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Preparation and Properties of Water-Soluble PAA-PAS/SiO
2
Hybrid
Materials
Kuo-Shien Huang
a
; Chiu Chun Lai
b
; Zong-Sian Lee
a
;Chien-Chung Hong
a
a
Department of Polymer Materials, Kun Shan University, Yung Kang, Tainan, Taiwan
b
Department of
Textile Engineering, Chinese Culture University, Taipei, Taiwan
Online publication date: 13 April 2010
To cite this Article Huang, Kuo-Shien , Lai, Chiu Chun , Lee, Zong-Sian andHong, Chien-Chung(2010) 'Preparation and
Properties of Water-Soluble PAA-PAS/SiO
2
Hybrid Materials', Polymer-Plastics Technology and Engineering, 49: 5, 462
466
To link to this Article: DOI: 10.1080/03602550903532182
URL: http://dx.doi.org/10.1080/03602550903532182
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Preparation and Properties of Water-Soluble PAAPAS/SiO
2
Hybrid Materials
Kuo-Shien Huang
1
, Chiu Chun Lai
2
, Zong-Sian Lee
1
, and Chien-Chung Hong
1
1
Department of Polymer Materials, Kun Shan University, Yung Kang, Tainan, Taiwan
2
Department of Textile Engineering, Chinese Culture University, Taipei, Taiwan
Copolymers with different weight ratios of AA/PAS (acrylic
acid/poly(DL-aspartic acid)) were synthesized and blended with
sol-gel precursors to prepare water-soluble PAAPAS/SiO
2
inor-
ganic/organic hybrid materials. The PAS polymer or its copolymer
in PAAPAS/SiO
2
formed hydrogen bonds with SiO
2
and the
amorphous structure of the hybrid material varied with the weight
ratio of PAA. The hybrid materials exhibited enhanced thermal
resistance over the copolymer alone. All hybrid materials were
water-soluble and relatively insoluble in organic solvents.
Keywords Copolymerization; FTIR; Hybrid materials; NMR;
Sol-gel
INTRODUCTION
The advancement in materials science, especially at the
nanoscale, exhibits a broad inuence over an array of
scientic disciplines. Nanometer-scale materials boast
many physical and chemical properties different from those
of traditional materials, including higher tensile strength
and resilience
[1,2]
. A composite material consists of two or
more materials; when the dispersive grain diameter of
the two constituents is within the nanometer range
(1100 nm), the material may be referred to as a nanometer
composite material
[3]
.
The sol-gel process has been widely used in the prep-
aration of organic=inorganic hybrid materials. The basic
process involves the hydrolysis of ester compounds or
metal alkoxides in an organic solvent by a catalytic amount
of acid or base. When the resulting precursor sol is evenly
distributed, other elements, or dopants, may be added. The
sol is gradually gelated through a series of cross-linking
polycondensation and agglomeration reactions. Depending
on the nal application, the sol may be cast into a thin lm
prior to complete gelation, or it may be dried and crushed
into a powder
[47]
.
PAS (poly(DL-aspartic acid sodium)) and PAA (poly
(acrylic acid)) are inexpensive, water-soluble, high-
molecular-weight materials. Previous reports have
indicated that PAA mixed with nanometer-scaled
materials, such as ne grains of SiO
2
or TiO
2
, can increase
the strength of the polymer through the formation of an
inorganic network structure, as well as form porous lms
on the polymer surface to enhance water permeability
[89]
.
In addition, PAS is a biodegradable and water-soluble
polypeptide. Therefore, it can be easily applied as a
dispersing agent or raw material in detergents, biomedicine,
and fabric processing applications
[1013]
.
In this study, we examined the synthesis of water-soluble
copolymers through the polymerization of different molar
ratios of AA and PAS. The copolymer was then blended
into a precursor silica sol to make PAAPAS=SiO
2
hybrid
materials. The inuence of polymer and copolymer compo-
sition on the physical properties of the hybrid materials
was thoroughly investigated.
EXPERIMENTAL
Materials
Reagent grade acrylic acid (AA), ammonium peroxydi-
sulfate, hydrochloric acid, tetrahydrofuran, dimethyl
sulfoxide, and ethyl alcohol were supplied by Pharmaceuti-
cal Corporation (Osaka, Japan). PAS (MW3,000) was
obtained from Aldrich (Milwaukee, WI, USA). Isopropyl
alcohol (IPA), tetraethoxysilane (TEOS), and vinyl-
triethoxysilane (VTES) were purchased from ACROS
(Morris Plains, NJ, USA).
METHODS
Preparation of the PAAPAS Copolymer
A solution of AANa was prepared by neutralizing 60 g
of AA with a NaOH solution (2.72 g of NaOH dissolved in
80 g of water), cooling to room temperature, and diluting
1:1 with water. Five grams of PAS, 20 g of AANa, 2 g
of VTES, 0.2 g of glycerin, and 0.3 g of ammonium persul-
fate were placed into a single reaction vessel. Ingredients
were added one by one with the exception of the initiator.
The reaction mixture was stirred, injected with helium for
20 min, and heated to 40

