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Oct 24, 2008

LG Chem / Research Park

Kisu Ro*, Ki-Soo Lee, Choong Hoon Lee

메탈로센 촉매에 의한 폴리올레핀 제조 기술

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Contents

1. Introduction

2. LG Metallocene Technology

3. LG Metallocene Product

4. Summary

3/31

HDPE

18%

LLDPE

12%

LDPE

12%PP

24%

PVC

19%

PS

7%

PET

5%

ABS

3%

�World Polymer Demand = 169.6 Million Metric Ton (2006)

� Polyolefins Demand accounts for 66% (112 Mil MT) among polymers.

* Chemical Market Associates (2007)

Polyolefin Biz

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Polyolefin Market Trends

Polyolefin new capacity will increase with rate of 30% by 2010 forcused

in Middle East and Asia � Cannot survive with commodities

Source : SRI (Feb. 2007)

Comparison of Commodity PO TollingComparison of Commodity PO Tolling

Transload

Ship

PE Conv

C2

PE Price

Pro. BuyUS ME

70

60

50

40

30

20

10

0

1540

1320

1100

880

660

440

220

0

Asia

U$/MTcent/lb

Transload

Ship

PE Conv

C2

PE Price

Transload

Ship

PE Conv

C2

PE Price

Pro. BuyUS ME

70

60

50

40

30

20

10

0

1540

1320

1100

880

660

440

220

0

AsiaPro. BuyUS ME

70

60

50

40

30

20

10

0

1540

1320

1100

880

660

440

220

0

Asia

U$/MTcent/lb

Global Global

CapaCapa..

신증설신증설

중동중동

신증설신증설

76 (2006년 현재)

4.6

9.4

신증설

(2007~2010)(2007~2010)

중동 +아시아 기타지역기타지역

중동중동 아시아아시아

18.4 (80%)

23(30%)

단위: 백만톤, %

18.4 (80%)

9 (39%)

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Polyolefin Market TrendsPolyolefin Market TrendsPolyolefin Market Trends

PE Market PP Market

mPO MarketPE

- New Plant only in ME and Asia

- Specialty product based on metallocene

PP

- New Plant in Worldwide

- Product range expansion to the ENPLA

mPO

- mPE CAGR >20%

- Maket leading by Dow and Exxon

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Contents

1. Introduction

2. LG Metallocene Technology

3. LG Metallocene Polyolefins

4. Summary

7/31

–– DefinitionDefinition

Group IV transition metal(Ti, Zr, Hf) coordinating Group IV transition metal(Ti, Zr, Hf) coordinating

at least one bulky ligand + Activator (MAO or at least one bulky ligand + Activator (MAO or NACsNACs))

–– CharacteristicsCharacteristics

Highly activeHighly active

Narrow molecular weight distribution of resulting polymerNarrow molecular weight distribution of resulting polymer

Easy to control polymer propertyEasy to control polymer property

Synthesis of new polyolefin (TPE, COC, PNB, PK etc)Synthesis of new polyolefin (TPE, COC, PNB, PK etc)

Zr

Cl

Cl

MAO

Zr

Me MAO

Free coordination site- cationic14-electron species- strong Lewis acid

Metallocene CatalystMetallocene CatalystMetallocene Catalyst

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Supported Catalysts: ComponentsSupported Catalysts: Components

Zr

Cl

Cl

1

Si Ti

N

Cl

Cl

2

Zr

Cl

Cl

3

N

O

ZrCl2

2

4

<

OOH OH

OH

Cocatalyst : Methylaluminoxane (MAO)

Silica Support

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Supported Catalysts: PolymerizationSupported Catalysts: Polymerization

Molecular

Weight

Zr

Cl

ClSi TiN

Cl

Cl

Zr

Cl

Cl N

O

ZrCl2

2

> > >

8.95101,38011,38818614

(1.0)

4

7.88279,27635,6101783

(1.0)

3

3.901,223,721314,25011802

(1.0)

2

2.20157,77971,62783001

(1.0)

1

PDIMwMnActivity

(g-PE/g-Cat)

Catalyst type

(mmol)

run no.

Supported Catalyst : Silica = Sylopol 948 (dehydrated at 200oC), MAO (5mmol)

Polymerization: ethylene pressure = 40 atm, temperature = 80oC, time = 1hr,

solvent = Hexane (1.2L), comonomer = 1-hexene(20ml)

Activity

Log(Molecular Weight)

2 3 4 5 6 7 8

dwf/dLog(m)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1

2

3

4

Zr

Cl

ClSi Ti

N

Cl

ClZr

Cl

ClN

O

ZrCl2

2

> > >

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Supported Catalysts: MWD ControlSupported Catalysts: MWD Control

29.63802,29027,12716972+4

(0.5+0.5)

6

3.55254,60082,00222661+2+4

(0.2+0.4+0.4)

9

3.09245,84079,39224901+2+3

(0.2+0.4+0.4)

8

53.04575,53610,86114802+4’

(0.5+0.5)

7

5.32740,590154,3727882+3

(0.5+0.5)

5

PDIMwMnActivity

(g-PE/g-Cat)

Catalyst type

(mmol)

run no.

