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i n t e r n a t i o n a l j o u r n a l o f g r e e n h o u s e g a s c o n t r o l 2 ( 2 0 0 8 ) 4 9 2 – 5 0 1
Crosslinking and stabilization of high fractional freevolume polymers for gas separation
Lei Shao a, Jon Samseth b,c, May-Britt Hagg a,*aDepartment of Chemical Engineering, Faculty of Natural Sciences and Technology, Norwegian University
of Science and Technology, Sem Saelandsvei 4, N-7491 Trondheim, Norwayb SINTEF Materials and Chemistry, N-7465 Trondheim, NorwaycAkershus University College, N-2001 Lillestrøm, Norway
a r t i c l e i n f o
Article history:
Received 12 December 2007
Accepted 1 April 2008
Published on line 20 May 2008
Keywords:
Poly(4-methyl-2-pentyne)
Crosslinking
Membranes
Gas separation
a b s t r a c t
Crosslinkable poly(4-methyl-2-pentyne) (PMP) membranes were cast from carbon tetra-
chloride solutions containing PMP and either 4,40-diazidobenzophenone or 4,40-(hexafluor-
oisopropylidene)diphenyl azide. The composite membranes were transparent and
homogeneous and were crosslinked by UV irradiation at room temperature or thermal
treatment at 180 8C. Low levels of the bis(aryl azide) (1–4.5 wt%) were effective in rendering
the membranes insoluble in cyclohexane and carbon tetrachloride, both are good solvents
for PMP, thus PMP can easily be converted to mechanically stable membranes with perme-
abilities and selectivities comparable or higher than those of the well-known poly(dimethyl-
siloxane) (PDMS). The permeabilities of O2, N2, H2, CH4 and CO2 were measured. Compared to
pure PMP, the crosslinked membranes containing bis(aryl azide) had lower permeabilities
and higher selectivities, consistent with a reduction in free volume.
# 2008 Elsevier Ltd. All rights reserved.
avai lable at www.sc iencedi rec t .com
journal homepage: www.e lsev ier .com/ locate / i jggc
1. Introduction
The use of polymeric materials for membrane gas and vapor
separation has been on the market for more than 25 years, and
the potential use is steadily increasing. High permeability and
high selectivity in favor of the permeating gas as well as good
durability and high mechanical strength of the material are
the important properties for a commercial gas separating
membrane. Poly(4-methyl-2-pentyne) (PMP) is an amorphous,
disubstituted acetylene-based high free volume glassy poly-
mer. It is one of the most permeable purely hydrocarbon-
based polymer known (Morisato and Pinnau, 1996). The high
permeation property and hence also low gas selectivity of PMP,
results from very poor polymer chain packing due to the
stiffness of the polymer chain as can be understood with
reference to its chemical structure (Fig. 1). The unique
* Corresponding author. Tel.: +47 73594033.E-mail address: [email protected] (M.-B. Hagg).
1750-5836/$ – see front matter # 2008 Elsevier Ltd. All rights reservedoi:10.1016/j.ijggc.2008.04.005
permeation property has been documented by several authors
(Merkel et al., 2002, 2003; He et al., 2002; Nagai et al., 2004,
2005). However, it has also been documented that the gas
permeability is not stable over time, and that it is sensitive to
processing history. PMP undergoes significant physical aging,
which is the gradual relaxation of non-equilibrium excess free
volume in glassy polymers (Merkel et al., 2003; Nagai et al.,
2004). For example, nitrogen permeability coefficient in PMP
has been reported to decrease by 25% over a period of 29 days
(Merkel et al., 2003). PMP is also soluble in some organic
compounds, leading to potential dissolution of the membrane
in process streams where its separation properties are of
greatest interest. These phenomena compromise the practical
utility of PMP.
Polymer modification by crosslinking has attracted inter-
est in membrane-based separation of gases or vapors. Today
d.
Fig. 1 – Chemical structure of PMP.
i n t e r n a t i o n a l j o u r n a l o f g r e e n h o u s e g a s c o n t r o l 2 ( 2 0 0 8 ) 4 9 2 – 5 0 1 493
crosslinked poly(dimethylsiloxane) (PDMS) is used commer-
cially as a vapor separation membrane material (Baker, 2004).
