Polypropylene Clarification s Nucleation. Dariusz ... - Creon

Moscow International Conference PP 2008
“Polypropylene Clarification & Nucleation”
Dariusz Lukaszewski & Dr. Tim Hauck, Milliken Europe
March 25th, 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 ®
Milliken, Moscow International Conference PP 2008
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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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Chemicals
Chemicals
Milliken, Moscow International Conference PP 2008
Floor Floor Covering Covering
Covering
Automotive
Automotive
Performance Performance Textiles
Textiles
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Milliken: Closer Look at Plastic Additives
Milliken is a full-service global provider of innovative solutions for
polyolefin clarification and nucleation
Products
Industry leadership in clarification
and nucleation of PP
Regional Technical Centers
and Sales Offices offering
services on a global basis
Milliken, Moscow International Conference PP 2008
Innovation
Opening new applications and
material substitution opportunities
for polypropylene & polyethylene
Value Creation Model
Market development
throughout the value chain:
resin producers, plastics
converters, brand owners,
retailers and consumers
Additives optimization studies
Resin grades formulation
Applications trials
Global Footprint Services
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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
Milliken, Moscow International Conference PP 2008
� 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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MILLAD ® 3988i STATE OF THE ART CLARIFIER
Milliken, Moscow International Conference PP 2008
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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)
Milliken, Moscow International Conference PP 2008
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NUCLEATING AGENTS vs CLARIFYING AGENTS
Nucleating Agents Clarifying Agents
Talc
Sodium Benzoate
Phosphor Ester Salts
Hyperform HPN-68L HPN 68L
Milliken, Moscow International Conference PP 2008
Acetal Sorbitols
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Nucleation and Crystal Growth
Differences in Nucleation Mechanism
Melt Phase
Normal PP
Nucleated PP
Clarified PP
Milliken, Moscow International Conference PP 2008
Nucleation Phase Semi-Crystalline Phase
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Percent Haze
Evolution of Polypropylene Clarifying Agents
DBS
1G
Adv. Nucleator
MDBS / EDBS
2G
Milliken, Moscow International Conference PP 2008
A
Sorbitol Acetals
Unclarified Polypropylene
Phosphate Ester Salts
Time
Adv. Nucleator
Millad® 3988i
3G
B
Adv. Nucleator
D
C
Trisamides
E
Millad®
NX8000
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Percent Haze
Evolution of Polypropylene Clarifying Agents
DBS
1G
Sorbitol Acetals
MDBS / EDBS
2G
Milliken, Moscow International Conference PP 2008
Unclarified Polypropylene
Sorbitol Acetals
DBS
MDBS / EDBS
Millad® 3988i
3G
Time
Primary Limitations vs Millad 3988i
Haze; Nucleation; Heat stability
Organoleptics
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PERFORMANCE MAPPING …
Millad ® 3988i outperforms MDBS in organoleptics
Milliken, Moscow International Conference PP 2008
Substituted Aldehydes
R 1
R 2
R1 R2
CHO
DBS 1G H H NO SMELL
MDBS 2G CH3 H STRONG
SMELL
MILLAD® 3G CH3 CH3 NO SMELL
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MDBS (2G) - PERFORMANCE MAPPING …
Regulatory Aspects
� EC Directive 89/109/EEC, Article 2:
Materials and articles must be manufactured in compliance 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 foodstuffs or
deterioration in the organoleptic
Milliken, Moscow International Conference PP 2008
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Percent Haze
Evolution of Polypropylene Clarifying Agents
Adv. Nucleator
Milliken, Moscow International Conference PP 2008
A
Phosphate Ester Salts
A
B / C
Unclarified Polypropylene
Phosphate Ester Salts
Primary Limitations vs Millad 3988i
Haze (esp. in higher MFR resins and thicker parts);
anisotropic shrinkage
Time
Adv. Nucleator
B
Haze; anisotropic shrinkage
Adv. Nucleator
C
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Percent Haze
Evolution of Polypropylene Clarifying Agents
Trisamides
Milliken, Moscow International Conference PP 2008
D
E
Unclarified Polypropylene
Primary Limitations vs Millad 3988i
Haze (esp. in higher MFR resins and thicker parts); lower
polymer Tc
Haze (esp. in higher MFR resins and thicker parts); lower
polymer Tc
Time
D
Trisamides
E
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Polypropylene Clarifier Review
Summary
Clarifying
Technologies
MDBS
Phosphate Ester Salts
Trisamides
Haze Performance (esp. in
thicker parts and higher
melt flow resins)
X
X
Milliken, Moscow International Conference PP 2008
Primary Limitations vs Millad 3988i
Organoleptics
(Taste and Odor)
X
Anisotropic Shrinkage
(Warpage)
X
Polymer Tc
(Cycle Time)
X
