Chemical Modifications of Lipids For Applications in Chemical Industry PDF

Ph. D. Thesis, Priya S.
Deshpande, NMU, Jalgaon, 2013

1

Chapter 1
Introduction and Literature Review:
Chemical modifications of lipids for applications in chemical industry
The chemical process industries, all over the world, have been facing the
challenges of developing innovative processes and products in the wake of highly
globalized trade competition and stringent environmental regulations
1
. The term Green
Chemistry has been coined to promote the movement towards more environmentally
acceptable and sustainable chemical processes and products. The Twelve Principles of
Green Chemistry, which were formulated in the 1990s, provide guidelines for chemists to
develop clean, environmentally benign methodologies that are sustainable for the long
term and that reduces or eliminates the use or generation of hazardous substances in the
design, manufacture and application of chemical products
2
.
According to the seventh principle of Green Chemistry, a raw material or feedstock
should be renewable rather than depleting whenever technically and economically
practicable. The term Renewable Resources primarily includes carbohydrates (starch,
cellulose, sugars) and lipids (animal and vegetable fats and oils, phospholipids etc.).
Carbohydrates are the most abundant organic compounds (around 75-80% of biomass) on
the planet. They constitute a suitable replacement for fossil fuels since they contain a
considerable amount of carbon and hydrogen. Utilization of natural products such as plant
oils and natural fats has attracted great attention in both scientific and industrial areas in
recent years. They can be used and are being used to produce valuable chemical
feedstocks and macrocyclic frameworks for natural product synthesis. The wide range of
renewable raw materials with varying properties and differing chemical compositions are
available at the annual production rate of approximately 170 billion tons
3
. Around 6
billion t/a (3.5%) are utilized in the form of timber, grain and other foodstuffs. The rapid
depletion of crude oil reserves, escalating fuel prices and the concern over climate change
catapulted into global interest for utilizing the remaining 96% (quantitatively in the order
of the total reserve of mineral oil) crop-based feedstocks as renewable alternatives to
petroleum-based feedstocks for energy generation and the synthesis of new platform
chemicals
4-6
. Bio-based chemicals typically are cheap, readily available, low in toxicity,
CO
2
sequestering, biodegradable and eco-friendly, making them prime candidates for an
alignment of industry to the principles of green chemistry and sustainability. In spite of
this fact, the applications that use biomass as starting materials are currently limited to
Ph. D. Thesis, Priya S. Deshpande, NMU, Jalgaon, 2013
2

only 10-12% of the overall organic chemical industry and include adhesives, textile and
leather chemicals, surfactants, cleaning agents, perfumes and flavours, cosmetics,
coatings/ paints, printing inks, crop protection, lubricants/ greases and dietary
supplements. Chemists have much to contribute to meet this challenge and the future of
green chemistry will depend on innovations that consolidate and integrate the Twelve
Principles as a framework for intentional design of routes for utilisation of renewable
materials. The detailed study of the chemistry of these renewable materials and the
exploration of their chemical derivatizations with due stress on techno-commercial
feasibility analysis, which is the objective of present investigations, is absolutely
necessary on the way to sustainable and economical usage of biomass as renewable
feedstock for organic chemical industries.
1.1 A. Vegetable oils and fats as feedstock for chemical industries, their world
production and economics
Lipids are water insoluble organic biomolecules that can be extracted from cells
and tissues by nonpolar organic solvents such as hexane, acetone, ether, chloroform etc.
and are widely distributed in nature. Lipids can be further classified as simple lipids (fats,
waxes), conjugated lipids (phospholipids, lipoproteins, glycolipids) and derived lipids
(terpenes, steroids, fat soluble vitamins [A, D, E, K], carotene, tocopherols, squalene).
The diverse utility as foods, fuels, lubricants and starting materials for other chemicals
result from the unique chemical structures and physical properties of lipids. Vegetable oils
are the most important renewable and readily available part of a large family of lipids.
The oils and fats of commerce are predominantly made up of triesters of glycerol
with fatty acids (FA) called triacylglycerol or triglycerides (Fig. 1.1). FA are almost
entirely straight chain aliphatic saturated, monounsaturated or polyunsaturated carboxylic
acids. The broadest definition includes all chain lengths, but most natural FA are C
4
to C
22
,
with C
18
most common. The principal raw materials from which the natural fatty acids are
derived are tallow, crude tall oil, coconut, palm kernel, sunflower, castor and soybean oils.
Crude oils or triglycerides, when first extracted (generally >95%), are accompanied by
diglycerides, monoglycerides and free FA, but they may also contain phospholipids, free
sterols and sterol esters, tocols (tocopherols and tocotrienols), triterpene alcohols,
hydrocarbons and fat-soluble vitamins. During refining, some of the minor components
are removed, wholly or in part, and useful materials may be recovered. For example,
phospholipids are separated during degumming, and deodoriser distillates contain fatty
acids, along with valuable sterols, sterol esters, tocols, etc.
3

R
3

O
O
O
O
R
1
O
O
R
2

Fig. 1.1 Structure of triglyceride (R
1
, R
2
, R
3
- alkyl

parts of different fatty acids)
The worlds production and consumption of natural oils and fats has grown from
79.2 million metric tones
7
(MMT) in 1990 to 117 MMT in 2001. The annual global
production of the major vegetable oils amounted in 2007/08 to 128 MMT, increasing in
2008/09 to 132 MMT, and in 2009/10 137 MMT are expected
8
. In addition, about 31
MMT of minor plant oils and animal fats were produced and consumed
9
. It is expected
that the average annual world oil production will increase in the years 2016 to 2020 to
184.7 MMT
10
. Sunflower seed oil is obtained from Helianthus annuus grown mainly in
Russia and Ukraine, Argentina, Western and Eastern Europe, China and the United
States
11
. World production of sunflower oil is around 9 MMT, amounting to 8% of the
total vegetable oil production
12
.

The projected production for 20082012, according to the
literature
10,13
, would be 12 MMT. Soybeans (Glycine max) are grown mainly in the United
States, Brazil, Argentina and China
11
. At almost 30 MMT per annum
14
(2006-10 forecast
33.6 MMT)
10
, soybean oil is produced in greater amounts than any other oil. Grown
mainly in Indonesia and the Philippines, the annual production of coconut oil [coconut
palm (Cocus nucifera)] exceeds 3 MMT
11,14
. Castor oil (Ricinus communis) is produced
mainly in India, Brazil and China at a world production level of 0.4-0.5 MMT
11,14
. India is
the worlds largest exporter of castor oil. Groundnut oil, obtained from the legume Arachis
hypogea, is also known as peanut oil, monkeynut oil or arachis oil. The plant is grown
widely, especially in India, China and the United States. Many of the nuts are consumed as
snacks, but crushing still yields about 5.5 MMT of oil each year
11,14
. In general, Malaysia,
Indonesia, and Argentina are prominent excess-supply producers of oils and fats while
India, the European Union countries, and China are notable high-demand areas that
supplement regional production through imports. In India, in the Oil Year 2007-08 (Nov.
2007- Oct. 2008), the net availability of edible oils from all domestic sources was 8.654
MMT while the consumption of Edible Oils was 14.262 MMT (source: Net availability
and consumption of edible oils: Directorate of Vanaspati, Vegetable Oils & Fats, India).
Thus the surplus requirement was met mainly through imports. Despite overall increases
4

in production of oils and fats, changes vary from year to year and individual oils may even
show a decline in particular years. The uneven changes from year to year result in
variations in the relation between supply and demand and consequently affect the stock
status. When stocks rise, prices fall, demand increases and production declines because it
becomes less profitable. On the other hand, when stocks fall, prices rise, demand is stifled,
but production then increases as profit margins grow. In this way the market takes care of
changes in agricultural production arising both from man-made decisions and from
changes in climate.
Oils and fats differ in composition of the alkyl chains depending on their origin.
Table 1.1 presents the FA composition of some commercially important vegetable oils.
Oils rich in saturated FA have poor low-temperature flow properties, and those rich in
polyunsaturated FA are of low oxidative resistance. Vegetable oils rich in
monounsaturated FA have optimum oxidative stability and low-temperature properties
15
.
The edible uses of vegetable oils include the preparation of shortening/ bakery fat,
vanaspati, margarines, and mayonnaise, besides routine use as cooking and frying oil and
as salad oil. In addition to food uses, the long-chain unsaturated FA vegetable oils such as
soybean, sunflower, and rapeseed have found their way into the plastics, pharmaceutical
products, inks, adhesives, coatings and many other industries. For example, the use of
soybean oil in lubricants
15
, oleochemicals
16
, and bioplastics
17
is reported. Vegetable oil-
based inks, which cost even less than the petroleum oil-based inks, have been formulated
for various specialized applications. Containing around 70% linoleic acid, the traditional
sunflower oil is semidrying oil and can be used, like soybean oil, in the manufacture of
resins for paint and press-ink formulations
18
.
Mineral-based lubricants lead the lubricant market. However, with the
advancement of the need for biodegradable products, vegetable oils have become popular,
because they are also better lubricants. Vegetable oils with high oleic (C
18:1
) content are
considered to be the potential environmentally friendly base fluids to substitute
conventional mineral oil-based lubricating oils, synthetic fuels (biodiesel, biogasoline) and
synthetic ester
19-21
. In view of the higher oxidative stability of high-oleic sunflower oil, it
is used as diesel and gasoline engine lubricant. The groundnut oil produced is virtually all
used within the countries of production for edible purposes. Coconut oil, the medium
chain saturated FA oil (mainly lauric C
12
and myristic C
14
FA), normally commands a
higher cost over other vegetable oils. It is an important source for the production of
emulsifiers, detergents, cosmetics etc. In toilet soap, high lauric content provides the quick
5

lathering properties. Castor oil differs from all other commercial oils in being rich in
ricinoleic acid (~90%, 12-hydroxyoleic). This hydroxy acid has several interesting
properties and is converted to a range of useful products to substitute those obtained from
petroleum such as lubricant, surface coating, nylon, perfumery chemicals and organic
intermediates for several industries. Long chain saturated FA (mainly stearic C
18
and
palmitic C
16
) oils such as palm oil, sal fat, mahuwa fat have relatively high oxidation
stability and provide the hard fat components of soaps.
1.1 B. Primary and secondary oleochemicals
The direct use of fatty oils for industrial purposes is limited to relatively small
applications. The chemistry and technology of oils and fats derived industrial products i.e.
oleochemicals run parallel to those of petrochemicals. Majority of the oleochemicals,
being derived from oils and fats, are straight long chain, even numbered, primary
functional compounds and their advantages including biodegradability and negligible
sulfur, nitrogen and heavy metal content can be illustrated by several of the principles of
green chemistry
22,24
.