Crosslinked polymer films offer obvious advantages as
membranes, particularly in terms of stability. Without
crosslinking the material will tend to swell when exposed
to certain gas mixtures, and hence separation properties are
affected. There is a lot of published literature on crosslinked
membranes for gas and liquid separation (Paul and Yam-
polskii, 1994; Lin et al., 2005; Staudt-Bickel and Koros, 1999;
Staudt-Bickel et al., 2007; Kita et al., 1994; Hsu et al., 1993;
Wright and Paul, 1997; Chung et al., 2004; DeForset, 1975; Liu
et al., 2001), with the most attractive processes being those
initiated thermally or photochemically. Jia and Baker (1998)
reported that crosslinking poly(1-trimethylsilyl-1-propyne)
(PTMSP) with bis(aryl azides) has been shown to increase the
Fig. 2 – Illustration of crossl
chemical and physical stability. Crosslinked PTMSP mem-
branes are insoluble in common PTMSP solvents such as
toluene, and the permeability of the crosslinked membranes
are reported to be constant over time. These results are
very interesting for the current work, as PTMSP and PMP
are both high free volume polymers. All these results
encouraged us to adapt the technique of crosslinking PMP
membranes in order to increase its stability. A plausible
mechanism for the crosslinking reactions is shown in Fig. 2
(Jia and Baker, 1998), under photochemical irradiation or
thermal treatment of the bis(aryl azide) decomposes to
nitrogen gas and reactive nitrenes, the resulting nitrenes
can add to double bonds to form aziridines or insert into
carbon–hydrogen bonds in PMP to form substituted amines.
In the current study, the procedure of crosslinking, char-
acterization and the permeability of crosslinked PMP mem-
branes are described, the implications of these results for the
mechanism of permeability decline in PMP are discussed as
crosslinking inevitably will lead to a reduced gas flux, while
selectivity will increase.
2. Background
2.1. Transport in polymers
The permeation of gases and vapors through a dense
polymeric membrane is generally described as a solution-
diffusion process, and the permeability, P, of a penetrant
molecule through a membrane is the product of its diffusivity,
D, and solubility, S, i.e.
P ¼ DS (1)
inking reaction of PMP.
i n t e r n a t i o n a l j o u r n a l o f g r e e n h o u s e g a s c o n t r o l 2 ( 2 0 0 8 ) 4 9 2 – 5 0 1494
The ability of a membrane to separate two molecules, for
example, A and B, is the ratio of their permeabilities and is
called the membrane ideal selectivity aA/B:
aA=B ¼PA
PB¼ DA
DB
� �SA
SB
� �(2)
where the first term on the right-hand side is the diffusivity
selectivity and the second is the solubility selectivity. The
balance between the solubility selectivity and the diffusivity
selectivity determines whether a membrane material is selec-
tive for molecule A or molecule B in a feed mixture (Toshima,
1992; Stern, 1994; Mulder, 1996).
The temperature dependency of solubility, diffusivity and
permeability may be expressed as the van’t Hoff–Arrhenius
relationships (Toshima, 1992; Stern, 1994; Mulder, 1996):
S ¼ S0 exp�DHS
RT
� �(3)
D ¼ D0 exp�Ed
RT
� �(4)
P ¼ P0 exp�Ep
RT
� �(5)
where S0, D0 and P0 are pre-exponential factors, DHS is the
enthalpy of sorption, Ed is the activation energy of diffusion, Ep
is the activation energy of permeation, R is the ideal gas
constant, and T is the absolute temperature.
The activation energy, Ep, of permeation is the sum of the
activation energy of diffusion, Ed, and the enthalpy of sorption,
DHS:
Ep ¼ Ed þ DHS (6)
2.2. Free volume
Molecular diffusion through a dense polymer depends
strongly on the amount of free volume that a material
possesses. A quantity frequently used to compare the amount
of free volume in polymers is the fractional free volume (FFV),
which is usually estimated according to Bondi’s method:
FFV ¼ V � 1:3VW
V(7)
where V is the polymer specific volume (i.e. reciprocal of
geometric density) and Vw is the specific van der Waals
volume, which can be calculated by group contribution meth-
ods (Ghosal and Freeman, 1994; Bondi, 1968; van Krevelen,
1997). The FFV of PMP is 0.28, which is one of the highest values
of any known polymer.
