1. G. Bogdanić: Group Contribution Methods for Predicting Properties of Systems Containing Polymers
13/10/2011
Group Contribution Methods for Predicting Properties of Systems Containing Polymers
Grozdana Bogdanić
Institute of Chemical Process Fundamentals ASCR, Prague

2. −M−M−M−M−M−M−M−M−M−M−
POLY − MER
many units
−M−M−M−M−M−M−M−M−M−M− or
−(M)n−

4. 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

5. 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

6. 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
2.2. Group contribution methods for predicting the properties
of polymer–polymer mixtures (polymer blends)
3. Conclusions

7. In: Polymeric Materials, Chapter 7
G. Bogdanić:
Additive Group Contribution Methods for Predicting the Properties of Polymer systems
In: Polymeric Materials, Chapter 7
Transworld Reserach Signpost, Trivandrum, India (2009).

8. 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).

9. Group Contribution Methods for Predicting Properties of Polymer – Solvent Mixtures (VLE)

10. Calculation of Free Volumes
Component T
[°C] d
[g cm-3] V
[cm3 mol-1] V* Vf
Benzene 25
0.8735
89.3
91.9
27.4
Acetone
0.7846
73.9
50.0
23.9
Toluene
0.8616
106.9
76.2
30.6
Cyclohexane
0.7749
108.4
78.6
29.8
Dioxane 20
1.0337
85.1
61.9
23.3
Poly(isobutylene)
0.9169
61.1
52.4
8.7
Poly(ethylene oxide)
1.126
39.1
30.9
8.2
Poly(vinyl acetate)
1.19
60.7
58.7
2.0
Polystyrene
1.05
99.0
80.4
18.6
Poly(vinyl alcohol)
1.27
34.6
32.1
2.5
Poly(vinyl pyrrolidone)
1.215

11. The UNIFAC-FV Model T. Oishi, J. M. Prausnitz, 1978.
combinatorial residual free-volume

12. The Entropic-FV Model
H. S. Elbro, Aa. Fredenslund, P. Rasmussen, 1990.
G. M. Kontogeorgis, Aa. Fredenslund, D. P. Tassios, 1993.
(UNIFAC)
The free-volume definition:

13. The GC-Flory EOS F. Chen, Aa. Fredenslund, P. Rasmussen, 1990.
G. Bogdanić, Aa. Fredenslund, 1994.
combinatorial FV attractive
N. Muro-Suñé, R. Gani, G. Bell, I. Shirley, 2005.

15. The GC-Lattice-Fluid EOS
M. S. High, R. P. Danner, 1989; 1990.
B. C. Lee, R. P. Danner, 1996.

16. [G. Bogdanić, Aa. Fredenslund, 1995]
UNIFAC-FV
Entropic-FV
GC-Flory
GC-LF (1990)
Prediction of infinite dilution activity coefficients versus experimental values for polymer solutions (more than 120 systems)
[G. Bogdanić, Aa. Fredenslund, 1995]

17. Prediction of infinite dilution activity coefficients versus experimental values for systems containing nonpolar solvents ( systems)
[B. C. Lee, R .P. Danner, 1997]

18. 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]

19. 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]

20. Activity of MEK in PS (Mn = 103000)
T = 383 K
T = 373 K
T = 322 K
Activity of 2-methyl heptane
in PVC
(Mn = 30000; Mn = )
Activity of ethyl benzene
in PBD (Mn = )
Activity of MEK in PS
(Mn = )
[G. Bogdanić, Aa. Fredenslund, 1995]

21. LLE
 Polymer solutions
 Polymer blends

23. PVAL–water binary mixture at 420 K
GM/RT versus molar fraction (GM/RT – se) versus molar fraction
of the polymer of the polymer

24. The Segmental Interaction UNIQUAC-FV Model(s)
G. Bogdanić, J. Vidal, 2000.
G. D. Pappa, E. C. Voutsas, D. P. Tassios, 2001.

26. Correlation (  ) of LLE PEG/water system by the UNIQUAC–FV model
[J. Vidal, G. Bogdanić, 1998]

27. 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= g/mol,   prediction
 Mw=44500 g/mol, prediction

28. 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 = g/mol,  correlation
 poly(S0.80-co-BMA0.20), Mw = g/mol, prediction

29. G. Bogdanić, Aa. Fredenslund, 1994.
The GC-Flory EOS
G. Bogdanić, Aa. Fredenslund, 1994.
G. Bogdanić, 2002.
LLE parameters

30. Coexistence curves for HDPE/n-hexane systems as correlated
by the GC-Flory EOS (  ) [G. Bogdanić, 2002]

31. Coexistence curves for PIB/n-hexane systems as correlated by
G. Bogdanić: Group Contribution Methods for Predicting Properties of Systems Containing Polymers
13/10/2011
Coexistence curves for PIB/n-hexane systems as correlated by
the GC-Flory EOS (  ) [G. Bogdanić, 2002]

32. The Mean-Field Theory R. P. Kambour, J. T. Bendler, R. C. Bopp, 1983.
G. ten Brinke, F. E. Karasz, W. J. MacKnight, 1983.
combinatorial residual

33. T = 473 K
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]

34. Miscibility behavior of PPO/poly(oFS-co-pClS) system ( ) correlated by the UNIQUAC-FV model [G. Bogdanić, 2006]

35. the UNIQUAC-FV model [G. Bogdanić, 2006]
T = 473 K
Miscibility of SPPO/poly(oBrS-co-pBrS) system (  ) correlated by
the UNIQUAC-FV model [G. Bogdanić, 2006]

36. 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.