it reacted was impracrical in this exploratory study. HoweiTer, reactions with relatively low initial olefin concentrations indicated that the yields of 1 to 1 adducts vary inversely with olefin concentration. I n general, the yields with higher olefins seem to be somewhat lower than those with ethylene. A few experiments with propylene, 1-hexane, 1-octene, and a-methylstprene are reported in Table I.
Initiators, Initiator Efficiency, and Additives. In many of the experiments with isopropyl alcohol reported here the charge consisted of 0.1 mole of tert-bury1 peroxide and 6.67 moles of alcohol. T h e yields of product amounted to 20 to 22 moles of telomeric compounds per
mole of initiator in many of the experiments. U r r y and others (70) reported higher product yields based on initiator charge. In a n attempt to explain this difference, isopropyl alcohol and ethylene were reacted using variable charges of initiator. T h e data (Figure 4) show that the initiator efficiency (measured as the ratio of telomer product to initiator) varies inversely with the initiator charge. Specifically, a threefold increase in product yield (per initiator charge) was realized by decreasing the initiator charge from 1.5 to 0.2 mole yo. Concurrently, the conversion of isopropyl alcohol decreased (nearly linearly with initiator charge) from about 34 to 23%. Many of the reactions reported here were initiated lvith tert-butyl peroxide. Urry and others (70) reported that simi-
Table IV.
Yield of High Molecular Weight Telomers Decreased a t Higher Total Pressure and Presence of Inert Diluent Yields of Higher Telomer,a Wt. % of Isopropyl -~Alcohol Charge Ethylene partial Pressure, P.S.I.G. No diluent 500 p.s.i.g.* 1000 p s.i.g.* 150
200 250
7.2
8.6 21.5 24.2
3.3
11.9
...
17.3
11.6
Product of reaction of four or more taxogen units per telogen unit.
* Piitrogen added.
lar tert-alkyl peroxides are effective initiators, while benzoyl peroxide, 01cumyl hydroperoxide, hexachloroethane, and azobis(isobutyronitri1e) are ineffective for telomerization initiation. I n this work, potassium persulfate, with and without added mercaptan, and dimethyl azodiisobutyrate were also found to be ineffective initiators for alcohol telomerization. Reaction was initiated by di-tert-butyl peroxydicarbonate, but the product had a higher molecular \.\.eight than that obtained with tert-butyl peroxide. ,4 few additives were also included in the charge of some experiments, as reported in Table I . Strong base, such as sodium methoxide, seemed to inhibit partially the telomerization or methyl alcohol. Water and glucose appeared to retard the telomerization of isopropyl alcohol, but the effect was small. These two substances apparently reduce the yield of 1 to 1 adduct and increase the yield of higher telomers. literature Cited
(1) Banes, F. I V . , Fitzgerald, W,P., Gilliland, E. R., Nelson, J. P. (to Standard Oil Development Co.), U. S. Patents 2,668,181 (Feb. 2, 1954), 2,671,121 (March 2, 1954). ( 2 ) Cadogan, J . I. G., Hey, D. H . , Quart. Revs. (London) 8, 308 (1954). (3) Choppin, A. R., Rogers, J. W., J.Am. Chem. Soc. 70, 2967 (1948). (4) Erchak, M., Jr. (to Allied Chemical and Dye Corp.), U. S.Patents 2,504,400 (April 18, 1950), 2,683,141 (July 6. 1954), 2,712,534 (July 5, 1955), 2,713,071 (July 12, 1955), 2,717,910 (Sept. 13. 1955), 2,779,754 (Jan. 29, 1957). (5) Erchak, M., Jr., Porter, Frank, Silsby, C. F. (to Allied Chemical and Dye Corp.), Ibid.,2,670,386 (Feb. 23, 19541. (6) Friedlander, H. N. (to Standard Oil Co. of Indiana), Ibid., 2,728,756 (Dec. 27. 1955). ( 7 ) Gilliland: E. R., Kallal, R. J . , C h i n . Eng. Progr. 49, No. 12, 647 (1953). ( 8 ) Kharasch, M. S.,Jensen, E. V.? Crry, 1%’.H., J . Am. Chem. Soc. 68, 154 (1946); 69, 1100 (1947). ( 9 ) Steacie, E. W. R., “Atomic and Free Radical Reactions,” Val. 2, p. 507. Reinhold, New York, 1954. (10) Lrry, W. H., Stacey, F. W., Huyser, E. S., Juveland: 0. 0.:J . Am. Chem. SOC. 76, 450 (1954).
RECEIVED for review May 4, 1959 ACCEPTED January 25, 1960 Division of Organic Chemistry, 135th Mceting, ACS, Boston, Mass., April 1959.
Flow Conditioning and Anticaking Agents-Correction I n the article “Flow Conditioning and Anticaking Agents” [R. R. Irani, C. F. Callis, and T. Liu, IND.ENG.CHEM.51, 1285 (October 1959)], the plots of Figures 1 and 2 on page 1286 have been interchanged so that Figure 1 and its
400
caption refer to the wrong plot. Hence, Figure 1 caption refers to drawing in column 2 and Figure 2 caption refers to drawing in column 1 above it. O n page 1287, column 3, the second sentence of paragraph 2 should read:
INDUSTRIAL AND ENGINEERING CHEMISTRY
Tricalcium phosphate, calcium silicate hydrate, and diatomaceous earth reduced the percentage caked to 10, 20, and 30%, respectively, but beyond 0.5% (weight) conditioners had no further effect.
