WAXES

STRUCTURE, COMPOSITION, OCCURRENCE AND ANALYSIS

1. Introduction
To my knowledge, there is no satisfactory definition of the word "wa" in chemical terms. It is derived
from the Anglo-Saxon word "weax" for beeswax, so a practical definition of a wax may therefore be "a
!u"!tanc# !i$i%ar in co$&o!ition and &'(!ica% &ro&#rti#! to "##!wa". Technologists se the term
for a variety of commercial prodcts of mineral, marine, plant and insect origin that contain fatty
materials of varios kinds. !iochemists link waxes with the thin layer of fatty constitents that cover the
leaves of plants or provide a srface coating for insects or the skin of animals. All of these tend to
contain wax esters as ma"or components, i.e. esters of long-chain fatty alcohols with long-chain fatty
acids.
The natre of the other lipid constitents can vary greatly with the sorce of the waxy material, bt they
inclde hydrocarbons, sterol esters, aliphatic aldehydes, primary and secondary alcohols, diols,
ketones, #-diketones, triacylglycerols, and many more.
Also, the chain-length and degree of nsatration and branching of the aliphatic constitents will vary
with the origin of the wax, bt other than in some waxes of marine origin or from some higher animals,
the aliphatic moieties tend to be satrated or monoenoic.
). Co$$#rcia% Wa#!
A nmber of waxes are prodced commercially in large amonts for se in cosmetics, lbricants,
polishes, srface coatings, inks and many other applications. Some of these are of mineral origin $e.g.
montan wax from brown coal%peat deposits&, and only those from living organisms are discssed here.
Amongst them are -
*##!wa - 'lands nder the abdomen of bees secrete a wax, which they se to
constrct the honeycomb. The wax is recovered as a by-prodct when the honey is harvested and
refined. It contains a high proportion of wax esters $() to *+,&. The hydrocarbon content is highly
variable, and mch may be "nnatral" as beekeepers may feed some to bees to improve the yield of
honey. The wax esters consist of -.+ to -./ moleclar species, based on 0/1+ and 0*1+ fatty acids some
with hydroxyl grops in the 2-3 and 2-( positions. In addition, some diesters with p to /. carbons may
be present, together with triesters, hydroxy-polyesters and free acids $which are different in composition
and natre from the esterified acids&.
+o,o"a - The "o"oba plant $Simmondsia chinensis&, which grows in the semi-arid regions of 4exico and
the 5.S.A., is ni6e in prodcing wax esters rather than triacylglycerols in its seeds, and it has become
a significant crop. It consists mainly of 0*10 $/,&, 3+10 $(),& and 3310 $7,& fatty acids linked to 3+10
$33,&, 3310 $30,& and 3.10 $.,& fatty alcohols. Therefore, it contains -(* to -.. esters with one doble
bond in each alkyl moiety. As methylene-interrpted doble bonds are absent, the wax is relatively
resistant to oxidation.
Carnau"a - The leaves of the carnaba palm, Copernicia cerifera that grows in !ra8il, have a thick
coating of wax, which can be harvested from the dried leaves. It contains mainly wax esters $*),&,
accompanied by small amonts of free acids and alcohols, hydrocarbons and resins. The wax esters
constitte -0/ to -3+ fatty acids linked to -(+ to -(. alcohols, giving -./ to -). moleclar species.
9ther vegetable "waxes" sch as bayberry or :apan wax are better described as "tallows" as they
consist mainly of high melting triacylglycerols.
Woo% wa -%ano%in. - The grease obtained from the wool of sheep dring the
cleaning or refining process is rich in wax esters $of 0- and 3-alkanols, and 0,3-diols&, sterol esters,
triterpene alcohols, and free acids and sterols. The natre of the prodct varies with the degree and type
of processing involved, bt can contain p to )+, wax esters and ((, sterol esters. A high proportion
of the sterol component is lanosterol. The fatty acid components are mainly satrated and iso- and
anteiso-methyl-branched-chain.
/. P%ant Sur0ac# Wa#!
;lant leaf srfaces are coated with a thin layer of waxy material that has a myriad of fnctions. This
layer is microcrystalline in strctre and forms the oter bondary of the cticlar membrane< it is the
interface between the plant and the atmosphere. It serves many prposes, for example to limit the
diffsion of water and soltes, while permitting a controlled release of volatiles that may deter pests or
attract pollinating insects. The wax provides protection from disease and insects, and helps the plants
resist droght. As plants cover mch of the earth=s srface, it seems likely that plant waxes are the most
abndant of all natral lipids.
The range of lipid types in plant waxes is highly variable, both in natre and in composition, and Table 0
illstrates some of this diversity in some of the main components.
Ta"%# 1. T'# $a,or con!titu#nt! o0 &%ant %#a0 wa#!.
n1A%2an#! ->($->3&x->(
30 to ()- -
odd nmbered
A%2(% #!t#r! ->($->3&x-99$->3&y->(
(. to /3- -
even
nmbered
3att( acid! ->($->3&x-99>
0/ to (3- -
even
nmbered
3att( a%co'o%!
-&ri$ar(.
->($->3&y->39>
33 to (3- -
even
nmbered
3att( a%d#'(d#! ->($->3&y->9
33 to (3- -
even
nmbered
4#ton#! ->($->3&x-9$->3&y->(
3( to ((- -
odd nmbered
3att( a%co'o%!
-!#condar(.
->($->3&x->9> $->3&y->(
3( to ((- -
odd nmbered
51Di2#ton#! ->($->3&x-9->3-9$->3&y->(
37 to ((- -
odd nmbered
Trit#r&#no%!
Sterols, ?-amyrin, #-amyrin, vaol, lpeol,
erythrodiol
Trit#r&#noid acid! 5rsolic acid, oleanolic acid, etc
In addition, there may be hydroxy-#-diketones, oxo-#-diketones, alkenes, branched alkanes, acids,
esters, acetates and ben8oates of aliphatic alcohols, methyl, phenylethyl and triterpenoid esters, and
many more.
