propylene polymerization using zieglerpropylene ......a. alshaiban and j.b.p. soares, macromol....
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Propylene Polymerization using ZieglerPropylene Polymerization using Ziegler--Natta Catalysts Natta Catalysts Mathematical Modeling, Polymerization Kinetics andMathematical Modeling, Polymerization Kinetics andMathematical Modeling, Polymerization Kinetics and Mathematical Modeling, Polymerization Kinetics and
Polymer Characterization StudyPolymer Characterization Study
Institute for Polymer Research Symposium May 10, 2011
U i it f W t lUniversity of WaterlooWaterloo, Ontario
Ahmad Alshaiban and João B. P. Soares
Department of Chemical Engineeringp g gUniversity of Waterloo
Waterloo, Ontario, Canada
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2011
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Outline
Background Background Polypropylene Ziegler-Natta Catalysts and Electron Donors
Results Modeling Polymerization Experiments: Kinetic Polymerization Experiments: KineticReactor SetupEstimation of Kinetic Constants
Polymerization Experiments: Characterization Polymerization Experiments: CharacterizationMolecular Weight / GPCTacticity / 13C NMRCrystallinity / CEF
2 Conclusions
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2011
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PolypropyleneBackground
Isotactic
CH3 CH3 CH3 CH3 CH3
PropyleneCHCH
CH2 CH2 CH2CH2
CH
CH2
CH
CH2
CH
CH
Atactic CHCH CH
CH3
CH
CH3
CH
CH3CH3CH3CH2CH
CH3
CHCH
CH2 CH2 CH2CH2
CH
CH2
CH
CH2
CH
Syndiotactic CHCH
CH3
CH
CH3
CH CH
CH3CH3 CH3
3
CH2 CH2 CH2CH2 CH2 CH2
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2011
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BackgroundZiegler‐Natta Catalyst
• Electron Donor Functionality
Donor :D
DDonor :D
DDonor :D
DDonor :DDonor :D
D
Low isotactic Inactive
:D
Low isotactic Inactive
:D
Low isotactic Inactive
:D
Low isotactic Inactive
:D
Ti PolymerVacancyMg ClTi PolymerVacancyMg ClTi PolymerVacancyMg ClTi PolymerVacancyMg ClTi PolymerVacancyMg ClTi PolymerVacancyMg Cl
Donor :D :DDonor :DDonor :D :DDonor D
Atactic Highly isotactic
Donor DDonor D
Atactic Highly isotactic
4Active site models for MgCl2·TiCl4 (Kakugo et al., 1988)
Ti PolymerVacancyMg ClTi PolymerVacancyMg ClTi PolymerVacancyMg ClTi PolymerVacancyMg Cl
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BackgroundIsotacticity and MWD
• Polypropylene tacticity and MWD have a significant effect on its properties.
• Electron donors control polypropylene tacticity.