C.
Address correspondence to Kuo-Shien Huang, Department of
Polymer Materials, Kun Shan University, Yung Kang, Tainan,
71003 Taiwan. E-mail: hks45421@ms42.hinet.net
Polymer-Plastics Technology and Engineering, 49: 462466, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0360-2559 print=1525-6111 online
DOI: 10.1080/03602550903532182
462
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At this point, the initiator was added and the polymer-
ization proceeded for 1 h in a nitrogen atmosphere. The
temperature was gradually increased to 70

C, and the poly-

merization process was allowed to continue for another 3 h
to produce the PAAPAS copolymer. The incompletely
reacted oligomer and unreacted monomer were removed
by ethanol extraction over 2 h. The resulting copolymer
was thoroughly dried, resulting in a fragmented solid.
Preparation of the PAAPAS/SiO
2
Complex Sol
TEOS was dissolved in 35 mL of IPA and 3.6 mL of
0.05 N HNO
3
and stirred for 60 min. The aforementioned
copolymer was mixed with the TEOS sol for 3 h at room
temperature, thereby obtaining a mixed sol containing
the water-soluble PAAPAS=SiO
2
complex. The complex
sol was heated at 80

C for 3 h in a vacuum oven to obtain

the hybrid material.
Analysis and Measurement
The molecular weight of the copolymers was measured
by gel permeation chromatography (GPC) in distilled
water at 20

C. The Fourier transform infrared spectro-

scopy=attenuated total reection (FTIR=ATR) spectra of
the samples were recorded with a Digilab FTS-200 spec-
trometer equipped with a mercurycadmiumtelluride
(MCT) detector (Bio-Rad, Hercules, CA, USA). A dia-
mond crystal was used as the internal reection element.
Single beam spectra were the result of 64 scans, and the
spectral resolution was 4 cm
1
.
13
C- and
29
Si-NMR spectra were measured with a
solid-state Avance 400 nuclear magnetic resonance (NMR)
spectrometer (Bruker Instruments, Billerica, MA, USA) at
100 MHz and 80 MHz. Spectra were observed under
cross-polarization with magic angle sample rotation and
power decoupling conditions using a 90

pulse and 4 s cycle

time. X-ray powder diffraction (XRD) data were obtained
on a Bruker-AXS D8 equipped with parallel beam optics,
Cu-target, scintillation counter, and rotating sampler
changer. Samples were run at 40 kV, 100 mA, 260

theta=2theta, with a 0.01

step size and 5 s counting time.

The surface morphology of the lms was evaluated
under a scanning electron microscope (SEM; model
JSM 6400; JEOL, Tokyo, Japan). Samples were coated
with gold to avoid surface charging. Thermal gravimetric
analyses (TGAs) of samples were measured using a
weight-loss analyzer (model 2200; DuPont, Wilmington,
DE, USA). To determine the initial decomposition
temperature (IDT), a 510-mg sample was placed in an
alumina crucible and subjected to a thermal ramp from
30 to 600

