POLYMERS FOR ADVANCED TECH OLOGIES

Polym. Adv. Technol, 2005; 16: 681-687

Published online in Wiley InterScience (www.interscience.wiley.com). 001: 10.1002/pat.644

Crosslinked styrene-maleic acid copolymer complexes of

some transition metals and their adsorption behavior
P. C. Deb*, L. D. Rajput, A. K. Agrawal, P. K. Singh, V. Hande and S. Sasane
Naval Materials Research Laboratory, Shil-Badlapur Road, MIDC Area, Addl. Ambernath, Ambernath (E)- 421506, India

Received 8 April 2005; Revised 23 May 2005; Accepted 4 July 2005

Transition metal complexes of linear and crosslinked styrene-maleic acid copolymer were prepared
in ethyl alcohol. The complexes appear as micro clusters fairly uniformly distributed in the copo-
lymer matrix. Vapor adsorption-desorption studies of the complex beads with methyl isobutyl
ketone (MIBK), toluene and ethyl alcohol show initial fast release followed by a steady and
slow release. Hydrogen adsorption at room temperature was studied for a few complexes up to
about 650torr, which showed initial slow adsorption followed by a rapid increase at about
550torr. Copyright © 2005 John Wiley & Sons, Ltd.

KEYWORDS: styrene-maleic acid copolymer; transition metal complexes; adsorption; crosslinking; matrix

INTRODUCTION Styrene and maleic anhydride are known to form alter-

nating copolymers over a wide range of monomer-pair
Metal complexes of organic compounds with functional
composition.18-21 Hydrolysis of this copolymer gives styrene-
groups have aroused intense interest in recent years in view
maleic acid copolymers of well-defined structure where
of their potential in catalysis, separation, absorption and bio-
each pair of carboxylic acid groups are separated by at least
medical applications.Y'" Of particular importance are the
one styrene unit. Crosslinked polymer beads of this copoly-
metal-organic frameworks which appear to retain substantial
mer are expected to contain immobilized functional groups
proportion of gases such as N2, CO2, H2 and organic vapors in
devoid of long-range interactions. Mostly the frozen seg-
the molecular pores at pressures of 1-20 etrnospheres.v '!
ments in between crosslinks that are near neighbors should
Hydrogen absorption and retention capacities reach as
react with metal ions and from identifiable clusters. These
high as 2% by weight at room temperature and lObar for
molecular clusters along with inherent porosity of the
representative metal-organic frameworks consisting of Zn-
crosslinked beads are expected to offer interesting properties
carboxylate complexes containing naphthalene and cyclo-
such as gas and vapor absorption and retention. Introduction
butylbenzene linkers having designed frarneworks.l '
of specific hosts" may also facilitate controlling the size of
Recently, it has been observed that metal complexes with
micro and nano pores thus allowing selective molecular
polymeric ligands such as polycaboxylic acid copolymers
retention of specific size, shape and chemical nature.
show unique properties like ion exchange, catalysis, electrical
In this article the preparation of linear and essentially
conductivity, etc.12-15 Kavlaket al.16 have carried out detailed
mono-dispersed crosslinked beads of styrene-maleic acid
studies on interaction of polytmaleic anhydride-alt-acrylic
copolymer, their reaction with metal ions such as Cu t 2, Ni+2,
acid) with transition metal ions through UV-vis spectroscopy
Co+2, Fe+3, Ti+4 and Pt+4 and vapor/gas uptake and
and viscometry. Their studies indicated preferential intra-
retention characteristics of the complexes are described.
chain complex formation, particularly at moderate-to-low
concentration of the polymer. Michinobu et al.l? have
described synthesis of micro-particles of Gd-polymethacrylic EXPERIMENTAL
acid complex and studies on their magnetic signals. Even
though multi-dentate organic molecules give rise to giant
Synthesis of linear and crosslinked copolyacid
Styrene was freed of inhibitor by the standard method, dried
molecular complexes with transition metals, use of well
and distilled. Maleic anhydride was recrystallisted from
defined nano and micro polymer ligands with reactive func-
chloroform just before use. Copolymerization of equimolar
tional groups provide an excellent opportunity to prepare
mixture of the monomers was carried out in l:4-dioxane
macro-molecular complexes as the size and shape of active
(AR grade from Merck) at 60°C under N2 atmosphere
macromolecules can be tailor-made through emulsion or
using 0.5 mg/ ml azo-bis-isobutyronitrile re-crystallized
suspension polymerization.
from methanol. The copolymer was precipitated in a large
excess of petroleum ether (40-60°C) and purified by repeated
dissolution-precipitation technique. The dried polymer was
'Correspondence to: P. C. Deb, Naval Materials Research Labora- dissolved in l(N) aq. NaOH solution and heated to about
tory, Shil-Badlapur Road, MIDC Area, Add!. Ambernath,
Ambernath (E)- 421506, India. 70°C with stirring for 24 hr to ensure conversion of anhydride
E-mail: pramil_cd@yahoo.co.in to acid. The product was precipitated in cone. HCI and