Supported Catalyst : Silica = Sylopol 948 (dehydrated at 200oC), MAO (5mmol)

Polymerization: ethylene pressure = 40 atm, temperature = 80oC, time = 1hr,

solvent = Hexane (1.2L), comonomer = 1-hexene(20ml)

- Bimodal PE having broad PDI obtained at run 6 & 7.

- The combination of 2+4 and 2+4’ was most effective to get broad MWD

� MWD of PE in continuous single reactor can be controlled.

Log(Molecular weight)

2 3 4 5 6 7 8

dwf/dLog(m)

0.0

0.2

0.4

0.6

0.8

1.0

5

6

7

8

9

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190℃ ARES Result

Run 6

Run 6-1

Run 7

Run 5

210℃ ARES Result

Run 6

Run 6-1

Run 7

Run 5

Supported Catalyst: Supported Catalyst: RheologiesRheologies of of mPEmPE

10-1 10

010

1

102

1.5x104

105

2x105

Frequency (rad/s)

Viscosity (P)

10-1 10

010

1

102

1.5x104

105

2x105

Frequency (rad/s)

Viscosity (P)

10-1 10

0101

102

1.5x104

105

2x105

Frequency (rad/s)

Viscosity (P)

10-1 10

0101

102

1.5x104

105

2x105

10-1 10

0101

102

1.5x104

105

2x105

Frequency (rad/s)

Viscosity (P)

- Processability can be controlled by optimization of catalyst compositions

- Bimodal PE from hybrid catalyst is more effective than that from

conventional cascade polymerization with Z/N catalyst

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Advanced Catalyst Engineering provides the capability to produce PE with

bimodal molecular weight distribution and bimodal compositional distribution

in a Single Reactor !

Recent Trend : Bimodal Polyethylene

Bimodal

mLLDPE

mLLDPE

Molecular Structure

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LG Metallocene PE HistoryLG Metallocene PE History

1993 1st Metallocene research group in Korea

1995 Pilot plant start up

1997 mPE Rotomolding grade

1998 Commercial trial of mPE in hexane slurry

process

1999 2nd generation catalyst development

2002 3rd generation catalyst development

- New concept of supported metallocene tech

2005 Super strength PE in a slurry loop process

2007 4th generation catalyst development

Commercial trial of Elastomer

Polymerization PilotPolymerization Pilot

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LG Metallocene CatalystsLG Metallocene Catalysts

� 2nd Generation Metallocene (Commercial)

- Narrow MWD / Narrow CD

- MDPE, HDPE

- (XL) Rotomolding, High-Speed Injection Applications

� 3rd Generation Metallocene (Commercial)

- Broad or Bimodal MWD / Narrow CD (in a Single Reactor !)

- LLDPE, MDPE, HDPE

- Film (Easy Processing), Injection & Pipe (High ESCR) Applications

� 4th Generation Metallocene (Commercial)

- Narrow or Broad MWD / Narrow CD

- LLDPE, Plastomer/Elastomer

- Film, Fiber, Wire&Cable, TPO Applications, etc

15/31

Contents

1. Introduction of Metallocene Catalyst

2. LG Metallocene Technology

3. LG Metallocene Product

4. Summary

16/31

LG PE-RT has outstanding Long-Term Hydrostatic Strength (LTHS) and

mechanical properties in hot/cold water pipe system without cross-linking

Excellent processability

Easier installation (Flexibility)

Cost effective

LG PE-RT

PE-RT : Polyethylene of Raised Temperature Resistance

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Under-floor & Wall Heating

Radiator connections

Hot and Cold Drinking Water Pipe

Snow Melt System

Multilayer Aluminum Pipe

ApplicationsApplications

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LG PELG PE--RT SP980 ResinRT SP980 Resin

Superior Mechanical StrengthHigher Resistance to

Slow Crack Growth(SCG)

Easy Processing High Stiffness Noble Polymer Architecture

� Metallocene Catalyst ensures excellent mechanical properties

- high mechanical strength

- good resistance against pressure

- greatly enhanced ESCR

- high clarity

� LG PERT SP980 resin allows for enhanced properties compared

with other pipe resins.