5(Chadwick et al, 2001)
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ModelingResults
Mathematical Modeling
6
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Modeling ModelingResults
Site Transformation:
Electron Donor D D
Atactic
Ti PolymerVacancyMg Cl
isotactic
Propagation: Ti + Ti
Termination: Ti + TiH H H +
trRP tfR
PpR
P7
tftrp
trtr RRR
P
tftrp
ftf RRR
P
tftrp
pp RRR
P
IP
R 20
11
-
Dynamic Solution Simulation ModelingResults
4 O ll M l l W i h Ti
20
25
x 10 4 Overall : Molecular Weights vs. Time
Normal
2 [M]
10
15
20
eigh
t (g/
mol
)
Normal Conditions 2 [Do]
2 [H2]Mw
0
5
Mol
ecul
ar W Mn
1 2 3 4 5 6 7 8
-5
Ti "S "
8
x 10 4Time "Sec"
A. Alshaiban and J. B. P. Soares, Macromol. Symp., 285, 8 (2009)
A. Alshaiban and J.B.P. Soares, Macromol. React. Eng., 5, 96 (2011)
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Monte Carlo Simulations ModelingResults
I i (79 9 %) St bl kI i (79 9 %) St bl k
1.00
1.50
dW /
d lo
g(M
W)
Isotactic (91.5 %)
Atactic (2.1 %)
Stereoblocks (6.4 %)
Atactic
IsotacticStereoblock
0 50
1.00
1.50
dW /
d lo
g(M
W)
Isotactic (79.9 %)
Atactic (13.0 %)
Stereoblocks (7.1 %)
Atactic
Isotactic
Stereoblock
1.00
1.50
dW /
d lo
g(M
W)
Isotactic (91.5 %)
Atactic (2.1 %)
Stereoblocks (6.4 %)
Atactic
IsotacticStereoblock
0 50
1.00
1.50
dW /
d lo
g(M
W)
Isotactic (79.9 %)
Atactic (13.0 %)
Stereoblocks (7.1 %)
Atactic
Isotactic
Stereoblock
0.00
0.50
1 2 3 4 5 6
log(MW)
d
0.00
0.50
1 2 3 4 5 6
log(MW)
0.00
0.50
1 2 3 4 5 6
log(MW)
d
0.00
0.50
1 2 3 4 5 6
log(MW)
0.5 x Do
Do
2 x Do
919.0019.5020.0020.5021.0021.5022.0022.5023.0023.50ppm downfield TMS
A. Alshaiban and J.B.P. Soares, Macromol. React. Eng., 5, 96 (2011)IP
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PolymerizationExperiments
Polymerization Experiments
10
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Reactor Set‐up PolymerizationExperiments
PCPCPC
Kinetic
rpmcontrol TIC
PI
FIPropylenerpm
control TICPI
FIPropylene
Cooling Water Cooling WaterCooling Water Cooling Water
Elect. HeatElect. Heat
Level-1 Level-2
Do/Ti (mol/mol) 1.5 0DCPDMS (D-Donor)
11
H2 (psi) 16 0
T (oC) 60 70
DCPDMS (D-Donor)Di cyclo pentyl di methoxy silane
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2011
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Estimation of Kinetic Constants PolymerizationExperimentsKinetic
k
Propylene Uptake Mathematical Formulation
tMVR Expp d
d, Vk
eeMCkR
tkKktK
pp
dad
a
1)1(
0tdK
ka
d1
2,2 ][min pExppkKk
RRa
p
12
*
kdIP
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Polymerization Experiments PolymerizationExperiments
60oCF t I II III IV
Kinetic
Factor I II III IV
Al/Ti (mol/mol) 900 (± 7.1%) 900 (± 16%) 900 (± 7.7%) 900 (± 7.2%)
Do/Ti (mol/mol) 1.5 (± 7.1%) 0 1.5 (± 9.6%) 0
H (psi) 0 0 16 (± 10%) 16 (± 10%)H2 (psi) 0 0 16 (± 10%) 16 (± 10%)
Yield (g‐PP∙g‐cat−1∙min−1) 7.6 (±15%) 6.1 (±15%) 17.3 (±2.5%) 8.4 (±6.5%)
0.0460 I 36
0 02
0.03
l/min)
60_I_36
60_I_37
60_I_40
0.01
0.02
R p (m
o
13
*
0.00
0 5 10 15 20 25 30 35
Time (min)
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2011
