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Polymerization Modeling for Relief Systems Design

1,3-Buatadiene Polymerization Case Study

By A Presentation to the
G. A. Melhem, Ph.D. DIERS USERS GROUP
melhem@iomosaic.com April 28-30, 2003, Philadelphia, PA

© 2003, ioMosaic Corporation, 93 Stiles Road, Salem, New Hampshire 03079, USA. All rights reserved
Incident statistics of reactive storage

• Survey recently completed by

the chemical safety
investigation board
• Storage vessels and drums
account for 32 % of all
accidents surveyed

Source: J. Murphy, CSIB Public Hearing Staff Preliminary Conclusions, May 2002, Paterson,
New Jersey.
GAM/Spring 2003 DIERS 2
 Millions of lbs
Thermoplastics

Polymerizations: How much do we know ? Polyethylene - Low Density

Polyethylene - Linear Low Density
7,578
7,227
Polyethylene - High Density 12,924
Polyvinyl Chloride and Copolymers 14,502
Polypropylene 13,825
• “Free radical polymerizations are the best studied Polystyrene 6,327
reactions in all of chemistry”[1] Acrylonitrile-Butadiene-Styrene 3,086

• “The kinetics of alkyllithium initiation for styrene and Thermosets

diene polymers in hydrocarbon solutions has been Phenolic 3,940

investigated extensively”[10] Urea
Unsaturated Polyester
2,581
1,713
Epoxy 639
• In 1998, the chemical and petrochemical industries Melamine 290
produced 87 Billion lbs of polymers including Synthetic Fibers
thermoplastics, thermosets, synthetic fibers, and
synthetic rubber[2] Polyester
Nylon
3,911
2,847
Olefin 2,800
• Many companies have developed and tuned Acrylic 346
polymerization models (anionic, free radical, etc.) Acetate and Rayon 365

that can be coupled with thermally initiated Synthetic Rubber

polymerization kinetics for relief design under
Styrene-Butadiene 960
runaway reaction scenarios[3][4][5] Polybutadiene 580
Ethylene-Propylene 321
Nitrile 89
Polychloroprene 72

Totals 86,923

GAM/Spring 2003 DIERS 3

The heats of reaction/polymerization are well known[6]

Heat of Heat of
Polymerization Polymerization
Monomer Bond Polymer Bond (Kcal/gmol) (BTU/lbmol)

C=C -C-C -20 -35,977

C=O -C-O -5 -8,994
C=N -C-N -1.4 -2,518
C≡N -C=N- -7.2 -12,952
C=S -C-S- -2 -3,598
S=O -S-O- -7 -12,592

GAM/Spring 2003 DIERS 4

The heats of reaction/polymerization are well known[7][8][9]

Heat of Heat of Heat of Heat of

Polymerization Polymerization Polymerization Polymerization
Monomer (kcal/gmol) (BTU/lbmol) (cal/g) (BTU/lb)
LOW
Methyl Styrene -8.4 -15,110 -71 -128
Methyl Methacrylate -13.5 -24,284 -135 -243
Styrene -16.7 -30,041 -160 -288
Vinylidene Chloride -18 -32,379 -186 -334
Methyl Acrylate -18.8 -33,818 -218 -393
Isobutene -12.3 -22,126 -219 -394
Vinyl Acetate -21 -37,776 -244 -439
Isoprene -17.8 -32,019 -261 -470
1,3-butadiene -17.4 -31,300 -322 -579
Vinyl Chloride -22.9 -41,193 -366 -659
Tetrafluoroethylene -37.2 -66,917 -372 -669
Propylene -20.5 -36,876 -487 -876
Ethylene -22.7 -40,834 -809 -1,456
HIGH

GAM/Spring 2003 DIERS 5

The mechanism of free radical polymerization involves three steps:
initiation, propagation, and termination[1][2][8][10]

kd
d[I ]
Initiation I → 2 R• − = kd [ I ]
dt

kp
d[M ]
Propagation M + M → M n•+1
•
n − = k p [ M • ][ M ]
dt

kt
d[M • ]
Termination • •
M + M → dead polymer
n m − = 2kt [ M • ]2
dt

At steady-state (> 1 min), the net rate of production of free radicals is

zero so that the initiation and termination rates are equal

GAM/Spring 2003 DIERS 6

Other important data can be estimated using the steady state assumption
such as termination rates and average degree of polymerization [1][2][8][10]

