Metallocene Catalyzed Polymers – Materials, Properties, Processing and Markets

Metallocene Catalyzed Polymers – Materials, Properties, Processing and Markets
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George Me Benedikt , Brian L Gooddl
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Metallocene Catalyzed Polymers – Materials, Properties, Processing and Markets
George Me Benedikt , Brian L Gooddl
Table of contents
Polyethylene
Polypropylene
Polystyrene
Ethylene-Olefin
Ethylene-Propylene-Diene (EPDM)
Nonbornene Copolymers
The Market
Special Attributes
Materials Economic Factors for the Production of Metallocene and Perfluorinated Boron Cocatalysts Polypropylene Reinvented
Cost of Using Metallocene Catalysts New Approaches for Ziegler-Natta Catalysts for Polypropylene UNIPOL?
Gas Phase Copolymerization with SSC Metallocene Technology High-Molecular-Weight Atactic Polypropylene from Metallocene Catalysts.
Influence of Ligand Structure and Polymerization Conditions on Molecular Weight Homo- and Co-polymers Derived from Multicyclic Olefin Monomers:
The Quest for Higher Tg Materials The Renaissance in Polyolefin Manufacturing Technology Mixed Metallocenes for Designer Polymers Advances in the Functionalized Polyolefins Synthesis and Applications SPS Crystalline Polymer: A New Metallocene-catalyzed Styrene Engineering Thermoplastic Ethylene/a-olefin Copolymers with Metallocene Catalysts in High Pressure Process Semicrystalline Polyolefins – Narrow MWD and Long Chain Branching: Best of Both Worlds Structure and Properties of Single Site Constrained Geometry Ethylene-Propylene-Diene, EPDM, Elastomers Enhancing Polyethylene Performance with INSITE? Technology and Molecular DesignProperties Morphological Investigation on Very Low Density Ethylene-Octene Metallocene Copolymers Using SAXS Further Studies on Metallocene ULDPE/PP Blends Impact-Morphology Relationships Morphology of Low to Very Low Density Ethylene-Octene Metallocene Copolymers Morphological Studies of Metallocene Plastomer Modified Polypropylenes Comparison of the Crystallization Behavior of Ziegler-Natta and Metallocene Catalyzed Isotactic Polypropylene Explaining the Transient Behaviors of Syndiotactic Polypropylene Equilibrium Melting Temperatures of Ethylene Copolymers: An Appraisal of the Applicability of the Flory and Sanchez-Eby Approaches Melt Rheology and Processability of Ethylene/Styrene Interpolymers Characterizing the Melt Relaxation Behavior of Metallocene Polyethylenes Studies on the Thermal Stability and Processability of Syndiotactic Polystyrene The Performance of Primary and Secondary Antioxidants in Polyolefins Produced with Metallocene Catalysts. Part 1. Preliminary Studies Comparing m-Syndiotactic and Isotactic Polypropylenes Metallocene Plastomer Modification of Clear Polypropylene for Impact Enhancement Frictional Behavior of Polyethylenes with Respect to Density and Melting Characteristics Crystallinity Dependence of Modulus and Yield Properties in PolyethylenesProcessing Processing Characteristics of Metallocene Propylene Homopolymers Performance – Property of Novel Glass Fiber Reinforced Polypropylene Compounds and Their Applications Injection Molding of Glass Fiber Reinforced Syndiotactic Polystyrene Injection Molding Optimization Procedures for Polyolefin Plastomers and Elastomers Potential Film Applications of Metallocene-based Propylene Polymers from Exxpol? Catalysis Effect of Various Polyethylene Structures on Film Extrusion An Innovative Approach to Understand Metallocene Based Polyolefins and Thermoplastic Resins for Film Applications Extrusion Behavior of Exxpol Metallocene Polypropylene The Effects of Long Chain Branching of the Processing-Structure-Property Behavior of Polyethylene Blown Film Resins Spherilene Process LLDPE for Conventionally Blown Shrink Film Blown Film Characterization of Metallocene Resins Made in the Phillips Slurry Loop Process Comparison of the Fiber-Spinning Properties of Ziegler-Natta and Metallocene Catalyzed Polypropylene Metallocene Linear Low Density Polyethylene Blends for Pouch Materials in High-Speed Hot-Liquid Filling Process Blends of SIS Block Copolymers with Ultralow Density Polyethylenes Preparation of Metallocene Plastomer Modified High Flow Thermoplastic OlefinsMarkets Metallocene Capabilities Drive Success of Innovative Packaging Manufacturer Impact of Technology on Global Polyethylene Technology Impact of Metallocene Based Polypropylene on Existing Polypropylene Technologies and Markets New Polyethylenes for Targeted Performance Based Applications Polyvinyl Chloride Replacement for Flexible Medical Tubing Index
A
abrasion resistance 374
acid neutralizer 20I
activation energy 181
active coordination site 28
active site 36
adhesion 81, 86, 330, 332
aging 164,200
alloys 243
amorphous 163,225
amorphous region 123
ansa-zirconocene catalyst 22
antiblock agents 305
antioxidants 193,201
Arrhenius plot 47
aspect ratio 151
atactic 24, 43,50, 157, 193
autoignition temperature 248
automobile parts 193
automotive 93, 247
Avrami equation 141
B
BASF 64
BFGoodrich 57
birefringence 318
blends 74, 85, 138, 328, 329, 348
block copolymers 85
bloom 166
blow molding 66,185,209
blown film 101, 185,278,291,299,305
blowup ratio 271
boiling point 182
borane moiety 87
boron-based cocatalysts 1
branch content 141
branching frequency 142
bridge length 29
bridging moiety 29
INDEX
Brintzinger’s catalyst 5
brittle failure 342
brittle matrix 138
brittle-ductile transition 138
bubble stability 271, 277
C
cable jacketing 122,373
calcium stearate 201
Capillary number 154
carbon monoxide 63
catalyst activity 48
decay 36
residue 201
systems
price ranges 14
return on investment 14
chain branching 271,291,369
length 106
transfer 108
transfer reaction 43
chain-end structure 38
chain-folding model 123
chemical resistance 89, 93
chemical shift 60
clarity 211, 305
cocatalyst 8
coefficient of friction 167
coextrusion 123
computer-aided design 121
constrained-geometry 6
cooling rate 250
copolymerization 32, 36, 57, 81, 99
copolymers 169, 179,216,329,339,369
Cox-Merz rule 114, 182 .