Copyright r 2005 John Wiley & Sons, Ltd.

682 P. C. Deb et at,
repeatedly washed with water to free from adhering salt and
acid. The styrene-maleic acid copolymer was then dried at
60°C under reduced pressure to constant weight. Acid con-
tent of the copolymer was obtained from back titration in
standard alkali solution.
Styrene-maleic acid crosslinked copolymer beads were
prepared as described earlier.r" The beads obtained were of
the size 200-800 urn. A batch of 400 ± 25 urn spherical beads
was obtained by sieving and used for further work. The beads
were hydrolyzed by refluxing with aq. l(N) NaOH solution
for 4hr, washed several times with water and finally
soxhletted with water to remove adhering alkali. The Na-
form of styrene-maleic acid copolymer beads so obtained
was used for acid content by subsequent acidification and
titration. The crosslinked beads had an acid equivalent of
340.
Soluble metal-copolyacid complex
For Cu+2-complex, stoichiometric amounts of copolyacid
and CuCh, 2H20 in ethanol were mixed slowly under
constant stirring. The mixture was left overnight at 50°C
when the color changed from green to deep bluish-green.
The solution was subsequently diluted with methyl
ethyl ketone when the bluish-green powder separated out.
The solid was washed repeatedly with water until free from
u
chloride and finally dried at 60 C under reduced pressure to
constant weight. For Ti+4 complex, copolyacid was dissolved
in dry isopropanol (2 g/100 ml). Stoichiometric amount of
Ti-isopropoxide in isopropanol was slowly added to the
polymer solution with constant stirring. After 20 min
the reaction mixture was slowly warmed to about 50°C
when the entire mixture turned into a transparent gel in
about 5 min. The gel was left at 50°C for about 2 hr and then
broken and dispersed in methyl ethyl ketone. Vigorous
stirring was required to precipitate the polymer formed
which was then repeatedly washed with methyl ethyl ketone
and finally with acetone. The product in the form of a
light powder was dried at 60°C under reduced pressure to
constant weight.
Metal-copolyacid beads
Appropriate quantity of the copolymer beads (Na-form) was
suspended in stoichiometric amounts of ethanol solution of
metal chlorides and evacuated at 10-2 atm pressure for
30 min to expel entrapped air from the beads. The mixtures
were then warmed to 50 C with constant but slow stirring.
In case of colored solutions such as those of Cu+2, Co+2,
Fe+3,Ni+2 and Pt+4, the progress of reaction was visually
monitored by the decrease in intensity of the color of
solutions and simultaneous change of color of the beads. In
the case of Ti f-4, the beads were suspended in isopropanol,
evacuated and requisite amount of Ti-isopropoxide in isopro-
panol was slowly added and stirred at 50°e. The reaction
with Ti-isopropoxide was carried out for about 2 hr.
All the reacted beads were washed with ethanol, water
and subsequently soxhletted with water for 24 hr allowing
8-10 cycles, to ensure removal of sodium chloride formed
as byproduct. The beads were finally washed with acetone
and dried at 60'C under reduced pressure to constant
weight.
Copyright r 2005 John Wiley & Sons, Ltd.
Vapor/gas absorption and retention
Definite weights of the beads were exposed to vapors of
methyl isobutyl ketone (MIBK), ethanol and toluene in desic-
cators for 24 hr to equilibrate. The containers were wiped dry
with absorbent papers and placed in a microbalance to moni-
tor weight loss as a function of time at 30 C in air.
Hydrogen adsorption studies were carried out in a
Sorptomatic 1990 of Thermo Finnigan, Italy. The instrument
records the fall in pressure of gases over an adsorbing surface
as a function of pressure and automatically converts the
same into amount adsorbed. About 1 g of the beads was
evacuated 00-6 torr) at 70"C for 12 hr in the glass sample
holder (previously calibrated) to ensure cleanliness of the
surface and availability of clean pores for adsorption.
Hydrogen gas was then introduced at 80 torr pressure and
allowed to attain equilibrium. A maximum deviation of
0.08 torr from the mean pressure was considered as an
indication of attainment of equilibrium. The fall in pressure
due to adsorption was automatically monitored. Gas is
further fed in and gas adsorption was measured as a function
of pressure. A typical measurement for a sample was
continued for about 24 hr.
Characterization
Infrared spectra of styrene-maleic acid copolymer and
complexes were taken in KBr using a FT-IR instrument
(Perkin-Elmer, 1650) and scanning electron micrographs
were taken in LEO 1455. Complex formation was studied
with UV-vis spectroscopy (Varian EL 0110 4642).
RESULTS AND DISCUSSION
Styrene-maleic acid copolymers had an acid equivalent of
150 ± 5 indicating slightly higher styrene content than true
alternating copolymer. IR spectra of the copolyacid, com-
plexed powder and beads are shown in Fig. 1. The stretching
vibration of the carboxylic acid group appears at about
1725 em -1 for the acid whereas tha t for the carboxylate anion
of the metal complexes 17 emerged at 1550-1600 ern 1 both for
the linear as well as crosslinked polymers. Intensity reduc-
tion of the carboxylate peak at 1725 em -I is indica tive of con-
sumption of acid and confirms the formation of metal
carboxy la tes.
The formation of a complex between the copolyacid and
CuCl2, 2H20 was also studied in ethyl alcohol by UV-vis
spectroscopy. The copolymer acid and CuCIz solutions in
ethanol have absorption maxima at 259 and 284 nm respec-
tively while the absorption maximum for Cu-poly(styrene-
maleic acid) appears at 288 nm. However, unique coordina-
tion number could not be iden tified as the absorption maxima
appeared almost the same for compositions containing less
than 1:3 of metal! solidus ligand ratio. This is expected
because in metal-copolyacid complexes intra and inter
coordination bindings are possible by near and distant
neighbors due to the flexible nature of the chains. This is
in contrast to clearly identifiable values reported by
Kavlak et al.16
Suspension polymerization of styrene-maleic anhydride
monomer pair along with divinylbenzene to obtain porous
crosslinked beads was successfully carried out earlier.:" In
PoIYIIl. Adv. Technoi. 2005; 16: 681-687