Oleochemicals derived from splitting (hydrolysis) or transesterification of natural
fats and oils such as fatty acids (FA), mono-alkyl (mostly methyl) fatty esters (biodiesel-
substitute for diesel fuel), and glycerol, are termed as basic oleochemicals. Further
processing of these basic oleochemicals and their various fractions by different unit
processes/ chemical modifications, such as transesterification and esterification (e.g.
sucrose polyesters, monoglycerides), saponification and coprecipitation (metallic soaps)
hydrogenation and hydrogenolysis (e.g. fatty alcohols), ethoxylation (e.g. alcohol ethers),
sulphonation and sulphation (e.g. ester sulphonates, turkey red oil), ammonolysis and
amidation (nitrogen derivatives), ozonolysis (azealic/ pelargonic acids), epoxidation and
hydroxylation, dimerization and polymerisation, pyrolysis, alkali fusion (Fig. 1.2),
produce secondary oleochemical or specialty chemical products for utilisation as
surfactants, emulsifiers, lubricants, plasticizers, additives, bactericides, fungicides, etc.
Sunflower oil, either traditional or high oleic, may be used in bio-carburant in the form of
methyl esters. The use of vegetable oils as a substitute for petroleum-based diesel has
been replaced by the use of their methyl or ethyl esters as biodiesel. The importance of
biodiesel as a partial or total substitute for petroleum-based fuels has increased in the last
two decades. The fatty acid methyl esters (FAME) of soyabean oil are blended with diesel
fuel at a ratio of 20:80 for use in ignition engines
25
. The caproic to capric (C
6
C
10
) fatty
acid fractions, comprising approximately 15% in coconut oil, are good materials for
6

plasticizer range alcohol and for polyol esters. The latter are used in high-performance oil
for jet engines and for the new generation of lubricants. These acid fractions are also the
basic material for the manufacture of medium-chain triglycerides, a highly valued dietary
fat. Glyceryl monoesters and wax esters find application as food emulsifiers, mold release
agents, and lubricants for the plastic industry. In a variety of polymer applications, such as
coatings, large amount of solvents has to be used. Use of hydrocarbon and chlorinated
solvents provide volatile organic emissions with photochemical ozone creation potential.
Ester solvents, typically produced from FA and/or fatty alcohols, represent the largest
group of green solvents
26
. The production of FAME of soyabean oil as environmentally
friendly solvent is reported
27,28
.
The main non-food use of oleochemicals is in the production of surfactants. The
amphiphilic properties of fatty acids, exploited for centuries in the use of soaps, can be
modified by changing the carboxyl group into other hydrophilic groupings, giving anionic,
cationic, amphoteric and nonionic surfactants. Soap is one of the oldest known
oleochemical surfactant manufactured from saponification of oils. Fatty amines, produced
by the reaction of fatty acids with ammonia and hydrogen, are the most important nitrogen
derivatives of fatty acids. Polyglycol ethers, produced by the reaction of fatty alcohol with
ethylene oxide, constitute the most important class of nonionic surfactants. Monoalkyl
phosphate, fatty alcohol ether phosphate, and fatty alcohol sulfosuccinate are some of the
specialty surfactants derived from fatty alcohol with specific applications in the cosmetics
and other chemical industries. Alkanolamides, formed by the reaction of fatty acids or
esters with monoethanolamine or diethanolamine are popularly used as foam boosters for
shampoos and detergent products.
Parallel to the growth of the petrochemical industry, the fats and oils industry has
grown, and the oleochemistry has become an important area of research and technology in
several institutions and industries over the years. For long it has been considered that oil
and fat consumption was shared between food, feed, and industrial use in the ratio 80:6:14,
but with increasing production of biodiesel this is probably now closer to 74:6:20
29
. Many
new FA plants, with a cumulative capacity of 1.5 MMT have been built in Southeast
Asia
30
(coconut and palm oil producing region). Consumption of fatty acids in the United
States, Western Europe, and Japan totaled 2.5 MMT in 2001. There was a sharp decline in
production and consumption of fatty acid in North America after the events of September
2001. However, growth is expected at the rate of 2.3% for the consumption of split acids
for the period 20002006. Growth in Western Europe is expected at the rate of 1.2%/yr for

7

Table 1.1 Fatty acid composition of major vegetable oils
Sr.
No.
Name of
the Oil
S. V. I. V.
% Fatty Acid Composition
C
14
C
16
C
18
C
18:1
C
18:2
C
18:3
C
20
Any special fatty acid
1 Castor
0.945-0.965/
25
0
C
177-187
H.V.-160
83-86 ---- 2.0 1.0 7.0 5.0 ---- ----
Ricinoleic:86-90; 9,10
Dihydroxy Stearic: 0.7
2 Coconut
0.917-0.919/
25
0
C
251-263
7.5-
10.5
13.0-
19.0
8.0-
11.0
1.0-
3.0
5.0-8.0 0-1.0 ----
0-
0.5
C
6
: 0-0.8, C
8
: 5.0-9.0, C
10
: 6.0-
10.0, C
12
: 44.0-52.0,
Palmitoleic: tr -2.5
3 Groundnut
0.910-0.915/
25
0
C
188-195
84-
100
----
6.0-
9.0
3.0-
6.0
52.0-
60.0
13.0-
27.0
----
2.0-
4.0
Lignoceric: 1-3, Behenic acid:
1-3
4 Mustard
0.906-0.910/
25
0
C
169-176
98-
110
---- 1.5 0.4 22.0 14.2 6.8 ----
Erucic: 47.0 Behenic:2.0
5 Soyabean
0.916-0.922/
25
0
C
189-195
128-
143
tr.0.5
7.0-
11.0
2.0-
6.0
22.0-
34.0
43.0-
56.0
5.0-
11.0
----
----
6 Sunflower
0.915-0.919 /
25
0
C
188-194
125-
140
----
3.0-
6.0
1.0-
3.0
14.0-
35.0
44.0-
75.0
----
0.6-
4.0
Behenic: 0.8
7 Cottonseed
0.915-0.926
/15
0
C
191-196
103-
115
0.4 20.0 2.0 35.0 42 ---- ----
----
8 Palm
0.921-0.925
/15
0
C
196-205 48-58
0.5-
2.0
32.0-
45.0
2.0-
7.0
38.0-
52.0
5.0-11.0 ---- ----
----
9 Linseed
0.931-0.938/
15
0
C
189-196
170-
180
----
4.0-
7.0
2.0-
5.0
12.0-
34.0
17.0-
24.0
35.0-
60.0
0.3-
1.0
----

: specific gravity, I. V.: Iodine value, S.V.: Saponification value, H.V.: Hydroxyl value, C
6
: Caproic acid, C
8
: Caprylic acid, C
10
: Capric acid,
C
12
: Lauric acid, C
14
: Myristic acid , C
16
: Palmitic acid, C
18
: Stearic acid, C
18:1
: Oleic acid , C
18:2
: Linoleic acid , C
18:3
: linolenic acid , C
20
:
Arachidic acid.
8

the period 20012006. Japans consumption is expected to decline
30
. Recent data for the
Philippines listed a capacity of 25,000 t of alcohol products from coconut oil by the fatty acid
hydrogenation process for Cocochem and 4,000 t for Colgate. Philippians Kao produced
30,000 t of alcohol products from coconut oil using the methyl ester hydrogenation process
31
.
In 2008, biodiesel production and capacity amounted globally to 11.1 and 32.6 MMT,
respectively
32
. This is most remarkable because biodiesel as fatty acid methyl ester can also
be used as chemical feedstock. Moreover, genetic engineering offers a new way of
optimizing the properties of oleochemicals by controlling the FA distribution. This allows us
to change the composition of plant oils to control the structures that produce oleochemicals
with better properties. Thus the oleochemical industry is fairly well developed and its future
share of chemical industries, which currently stands at 10%, may go up because of a reliable
supply of raw materials.
1.1 C. Chemical modifications of vegetable oils for synthesis of oleochemicals
The physical and chemical properties of oils and fats can be modified through the use
of diverse derivatization pathways as shown in Fig. 1.2. In fact, chemical modifications of
vegetable oils constitute an important route to develop new efficient and environmentally
friendly reaction pathways leading to new products or to find new applications for already
existing oleochemicals
33
.This strategy can contribute to decrease our dependence on non-
renewable, and therefore limited, natural resources such as mineral oil. For example, a high
degree of multiple C=C unsaturations in the fatty acid (FA) chain (mainly linoleic C
18:2
and
linolenic C
18:3
FA) of many vegetable oils (e.g. soybean/ linseed/ sunflower/ safflower etc.)
causes poor thermal and oxidative stability and confines their use as lubricants to a modest
range of temperature. The bis allylic protons in FA chain are highly susceptible to radical
attack and subsequently undergo oxidative degradation to form polar oxy compounds, which
ultimately results in insoluble deposit formation and an increase in oil acidity and viscosity
34
.
Vegetable oils also show poor corrosion protection and the presence of ester functionality
renders these oils susceptible to hydrolytic breakdown. Although use of additives
35

(antioxidants and pour point depressants) can overcome these shortcomings to some extent,
the major way to improve these properties of vegetable oils is chemical modifications of fatty
acid chains of triglycerides at the sites of double bonds and carboxyl groups.
Thus the chemical modifications through application of various unit processes, as
shown in Fig. 1.2, are essential for obtaining oleochemicals with multifunctionality,
improved oxidative, thermal and photostability and good low temperature properties for
explorations in chemical industries
36,37
.
9

Fig. 1.2 Oleochemicals derivatization pathways
Hydro
-genation
Sulfonation
Diols /
Polyols
Hydroxylation
Fatty alcohol
sulfates
Azealic /
Pelargonic acids
Sebacic acid /
Octanol
Hydrogenated
Castor oil
Turkey red oil
Splitting

FAME/
bio-
diesel
Ozonolysis
Alkali fusion
Amidation
Epoxidation
Ethoxylation / Propoxylation
Hydrogenation
Sulfation
Esterification
Transesterification
F
a
t
t
y

A
l
c
o
h
o
l

Chlorination
Ethoxylation
Propoxylation
Sulfation
Esterification
Esters
-Sulfo FA esters
FA
alkanolamides
Epoxidised
triglycerides
Alkoxylated
triglycerides
Fatty alcohol
alkoxylates
Alkyl chlorides
Guerbet alcohols
Fatty alcohol
ether sulfates
Fatty alcohol
ether
phosphates
Fatty alcohol
sulfosuccinates
Phosph-
atization
Sulfitation
Sulfation
Guerbet
reaction
Esterification
Epoxidation
Ethoxylation
Polymerisation
Conjugation
Esterification
F
a
t
t
y

A
c
i
d
s

(
F
A
)

Self
Metathesis

Dibasic esters,
Hydrocarbons
Dimer acids
Saturated FA
Partial glycerides
Triacetin
Fatty Acid esters
Alkyl epoxy esters
FA ethoxylates
Conjugated FA
Glycerol
Hardening
O
i
l
s

a
n
d

F
a
t
s

10

The exact FA composition of various plant oils (Table 1.1) gives indications of the
most likely transformations and the probable characteristics of the oleochemicals formed
after chemical modifications, which are required to improve the physicochemical and
performance characteristics of these derivatives. The main compositional difference is the
chain-length distribution of the fatty acids associated with the fats or oils. The chain length of
the feed stock, C
12
-C
14
from lauric oils, C
22
from high erucic rape and fish oils, and C
16
-C
18
from most other sources, can be used to modify solubility, hydrophobicity and other
characteristics. The chemical modification of triglycerides is performed using the reactivity
of the functional groups in their structure. In respect of chemical modifications, oils and fats
carry following active chemical sites that can be used for derivatisation, functionalisation or
polymerization:
i) The terminal functional group mostly ester or carboxyl group- Traditionally,
industrial oleochemistry has concentrated predominantly on exploiting synthetic methods-
esterifications
38
, transesterifications
39
, hydrogenolysis, saponifications, acylation
40
etc.
applied to the carboxylic group of FA to synthesize major industrial oleochemicals.
ii) Single or multiple double bonds- Chemical modification of seed oils at the
unsaturated bond sites results in changes to the physical properties of the substrate and allows
products to be tailored to meet specific applications. Currently less than 10% of the
modifications have involved the hydrocarbon backbone of the fatty acid
41,42
.
iii) Carbon atom to the functional group- although the most reactive sites in fatty
acids are the carboxyl group and double bonds, methylenes adjacent to them are activated,
increasing their reactivity. Only rarely do saturated chains show reactivity.
iv) Secondary OH group- The presence of hydroxyl group on castor oil makes it vital
industrial raw material.
v) Other special functional groups- e.g. epoxy group in Vernolic acid present in oil
obtained from Euphorbia lagascae.
Carboxyl groups and unsaturated centers usually react independently, but when in
close proximity, both may react through neighboring group participation. The industrial
exploitation of oils and fats, both for food and oleochemical products, is based on chemical
modification of one of these five active sites. The continued development of oleochemistry
opens up for several reaction routes involving selective transformation of the alkyl chain, for
example sulfonation, with the potential of producing new highly-branched and charged
hydrophobes from abundant natural material
43
. The transformations by reactions of the
11

