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t echnische universit t
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Chair of Thermodynamics

Phase Behavior of
Hyperbranched Polymer in
Mixed Solvents

Tim Zeiner
1
, Philipp Schrader
2
, Christina Browarzik
2
,
Mahmudian Jergarluee Puyan
2
and Sabine Enders
2

1
Chair of Fluid separation, TU Dortmund
2
Chair of Thermodynamics, TU Berlin
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Chair of Thermodynamics

2
Outline
Motivation
Lattice Cluster Theory
Wertheim Association Theory
Results
Conclusion
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Chair of Thermodynamics

3
Motivation
Hyperbranched polymers:
- treelike structure
- functional groups
tailor-made polymers
Application:
- process engineering
- drug delivery system
- functional food

K. Inoue, Prog. Polym. Sci. 25 (2000) 453.
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Chair of Thermodynamics

4
Motivation
360
364
368
372
0.0 0.2 0.4 0.6 0.8 1.0
Dorozewsky and Polansky, 1910
LCT (Ac
n-propanol-water
/k
B
=64K)
P=1.013 bar
X
n-Propanol

T
/
K
0.00 0.25 0.50 0.75 1.00
0.00
0.25
0.50
0.75
1.00
0.00
0.25
0.50
0.75
1.00
u
p
o
l
y
m
e
r

u
w
a
t
e
r

Exp. Boltorn H20 /n-propanol/water
LCT Ac
n-propanol-water
/k
B
=64K
LCT Ac
n-propanol-water
/k
B
=45K (fitted on LLE)
T=353,15 K
Ac
polymer-water
/k
B
=46.893K
Ac
n-propanol-polymer
/k
B
=18.96K
u
n-propanol

T. Zeiner and S. Enders, Chemical Engineering Science, 66 (2011) 5244-5252.
Hyperbranched polymer in mixed solvent n- propanol/water
Interaction parameter of LCT was fitted on VLE
Qualitative prediction of the phase behavior
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Chair of Thermodynamics

5
Lattice Cluster Theory
General description of hyperbranched polymers
n
0
number of segments of the core
n separator length
g degree of branching
Chain length
( )
0 0
4 2 1 = = +
g
P
N M n n
( )
3
4 2 1 2 = +
g
b
Branching degree of 3 points
Branching degree of 4 points
4
0 = b
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Chair of Thermodynamics

6
Wertheim Association Theory
1 2 2 1 2 2
,

B A B A C D
R OH H O H
functional groups / n-butanol water
exp 1
(
| |
A =
( |
\ .

i
i i
B
K
k T
c
E. Nies et al., J. Phys. Chem. B 110 (2006) 5321-5329
Determination of parameters:
K
water/n-butanol
; c
water/n-butanol
Vapour pressure
K
polymer
; c
polymer
LLE of polymer solution
K
Mix
;c
Mix
Combining rule (k
ij
for interaction)
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Chair of Thermodynamics

7
Results
260
280
300
320
340
360
380
400
0.0 0.2 0.4 0.6 0.8
Stephenson et al. (1986)
Prochazka et al. (1975)
LCT Ac/k
B
=84.622K
LCT + Wertheim

Segmentfraction (Butanol)
T
/
K
LLE of water + n-butanol
LCT:
Ac/k
B
=84.622K

LCT +Wertheim:
Ac/k
B
=57.5 K
c
water
=1800 K
c
butanol
=1710 K
k
water
=0.01
k
butanol
=0.01
k
ij
=0.03
T= 353.15 K
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Chair of Thermodynamics

8
Results
340
350
360
370
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Boltorn H20 + Butanol
LCT
LCT+Wertheim
Experimental Data
Boltorn H20 + Water
LCT
LCT+Wertheim
Experimental Data
Segmentfraction Polymer [-]
T
/
K
Binary LLE of Boltorn H20 in water and in n-butanol
Boltorn H20 + n-butanol:
k
ij
=0.035
Boltorn H20 + water:
k
ij
=0.06
T. Zeiner, P. Schrader, D. Browarzik, S. Enders, Fluid Phase Equilibria ,302 (2011) 321-330
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Chair of Thermodynamics

9
Results
0.00 0.25 0.50 0.75 1.00
0.00
0.25
0.50
0.75
1.00
0.00
0.25
0.50
0.75
1.00
3 Phases
u
n-butanol
u
p
o
l
y
m
e
r
u
w
a
t
e
r
prediction of a three
phase equilibrium
not in agreement
with experiments
Can the
result be
improved ?
T= 353.15 K
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Chair of Thermodynamics

10
Results
0.00 0.25 0.50 0.75 1.00
0.00
0.25
0.50
0.75
1.00
0.00
0.25
0.50
0.75
1.00
u
p
o
l
y
m
e
r
u
n-butanol
u
w
a
t
e
r
T= 353.15 K
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Chair of Thermodynamics

11
Conclusion
LCT predicts the critical composition of binary systems
by knowledge of chemical structure
LCT + Wertheim Theory allows to model exactly the
cloud-point curves of the binary polymer solutions
LCT cannot predict the ternary phase behavior
LCT + Wertheim Theory allows the prediction of the
ternary phase behavior without adjustable parameter
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12
Thank you for your attention!
Max-Buchner Forschungsstiftung
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Chair of Thermodynamics

13
Lattice Cluster Theory
Development of the Helmholtz energy using double series expansion
in inverse coordination number 1/z and in interaction energy c/kBT
taking into account the polymer architecture.
(J. Dudowicz, K.F. Freed, Macromolecules 24 (1991) 5076-5095)
A = A + A
int LCT ath
a a a
c
P
interaction energy between polymer segments
c
S
interaction energy between solvent segments
c
PS
- interaction energy between polymer and solvent segments
Truncation of the series at second
order of 1/z and at second order of c/k
B
T
PP SS PS
2 Ac = c + c c
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Chair of Thermodynamics

14
Wertheim Association Theory
- perturbation theory for molecules
with different association sites
(M.S. Wertheim, J. Chem. Phys. 42 (1986) 477 -
492) eventuell weg

- derivation of the theory by expanding
the Helmholtz energy in a integral
series
-broadly used in the SAFT-EOS family
(E.A. Mller, K.E. Gubbins
Ind. Eng. Chem. Res. 40 (2001) 2193-2211)
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Chair of Thermodynamics

15
Wertheim Association Theory
2 2
ln
i
i
i
A
asso i
i A
i A
X
a M
X
RT
| |
| |
= u +
|
|
|
\ .
\ .

Mi - number of association-sites at the molecule i
X
Ai
- volume fraction of molecules not bonded at site Ai
i
A
1
X =
1+
i j
j
j
AB
j B
j B
X u A

A
A
i
B
j
- the association strength depending on association
energy and association volume