100.0
90
80
70
60
50
%T
40
30
20
10
O.O+- -.
4000.0 3000
Figure 1. IR spectra of: (a) copoly[styrene-maleic
(c) Ti-copolyacid complex.
the present work, the copolymerization recipe and tempera-
ture were adjusted to get beads of about 400 urn diameter.
Fairly uniform sized beads could be obtained with an acid
equivalent of 340 indicating higher styrene content in the
copolymer that may be due to dissolution of some maleic
anhydride in water and the presence of a substantial amount
of crosslinker in the copolymer beads. Rupture of beads was
not observed during hydrolysis to maleic acid. However,
micro-cracks and surface roughness were observed after
complexation as revealed in Scanning electron microscopy
(SEM) studies. The progress and extent of metal uptake by
the copolyacid could be followed visually as well as by
estimation of metal in the reaction mixture periodically. It
was observed that about 95% of metal uptake (corresponding
to simple carboxylate formation) was complete in 24 hr at
50°C. Further reaction was very slow probably due to
hindrance to entry of metal ions into the interior of the beads
due to network formation in the pores of the beads by the
metal carboxylates. Gravimetric estimation showed that in all
cases the extent of reaction was about 95%. Only in the case of
Pt+4 and its mixture the gravimetric yield was about 60-70%.
The progress of reaction was also evident from the formation
of sodium chloride in the proximity of the complex cluster as
was revealed in preliminary SEM studies. EDAX showed 1:1
ratio of Na and Cl in the cluster pockets, which could be
removed completely by extensive soxhletting. In all the
experiments it has been assumed that the carboxylic acid
group is bi-dentate in the Na-forrn, hydrogen bonding and
other associations can be considered absent and the mildly-
alkaline nature of the Na-carboxylate should not hinder this
ability of the carboxylate group?2 Metal carboxylate com-
plexes have characteristic color of the metal ions, e.g. Cu-
complexed beads are greenish-blue, Fe-complex brick-red,
Co-complex pink, Ni-complex pale green, Ti-complex white.
Pt-complex was made in aqueous alcoholic solution using
chloroplatinic acid and the resulting beads were light yellow
in color. In addition, mixed metal complexes were also made
for Fe-Ti, Ni-Ti, and Pt-Ni combinations. In such cases, half of
Copyright © 2005 John Wiley & Sons, Ltd.
Transition metal complexes 683
-r -, .- ~
2000 1500 1000 450.0
em-I
acid], (b) Cu-copolyacid complex,
the carboxylic groups were first reacted with the less reactive
metal chloride. The partial complexes so formed were
purified as already described and dried before further
complexation with the second metal ion. In the case of metal
complexes, the apparent fastness of reaction was in the order
Ti+4 > Fe+3 > Cu+2 > Co+2 > Ni+2 > Pt+2 This difference in
reactivity of inorganic species and enrichment using both the
soluble (linear) and crosslinked form of styrene-maleic acid
copolymer can be used23 in the liquid-phase polymer
retention technique (LPR) and metal recovery by insoluble
polymer network. The present study is, however, limited to
adsorption of vapors/ gas and the extent of their retention by
the metal-polymer complex beads.
Scanning electron micrographs of a few of the complexes
are shown in Fig. 2. Fairly uniform distributions of metal
complex clusters of size ranging from 0.2-2 urn are clearly
seen. Metal content in these clusters vary over a wide margin.
Compared to calculated amount of about 5-10% of metal
when uniformly distributed in the polymer beads through
complexation, percentage content vary from 5-20% in the
clusters as revealed through energy dispersire X-ray analysis
(EDX). Since the polymer is not truly alternating local areas
exist where carboxyl content is less than theoretical. Higher
metal content in many locations thus indicate possible
framework formation where an individual functional group
is associated with more than one metal ion through primary
bond formation and coordination. This is facilitated also
possibly through network formation and the closer proximity
of maleic acid components of segments inbetween crosslinks.
This is particularly true for Ti complexes (where metal
content sometimes reaches 40%) and it appears that Ti404
ring cluster/" cores might be present in the Ti complexes of
styrene-maleic acid copolymer.
Liquid vapor adsorption behavior
In view of apparently uniform distribution of metal complex
clusters throughout the crosslinked polymers, it was consid-
ered interesting to study vapor adsorption and retention
Po{ym. Adv. Technol. 2005; 16: 681-687
684 P. C. Deb et al.

a b

c d

sq,.A-RISD o..:SODM2O(W
PtIOb:I".·~79 UM:16:2t:33

e f
Figure 2. SEM photographs of complexes with styrene-maleic acid copolymer with various transition
metals: (a) Co+2, (b) Cu+2, (c) Fe+3, (d) Ni+2, (e) Pt+4 and (f) Ti+4.

