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Kingdom of Saudi Arabia Ministry of Higher Education
Umm Al-Qura University Faculty of Applied Science
Chemistry Department
"Synthesis of Some Surface Active Agent From Fatty Matter
Extracted From Wastes of Some Vegetable Seeds"
By
Basmah Ahmad Mahi
B.Sc. ( Chemistry)
A thesis Submitted in Partial Fulfillment of the Requirement for
the Degree of Master of Science ( Chemistry)
Supervised by
Prof. Dr. Wagdy Ibrahim Ahmad El-Dougdoug
Professor of Applied Organic Chemistry, Chemistry Department,
University College, Umm Al– Qura University.
1434 H. / 2013 AD.
ACKNOWLEDGEMENT
Acknowledgement=======================================================================
Acknowledgement
My greatest thanks and indebtedness are directed first always
first to "ALLAH" .
I would like to express my deep thanks and gratitude to Prof. Dr. Wagdy Ibrahim
Ahmad Ali El-Dougdoug, prof. of Applied Organic Chemistry, in Chemistry
Depart , University College, Umm Al-Qura University, Makkah Al-Mukarramh, for
suggesting this work; supervision and his careful guidance and invaluable
discussions during this study.
I would like to express my deep thanks to Prof. Dr. Khalid Khairu, head o f
Chemistry Department, Faculty of Applied Science, Al-Qura University, MaKKah
Al-Mukarramh for his guidance and support.
Finally , the author thanks to all staff members of Chemistry Department Faculty
of Applied Science , specially Girls branch for cooperation, and continuous help.
Last but not least this work would not have been possible without the love,
encouragement, patience and support from my husband and my parents, sisters,
brother, and children.
CONTENTS
............................................................................................................................................................CONTENTS
i
CONTENTS
ACKNOWLEDGEMENT.........................................................................
CONTENTS ..........................................................................................ii
LIST OF TABLES....................................................................................v
LIST OF FIGUERS.................................................................................vi
GENERAL INTRODUCTION.............................................................vii
1. REVIEW OF LITERATURE.......................................................1
Synthetic surface active agents…….……...……………….......................1
a-Nonionic surfactants……………….…………............................2
Condensate with carboxylic acid……….................................3
Condensate with long- chain fatty alcohol…..........................5
b-Anionic surfactants…………………….......................................7
Sulfates………………..………………...................................8
Sulfonates…………………………..……..….........................8
Sulfates oils…………………………......................................8
Sulfated monoglycerides……………..…................................9
Fatty alcohol sulfates………………........................................9
Alkyl ether sulfates………………….....................................10
α -Sulfonated fatty acids and esters........................................13
Ester sulfonates……..........…….............................................14
Sulfonated esters from dicarboxylic acids..............................17
c-Cationic surfactants....................................................................20
d-Amphoteric surfactants..............................................................20
............................................................................................................................................................CONTENTS
ii
Application of nonionic and anionic surfactants.................................21
Biodegradability.....................................................................................22
2-MATERIALS AND METHODS.......................................................24
2.2. Oil extraction............................................................................25
2.2.1.Chemical Characteristics of Al-Cedre oil.............................25
2.3. Analysis...................................................................................29
2.4. Methods....................................................................................30
a- Fatty acids composition.......................................................30
b- Separation of saturated F. A from unsaturated F. A …... 30
c- Propenoxylation...................................................................30
d- Sulfation of oxypropylation fatty acids................................31
e- Fatty alcohol.........................................................................31
f- Alkyl acrylate esters............................................................31
g- Sulfo - fatty esters................................................................31
2.5. Surface Properties.................................................................31
2.6.Biodegradability...................................................................... 33
3. RESULTS AND DISSCUSSION......................................................34
Chemical chracteristics...........................................................34
Fatty acids composition of Al-Cedre Oil...............................34
Separation of saturated F. A. from unsaturated F. A…......34
Preparation of anionic surfactants from fatty acids................35
Surface active properties........................................................................39
Critical micelle concentration................................................................41
Hydrophile – lipophile Balance.............................................................41
............................................................................................................................................................CONTENTS
iii
Sulfonated surface active agents from fatty alcohols...............................41
Preparation of mixed fatty alcohols..........................................................41
Preparation of alkyl acrylate....................................................................42
Preparation of Sulfo-fatty esters ............................................................42
The surface active properties...................................................................45
Biodegradation.........................................................................................45
Tables......................................................................................................46
Figures.....................................................................................................57
4.REFRENCES.......................................................................................73
5.ARABIC SUMMARY........................................................................a-c
............................................................................................................................................................CONTENTS
iv
LIST OF TABLES:
1- Fatty acids composition and chemical characterizatics of
Al-Cedre oil.
2- Surface properties of sulfated oxypropylated fatty acids of
Al-Cedre oil .
3- Surface properties of sulfated oxypropylated saturated fatty
acids of Al-Cedre oil .
4- Surface properties of sulfated oxypropylated unsaturated
fatty acids Al-Cedre oil .
5- CMC for some prepared oxypropylated fatty acids sulfated.
6- Reduction characteristics of fatty alcohols .
7- Physical characterization of sulfonated acrylated esters.
8- Spectral data for fatty alkyl acrylate esters and sulfonated
fatty alkyl Acrylate esters.
9- Surface properties of sulfonated product of fatty alkyl
acrylate .
10- Biodegradability of sulfated oxypropylated of pure
Individual fatty acids.
11- Biodegradability of sulfated oxypropylated fatty acids of
Al-Cedre oil .
............................................................................................................................................................CONTENTS
v
LIST OF FIGURES:
1- GLC of Al-Cedre oil .
2- 1HNMR spectra of compound [ΙΙΙa].
3- 1HNMR spectra of compound [ΙΙb].
4- IR spectra of compound [ ΙVb].
5- 1HNMR spectra of compound [ΙVc].
6- IR spectra of compound [VΙa].
7- 1HNMR spectra of compound [VΙΙa].
8- 1H NMR spectra of compound [VΙΙb].
9- 1H NMR spectra of compound [VΙΙc].
10- IR spectra of compound [VΙΙΙc].
11- IR spectra of compound [VΙc].
12- 1H NMR spectra of compound [ΙΧf].
13- IR spectra of compound [ΧΙe].
14- 1H NMR spectra of compound [ΧΙe].
15- 1H NMR spectra of compound [ΧΙΙd].
16- IR spectra of compound [ΧΙΙd].
17- Biodegradability of oxypropylated stearate sulfate.
GENERAL
INTRODUCTION
………………………………………………………………………………........GENERAL INTRODUCTION
vii
GENERAL INTRODUCTION
Crude oil obtained from the waste can be successfully used to prepare
a variety of fatty derivatives.
Fatty acids and their derivatives play an important role in the chemical
industry because they are used as raw materials for a wide variety of
industrial products utilized in different aspects like, textile, paints, rubber,
cosmetics, food, pharmaceuticals and surfactants. The production of fatty
acids from non-edible oil resources upgrades them to be suitable for the
manufacture of all types of surfactants and other products. All organic
surfactants comprise a specific character, in their molecular structure.
The molecule must contain a portion which has affinity to oil (
lypophilic.), where as the opposite end of the molecule, at the same
distance has an attraction for water or aqueous solutions ( hydrophilic).
This ability within the same molecule will be a dual affinity for
substances of entirely different natures, such character gave these
substances surface active property in quite dilute solutions. This function
is done to the tendency of the molecules to concentrate at interfaces
between the solvent and a gas, solid or other immiscible liquids. From
this phenomenon, the tern of surface active agents or surfactants was
derived. At the boundaries of the solvent, the molecules are oriented in
such that; the hydrophobic hydrocarbon chain or “tail” of the molecule is
directed towards the hydrophobic or oily phase and the hydrophile or
polar “head” is directed or embedded into a gas or polar phase. This
property leads to the ability of these materials to reduce surface tension,
to cause foaming, and to exhibit other unique properties. Therefore,
surfactants find utility in many fields, the principle use being as
detergents, wetting agent, dispersing agents and floating agents.
Consequently, they are widely incorporated in house hold cleaning
products and in such diverse applications as agricultural sprays,
cosmetics, floatation, foods, emulsifiers, lubricants, leather manufacture,
inks, synthetic elastomer production and oil recovery operations.
………………………………………………………………………………........GENERAL INTRODUCTION
viii
The following is a concise review of literature covering some
important aspects of synthetic surface active agents, sulfated oils, sulfated
monoglycerides, would present the necessary knowledge on the
concerned subject. It is observed that the acids obtained by hydrolysis of
vegetable fats are very largely saturated or unsaturated acids containing
more than 18 carbon atoms. The work done in this thesis synthesis of
anionic surface active agents (Sulfated and Sulfonated) obtained from the
non-edible Al-Cedre oil which wide spread through out the Kingdom of
Saudi Arabia were , considered because of the remarkable properties and
wide variety of uses of these compounds. This study has been represented
in the following sections.
SECTION I:
It includes the preparation of the oil samples by cold extraction with n-
hexane. The extracted oil was subjected to the chemical characteristics
and fatty acids composition via G.L.C., the saturated fatty acids was
separation from the unsaturated fatty acids using lead acetate method.
The modified anionic surfactants was prepared by addition of propylene
oxide (P.O.) 1,3,5and7 moles respectively, followed by reacting with
fuming sulfuric acid and neutralization using NaOH to pH=7.
The structure of the synthesized surfactant was confirmed by
examination of their I.R and 1HNMR spectra.
SECTION II:
Was concerned with the synthesis of sulfonated fatty esters as follow :
a- The proposed mixed fatty ester of saturated acids, unsaturated
acids and / or mixed fatty acid of Al-Cedre oil was subjected to
reduction with (LiAlH4) to the corresponding fatty alcohols the %
of reduction was confirmed via S.V of ester and reduced products
respectively.
b- Esters was synthesized by esterification of acrylic acid with fatty
alcohols of (CI6:0, C18:0, C18:1, C18:2, mixed saturated, mixed
………………………………………………………………………………........GENERAL INTRODUCTION
ix
unsaturated, mixed Fatty acids of Al-Cedre oil) respectively,
followed by addition of NaHSO3 forming bisulfite adduct.
The structure of the prepared surfactant was confirmed by spectral
data. The surface active properties , biodegradability of the prepared
surfactant were evaluated and illustrated in (11Tables) and (17 Figures) .
The preparation of dual functionality materials having anionic and
nonionic groups in the same molecule, to adjust the foam height and Ca+2
stability , which can be used as detergent additives for washing machines
from economic sources.
In general the surface active properties in this study were quite
satisfactory and it is hoped that, they will find uses in some industrial
applications.
REVIEW
OF
LITERATURE
……………………………………………………………………………………… REVIEW OF LITERATURE
1
1. REVIEW OF LITERATURE
The following is a concise of literature survey concerning the aspects
of the present study. It includes synthetic surface active agent, sulfated
oils, sulfated monoglycerides, fatty acids, fatty alcohol sulfates, fatty
alcohol ether sulfates, sulfonated dicarboxylic acids and esters,
biodegradability and field of applications:
Synthetic surface active agents:
Surfactants are substances with molecular structures consisting of a
hydrophilic and a hydrophobic part. The hydrophobic part is normally a
hydrocarbon (linear or branched), where the hydrophilic part consists of
ionic or strongly polar groups, e.g. polyglycol ether groups.