Termination
• •
kt
d[M • ]
M + M → dead polymer
n m − = 2kt [ M • ]2 = 2kd f [ I ]
dt
Average Degree of Polymerization*
[M ] kp
DP = k ′′ where k ′′ =
[I ] 2 k d kt f

* Molecular weight of polymer / molecular of monomer

GAM/Spring 2003 DIERS 7

Often, the free radical rate expression is simplified such that the rate of
polymerization is represented using a composite form[1][2][8]

1 dN monomer
− = kc [ N monomer ] [ I ]
Vl dt
N is the number of moles in ( kmol ) and[ ] is in (kmol / m3 )
1
 kd  2
kc = k p  f  where f is the initiator efficiency
 kt 
 E  Ad 1
kc = Ac exp  − c  where Ac = Ap f and Ec = E p + ( Ed − Et )
 T  At 2
 E  dI
kd = Ad exp  − d  and = − kd I
 T  dt
Vl = Total liquid volume in m3 , k p and kt are in (m3 / kmol / s ) and kd is in s −1

GAM/Spring 2003 DIERS 8

There are many published values for kd[1][8][11]
sqrt(Kd/K*)
INITIATOR REFERENCE SOLVENT Ad Ed (/K) Kd at 50 C at 50 C

2,2-Azo-bis-isobutyronitrile (AIBN) Polymer Handbook Benzene 1.438E+15 15,449 2.485E-06 1.189

2,2-Azo-bis-isobutyronitrile (AIBN) Principles of Polymerization Benzene 1.881E+14 14,842 2.129E-06 1.100

Benzoyl peroxide Polymer Handbook Benzene 5.281E+12 13,990 8.349E-07 0.689

Benzoyl peroxide Principles of Polymerization Benzene 7.390E+13 14,950 5.983E-07 0.583
Benzoyl peroxide ATOFINA Catalogue 3.184E+14 15,318 8.254E-07 0.685

Butadiene Polyperoxide Butadiene Safety Manual 2.400E+07 9,864 1.329E-06 0.869

Cumyl peroxide Polymer Handbook Benzene 1.318E+18 20,481 3.933E-10 0.015

Cumyl peroxide Principles of Polymerization Benzene 1.290E+18 20,482 3.832E-10 0.015

Lauroyl Peroxide Polymer Handbook Benzene 2.142E+15 15,298 5.907E-06 1.833

Lauroyl Peroxide* ATOFINA Catalogue 1.300E+16 16,272 1.759E-06 1.000

tert-Butyl hydroperoxide Polymer Handbook Benzene 3.223E+15 20,531 8.228E-13 0.001

tert-Butyl hydroperoxide Principles of Polymerization Benzene 2.868E+15 20,531 7.342E-13 0.001
tert-Butyl hydroperoxide ATOFINA Catalogue 1.523E+12 17,321 8.033E-12 0.002

tert-Butyl perbonzoate Polymer Handbook Benzene 2.314E+15 17,462 7.886E-09 0.067

tert-Butyl perbonzoate ATOFINA Catalogue 1.754E+14 16,465 1.307E-08 0.086

tert-Butyl peroxide (TBP) Polymer Handbook Benzene 8.568E+13 17,110 8.685E-10 0.022
tert-Butyl peroxide (TBP) Principles of Polymerization Benzene 3.236E+14 17,668 5.825E-10 0.018

GAM/Spring 2003 DIERS 9

There are many published values for kp, and kt[1][8]

Monomer Ap Ep kp at 60 C At Et kt at 60 C kp/kt

Vinyl Chloride 3.300E+06 1,924 10,231 1.474E+12 2,117 2.564E+09 3.990E-06

Vinyl Acetate 1.532E+06 2,165 2,307 7.899E+10 2,634 2.910E+07 7.926E-05
Acrylonitrile 6.813E+05 1,948 1,965 2.719E+11 2,717 7.800E+07 2.519E-05
Methyl acrylate 1.000E+08 3,572 2,205 2.884E+10 2,670 9.534E+06 2.313E-04
Methyl methacrylate 8.700E+06 3,175 631 1.876E+09 1,431 2.555E+07 2.471E-05
Styrene 4.500E+06 3,127 377 1.079E+09 962 6.008E+07 6.281E-06
Ethylene 1.862E+05 2,213 243 8.636E+08 156 5.401E+08 4.494E-07
1,3-Butadiene 1.200E+07 2,923 1,859
1,3-Butadiene [15] 8.050E+07 4,292 205 1.130E+10 711 1.337E+09 1.530E-07

