‫بسم الله الرحمن الرحيم‬

Islamic University – Gaza

Faculty of Science
Chemistry Department

Title of Research
Synthesis and application of
Diethylentriamine polysiloxane
Immobilized ligand

Prepared by :

Mohammad Hassan raidah & Ahmad

marwan alashi

Supervised by :
Dr. Nizam M. El Ashgar

Submitted in Partial Fulfilment

Of the Requirements for B.S Degree

July 2008
 ‫بسم الله الرحمن الرحيم‬
‫ل(‬ ‫قل هل يستوي الذين يعلمون والذين‬
‫)يعلمون‬
‫صدق الله العظيم‬

‫) سورة الزمر – آية ‪(9‬‬

‫‪2‬‬
We very pleased to thanks my God , who give us these
successful because he said in holy Qurane .
‫قل هل يستوي الذين يعلمون والذين ل يعلمون‬
Special thanks to us guides DR. Nizam M. El-Ashgar we very
greatful for his advices and information which helped us in this
research .
We thanks all who works in chemistry department to all help us
in doing this research , and teach us for four years

3
For my best guides … who have been
with me in every step in my scientist
way .
For us dears fathers , mothers , brothers
and sisters .

For all Palestinian Materies

ABSTRACT

4
 Porous solid polysiloxane ligand system have been prepared
using sol-gel process either before or after polymerization.
The ligand is triamine.
Polymer name is diethylenetriaminepolysiloxane
The polysiloxane-Immoblized ligand system show high potential for
extraction of some heavy metal ions including Copper, Nickel and
,Cobalt. uptake of metal ions increases in the order:
Cu2+ > Ni2+ > Co2+

Several conditions such as :time , pH ,Concentration ,buffer type ,

particle size and , shaking were used to reach the optimum metal
uptake capacity
We introduction onto polysiloxane net work the new functionlized
ligand system exhibit high capacities for uptake of metal ions
The ligand system also show high selectivity to separate a mixture of
metal ion.
These immobilized ligand systems were also, used and tested for
removal of toxic heavy metal ions from wastewater.

The optimum pH appeared to be pH=5.2 using acetate buffer as an

eluent, th preconcentration chemisorbed metal ions were regenerated
from the solid extraction using 0.5M HCl

5
 This research is concerned with the preparation of some functionalized
insoluble inorganic polymers and using them as metal-extraction agents from aqueous

6
solution.
Fundamentally, two types of polymeric matrices can be considered, organic
and inorganic matrices. Recently, attention has been turned to inorganic polymeric
compounds because of their thermal stability at high temperature, rigidity and general
chemical inertness. Many organic polymers suffer from defects such as variable degrees
of swelling in solvents and limited thermal stability(1).
The polysiloxane-immobilized ligands are important class of inorganic supports,
particularly silica-based matrices, with chemical composition and properties give them
an intermediate position between typical inorganic matrices (silica, silicates, quarts,
etc.) and organic polymers, since they contain both a silica-oxygen, framework and
organic radicals (functional groups) attached to silicon atoms(2).
The aim of the present work is to exploit the potential of the functionalized
chelating polysiloxane for analytical applications such as extraction and separation of
some toxic heavy metals such as Cu2+, Ni2+, Co2+. Cadmium is considered as a highly
toxic element, and tends lo be accumulated with even very low exposures because
its excretion is extremely slow. It also causes on low chronic exposure, hypertension
and kidney damage. Zinc and copper have relative toxicity. The choice of chelating
functional groups over others as extractants is due to the high stability constants
associated with them, thus making them suitable as extractants even for heavier metal
ions in dilute solutions(3). These materials find many applications in catalysis, water,
and wastewater treatment, hydrometallurgy, industrial processes, and miscellaneous
applications in analytical chemistry(4).

1. Polymeric Supports.

Polymeric matrices are classified into two categories,

1.1 Organic Polymeric Supports.

Insoluble organic polymers usually have a three dimensional, cross-linked

matrix of hydrocarbon chains resulting from the polymerization of a suitable mixture of
monomers, to form a cross-linked network in such away the functional ligand groups
can later be introduced. The degree of cross-linking determines the properties of

7
polymeric structure and its solubility.

Linear non-cross-linked polymers are soluble, while highly cross-linked

polymers limit the mobility of the functionalized organic side chains. Hence prop
adjustments of the degree of cross-linking must be carried out to obtain a suitable
support. The organic polymeric matrices are formed in two general ways.

a) Addition Polymers:

These polymers have cross-linked structures formed by free-radical

polymerization of mixtures of olefinic and diolefinic organic compounds(5). A
well-known example of this type is the polymerization of styrene with difunctional
divinylbenzene (DVB). By varying the amount of divinylbenzene in the reactants
mixture, the degree of cross-linking can be adjusted (Scheme 1.1)

CH=CH2 CH2CH2-CH-CH2-
CH=CH2

+
CH=CH2 -CH-CH2-CH-CH2-

Scheme 1.1

8
b) Poly condensation Polymers:

These are cross-linked structures with high molecular weight, usually formed
by ionic organic reactions from small poly functional monomers through the removal
of small molecules such as water, alcohol or ammonia. New C-C, C-N, C-O or other
bonds are formed(5). For example; p-substituted phenol may condense with
formaldehyde to yield linear condensation polymers with no cross-linking. The Para -
position is occupied and the meta- position is inaccessible to the aldehyde (Scheme
1.2)

OH OH OH
O

+ C
CH2 CH2- + H2O

H H
R R R

Scheme 1.2

On the other hand, if unsubstituted phenol is added, across-linked polymeric matrix is

formed and hence a rigid three-dimensional structure may be obtained (Scheme 1.3).

OH OH OH
OH
H2CO
+ CH2 CH2- + H2O

R R CH2
OH

CH2-

Scheme 1.3

By varying the content of phenol its the reaction mixture the degree of cross linking
can be adjusted. Such organic condensation polymers have poor chemical am

9
mechanical stability as they can easily undergo hydrolytic and cleavage reactions.