A number of techniques have been using to study free
volume in polymers, including spin probe methods (Yampolskii
et al., 1999), molecular modelling (Hofmann et al., 2002, 2003),
inverse gas chromatography (Yampolskii et al., 1986), small-
angle X-ray scattering (Roe and Curro, 1983), 129Xe NMR
(Golemme et al., 2003), and positron annihilation lifetime
spectroscopy (PALS) (Kobayashi et al., 1994; Yampolskii et al.,
1993; Consolati et al., 1996). PALS is one of the most widely
applied techniques and provides the most direct and detailed
information on the size and concentration of free volume
elements in the materials.
3. Experimental
3.1. Instrumental characterization
NMR spectra were recorded on Bruker Avance DPX 400
with chemical shifts referenced to tetramethylsilane for
deuteriochloroform. FT-IR spectra were recorded on a Thermo
Nicolet FT-IR Nexus spectrometer. NMR and FT-IR spectra
were used to confirm chemical structure. UV–vis spectra were
recorded on a Varian Cary 50 UV–vis spectrophotometer.
Differential scanning calorimetry (DSC) was done by a Q500
(TA Instruments, New Castle, DE, USA) under a nitrogen
atmosphere at a heating rate of 10 8C/min. DSC measures the
heat flow associated with transitions in the materials as a
function of time and temperature in a controlled atmosphere.
3.2. Sorption measurement
The solubility of gases in uncrosslinked PMP and crosslinked
PMPmembranesweremeasuredwith asorption apparatus. The
experimental method and setup is described elsewhere (Lind-
brathen, 2005; Lindbrathen and Hagg, 2005). After the mem-
brane was loaded into the sample chamber, the sorption system
was evacuated for at least 24 h prior to each test. The sorption
was measured as cm3 (STP) gas adsorbed per cm3 material. The
tests wereperformed at 35 8C with thepressure range of 1–4 bar.
3.3. Polymer synthesis
PMP was synthesized as described in literature (Morisato and
Pinnau, 1996; Khotimsky etal., 2003; Pinnau and Morisato, 1998).
The monomer, 4-methyl-2-pentyne (Lancaster, Inc.) was dried
over calcium hydride for 24 h, and was then distilled in an
atmosphere of high-purity nitrogen. The catalysts, niobium
pentachloride (NbCl5) and triphenyl bismuth (Ph3Bi) (Aldrich
Chemicals) used without further purification. A solution of
0.33 g of NbCl5, and 0.54 g Ph3Bi in 47 mL cyclohexane was
stirred at 80 8C for 10 min under dry nitrogen. Then the
monomer solution of 5 g 4-methyl-2-pentyne in 7 mL cyclohex-
ane was added dropwise to the catalyst solution, and the
mixturewas reacted at80 8C for 4 h.The viscosity of the solution
increased very rapidly. The resulting gel was precipitated in
methanol, filtered to recover the precipitated polymer, and
dried under vacuum. The polymer was dissolved in cyclohex-
ane and reprecipitated twice from methanol to remove excess
monomer, oligomers and catalysts. The polymer yield was 85%.1H and 13C NMR and FT-IR analyses of the polymer confirmed
the chemical structure of PMP (Fig. 1).
3.4. Synthesis of crosslinking agents
The syntheses and structures of bis(aryl azide) crosslinking
agents are shown in Fig. 3. 4,40-Diazidobenzophenone (BAA),
Fig. 3 – Syntheses of 4,40-diazidobenzophenone (BAA) and 4,40-(hexafluoroisopropylidene)diphenyl azide (HFBAA).
Fig. 4 – DSC heating and cooling curves for PMP/3 wt%
HFBAA. The dip in the heating curve corresponds to the
decomposition of HFBAA and the loss of N2. Conditions:
heating and cooling, 10 8C/min under N2 atmosphere.
i n t e r n a t i o n a l j o u r n a l o f g r e e n h o u s e g a s c o n t r o l 2 ( 2 0 0 8 ) 4 9 2 – 5 0 1 495
and 4,40-(hexafluoroisopropylidene)diphenyl azide (HFBAA)
were obtained by diazotization of the corresponding amines
(Aldrich Chemicals) followed by nucleophilic displacement of
the diazonium salt with NaN3. The synthetic procedure
follows that reported in the literature (Ling et al., 1992; Wiley
and Sons, 1973; Hepher and Wagner, 1958; Coe, 1967).
