Illl

EG9601796
Ionic Membranes Obtained by Radiation-Induced Graft
Copolymerization. I.Preparation
H.A.ABDE1-REHIM*,A.M.I.ALI**,H.G.NOWIER**,E.A.HEGAZY*
and H.F.ALY**

(*) National Center for Radiation Research and Technology, Atomic Energy Authority..P.O.Box 29,
Nasr City, Cairo, Egypt.
(**) Hot Labs. Center P.O. Box 13758, Atomic Energy Authority., Inshas, Egypt.

ABSTRACT
A study has been made on the preparation of ionic membrane by radiation-induced graft
copolymerization of acrylic acid (AAc) onto low density polyethylene (LDPE) films. The suitable
conditions at which the grafting process proceeds homogeneously were determined. To minimize
the homopolymerization process of AAc during irradiation process, different types of inhibitors
were investigated to find that the addition of FeCb (1.5 wt%) effectively reduced such process if
compared with other inhibitors used. The suitable diluent for this grafting system is found to be
distilled water, methanol, and methanol-water mixture. The effect of diluent mixture composition,
irradition time, addition of mineral or organic acid, and metal chlorides on the grafting yield
increased as the content of water increased in MeOH/I-^Q -mixture. The addition of oxalic acid to
the reaction medium enhanced the grafting process. However, the addition of HCl or H2SO4 resulted
in a more homogeneous grafting. The same effect was also observed when salts of NH4CI, NaCl
and CuCh were added and resulted in homogeneous grafted membranes. The swelling and
permeability of the prepared grafted films were also investigated. The results showed a great
promise for the possible practical use of such prepared graft copolymers as a good hydrophilic
membrane. The possibility of its use as ion-exchange membrane for waste treatment will be
considered.

INTRODUCTION
High energy radiation grafting processing is known to improve the physicochemical
qualities of many polymer products*!). With this principle polyethylene (PE), the cheapest
polymer compound, can be largely expanded of its utilization using radiation method. This trend
is envisaged to be continuously growing to form a big application field of PE products. The
grafting of hydrophilic monomers into PE films generates perm-selective membranes with
interesting properties.(2>3) The radiation-induced grafting of acrylic acid (AAc) onto PE is of

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great importance as modified PE which is of interest for various applications^ . The grafting of
AAc and properties of modified surface of PE have been described in details(5)
In the present work, the preparation of ion-exchange membranes, which could be of
practical interest in the field of waste treatment, is studied. The preparation of such membranes
was carried out using the technique of direct radiation-induced graft copolymerization of acrylic
acid onto low density polyethylene films.

EXPERIMENTAL
Materials:
Low density polyethylene films (LDPE) of thickness 60 urn was supplied from El-Nasr
chemical co. Ltd., Egypt, were washed with acetone and dried at 60°C. Acrylic acid (AAc) of
purity 99.99 % (Merck, Germany) was used as received. The other chemicals used are of reagent
grade.
Graft Copolymerization :
The direct radiation grafting method was used as a technique. The glass ampoules that
containing the polymer film and monomer mixture were then subjected to Co-60 gamma rays, at
a dose rate ranged from 1.35 to 1.41 Gy/s.The grafted films were removed and washed
thoroughly with distilled water to extract the residual monomer and the homopolymer.The films
were dried in vacuum oven at 50-60 °C for 24 h and weighed. The degree of grafting was
determined by the percentage increase in weight as follows:

Degree of grafting (% ) = [(W -W o )/ W o ] X 100

where W o and W represent the weights of initial and grafted films , respectively.

RESULTS AND DISCUSSION

This work deals with the preparation of ion exchange membranes of practical interest in the
field of waste treatment. The preparation of such membranes was carried out using the technique
of direct radiation graft copolymerization of acrylic acid onto low density polyethylene.
The influence of some grafting parameters such as; solvent mixture composition, inhibitor type
and its concentration to inhibit the homopolymerization process, and irradiation dose on the yield
and homogenity of grafting, was investigated. The addition effect of organic and mineral acids and
also some metal salts to the reaction medium, on the grafting process was also studied.
 Solvent Effect:

