1

R H E O LO G I C A L P R O P E R T I E S O F TA I LO R - M A D E M E TA L LO C E N E A N D Z I E G L E R - N AT TA B A S E DC O N T R O L L E D R H E O LO GY P O LY P R O P Y L E N E S

Presenter: Shouliang NieSupervisor: Prof. Costas Tzoganakis

Department of Chemical Engineering University of Waterloo

2015 IPR Symposium

Introduction

2 . O r i g i n o f C o n t r o l l e d R h e o l o g y P o l y p r o p y l e n e s ( C R P P )

ZN-PP: broad MWD;

high MW and viscosity.

CRPP:narrower MWD;

Controlled rheological properties.

Random scission by peroxide

2

Introduction

3.Purpose of this study

1 . Z i e g l e r - N a t t a , m e t a l l o c e n e b a s e d p o l y p r o p y l e n e ( Z N - P P a n d m P P )

CRPPs with same

MW/MFR

Rheological properties

CRPP technique

Rheometer

mPP

ZN-PP

Extruder Extrusion behavior

Discrete GPC output of polypropylenes

3

Modell ing study of CRPP

)exp(*)][(

][ 21

2

3

0

2

2

3 dtP

P nn

)](log/[**10ln

][2

0

Mddwnm

P Pn

CRPP

reaction kinetics

2 . M o d e l l i n g r e s u l t s f o r C R P P s

1 . M o d e l l i n g p r o c e s s

• PDI down to the “most probable distribution”, 2

•From ZN-PP

•From mPP

• From ZN-PP: MW ↓; PDI lowered sharply.

• From mPP: MW↓, however, PDI keeps ca. 2.

We can make CRPPs with tailor-made MW and MWD from different origins.

Modelling study of CRPP

η0 = 7×10-16*Mw3.49

1. Raw Materials & Equipment:

4

Original PPs: Peroxide:

Experimental study of CRPP

2. MW/MFR of CRPPs :

MFR tester

Mw monitored by η0

Evolution of MW

CRPP series to find peroxide level for target MW

CRPP series to find peroxide level for target MFR

Batch Mixer:

@ 210 ◦C*3min

Experimental study of CRPP

Target

500

Mw from modelling

0

500

1000

1500

2000

2500

3000

3500

0 100 200 300 400 500

η0

(18

0 C

, Pa*

s)

Lupreox101 conc.(ppm)

from PPC

target

0

20

40

60

80

0 100 200 300 400 500 600

MFR

,(g/

10

min

)

Lupreox101 conc.(ppm)

from PPC

target

ω

Evolution of MFR

Rotational rheometer

5

Extrusion study of CRPPs and their rheological characters

Rheomix252

Rheocord 90

Melt Pressure

Zone1 Zone3Zone2Zone4 Zone5

Thermocouples

Melt temp

Water Bath

Extrusion set-up for CRPPs

D= 0.0315" (0.89mm)

6.12

9.50

2α

L

20.00

40.00

Drawing of the extrusion dieD=0.0315’, L/D=9

300

600

900

1200

1500

1800

0 5000 10000 15000

Pre

ssu

re d

rop

(p

si)

ẏapp (s-1)

Pressure dorp during extrusion of PPD at different die temperature

140°C160°C180°C200°C

On-set zone of

melt fracture

Development of melt-fracture

with extrusion rate of the extrudate

Extrusion speed / shear rate

Extrusion study of CRPPs

P

6

100

1,000

0.01 0.1 1 10 100 1000

η*

(P

as)

ω (rad*s-1)

CRPPs with the similar zero-shear viscosity

A880

B100

C390

PPD

A880 fit

B100 fit

C390 fit

PPD fit

300

600

900

1200

1500

1800

0 2000 4000 6000 8000 10000 12000

Pre

ssu

re d

rop

(psi

)

ẏapp (s-1)

Extrusion pressure drop of CRPPs with same MFR

PPD

A480

B40

C190

Extrusion study of CRPPs and their rheological characters

A480 B40C190

PPA

PPB

PPC

PPD as target

0

10

20

30

40

MFR

,(g/

10

min

)

PP Sample

Origin PPs CRPPs with similar MFR

300

600

900

1200

1500

1800

0 5000 10000 15000

Pres

sure

dro

p (p

si)

ẏapp (s-1)

Extrusion pressure drop of CRPPs with same MW

PPD

A880

B100

C390

strength of shear-thinning

η0

target MFR

onset of melt-fracture

ẏapp(s-1)

ẏapp(s-1)

