1.

Theory

1.1.1

Jatropha Oil
Oil content in jatropha (Jatropha L.) is quite high, but it contained the poison.

It can not be used as edible oil. In the Jatropha oil is contained the double bond
resulted in oil becoming unstable. Therefore, it is necessary to do research for seeking
alternative solution. One alternative product is for the manufacture of epoxy as a raw
materials for the manufacture of lubricant base (automotive engine lubricants).
Oils and fats in general is often called triglycerides or triasigliserol. The other
components of triglecerides is mentioned by fraction was saponified and free fatty
acids which is comprised less than 3% of the total oils and fats. The differences
between oils and fats is one of the fatty acid composition. Jatropha oil is obtained
from the seeds of Jatropha oil plant (Ricinus communis L.),which includes family
Euphorbiaceae. This plant is an annual plant that lives in the tropical and sub-tropical
and can grow at an altitude of 0-800 meters above sea level and the plant has been
known for a long distance in Indonesia. (Ketaren, 1986).
Jatropha oil is pale yellow, but after the process of refining and bleaching the
color is lost so that it becomes almost colorless. Crude oil has a distinctive odor and
offensive but is easily removed. Jatropha oil can be stored and does not easily become
rancid. Jatropha oil is relatively high solubility in alcohols, as well as in the ether,
chloroform and glacial acetic acid. Jatropha oil is not soluble in mineral oil except
when mixed with other vegetable oils. Jatropha oil which is dominately in the form of
triglycerides, especially resinolenin with ricinoleic acid: Synthesis of N-ethanol
stearamide -9,10,12- trihydroxy-derived from Jatropha oil, The fatty acid component.
Tocopherol content is relatively small component (0.05%) and essential fatty acid
content is very low causing Jatropha oil is different from other vegetable oils (Weiss,
1983).

Table 1.1. Fatty Acid Content of Caster Oil

Source : Marlina, dkk (2004)

Oil cake obtained from processing Jatropha oil has a fairly high protein
content, but contain toxins that are strong enough. The poison contained in the form
of ricin, risinin, and heat-stable allergen. Risinin is an alkaloid derived from nicotinic
acid, where in the carboxyl group is converted into a nitrile by dehydration of
nicotinamide ( Torsell, 1984 ).
Jatropha oil is a versatile oil, this is mainly due to the high acid content its
risinoleat. Jatropha oil can be used directly in the manufacture of non-dried alkyd
resins, as plasticizer in nitrocellulose and urethane. A large number of Jatropha oil
was converted to the derivative dehydrated Jatropha oil (DCO) that is used as a
substitute for oil terkonjungasi. resulting the DCO is usually done catalytic
dehydration by using a catalyst such as sulfuric acid, sodium bisulfite , lipase
enzyme.(Guner, 1997).
1.1.2 Asam Risinoleat
Ricinoleic acid is an unsaturated fatty acid monohydroxy (figure 2.1) with a
molecular formula C18H34O3. (R) -12-hydroxy (Z) -9-oktadekenoat which is the
main fatty acid groups of Jatropha oil. This fatty acid is slightly toxic demonstrated
by the activity of the resulting laxative when consumed

Picture 1. The chemical structure of ricinoleic acid

Ricinoleic acid which has been esterified to methyl ricinoleic when reduced
with a reductant dissolved metals then that will be reduced only methyl ester and does
not attack the double bonds, which will form resinoleil alcohol and if acetylated will
be formed d-12-acetoxy-cis-9-oktadekenol. Ricinoleic acid can be esterified with
long-chain aliphatic alcohols (C10 -C18) enzymatically or by enzymatic reactions
directly without damaging alcoholic OH groups existing on the ricinoleic. Alcoholic
fatty acids of Jatropha oil with a specific lipase as mocor miehei, can produce
monoglycerides as by-products. Monohydric alcohol esters of long chain of ricinoleic
acid is a base material with the potential to manufacture surfactants. Oils containing
hydroxyl fatty acid is a very important ingredient. Hydroxyl fatty acid is used in the
manufacture of polymers such as nylon 6.6, coatings, and paints . Ricinoleic methyl
compound has a double bond then the bond can be oxidized. Double bonds can be
dioxide into a variety of products, depending on the reagents used. The reaction involves
the oxidation of carbon-carbon double bond can be grouped into two general groups:
1. Oxidation bond without breaking the pi sigma bond.
2. Oxidation of pi bonds which decides sigma bond.
Production oxidation without termination of sigma bond is an epoxide or 1,2-diol.
The most popular reagents used to convert alkenes into a 1,2-diol is a potassium
permanganate solution (in water) under alkaline conditions and cold (though usually
these reagents provide a low yield). Tetraoksida osmium (OsO4) followed by reduction
with reagents such as Na2SO3 or NaHSO3 to produce diol with a better yield, but of
limited use because of expensive and toxic (Fessenden, R.J., 1999)