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Polymerization Experiments PolymerizationExperiments
Rp Experimental vs. Calculated at 60ºC
Kinetic
(D, —)
(—, —)
0.08 60_I_exp
60 II exp ( , )
(D, H)
(—, H)0.04
0.06
mol/m
in)
60_II_exp
60_III_exp
60_IV_exp
60 I cal
0.02
R p (m
60_I_cal
60_II_cal
60_III_cal
60 IV cal0
0 5 10 15 20 25 30 35
Time (min)
60_IV_cal
14
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Polymerization Experiments Results
Rp Experimental vs. Calculated at 70ºC
0.08 70_I_exp
70 II exp
(D, —)
(—, —)
0.04
0.06
mol/m
in)
70_II_exp
70_III_exp
70_IV_exp
70 I cal
( , )
(D, H)
(—, H)
0.02
R p (m
70_I_cal
70_II_cal
70_III_cal
70 IV cal0
0 5 10 15 20 25 30
Time (min)
70_IV_cal
15
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Polymerization Experiments PolymerizationExperiments
Group II (D, —) 2C70,C60,2 ])()[(min pExpppExppkKk
RRRRa
p
Kinetic
kd
0.030
0.040
min)
60_II_exp
60_II_cal
70_II_exp
70_II_cal
0.010
0.020
R p (m
ol/
60 70 E
0.000
0 5 10 15 20 25 30 35
Time (min)
60oC
70oC
E kcal/mol
Ka(min)–1 0.33 0.89 22.8
k (L mol–1 min–1) 1 7x103 2 5x103 8 6
16
kp (L·mol 1· min 1) 1.7x103 2.5x103 8.6
kd (min)–1 0.010 0.041 31.8 *
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Polymerization Experiments PolymerizationExperimentsKinetic
30
35
l‐1)
EA Ep Ed
20
25
ergy
(kcal.m
o
5
10
15
Activation En
e
0
I (D, −) II (−, −) III (D, H) IV (−, H)
A
17*
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Summary of the Estimated Kinetic Constants PolymerizationExperiments
K increases as T increases
Kinetic
Ka increases as T increases.Ka increases by adding H2 in absence of Do.
Ka get’s the highest value at the presence of H2only (IV).
Kp increases as T increases. kp get’s the highest value at the presence of kp get s the highest value at the presence of Do & H2 (III).
kp increases by adding H2 (III) & (IV).
kd increases as T increases.kd increases by adding H2 in absence of Do (IV).
18*
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Conclusion Conclusion
Developed a detailed mathematical model that describes
Kinetic
Developed a detailed mathematical model that describespropylene polymerization kinetics and polypropylenemicrostructure, taking in consideration the effect of externalelectron donors.(*)
Estimated the activation energies of activation, propagation, anddeactivation of a commercial heterogeneous Ziegler Nattacatalyst for propylene polymerization in order to be integratedwith the commercial process simulator.
A. Alshaiban and J. B. P. Soares, Macromol. Symp., 285, 8 (2009)(*)
19
A. Alshaiban and J.B.P. Soares, Macromol. React. Eng., 5, 96 (2011)IP
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PolymerizationExperiments
Characterization
GPC A l iGPC Analysis
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GPC Analysis PolymerizationExperiments
Mn decreases with H2 at
Characterization
Mn decreases with H2 at the same T.
Mn increases with T in the presence of Do andthe presence of Do and vice versa.
PDI decreases with H2.2
PDI decreases with increasing T.