Prof. Costas Tzoganakis

Dr. Yasaman Amintowlieh

Dr. Shuihan Zhu

Dr. Xiaochuan Wang (NOVA Chemicals)

Acknowledgements

7Acknowledgements

Polypropylene Peroxide

HAAKE Rhoemix 3000 inner mixer

0

2000

4000

6000

8000

10000

0 1 2 3 4 5 6 7

Mixi

ng tor

que(

m.g)

Time (min)

Mixing of CRPP @210C 80rpm in HAAKE mixer

Load PP

add L101

Mixing recipe of CRPPs:

Polypropylene:Ingenia ground gradesMFR: 13.5 g/10min (230C*2.16kg)

Peroxide:Luperox® 101, SIGMA-ALDRICH (L101),2,5-Bis(tert-butylperoxy)-2,5-dimethyl hexane (DHBP).t1/2 @210C: 13.5s .

Mixing condiction:Temp: 210CRoter speed: 80rpm Reaction time: 3min

Sample L101/ppm Acetone,ml Liquid add typeA1 500 0 directlyA2 1000 0 directlyA3 1500 0 directlyA4 2000 0 directlyB4 2000 20 directlyC4 2000 20 pre-mix

Product ion of CRPP

8

Supporting data1: CRPP production

Initiation:

Chain scission (β-scission):

Transfer:

Thermal degradation:

Termination:

KdI 2R·

K 1Pn + R· Pr· + Pn-r + R

K 2Pn + Pr· Pr + Ps + Pn-s·

K 3Pn Pr· + Pn-r·

K 4Pn· + Pr· Pn + Pr

Reaction kinetics of peroxide-induced CRPP

C. Tzoganakis, J. Vlachopoulos, and A.E. Hamielec,

Polym. Eng. Sci., 28, 170 (1988).B. Krause, M.Stephan,S.Volkland,D.Voigt,

L.Haubler,H.Dorschner,J.App.Polym.Sci.,Vol.99,260–265(2006)

9

Supporting data2: Reaction kinetics of CRPP

)exp(*)][(

][ 21

2

3

0

2

2

3 dtP

P nn

P

d mIfk

0

1

][2

n12

][*21

3

n

nP

dt reaction time increment

m0 molecular weight of monomer

ρP polymer density

[Pn] concentration of polymer chain

n chain length

[I] initiator concentration

Kd decomposition rate constant of the initiator

f initiator efficiency

)exp(][][ 0 dtkII d

S. T. BALKE, D. SUWANDA, and R. LEW,

J. of Polym. Sci.: Part C, Vol. 25, 313-320 (1987)

Quantitation of GPC data

[dw/d(logM)] ordinate data in the normalized

differential GPC curve

)](log/[**10ln

][2

0

Mddwnm

P Pn

R. LEW, D. SUWANDA, and S. T. BALKE,

J. of App. Polym. Sci., Vol. 35, 1049-1063 (1988)

0

0.2

0.4

0.6

0.8

2 3 4 5 6 7 8

dw

/d(l

ogM

)

logM

Differencial GPC Curve

d(logM)

logMi logMi+1

d(logM)

logMi logMi+1

dw/d(logM)

10

Model

GPC output

Supporting data3: Model for CRPP process

Prediction procedure of the peroxide concentrations for CRPPs from PPA/PPB/PPC are:

880/100/390 respectively

1. CRPPs series production for similar MW (η0) *

11

* The MW level of CRPPs was characterized by the zero-shear viscosity η0.

A

B

C

D

E

y = 7E-16x3.4874

R² = 0.9997

10

100

1000

10000

100000

10000 100000 1000000

η0

(Pa

*s)

Mw(g/mol)

Denpendence of η0 on Mw

Mw vs n0

Supporting data4: CRPPs series with same MW/MFR

0

10

20

30

40

50

60

70

80

0 100 200 300 400 500 600

MFR

,(g/

10

min

)

Lupreox101 conc.(ppm)

from PPC

0

10

20

30

40

50

60

70

80

0 200 400 600 800 1000

MFR

,(g/

10

min

)

Lupreox101 conc.(ppm)

from PPA

Prediction procedure of the peroxide concentrations for CRPPs from PPA/PPB/PPC are:

480/40/190 respectively

2. CRPPs series production for similar MFR

12

0

10

20

30

40

50

60

70

80

0 100 200 300 400 500 600

MFR

,(g/

10

min

)

Lupreox101 conc.(ppm)

from PPC

100

1,000

10,000

0.01 0.1 1 10 100 1000

η*

(Pas

)

ω (rad*s-1)

CRPPs with the similar MFR

A480

B40

C190

PPD