Solvents are basically used in radiation grafting experiments to enhance the degree of
accessibility of monomer to grafting sites within the polymer brought about the great ability of
the added solvent to swell the base polymer. Table (1) shows the effect of different solvents on
radiation induced grafting of AAconto LDPE films at20kGy. It can be seen that the higher
degree of grafting of such monomer-polymer system is obtained in case of using distilled water as a
diluent, but the absence of inhibitor during irradiation process results in enhancement of
homopolymerization process of AAc. Under such condition, the resulting grafted films are
difficult to be extracted from the reaction medium. By using MeOH/FkO mixture, it gives a
lower degree of grafting, but the grafted films are easily extracted from the reaction
medium. Under the same experimental conditions, benzene as a diluent gives a reasonable
grafting yield (74%). However, the homopolymerization is much less than that formed in
other diluents used and the grafting process proceeded homogeneously. This can be reasonably
understood by considering the energy transfer effect and it is caused by resonance stabilization of
benzene ring which act as an inhibitor for the homopolymerization of AAc during irradiation

process.
(6)
In general, the influence of solvent on the grafting process may be ofdifferent features :

(a) Solvent may swell polymer substrate to facilitate accessibility and diffusion of monomer to
active site .
(b)Solvent may act as a chain transfer agent.
(c)Addition of solvent may modify the thermodynamic equilibrium of the polymer in the
particular monomer-solvent mixture,
(d) Solvent will "dilute" the monomer, thus reducing the rate of propagation and the kinetic
length.
Results revealed that the most suitable diluents for this grafting system are distilled water
or a mixture of methanol and water. However, the addition of a suitable inhibitor to minimize
the homopolymerization process is very necessary. Benzene also is a good solvent, but from the
economical point of view it is preferable to use water or water-methanol mixture.

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Table(l):
Effect of different solvents on the grafting of AAc (30%) onto LDPE
films at Irradiation dose of 20 kGy
Solvent Degree of Remarks
grafting (%)
Butanone 8.7 easily extractable
Benzene 74.3 easily extractable
Distilled water 420 difficulty extracted
MeOH/H2O(30/70 257 extractable
wt%)
MeOH/H2O(70/30 82 extractable
wt%)
MeOH 12 extractable
Dioxane not can not extracted
determined
Chloroform not can not extracted
determined
DMF not can not extracted
determined

Table(2):
Effect of inhibitor type on the grafting of aqueous acrylic acid (30
wt%) onto LDPE , irradiation dose ; 20 kGy
Diibitor type Inhibititor concn. Degree of Remarks
wt% grafting %
FeCl3 1.5 140 littel gel formed
FeCl3 2.5 120 littel gel formed
CuCl2 2.5 53.42 No homopolymer
CuCl 2.5 55.43 No homopolymer
Mohr's salt 2.5 72.87 No homopolymer

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Effect of Inhibitor Type:

In general, one of the disadvantages of the direct radiation grafting of water soluble
monomers is the fast homopolymerization without significant grafting yield. When this technique
is applied to radiation sensitive monomers such as acrylic acid, methacrylic acid, the
polyfiinctional acrylates and their esters, the homopolymer is formed more rapidly than the graft (7)
. To avoid homopolymer formation, several methods have been applied which involved the
inclusion of metal cations such as Cu and Fe. Ferrous ammonium sulfate has been commonly
used as a homopolymerization inhibitor in many radiation-chemical grafting systems. (8) It had
been reported by Hegazy et al. ( 9 ) that FeCb effectively inhibits the homopolymerization process of
methacrylic acid during its radiation grafting onto fluorinated polymers.

Therefore, the addition of redox compounds or inhibitors to the reaction medium is

necessary to minimize such homopolymer formation.In this connection, different types of
inhibitors are investigated for this grafting system; namely; FeCb , Cu Cb and ammonium ferrous
sulfate (Mohr's salt). The influence of inhibitor type on the grafting process is shown in Tables 2
and 3 in water and in methanol/water mixture, respectively. It can be seen that FeCl 3 and also
Mohr's salt are the most reasonable inhibitors in which the grafting process proceeds effectively and
higher degree of grafting was obtained as compared with that obtained in other inhibitors
investigated here. This behaviour is observed in Tables 2 and 3 for both diluents used (water and
methanol/water mixture).