Hydrophobic Hydrophilic
(Tail) (head)
The arrangement of the hydrophilic as well as the hydrophobic part
can vary, as shown below :
Due to this characteristic structure, these compounds have a special
property, namely the interfacial activity, that sets them, apart from
……………………………………………………………………………………… REVIEW OF LITERATURE
2
organic compounds in general. In solvents such as water, the surfactant
molecules distribute in such a manner, that their concentration at the
interfaces is higher than in the inner regions of the solution. This behavior
is attributable to their amphiphilic structure (hydrophilic part,
hydrophobic part). At the phase borders, an orienting alignment of the
surfactant molecules occurs. This results in a change of system
properties, e.g. a lowering of interfacial tension between water and
adjacent phase, a change of wetting properties, as well as formation of
electrical double layers at the interfaces. Inside the solution, on exceeding
a certain surfactant concentration. The surfactant aggregates
(micelles).Surfactants are primarily applied in aqueous solutions, so that,
classification by type of hydrophilic group is appropriate.
a- Nonionic surfactants; b- Anionic surfactants,
c Cationic surfactants; d - Amphoteric surfactants.
a-Nonionic surfactants, are surface active substances which in aqueous
solutions do not dissociate into ions. Polar groups such as polyglycol
ether groups or polyol groups provide the solubility of these substances in
H2O.
Ethylene and propylene oxide condensation is one of the principal
processes employed to introduce hydrophilic functional group into the
molecular structures of organic compounds. The ultimate objective of the
process is the production of surface active agents having the desired
hydrophile- lipophile balance for such commercial applications as
……………………………………………………………………………………… REVIEW OF LITERATURE
3
detergency, emulsification, wetting, textile processing, etc. Ethylene or
propylene oxide is characterized by great reactivity, three-member ring is
under great strain and can readily be opened, and is therefore, easily
added to compounds having active hydrogen atom contained in a
functional group with which, it is being condensed to form a
hydroxyethyl or hydroxypropyl derivatives. The active hydrogen of
hydroxyethyl or hydroxypropyl derivative is then available for reaction
with an additional epoxide group and by repetition of this process, a
polyoxyethylene or polyoxypropylene compound can be formed. Most of
the important nonionic surfactants are synthesized in an anhydrous media
in the presence of an alkaline catalyst.
Classification of nonionic surfactants:
1 - Condensate with Carboxylic acid: The addition of ethylene oxide or
propylene oxide to a carboxylic acid takes place as follows:
R-COOH + RCOOCH2-CH2-OH
CH3 CH3
R-COOH + RCOO- CH-CH2-OH
This results in the production of the monoglycol ester of the
carboxylic acid. The ethenoxylation and or propenoxylation will then
continue with the formation of polyethylene glycol mono esters or poly
propylene glycol mono ester, respectively as follows:
RCOOCH2-CH2-OH + n RCOO(CH2-CH2-O)n+1H
……………………………………………………………………………………… REVIEW OF LITERATURE
4
CH3 CH3 CH3
RCOO -CH-CH2-OH +n R-COO(CH-CH2-O)n+1H
Formation of the diesters will take place by transesterification if
alkaline catalysts are used.
2RCOO(CH2-CH2-O)nH 2RCOO(CH2-CH2-O)nCOR + HO(CH2-CH2-O)nH
CH3 CH3
2R-COO(CH-CH2-O)n+1H RCOO(CH-CH2O)COR
CH3
HO-(CH-CH2-O)nH
The polyethylene or polypropylene glycols are produced and the
products will consist of mono and diesters for polyethylene or
polypropylene glycols and free polyethylene or polypropylene glycols,
respectively. A similar reaction takes place in case of one molecule of
polyethylene or polypropylene glycol . The ester structure of these
surfactants makes them generally unsuitable for use in strong acid or
alkali solutions due to the tendency to hydrolyze. The properties of the
products, can be changed considerably by varying the molar proportion of
ethylene oxide, i.e. by changing the length of the polyethenoxy chain.
The products are usually specified in terms of the number of moles of
ethylene oxides, which has reacted with one mole of the hydrophobic
starting material during the preparation. The polyethenoxy chain is a less
powerful solubilizer than the ionogenic groups such as -SO3H, -COOH or
quaternary nitrogen. It solubilizes by virtue of the power of the ether
oxygen to hydrate [1-3]. The polyethenoxy surfactants tend to become
……………………………………………………………………………………… REVIEW OF LITERATURE
5
markedly less soluble at increased temperature. The “cloud point” or
temperature at which an aqueous solution of a specified concentration
begins to separate into two phases is used as one of the control
specifications of these materials [4].
In general the longer the ethenoxy chain, the higher the solubility of
the surfactant in water. Sodium salts in much the same way as the
ionogenic surfactants salt out these detergents. Calcium salts, however,
frequently increase the solubility of the nonionics, presumably by
forming complex with them [5]. In solution the nonionics show no ions,
but there is some evidence that their micelles migrate in an electric field.
This is characteristic of all colloidally dispersed materials. In previous
literature on nonionics, the impression was sometimes given that ethylene
oxide and propylene oxide are practically interchangeable in producing
surfactants.
2-Condensate with long-chain fatty alcohols.
Ethylene or propylene oxides add to alcohols to yield ether adducts:
ROH + ROCH2CH2-OH
ROC2H4OH + ROC2H4OC2H4OH, etc.
CH3
ROH + ROCH(CH3)CH2-OH
ROCH(CH3)CH2-OH + RO(CH(CH3)CH2-O)2H, etc.
Most of the aliphatic alcohols with more than eight carbon atoms
where sulfates are commercially available, are converted to polyethenoxy
ethers, which have appreciable surface activity. Among these compounds,
……………………………………………………………………………………… REVIEW OF LITERATURE
6
the relationships between the structure of the alcohols and the surface
action properties of the polyethenoxy ether are similar to the relationship
observed in the case of fatty alcohol sulfates. The higher fatty alcohols of
beeswax and other natural waxes have also been converted to
polyethenoxy derivatives. These materials are finding increasing use in
cosmetic and pharmaceutical preparations [6].
Propylene oxide forms a large number of condensed products with
fatty acids, alcohols, and mercaptans, amines and amides that have good
detergent properties. The availability of propylene oxide at a relatively
low price, coupled with its ability of reaction to form polyoxypropylene
glycols opens the way to an almost unlimited number of relatively
inexpensive base materials for the synthesis of nonionic surface active
agents. Propylene oxide resembles ethylene oxide except that hydrophilic.
Locally produced non-edible oils, namely, rice bran oil were utilized as
starting materials for preparing nonionic surfactants [7]. The mixed fatty
acids of rice bran oil were converted to methyl-ester and then reduced
with LiAlH4 to the corresponding fatty alcohols. The alkali-catalyzed
reaction of propylene oxide with the fatty acids or alcohols of rice bran
oil, was carried out to obtain nonionic surfactants covering a range of 10-
20 propylene oxide moles molecule, RCO(OCH(CH3)-CH2)11-OH
and R (OCH(CH3)CH2)n-OH. The reaction rate of alcohols was higher
than that of the corresponding acid[8]. Oxypropylated diol monoesters of
palmitic and oleic acids was prepared by reacting oxypropylated diol with
boric acid, esterifing the resultant borate with fatty acid, and selectively
hydrolyzing the borate ester; their surface active properties were
evaluated[9]. Nonionic surfactants with an amido- oxime terminal group
were prepared from fatty acids of rice bran oil by reacting with propylene
oxide in presence of KOH as catalyst [10-12]. Also, oxypropylated
p-hydroxy phenyl octadecanol and p-hydroxyphenyl octadecanoic acid
were prepared by reacting the mentioned substrate with propylene oxide
followed by the conversion of the product to nonionic surface active
agents with hydroximic acid group [13]. The simplest of these are the
straight chain fatty acids esters of polyethylene glycol :
……………………………………………………………………………………… REVIEW OF LITERATURE
7
RCOO(-C2H4O-) nH, wich may be produced by reacting the fatty acids
with ethylene oxide under pressure, in the same manner as the
polyoxyethylene ether [ 14]. They are however more usually made, by
esterifyng the previously prepared polyethylene glycol with a fatty acid.
The polyethenoxy esters of tall oil acids are doubtless used in larger
amounts than any other class of nonionic surfactant. This ester is an
excellent detergent but produces very little foam. In admixture with
inorganic builders, it is used in commercial laundering and as a heavy-
duty household detergent. Among the interesting polyethenoxy esters,
which exhibit good detersive properties, are those made from the fatty
acids of oxidized paraffin wax. Naphthenic acids have also been reacted
with ethylene oxide to form strongly surface active esters. A sides from
ethylene oxide and polyethylene glycol, several polyethenoxylated
polyols have been used to convert fatty acids, by esterification, into non-
ionic surfactants. Among the best known and most widely used nonionic
surfactants, which do not possess a polyethenoxy chain in their structure,
are the esters of the sugar alcohols, sorbitol and manitol. As produced,
they are probably mixtures of esters in which the sorbitol portion of the
molecule is partly esterified and partly dehydrated before esterification to
form the cyclic inner ether monoanhydrosorbitol and dianhydrosorbitol.
These inner ethers are collectively referred to as sorbitan (or mannitan).
They have been isolated in relatively pure state and they can be etherized
as well as esterified. The sorbitan ester can be prepared by direct
esterification with fatty acids at high temperatures or with a fatty acid
chloride. Since sorbitol and Sorbitan contain more than one hydroxyl
group, the possibility exists to produce di- and polyesters [15], which are
not sufficiently water soluble to be used as surfactants. Fatty acid esters
of the diol polysaccharides have been prepared and described. The
monoesters are water dispersible and surface-active agents.
b-Anionic surfactants: are surface active substances in which, e.g. one
hydrophobic hydrocarbon group is connected with one or two hydrophilic
groups. In aqueous solution, dissociation occurs into a negatively charged
ion (anion) and positively charged ion (cation). The anion is the carrier of
……………………………………………………………………………………… REVIEW OF LITERATURE
8
the surface-active properties. The sulfated and sulfonated materials
represent the largest group of surface-active agents, exclusive of soap.
Chemically, these products are divided into two categories:
Sulfates: Compounds in which sulfur is attached to the carbon chain
through an oxygen:
Sulfonates: Compounds in which the sulfur is attached directly to the
carbon chain. A large number of sulfated and sulfonated surface-active
agents are commercially available.
Sulfated oils: The sulfation of fatty materials to yield surface- active
compounds was discovered by Fremy [16] almost 150 years ago, when
he treated olive oil with sulfuric acid. Historically, it is the earliest
reported example of a non-soap organic surfactant. This so-called
“sulfuric acid oil” was used as a mordant and was found to be superior to
untreated olive oil which was also used for this purpose [17]. in 1874,
castor oil was sulfated and the resultant product was used in dying with
alizarin red.
……………………………………………………………………………………… REVIEW OF LITERATURE
9
Sulfated monoglycerides:
Sulfated fatty monoglycerides were introduced in the United States in
the early 1940 by the Colgate-Palmolive Co. [18-22]. Sulfated
monoglycerides are produced by the reaction of three relatively
inexpensive raw materials: fat (coconut oil), glycerol, and sulfuric acid:
CH2-O-COR CH2-OH a)H2SO4 CH2-O-COR
CH -O-COR + CH2-OH CH -OH + 3H2O
CH2-O-COR CH2-OH b)NaOH CH2-OSO3-Na
+
Coconut oil monoglycerides were used for many years by Colgate -
Palmolive Co. in a number of major products, including a synthetic
detergent bar (Vel), light-duty detergents, shampoos (Halo), and
toothpaste. The surface active properties of pure monoglycerides sulfates
were reported by Biswas and Mukherji [23-24], who found that the C14
homologues have the best foaming power and exhibit the greatest surface
tension- lowering effect.
Fatty alcohol sulfates:
The fatty alcohols are normally derived from fatty acids by catalytic
hydrogenation under pressure [25], Various glycerides and simple esters
have been reduced to fatty alcohols with either sodium- alcohol [26],
lithium aluminum hydride (LAH) [27], catalytic hydrogenolysis or by
sodium borohydride in a mixture of t-butanol and methanol [28].