Multidentate ligand groups can be introduced in these cross-linked polymer (Schemes,

1.1, 1.2 and 1.3) by substitution before or after polymerization.

1.1.1 Advantages and disadvantages of Organic Polymeric Supports.

Organic polymers can be modified by functionalization of ligand groups of

practical applications. These polymers have a number of advantages including:

i- Their chemistry is well established and well known.

ii- Selecting the appropriate functional groups.

iii- Their pore size can be adjusted.

iv- Their structural rigidity can be controlled.

v- They can be obtained as porous spherical beads.

vi- High degree of functionalization can be achieved, particularly for polymer,

containing aryl groups.

On the other hand, organic polymeric matrices have some disadvantages:

i- They are unstable under high pressure and disintegrate into smaller fragments, so
clog up columns at high pressure chromatographic operations(5).

ii- They are sensitive to high temperature and radiation.

iii- They swell in most organic solvents.

iv- Lack of chemical and mechanical stability.

So it is very important to search for other polymeric matrices which have superior
properties.

1.2 Inorganic Polymeric Supports.

Inorganic polymers are normally utilized for supporting functional groups. Examples
are: silica, glass: beads, clays, zeolites and polysiloxanes(4). These inorganic supports,

10
particularly the silica-based matrices, offer several advantages over organic polymeric
supports, including:

i- Physical rigidity and high mechanical resistivity.

ii- Negligible swelling in both aqueous and organic solutions.

iii- Chemical inertness (low interaction with analytes and lower poisoning by

irreversible side reactions).

iv- High biodegradational, photochemical and thermal stability.

v- Good mechanical and heat transfer properties.

vi- Have a good ability to withstand high pressure .

vii- Greater control for diffusion factors which is inaccessible with organic polymers
because of variation of swelling as a function of solvent and pressure .

The main disadvantages of these inorganic polymers is its susceptibility to

degradation by basic solutions pH (6).

1.2.1 Silicon Compounds.

Compounds of silica are widely used for obtaining inorganic polymeric matrices and
play an important role in technology(7).

Silicon resembles carbon in the ability of forming covalent compounds, such as silica
gel and polysiloxane materials The chemical bond between the silicon and oxygen
atoms, Si-O, is called the (siloxane bond). The most frequently used inorganic
supports are silica and polysiloxanes. The backbone of these silica-based supports are
Si-O-Si linkages. The Si-O bond is formed by the (σ) bonding of the hybridized s and
p electrons of the silicon atom with the p electrons of oxygen. There is an additional
(π) bonding interaction of the unshared p electrons of the oxygen with the 3d orbital
of the silicon called p(π)-d(π) conjunction. The nature of p(π)-d(π) bonding measures

11
the differences in the structure and the properties of the corresponding silicon and
carbon atoms (4).

The Si-O bond is very stable, its average bond energy which calculated from heats of
combustion is in the range (422-494 KJ/mol): and its bond length is 1.64 ± 0.03 A0 ,
which is substantially smaller than the length of the Si-O bond (1.83 A0), calculated
from individual atomic radii . The strength of the Si-O bond can be explained by its
substantial ionic character (40-50%) in addition to partial double bond character, due
to p(π)-d(π) interactions. The larger Si-O bond dissociation, energy compared with
that of C-O (35S KJ/mol) and Si-C bond energy (318 KJ/mol) bear testimony to the
strength of Si-O bond due to the existence of p(π)-d(π) interaction .

From practical point of view, it is useful to study silane-coupling agents, which are
special types of organosilicon compounds as they considered to be the starting and
intermediate products in the siloxane materials

1.2.2 Silane Coupling Agents.

Silane coupling agents have been used widely to modify surfaces for chemical.
applications, and lo immobilize chelating functional groups on silica gel and on
prepare organofunctionalized polysiloxane polymers.

Silane coupling agents have the general form X3Si-R where X is hydrolyzable group
and R represents an organo functional group. The organofunctional groups are chosen
for reactivity with the polymer, while the hydrolyzable groups X (Cl or OR) are
merely intermediates in formation of silanol groups for bonding to mineral surface.
Ordinarily, trialkoxysilane is used because it is easier to handle than the
trichlorosilane and the corrosive HC1 formed as a by product of hydrolysis is
undesirable(4).

Silane coupling agents combine the organic chemistry of organofunctional groups

12
with inorganic chemistry of silicates to bridge the hydrophilic interface between
mineral substrate and organic polymer.

To form a bond between a ligand and the surface of silica, a molecule containing an
organofunctional ligand group, is reacted with the surface silanols. In principle this
can be achieved in several ways, all of which have been used to bond
organofunctional groups to inorganic structures (Scheme 1.4).

(i)ROH
OH2 SiOR
RNH2
ClH
SiNHR
(ii)SOCl2
SiOH HSOCl SiCl
LiR or XMgR
Surface silanol SiR
(iii)RSiX3
HX SiOSi(X2)R

Where: R = an organofunctional group,

X= a readily hydrolysable group such as Cl. OR, NH2. OCOR.

Scheme 1.4

Method (iii) is preferred for bonding groups to silica because:

a) It produces an Si-C unit at the surface which is much more hydrolytically and
thermally stable than either an Si-O-C or Si-N-C unit.

b) Many organofunctional compounds of the type RSiX3 are readily available

c) It is a one-step reaction that is simple to carry out under mild conditions.

Therefore in principle any ligand that forms part of an organic molecule of the type
RSiX3 and hence bind to silica surface. However practically it is sometimes easier to
modify or replace an organic group already attached to the surface.

13
1.3 The Polysiloxane Supports.

Polysiloxane-immobilized ligands or polyorganosiloxanes are intermediates in

composition between the pure inorganic silica and organic polymers such as
polystyrene. They are chemically modified insoluble polyorganosiloxane materials.
The term "siloxane" was adopted for these polymers initially in analogy to ketone
since the structural unit of the chain R2SiO appears to correspond the ketone R2CO
(Scheme 1.5) however siloxane is a more appropriate term identifying the (Si-O)
bond(4).

