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Article history:
Received 4 March 2015
Received in revised form
5 June 2015
Accepted 7 June 2015
Available online 10 June 2015
In this study, the thermal and rheological properties of polystyrene-block-poly(4-vinylpyridine) (PS-bP4VP) diblock copolymers are investigated in order to get information about the optimum foaming
temperature. Foams of these diblock copolymers were prepared using the technique of batch foaming
with carbon dioxide as environmentally-benign blowing agent. The tailored PS-b-P4VP diblock copolymers with different molecular weights and a cylindrical morphology were prepared and analysed
regarding their thermal stability. High-pressure differential scanning calorimetry exposes the plasticising
effect of the blowing agent which yields a decrease of the glass transition temperature of the polystyrene
and the poly(4-vinylpyridine) blocks. Sorption measurements were performed in order to measure the
uptake of carbon dioxide in the diblock copolymer. Additionally, rheological experiments in the oscillatory mode were conducted which conrmed a microphase-separated structure of the PS-b-P4VP
diblock copolymers by a plateau of the storage and loss moduli in the temperature range of processing. In
shear and melt elongation, the transient shear viscosity and the transient elongational viscosity were
much smaller than the linear viscoelastic prediction at later times. The analysis of the foam morphology
revealed that the foam density of the diblock copolymers as measured via Archimedes' principle exhibits
the lowest foam density at a molecular weight in the order of 160 kg mol1.
2015 Elsevier Ltd. All rights reserved.
Keywords:
Polymer foams
Diblock copolymers
Rheology
Microphase separation
1. Introduction
Block copolymers have attracted much interest as promising
materials due to their ability of microphase separation. These
materials combine the characteristics of thermoplastic polymers
and the possibility of creating self-assembled structures on the
microscopic level [1e4]. By employing the technique of living
anionic polymerisation, the design of tailored block copolymers
with a dened molecular weight and a small polydispersity is
realisable [5e7]. Hence, block copolymers can be applied in
numerous elds in industry, e.g., as insulation, absorbants or
membranes [8,9]. The covalent bonding of different types of
monomers in block copolymers allows for combining different
properties, e.g., for enhancing the toughness of polymers by
incorporation of a soft block or for the compatibilisation of polymer blends [10e13]. In addition, the phenomenon of microphase
* Corresponding author.
E-mail address: ulrich.handge@hzg.de (U.A. Handge).
http://dx.doi.org/10.1016/j.polymer.2015.06.005
0032-3861/ 2015 Elsevier Ltd. All rights reserved.
89
2. Experimental section
2.1. Synthesis of PS-b-P4VP diblock copolymers
PS-b-P4VP diblock copolymers were synthesised via sequential
anionic polymerisation of styrene and 4-vinylpyridine [51,53]. All
reactants were puried by the following procedures: Tetrahydrofuran (THF) (Th. Geyer, Renningen, Germany) was successively
distilled under argon atmosphere. Styrene (Sigma Aldrich, Taufkirchen, Germany) was puried with dibutyl magnesium (MgBu2)
and lately distilled before use. 4-vinylpyridine (Sigma Aldrich) was
distilled and kept on calcium hydride (CaH2). After purifying twice
with ethylaluminum dichloride (EtAlCl2), 4-vinylpyridine was
distilled once again.
The reaction was carried out at 78 C with THF as solvent and
sec-butyl lithium (sec-BuLi) (Sigma Aldrich) as initiator. THF was
put into the reaction vessel with lithium chloride (LiCl) (Sigma
Aldrich) and stirred overnight. The rst block was polymerised by
adding styrene in a rst and sec-BuLi in a second step to the solution. This was left under stirring for 4 h. After adding 4vinylpyridine, the mixture was stirred further overnight. To
terminate the reaction, the solution was quenched with puried
methanol. Finally, THF was removed under reduced pressure and
the polymer solution was precipitated into water before ltering
and drying the obtained polymer powder.
90
Mt
4
M
r
Dt
pl2
(1)
Table 1
Synthesised diblock copolymers and the results of molecular characterisation.
Diblock copolymera
PS [wt%]
P4VP [wt%]
Mn [kg mol1]
PDI
PS80-b-P4VP50
20
PS80-b-P4VP164
20
PS80-b-P4VP183
20
PS80-b-P4VP220
20
PS76-b-P4VP50
24
PS77-b-P4VP106
23
PS78-b-P4VP116
22
PS77-b-P4VP134
23
80
80
80
80
76
77
78
77
20
20
20
20
24
23
22
23
50
164
183
220
50
106
115
134
1.05
1.06
1.07
1.15
1.05
1.09
1.08
1.09
479
1572
1754
2108
479
1016
1111
1284
a
Subscript numbers indicate the weight percentage of each block and superscript
numbers indicate the total number averaged molecular weight in kg mol1.
91
92
Fig. 1. Transmission electron micrographs of PS-b-P4VP diblock copolymers with a number average molecular weight of a) 106, b) 134, c) 164 and d) 220 kg mol1. P4VP
microphases appear dark, whereas the PS microphase appears bright.
220 kg mol1 were analysed. For comparison, the data for a pristine
PS homopolymer (Polystyrene PS 158K, BASF SE, Ludwigshafen,
Germany, Mn 120 kg mol1) and a pristine P4VP homopolymer
(Sigma Aldrich, Mw 60 kg mol1) is shown as well. The evaluation
of the Tg for the diblock copolymers was only feasible for the PS
microphase up to CO2-pressures of 20 bar due to weak signals at
higher CO2-pressures. The glass transition temperature Tg for the
P4VP microphase in the diblock copolymers was not analysable
because of the lower P4VP fraction compared to the PS fraction in
the diblock copolymer.