characteristics of these materials. The materials were exposed
separately to saturated vapor of three organic liquids,
namely, toluene, ethanol and MIBK at 30°C in a dessicator
for 24 hr. Desorption behavior was gravimetrically followed
at 1 atmospheric pressure in air. Though this method may
lack stringent accuracy, it gives a fairly good estimate of com-
parative adsorption and retention behavior of the complex
beads. Figure 3 shows the release pattern of MIBK from the
beads. As is evident, Pt-complexed beads give higher absorp-
tion and retention at 30°C and 1 atmosphere pressure. In all
these cases, initial release is sharp for about 10 min. subse-
quent release rate being almost constant. Moreover, the
slopes of most of the plots in the linear region are almost equal
indicating a uniform mechanism. This is most possibly the
free space inside the pores where liquid vapors get entrapped
under saturated vapor pressure of the liquids. Retained sol-
vent molecules after 2 hr at room temperature could only be
those tightly held into the sub-micron molecular pores
formed by complex formation. While uncomplexed polyacid
beads retain about 7% of MIBK, the complexed beads retain
as high as 17% for Co and 26% for Pt. which could be removed
only on prolonged application of vacuum and higher
temperature. Retention and release behavior of the beads
followed the same pattern for toluene and ethanol but the
order of retention was Ti > Ni > Cu > Fe > Pt > UC > Co
and Ti > Fe > Co > Ni > Cu > Pt > UC (UC represents un-
complexed polyacid beads) respectively for the two liquids
as shown in Figs. 4 and 5. It is seen that on complexation

Copyright © 2005 John Wiley & Sons, Ltd. Polym. Adv. Technol . 2005; 16: 681-687
 Transition metal complexes 685
Retention of MERK

50.00

45.00

40.00

35.00

30.00
-+-Raw
.••• Cu

25.00
-trNi
""*,""Co
••••• Fe
20.00
..••. Ti

15.00 -PI
•••• Zn

10 .00

5.00

0.00 +-----------~------------~----------~------------~----------~----------~
20 40 60 80 100 120
Time (min)

Figure 3. MIBK vapor retention behavior of metal-styrene maleic acid copolymer complexes: (a) Co+2,
(b) Cu+2, (c) Zn+2, (d) Ni+2, (e) Fe+3, (f) Pt+4, (g) Ti+4 and (h) raw (uncomplexed polymer).

with metal ions, the extent of vapor uptake and retention
change resulting in an increase in these properties. Polarity
and molecular dimension also play important roles as evi-
dent from the extent of absorption of the three liquids. Except
for Pt-complex/MIBK, adsorption and retention of all the
three vapors were higher in Ti complexes. i-Ti, i-Pt, and
Fe-Ti mixed metal complexed beads were exposed to MIBK
to see the effect of binary metals in complexes on adsorption.
The extent of adsorption and retention pattern were similar to
those obtained for single metal complexes and do not show
any peculiar behavior. In these cases, however, the content
of the second metal in the complex was much lower than

Retention of Toluene

40.00

35.00

30.00

-+-Cu
__ Co
25.00
__ Ni
c:
0
~
.!
-..-Ti
20.00
••
a:
-"-Fe
;!!. -+-Pt
--Raw
15.00
--Zn

10.00

5.00

0.00
0 20 40 60 80 100 120
Time(min)

Figure 4. Toluene vapor retention behavior of metal-styrene maleic acid copolymer complexes:
(a) Co+2 , (b) Cu+2, (c) Zn+2, (d) Ni+2, (e) Fe+3,(f) Pt+4, (g) Ti+4 and (h) raw (uncomplexed polymer).