R R R
O Si O Si O Si

R R R

Scheme 1.5

Most work on polysiloxanes seems to be hidden in patents. They find use in many
applications ranging from electric insulation, biomaterials, catalyst supports,
stationary phase in liquid chromatography and separation of metal ions from
solutions. Siloxane polymers are made from organosilane intermediates (monomers)
which are compounds of the general type X4-nSiRn, where R is alkyl or aryl group and
X is a group which can be hydrolyzed to ≡SiOH such as chlorine or alkoxy, where 3
≥ n ≥ 1. The repeating unit of polyorganosiloxane consists of alternating silicon and
oxygen atoms in which organic radicals are attached to each silicon atom (Scheme

14
1.5).

These polysiloxane-immobilized ligands usually prepared by the sol-gel process which(8,9)

proceeds via hydrolytic polycondensation of metal alkoxides. This process, which takes place
at room temperature includes two steps that may occur simultaneously Acid or base catalysis
may be used to enhance or control the sol-gel process.

15
1.4.1 Preparation of Polysiloxane Immobilized Ligand System.
Insoluble polysiloxane ligand systems can be prepared by two methods:

Method 1:

Hydrolytic polycondensation of a mixture of tetraethyl orthosilicate (TEOS) and the

appropriate silane coupling agent in a definite mole ratio() (Khatib, 1985) through the
sol-gel process(9) (Hench and West, 1990). Acid or base (10)catalysis can be used to
enhance the two-step process, which, takes place at room temperature (Aelion, et al.,
1950).

Method 2:

Modification of the preformed polysiloxane immobilized ligand system by the

appropriate ligand group(12).

1.4.2 Sol-gel Process.

The sol-gel process, a method for the production of inorganic materials at

ambient temperature, was first reported some 150 years ago (Ebelman, 1846 and
Graham, 1864). The process is gaining renewed interest because it provides a
convenient way for incorporation, immobilization, entrapment, and encapsulation for
large variety of materials include; organic, inorganic, biomolecules, microorganisms,
tissue and indicators(13) (Hench, and west, 1990; Brinker and Scherer, 1989; Klein
and dun, 1988; Zusman and Rottman, 1990; Samuel, et al., 1994)

1.4.3 Steps of the Sol-gel Process.

The synthetic method of polysiloxanes by sol-gel process as its name implies,

involves the formation of a colloidal suspension (sol) and gelation of the sol to
form a wet gel (a globally connected solid matrix), which after drying forms "dry

16
 gel" state (xerogel) (12) (Brinker, 1988 and 1994).

The following steps summarizes the preparation of polysiloxane by the sol-gel

process.

1.4.3.1 Hydrolysis.

Most sol-gel techniques use water and low molecular weight tri- or/and tetra-
alkoxysilanes as gel precursors. Because alkoxysilanes are not miscible with water, a
common solvent is used for homogenization, although in some cases the released
alcohol can provide sufficient homogenization. Generally the hydrolysis reaction is
promoted by the addition of a catalyst. Hydrolysis leads to the formation of silanol
groups. Soluble intermediates produced in the alcohol-water medium include,
silanols, ethoxy silanols and oligomers of low molecular weight which formed at the
first stages of the process(12) (Hench and west, 1990)

≡SiOR + H2 O ≡SiOH + ROH

Two models for the hydrolysis reaction have been proposed, one in which a
trivalent (Swain, et al., 1949) and another in which a pentavalent (Keefer, 1984),
transition state is formed. Raman spectroscopic studies on the hydrolysis of TMSO
indicate that the model involving a pentavalent transition is correct(12) (Hench and
West, 1990).

Hydrolysis can be readily occur under acidic or basic catalysts.

1.4.3.2 Acid Catalyzed Hydrolysis:

In general, acids accelerate the hydrolysis process of alkoxysilane, the most frequently
used acid is hydrochloric acid. Other acids such as, acetic acid, phosphoric acid or
sulfuric acid have been used (Zhitova, 1969 and Segal, et al., 1960). It has been
suggested that the resulting gels are much the same whichever acid is used(12)
(Yurchenko, et al., 1970).

17
It is proposed that the mechanism of hydrolysis under acidic condition is proceeded as
follows (Scheme 1.6).

Where: R = CH3 or C2H5.

H

H3O+ + Si-OR Si-OR

+
H2O

Si-OH + R-OH + H+
Scheme 1.6
The proton is attracted by the oxygen atom of the OR group. This causes a shift of the
electron cloud of the Si-O bond toward oxygen, and the result the positive charge of
the silicon atom increases. A water molecule can now attack the silicon atom, and a
transition state is formed(12). (Hench and West, 1990).

1.4.3.3 Base Catalyzed Hydrolysis:

In case of base catalysis ion, the reaction is caused by a hydroxyl ion (Scheme 1.7).

OH + Si-OR Si-OR

OH

Si-OH + OR

here: R = H3 or C2H5.

Scheme 1.7
The OH- ion has high nucleophilic power and is able to attack the silicon atom
directly. These attacks are aimed toward the silicon atom as the Si atom carries the
highest positive charge.

1.4.3.4 Polycondensation.

The polycondensation of alkoxysilanes can be summarized in terms of two

18
reactions: silanol-silanol condensation and silanol-ester condensation(12) (Hench and
west, 1990), (Scheme 1.8).

≡SiOH + ≡SiOH ≡Si-O-Si≡ + H2O

or

≡SiOR + ≡SiOH ≡Si-O-Si≡ + ROH

Where: R = CH3 or C2H5.

Scheme 1.8
For example the formation of the solid product from TMOS, (Scheme 1.9), (Hench
and West 1990).

