I
T h e other is a n ether linkage. as shown in the figure. T h e spectrum for the oxo bottoms product sho\vs peaks at 9 microns (ether) a n d 9.6microns (alcohol). T h e comparative infrared data on the C,6 ether were obtained on a synthetic product made by condensing 2 moles of Cg oxo alcohol in thi: presence of a toluenesulfonic acid c a t a l y t . Data on the C,, alcohol \cere obtained using a branched CI6alcohol ( 9 ) . O n the basis of the above data, the oxo bottoms product is probabl>-a C,; ether alcohol similar to the componds synthesized recently by Buchner (2).
JEFFREY HOBART BARTLETT, ISIDOR KIRSHENBAUM, and CLIFFORD W. MUESSIG Esso Research and Engineering Co., Linden, N. J.
Oxo Ether Alcohols Promising Detergent Compounds
OVLR
90~000:000pounds of synthetic alcohols are produced annually by the oxo or hydroformylation reaction ( 3 ) . This reaction, discovered in the 1930's ( 7Hj 77). involves the addition of carbon monoxide a n d hydrogen to a n olefin to form a saturated aldehyde. which is readily hydrogenated to the corresponding alcohol. hfore than one isomer is usually formed, a n d isomer distribution depends upon reaction conditions (7). Commercially available oxo alcohols include those in the Cg to C,, range; two principal alcohols are the Cg a n d Clo. Both are mixtures of isomers, produced from branched C: a n d C9 olefins. A typical analysis of a n oxo Cs alcohol is shown in Table I. M a n y laboratories have studied the mechanism a n d kinetics of this reaction ( 7 . 2. J . 6-7.7.79-21). However. publications are concerned primarily with principal products formed rather than side reactions a n d by-products. Actually a number of side reactions lead to compounds which boil a t temperatures higher than the principal products-e.g., byhen a C g alcohol having a boiling point of about 185' C. is made, compounds are also produced which boil in the range of 210' IO 220" C. a t 50 m m . of mercury. T h e amount of such by-products depends upon reaction conditions. Little is knobcn about these higher boiling mixtures (oxo bottoms) ; therefore a study was undertaken to identify the principal components. Hydroxyl groups are present and it \cas believed that the principal components \vere alcohols. .-lctually. ho\vever. one is a n ether alcohol, \vith lesser amounts of saturated a n d unsaturated ethers.
R-CH-CH.-O-CrH
Properties of Distilled O x o Bottoms from Ci Olefin Oxonation (4iVo heart c u t )
Molecular weight Hydroxyl No., mg. KOH 'g. Oxygen, 70 Carbon, 70 Hydrogen, 70 Boiling range, 50 mm. Hg
*
kH20H .4n alternative possibility is
2 69
C;Hi,-CH--O-CsHij
204 11.1
75.2 13.7 210-18' C.
T h e 11.1% oxygen in the purified oxo bottoms from C; oxonation shows the presence of two oxygens per molecule: but the hydroxy number of 204 indicates that only one is a hydroxyl group.
CsH1,-O-CH=CH-CGHIa
:;
0x0 +
Li?OH These conclusions were confirmed b!s!-nthesis a n d mass spectrometer analysis. A synthetic C,; ether alcohol was prepared from Ca oxo alcohol and Cg oxo aldehyde a n d shown to be identical in properties with the ether alcohol derived from oxo bottoms.