Sulfuric acid, chlorosulfonic acid, amidosulfonic acid and also gaseous
sulfur trioxide maybe utilized in the production of primary fatty alcohol
sulfates:
R-OH + H2SO4 ROSO3H + H2O
R-OH + ClSO3H ROSO3H + H2O
……………………………………………………………………………………… REVIEW OF LITERATURE
11
R-OH +NH2-SO3H ROSO3- NH4
+
R-OH + SO3 ROSO3H
The chain length and degree of branching of fatty alcohols mainly
determine the properties of the fatty alcohol sulfates. Generally intensive
is an effective surfactant that possess high interfacial activity. The
solubility decreases with increasing carbon chain length, while hardness
sensitivity increases. The unsaturated C16-C18 alkenyl sulfates show an
improved solubility as compared to the saturated alkyl sulfates.
Alkyl ether sulfates: The starting materials for the preparation of ether
sulfates are primarily fatty alcohols with carbon chain length of C12 —
C14 or (C12 — C18) to which ethylene oxide is added, forming the
respective alcohol ethoxylates respectively.
R- O (CH2 - CH2 - O)n- H + SO3 R- O (CH2 - CH2-O)n- SO3H
Ether sulfates differ from alkyl sulfates by the glycol ether units
positioned between the hydrophobic alkyl chain and the hydrophilic
sulfate group:-
ROSO3‾ Na+ RO-(CH2-CH2-O )n-SO3
‾ Na
+
Alkyl sulfates Ether sulfates
The solubility of the ether sulfates is influenced by the hydrophilic
polyglycol ether group and is noticeably higher than that of the respective
alkyl sulfates [29]. The solubility of the calcium salts is very significant
white ether sulfates are quite insensitive to water hardness [30]. The
reaction of alkylene oxides with active hydrogen containing compounds
is the chief method of preparing nonionic surfactants [31]. Up till now,
the reaction of these compounds with ethylene oxide has attracted
considerably more attention, for these compounds always give only one
kind of poly adduct. In the reaction of propylene oxide with alcohols,
alkyl phenols or various other compounds commonly used for the
synthesis of nonionic surfactants, two different of poly adducts may be
……………………………………………………………………………………… REVIEW OF LITERATURE
11
formed depending on the properties of the catalyst. In order to obtain only
one series poly adducts, the oxypropylation reaction is usually carried
out in the presence of basic catalyst such as sodium or potassium
alkoxylates or hydroxides. Under such conditions, in the first stage of the
reaction of propylene oxide with alcohols, mono-ethers of 1- alkoxy
propanol-2 are fonned which exhibit a lower acidity and a lower
reactivity than the starting alcohol [32-35].
CH3 RO‾ Na+
R-OH + R-O-CH(CH3)-CH2-OH
O
Propylene glycol alkyl monoether thus formed, may be further reacted
with propylene oxide to give a poly disperse mixture of alkyl monoesters
of polyoxypropylene glycols:
CH3 CH3 RO‾ Na+
R-O-CH- CH2-OH + (n–1) R-O-CH(CH3)-CH2-OH
O
The composition of the reaction mixture depends on the molar ratio of
the substrates and the acidity of the starting alcohol. The molecular
weight distribution values for the products of poly oxypropylation of
aliphatic alcohols often differ considerably, however, the values for
higher fatty alcohols are almost constant [36-37]. The polyoxypropylation
products of higher alcohols are, similarly to starting alcohols, insoluble in
water, because the polyoxypropylene chain possess hydrophobic
properties as well. In order to increase their solubility in water, these
products are subjected to polyoxyethylation that leads to RPE- type
nonionic surfactant foundation [38- 40]. Weil et all [36,40], reported the
preparation of anionic surfactants through sulfation of the
polyoxypropylation products of certain fatty alcohols. Matsuda et al.,
……………………………………………………………………………………… REVIEW OF LITERATURE
12
[41], obtained similar compounds through sulfation of polyoxypropylated
lauryl alcohol. Chiebicki et al.[42] reported that, polyoxypropylene
glycol alkyl monoethers were obtained from C8- C18 aliphatic alcohols
and propylene oxide in the presence of a basic catalyst. These compounds
were used to synthesize a series of sulfate- type anionic surfactants CnPm
OSO3‾ Na+. It was also found that, the presence of oxypropylene units in
a molecule of the compound enhances the surface activity and wetting
ability of these surfactants.
The sulfation of fatty alcohols and fatty alcohol ethoxylates gives fatty
alcohol sulfates and fatty alcohol ether sulfates, respectively. These
sulfates are representative of the anionic surfactants, and their detergency
depends on alkyl chain length, oxyethylene chain length and nature of the
cations. Lauryl sulfates have good foaming ability and biodegradability,
so they have been widely used as detergents or emulsifiers. Sodium lauryl
sulfate is superior in detergency and has been used for household
products and industrial applications. It is often used as a foaming agent or
a dispersing for cosmetics and as an emulsifier for emulsion
polymerization. Triethanolamine lauryl sulfate possesses good foaming
ability against sebaceous soil and it is used in liquid dishwashing
detergents or in cosmetic products, especially in shampoos. Ammonium
lauryl sulfate is used in liquid dishwashing detergents and shampoos as a
good foaming agent. Lauryl ether sulfates are more soluble in water and
less irritative to the skin or eyes than lauryl sulfates. Sodium lauryl ether
sulfate is used in liquid dishwashing detergent and liquid shampoo [43].
Sodium oleyl sulfate is an example in which the CH2-OSO3‾ Na
+ group
replaces the carboxyl group and the molecule is further solubilized by the
presence of a double bond. Sodium oleyl sulfate has not been as well
characterized as the sodium alkyl sulfates of the saturated alcohols,
principally because the usual sulfating agents react both with the double
bond and the hydroxyl group of oleyl alcohol [44].
El-Sawy et. al. [45], reported that, 2-sulfated fatty acids derivatives of
myristic, palmitic and stearic, were prepared by reacting with
……………………………………………………………………………………… REVIEW OF LITERATURE
13
chlorosulfonic acid in CCl4 as solvent. Cis and trans-2- n-alkyl-5-
hydroxy-l,3-dioxans were subjected to sulfation reaction with SO3-
pyridine complex, followed by neutralization, to obtain mixtures of sod
cis- and trans- (2- n-alkyl -l ,3-dioxan -5-yl) sulfates [46-48].
Higher alcohol ethoxylat sulfates [49], (C8 - C20), linear or branched,
are prepared by sulfation of RO-(C2H4)nOH (R1, n = same as above),
using SO3 diluted to 0.1 - 3 vol. % with an inert gas to give 93.3 %
sulfated products. On other hand: sulfates were prepared from
oxypropylated alkyl glucosides by reacting with chlorosulfonic acid in
cooled system [50]. The α – sulfonation of saturated fatty acids has been
accomplished in the past by leading sulfur trioxide vapur over the surface
of a carbon tetrachloride solution [51]. Also,by the reaction of
chlorosulfonic acid or sulfur trioxide with the molten acid [52], and
refluxing with chiorosulfonic acid in carbon tetrachloride solution [53].
The sulfonation of the soap, acid, alkyl ester with sulfur trioxide in sulfur
dioxide solution [54-55], and by the reaction of sulfites with α-
bromoacids [56-57], could be achieved.
α-Sulfonated fatty acids and esters: α - Sulfonated fatty acids and esters,
because of their wide— range of application and biological properties,
……………………………………………………………………………………… REVIEW OF LITERATURE
14
represent an interesting class of surfactants. A technical method for the
preparation of α-sulfonated fatty acids is described [58]. Under special
reaction conditions, it is possible to prepare α -sulfonate saturated fatty
acid esters directly without the use of solvents. The use of SO3 gives the
product in more than 97 % yield. Sod. α- sulfopelargonic acid [59]
displays little evidence of surface active properties, but becomes an
efficient wetting agent upon esterification with n-octanol to form sodium
octyl α-sulfopelargonate, a compound with the hydrophilic group at about
the middle of the molecule and with hydrophobic alkyl groups of about
equal chain length. On the other hand, sod α-sulfo–n-decanoic acid was
prepared by the α-sulfonation of n-decanoic acid using chlorosulfonic
acid in CC14. The mono-sodium salt was prepared by adding aqueous
sodium sulfate to a hot aqueous solution of the crude α- sulfo-acid and
cooling to room temperature [60].
A novel series of glycerol-based double or triple– chain surfactants
with two sulfonate, two sulfate or two carboxylate groups was
conveniently prepared by reactions of 1 -O-alkyl glycerol diglycidyl ether
with long chain fatty alcohols, and followed by reactions with
propanesultone, chlorosulfonic acid or bromoacetic acid, respectively
[61]. The sulfate and carboxylate types of compounds have higher water
solubilities than the corresponding sulfonate type of compounds bearing
the same lipophilic groups. The triple chain surfactants show excellent
surface-active properties, such as micelle forming and ability to lower
surface tension, compared not only with the corresponding single chain
anionic surfactants, but also with the corresponding double chain
surfactants.
Ester sulfonates:
Sulfonates with an intermediate ester between the hydrophobic fatty
chain and the sulfonate group were introduced in Germany by I.G.
Farben industries in 1930 under the Igepon A [62].
R-COO-CH2-CH2 - S03‾ Na+
……………………………………………………………………………………… REVIEW OF LITERATURE
15
The Igepon surfactants are prepared by reacting isethionate with a
fatty acid chloride or directly with the fatty acid. The acid chlorides are
manufactured from the fatty acids by reaction with phosphorus trichloride
or with thionyl chloride
3RCOOH + PCl3 3 RCOCl + H3PO3
RCOOH + SOCl2 RCOC1 + HC1 + SO2
The reaction of the acid chloride with isethionates is carried out in a
stainless steel vessel with a slow heavy – duty agitator. High vacuum is
applied to remove the HC1 formed in the reaction.
RCOCl + HOC2H4 SO3‾Na
+ 70- 90°C RCOO C2H4 SO3
‾Na
+ + HCI
The efficiency of hydrochloric acid removal affects yield and quality,
continuous processes for the manufacture of Igepon A have also been
reported [63]. Salts, of α-sulfonated fatty esters have been known for a
considerable period of time. Their chemical formulas are:
R- CH- COOH R-CH-COOR
SO3H SO3H
α - sulfonated acid α- sulfonated fatty esters
Because of their superior properties, the ester sulfonates (ES) are of
greater practical importance than are fatty acid sulfonates (FAS).
However, because of the lack of a simple, economical manufacturing
process, they have received little attention. Therefore, at the end of the
1950’s they began to develop a technically practical method for preparing
ES of exceptional quality [64]. On economic grounds this could only
proceed by direct sulfonation of fatty esters, especially methyl esters.
Sodium α-sulfonated fatty acid polyethylene glycol monoesters
[CmH 2m+1CH(SO3‾Na+)COO-(C2H4O)nH] and diesters
[CmH2m +1 CH(SO3‾Na+ )n-COO-(C2H4O)n COCH-(SO3
‾Na
+) CmH2m+1],
……………………………………………………………………………………… REVIEW OF LITERATURE
16
where m = 10-16 and n = 1-35, were prepared by esterification of α-
sulfonated fatty acids with poly ethylene glycol followed by
neutralization with NaOH. Crude products were purified by reversed –
phase column chromatography on an octadecyl – modified silica gel
[65]. The structural effects of sodium α-sulfonated fatty acid higher than
alcohol esters on surface-active properties were reported, [66] where
some characteristic features, such as low interfacial tension, good
emulsifier ability and extremely low foaming properties were elucidated.
Most of them, however, had relatively high kraft points, perhaps resulting
in restricted practical applications. A series of polyethylene glycol esters
of sodium α- sulfonated, fatty acids was then prepared to attain more
hydrophilic character. Esterification of polyethylene glycol and α-
sulfonated fatty acid simultaneously produces monoesters and diesters. A
molecule of sodium α- sulfonated fatty acid polyethylene glycol
monoesters consists of one hydrophobic alkyl chain and two hydrophilic
residues, i.e., a nonionic oxyethylene (EO) unit and anionic sulfonate
group, located on the same carbon atom. The structure of the α-
sulfonated fatty acid polyethylene glycol monoester molecule is
significantly different from alkyl ethoxy sulfate (AES), which has an
anionic sulfate group attached to the end of the (EO) chain, and
simultaneously possesses well-known and favorable surface – active
properties [67-68]. There are few studies, however, concerning sodium α-
sulfonated fatty acid polyethylene glycol monoesters, except for the work
by Micich et al. [69], which deals with sodium α-sulfonated palmitic and
stearic acid monoethylene glycol mono esters. Sodium α- sulfonated fatty
acid polyethylene glycol diesters are examples of amiphiphatic
compounds with double lipophilic groups and double hydrophilic groups.