Hydrolysis:

OCH3 OH
CH3O Si OCH3 + 4 H2 O OH Si OH + 4 CH3OH
OCH3 OH

Condensation:
OH OH OH OH

OH Si OH + OH Si OH OH Si O Si OH + H2O

OH OH OH OH

Scheme 1.9

Further polycondensation occurs to produce SiO2 network (Scheme 1.10).

19
 OH OH
HO Si O Si OH + 6 Si(OH)4
OH OH

OH OH
HO Si OH HO Si OH
OH O O OH

HO Si O Si O Si O Si OH

OH O O OH
HO Si OH HO Si OH
+ 6 OH2
OH OH

Scheme 1.10
Many different intermediates are possible. This means that it is very hard to
give an exact thermodynamic description of what might be possible or not, in the sol-
gel reaction paths. The effect of the different reaction parameters (Organic radical of
the OR group, solvent, catalyst, temperature and concentration) has to be investigated
experimentally, and the conclusions have to drawn from these results (Schmidt, 1984).

The H2O and alcohol expelled from the reaction remain in the pores of the network.

The hydrolytic ability of the Si-O-Si bond is responsible for the differences between
organic and inorganic polycondensation. Organic polymers evolve through the
formation of dimmers, trimmers, and linear chains, which cross-link to form the gel
state. Inorganic particles, however evolve either through aggregation of small colloids
or by addition of low molecular weight particles to larger ones (Lev, et al., 1995).

1.4.3.4 Gelation.

Gelation of the sol formed when interconnection between particles of the sol increases
forcing the sol to become more viscous (gel-point) so lose its fluidity. At the initial
stages of polymerization, the silanol functional groups at the surface of the growing
particles are partly deprotonated and their negative charge provides a repulsion barrier
that stabilizes the sol. Latter, solvent evaporation and water consumption by alkoxy
silane hydrolysis concentrated the solution and destabilize the suspension (12) (Lev, et
al., 1995).

20
1.4.3.5 Drying .

During the last stages of gelation, water and the organic solvent evaporate from the
pores of the glassy material and the volume of the solid shrinks gradually (In some
cases, the final volume of the xerogel is < 10% of the initial volume of the gel).
During the drying phase, some of the larger pores are emptied while smaller pores
remain wetted by the solvent, creating large internal pressure gradients. This process
causes cracking and fracture in large monoliths. Addition of surfactants, such as
Triton-X, were suggested to prevent these fractures (Lev, et al., 1995). Drying the wet
gel under monitored conditions also, give free cracks monolith (Hussien, 2001).

1.4.3.6 Aging.

In this stage, the polycondensation reactions, formation of new bonds, water

and alcohol are still occurs as a function of time (Dave, et al., 1994). Additional cross-
linking and spontaneous shrinking occurs. As a result composition, structure and
properties of the gel continue changing with time (Shibayama and saigo, 1995;
Campostrini, et al., 1996). The gel is aged to complete the reaction, which include
further hydrolysis and resterification. The strength of the gel increases with aging
(Scheme 1.11).

≡SiOR + H2 O ≡SiOH + ROH

≡SiOH + ROH ≡SiOR + H2O

Scheme 1.11

1.4.4 General methods of Preparation.

The basic synthetic method of functionalized polysiloxane through the sol-gel process
is the hydrolytic polycondensation of a mixture of tri- and tetra- silane agents
(monomers); [R’Si(OR)3 and Si(OR)4](10) (Khatib and Parish, 1989). More than two
components of alkoxysilane may be used to form the functionalized polysiloxane.
Tetraalkoxysilane (eg. TEOS) is the base component which gives the polysiloxane its
rigidity due to the cross-linking polymerization (Khatib, 1985), (Scheme 1.12).

21
 O
H2O/Cat. O SiR'
Si(OR)4 + (RO)3SiR'
ROH
O

R = Me or Et R’ = Organofunctionalized ligand

Scheme 1.12
The porous structure of the functionalized polysiloxane can be modified by
varying the conditions of gelation, such as pH of the reactants sol, temperature during
gel sedimentation and drying conditions of the gel, etc., (6) (Jaber, 1983).

The first preparation of functionalized polysiloxane was by Neimark and

coworkers (15) (Chuiko, et al., 1966). It was based on the hydrolytic polycondensation
of TEOS and 3-aminopropyltrimethoxysilane in the presence of methanol as solvent
in alkaline media.

Solid ligands was firstly prepared by Khatib(10) by hydrolysis and

condensation tetraethylorthosilicate with alkoxysilane agents carrying functional
groups in appropriate molar ratio of the mixture (Khatib, 1985).

Recently, during the last twenty years several fucntionalized polysiloxanes

have been prepared (16,24) (El-Nahhal and Parish, 1993; Parish et al., 1989, 1993,
1999; Ahmed and Parish, 1993; El-Nasser and Parish, 1999; El-Nahhal et al., 1999,
2000, 2001, 2002) and their structure have been characterized (25,26) (El-Nahhal, et al,
1996; Yang, el al. 1997; El-Nahhal et al 2001) and different applications based on the
prepared polysiloxanes have been studied(16,24) (El-Nahhal et al., 2000, 2001, 2002).

1.4.4.1 Sol-Gel Method.

Polysiloxanes bearing halide groups (I or Cl) were prepared by hydrolytic

condensation of a mixture of TEOS and 3-halopropyltrimethoxysilane to give
functionalized 3-halopropyl polysiloxane. The reaction was catalyzed by

22
 Bu2Sn(OAc)2 or HCl(16,24).(Khatib, 1989; Ahmed, 1993). The optimum ratio of
TEOS/Halopropyltrimethoxysilane is 2:1(10,17). (Khatib, 1985; Ahmed, 1993)
(Scheme 1.13).

O
OH2 O Si(CH2)3X
Si(EtO)4 + (CH3O)3Si(CH2)3X
ROH
O
Where, X= Cl or I

Scheme 1.13
1.4.4.2 The Modification Method.

Since few number of silane coupling agents is available, the modification

method was used to prepare the appropriate polysiloxane ligand systems.