It can be concluded that the addition of either FeCb or Mohr's salt to the reaction
medium is very effective to reduce the homopolymerization of AAc during irradiation process.
The use of Mohr's salt as a redox system resulted in a more homogeneous grafted films, however,
the yield of grafting is lower compared to that for FeCb . Therefore, both inhibitors are used in
this work depending on the preparation conditions and the required yield of grafting (if high, so
is preferable for such purpose).

Effect of FeCb Concentration

The influence of FeCb concentration on the grafting process of aqueous and alcoholic
AAc solutions onto LDPE films is investigated as shown in Figs. 1 and 2, respectively. It is
obvious that, as the concentration of FeCb increases the degree of grafting in aqueous medium

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Table(3):
Effect of inhibitor type on the grafting of AAc (30%) in presence of
MeOH/H2O- mixture (30/70 wt%) onto LDPE films at 20 kGy.
Inhibitor Inhibititor Degree of Remarks
type concn., wt% grafting, %
FeCl3 1.5 142 littel gel formed
FeCl3 2.5 121 littel gel formed
CuCl2 2.5 50 No homopolymer
CuCl 2.5 51 No homopolymer
Mohr's salt 2.5 61 No homopolymer

Table (4):
Effect of metal salt on the grafting yield of aqueous AAc (30% wt % )
onto LDPE films. Irradiation dose; 20 kGy, Mohr's salt; 2.5 wt %.
Metal salt Degree of grafting
Metal free 71
BaCl2 74
CaCl2 69
NRtCl 70
ZnCl2 73
NaCl 73
KC1 73
CuCl2 62

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 20
000 0-60 1-60 2-40 300 000 0-30 060 0-90
FeCl Concentration wt%J FeC I Concentration ( w t °U)
3

Fig( 1) Effect of FeCl 3 concentration on the grafting yield of aqueous Fig(2) Effect of F e d 3 concentration on the grafting yield of AAc 30
AAc 30 wt.% onto LDPE; irradtion dose 20 kGv. wt.% onto LDPE; Irradtion dose 20 kGy; in water-methanol diluent.
significantly increases, but it tends to level off above 2.5 wt % FeC^ (Fig.l). By using methanol as
a diluent for AAc, the degree of grafting slightly increases with FeCb concentration to reach an
optimum value at 0.2 wt %. Thereafter it sharply decreases as the FeCb concentration increases.

It can be reasonably concluded that the addition of 2.5 wt% and 0.2 wt%FeCl3 to the
aqueous and alcoholic AAc solution, respectively, inhibited effectively the homopolymerization
process. Further increase in FeCb concentration may resulted in its diffusion into the interior region
of polymer matrix and thus reducing both the grafting and homopolymerization processes. This is
caused by the energy transfer effect which decreases the efficency of formed free radicals and
growing graft chains without initiating new grafting sites. Such a case is more pronounced in
alcoholic medium in which the diffusion of Fe3+ is high and may enhances the decay of free
radicals. Therefore, lower grafting yield is achieved in alcoholic medium compared to that
obtained in aqueous medium.

Effect of Solvent-Mixture Composition

The influence of methanol -water composition on the grafting yield of AAc (30 wt%) onto
LDPE films is determined as shown in Fig.(3 ). It can be seen that the grafting degree increases
with decreasing MeOH content reaching a maximum degree of grafting in the pure aqueous AAc
solution. This result shows that the higher diffusivity of monomer through the grafted layer of
LDPE film is enhanced in the pure aqueous monomer solution due to the improvement of
hydrophilic properties. This is gained by grafting of acrylic acid onto LDPE specially at the first
stage of grafting which occurred near the film surface. It can be concluded that, the use of
distilled water as a diluent is very reasonable without addition of organic solvent. This is a good
advantage from the economical point of view for practical applications.