Recently, Rosen, Okahara, and their coworkers, [70-75] have studied
such surfactants, and many favorable features, such as low kraft point and
low critical micelle concentration (CMC), were determined.
……………………………………………………………………………………… REVIEW OF LITERATURE
17
Sulfonated esters from dicarboxylic acids:
Sulfonated succinic acid alkyl esters [76-80], are generally produced
from maleic anhydride, but maleic acid or fumaric acid may also be used.
For example, by reaction of maleic anhydride with an excess (>2 moles)
of an alcohol, maleic dialkyl esters are obtained. Azeotropic agents such
as benzene, toluene, or xylene are used in this reaction to azeotropically
remove the released water from the reaction mixture. Suitable
esterification catalysts such as toluene sulfonic acid, amidosulfonic acid
or sulfuric acid, are used.
The reaction is completed 4-5 hours at temperature range of
approx. 80-100 °C, after neutralization of the reaction mixture with
NaOH or NaHCO3, the excess alcohol and the azeotropic solvent are
removed from the reaction mixture by vacuum distillation. Sulfo-
succinic dialkyl esters are formed by reaction of dialkylmaleate ester
with NaHSO3. When, the reaction carried out in methanol / water
mixture, under pressure in an autoclave it may shorten the reaction
time of approx. 8-10 hours. Any remaining excess NaHSO3 is
filtered off. After removal of the solvent, the sodium Salt of sulfo-
succinic acid ester is obtained in anhydrous form.
……………………………………………………………………………………… REVIEW OF LITERATURE
18
The maleic acid mono-esters are prepared without solvent by reacting
maleic acid anhydride with equimolar quantity of alcohol in the presence
of an acidic catalyst. The reaction is completed in approx. 2 hrs at 70-
100°C,. The reaction of the mono-ester with NaHS03 is carried out with
equimolar amounts of mono-ester and sulfite. The pH of the reaction
mixture is adjusted with NaHC03 or NaOH to approx. pH 5-8 ,so that, a
neutral product results after workup. Both, straight and branched chain
alcohols are used in the esterification of maleic acid and maleic
anhydride. Alcohols with five to eight carbon atoms, or fatty acid ethanol
amides are preferred for the diesters. Mono-esters are prepared from fatty
alcohols, fatty alcohol ethoxylates or fatty acid alkanol amides. Sulfo-
dialkylsuccinate ester based on alcohols with a total of less than nine
carbon atoms are water– soluble. The solubility is improved by branching
in the alkyl groups. Ethoxylated alcohol-based sulfo-succinic acid half
esters were synthesized by esterification of the above ethoxylated product
with maleic anhydride at (90-95 °C) molar ratio (1:1), in nitrogen
atmosphere, followed by sulfation in aqueous solution sodium sulfite at
(70- 75°C) and molar ratio (1:1) [81].
……………………………………………………………………………………… REVIEW OF LITERATURE
19
A series of anionic surface active agents were prepared from salicylic
acid by esterification with fatty alcohols [Ia-i] [ decyl C10: 0 , dodecyl
C11: 0, tetradeyl C14 : 0, hexadecyl C16 : 0, octdecyl C18 : 0 , octdec 9-enyl
C18 : 1, octdec 9,12-dienyl C18 : 2 , mixed fatty alcohol of Juagafa seed
fat and mixed fatty alcohols of Grape oil ], in the presence of p-toluene
sulfonic acid as catalyst , to afforeded an alkyl salicylates [IIa-i], which
are converted to anionic sulfated, sulfonated fatty alkyl salicylate [IVa-
i] respectively. Also, the prepared esters [IIa-i] were oxypropylated with
various unit of propylene oxide (2, 4 and 6 moles) to give [IIIa-i]. These
compounds were converted to a modified anionic surfactants [Va-i] as
molecular aggregations and surface active agents in aqueous media[82]
as shown in the following scheme.
COH
O
OH+ CH3(CH2)x CH2-OH
p-Tol.Sulf. AcidC
O-CH2-(CH2)x-CH3
O
OH
I a-i
IIa-i
a)
b)
dry benzene
CO-CH2-(CH2)x-CH3
O
OH IIa-i
+
O
H3C
nN(CH2-CH3)3
70-80
CO-CH2-(CH2)x-CH3
O
O (O)n H
ClSO3H / CCl4i)
ii) NaOH
CO-CH2-(CH2)x-CH3
O
O (O)n SO3
CO-CH2-(CH2)x-CH3
O
OSO3 NaNa
ClSO3H / CCl4i)
ii) NaOH
IIIa-i
IVa-i
x = 8, 10,12, 14,16, 16:1 , 16:2 ,mixed alcohol of Juagafa Fat and mixed alkyl of grape oil
n = 2, 4, 6 mole propylene oxide add
Na O3SNa O3S
(Va-i ) 2,4 and 6
C
……………………………………………………………………………………… REVIEW OF LITERATURE
21
c- Cationic surfactants: which also contain a hydrophobic hydrocarbon/
group and one or several hydrophilic groups, dissociate in aqueous
medium also into cation and anion. However, the cation is the carrier of
the surface active properties.
d- Amphoteric surfactants: contain in aqueous solution both positive and
negative charge in the same molecule. Depending on the composition and
conditions of the medium (pH value), the substances can have anionic or
cationic properties.
X = - R2N+- CH2 - COO‾ and / or -R2N
+ - (CH2)3 SO3‾
……………………………………………………………………………………… REVIEW OF LITERATURE
21
Application of anionic surface active agents
The applications of anionic surfactants are very widely distributed
throughout science technology, and every day life. Examples, which at
once come to mind are the washing, wetting out of textile materials, the
preparation of dispersions and emulsion, the application of agricultural
and horticultural sprays, and a wide variety of special uses, the number
of which is continually increasing. Fatty alcohol sulfates and fatty alcohol
polyglycol ethers have found acceptance. Furthermore, fatty acid esters of
glycerin or sorbitol are being emulsified. The primary application for
surfactants in the plastics industry is in the preparation of plastics
dispersions. The polymerization of vinyl monomers is carried out with
usage of anionic or nonionic surfactants as emulsifiers. Also known is the
application of α.- sulfo fatty acids, α- sulfo fatty acid esters.
In the styrene polymerization process, primarily alkyl aryl sulfonates,
alcohol sulfates, as well as polyglycol ethers are being employed [83].
The manufacture of acrylonitrile, mixed polymerizes and graft
polymerizes certain protective colloids, soaps, alkyl aryl sulfonates,
sulfo-succinic acid esters, alkyl phenol polyglycol ethers and alkyl phenol
ether sulfates are approved for usage in the food sector [84]. Recent
systematic evaluations of α- sulfo-fatty acid esters in the emulsion
polymerization process show that this surfactant class is superior to
common emulsifier systems in essential application properties [85-86].
The application of different kinds of natural surface– active agents mono
acyloglycerols (monoglycrides) are the most widely used emulsifiers in
the food industry [87]. Dioctyl sulfo-succinate salt was used for cleaning
petroleum – contaminated surfaces [88]. As potentially suitable
surfactants in the tertiary petroleum recovery, petroleum sulfonates, alkyl
aryl sulfonates, alkane sulfonates, olefin sulfontes, ether sulfates, ether
sulfonates, and ether carboxylates may be applied in oilfield industry.
Hovever, surfactants are presently being applied only in field tests. In the
USA the production of crude oil by tertiary recovery methods in 1982
……………………………………………………………………………………… REVIEW OF LITERATURE
22
amounted to 19 MM tons, primarily by the steam flooding process and to
a small extent by the carbon dioxide process.
Biodegradability:
The use of different surfactants has led to very considerable problems
in the purification of sewage. The difficulties are mainly caused by the
insufficient biological degradation of the detergents most commonly
used. The compounds partly undegraded pass through the sewage
treatment plants and they can cause, together with other organic
compounds, such as proteins, excessive and trouble some foam in the
rivers. The biological degradation of the surfactants varies greatly.
Biologically soft surfactants, like straight chain alkyl sulfates and
sulfonated amides or esters, are removed in warm weather by ordinary
biological treatment within 20-30 hours, while the half – life of
biologically hard surfactants such as branched alkyl benzene sulfonate
and various ethylene oxide adducts is 7-16 days. Several testing methods
are used for evaluating the biodegradability of the surfactants.
The biochemical oxygen demand (BOD) method is employed in the
laboratory tests. The BOD method is based on the assumption that the
amount of oxygen consumed under the influence of bacteria is
proportional to the amount of organic oxidizable substance present .The
result is expressed as ppm. of oxygen consumed [89]. The test is often
carried out in a Warburg respirmeter. In the river- die away tests, the
amount of surfactant present in river water is determined at certain time,
time, intervals. Measurements of surface tension or of foaming properties
can be sued if no other analytical methods are available [90]. It must be
remembered that, no indication of the extent of degradation can be
obtained for the compounds that have lost their surface active and
foaming properties.
Other testing procedures are the shake flask test using microbial
cultures and the anaerobic die- away test. Furthermore continuously
operating pilot plants, which simulate the activated sludge process and
……………………………………………………………………………………… REVIEW OF LITERATURE
23
trickling filter processes are used [91]. The surfactant biodegradation is
an oxidation process. There are three-biochemical mechanisms
encountered [92], as follows:
a- β- Oxidation b- Methyl oxidation. c- Aromatic oxidation.
a-β-oxidation
This mechanism causes the degradation of the fatty acids.The carboxyl
group of fatty acid is first esterified with coenzyme A (complex organic
mercaptans compound). Dehydrogenation gives the α,β-unsaturated fatty
acid coenzyme A ester, which is converted to the β-keto derivative by
hydration and dehydrogenation. Another coenzyme A reaction then takes
place between the α- and β- carbon atoms of the fatty acid. Finally,
acetyl-coenzyme A splits off, leaving a fatty acyl-Coenzyme A ester
shorter by two carbon atoms. Further fatty acid degradation then takes
place in similar steps.
b- Methyl oxidation.
This involves the oxidation of a terminal methyl group to carboxyl
group . This can then be followed by β - oxidation.
c- Aromatic oxidation.
This process breaks down the aromatic rings; benzene phenol,
salicylic acid or other derivatives are first oxidized to catechol. The
benzene ring is then splitted between the two hydroxyl groups, giving the
dicarboxylic acid, and this is converted by three successive
rearrangements into B-keto-adipic acid. The latter can then be
biodegraded by the β -oxidation mechanism.
Biodegradation of anionic surfactants by isolated bacteria from
activated sludge gave the result that growth of simple bacteria such as
Acinetobacter or Pseudomonas in household and industrial sewage can be
cost effective method anionic surfactants elimination [93].
MATERIALS
AND
METHODS
………………………………………………………..…………………………..MATERIALS AND METHODS
42
2.MATERIALS AND METHODS
2.1. MATERIALS
Sodium Carbonate Sigma
Calcium Chloride Laba Chemic
Sodium Sulfate Anhydrous Scharlau
Sodium bisulfate Aldrich
Sodium Hydroxide Aldrich
P-toluene Sulfonic acid Aldrich
Hydrochloric Acid Aldrich
Potassium Hydroxide Laboratory Rasayan
Sulfuric Acid (fuming) Sigma
Stearic Acid BDH
Palmitic Acid BDH
Oleic Acid BDH
1-Hexadecanol Aldrich
1-Octadecanol Aldrich
All the solvents that were used here are of annular analysis.
