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Moscow International Conference PP 2008
“Polypropylene Clarification & Nucleation”
Dariusz Lukaszewski & Dr. Tim Hauck, Milliken Europ e
March 25th, 2008
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Milliken, Moscow International Conference PP 2008
Outline
� Milliken: Solution Provider
� Millad ® 3988i Clarified PP and its Applications Versatility
� Differences in Nucleation & Clarification
� Overview on commercial Clarifiers & Nucleators
� Brand New Clarifier Millad ® NX 8000
� PP nucleated with Hyperform ®
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Milliken, Moscow International Conference PP 2008
• Founded in 1865• One of the world’s largest privately held chemical and textile companies
•11,000 associates
• 50 facilities worldwide
• Headquarters in Spartanburg
• Recognized for leadership in
• Quality & safety,
• Environmental excellence
• Innovation
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Milliken, Moscow International Conference PP 2008
Floor CoveringFloor CoveringFloor CoveringFloor Covering
Performance TextilesPerformance TextilesPerformance TextilesPerformance Textiles
AutomotiveAutomotiveAutomotiveAutomotive
ChemicalsChemicalsChemicalsChemicals
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Milliken, Moscow International Conference PP 2008
Milliken: Closer Look at Plastic Additives
Milliken is a full-service global provider of innovative solutions for polyolefin clarification and nucleation
Innovation
Value Creation Model Products
Industry leadership in clarification and nucleation of PP
Market development throughout the value chain:
resin producers, plastics converters, brand owners,
retailers and consumers
Regional Technical Centers and Sales Offices offering services on a global basis
Additives optimization studiesResin grades formulation
Applications trials
Global Footprint Services
Opening new applications and material substitution opportunities for polypropylene & polyethylene
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Milliken, Moscow International Conference PP 2008
Plastic Applications & Technical Service Lab
� Optimization of resin additive formulation
� Evaluate commercial resins (crystallization temperature, optical properties, mechanical properties…)
� Evaluate the properties of Millad® 3988i compared to other clarifying agents and nucleating agents in specific resin/fluff
� Quality control of 1packs, masterbatch and resin
� Evaluation of commercial parts (optical as well as mechanical properties)
� Assistance at trials at PP producers as well as converters/transformers
� Assistance in application development
� Assistance in processing optimization
� Run trials in-house on TWIM, EBM, TF and ISBM equipment
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Milliken, Moscow International Conference PP 2008
MILLAD ® 3988i STATE OF THE ART CLARIFIER
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Milliken, Moscow International Conference PP 2008
Advantages for clarified Polypropylene (cPP)
� Low Density, Light Weight
� Cost Effective
� Excellent Thermal Resistance
� Moisture/Vapor Barrier
� Stiffness, Flexibility and Impact: highly adaptive properties
� Chemical Resistance
� Hot fill properties
� Ability to Clarify (cPP)
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Milliken, Moscow International Conference PP 2008
NUCLEATING AGENTS vs CLARIFYING AGENTS
Nucleating Agents Clarifying AgentsNucleating Agents Clarifying Agents
TalcTalcSodium BenzoateSodium Benzoate
Phosphor Ester SaltsPhosphor Ester SaltsHyperform HPNHyperform HPN--68L68L
Acetal Acetal SorbitolsSorbitols
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Milliken, Moscow International Conference PP 2008
Melt Phase
Normal PP
Clarified PP
Nucleated PP
Nucleation Phase Semi-Crystalline Phase
Nucleation and Crystal GrowthDifferences in Nucleation Mechanism
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Milliken, Moscow International Conference PP 2008
Evolution of Polypropylene Clarifying Agents
Time
Per
cent
Haz
e
Unclarified Polypropylene
Millad®
NX8000
DBS
1G
MDBS / EDBS
2G
Sorbitol Acetals
Phosphate Ester Salts