carbon-carbon double bonds in the fatty acids such as epoxidation and epoxy ring-opening
20

hydrogenation
44
, hydroformylation, hydrocarboxylation, ozonolysis, estolides formation
45
,
metathesis
46
and dimerization, are becoming increasingly important industrially for the
improvement in the oxidative stability and attaining the optimal characteristics for extreme
applications
47
. There is also scope for functionalizing the aliphatic chain, but this has not
been widely used commercially. Introducing functionality to the alkyl chain through radical,
electrophilic, nucleophilic, pericyclic, and transition metal catalyzed addition to carbon-
carbon double bonds leads to novel compounds with commercial potential. The chemical
transformation of triglycerides affords a wide variety of monomers for the synthesis of
linear
45
, hyper-branched
48
or cross-linked structures
49
.
Subsequent sections present literature review on chemical modifications undertaken
in present investigations.
1.2 Sucrose esters
Although scientists have reported numerous ways of making surfactant linkages
(amphiphilic) for a large number of different carbohydrates used, it is clear from an industrial
perspective that only a few carbohydrates such as sucrose fulfil the criteria of price, quality,
and availability to be an interesting raw material source. Sucrose (C
12
H
22
O
11
) is one of the
most abundant, renewable and inexpensive international agricultural carbohydrate products in
the world, found in sugar cane, sugar beet and many other plants. It is produced at a very high
scale of production volume of 130 MMT per annum [The figure, estimated by Cerestar,
Henkel, is based on the crop cycle of 2002-03]. According to the revised estimate of ISMA
(Indian Sugar Mill Association), the annual production of sugar in 2012 at the end of
sugarcane season would be 24.3 MMT. The data indicates the abundant availability of sugar
as raw material for chemical industries. Chemical transformations of sucrose are much
developed in the fermentation domain, in order to produce alcohol, yeast, organic acids, etc.
Another strategy (sucrochemistry) is to keep the disaccharidic structure with the goal of
taking advantage of its physical properties (polarity, hydrophilicity, biodegradability, higher
compatibility with biological systems, low toxicity, skin-compatibility etc.) and bringing
them into a new molecule. In this respect, the targets are nonionic surfactants, eco-friendly
detergents, associative polymers, rheology modifiers, sweeteners, body builder, fat
substitutes, non digestible oligosaccharides etc
50-52
.
Sucrose monoester (SE) is a green surfactant while sucrose polyester (SPE) is a low
calorie fat substitute, both being derived by transesterifying sucrose with edible oil/ fatty
acids or esters either by chemical or enzymatic processes. Development of the technique for
12

synthesis of sucrose esters was one of the first major achievements of the Sugar Research
Foundation
53
.
1.2.1 Synthesis and characterization of sucrose esters
Considering the amphiphilic structure of a typical surfactant with a hydrophilic head
group and a hydrophobic tail, it has always been a challenge to attach a sucrose molecule as
the perfect hydrophilic group, due to the numerous (eight) hydroxyl groups, to a fat and oil
derivative such as fatty acid/ester/ alcohol
54
. Sucrose is a disaccharide of -glucose and
fructose. These two moieties are connected at their anomeric carbon atoms. It does not
contain a hemi-acetal linkage and so, it is a nonreducing sugar. Its chemistry is then limited to
its eight hydroxyl groups, of which three are primary (C
1
, C
6
and C
6
) and five are secondary,
which compete during the derivatization step with methyl esters of fatty acids derived from
edible fats and oils including hydrogenated fats and oils such as stearic acid, palmitic acid,
erucic acid and other fatty acids. The primary site for transesterification appears to be the 6
th

position of the glucose portion of the molecule
55
. The base catalyzed transesterification
reaction proceeds faster than its acid catalyzed counterpart
56
.
Typically, the sucrose esters are prepared through the base catalyzed
transesterification of sucrose with vegetable oils/ fatty acid methyl esters, using sodium
methoxide or potassium carbonate or alkali metal soaps as a catalyst and in the presence of
suitable basic solvents such as dimethyl formamide (DMF), dimethyl sulfoxide (DMSO),
isobutanol, or methyl ethyl ketone
57,58
(Fig. 1.3). Methanol is released as a by-product
through this reaction. Its removal by distillation during synthesis (semi-batch process) drives
the equilibrium in favor of the sucrose ester and improves the yield of the desired product.
Lithium soap, as catalyst, will shorten ester exchange time 2-3 hr relative to other method and
the yield of production is high. In general, mixed alkali metal soap (lithium oleate and
sodium oleate) with proper ratio as catalyst can improve the yield of sucrose ester
59
. A
complex product mixture consisting of mono-, di-, tri, tetra-, and pentaesters is formed. The
reaction is stopped by the addition of lactic acid to neutralize the reaction mixture. Through
the choice of sucrose to fatty acid mole ratio, reaction time, speed of methanol removal, the
ratio of mo-, di-, and polyester can be influenced. It is difficult to obtain pure monoesters by
this route because they disproportionate to sucrose and diesters. Hence diester predominates
at lower reactant ratios
60
(2:1). Co-proportionation of diesters with sucrose resulted in
monoesters which still contained 10% diester. By varying the degree of esterification of the
sucrose molecule it is possible to obtain emulsifiers with HLB values ranging from 1 up to 16
13

for the high SE content. SPE products (higher degree of substitution) are very hydrophobic
and of limited application potential.

O
O H
OH
OH
O
OH
O H
O
OH
OH
OH
O
OR
OR
OR
O
OR
OR
O
OR
OR
OR
R'COOMe
MeOH
+
-
Sucrose
Sucrose ester
R= RCO, H
R= C
12
, C
16
, C
18
, C
18:1

Fig. 1.3 Synthesis of sucrose esters by base catalysed (K
2
CO
3
) transesterification with
FAME.
The conventional base-catalyzed high temperature production of sucrose esters has a
low selectivity, forming coloured derivatives as side products
61,62
. Several methods have been
developed to achieve higher selectivity in the reaction or provide economical purification
procedures and, as a result, a high quantity of hydrophilic monoester or hydrophobic
polyester. Increase in the monoester content was achieved in a sucrose laurate product by
alcoholysis with methanol
63
. An alternate improved one-step process involves dissolving
sucrose ester in propylene glycol and emulsifying methyl esters into this solution followed by
thin film reactive distillation. The glycol is distilled off and in the distillation process,
transesterification takes place. It permits greater yields of the polyesters at 110-145
0
C within
5 hrs, eliminating use of toxic solvents and more efficient removal of byproducts
64,65
. Procter
& Gamble holds two patents on synthesis of SPE
66,67
during 2005-06. The direct esterification
of sucrose with fatty acid chlorides
68
is reported. Powdered white granulated sugar and
methyl carbityl palmitate were reacted using different metal soaps as catalyst at 185
0
C
59
.The
base-catalyzed synthesis of four sucrose fatty acid esters (caprylate, laurate, myristate, and
palmitate) was performed in DMSO by transesterification of sucrose with the corresponding
vinyl esters using disodium hydrogen phosphate as catalyst. In using a molar ratio sucrose/
vinyl ester 4:1 and mild reaction conditions (40
0
C and atmospheric pressure), yields were
higher than 85%. The isolated sucroesters had a higher percentage of monoesters (around
90%) and a lower content of diesters in comparison with commercial derivatives. In all cases,
2-O-acylsucrose was the major product (around 60%) in the monoester fraction. For example,
72% yield of 2-O-lauroyl sucrose was obtained at 40
0
C for 5 hrs with vinyl laurate as acyl
donor
69
. The author holds patent for this improved procedure
70
. A highly regioselective
14

conversion of sucrose into 6-O-acyl derivatives is reported. First sucrose was transformed
into the dibutyltin acetal, thus enhancing the nucleophilicity at the C
6
oxygen and restricting
the subsequent acylation reaction
71
. The enzyme-catalyzed synthesis of sugar esters provides
regio- and stereo selective products
72-74
. Enzymatic sugar ester syntheses catalyzed by an
immobilized lipase were investigated, including the solubility, water content, molar ratio of
sugar/acyl donor, and enzyme stability
75
. Enzymatic synthesis of fatty acid esters of di- and
tri-saccharides is limited by the fact that most biological catalysts are inactivated by the polar
solvents (e.g. DMSO, DMF) where these carbohydrates are soluble. To overcome this
limitation, the uses of mixtures of miscible solvents (e.g. DMSO and 2-methyl-2-butanol)
were proposed as a general strategy to acylate enzymatically hydrophilic substrates.
However, most of the above methods remain limited to laboratory scale because of
the process economics. Standard technology (conventional method, Fig. 1.3) for production
of SE/ SPE is still the transesterification combined with a series of purification steps to
remove impurities and residual solvents. The purification procedures include the use of
solvents, special extraction and crystallization techniques, and equilibrium reactions. The
sugar was precipitated from the reaction mixture by adding toluene, xylene, butanol or
isobutanol as a solvent. The solvent permits separation into a plurality of layers containing
sucrose esters of different degrees of substitution, which are recovered from the separate
layers. Mixing with water and freeze-drying the aqueous mixture may further refine the
separate layers. Reaction and extraction solvents and methanol are removed by the distillative
concentration/ purification processes. Vacuum may be applied to accomplish the distillation
at lower temperature. As a consequence of the manufacturing process, several trace
impurities may be found in the final purified products. An optimized solvent-free process
using water for removal of impurities and spray process for drying of product has been
described
76
. Transesterification of sucrose in excess FAME (without additional solvent) at
about 140
0
C (around 20 hrs) and simultaneous removal of methanol to form sucrose esters
with a high degree of esterification (DE= 4), subsequent alcoholysis of the sucrose ester by
addition of methanol at 75
0
C in two steps (step 1 transesterification: 45 min, step 2
transesterification: 75 min) to form sucrose monoester and FAME, and removal of residual
methanol and FAME using a thin-film evaporator (160
0
C, 0.20.3 mbar)
63
permit high yield
of sucrose monoesters. Product analysis by high-performance liquid chromatography shows
the increase of the sucrose monoester (SE) content to 48% (DE= 1.8, reaction A) and 57%
(DE= 1.6, reaction B) relative to sucrose diester and sucrose oligoesters (SPE). The Japanese
15

firm of Dai- Nippon has utilized large excess of sucrose and K
2
CO
3
as a catalyst, for
manufacture at 90
0
C under vacuum
77
. Today, the major producers of sucrose esters are Dia-
Ichi Kogyo Seiyaku and Mitsubishi in Japan, Croda in the United States, Sisterna (a joint
venture of Dai-Ichi with Suiker Unie from The Netherlands), and Goldschmidt in Germany.
Thin layer chromatography (TLC) has been widely used as a preliminary qualitative
technique for the analysis of SE/ SPE to give an impression of the reaction. This technique is
considered as a rapid, advantageous and simple method for the preliminary investigation of
SE/ SPE synthesis. HPLC is an efficient tool for analyzing and quantifying SE/ SPE in a
reaction mixture. This technique is more convenient than gas chromatography as it does not
require previous derivatization of the sample. Many procedures for SE/ SPE separation with
HPLC were reported with the different eluent systems.
1.2.2 Reaction mechanism and kinetics of synthesis of sucrose esters
The transesterification reaction mechanism
78
of base catalyzed synthesis of sucrose
esters is shown in Fig. 1.4 which proceeds by a two stage transesterification process.
n
C H
3
O
OCH
3
+
Sugar
-
O
n
C H
3
OCH
3
O
-
O
Sugar
n
C H
3
O
O
Sugar
+ C H
3
O
-
n
C H
3
OCH
3
O
-
O
Sugar
Sugar OH
+
Base Sugar O
-
+
Base H
+

