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NATURAL & SYNTHETIC WAX EMULSIFICATIONS

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Proceedings of the 36th Annual International Conference Minna, Nigeria
Copyright © Chemical Society of Nigeria
All right of reproduction in any form reserved
NATURAL & SYNTHETIC WAX
EMULSIFICATIONS
R.U. Duru, G.I. Airuehia and J.O. Otaigbe
Department of pure and Industrial Chemistry
University of Port Harcourt
E-mail: rudchem@yahoo.com
ABSTRACT
A synthetic wax, capable of acting as a non-ionic emulsifier
has been prepared. The Hydrophile- Lipophile Balance (HLB)
of its combination with an ionic emulsifier suitable for the
formation of O/W emulsions of paraffin wax and Beeswax was
determined. Blends of the synthetic wax with paraffin and
Beeswax respectively, (natural waxes) were used to formulate
O/W emulsions with good stability.
Keywords: Hydrophile-Lipophile Balance, Natural wax, Non-
ionic emulsifier, Oil in water emulsions, Synthetic wax.
1.0 INTRODUCTION:
The name “Wax” is derived from the Anglo-Saxon
term, wax – the natural material from honeycomb of the bee. In
recent times, the name wax has been used in a wider sense and,
it applies to all wax-like materials, solids or liquids that are
composed of esters of higher fatty acids and long chain
monohydric alcohols (1, 2). They may also contain any of high
molecular weight acids, ketones, hydrocarbons, sterols,
diesters, etc. (1)
Generally, waxes have the following physical properties:
1. They are non-greasy and are harder than fats.
2. Waxes are solids at 200C and crystalline melt above
400C without decomposition.
3. They have relatively low viscosity above their melting
point.
4. Their solubility and consistency properties are
strongly dependent on temperature.
5. Waxes are cable of being polished under slight
pressure.
A wax is either synthetic or natural and depending on
the source, natural
wax is either of vegetable, insect, animal or mineral origin.
Some of the well-studied waxes are as follows: -
1.2 VEGETABLE WAXES
471
Carnauba wax: Extracted from the leaves of a Palm
tree species called carnauba Palm (Corpernecia Prunicia) that
grows almost exclusively in North Eastern Brazil, Particularly,
in the State of Ceara and Piani.
Candellila wax: Euphorbia antisiphilitica, Euphorbia
Cerifera and Pedilanthus are the three species of leafless desert
shrubs that exist in Mexico and South-Western United States of
America from which candellila wax is obtained. Unlike most
other waxes, the candellila wax exhibits little change in volume
on phase change(4). A refined candellila wax is brownish in
colour.
Sugar cane wax: Recovered as a by-product when
sugar cane is processed in a very large quantity (as in Cuba).
The dull yellow wax which is hard and brittle is composed of
about 80% wax esters and some free acids, alcohols and
hydrocarbons(3).
Others are Japan wax, Bayberry wax, Jojoba wax and
Rice bran wax.
1.3 INSECT AND ANIMAL WAXES
Beeswax: Beeswax is the first wax ever known and
the most studied of the natural waxes. It is secreted by the hive-
bee, Apis Indica, Apis dorsata, Apis flores and Apis Mellifera
to build the honeycomb. The wax is harvested by melting the
comb in boiling water, after removing the honey. The melt is
then filtered and cast into cakes. The brittle wax is yellow when
refined and white when bleached. Beeswax chemical
constituents vary in their percentage composition as they
depend on the geographical origin. However, they generally
contain alkyl esters of monocarboxylic acids, lactone, free
alcohols, free wax acids, hydrocarbons(3), colouring matter (for
the unbleached wax), moisture and mineral impurities.
Spermaceti wax: The source of spermaceti wax is an
oil derived from the head of the sperm whale. The oil contains
a considerable amount of ester made up of unsaturated alcohols
and acids which yields the wax when saturated.
1.4 MINERAL WAXES
Montan wax: Derived from lignites and brown coal
that are of German origin. It is also produced in some parts of
the United States of America.
Ozokerite wax: Also known as ceresin wax is an
earth wax mined in Poland, Austria and Commonwealth of
Independent States.
Petroleum wax: About 90% of all waxes used in the
industry today are produced primarily from lubricating oil
fractions of petroleum(1). Petroleum wax is essentially of two
types; paraffin wax (macrocrystalline) and petrolatum
(microcrystalline). The paraffin wax has an average molecular
Proceedings of the 36th Annual International Conference Minna, Nigeria
Copyright © Chemical Society of Nigeria
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weight of 350-420(3) and is composed of about 40-90% by RICE