C,HIjO-CH-CH--CrH,
* (ether alcohol 1
CHzOH Exact positions of double bond and methylol group are not howm
THESPECTRA'ARE' DISPLACED TO ALLOW
'
I
(3)
I
Identification of Ether Alcohols T h e higher boiling fractions obtained by oxonation of C;, Cg. a n d C,? olefins \vere separated from the Cg, Clo. a n d C,, product alcohols by distillation. Heart cuts of 4' a n d 90%: prepared by redistilling in a 20-plate column a t a reflux ratio of 10 ta 1 were analyzed chemically by infrared a n d mass spectrometer. -4 sample purified by the borate ester technique (78) gave the same analytical results as those for the distilled products. ~
MICRONS Infrared spectrum shows presence of ether alcohols in oxo bottoms VOL. 51, NO. 3
MARCH 1959
257
T h e oxo acetal was prepared in the presence of toluenesulfonic acid (catalyst) a n d toluene (entraining agent). T h e acetal was purified by distillation and then oxonated a t 175’ to 185’C., usinga cobalt catalyst. T h e product consisted of the C1; ether alcohol, some CS alcohol. and less than 15y0 of products boiling above the CI7 ether alcohol range. I n another preparation, the acetal was first heated a t 250’ C. (as indicated in Equation 2) to give a n unsaturated ether, which was oxonated and hydrogenated to form a C,; ether alcohol. T h e synthetic ether alcohols had the same chemical and infrared characteristics as the material isolated from oxo bottoms. Data are given in Table 11, with the analytical values theoretically expected for a C l i ether alcohol. Mass spectrometer analysis of the oxo bottoms C!; ether alcohol gave a fragmentation pattern which was not one of a simple primary alcohol, but was entirely consistent with either the following or closely related skeletal structures. or Cs-C-C--O-Cs
CS-C-C-O-C~
I
COH
LOH
Oxo bottoms fractions obtained in the manufacture of C I O and Cj3 alcohols (from C9 and CIU olefin oxonations) contained substantial amounts of ether alcohols. By using the techniques described above, it was shown that their principal components are the C21 and C2, ether alcohols, respectively.
Nonionic Detergents from Ether Alcohols Sonionic detergents were prepared by reaction of the ether alcohols with ethylene oxide. T h e ethvlene oxide adds
Table I.
readily in the presence of sodium methoxide a t about 150’ C. T h e reaction mixture was treated with a n ion exchange resin, filtered, and then stripped under vacuum to remove traces of moisture. T h e amount of ethylene oxide required for maximum detergency was approximately that needed for the nonionic to have a water solubility of about 47,. T h e compositions were: 12 moles of ethylene oxide per mole of CI, ether alcohol and 15 moles of ethylene oxide per mole of Cy1 ether alcohol. Derergency \vas determined by the Terg-o-Tometer test (.5)! using a standard soiled cotton cloth obtained from the United States Testing Co. Comparisons were made with a nonylphenol nonionic containing 9.4 moles of ethylene oxide per mole of the phenol. Evaluations were carried out in both medium hard (120 p.p.m.) and hard (300 p.p.m.) ivater (Table 111). T h e ether alcohol nonionics are fully equivalent in this detergency test to the premium nonylphenol nonionic. .4s anticipated, rhe ether alcohol nonionics: as well as that from non>-lphenol, were slightly less effective in hard water than in medium hard. Differences were found in the \vetting characteristics of these nonionics. T h e C,; ether alcohol nonionic was somewhat better than the nonylphenol detergent
Discussion and Conclusions T h e oxonation process is much more complex than is usually described. Side reactions lead to higher boiling fractions, whose principal components are ether alcohols. Nonionic surfactants prepared from the ether alcohols show advantages over nonylphenol nonionics in laboratory surfactant tests.
Commercial C, Oxo Alcohol Is a Mixture of Isomers Rtruccure
I-om er 3,4-Dimethyl-l-hexanol 3,5-Dimethyl-l-hexanol 4,5-Dimethyl-l-hexanol 3-Methyl-1-heptanol 5-Methyl- 1-heptanol Other isomers
W t
CHBCH&H(CHIj CH(CH3j CHzCH2OH CHsCH(CHB)CH2CH(CH3)CH2CH20H CHBCH(CHI)CH( CHB)CH2CH2CH20H
FC
20 30 25
C H ~ C H & H ~ C H ~ C H ( C H I ) C H ~ C H ~ ~15 H\ CH?CHgCH(CH,) CH?CH?CH.CH?OH, 10
Table II.