3.4.1. 4,40-Diazidobenzophenone4,40-Diaminobenzophenone (0.50 g, 2 mmol) was dissolved in
2 mL of water containing 1.1 mL of concentrated HC1, and
cooled to 0 8C, then treated dropwise with a solution of sodium
nitrite (0.34 g, 5 mmol) in 1.2 mL of water. After the addition,
the reaction was maintained at 0–5 8C for 1.5 h. To the
resultant clear orange solution was added dropwise 0.31 g
(5 mmol) of sodium azide in 1.2 mL of water. The solution was
stirred for 15 min, as a white precipitate formed. The solid was
collected, washed with water, allowed to dry, dissolved in
dichloromethane, and heated with activated charcoal. Filtra-
tion and solvent evaporation gave 0.51 g (84%) of pale yellow
4,40-diazidobenzophenone. 1H and 13C NMR and FT-IR ana-
lyses of the product confirmed the chemical structure of BAA
(see Fig. 3).
3.4.2. 4,40-(Hexafluoroisopropylidene)diphenyl azide4,40-(Hexafluoroisopropylidene)dianiline (0.70 g, 2 mmol) was
dissolved in 2 mL of water containing 1.1 mL of concentrated
HC1, and cooled to 0 8C, then treated dropwise with a solution
of sodium nitrite (0.34 g, 5 mmol) in 1.2 mL of water. After the
addition, the reaction was maintained at 0–5 8C for 1.5 h. To
the resultant clear solution was added dropwise 0.31 g
(5 mmol) of sodium azide in 1.2 mL of water. The solution
was stirred for 15 min, as a white precipitate formed. The solid
was collected, washed with water, allowed to dry, dissolved in
dichloromethane, and heated with activated charcoal. Filtra-
tion and solvent evaporation gave 0.63 g (82%) of 4,40-
(hexafluoroisopropylidene)diphenyl azide. 1H and 13C NMR
and FT-IR analyses of the product confirmed the chemical
structure of HFBAA (see Fig. 3).
3.5. Membrane preparation and modification
The PMP was dissolved in carbon tetrachloride to form a
1.2 wt% polymer solution, poured into a casting ring placed on
a glass plate and covered with a funnel to allow for slow
solvent evaporation. The membrane was dried at ambient
temperature for 5 days and then placed in a vacuum oven at
room temperature for at least 24 h to remove any residual
solvent. The final as-cast membrane thicknesses varied from
40 to 50 mm. To prepare modified membranes, PMP and a small
amount of the appropriate bis(aryl azide) were codissolved in
carbon tetrachloride, and membranes were then cast from the
solution after filtration.
Crosslinking of the bis(aryl azide) containing membranes
was induced by either UV irradiation at room temperature or
thermal treatment at 180 8C. In both cases, the crosslinking
reactions were performed under an inert atmosphere (see
Fig. 2).
The temperature used to initiate thermal crosslinking,
180 8C, was determined from DSC measurements (Fig. 4) as
the onset of N2 loss from PMP/azide composites (see Fig. 2). The
irradiating wavelength for photochemical crosslinking was set
to correspond to the peak of the absorption band for the azide.
For fluorinated azide HFBAA, the peak of the absorption is near
254 nm while the absorption spectrum of the benzophenone-
based azide BAA is red-shifted, with a peak near 302 nm (Fig. 5).
Thus 254 and 302 nm light was used for crosslinking PMP/
HFBAA and PMP/BAA composite membranes, respectively.
Photochemical crosslinking of membranes with bis(aryl
azide), BAA, was performed at 302 nm for 60 min using a lamp
in a vacuum oven. Photochemical crosslinking of membranes
Fig. 5 – UV–vis spectra of the bis(aryl azide) crosslinking
agents used for crosslinking PMP membranes.
i n t e r n a t i o n a l j o u r n a l o f g r e e n h o u s e g a s c o n t r o l 2 ( 2 0 0 8 ) 4 9 2 – 5 0 1496
with fluorinated bis(aryl azide), HFBAA, was performed at
254 nm using a lamp for 30 min in a vacuum oven. After
photochemical treatment, membranes were slightly curled
toward the side that was exposed to UV light. Thermal
crosslinking of the membranes was achieved by heating flat
membranes in a vacuum oven at 180 8C for 90 min. Thermally
treated membranes remained flat after crosslinking.
