Model-guided design of polymerization processes

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

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Model analysis: explicit visualization (1)

16

Methusalem International Advisory Board meeting, Ghent, Belgium, 19/06/2014

Model analysis: explicit visualization (2)

17

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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

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Branching in acrylate radical polymerization

21

0 0

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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