weight of normal paraffins(4), the remainder being C28 – C36 BRAN
isoalkanes and cycloalkanes. On the contrary, the petroleum WAX
with an average molecular weight of 600-800 contains a
substantial number of hydrocarbons that are not normal INSECT/ MONTAN 82- 48 - 112
alkanes. The quality of wax derived from crude petroleum
ANIMAL WAX 87
varies with the source of the crude. Crude from the United - - -
States, Venezuela and Romania, for example, contains high WAX
concentrations of petroleum wax. Some of the physical PARAFFIN 46-
WAX 68 - - -
properties of the waxes are presented in Table 1.

1.5 SYNTHETIC WAXES PETROLA 60-

TUM 93
Polyethylene wax: When polymerization of ethylene
is carried out under controlled conditions, polyethylenes of low
molecular weight (< 2000) are produced. These polyethylenes
having wax-like properties are used in conjunction with SYNTHE POLYETH 106- - - -
petroleum wax in food packaging applications. TIC WAX YLENE 115
Other Synthetic waxes are Polymethylene wax and WAX
carbowax - - -
POLYMET
Table 1: SOME PHYSICAL PROPERTIES OF WAXES (3,1,4,) HYLENE 45-
WAX 106
TYPE NAME OF MEL ACI IOD SAP
OFWAX WAX TING D INE ONIF