- high productivity � cost benefit

- the most flexible choice over PB, PVC, PEX

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ISO9080 for PEISO9080 for PE--RT pipes from SP980RT pipes from SP980

※ MRS : Minimum Required Strength, LPL : Lower Prediction Limit

The regression curves show no presence of a soThe regression curves show no presence of a so--calledcalled

““Knee (Brittle Fracture)Knee (Brittle Fracture)”” at any test temperature.at any test temperature.

; With respect to the valid ISO 9080 document, a ductile (; With respect to the valid ISO 9080 document, a ductile (σσLPLLPL) long) long--termterm

strength value of strength value of 9.2MPa9.2MPa at 50 years at 20at 50 years at 20℃℃..

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Ethylene Ethylene ElastomersElastomers are ethylene and are ethylene and αα--olefin copolymers (0.860~0.910 g/cc) olefin copolymers (0.860~0.910 g/cc)

as a kind of thermoplastic as a kind of thermoplastic elastomerelastomer like synthetic rubbers.like synthetic rubbers.

POE (Polyolefin POE (Polyolefin ElastomerElastomer))

Polyethylenes Olefin Elastomers

� HDPE (0.940~0.970 g/cc)

� LLDPE (0.905~0.940 g/cc)

� LDPE (0.917~0.935 g/cc)

Olefin Elastomer

(0.855~0.910 g/cc)

• Tech.: Metallocene + Solution

• Supplier: Dow, Mitsui, Exxonα-olefin

Ethylene

Crystallinity

Propylene

Crystallinity

Crystallinity

HCPP

PP

RCPP

Propylene

Plastomers

& Elastomers

Amorphous

HDPE

LLDPE &

LDPE

VLDPE

Ethylene

Plastomers

& Elastomers

Block

Copolymers

Ziegler-

Natta

EP(D)M

Metallocene

& SSC

*SSS: Single-Site Catalyst

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LG Polyolefin LG Polyolefin ElastomersElastomers are produced by optimum combination of our are produced by optimum combination of our

unique metallocene catalyst and solution process technologies.unique metallocene catalyst and solution process technologies.

LG POELG POE

� Unique Metallocene Structure for PO Elastomers

- high thermal stability

- high activity

- high molecular weight

- excellent comonomer incorporation

� Characteristics of LG PO Elastomers

- Solution process retrofitting

- Wide density window (0.860 ~ 0.910 g/cc)

- Uniform MW & comonomer distribution

- Transparent & elastic

Unique Catalyst

Elastomer Resin

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Major POE ApplicationsMajor POE Applications

Hard & Soft TPO CompoundsHard & Soft TPO Compounds

Auto ExteriorAuto Exterior

Footwear & FoamsFootwear & Foams

Slipper SolesSlipper Soles

Molded GoodsMolded Goods

Soft GripsSoft Grips

MultiMulti--purposepurpose

WheelsWheels

•• Excellent Physical Properties (Elasticity, Toughness)Excellent Physical Properties (Elasticity, Toughness)

•• Excellent Impact ResistanceExcellent Impact Resistance•• More Flexible & Elastic, Lighter WeightMore Flexible & Elastic, Lighter Weight

•• Improved Look & FeedImproved Look & Feed

•• Tough yet FlexibleTough yet Flexible

Auto InteriorAuto InteriorAuto ExteriorAuto Exterior Mid Sole FoamsMid Sole Foams

23/31

Key Asset of LG Metallocene TechnologyKey Asset of LG Metallocene Technology

Unique Portfolio of

Metallocene Precursor

Unique Portfolio of

Metallocene Precursor

Heterogenization and

Catalyst Scale-up

Heterogenization and

Catalyst Scale-up

Process Innovation

& Retrofitting Eng.

Process Innovation

& Retrofitting Eng.

Pilot Plant Work &

Commercial Trial

Pilot Plant Work &

Commercial Trial

Analytic Method and

Characterization of

PE Product

Analytic Method and

Characterization of

PE Product

Open-up New Market &

Global Marketing

Open-up New Market &

Global Marketing

Supported Catalyst

SolutionSlurry

“VALUE CHAIN”

Total Technical Support Basis for the Specialty mPETotal Technical Support Basis for the Specialty mPE

24/31

SummarySummary

LG Metallocene Technology

� LG Chem developed proprietary metallocene catalysts which cover

full ranges of Polyethylene (PE) products.

� LG Chem carried out several commercial campaigns using own 2nd

Generation in hexane slurry HDPE process.

� Especially, 3rd Generation is a new promising catalyst to produce

broad or bimodal PE in a Single Reactor and commercialized in loop

slurry process !

� LG Chem newly launched Polyethylene Elastomer.