Princess Janine B.
Catral BSChE 5 Animal Waxes
Assignment in Biochemical Engineering 11/23/16
Waxes
 Mixtures of esters of long-chain carboxylic
acids(16-36 C atoms) with long chain
alcohols(24-36 C atoms)
 Can be seen in most fruits, berries, and leaves
which act as a protective coating
 Hydrophobic, malleable solids near ambient
temperature, melting point at greater than or
equal to 400C
 Soluble in nonpolar organic solvents
 All waxes are water-resistant materials made up
of various substances including
hydrocarbons (normal or branched alkanes and
alkenes), ketones, diketones, primary and
secondary alcohols, aldehydes, sterol esters,
alkanoic acids, terpenes(squalene) and
monoesters (wax esters), all with long or very
long carbon chains (from 12 up to about 38
carbon atoms) and solid in a large range of
temperature (fusion point between 60 and
100°C).
 More commonly, waxes are esters of an alcohol
other than glycerol (long
chain alcohol, sterol, hydroxy carotenoids, and
vitamin A) and a long chain acid (wax esters).
 Wax esters are saponified by hot alkaline
solutions and give a fatty acid and an alcohol.
They are soluble in aromatic solvents,
chloroform, ethers, esters and ketones.
Beeswax.
Triacontanylpalmitate, main component of beeswax
This wax is an abdominal secretion of bees (Apis
mellifera), its colour being dependent of the flowers
gathered by these insects. Bees used it to form the hive
cells. It is easily saponifiable and emulsifiable because of
its content in free fatty acids, diols and hydroxyacids. Its
main components are palmitate, palmitoleate,
hydroxypalmitate and oleate esters of long-chain alcohols
(C30-32) (about 70 to 80% of the total weight). The ratio
of triacontanylpalmitate (or melissylpalmitate, C30
alcohol esterified by C16 fatty acid) to cerotic acid
(C26:0), the other major component of bee wax is 6:1.
Ethyl esters are also present, the most abundant species
being ethyl palmitate, ethyl tetracosanoate, and ethyl
oleate (Jimenez JJ et al., J Chromatogr A 2004, 1024,
147). Aliphatic hydrocarbons (from 10 to 18 % of
heptacosane and nonacosane and other species from 17 up
to 35 carbon atoms), unsaturated hydrocarbons from 21
up to 35 carbon atoms with one or two double bonds,
sterols (up to 2% as cholesterol, lanosterol, b-sitosterol),
pheromones (geraniol, farnesol) and terpenoids are also
found. Its melting point is 62-65°C. A chemometric
method based on the use of high-temperature gas
chromatography has been reported for the detection of bee
wax adulteration with mineral paraffin.
Beeswax is used since ancient times since its presence
was detected in the wall pictures of the Lascaux cave and
in Egyptian mummies. Ancient Egyptians used it also for
its adhesive and coating properties, and in shipbuilding.
In the Roman period, bee wax was used as a
waterproofing agent and treatment for painted walls
(medium for the "Fayum portraits"). In the Middle Ages,
this wax was valuable and exchanged as a form of
currency. In recent times, bee wax was used as a modeling
material, as component of seals, coatings, polishes, and
candles. The world production amounts to about 7000
tons per year and 60% are used in cosmetic and pharmacy.
Chinese wax (insect wax). This wax is secreted by insects
(Coccus ceriferus) and laid on tree branches (1500 insects
are needed to produce 1g chinese wax). That insect is
cultivated in China. Besides an important content in esters
(about 83%), this wax includes some free acids, alcohols
(up to 1%) and hydrocarbons (2 to 3%). Chemically, the
esters are formed of chains with 46 up to 60 carbon atoms,
the majority of alcohols and acids having 26 or 28 carbon
atoms. The purified wax is used to make candles and
polish.
Shellac wax.
This wax (known also as lac wax) is produced by a
cochineal insect (Tachardia lacca) native of India. It
contains a majority of fatty esters (70-82%), free fatty
alcohols (8-14%), acids (1-4%) and hydrocarbons (1-6%).
The esters are formed of chains of 28 up to 34 carbon
atoms. This wax is used in varnish industry and may
replace carnauba wax.
Whale spermaceti.