3.6. Gas permeability
The membranes were masked using an impermeable alumi-
num tape, leaving open a defined permeation area. Epoxy was
then applied along the interface of the tape and the
membrane. A sintered metal disc covered with a filter paper
was used as support for the membrane in the test cell. Single
gases (O2, N2, H2, CH4 and CO2) were measured at 35 8C
with feed pressure of 2.0 bar using a constant volume/
variable-pressure method in a standard pressure-rise setup
(MKS Baratron1 pressure transducer, 0–134 mbar range)
Fig. 6 – FT-IR spectra of PMP/3 wt% HFBAA composite membra
with LabView1 data logging. The experimental method and
equipment was described elsewhere (O’Brien et al., 1986; Lie,
2005).
The membrane thickness was measured by an electronic
Mitutoyo 2109F thickness gauge (Mitutoyo Corp., Kanagawa,
Japan). The gauge was a non-destructive drop-down type with
a resolution of 1 mm. Flat sheet membrane was scanned at a
scaling of 100% (uncompressed tiff-format) and analyzed by
Scion Image (Scion Corp., MD, USA) software. This image tool
is available from http://www.scioncorp.com/ at no cost. The
effective area was sketched with the draw-by-hand tool both
clockwise and counter-clockwise several times.
4. Results and discussion
The bis(aryl azide)s dissolved easily in PMP to form homo-
geneous mixtures. At high loadings (>4.0 wt% BAA and
>4.5 wt% HFBAA), the membranes became cloudy and optical
microscopy confirmed phase separation of crosslinker and
polymer. All crosslinking studies reported here were per-
formed on clear membranes which showed no apparent signs
of phase separation. The dried membranes were clear, and
UV–vis and FT-IR spectra show that the spectra of the as-
prepared membranes are simply the linear combination of the
spectrum of PMP and that of the azide crosslinker. The
stretching vibration for the azide at 2110 cm�1 is easily
monitored in the FT-IR, and the loss in its intensity can be
correlated with the progress of the crosslinking reaction
(Fig. 6). Double bonds on the PMP backbone and methyl groups
on the side chains are two possible crosslinking sites, but the
latter is more likely since access to the double bonds is
sterically hindered.
A preliminary indication of significant crosslinking is the
lack of solubility of crosslinked membranes in known solvents
for PMP. In this regard, crosslinked PMP was insoluble in
cyclohexane and carbon tetrachloride, which are known to be
nes: (A) as cast, (B) after irradiation and (C) after heating.
Table 1 – Gas permeabilities (Barrer)a of uncrosslinked and photochemically crosslinked PMP membranes at 35 8C and feedpressure of 2.0 bar
Crosslinking agent Before crosslinking After crosslinking
Azide wt% azide N2 O2 H2 CH4 CO2 N2 O2 H2 CH4 CO2
Noneb 0 950 1780 3970 1790 6700 870 1670 3810 1560 6420
BAA 1.0 810 1570 3680 1530 6230 450 1340 3580 890 5130
2.0 750 1530 3650 1420 6190 340 1250 3480 710 4910
3.0 680 1440 3520 1180 5820 280 1130 3410 630 4450
Nonec 0 950 1780 3970 1790 6700 490 1490 3640 920 4860
HFBAA 1.1 790 1580 3660 1500 6250 380 1190 3420 810 4710
2.0 730 1540 3610 1430 6100 290 1080 3380 630 4320
3.0 690 1420 3490 1070 5710 230 990 3300 510 3950
a Permeability is in unit of Barrer (1 Barrer = 10�10 cm3(STP) cm cm�2 s�1 cmHg�1).b Irradiated at 302 nm for 60 min.c Irradiated at 254 nm for 30 min.
i n t e r n a t i o n a l j o u r n a l o f g r e e n h o u s e g a s c o n t r o l 2 ( 2 0 0 8 ) 4 9 2 – 5 0 1 497
good solvents for uncrosslinked PMP (Morisato and Pinnau,
1996). It was found that when the bis azides concentration
were about BAA 0.9 wt% and HFBAA 1.0 wt% or higher, PMP
membranes were insoluble in carbon tetrachloride. The
insolubility of crosslinked PMP membranes is defined when
there is less than 0.5% weight loss in a dry membrane before
and after soaking in carbon tetrachloride for 24 h.