Fig. 1.4 Reaction mechanism of base catalyzed transesterification between sugar
polyols and FAME
78

Potassium soaps provide a homogeneous melt of sucrose and fatty acid methyl esters.
Initially, the base reacts with the alcohol, producing an alkoxide and the protonated catalyst.
The alkoxide then attacks the carbonyl group of the fatty acid methyl ester. This nucleophilic
attack generates a tetrahedral intermediate. The alkyl ester and the anion of the fatty acid are
then formed. The anion deprotonates the catalyst and generates an active species which reacts
with a molecule of the alcohol, starting another catalytic cycle.
The rate constants, activation energies, Arrhenius factor and mechanism of inhibition
for base catalyzed hydrolysis of sucrose laurate, sucrose sulphenyl laurate and sucrose ethyl
laurate were investigated at several temperatures in pH 11 buffer. At 27
0
C sucrose laurate
16

hydrolyzed fastest and sucrose ethyl laurate slowest
79
. A kinetic model for the synthesis of
the sucrose esters without solvent is developed. It implies a solid/solid/liquid reaction
between sucrose (solid) and methyl palmitate (liquid). The second solid (potassium
carbonate) acts as a catalyst. The reaction medium is heterogeneous and pasty. The viscosity
increases with the chemical reaction extent. Activation step of sucrose (solid) by potassium
carbonate (solid) is taken into account which corresponds to the overcrossing of the
interfacial barrier and the contact between the two solids and is associated to the viscosity of
the medium. The second important parameter is molar ratio, which takes into account the
hydrophobic effect during the formation of diesters
80
. The literature describes several
molecular models of heterogeneous kinetics, for example:
Park and Levenspiel model
81
: it represents conversion versus time with S shape
curves.
Hao-Tanaka model
82
: it describes the reaction between two solids and takes into
account the number of contact points between the particles.
The shrinking core model and the uniform conversion model
83
.
1.2.3 Properties and applications of sucrose esters
Sucrose esters (SE/ SPE) occur as white to yellow-brown powdery or massive
substances, or as colourless to red-brown, viscous resinous or liquid substances. Sucrose
monolaurate forms clear, low viscous aqueous solutions at 30% strength while those of C
16
-
C
18
fatty acids forms gels. SPEs, however, are completely water insoluble. They are stable at
pH 4 to 8 and at temperatures up to 180
0
C. Sucrose monooleate, however, decomposes at
120
0
C. The physical and chemical properties, including the lipophilic character, of the
sucrose esters vary depending on (i) the alkyl chain length of acyl group, (ii) the degree of
substitution or number of hydroxyl groups replaced by ester groups in the compound, (iii) the
degree of unsaturation of the acyl chain.
i) SE as non-ionic surfactant
Sucrose ester with three or lesser fatty acids is suitable as surfactants and food
additives because of their emulsifying, stabilizing, and conditioning properties
84,85
. The
amphiphilic behavior of sucrose based surfactants result from the hydrophilic free hydroxyl
groups and hydrophobic alkyl chain. The uses of surfactants are determined by the particular
functionality with respect to their solubility in oil and water which can be expressed and
quantified as their hydrophilic-lipophilic balance or HLB value. Wide range of HLB values
ranging from zero to twenty, are obtained by changing the characteristics of the fatty acid
used in their preparation
86
. Unlike the alkyl ethoxylates, the sucrose esters do not
17

significantly change their HLB with increasing temperature. Consequently, increasing the
temperature does not induce a phase inversion in micro emulsion systems based on sucrose
esters, as was observed in micro emulsions based on alkyl ethoxylate
87
. The properties of
sucrose esters can range from water soluble surfactants (high HLB, most hydrophilic) to oil
soluble surfactants (low HLB, most hydrophobic) as shown in Table 1.2. HLB values of
some pure SE is as given below
88
: sucrose monostearate(C
18
)-11.2, sucrose
monopalmitate(C
16
)-11.8, sucrose monomyristate(C
14
)-12.4. Thus with decrease in chain
length from C
18
to C
14
, the hydrophilicity of SE increases. The softening temperature and
surface tension of 1% solution of sucrose monolaurate were 90-91
0
C and 33.4 dynes/cm.
respectively
89
. The CMC (mol/lit) of 6-O-lauroyl sucrose and 6-O-myristyl sucrose at 30
0
C
were found to be 5.14-5.31 X 10
-4
and 0.71-0.88 X 10
-4
, respectively. These CMC values are
lower than those of ethoxylates
71
. Thus SE of fatty acids having 12 or more carbon atoms (at
low degree of substitution, preferably monoester) are expected to display surface active
properties. Long chain SE have shown promise as surfactant and compare well in foaming,
wetting, emulsification and overall detergency performance with other surface-active
compounds and for some applications even superior
58,90
. They are not sensitive to hard water,
and some of the SEs are moderate foaming agents
91
. Mixtures of regioisomers, as well as
mono-, di- and triesters are used as emulsifiers, whose resulting physicochemical properties
depend on the average degree of substitution and fatty acid chain length.
Table 1.2 Approximation of HLB values of surfactants as a function of their solubility in
water
92

Solubility in water HLB Values* Description
Insoluble 4-5 Water in oil emulsifier
Poorly dispersible 6-9 Wetting agent
Translucent to clear 10-12 Detergent
Very soluble 13-18 Oil in water emulsifier

*HLB = (L/T) x 20 (L and T referred to the molecular weight of the hydrophilic (sucrose) part of the
molecule and the total molecular weight, respectively)
Sucrose esters have a wide variety of applications. SE has excellent non ionic
surfactant and emulsifier properties that are desirable and promising in food, personal care,
detergent, bleaching booster, cosmetic, fine chemical, oral-care and medical applications
93-97
.
Besides this, they have received considerable attention due to their recent availability in
commercial quantities, together with their tasteless, odourless, nontoxic, biocompatible,
biodegradable and noncumulative characters
98,99
. SEs were approved in 1959 for use as food
18

additives in Japan
90
. They are mild toward the skin and eye and possess lower hemolytic
activity than many other types of surfactants. However, depending on the nature of the
hydrophobic moiety, some sugar-based surfactants possess rather high haemolytic activity.
Sucrose esters have been studied for effective preservation of the quality of fresh produce
100
.
Phosphorylated sucrose stearate showed a higher solubility and better emulsifying properties
than sucrose stearate and improved the thermal behaviour of potato starch by increasing the
gelatinization temperature, decreasing the viscosity and inhibiting retrogradation
101
.
Fatty acid esters of mono- and di-saccharides, produced commercially by Mitsubishi-
Kagaku (Tokyo, Japan) and Sisterna PV (Roosendaal, Netherlands), are effective emulsifiers
found in a variety of food, cosmetic, and pharmaceutical products such as chocolate,
toothpaste, lotions, shampoo, and lipstick
87,102,103
. They possess excellent antimicrobial
activity as well
104
. Some possible applications for sucrose based polymers are drug delivery
systems, dental medicine, bioimplants, contact lenses, and tissue engineering
105,106
. The most
common pharmaceutical application of SE is for the modification of bioavailability, often
with the hot-melt method. Use of SE as surfactants in the development of microparticulate
systems for parenteral delivery of protein and gene medicines was investigated
107
.
SE has shown remarkable use as surfactant in stabilized synthesis of nanoparticles.
Huang
108
synthesised indium sulfide nanorods in water-in-oil (w/o) microemulsion system
using food grade SE as biosurfactant. Titanium dioxide nanoparticles were prepared via
hydrothermal processing route, which utilized SE as a stabilizing agent
109
.
Sucrose esters are more soluble in t-pentanol than glucose esters. Dimethyl sulfoxide
provides good solvency, especially in the case of glucose and sucrose monoesters
110
. Sucrose
esters display significant activity against several clinical isolates. They have increasing
interest due to advantages with regard to the performance, the consumer health and the
environmental compatibility compared to petrol-derived standard products
62
. They have
antibacterial properties and can also be used as lubricants
97
. SE also shares a number of
insecticidal properties with other surfactant
111
. SEs composed of C
6
-C
12
fatty acids have
desirable insecticidal properties against many soft-bodied arthropod pests
112
. Sucrose esters
are currently used as additives in the food industry which makes them especially attractive as
safe and effective insecticides. The combination of particular characteristics such as
emulsifying, anti-adhesive (inhibition and disruption of biofilms formed in food contact
surfaces) and antimicrobial activities presented by sucrose esters suggests potential
application as multipurpose ingredients or additives
113
.
19

ii) Sucrose polyesters (SPE) as fat substitute
SPE has physical and organoleptic properties similar to those of cooking and frying
fats and are digested as a blend of sucrose and fatty acids in the stomach
93
. Olestra, a non-
caloric fat substitute, is a SPE with moderate to high degree of substitution (six or more fatty
acids per sucrose molecule) and has been developed by Proctor and Gambel in the early
1970s and marketed under the brand name Olean
114
. It has been approved by the FDA as a
food additive used in preparing low-fat deep-frying foods such as savoury snacks. These
compounds are lipophilic, nondigestible and nonabsorbable molecules with physical and
chemical properties similar to those of triglycerides, but it is not digestible by lipolytic
enzymes.
1.3 Epoxidation of vegetable oils and fatty acids
Epoxidation is the reaction (Fig. 1.5) between double bonds in olefinic compounds
(unsaturated fatty acid, alkyl ester, or oil) and organic peroxy acid [RC(=O)OOH, oxygen
transfer reagent] to obtain (three-membered) cyclic ethers called epoxides. The reaction is
catalysed by homogeneous catalysts such as H
2
SO
4
, p-toluene sulfonic acid
115
, heterogeneous
catalysts such as transition metals of variable valence, acidic ion exchange resin
116
or
enzymes
117
. The peracid is either preformed or prepared in situ by equilibrium reaction (Fig.
1.5) between hydrogen peroxide (preferably high strength e.g. 70% w/w) and carboxylic acid
[formic or acetic acid or other acids]/ corresponding anhydride or acid chloride. The
carboxylic acid is regenerated after epoxidation which proceeds by a concerted mechanism,
giving cis stereospecific

addition
118
(Fig. 1.6). Thus, a cis olefin leads to a cis epoxide and a
trans olefin to a trans epoxide. For example, epoxidation of oleic acid generates cis-9, 10-
epoxy stearic acid, while that of linoleic acid gives a mixture of two cis, cis diastereoisomeric
bis- epoxides. The carboxylic acid produced is a stronger acid than the strongly hydrogen
bonded peracid and may lead to subsequent ring opening reactions especially in the case of
formic acid producing dihydroxy and hydroxy carboxylates as byproducts. Hence complete
epoxidation is never achieved in the acidic medium.
RCOOH
+
H
2
O
2
H
+
R
O
O OH
+
O H
2
+
C H
3
C H
3
CH
3
CH
3
RCOOH
+
C H
3
C H
3
CH
3
CH
3
O
R
O
O OH