………………………………………………………..…………………………..MATERIALS AND METHODS
42
2.2. Oil Extraction :
The fresh seeds obtained from the farm , were cleaned , dried in a
vacuum oven at 60ºC and crushed . The oil sample was extracted by cold
extraction with n-hexane , dried over anhydrous sodium sulfate , the
solvent evaporated under reduced pressure afforded oil sample. The
extracted oil sample was subjected to chemical characteristics and fatty
acids composition .
2.2.1.Chemical characteristics of Al- Cedre Seed oil :
2.2.1.a.Acid value (A.V) :
It is defined as the number of milligrams of alcoholic potassium
hydroxide required to neutralize the free acids in one gram of oil . The
results of this determination are often expressed as free fatty acids
calculated as the oleic acid percent in a sample [94] .
Procedure :
About (2-10 gm) of the well mixed fat was accurately weighed in 250
ml conical flask and 100 ml of neutral (ether – ethanol )mixture (1:1 ,
v:v) were added and the solution allowed just to boil while constant
shaking . The solution was titrated while hot with N/10 alcoholic
potassium hydroxide, the acid value was calculated according to the
following equation :
N × 0.005611 × 1000
A.V =
W
………………………………………………………..…………………………..MATERIALS AND METHODS
42
Where :
N= Number of ml. ( 0.1) N alcoholic KOH) added.
W= weight sample in gm .
2.2.1.b.Saponification value (S.V) :
Saponification value may be defined as weight in milligram of
potassium hydroxide required to saponify one gram of oil .
Procedure :
A sample of (0.5 gm) of dry oil was accurately weighed into a 250 ml
round flask, (alkali resisting glass), and mixed with 20 ml of neutral ethyl
alcohol. The semi-normal alcoholic potash (exactly 25 ml) was run with
constant stirring and at a constant rate. The contents of the flask were
gently boiled with occasional shaking for half an hour under reflux
condenser. The soap solution was titrated while hot against semi-normal
HCl in the presence of phenolphthalein as indicator. A blank test was
carried out under the same conditions in order to standardize the
potassium hydroxide solution [94].
Calculation :
The saponification value (S.V)is given by the equation :
(C1–C2) × N ×56.1
S.V =
W
Where :
C1 and C2 : represent the quantity in ml of standard HCl solution
………………………………………………………..…………………………..MATERIALS AND METHODS
42
used in blank and tested sample, respectively.
N : Exact normality of HCl solution.
56.1 : Molecular weight of KOH.
W : Weight in grams of oil taken.
2.2.1.c.Unsaponifiable matter :
Unsaponifiable fraction is the part of the oil that cannot be changed to
a water-soluble product by the process of saponification. It was
determined according to the Am. Oil Chem. Soc. (AOCS) method [94].
2.2.1.d.Iodine value :
Iodine value is an average measure of total unsaturation of the oil. It is
defined as the weight of halogen absorbed by 100 grams of the fatty
material. The Iodine value was determined according to Kaufman
method [95].
Procedure :
The oil sample (ca. 0.2 gm) was accurately weighed into 500ml.
iodine determination flask, dissolved in 10ml chloroform and then exactly
25ml of 0.1N bromine solution were added. Bromine solution was
prepared by adding 5.2ml of bromine to 1000ml saturated solution of
sodium bromide in methanol. The stoppers of the flasks were moisture
with potassium iodide solution to prevent any bromine vapours from
escaping . The content, of the flask was kept in the dark for tow hour,
then 15-20 ml of 10% KI solution were added and sides of the flask and
the stopper was washed with distilled water (ca. 100 ml). The unreacted
equivalent iodine was titrated against standard 0.1N sodium thiosulfate
solution using starch as indicator. A blank determination was also carried
out under the same conditions without sample.
………………………………………………………..…………………………..MATERIALS AND METHODS
42
Calculation :
(b – a) × 1.269
I.V =
W
Where :
b = Volume of sodium thiosulfate required in blank.
a = Volume of sodium thiosulfate required in tested sample.
W = Weight of sample.
2.2.1.e.Hydroxyl value (H.V) :
The hydroxyl value is defined as the number of milligrams of
potassium hydroxide equivalent to the hydroxyl content of sample based
on weight of unacetylated sample [96].
Reagents :
1- Hydrochloric acid, 0.5 N accurately standardized.
2- Sodium sulfate, anhydrous.
3- Phenolphthalein indicator, 1% in 95% alcohol.
4- Alcoholic potassium hydroxide, 0.5 N.
5- Acetic anhydride 95 to 100% actual acetic anhydride.
Procedure :
1- Boil a mixture of 2 gm of sample and 2ml of acetic anhydride for 2
hours in 100ml round bottom flask under a reflux condenser.
………………………………………………………..…………………………..MATERIALS AND METHODS
42
2- Pour the mixture into a beaker containing50 ml of distilled water
and boil for about 15 minutes.
3- Discontinue boiling, cool slightly and remove the water, and add
another 50 ml of distilled water and boil again.
4- Extract the acetylated sample by petroleum ether and remove the
wash water, wash again with two 50 ml portions of warm (60 to
70ºC) distilled water.
5- Extracted acetylated matter, dried over anhydrous sodium sulfate.
6- Determine the saponification values of the acetylated and
unacetylated portions as recorded in Am. Oil Chem. Soc. (AOCS)
official methods.
Calculation :
S` – S
Hydroxyl value =
1.000 – 0.00075 S`
Where :
S = Saponification value before acetylation.
S`= Saponification value after acetylation.
2.3.Analysis :
2.3.1.Gas liquid chromatography :
This was done using Varian 3700 dual flame ionization detector under
the following conditions :
Column packages 10% diethylene glycol adipate on chromosorb W.
………………………………………………………..…………………………..MATERIALS AND METHODS
03
(60 -30 mesh),and operated at 190 ºC.
Injection temperature 210 ºC .
Detector temperature 220 ºC .
Chart speed was adjusted at 5 mm/min.
Carries gas (N2) flow rate 35 ml/min.
the prepared surfactants was carried out in microanalysis center.
2.3.2.I.R – spectra :
IR spectra were carried out using a. SHIMADZU IR-470, double
beam spectrophotometer in the micro-analytical center in Chemistry
Department ,Faculty of Science, King Abdul-aziz University.
2.3.3.1H- NMR – spectra :
1H-NMR spectra were measured on a BRUKER 600 MHz.
Spectrophotometer in Deut. chloroform (CDCl3) and/or DMSO and TMS
as internal standard.
2.4. Methods:
a)Fatty acids composition of Al-Cedre oil :
The fatty acids were determined as methyl esters using G.L.C. [97].
b)Separation of Saturated fatty acids from unsaturated fatty acids :
The separation of Saturated fatty acids from unsaturated fatty acids
using lead acetate- method [98,99] .
c) Propenoxylation :
This was done followed the procedure was described by El-Sawy
et.al.[8]. The mixed fatty acids, propylene oxide and KOH were charged
to the propenoxylated apparatus to afford oxypropylated fatty acids
………………………………………………………..…………………………..MATERIALS AND METHODS
03
VΙΙΙ a-d of Al-Cedre seeds oil , with relative ratio of propylene oxide n =
1,3,5 and 7 respectively.
d)Sulfation of propenoxylation fatty acids:
The sulfation of oxypropylated fatty acids was made by added fuming
sulfuric acid gradually and neutralized with NaOH to pH=7 [8].
e)Fatty alcohols :
Fatty alcohols of Al-Cedre seeds oil, were prepared by reduction of
the corresponding mixed methyl esters using Lithium aluminum hydride
(LAH)[27]. Pure fatty alcohols were obtained from the above prepared
products by saponification to remove the unreacted fatty ester, followed
by extraction with diethyl ether.
f)Alkyl acrylate esters :
Hexadecanol, octadecanol, octadeca9-enol, octadeca9,12-dienol and/
or fatty alcohols obtained from Al-Cedre seeds oil were esterified with
acrylic acid in presence of P-toluene sulfonic acid as catalyst and dry
benzene as solvent using Dean-stark adapter [100].
g)Sulfo-fatty esters :
Sulfo-derivatives of alkylacrylate are formed by the reaction of the
above esters with NaHSO3 in saturated solution of Na2SO4 inless
amount of water and the reaction may be carried out in a methanol /water
mixture. The reaction time 8-10 hrs.[78], to afford anionic surface active
agents as shown in scheme 2.
2.5.Surface properties :
Surface and interfacial tension [101], foam height [102], wetting
[103], were measured by standard methods.
………………………………………………………..…………………………..MATERIALS AND METHODS
04
Emulsion stability :
The tested samples were prepared from liquid toluene (6 ml) and 20 m
mole solution (10.0 ml) . The sample was shaken 15 times (5sec. each) at
40 ºC. The time in seconds for 9.0 ml of the aqueous phase to separate
was recorded [104].
Stability to hydrolysis :
A mixture of 10 ml(10mmole) surfactant and 10 ml of 2 N sulfuric
acid was placed in a thermostat at 40ºC. The time it takes for a sample
solution to the clouded as the result of hydrolysis shows the stability of
the surfactant to hydrolysis [105].
Kraft point :
The temperature at which 1% solution becomes clear on gradual heating
is a convenient measure of aqueous solubility [106].
Ca+2
Stability :
Ca+2
stability of compounds was determined by a modified Hart
method [107] the surfactant (10-mmole) solution was titrated against
calcium chloride (0.1 N) solution. The end point was determined by
visual observed of cloudiness of the surfactant solution.
Critical micelle concentration (CMC) :
The CMC values of aqueous solutions of the synthesized surfactant were
determined by the surface tension method[108].
Hydrophilic / Lipophilic Balance :
HLB was measured according to the Griffin method [109]:
Mh
HLB = 20 ×
M
………………………………………………………..…………………………..MATERIALS AND METHODS
00
Where :
Mh : Molecular weight of hydrophilic groups .
M : Molecular weight of all molecule .
2.6.Biodegradabilition :
Samples taken daily, or even more frequently, were filtered through
Whitman filter paper number I, measuring the surface tension
measurements were made periodically (each day ) on each sample during
the degradation test.
Biodegradation % D, was calculated from the following equation[110]:
D = γt - γº / γbt - γº × 100
Where :
γt = Surface tension at time t.
γº = Surface tension at time zero.
γbt = Surface tension at of the blank exp. At time t (without sample).
RESULTS
AND
DISCUSSION
……………………………………………………………………………….……RESULTS AND DISCUSSION
34
3.RESULTS AND DISCUSSION
Al-Cedre oil sample obtained by solvent extraction using n-hexane
was investigated to determine the chemical characteristics and fatty acid
compositions .
3.1.Chemical Characteristics:
It is shown that, acid value (A.V.) of the solvent extracted oil is
0.338 on other hand, saponification value (S.V.), unsaturated characters
as represented by Iodine value (I.V.) and unsaponifable matter (Unsap.)
are 199.0, 74.03 and 2.03 respectively (cf. Table 1).
3.2.Fatty acids composition of Al-Cedre Oil:
The fatty acids mixture obtained according to kush et. al. [97],
analyzed by G.L.C as shown in (Table 1 and Fig. 1). The result indicated
that, Al-Cedre fatty acids are nearly 78% saturated , on the other hand,
the unsaturated are nearly 22% (cf. Table 1 and Fig.1).
3.3.Separation of saturated from unsaturated fatty acid.
The mixed saturated fatty acids was separated from the unsaturated
fatty acids using lead-salt ethereal method [98,99].