POIN NUM - 1.6 EMULSIONS: AN OVERVIEW

T BER ICAT
An emulsion is a colloidal dispersion consisting of two
ION
RAN incompletely miscible liquids, one (the dispersed or internal
phase) being distributed in finite globules in the other (the
GE NUM
continuous or external phase). The diameter of the globules of
BER the dispersed phase is normally between 0.1micron and
(0OC)
10micron for usual emulsion types. A third component, the
emulsifying agent, without which the emulsion may
VEGETA CARNAUB 82- 8 10 80
immediately break down into layers is usually present at the
BLE A WAX 86 interface between the two phases. An emulsifying agent,
14 33 55 therefore, promotes the ease of formation and the stability of
WAX CANDELL 68- emulsions.
ILA WAX 74 - - -
1.7 EMULSION TYPES AND CHARACTERISTICS:
SUGAR 79- 18 - 217 Water and oil emulsions are the most widely studied.
WAX 81 The industries are mostly concerned with the emulsification of
15 - 220 oil and water. As a result, for emulsions of varied compositions,
JAPAN 51- the term oil-in-water (O/W) is used to designate emulsions
- 6 - when the dispersed phase is oil or oil-related liquids.
WAX 53
Conversely, Water-in-oil (W/O) is used to designate emulsions
- 20 75- when the dispersed phase is water or related liquids.
BABERRY 42-
120
WAX 48 In most cases, the relative volumes of the two phases determine
the type of emulsion formed. The higher its phase volume, the
JOJOBA - more likely a liquid is to become the continuous phase.
WAX However, the dispersed phase may occupy up to 74% of the
75-80 total volume when the particles are uniformly spherical. Stable
emulsions above 74% of the dispersed phase may also be
possible when the droplets are not of uniform size and can,
472
Proceedings of the 36th Annual International Conference Minna, Nigeria
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therefore, be packed more densely or be deformed into
polyhedral particles in close contact(5). In practice, for
concentrations of the phase above 70%, the emulsion will either
contain deformed polyhedral particles in close contact or tend
to invert into emulsions of the opposite types with less than
30% of the dispersed phase.
There are handy tests to determine whether an emulsion is O/W
or W/O type viz: -
i The emulsion mixes readily with a liquid which is
miscible with the continuous phase
ii The emulsion is readily coloured by dyes that are
soluble in the continuous phase.
iii O/W emulsion usually exhibit higher electrical
conductivity than W/O emulsions.
The gross properties of an emulsion are in general determined
by the nature of the continuous phase. For example, milk, an
O/W emulsion, is watery, whereas butter, a W/O emulsion is
greasy. For both O/W and W/O emulsions, the physical
appearance is controlled by the particle size and the difference
in the refractive index of the continuous and the dispersed
phases (5). This ranges from transparency, when the dispersed
phase is very small (less than 0.05 microns) or for two phases
of the same refractive index to distinguishable phases when the
particle size of the dispersed phase is far above 1micron. In
between these two, emulsions may appear grey-
semitransparent, blue-white or milky in their increasing order
of particle size.
1.8 EMULSION STABILITY: Usually, emulsion stability is
thought of with reference to two major phenomena; creaming
and coagulation. Creaming describes the settling or rising of
the droplets of the dispersed phase in the system. The rising or
settling depends on the specific gravities of the two phases and
as the creaming continues, the droplets of the dispersed phase
crowds together more and more and this may eventually lead
to phase separation. The greater the difference in the specific
gravities between the two phases, the higher the rate of
creaming. Creaming tendencies can be reduced by producing
finer particle size and greater electrical charge of the dispersed
phase as well as increased viscosity of the continuous phase.
Coagulation is as a result of collisions of the internal
phase droplets leading to the formation of large globules and
consequently, phase separation. In order words, this is the
actual breakdown of the emulsion as it occurs when the
interfacial film ruptures at the point of juncture of the two
phases’ particles. A careful choice of the type and quantity of
the emulsifier employed provides stability against
coagulation.
There are other stability requirements that may be
considered in relation to the application of the emulsion, e.g.
473
stability to freezing and stability to elevated temperature. It
can generally be stated that the stability of emulsions depends
on several factors, such as particle size of the internal phase,
the density difference between the two phases, viscosity, the
presence of emulsifying agent, the electrical double layer
repulsions(6), the interfacial tension and the age of the
emulsion.
1.9 EMULSIFYING AGENTS AND THEIR
PROPERTIES
Emulsions formed without the third component, an
emulsifying agent will almost immediately separate into its
two phases especially, at a higher concentration of the
dispersed phase. An emulsifying agent is a surface-active
agent (surfactant) that facilities the ease of formation and the
stability of emulsions.
Surfactants generally have the tendency of being
soluble in both water and oil or their equivalents. This special
characteristic is accomplished by the possession of a polar
hydrophilic group, which may be anionic or cationic, as well
as a non-polar lipophilic chain which makes it soluble in oil.
There also exists a non-polar surface-active agent that contains
units or groups that also exhibit a strong affinity for water, for
example, the monomer units of polyethylene oxides.
Emulsifiers may, therefore, be classified as cationic, anionic
and non-ionic or ampholytic according to the charge they
possess.
Because of their dual solubility nature, emulsifiers tend to be
strongly adsorbed at the O/W interfaces to form an oriented
monomolecular layer, hence the term “Surface activity”. The
phenomenon favours an expansion of the interface and this
must be balanced against the tendency for the interface to
contract under normal surface tension forces. Assuming π to be
the surface pressure of an adsorbed layer of the emulsifier, then,
the interfacial tension (Io) will be lowered to a value;
I = Io - π (5)
Thus, on addition of an emulsifier to a value where π ≥ Io,
emulsification will readily take place.
1.10 THE HYDROPHILE-LIPOPHILE BALANCE
(HLB) IN EMULSION FORMATION: The type of
emulsion which tends to form depends on the balance between
the hydrophilic and the lipophilic properties of the emulsifier.
HLB is an expression of the relative simultaneous attraction of
an emulsifier for two phases of the emulsion being considered.
A high HLB value means a stronger attraction for the water
phase (hydrophilic) and tendency to form O/W emulsion.
Conversely, lipophilic emulsifier will have a low HLB value
and favour W/O emulsions.
A study too has however shown that emulsions stabilized with
non-ionics such as polyoxyethylene alkyl or alkyl aryl ethers
Proceedings of the 36th Annual International Conference Minna, Nigeria
Copyright © Chemical Society of Nigeria
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form O/W type of emulsions at lower temperatures and W/O

type of emulsions at higher temperatures.

