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Preparation of maleinized castor oil (MCO) by conventional method and it's

application in the formulation of liquid detergent

Article · January 2013

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 International Journal of ChemTech Research
CODEN( USA): IJCRGG ISSN : 0974-4290
Vol.5, No.4, pp 1886-1896, April-June 2013

Preparation of Maleinized Castor oil (MCO) By Conventional

Method And It’s Application in the Formulation of Liquid
Detergent.

Bhalchandra P. Vibhute¹*, R.R.Khotpal¹,

Vijay Y. Karadbhajane², A.S.Kulkarni²

¹Department of Oil, Fats & Surfactant Technology, Laxminarayan Institute of

Technology(L.I.T), Nagpur ,M.S., India
²Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur, M.S., India-440033

*Corres. Author: [email protected]

Contact No : +919730020505

Abstract: Castor (RicinusCommunis L.) seed oil has found wide application in the coatings, cosmetics &
detergents.India is the largest exporter of castor oil in the world.35-55% of the seed content is a valuable drying
oil with many industrial applications.In the present study, modification of castor oil through the melainization of
castor oil carried out with the use of maleic anhydride to form maleinized castor oil.In this method of addition of
unsaturation compound to the unsaturated part of the oil molecule, thus increasing its complexity and heat
reactivity.The product obtained from maleic addition is known as the adduct which when neutralized with
inorganic alkali, ammonia gives water miscible oils. Their solubilized oils may be used for different applications
like cosmetics,detergents etc. The application of melainized castor oil has been done in the formulation of liquid
detergent Liquid detergents prepared by this resin with acid slurry in different proportions are giving excellent
results in comparison with that of commercial products.This research was undertaken to develop products which
are based on naturally available raw materials specifically not of petroleum origin .This is an attempt to make
the novel products useful for society and to reduce percentage of non-renewable product usage in day to day life
thus solving problem of environmental pollution to some extent and thus favor eco-friendly products
technology.
Keywords: Castor oil; Maleinized Castor oil ; Liquid Detergents ; Maleic anhydride.

1.Introduction1-5

Castor (RicinusCommunisL.) is cultivated around the world because of commercial importance of its oil. Castor
grows best under tropical conditions. It is extensively cultivated in a few states in India namely, Rajasthan,
Gujarat and Andhra Pradesh which have suitable climatic conditions. India produces on an average, around
800,000 tons of castor seeds annually, accounting for about 75% of the total world production. Brazil and China
constitute the balance global castor seed production. In recent years however, Brazil and China have
experienced stagnation in castor crops. In India, castor is planted during July/August and harvesting commences
Bhalchandra P. Vibhute et al /Int.J.ChemTech Res.2013,5(4) 1887

around December/ January. The castor seed and its oil can be stored for long time without affecting its quality.
The Indian variety of castor oil has an oil content of about 48%. The castor seed products are oil and cake,
where the oil has large industrial uses like paints, lubricants, pharmaceuticals, textiles, plastics etc. and the cake
is used as organic manure in agriculture field.
The castor bean contains 50-55% oil. The oil itself contains a number of fatty acids similar to those in cooking
oils, such as oleic acid, linoleic acid, stearic acid and palmitic acid. However, among vegetable oils, castor oil is
distinguished by its high content (over 85%) of ricinoleic acid. No other vegetable oil contains so high a
proportion of fatty hydroxyacids. Castor oils unsaturated bond, high molecular weight (298), low melting point
(50C) and very low solidification point (-120C to -180C) make it industrially useful, most of all for the highest
and most stable viscosity of any vegetable oil (Bonjean, 1991).
2. Market And Market Potential1-5
Castor oil is sold either for pharmaceutical or industrial use. Specification for pharmaceutical use can be
found in the European Pharmacopeia. The industrial type may be divided into first, second and third quality.
Only pressed castor oil, extracted without solvents, can be called first quality. These oils, produced in Europe,
are virtually colourless and have very low acidity. Second and third quality oil are commercial names, meaning
that the oil has been extracted using solvent.35-55% of the seed content is a valuable drying oil with many
industrial applications.
The primary use of Castor oil is as a basic ingredient in the production of nylon 11, sebacic acid, plasticizers and
jet engine lubricants, nylon 6-10, heavy duty automotive greases, coatings and inks, surfactants, polyurethanes,
soaps, polishes, flypapers, paints, varnishes, lubricants, and many other chemical derivatives and medicinal,
pharmaceutical and cosmetic derivatives.
The plant is also used for fibre, an insecticide and repellent. Cellulose from the stems is used for making
cardboard and paper products.
The oil from the seed is a very well known laxative and purgative that has been widely used for over 2,000
years. It is so effective that it is regularly used to clear the digestive tract in cases of poisoning. The oil has a
remarkable antidandruff effect. The oil is well tolerated by the skin and so is sometimes used as a vehicle for
medicinal and cosmetic preparations. Castor oil congeals to a gel-mass when the alcoholic solution is distilled in
the presence of sodium salts of higher fatty acids. This gel is useful in the treatment of dermatitis and is a good
protective in cases of occupational eczemas and dermatitis. Medicinal applications consume a tiny fraction of
total production.

