Monohydric Alcohols. Manufacture, Applications, and Chemistry

223 Pages·1981·2.8 MB·English

by  Edward J. Wickson (Eds.)

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In Monohydric Alcohols; Wickson, E.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
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In Monohydric Alcohols; Wickson, E.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
Monohydric Alcohols
Manufacture, Applications, and
Chemistry
Edward J. Wickson, EDITOR
Exxon Chemical Company
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1/ Based on a symposium
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8 Industrial and Engineering Chemistry
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March 25-26, 1980.
ACS SYMPOSIUM SERIES 159
AMERICAN CHEMICAL SOCIETY
WASHINGTON, D. C. 1981
In Monohydric Alcohols; Wickson, E.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
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98 Library of Congress Data
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02 (ACS symposium series 159; ISSN 0097-6156)
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0. Includes bibliographies and index.
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doi: I1.. WAlcicokhsoolsn—, ECdownagrredss eJs.., 1920- II. American
1 | Chemical Society. Division of Industrial and Engi
8 neering Chemistry. III. Series.
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15, 1 TISPB2N48. A0-58M4162-606 37-6 661'.82 8A1A-5C9R502
ne ASCMC 8 159 1-222 1981
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In Monohydric Alcohols; Wickson, E.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
ACS Symposium Series
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0 M. Joan Comstock, Series Editor
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W. Jeffrey Howe Davis L. Temple, Jr.
James D. Idol, Jr. Gunter Zweig
In Monohydric Alcohols; Wickson, E.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
FOREWORD
01 The ACS SYMPOSIUM SERIES was founded in 1974 to provide
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1- IN CHEMISTRY SERIES except that in order to save time the
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9 papers are not typeset but are reproduced as they are sub
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bk- mitted by the authors in camera-ready form. Papers are re
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2 viewed under the supervision of the Editors with the assistance
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0. of the Series Advisory Board and are selected to maintain the
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98 and reports of research are acceptable since symposia may
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In Monohydric Alcohols; Wickson, E.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
PREFACE
Unsubstituted monohydric alcohols are the largest single class of oxy
genated hydrocarbons made in the chemical industry. In fact, three
of the alcohols—methanol, ethanol, and isopropyl alcohol—are in Chemi
cal and Engineering News "Top 50 Chemicals" for 1979. These alcohols
are used in a myriad of applications, some very large and others quite
small. Solvents, fuels, antifreeze, germicides, frothers, antifoams, and inks
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00 are examples of where the alcohols are used as such. Derivatives cover an
pr
9. even wider range of applications, including resins, solvents, plasticizers,
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01 surfactants, lubricants, flavors, fragrances, capacitor fluids,a nd the fast
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8 growing gasoline additive MTBE, to name a few. In this sense, alcohols
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k- differ markedly from some of the very large volume organics such as
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1/ ethylene, propylene, toluene, p-xylene, and urea, which are used in very
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10 large volumes but have relatively few end uses.
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oi: 1 It is common practice to divide alcohols into lower alcohols (C1-C5)
d and higher alcohols (C and higher). In turn, higher alcohols are gen
81 | erally subdivided into (p6olyvinyl chloride) plasticizer range (C-C or
15, 19 C6-C12) and detergent range (C11 or C12 and higher). Actual6ly, 11the
e dividing line is not this clear cut, and one finds the lower alcohol n-butanol
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Ju used in butyl benzyl phthalate and the detergent-range tridecyl alcohol
ate: used in ditridecyl phthalate. Both of these esters are important polyvinyl
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n chloride plasticizers. Also, detergents based on mixed alcohols, including
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ati C , are produced commercially, and there are many surfactants, such as
blic di1-12-ethylhexyl sulfosuccinate, based on the so-called plasticizer-range
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P alcohols.
In developing the symposium on which this book is based, our objec
tive was not to cover all monohydric alcohols, but to cover representative
lower and higher alcohols with special attention, when possible, to new
developments and applications.
The book starts with a review of the chemistry of monohydric alco
hols with references to many of the common reactions used in industry.
Much attention has been devoted in the professional journals and in
the press to gasohol, and announcements of new ethanol plants and process
improvements seem unending. A perspective on the problems and promise
of gasohol is covered along with a status report on work in Brazil on
(fuel) methanol from wood, not by destructive distillation used in the