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…for the ultimate in clear polypropylene
Milliken, Moscow International Conference PP 2008
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80
60
20
Haze, % 40
10
5
3
1
0
Mapping of Millad ® NX8000 Clarified PP
Clarified PP
(1G) RACO
20-30
Note: 1.25 mm plaques
Milliken, Moscow International Conference PP 2008
Haze Continuum for Selected Plastic Materials
Unclarified PP
(RACO)
40-50
Clarified (3G)
PP (HOMO)
15-20
Clarified (3G)
mPP (HOMO)
Clarified (3G)
PP (RACO)
10-15
Clarified
(Milad NX8000) PP
(RACO & HOMO)
3.5-7.0
Glass
Unclarified PP
(HOMO)
50-70
13-16 Clarified (3G)
PET
PMMA
mPP (RACO)
9-11
PS
Unclarified HDPE
80+
PC
Evolutionary Improvements
in Polypropylene Clarity
“Water White”
Clarity (1–3)
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Opportunities to
replace glass like materials:
PS
SAN
PET
COC
PVC
PMMA
Ionomers
Glass
use environmently friendly PP
reduce raw material cost
…for the ultimate in clear polypropylene
Milliken, Moscow International Conference PP 2008
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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
Milliken, Moscow International Conference PP 2008
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
Performance and Benefit Options Increase
Hyper
• Hyperfom family
• Highest T c
• Isotropic – Low Warpage
• Pigment Leveling
• Ideal Stiffness/Impact Balance
• High HDT
• Low CLTE
• Tailored dimensions
1960s-1980s 1980s-1990s 2000s +
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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
Milliken, Moscow International Conference PP 2008
� Thermoforming
� Injection Molding
(Houseware, TWIM containers, DVD cases)
� Caps & Closures
(extrusion compression molding & injection
molding)
� Automotive
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Hyperform ® Commercial Applications
Polymer Type
Homopolymer
Block Copolymer
Random Copolymer
MFR
2-5
14-35
40-55
1-2
6-8
7-40
70-100
2-30
Milliken, Moscow International Conference PP 2008
Applications
Thermoforming, Closures
Medical, Housewares, Hangers, Furniture, Appliances
TWIM, DVD Cases, General IM
TF, EBM
ECM Closures
Automotive, Housewares, Buckets, Material Handling, Trays, etc
DVD Cases, General IM
Housewares, Appliances, Film, ISBM
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Resin: HP (MFR=4)
Part: Portion cup (Ø=93mm – h=51mm)
Equipment: Illig RDM54K
Milliken, Moscow International Conference PP 2008
Increased productivity due to high Tc
Maximum cycle speed (cpm)
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23
22
21
20
19
18
17
16
15
Control
Adv. Nucl. B
110 115 120 125 130
Crystallisation temperature (°C)
Increase in crystallisation speed - provides higher productivity
Adv. Nucl. A
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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 reduced
Improved optical properties
� HPN-68L compounded resin
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 addon
cost
Milliken, Moscow International Conference PP 2008
Recent case study on industrial part
NaBz HPN68L
Benefits
� 14% higher productivity
� Value creation 74 USD / mt resin
� Less „out-of-spec“ parts“
� Better transpareny
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Hyperform ® Application Case Study: Material Handling
� Resin: Impact Copolymer
� Part Details: Pallet
� Process: Injection Molding
� Previous Nucleation: Sodium benzoate
Benefits
– Cycle Time Reduction
– Warpage Control
– Leveling of Recycled Resin
– Value creation 150 USD/mt resin
Milliken, Moscow International Conference PP 2008
HPN68L
Control
Cycle Time (sec)
12% Improvement using Hyperform
240 250 260 270 280 290 300
Cycle Time (sec)
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 addon
cost
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A Broad Portfolio of Clarification & Nucleation Technologies
Milliken Offering Resin Technology
End Use Process
Milliken, Moscow International Conference PP 2008
POLYPROPYLENE
Random Copolymer
Homopolymer
POLYPROPYLENE
Random Copolymer
Homopolymer
Impact/Block Copolymer
Injection Molding
Extrusion Blow Molding
Extrusion / Thermoforming
Injection Stretch Blow Molding
Blown Film
Injection Molding
Extrusion / Thermoforming
Blown Film
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Please contact us at one of our
Regional Technical Centers
or in person during this conference
www.millikenchemical.com
North America
Spartanburg, South Carolina
Phone: 864-503-2200
Email: millichem@milliken.com
Asia Pacific
Singapore
Phone: 65-6377-0770
Email: asiachem@milliken.com
Milliken, Moscow International Conference PP 2008
Thank You
Europe & Middle East
Gent, Belgium
Phone: 32-9-265-1084
Email: eurochem@milliken.com
China
Shanghai, China
Phone: 86-21-6113-2228
Email: asiachem@milliken.com
Meet us @
24-30 April 2008
Hall 10 - Stand A06
Düsseldorf, Germany
Latin America
Sao Paulo, Brazil
Phone: 55-11-3043-7170
Email: lachem@milliken.com
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