A number of different formulae have been established for

calculating HLB values from composition data(5). Two of the
formulae are as follows:-

1. HLB = E/5, where E is the weight percentage of the

hydrophilic portion of the molecule. For example, the
hydrophilic portion of the polyoxyethlene stearate
which is the oxyethylene was determined to be 85%,
HLB = 85/5 =17.

2. HLB = 20(1 – S/A) where S is the saponification value

and A is the acid number of the emulsifier. For example, the
saponification value and acid number of a grade of sorbitan
monolaurate was determined to be 164 and 290 respectively.
HLB = 20 (1 – 164/290) = 8.7. For some non-ionics and most
ionics however, the above formulae may not be satisfactory
for calculating their HLB, in which case they are
experimentally determined. The HLB values for many
surfactants have been published(5) and some are presented in
the table II below.

1.11 FORMULATION OF WAX EMULSIONS:

For every emulsion formulation, the first procedure is
the selection of the required HLB system for that particular
formulation. In most cases, a blend of two emulsifiers is
usually preferred. If x is the proportion of one of the
emulsifiers having an HLB of A and the other has an HLB B,
the combined HLB is calculated as

XA + (1-X) B

For wax emulsions, the range of the HLB to be selected depends

on the type of emulsion desired, i.e. whether O/W or W/O and
this, in turn depends on the expected application of the
emulsion.

Using the best HLB selected for a particular formulation, blend

of the emulsifier types available are also tried to determine the
best blend to be used. In the formulation process, the wax is
heated to 5 – 100C over the melting point of the wax. All the
oil-soluble materials such as dyes, medicine and pesticides that
may be required in the formulation including the lipophilic
portion of the emulsifier are added or dissolved in the melted
wax to form the oil phase. The water phase is heated to about
30C over the temperature of the melted wax. As with the oil
phase, the water-soluble ingredients are added to the water
phase.

TABLE II: HLB VALUES OF SOME SURFACTANTS (5)

474
Proceedings of the 36th Annual International Conference Minna, Nigeria
Copyright © Chemical Society of Nigeria
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agitation of the later. The mixture becomes cloudy at first and

then assumes a milky cast as the viscosity increases thereby
TYPE CHEMICAL DESIGNATION TRADE NAME HLB giving rise
to a W/O
CATIONICS POLYOXYETHLENE AKLYL AMINE Atlas G-3780A 15.5 emulsion.

If the
N-ETHYL MORPHOLINIUM
addition of
the water
ETHOSULPHATE
phase is
continued,
QUATERNARY AMMONIUM
at a point
called the
DERIVATIVE Atlas G-263A 25.30
inversion
point, the
HIGH MOLECULAR WEIGHT AMINE
viscosity
suddenly
BLEND Atcos G- HC 18.5
decreases
and this is
HIGH MOLECULAR WEIGHT FATTY AMINE suggestive
BLEND of the fact
Atlas G- 3570 4.5 that the
emulsion
ANIONICS ALKYL ARYL SULPHONATE Atlas G-3300 11.7 has
changed
TRIETHANOLAMINE OLEATE - 12 from W/O
to O/W
SODIUM OLEATE - 18 emulsion.
POTASSIUM OLEATE - 20 There
are other
NON IONICS SODIUM MONOPALMITE Span 40 6.7 methods of

