2011.

2017

Propylene-based Elastomer
An Innovation for the Masterbatch Industry

Master Batch Asia 2012 - Singapore Pradeep Patki ExxonMobil Company India Pvt. Ltd March 27, 2012

Agenda
Masterbatch (MB) background and carrier materials Manufacturing process and equipment Technical study Vistamaxx propylene-based elastomer benefits for compounders and endusers
Filler MB
Calcium carbonate (CaCO3) Carbon black (CB) Flame retardant (FR)

Conclusions

Masterbatch background
Resin compounds with color or additives encapsulated in the polymer to impart color, aid processability or enhance end-use properties Divided into four major categories Color MB
Black MBs White MBs Colored MBs Additives MBs

Typical dosage ranges from 1 to 20% by weight depending on end use applications and cost/performance requirements Dry-blended with base polymer in mixing/dosing hopper loaders Filler MB

Masterbatch polymer carrier material

Dominated primarily by polyethylene (PE) and polypropylene (PP) material with some ethylene vinyl acetate (EVA) for niche applications
PP primarily used in color and functional MBs for PP-based housewares, toys, fibers and bi-axially oriented PP film modifications
Limited filler acceptance compared to Vistamaxx propylene-based elastomer, PE or EVA

PE used for all four types of black, white, color and additive MBs primarily for film, blow molding and consumer durable applications EVA used for applications requiring high filler loading or compounding at lower temperatures for heat sensitive additives or carrier for universal MB

Manufacturing process and equipment

Pellets sometimes cryogenically ground into small particles for better mixing and dispersion with powder pigments Waxes also used as processing aids, but may lead to blooming issues which will affect surface appearance and cause printing problems Accurate dosage of organic or inorganic pigments along with process control important, as pigments can vary in price significantly Strand-cut/water bath cooling system typically used for small batch size color MB Die-face cutting or underwater pelletizing used for high volume filler or commodity black/white MB Pellet size and shape important to ensure accurate quantity using volumetric dosing unit

Benefits
Delivered features
Unique product morphology using ExxonMobil Exxpol metallocene catalyst

Derived benefits
Excellent heat stability and less polymer degradation or formation of cross-linked gels Narrow molecular weight distribution Transparent pellets Energy saving for compounding at lower temperature and shorter cycle time Universal carrier for both PE or PP based MB allows consolidation of grade mix offered to end customers Less corrosive to compounding equipment Food contact applications

Importance to you
Broad processing window in various types of compounding machines Better dispersion and wetability of pigments and fillers Easy color matching with various pigments Energy cost savings and less thermal degradation of polymer carrier Excellent carrier for heat sensitive additives such as blowing agents or flame retardants Reduced number of grades and better inventory control would allow better cash flow and less product wastage Lower equipment maintenance cost Meet increasing end-user demand for food law compliance and certification

Low melt temperature

Compatible with BOTH polyethylene (PE) and polypropylene (PP) Inert polymer with no odor and broad compliance to US, European and Japanese food laws

Technical study
Materials MB formulations and sample preparation Dispersion evaluation by optical control system (OCS) film appearance rating (FAR) dispersion evaluation
CaCO3 MB (ExxonMobil test method) CB MB (OCS Equipment Company test method)

Physical property improvement for end use products Lower processing temperature

Materials
MFR 230C/2.16 kg ASTM D1238 (g/10 min) 20 17 --50 MI 190C/2.1 6 kg ASTM D1238 (g/10 min) Density D23C ASTM D1505 modified (g/cm) 0.861 -0.926 Density ASTM D1513 kg/cm lbs/ft

Manufacturer

Grade

ExxonMobil Chemical Sunoco Chemicals ExxonMobil Chemical

Vistamaxx 6202 propylenebased elastomer F180A homopolymer polypropylene (hPP) ExxonMobil LLDPE LL 6201RQ resin ExxonMobil PP4712E1 polypropylene homopolymer resin Hubercarb M4 Calcium Carbonate (CaCO3) Vulcan 9A32 carbon black (CB)

----

----

ExxonMobil Chemical Huber Engineered Materials Cabot Corporation

2.8

--

0.9

--

--

mean particle size 4.5 m less than or equal to 19 nm particle size

---

-352

40 --

Note: Values obtained from product data sheet for each material.