Cross model 179
crosslinking 280
crossover frequency 180
crystal382
density 142
perfection 167
thickness 130, 142
crystalline domains 89
crystallinity 84,116,127,160,165,199,
231,280
crystallization 157, 315
D
dart impact 102, 309, 371
deactivation 81
Deborah number 185
deflection temperature 91
degradation 178
density 64, 100, 135,217,223,300,305,
316,339,371
development cost 3
Dex Plastomers 67
Dexco 330
dielectric strength 92
dimensional stability 91, 247
discoloration 193
dispersed phase 335
dispersion 149
dissipation factor 92
DMA 137, 165,332
dominant defect 142
Dow 21,64,66, 103, 127, 141, 171, 177,
330,369
drawdown ratio 271
DSC 79, 114, 130, 136, 141, 158, 194,217,
249,279
DSM66
ductility index 341
dyeability 81
E
electrical housing 193
electrical properties 89
electron-donating groups 28
Elf Atochem 64
elongation 374
Metallocene-catalyzed Polymers
enantioface 24
enchainments 58
endotherm peak 325
energy consumption 271
Eni~hem 64, 331
entanglement 167
enthalpy of melting 159
EPDM 71,113,359
ethylene 77
ethylene/a-olefin copolymer 97
ethylene-propylene copolymer 12, 359
EVA 65,100,281,348,354,374
EVAc 323
extensional flow 232
extensional viscosity 277
extraction 84
extruder 156, 185,215,231,240,316,324,
339
extrusion 200,202,233,271,283
Exxon 21,66,73,231,261,283,330
F
ferrocene 1
fiber 236
fiber spinning 231
fibers 315, 363
fibrils 139
filaments 316, 363
film 236,262,271
film applications 123
film blowing 271, 277, 291
film casting 231
Fina 21, 163, 199,359
flexural modulus 123,225
Flory equation 169
F1ory-Vrij equation 169
flow direction 250
fractionation 84, 100, 158
free radical polymerization 64
friction 219
frictional stress 224
fringed micellar crystals 127Index
frost-line height 271
FTIR 114, 157, 158
functional cost analysis 2, 4
G
Gardner impact 91, 241
gas phase 63, 360
gas phase copolymerization 35,37,39,41
Gibbs-Thomson equation 146
glass fibers 239, 247
glass reinforced 89
glass transition temperature 57, 61,114,135
GPe 53, 194,294
graft copolymers 85
383
impact energy 213
impact strength 91, -292
injection molding 123,240,247,253
injection pressure 94, 256
injection time 254
insoluble fraction 59
interface 139
interfacial tension 149
interfacial thickness 129
intrinsic viscosity 100
ionomer resins 278, 354
irradiation 277
isotactic 27,57, 79, 84, 157, 163,200,203,
315,359
H
hardness 256, 329, 333
haze 212,263,311
HDPE 65,66,188,271,278,292
heat deflection temperature 240
heat of fusion 142, 250, 283
heat resistance 90, 247, 325
heat seal temperature 100, 305
heat sealing 163
heat shrink film 277
heat-sealable material 323
hemi-isotactic structure 25
heteronuclear correlation 61
high pressure 63
Hoechst 71,261
Hoffman-Weeks method 159
Hoffman-Weeks plot 141, 169
hydride elimination 40
hydrogen 77
hydrophilic functional groups 85
hydrophobic 86
hydrotalcite 206
hydrotrimers 60
I
Idemitsu 193
image analysis 150
L
labor cost 6
lamellae 123, 142, 161
lamellar thickness 101, 171
LDPE 11,271,278,299,323,353
Lewis acid 81, 103
lids 125
life-cycle 2
ligand structure 37,97
ligands 1
liquid crystal polyester 91
LLDPE 11,21,40,66,97; 102, 105, 121,
145,186,216,271,292,299,323,352,369
long chain branching 39, 57, 103
loss modulus 119,271
M
market sectors 354
Mark-Houwink-Sakurada parameter 52
medical applications 213
melt 177
melt elasticity 286
melt flow rate 99, 149,201,212
melt fracture 294,371
melt index 37, 64, 69, 200, 279, 339
melt strength 119, 177
melt viscosity measurements of several384
polymers 93
melting behavior 141
melting index 196
melting point 27, 28, 90,101,159,169,193,
280,283
metallocene
capital investment 11
comparison 7
cost contributions 7
cost of use 11
isospecific 24