Spermaceti is extracted by cooling (11% of the initial oil)
from adipose tissues and also collected from a big cavity
in the head of a cachalot (Physeter macrocephalus) known
as sperm whale. The frontal organ, used as a sonar by the
animal, contains about 3 tons spermaceti for a 15 meters
animal. This product contains fatty esters (65-95%) but
also triglycerides (5-30%), free alcohols (1-5%) and acids
(0-3%). Adipose tissues (9-10 tons of lard for a 15 m
animal) contain only 10-12% spermaceti wax. Fatty esters
are formed essentially of cetyl palmitate (C32) and cetyl
myristate (C30). Purified spermaceti has an aspect of a
light mass of white crystals which can be powdered. It can
be fused with bee wax and other fatty compounds (oils,
fatty acids). Its melting point is 42-50°C. Spermaceti was
used in medicine in England (15th century) and later in
cosmetics, pharmacy and also in candles but, after the
recent international regulation concerning whale captures,
it is no longer produced and sold. It is now replaced by
synthetic spermaceti made of pure cetyl palmitate or
mixtures based on jojoba.
Lanolin (wool wax). This material is secreted by sheep
sebaceous glands and collected from crude wool by dilute
alkali or detergent washing. Unwashed wool contains
about 10-24% of greasy matter and a small proportion of
salts of long-chain fatty acids. Lanolin contains fatty
esters (14-24%), sterols and triterpene alcohol esters (45-
65%), free alcohols (6-20%), sterols (cholesterol,
lanosterol) and terpenes (4-5%). Hydroxylated fatty acids
(mainly hydroxy palmitate) are found either free or
esterified. Fatty acid chains have from 14 up to 35 carbon
atoms, many of them having branched chains (iso or
anteiso conformations). Its melting point is 35-42°C. The
crude lanolin contains about 17% of primary alcohols and
9% of diols. Among monoalcohols, 9% have a normal
chain, 38% belong to the iso series and 53% to the anteiso
series. Two third of the diols belong to the iso series
(Fawaz F et al., Ann Pharm Fr 1974, 32, 215). Among
acids, 27% are a-hydroxylated, 5.2% are w-hydroxylated
and 4.7% are poly-hydroxylated (Fawaz F et al., Ann
Pharm Fr 1974, 32, 59). As bee wax, lanolin is used since
very ancient times in cosmetic and dermatology but is
actually used in industry (fabric, ink, lubricant).
Plant waxes
Carnauba wax.
This wax (known as "queen of waxes") is secreted by
leaves of a Brasilian palm tree (Copernicia prunifera
cerifera), about 100 g for one tree in a year. It contains
mainly fatty esters (80-85%), free alcohols (10-15%),
acids (3-6%) and hydrocarbons (1-3%). As a peculiarity,
carnauba wax contains esterified fatty dialcohols (diols,
about 20%), hydroxylated fatty acids (about 6%) and
cinnamic acid (about 10%). This last phenolic acid
compound (antioxidant in free form) may be
hydroxylated or methoxylated. This wax is the hardest
and highest melting of the natural waxes (melting point :
78-85°C) and is used mainly mixed to bee wax to make
various polishes for shoes, floor and furniture but also in
cosmetics (lipsticks, creams) and in food industry (glazes
for candies, gums, fruit coatings ...). It is used also in the
paper industry for paper coating (the largest application in
the USA).
Ouricouri wax. It was extracted from the ouricouri palm
(Syagrus coronata, Cocos coronata) by scraping the wax
from the leaf surface. Its melting point is 81-84°C.
Ouricouri resembles carnauba wax in its physical
properties, thus, it was used as substitute in carbon paper
inks, mould release lubricants and polishes.
Jojoba oil.
This wax is fluid (melting point: about 7°C) and produced
by pressing from seeds of the jojoba tree (Simmondsia
chinensis, Euphorbiacae), now cultivated in Mexico
(Sonora), Arizona and California. The cultivation of
jojoba is also experimented in Israel, Africa, Australia,
and China. It is formed quite exclusively of alcohols
esterified with long-chain fatty acids (more than 98%)
with a total of 38 to 44 carbon atoms. The fatty acids are
18:1n-9 (about 10%), 20:1n-9 (about 70%) and 22:1n-9
(15-20%), while the fatty alcohols have predominantly 20
and 22 carbon atoms and one double bond. Jojoba oil is
very resistant to oxidation and is largely used in cosmetic
applications (soaps, shampoos, skin cream, anti-solar
oils). Industries use sulfonated or hydrogenated oil as
lubricant, polishes, candles and coatings. Future uses
could be as foam control agent and low-calorie food
additive.