The amont of each lipid class and the natre and proportions of the varios moleclar species within
each class vary greatly according to the plant species and the site of wax deposition $leaf, flower, frit,
etc.& and some data for some well-stdied species are listed in Table 3.
Ta"%# ). R#%ati6# &ro&ortion! -wt 7. o0 t'# co$$on wa
con!titu#nt! in !o$# &%ant !&#ci#!.
8ra&#
%#a0
Ra&#
%#a0
A&&%#
0ruit
Ro!#
0%ow#r
P#a
%#a0
Su9ar
can#
!t#$
:(drocar"on! 3 (( 3+ )*
.+-
)+
3-*
Wa #!t#r! / 0/ 0* 00
)-
0+
/
A%d#'(d#! / ( 3 - ) )+
4#ton#! - 3+ ( - -
S#condar( a%co'o%! - * 3+ @ 7 -
Pri$ar( a%co'o%! /+ 03 / . 3+ )-3)
Acid! * * 3+ ) / (-*
9ther components present inclde varios diol types and triterpenoid
acids
;. S2in Li&id!
In most animals, the main wax prodction is associated with the sebaceos glands of the skin. 4ost of
these glands are associated with hair follicles, bt there are also related strctres on the eyelids
termed 4eibomian glands. Sebaceos glands secrete mainly non-polar lipids in the form of sebm onto
the skin srface, where they are easily recovered for analysis. Althogh relatively few species have
been stdied in real detail, it is evident that a wide range of lipid classes are present and that these vary
greatly in amont and natre between species $there may also be variation with age&. The composition
of hman sebm differs appreciably from that of other species, especially in the high content of
triacylglycerols and in fatty acid composition. Some typical data are listed in Table (.
Ta"%# /. R#%ati6# co$&o!ition -wt 7 o0 t'# tota%. o0 t'# non1&o%ar %i&id! o0 0ro$
t'# !2in !ur0ac# o0 6ariou! !&#ci#!.
S<ua%#n# St#ro%!
St#ro%
#!t#r!
Wa
#!t#r!
Di#!t#r!
8%(c#r(%
#t'#r!
Triac(%1
9%(c#ro%!
3r##
acid!
3r##
a%co'o%!
:u$an 03 0 ( 3) .0 0/
S'##& 03 ./ 0+ 30 00
Rat 0 / 37 07 30 * 0
Mou!# 0( 0+ ) /) /
Adapted from Aowning, A.T. 4ammalian waxes. In1 Chemistry and Biochemistry of Natural
Waxes. $Bd. ;.B. Colattkdy, Blsevier, Amsterdam& $0@7/&.
Sebaceos glands appear to be the only sorce of wax esters in mammalian tisses and the only tisse
where s6alene accmlates in significant amonts. A high proportion of the fatty acid constitents of
sebm lipids can be branched chain, which are not common in other organs. >man sebm is ni6e in
containing cis-/-hexadecenoic acid $/-0/10 or DsapienicE acid&, which is the single most abndant
component indeed, and is accompanied by an elongation and desatration prodct ),*-octadecadienoic
acid $DsebaleicE acid&, also ni6e to hman skin. Sapienic acid is formed in the sebaceos glands by a
distinctive F/ desatrase and has powerfl antibacterial properties.
Skin also contains a wide range of more polar lipids based on the ceramide backbone. They have been
most stdied in the skin of the pig, where a range of nsal ceramides per se have been identified,
some of which contain linoleic acid $a& esterified to a hydroxy acid $"& that is in trn linked to a long-
chain base $c&. In addition, several moleclar forms of glcosylceramide, based on similar strctres,
have been characteri8ed $see or web pages on c#ra$id#!& for frther information.
The composition depends on the particlar layer of the skin $epidermis, stratm cornem, etc.&. Ghether
they shold trly be called waxes is dobtfl.
=. Ot'#r Wa#!
In!#ct wa#!. The srface of insects is covered by a layer of wax that, amongst other fnctions, serves
to restrict movement of water across the cticle and prevent desiccation. The natre of this lipid is
dependent on species, bt in general a high proportion tends to be satrated alkanes $-3( to -(0& often
with one or two methyl branches. In addition, wax esters, sterol esters, and free fatty alcohols and acids
may be present. Some species of insect secrete triacylglycerols in their waxes together with free sterols
and other terpenoid components. The composition of beeswax is discssed above.
Marin# wa#!. 4any marine animals from invertebrates to whales contain
appreciable amonts of waxes in the form mainly of hydrocarbons and wax esters. In addition, glycerol
ethers and sterols cold be classified as wax components in some species. They are fond in a variety
of tisses from fish roe, to liver and mscle tisses. The wax esters consist of the normal range of
satrated, monoenoic and polynsatrated fatty acids typical of fish, esterified to mainly satrated and
monoenoic alcohols often with the 0*10 fatty alcohol as the main component. S6alene and other
terpenoid hydrocarbons are often ma"or components of the hydrocarbon fraction, and can be
accompanied by satrated $straight-chain and methyl-branched&, monoenoic and polyenoic
components. Gaxes appear to have a variety of fnctions in fish, from serving as an energy sorce to
inslation, boyancy and even echo location. Spermaceti or sperm whale oil $wax esters, 7/,<
triacylglycerols, 3(,& was once in great demand as a lbricant bt now is proscribed.
*ird wa#!. The ropygial glands of birds secrete waxes that consist largely
of wax esters. The fatty alcohol components of these are sally relatively simple in natre, consisting
largely of normal -0/ and -0* satrated componds, althogh those with branched-chains can make p
an appreciable proportion in some species. >owever, the fatty acids can be highly complex and are
often shorter chain than sal with p to for methyl branches. The main prpose of the waxes is
presmed to be to give a water-proof layer to the feathers, bt other fnctions have been sggested.
Micro"ia% wa#!. Gaxes are not common in prokaryotes, bt the mycobacteria prodce waxes, termed
=mycoserosates=, based on branched-chain alcohols or =phthiocerols=. These are -(. or -(/ branched-
chain componds with hydroxyl grops in positions @ and 00, or 00 and 0(. These are esterified with
long-chain fatty acids varying in chain length from -0* to -3/ and with two to for methyl branches that
may occr at the 3, ., /, and * positions. The dimycocerosate esters are ma"or virlence factors of
pathogenic mycobacteria inclding Mycobacterium tuberculosis and M. leprae.
