360
Answers to the Quickies
form (dark-colored) sulfonic acid. This is
bleached and then neutralized with caustic
soda to form the sulfonate. In total, there
are four processing steps. To synthesize
LABS, benzene is alkylated with long-chain
alkenes to alkylbenzenes, sulfonated, and
finally, the sulfonic acids are neutralized. In
total, there are three steps. The AES therefore require an additional step, bleaching
with hydrogen peroxide. However, this
bleaching process could be omitted if the
consumer would accept a slightly colored
detergent.
2. In this book, you have already learned a
whole range of possibilities for obtaining
oleochemical di- and polyols:
5 Castor oil is used which contains up to
three molecules of ricinoleic acid with one
hydroxyl group each (7 Sect. 2.2.7).
5 You use (poly)unsaturated triglycerides,
which are epoxidized by performic acid.
These epoxides can then be converted
into hydroxyl compounds by hydrolysis or
alcoholysis (. Fig. 4.4).
5 You perform a direct bishydroxylation
of unsaturated fatty compounds with
hydrogen peroxide catalyzed by tungsten
or rhenium (. Fig. 4.5).
5 You hydroformylate polyunsaturated
triglycerides, e.g. soybean oil, and hydrogenate the resulting polyaldehydes to
polyalcohols (7 Sect. 4.2.2.1).
5 You dimerize unsaturated fatty acids
catalyzed by montmorillonite to dimer
fatty acids and reduce them to dimer diols
(7 Sect. 4.2.2.3). You can also hydrogenate
unsaturated fatty acids to unsaturated fatty
alcohols (. Fig. 3.12) and then dimerize
them to dimer diols.
5 You carry out a metathesis of unsaturated
fatty alcohols, e.g. ocenol, with itself
(self-metathesis) or with petrochemical
unsaturated alcohols, e.g. with allyl alcohol
(cross-metathesis, 7 Sect. 4.2.2.4).
5 You carry out an (isomerising) methoxycarbonylation of methyl oleate
(. Fig. 4.25) and then reduce the resulting
diester to the corresponding diol.
3. Ozonolysis of oleic acid (C18:1, Δ9/c.)
results in pelargonic acid (C9) and azelaic
acid (C9). With erucic acid (C22:1, Δ13/c.),
again pelargonic acid (C9) is formed as
monocarboxylic acid, but the industrially
important brassylic acid (tridecanedioic
acid, C13) is formed as diacid.
4. Hydroformylation is a homogeneously catalyzed reaction. The transition metal catalyst,
usually a cobalt or rhodium complex, can be
used to control the addition of the formyl
group. The electronic and steric properties of the complex ligands are of decisive
importance.
5. There are different ways to branched fatty
acids (or their esters):
5 Alkali catalyzed condensation of (identical
or different) fatty alcohols produces the
branched Guerbet alcohols, which can be
oxidized to branched Guerbet acids
(. Fig. 3.21).
5 During the production of dimer fatty
acids, monomeric fatty acids are formed
as by-products. These are predominantly
methyl-branched isostearic acids
(7 Sect. 4.2.2.3).
5 Cooligomerization of conjuenic acids
with ethene leads to the formation of
alkyl-branched fatty acids under rhodium
catalysis (. Fig. 4.21).
6. 1-Tridecene and ω-heptenoic acid are
formed during the ethenolysis of petroselinic acid.
7. Depending on the linkage, either 1-decene
and 11-chloro-9-undecenoic acid methyl
ester or 1-chloro-2-undecene and
9-decenoic acid methyl ester are formed.
8. Typical ruthenium metathesis catalysts
contain a ruthenium-carbon double bond.
Chlorine, phosphines and/or carbenes are
bound to ruthenium as ligands
(. Fig. 4.11).
9. The isomerization to conjuenic acids can
take place by prolonged heating at high temperatures in the presence of alkali catalysts.
10. Typical catalysts for the hydrogenation of
C=C double bonds in fatty compounds are e.g.:
5 heterogeneous metal catalysts, e.g. of
nickel or palladium
5 homogeneous transition metal complexes,
e.g. of platinum or palladium
5 Ziegler/Sloan/Lapporte catalysts of nickel
and cobalt activated by aluminum alkyls
5 Palladium nanocatalysts (easy to produce,
very active and easy to recycle).