Most of the insoluble functionalized polysiloxanes can be modified with new ligand
groups. This method was used for the synthesis of many modified polysiloxanes,
where the silane coupling agent is not available. The produced polysiloxane
immobilized ligand systems exhibit higher density of ligand groups or ligand sites
than silica functionalized with the same ligand groups(16,24) (Khatib and Parish,
1989).

New polysiloxane ligand systems were prepared by the reaction between the
iodopropyl polysiloxane ligand system (P-I) and diethyliminodiacetate
HN(CH2COOEt)2 which then was hydrolyzed to give the functionalized
polysiloxane immobilized iminodiacetic acid (P-IDA) (12) (scheme 1.14).
Scheme 1.14

O Si (CH2)3-X + HN(CH2COOEt)2

O
O O
O CH2 C OC2H5 O CH2 C OH
HCl
O Si(CH2)3 N O Si(CH2)3 N

O CH2 C OC2H5 CH2 C OH

O
O O

23
The diethyliminodiacetate polysiloxane ligand system was then modified with
ethylenediamine and diethylenetriamine by direct reaction (12) (Scheme 1.15).

O CH2 C NH NH2
O Si N

O CH2 C NH NH2
H2N(CH2)2NH2
O
O

O Si(CH2)3N(CH2COOEt)2
O
O

O CH2 C NH NH NH2
N
H2N(CH2)2NH(CH2)2NH2 O Si
CH2 C NH NH NH2
O
O

Scheme 1.15a
Another new polysiloxane immobilized ligand system was prepared by the reaction
between iodopropyl ligand system (P-I) with ethy-2-aminobenzoate (EAB) (12)
(Scheme1.15).

O O
H2N H
Et3N Si (CH2)3 -N
O Si (CH2)3-I + O
-HI
O EtOOC O
EtOOC

O O
H H
Si (CH2)3 -N HCl O Si (CH2)3 -N
O

O O
EtOOC HOOC

(scheme 1.15b)

24
 The ethyl-2-iminobenzoate polysiloxane ligand system was then modified with either
ethylenediamine or diethylenelriamine by direct reaction(12) (Scheme 1.16)

O
H
H2N(CH2)2NH2 O Si N

O H2 N N
O C
H H
O Si (CH2)3 -N O

O
EtOOC

O
O H
Si N
H2N(CH2)2NH(CH2)2NH2
O
H2 N NH NH
C
O

(Scheme 1.16)

1.16
a

Scheme1.16a

25
26
Preparation of polysiloxane-Immobilized Triamine Ligand System (PTA)

Diethylenetriamine has been used as Chelating ligand for many decades interoduce
into the polysiloxane by direct reaction with halogenofunctionalized polysiloxane (19)
Prepared this ligand system by the reaction of 3-Iodopropylpolysiloxane with an
excess diethylenetriamine in the presence of triethylamine
This reaction carried out under nitrogen ,for 48 hours. The solid material was washed

27
and dried under vacuum ,

1.4.5 Characterization of Functionalized Polysiloxanes.

Many attentions have been exerted in the past on the preparation of new
functionalized polysiloxanes but few studies have been reported to characterize these
new insoluble polymeric systems.
Elemental analysis was the essential technique used to characterize such
polymers by many workers (Khatib, 1985; Ahmed, 1991; Habibi, 1988; Parish, et al.,
1989; El-Nahhal, et al, 1993; El-Kurd, 1998; El-Ashgar, 1999; Nassar, 2001). As the
polysiloxanes are insoluble in solvents they are difficult to be characterized by
classical spectroscopic instruments such as UV, VIS, NMR. Only limited methods are
available (Ahmed, 1991). IR spectra have been used for the identification of the main
functional groups attached to these ligand systems(16,24), (Ahmed, 1991; El-Kurd,
1998; El-Ashgar, 1999, El-Hashash, 2000, Nassar; 2001).
Recently, in the last ten years great efforts have been exerted to characterize the
structures of functionalized polysiloxanes using high resolution solid state NMR
technique as well as other techniques (24,25) (Yang, et al., 1996; Yang et al., 1997; El-
Nahhal, et al., 1996; Yang et al., 1997; El-Nahhal et al., 2000).
Valuable information was obtained from solid state 29Si, 15N, 13C, and 1H NMR
spectra, which assist characterization of these polysiloxane-immobilized ligand
systems. Other techniques such as XPS, TGA and TDG were also help in
characterization. Characterization of functionalized polysiloxanes include: the matrix
(Si-O)n, net work , the polysiloxane surface and the functional groups. A brief

28
explanation of the different technical methods will be discussed in the following
sections.

1.4.5.1 CP-MAS NMR.

When magnetically active nuclei in the solid state placed into a magnetic field, no
given nucleus will resonate at a precise value, but will resonate over a fairly wide
frequency range. This line broadening is generally severe enough to prevent the
observation of NMR fine structure(12).

A new technique, based on Magic Angle Spinning, (MAS), is used for solids
and highly viscous samples(27) (Engelhard & Michel, 1987; Bleam, 1991). This
technique is based on the appropriate averaging of the various solid-state interactions,
by spinning the sample at a certain angle to the applied magnetic field. In other hand,
the relaxation times of nuclei from their ground state can be very long in solid matrix.
Therefore modern solid state NMR spectrometers have the possibility of cross-
polarization, (CP) (28), (Engelhard & Michel, 1987; Bleam, 1991). This cross
polarization was originally designed to enhance the sensitivity of nuclei with a low
magnetogyric ratio (γ) or a low natural abundance. It is used in solid state for
permitting an improvement of the signal to noise ratio.

1.4.5.2 29Si NMR

29
Si CP-MAS NMR spectra are expected to provide valuable information about the
nature of attachment of the various silicon atoms and on the stability of the attachment
of these ligands.

