(high melt strength pp) · 2007-12-04 · the r&d trends of high performance polypropylene...
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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.
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DAEDUK R&D Center
목차목차목차목차
호남석유화학㈜ 소개(롯데 유화 3사)
대덕연구소 소개
폴리올레핀 기술 개발 동향
고용융장력 폴리프로필렌
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DAEDUK R&D Center
개요개요개요개요l
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DAEDUK R&D Center
롯데롯데롯데롯데 유화유화유화유화 3사사사사 연혁연혁연혁연혁l
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DAEDUK R&D Center
지분지분지분지분 구조구조구조구조l
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DAEDUK R&D Center
사업장사업장사업장사업장l
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DAEDUK R&D Center
사업군사업군사업군사업군 위치위치위치위치l
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DAEDUK R&D Center
주요주요주요주요 생산생산생산생산 품목품목품목품목l
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DAEDUK R&D Center
위상위상위상위상l
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DAEDUK R&D Center
신규사업신규사업신규사업신규사업l
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DAEDUK R&D Center
비전비전비전비전l
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DAEDUK R&D Center
대덕연구소대덕연구소대덕연구소대덕연구소 개요개요개요개요l
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DAEDUK R&D Center
역할역할역할역할l
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DAEDUK R&D Center
위상위상위상위상l
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DAEDUK R&D Center
비전비전비전비전l
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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
Trends of Polyolefin Characterization
High Melt High Melt StrengthStrengthHigh FlowHigh Flow
Low Density
PolarPolarPropertiesProperties
High High StiffnessStiffness
Metallocene
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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
Evaluation of Melt Strength
Equipment : Molten Rheometer (Toyoseiki, Japan)
Oil Bath
Specimen Silicon Oil
Load Cell
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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
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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DAEDUK R&D Center
Thank you very much for your attention!
Daeduk R&D Center
Honam Petrochemical Corp.