Answers to the Quickies
form (dark-colored) sulfonic acid. This is
bleached and then neutralized with caustic
soda to form the sulfonate. In total, there
are four processing steps. To synthesize
LABS, benzene is alkylated with long-chain
alkenes to alkylbenzenes, sulfonated, and
finally, the sulfonic acids are neutralized. In
total, there are three steps. The AES therefore require an additional step, bleaching
with hydrogen peroxide. However, this
bleaching process could be omitted if the
consumer would accept a slightly colored
detergent.
2. In this book, you have already learned a
whole range of possibilities for obtaining
oleochemical di- and polyols:
5 Castor oil is used which contains up to
three molecules of ricinoleic acid with one
hydroxyl group each (7 Sect. 2.2.7).
5 You use (poly)unsaturated triglycerides,
which are epoxidized by performic acid.
These epoxides can then be converted
into hydroxyl compounds by hydrolysis or
alcoholysis (. Fig. 4.4).
5 You perform a direct bishydroxylation
of unsaturated fatty compounds with
hydrogen peroxide catalyzed by tungsten
or rhenium (. Fig. 4.5).
5 You hydroformylate polyunsaturated
triglycerides, e.g. soybean oil, and hydrogenate the resulting polyaldehydes to
polyalcohols (7 Sect. 4.2.2.1).
5 You dimerize unsaturated fatty acids
catalyzed by montmorillonite to dimer
fatty acids and reduce them to dimer diols
(7 Sect. 4.2.2.3). You can also hydrogenate
unsaturated fatty acids to unsaturated fatty
alcohols (. Fig. 3.12) and then dimerize
them to dimer diols.
5 You carry out a metathesis of unsaturated
fatty alcohols, e.g. ocenol, with itself
(self-metathesis) or with petrochemical
unsaturated alcohols, e.g. with allyl alcohol
(cross-metathesis, 7 Sect. 4.2.2.4).
5 You carry out an (isomerising) methoxycarbonylation of methyl oleate
(. Fig. 4.25) and then reduce the resulting
diester to the corresponding diol.
3. Ozonolysis of oleic acid (C18:1, Δ9/c.)
results in pelargonic acid (C9) and azelaic
acid (C9). With erucic acid (C22:1, Δ13/c.),
again pelargonic acid (C9) is formed as
monocarboxylic acid, but the industrially
important brassylic acid (tridecanedioic
acid, C13) is formed as diacid.
4. Hydroformylation is a homogeneously catalyzed reaction. The transition metal catalyst,
usually a cobalt or rhodium complex, can be
used to control the addition of the formyl
group. The electronic and steric properties of the complex ligands are of decisive
importance.
5. There are different ways to branched fatty
acids (or their esters):
5 Alkali catalyzed condensation of (identical
or different) fatty alcohols produces the
branched Guerbet alcohols, which can be
oxidized to branched Guerbet acids
(. Fig. 3.21).
5 During the production of dimer fatty
acids, monomeric fatty acids are formed
as by-products. These are predominantly
methyl-branched isostearic acids
(7 Sect. 4.2.2.3).
5 Cooligomerization of conjuenic acids
with ethene leads to the formation of
alkyl-branched fatty acids under rhodium
catalysis (. Fig. 4.21).
6. 1-Tridecene and ω-heptenoic acid are
formed during the ethenolysis of petroselinic acid.
7. Depending on the linkage, either 1-decene
and 11-chloro-9-undecenoic acid methyl
ester or 1-chloro-2-undecene and
9-decenoic acid methyl ester are formed.
8. Typical ruthenium metathesis catalysts
contain a ruthenium-carbon double bond.
Chlorine, phosphines and/or carbenes are
bound to ruthenium as ligands
(. Fig. 4.11).
9. The isomerization to conjuenic acids can
take place by prolonged heating at high temperatures in the presence of alkali catalysts.
10. Typical catalysts for the hydrogenation of
C=C double bonds in fatty compounds are e.g.:
5 heterogeneous metal catalysts, e.g. of
nickel or palladium
5 homogeneous transition metal complexes,
e.g. of platinum or palladium
5 Ziegler/Sloan/Lapporte catalysts of nickel
and cobalt activated by aluminum alkyls
5 Palladium nanocatalysts (easy to produce,
very active and easy to recycle).