The 29Si NMR spectra of the immobilized polysiloxanes ligand systems show two
regions of major intensities occurred at about -105 and -60 ppm. These two positions
correspond to Si(-O-)4 and RSi(-O-)3 units, respectively, where R is an
organofunctional group. The -105 ppm pattern is composed of at least three
contributions, at about -91, -100 and -108 ppm, due to the following typesof species;
(≡Si)2Si(OR')2, (≡SiO)3SiOR' and siloxane bridges (≡Si)4Si respectively, where R'=Et,
Me or H. These types are often referred to as Q2, O3 and Q4 sites respectively (12)
(Yang et al., 1997).

29
In 29Si NMR spectroscopy, siloxane bridges and different surface silanols, which are
single (either isolated or vicinal) and double (geminal), (Scheme, 2.24) have been
distinguished (Vansant, 1995; Maciel and Sindrof, ). The single silanols are referred as
Q3 sites (-94 ppm) and the double Q2 sites (-100 ppm).

OH OH OH OH
HO
Si Si Si
O Si
O O O O O O
O O O

Geminal (Q2) Isolated (Q3) Vicinal (Q3)

-94 ppm -100 ppm -100 ppm

Scheme 1.17

Further observations of polysiloxanes surface obtained by hydrolytic

polycondensation are confirmed using 29Si CP MAS. Based assignments of spectra
have been elaborated by De hann and co-workers by studying aminopropyltrimethoxy
silane modified polysiloxane(29) (De Hann, et al., 1986). Comparing the shielding
effects of ethoxy and hydroxy substituents, they proposed that and hydrolyzed and
non-hydrolyzed monodentate species have a different peak positions (Scheme 2.25).

R O Si R OR' R R
Si Si EtO Si OEt HO Si OH
O O OO O O

-67 ppm -59 ppm -52.9 ppm -49 ppm

Scheme 1.18
1.4.5.3 1H NMR.

The proton NMR should in principle be an extremely useful tool in the

30
characterization of surface hydroxyls. This technique is complementary to silicon
NMR, for the identification of silanol groups, since it discerns free and bridged
hydroxyls as not as silicon NMR single and geminal hydroxyls.

However, proton NMR on solid samples is encumbered by the severe broadening

effects of strong 1H-1H magnetic dipolar interactions. If these effects are not too large,
because of the large 1H-1H internuclear distances and/or fast motional averaging, then
sharp 1H NMR resonances can often be achieved by magic-angle-spinning (MAS) (12)
(Vansant, et al., 1995).

A well resolved 1H NMR of silica surface was not produced before 1988 by
Bronnimann's technique (Bronnimann, et al., 1988), which was further developed by
Haukka and co-workers(30,31) (Haukka, 1993; Haukka, 1994).

The 1H MAS NMR spectra of surface silanol resemble infrared spectra: one broad
peak is attributed to hydrogen bonded silanols and one sharper peak to the isolated
silanols.

1.4.5.4 13C NMR.

Solid state 13C CP-MAS NMR spectroscopy is very useful for characterizing the
pendent groups of the polysiloxane-immobilized ligand systems. Chemical shifts
reveal details of chemical form or structure and both chemical shifts and line widths
provide some information on the nature of interactions (e.g., hydrogen bonding) of the
ligand groups with the polysiloxane framework or with other ligand groups.

In addition to characterize functionalized ligand groups of polysiloxanes, this

technique is used to detect the extent of hydrolysis the alkoxy groups during sol-gel
process.

The 13C NMR indicates a loss of ethoxy groups as no peaks are observed at
57.6 ppm (-OCH2-) and 15.9 ppm (-OCH2CH3) (25,26) (Yang et al., 1996; Chiang et
al., Yang et al., 1997).

Other valuable information could be obtained from 13C NMR included:

detection of leaching soluble oligomers from the polysiloxane matrix upon treatment

31
with acidic and basic solutions due to the hydrolysis of the polysiloxane networks
under these conditions (25,26) (Yang, et al., 1997).

It is also used to indicate how the organic functionalities distributed in the

polysiloxane matrices (Yang 1997).

1.4.5.5 15N NMR.

15
N CP-MAS NMR spectra of amine ligand systems can be expected to provide useful
information about the environments of the amine groups and their interactions with
each other or with proton donors or acceptors, e.g., silanols of silica-like regions of
the polysiloxane framework. (Yang, et al., 1997). It is also used to confirm the
coordination behavior between the amine binding ligands and metal ions(25,26) (Yang
et al., 1997).

1.4.5.6 FTIR Studies.

Infrared spectroscopy has been widely applied when studying the silica and
polysiloxane surfaces (Vansant, 1995). The FTIR spectroscopic studies for
polysiloxanes-immobilized ligand systems show three main regions as given in the
following Table.

Frequency cm-1 Species

3746 Free OH
3742 Geminal OH
3730-3720 Hydrogen perturbed OH
3650 Intraglobular OH
3520 Oxygen perturbed OH
3400-3500 Molecular adsorbed H2O
2000-1870 Skeleton overtone vibrations
1625 Bending O-H (molecular water)

32
 1285-985 Asymmetrical Si-O-Si stretching
970 Si-O-(H….H2O) bending
870 Bending O-H (silanol)

FTIR spectra also used to detect many functional groups at their ordinary
assignments, such as amines (El-Nahhal, et al., 2000;El-Nahhal, et al., 2001, Zaggout,
et al., 2001)) amides, (El-Nahhal, et al, 1999) carboxylic and .esters(12) (Parish, et al.,
1999; El-Nahhal, et al., 1999; El-Nahhal, et al., 2000, Leyden, 1980).

1.4.6 APPLICATIONS.

These materials have several applications. These applications include:

preconcentration and extraction of divalent metal ions from aqueous solutions ions. It
also used as solid phase for separation of a mixture of metal ions. These immobilized
ligand systems were also, used and tested for removal of toxic heavy metal ions from
wastewater(12).

33
34
2. Experimental
2.1. Reagents and Materials.