4.1. Photochemical crosslinking
Permeability data in Table 1 show membranes with different
amounts of crosslinker. For all gases considered, the addition
of bis(aryl azide)s to PMP decreased the permeability only
slightly before photo-irradiation, with hardly any improve-
ment of selectivity (Table 2). The crosslinked membranes
show a significant decrease in permeabilities (Table 1), steadily
decreasing as crosslinker content increase. The selectivities of
O2/N2, H2/N2, CO2/N2, CO2/CH4 and H2/CH4 increased with
increasing crosslinker. Higher degrees of crosslinking resulted
in a lower gas permeability and higher selectivity.
Blanks were run for photochemical reactions, to study the
effects of irradiation on the properties of pure PMP. When
irradiated at 302 nm for 60 min (the condition used for the
Table 2 – Selectivitiesa of various gas pairs in uncrosslinked a
Crosslinking agent Selectivity (before crosslinking
Azide wt% azide O2/N2 H2/N2 CO2/N2 CO2/CH4
Noneb 0 1.9 4.2 7.1 3.7
BAA 1.0 1.9 4.5 7.7 4.1
2.0 2.0 4.9 8.3 4.4
3.0 2.1 5.2 8.6 4.9
Nonec 0 1.9 4.2 7.1 3.7
HFBAA 1.1 2.0 4.6 7.9 4.2
2.0 2.1 4.9 8.4 4.3
3.0 2.1 5.0 8.3 5.3
a Selectivity is the ratio of the permeabilities for the pure gases.b Irradiated at 302 nm for 60 min.c Irradiated at 254 nm for 30 min.
irradiation of PMP/BAA composites), PMP membranes showed
only a slight change in permeabilities and selectivities; a more
noticeable change can however be seen for N2 and partly CH4.
When membranes were irradiated at 254 nm for 30 min (the
condition used for the irradiation of PMP/HFBAA composites),
the selectivities of O2/N2, H2/N2, CO2/N2, CO2/CH4 and H2/CH4
improved and the permeabilities decreased. Again, there is a
large reduction in permeation for N2 and CH4.
As mentioned above, PMP is a disubstituted acetylene-
based glassy polymer, its chain consists of conjugated double
bonds in the cis or trans configurations, the content of which
depends on the temperature of polymerization. The trans
isomer is the thermodynamically stable form. Under UV
irradiation cis! trans isomerization of PMP readily takes
place (Rolland et al., 1980; Cernia et al., 1984), this strongly
reduced chain mobility of polymer, intersegmental packing
may become much denser and intrasegmental mobility
smaller than in non-irradiated polymer, which causes the
change of the free volume in polymer membranes (decrease),
hence the gas permeability is decreased.
For photochemical crosslinking, the permeability changes
in going from pure PMP, to PMP with azide additives, to the
crosslinked membrane were predictable. For example, the
nd photochemically crosslinked PMP membranes
) Selectivity (after crosslinking)
H2/CH4 O2/N2 H2/N2 CO2/N2 CO2/CH4 H2/CH4
2.2 1.9 4.4 7.4 4.1 2.4
2.4 3.0 7.9 11.4 5.7 4.0
2.6 3.7 10.2 14.5 6.8 4.9
3.0 4.0 12.2 15.9 7.1 5.4
2.2 3.0 7.4 9.9 5.3 4.0
2.4 3.1 9.0 12.3 5.8 4.2
2.5 3.8 11.7 14.9 6.9 5.4
3.3 4.3 14.4 17.2 7.8 6.5
Table 3 – Gas permeabilities (Barrer)a of uncrosslinked and thermally crosslinked PMP membranes at 35 8C and feedpressure of 2.0 bar
Crosslinking agent Before crosslinking After crosslinking
Azide wt% azide N2 O2 H2 CH4 CO2 N2 O2 H2 CH4 CO2
Noneb 0 950 1780 3970 1790 6700 890 1720 3820 1650 6640
BAA 1.0 810 1570 3680 1530 6230 610 1510 3620 980 5780
2.0 750 1530 3650 1420 6190 540 1470 3560 810 5310
3.0 680 1440 3520 1180 5820 460 1390 3510 720 4920
HFBAA 1.1 790 1580 3660 1500 6250 570 1490 3640 950 5690
2.0 730 1540 3610 1430 6100 480 1380 3570 770 5210
3.0 690 1420 3490 1070 5710 390 1260 3420 570 4320
a Permeability is in unit of Barrer (1 Barrer = 10�10 cm3(STP) cm cm�2 s�1 cmHg�1).b Thermal treatment at 180 8C for 90 min.