Table No:1-Properties of Castor oil:

Density (20 oC) 0.956 - 0.963 g/ml
Viscosity (20 oC) 9.5-10.0 dPa.s
Refraction index n2d 1.477 -1.479
Saponification value 177- 187
Iodine value 82 – 88
Unsaponifiable matter 0.3 -0.5%
Hydroxyls 160 minimum

3.Aim and Objective of Present Research Work1-5:

The present work is aimed at developing the Oleo-chemicals based on Castor oil which can be used in liquid
detergents. In the first stage of the work, preparation of Maleinized Castor oil has been standardized by
choosingproper ratio of reactants, time of heating and cooking schedule to get desirable properties. This
Maleinized Castor oil is used as substitute of conventional ingredients in liquid detergents. Thus, several
formulations of liquid detergents have been attained in which a part of Acid Slurry has been replaced with
Malenized Castor oil.
Bhalchandra P. Vibhute et al /Int.J.ChemTech Res.2013,5(4) 1888

This research is undertaken with the objective to develop products which are based on naturally available raw
materials specifically not of petroleum origin .This is an attempt to make the novel products useful for society
and to reduce percentage of non-renewable product usage in day to day life thus solving problem of
environmental pollution to some extent.
4.Malenized Castor Oil

A number of methods have been suggested for improving the properties of drying oil which involve the
separation of better drying from the poorer drying components (segregation), removal of water to introduce a
new double bond (dehydration).
There is a method of adding unsaturation compound to the unsaturated part of the oil molecule, thus
increasing its complexity and heat reactivity. The compound referred to is maleic anhydride and the oils are
known as maleic treated or Maleinized oils. Since the maleic is added far or near the unsaturation section of the
fatty acid radical, it retards oxidation slightly so that maleic treated oils do not show greatly increased air drying
properties. However, they are definitely faster bodying and have better color and at equal viscosity, better water
resistance in the dried fillers.

Maleic Anhydride: - It is a dibasic acid, which reacts with both conjugated and isolated double bonds in the
following manner-
OH HC CH HO

C C C C C + C C C C C C C

O O O HC CH 2

C C

O O O

The product obtained from maleic addition is known as the adduct which when neutralized with
inorganic alkali, ammonia or amine gives water miscible oils. Their solubilized oils may be used for different
applications like cosmetics, water paints of emulsion type disinfectants etc. based on the amount of maleic
allowed to react with the oil. Usually 10-25% of maleic anhydride is sufficient to produce the desired increase in
neat reactivity in the non-conjugated oils. However, up to 15% maleic is made to form an adduct with the
unsaturation portion of the fatty acid radicals in drying oils to get optimum desirable properties.