Tetraethylorthosilicate, diethylenetriaminopropytrimethoxysilane, were purchased

from MERCK and used as received. Diethyl ether and methanol (spectroscopic grade) were
used as received. Solutions of metal ions of the appropriate concentrations were prepared by
dissolving the metal chloride (analar grade) in deionized water. pH range of 3-6 was
controlled by using acetic acid (0.1 M)/sodium acetate (0.1 M) buffer solutions.

2.2. General Techniques.

Analysis for carbon, hydrogen and nitrogen was carried out, using an Elemental
Analyzer EA 1110-CHNS CE Instrument. The concentrations of metal ions in their aqueous
buffer solutions were measured using a Perkin-Elmer A Analyst-100 spectrometer. The
infrared spectra for the materials were recorded on a Perkin-Elmer FTIR spectrometer using
KBr disk in the range 4000 to 400 cm−1. All pH measurements were carried out using HM-40
V pH Meter.

2.3. Preparation.
2.3.1. Preparation of Polysiloxane-Immobilized Diethylenetriamine Ligand
System (P-DTA).

Polysiloxane-Immobilized diethylenetriamine (P-DTA) was prepared by adding

diethylenetriaminopropytrimethoxysilane (13.27, 50 mmol) to a stirred solution of
tetraethylorthosilicate (20.83 g, 100 mmol) in 15 mL methanol and HCl (4.95 mL, 0.42 M).
Gelation occurred within few seconds. The product was left to stand for 12 hours then dried
in vacuum oven at 90 oC. The material was crushed, sieved, washed successively with 50 mL
portions of 0.025 M NaOH, water, methanol and diethyl ether and then dried in vacuum oven
at 90 oC at 0.1 torr for 10 hours.

2.4. Batch Experiments.

A 100 mg of the functionalized polysiloxane-immobilized ligand system, P-DTA was

shaken with 25 cm3 of 0.02 M aqueous solution of the appropriate metal ions (Co2+, Ni2+ and
Cu2+) using 100-cm3 polyethylene bottles. Determination of the metal ion concentration was

35
carried out by allowing the insoluble complex to settle down, withdrawing an appropriate
volume of the supernatant using a micropipette and then diluting to the linear range of the
calibration curve for each metal using AAS. The maximum metal ion uptake capacity was
calculated as mg of M2+/g ligand. Each study was performed at least in a triplicate.

2.5. Column experiments.

2.5.1. Preconcentration Experiment.
A glass column (250 mm long, 10 mm diameter) was washed sequentially with 0.1 M
nitric acid, water and acetone. It was then oven-dried and packed with a bed (5.0 g, 60-80
mesh) of the diethylenetriamine immobilized ligand system, P-DTA. The packed material
was activated for each run by washing with 15 cm3 of aqueous solution of 0.5 M
hydrochloric acid, followed by deionized water and finally with acetate buffer solution at pH
5.5. Solutions (50 cm3, 100 ppm) of each metal ion at different pH values were eluted with a
flow rate at 1.0-1.5 cm3 min-1 by gravity. When needed, vacuum pump was used to reach the
desired flow rate. In another experiment, the column containing the bed (5.0 g, 60-80 mesh)
of P-DTA, was activated as mentioned previously and solutions of different concentrations
(0.0005 – 1.0 M) buffered at pH 5.5 were passed through the column with a flow rate at 1.0-
1.5 cm3 min-1. The chemisorbed metal ion was eluted by passing 50 cm3 of an aqueous 0.5 M
hydrochloric acid. The metal ions were quantified by atomic absorption spectroscopy.

2.5.2. Column Separation Experiment.

The column was packed with the functionalized diethylenetriaminopolysiloxane, P-
DTA (5.0 g, 60-80 mesh). After each use the column was flushed with 0.50 M hydrochloric
acid, followed by deionized water, to remove any uneluted metal contaminant. Before any
sample injection, the column was preconditioned by passage of 25 cm3 of the appropriate
buffered aqueous solution to equilibrate the column as that of the working solution. Solution
of a mixture of metal ions (Co2+, Ni2+ and Cu2+, each of 100 ppm) was injected in the column.,
then buffered solutions of controlled pH were passed through the column at a flow rate of 1.0
-1.5 cm3 min-1 by gravity. The eluates were collected in fractions with a volume range 5-10
cm3. Each fraction was diluted to 50 cm3 and the amount of metal ion (mg) in each fraction
was determined using atomic absorption spectroscopy. The retained metals on the ligand
system were eluted with 10 cm3 of 0.50 M hydrochloric acid. The solution was then diluted
to 50 cm3 and the metal concentrations in the solution were determined by using atomic

36
absorption spectroscopy.

37
1.1.13. Results and Discussion
3.1 Synthesis of Polysiloxane-immobilized Triamine Ligand System (P-DTA).
The diethylenetriamine polysiloxane ligand system (P-DTA) was made by hydrolytic
polyucondnsation between TEOS and diethylenetriaminopropyltrimethoxysilane (Scheme 1).
The elemental analysis results of the prepared polysiloxane are given in Table 1. The
functional group content of the ligand system is higher than previously reported results [15].
It is found that percentages of C and N are slightly lower than expected due to formation of
small oligomers which leached during the washing process [10, 30-32]. Formation of these
small oligomers is enhanced by the presence of self base catalyzed amino groups which lead
to rapid gelation, so small amounts of non-cross linked oligomers are formed [10, 30-32].
The equal ratios of both expected and found results confirm that complete functionalized
ligand leached.

H2O/Ethanol
(CH3O)3Si(CH2)3NH(CH2)2NH(CH2)2NH2 + TEOS

O
H
N NH2
O Si N
H
O

Scheme 1

Table 1: Elemental analysis for polysiloxane-immobilized triamine ligand system (P-

DTA).