Helated strctres have a phenol grop at the termins of the alkyl chain, and the hydroxyl of this can
be attached to carbohydrate moieties of varying complexity. 4ycobacteria are nsal in a nmber of
other ways in that their lipids can contain triac(%9%(c#ro%!, and the distinctive $(co%ic acid!, for
example.
>. *io!(nt'#!i! o0 Wa#!
!ecase of their biochemical importance and relative ease of stdy, the waxes of the plant cticle have
received most stdy. All the aliphatic components of plant waxes are synthesised in the epidermal cells
from satrated very-long-chain fatty acids $commonly -3+ to -(.&. 0/1+ and 0*1+ fatty acids are first
synthesised in the stroma of plastids by the solble en8ymes forming the fatty acid synthase complex
$see or web page on 0att( acid "io!(nt'#!i!&. The second stage involves mltiple elongation steps
and is catalysed by membrane-associated mlti-en8yme complexes, known as fatty acid elongases
otwith the plastids. As in fatty acid synthesis de novo, each two-carbon extension of the chain involves
for reactions1 condensation between a -oA-esterified fatty acyl sbstrate and malonyl--oA, followed
by a #-keto redction, dehydration and an enoyl redction. 4any different forms of the elongases have
been identified, and these mst interact in some manner to prodce the chain-length specificity
observed.
There are then two main pathways for biosynthesis of wax components1 an acyl redction pathway,
which yields primary alcohols and wax esters, and a decarbonylation pathway that reslts in synthesis
of aldehydes, alkanes, secondary alcohols and ketones. In the redctive pathway, acyl--oA esters
prodced by chain elongation are redced in a two-step process via a transient aldehyde intermediate,
catalysed by a single en8yme, an acyl--oA redctase $thogh it was once thoght that two distinct
en8ymes were involved&.
The fatty alcohol prodced can then be esterified via an acyl--oA alcohol transacylase to form a wax
ester. Similar mechanisms have been observed in stdies with insects, algae and birds $ropygial
glands&. It seems probable that wax diols are prodced by insertion of a hydroxyl grop into the alkyl
chain of an acyl--oA precrsor.
In the decarbonylation pathway for the synthesis of wax constitents, the first step is again the redction
of acyl--oA ester to an aldehyde by means of an acyl--oA redctase. Hemoval of the carbonyl grop by
an aldehyde decarbonylase yields an alkane, with one fewer carbon atom than the fatty acid precrsor.
Irther metabolism of the hydrocarbon is then possible, for example by insertion of a hydroxyl grop
into the chain via a hydroxylase or mixed-fnction oxidase to form a secondary alcohol. The position of
the sbstittion depends on the species, and the specificities of the en8ymes involved. Secondary
alkanols can in trn be esterified to form a wax ester. Alternatively, the hydroxyl grop can be oxidi8ed
with formation of a long-chain ketone. An associated pathway leads to the formation of #-diketones and
3-alkanols. Again, these processes have been stdied most in plants, bt similar biochemical reactions
appear to occr in insects and birds.
The final step in the prodction of wax esters from long-chain alcohols and fatty acids involves the
action of an acyl--oA1alcohol transacylase. In animal tisses, this is an en8yme that is also re6ired for
triacylglycerol biosynthesis, i.e. an acyl -oA1diacylglycerol acyltransferase $A'AT& or more specifically
an isoform of the en8yme known as A'AT0. The same en8yme synthesises retinyl esters also.
Similarly, in prokaryotes, an en8yme that is strctrally distinct from that in animals is both a
diacylglycerol acyltransferase and a wax ester synthase. In plants, -0/ and -0* fatty acids from the fatty
acid synthetase are converted to -oA esters and sb"ected to chain elongation prior to wax formation.
An active fatty acyl -oA1fatty alcohol acyltransferase has been isolated from microsomal fractions of
seeds of the "o"oba plant that is responsible for prodction of the storage wax, bt also appears to be
strctrally related to the wax synthases involved in the synthesis of the epicticlar waxes.
9nce synthesised, the wax components mst be exported from the sites of lipid synthesis in the plastid
and the endoplasmic reticlm to the plasma membrane and throgh the cell wall. They mst then pass
into the ctin layer $a lipid-based polyester J see or web page on '(dro( 0att( acid!& that provides a
matrix within and pon which the waxes are deposited. Kery little is known of how wax is exported, bt
two grops of transport molecles have been identified recently that are known to facilitate this process.
?. Ana%(!i!
Thin-layer and high-performance li6id chromatography have been sed widely to isolate individal
classes of waxes for more detailed analysis. 9n the other hand, mch of the more recent pblished
work has made se of high-temperatre gas chromatography following trimethylsilylation, often in
combination with mass spectrometry, so that simltaneos identification and 6antification of the varios
moleclar species can be achieved.
'tt&@AAwww.%i&id%i"rar(.co.u2ALi&id!Awa#!Aind#.'t$
WAXES AND OT:ER ESTERS
Gaxes is a general term sed to refer to the mixtre of long-chain
apolar lipids forming a protective coating $ctin in the cticle& on
&%ant leaves and frits bt also in ani$a%! $wax of honeybee,
cticlar lipids of insects, spermaceti of the sperm whale, skin lipids,
ropygial glands of birds, depot fat of planktonic crstacea&, algae,
fngi and bacteria. Some waxes are of $in#ra% origin. 4ontan wax
originates from mob or lignite, that fossili8ed compond representing
a late step of the transformation of vegetal into hydrocarbons.
The varios materials named waxes do not form a chemically
homogeneos grop. All waxes are water-resistant materials made
p of varios sbstances inclding '(drocar"on! $normal or
branched alkanes and alkenes&, ketones, diketones, primary and
secondary alcohols, aldehydes, sterol esters, alkanoic acids,
t#r&#n#! $s6alene& and monoesters $wax esters&, all with long or
very long carbon chains $from 03 p to abot (* carbon atoms& and
solid in a large range of temperatre $fsion point between /+ and
0++L-&.
