TSINGHUA SCIENCE AND TECHNOLOGY

nSSN 1007-0214 12/24 pp172 - 175

Volume 5, Number 2, June 2000

Crosslinking of PVA Pervaporation Membrane by Maleic Acid *

MENG Pingrui (ifu:+~), CHEN Cuixian (~*-¥{L1J) ,YU Lixin (*"iL~ff),

LI Jiding (*~I*5E), JIANG Weijun (~~t$)])

Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Abstract Maleic acid (MA) crosslinked polyvinyl alcohol (PVA) membrane is prepared using a high
temperature esterification reaction between PVA and MA in the presence of sulfuric acid as a catalyst. The
crosslinking reaction mechanism is investigated using FT -IR spectral analysis. The results indicate that maleic
acid reacts with hydroxyl groups in PVA to form mono- and bis-ester in a two-step process.

Key words pervaporation; polyvinyl alcohol (PVA); maleic acid (MA); crosslinking mechanism; Fourier
transform-Infrared (FT -IR) spectrometry

conventional extraction dis tillation process [5J •

Introduction Priority in pervaporation research has been
There has been much progress in the research given to the development of polymer membranes
and development of membranes and their uses in with high selectivity, acceptable flux, and good
pervaporation processes for the separation of stability and/or durability. For example, the
varIOUS organic liquid mixtures and for the dehydration of highly-concentrated ethanol
dehydration of organic mixtures. Currently, much solutions above 95 % (mass fraction) needs a
a ttention is still being paid to pervaporation , membrane which preferentially allows the passage
because, as an energy saving separation method, it of water. The pioneer pervaporation membrane
might partly replace traditional distillation of used in ethanol-water separation was the GFT
aqueous alcohol solutions and azeotropic membrane, which was developed by GFT
rnixt uresl v':'. In addition, it has the advantage of (Germany) at the beginning of the 1980s. It is a
simplifying the process design and avoiding the composite membrane with a polyvinyl alcohol
pollution of products caused by the substances (PVA) active layer coated on a polyacrylonitrile
used in distillation processes to break up azeotropic (PAN) ultrafiltration membrane.
mixtures. Huang and Y eom [6J reported the effect of the
Sander investigated a pilot plant combining concentration of a cross-linking agent (arnic acid)
pervaporation and extraction dis tillation , and on the PVA membrane performance. Nobrega et
reported that the operating cost of the hybrid al. [7] investigated the effect of chemical and
process was 1/3 to 1/4 less than that of a thermal treatment on the PVA membrane
performance. Spitzen et al. [8,9J reported on the
Received: 1998-09-14; revised: 1999-06-11
water permselectivity of PVA/PAN membranes
* Supported by a Ninth-Five-Year National Project (No.
used in pervaporation processes. All the results of
96-A13-01-06) and the National Natural Science
Foundation of China (No. 29231620-02) these investigations show that after crosslinking
* * To whyjl::9frHndence should be addressed the water permselectivity and durability of a PVA
membrane can be remarkably improved.
 MENG Pingrui (~3f~) et al . Crosslinking oj PYA Pervaporation Membrane by Maleic Acid 173

This paper describes the preparation of a (provided with the instrument). C=O group's
1
maleic acid (MA) crosslinked PVA membrane IR spectra (vc=o 1750 - 1700 cm- ) were fit with
through an esterification reaction between PVA the Calactic Peaksolve curve fitting program (also
and MA in the presence of sulfuric acid as catalyst, provided with the ins trumen t ),
investigates the reaction mechanism using Fourier
transform-infrared (FT- IR) spectrometry, and
2 Results and Discussion
correla tes the crosslinking structure with the
2. 1 Hot water durability of PVA-MA membranes
membrane's pervaporation properties.
The water durability of various PVA-MA and
1 Experimental PVA homogeneous membranes are shown In
Table 1.
1. 1 Preparation of PVA-MA membranes
Table 1 Water durability of various PVA-MA
PVA aqueous solution is first prepared by and PV A homogeneous membranes
dissolving PVA in hot water in a flask. Maleic acid theoretical crosslinking hot water durability at 100°C
and sulfuric acid are added to an 8 % PVA aqueous degree of PYA by MA( %)