D
Trisamides
E
Millad® 3988i
3G
Adv. Nucleator
A
Adv. Nucleator
B
Adv. Nucleator
C
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Milliken, Moscow International Conference PP 2008
Evolution of Polypropylene Clarifying Agents
Time
Per
cent
Haz
e
Unclarified Polypropylene
DBS
1G
MDBS / EDBS
2G
Sorbitol Acetals
Millad® 3988i
3G
OrganolepticsMDBS / EDBS
Haze; Nucleation; Heat stabilityDBS
Primary Limitations vs Millad 3988iSorbitol Acetals
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Milliken, Moscow International Conference PP 2008
PERFORMANCE MAPPING …
Millad ® 3988i outperforms MDBS in organoleptics
CHOR1
R2
R1 R2
DDBBSS 11GG HH HH NNOO SSMMEELLLL
MMDDBBSS 22GG CCHH33 HH SSTTRROONNGG SSMMEELLLL
MMIILLLLAADD 33GG CCHH33 CCHH33 NNOO SSMMEELLLL
Substituted Aldehydes
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Milliken, Moscow International Conference PP 2008
MDBS (2G) - PERFORMANCE MAPPING …
Regulatory Aspects
� EC Directive 89/109/EEC, Article 2 :
Materials and articles must be manufactured in comp liance with good manufacturing practice so that, under their normal or foreseeable condition of use, they do not transfer their constituents to foodstuff in quantities which could:- endanger human health- bring about an unacceptable change in the composition of the foods tuffs or deterioration in the organoleptic
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Milliken, Moscow International Conference PP 2008
Evolution of Polypropylene Clarifying Agents
Time
Per
cent
Haz
e
Unclarified Polypropylene
Adv. Nucleator
A
Haze (esp. in higher MFR resins and thicker parts); anisotropic shrinkage
B / C
Haze; anisotropic shrinkageA
Primary Limitations vs Millad 3988iPhosphate Ester Salts
Phosphate Ester Salts
Adv. Nucleator
B
Adv. Nucleator
C
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Milliken, Moscow International Conference PP 2008
Evolution of Polypropylene Clarifying Agents
Time
Per
cent
Haz
e
Unclarified Polypropylene
Haze (esp. in higher MFR resins and thicker parts); lower polymer Tc
D
Haze (esp. in higher MFR resins and thicker parts); lower polymer Tc
E
Primary Limitations vs Millad 3988iTrisamides
D
Trisamides
E
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Milliken, Moscow International Conference PP 2008
Polypropylene Clarifier ReviewSummary
XXTrisamides
XXPhosphate Ester Salts
XMDBS
Polymer Tc (Cycle Time)
Anisotropic Shrinkage (Warpage)
Organoleptics (Taste and Odor)
Haze Performance (esp. in thicker parts and higher
melt flow resins)
Primary Limitations vs Millad 3988i
Clarifying Technologies
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Milliken, Moscow International Conference PP 2008
…for the ultimate in clear polypropylene ™
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Milliken, Moscow International Conference PP 2008
Mapping of Millad ® NX8000 Clarified PP
Haze Continuum for Selected Plastic Materials
PMMA
PET
PS
PC
Glass
Clarified (Milad NX8000) PP(RACO & HOMO)
3.5-7.0
Clarified PP (1G) RACO
20-30
Clarified (3G) PP (HOMO)
15-20 Clarified (3G) PP (RACO)
10-15
Clarified (3G) mPP (HOMO)
13-16 Clarified (3G) mPP (RACO)
9-11
Unclarified PP(HOMO)
50-70Unclarified PP
(RACO) 40-50
Unclarified HDPE 80+
“Wat
er W
hite
”C
larit
y (1
–3)
Evo
lutio
nary
Impr
ovem
ents
in
Pol
ypro
pyle
ne C
larit
y
Note: 1.25 mm plaques
Haz
e, %
40
80
60
20
10
3
1
5
0
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Milliken, Moscow International Conference PP 2008
…for the ultimate in clear polypropylene ™
Opportunities to
replace glass like materials:PSSANPETCOCPVCPMMAIonomersGlass
reduce raw material cost
use environmently friendly PP
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Milliken, Moscow International Conference PP 2008
PP nucleated with Hyperform ®
PP Nucleating Agents and their Evolution
Conventional
• NaBz, Talc, Pigments, etc
• Low T c (generally)
• Anisotropic (few exceptions)
• High use level
• Good for “moderate” performance
• Generally low cost
Advanced
• Ph. Ester Salts (and Sorbitol Clarifiers)
• Higher T c
• Very Anisotropic (P. Ester Salts only)
• Potential for warpage (P. Ester Salts)
• High Stiffness (flex mod)
• High HDT