SORBITAN TRIOLEATE Span 85 1.8

GLYCEROL MONOSTEAATE Tergin 515 3.8

POLYOXYETHYLENE

MONOSTEARATE S 541 11.6

POLYOXYETHYLENE SORBITAN

MONOSTEARATE Tween 60 14.9

POLYOXYETHYLENE ALKYL PHENOL Igepal CA-630 12.8

POLYOXETHYLENE

MONSTEARATE Myrj 53 17.9

formulating wax emulsions but the above description covers a

simple laboratory technique. Generally, a good formulation
The next stage which is the emulsification process proper is the depends on a proper choice of the emulsifiers and the extent to
mixing of the two phases. It involves a slow addition of the which one of the phases is dispersed in the other, and for each
water phase into the container of the oil phase with sufficient formulation, a specific procedure must be worked out.

475
Proceedings of the 36th Annual International Conference Minna, Nigeria
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1.12 APPLICATION OF WAX EMULSION: Usually,
possible applications of emulsion come to mind even before the
formulation. This guides the formulator on the choice of the
water phase, the emulsion type, the emulsifier to be employed
and other concentrates that may be required.
One of the major areas of application of wax
emulsions is in polishes. Floor polishes used on wood floors
and linoleum, asphalt, rubber and other types of flooring consist
of waxes blended in a liquid emulsion form with an organic
solvent or water in some cases. Wax polish emulsions contain
between 12 to 20% of wax and are easily applied by a manual
or mechanical process to produce high gloss without buffing(2).
Some of the waxes commonly used in these formulations
include Carnauba wax, Beeswax, Ozokerite wax and Paraffin
wax. In this regard, Carnauba wax has the peculiar ability of
gelling high concentrations of organic solvent and oils.
In addition, cream or solvent polishes for furniture,
shoes and leathers are common products of wax
emulsifications.
An appreciable percentage of wax emulsions is used
in the preparation of cosmetics and pharmaceutical ointments
such as cold creams, soaps, varnishes and lipsticks.
Several other areas of wax applications are known,
whilst some others are yet to be exploited as improved
extraction and purification processes have increased wax
derivation from many other sources.
2.0 RESEARCH OBJECTIVES:
This research work is aimed at investigating the
suitability of a blend of natural and synthetic wax as an
important source of stable emulsions. It is also intended to
compare the wax emulsion properties with respect to their
envisaged applications. As a result of the unavailability of
desired synthetic waxes, the research work was also aimed at
the possibility of synthesizing a wax in the laboratory.
3.0 MATERIALS AND EQUIPMENT
i. Commercial grades of Beeswax, propylene glycol and
stearic acid samples were supplied by MC Anak Nigeria
Limited, Lagos. Paraffin wax and organic solvents were
obtained from the stock of Department of Pure and Industrial
Chemistry of University of Port Harcourt. Adopol and Teepol
emulsifiers were respectively provided by Gamor Chemical and
Allied Limited and National Oil and Marketing Company, all
in Port Harcourt.
ii. Capillary tube method was used to determine all
melting points and are uncorrected.
iii. Viscosity measurements were carried out with the aid
of Fann Viscometer, model 34.
476
iv. Stuart’s Flask shaker was used for mechanical
agitation
v. For all weighing, Metler balance, model AE 240 was
used.
3.1 WAX EMULSIFICATIONS WITH ADOPOL
AND TEEPOL EMULSIFIERS
A-1 Paraffin wax emulsification with a combination
of Adopol and Teepol emulsifiers.
Into a 250ml conical flask, was introduced, paraffin
wax (20g) which was warmed to melting and then kept
at 700C. A mixture of Teepol (12ml) and Adopol (8ml)
was next added into a beaker (250ml) containing
deionised water (50ml) and was then heated to 75 0C.
The conical flask was agitated with the aid of a
mechanical shaker and while this was on, the contents
of the beaker were slowly but steadily added to it. Cold
water (20ml) was added at room temperature after the
formation of the primary emulsion (low energy