solution which is stirred to obtain a homogeneous o (not crosslinked) completely dissolved

solution. The amount of maleic acid corresponds to
a desired theoretical degree of crosslinking in the
PVA membrane. After the air bubbles
removed from the solution, the solution is spread
on a glass plate. After the water evaporates,
membranes are obtained with a thickness of about
60 p.m. The membrane is then heated in an oven at
a specified temperature for a certain period of time
for the esterification reaction to take place to form
the desired crosslinking structure. Cooling
produces the final PVA membranes crosslinked by
maleic acid. These PVA membranes are tested for
water durability and analyzed using FT-IR analysis
to determine the reaction mechanism.
Spreading the PVA solution containing maleic
acid and sulfuric acid on a PAN microporous
support membrane instead of on a glass plate
serious wrinkles appear
almost unchanged with a slight
decrease of transparency
are 10 almost unchanged with a slight
decrease of transparency
The results in Table 1 show that the water
durability of crosslinked PVA membranes is much
improved. This is mainly due to the crosslinking of
PVA. The decrease of hydrophilic hydroxyl groups
might also have some effect.
2. 2 Pervaporation experiment
Composite membranes with a PVA active
layer crosslinked by maleic acid were tested in a
pervaporation unit for the dehydration of ethanol.
The concentration of the feed ethanol was 95 %
(mass fraction). The operating temperature was
70 e . The experiment data are listed in Table 2.
o

produces a composite membrane with a thin PVA
active layer. The PVA thickness is several microns
(3 - 4 p.m in general). This type of composite
membrane was tested in a pervaporation unit to
determine the separation factor and flux data.
For comparison, the separation factor and the flux
of the uncross linked membranes are Q' = 300 - 400
and J (flux) = 300 - 400 g/ (m 2 • h).
Table 2 Pervaporation data of MA crosslinked
PV Alp AN composite membranes

1. 2 F1L-][R spectral analysis theoretical crosslinking cros linking flux separation

crosslinking temperature reaction time J factor
FT-IR spectral analysis can be used to obtain degree (%) caC) (h) (g/ (m 2 • h)) a

the structural information of polymcr s-l'". PYA 1 100 2 135 688

1 120 1 88 344
and PVA-MA homogeneous membranes were
1 140 o. 5 321 116
tested using an FT- IR spectroscope (Model Fis 5 110 1.5 61 478
165, Rio-Rad Co. , USA) with an analysis range 5 120 1 98 191
of 500 - 4000 cm- 1 , a resolving power of 4 cm- 1 5 140 o. 5 197 306
10 110 1.5 55 205
and a scanAl~jmf 16. Second derivative spectra 10 120 1 59 236
were obtained usmg the OMNIC program 10 140 o. 5 158 49
 174 Tsinghua Science and Technology, June 2000, 5 (2): 172 - 175

unreacted maleic acid. The absorption at

2. 3 F1L-][R analysis results 1
1712.29 cm- is caused by C=O groups in the
The FT-IR spectra of PVA-MA and PYA are bis-ester product. The absorption at 1703. 08 cm- 1
shown in Fig. 1. For PVA-MA membranes, the is caused by C=O groups in the mono-ester
v c=o stretching vibration absorption can be product[1l-13] .
observed at 1750 - 1700 cm- 1, which indicates the
existence of C=O groups in the membranes, but
the crosslinking structure can not be fully
identified from the single peak.

