The R&D Trends of HighThe R&D Trends of HighPerformance Polypropylene Performance Polypropylene

(High Melt Strength PP)(High Melt Strength PP)

Daeduk R&D Center

2007. 10. 26.

DAEDUK R&D Center

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호남석유화학㈜ 소개(롯데 유화 3사)

대덕연구소 소개

폴리올레핀 기술 개발 동향

고용융장력 폴리프로필렌

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롯데롯데롯데롯데 유화유화유화유화 3사사사사 연혁연혁연혁연혁l

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주요주요주요주요 생산생산생산생산 품목품목품목품목l

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Polypropylene

Chemical Structure

Crystalline Polymer

Crystallinity : 52%

Non-Polar PolymerWetting Tension : 29~31 dynes/cm( PA : 33 ~ 46 dynes/cm )

34Triclinicγ form

31Pseudohexagonalβ form

31Monoclinicα form

HelixCrystal SystemForm

POM Image of Spherulites

Black : CarbonWhite : Hydrogen

CH2 CH

CH3

n

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Feature of Polypropylene

AdvantagesMechanical Properties, Chemical Resistance, DurabilityHeat ResistanceProcessibility : Injection, ExtrusionClean, Eco-Friendly MaterialLow Cost

DisadvantagesLow Melt Strength : � Poor processibility for Foam, Thermoforming

Poor Adhesive Properties : � Hard to Paint, Print, and Dye� Poor Compatibilities with Polar Material

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Trends of Polyolefin Characterization

저밀도

High High StiffnessStiffness

High Melt High Melt StrengthStrength

High FlowHigh FlowPolar Polar

PropertiesProperties

Low Low DensityDensity

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Nano HybridReactor Made

Trends of Polyolefin Characterization

High FlowHigh FlowPolar Polar PropertiesProperties

High

Stiffness

Low Low DensityDensity

High Melt High Melt StrengthStrength

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Trends of Polyolefin Characterization

High High StiffnessStiffness

High Melt High Melt StrengthStrength

High High FlowFlow

Low Low DensityDensityPolar

Properties

Solution Reactive Extrusion

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Trends of Polyolefin Characterization

High Melt High Melt StrengthStrengthHigh FlowHigh Flow

Low Density

PolarPolarPropertiesProperties

High High StiffnessStiffness

Metallocene

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Process of High Melt Strength PP

Polar Polar PropertyProperty

Low Low DensityDensity

High Melt Strength

High High StiffnessStiffness

High High FlowFlow

○○○○◎◎◎◎××××Cost

◎◎◎◎△△△△◎◎◎◎Performance

Maker

Reactive Extrusion

Reactor Made Type

Ionizing Electron Radiation

Method

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Melt Strength Behavior of Polymer

Crystalline Polymer :

���� Very Narrow Processing Temperature Window

Tg Tm

Temperature

Mel

t Str

engt

h

Crystalline Polymer

Amorphous Polymer

OptimumMelt Strength for Expansion

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Melt Strength

FactorMolecular Weight

Side Chain

Intermolecular Interaction

Influence on Processing Blow Molding : Parison Draw Down

Thermoforming : Deep Drawing

Inflation Film : Bubble Rupture

Foaming : Cell Growth, Coalescent & Rupture

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Why HMS-PP ?

Material UnificationRecycling : Need not Classify

Food PackageLess OdorMicrowave Oven

Plank FoamBetter Impact & Chemical ResistanceLess Harmful Combustion Gas

Automotive Door TrimPP Core

X-linked PP Foam(Urethane Foam)

TPO Skin

PP Core

HMSPP Foam

TPO Skin

PS FoamPS Thermoform

HMSPP FoamHMSPP Thermoform

PS Foam HMSPP Foam

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Evaluation of Melt Strength

Equipment : Molten Rheometer (Toyoseiki, Japan)

Oil Bath

Specimen Silicon Oil

Load Cell

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Melt Strength with Molecular Weight

0

2

4

6

8

10

12

14

0 10 20 30 40 50

Time(sec)

Melt T

ensi

on(g

)

MI : 0.5

MI : 1.0

MI : 2.0

MI : 4.0

313,200425,900415,800492,000

Mw

53,70074,50078,00096,400

Mn

4.01.0

Homo PP

2.00.5

Block PP

MI(g/10min)

Test Temperature : 200 ℃℃℃℃

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High Melt Strength is not Real Solution!