Masterbatch formulation and sample preparation

CaCO3 LLDPE 20 (granular) 20 60 hPP Vistamaxx propylene-based elastomer CaCO3 CB hPP CB LLDPE 60 (pellet)

MB Samples ExxonMobil LLDPE LL 6201RQ resin F180A hPP Vistamaxx 6202 propylene-based elastomer CaCO3 CB

20 80 80 80

60 40 40 40

CaCO3 MB samples compounded in twin-screw compounder (1 step) CB MB samples made in two step mixing process:
1. Mixing in banbury and pelletizing 2. Enhanced mixing in twin screw compounder

Dispersion evaluation by OCS film appearance rating

Optical Control System (OCS) film appearance rating (FAR) testing used to evaluate dispersion of CaCO3 and CB in MB samples
Defects on film captured and measured

Cast film

CaCO3 dispersion evaluation

Distribution (%)

MB samples of CaCO3-LLDPE, CaCO3hPP and CaCO3-VistamaxxTM propylenebased elastomer dry blended in hPP at 2% by weight and extruded in cast film CaCO3-Vistamaxx propylene-based elastomer masterbatch has comparable dispersion to CaCO3-hPP MB and better dispersion than CaCO3-LLDPE MB in hPP film
Particle size distribution Vistamaxx as carrier

80 60 40 20 0 50

Particle size distribution hPP as carrier

100

150 200 300 Particle size (m)

500

700

Particle size distribution LLDPE as carrier 80 Distribution (%) 60 40 20 0 50 100 150 200 300 Particle size (m) 500 700

Distribution (%)

80

60 40 20 0 50 100 150 200 Particle size (m) 300 500

Carbon black dispersion evaluation

Particle size distribution hPP as carrier

Distribution (%)

MB samples of CB-LLDPE, CB-hPP and CBVistamaxx propylene-based elastomer blended in hPP at 2% by weight and extruded in cast film CB-Vistamaxx propylene-based elastomer masterbatch has better dispersion compared to CaCO3-hPP MB and CaCO3-LLDPE MB in hPP film
Particle size distribution Vistamaxx as carrier

100 80 60 40 20 0 100 200 300

Particle size (m)

400

500

600

700

800

Particle size distribution LLDPE as carrier

100

100

Distribution (%)

Distribution (%)

80 60 40 20 0 100 200 300 400 500 600 700 800

80 60 40 20 0 100 200 300 400 500 600 700 800

Particle size (m)

Particle size (m)

Dispersion evaluation
Statistic results of CaCO3 and CB MB
CaCO3 MB CaCO3 - Vistamaxx 6202 CaCO3 - hPP CaCO3 - LLDPE Mean Particle Size (m) 72.2 71.2 89.2 Standard Deviation (m) 58.6 64.6 88.9