Table 4 – Selectivitiesa of various gas pairs in uncrosslinked and thermally crosslinked PMP membranes
Crosslinking agent Selectivity (before crosslinking) Selectivity (after crosslinking)
Azide wt% azide O2/N2 H2/N2 CO2/N2 CO2/CH4 H2/CH4 O2/N2 H2/N2 CO2/N2 CO2/CH4 H2/CH4
None 0 1.9 4.2 7.1 3.7 2.2 1.9 4.3 7.5 4.0 2.3
BAA 1.0 1.9 4.5 7.7 4.1 2.4 2.5 5.9 9.5 5.9 3.7
2.0 2.0 4.9 8.3 4.4 2.6 2.7 6.5 9.8 6.6 4.4
3.0 2.1 5.2 8.6 4.9 3.0 3.0 7.6 10.7 6.8 4.9
HFBAA 1.1 2.0 4.6 7.9 4.2 2.4 2.6 6.3 10.0 6.0 3.8
2.0 2.1 5.0 8.4 4.3 2.5 2.9 7.4 10.9 6.8 4.6
3.0 2.1 5.1 8.3 5.3 3.3 3.2 8.8 11.1 7.6 6.0
a Selectivity is the ratio of the permeabilities for the pure gases.
Fig. 7 – Nitrogen sorption in uncrosslinked PMP and
crosslinked PMP containing 3.0 wt% HFBAA at 35 8C.
i n t e r n a t i o n a l j o u r n a l o f g r e e n h o u s e g a s c o n t r o l 2 ( 2 0 0 8 ) 4 9 2 – 5 0 1498
azide additive in composite membranes is expected to occupy
much of the free volume in the polymer and thus the
permeability is lower compared to pure PMP membranes.
Crosslinking connects adjacent chains, increases the local
segment density, and causes a further decline in the
permeability.
4.2. Thermal crosslinking
After crosslinking, the membranes were insoluble in good
solvents for PMP such as cyclohexane and carbon tetra-
chloride. Permeability data in Table 3 show membranes
with different amounts of crosslinker. For all gases consid-
ered, the addition of bis(aryl azide)s to PMP decreased the
permeability slightly before thermal crosslinking, with
hardly any improvement of selectivity (Table 4). After thermal
treatment, the crosslinked membranes show decreased
permeabilities. The permeabilities decreased as crosslinker
content increased for the crosslinked membranes, hence the
selectivities of O2/N2, H2/N2, CO2/N2, CO2/CH4 and H2/CH4
increased with increasing crosslinker. Thermally crosslinked
membranes show higher permeabilities and lower selectiv-
ities compare to photochemically crosslinked membranes. It
may be assumed there is a more open network structure for
the thermally cured membranes compared to membranes
crosslinked using UV irradiation. After crosslinking, the free
volume fraction in the membranes decreased, with the
photochemically crosslinked membranes having lower free
volumes than thermally crosslinked membranes.
Blank was run for thermal reaction, to study the effect
of thermal treatment on the property of pure PMP. When
treated at 180 8C for 90 min (the condition used for the
thermal treatment of PMP/azide composite membrane), PMP
membrane showed very slight change in permeabilities or
selectivities.
4.3. Solubility
Fig. 7 presents nitrogen sorption isotherms in uncrosslinked
PMP and crosslinked PMP containing 3.0 wt% HFBAA cross-
linker at 35 8C. Within experimental uncertainty, nitrogen
sorption levels in uncrosslinked PMP and crosslinked PMP are
Fig. 8 – Methane sorption in uncrosslinked PMP and
crosslinked PMP containing 3.0 wt% HFBAA at 35 8C.
Fig. 10 – Temporal stability of PMP, photochemically
crosslinked PMP/bis(aryl azide) composite membranes
measured as oxygen permeability. Temperature: 35 8C;
feed pressure: 2.0 bar.
