Propylene Polymerization using ZieglerPropylene ......A. Alshaiban and J.B.P. Soares, Macromol. React. Eng., 5, 96 (2011) IPR 2011 Polymerization Experiments Polymerization Experiments

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

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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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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BackgroundZiegler‐Natta Catalyst

• Electron Donor Functionality

Donor :D

DDonor :D

DDonor :D

DDonor :DDonor :D

D

Low isotactic Inactive

:D


:D


:D


: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

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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 %)


Atactic

Isotactic

Stereoblock

1.00

1.50

dW /

d lo

g(M

W)

Isotactic (91.5 %)

Atactic (2.1 %)


Atactic

IsotacticStereoblock

0 50

1.00

1.50

dW /

d lo

g(M

W)

Isotactic (79.9 %)

Atactic (13.0 %)


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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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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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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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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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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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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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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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

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

Documents

Propylene Polymerization using ZieglerPropylene ......A. Alshaiban and J.B.P. Soares, Macromol. React. Eng., 5, 96 (2011) IPR 2011 Polymerization Experiments Polymerization Experiments