5.Mechanism Of Adduct Formation:

Clocker in U.S. patent 2,275,843 proposed that additions of maleic takes place at double bonds as
follows:

H H HC CH H H

R C C R’ + C C R C C R’

O O O HC CH

C C

O O O
Bhalchandra P. Vibhute et al /Int.J.ChemTech Res.2013,5(4) 1889

However, this mechanism does not appear to be likely because it would be difficult to form a four-member ring
under specified conditions and this type of ring structure is not very stable.

A Diels- Alder type of addition is entirely possible for oils with conjugate unsaturation.

This type of reaction does not take place with oils having non-conjugated unsaturation unless the
conditions are such that the oil isomerizes to the conjugated form during the reaction. Wheeler Et Al has stated
in the studies of maleic treated methyl ester type of isomerization and addition occurs with methyl linoleate and
maleic anhydride.
From this result, they concluded that transfer of a hydrogen atom from the fatty acid chain to the maleic
anhydride formed a substituted succinic anhydride as follows;

Wheeler et al also found that the first molecule of maleic anhydride reacting with methyl linoleate reacts
mostly to saturate one double bond, and the second one adds without affecting the unsaturation, in addition, they
also found that the first two molecules of anhydride reacting with methyl linoleate react mostly to saturate one
double bond each, and the third molecule adds without affecting the unsaturation. The unsaturation was
determined by the Wij’s iodine method, and it was recognized that this method is not accurate if conjugated
unsaturation has been formed. Therefore these works for the linoleate and linoleate adducts gave no structures.
Kappelmeir believes that, with oleic radicals, the addition takes place as indicated above with the
formation of a succinic anhydride derivative without affecting the double bonds.
With the linoleic esters, the first molecule adds to form the succinic anhydride derivative and shift in the
unsaturation occurs to form the conjugated type. The second molecule of maleic anhydride then adds to the
conjugated unsaturation occurs to form the conjugated type. The second molecule of maleic anhydride then adds
to the conjugated unsaturation by the Diels-alder type of reaction. Therefore the structure obtained from the
addition of one and two molecules of maleic would be as follows :

One molecule of maleic added:

Bhalchandra P. Vibhute et al /Int.J.ChemTech Res.2013,5(4) 1890

Two molecules of maleic added:

In case of the linoleic radicals Kappelmeir believes that a molecule of maleic anhydride may be added
simultaneously to both ends of the unsaturated portion with the consequent formation of a triple conjugate
system. This would be followed by the addition of a third molecule of maleic anhydride may be added
simultaneously to both ends of the unsaturated portion with the consequent formation of a triply conjugate
system.
This would be followed by the addition of a third molecule of maleic by a Diels-Alder mechanism to
give the structure shown below:

Two molecules of maleic added:

Three molecules of maleic added:

Kappelmeir describes a possible method for determining the extent of the maleic addition from the fact that
dimethyl aniline forms a highly coloured product with free maleic anhydride.

6. Materials and Methods1-5:

Chemicals Required: Wij’s solution, KI, water, Sodium indicator, carbon tetrachloride,0.5 Nalco. KOH, 1%
phenolphthalein indicator, 0.5 N hydrochloric acid, Neutral alcohol 0.1 N, Phenolphthalein Indicator, Oxalic
acid, 0.1 N Alco. KOH
Apparatus: Conical flask burette, pipette, balance, water bath & heater,Flat bottom flasks (250 ml capacity),
reflux condenser, burette, balance,I.V. bottles,Ford cup No. 4 , refractometer.
Bhalchandra P. Vibhute et al /Int.J.ChemTech Res.2013,5(4) 1891