4ore commonly, waxes are esters of an alcohol other than glycerol
$long chain a%co'o%, !t#ro%, '(dro(carot#noid!, 6ita$in A& and a
long chain acid $wax esters&. Gax esters are saponified by hot
alkaline soltions and give a fatty acid and an alcohol. They are
solble in aromatic solvents, chloroform, ethers, esters and ketones.
H0 et H3 have commonly 0+ to 3+ carbon atoms or more. Bxample of
wax esters are1 dodecyl hexadecanoate $laryl palmitate&, octadecyl
octadecanoate $stearyl stearate&, etc. The acid or the alcohol chain
can be nsatrated. In plants and some algae, phytol may be the
alcohol component of was esters protecting leaves against
dessication and parasites. Gax monoesters accont for abot 3), of
sebm lipids in hman, this wax being characteri8ed by a high
amont of an nsal fatty acid, 1>@1n11B.
The physical characteristics of wax have maximi8ed their sage in
varios indstries, particlarly in cosmetics. Gax are formlated in
nmeros personal care prodcts de to their excellent emollient
behavior. Gax esters are fine chemicals which are prodced in low
volme bt are highly priced. +o,o"a oi% and !&#r$ w'a%# oi% are
natral waxes that fall within that fine chemicals grop. Several
attempts have been made to synthesi8e wax esters with cheap
starting materials. Ths, waxes were synthesi8ed from palm oil
throgh en8ymatic transesterification with oleyl alcohol sing
Mipo8yme H4 I4 as the catalyst $Keng PS et al. !nd Crops Prod
"##$ "$ %&&.
In the ropygial gland of birds, the acids of wax esters may have a
mono- or mlti-branched chain $diester waxes&. The physiological
fnction of these waxy material is still a matter of debate bt may
contribte to protect birds against wetting, to make the feather
flexible, to play a role as antiparasitic componds or to provide 5K
protection. It has been shown that ropygial waxes shifted their
strctre dring the mating season from a monoester type to one of
two diester types.
Gaxes of type 0 are based on -* to -0/ -hydroxy acids $H3&
esterified with -/ to -0/ fatty acid $H0& at the -hydroxy position and
with -0/ to -3+ fatty alcohol $H(& at the carboxyl grop. These -(+-
-)+ diester waxes have been described in several shorebirds
$Rijpstra WI et al. ' Nat Prod "##& &# ()#*& and in female
mallards $+nas platyrhynchus& $Kolattukudy PE et al. ' ,ipid -es
($)& ") .)"&. Gaxes of type 3 are based on -03--3( alkane-0,3-
diols $or 3,(-diols, sometimes named ropygiols& esterified with -0+-
-3+ acids at the two hydroxyl grops. These diester waxes have
been described first in chicken $/aahti 01 e al. ' ,ipid -es ($2& )
(%(& and then in trkey $/ansen !+ et al. ' ,ipid -es ($2$ (# "2&&,
in the pheasant $Phasianus colchicus& $Saito K et al. ' Biochem
($&# 2& )*(& and in the red knot $Calidris canutus& $Sinninghe
3amste 'S et al. ' Nat Prod "### 2% %)(&.
;olar 8ooplancton species are known for the storage of wax esters
as natral energy reserves. Ths, in the antarctic Bphasiid
4hysanoessa macrura the wax deposits reach p to 7+, of the total
body lipids and contain high levels of 0*10$n-@& and 0*10$n-7&
alcohols $Kattner 5 et al. Mar 0col Prog Ser ($$2 (%* "$.&.
-arnivoros 8ooplankton species are characteri8ed by the presence
of shorter-chain alcohols $0.1+, 0/1+& while herbivoros species, as
the calanoid copepods, contain mainly long-chain alcohols $3+10,
3310&.
Triacontanylpalmitate is the main component of bee wax. ;almitic
acid $-0/1+& is esterified by a -(+ chain, triacontanol $or melissyl
alcohol&.
Aon=t forget that the word "wax" is derived from the old Bnglish
"6eax" for the honeycomb of the bee-hive. Ths, bee wax can be
considered as the reference wax.
In plants the oter covering consists of an hydroxy fatty acid polymer
called ctin. The ndergrond parts and healed wond srfaces of
plants are covered with an analogos sbstance, sberin. These
sbstances are fre6ently mixed with other lipids and form a complex
mixtre called epicticlar wax. -tin is a lipidic polymer containing
-0/ and -0* families of acids. The former is more abndant in
growing parts, the later is present in the cticle of slower-growing
plants. These acids may be satrated, nsatrated, mono- or di-
hydroxylated. In the ctin strctre, a polyester strctre exists where
cross-linking depends on the availability of secondary hydroxyl
grops. It has even been sggested that a biopolymer called
"algaenan" consisting mainly of linear polyester chains cross-linked
by ether bridges is present in cell wall of green microalgae $Blo77er P
et al. Phytochemistry ($$) *$ 2$(&. In some microalgae $Chlorella
Scenedesmus 4etraedron&, the presence of complex ester waxes
with long-chains $p to -*+& have been described $+llard B et al.
Phytochemistry "##( .& *.$&. In contrast, the ma"or carbon chains
of sberins are -hydroxy acids and dicar"o(%ic acids, all with very
long chains $N3+ carbon atoms&.
Among the least polar components of plant srface lipids
hydrocarbons with the odd nmber carbon chains $-0) p to -((&
are predominant. Aliphatic alcohols in the -3+--(. range are also
widespread in plant srface lipids.
;yrethrins are natral or synthetic organic componds that have
potent insecticidal activity. All are formed from a cyclopropane fatty
acid esterified by an allylic alcohol having a cyclopropane core. The
natral forms are pyrethrin I and II. They differ by the strctre of the
grop H of the acid moiety.
;yrethrin I 1 H O ->
(
;yrethrin II 1 H O -9
3
->
(

The pyrethrins are contained in all parts of several species of
Chrysanthemum were they were first discovered. Pow, all pyrethrins
are synthesi8ed by chemists from varios precrsors.