Copyright c 2005 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2005; 16: 681-687
686 P. C. Deb et al .
45.00

40.00

-+-Cu
___ Co
___ Ni
35.00
___ Fe

30.00 -+-Ti
--PI
--Raw
g 25.00
~ --'-Zn

!
~ 20.00

15.00

10.00

5.00

0.00 +-------,-------~----~----~----___,----~
o 20 40 60 80 100 120
TIme (min)

Figure 5. Ethanol vapor retention behavior of metal-styrene maleic acid copolymer

complexes: (a) Co+2, (b) Cu+2, (c) Zn+2, (d) Ni+2, (e) Fe+3, (f) Pt+4, (g)Ti+4 and (h) raw
(uncomplexed polymer).

expected possibly due to impeded reaction of the second they are present in minor quantities mostly control the
metal in the presence of the random complex already formed. adsorption behavior.
Virtual freezing of active groups allows only restricted All the complexed beads contammg residual vapor
approach of the second metal ion to the reactive sites. Preli- (6-25%) after room temperature desorption studies at
minary adsorption studies of mixed metal complexes show ambient pressure were heated to 75°C at 10-3 torr for 3 hr.
that metals having higher adsorption capacity even though They still retained 3-6% of the vapor indicating either

20

18

16

14 -+-(a)
E ___ (b)
~ 12
E
.£.
al
.0
10 ~(C)
5
III
-g 8 --(d)
~
6

0"__
o 100 200 300 400 500 600 700
p/pO

Figure 6. Hydrogen adsorption isotherms of metal-styrene maleic acid copolymer complexes:

(a) Fe+3 , (b) Co+2, (c) Ti+4 and (d) uncomplexed polymer.

Copyright r: 2005 John Wiley & Sons, Ltd. PofylIl. Adv. Technof. 2005; 16: 681-687