1 Barrer = 10S10 cm3(STP) cm cmS2 sS1 cmHgS1.
i n t e r n a t i o n a l j o u r n a l o f g r e e n h o u s e g a s c o n t r o l 2 ( 2 0 0 8 ) 4 9 2 – 5 0 1 499
almost identical. The permeability (P) is the product of the gas
diffusivity (D) and solubility (S) (Eq. (1)), it is most likely that the
decrease in permeability in crosslinked PMP is due to a
decrease in the diffusivity caused by a reduced FFV. This trend
would also be expected for an ideal gas like nitrogen with very
low sorption level. The same trend is documented for methane
(Fig. 8), a gas which is less ideal but has about the same
molecular size as nitrogen. Hence it seems to be a general
trend applying to gas transport in crosslinked PMP; at least in
this low pressure region (!4 bar).
Fig. 8 presents methane sorption isotherms in uncros-
slinked PMP and crosslinked PMP containing 3.0 wt% HFBAA
crosslinker at 35 8C. The isotherms are slightly concave to the
pressure axis, which is typical behavior for gas sorption of
non-ideal gases in glassy polymers (Ghosal and Freeman,
1994). Consistent with the nitrogen data provided in Fig. 7,
methane sorption data in PMP are independent of HFBAA
crosslinker content, indicating that methane solubility in PMP
Fig. 9 – Temporal stability of uncrosslinked PMP,
photochemically crosslinked PMP/bis(aryl azide)
composite membranes measured as nitrogen
permeability. Temperature: 35 8C; feed pressure: 2.0 bar.
1 Barrer = 10S10 cm3(STP) cm cmS2 sS1 cmHgS1.
containing varying amounts of HFBAA is virtually identical to
that in the pure polymer—again in this low pressure region.
4.4. Membrane stability
The stability of the uncrosslinked PMP and photochemically
crosslinked PMP/bis(aryl azides) composite membranes stored
in air were checked over time. The results are shown in Figs. 9
and 10. The nitrogen and oxygen permeabilities of photo-
chemically crosslinked PMP/bis(aryl azides) composite mem-
branes were almost constant over a fairly long time. The
uncrosslinked PMP membranes showed a large decrease in the
nitrogen and oxygen permeabilities during the same time. The
permeability stability of crosslinked PMP for the gases is
clearly improved. After crosslinking, the PMP can be easily
converted to mechanically stable membranes with perme-
abilities and selectivities comparable or higher than those of
poly(dimethylsiloxane).
5. Conclusions
Crosslinkable poly(4-methyl-2-pentyne) membranes were
cast from carbon tetrachloride solutions containing PMP
and either BAA or HFBAA crosslinker. The composite
membranes were transparent and homogeneous and were
crosslinked by UV irradiation at room temperature or thermal
annealing at 180 8C. After crosslinking, the membranes were
insoluble in solvents that typically dissolve PMP. Thus, the
effect is a significant increase in the chemical stability due to
crosslinking. The process is simple and effective, and thus
PMP can be easily converted to mechanically stable mem-
branes.
For all gases considered permeability decreased as amount
of crosslinking agent increased. The permeability decrease
can be correlated with the fractional free volume decrease.
The permeability of PMP decreased with increasing cross-
linking due to the loss in FFV. The selectivities of O2/N2, H2/N2,
i n t e r n a t i o n a l j o u r n a l o f g r e e n h o u s e g a s c o n t r o l 2 ( 2 0 0 8 ) 4 9 2 – 5 0 1500
CO2/N2, CO2/CH4 and H2/CH4 increased as the FFV decreased,
showing that crosslinked PMP is more size selective to gases
than uncrosslinked PMP. The permeability stability of cross-
linked PMP for the gases is clearly improved. The increased
stability may be caused by crosslink constraining the PMP
chains and not allowing relaxation of the excess, non-
equilibrium FFV that is inherent in PMP.
The sorption levels of N2 and CH4 were measured and
found to be independent of crosslinker content (i.e. the
solubility remains relatively constant), within experimental
uncertainty. Therefore gas solubility in PMP does not seem to
be affected by the FFV decrease accompanying the increase in
crosslinker content. The permeability (P) is described as the
product of the gas diffusivity (D) and solubility (S), hence the
decrease in permeability in crosslinked PMP is most likely due
to a decrease in the diffusivity.
Acknowledgements
The authors want to thank the Norwegian Research Council
for the financial support to the work. We also gratefully
acknowledge Dr. Keith Redford and Siren M. Neset from
SINTEF Oslo for valuable help with synthesis and analysis
work.
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