As several componds containing the allyl grop have a high activity
as insecticides, acaricides, and insect repellents, allyl esters of fatty
acids were synthesi8ed. As an example, allyl esters of fatty acids
have been proposed as wood preservatives, allyl pentanoate having
the highest activity on termites $8oshida S et al. 'pn Patent 'P
#)(%%$#$ "##29. Allyl esters of fatty acids $from ( to 07 carbon
atoms& have been synthesi8ed. All have ovicidal effect on an insect
$Cydia pomonella&, the activity being inversely related to the alyl
chain length $0scriba M et al. ' +gric :ood Chem "##$ .& *)*$&.
In bacteria, Mycobacterium spp, characteristic waxes $&'t'ioc#ro%
wa#!& were described in the wall cell lipids. These waxes are
diesters of the &'t'ioc#ro%!, inclding phthiodiolone and phthiotriol,
with $(coc#ro!ic acid!. Ths, they are named di$(coc#ro!at#
#!t#r!.
m O 3+, 33
n O 0/, 0*
p O 3-)
H O ->
3
-->
(
or ->
(

These waxes were shown to play a role in the virlence of the cell bt
also in its architectre and permeability $Camacho ,- et al. ' Biol
Chem "##( "&2 ($)*.; Onwueme KC et al. Prog ,ipid -es "##.
** ".$9.
A review on waxes may be fond in the book pblished in "The 9ily
;ress" by >amilton H: $Waxes< chemistry molecular biology and
functions ($$.&.
Gaxes are largely sed in cosmetics, in pharmacetical indstries, as
lbricants, polishes, plastici8ers and in food indstries. As natral
sorces of waxes are expensive and limited in access, they are
fre6ently synthesi8ed by en8ymatic $/allberg M, et al. '+1CS
($$$ &2 ()%& or chemical procedres $+racil ' et al. =eolites ($$"
(" "%%&.
Ge give below a description of some waxes of indstrial importance.
Ani$a% wa#!
*## wa
This wax is an abdominal secretion of bees $+pis mellifera&, its color
being dependent of the flowers gathered by these insects. !ees sed
it to form the hive cells. !ee wax is easily saponifiable and
emlsifiable becase of its content in free fatty acids, diols and
hydroxyacids.
Its main components are palmitate, palmitoleate, hydroxypalmitate
and oleate esters of long-chain alcohols $-(+-(3& $abot 7+ to *+,
of the total weight&. The ratio of triacontanylpalmitate $or
melissylpalmitate, -(+ alcohol esterified by -0/ fatty acid& to cerotic
acid $-3/1+&, the other ma"or component of bee wax is /10. Bthyl
esters are also present, the most abndant species being ethyl
palmitate, ethyl tetracosanoate, and ethyl oleate $'imene> '' et al. '
Chromatogr + "##* (#"* (*&&. Aliphatic hydrocarbons $from 0+ to
0* , of heptacosane and nonacosane and other species from 07 p
to () carbon atoms&, nsatrated hydrocarbons from 30 p to ()
carbon atoms with one or two doble bonds, sterols $p to 3, as
cholesterol, lanosterol, b-sitosterol&, pheromones $geraniol, farnesol&
and terpenoids are also fond. Its melting point is /3-/)L-.
!ee wax is sed since ancient times since its presence was detected
in the wall pictres of the Mascax cave and in Bgyptian mmmies.
Ancient Bgyptians sed it also for its adhesive and coating
properties, and in shipbilding. In the Homan period, bee wax was
sed as a waterproofing agent and treatment for painted walls
$medim for the "Iaym portraits"&. In the 4iddle Ages, this wax was
valable and exchanged as a form of crrency. In recent times, bee
wax was sed as a modeling material, as component of seals,
coatings, polishes, and candles.
The world prodction amonts to abot 7+++ tons per year and /+,
are sed in cosmetic and pharmacy.
C'in#!# wa -in!#ct wa.
This wax is secreted by insects $Coccus ceriferus& and laid on tree
branches $0)++ insects are needed to prodce 0g chinese wax&. That
insect is cltivated in -hina. !esides an important content in esters
$abot *(,&, this wax incldes some free acids, alcohols $p to 0,&
and hydrocarbons $3 to (,&. -hemically, the esters are formed of
chains with ./ p to /+ carbon atoms, the ma"ority of alcohols and
acids having 3/ or 3* carbon atoms. The prified wax is sed to
make candles and polish.
S'#%%ac wa
This wax $known also as lac wax& is prodced by a cochineal insect
$4achardia lacca& native of India. It contains a ma"ority of fatty esters
$7+-*3,&, free fatty alcohols $*-0.,&, acids $0-.,& and
hydrocarbons $0-/,&. The esters are formed of chains of 3* p to (.
carbon atoms.
This wax is sed in varnish indstry and may replace carnaba wax.
W'a%# !&#r$ac#ti
Spermaceti is extracted by cooling $00, of the initial oil& from
adipose tisses and also collected from a big cavity in the head of a
cachalot $Physeter macrocephalus& known as sperm whale. The
frontal organ, sed as a sonar by the animal, contains abot ( tons
spermaceti for a 0) meters animal. This prodct contains fatty esters
$/)-@),& bt also triglycerides $)-(+,&, free alcohols $0-),& and
acids $+-(,&. Adipose tisses $@-0+ tons of lard for a 0) m animal&
contain only 0+-03, spermaceti wax. Iatty esters are formed
essentially of cetyl palmitate $-(3& and cetyl myristate $-(+&. ;rified
spermaceti has an aspect of a light mass of white crystals which can
be powdered. It can be fsed with bee wax and other fatty
componds $oils, fatty acids&. Its melting point is .3-)+L-.
Spermaceti was sed in medicine in Bngland $0)th centry& and later
in cosmetics, pharmacy and also in candles bt, after the recent
international reglation concerning whale captres, it is no longer
prodced and sold. It is now replaced by synthetic spermaceti made
of pre cetyl palmitate or mixtres based on "o"oba.
Lano%in -woo% wa.
