2. LG Metallocene Technology

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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

Contents

1. Introduction

2. LG Metallocene Technology

3. LG Metallocene Product

4. Summary

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HDPE 18%

LLDPE 12%

LDPE PP 12%

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

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 Tolling Comparison of Commodity PO Tolling

Transload Ship PE Conv C2 PE Price Pro. Buy

US ME

70 60 50 40 30 20 10 0

1540 1320 1100 880 660 440 220 0 Asia

U$/MT cent/lb

Transload Ship PE Conv C2 PE Price Transload Ship PE Conv C2 PE Price Pro. Buy

US ME

70 60 50 40 30 20 10 0

1540 1320 1100 880 660 440 220 0 Pro.AsiaBuy

US ME

70 60 50 40 30 20 10 0

1540 1320 1100 880 660 440 220 0 Asia

U$/MT cent/lb

Global Global Capa Capa..

신증설신증설

중동 중동신증설 신증설

76 (^{2006년 현재})

4.6

9.4

신증설 (2007~2010) (2007~2010)

중동 + 아시아 기타지역기타지역

중동중동 아시아아시아

18.4 ^(80%)

(30%)23

단위: 백만톤, %

18.4 ^(80%)

9 ^(39%)

Theories and Applications of Chem. Eng., 2008, Vol. 14, No. 2 4073

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Polyolefin Market Trends Polyolefin Market Trends

Polyolefin Market Trends

PE Market PP Market

mPO Market _PE

- 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

Contents

1. Introduction

2. LG Metallocene Technology

3. LG Metallocene Polyolefins

4. Summary

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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 active Highly active

Narrow molecular weight distribution of resulting polymer Narrow molecular weight distribution of resulting polymer Easy to control polymer property

Easy 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 Catalyst Metallocene Catalyst Metallocene Catalyst

Supported Catalysts: Components Supported Catalysts: Components

Zr Cl Cl

1

Si Ti N

Cl Cl

2

Zr Cl

Cl

3

N O ZrCl2

2

4

<

OH OH O OH

Cocatalyst : Methylaluminoxane (MAO)

Silica Support

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Supported Catalysts: Polymerization Supported Catalysts: Polymerization

Molecular Weight

Zr Cl Si Ti Cl

N Cl

Cl Zr

Cl

Cl N

O ZrCl2

> > > 2

8.95 101,380 11,388 1861 (1.0)4

4

7.88 279,276 35,610 178

(1.0)3 3

3.90 1,223,721 314,250 1180

(1.0)2 2

2.20 157,779 71,627 8300 (1.0)1

1

PDI Mw Mn Activity (g-PE/g-Cat) Catalyst type

(mmol) run no.

Supported Catalyst : Silica = Sylopol 948 (dehydrated at 200^oC), MAO (5mmol) Polymerization: ethylene pressure = 40 atm, temperature = 80^oC, time = 1hr,

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

Activity

Log(Molecular Weight)

2 3 4 5 6 7 8

dwf/d Log(m )

0.0 0.2 0.4 0.6 0.8 1.0 1.2

12 34

Zr Cl

Cl Si Ti

N Cl

Cl Zr

Cl Cl N

O ZrCl2

> 2 > >

Supported Catalysts: MWD Control Supported Catalysts: MWD Control

29.63 802,290 27,127

1697 (0.5+0.5)2+4

6

3.55 254,600 82,002

2266 1+2+4

(0.2+0.4+0.4) 9

3.09 245,840 79,392

2490 1+2+3

(0.2+0.4+0.4) 8

53.04 575,536 10,861

1480 (0.5+0.5)2+4’

7

5.32 740,590 154,372 788

(0.5+0.5)2+3 5

PDI Mw Mn Activity (g-PE/g-Cat) Catalyst type

(mmol) run no.

Supported Catalyst : Silica = Sylopol 948 (dehydrated at 200^oC), MAO (5mmol) Polymerization: ethylene pressure = 40 atm, temperature = 80^oC, 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/d Log(m )

0.0 0.2 0.4 0.6 0.8 1.0

5 67 89

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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: Rheologies Rheologies of of mPE mPE

10^-1 ¹⁰⁰ ¹⁰¹ 10²

1.5x 10⁴ 10⁵ 2x10⁵

Frequency (rad/s) Visc

osity (P)

10^-1 ¹⁰⁰ ¹⁰¹ 10²

1.5x 10⁴ 10⁵ 2x10⁵

osity (P)

10^-1 ¹⁰⁰ ¹⁰¹ 10²

1.5x10⁴ 10⁵ 2x10⁵

osity (P)

10^-1 ¹⁰⁰ ¹⁰¹ 10²

1.5x10⁴ 10⁵ 2x10⁵

10^-1 ¹⁰⁰ ¹⁰¹ 10²

1.5x10⁴ 10⁵ 2x10⁵

osity (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 History

1993 1^stMetallocene research group in Korea 1995 Pilot plant start up

1997 mPE Rotomolding grade

1998 Commercial trial of mPE in hexane slurry process

1999 2^ndgeneration catalyst development 2002 3^rdgeneration catalyst development

- New concept of supported metallocene tech 2005 Super strength PE in a slurry loop process 2007 4^thgeneration catalyst development

Commercial trial of Elastomer

Polymerization Pilot Polymerization Pilot

LG Metallocene Catalysts

2^ndGeneration Metallocene (Commercial) - Narrow MWD / Narrow CD

- MDPE, HDPE

- (XL) Rotomolding, High-Speed Injection Applications 3^rdGeneration Metallocene (Commercial)

- Broad or Bimodal MWD / Narrow CD (in a Single Reactor !) - LLDPE, MDPE, HDPE

- Film (Easy Processing), Injection & Pipe (High ESCR) Applications 4^thGeneration Metallocene (Commercial)

- Narrow or Broad MWD / Narrow CD - LLDPE, Plastomer/Elastomer

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

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Contents

1. Introduction of Metallocene Catalyst 2. LG Metallocene Technology

3. LG Metallocene Product 4. Summary

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

Applications

LG PE

LG PE--RT SP980 ResinRT SP980 Resin

Superior Mechanical Strength Higher 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 PE

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

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

The regression curves show no presence of a so The 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 9.2MPa9.2MPaat 50 years at 20at 50 years at 20℃℃..

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Ethylene

Ethylene ElastomersElastomersare 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 elastomerelastomerlike synthetic rubbers.like synthetic rubbers.

POE (Polyolefin

POE (Polyolefin Elastomer Elastomer) )

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, Exxon

α-olefin

Ethylene Crystallinity Propylene

Crystallinity

Cry stal linity

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 ElastomersElastomersare 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 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

Major POE Applications

Hard & Soft TPO Compounds Hard & Soft TPO Compounds

Auto Exterior Auto Exterior

Footwear & Foams Footwear & Foams

Slipper Soles Slipper Soles

Molded Goods Molded Goods

Multi Multi--purposepurpose

Wheels Wheels

••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 Interior Auto InteriorAuto Exterior

Auto Exterior Mid Sole FoamsMid Sole Foams

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Key Asset of LG Metallocene Technology

Unique Portfolio of Metallocene PrecursorUnique 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 mPE Total Technical Support Basis for the Specialty mPE

Summary Summary

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 2^nd Generation in hexane slurry HDPE process.

Especially, 3^rdGeneration 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.