……………………………………………………………………………….……RESULTS AND DISCUSSION
35
3.4.Preparation of anionic surfactants from fatty acids:
The availability of propylene oxide at a relatively low price, coupled
with its ease of reaction to from polypropylene glycols opens the way to
an almost unlimited number of relatively base materials for the synthesis
of nonionic surface active agents. Nonionic surfactants, being efficient
wetting agents low foam and effective emulsifiers are applied in a broad
area of domestic and industrial applications. The sulfation of nonionic
surfactants may have considerable effect on the properties of course
because changes the oxyalkylated compounds from nonionic to anionic
surface active agents, and the product is an ester like alcohol sulfate, it
may have both anionic and nonionic characteristics. Anionic surface active
agents of oxypropylated fatty acids were prepared by addition of
propylene oxide (molar ratio 1,3,5 and 7 respectively) to a mixed fatty
acids of Al-Cedre oil (Ιa), mixed saturated (Ιb), mixed unsaturated
(Ιc), Hexadecanoic C16:0, Octadecanoic C18:0, Octadec9-enoic C18:1 and/or
Octadec9,12-dienoic acid C18:2 (Ιd- g ) respectively in the presence of OH
as catalyst at 170 C according to El-Sawy et.al. [8]. The oxypropylated
derivatives (ΙΙ – V)a-g were subjected to sulfation using fuming sulfuric
acid in carbon tetrachloride as solvent. Finally, the products were
neutralized with sodium hydroxide solution (0.5N), to afford sodium salt
of oxypropylated fatty esters as the improved anionic surface active agents
……………………………………………………………………………….……RESULTS AND DISCUSSION
36
(VΙ-ΙΧ)a-g (cf. Scheme1). The structure of the prepared compounds were
confirmed by spectral data. The IR spectra of oxypropylated fatty acids
showed characteristic bands of the ether linkage of poly propenoxy chain υ
(C-O-C) at 1100 – 1120 Cm-1
and at 1735 Cm-1
characteristics for υ C=0
of ester, for example compound (ΙVb) gave the following characteristics
peaks at 3382.4 Cm -1
for (O-H in P.O), 2923.4, 2856.39 cm-1
for (C-H
aliphatic in fatty chain ),1733.92 cm-1
(C= O of ester); broad peak at 1250-
1098 cm-1
for (C-o ) respectively (cf. Fig. 4) and compound (VΙa)
recorded the following bands at 2924.8 cm-1
(C-H aliphatic in fatty chain
),1735.38 cm-1
(C= O of ester); broad peak at 1250-1098 cm-1
(C-o )
respectively,933.79-776.20 (SO2-S-O) (cf, Fig. 6).
1H-NMR spectra showed that, the characteristic protons of propenoxy
group at δ=3.29 – 3.98ppm. For example compound (ΙΙΙa), recorded the
following characteristic peak, =0.8-0.9ppm (t,3H, terminal CH3 ); =1.1-
1.4ppm (m,8H, CH3-(CH2)4 -CH=CH ), =1.9-2.5ppm (m, 14H, CH=CH-
(CH2)7-C-OO) , =3.2-4.2ppm (m,9H , CH-CH2-O in P.O ), =4.9-
5.2ppm(t,2H, (CH2)4-CH=CH ), =5.2-5.4ppm(t,2H, CH=CH-(CH2)7
-C-O) (cf. Fig. 2).
On the other hand, compound (ΙΧf) gave =0.8-0.9 ppm
(t,3H,terminal, CH3), =1.0-1.4ppm (m, 14H, CH3(CH2)7- ), =2.4-
……………………………………………………………………………….……RESULTS AND DISCUSSION
37
2.5ppm (t,2H,CH2-COO-), =3.2-4.1ppm (m,21H, CH-CH2-O in P.O),
=4.4-4.7ppm (t,2H, CH=CH) with discharge hydroxyl proton in
oxypropylated fatty acids sulfate (cf. Fig. 12). The same characteristics
signals are recorded for compounds IIb and IVc respectively (cf. Fig. 3 and
5).
……………………………………………………………………………….……RESULTS AND DISCUSSION
38
Al-Cedre Oil
Alc. NaOH
Free Fatty Acids
Ia
Mixed saturatedfatty acids
Mixed unsaturated
fatty acids Ic
P. O / KOH170 C
RC
O
O
OH
n
Ib
C16:0; C18:0C18:1 and C18:2
Id-g
(II-V) a-g
( n= 1,3,5 and 7 propylene oxidemole respectively).
RC
O
O
OSO3 Na
n
Fuming H2SO4NaOH
(VI-IX) a-g
VI- IX( n- 1,3,5 and 7 propylene oxide
mole respectively).
Scheme (1)
Urea-Lead acetate method
……………………………………………………………………………….……RESULTS AND DISCUSSION
39
3.5.Surface active properties:
3.5.1. Surface and interfacial tensions: of the prepared sulfated
oxypropylated fatty acid (VΙ-ΙΧ) a-g are given in (Table 2-4) respectively.
The values of surface and interfacial tensions decrease as the number of
propylene oxide unite increases in the molecule from 1,3,5 and 7
respectively[8].
3.5.2. Kraft point: (Tables 2-4) , showed that propenoxylated saturated
fatty acids (VΙ-ΙΧ)b-d and e have higher values than the corresponding
unsaturated fatty acid (VΙ-ΙΧ)c-f and g with the same number of carbon
atoms .The last compounds can be used at lower TKp [42].
3.5.3. Emulsification stability: Studies are still being carried out on the
utilization of surfactants in emulsion formation , which is of immense
importance to technological development. It was proved that, the
emulsifying stability of propenoxylated fatty acids sulfate (VΙ-ΙΧ) a-g
(Tables 2-4) decrease by increasing numbers of carbon atoms in alkyl
chain length and increase with increasing number of propylene oxide
units through the surfactant moiety, also the polarity in the molecule
increase when the number of double bonds and emulsifying stability
increase with its ability to improve the surface activity [116].
……………………………………………………………………………….……RESULTS AND DISCUSSION
41
3.5.4. Wetting properties: The ease of which a surface can be wetted by
water as other liquids is an important property for many applications. The
wetting time values for propenoxylated fatty acids sulfate (VΙ-ΙΧ) a-g
(Tables 2-4), increase by increasing number of carbon atoms and
decreasing the number of propylene oxide . On the other hand, the
wetting values for saturated fatty acids (VΙ-ΙΧ)b-d and e are higher than
unsaturated fatty acids (VΙ-ΙΧ)c-f and g [116].
3.5.5. Foam height: It was reported that, the efficiency of surfactant as
a foamer increases with increasing number of carbon atoms in alkyl
chain length [117]. In general , the foam height increases by increasing of
propylene oxide unit in surfactant molecule [116] .
3.5.6. Stability towards acids: All prepared surfactants were high stable
in acidic media. From the values recorded in |(Tables 2-4); the stability
increase with increasing the number of propylene oxide cooperated with
number of carbon atoms in alkyl chain [118].
3.5.7. Ca+2
stability: From the data showed in (Tables2-4) , it was found
that , the Ca+2
stability increase by increasing the number of propylene
oxide unit and the number of carbon atoms in alkyl chain in the
surfactant molecule [8] .
……………………………………………………………………………….……RESULTS AND DISCUSSION
41
3.5.8 Critical micelle concentration: The (CMC); of the synthesized
surfactants were determined by the surface tension method [108]. The
values recorded for (CMC) in (Table 5) for compounds (VΙd, VΙe, ΙΧf),
decrease with increasing the number of carbon atoms in alkyl chain [118].
3.5.9. Hydrophile – lipophile Balance :
The (HLB), was determined according to Griffin equation [109]
Mh
HLB = 20 ×
M
Hydrophilic – lipophilic balance of the synthesized surfactants
showed values ranging from (9.23-14.50) , however , it is a disable to use
them as emulsifiers perhaps or as anionic detergent , the values increased
by increasing number of propylene oxide unit in their molecules and
number of carbon atoms in their alkyl chain (Tables 3-4) [108] .
3.6. Sulfonated surface active agents from fatty alcohols:
3.6.1.Preparation of mixed fatty alcohols: Mixed fatty alcohols, mixed
saturated fatty alcohols and mixed unsaturated fatty alcohols has been
prepared in about 75 – 79 % yield by reduction of methyl esters of the
corresponding acid using (LiAlH4) as described by Micovic V. M.
et.al.[113].
……………………………………………………………………………….……RESULTS AND DISCUSSION
42
3.6.2. Preparation of alkyl acrylate: Alkyl (hexadecyl, octadecyl,
octadeca9-enyl, octadeca9, 12-dienyl and / or alkyl of mixed fatty
alcohol of (Al-Cedre oil) acrylates (ΧΙ)a-g were prepared by direct
esterification of acrylic acid with the above alcohols [102]. The obtained
esters were confirmed by IR and 1
HNMR spectra. The IR spectrum of
octadecyl acrylate (ΧΙ)e(C18:0) revealed that, characteristics bands at
2960, 2870, 1735, 1620, 1460, 1060cm-1
respectively (cf.Fig.13). On the
other hand, 1
HNMR for compound (ΧΙ)e (C18:0); gave the following
characteristics signals at δ = 0.9ppm (t,3H ,terminalCH3), δ = 1.0-
1.6ppm (m,(CH2)16 chain); δ =4.1ppm(t,2H; CH2 -O-CO ), and olefin
protons at δ = 5.8ppm (d,1H, Ha HbC=CHc-COO-), δ = 6.1ppm (t,1H,
HaHbC=CHc-COO-) and δ = 6.4ppm (d, 1H, HaHbC=CHc-COO-)
(cf.Fig.14).
3.6.3. Preparation of Sulfo-fatty esters: Sulfonated derivatives from the
above fatty esters were prepared by the reaction with NaHSO3 in
methanol as solvent and in presence of Na2SO4 as catalyst [78], to afford
(ΧΙΙ)a-g respectively as anionic surface active agents according to
(Scheme 2). The structure of sulfated esters was characterized by their
physical properties (cf. Table 7) and spectra data. 1HNMR spectrum of
compound (ΧΙΙ)d (C16:0); showed , δ =0,75ppm (t,3H, terminal CH3); δ
=1.1- 1.8ppm(m,36H, CH2 chain ); δ=3.2ppm (d, 3H,
……………………………………………………………………………….……RESULTS AND DISCUSSION
43
CH3- (SO3-Na
+)CHCOOCH2-); δ =3.4ppm (t, 1H, CH3-CH
SO3-Na
+COOCH2); and reversed adduct at δ = 3.5, 3.8ppm respectively
;(cf.Fig15). IR spectrum of compound (ΧΙΙ)d (C16:0) showed stretching
bands at 1730 Cm-1 for υC=O of ester , 1180, 1090, 640 cm
-1υSO2, υS-O in
SO3-Na
+ group (cf. Fig 16) .
……………………………………………………………………………….……RESULTS AND DISCUSSION
44
Al-Cedre Oil
Alc. NaOH
Free Fatty Acids
MeOH / H / dry Toluene4 hrs.
Mixed fatty methyl ester of Al-Cedre oil;Mixed fatty
saturated ; Mixed fatty unsaturated; C16:0;C18:0;
C18:1 and C18:2 respectively.
RCOOMe
Fatty Alcohols
R-OH
( X )a-g
CH2=CHCOOH
P-Tol. Sulfonic acid
Dry Tolu .
CH2=CHCOOR
( XI )a-g
SO3-Na+
CHCOORH2C
H
( XII )a-g
Scheme (2)
LAH
NaHSO3/Ethanol
……………………………………………………………………………….……RESULTS AND DISCUSSION
45
3.6.4.The surface active properties: given in (Table 9), show that, the
products obtained have a pronounced surface activity. The results of
emulsification, wetting time, calcium stability, stability to hydrolysis and
foaming properties for sulfonated alkyl acrylate (ΧΙΙ)a-g reflect the
following facts :
1- These types of surfactants were very effective wetting agent in
distilled water solution.
2- All the prepared sulfo-esters are stable to hydrolysis in acid media
, which might indicate that the sulfate group protects the ester
linkage through steric hindrance.
Most of the prepared sulfo-esters have good or excellent
calcium stability and their stability increase with increasing the
number of carbon atoms in alkyl chain of fatty alcohols , also, fatty
acids of Al-Cedre seed oil , have excellent Ca+2
stability, and can
be used in several industrial applications[83].
