You are on page 1of 28

Synthesis And Application of

Ethylenediamine Triaceticacid
Polysiloxane Immobilized Ligand
System
Prepared by
Mohammad R. Matar & Hussein Al. Shayah
Chemistry Department
Islamic University of Gaza
Supervised by :
Dr. Nizam M. El-Ashgar

Polymeric Supports
Organic Polymeric Supports.
are formed in two general ways.
a) Addition Polymers:
1.

CH=CH2

CH=CH2

CH2CH2-CH-CH2-

+
CH=CH2

-CH-CH2-CH-CH2-

b) Poly condensation Polymers:

OH

OH

OH

C
H

CH2

CH2-

H
R

H2O

Disadvantages of Organic Polymers


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

2- Inorganic Polymeric Supports


Polymers synthesis from elements other than carbon
they are macromolecules in which a metal or
metalloid is part of the main chain backbone (soil,
diamond, glass, stones, graphite silica gel,..)

R
P
R

N
n

Polyphosphazene

Si

Si

Polysilane

R
Polysiloxane

Advantages

Physical rigidity and high mechanical resistivity.


Negligible swelling in both aqueous and organic
solutions.
Chemical inertness to analyte or production of side
reactions.
High biodegradational, photochemical and thermal
stability.
Good mechanical and heat transfer properties.
Have good ability to withstand high pressure.
Greater control for diffusion factors.

Polysiloxanes Immobilized Ligand


Systems.

Functionalized polysiloxane sorbents


(Polyorganosiloxanes).
Insoluble cross-linked organosilicon polymers with a
controllable porous structure.
They are intermediates in composition between the
pure inorganic silica and organic polymers such as
polystyrene.
Although the chain is entirely inorganic, with
alternating Si and O atoms, organic side groups are
attached to the silicon atoms.
Has an extraordinary flexibility of the siloxane
backbone.
Si-O bond is significantly longer than the C-C bond.
Si-O-Si bond angle of 143 > tetrahedral angle.

Preparation of Polysiloxane
immobilized Ligand System
Method 1: The Sol Gel Process:
Hydrolytic polycondensation of a mixture of tetraethyl
orthosilicate (TEOS) and the appropriate silane
coupling agent in a definite mole ratio using acid or
base catalysts.
Method 2: Modification of the preformed polysiloxane
immobilized ligand system by the appropriate ligand
group.
Sol-gel Process.
Used for incorporation, immobilization, entrapment,
and encapsulation for large variety of materials
include; organic, inorganic, biomolecules,
microorganisms, tissue and indicators .

Steps of the Sol-gel Process

1- Hydrolysis.
By mixing low molecular weight tri or/and tetra
alkoxysilanes with water in present of a
homogenization agent. The hydrolysis catalyzed by
acid or base.
SiOR + H2O SiOH + ROH

2- Polycondensation.
Through silanol-silanol condensation
SiOH + SiOH
Si-O-Si + H2O
silanol-ester condensation.
SiOR + SiOH Si-O-Si + ROH
Where: R = CH3 or C2H5.

Formation of Solid Silica:


Hydrolysis:
OCH3
CH3 O

Si

OH

OCH3

OCH3

CH3 O

OCH3

Si

OH

H2O/Cat
Solvent

HO

OCH3

Si

OH

HO

OH

Si

OH

Condensation.
OH
HO

Si
OH

OH

+ HO

Si
OH

OH

OH

OH

HO
-H2O

Si
OH

Si
OH

Further polycondensation to form SiO2 net work

OH

OH

n HO

Si
OH

Si
OH

Si

O
O

Si

Si
O

O
O

Si

Si
O

Si

O
O

O
O

Si

Si

O
O

Si

The H2O and alcohol expelled from the reaction remain in


the pores of the network.

Gelation, Drying and Aging.


Gelation.
Interconnection between particles of the sol increases forcing the
sol to become more viscous (gel-point) so lose its fluidity.
Drying .
*Evaporation of water and organic solvent from the pores of the
glassy material.
*Shrinking of solid gradually (In some cases, the final volume of
the xerogel is 10% of the initial volume of the gel).
* Large internal pressure gradients in the wet pores. This process
causes cracking and fracture in large monoliths. Addition of
surfactants, such as Triton-X, were suggested to prevent these
fractures
* Drying the wet gel under monitored conditions also, give free
cracks monolith

Aging.

Structure and properties of the gel continue


changing with time.
The reaction, is completed further hydrolysis and
resterification.
Polycondensation reactions New bonds
formation - are still occurs as a function of time.
Additional cross-linking and spontaneous
shrinking occurs
The strength of the gel increases with aging
SiOR +
H 2O
SiOH + ROH
SiOH +
SiOH
SiOSi + H2O

Preparation Methods Polysiloxanes


1- Sol-Gel Method.
O
Si(OR)4 +

(RO)3SiR'

H2O/Cat.
ROH

SiR'

O
R = Me or Et

R = Organofunctionalized ligand

2- Modification Method
O
O
O

O
Si(CH2)3Cl

NaI

Acetone
o

48 hr, 70 C

Si(CH2)3I

Advantages of Polysiloxane Immobilized


Ligand Systems.