Candelilla wax. This wax is produced by small shrubs
from Mexico, Euphorbia cerifera and E. antisyphilitica
(Euphorbiaceae). The wax is extracted by boiling the
plant (to separate the wax and the plant material). The wax
floats to the top of the water and is skimmed off and
processed. It contains hydrocarbons (about 50% of C29 to
C33, mainly C31), esters (28-29%), alcohols, free fatty
acids (7-9%), and resins (12-14% triterpenoid esters). Its
melting point is 67-79°C. It has been used mainly mixed
with other waxes to harden them without raising the
melting point. This wax is used in cosmetics (lip balms
and lotion bars), pharmaceutics and in food stuffs (E 902,
GRAS) to improve stability and texture as a substitute to
beeswax (melting point : 66-71°C). One of candelilla's
major outlets was a binder for chewing gums.
Esparto wax This wax is a by-product in the artisanal
preparation of paper from a reed known in northwest
Africa and southern Spain as "Halfah grass", Stipa
tenacissima, it melt at 73°C. While its composition is
highly variable, it contains hydrocarbons, esters, alcohol
(C28) and triterpenoids.
Rice bran oil. Rice bran from the milling of rice, Oryza
sativa, contains a wax mixed with triglycerides. The
melting point of the pure wax is 75-80°C. It contains
esters of fatty acids (26 to 30 carbon atoms) and long-
chain alcohols (C26 to C30) and a large amount of
unsaponifiable matter (55-67%). That wax is much used
as a constituent of chocolate enrobers, various fruit and
vegetable coating and as a lipstick.
Mineral waxes
Ozocerite (or ozokerite). This wax is found in lignite beds
in Galicia in the Carpathian mountains, Russia, Iran, and
United States (Utah). Most ozocerite consists of
hydrocarbons (C20-C32) and its melting point is about
90°C. It is used in making lubricants, lipsticks,
deodorants, polishes, and adhesives.
Montan wax. This wax is derived by solvent extraction of
lignite or brown coal (sub-bituminous coal). As it has
been preserved in the coal it is really fossilized plant wax.
Thus, it has many characteristics similar to those of
vegetal waxes. The earliest production on a commercial
scale was in Germany during the latter half of the
nineteenth century, and Germany continues to supply the
majority of the world’s production of Montan wax. The
composition of Montan wax depends on the material from
which it is extracted, but all contain varying amounts of
wax, resin, and asphalt. Resins must be removed by
extraction with solvents (diethyl ether, acetone). The wax
component of Montan is a mixture of long. chain (C24-
C30) esters (62-68 wt %), long-chain acids (22-26 wt %),
and long. chain alcohols, ketones, and hydrocarbons (7-
15 wt %). Montan wax is hard and is one of the most
resistant to oxidation. Carbon papers were the largest
consumer of crude Montan wax. The highest present part
(30%) of Montan wax is used in car polishes. Additional
applications are shoe polishes, electrical insulators, and
lubricant in plastics and in paper industry.
Synthetic waxes and esters
As natural waxes are versatile, they can suffer inherent
variability in quality and availability, cosmetic product
include more and more frequently synthetic waxes. They
are made of ethylene glycol diesters or triesters of long-
chain fatty acids (C18-C36). Their melting points range
between 60-75°C and can be used to confer rigidity to
sticks and to modify the product's crystallinity. While
having the structure of waxes, esters of alcohols and fatty
acids either with a straight or branched chain, but shorter
than for waxes, are manufactured for cosmetic
applications. Depending on the chain length and structural
arrangement of the two starting materials, esters are
tailored to provide different physical properties and types
of emolience.
Straight chain esters, such as cetyl palmitate and
cetostearyl stearate, which are solid at room temperature,
are used to increase the viscosity of emulsions. Liquid
branched chain esters, such as isopropyl myristate or
cetostearyl ethylhexanoate, provide products with good
spreading properties. Furthermore, the choice of the ester
influences both the solubility and spreadability of
sunscreen agents and their ability to penetrate the skin.