Table No:2-Various raw materials were used in this project. Their properties, grades and sources are tabulated
below-
Raw Materials Grade Source Properties
Castor oil Specific Gravity:0.958
Boiling pt.: 0.950 to 0.970
Refractive Index:1.4790
Sap value:176-187
Iodine Value: 83-89
Acetyl value:150
Unsaponifiable matter:0.3 to 0.37
KOH Laboratory S.D.Fine Appearance:
chemical Chemical White deliquescent solid
s Specific Gravity: 2.04
pH: 13.5 (0.1 molar solution)
Boiling Point: 1320 0C
Melting Point: 3600C
Sorbitol Laboratory Samar Physical state and appearance: Solid
chemical Chemical Molecular wt.:182.17 gm/mole
s Boiling Pt.:decomposes
Melting pt.:111.50C
Sp. Gravity:1.489
Tween-20 Laboratory Ranbaxy Mol. Formula: C18H34O6
chemicals fine Mol. Wt:346.5
chemical Boiling pt: 1000C
s Density: 1.11 gm/ml at 200C
Refractive Index:1.468
SLS Mol. Formula: CH3(CH2)10CH2OOSOONa
Mol. Wt.:288.38 gm/mole
Colour : Whitish to yellow
Melting pt:2040C
SLES Mol. Structure:

Mol.wt.376.48
Mol. Formula: C12H25O.(C2H4O)2.SO3.Na

7. Experimental Setup:
Experimentation has been done in following stages –
1)Analysis of castor oil was done by determination of it’s acid value (A.V.) , Saponification Value(S.V.) ,
Iodine value(I.V.), Acid Value(A.V.), viscosity, refractive index, density, color and consistency…etc.
2) Saponification byConventional method
3) Maleinization of castor oil:
a) Analysis of Maleinized oil
b) Applications of Maleinized castor oil
Bhalchandra P. Vibhute et al /Int.J.ChemTech Res.2013,5(4) 1892

THE REACTOR SETUP

Saponification process of castor oil :

Conventional process : Weigh 100 gms Of Castor oil .According to its sap. Value, weigh KOH (dissolved in
minimum amount of water) .Add 2-3 ml. of neutral alcohol to this KOH. Add this alco. KOH solution to the
sample & heat the mixture for 1-2 hrs. till the mass becomes homogenous. Mixing of two layers shows that the
saponification is complete.
Analysis of Saponified oil :
After saponification process, the sample was checked for its solubility in water. Mass which is completely
soluble in water and forms a turbid solution with water is said to be completely saponified.

8.Synthesis of Maleinized oil

1) The Reactor: The preparation of maleinized oil was carried out in a glass reactor. The reactor consists of two
parts. Lower part of the reactor is a round bottom vessel with very wide mouth. The capacity of the flask is
about 2 liters. The upper part of the reactor is its lid, having four necks with standard joints. A motor driver
stirrer was inserted in the reactor through the central neck, while another neck was used for thermometer. A
condenser was fitted with the reactor through the third neck. And the fourth neck was used for dropping the
chemicals into the reactor. The reactor was heated by an electric heating mantle having special arrangement for
smooth control of the temperature of the reactor. A regulator controlled the speed of the stirrer. The reaction
vessel and its lid were tied together with the help of clamp

2) Methodology & Cooking Schedule Of Maleinized Oil Synthesis: The reaction, temperature & addition of
ingredients are detailed below;
Step 1) Maleic Anhydridewas added in approximate quantity of castor oil to form a slurry. Step 2) The slurry
was then introduced in the reactor and heated with agitation to a temp. of 100 0C in 1 hr.
Step 3) The slurry was further heated for one and a half hour at 125°C
Step 4) Heating was continued for another one and a half hour at 180°C.
Step 5) the darkening and thickening (i.e. viscosity) of treated oil was observed periodically and the reaction
was terminated when sufficient viscous mass was observed giving an indication of almost complete reaction of
maleic with oil.
Bhalchandra P. Vibhute et al /Int.J.ChemTech Res.2013,5(4) 1893

Flow-sheet No:1

Procedure : Total Charge 1 Kg

Castor Oil half quantity +Maleic anhydride

Mix all ingredients into the reactor

Heat at 1000C with continuous stirring for complete mixing

Raise the temperature upto 1250C for 1.5 hrs.

Raise the temperature upto 1800C for 1.5 hrs

Cool down the batch and withdraw.

9. Application of Maleinized Castor Oil in Liquid Detergents:-

To use the preparedmaleinized oil in a liquid detergent it is necessary to neutralize it by using
Triethanolamine so that its acid value becomes zero. Neutralized maleinized oil prepared by above method is
used in the liquid detergents having composition shown in the table below. This resin is used in the liquid
detergent in various proportions with acid slurry and analyzed for its effect on the properties such as foam
height, surface tension etc.