Biodegradation: The results cited in (Tables 10-11) and (Fig. 17),
revealed the fact that, the biodegradability increase by increasing the
number of double ponds in unsaturated fatty acids and the rate of
biodegrade decrease when the number of carbon atoms increase[83].
TABLES
............................................................................................................................................ ............................................................................................................................. .............................TABLES
46
Table 1 : Fatty acids composition and chemical characteristics of Al-Cedre oil .
F.A composition
peak area %
Chemical characteristics
Saturated Fatty acids:
Palmetic (C16 :0) 14.030
Stearic (C18 :0) 63.578
Unsaturated Fatty acids:
Palmitoleic (C16 :1) 00.877
Oleic (C18 :1) 15.381
( ῳ -9)
Linoleic (C18 :2) 04.380
( ῳ -6)
Linolenic (C18 :3) 01.754
(ῳ-3)
- A.V 00.338
- I.V 74.03
- S.V 199.00
- Unsap. 002.03
- H.V 000.06
............................................................................................................................................ ............................................................................................................................. .............................TABLES
47
Table 2: Surface properties of sulfated oxypropylated fatty acids of Al-Cedre oil .
Compd. no
No.
P.O
S.T
0.1%
(dyne/cm)
I.F.T
0.1%
(dyne/cm)
Kraft p.
1% 0C
Emu. stab.
10 mmole
(sec.)
Wetting t
1%
sec.))
Foam h.
1%
(mm)
Stab. to
hyd. acid
min :
Sec.))
Stab. to
Ca++
(ppm)
VΙa
VΙΙa
VΙΙΙa
ΙΧa
1
3
5
7
40.0
38.0
37.5
37.0
17.0
16.0
15.5
14.5
5
3
0
0
250
260
360
375
132
124
97
89
320
340
370
500
42 : 43
47 : 26
51 : 04
60 : 11
1550
1650
1800
1900
VΙb
VΙΙb
VΙΙΙb
ΙΧb
1
3
5
7
41.0
39.5
40.5
38.0
18.0
17.5
17.0
16.5
18
14
11
4
240
255
270
315
145
134
128
113
305
310
360
400
48 : 00
52 : 33
58 : 27
64 : 42
1600
1650
1750
1800
VΙc
VΙΙc
VΙΙΙc
ΙΧc
1
3
5
7
39.5
37.0
36.5
36.0
16.5
15.0
14.0 13.5
4
3
0
0
180
225
240
270
122
114
95
86
500
600
650
700
50 : 21
56 : 42
64 : 24
72 : 32
1600
1750
2000
2100
............................................................................................................................................ ............................................................................................................................. .............................TABLES
48
Table 3 : Surface properties of sulfated oxypropylated saturated fatty acids .
Compd. no
No.
P.O
S.T
0.1%
(dyne/cm)
I.F.T
0.1%
(dyne/cm)
Kraft p.
1% 0C
Emu. stab.
10 mmole
(sec.)
Wetting t
1%
sec.))
Foam h.
1%
(mm)
Stab. to
hyd. acid
min : Sec.))
Stab. to
Ca++
(ppm)
HLB
VΙd
VΙΙd
VΙΙΙd
ΙΧd
1 3 5 7
41.5 40.5
39.5
38.5
17.5
17.0
16.0
15.5
3 0C
50C
0 0C
0 0C
310 330
345
360
125 119 109 103
320
340
450
490
52 : 32
54 : 11
59 : 38
64 : 00
1350
1450
1550
1600
09.90 12.10 13.50 14.50
VΙe
VΙΙe
VΙΙΙe
ΙΧe
1 3 5 7
43.0
42.5
41.0
40.0
18.5
17.0
16.5
15.5
9
7 5
0
190
220
270
290
142
134
130
122
330
390
440
520
55 : 48
59 : 22
63 : 25
69 : 32
1500
1600
1650 1700
09.23 11.46 12.93 14.00
............................................................................................................................................ ............................................................................................................................. .............................TABLES
49
Table 4: Surface properties of sulfated oxypropylated unsaturated fatty acids .
Compd. no
No.
P.O
S.T
0.1%
(dyne/cm)
I.F.T
0.1%
(dyne/cm)
Kraft p.
1% 0C
Emu. stab.
10 mmole
(sec.)
Wetting t.
1%
sec.))
Foam h.
1%
(mm)
Stab. to hyd.
acid
min : Sec.))
Stab. to
Ca++
(ppm)
HLB
VΙf
VΙΙf
VΙΙΙf
ΙΧf
1
3
5
7
40.0
39.5
38.0
37.5
17.0
16.5
15.5
15.0
0
0
0
0
191
215
320
330
139 132
124
118
520
690
860
910
58 : 32
66 : 02
69 : 38
73 : 00
1650
1700
1900
2000
09.30
11.51
13.00
14.00
VΙg
VΙΙg
VΙΙΙg
ΙΧg
1
3
5
7
38.5
39.0
38.0
37.5
13.5
13.0
12.5
12.0
0
0
0
0
195
200
315
325
137
134
128
121
400
360
400
410
57 : 18
59 : 20
64 : 07
69 : 51
1700
1850
2050
2150
09.32
11.55
13.01
14.04
............................................................................................................................................ ............................................................................................................................. .............................TABLES
51
Table 5 : CMC for some prepared oxypropylated fatty acids sulfated .
γcmc CMC Compound n.
39 1.5x10-2 VΙd
43 1.5x10-3 VΙe
38 1.5x10-3 ΙΧf
............................................................................................................................................ ............................................................................................................................. .............................TABLES
51
Table 6: Reduction characteristics of fatty alcohols .
Compd. n S.V H.V I.V
* Red. Yield% Ester Red. Prod. Ester Red. Prod. Ester Red. Prod.
Χa 199.0 45.30 ---- 194.50 74.03 71.40 77.24 Χb
195.5 39.50 ---- 187.00 01.02 00.81 79.79 Χc 197.0 41.50 ---- 189.00 108.6 93.40 78.93 Χd 189.0 46.50 ---- 196.00 01.01 00.67 75.39 Χe 198.5 43.20 ---- 197.00 01.03 00.92 78.35 Χf 196.5 46.00 ---- 191.02 91.70 88.20 76.44
*(s.vester - s.vred.prod. / s.vester) x 100
............................................................................................................................................ ............................................................................................................................. .............................TABLES
52
Table 7: Physical characterization of sulfonated acrylated esters .
Compd. No Mol. Formula M. wt colour Solvent of
crystallization
Yield %
ΧΙΙa
- * Semi-solid
waxy
Isopropanol 74
ΧΙΙb
- * White Ethanol 88
ΧΙΙc
- * Pale yellow Isopropanol 75
ΧΙΙd
C19 H37 SO5Na 400.55 White Ethanol 89
ΧΙΙe
C21 H41SO5Na 428.60 Pale Yellow Ethanol 82
ΧΙΙf
C21 H40S2O8Na2 530.65 Pale Yellow Isopropanol 84
ΧΙΙg
C21 H38S2O8Na2 528.63 Pale Yellow Isopropanol 79
*Mixed Mol. Wt. of fatty alcohol.
............................................................................................................................................ ............................................................................................................................. .............................TABLES
53
Table 8: Spectral data for fatty alkyl Acrylate esters and sulfonated fatty alkyl Acrylate esters .
Compd No. 1HNMR ( = ppm) IR (/ cm-1)
ΧΙe 2CH; chain); δ =4.1(t,2H16 )2(CH1.6 (m,-), δ = 1.03CHδ = 0.9ppm (t,3H ,terminal
), δ = 6.1 (t,1H, -COO-cC=CHbH aHCO ), and olefin protons at δ = 5.8(d,1H, -O-
) -COO-cC=CHbHa) and δ = 6.4 (d, 1H, , H-COO-cHCC=bHaH
3460 cm-1
(O-H ); 3223 cm-1
(C-Holefinic proton); 2980,
2930 cm-1
(C-H aliphatic),1740 cm-1
(C= O of ester);
1650 cm-1
(C=C )and1450, 1260, 1150 cm-1
(C-o )respectively.
ΧΙΙd chain ); δ = 3.2ppm (d, 2CH1.8(m,36H, -); δ =1.13CHδ =0,75ppm (t,3H, terminal
); 2COOCH+
Na-
3SO CH-3); δ =3.4ppm (t, 1H, CH-2)CHCOOCH+
Na-
3(SO-3CH3H,
and reversed adduct at δ = 3.5, 3.8ppm respectively
1725 cm-1 for υC=O of ester , 1180, 1090, 640 cm
-1υSO2, υS-O
in -SO3-Na
+ group
............................................................................................................................................ ............................................................................................................................. .............................TABLES
54
Table 9 : Surface properties of sulfonated product of fatty alkyl acrylate .
Compd. No
S.T
0.1%
(dyne/cm)
I.F.T
0.1%
(dyne/cm)
Kraft p.
1% 0C
Emu. stab.
10 mmole
(sec.)
Wetting t.
1%
sec.))
Foam h.
1%
(mm)
Stab. to hyd.
acid
min : Sec.))
Stab. to hyd.
Base
min : Sec.))
Stab. to
Ca++
(ppm)
ΧΙΙa
42.0 14.0 10.0 440 131.0 400 73 : 31 169 : 41 1850
ΧΙΙb
40.5 14.5 9.0 420 128.0 415 69 : 14 166 : 30 1900
ΧΙΙc
39.5 13.5 8.0 415 130.0 390 71 : 15 167 : 34 2000
ΧΙΙd
38.5 09.0 2.0 350 90.0 350 58 : 20 132 : 14 2400
ΧΙΙe
39.0 11.0 4.0 365 98.0 390 60 : 34 142 : 03 2200
ΧΙΙf
37.5 12.0 2.0 380 114.0 405 64 : 12 150 : 32 1850
ΧΙΙg
36.5 11.5 0 405 121.0 410 67 : 51 161 : 47 1750
............................................................................................................................................ ............................................................................................................................. .............................TABLES
55
Table 10: Biodegradability of sulfated oxypropylated fatty acids of Al-cedre oil.
Compd. No
No.
P.O 1 st. day day nd.2 3
th. Day 4
th. day 5
th. Day 6
th. day 7
th. day
VΙa
VΙΙa
VΙΙΙa
ΙΧa
1 3 5 7
37.0 35.0
33.0
31.0
43.0 40.0 39.0 37.0
56.0 54.0 51.0 49.0
68.0 67.0 66.5 63.0
76.0 75.0 73.5 72.5
88.0 87.0 86.5 84.5
95.0 94.0 92.0 91.0
VΙb
VΙΙb
VΙΙΙb
ΙΧb
1 3 5 7
35.0 34.0
33.5 31.0
42.5 40.0 38.5 37.0
57.5 54.0 51.0 48.5
74.0 73..0 73.0 72.0
78.0 77.5 76.5 75.5
88.0 86.5 86.0 85.5
94.5 93.0 91.0 90.0
VΙc
VΙΙc
VΙΙΙc
ΙΧc
1
3
5
7
38.5 38.0 37.5 37.0
43.5 42.5 42.0 41.0
56.5
56.0 54.5 54.0
77.0 74.5 73.5 71.5
80.0 78.0 77.0 76.5
89.0 88.0 87.0 86.0
-
96.0
92.5
91.0
............................................................................................................................................ ............................................................................................................................. .............................TABLES
56
Table 11: Biodegradability of sulfated oxypropylated of pure Individual fatty acids
Compd. No
No.