CB MB CB - Vistamaxx 6202 CB - hPP CB - LLDPE

Mean Particle Size (nm) 199.3 233.0 228.9

Standard Deviation (nm) 112.9 132.4 128.7

Mean particle size of Vistamaxx propylene-based elastomer masterbatch is

smaller than LLDPE or hPP MB

Vistamaxx propylene-based elastomer masterbatch has comparable or better

dispersion than LLDPE MB or hPP MB in hPP film

High filler loading capability

Hardness
Viscosity at 1200 1/s(pa.s)
Test method: ASTM D2240

400 350 300 250 200 150 100 50

LCR
Test method: ExxonMobil TPE-0200

100 Hardness Shore A 80 60 40 20 Shore D

50

65

75

80

85

65

75

80

wt% CaCO3 in Vistamaxx 6202 propylene-based elastomer

wt% CaCO3 in Vistamaxx 6202 propylene-based elastomer

Elongation at Break
Test method: ASTM D638

1200

Vistamaxx 6202

Eb, %

Up to 85% by weight CaCO3 can be

loaded into Vistamaxx propylenebased elastomer

800
Vistamaxx 3000

400 RCP 0 50 60 65

LDPE 70 75

wt% CaCO3 in blends with different carriers

Higher MB loadability in end use product

Hardness 73 Hardness, Shore D 30 Tb, MPa 71 20 10 0 Tensile Strength at Break

69

67 0 20 30 MB% in hPP blends Elongation at Break 120 Eb, % 80 40 0 40

Test method: ASTM D2240

20 30 MB% in hPP blends

40

Test method: ASTM D638

MB samples of CaCO3-LLDPE, CaCO3-hPP and CaCO3-Vistamaxx propylene-based elastomer blended into hPP using twin screw Up to 40% by weight of CaCO3-Vistamaxx propylene-based elastomer masterbatch can be loaded into hPP while maintaining physical integrity vs. only 30% by weight of CaCO3LLDPE MB or CaCO3-hPP MB
0 20 30 MB% in hPP blends 40
MB LLDPE MB hPP MB Vistamaxx propylene-based elastomer
Test method: ASTM D638

Physical property enhancement in end use product

Elongation Elongation at @Break Break
140 120 120 100 80 60 40 20 0 0 Notch Izod, J/M

Notched Izod
39 37 35 33 hPP LLDPE MB

Eb % Eb, %

hPP LLDPE MB hPP MB PP4712E1 LL MB PP MB Test method: ASTM D638 Type of MB

VM MB Vistamaxx 6202

hPP MB

Type of MB
Test method: ASTM D256 Method A

Vistamaxx MB

Melt Flow Rate

MFR, g/10mins 4 3 2 1 0 hPP LLDPE MB hPP MB Type of MB Vistamaxx MB

20% MB samples of CaCO3-LLDPE, CaCO3-hPP and CaCO3-Vistamaxx propylene-based elastomer dry-blended with hPP MB using Vistamaxx propylene-based elastomer gives:
Higher MFR for easy processing Better elongation for increased flexibility Higher impact strength

Test method: ISO1133 Method B

Lower processing temperature

DSC Melting Scan
Vistamaxx 6202 F180A hPP ExxonMobil LLDPE 6201RQ Vistamaxx 6202 LLDPE hPP

50

100

150

200

Temperature (C)

Low melt temperature of Vistamaxx 6202 propylene-based elastomer allows lower mixing temperature during MB compounding process
Minimize gel generation due to polymer cross-linking at higher temperatures Protect heat sensitive additives in MB compound

Other possibilities FR dispersion improvement

Thermoplastic olefin (TPO) single-ply roof membrane
Control formulation: 60% polymer, 30% FR (Magnesium Hydroxide), 5% UV stabilizer; 5% white pigment

Vistamaxx propylene-based elastomer used as modifier delivers following benefits

Improved dispersion of FR for improved performance or reduction in FR for lower weight and cost

15um

15um

15um

Control

5% Vistamaxx 6102 propylene-based elastomer replacement of polymer

20% Vistamaxx 6102 propylene-based elastomer replacement of polymer

Horizontal burn (HB) rate improvement

Burning rate improved 46% when control material substituted with just 5% Vistamaxx 6102 propylene-based elastomer due to enhanced dispersion of FR
TPO Roofing Sheet Burning Rate Average (BRA)
BRA V=60L/t mm/min UL94
70.00 60.00 50.00 40.00 30.00 20.00 10.00 0.00 Control 5% VM 10% VM 15% VM 20% VM

Vistamaxx 6102 propylene-based elastomer (%)

UL94 HB for classifying materials

Conclusions
Looking for:
Lower cost and higher performing solutions Better dispersion Higher loading Lower melt temperatures

Vistamaxx propylene-based elastomer expands your possibilities in filled and color MBs!

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March 27, 2012