Embed Size (px)
DESCRIPTION
exxonmobil
Citation preview
Propylene-based ElastomerAn Innovation for the Masterbatch Industry
Master Batch Asia 2012 - Singapore
Pradeep Patki
ExxonMobil Company India Pvt. Ltd
March 27, 2012
2011.2017
Agenda
• Masterbatch (MB) background and carrier materials
• Manufacturing process and equipment
• Technical study
• Vistamaxx propylene-based elastomer benefits for compounders and end-users• 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• 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
Color MB
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 Derived benefits Importance to you
• Unique product morphology using ExxonMobil Exxpol™ metallocene catalyst
• Excellent heat stability and less polymer degradation or formation of cross-linked gels
• Narrow molecular weight distribution
• Transparent pellets
• Broad processing window in various types of compounding machines
• Better dispersion and wetability of pigments and fillers
• Easy color matching with various pigments
• Low melt temperature • Energy saving for compounding at lower temperature and shorter cycle time
• Energy cost savings and less thermal degradation of polymer carrier
• Excellent carrier for heat sensitive additives such as blowing agents or flame retardants
• Compatible with BOTH polyethylene (PE) and polypropylene (PP)
• Universal carrier for both PE or PP based MB allows consolidation of grade mix offered to end customers
• Reduced number of grades and better inventory control would allow better cash flow and less product wastage
• Inert polymer with no odor and broad compliance to US, European and Japanese food laws
• Less corrosive to compounding equipment
• Food contact applications
• Lower equipment maintenance cost• Meet increasing end-user demand for food
law compliance and certification
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
Manufacturer Grade
MFR 230ºC/2.16 kg ASTM
D1238 (g/10 min)
MI 190ºC/2.1
6 kg ASTM D1238
(g/10 min)
Density D23ºC ASTM D1505
modified (g/cm³)
DensityASTM D1513
kg/cm³ lbs/ft³
ExxonMobil ChemicalVistamaxx™ 6202 propylene-based elastomer
20 0.861 -- --
Sunoco ChemicalsF180A homopolymer polypropylene (hPP)
17 -- -- -- --
ExxonMobil ChemicalExxonMobil™ LLDPE LL 6201RQ resin
-- 50 0.926 -- --
ExxonMobil ChemicalExxonMobil PP4712E1 polypropylene homopolymer resin
2.8 -- 0.9 -- --
Huber Engineered Materials
Hubercarb® M4 Calcium Carbonate (CaCO3)
mean particle size 4.5 µm -- -- 40
Cabot CorporationVulcan® 9A32 carbon black (CB)
less than or equal to 19 nm particle size
-- 352 --
Note: Values obtained from product data sheet for each material.
Masterbatch formulation and sample preparation
MBSamples
CaCO3
Vistamaxx™ propylene-based elastomer CB
LLDPE hPP CaCO 3 CB hPP LLDPE
ExxonMobil™ LLDPE LL 6201RQ resin
20(granular)
60(pellet)
F180A hPP 20 60
Vistamaxx 6202 propylene-based
elastomer 20 60
CaCO3 80 80 80
CB 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
• MB samples of CaCO3-LLDPE, CaCO3-hPP and CaCO3-VistamaxxTM propylene-based 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
80
Particle size ( µµµµm)
0
20
40
60
80
50 100 150 200 300 500 700
Dis
trib
utio
n (%
)
Particle size distribution – LLDPE as carrier
0
20
40
60
Particle size ( µµµµm)
Particle size distribution – Vistamaxx as carrier
50 100 150 200 300 500
Dis
trib
utio
n (%
)
0
20
40
60
80
50 100 150 200 300 500 700
Particle size distribution – hPP as carrier
Particle size ( µµµµm)
Dis
trib
utio
n (%
)
• MB samples of CB-LLDPE, CB-hPP and CB-Vistamaxx™ 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
Dis
trib
utio
n (%
)
Particle size ( µµµµm)100 200 300 400 500 600 700 800
40
20
60
80
100
0
Particle size distribution – hPP as carrier
100
100 200 300 400 500 600 700 800
40
20
60
80
0
Particle size ( µµµµm)
Dis
trib
utio
n (%
)
Particle size distribution – Vistamaxx as carrier
100 200 300 400 500 600 700 800
40
20
60
80
100
0
Particle size ( µµµµm)
Dis
trib
utio
n (%
)
Particle size distribution – LLDPE as carrier
Carbon black dispersion evaluation
Dispersion evaluation
• 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
Statistic results of CaCO 3 and CB MB
CaCO3 MB Mean Particle Size ( µµµµm) Standard Deviation ( µµµµm)
CaCO3 - Vistamaxx 6202 72.2 58.6CaCO3 - hPP 71.2 64.6
CaCO3 - LLDPE 89.2 88.9