chemical transformation or tight entrapment inside
molecular pores.
Hydrogen adsorption
Metal organic frameworks are considered a class of promis-
ing materials for hydrogen adsorption. The present materials
are expected to form molecular networks that may entrap and
retain hydrogen under normal/higher pressure and tem-
perature. There have been limited studies on the role of poly-
mer25-27 for hydrogen adsorption and the results have
remained inconclusive. Studies on "Polymer dispersed metal
hydrides" (PDMH) involving select polymers such as polya-
niline, polytetrafluoroethylene, polyamide polyetherether-
ketone etc. have shown negligible hydrogen adsorption in
the absence of metal hydrides.P Polyphenylene dendrites
are characterized by rigidity in amorphous systems that
result in formation of micro pores and cavities.i" It is also
reported that enhanced adsorption of hydrogen through
conducting polymers and suitable doping27 However, these
studies are preliminary and results are not fully established.
The instrument Sorptomatic 1900, which allows accurate
measurements up to 900 torr, has been used in this study.
Figure 6 shows adsorption behavior of a few metal complexes
along with that of uncomplexed beads in acid form. In all
cases it was observed that the first positive adsorption starts
at about 300 torr for most samples. Thereafter adsorption
increases slowly with increasing pressure till 550-600 torr. At
this point, there is a sharp increase in adsorption with very
little increase in loading pressure. These beads seem to
adsorb through pores of varying dimensions. It appears that
once the larger pores are filled up, the pressure developed
leads to opening up of smaller and smaller pores connected to
the larger ones. This multi-step filling up possibility seems to
be unique for these type of materials. This is also indicated by
the fact that in most cases adsorption continued even after
24-48 hr and no final value for extent of adsorption could be
ascertained. Adsorption studies at liquid nitrogen tempera-
ture could not be successfully carried out in view of
brittleness at very low temperature (glass transition tem-
perature, Tg- of the parent copolymer is about 125°C, which is
expected to be further increased by crosslinking, hydrolysis
and complex formation). Studies of adsorption at higher
pressures may reveal interesting properties of metal-copoly-
mer complexes and their utility as adsorbing materials.
CONCLUSION
Transition metal complexes of maleic acid component of lin-
ear and crosslinked styrene-maleic acid copolymers were
prepared in ethyl alcohol under mild reaction conditions.