Fig. 1.5 I n situ peracid epoxidation reaction
20

+
O
R
O
O
H
CH
3
C H
3
CH
3
C H
3
O
CH
3
C H
3
CH
3
C H
3
+
O
R
OH

Fig. 1.6 Mechanism of peracid epoxidation
118

1.3.1 The performic/ peracetic epoxidation process
The industrial scale epoxidation process, referred as Prileschajew reaction, is most
frequently carried out with preformed or in situ generated peroxyacetic acid or peroxyformic
acid due to their low cost (particularly the peracetic acid process) and easy availability
119,120
.
Moreover epoxidation with peracids is irreversible (if the acid does not contain
admixtures). On the other hand, problems related to this method are associated with the
strongly exothermic character of this reaction and the risk of explosion resulting from the
necessity of operations with concentrated solutions of peracids. These problems imply the
necessity for strict control of temperature and reaction time. The in situ generation of
peracids is mostly preferred because, when the organic peroxyacid is preformed, there are
some safety issues associated with its storage since the concentrated peroxyacid is unstable
and explosive
121,122
. Moreover the in situ process operates with a lower concentration of
aliphatic acids. On the other hand, the presence of an acid during in situ epoxidation causes
the opening of the oxirane ring with formation of undesirable secondary products. In ex situ
process, the acid is eliminated from preformed peracid by neutralizing it with a buffer or
filtering. With preformed peroxyacetic acid, the conversions, yields and selectivity were
higher than those with the in situ formed peroxyacetic acid.
The rate of generation of peroxyformic acid is much greater than that of peracetic
acids. Formation of peroxyacetic acid requires an acidic catalyst such as sulfuric acid
123
.
Between the in situ-generated performic and peroxyacetic acid, latter has certain advantages
such as need of minimum amounts of reactants in the preparation of epoxidizing reagent and
convenience and safety of preparation, handling and stability of peroxyacetic acid at
moderate temperatures
124
. Patwardhan et al
125
worked on the epoxidation of cottonseed oil
using in situ generated peracetic/ performic acid catalysed by liquid inorganic acid. While the
rate of formation of oxirane was higher with formic acid, acetic acid was more effective
oxygen carrier, promoting the transport of the oxygen from the aqueous phase to the oil
phase
126
. It also functions as a catalyst in the formation of the oxirane ring
127
. H
2
SO
4
was
found to be the most efficient and effective catalyst. But being strong acid, it leads to many
side reactions such as oxirane-ring opening to diols, hydroxyesters, estolides and other dimer
21

formations. Furthermore it causes the equipment corrosion and must be neutralized and
removed from the end product
128
. Ikhuoria et al
129
observed that the in situ peracetic acid
epoxidation of the methyl esters of parkia biglobosa seed oil could be carried out in a
moderate temperature range of 50-70
0
C. Peracetic acid resulted in a 10% higher conversion
of double bonds to oxirane
116
and caused the lower amount of undesirable products formed
over that by performic acid. An explanation for this is that due to the very high activity of the
formic acid, the hydrogen peroxide is rapidly decomposed leaving the batch oxygen
depleted
37
. Cationic ion-exchange resins are versatile heterogeneous catalysts and offer
several advantages over the homogeneous acid catalysts. Use of acidic ion exchange resin
catalysts would reduce corrosion problem, avoid disposal of strong acids, and present better
product recovery. The catalyst can be recycled, shows better selectivity, and avoids side
reactions
130
. However the rate of resin catalysed epoxidation slows down in comparison to
that of homogeneous epoxidation. The heterogeneous method seems to be tedious due to the
difficulty of separating the product from the resin.
1.3.2 Other techniques of epoxidation
A cheap and green epoxidiser would be molecular O
2
.

But when used in the
epoxidation of vegetable oil, it leads to the degradation of the oil to low molecular weight
volatile compounds such as aldehydes and ketones as well as short chain dicarboxylic
acids
131
. Organic peroxy acids, other than peroxyformic or peroxyacetic acids, may be more
convenient in the laboratory or for small-scale reactions. These include the peroxy acids
derived from trifluoroacetic, lauric, benzoic, m-chlorobenzoic acids, and m-nitrobenzoic acid.
Monoperoxy acids derived from succinic, maleic, and phthalic anhydrides can also be used.
The order of reactivity of some peracids is: m-chloroperbenzoic > performic > perbenzoic >
peracetic; electron withdrawing groups promote the reaction. Some of these can be safely
stored at 0-20
0
C to avoid hazards of its decomposition. Small scale reactions are carried out
with m-chloroperbenzoic acid in a halocarbon or aromatic solvent, in the presence of
bicarbonate to neutralize the carboxylic acid as it is formed
132
.
Recent studies have attempted enzymatic procedures to improve the efficiency of
epoxidation under milder conditions that minimize the formation of byproducts. Chemo-
enzymatic epoxidation
133
uses the immobilized lipase from Candida antartica (Novozym
435) to catalyze conversion of fatty acids to peracids with 60% hydrogen peroxide. The fatty
acid is then self-epoxidized in an intermolecular reaction. The lipase is remarkably stable
under the reaction conditions and can be recovered and reused 15 times without loss of
activity. Competitive lipolysis of triacylglycerols is inhibited by small amounts of fatty acid,
22

allowing the reaction to be carried out on intact oils
134
. Rapeseed oil with 5% of rapeseed
fatty acids was epoxidised in 91% yield with no hydroxy byproducts. Sunflower, soybean,
and linseed oils have been satisfactorily epoxidised by this route using 35% hydrogen
peroxide with 5 mol% of free fatty acid
134
and in a batch stirred tank reactor at atmospheric
pressure
135
. Corn oil rich in oleic and linoleic acids, was also epoxidized in a similar manner
but using stearic acid as an active oxygen carrier
136
. Methyl esters are also epoxidized
without hydrolysis under these conditions.
Epoxidation is also feasible with dimethyl dioxirane (DMDO), made from potassium
peroxymonosulfate (KHSO
5
) and acetone. The most common of inorganic peroxides is nitrile
hydrogen peroxide, which catalysed by a transition metal catalyst
131
. Halohydrines, using
hypohalous acids (HOX) and their salts as reagents, are also used for the epoxidation of
olefins with electron deficient double bonds. But the process is not ecofriendly.
Different novel approaches to epoxidation have recently been reviewed
137,138
.
Compounds of second-row transition metals- rhodium and ruthenium and the oxides of
rhenium and tungsten have attracted particular interest as catalysts to affect the epoxidation
of olefins, some with excellent regio-, stereo- and enantio- selectivities. Silver, however,
produces very low rates of double bond conversion and is also only effective on very simple
ethylenic substances. Methyltrioxorhenium (MTO, MeReO
3
) or tungstates catalyses direct
epoxidation by hydrogen peroxide. MTO reacts with hydrogen peroxide to give
organorhenium peroxo complexes. The reaction is carried out in presence of large excess of
nitrogenous bases, particularly pyridine under biphasic conditions, avoiding acidic conditions
detrimental to high epoxide yield and uses less concentrated hydrogen peroxide (30%) than
other methods
139
.This method epoxidized soybean
140
and metathesized soybean oil in high
yield
141
with higher product selectivity and catalyst lifetime. The epoxidized metathesized oil
was more stable to polymerization than that produced using m-chloroperbenzoic acid,
presumably because it was free of acidic impurities. Hyeon et al
142
fabricated molybdenum
oxide nanoparticles incorporated into a mesoporous silica shell that are coated on dense
silica-coated magnetite nanoparticles and demonstrate a magnetically recyclable epoxidation
catalyst. Alumina catalysed sol-gel process was evaluated for the epoxidation of unsaturated
fatty esters using anhydrous or aqueous hydrogen peroxide as oxidant and ethyl acetate as
solvent. The alumina shows a good catalytic activity and excellent selectivity towards the
epoxides. The sol-gel alumina was more efficient and when using aqueous hydrogen
peroxide, it could be recycled several times
143
. None of these methods have yet found
feasibility at industrial scale.
23

1.3.3 Influence of reaction parameters on extent of epoxidation and kinetic and
thermodynamic modelling of epoxidation
Epoxidation is a consecutive reaction and its success depends on the control of
available conditions for minimisation of opening the rings. The rate of performic acid
production, for ex situ process, is at least 4 X 10
4
faster than the rate of epoxidation
144
. This
means that whenever a performic acid molecule reacts, another performic acid molecule is
generated before any further epoxidation occurs. On the other hand, peracids are unstable,
and the reaction is exothermic. The concentration of peracid is therefore kept low by using a
low concentration of the carboxylic acid either in the neat oil or in a hydrocarbon solvent.
Industrial epoxidation is conducted in two-phase polar (aqueous H
2
O
2
)-organic (oil plus
solvent) systems. The presence of an inert solvent (e.g. xylene, toluene) in the reaction
mixture appeared to stabilize the epoxidation product and minimize the side reaction such as
the opening of the oxirane ring, especially at higher temperatures
145
. It is important to
minimize the presence of protons originating from either the acid or the catalyst and work at
low temperatures. Ring opening cannot be totally avoided, but proper control may be attained
by working at low temperatures, say 20-35
0
C. The progress of the epoxidation reaction, as
measured by the changes of the hydroxyl value, iodine number and epoxy number, is used to
estimate the fractional conversion, yield, and the selectivity of transformation to epoxidized
oil/ fatty acids/ ester. The structures of the products are confirmed by thin layer
chromatography (TLC), fourier transform infrared spectroscopy (FTIR), and nuclear
magnetic resonance (NMR) analysis.
The influence of the several reaction parameters such as temperature, hydrogen
peroxide: peracid: vegetable oil molar ratio, type of peracid, type and loading of catalyst,
stirring speed and reaction period on epoxidation rate as well as the oxirane ring stability for
the in situ inorganic acid catalysed (homogeneously catalysed) peroxyacid epoxidation of
rapeseed oil
146
, mahua oil
131
(Madhumica indica), cottonseed oil
125
, soybean oil and jatropa
oil
147
were examined. Elevation of the temperature from 30 to 60
0
C caused a decrease of the
iodine number, while the value of the epoxy number rapidly decreased above 60
0
C for the
formation of epoxidised rapeseed oil. Increasing temperature showed a favorable effect on
the formation of peracetic acid during the epoxidation of mahua oil. Acetic acid was found to
be superior to formic acid for the in situ cottonseed oil epoxidation. In general, with an
increase in hydrogen peroxide-to-ethylenic unsaturation molar ratio, there was a progressive
increase in the rate of oxirane formation. However, the correlation between decrease in the
final iodine value and the corresponding increase in the final oxirane value were relatively
24

less when the ratio was increased beyond particular magnitude, specific to individual oils.
This may be attributed to the higher hydrogen peroxide concentration leading to an
accelerated rate of oxirane ring decomposition. To attain the maximum oxirane oxygen
content in peroxyacetic acid epoxidation, the optimum level of the acetic acid should be used
where both the effects (catalytic effect counteracting hydrolysis) are balanced considering the
amount of acid required in the formation of peracetic acid. The maximum reaction conversion
was 83.3% for the epoxidation of soybean oil and 87.4% for the epoxidation of jatropha oil. It
was possible to obtain up to 78% relative conversion to oxirane with very less oxirane
cleavage by in situ sulfuric acid catalysed epoxidation of cottonseed oil. The order of
effectiveness of catalysts was found to be sulfuric acid > phosphoric acid > nitric acid >
hydrochloric acid. For a two-phase epoxidation reaction mixture, different solubility of
peracid in the organic phase can have a large effect on the kinetics. Thus to safely avoid mass
and heat transfer effects, a stirring speed of higher order feasible with the given system
should be chosen. Okieimen et al
121
have shown that the negligible oxirane cleavage and
almost complete epoxidation of rubber seed oil by in situ peroxyacetic acid process could be
achieved.
In a similar manner, the effect of different reaction variables on heterogeneous in situ
cationic exchange resin- Amberlite IR-120 catalysed peracid epoxidation of soybean oil
148
,
jatropha oil
124
and castor oil
149
was evaluated. With an acidic ion exchange resin as the
catalyst for the epoxidation of vegetable oils, the porous structure of the solid catalyst and the
size of the natural unsaturated triglycerides were found to minimize side reactions and thus
improve selectivity
150
. At lower temperatures (30, 50 and 70
0
C), peroxyformic acid was
found to be more efficient, while at higher temperature (85
0
C), peroxyacetic acid was equally
good and an optimum in the ion exchange resin catalyst reactivity was observed at 70
0
C for
the formation of epoxidised jatropha oil. The extent of the side reaction is negligible with
peracetic acid in the entire temperature range and somewhat higher with performic acid at
85
0
C for epoxidation of castor oil. The optimal conditions (91% conversion, 5.99% epoxide
content in product) for peracetic epoxidation of soybean oil were found to be: 0.5 mole of
glacial acetic acid and 1.1 mole of hydrogen peroxide (30%) per mole of ethylenic
unsaturation, 75
0
C, 8 hrs, 5 wt% of the resin catalyst
148
.
The rate law that holds for epoxidation of all oils and FAME is shown in Eq. 1.1:
d[DB]
r = = k [DB] [PFA] Eq. 1.1
dt