This material is secreted by sheep sebaceos glands and collected
from crde wool by dilte alkali or detergent washing. 5nwashed
wool contains abot 0+-3., of greasy matter and a small proportion
of salts of long-chain fatty acids. Manolin contains fatty esters $0.-
3.,&, sterols and triterpene alcohol esters $.)-/),&, free alcohols
$/-3+,&, sterols $cholesterol, lanosterol& and terpenes $.-),&.
>ydroxylated fatty acids $mainly hydroxy palmitate& are fond either
free or esterified. Iatty acid chains have from 0. p to () carbon
atoms, many of them having branched chains $iso or anteiso
conformations&. Its melting point is ()-.3L-.
As bee wax, lanolin is sed since very ancient times in cosmetic and
dermatology bt is actally sed in indstry $fabric, ink, lbricant&.
C#9#ta% wa#!
Carnau"a wa
This wax $known as "6een of waxes"& is secreted by leaves of a
!rasilian palm tree $Copernicia prunifera cerifera&, abot 0++ g for
one tree in a year. It contains mainly fatty esters $*+-*),&, free
alcohols $0+-0),&, acids $(-/,& and hydrocarbons $0-(,&. As a
pecliarity, carnaba wax contains esterified fatty dialcohols $diols,
abot 3+,&, hydroxylated fatty acids $abot /,& and cinnamic acid
$abot 0+,&. This last phenolic acid compond $antioxidant in free
form& may be hydroxylated or methoxylated.
This wax is the hardest and highest melting of the natral waxes
$melting point 1 7*-*)L-& and is sed mainly mixed to bee wax to
make varios polishes for shoes, floor and frnitre bt also in
cosmetics $lipsticks, creams& and in food indstry $gla8es for candies,
gms, frit coatings ...&. It is sed also in the paper indstry for paper
coating $the largest application in the 5SA&.
Ouricouri wa
It was first exported from !ra8il in 0@(7 bt has fallen in se in recent
times.
It was extracted from the oricori palm $Syagrus coronata Cocos
coronata& by sraping the wax from the leaf srface. Its melting point
is *0-*.L-. 9ricori resembles carnaba wax in its physical
properties, ths, it was sed as sbstitte in carbon paper inks,
mold release lbricants and polishes.
+o,o"a oi%
This prodct reslted from the pressre on governments to replace
spermaceti.
This wax is flid $melting point1 abot 7L-& and prodced by pressing
from seeds of the "o"oba tree $Simmondsia chinensis,
0uphorbiacae&, now cltivated in 4exico $Sonora&, Ari8ona and
-alifornia. The cltivation of "o"oba is also experimented in Israel,
Africa, Astralia, and -hina.
It is formed 6ite exclsively of alcohols esterified with long-chain
fatty acids $more than @*,& with a total of (* to .. carbon atoms.
The fatty acids are 0*10n-@ $abot 0+,&, 3+10n-@ $abot 7+,& and
3310n-@ $0)-3+,&, while the fatty alcohols have predominantly 3+ and
33 carbon atoms and one doble bond.
:o"oba oil is very resistant to oxidation and is largely sed in cosmetic
applications $soaps, shampoos, skin cream, anti-solar oils&.
Indstries se slfonated or hydrogenated oil as lbricant, polishes,
candles and coatings. Itre ses cold be as foam control agent
and low-calorie food additive.
Cand#%i%%a wa
This wax is prodced by small shrbs from 4exico, 0uphorbia
cerifera and 0. antisyphilitica $0uphorbiaceae&. 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 $abot )+, of -3@ to -((&, esters $3*-
3@,&, alcohols, free fatty acids $7-@,&, and resins $03-0.,
triterpenoid esters&. Its melting point is /7-7@L-. It has been sed
mainly mixed with other waxes to harden them withot raising the
melting point. This wax is sed in cosmetics $lip balms and lotion
bars&, pharmacetics and in food stffs $B @+3, 'HAS& to improve
stability and textre as a sbstitte to beeswax $melting point 1 //-
70L-&. 9ne of candelilla=s ma"or otlets was a binder for chewing
gms.
E!&arto wa
This wax is a by-prodct in the artisanal preparation of paper from a
reed known in northwest Africa and sothern Spain as ">alfah
grass", Stipa tenacissima it melt at 7(L-. Ghile its composition is
highly variable, it contains hydrocarbons, esters, alcohol $-3*& and
triterpenoids.
+a&an wa
That prodct is not a tre wax bt is more like a vegetable tallow
fond in the kernel and oter skin of the berries of -hus and
4oxicodendron species, inclding those yielding :apanese lac6er. It
contains a high amont of palmitic acid triglycerides $@(-@7,&, long
chain dicarboxylic acids inclding -33 and -3( chains $.-).),& and
free alcohols $03-0./,&. Its melting point is .)-)(L-. That wax is
mch sed in :apan in cosmetics, ointments and to make candles
bt becomes rancid with age.
Ric# "ran oi%
Hice bran from the milling of rice, 9ry8a sativa, contains a wax mixed
with triglycerides. The melting point of the pre wax is 7)-*+L-. It
contains esters of fatty acids $3/ to (+ carbon atoms& and long-chain
alcohols $-3/ to -(+& and a large amont of nsaponifiable matter
$))-/7,&.
That wax is mch sed as a constitent of chocolate enrobers,
varios frit and vegetable coating and as a lipstick.
Min#ra% wa#!
ODoc#rit# -or oDo2#rit#.
This wax is fond in lignite beds in 'alicia in the -arpathian
montains, Hssia, Iran, and 5nited States $5tah&. 4ost o8ocerite
consists of hydrocarbons $-3+--(3& and its melting point is abot
@+L-. It is sed in making lbricants, lipsticks, deodorants, polishes,
and adhesives.
