iv moscow international conference «polypropylene 2007 · iv moscow international conference ......

IV Moscow International Conference «Polypropylene 2007

New Horizons in Clarification and Nucleation of Polyolefins

Mr. Darek Lukaszewski & Dr. Tim Hauck, Milliken Chemical

Milliken & Co, September 21 (2005) – PolyPropylene 2005 (Maack Business Services) 2Polypropylene 2007, Moscow

Outline

� Intro to Milliken & Co.

� Clarified PP market perspective

� Mechanism of PP clarifying and nucleating agents

� 3 Generations of clarifiers

� Intro to Milliken & Co.

� Clarified PP market perspective

� Mechanism of PP clarifying and nucleating agents

� 3 Generations of clarifiers


Milliken & Company : Corporate Profile

� Founded in 1865

� World’s Largest Privately Held Textile &

Chemical Company

� Global Headquarters in Spartanburg, SC USA

� Manufacturing 19,000 products with

� over 10,000 Associates at

� 60+ locations in

� 12 countries

� Founded in 1865

� World’s Largest Privately Held Textile &

Chemical Company

� Global Headquarters in Spartanburg, SC USA

� Manufacturing 19,000 products with

� over 10,000 Associates at

� 60+ locations in

� 12 countries


InnovationInnovation


USA

Belgium

Brasil

China

Singapore

Customer supportCustomer support

Spartanburg, USASpartanburg, USA SingaporeSingaporeSao Paulo, BrazilSao Paulo, BrazilGent, BelgiumGent, Belgium


QualityQuality


PRODUCT PERFORMANCE OFFERING FOR PP

� Millad®

Clarifying agents for polyolefins

� Hyperform®

Nucleating agents for fast processing and excellent physical properties

� ClearTint®

Colourants for plastic packaging, containers and moulded products

� AlphaSan®

Antimicrobials for plastics

� Millad®

Clarifying agents for polyolefins

� Hyperform®

Nucleating agents for fast processing and excellent physical properties

� ClearTint®

Colourants for plastic packaging, containers and moulded products

� AlphaSan®

Antimicrobials for plastics


MILLAD® 3988 STATE OF THE ART CLARIFIER

Outstanding Clarity and Organolpetics in PP


Benefits of Polypropylene

• Light Weight

• Cost Effective

• Hot Fillability

• Microwaveability

• Moisture / Vapor Barrier

• Stiffness / Flexibility / Impact

• Chemical Resistance

• Ability to Make Clear

• Competitive Productivity


Injection Molding

Medical

• Syringes

•Labware

Media

• Media Packaging

Blow Molding

• Food Packaging

• Non-Food Pkging

TF / Extrusion

• Food, Cups

• Semi-durable Housewares

cPP Market Segmentation

� cPP (clarified PP) is a versatile raw material that has found a home in many applications and processes

Packaging

• Thinwall Food,Non-food

• Pill Vials / Reusable Pkgs

• Food Storage

•Totes /

Home Org.

Housewares


Global PP and cPP Demand

*Indexed to clear PP volume in 1995

� Over the past 10 years, growth for clarified polypropylene (cPP) has outpaced overall PP growth

� For the forecast period through 2009, cPP will continue to grow faster than overall PP but at a lower multiple

8.2%6.8% 6.1%

19.3%

11.9%

7.6%

0.0%

5.0%

10.0%

15.0%

20.0%

25.0%

1995 - 2001 2001-2004 2004-2009

Time interval

Dem

and g

row

th (

CA

GR

%)

Overall PP cPP

Source: PTAI (2006) / Milliken Estimates

0

10

20

30

40

50

60

19

95

19

96

19

97

19

98

19

99

20

00

20

01

20

02

20

03

20

04

20

05

20

06

20

07

20

08

20

09

PP

Re

sin

De

ma

nd

(M

M T

on

s)

0

1

2

3

4

5

6

cP

P R

es

in D

em

an

d*

Overall PP cPP


cPP Demand by Market Segment and Region

Eur

26%

A/P

34%

LA

8% NA

32%

By Region

By Segment

Source: Milliken Estimates

Media

4%Medical

9%

Packaging

18%

Blow Molding

12%

TF/Extrusion

11%Housewares

46%

� Housewares and packaging applications accounted for 2/3 of cPP demand in 2005


Nucleating Agents / Clarifying Agents

How do they work?

Nucleating Agents Clarifying AgentsNucleating Agents Clarifying Agents

TalcSodium BenzoatePhosphor SaltsHyper-Nucleator

Acetal Sorbitols


Semi-Crystalline PhaseMelt Phase

Regular PP

Clarified PP

Nucleated PP

“Nucleation Phase”

Nucleated vs. Clarified PP (cPP)


Criterion Why Important

Clarity

Organoleptics

Processability

Nucleation

Consumer Appeal

Food Contact Applications

High Temperature Processing

Faster Production and Improved Physical Properties

Key Performance Criteria for Clarifiers


Generations of Sorbitol Acetal Clarifiers for PP

R1

R1

o

oo

o

OH

HO

R2

R2

R1 R2

DBS 1G H H

MDBS 2G CH3 H

Millad 3G CH3 CH3


DBS Food ContactHeat Stability

Clarity

Millad®

3988(DMDBS)

ClarityFood ContactNucleation

Heat Stability

NONE

MDBSClarity

NucleationTaste & Odor

225 °C

285 °C

250 250 °°CC

Max. TDrawbacksAdvantagesProduct

Advantages and Drawbacks of Clarifiers


Chemical degradation forms the aldehyde

R2

R1

R1

o

oo

o

OH

HO

H + R2

o

oo

OHHO

+R1

R2

CHOR1

R2

� Thermal oxidation of sorbitol based

clarifier – deterred through the addition of antioxidants

� Residual aldehydes (100-200ppb

threshold detection)*

� Chemical degradation of sorbitolacetals during processing of the polymer*

*T. Roth, V. *T. Roth, V. DudlerDudler (Swiss Federal Office of Public Health) et al., Mitt. (Swiss Federal Office of Public Health) et al., Mitt.

LebensmLebensm. . HygHyg. 91 (2000), 143. 91 (2000), 143--148148


MILLADMILLAD®®MDBS

Substituted aldehydes

CHOR1

R2

R1 R2

DBS 1G H H NO SMELL

MDBS 2G CH3 H STRONG SMELL

MILLAD 3G CH3 CH3 NO SMELL


European law: Framework directive 89/109

• 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

characteristics thereof

NO CHANGE IN TASTE ALLOWED


Clarifying agent for polypropyleneClarifying agent for polypropylene

M I LL I K E NB Y M I LL I K E NB Y

Milliken solutions for polyolefines


MI LLIKENBY MI LLIKENBY

High speed nucleating agent High speed nucleating agent

for polypropylenefor polypropylene



NucleatorNucleator for polypropylene andfor polypropylene and

polyethylenepolyethylene


PolyethylenePolyethylene

PolypropylenePolypropylene


THANK YOU

Visit us at:

www.millikenchemical.com

www.clearPP.com

www.specialchem4polymers.com

iv moscow international conference «polypropylene 2007 · iv moscow international conference ......

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