P.O 1 st. day day nd.2 3
th. Day 4
th. day 5
th. Day 6
th. day 7
th. day
VΙd
VΙΙd
VΙΙΙd
ΙΧd
1 3 5 7
39.5 37.5
37.0
36.0
56.5 55.0 54.5 54.0
68.5 67.5 66.0 65.5
79.5 78.0 77.0 74.5
89.5 88.0 86.5 85.5
95.0 94.0 92.5 91.5
- 98.0 96.5 94.0
VΙe
VΙΙe
VΙΙΙe
ΙΧe
1 3 5 7
38.0 37.0 36.5 35.5
53.0 52.0 51.5 50.0
67.5 67.0 65.5 64.5
79.0 78.0 76.5 74.0
88.5 88.0 86.0 85.0
94.0 93.0 92.0 91.0
- 97.0 95.0 93.0
VΙf
VΙΙf
VΙΙΙf
ΙΧf
1
3
5
7
43.5 42.5 41.5 41.0
55.0 54.5 54.0 53.0
69.0 67.5 66.5 66.0
78.5 76.5 75.5 75.0
89.0 88.0 87.5 87.0
95.5 94.0 93.0 92.0
-
97.5
93.0
91.0
VΙg
VΙΙg
VΙΙΙg
ΙΧg
1
3
5
7
46.5 44.5 43.0 41.5
57.5 56.5 56.0 55.0
70.0 68.5 67.5 65.5
79.5 79.0 78.5 77.5
88.5 88.0 85.5 85.0
94.5 93.5 91.5 89.0
-
-
97.0
93.5
FIGURES
............................................................................................................................. .......................................................................................................................................................................FIGURES
57
Fig. (1) : GLC of Al-Cedre oil .
............................................................................................................................. .......................................................................................................................................................................FIGURES
58
Fig. (2): 1HNMR spectra of compound [ΙΙΙa]
............................................................................................................................. .......................................................................................................................................................................FIGURES
59
Fig.(3): 1HNMR spectra of compound [ΙΙb]
............................................................................................................................. .......................................................................................................................................................................FIGURES
61
Fig.(4): IR spectra of compound [ ΙVb]
............................................................................................................................. .......................................................................................................................................................................FIGURES
61
Fig.(5): 1HNMR spectra of compound [ΙVc]
............................................................................................................................. .......................................................................................................................................................................FIGURES
62
Fig.(6): IR spectra of compound [VΙa]
............................................................................................................................. .......................................................................................................................................................................FIGURES
63
Fig.(7): 1HNMR spectra of compound [VΙΙa]
............................................................................................................................. .......................................................................................................................................................................FIGURES
64
Fig.(8): 1HNMR spectra of compound [VΙΙb]
............................................................................................................................. .......................................................................................................................................................................FIGURES
65
Fig.(9): 1HNMR spectra of compound [VΙΙc]
............................................................................................................................. .......................................................................................................................................................................FIGURES
66
Fig.(10): IR spectra of compound [VΙΙΙc]
............................................................................................................................. .......................................................................................................................................................................FIGURES
67
Fig.(11): IR spectra of compound [VΙe]
............................................................................................................................. .......................................................................................................................................................................FIGURES
68
............................................................................................................................. .......................................................................................................................................................................FIGURES
69
Fig.(12): 1HNMR spectra of compound [ΙΧf]
............................................................................................................................. .......................................................................................................................................................................FIGURES
71
Fig.(13): IR spectra of compound [ΧΙe]
Fig.(14): 1HNMR spectra of compound [ΧΙe]
............................................................................................................................. .......................................................................................................................................................................FIGURES
71
Fig.(15): 1HNMR spectra of compound [ΧΙΙd]
............................................................................................................................. .......................................................................................................................................................................FIGURES
72
Fig.(16): IR spectra of compound [ΧΙΙd]
............................................................................................................................. .......................................................................................................................................................................FIGURES
73
Fig.(17) :Biodegradability of oxypropylated stearate sulfate.
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ARABIC
SUMMARY
....................................................................................................................................................................................................الملخص العربي
a
بسم هللا الرحمن الرحيم
بسمة أحمد محمد صالح ماحي :اسم الطالبة
:عنوان الرسالة
تحضير بعض المركبات ذات النشاط السطحي من المادة الدهنية المستخلصة"
"من مخلفات بعض البذور النباتية
المستخلصة دة الدهنيةتتضمن هذه الرسالة دراسة إمكانية استغالل الما: موضوع الرسالة
في , شجرة السدرمن بذور بعض األشجار المنتشرة في ربوع المملكة العربية السعودية وهي
تحضير بعض المركبات األنيونية ذات النشاط السطحي والتي لها استغالل المادة الدهنية ل
. ةالصناعي تاستخدامات تطبيقية متعددة في المجاال
:ة من خالل األجزاء التالية وقد تم تقديم هذه الرسال
:مقدمة تاريخية عن اآلتي
كاتيونية , أنيونية, ونية يغير أ)بأنواعها المختلفة المركبات ذات النشاط السطحيتعريف -
(مترددةال وكذلك
.الكحوالت الدهنيةو نيوكسي إثير من األحماض يمركبات غير أيونية وتشمل بولي إيثيل -
.كبات األمونيوم الرباعيةمركبات كاتيونية وتشمل مر -
الجلسريدات األحادية , المسلفنة مركبات أيونية وتشمل مركبات الزيوت -
, سلفونات األحماض الدهنية –ألفا , الكحوالت الدهنية المسلفنة , المسلفنة
.سلفانات األحماض ثنائية مجموعة الكربوكسيل, اإلسترات
يقات الصناعية لهذه المركبات غير وتنتهي المقدمة التاريخية بنبذة عن التطب
.أيونية و األيونية ودراسة التكسير الحيوي لها
....................................................................................................................................................................................................الملخص العربي
b
:الجزء العملي ويتناول األجزاء التالية -2
:الجزء األول -
تجهيز البذور وتنظيفها وتجفيفها وطحنها واستخالص الزيت منها ومن ثم اجراء -1
رقم الحموضة والرقم اليودي والرقم )الزيت مثل التحاليل الكيميائية الالزمة لدراسة خواص
(. الهيدروكسيلي ورقم التصبن واألجزاء الغير متصبنة
التعرف على تركيب األحماض الدهنية المكونة لزيت السدر عن طريق استخدام جهاز -2
(.غاز/ سائل )التحليل الكروماتوجرافي
و -باستخدام طريقة خالت الرصاصفصل األحماض الدهنية المشبعة عن الغير مشبعة -3
.اليوريا
.األحماض المشبعة والغير مشبعة إلى كحوالت دهنيةتحويل -4
:الجزء الثاني
من ويشمل هذا الجزء تحضير بعض المركبات ذات النشاط السطحي األنيونية المحسنة . األحماض الدهنية
, 3, 1)تد لألحماض الدهنية المضافة لها سلفنة أوكسي بروبيليمتحضير مركبات :أواًل
:كما يلي( ين يلمن أكسيد البروب مول 7و 5ومخلوط , ين إلى مخلوط األحماض الدهنية لزيت السدر يلإضافة أكسيد البروب -1
ومخلوط األحماض الدهنية الغير مشبعة وكذلك , األحماض الدهنية المشبعة
.ى حدةاألحماض الدهنية المكونة لزيت السدر كالً عل
المدخن الكبريتيكعملية السلفنة لنواتج اإلضافة باستخدام حامض إجراء -2
.ومعادلة المركبات الناتجة بمحلول هيدروكسيد الصوديوم
وقد تم التعرف على التركيب الكيميائي للمركبات الناتجة عن طريق جهاز -3
.الرنين النووي المغناطيسي واألشعة التحت حمراء
التوتر السطحي , التوتر السطحي)ة لهذه المركبات مثل تعيين الخواص السطحي -4
درجة الثبات , درجة االستحالب, زمن البلل, طول الرغوة, درجة العكارة, البيني
(. تجاه األحماض
....................................................................................................................................................................................................الملخص العربي
c
من الكحوالت مكبرتة تحضير مركبات ذات نشاط سطحي أنيونية :ثانيًا :الدهنية
, ة المكونة لزيت السدرتحضير الكحوالت الدهنية لألحماض الدهني -1
.هيدريد الليثيوم واأللومنيوموذلك باختزالها بواسطة
كبريتيت كبرتتها بإضافة تحضير أكريالت اإلستر للكحوالت الدهنية ثم -2
.الصوديوم الهيدروجينية
التعرف على التركيب الكيميائي للمركبات الناتجة باستخدام جهازي -3
. لمغناطيسياألشعة تحت الحمراء والرنين النووي ا
التوتر , التوتر السطحي)تعيين الخواص السطحية لهذه المركبات مثل -4
زمن , طول الرغوة, درجة العكارة, السطحي بين سائلين غير ممتزجين
(. درجة الثبات تجاه األحماض, درجة االستحالب, البلل
شاط السطحي السطحية للمركبات ذات النودراسة الخواص قد تم عرض النتائج ومناقشاتها
في العديد هاستخداما أظهرت إمكانية والتي , ( منحنى 17)و( جدوالً 11)المحضرة من خالل
وصناعة النسيج , صناعة األسمنت , صناعة الكيماويات الدوائية ) من المجاالت الصناعية
.والتي لها أهمية اقتصادية عالية( الخ..................
كما أنها صديقة للبيئة فهي ال , عالية في الماء العسر يةباتثات درجة وقد وجد أن لهذه المركب
وبشكل عام نأمل العثور على تطبيقات أخرى. تسبب التلوث ألن التحلل البيولوجي لها جيد
.المختلفة لهذه المركبات في النواحي الصناعية إضافية
الملخص العربي
شكر و اهداء
بسم اهلل الرمحن الرحيم هلل حمد الشاكرين الحمد هلل على نعمه وتوفيقه وامتنانه ف له الفضل والشكر أولا الحمد
. اا وباطن وظاهراا وأخراا
الذي . وجدي إبراهيم الدجدج /لمشرفي الف اضل األستاذ الدكتوروالشكر بعد الشكر هلل رشد م المعلم والملم يبخل علي بعلمه ووقته وجهده ورغم كثرة انشغالته إل أنه كان نع
. أخالقه فجزاه اهلل خير الجزاء في الدنيا واآلخرة وزاده من فضله و بعلمه والموجه كريماا
العلوم بكلية رئيسة قسم الكيمياءعميدة كلية العلوم التطبيقية و من والشكر موصول لكالا وأعضاء هيئة التدريس بقسم الكيمياء وفنيات المختبر ومنسوبي كلية العلوم التطبيقية
.طبيقية وجامعة أم القرى الت
وهذا البحث لم يكن ليرى النور لول فضل اهلل ثم مساندة أقرب الناس إلي ولذا أقدم / لي يهم دعواتي وأبدأهم بزوجي الغاهدأوتقديري وامتناني واعتذاري لهم و شكري
.فجزاه اهلل عني خيراا ومادياا اا الذي صبر علي وساندني معنوي. ياسر محمد العمري
ي العزيزين اللذان أكرماني بدعمهما وتشجيعهما ودعائهما داجب علي شكر والوو رب ) أنهما من أنجباني وربياني وعلماني لن أوفيهما حقهما ويكفيني فخراا ومهما ق لت
( . ارحمهما كما ربياني صغيراا
. لن أنسى بالطبع ابني وابنتي باسل ولنا العمري بارك اهلل لي فيهما ورزقني برهما و
إخوتي وأهلي وصديق اتي وكل من شاركني بمعلومة أو نصيحة أو خصني وأشكر أيضاا . بدعاء أو تفضل علي بجزء من وقته وعلمه فجزا اهلل الجميع خير الجزاء ورفع درجاتهم
: قال تعاىل وما توفيقي إال باهلل عليه ))
((توكلت وإليه أنيب(88)آية سورة هود
المملكة العربية السعودية
جامعة أم القرى بمكة
كلية العلوم التطبيقية
قسم الكيمياء
تحضير بعض المركبات ذات النشاط السطحي من المادة الدهنية "
"المستخلصة من مخلفات بعض البذور النباتية
رسالة مقدمة من الطالبة
لح ماحيبسمة أحمد محمد صا
( كيمياء بكالوريوس علوم)
كجزء من المتطلبات للحصول على درجة الماجستير في الكيمياء العضوية
رافـــــــــــشإ
وجدي إبراهيم أحمد علي الدجدج/ د . أ
أستاذ الكيمياء العضوية التطبيقية
جامعة أم القرى -مكة المكرمة الكلية الجامعية ب -قسم الكيمياء
م3144/هـ 4141