Oxo Bottoms and Synthetic C17 Ether Alcohols Are Comparable Analytiral Data Oxo Bottom? SynthetiL Theoleti( a1
Molecular weighta Oxygen, 7% Carbon, yo Hydrogen, 74 Hydroxyl No., mg. KOH/g.b Infrared spectra Ether peak at 9 microns Alcohol peak at 9.6 microns
Determined by cryosLopic method.
258
269 11.1 75.2 13.7 204
267 10.8 75.7 13.5
...
272 11.7 74.9 13.4 206
Yes Yes
Yes Yes
Yes Yes
* By acetic anhydride-p> I idiiie
INDUSTRIAL AND ENGINEERING CHEMISTRY
h-titiat~oli
Table 111.
Ether Alcohols Form Good Nonionics
f Detergenvy
relative to nonyipheiiol iioiiioi~ic iii medium hard water) - Relative Detergency --. h l edium hard water Hard Rater Nonionic (120 p.p.m.) (300 u.p.ni.)
C17 ether alcohol C?Iether alcohol Nonylphenol
100 98 100
93 94 93
Acknowledgment T h e authors thank Nelson C. Edwards and Russell C. Doeringer for help in carrying out the experiments.
literature Cited (1) Adkins, H., Krsek, G., J . A m . Chenr. Soc. 70, 383 (1948). ( 2 ) Buchner, K., German Patent .\PPI., R-9579 (March 29, 1956). (3) Chem. En?. :Teres 35, 16 (Siarch 18, 1957). (41 Goldfarb, I. J., Orchin, lt., 1st International Congress on Catalysis, Philadelphia, Pa., September 1956. (5) Harris, J. C., “Detergency Evaluation and ‘Testing,” Interscience, S e w York, 1954. (6) Hatch, L. F., “Higher Oxo ;ilcohols,” Wiley, New York, 1957. (7) Hughes, V. L., Kirshenbaum, I., ISD. ENG.C H E M . 49, 1999 (1957). (8) Martin, .4.R., Chem. Ind. (London) 50. 1536 11954). (9) &Iason,‘R. B., LJ. S. Patent 2,811,567 (Oct. 29, 1957). (10) Natta, Giulio, Beati, Ernesto, Chimzra @ industrra 27, 88 (1945). (11) Natta, G., Ercoli, R., [bid., 34, 503 (1932). (12) Natta, G., Ercoli, R., Castellano, S., Barbieri, F. H.. J . Am. Chem. Soc. 76, 4049 (19541. (13) Orchin, M., “Chemistry of Petrolrum Hydrocarbons,” vol. 111, Chap. 53, Keinhold, New York, 1955. (14) Orchin, M., Schroeder, \V. C . , “Unit Processes in Organic Synthesis,“ 4th ed., Chap. 9, McGraw-Hill, New York, 1952. (15) Orchin, &Wfnder, I., I., “Encyclopedia of Chemical Technoloqy,” vol. 9, Interscience Encyclopedia, New York, ’
1952.
(16) Roelen, O., c‘. S. Patent 2,327,066 (1 943) ; German process patent applied for. 1938. (17) Smith, D. F., Hawk, C . D., Golden, P. L., J . A m . Chem. SOC. 52, 3221 (1930). (18) U. S. Naval Tech. htission, Rept. 248-45, 86-8 [PB-22841). (19) Wender, Irving, Meltin, S., Ergun, S., Sternberg, H. \V., Greenfield, H., J . Am. Chem. SOG.78, 5401 [l9561. (20) Wender, Irving, Sternberg, H. LV., 594-608, Adrsunces zn Catalysis 9 (19571. (21) Wender, I., Sternberg, H. LY., Orchin, M.. ”Catalysis,” ed. by P. H. Emmett, vol. V, Chap. 2. Reinhold, New York, 1957. RECEIVED for review .June 2, 1958 .ACCEPTED October 31, 1958 Division of Petroleum Chemistry, Symposium on Recent Developments in Chemicals from Petroleum, 133rd Meeting, .4CS; San Francisco, Calif., April 1958.