Kp = Ap exp ( -Ep/T)
Kt = At exp (-Et/T)
Ep and Et are in /K
Ap and At are m3/kmol/s
References [1] and [8] provide guidance and typical values on activation energies, pre-exponential factors, rate
constants, and rate constant ratios

GAM/Spring 2003 DIERS 10

1,3-Butadiene thermally initiated polymerization occurs in both the
vapor and liquid phases[16][11]
• Thermal dimerization of butadiene to form vinylcyclohexene proceeds
according to the rate equation (dominant dimerization reaction at 600
BTU/lb of BD) and is second order in BD.
1 dN BD  −12,344 
= −3.47 ×107 exp   [CBD ]
2

V dt  T 

• Thermal dimerization of butadiene to form 1,5-cyclooctadiene proceeds

according to the rate equation (a few percent of COD typically formed)
1 dN BD  −14,312 
= −1.8 ×108 exp   [CBD ]
2

V dt  T 

• Thermal trimerization of butadiene to form ∆3,3’-octahydro diphenyl

proceeds according to the rate equation
1 dN BD  −19,122 
= −8 ×1013 exp   [CBD ][CVCH ]
V dt  T 

Where N is the number of moles (kmol), V is the total liquid volume (m3), T is the temperature in (K), t is the time
in (s), and CBD is concentration of butadiene in (kmol/m3).

GAM/Spring 2003 DIERS 11

We conducted several adiabatic calorimetry tests to verify the
butadiene kinetics reported in the literature
• The TBC was removed by vacuum distillation
• Test A, B, and C were conducted in the accelerating rate calorimeter
(ARC)
• Test D was conducted in the advanced pressure tracking adiabatic
calorimeter (APTAC)
• Lauroyl peroxide was used to simulate the effect of butadiene
polyperoxide on butadiene polymerization
• The test data clearly shows (as stated in various literature sources) that
the onset temperature of the butadiene polymerization is lowered
considerably in the presence of active oxygen

GAM/Spring 2003 DIERS 12

GAM/Spring 2003 DIERS 13
 100
Test A Test B Test C
Inert gas Argon Argon Argon
1,3-Butadiene Sample Mass (g) 2.089 2.057 4.345

Active Oxygen Concentration (ppmw) 0 557 2,682

Test Cell Weight (g) 10.447 10.414 6.834
Test Cell Volume (ml) 9 9 9
Test Cell + Fittings Weight (g) 21.157 21.087 17.55
Detection Sensitivity (C/min) 0.02 0.02 0.02
10 Start Temperature (C)
Heat Step (C)
28.8
3
18.65
3
23.2
3
Wait Time (min) 20 20 20 Test A
Starting Pressure (psia) 40.5 33.4 38.1
Detected Onset Temperature (C) 112 73 55
dT/dt (C/MIN)

0.1 Test B
Test C

0.01
0 100 200 300 400 500
TEMPERATURE (C)

GAM/Spring 2003 DIERS 14

 500

400

Test A
TEMPERATURE (C)

300

Test C
200

100
Test B

0
0 1000 2000 3000 4000
TIME (MIN)

GAM/Spring 2003 DIERS 15

 1500
Test A Test B Test C
Inert gas Argon Argon Argon
1,3-Butadiene Sample Mass (g) 2.089 2.057 4.345

Active Oxygen Concentration (ppmw) 0 557 2,682

Test Cell Weight (g) 10.447 10.414 6.834
Test Cell Volume (ml) 9 9 9
Test Cell + Fittings Weight (g) 21.157 21.087 17.55
Detection Sensitivity (C/min) 0.02 0.02 0.02
Start Temperature (C) 28.8 18.65 23.2
Heat Step (C) 3 3 3
Wait Time (min) 20 20 20
Starting Pressure (psia) 40.5 33.4 38.1
1000 Detected Onset Temperature (C) 112 73 55
PRESSURE (PSIA)

Test C

Test A
500 Test B

0
0 1000 2000 3000 4000
TIME (MIN)

GAM/Spring 2003 DIERS 16

 1200

1100 Inert gas

Test A
Argon
Test B
Argon
Test C
Argon
1,3-Butadiene Sample Mass (g) 2.089 2.057 4.345
Active Oxygen Concentration (ppm) 0 557 2,682
1000 Test Cell Weight (g) 10.447 10.414 6.834
Test Cell Volume (ml) 9 9 9
Test Cell + Fittings Weight (g) 21.157 21.087 17.55
Detection Sensitivity (C/min) 0.02 0.02 0.02
900 Start Temperature (C) 28.8 18.65 23.2
Heat Step (C) 3 3 3
Wait Time (min) 20 20 20
800 Starting Pressure (psia)
Detected Onset Temperature (C)
40.5
112
33.4
73
38.1
55
PRESSURE (PSIA)