emulsification technology, LEE 8). The shaking was
continued until the temperature decreases to 400C.
A-2 Beeswax emulsification with a combination of
Adopol and Teepol emulsifiers.
The procedure as outlined in A-1 above was repeated
except that Beeswax (20g) was used.
A-3
The same experimental procedure as outlined in A-1
and A-2 above were separately repeated, except that
Adopol (15ml) and Teepol (15ml) were used in each
of the experiments.
3.2 B Preparation of Propylene Glycol
Monostearate (PGMS)
Stearic acid (50g, 0.17 mol), propylene glycol (25ml,
0.342 mol) and a catalytic quantity of 3% concentrated
sulphuric acid was refluxed (11/2hrs) in a flat bottom
flask (250ml). At the beginning of heating, the
solution was clear but became more viscous after
about 45 minutes of refluxing. At the end of the
refluxing, the resulting water content was separated
with the aid of a separating funnel. The remaining oily
product was washed with warm water and it became
solid on cooling. On weighing the resulting solid
product after 24 hours, it gave a material in 84.2%
(53.3g) and a melting point of 580C.
3.3 WAX EMULSIFICATIONS WITH TEEPOL
AND PGMS
Proceedings of the 36th Annual International Conference Minna, Nigeria
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C-1.1 Paraffin wax emulsification with a
combination of Teepol and Propylene glycol
monostearate emulsifiers.
A mixture of paraffin wax (20g) and propylene glycol
monostearate (5g) was melted and warmed in a 250ml conical
flask of 700C. The flask was agitated mechanically. Whilst the
agitation was on, a solution of Teepol (3ml) in deionized water
(50ml) at 750C was gradually added to the conical flask
containing a mixture of the paraffin wax and propylene glycol
monostearate. More water (25ml, cold) was added at room
temperature. The shaking was continued until a temperature of
less than 400C was attained.
C-1.2 Paraffin wax emulsifiers with a
combination of Adopol and Propylene
glycol monostearate emulsifiers.
Adopol (7.5ml) and PGMS (3g) was respectively used
in place of the 3ml Teepol and 5g PGMS in C-1.1 above. The
same procedure in the C-1.1 was repeated.
C-2 Beeswax emulsifiers with Teepol and
propylene glycol monostearate emulsifiers.
The procedure in C-1.1 was repeated except that 20g Beeswax
and 5.6g PGMS were used.
3.4 (D-1, D-2……….D-6) Emulsifications with Organic
Solvents
60ml each of Acetone, 1-Butanol and chloroform were
separately used in place of water as the continuous phase, first
with the paraffin wax (D-1 to D-3) and then with the Beeswax
(D-4 to D-6). In each of the cases, the procedure in C-1.1 was
adopted.
3.5 WAX EMULSIFICATIONS WITH STEARIC
ACID AND PROPYLENE GLYCOL.
(E-1, E-2………E-4) Paraffin wax and
Beeswax emulsification with stearic acid
and propylene glycol.
The stearic acid was warmed with the paraffin wax
and the propylene glycol was added to the water. Procedure C-
1.1 and C-2 as outlined earlier (see above) was carried out
separately for each of the paraffin wax and the Beeswax.
3.6 EMULSIFICATION OF SYNTHETIC AND
NATURAL WAX BLENDS
F Emulsification of PGMS Using
Teepol
477
Propylene glycol monostearate (10g) was melted in a
250ml conical flask and then maintained at 700C. Teepol (2ml)
was added to a beaker containing deionized water (40ml) and
then warmed to 750C. With mechanical agitation of the flask,
the contents of the beaker were slowly added to it. A balance of
10ml water was added at room temperature. The shaking was
continued until the temperature of the flask fell below 40 0C.
G Emulsification of PGMS and
Paraffin wax blend with Teepol
emulsifier
PGMS (10g) and paraffin wax (10g) were melted
together and the procedure as described in F above was
repeated, except that a solution of Teepol (4ml) in water (55ml)
at 750C was used and more 25ml water at room temperature
added after the primary emulsion had been formed.
H Emulsification of PGMS and
Beeswax blend with Teepol
emulsifier
Beeswax (10g) and PGMS (10g) was melted in a
250ml conical flask and then maintained at 70 0C. The same
experimental procedure as described in G above was repeated