The physical rigidity of their structures.


High abrasion resistively.
Negligible swelling in both aqueous and organic solutions.
Chemical inertness (low interaction with analytes).
Slower poisoning by irreversible side reactions.
High biodegradation, photochemical and thermal stability.
High capacity of functionalized groups.
Uniform distributions of ligand sites within the polymer
particles.
Readily modified by a variety of functional groups to be
immobilized either before or after polymerization.

Drawbacks of Polysiloxanes.
Hydrolysis at high pH pH 12).
Unstable for certain reaction conditions.
Leaching of the functional groups from the
support surface into the solution.

Application of Polysiloxane Immobilized


Ligand Systems.
The extraction and and isolation of metal ions.
Metal ion separation in columns
chromatography.
As catalysts in a variety of reactions.

Preparation of ethylenediaminetriacetic
acid polysiloxane immobilized ligand
system
1- Preparation of the silane agents by the reaction of 3ethylenediaminetrimethoxysilane with
ethylchloroacetate by the ratio of 1:2

(CH3O)3Si(CH2)3NH(CH2)2NH2 +

3 ClCH2COOC2 H5

(CH3O)3Si(CH2)3N(CH2COOC2 H5)(CH2)2N(CH2COOC2 H5)2

2- Hydrolytic polycondensation of the


triethyldiminotriacetatetrimethoxysilane agent with
tetraethylorthosilicate (TEOS), in the ratios 1:2
respectively.
3- The new functionalized ligand system P-EDTA was
obtained by acidic hydrolysis of the ester products.

(CH3O)3Si(CH2)3N(CH2COOOH)(CH2)2N(CH2COOC2 H5)2 + n (C2H5O)4Si

CH2COOC2H5
O

CH2COOC2H5
SiCH2-CH2-CH2-N(CH2)2N

CH2COOC2H5

O
HCl

CH2COOH
O
O

CH2COOH
SiCH2-CH2-CH2-N(CH2)2N
CH2COOH

O
P-EDTA

Characterization of Functionalized
Polysiloxanes.
1- Elemental Analysis:
Polysilox
ane
PEDTE
A
P-EDTA

%C

%H

%N

C/N

Expected

38.4

5.8

5.3

8.5

Found

30.4

4.3

4.3

8.2

Expected

23.2

3.4

4.9

5.5

Found

25.8

3.5

4.7

6.4

2- FTIR

Metal Uptake Capacity


Maximum Uptake

Co2+

Ni2+

Cu2+

mg M2+/g Ligand

23.1

44.1

48.5

mmol M2+/g Ligand

0.39

0.74

0.76

Effect of pH
60

mg M(II)/g Ligand

50
40
30
20
10
0
3

3.5

4.5

5.5

pH
mg Co(II)/g

mgl Ni(II)/g

mg Cu(II)/g

Uptake of metal ions by P-EDTA versus pH values, (72 hr shaking time)

Chromatographic study
Effect of pH on metal desorption

Cu(II) desorbed at different pH values


3

mg Cu(II) desorbed

2.5
2
1.5
1
0.5
0
-0.5

50

100

150

200

250

Volume of eluent (mL)


pH 3.6

pH 4

pH 4.4

pH 4.8

pH 5.2

Amount of Cu(II) desorbed as a function of eluent volume at


different pH values (flow rate 1.5 mL/min)

Relation between total amount of Cu(II)


desorbed & adsorbed as a function of pH
Cu(II) desorbed and retained versus pH values
35
30

mg Cu(II)

25
20
15
10
5
0
3

3.5

4.5

5.5

pH
Cu(II) desorbed

Cu(II) retained

Amount of Cu(II) desorbed and retained at different pH values


(flow rate 1.5 mL/min).

Metal ions Separation


Separation of Cu(II), Ni(II) and Co(II)

3
pH 5.2

pH 4

pH 3.6

mg of M(II) desorbed

2.5

1.5

0.5

0
0

100

200

300

400

500

600

700

Volume of Eluent
mg Ni(II) desorped

mg Co(II) desorped

mg Cu(II) desorped

Separation of Co(II), Ni(II) and Cu(II) at different pH values


(flow rate 1.5 mL/min

800

Conclusion
The immobilized ethylenediaminetriacetic acid
ligand system was prepared by the sol-gel
method. This immobilized ligand system exhibits
high potential for extraction and separation of
Cu(II), Ni(II) and Co(II) from aqueous solution..
The ligand system has been shown to be an
effective solid-phase for metal ion recovery at
the optimum pH.

Thank You