I
W. LORZ, G. A. MILLS, H. SHALIT, and T. C. MICHAEL Houdry Process Corp., Marcus Hook, Pa.
c
2
60
t-
W o _I
W v)
50
40
50
CONVERSION,
60 WT. %
Figure 4. Selectivity-conversion values of diisopropyl dehydrogenaton show constant yield per pass of approximately 30y0with optimum catalyst VOL. 53, NO. 1 1
NOVEMBER 1961
875
fin-2,3-diniethyl-2-butenecut into a material containing the 2,3-dimethyl-2butene in 8570 purity. By suitable treatment the last cut can provide 95y0 purity 2,3-dimethyl-2-butene. Applications for Products. 4 number of uses of tert-butylethylene for chemical applications have been suggested involving. reactions such as epoxidation, oxidation, hydration, and hydroformylation. Certain interesting products can be made-for example, pivalic acid by oxidation. I t was originally expected that tert-butylethylene would be of immediate polymer interest since the next higher homolog (4,4dimethyl-I-pentene) forms a stereoregulated polymer of melting point above 320’ C. (70). However, in spite of occasional literature reference to the polymer of tert-butylethylene ( I ) , samples submitted for such polymerization have not met with success, presumably because of steric hindrance. Molecular models show the availability of the double bond, but the spatial requirements of the catalyst are not known. T h e stereospecific polymerization of tert-butylethylene, therefore, remains as a challenge to polymer chemists. Several interesting possibilities also arise from the dehydrogenation prod-
Table IV.
ucts of 2,3-dimethylbutane. The only possible diolefin from this reaction, 2,3-dimethyl-1,3-butadiene,has been used in the past, notably in Germany, as the monomer for synthetic rubber production. Other elastomers became available and “methyl” rubber was abandoned; however, the development of Ziegler-Natta type polymerization has opened u p new possibilities, and interest in the polymers of this diolefin has been revived. A cis-1,4-polymer has been prepared (75), which is a plastic with a melting point of 189’ to 192’ C.; trans-forms have also been prepared ( 3 , 76) which have even higher melting points, u p to 263’ C. The two monoolefins in this series, 2,3-dimethyl-1-butene and 2-butene, are also potentially useful as monomers in polymerization or intermediates in chemical synthesis requiring particular structures.
Acknowledgment
Most of the analyses were performed by James Terrell, who had also worked out detailed analytical procedures. T h e authors thank the Houdry Process Corp. for permission to publish this report.
Three Sets of Conditions Correspond to Optimum Production Possible Products. Wt.
Conditions“
Product 2,3-Dimethyl-l-butene
31.4
2,3-Dimethylbutadiene
A
B C
Total 2,3-dimethylbutenes Total 2,3-dimethylbutenes 2,3-dimethylbutadiene
+
See Figure 3.
876
Selectivity
INDUSTRIAL AND ENGINEERING CHEMISTRY
of Three
7 0 Yield/pass
(1) Bawn, C. E. H., J . Inst. Petrol. 46, 374 (1960). (2) Bloch, H. S., Donaldson, G. R., Haensel, V., 135th Meeting, ACS, Boston, Mass., April 1959. (3) Brown, J. F., Jr., White, D. M., 133rd Meeting, ACS, San Francisco, Calif., April 1958. (4) Frey, F. E. (to Phillips Petroleum Co.), U. S. Patent 2,438,315 (March 23, 1948). (5) Grosse, A. V., Ipatieff, V. N., J. Org. Chem. 8, 438 (1943). (6) Hornaday, G. F., Ferrell, F. M., Mills, G. A. in ”Advances in Petroleum Chemistry and Refining,” Vol. IV, Interscience, New York, 1961. (7) Horton, A. W., Icellett, J., I11 (to Socony-Vacuum Oil Co.), U. S. Patent 2,406,688 (Aug. 27, 1946). (8) Kilpatrick, J. E., Prosen: E. J., Pitzer, K. S., Rossini, F. D., J . Research N a t l . Bur. Standards 36, 559 (1946). (9) Lorz; W., Mills, G. A,, Shalit, H., Michael, T. C., Houdry Process Corp., Marcus Hook, Pa., unpublished data, 1960. (10) Reding, F. P., J . Polymer Sci. 21, 547 (1956). (11) Rossini, F. D., “Selected Values of Physical and Thermodynamic Properties of Hydrocarbons and Related Compounds,” API Research Project 44, Carnegie Press, Pittsburgh, Pa., 1953. (12) Sachanen, A. N., in “The Chemistry of Petroleum Hydrocarbons,” Vol. 11, Chap. 24: Reinhold, New York, 1955. (13) Whitmore, F. C., Meunier, P. L., J.Am. Chem. Sac. 55, 3721 (1933). (14) Whitmore, F. C., Rothrock, H. S., Zbid., 5 5 , 1107 (1933). (15) Yen, T. F., J. Polymer Sci. 35, 533 (1959). (16) Zbid.,38, 272 (1959). RECEIVED for review December 20, 1960 ACCEPTED May 3, 1961 Division of Petroleum Chemistry, 139th Meeting, ACS, St. Louis, Mo., March 1961.
10.3
8.9
4.0
18.9
10.0
41.5 9.1 19.3
13.7 10.2
7.2 51.7
2.4 23.0
4.0
21.3
11.3
72.9 18.0
24.0
8.0
20.2
80.1
26.4 31.0
69.7 59.5
Literature Cited
8.0
31.5
Correction
Hydrogenation and Dehydrogenation In this unit processes review article by Bruce T. Alexander, Doris J. Batliner, W. M. Keely, and F. J. O’Hara [IND. ENG. CHEM.53, 767 (1961)], the AD1 prices for microfilm and photostat copies of the complete annotated bibliography have been reversed in the coupon on p. 767 and in the footnote on p. 771. T h e prices will be $1.75 for microfilm and $2.50 for photostat copies.