CB MB Mean Particle Size (nm) Standard Deviation (nm)
CB - Vistamaxx 6202 199.3 112.9CB - hPP 233.0 132.4
CB - LLDPE 228.9 128.7
High filler loading capability
• Up to 85% by weight CaCO3 can be loaded into Vistamaxx™ propylene-based elastomer
wt% CaCO 3 in Vistamaxx 6202 propylene-based elastomer
20
40
60
80
100
50 65 75 80 85
Shore A
Shore D
Har
dnes
s
LCR
Test method: ASTM D2240
Hardness
50 65 75 80
400
100
150
200
250
300
350
Vis
cosi
tyat
1200
1/s(
pa.s
)
wt% CaCO 3 in Vistamaxx 6202 propylene-based elastomer
Elongation at Break
Eb,
%
050 65
400
800
1200
60 70 75
Vistamaxx 6202
Vistamaxx3000
LDPERCP
Test method: ASTM D638
wt% CaCO 3 in blends with different carriers
Test method: ExxonMobil TPE-0200
Higher MB loadability in end use product
• 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 CaCO3-LLDPE MB or CaCO3-hPP MB
Tb,
MP
a
67
69
71
73
0 20 30 40
Har
dnes
s, S
hore
D
MB% in hPP blends
Hardness
0
10
20
30
0 20 30 40MB% in hPP blends
Tensile Strength at Break
0
40
80
120
0 20 30 40
Eb,
%
Elongation at Break
Test method: ASTM D2240
Test method: ASTM D638
Test method: ASTM D638
MB% in hPP blends
MB LLDPE
MB hPP
MB Vistamaxx propylene-based elastomer
Physical property enhancement in end use product
33
35
37
39
Not
ch Iz
od, J
/M
Notched Izod
hPP LLDPE MB hPP MB VistamaxxMB
Elongation at Break
hPP LLDPE MB hPP MB VM MB0
40
80
120
Eb
%
0
1
2
3
4
MF
R, g
/10m
ins
hPP LLDPE MB hPP MB VistamaxxMB
Melt Flow Rate
Test method: ASTM D638
Test method: ISO1133 Method B
Test method: ASTM D256 Method A
Type of MB
Type of MB
Elongation @ Break
020406080
100120140
PP4712E1 LL MB PP MB Vistamaxx6202 Type of MB
Eb,
%
• 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
Lower processing temperature
Vistamaxx 6202
F180A hPP
ExxonMobil™ LLDPE 6201RQ
LLDPEhPP
Temperature (ºC)
Vistamaxx 6202
DSC Melting Scan
50 100 150 200
• 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
Control • 5% Vistamaxx 6102propylene-based elastomer replacement of polymer
• 20% Vistamaxx 6102 propylene-based elastomer replacement of polymer
0 15um 0 15um 0 15um
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
UL94 HB for classifying materials
TPO Roofing Sheet Burning Rate Average (BRA)
0.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
Control 5% VM 10% VM 15% VM 20% VM
Vistamaxx 6102 propylene-based elastomer (%)
BR
A V
=60L
/t m
m/m
in U
L94
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!
©2012 ExxonMobil. To the extent the user is entitled to disclose and distribute this document, the user mayforward, distribute, and/or photocopy this copyrighted document only if unaltered and complete, including all of itsheaders, footers, disclaimers, and other information. You may not copy this document to a Web site. ExxonMobildoes not guarantee the typical (or other) values. Analysis may be performed on representative samples and not theactual product shipped. The information in this document relates only to the named product or materials when notin combination with any other product or materials. We based the information on data believed to be reliable on thedate compiled, but we do not represent, warrant, or otherwise guarantee, expressly or impliedly, themerchantability, fitness for a particular purpose, suitability, accuracy, reliability, or completeness of this informationor the products, materials, or processes described. The user is solely responsible for all determinations regardingany use of material or product and any process in its territories of interest. We expressly disclaim liability for anyloss, damage, or injury directly or indirectly suffered or incurred as a result of or related to anyone using or relyingon any of the information in this document. There is no endorsement of any product or process, and we expresslydisclaim any contrary implication. The terms, “we”, “our”, "ExxonMobil Chemical", or "ExxonMobil" are used forconvenience, and may include any one or more of ExxonMobil Chemical Company, Exxon Mobil Corporation, orany affiliates they directly or indirectly steward. ExxonMobil, the ExxonMobil Logo, the Interlocking "X” Device, andall other product names used herein are trademarks of ExxonMobil unless indicated otherwise.
2012 Master Batch Asia - Singapore
Pradeep Patki
ExxonMobil Company India Pvt. Ltd
March 27, 2012