Melt Strength

PP(MI : 0.5) >> LDPE(MI : 5.3)

Processibility of Foaming

PP(MI : 0.5) << LDPE(MI : 5.3)

���� Processing Window of PP is not improved.���� Too High Melt Strength is not good for

Cell Growth at early stage in Foaming Process

Other Factor is more Important

in Crystalline Polymer for Foaming!

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Melt Strength with Side Branch

Elongational Viscosity

dtdt

dLd

dt

dL

Ldt

d )ln(1 === εε&0

lnL

L=ε

extensionofrate

stresstensile

=λεσσ&

=⋅

=

dt

dL

L

1

100 101 102

103

104

105

Vis

co

sit

y (

Pa

.s)

Time (sec)

Te

nsio

n (

g)

Time (sec)

10 20 30

5

10

15Strain Hardening

HDPE

LDPE

HDPE

LDPE

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Basic Idea

Improve Processing Window of PPCross-Linking : Non-recyclable, High Cost

Decreasing Crystallinity : Decrease Mechanical Properties

Introducing Side Branch : Improve Strain Hardening

HMSPP

General PP

20105210.50.2

0.2

20

10

5

2

1

0.5

MI (g/10min)

Me

lt T

en

sio

n (

g)

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Characteristic of HMSPP – Molecular Weight

HMS PPConventional PP

2.734.121,208,000443,300107,6000.5Conventional PP

2.985.811,277,000428,30073,8003HMSPP

Mz/MwMw/MnMzMwMnMIPP

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Characteristic of HMSPP – Melt Strengthl

Time(sec)

0 10 20 30 40 50

Mel

t Ten

sion

(g)

0

1

2

3

4HMS PP (HPC)HMS PP (Maker A)Conventional PP

Test Temperature : 200 ℃℃℃℃

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Characteristic of HMSPP – Elongational Viscosity

Time(sec)

1 10 100

Visc

osity

(pois

e)

1e+5

1e+6

HMS PP (HPC)HMS PP (Maker A)Conventional PP

Test Temperature : 200 ℃℃℃℃

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Characteristic of HMSPP – Mechanical Properties

℃℃℃℃

Mpa

kg ∙∙∙∙cm/cm

Mpa

g/10min

Unit HonamMaker AItem

333MI

Homo PP

116

35

4.6

1,650

Conventional

PP

Homo HMSHomo HMSNotes

12.26.7IZOD Impact Strength

4037Tensile Strength

135

2,1001,620Flexural Modulus

118Heat Distortion Temp .

HMSPPMechanical Properties

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Characteristic of HMSPP – Foaming Processibility

20 times Foaming20 times Foaming 6060 times Foaming times Foaming

Process : Extrusion FoamingBlowing Agent : CO2Processing Temperature : 160 ~ 200 ℃℃℃℃

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Applications of HMSPP

Foam SheetPlank Foam : Construction & IndustryFood Tray Automotive Interior Parts Stationery Cover Sheet

ThermoformingTrayCup

Extrusion CoatingLamination Film : Improve neck-in

Blow Molding

Blown Film

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Conclusions

Introduction of long chain branch on linear PP back -bone increase melt strength and strain hardening remarkably.

High melt strength PP has improved mechanical properties.

It can make extend processing temperature window, because of the strain hardening effect which can increase melt strength of polypropylene melt at hi gh temperature.

High melt strength PP which has high strain hardening effect can make 20 ~ 60 times expanded foam in no cross-linking.

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Thank you very much for your attention!

Daeduk R&D Center

Honam Petrochemical Corp.