Table No:3-Formulation for Liquid Detergent.

Sr. No. Raw materials Composition ( % by weight )
I II III IV V
1) Acid slurry 8 12 16 0 10
2) Neutralized resin 12 8 4 20 10
3) NaOH 4.4 4.4 4.4 4.4 4.4
4) TSP 6 6 6 6 6
5) Urea 12 12 12 12 12
6) SLES 12 12 12 12 12
7) Water 145.6 145.6 145.6 145.6 145.6
Bhalchandra P. Vibhute et al /Int.J.ChemTech Res.2013,5(4) 1894

Analysis of liquid Detergents:-

Liquid detergents were analyzed for the moisture content, foam height and surface tension as per standard
methods.

10. Results& Discussion

Results of different analysis done in present project are tabulated below.

Table No.:4-Analysis of Castor oil.

Sr.No. Properties Value
1 Sap. Value 180
2 Iodine Value 85
3 Refractive Index 1.4790
4 Specific Gravity 0.958
5 Color & Consistency Dark yellow and viscous

Table No.:5-Analysis of Maleinised Castor oil (M.C.O.).

Sr.No. Properties Value
1) Acid Value 40.07
2) Sap. Value 284.6
3) Iodine Value 72.6
4) Refractive Index 1.487
5) Density 0.985
6) Colour & Consistency Dark Brown
7) HLB Value 12.8

Table No.6-Analysis of Liquid Detergents.

Sr. Properties I II III IV V
No. 8:12 12:8 16:4 0:20 1:1
1) % Solid Content 31.4 32.4 33.6 32 32.1
2) Foam % solution 1 0.5 1 0.5 1 0.5 1 0.5 1 0.5
Height i) 0 min. 0 0 350 260 250 220 0 0 320 250
ii) 5 min. 0 0 130 200 200 185 0 0 140 150
iii)10 min 0 0 120 170 150 150 0 0 120 100
iv) 15 min. 0 0 120 170 150 150 0 0 100 100
3) Surface tension - - 55.1 55.3 70.3 84.6 - - 59.2 60.2
( dyne/cm)
3) pH 7.5 7.5 7.5 7.5 7.5

Table No.7-Analysis of commercial Detergents

Composition % Foam Height Surface Tension
conc. 0 5 10 15 (dyne/cm)
Surf Excel 0.5 340 315 295 270 36.944
1 390 370 345 315 29.160
Nirma 0.5 310 295 270 255 36.909
1 360 335 300 275 30.253
Bhalchandra P. Vibhute et al /Int.J.ChemTech Res.2013,5(4) 1895

Graph No.1

Graph No.2

Graph No.3
 Bhalchandra P. Vibhute et al /Int.J.ChemTech Res.2013,5(4) 1896

Commercial Products:

Graph No.4

Graph No.5

12.Conclusions:
1. Saponification of castor oil is carried out to a greater extent by the conventional method.
2. Maleinized castor oil has been prepared using maleic anhydride and castor oil for improvement in its
properties like acid value, viscosity etc.
3. Petroleum jelly, mineral oil and lanoline can be replaced by maleinized castor oil. So our products are
eco-friendly.
4. Liquid detergents prepared by above resin with acid slurry in different proportions are giving excellent
results. Some of them like I, III & V are having stable foam, while formulations II & IV form foamless
detergents.

13. References:
1. Brittany L. Hayes, ‘Microwave Synthesis Chemistry’, CEM Publications.
2. Payne, I.I.F., Organic Coating Technology, Vol. II, John Wiley Sons, New York, 1961.
3. Sagarin E Science and Technology ( Interscience Publishers, John Wiley and Sons, Newyork) 3rd Edition.
4. Swern, Daniel, ‘Bailey’s Industrial Oil and Fat Products’, Vol. I, 4th Edition.
5. W. M. Morgan, Vol. I, 4th Edition.

*****

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