Element C% H% N% C/N mmol N/g

Expected 26.56 5.73 13.28 2.33 9.5
Found 24.34 5.9 11.89 2.38 8.5

3.2. FTIR Spectrum.

38
 The FTIR spectrum of the immobilized diethylenetriaminepolysiloxane, P-DTA
ligand system is given in Fig. 1. The figure shows three characteristic absorption regions at
3500-3200 cm-1 due to ν(OH), ν(NH) or ν(NH2), 1650-1560 cm-1 due to δ(OH), δ(NH2) or δ
(NH) and 1200-900 cm-1 due to ν(Si-O) respectively. The s strong bands at 3453 cm-1 and
1641 cm -1
are due to ν(NH2/NH/OH) and δ( NH2/NH/OH) vibrations respectively. This
confirms that the diethylenetriamine functional group is chemically bonded to the
polysiloxane surface.
88.1
85

80

75
582.04
70
2952.02 1520.75 789.93
65
461.28
60
Fig. 1. FTIR spectrum of P-DTA.

1641.17
55
%T %T
50

45

40

35 1067.68

30

25 3453.84

20.5
4000.0 3000 2000 1500 1000 400.0
cm-1 cm-1
39
3.3 Metal Uptake Capacity of P-DTA
The metal ion uptake capacity of Co2+, Ni2+ and Cu2 +, was determined by shaking the
functionalized ligand system, P-DTA with buffered metal ions solutions for 48 hours. The
results in mg M2+/ g ligand are given in Table 2. The elemental analysis of nitrogen of the
immobilized ligand (P-DTA) as given in Table 1 was 11.89% i.e. 2.8 mmol N/g ligand.
Comparing this value with the maximum metal ion uptake, it is possible to suggest that not
all functional groups are accessible to binding with the metal ions assuming the ligand to
metal complexation ratio is 1:1. It is clear that uptake of metal ions increases in the order:
Cu2+ > Ni2+ > Co2+

Table 2: Maximum metal uptake by P-DTA

Maximum Uptake Co2+ Ni2+ Cu2+

mg M2+/g Ligand 97 104.2 129
mmol M2+/g Ligand 1.64 1.77 2.03

3.4. Effect of pH on the metal ions chemisorption.

The influence of pH of the aqueous solution on the retention of cobalt, nickel and
cupper was investigated in the pH range 3-6 by using acetate buffer solution. The results are
depicted in Fig. 2. The recovery values of the analyte ions were generally found to be very
small at low pH values and increases by increasing pH. Maximum retention occurs at pH 5.5.
In case of cupper about 100% was retained while 93% and 88 % were retained in case of
nickel and cobalt respectively.

40
 120

% of metal ion retained 100

80

60

40

20

0
2.5 3 3.5 4 4.5 5 5.5 6 6.5
pH

Cu(II) retained Ni(II) retained Co(II) retained

Fig. 2. Chemisorption of metal ions by P- DTA versus pH values.

3.4. Preconcentration of metal ions.

The ability of P-ABT to preconcentarte metal ions from aqueous solution was
evaluated using aqueous solutions of metal ions at different concentartions. The results are
given in Fig. 3. The amount of metal ion recovered by the ligand system increases with
increasing concentration up to the maximum value. Based on elemental analysis of N (11.89
%) of the ligand system (each ligand contains 3 N atoms), there was 2.8 mmol ligand per
gram of immobilized system. Assuming 1:1 complex formation of M:L mole ratio the
maximum loading (theoretically) of metal ion would be 179 mg Cu, 164 mg Ni and 165 mg
Co per gram ligand system. The maximum chemisorption values were obtained at
concentration of 0.5 M of the eluted metal ions and found to be 128 mg Cu, 104 mg Ni and
97 mg Co per gram ligand system. These values represent preconcentration efficiency of the
column in percentages of 73.5 %, 63.4 % and 58.8 % for copper, nickel and cobalt
respectively. At low metal ios concentration, ∼100 % extractions were achieved. This
promises the column to be an excellent preconcentration system for these metal ions.

41
 140

mg of metal ion retained

120
100
80
60
40
20
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2
Con. of metal ion (M)

Co(II) Ni(II Cu(II

Fig. 3. Preconcentration of Co(II), Ni(II) and Cu(II) as a function of concentration (5.0

g of ligand system, flow rate 1.0 -1.5 cm3 min-1 , pH = 5.5).

.Separation of metal ions .3.5

Separation of a mixture of metal ions Cu(II), Ni(II) and Co(II) was performed by
elution with buffer solutions at different pH values. Three bands were observed by pH
control. A blue color band of Cu(II) was observed upstream followed by a green and a pink
bands of Ni(II) and Co(II) respectively. These metal ions were eluted cleanly from the
mixture by pH control. Fig. 4 shows the separation of Cu(II), Ni(II) and Co(II) metal ions as
a function of elution volume at variable pH values. Complete separation of Co(II), Ni(II) and
Cu(II) from solution mixture was performed and improved by stepwise pH control of the
eluent . The desorbed amount of metal was calculated from the total fractions of 500 cm3.
Three well resolved peaks of cobalt, nickel and copper ions were obtained, at pH 4.5, 4 and
0.1 N HNO3 respectively. This promises the ligand system to be efficient in a clean
separation of these metal ions.

42
 40
pH 4.5
35 0.1 M HNO3
pH 4
30
mg M(II) desorbed

25

20

15

10

0
0 50 100 150 200 250 300 350 400 450 500 550
Volume of eluent (mL)

Ni(II) Co(II) Cu(II)

Fig. 4. Separation of a mixture of Co(II), Ni(II) and Cu(II), (5.0 g of ligand system, flow
rate 1.0 -1.5 cm3 min-1 , pH = 5.5, total eluent volume = 500 cm3).

Conclusion
The immobilized diethylenetriamine ligand system was prepared by direct sol-gel
hydrolytic polycondensation reaction of diethylenetriaminopropyltrimethoxysilane and
tetraethylorthosilicate monomers at ambient temperature. This ligand system has been shown
to be an effective solid-phase preconcentration agent for cobalt, nickel and copper at pH 5.5.
The ligand system exhibits high potential for separation of a mixture of Co2+, Ni2+ and Cu2+
metal ions from aqueous solution by pH control.

43
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45