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GPC Analysis PolymerizationExperimentsCharacterization
0 15
0.2
0.25
0.3
0.35
2
IIIIIIIV
(donor, no H2)(no donor, no H2)
(donor, H2)(no donor, H2)
0 15
0.2
0.25
0.3
0.35
2
IIIIIIIV
0 15
0.2
0.25
0.3
0.35
2
IIIIIIIV
(donor, no H2)(no donor, no H2)
(donor, H2)(no donor, H2)
0.6
0.7
0.8Exp.# 0395 Site Types
2= 0.00496 0
0.05
0.1
0.15
2 3 4 5 6 70
0.05
0.1
0.15
2 3 4 5 6 70
0.05
0.1
0.15
2 3 4 5 6 7
0 3
0.4
0.5
W/d
(log
MW
)
Number of Site TypeNumber of Site TypeNumber of Site Type
0.1
0.2
0.3dW
02 3 4 5 6 7 8 9
log MW
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2011
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GPC Analysis PolymerizationExperiments
60oC
Characterization
ParameterI
(D, —)II
(—, —)III
(D, H)
IV
(—, H)
Mn (g∙mol−1) 30.1 x 103 22.5 x 103 18 x 103 19 x 103
Mw (g∙mol−1) 151.6 x 103 140.3 x 103 82.9 x 103 77.3 x 103
PDI 5.0 6.2 4.6 4.1
Number of site types (n) 5 5 5 5
70oC
ParameterI
(D, —)II
(—, —)III
(D, H)
IV
(—, H)
M (g∙mol−1) 84 1 x 103 13 7 x 103 27 5 x 103 9 4 x 103Mn (g∙mol ) 84.1 x 103 13.7 x 103 27.5 x 103 9.4 x 103
Mw (g∙mol−1) 499.4 x 103 72.5 x 103 95.5 x 103 32.6 x 103
PDI 5.9 5.3 3.5 3.5
Number of site types (n) 5 5 4 4Number of site types (n) 5 5 4 4IP
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PolymerizationExperiments
Characterization
13C NMR Analysis
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13C NMR Analysis PolymerizationExperiments
19.868
19.943
20.090
20.166
20.299
20.329
20.605
20.858
21.061
21.181
21.357
21.594
21.675
21.699
21.714
21.730
21.738
21.746
21.754
21.762
21.770
21.778
21.786
21.794
21.851
21.884
21.892
21.900
21.908
21.916
21.924
21.932
Characterization
19.867
19.946
20.090
20.169
20.298
20.342
20.691
20.857
20.898
20.936
21.060
21.182
21.371
21.593
21.632
21.674
21.698
21.729
21.737
21.745
21.753
21.761
21.769
21.777
21.785
21.793
21.850
21.883
21.891
21.899
21.907
21.915
1919202020202020212121212121212121212121212121212121212121212121
17.518.018.519.019.520.020.521.021.522.022.5 ppm
1.052
0.873
0.904
1.258
1.841
2.252
56.443
1.000
III (D, H)
IV ( H)
17.518.018.519.019.520.020.521.021.522.022.5 ppm
849
805
051
622
948
207
101
170
000
IV (—, H)
1.8
1.8
2.0
3.6
3.9
5.2
0.1
59.11.0
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13C NMR Analysis PolymerizationExperiments
Seq.# Range ( d )* I(D, —)
II(—, —)
III(D, H)
IV(—, H)
1 mmmm 22.0 − 21.7 83.78 61.25 93.77 76.46
Characterization
1 mmmm 22.0 21.7 83.78 61.25 93.77 76.46
2 mmmr 21.7 − 21.4 3.73 9.51 3.06 6.73
3 rmmr 21.4 − 21.2 0.53 1.87 0.00 0.00
4 mmrr 21.2 − 21.0 4.17 7.76 2.48 4.96
5 mmrm + rmrr 21.0 − 20-7 2.01 6.38 0.00 4.60
6 rmrm 20.7 − 20.5 0.00 1.67 0.00 0.00
7 rrrr 20.5 − 20.25 2.90 3.55 0.00 2.61
8 rrrm 20.25 − 20.0 1.67 5.18 0.00 2.29
9 mrrm 20.0 − 19.7 1.21 2.82 0.69 2.35
•Range of d reported by Busico et al.(2001) IP
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13C NMR Analysis: Simulated H2 effect on polypropylene tacticityPolymerizationExperiments
Characterization
1/2 x H2
12.70%4.28%
H2
7.19%6.04%
2 x H2
3.90%7.45%
83.01% 86.77% 88.65%
Isotactic chains in wt% Atactic chains in wt% Stereoblock chains in wt%
A. Alshaiban and J. B. P. Soares, Macromol. Symp., 285, 8 (2009)A. Alshaiban, 2008, MASc. Thesis, University of WaterlooA. Alshaiban and J. B. P. Soares, Macromol. Symp., 285, 8 (2009) A. Alshaiban and J.B.P. Soares, Macromol. React. Eng., 5, 96 (2011)