Effect of Metal Cations On The Grafting Process:

Inorganic metal salts were added to the reaction mixture in an attempt to optimize the
grafting conditions. Inclusion of appropriate additives in the grafting solution may enhance the
properties of resulting system, in particular, their presence may lead to an increase in
copolymerization grafting yield.
In the present work the effect of different cations, such as Ba2+ , Ca2+ , Zn2+, Na+ , K+,
Cu2+ and N H / on the graft polymerization of AAc onto LDPE films is shown in Table (4). It

23U
 500

ro

100 80 60 40 0 Me OH 1 2 3
20
0 20 40 60 80 100 HO Irradiation Time( h )
2

Fig(3) Effect of solvent composition on the grafting of AAc onto LDPE F«g(4) Effect of total irradiation dose on the grafting of AAc onto LDPE
films. Monomer concentration; 30 wt.% and irradiation dose; 20 kGy. aims. Monomer concentration; 30 wt.%.
can be deduced that the grafting yield is somewhat affected by the addition of such metal cations.
However, a pronounced effect of homogenity in grafting is observed in case of addition of N H / ,
K+ , and Na + (monovalent cations). The little enhancement of grafting due to the addition of the
aforementioned cations may attributed to the formation of a complex between the metal salt and
carboxylic acid groups of acrylic acid . Such a complex formation may raise the polarity of the
monomer and leading to an increase in the conjugation energy of Fl-electron of the C=C of vinyl
group of A A c ( I 0 ) . Therefore, in such a case the formation of longer grafted chains is expected, and
higher degrees of grafting are obtained. Such complexation process is also resulted in highly
homogeneous distribution of graft chains in the whole bulk of polymer.

Effect of Mineral and Organic Acid As Enhancer for Graft Polymerization

Recently, the acid enhancement effect in radiation grafting of monomers onto PE and the
use of these copolymers for enzyme immobilization and related reactions was reported by Garnett

e tal.<">.

In the present study, the effect of different mineral and organic acids on the radiation-
induced graft polymerization of aqueous acrylic acid onto LDPE films is shown in Table (5). It
can be seen that, there is a significant enhancement observed when oxalic acid is added to the
reaction medium. However, all other mineral acids used have no enhancement effect and the
grafting yield is somewhat reduced. However, a more homogeneous grafting is obtained when
these acids are added to the monomer solution.
The enhancement of graft copolymerization in the presence of oxalic acid can be explained
by assuming that the acid facilitates the hydrogen abstraction reaction from an adjacent polymer

molecule (PH) by monomer solution radicals MR* to give more grafting sites ( P )by the

following mechanism (I2) :-

PH + M R ' - H ^ P * +MRH

Thus, the effect of acid would appear to be predominantly to a radiation chemistry phenomenon
(13)
consistent with the observation by Bexedale and Hellows that the addition of acid to
methanol increases G-value of hydrogen {G(H )} appreciably.

236
Table(5) :
Effect of different mineral and organic acids on the grafting of AAc
onto PE Films; Monomer concentration (30 wt.%); Dose; 10 KGy
Acid % Grafting
HC1 78.16
H2SO4 93.66
HOCI4 70.6
(COOH)2 160.13
HNO3 96.1
Acid free 121

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Effect of Irradiation Time:
60

As this graft polymerization is initiated by gamma radiation Co in which the reaction

proceedes by radical mechanism. Therefore, the grafting is governed by the concentration of free
radicals formed in both polymer substrate and monomer solution. The influence of irradiation
time on the grafting yield of aqueous AAc onto LDPE film is investigated and shown in Fig.(4 ). It
is clear that the degree of grafting at the initial stage, almostly increases linearly with irradiation
time up to 100 min. Thereafter, at the second stage, it tends to level off at higher irradiation time.
These results are reasonably coincident with the typical behaviour of the concentration
of formed free radicals as a function of irradiation time (exposure dose); in which the amount of
free radical increases with dose to reach a maximum at a certain dose. Such saturation dose is
varied from system to other depending on the chemical structure and morphology of the
polymeric materials.
CONCLUSION
It can be concluded that the homogeneous PE-PAAc graft copolymer films of practical
interest can be obtained by using water and/or methanol-water mixture as a diluent and FeCb or
Mohr's salt should be added to inhibit the homopolymerization process. The presence of oxalic acid
as enhancer can be used to obtain homogenous graft copolymer films having high degree of grafting
. The addition of metal cations to the grafting reactants resulted in high homogenous distribution of
graft chains in the whole bulk of polymer.
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