25

Where r is the rate of disappearance of carbon-carbon double bonds, [DB] is the
concentration of double bonds, [PA] is the concentration of peracid and k is the second-order
rate constant. For ex situ and sometimes for in situ process, the epoxidation reaction can be
assumed to be pseudo-zero order in peracid concentration because the rate of formation of
peracid is much faster than the rate epoxidation. The epoxidation and ring opening for in situ
epoxidation of anchovy oil with partially preformed peracetic acid in the presence of a resin
catalyst
151
were described, by applying the principle of the stationary state, by a pseudo first-
order reaction. Two studies of the kinetics of the in situ epoxidation of oleic acid with
hydrogen peroxide and acetic acid and of methyl esters of palmolein by performic and
peracetic acid, both carried out in the presence of sulfuric acid as a catalyst, concluded that
the rate-determining step of the epoxidation process was the formation of peracetic (or
performic) acid
145,152
. Rangarajan et al
120
reported kinetic parameters for the in situ
epoxidation of soybean oil by peracetic acid, again in the presence of sulfuric acid as the
catalyst, but treated it as a two-phase system. Significantly higher rates were obtained in
kinetically controlled regimes. Jankovic et al
153
proposed the mathematical model that
describes the kinetics of reaction systems for the in situ epoxidation of unsaturated fatty acid
esters or triglycerides with organic peracids. Kinetic studies of epoxidation of soybean oil
with peroxoacetic acid and peroxoformic acid have been reported and found to be pseudo-
first order with respect to both double bonds as well as peroxy acid
37
.
The magnitude of rate constants (k
epo
) in cm
3
mol
-1
s
-1
and the energy of activation
(E
a
) in Kcal/mol for conc. sulfuric acid catalysed preformed (ex situ) peracetic epoxidation of
undecylenic acid, methyl undecylenate, and ethyl undecylenate undecylenic acid over 25-
35
0
C were found to be- 0.06-0.09 and 20.78, 0.096-0.12 and 6.95 and 0.046-0.11 and 15.34,
respectively
130
. The apparent activation energy using Arrhenius relationship, for the in situ
formation of epoxidised jatropha oil was found to be 53.6 kJ/mol
124
which compared well
with the corresponding value of 48.6 kJ/mol, as obtained by
154
for a similar acidic ion
exchange resin catalysed epoxidation of a vegetable oil. The epoxidation of castor oil with
performic and peracetic acid generated in situ in presence of cation exchange resin
(Amberlite IR-120) was found to be first order with respect to the conversion of ethylenic
unsaturation. The rate constants for the epoxidation with peracetic acid were 0.067, 0.184,
0.55, and 1.12 (hr
-1
) at 30
0
C, 50
0
C, 70
0
C and 85
0
C, respectively, while those for the
performic acid were 0.125, 0.287, 0.645, and 0.981 (hr
-1
). Activation energies of the peracetic
acid and performic acid epoxidation were found to be 48.2 kJ/mol and 35.4 kJ/mol,
respectively
149
. The kinetic modelling of Novozym 435 catalysed epoxidation of oleic acid
26

based on ternary complex mechanism was reported
155
. Following kinetic parameters were
deduced at 30
0
C: V
max
= maximum epoxidation velocity=2.229 X 10
5
-3.614 X 10
5

(mmol/L/min/g enzyme) and K
iA
= dissociation constant for enzyme-oleic acid complex
59.986- 65.618 (mmol/L/g enzyme). At low temperatures, the rate of epoxidation was faster
than the rate of deactivation of the enzyme by hydrogen peroxide.
Table 1.3 provides the kinetic constants (k
epo
and E
a
) and thermodynamic parameters
[enthalpy of activation-H, average entropy of activation- S, and free energy of activation-
G ] reported by different investigators for sulphuric acid catalysed peracetic acid in situ
epoxidation of different oils/ esters. These thermodynamic data show that the epoxidation is
a non-spontaneous process.
In Eq. 1.1, if triglyceride structure is going to have any effect on epoxidation reaction
kinetics, the only parameter that can be affected is the rate constant implying likely influence
of the FA composition on the value of the rate constant. The rate constants of noncatalysed,
ex situ epoxidation were determined by reacting preformed formic acid with a number of oils
(cottonseed/ corn/ olive/ soybean oil etc.) model triglycerides (triolein, trilinolein) and model
fatty acid methyl esters (FAME)
144
. In triglycerides, the double bonds of oleic acid and
linoleic acid were equally reactive, and the double bonds of linolenic acid were
approximately three times more reactive than oleic and linoleic acids. For FAME, the rate
constants of epoxidation increased as the level of unsaturations increased. Furthermore, the
rate constants of epoxidation for the FAME were higher than their respective triglycerides.
These results showed that the FA composition had a significant effect on the value of the
epoxidation rate constant and were interpreted on the basis of the steric and electronic effects
on epoxidation kinetics. The double bonds further from the glycerol center are more reactive
than double bonds near the glycerol center and double bonds on different FA have different
reactivities. Steric factors inherent in the triglycerides structure reduce the reactivity of the
unsaturated sites in comparison to the same site on FAME. As the number of double bonds
increases, the electron density increases, this causes an increase in the rate constant for
epoxidation of linolenic acid. These results were used to derive a model that predicts the
epoxidation kinetics of oils from their FA composition. The relative rates of epoxidation for
oleic, linoleic and linolenic acids are 1.0, 1.0 and 1.7, respectively. The triacylglycerols are
slightly more reactive than the acids with values of 1.9, 3.0 and 4.9, respectively
11
.
Twelve epoxidised oil derivatives based on rubber seed oil, Madhuca oil (Mee oil)
and Neem oil and their hydrolysed products were prepared by optimised conditions on a
comparatively large scale without solvent extraction procedures. It was found that more than
27

80% of the reaction was completed within three hours at 60
0
C. The level of epoxidation could
be controlled reasonably by limiting the reagents. The solubility parameter values calculated
from the molar attraction constant values G, using Smalls equation, were comparable with
those of conventional plasticizers used in the PVC industry
156
.
Table 1.3 Kinetic and thermodynamic parameters for sulphuric acid catalysed peracetic
acid in situ epoxidation of different oils/ esters
Oil/ esters
Kinetic constants Thermodynamic parameters
Literature
reference
k
epo,
L mol
-1
s
-1

E
a
H S G
Cotton
seed oil
0.39-5.42
X 10
-6

(temp. range
3075
0
C)
11.7
kcal/mol
11.0
kcal/mol
-51.4 cal
mol
-1
K
-1

28.1
kcal/mol
125
mahua oil
0.2-6.8
X 10
-6

(temp. range
3085
0
C)
14.5
kcal/mol
13.8
kcal/mol
-51.1 cal
mol
-1
K
-1

30.6
kcal/mol
131
methyl esters
of parkia
biglobossa
seed oil
3-5 X 10
-7

(temp. range
50-70
0
C)
51.963
kJ/mol
13.8
kJ/mol
-3.55 kJ
mol
-1
K
-1

1.51
kJ/mol
129
1.3.4 Ring opening and synthesis of multifunctional derivatives
A lot of trifunctional compounds (introduction of hydroxyamines, hydroxynitriles,
diols, etheralcohols, hydroxyalkylamides etc. in FA or triglycerides) are the result of splitting
of oxirane ring by nucleophilic compounds (secondary amines, hydrogen cyanide, water,
alcohols, amides etc.). Applications for these interesting oleochemicals have not yet been
fully investigated.
The three-step synthesis of several diesters from commercially available oleic acid
and common fatty acids was reported
157
. The key step of ring opening of epoxidized oleic
acid with different fatty acids (octanoic, nonanoic, lauric, myristic, palmatic, stearic and
behenic acids) was achieved using p-toluenesulphonic acid (PTSA) as catalyst. The
esterification reaction of these compounds with octanol was further carried out in the
presence of H
2
SO
4
giving diester compounds. This study described a systematic approach to
improve the low temperature pour property of oleic acid derivatives. Salimon et al
24
also
reported the oxirane ring opening of epoxidized oleic acid using behenic acid and PTSA as
catalyst followed by esterification with octanol and 2-ethylhexanol to form diesters for
28

industrial biolubricant applications. Moser
158
also reported the preparation of branched chain
ethers from oleic acid in a three-step synthesis. Esterification of oleic acid was followed by
the epoxidation of double bond and then a ring-opening step by an alcohol (alkyl: propyl,
isopropyl, octyl, 2-ethylhexyl) using propionic and octanoic acid medium without the need
for either solvent or catalyst.
O
O
O
O
O
O
CH
3
O
CH
3
O
O
O
O
C H
3
O
O
O
O
O
O
CH
3
CH
3
C H
3
OH
OR
OR
OH
OR OH
OR OH OH OR
ROH, H
2
SO
4
120
0
C, 3Hrs

Fig 1.7 Ring opening of epoxidised oils
For the production of lubricants from vegetable oils, the oils are first epoxidized, and
then the oxirane ring is opened with either acetic acid or a low chain aliphatic alcohol like
methanol or ethanol
159
. Epoxidized oils were ring opened by a one-pot, one-step process by
using a predetermined amount of allyl alcohol mixed with tetrafluoroboric acid catalyst.
Allylic double bonds were successfully incorporated into triglycerides of epoxidized oils
through a ring-opening nucleophilic addition reaction of allyl alcohol. The reaction is facile
with high conversion under mild conditions
160
. The epoxidation of natural oils and
subsequent ring opening with acrylic acid has been well studied
161
. Acrylation kinetic model
that predicts rate constants from fatty acid distributions in the oil were established
144
. Thus,
the rate constant of acrylation increased as the number of epoxides per fatty acid decreased.
Multiple epoxides per fatty acid decrease the reactivity of the epoxides because of steric
hindrance effects and the oxonium ion, formed as an intermediate during the epoxy-acrylic
acid reaction, is stabilized by local epoxide groups.
Ring-opening polymerization of epoxidized soybean oil (ESO) catalyzed by boron
trifluoride diethyl etherate (BF
3
.OEt
2
) in methylene chloride was conducted in an effort to
develop useful biodegradable polymers
162
. Epoxidized diethanolamides were synthesized by
reacting diethanolamine (DEA) with mixture of epoxidized palmolein (40% w/w) and refined
29

bleached deodorized palmkernel olein (60% w/w) at 1:3 molar at 80
0
C for 5 hrs and
continued at 110
0
C for another 4 hrs of reaction time. Synthesized diethanolamides with high
content of epoxides were reacted with isocyanate in the presence of AlCl
3
-THF complex
catalyst to produce oxazolidone linkages in polyurethane network. The rigid polyurethane
foam produced is of better quality as compared to the commercially available foam
163
.
The kinetic study on the oxirane cleavage of palmolein methyl ester
164
has been
reported. The first degradation reaction is first order with respect to the epoxide concentration
and second order with respect to the solvated acetic acid
126
[k
AA
(70
0
C) = 4.27 0.1210
-5