past, but by modern synthetic chemistry. Other promising new uses for
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In Monohydric Alcohols; Wickson, E.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
methanol are covered that together suggest enormous growth for this first
member of the monohydric alcohol series.
A detailed discussion on surfactants from secondary alcohols which
are relatively little known in the U.S. is included, together with a review
of linear alcohol processes (Oxo and Ziegler) and detergent applications
of the Ziegler alcohols. Also covered is a discussion of the revolutionary
rhodium oxo process which has already resulted in a number of new
plants—announced, under construction, or in operation, worldwide—for
the manufacture of n-butanol and 2-ethylhexanol. Applications of these
alcohols are also discussed.
The application of branched-chain alcohol diesters in part-synthetic
lubricants is covered as one of the ways the petroleum industry is respond
1 ing to the challenges brought on by the trend toward new smaller cars
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pr0 with more demanding lubricant requirements.
59. The history of monohydric alcohol-based ester-type plasticizers for
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1-0 polyvinyl chloride is reviewed, and a prediction of the future for these
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9 plasticizers in the eighties is made. Finally, although not in the large
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bk- volume category compared to many monohydric alcohols, the rather
21/ sophisticated chemistry used to produce monohydric alcohols for the
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1 | EDWARD J. WICKSON
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In Monohydric Alcohols; Wickson, E.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
1
Chemistry of Monohydric Alcohols
F. M. BENITEZ
Exxon Chemical Company, Specialties Technology Division, P.O. Box 241,
Baton Rouge, LA 70821
1 Alcohols can be regarded as hydroxyl derivatives of hydro
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9.c groups (monohydric, dihydric, etc.), according to their struc
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1 ture (primary, secondary or tertiary), and by the structure of
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1- the hydrocarbon function to which the hydroxyl is attached
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19 (aliphatic, cyclic, saturated or unsaturated).
bk- This chapter is concerned almost exclusively with the
21/ chemistry of saturated aliphatic monohydric alcohols with
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1 particular emphasis on the reactions used in the conversion of
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1 these alcohols to other useful compounds. Manufacture of many
oi: of the alcohols is covered in other chapters.
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19 Acidity and Basicity
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The acidity of the hydroxyl group can be seen in the rapid
proton-deuteron exchange that can take place when alcohols are
dissolved in D^O (Reaction I), alkali metals (Reaction II) and
organometallic reagents (Reaction III and IV).
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0097-6156/81/015 9-0001 $05.00/ 0
© 1981 American Chemical Society
In Monohydric Alcohols; Wickson, E.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
2 MONOHYDRIC ALCOHOLS
The most complete measurements of the acidity of alcohols
in water were made some time ago by Long and Ballinger (1,2_,3)
using conductivity methods. The pKa values for substituted
methanols (RCHOH) (2) are a linear function of the Taft a*
2
constants (4,J5; for the R substituents, allowing the prediction
of the actual pKa by using the formula: pKa = 15.9 - 1.42 a*.
In recent years the question of acidity and basicity has
been reopened by the development of techniques to measure them
in the gas phase(6^). The results available reemphasize the
fact that solvation factors have a profound influence on the
course of acid-base reactions.
Brauman and Blair have determined (6) that the acidity of
some substituted alcohols increases as the size and number of
substituents increase. This is exactly the opposite effect
seen in solution measurements. The conclusion that must be
01 deduced from this is that there are two kinds of acidity that
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81- (b) a practical liquid phase acidity in which solvation effects
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oi: Categories of Chemical Reactions of Alcohols
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5, reactions of alcohols, (B) displacement of the hydroxyl group,
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ate: Under each one of these categories the different types of
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atio given, but by no means are all the different types of alcohols
c covered. The reader is asked to extend the analogies and use the
ubli references given to pursue his areas of interest.
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Nucleophilic Reactions
Any species having an unshared pair of electrons may act as
a nucleophile, whether it is neutral like an alcohol or negative
like the alkoxide ion. The rate of S^l reactions is independent
of the structure and charge of the nucleophile. For S^2 re
actions, factors like the charge of the nucleophile, its degree
of solvation and nucleophilicity determine the rate of the
reaction (6A).
The major trend in nucleophilicity is to parallel base
strength. However, sometimes differences between basicity and
nucleophilicity of a species occur because the two are somewhat
different. Basicity measures attack on hydrogen and it is
In Monohydric Alcohols; Wickson, E.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1981.