Montan wa
This wax is derived by solvent extraction of lignite or brown coal $sb-
bitminos coal&. As it has been preserved in the coal it is really
fossili8ed plant wax. Ths, it has many characteristics similar to those
of vegetal waxes. The earliest prodction on a commercial scale was
in 'ermany dring the latter half of the nineteenth centry, and
'ermany contines to spply the ma"ority of the worldEs prodction of
4ontan wax. The composition of 4ontan wax depends on the
material from which it is extracted, bt all contain varying amonts of
wax, resin, and asphalt. Hesins mst be removed by extraction with
solvents $diethyl ether, acetone&. The wax component of 4ontan is a
mixtre of long. chain $-3.--(+& esters $/3-/* wt ,&, long-chain
acids $33-3/ wt ,&, and long. chain alcohols, ketones, and
hydrocarbons $7-0) wt ,&. 4ontan wax is hard and is one of the
most resistant to oxidation. -arbon papers were the largest
consmer of crde 4ontan wax. The highest present part $(+,& of
4ontan wax is sed in car polishes. Additional applications are shoe
polishes, electrical inslators, and lbricant in plastics and in paper
indstry.
S(nt'#tic wa#! and #!t#r!
As natral waxes are versatile, they can sffer inherent variability in
6ality and availability, cosmetic prodct inclde more and more
fre6ently synthetic waxes. They are made of ethylene glycol
diesters or triesters of long-chain fatty acids $-0*--(/&. Their melting
points range between /+-7)L- and can be sed to confer rigidity to
sticks and to modify the prodct=s crystallinity.
Ghile having the strctre of waxes, esters of alcohols and fatty
acids either with a straight or branched chain, bt shorter than for
waxes, are manfactred for cosmetic applications. Aepending on
the chain length and strctral arrangement of the two starting
materials, esters are tailored to provide different physical properties
and types of emolience.
Straight chain esters, sch as cetyl palmitate and cetostearyl
stearate, which are solid at room temperatre, are sed to increase
the viscosity of emlsions. Mi6id branched chain esters, sch as
isopropyl myristate or cetostearyl ethylhexanoate, provide prodcts
with good spreading properties. Irthermore, the choice of the ester
inflences both the solbility and spreadability of snscreen agents
and their ability to penetrate the skin.
Aari wikipedia 1
Carnauba is a wax of the leaves of the palm, Copernicia prunifera, a plant native to
and grown only in the northeastern Brazilian states of Piau, Cear, and Rio Grande
do Norte.
[1]
It is known as "queen of waxes"
[2]
and usually comes in the form of hard
yellow-brown flakes. It is obtained from the leaves of the carnauba palm by collecting
them, beating them to loosen the wax, then refining and bleaching the wax.
Contents
[hide
1 Composition
2 ses
! "e#hni#al
#hara#teristi#s
$ Re%eren#es
& 'xternal lin(s
[edit] Composition
!arnauba palm
!arnauba wax contains mainly esters of %att) a#ids "#$-#%&', %att) al#ohols "($-
()&', acids "*-)&' and h)dro#arbons "(-*&'. +pecific for carnauba wax is the
content of esterified fatty diols "about ,$&', hydroxylated %att) a#ids "about )&' and
#innami# a#id "about ($&'. !innamic acid, an antioxidant, may be hydroxylated or
methoxylated.
[edit] ses
!andy coated with carnauba wax
!arnauba wax can produce a glossy finish and as such is used in automobile waxes,
shoe polishes, food products such as sweets, instrument polishes, and floor and
furniture waxes and polishes, especially when mixed with beeswax and with
turpentine. It is used as a coating on dental %loss. -se for paper coatings is the most
common application in the -nited +tates. It is the main ingredient in sur%board wax,
combined with #o#onut oil.
.ecause of its h)poaller*eni# and emollient properties as well as its shine, carnauba
wax appears as an ingredient in many #osmeti#s formulas where it is used to thicken
lipstick, eyeliner, mas#ara, eye shadow, foundation, deodorant, various skin care
preparations, sun care preparations, etc.
[citation needed
It is also used to make Cutler+s
resin.
It is the finish of choice for most briar tobacco or smoking pipes. It produces a high
gloss finish when buffed on to wood. /his finish dulls with time rather than flaking
off "as is the case with most other finishes used.'
In %oods, it is used as a formulation aid, lubricant, release agent, anticaking agent, and
surface finishing agent in baked foods and mixes, #hewin* *um, confections,
%rostin*s, fresh fruits and 0uices, gravies, sauces, processed fruits and 0uices, soft
sweets, "i# "a#s and ,ltoids.
/hough too brittle to be used by itself, carnauba wax is often combined with other
waxes "principally beeswax' to treat and waterproof many leather products where it
provides a high-gloss finish and increases leather1s hardness and durability.
It is also used in the pharmaceutical industry as a tablet coating agent.
In (#2$, Charles "ainter patented the use of carnauba wax on phono*raph
#)linders as a replacement for a mixture of para%%in and beeswax.
3hen used as a mold release, carnauba, unlike sili#one or P"-', is suitable for use
with liquid epoxy, epox) molding compounds "45!' and some other plastic types.
!arnauba wax is compatible with epoxies and generally enhances its properties along
with those of most other engineering plastics.
6n aerosol mold release is formed by suspending carnauba wax in a solvent. /his
aerosol version is used extensively in molds for semiconductor devices.
+emiconductor manufacturers also use chunks of carnauba wax to break in new epoxy
molds or to release the plunger when it sticks.
!arnauba is used in melt7castable explosives to produce an insensitive explosive
formula such as Composition B, which is a blend of R./ and "N".
Tentang waxes nya..
0ax refers to beeswax or another substance with similar properties. /he traditional
meaning, beeswax, refers to a substance secreted by bees and used by them in
constructing their hone)#ombs. /he term has come to refer more generally to a class
of substances with properties similar to beeswax, enumerated below8
plasti# "malleable' at normal ambient temperatures
a meltin* point above approximately 9% :! "((* :;' "which differentiates
waxes from %ats and oils'
a relatively low 1is#osit) when melted "unlike many plasti#s'
insoluble in water
h)drophobi#
0axes may be natural secretions of plants or animals, artificially produced by
purification from natural petroleum or completely synthetic. In addition to beeswax,
#arnauba "a plant epi#uti#ular wax' and para%%in "a petroleum wax' are commonly
encountered waxes which occur naturally. Earwax is an oily substance found in the
human ear. +ome artificial materials such as sili#one wax that exhibit similar
properties are also described as wax or waxy.