700
Test C
600
Test A
500

400

300

200 Test B

100

0
0 100 200 300 400
TEMPERATURE (C)

GAM/Spring 2003 DIERS 17

 100
Test D
Inert gas None
1,3-Butadiene Sample Mass (g) 60.31
Active Oxygen Concentration ppmw 570
Test Cell Weight (g) 34.82
Test Cell Volume (ml) 133
Test Cell + Fittings Weight (g) 38.88 Dimerization
10 Detection Sensitivity (C/min) 0.06
Start Temperature (C) 25
Heat Step (C) 2
Wait Time (min) 20
Starting Pressure (psia) 56
Dead End
dT/dt (C/MIN)

Detected Onset Temperature (C) 50

Polymerization
1

0.1

0.01
0 50 100 150 200
TEMPERATURE (C)

GAM/Spring 2003 DIERS 18

 1000 Test D
Inert gas None
1,3-Butadiene Sample Mass (g) 60.31
Active Oxygen Concentration ppmw 570
Test Cell Weight (g) 34.82
Test Cell Volume (ml) 133
100 Test Cell + Fittings Weight (g) 38.88
Detection Sensitivity (C/min) 0.06
Start Temperature (C) 25
Heat Step (C) 2
Wait Time (min) 20
Starting Pressure (psia) 56
Detected Onset Temperature (C) 50
dP/dt (PSI/MIN)

10

0.1

0.01
0 50 100 150 200
TEMPERATURE (C)

GAM/Spring 2003 DIERS 19

 Model fit for free radical and thermally initiated 1,3-butadiene kinetics
1 dN BD  −13, 786  Where N is the number of moles (kmol), V
= −2.7815 ×1010 exp   [CBD ] Cactive, ppmw
1000 V dt  T  is the total liquid volume (m3), T is the
temperature in (K), t is the time in (s), CBD
where
is concentration of butadiene in (kmol/m3),
1
and Cactive is the concentration of active
100  −13, 786   kd  2 oxygen/free radicals in ppm
2.7815 ×1010 exp   = k p f 
 T   kt 

Model Predictions
10
dT/dt (C/MIN)

Dead End
Polymerization
1

Experimental

0.1

Dimerization
0.01 Note that dimerization kinetics
are based on known
literature data and were not fit
from this data set.
0.001
0 100 200 300 400 500
TEMPERATURE. F
Source: SuperChems Expert Version 5.2
GAM/Spring 2003 DIERS 20
 Model fit for free radical and thermally initiated 1,3-butadiene kinetics

10000

1000

Experimental

100
dP/dt (PSI/MIN)

10

1
Model Predictions

0.1

0.01
0 100 200 300 400 500
TEMPERATURE. F
Source: SuperChems Expert Version 5.2
GAM/Spring 2003 DIERS 21
Dilute concentrations of butadiene polyperoxide decompose at higher
temperatures than Lauroyl peroxide[11][12]
The decomposition rate of Lauroyl (LP) and
1 butadiene polyperoxide (BDP) at dilute
concentrations are give by the following rate
expressions:
0.9
dC
=−k C
0.8 dt
 9,864 
0.7 BDP k BDP = 2.4 × 107 exp  − 
C/Co AFTER 60 MINUTES

 T 
 16,172 
0.6 k LP = 1.3 ×1016 exp  − 
 T 

0.5 Where C is in ppm, k is in /s and T is in Kelvins.

0.4
LP

0.3

0.2

0.1

0
0 100 200 300 400
TEMPERATURE. F

GAM/Spring 2003 DIERS 22

The presence of active butadiene popcorn polymer increases the rates
of the butadiene free radical polymerization and lowers its onset
temperature[15]

• Active butadiene popcorn polymer always contains peroxides, which are

formed by the peroxidation of butadiene by dissolved oxygen
• The peroxide, required for the formation of popcorn polymer, and the
peroxide containing butadiene popcorn polymer itself are known to initiate
the free radical polymerization of butadiene at low temperatures
• Adiabatic data indicate the potential for a runaway reaction at a
temperature at least 50 C lower than would be expected for neat
butadiene