except that warm water (60ml) and cold (r.t) water (45ml) were
used.
4.0 RESULTS AND DISCUSSION
A. Wax emulsifications with Adopol and Teepol
emulsifiers (A series)
The emulsifications reported in section three above
were all aimed at formulating O/W emulsions. The ‘A
series’ consist of test formulations, involving the use of
different concentrations of the two emulsifiers available
(Adopol and Teepol) separately as well as their
combinations. Three of these series were presented as A-1,
A-2 and A-3 (see section 3) in which a very high
concentration of the emulsifiers were employed. In all of
this series, emulsions were not formed.
A near success was achieved in an attempt to prepare
a non-ionic emulsifier -propylene glycol monostearate,
however, it is believed that in the process of reacting stearic
acid and propylene glycol, a simple acid catalyzed
esterification reaction took place in the main (9).
CH3(CH2)16CO2H + CH3CH(OH)CH2OH
CH3(CH2)16 CO2CH2CH(OH)CH3 + H2O
Although confirmatory qualitative analysis was not
carried out on the resulting product, simple physical
Proceedings of the 36th Annual International Conference Minna, Nigeria
Copyright © Chemical Society of Nigeria
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test/observation (melting point, odour) showed that a new
product as well as an ester may have been formed from the
reaction. It may have been possible for the reaction to take place
in the secondary alcohol of the glycol to give a mixture of the
mono- and the di-stearates in the product, but this should be
limited by the stoichiometric equivalents of the reactants used.
Therefore, di-stearate, if formed at all, will be negligible so that
the product may be reported as the monostearate.
C. Wax Emulsifications with Teepol and PGMS (C
series)
Propylene glycol monostearate (PGMS) was used as a
non-ionic co-emulsifier with Adopol and Teepol ionic
emulsifier to formulate emulsions in the C series
The trial series consist of two sets of six blends in which Adopol
constituted one set while Teepol represented the other and they
were combined with the PGMS in different proportions to attain
an HLB of 10, 12, 14, 16, 18 and 20. For the set involving
Teepol and PGMS blend, the wax was emulsified at the HLB
of 17-20. This was repeated, but only with blends of HLB
values of 16.7, 16.9 and 17.2.
Similarly, the set containing Adopol was emulsified
with the paraffin wax at the HLB range, 10-20. Adjustments
were made for lower HLB values and the best formation was
observed at HLB values of 9.3 and 9.4
The procedure as presented in C-1.1 and C-1.2 (pgs.
16 & 17) respectively are the final formulations that produced
stable emulsions using the PGMS with Teepol and Adopol
respectively.
HLB Calculations
C-1.1 Teepol - 3ml, HLB = 40 (Aprox)(2)
PGMS – 5g, HLB = 3.4
HLB (blend) = x (HLB Teepol) + (1 –X) HLB PGMS (see Pg.
11)
X = Proportion of Teepol in the
blend
HLB (blend) = 0.375 x 40 + (1 – 0.375) 3.4
= 7. 125
C – 1.2 Adopol – 17. 5ml, HLB = 11.7
478
PGMS - 3g, HLB = 3.4
HLB (Blend) = X(HLB Adopol) + (1- X) HLB PGMS.
X = Proportion of Adopol in the blend
HLB (Blend) = 0.714 x 11.7 + (1 – 0.714) 3.4 = 9.32
After a period of 48 hours, it was observed that the
emulsions formed by the Adopol and the PGMS blend had lost
consistency in texture. In line with the objectives of this
research, the rest of the work was therefore continued with that
of Teepol and PGMS blend.
Further adjustments were made on the HLB of the Teepol and
PGMS blend during formulations with Beeswax. C-2 (Page 17)
represents the best result with the Beeswax and it was obtained
at an HLB of 16.
HLB Calculations
Teepol – 3ml, HLB = 40
PGMS – 5.6g, HLB = 3.4
HLB (blend) = X(HLB Teepol ) + (1-X) HLB PGMS
X = proportion of Teepol
HLB (blend) = 0.349 x 40 + (1- 0.349) 3.4
= 16.2
Apart from the adjustment in the HLB, it was observed
that the Beeswax had a higher change in volume on
emulsification when compared with the paraffin wax. In other
words, the Beeswax required about one and half times more
water phase to produce an emulsion of the same texture.
