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Functional Polyolefins Through Polymerizations by Using Bis(indenyl) Zirconium Catalysts

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Polyolefins: 50 years after Ziegler and Natta II

Part of the book series: Advances in Polymer Science ((POLYMER,volume 258))

Abstract

The discovery of metallocene catalysts has enabled synthesis of new polyolefin structures through the ability to incorporate comonomers that are not applicable using Ziegler–Natta or other conventional olefin polymerization catalysts. Extensive research has been carried out on the copolymerization behavior of different bis(indenyl) zirconium catalysts in order to understand their comonomer response, chain termination mechanisms, and chain-end isomerization. Metallocene-catalyzed copolymerization enables unforeseen material structures, leading to functional polyolefins with strongly or weakly interacting comonomers or long-chain branches. These copolymers show interesting technical properties like reactive functionality, compatibility, adhesion properties, and modified rheology.

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Abbreviations

Ar:

Aryl

a T :

Shift factor, a T = η 0(T)/η 0(T 0)

Bn:

Benzyl

Bu:

Butyl

Bz:

Benzoyl

cat:

Catalyst

CD:

Composition distribution

CGC:

Constrained geometry catalyst

-co-SiF:

-co-7-octenyldimethylfluorosilane

-co-SiPh:

-co-7-octenyldimethylphenylsilane

Cp:

Cyclopentadienyl

CSTR:

Continuous stirred tank reactor

E a :

Flow activation energy, a T = exp [(E a/R) × (1/T − 1/T 0)] (kJ mol−1)

Et:

Ethyl

FTIR:

Fourier transform infrared spectroscopy

G*:

Complex modulus, G* = [(G')2 + (G″)2]1/2 (Pa)

G′:

Storage modulus, G′ = cos δ (σ/γ) (Pa)

G″:

Loss modulus, G″ = sin δ (σ/γ) (Pa)

HDPE:

High-density polyethylene

HMW:

High molecular weight

Ind:

Indenyl

i-Pr:

Isopropyl

LCB:

Long-chain branching

LDPE:

Low-density polyethylene

LLDPE:

Linear low-density polyethylene

LVE:

Linear viscoelasticity

MAO:

Methylaluminoxane

M 0 :

Molecular weight of the repeat unit, for PE, M 0 = 14.027 g/mol

M c :

Critical molecular weight above which η 0 scales with \( M_{\mathrm{ w}}^{3.6} \) for PE, M c = 3,500 g/mol

M e :

Chain length for entanglements for PE, M e = 1,300 g/mol

M n :

Number-average molecular weight

M w :

Weight-average molecular weight

Me:

Methyl

MFR:

Melt flow rate

mLLDPE:

Metallocene-catalyzed linear low-density polyethylene

mol:

Mole(s)

MTR:

Mass transfer resistance

MWD:

Molecular weight distribution, M w/M n, as determined by size exclusion chromatography

NMR:

Nuclear magnetic resonance

p E :

Ethylene partial pressure in polymerization

Ph:

Phenyl

Pr:

Propyl

r C :

Reactivity ratio of comonomer

r E :

Reactivity ratio of ethylene

r H :

Reactivity ratio of comonomer (1-hexene)

rt:

Room temperature

SEC:

Size exclusion chromatography

SEC-MALLS:

Size exclusion chromatography coupled with multi-angle laser light scattering

-Si(CH3)2Ph:

Dimethylphenylsilane

-Si(CH3)3 :

Trimethylsilane

SSC:

Single-site catalyst

T :

Measurement temperature

T 0 :

Reference temperature

tan δ :

Loss tangent, tan δ = G″(ω)/G′(ω) [−]

t-Bu:

tert-Butyl

TMS:

Trimethylsilyl

T p :

Polymerization temperature

ZN:

Ziegler–Natta

γ :

Shear strain [−]

γ :

Shear rate (s−1)

δ :

Phase angle, phase shift between stress and strain vectors

ε :

Tensile strain [−]

η :

Shear viscosity, η = σ/γ (Pa s)

η*:

Complex viscosity, η* = G */ω (Pa s)

η 0 :

Limiting viscosity at zero shear rate (Pa s)

η E :

Steady-state extensional (tensile) viscosity, η E = σ E/ε (Pa s)

μSi:

Microsilica

σ :

Shear stress (Pa)

σ E :

Steady state tensile stress (Pa)

ω :

Angular frequency (rad s−1)

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Authors and Affiliations

  1. Department of Biotechnology and Chemical Technology, Aalto University, Espoo, Finland

    Jukka Seppälä & Barbro Löfgren

  2. Borealis Polymers Oy, Porvoo, Finland

    Esa Kokko & Anneli Pakkanen née Malmberg

  3. Neste Oil Corporation, Technology Centre, Porvoo, Finland

    Petri Lehmus

  4. Borouge Pte Ltd, Innovation Centre, Ruwais, United Arab Emirates

    Kimmo Hakala

  5. Styrochem Finland Oy, Porvoo, Finland

    Sami Lipponen

Authors
  1. Jukka Seppälä
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  2. Esa Kokko
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  3. Petri Lehmus
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  4. Anneli Pakkanen née Malmberg
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  5. Kimmo Hakala
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  6. Sami Lipponen
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  7. Barbro Löfgren
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Correspondence to Jukka Seppälä .

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  1. Dept. of Chemistry Inst. for Techn. and Macromol. Chemistry, University of Hamburg, Hamburg, Germany

    Walter Kaminsky

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Seppälä, J. et al. (2013). Functional Polyolefins Through Polymerizations by Using Bis(indenyl) Zirconium Catalysts. In: Kaminsky, W. (eds) Polyolefins: 50 years after Ziegler and Natta II. Advances in Polymer Science, vol 258. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_2013_210

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