The value of Tg of the PS microphase decreased when increasing
the pressure of the CO2-atmosphere from ambient pressure to
Fig. 2. a) Diameter of the P4VP microphases in the PS matrix and b) distance of the centre of P4VP microphases as a function of the molecular weight of the diblock copolymer
determined by analysis of the two-dimensional ultrathin sections.
93
Fig. 4. Glass transition temperature Tg as a function of pressure p in a CO2-atmosphere of a) the polystyrene microphase for three PS-b-P4VP diblock copolymers with molecular
weights of 50, 134 and 220 kg mol1 and pristine PS and b) pristine poly(4-vinylpyridine) using high-pressure DSC measurement.
94
Table 2
Specic uptake of carbon dioxide in the diblock copolymers and diffusion coefcient
of the diblock copolymers at a pressure of 40 bar and a temperature of 30 C. For
comparison, measurements of pure PS and P4VP are shown.
Diblock
copolymer
Densitya
[g cm3]
Specic
CO2-uptake
[wt%]
Diffusion
coefcient
[107 cm2 s1]
PS76-b-P4VP50
24
PS77-b-P4VP106
23
PS77-b-P4VP134
23
PS80-b-P4VP164
20
PS80-b-P4VP183
20
PS80-b-P4VP220
20
120
PS100
60
P4VP100
1.0967
1.0950
1.0917
1.0897
1.0883
1.0840
1.0708
1.1884
6.21
6.72
6.33
6.46
6.45
6.48
5.89
7.18
2.00
1.03
1.32
0.90
0.45
0.68
0.72
0.43
95
Fig. 6. Master curves of G0 and G00 as a function of angular frequency u of two different PS-b-P4VP diblock copolymers with molecular weights of a) 50 kg mol1 and b) 183 kg mol1.
The reference temperature was 160 C and the shift factor is denoted by aT. The entanglement plateau is mainly caused by the contribution of the PS microphase.
Fig. 7. Results of stress-growth tests with a constant shear rate: Transient viscosity h as a function of time t for a) a selected diblock copolymer with a molecular weight of
134 kg mol1 and b) as a function of the molecular weight for two different shear rates.
Fig. 8. Steady-state value of the shear viscosity as a function of shear rate g_ 0. The test
temperature was 220 C.
(here CO2) and the second step is the foaming of the polymer by
nucleation of foam cells and expansion of the dissolved gas through
pressure drop and/or increase in temperature. Therefore, the processing parameters were chosen to guarantee a saturation of the
sample with CO2 at a pressure of 40 bar provided by the gas source.
The achieved density of the PS-b-P4VP diblock copolymer foams
strongly depends on the foaming temperature and the molecular
weight of the foamed diblock copolymers (Fig. 12). Low densities in
the order of 0.15 g cm3 are obtained for diblock copolymers with a
high molecular weight at a foaming temperature of 110 C. Foaming
Fig. 9. Scheme of the deformation of the morphology during shear ow. The cylindrical domains of the P4VP blocks are surrounded by a shell of PS blocks. At high shear
rates, the cylinders with the shell slide on each other. This deformation mechanism
dominates the viscous response.
96
Fig. 10. Apparent elongational viscosity he;app as a function of time for three different Hencky strain rates _ 0 and two diblock copolymers of this study ((a) PS77-b-P4VP106
23 and
(b) PS80-b-P4VP220
20 diblock copolymers). The measurement temperature was 220 C. The linear viscoelastic prediction of the elongational viscosity (LVE) and the results of the
transient shear viscosity measurements (multiplied by the Trouton ratio) are also shown. The solid symbols are the data in elongation and the open symbol correspond to the shear
data.
Fig. 11. Scheme of a two-step batch foaming process with the processing parameters
T0 as loading temperature, p0 as saturation pressure, Dt as loading time, Tfoam as
foaming temperature, Dp as pressure drop down to ambient pressure and tfoam as
foaming time.
97
Fig. 12. Foam density of the PS-b-P4VP diblock copolymers as a function of the foaming temperature for the block copolymers with (a) a PS fraction of 77 wt% and (b) a PS fraction of
80 wt%. The number average Mn of the molecular weight is indicated.
Fig. 13. Scanning electron micrographs displaying i) the inuence of the foaming temperature on a 164 kg mol1 PS-b-P4VP diblock copolymer foam with temperatures of a) 100 C,
b) 110 C, c) 120 C and ii) the inuence of the molecular weight of PS-b-P4VP foams with d) 106 kg mol1, b) 164 kg mol1, e) 220 kg mol1 at a foaming temperature of 110 C.
diblock copolymers had a similar foam density at a foaming temperature of 110 C (see Fig. 12).
Whereas the effect of foaming temperature is clearly seen by its
inuence on melt viscosity and foam density, the explanation of the
effect of molecular weight is less obvious. Our rheological experiments in shear and elongation suggest that it is not the macroscopic
viscosity which inuences the nal foam density, but the microrheological deformation of the cylindrical structure which appears
when a gas bubble expands in the microphase separated structure.
Such a microrheological analysis is beyond the scope of this study.
4. Conclusions
The present study elucidates the inuence of thermal and
rheological properties on the foaming behaviour of PS-b-P4VP
diblock copolymers using CO2 as blowing agent. The synthesis via
living anionic polymerization led to diblock copolymers with
dened molecular weight and composition and allows the investigation of the impact of morphology on the foaming process.
DMTA experiments and transmission electron microscopy
98
Fig. 14. Cell size distribution of PS-b-P4VP diblock copolymer foams with molecular weights of (a)e(c) 220 kg mol1 and (d) 164 kg mol1 processed at foaming temperatures
between 100 C and 120 C indicated in the graphs. The mean cell diameter dc and its deviation are denoted.
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