Fig. 2 Absorption of three different

types of C=O groups
(cross linking conditions: 100°C, 2 h , theoretical
crosslinking degree of 10%)
1750 1700 1650 1600
wave number tcm'")
Table 3 gives some results of the percentage
of different types of C=O groups in maleic acid
crosslinked PV A membranes at different cross-
Fig. 1 infrared spectra of PV A membranes crosslinked linking conditions. The percentage distribution
by MA at different crosslinking degrees shows that:
(a, PVA; b , 1 % crosslinked; c , 5 %; d , 10%) (1) crosslinking reaction takes place to form
PV A and maleic acid can react to form either the desired crosslinking s tructure which leads to
mono-esters or bis-esters as shown below[ll]: good durability in hot water;
(2) crosslinking reaction takes place in a two-
-CH-CHz-CH-CH z- + CH-COOH
step sequence with mono-ester as an intermediate
I I I
OH OH CH-COOH product;
D (3) crosslinking reaction is a slow reaction.
-~ -CH-CHz-CH-CH z-
Unlike the ordinary reversible esterification
I I
o 0 reaction in the liquid phase, the esterification here
I I can be regarded as irreversible due to the prompt
C=O C=O removal of the water produced.
I I Theoretically, increasing the crosslinking
CH CH
I I degree will reduce the flux of the PV A membranes
CH CH because of the increased resistance imposed on the
I I water and ethanol as they pass through the
COOH C=O
membrane while the separation factor will increase
I
OH 0 because the ethanol is a larger molecule. But if not
I I all the maleic acid reacts to bis-ester structure, the
-CH-CHz-CH-CH z- unreacted maleic acid and the mono-ester structure
in the membrane might lead to other tendencies in
The C=O groups that cause the absorption
the variation of the flux and separation factor
at 1750 - 1700 ern -1 can come from either the
mono-ester, the bis-ester and the unreacted maleic which complicates the analysis of the pervaporation
acid. However, the single peak can be clearly split data in Table 2. Interestification reaction which
into three peaks using second derivative spectra consumes hydroxyl groups in the same PV A chain
analysis (see Fig. 2 ). The a bsorption at might also take place, leading to a more
1722. 34 cW--ni~)[~sed by C=O groups in the complicated situation In explaining the
carboxyl groups of the mono-ester product and the pervaporation data.
 MENG Pingrui (~3f~) et al . Crosslinking oj PYA Pervaporation Membrane by Maleic Acid 175

Table 3 influence of reaction conditions on crosslinking

crosslinking conditions theoretical (v c=o peak area percentage (%)
crosslinking
time (h) temperature (OC) degree (%) 1722. 34 cm- 1 1712.29cm- 1 1703. 08 cm- 1

2 100 1 5. 94 92. 21 1. 85
2 100 5 20. 21 75. 78 4.01
2 100 10 16.68 66. 75 16.57
1 120 10 30. 38 58.05 11. 57
o. 5 140 10 26. 23 54. 23 19.54

[7J Nobrega R, Harbert A C, Garcia M E F, et al.

3 Conclusions Separation of ethanol water mixtures by
pervaporation through polyvinyl alcohol (PVA)
Maleic acid crosslinked homogeneous PVA
membranes [A]. Bakish R, ed. Proceedings of the
membranes and PV AlP AN composite membranes
3rd International Conference on Pervaporation
were produced. The FT- IR analysis of the Processes in the Chemical Industry[C]. Englewood,
homogeneous membranes indicates that the Bakish Materials Corp, NJ, 1988. 326.
crosslinking reaction mechanism is a two-step [8J Spitzen J W F, Elsinghorst E, Mulder M H V, et al.
esterification sequence. The pervaporation data Solution-diffusion aspects In the separation of
from the composite membranes were then analyzed ethanol/water mixtures with PYA membranes[A].
using FT- IR analysis but the data could not be Bakish R, ed. Proceedings of the 2nd International
Conference on Pervaporation Processes In the
clearly interpreted because of the many factors
Chemical Industry[C]. Englewood, Bakish Materials
which affect the process.
Corp, NJ, 1987. 209.
[9J Spitzen J W F, Koops G H, Mulder M H V, et al.
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