grozdana bogdanić institute of chemical process fundamentals ascr, prague group contribution...
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Grozdana Bogdanić
Institute of Chemical Process Fundamentals ASCR, Prague
Group Contribution Methods for Predicting Properties of Systems Containing Polymers
POLY − MER
many units
−M−M−M−M−M−M−M−M−M−M−
or
−(M)n−
Modeling
description of thermophysical properties (vapor pressures, viscosities, caloric data, etc.) of pure components and mixtures
properties of different apparatuses like reactors, distillation columns, pumps, etc.
chemical reactions and kinetics
environmental and safety-related data
Two main different types of models can be distinguished:
Rather simple equations and correlations where parameters are fitted to experimental data
Predictive methods where properties are estimated
1. VLE
1.1. Group contribution methods for predicting the properties of polymer–solvent mixtures
Activity coefficient models Equations of state
2. LLE
2.1. Group contribution methods for predicting the properties of polymer–solvent mixtures
Activity coefficient models Equations of state
2.2. Group contribution methods for predicting the properties of polymer–polymer mixtures (polymer blends)
3. Conclusions
G. Bogdanić:
Additive Group Contribution Methods for Predicting the Properties of Polymer systems
In: Polymeric Materials, Chapter 7
Transworld Reserach Signpost, Trivandrum, India (2009).
G. Bogdanić, I. Wichterle, A. Erceg Kuzmić:
Collection of Miscibility Data and Phase Behavior of Binary Polymer Blends based on Styrene, 2,6-Dimethyl-1,4-Phenylene Oxide and of Their Derivatives
Transworld Research Signpost, Trivandrum, India (2010).
jjj
ii
jj
ii Mx
Mxm
mw
iiiii w = x = a
Group Contribution Methods for Predicting Properties of Polymer – Solvent Mixtures (VLE)
Calculation of Free Volumes
Component T[°C]
d[g cm-3]
V[cm3 mol-1]
V*
[cm3 mol-1]
Vf
[cm3 mol-1]
Benzene 25 0.8735 89.3 91.9 27.4
Acetone 25 0.7846 73.9 50.0 23.9
Toluene 25 0.8616 106.9 76.2 30.6
Cyclohexane 25 0.7749 108.4 78.6 29.8
Dioxane 20 1.0337 85.1 61.9 23.3
Poly(isobutylene) 25 0.9169 61.1 52.4 8.7
Poly(ethylene oxide) 25 1.126 39.1 30.9 8.2
Poly(vinyl acetate) 25 1.19 60.7 58.7 2.0
Polystyrene 25 1.05 99.0 80.4 18.6
Poly(vinyl alcohol) 25 1.27 34.6 32.1 2.5
Poly(vinyl pyrrolidone) 25 1.215 34.6 32.1 2.5
The UNIFAC-FV Model
i
FV
i
resid
i
comb
i ln + ln + ln = ln
combinatorial residual free-volume
1
v~i1/31
-11-v~M
v~iCi - 1-v~M
1/31-v~i
1/3lnCi3 = i
FVln
T. Oishi, J. M. Prausnitz, 1978.
The Entropic-FV Model
i
attr
i
entr
i ln + ln = ln
x - 1 +
x ln = ln
i
i
FV
i
i
FV
i
entr
The free-volume definition:
v - v = v *iiif, v = v iw,
*i
H. S. Elbro, Aa. Fredenslund, P. Rasmussen, 1990.G. M. Kontogeorgis, Aa. Fredenslund, D. P. Tassios, 1993.
i
attr
i
attr lnln (UNIFAC)
