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Laboratory for Chemical Technology, Ghent University
http://www.lct.UGent.be
Model-guided design of polymerization processes
Dagmar R. D’hooge
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Outline
2
1. Principle of radical polymerization:
a. Conventional free radical polymerization
b. Controlled radical polymerization
2. Modeling goals and techniques
3. Case study 1: model-based optimization of bulk CRP of
styrene
4. Case study 2: model-based optimization of miniemulsion CRP
of styrene and acrylates
5. Conclusions
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Conventional free radical polymerization (FRP)
3
2 populations: R and P
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Controlled radical polymerization (CRP)
4
3 populations: R, P, RX
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Outline
5
1. Principle of radical polymerization:
a. Conventional free radical polymerization
b. Controlled radical polymerization
2. Modeling goals and techniques
3. Case study 1: model-based optimization of bulk CRP of
styrene
4. Case study 2: model-based optimization of miniemulsion CRP
of acrylates
5. Conclusions
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Modeling goals : status 2013
6
Monomer A units (-)
Cha
in le
ngth
(-)
Copolymer compositionchain length distribution
(CoC-CLD)
Cha
in n
umbe
r(-
)
Chain position (-)
individual monomersequences
Macromolecular structural detail
Mod
el c
ompl
exity
Num
ber
frac
tion
(-)
0 100 200150500
0.02
0.01
0 100 200150500
0.02
0.01
Chain length (-)
chain lengthdistribution
(CLD)
xn
xm
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Modeling goals: update 2014
7
also branch formation(homogeneous)
PSD: monodisperse(heterogeneous)
ARGET ATRP simulation
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
LCT multi-scale modeling platform
8
moleculardiffusion
apparent reactionrates
(MICRO-scale)
LCT solver for kinetics withkMC and deterministic
module
chemical composition
distribution (CCD)
(monomer) conversion
reactor configuration
reactor model (MACRO-scale)
chain lengthdistribution
(CLD)
kinetic lab scale tests
(co)monomer(s),initiator(s), mediating
agent, …
polymerizationconditions
intrinsic kinetics & thermodynamics
reactionnetwork
ab initiocalculations
explicit microstructure
particle sizedistribution
(MESO-scale)
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Micro-scale: apparent reaction rates (1)
9
kchemk+diff
k-diff
kapp
A + B AB C A + B C
ABAdiff DNk σπ4=
1
�����
1
����
1
���
Termination:
General:Encouter pair model
LCT/KIT collaboration ondevelopment generic methodfor quantification of kt
Derboven et al. 2014 in preparation
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Micro-scale: apparent reaction rates (2)
10
Coupled encounter pair model
D’hooge et al. Macromol. React. Eng. 2013, 8, 362
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Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Outline
11
1. Principle of radical polymerization:
a. Conventional free radical polymerization
b. Controlled radical polymerization
2. Modeling goals and techniques
3. Case study 1: model-based optimization of bulk CRP of
styrene
4. Case study 2: model-based optimization of miniemulsion CRP
of acrylates
5. Conclusions
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
NMP side reactions
12
DIMER
DEAD POLYMER
Thermal initiation
Chain transfer to dimer and monomer
•
+ +•
++•
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Regression analysis for kchem,NMP
13Fierens et al. Chem. Eng. J. 2014 submitted
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Model versus experiment
14
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Model analysis: relevance NMP initiator
15
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Model analysis: explicit visualization (1)
16
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Model analysis: explicit visualization (2)
17
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Model-based optimization: T program
18
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Outline
19
1. Principle of radical polymerization:
a. Conventional free radical polymerization
b. Controlled radical polymerization
2. Modeling goals and techniques
3. Case study 1: model-based optimization of bulk CRP of
styrene
4. Case study 2: model-based optimization of miniemulsion CRP
of acrylates
5. Conclusions
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Principle of NMP miniemulsion
20
emulsifier
acrylate droplet (nm)
NMP initiator R0X
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Branching in acrylate radical polymerization
21
0 0
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Model analysis: importance of backbiting
22TCL= 300, T= 112°C; dp= 60 nm
lower kbb
higher kbb
All model parameters: literature data
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
23
Model analysis: relevance X partitioning
Part. Coeff.= 50 (org/aq)
Part. Coeff.= ∞ (org/aq)
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Model-guided optimization: selection of dp
24TCL= 300, T= 112°C; dp= 60 nm; conversion: 0.7
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Part. Coeff.= 50 (org/aq) Part. Coeff.= ∞ (org/aq)Part. Coeff.= 5000 (org/aq)
Outline
25
1. Principle of radical polymerization:
a. Conventional free radical polymerization
b. Controlled radical polymerization
2. Modeling goals and techniques
3. Case study 1: model-based optimization of bulk CRP of
styrene
4. Case study 2: model-based optimization of miniemulsion CRP
of acrylates
5. Conclusions
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Conclusions
26
1. A versatile multi-scale modeling platform has been developed at the LCTallowing the simulation of
� Homogeneous polymerization: bulk and solution polymerization
� Heterogeneous polymerization: suspension, miniemulsion andmicroemulsion polymerization
2. The platform has been successfully applied for model-guided design of
� Controlled radical polymerization
� Living polymerization
� Free radical polymerization
3. The modeling platform is generic that it can be extended to any otherpolymerization technique
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
Acknowledgments
27
1. Fund for Scientific Research Flanders (FWO Vlaanderen)
2. The Long Term Structural Methusalem Funding by the FlemishGovernment
3. The Interuniversity Attraction Poles Program - Belgian State -Belgian Science Policy (BELSPO)
Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014