C, at a heating rate of 20

C min
1
under a
nitrogen ow speed of 20 cc min
1
. Solubility measure-
ments were conducted by stirring each sample individually
with different solvents such as water, IPA, THF, DMSO,
and ethanol.
RESULTS AND DISCUSSION
Molecular Weight of Copolymers
The molecular weight of each copolymer increased with
the weight percentage of AA, as shown in Table 1. This was
likely due to higher rates of AA homopolymerization and
the subsequent formation of long blocks of poly(AA),
versus the heteropolymerization rate of AA with PAS.
FTIR
Figure 1 shows the FTIR spectra obtained for PAS, the
copolymer, and hybrid PAAPAS=SiO
2
materials. With
the exception of PAS, the other materials exhibited
clear >C
=
O absorption peaks at approximately 1710
1717 cm
1
, which correspond to the presence of AA. All
materials exhibited an absorption peak at 1402 cm
1
due
to CH
2
C=O groups in PAS.
In addition, the copolymer spectra showed signicant
differences in the position of the OH, COONa, and
COOH absorption peaks relative to the corresponding
TABLE 1
Molecular weight of PAA=PAS copolymers
Properties
Materials
1
M
w
M
n
M
w
=M
n
1=4 16,200 12,320 1.315
2=3 21,710 14,600 1.487
2.5=2.5 24,050 15,950 1.508
4=1 32,400 20,070 1.614
1
Copolymers synthesized from different molar ratios of AA=
PAS.
FIG. 1. FTIR spectra of copolymer and hybrid materials ((A) PAS,
weight ratio of PAA=PAS: (B) 2=3 (TEOS 0%), (C) 2=3 (TEOS 2%),
(D) 2=3 (TEOS 6%)).
PROPERTIES OF WATER-SOLUBLE PAA-PAS/SiO
2
HYBRID MATERIALS
463
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peak positions in the hybrid material. The OH absorp-
tion peaks in the copolymer spectra shifted from
3422 cm
1
to 3262 or 3300 cm
1
. The >C=O absorption
peak also shifted to a lower frequency from 1717 cm
1
to
about 1710 or 1700 cm
1
. These shifts suggest that hydro-
gen bonds were formed between the COONa or COOH
groups in the copolymer and SiO
2
groups in the sol-gel
component of the hybrid material.
With increasing weight ratios of PAS, as shown in
Figure 2, the OH absorption peak shifted to between
3000 and 3600 cm
1
. This was likely due to intramolecular
hydrogen bonding. However, as discussed above, signi-
cant hydrogen bonding with the SiO
2
matrix was observed
at higher proportions of PAA. Compared to the OH
absorption peak at between 3000 and 3600 cm
1
in
Figure 2B or 2C, the >C
=
O absorption at 1710 cm
1
in
Figure 2D is not easily recognized.
NMR
13
C-NMR spectra, obtained from all hybrid materials
described herein, are presented in Figure 3. With increasing
levels of PAS, the peak at 120130 ppm became more
apparent, corresponding to the ring structure formed by
intramolecular hydrogen bonding in PAS. Conversely, with
increasing proportions of PAA, the CO peak at approxi-
mately 6065 ppm increased in intensity. The addition of
TEOS had little inuence on the >C
=
O peak in hybrid
materials. This implies that with the addition of 2% TEOS,
the hydrogen-bonding capacity of the resulting SiO
2
was
saturated by interactions with the copolymer.
29
Si-NMR spectra of copolymer and hybrid materials
are shown in Figure 4. The peak corresponding to
SiOSi bonds in VTES shifted from 72.02 to
80ppm in Figure 4A, to between 61.33 and 77.76 ppm
in Figure 4B, and further to between 77.53 and
FIG. 2. FTIR spectra of hybrid materials (weight ratio of AA=PAS:
(A) 1=4, (B) 2=3, (C) 2.5=2.5, (D) 4=1).
FIG. 3.
13
C-NMR spectra of hybrid materials (weight ratio of AA=PAS:
(A) 1=4 (2% TEOS), (B) 2.5=2.5 (2% TEOS), (C) 4=1 (2% TEOS), (D)
2.5=2.5 (6% TEOS)).
FIG. 4.
29
Si-NMR spectra of copolymer and hybrid materials (weight
ratio of AA=PAS: (A) 2=3 (0% TEOS), (B) 2=3 (2% TEOS), (C) 2=3
(6% TEOS)).
FIG. 5. X-ray diffraction data of copolymer and hybrid materials ((A)
PAS, weight ratio of AA=PAS: (B) 1=4, (C) 2.5=2.5, (D) 4=1, (E)
2.5=2.5 (hybrid materials, 2% TEOS)).
464 K.-S. HUANG ET AL.
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81.73 ppm in Figure 4C. Secondly, all there is the absorp-
tion Feng of Q
4
(112 ppm) in Figure 4B and 4C, this pre-
sents in the hydrolytic process for TEOS of special absorb
peak. These results suggest that the addition of more TEOS
leads to a reduction in the Si content in VTES as a result of
hydrogen bonding between TEOS and the copolymer.
XRD and SEM
XRD data acquired on several different copolymers and
hybrid materials are shown in Figure 5. With the exception
of PAS, a diffraction peak was observed at 2h 9

, corre-
sponding to PAA. With increasing proportions of PAA,
the diffraction peak at 2h 20

became more apparent.