The GC-Flory EOS
combinatorial FV attractive
VE+
1-v~C+v~
V
RTn = P
attr
1/3
1/3
i
attr
i
FV
i
comb
i ln + ln + ln = ln
F. Chen, Aa. Fredenslund, P. Rasmussen, 1990.G. Bogdanić, Aa. Fredenslund, 1994.
N. Muro-Suñé, R. Gani, G. Bell, I. Shirley, 2005.
x - 1 +
x ln = ln
i
i
i
ii
comb
j
jijiiiiiiattri )RT/(exp ln - 1 + )]v~(-)v~([
RT
1 qz1/2 = ln
k
kik
jij
j /RT)(-exp
/RT)(-exp -
v~v~ ln C -
1 - v~1 - v~ln )C + 3(1 = ln i
i1/3
1/3i
iFVi
The GC-Lattice-Fluid EOS
T~ -
v~1-q/r+v~
ln2
z +
1-v~v~
ln = T~P~ 2
T~ -
T~
2q +
v~1)-v~(
1)-v~(
v~ln q +
v~v~ ln + wln - ln= ln
i
pi,i
i
ii
iiii ii
i ln2
qz +
M. S. High, R. P. Danner, 1989; 1990.
B. C. Lee, R. P. Danner, 1996.
T~ -
T~
2q +
v~1)-v~(
1)-v~(
v~ln q +
v~v~ ln + wln - ln= ln
i
pi,i
i
ii
iiii ii
i ln2
qz +
Prediction of infinite dilution activity coefficients versus experimental values for polymer solutions (more than 120 systems)
[G. Bogdanić, Aa. Fredenslund, 1995]
UNIFAC-FV Entropic-FV
GC-Flory GC-LF (1990)
Prediction of infinite dilution activity coefficients versus experimental values for systems containing nonpolar solvents (215-246 systems)
[B. C. Lee, R .P. Danner, 1997]
Predictions of infinite dilution activity coefficients versus experimental values for systems containing weakly polar solvents (cca 60 systems)
[B. C. Lee, R. P. Danner, 1997]
Predictions of infinite dilution activity coefficients versus experimental values for systems containing strongly polar solvents (cca 30 systems)
[B. C. Lee, R. P. Danner, 1997]
Activity of ethyl benzene in PBD (Mn = 250000)
T = 373 K
Activity of MEK in PS (Mn = 103000)
T = 322 K
Activity of 2-methyl heptane in PVC (Mn = 30000; Mn = 105000)
T = 383 K
[G. Bogdanić, Aa. Fredenslund, 1995]
0G
P,T
21
2
0GG32
3
22
2
0lnln
22
12
2
1
LLE
Polymer solutions Polymer blends
GM/RT versus molar fraction (GM/RT – se) versus molar fraction of the polymer of the polymer
PVAL–water binary mixture at 420 K x 1
04
The Segmental Interaction UNIQUAC-FV Model(s)
G. Bogdanić, J. Vidal, 2000.G. D. Pappa, E. C. Voutsas, D. P. Tassios, 2001.
i
resid
i
entr
i ln + ln = ln
x - 1 +
x ln = ln
i
i
FV
i
i
FV
i
entr
)i(kk
k
)i(k
residi lnlnln
nseg
mnseg
nnmn
kmmnseg
mmkmkk ln1Qln
ncomp
j
nseg
m
)j(mj
ncomp
i
)i(ki
k
x
xX
02,mn1,mnmn TTaaa
Correlation ( ) of LLE PEG/water system by the UNIQUAC–FV model
[J. Vidal, G. Bogdanić, 1998]
Correlation and prediction of LLE for PBD/n-octane by the UNIQUAC-FV model [G. Bogdanić, J. Vidal, 2000]
Mv=65000 g/mol, correlation Mv=135000 g/mol, prediction Mw=44500 g/mol, - - - - prediction
Correlation and prediction of LLE for poly(S-co-BMA)/MEK by the UNIQUAC-FV model [G. Bogdanić, J. Vidal, 2000]
poly(S0.54-co-BMA0.46), Mw = 40000 g/mol, correlation poly(S0.80-co-BMA0.20), Mw = 250000 g/mol, - - - - prediction
The GC-Flory EOS
LLE parameters
G. Bogdanić, Aa. Fredenslund, 1994.
G. Bogdanić, 2002.
εnn , Δεnm
0.00 0.02 0.04 0.06 0.08 0.10390
400
410
420
Mn=60400, Mw=82600
Mn=97700, Mw=135900
Mw=180000
T/K
Mass fraction of polymer
Coexistence curves for HDPE/n-hexane systems as correlatedby the GC-Flory EOS ( ) [G. Bogdanić, 2002]
0.00 0.05 0.10 0.15 0.20 0.25250
275
300
325
350
375
400
Mv=98000
Mv=191000
Mv=380000
T/K
Mass fraction of polymer
Coexistence curves for PIB/n-hexane systems as correlated by the GC-Flory EOS ( ) [G. Bogdanić, 2002]
The Mean-Field Theory
21blend22
21
1
1M
+ ln N
+ ln N
= TR
G
BDBCADACblend yx + ) y - 1 (x + y )x - 1 ( + ) y - 1 ( )x - 1 ( =
CDAB ) y - 1 ( y - )x - 1 (x -
combinatorial residual
R. P. Kambour, J. T. Bendler, R. C. Bopp, 1983.G. ten Brinke, F. E. Karasz, W. J. MacKnight, 1983.
(A1-xBx)N1/(C1-yDy)N2:
Miscibility of poly(S-co-oClS)/SPPO Miscibility of poly(S-co-pClS)/SPPO
() one phase; () two phases; ( ) predicted miscibility/immiscibility boundary by the mean-field model [G. Bogdanić, R. Vuković, et. al., 1997]
T = 473 K
Miscibility behavior of PPO/poly(oFS-co-pClS) system ( ------ ) correlated by the UNIQUAC-FV model [G. Bogdanić, 2006]
Miscibility of SPPO/poly(oBrS-co-pBrS) system ( ) correlated by the UNIQUAC-FV model [G. Bogdanić, 2006]
T = 473 K
Thermodynamic Databases for Polymer Systems
H. Wen, H.S. Elbro, P. Alessi, Polymer Solution Data Collection, Dechema Chemistry Series, Frankfurt, 1992.
M.S. High, R.P. Danner, Polymer Solution Handbook; DIPPR 881 Project. Design Institute for Physical Property Data, 1992.
C. Wohlfarth, Vapor-Liquid Equilibrium Data of Binary Polymer Solutions, Elsevier, Amsterdam, 1994.
P.Zoller, D.J. Walsh, Standard Pressure-Volume- Temperature Data for Polymers, Technomics Publishing Co., Lancaster, 1995.
Why so many different models have been developed for polymer systems?
The choice of a suitable model depends on: the actual problem and on the type of mixture type of phase equilibrium (VLE, LLE, SLE) conditions (temperature, pressure, concentration) type of calculation (accuracy, speed, yes/no answer, or complete design)
Many databases and reliable GC-methods are available for estimating:
pure polymer properties phase equilibrium of polymer solutions
VLE: GC - models based on UNIFAC + FV GC - EOS
LLE simple FV expression + local composition
energetic term (UNIQUAC)