!ommercial hone)#omb foundation, made by pressing beeswax between patterned
metal rollers.
Contents
[hide
1 0ax #hemistr)
2 ses o% wax
! 0ax t)pes
o !21 ,nimal waxes
o !22 3e*etable waxes
o !2! 4ineral waxes
o !2$ Petroleum
waxes
o !2& 5)ntheti# waxes
$ 5ee also
& Re%eren#es
6 'xternal lin(s
[edit] 0ax #hemistr)
!hemically, a wax is a type of lipid that may contain a wide variety of long-chain
al(anes, esters, pol)esters and hydroxy esters of long-chain primar) al#ohols and
%att) a#ids. /hey are usually distinguished from %ats by the lack of tri*l)#eride esters
of *l)#erin "propan-(,,,*-triol' and three fatty acids. In addition to the esters that
contribute to the high melting point and hardness of carnauba wax, the epi#uti#ular
waxes of plants are mixtures of substituted long-chain aliphati# h)dro#arbons,
containing al(anes, fatty acids, primary and se#ondar) al#ohols, diols, (etones,
aldeh)des.
[1]
<araffin waxes are h)dro#arbons, mixtures of al(anes usually in a
homolo*ous series of chain lengths.
[edit] ses o% wax
3axes are used to make wax paper, impregnating and coating paper and card to
waterproof it or make it resistant to staining, or to modify its surface properties.
3axes are also used in shoe polishes, wood polishes, and automotive polishes, as
mold release a*ents in mold ma(in*, as a coating for many #heeses, and to
waterproo% leather and fabric. 3ax has been used since antiquity as a temporary,
removable model in lost7wax #astin* of *old, sil1er and other materials.
3axes and hard fats such as tallow have long been use to make #andles, used for
lighting and decoration in a number of religious traditions, including !hristianity and
=induism, as well as various neo-pagan religions such as 3icca. /he 4mperor
!onstantine is reported to have called for the use of candles during an 4aster service
in the 9th century 6>. !andles continue to be used today by !hristians
[2]
in worship
as symbols of the light of !hrist. In the ?oman !atholic !hurch, beeswax candles are
used, since a colony of bees is a celibate sisterhood with a single mother.
[!]
!andles of
wax or tallow took the place of lamps used in various @ewish rituals such as the
+abbath lightsA in the =avdalah ceremonyA and the =anukkah lights. 6 synagogue had
to be well lit, and pious folk used to donate candles for the purpose. Bn the basis of
the verse8 1/he soul of man is a candle of the Cord1 a special candle which burns
twenty-four hours is kindled on the anniversary of the death of a near relative
"DahrEeit' and often two lighted candles are placed at the head of the corpse awaiting
burial.
[$]
. !andles have also played a role in pa*an religions and in modern humanist
festivals. Firtually all rituals in 0i##a include the lighting of altar candles, where two
main candles are often used to represent the God and the GoddessA and the lighting of
candles is a central theme at the 3iccan holiday of .rigid or Imbolc, which is also
known as !andlemas or the ;east of the 3axing Cight. 3ax candles were also used in
se#ular life for lighting, signals in warfare, safety in travel and for time keeping, and
are still in popular use today to provide soft lighting for meals and other social
activities.
3ax-decorated 'aster e**s as made in the Cze#h Republi#
3ax with colored pigments added has been used as a medium in en#austi# paintin*,
and is used today in the manufacture of #ra)ons and colored pen#ils. Carbon paper,
used for making duplicate t)pewritten documents was coated with #arbon bla#(
suspended in wax, typically montan wax, but has largely been superseded by
photo#opiers and #omputer printers. In another context, lipsti#( and mas#ara are
blends of various fats and waxes colored with pigments, and both beeswax and
lanolin are used in other #osmeti#s. 6lso, the sports of surfing, s(iin*,
snowboardin* and s(ateboardin* often use wax to enhance the performance.
.eeswax or coloured synthetic wax is used to decorate 'aster e**s in the Cze#h
Republi#. <araffin wax is used in making chocolate covered bon-bons. 3ax is also
used in wax bullets, which are used as simulation aids.
[edit] 0ax t)pes
E#ditF Ani$a% wa#!
Beeswax - produced by hone) bees
Chinese wax - produced by the s#ale inse#t Ceroplastes ceriferus
'ar wax - found in the human ear.
8anolin "wool wax' - from the seba#eous *lands of sheep
5hella# wax - from the la# inse#t Kerria lacca
5perma#eti - from the head cavities and blubber of the sperm whale
E#ditF C#9#ta"%# wa#!
Ba)berr) wax - from the sur%a#e wax of the %ruits of the bayberry shrub,
Myrica faya
Candelilla wax - from the 5exican shrubs Euphorbia cerifera and
Euphorbia antisyphilitica
Carnauba wax - from the leaves of the !arnauba palm, Copernica cerifera
Castor wax - catalytically hydrogenated #astor oil
'sparto wax - a byproduct of making paper from esparto *rass, "Macrochloa
tenacissima'
9apan wax - a vegetable tri*l)#eride "not a true wax', from the berries of
Rhus and Toxicodendron species
9o:oba oil - a replacement for sperma#eti, 0o0oba is pressed from the seeds of
the :o:oba bush, Simmondsia chinensis
;uri#ur) wax - from the .raEilian feather palm, Syagrus coronata.
Ri#e bran wax - obtained from ri#e bran "Oryza sativa'
5o) wax - from soybean oil
E#ditF Min#ra% wa#!
Ceresin waxes
4ontan wax - extracted from li*nite and brown #oal
;zo#erite - found in lignite beds
Peat waxes
E#ditF P#tro%#u$ wa#!
Para%%in wax - made of long-chain al(ane h)dro#arbons
4i#ro#r)stalline wax - with very fine crystalline structure
E#ditF S(nt'#tic wa#!
Pol)eth)lene waxes - based on pol)eth)lene
-is#her7"rops#h waxes
Chemi#all) modi%ied waxes - usually esteri%ied or saponi%ied
substituted amide waxes
pol)merized <7ole%ins
!arnauba waxes
+truktur waxes