D. Wax Emulsification with Organic Solvents (D series)
In the D series, emulsion formulations were separately
tried with Acetone, 1-Butanol and chloroform as organic
solvents. For both the paraffin wax and the Beeswax, and at
various proportions of the emulsifier blends, no emulsion was
formed. Formations with non-aqueous solvents are usually
based on trial and error process (2). The HLB system may exhibit
some effectiveness if one of the phases is strongly hydrophilic.
The basis of operation of the system which is the attraction to
an aqueous phase is not present. It is only therefore a matter of
chance if correlation exists.
In general, non-aqueous emulsions are much more
difficult to form and stabilize than their aqueous counterparts.
Proceedings of the 36th Annual International Conference Minna, Nigeria
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E Wax Emulsification with Stearic acid and
Propylene Gycol (F series)
Stearic acid and propylene glycol are used directly in
some formulations in combination with other modifiers and/or
co-emulsifiers (8). In the E series stearic acid and propylene
glycol, as precursors to the PGMS were employed directly. In
this experiment, there was an initial formation of emulsions
with both the Beeswax and the paraffin wax, but a clear
separation of the two phases was observed after 24 hours,
indicating unstable emulsions.
F-H Emulsifications of Synthetic and Natural Wax Blends
(F-H series)
At a ratio of 1: 1, PGMS (a synthetic wax) was blended
with paraffin wax in G, and with Beeswax in H to produce very
stable emulsions. 4ml Teepol per 10g of the PGMS being the
optimum value was used to form the emulsions. This gave an
HLB value of 18.58 for both the Beeswax and the paraffin wax.
The use of PGMS as an emulsifiable synthetic wax had earlier
been confirmed in formulation F where a stable emulsion was
formed by the use of 2ml Teepol per 10g of the wax (HLB,
15.0).
CONCLUSION
The synthesis of the propylene glycol monostearate
was as a result of necessity and it served a dual purpose; a non-
ionic emulsifier in formulations C, F-H and as a synthetic wax
in formulations F-H.
Emulsion formation with Teepol and Adopol,
separately, as well as in the combined state was not possible.
This is exemplified by the formulations in the ‘A’ series.
Furthermore, direct use of its precursors, stearic acid and
propylene glycol could not form a stable emulsion.
All the emulsions formed were observed for over a
period of days, ranging from 0 to 100 days. Within this period,
they were subjected to other physical stability test viz.: Heating
to 90oC and then cooling to room temperature, viscosity
measurements and freeze-thaw cycles. Arising from these tests,
observations for emulsions from formulations presented in the
C-series and F-H showed neither a significant separation of
phases or the constituent reagents, nor loss in the consistency
of the texture.
The Hydrophile-lipophile balance established in this
work serves to guide any formulator of similar emulsions when
employing other emulsifier blends. However, serious
adjustments may be required in some blends since HLB value
for Teepol is only an approximation and may therefore vary
with source.
479
Aside from the use in this study, the emulsifier
synthesized may be useful in other applications, especially in
formulations that may require non-toxic materials such as in
food and in medicine.
The emulsions formed as described in this report,
would serve as suitable base formulae in cream and lotion
productions. In some commercially available products of good
quality, the use of natural waxes had already been established.
Blending with propylene glycol monostearate as a wax as well
as an emulsifier provides a means of reducing cost of the natural
waxes and a mere co-emulsifier without reducing the desired
quality of the final product.
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Proceedings of the 36th Annual International Conference Minna, Nigeria
Copyright © Chemical Society of Nigeria
All right of reproduction in any form reserved

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