• Primarily used in Auto and TF
Hyper
• Hyperfom family
• Highest T c
• Isotropic – Low Warpage
• Pigment Leveling
• Ideal Stiffness/Impact Balance
• High HDT
• Low CLTE
• Tailored dimensions
Performance and Benefit Options Increase
1960s-1980s 1980s-1990s 2000s +
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Milliken, Moscow International Conference PP 2008
Hyperform ® Nucleation Performance Benefit in PP
Unique Benefits in PP Typical Applications Examples
� Productivity Enhancement
� Warpage Reduction
� Equalization of nucleation of pigments
� Physical Properties Enhancement
� Thermoforming
� Injection Molding (Houseware, TWIM containers, DVD cases)
� Caps & Closures (extrusion compression molding & injection molding)
� Automotive
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Milliken, Moscow International Conference PP 2008
Hyperform ® Commercial Applications
Housewares, Appliances, Film, ISBM2-30Random Copolymer
DVD Cases, General IM70-100
Automotive, Housewares, Buckets, Material Handling, Trays, etc7-40
ECM Closures6-8
TF, EBM1-2
Block Copolymer
TWIM, DVD Cases, General IM40-55
Medical, Housewares, Hangers, Furniture, Appliances14-35
Thermoforming, Closures2-5
Homopolymer
ApplicationsMFRPolymer Type
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Milliken, Moscow International Conference PP 2008
Resin: HP (MFR=4)
Part: Portion cup (Ø=93mm – h=51mm)
Equipment: Illig RDM54K
1516171819202122232425
110 115 120 125 130
Crystallisation temperature (°C)M
axim
um c
ycle
spe
ed (
cpm
)
Increased productivity due to high Tc
Increase in crystallisation speed - provides higher produc tivity
Adv. Nucl. A
Adv. Nucl. B
Control
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Milliken, Moscow International Conference PP 2008
Recent case study on industrial part
Drinking cup
� Off-line system� 1.1mm sheet – 15 cavity mould� Reference: NaBz resin – MFR=5
� Thermoforming���� Standard speed: 14 cycles/min ���� With HPN-68L: 16 cycles/min
Reject rate strongly reducedImproved optical properties
� HPN-68L compounded resin
NaBz HPN68L
Benefits
� 14% higher productivity
� Value creation 74 USD / mt resin
� Less „out-of-spec“ parts“
� Better transparenyDefinition of value creation: actual cost savings, based on increased productivity and expressed as cost savings per ton resin consumed after subtraction of the Hyperform add-on cost
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Milliken, Moscow International Conference PP 2008
Cycle Time (sec)
240 250 260 270 280 290 300
Control
HPN68L
Cycle Time (sec)
12% Improvement using Hyperform
Hyperform ® Application Case Study: Material Handling
� Resin: Impact Copolymer
� Part Details: Pallet
� Process: Injection Molding
� Previous Nucleation: Sodium benzoate
– Cycle Time Reduction– Warpage Control– Leveling of Recycled Resin– Value creation 150 USD/mt resin
Benefits
Definition of value creation: actual cost savings, based on increased productivity and expressed as cost savings per ton resin consumed after subtraction of the Hyperform add-on cost
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Milliken, Moscow International Conference PP 2008
A Broad Portfolio of Clarification & Nucleation Tech nologies
Milliken Offering End Use ProcessResin Technology
Injection MoldingExtrusion Blow Molding
Extrusion / ThermoformingInjection Stretch Blow Molding
Blown Film
POLYPROPYLENERandom Copolymer
Homopolymer
Injection MoldingExtrusion / Thermoforming
Blown Film
POLYPROPYLENERandom Copolymer
HomopolymerImpact/Block Copolymer
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Milliken, Moscow International Conference PP 2008
Thank You
Please contact us at one of our
Regional Technical Centers
or in person during this conference
www.millikenchemical.com
North America
Spartanburg, South CarolinaPhone: 864-503-2200Email: [email protected]
Europe & Middle East
Gent, BelgiumPhone: 32-9-265-1084Email: [email protected]
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Asia Pacific
SingaporePhone: 65-6377-0770Email: [email protected]
China
Shanghai, ChinaPhone: 86-21-6113-2228Email: [email protected]
Meet us @
24-30 April 2008Hall 10 - Stand A06Düsseldorf, Germany