l
2
mol
-2
min
-1
; E
aAA
= 12.9 0.64 kcal mol
-1
]. The degradation increases notoriously the lower
the pH of the reacting media is; the increase is directly proportional to the concentration of
protons, as is usually found in homogeneous catalysis (for very low pH, the reaction is almost
instantaneous). Likewise, the degradation reaction with peracetic acid is first order with
respect to the epoxide [k
PAA
(70
0
C) = 4.31 10
-4
l
2
mol
-2
min
-1
; E
aPAA
= 10.6 0.38 kcalmol
-1
]
and it also increases linearly with proton concentration. Although the specific attack on the
ring by the peracid is almost 10 fold harsher, acetic acid is constantly being regenerated
during the industrial process, so that its concentration is always far larger than that of
peracetic acid. Thus, under process conditions the degradation of the oxirane ring is mostly
caused by the carboxylic acid. A systematic investigation of the impact of the various
consecutive reactions of oxirane ring-opening on the yield of the epoxidised soybean oil was
carried.
1.3.5 Applications of epoxidised oils and fatty acids
Oils, mainly soybean and linseed, are epoxidized on an industrial scale (0.2 MMT per
year) for utilization as stabilizers and plasticizers for PVC polymers
11
. Epoxidised oils are
also used as plasticizer in the production of packing materials such as wrapping foils.
Plasticizer is an additive for plastic formulations to enhance their plastic workability and
flexibility and is generally produced from petroleum derivatives such as phthalate
compounds. The plasticizing efficiency of epoxidised oils is equivalent to that of dioctyl
phthalate. Besides this, epoxidised oils also improve UV light and heat stability of PVC
plastic due to the presence of the oxirane rings
36,45,165,166
. The typical stabilization action for
PVC
167
is derived from the fact that the reactive epoxide groups scavenge hydrogen chloride
produced by the degradation of the PVC polymer
168,169
, interrupt the formation of polyene
sequences in the polymer
170
and retard the apparition of discoloration
171
. They are generally
regarded as secondary stabilizers used to enhance the effectiveness of metal soaps. The
marked effect on the thermal stabilization of PVC by epoxidised oils requires the synergistic
30

presence of metallic soaps
172,173
. The esterification and etherification reactions which occur
with allylic chlorine groups in PVC provide an explanation for the synergism observed in the
stabilization of PVC containing a combination of an epoxy compound with metal soap
168,171
.
Epoxidized oils transesterified with low-molecular weight alcohols are also used as
plasticizers of polyvinyl chloride
174-176
. In particular, methyl esters of epoxidized soybean oil
represent a renewable substrate that is readily converted into surfactants, fuel additives, and
other industrial products
177
.
A significant lubricant market of some nine million metric tons per year of industrial
and automotive lubricants exists and there has been a constant demand for environmentally
friendly or green lubricants. As lubricants, vegetable oils possess superior lubricity, good
anticorrosive properties, better viscosity-temperature characteristics and low evaporation loss
which are important in industrial applications such as rolling, cutting, drawing, quenching
operations, and greases
159,178
. Their low volatility and narrow range of viscosity changes with
temperature are due to the high molecular weight of the triglyceride molecule. Polar ester
groups in vegetable oils are able to adhere to metal surfaces and, therefore, possess good
boundary lubrication properties. In addition, vegetable oils have high solubilizing power for
polar contaminants and additive molecules. From the environmental point of view, their
importance is evident especially in areas of total loss lubrication, military applications, and in
outdoor activities such as forestry, mining, railroads, dredging, fishing and agriculture
hydraulic systems. In spite of these facts, vegetable oils currently provide only a fraction of
the lubricant market due to the poor stability and low temperature properties. For the
production of lubricants from vegetable oils with improved oxidation stability and pour point
characteristics, the oils are first epoxidized, and then the oxirane ring is opened with either
acetic acid or a low chain aliphatic alcohol like methanol or ethanol
159
followed by the
reaction of the epoxide function with linear and branched-chain alcohols. Epoxy esters
144
, due
to the overall good lubrication characteristics, are being actively investigated as biolubricants.
Salimon et al
24
reported the oxirane ring opening of epoxidized oleic acid using behenic acid
and p-toluenesulfonic acid as catalyst followed by esterification reaction with octanol and 2-
ethylhexanol to form diesters for biolubricant industrial applications. Epoxidized soybean oil
functionalized with diamine is an excellent antioxidant and lubricant, and has been proven as
an antifriction agent. Because of its amphiphilic character it is added to base grease oils to
improve their application properties
179
. Activity of epoxidised oils is essentially related to the
amount of oxirane oxygen, but the plasticization, lubrication and cost parameters play a role
in their selection and use.
31

Due to the high reactivity of the oxirane ring in epoxidized oils, they are used as
renewable raw materials for manufacturing such intermediate products as alcohols, glycols,
alcoxyalcohols, hydroxyesters, N-hydroxyalkylamides, mercaptoalcohols, hydroxynitriles,
alkanolamines, and carbonyl compounds
131,180
. Thus, epoxidised oils/ fatty acid derivatives
are used as intermediates for a large number of commodities such as agricultural and
pharmaceutical molecules, flavors and fragrances, surfactants, adhesives, sealants
181-184
. With
sodium iodide and an appropriate solvent, epoxy esters are converted to keto esters
(RCOCH
2
R and RCH
2
COR). Natural vernolic acid (12, 13-epoxyoleic acid) is being
examined as an antirust additive (as its C
4
-C
6
amides) and as a source of dibasic acids and of
high-value products such as the pheromone bombykol (CH
3
(CH
2
)
2
CH=CH CH=CH(CH
2
)
8
CH
2
OH) and the plant wound hormone traumatic acid (HOOC(CH
2
)
8
CH=CHCOOH).
Limonene epoxide has traditionally been used as a precursor for the synthesis of perfumes,
drugs, and food additives
185
.
Petrochemical based resins such as epoxy, polyester and vinyl ester find more
engineering applications because of their advantageous material properties such as high
stiffness and strength. However these resins have serious drawbacks in terms of
biodegradability, initial processing cost, energy consumption and health hazards. Renewable
epoxy esters can be used as diluents in paints and so replace volatile organic solvents.
Reaction of epoxidised oils or fatty acids with acrylic acid (CH
2
=CHCOOH) gives an
acrylate which can be cured by exposure to UV photoinitiated free radical or cationic
polymerization
186-188
. Polyhydroxy compounds produced by reaction of epoxides with diols
and triols (glycerol) serve as a source of polyurethanes through reaction with isocyanates
155
.
Green nanocomposite coatings with excellent film properties and good biodegradability have
been obtained with epoxidised soybean and linseed oil and -glycidoxypropyl
trimethoxysilane
189
.
1.4 Synthesis and characterization of dimer acids
One finds number of patents on polymers based on vegetable oils
190
as number of
different dimers and oligomers are produced from fatty acids and alcohols. The term dimer
acid
191-195
is applied to the branched-chain acyclic or cyclic dicarboxylic acids (predominantly
the C
36
) formed by the thermal (260-400
0
C) or catalytic (acid activated clay or other cationic
catalysts) polymerization reactions of two or more C
18
unsaturated fatty acids or monohydric
esters of semi-drying oils such as tall oil, sunflower, soybean and rapeseed oils or drying oils
such as dehydrated castor oil. Typical manufacturing conditions
196
are: 4% montmorillonite
clay catalyst at 230
0
C for 4-8 hours under steam pressure. Dimerization is usually carried out
32

in the presence of a little water (1-2%) to prevent decarboxylation at high temperature. The
extent of reaction was determined by measuring changes in refractive index, molecular
weight and acid values of the dimerized oil samples. After the desired reaction is complete,
the mixture is cooled, a metal complexing agent, usually phosphoric acid, is added and the
crude product is filtered. The product is a complex mixture of acyclic, cyclic, and bicyclic C
36
dimer acids as the main product (Fig. 1.8), apart from some C
54
tricarboxylic trimer acids and
higher condensed polymer acids as well as unreacted and structurally modified (e.g. isostearic
acid) monocarboxylic acids
42
. The monomers are recovered as overhead product by vacuum
distillation. The separation from trimer and higher homologs is achieved by molecular
distillation or wiped film evaporator.
C H
3
OH
O
C H
3
OH
O
C H
3
OH
O
4%Montmorillonite clay
230
0
C, 4-8 hrs

Fig. 1.8 Dimerization of polyunsaturated fatty acid
Other catalysts investigated for this reaction include peroxides
197
, hydrofluoric acid
198

and sulphonic ion exchange resin
199
. The reaction also has been investigated under corona
discharge
200
. Catalysis by super acids has received considerable attention in recent years
201-
205
. The sulphate-treated zirconia super acid catalyst has high chemical stability, and being a
solid does not pose any corrosion problems. Dimerization of fatty acids derived from
dehydrated castor oil and safflower oil was carried out on the sulphate-treated zirconia
catalyst and trifluoromethane sulphonic acid (triflic acid) under autogeneous pressure in the
temperature range of 160-240
0
C. Triflic acid was observed to be highly active; however, the
product obtained was deeply colored. Zirconia exhibited high activity for the reaction. The
important features of this catalyst were the lower cost in comparison to triflic acid, the high
selectivity for dimer (low yields of trimer) and no significant coloration of the products
206
.
Anyaogu et al
207
as well as Boot and Speek
208
have reported the optimum condition for the
polymerization of soybean oil to include 350
0
C, 0.0025% iodine catalyst and a reaction time
of 20 min under inert atmosphere. None of these methods has succeeded commercially.
The diversification of the sources of precursors for the production of dimer acids will
reduce the pressure on the regular oils which are already in use in many domestic and
industrial applications. The physical properties of dimer are affected by the raw materials
used in the manufacture, reaction conditions and content of monomer, dimer and trimer.
33

These branched dibasic compounds possess significantly lower melting points than straight
chain structures of similar molecular weight. All the dimer acids are liquid at 25
0
C, even
though their molecular weight is about 560. This phenomenon can be attributed to the
presence of large number of isomers which tend to lower the melting point. Dimer and trimer
acids as well as monomer acids derived from dimer acid processing are neither flammable
nor combustible. Fully saturated dimers have excellent oxidative stability. This and their
extended liquid range are exploited in their use as lubricants and cosmetic additives. Dibasic
dimer acids react with polyamines to give reactive polyamides as epoxy curing agents in the
formulation of anticorrosive coatings and nonreactive polyamides for utilization in printing
inks hot melt adhesives and petroleum exploration operations with outstanding chemical,
physical and mechanical properties
209
. Imidazole derivatives are used as corrosion inhibitors
and esters as lubricants. Dimer acids also find wide applications as source of polybasic acids
for the synthesis of polyester and polyamidoamines. Isostearic acids, byproduct in dimer
production, are important intermediates in the production of biodegradable lubricants,
emollients, and hydraulic fluids. The scope and potential of the zeolite-catalyzed synthesis of
isostearic acids starting from oleic acid is examined
210
.
1.5 Alkali fusion of castor oils
The broad and versatile use of castor oil is because of its unique structure and comes
from its main component, ricinoleic acid (12-hydroxy-9-cis-octadecenoic acid), which
represents 90% of the vegetable triglycerides. This triglyceride has three chemical groups
subject to modifications: hydroxyl (C
12
), C-C double bond (C
9
), and acid carbonyl, giving a
variety of derivatives
217
. The hydroxyl group at 12
th
position is so reactive that the molecule
can be split at that point by high-temperature pyrolysis and by caustic fusion to yield useful
products of shorter chain length. Sebacic acid (1,8-octane-dicarboxylic acid or decanedioic
acid), a linear saturated C
10
dicarboxylic acid, is manufactured by heating castor oil to high
temperatures (about 250
0
C) with alkali. This treatment results in saponification of the castor
oil to sodium ricinoleate that is then cleaved to give capryl alcohol (2-octanol) and sebacic
acid (Fig. 1.9).
Although the sebacic acid yields by above route are low, the route has been found to
be cost competitive and used commercially by Union Camp in Dover, Ohio and by Hokoku
Oil Company, Japan
196
for mass production of sebacic acid in either a batch or continuous
process. The castor oil or ricinoleic acid and caustic are fed to a reactor at a temperature of
180-270
0
C, where the ricinoleic acid undergoes the series of reaction with evolution of
hydrogen to give disodium sebacate and capryl alcohol. When the reaction is complete, the
34

soaps are dissolved in water and acidified to a pH of about 6. At this pH, the soaps of
monobasic acids are converted to free acids that are insoluble in water. The disodium
sebacate is the only partially neutralised to the half acid salt, which is water soluble. The oil
and aqueous layers are separated. The aqueous layer containing the half salt is acidulated to a
pH of about 2, causing the resulting sebacic acid to precipitate from the solution. It is then
filtered, water washed, and finally dried. 2-Octanol, 2-octanone, and sebacic acid were
determined by GC and GC/MS analysis, and purity of sebacic acid was further assessed by its
acid value (444) and melting point (134
0
C). The crystals of sebacic acids are monoclinic
leaflets (-1.231). It is only slightly soluble in water even at 110
0
C. It is soluble in alcohol
and ether but nearly insoluble in benzene.
Castor oil + 3 NaOH 3 Sodium Ricinoleate +
Glycerol
Sodium Ricinoleate
NaOH,180-250
0
C
(CH
2
)
8
O
ONa
O
NaO +
C H
3
(CH
2
)
5
CH(OH)
CH
3
C H
3
(CH
2
)
5
CH(OH)
CH
2
CH CH(CH
2
)
7
C
O
ONa
Disodium Sebacate
Capryl alcohol

