rheological properties of tailor-made … · 1 rheological properties of tailor-made metallocene...
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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
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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) *
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* 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