SEM pictures show metal complex clusters fairly uniformly
Copyright © 2005 John Wiley & Sons, Ltd.
Transition metal complexes 687
the distributed in the polymer beads with local concentrations
of metal higher than stoichiometric amounts. Vapor adsorp-
tion for MIBK, toluene and ethyl alcohol showed good
adsorption and retention characteristics. Hydrogen adsorp-
tion isotherms show slow adsorption followed by a rapid
one at about 300 torr. Saturation levels could not be achieved
even in 48 hr.
Acknowledgments
The authors thank Dr J. Narayanadas, Director, Naval Mate-
rials Research Laboratory for his keen interest and support.
Thanks are also due to Mrs L. Chandrasekkhar and Mrs S.
Sontakke for experimental assistance.
REFERENCES
1. Michalska ZM, Strzelec K, Sobczak JW. J. Mol. Catal. A
(Chem.) 2000; 156: 91.
2. Tsuchida E, Nishida H. Adv. Polym. Sci. 1997; 24: 1-87.
3. Breslow R, Belvedere S, Gershell L, Leung D. Pure Appl.
Chem. 2000; 72: 333.
4. Rivas BL, Seguel GV. Polyhedron 1999; 18: 2511.
5. Reedijk J. Polymer-metal complexes in living systems. In
Macromolecules-Metal Complexes, Ciardelli F, Tsuchida E,
Wohrle 0 (eds). Springer: Berlin, 1996.
6. Eddaoudi M, Moler DB, Li H, Chen B, Reineke TM, O'Keefe
M, Yaghi OM. Acc. Chem. Res. 2001; 34: 319.
7. Li H, EddaoudiM, O'Keeffe M, Yaghi OM. Nature 1999; 402:
276.
8. Eddaoudi M, Li H, Yaghi OM. J. Am. Chern. Sac. 2000; 122:
1391.
9. Rosi N, Eckert J, Eddaoudi M, Vodak 0, Kim J, O'Keefe M,
Yaghi OM. Science 2003; 300: 1127.
10. Li H, Eddaoudi M, Groy TL, Yaghi OM. J. Am. Chem. Soc.
1998; 120: 8571.
11. James SL. Chem. Soc. Rev. 2003; 32: 273.
12. Rivas BL, Pereira ED, Moreno-Villoslada I. Prog. Polym. Sci.
2003; 28: 173.
13. Kuriki K, Koike Y, Okamoto Y. Chem. Rev. 2002; 102: 2347.
14. Kido J, Okamoto Y. Chern. Rev. 2002; 102: 2357.
15. Kavlak S, Kaplan Can H, Guner A, Rzaev Z. J. Appl. Polym.
Sci. 2003; 90: 1708.
16. Kavlak S, Kaplan Can H, Guner A. J. Appl. Polym. Sci. 2004;
92: 2698.
17. Michinobu T, Sasao N, Nishide H. J. Polym. Sci. A 2004; 42:
1912.
18. Tsuchida E, Tomono T. Makromol. Chern. 1971; 141: 265.
19. Tsuchida E, Tomono T, Sano H. Makromol, Chem. 1972; 151:
245.
20. Deb PC, Meyerhoff G. Polymer 1985; 26: 629.
21. Mathew A, Deb rc. J. Polym. Sci. A 1996; 34: 1605.
22. Spivakov BYa, Geckeler K, Bayer E. Nature 1985; 315:
313.
23. Rivas BL, Moreno-Villoslada 1. Chem. Lett. 2000; 166.
24. Fester A, Bensch W, Tromel M. Inorg. Chim, Acta 1992; 193:
99.
25. Schmidt WR. Proc DOE Hydrogen Program Review,
Baltimore, MD, April 17-19, 2001.
26. egri F et al. J. Camp. Methods Sci. Eng. 2002; 2: 441.
27. Polymers pack in the hydrogen. Science NOW August, 23,
2002.
PoIYIII. Adv. Technol . 2005; 16: 681-687