The addition of TEOS to produce the hybrid material
resulted in diffraction peaks at 31

, 34

, and 38

, corre-
sponding to diffraction from SiO
2
generated during the
sol-gel process. The little changes in the XRD data with
increasing proportions of AA indicate that the composition
of the copolymer, in addition to the presence of TEOS, was
not inuenced the amorphous of the hybrid materials.
SEM images of the hybrid materials are shown in
Figure 6. The surface morphology varied with TEOS con-
centration, with the surface of the copolymer alone being
nearly smooth. With the addition of 2% TEOS, miniscule
grains of SiO
2
appeared on the surface. At 6% TEOS, the
grains became more compact and showed evidence of con-
densation due to increased SiO
2
content and increasing
hydrophilicity of the hybrid material. The possibility exists
that water, released as a product of polymerization and
sol-gel condensation reactions, may not have been com-
pletely removed during drying.
TGA
Table 2 shows the thermal decomposition data obtained
on each copolymer and hybrid material. In the table, A
refers to the PAAPAS copolymer, B corresponds to the
FIG. 6. SEM images of hybrid materials (TEOS concentration: (A) 0%, (B) 2%, (C) 6%). Weight ratio of AA=PAS is 2=3.
TABLE 2
Thermal properties of copolymer and hybrid materials
Properties
Samples T
10
1
(

C) First Td (

C) Second Td (

C) Chard yield
2
(%)
PAA-PAS (A) 206 295 382 46.9
PAA-PAS-VTES (B) 212 320 397 51.2
PAA-PAS-VTES=SiO
2
(C) 252 331 410 52.3
1
Temperature of lost 10% weight.
2
Heated to 600

C.
PROPERTIES OF WATER-SOLUBLE PAA-PAS/SiO
2
HYBRID MATERIALS
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PAAPASVTES copolymer, and C refers to the PAA
PASVTES=SiO
2
hybrid material. Relative to A, a greater
residual mass was obtained with B due to the reaction
between VTES and copolymer, and the incorporation of
Si into the copolymer structure. B also exhibited greater
thermal stability, with higher temperatures at 10% weight
loss (T
10
), rst stage T
d
, and second stage T
d
. This was
likely due to the formation of a silica network structure
in the PAAPASVTES hybrid material. The greatest ther-
mal resistance was observed for C and can be attributed to
the formation of an even larger silica network.
Solubility
Table 3 shows the solubility of PAAPAS=SiO
2
hybrid
materials produced with different weight ratios of AA
Na=PAS and varying amounts of TEOS in different sol-
vents. The PAAPAS=SiO
2
hybrids were soluble in water
but not in organic solvents. This was due primarily to the
water-solubility of PAANa, which is insoluble in
nonpolar-to-polar esters, ethylene glycols, and most
organic solvents, including THF, IPA, and ethyl alco-
hol
[14]
. Despite the tight mesh structure of the extensive
silica network in PAAPAS=SiO
2
hybrids, water-solubility
was maintained on account of the highly water-soluble
PAANa.
CONCLUSIONS
This report describes the preparation and physical
properties of PAAPAS=SiO
2
hybrid materials. FTIR
analyses showed that the PAS polymer or copolymer in
PAAPAS=SiO
2
hybrid materials was subjected to hydro-
gen bonding with SiO
2
. The amorphous structure of the
PAAPAS copolymers were not varied considerably with
increasing weight ratios of PAA. The hybrid materials,
when synthesized with appropriate concentrations of
TEOS, exhibited enhanced thermal resistance over the
copolymer alone. All hybrid materials described herein
were water-soluble and relatively insoluble in organic
solvents.
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Fan, W. Inuence of organophilic clay and preparation methods on
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4. Ro, J.C.; Chung, I.J. Structures and properties of silica gels prepared
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1992, 143, 121132.
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7. Osseo-Asare, K.; Arriagada, J.F. Synthesis of nanosize silica in aero-
sol OT reverse microemulsions. J. Coll. Interf. Sci. 1995, 170, 817.
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11. Huang, K.S.; Nien, Y.H.; Hsiao, K.C.; Chang, Y.S. Application of
DMEU=SiO
2
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fabrics. J. Appl. Polym. Sci. 2006, 102, 41364143.
12. Huang, K.S.; Yang, K.L.; Lin, S.J.; Lian, W.T. Antiwrinkle treatment
of cotton fabric with a mixed sol of TEOS-TTB=DMDHEU. J. Appl.
Polym. Sci. 2007, 106, 25592564.
13. Natallia, M.; Alexander, P.; Llia, V.B. Water-soluble hybrid
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for biological imaging. Biophys. J. 2005, 89, 572580.
14. Shiao, H.R. Applied Chemistry, National Chiao Tung University
Press: Taipei, 2002.
TABLE 3
Solubility of hybrid materials
Weight
ratio of
AA=PAS
Conc.
of TEOS
(%)
Solvents
H
2
O IPA THF DMSO Ethanol
1=4 0
1

2

1
2
4
6
2.5=2.5 0
1
2
4
6
4=1 0
1
2
4
6
1
: soluble;
2
: insoluble.
466 K.-S. HUANG ET AL.
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