Synthesis of Some Surface Active Agent From Fatty …libback.uqu.edu.sa/hipres/FUTXT/16793.pdf · "Synthesis of Some Surface Active Agent From Fatty Matter ... Biodegradation

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.


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


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


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


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


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


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,


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 :


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


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.


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


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


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.,


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


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,


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+


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],


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.


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.


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].


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


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‾


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


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


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.


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


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


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.


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.


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.


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


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.


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


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].


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


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-


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).


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


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].


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] .


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].


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,


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) .


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


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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........................................................................................................... ................................................REFERENCES

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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

Documents

Synthesis of Some Surface Active Agent From Fatty …libback.uqu.edu.sa/hipres/FUTXT/16793.pdf · "Synthesis of Some Surface Active Agent From Fatty Matter ... Biodegradation