manufacturing 4
manufacturing cost 13
moisture sensitivity 2
molecules 1
prices 9
production cost 1
purit-y 74
yield 4
methylaluminoxane 11
microstructure 84,116,121,315
microtacticity 79
Mitsubisll.i Petrochemical 64
Mitsui Petrochemical 66
mixing 339
mobility 118
moisture sensitivity 89
mold flow 94
moldability 105
molecular design 121, 122
molecular motion 180
molecular movement 163
molecular weight 37, 43,57, 73, 103, 128,
158,169,171,178,231,253,271,283,305
monomer concentration 44
monomer pressure 99
Monte Carlo simulation 103
Mooney viscosity 114
morphology 31, 85, 127, 135, 185,225,268
multicyclic monomer 57
MetaUocene-catalyzed Polymers
N
Newtonian fluid 155
Newtonian plateau 232
Nippon Oil 70
~47,53,59,83, 158,293
norbomene 57
Nova 66
nucleating agents 209, 315
nucleation 199, 318
o
orientation 235,315
oxidation 193
p
packaging 345
paintability 81
particle size 138, 149, 151
patents 21
Phillips 67, 103,227,291,305
phosphites 202
pilot plant 3, 100
pinhole 302
platelet-like structure 146
PMMA85
Poisson’s ratio 225
poly- phenylene sulfide 91
polycycloolefins 359
polydispersity 37, 104, 128, 141
polyethylene 21, 37, 57, 64,82,121,139,
179,185,211,215,225,271,277,291,305,
329,346,353,359
polyethylene terephthalate 209,323
polyethylenes 11, 169
polymer backbone 81
polymer segment 85
polymerization 52
polymerization temperature 43,47, 51
polyolefins 4,63,81, 103,240,253,277,
305,351,359
polyphthalamide 91
polypropylene 11, 18,21,22,43,57,83,Index
138,149,157,163,199,209,231,239,262,
283,315,339,359
polypropylenes 157
polystyrene 57, 89, 179, 193,247
Porod Law 130
Porod region 129
pouch 323
printability 81
processability 89, 105
propagation 108
propagation rate 43
propylene-ethylene copolymer 50
puncture resistance 334
purification steps 4
PVC 253
R
random copolymers 32
reactive groups 81
reactivity 99
reactor impurities 74
recycling 289
reinforcement 239
relaxation time 185
reptation 185
Rexene 64
rheology 177,186,281,291
S
Sanchez-Ebyequation 169
SANS 149
SAXS 127, 142, 171
sealant 124
sealing 371
SEM 86,136, 149
semicrystalline 225, 255
shear strength 218
shear thinning 104
shear zone 250
Shell 71,330
short chain branching 64, 135
shot size 256
385
shrinkage 241, 263, 299
shrink film 299
side reactions 81
silica support 12
single site catalyst 11,63
slurry loop process 63, 305, 360
solution phase 63
specific gravity 93
spherulites 101, 127, 142,204
spinneret 234
stereochemical sequence 60
stereoisomers 60
stereoregularity 157, 199
stereorigidity 98
stereospecific polymerization 23
steric barrier 106
stiffness 209, 225, 236, 263
storage modulus 119,271
stress relaxation 186
surface tack 329
syndiotactic 22, 47,57, 163, 193, 199,203,
247,359
T
tacticity 30, 61, 261
Taylor’s equation 154
tear strength 104, 292, 305, 332, 333
tensile modulus 91
tensile strength 92, 102, 116,241,334,374
tennination 77
TGA 194,248
thennal expansion 251
thennal stability 178, 193
thickening 280
thickness 305
Thompson-Gibbs plot 169
Thompson-Gibbs relationship 169
tie chain 370
tie molecules 123
titanocene dichloride 1
torque 288
Tosoh 66386
toughness 305
U
ULDPE 135, 374
uniaxial tension 142
Union Carbide 35, 70
V
vanadium systems 23
vinyl unsaturation 105
visbreaking 232, 283
viscoelastic behavior 271
viscosity 152, 179, 231, 248, 277, 286
VLDPE65
volatiles 236, 305
w
\vater absorption 92
WAXD 141
Wu’s model 149
y
yellowness index 201
yield point 142
Young’s modulus 116, 225
Z
Ziegler-Natta 21,38,64,81,103, 121, 135,
157,165,188,199,209,231,240,315,329,
360
zirconocene catalyst 58
zirconocene dichloride 1, 5
zirconocene system 11
MetaUocene-catalyzed Polymers

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