Epoxidation
Epoxidation is an oxidation reaction by active oxygen double bond form

epoxide compounds. In general, oil epoxidation using hydrogen peroxide as reagents.

The nature of hydrogen peroxide as the oxidizing agent is not strong enough to be
transformed into a more active form (peroxyacids). According to D. Swern (Swern
D., et al, 1945) that the peroxy acid formed from the reaction of hydrogen peroxide
with a lower aliphatic acids (formic acid and acetic acid) is a reactive form.
Peroxyacids can react very quickly with unsaturated compounds. The nature of the
strong formic acid can also open the oxirane ring to produce a compound derived
hydroxy-formoksi. With the water will form dihidroksil compound and formic acid.
Epoxide of vegetable oil is important and very useful especially in the case as a
stabilizer and plasticizer polymer materials. Based on the high reactivity of the
oxirane ring, epoxides can also be used for various types of chemicals namely
alcohol, glycol, alkanolamine, carbonyl compounds, olefin compounds, and polymers
such as polyesters, polyurethanes and epoxy resins. In general the reaction
epoxidation followed by hydrolysis written as follows
There are four techniques that can be used to produce olefin epoxide molecules:
1. Epoxide with perkarboksilat acid that is often used in industry and
accelerated with the aid of a catalyst or enzyme.
2. Epoxides with organic peroxides and inorganic, including alkali epoxide
nitrile with hydrogen peroxide and transition metal catalyzed epoxide.
3. Epoxides with halohydrin, using hipohalogen acid with salt as a reagent,
and olefin epoxides with electron deficient double bond.
4. Epoxides using molecular oxygen, for the edible oil is rarely used because
it can lead to the relegation of the oil into smaller compounds such as
aldehydes and ketones dicarboxylic acid short-chain so that oxidation with
O2 is an inefficient method for epoxide vegetable oils

1.1.1

Enzymatic Epoxidation
Methyl epoxyricinoleate was prepared in high yield by the lipase-catalyzed..

epoxidation of methyl ricinoleate with H2O2. A high molecular weight

polyepoxyricinoleate (PER) with a maximum weight average molecular weight (Mw)
of 272,000 was enzymatically prepared by the polycondensation of methyl
epoxyricinoleate using immobilized lipase from Burkholderia cepacia (lipase PS-IM).
Enzymatic epoxidation with lipase and hydrogen peroxide is an attractive oxidation
process because of their mild and safe reaction, high conversion rate and easy
removal of the catalyst. Furthermore, only water is produced in the reaction . Miao et
al. reported the enzymatic epoxidation of oleic acid followed by ring-opening
polymerization with heating . Enzymatic epoxidation is regarded as an
environmentally benign process, and thus is effective for the synthesis of biobased
derivatives. In this report, a series of high molecular weight polyepoxyricinoleate
(PER) polymers were prepared by enzymatic epoxidation with subsequent
polycondensation of methyl ricinoleate using a lipase. The PER was then crosslinked
using diacid anhydrides with the aim of creating novel biobased thermosetting resins
(Scheme I). The thermal and mechanical properties, biodegradability of the PER and
crosslinked PER polymers were measured.

Picture 2. Enzymatic synthesis and crosslinking of high molecular weight

polyepoxyricinoleate.