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PolymerizationExperiments
CEF Analysis
Characterization
CEF Analysis
Injection Crystallization Elution
F
Injection Crystallization Elution
FFE
TfTiTfTi
TREFFE
TfTiTfTi
TREF
FEFcCEF
FEFcCEF
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CEF Analysis PolymerizationExperimentsCharacterization
30
35 A_70_I_158 A_70_I_159 A_70_II_157 A_70_II_147
(D, —) (—, —)
( D H) ( H)
20
25
30
dT
A_70_III_154 A_70_III_155 A_70_IV_151 A_70_IV_153( D, H) (—, H)
10
15dW/d
0
5
18 38 58 78 98 118
Temperature (oC)
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CEF Analysis PolymerizationExperimentsCharacterization
20 A_60_I A_60_II A_60_III A_60_IV(D, —) (—, —) ( D, H) (—, H)
15
W/dT
5
10dW
0
18 38 58 78 98 11818 38 58 78 98 118
Temperature (oC)
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2011
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CEF Analysis PolymerizationExperiments
15
20
A 60 I A 70 I
116.7°C
Group I (D, —)
Characterization
5
10dW/dT
A_60_I A_70_I
112.1°CMn
g/mol
PDI mmmm
%
30.1 x 103 5.0 83.78
30
0
5
18 38 58 78 98 118
T (oC)
84.1 x 103 5.9 95.5
20
25
30Temperature (oC)
Group II (—, —)
5
10
15
dW/dT
A_60_II A_70_II
109.9°C110.8°C
Mn g/mol
PDI mmmm
%
22.5 x 103 6.2 61.25
13 7 x 103 5 3 63 00
0
5
18 38 58 78 98 118
Temperature (oC)
13.7 x 103 5.3 63.00IP
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CEF Analysis PolymerizationExperiments
15116.3°C
Group III (D, H)
Characterization
5
10
dW/dT
A_60_III A_70_III114.9°C Mn
g/mol
PDI mmmm
%
18 x 103 4.6 93.77
0
18 38 58 78 98 118
27.5 x 103 3.5 96.90
Temperature (oC)
15
20
T
Group IV (—, H)
M PDI mmmm
5
10dW/dT
A_60_IV A_70_IV111.5°C 111.9°C
Mn g/mol
PDI mmmm
%
19 x 103 4.1 76.46
9.4 x 103 3.5 74.85
0
18 38 58 78 98 118
Temperature (oC)
9.4 x 10 3.5 74.85IP
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Conclusion Conclusion
Conducted a systematic polymerization kinetics and microstructural studies forpolypropylene produced using 4th generation ZN catalyst and compared thehydrogen effect with the simulation results obtained from the developedhydrogen effect with the simulation results obtained from the developedmathematical model.
Adding Do increases Mn; and at Do presence, Mn increases with T as in groups I(D,—) & III (D,H).( , ) ( , )
Mn decreases with H2 at the same T as we go from II (—, —) to IV(—, H) and from I(D,—) to III (D,H)
Number of site types decreased by one at high T in the presence of H Number of site types decreased by one at high T in the presence of H2.
No significant change in pentad assignments with T except for group I (Do, —)
Introducing H2 tends to increase the tacticity [ I (D,—)III (D,H) ] and [ II (—, —)IV( H) ] hi h i i t ith i l ti f th d l d th ti l(—, H) ] which is in agreement with our simulation of the developed mathematicalmodel.
Group III (D, H) shows the highest crystallization peak temperature.
Crystallinity increases with T in the presence of Do, I (D,—) & III (D,H).
A. Alshaiban and J. B. P. Soares, Macromol. Symp., AcceptedA. Alshaiban and J. B. P. Soares, Macromol. Symp., 285, 8 (2009)
A. Alshaiban and J. B. P. Soares, Macromol. React. Eng., 5, 96 (2011)
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The End
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2011
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