GAM/Spring 2003 DIERS 23

Popcorn kinetics model predictions based on 1950s data[11][13][14]

40
PREDICTED POPCORN MASS RATIO. M/Mo

30

dM
20 =k M
dt
 10,131 
k = 8.0 × 107 exp  − 
 T 
where T is in Kelvins, k is in /s, and
M is the BD popcorn mass
10

0
0 10 20 30 40
EXPERIMENTAL POPCORN MASS RATIO. M/Mo

GAM/Spring 2003 DIERS 24

The free radical model established for 1,3-butadiene using lauroyl
peroxide can easily be extended to other free radical initiators
1

1 dN BD  −13, 786   kd  2
= −2.7815 ×1010 exp     [CBD ] Cactive, ppmw
V dt  T   kd , LP 
dCactive , ppmw  Ed 
= − kd exp  − 
dt  T 
For 2,2-Azo-bis-isobutyronitrile, benzoyl peroxide, and butadiene polyperoxide
1
 kd  2

  ≈1 at 50 C
 kd , LP 

GAM/Spring 2003 DIERS 25

 An Example of an anionic radical polymerization for acrylonitrile
Test cell becomes
100 ARC test / Thermal Inertia = 1.81 liquid full due to expansion
Total sample mass = 3.6 g (20 % Active A)
Anionic species mass = 0.6 g

Thermally initiated
10 Anion initiated
polymerization
polymerization
dT/dt (C/MIN)

0.1

0.01
0 100 200 300
TEMPERATURE (C)

GAM/Spring 2003 DIERS 26

Summary / Conclusions
• Polymerization reactions are the best studied reactions in all of chemistry
• Well known heats of polymerization and thermal polymerization models
• Free radical and anionic polymerizations of many common polymer systems
can easily be established and modeled:
– (a) using literature data, or
– (b) Established experimental techniques of adiabatic/isothermal calorimetry, or
– (c) in-house proprietary production kinetic models.
• Free radical polymerization models should be run in parallel with thermally
initiated polymerization models
• It is possible for a free radical/anion initiated polymerization to “jump-start”
thermally initiated polymerizations if sufficient initiator is present
• Polymerization models are simple and can easily be applied in SuperChems
for DIERS or other simulation computer codes for performing relief design for
reactive systems and process optimization as well

GAM/Spring 2003 DIERS 27

References
[1] “Polymer Chemistry, An Introduction”, R. B. Seymour and C. E. Carraher, Jr., Mercel Dekker, NY, 1981
[2] http://www.stanford.edu/class/cheme160/lectures/lecture1.pdf
[3] “Identification and Validation of a VSL Polymerization Reactor Model”, Bayer Inc., Sarnia, Canada, 1998-2002,
http://www.uni-bayreuth.de/departments/math/~kschittkowski/proj_bay.htm
[4] “Styrene-butadiene rubber synthesized by anionic polymerization, M. C. Iovu et al., 2000,
http://www.sun.ac.za/unesco/Conferences/Conference2000/Abstracts2000/Iovu/IOVU.pdf
[5] “Modeling of ionic polymerization process: styrene and butadiene”, A. Sirohi and K. Ravindranath, AIChE Spring 1999 Meeting, Houston.

[6] http://www.stanford.edu/class/cheme160/lectures

[7] G. Moad and Solomon, The Chemistry of Free Radical Polymerization, Pergamon, ISBN 0080420788

[8] G. Odian, Principles of Polymerization, 3rd Edition, Wiley, 1991

[9] http://www.chem.warwick.ac.uk/ug/ugcourses/year3/ch3a4/downloads/Background.pdf

[10] “Anionic Polymerization, Principles and Practical Application”, H. L. Hsieh and R. P. Quirk, Mercel Dekker, 1996

[11] Butadiene Safety Manual, D. G. Hendry and F. R. Mayo, Stanford Research Institute, 1966

[12] ATOFINA Peroxide Catalogue

[13] Butadiene Popcorn Polymer, G. H. Miller et al., Journal of Polymer Science, 1952, pp. 453-462

[14] Proliferous Polymerization, Encyclopedia of Polymer Science and Engineering, Wiley, 1988, 2nd Edition, pp. 453-463

[15] H. G. Fisher, DIERS Users Group Presentation, May 11, 2002

[16] International symposium on runaway reactions, effluent handling and pressure relief design, G. A. Melhem and H. G. Fisher, Editors,
AIChE, 1998.

GAM/Spring 2003 DIERS 28