1.1.2

Characteristic of Epoxide
The characteristics of the epoxide compound is the oxirane group formed by

oxidation of compounds olefinic double bonds or aromatic compounds. To prevent

uncontrolled exothermic reaction and to optimize the epoxidation, the peroxide
solution is added gradually with stirring, and maintaining the temperature of the
reaction. When the substrate iodine number has been reduced to the desired point, the
reaction is stopped and the substrate epoxidized separated from the solution. Because
epoxidation reaction is reversible and there is a possibility of side reaction,
epoxidation endeavored to occur at low temperatures and a short time [Kirk-Othmer,
vol.9, 251].
Epoxidized esters have a higher density and lower volatility and greater
resistance to oxidation. Epoxidation improve thermal oxidative stability and reduce
the rate of increase in the acid number [Gan L.H. et. Al, 1995]. Epoxidation reaction
temperature is often set at 30 and 140oC. Epoxidation reaction can be carried out in
batch, semi-continuous, or continuous [Escrig, Pilar De Frutos et. Al, 1998].

1.1.5 Usability of Epoxide

One of the products of epoxides which can be produced using vegetable oils
as the raw material is polyhydroxy compound triglycerides. Polyhydroxy
triglycerides are compounds derived from oil or fat has hydroxyl groups of more than
2. triglycerides polyhydroxy compound is widely used as an ingredient for the
manufacture of polyurethane, additives for plastics, lubricants, surfactants and others
so that the need for these compounds to be very high.
Triglycerides polyhydroxy compound is produced through hydroxylation
reactions. Hydroxylation reaction involves two steps reactions, epoxidation reaction
formation of the epoxide rings (oxiranes) and followed by oxirane ring opening
reaction. Triglycerides unsaturated compounds contained in the vegetable oil is

diepoksidasi using peroxy acid (which is made of a carboxylic acid and hydrogen
peroxide), and will produce epoxide compound whose numbers can be expressed in
numbers oxiranes.
Epoxide oil can be used directly as a plasticizer in a polymer matrix to
produce a material suitable for polyvinyl chloride (PVC), it is very important to
control the viscosity of the PVC during the manufacturing process and as a stabilizer
of PVC resin to improve flexibility, elasticity, strength and to maintain the stability of
the polymer to heat and UV radiation. Oxirane ring high reactivity causes epoxy can
also be used as a feedstock for some chemicals, such as alcohols, glycols,
alkanolamine, carbonyl compounds, olefin compounds, and polymers such as
polyesters, polyurethanes and epoxy resin (Gan, 1992).

Daftar Pustaka
Escrig, Pilar De Frutos, and Martin, Jose Miguel Campos, (2000), Process
for Epoxidation of Olefinic Compound with Hydrogen Peroxide, U.S.
Patent No. 6,160,138
Fessenden, R. J., Fessenden, J. S. (1999), Kimia Organik, Jilid 1, Edisi ketiga,
Penerbit Erlangga, Jakarta
Gan, L.H., Goh, S.H., and Ooi, K.S., (1995). Kinetic Studies of Epoxidation
and Oxirane Cleavage of Palm Olein Methyl Esters. JAOCS. vol. 69,
pp. 347 351
Gan, L.H. Goh, S.H. and Ooi, K. S. 1992. Effect Of Epoxidation On The
Thermal Oxidative Stabilieties Of Fatty Acid Esteis Derived From
Palm Olein. JAOCS. Vol 72
Ketaren,S. 1986. Minyak dan Lemak Pangan. Cetakan I. Jakarta. UI Press
Marlina, dkk. 2004. Component of Caster Oil. Erlangga :Jakarta 35-45
Hamilton,R.J. dan Rossel,J.B. 1986 . Analysis of Oils and Fats. New York.
Elsevier

Weiss,T.J.1983. Food Oil and Their Uses. Second Edition. New York. Avi
Publishing Company Inc
Torsell, K. B. G. 1983. Natural Products Chemistry, A Mechanistic and
Biosynthetic Approach to Secondary Metabolism. New York : John
Wiley And Sons Limited.