Fig. 1.9 Alkali fusion of castor oil
The mechanism for the conversion of ricinoleic acid to sebacic acid
218
is shown Fig.
1.10. The first step is the dehydrogenation of ricinoleic acid to a , -keto acid, followed by
isomerisation of double bond to give , -unsaturated keto acid intermediate in the presence
of alkali. At elevated temperature, this intermediate should undergo a retro- aldol type of
reaction to give a saturated ketone and a -aldehydo acid in the presence of water. The
methyl hexyl ketone takes hydrogen from the first step of dehydrogenation for reduction to
form 2-octanol. On the other hand, two possible reactions may take place with the aldehyde
of decanoic acid. One reaction is a reversible reaction of hydrogenation (the hydrogen being
made available from the first step of dehydrogenation) to form 10-hydroxy decanoic acid,
while in the presence of strong alkali at elevated temperature, the -aldehydo acid would
undergo an irreversible oxidation to yield sebacic acid. Since only one mole of hydrogen is
available in situ after dehydrogenation of ricinoleic acid and the same is likely to get
distributed for the subsequent hydrogenation of methyl hexyl ketone and aldehyde of
decanoic acid, the presence of suitable catalyst, which may work as oxygen donor, favours
the oxidation reaction of aldehyde of decanoic acid. Longer reaction period (such as 13 hrs),
35

lower temperature range (458-463 K) and use of 1 mol of sodium or potassium hydroxide per
ricinoleate promote formation of 10-hydroxydecanoic acid. Using 2 mol of alkali per 1 mol
of ricinoleate at 513-549 K and with a shorter reaction cycle produces sebacic acid. Hydrogen
was also formed with excess alkali
219
.
A number of process improvements have been described and include the use of white
mineral oil having a boiling range of 300-400
0
C or the use of mixture of cresols
220
. These
materials act to reduce the reaction mixtures viscosity and thus improve mixing. The
normally expected theoretical yields of 2-octanol and sebacic acid from alkali pyrolysis of
castor oil containing 84% ricinoleic acid are 35.7 and 43.6%, respectively. Higher sebacic
acid yields are claimed by the use of catalysts such as barium salts
221
, cadmium salts
222
, lead
oxide and salts
223
, sodium nitrate
224
and zinc oxide
225
. The presence of barium is to provide a
process which enables the recovery of sebacic acid without neutralisation of fusion bath. The
role of adjuncts in enhancing the yields of the desired products is, however, not very explicit
in the literature. Alkali pyrolysis at 280 2
0
C for 5 hrs using an overall ratio of alkali to
diluent (white mineral oil) of about 8:27 and 1% red lead catalyst in a cylindrical reactor
yielded 70.1% 2-octanol and 72.5% sebacic acid on the basis of their respective theoretical
yields
226
. The oxygen donating effect of Pb
3
O
4
may play an important role in increasing the
yield of sebacic acid by oxidation of aldehyde of decanoic acid and suppressing the other
forward reaction of hydrogenation of the aldehyde of decanoic acid to form 10-hydroxy
decanoic acid.
Heating and driving chemical reactions by microwave energy has been an
increasingly popular theme in the scientific community
227
. Azcan et al
228
studied the effect of
microwave irradiation on alkali fusion of castor oil using different NaOH/oil ratios (8:15,
12:15, and 14:15), reaction temperatures (473, 493, 503, 513, and 523 K), and reaction times
(15, 20, 25, and 30 min) in the presence of 1% Pb
3
O
4
catalyst. Maximum yields of
oleochemicals were obtained using methylated then presaponified castor oil (sodium
ricinoleate), 14/15::NaOH/oil ratio at temperature 513 K and 20 min reaction time.
Sebacic acid finds applications as monomeric and polymeric plasticizers for PVC,
dioctyl sebacate for jet engine lubricants and air-cooled combustion engines and polymer
intermediates for 6,10 nylons, polyesters and polyurethanes used in adhesives, coatings,
fibers, inks and resins. It is also used as a mineral floatation agent and for producing
emulsifiers, defoaming and anti-bubbling agents. 2-Octanol (capryl alcohol) is used in
plasticizers in the form of dicapryl esters of various dibasic acids
229
.
36

C H
3
CH
2
CH
OH
CH
2
CH CH CH
2
COO
-
5 7
Dehydrogenation
C H
3
CH
2
C
O
CH
2
CH CH CH
2
COO
-
5 7
Isomerisation
5
C H
3
CH
2
C
O
CH CH CH
2
COO
-
8
Retro - Aldol fission
5
C H
3
CH
2
C
O
CH
3
OHC CH
2
COOH
+
(2 - Octanone) C -10 Aldehydo acid
5
C H
3
CH
2
CH
OH
CH
3
2 - Octanol
8
CH
2
CH
2
COOH O H
8
HOOC CH
2
COOH
8
Sebacic acid
10 - Hydroxydecanoic acid

Fig. 1.10 Mechanism of alkali fusion of castor oil
218

Background of present investigations
Structurally, fatty acids and esters closely resemble materials (petroleum
hydrocarbons) already recognized and understood by the current chemical industry based on
nonrenewable feedstock. Raw material familiarity will be an important component in
transitioning the industry from nonrenewables to renewables, and general technology and
equipment/ plant design present in the chemical industry today can be easily adapted/
retrofitted to the production of oleochemicals. Epoxidation of olefins present the glaring
example of this transition. Current research efforts in oleochemicals have focused only on
biodiesel as an area of investigation which is simply one of many products that are derived
37

from the oleochemical unit operations. The state of the art in chemical modification of fatty
acids/oils focuses almost entirely on simple, incremental changes at the COOH group of the
molecule. Shifting the focus from a single product to the much broader oleochemical
platform, as stated under initial para of introduction, is absolutely necessary on the way to the
sustainable and economical usage of lipids as renewable feedstock for organic chemical
industries. For example, application of mature technologies well known to the chemical
industry could lead to some of their traditional building blocks when applied to low value
mixed fatty acids. This research work will detail important R&D opportunities for
development of different chemical modification technologies for fatty acid/oil conversions.
A key barrier to the oleochemical unit operation is acceptance of a new form of raw
material by the chemical industry. The hydrocarbon nature of fatty acids and esters, with
appropriate development of new technology, can serve as an important transitional raw
material as the chemical industry evolves from nonrenewable to renewable raw materials.
However, use of crude oil still dominates the industry, while oleochemistry remains a
specialty sidelight. This situation, as is the case with any commodity technology, could
change radically upon introduction of new conversion technology for the raw materials and a
realization of their potential by the chemical industry. Demonstration of that potential and
addressing the important barriers in utilization of oils and fats are the objectives of present
investigations.
The broad range of vegetable oil sources lead to diverse fatty acid structures. These
structural units can be used to introduce new functionality that can be translated into
marketplace properties. The major vegetable oil sources in the U. S. are soybean and
cottonseed while those for European Union are rapeseed and sunflower oil. The economics of
Malaysia is governed by palm and palmkernel oil. India is the largest producer of groundnut
oil, castor oil and many native nontraditional oils. Developing of new or optimization of
technologies for the invention of next generation products are feasible in the most promising
growth areas such as surfactants, lubricants, additives and polymers. Improved products and
technology, exhibiting properties deemed of value, will allow capture of a greater proportion
of these markets by renewable oils and fats. Research efforts in the areas of transformations
related to the COOH group, in present work, is mainly concentrated on process optimization
and modeling studies in synthesis of sucrose ester. From a research viewpoint, a great
opportunity exists to develop cost effective and efficient technology for the selective
structural modification of fatty acid side chains. The chemical transformations in
hydrocarbon chain of fatty acids have the additional advantage of being able to draw on the
38

broad knowledge possessed by the petrochemical industry. Thus it is essential to explore the
breadths of the catalytic processes (alkali fusion in present work) available and examine their
feasibility. In a similar manner, the examination of unsaturated oils and their transformations
(epoxidation, ring opening, Dimerization in present work), which may fulfill the interests of
the oleochemical industry, was undertaken.
1. Surfactants and specialty chemicals: An area of potential opportunity is in the production
of sucrose ester.

These are surfactants based entirely on renewables as starting materials, and
are the result of the reaction between a carbohydrate (sucrose) and a fatty acid methyl ester/
oil to give an amphiphilic molecule possessing a polar sugar based head group and a long
nonpolar oleochemical tail. The research challenge in producing these materials arises in
developing technology suitable for the selective reaction of a fatty acid at a single site of the
carbohydrate molecule without the requirement of a complex series of protection/
deprotection sequences. While there are currently commercial products based on this
technology, the materials are mixtures of mono, di, and triesters, which limit their utility to
particular applications. Given that the performance of these materials will be based on their
structure, process optimization for selective transesterification and modeling studies based on
the concepts of Reaction Engineering were the objectives of research investigations.
2. Polymers and coating: Another very large potential market for consumption of fatty acid
derivatives is the polymer market. Use of oleochemicals, particularly diacids, as polymer
components is known but its share of the otal polymer market is very small. The portion of
the polymer market is dominated (87%) by materials such as adipic or terephthalic acid,
while use of oleochemically derived diacids accounts for only 0.5% of the total. Displacing
the commodity acids will be difficult; however, the use of oleochemical diacids offers access
to an interesting suite of properties including elasticity, flexibility, impact strength, hydrolytic
stability, hydrophobicity, lower T
g
, and flexibility
42
. In present research, synthesis of diacids
such as sebacic acid by catalytic alkali fusion of castor oil and dimer acids by catalytic
thermal polymerisation of polyunsaturated oils and fatty acids/ esters have been carried.
3. Additives and lubricants: The market opportunity exists in the production of
biolubricants from oleochemicals. Petrochemically derived lubricants possess an
environmental problem in that they are often released during their use, for example, in
various engines, metal working, chain saws, etc.

Epoxidation of the double bonds in fatty
acids is an area of current interest, as oil epoxides have utility as additives for PVC. Mustard
oil has been epoxidized and ring opening studies have been carried to obtain biolubricants.
39

The kinetic and thermodynamic studies on epoxidation and ring opening reactions and
comparative engineering evaluations of different reactor options were also focused.
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