Chinaplas Seminar, Shanghai, 2016 Innovation that works for you Vistamaxx performance polymer in compounding
Agenda Introduction of ExxonMobil Chemical Vistamaxx in compounding New possibilities for PP modification An innovation for masterbatch industry Introduction of Vistamaxx performance polymers Question and answer
Welcome!
ExxonMobil Chemical
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Expanding the possibilities for polypropylene modification
Agenda hpp/rcp modification ICP modification What is stress whitening issue? Quantitative stress whitening test method effectively reduce stress whitening help achieve balance of properties in ICP compounds
Maintaining clarity of RCP Haze, % Test based on ASTM D1003 100 80 60 40 20 0 Haze of RCP/ modifier blends (2 mm) Vistamaxx 6202 Vistamaxx 3000 Exact 9371 0 5 10 15 Modifier, wt.% Utilize Vistamaxx 3000 series grades for your most demanding clear applications Unlike plastomer, Vistamaxx performance polymers maintain clarity when blended with RCP 12
Superior RCP impact performance improvement Failure Mode Test based on ASTM D3763 D DB BD B 5 wt.% modifier in RCP at RT Exact 9371 RCP Vistamaxx 6202 Vistamaxx 3000 Exact 9371 Failure Mode Test based on ASTM D3763 D DB BD B 10 wt.% modifier in RCP at RT Exact 9371 RCP Vistamaxx 6202 Vistamaxx 3000 Exact 9371 Modifier/% Modifier/% 15 wt.% modifier in RCP at RT Failure Mode Test based on ASTM D3763 D DB BD B Exact 9371 RCP Vistamaxx 6202 Vistamaxx 3000 Exact 9371 Improve impact resistance with as little as 5% Vistamaxx performance polymers Modifier/% Note: D = Ductile DB = Ductile Brittle BD = Brittle Ductile B = Brittle Exact = Exact plastomer 13
Improve RCP impact performance at low temperature Impact strength - Notched Izod at 0, J/m Vistamaxx 6202, % 0% 10% 30% 50% 70% RCP 22 C 52 C 713 NB 820 NB 631 NB C = complete failure; P = partial failure, NB = No break 50 / 50 blend of Vistamaxx 6202 / RCP blends exhibit ductile behavior down to -20 C Addition of Vistamaxx performance polymers improves impact performance as long as temperatures stay above the glass transition temperature (T g Vistamaxx 6202 = -28 C) 14
Mechanical properties with RCP Flexural Modulus/MPa Test based on ASTM D790 1400 1200 1000 800 600 400 200 0 Flexural Modulus of RCP/modifier blends Vi stam axx 6 20 2 Vi stam axx 3 00 0 Exact 9371 0 5 10 15 Modifier, wt.% Ultimate tensile strength/mpa Test based on ASTM D638 35 30 25 20 15 10 5 0 Ultimate tensile strength of RCP/modifier blends 0 5 10 15 Modifier, wt.% Vistamaxx 6202 Vistamaxx 3000 Exact 9371 Mechanical performance of Vistamaxx performance polymers are similar to plastomers Improved flexibility, reduced tensile strength 15
Create unique products at high concentrations 80 Hardness Dry-Blending 1600 Flexural Modulus Dry-Blending Hardness, Shore D Test based on ASTM 2240 60 40 20 HPP RCP Flexural Modulus, MPa Test based on ASTM D790 1200 800 400 HPP RCP 0 0 10 30 50 70 0 0 10 30 50 70 Vistamaxx 6202, wt.% Vistamaxx 6202, wt.% Blends of Vistamaxx performance polymers with above 30% in PP have significantly improved softness and flexibility 16
Reduce Stress Whitening
ICP challenge: stress whitening/blush ICP is a two-phase system with hpp as matrix and EP rubber as dispersed phase In injection molding or other converting processes, hpp shrinks more in comparison to EP rubber phase, and hence the EP rubber particles are under compressive stress Under impact conditions, the EP rubber particles release the compressive stress by voids, cavitation, or crazes, and hence stress whitening hpp Ethylene- Propylene Rubber
Industry trends Increasing stringent requirements for lower stress whitening in ICP applications Rigid packaging Luggage shells Automotive parts Small appliance Toys Furniture Material handling Ways to reduce stress whitening Solution HDPE, LLDPE Polybutene Nucleating agent + PE Challenge Incompatible to ICP Naturally expensive No significant improvement* Your next best solution as shown in this study! 19 *only can reduce stress from molding pressure due to faster de-molding, no impact on material property for blush resistance
Technical study Process Dry blending for 30 minutes Sample plaque made by injection molding process for property test Design boundary Vistamaxx performance polymers from 0 to 30% LLDPE 6101XR from 0 to 30% Binary blend, ICP/ LLDPE and ICP/ Vistamaxx polymers Tri-blend, ICP/ LLDPE/ Vistamaxx polymers Material selection Grades ExxonMobil ICP PP7033E3 ExxonMobil LLDPE 6101XR MFR 230 C/2.16 kg g / 10 min 8 (test based on ASTM D1238) 20 (MI 190 C/2.16 kg) (test based on ASTM D1238) Density g / cm 3 0.9 (test based on ExxonMobil method) 0.924 (test based on ExxonMobil method) Vistamaxx 6202 Vistamaxx 3000 20 (test based on ExxonMobil method) 8 (test based on ExxonMobil method) 0.863 (test based on ASTM D1505) 0.873 20 (test based on ASTM D1505)
The quantitative measurement of whitening ExxonMobil test method Equipment: Gardner ambient impact tester, colorimeter Test specimens: injection molded 10cm disc (thickness: 3mm) Impact condition: 1.8kg; 12.7cm Quantified by measuring the L value of color using a colorimeter L is the measurement of whiteness The degree of whitening is recorded as ΔL L B ΔL= L A - L B L A The lower ΔL, the less stress whitening 21
Visual comparison of impact whitening Impact discs are molded from dry blending ExxonMobil ICP PP 7033E3 with LLDPE 6101XR and Vistamaxx 3000 at respective ratio Pictures of sample are after impacted with Gardner impact tester Pure ICP 70 / 30 / 0 70 / 0 / 30 85 / 7.5 / 7.5 70 / 15 / 15 55 / 22.5 / 22.5 ICP / LLDPE / Vistamaxx polymers Tests performed in Shanghai Technology Center (STC) following ExxonMobil test methods, some of which are based on certain versions of industry standards (ASTM/ISO). Color was tested in STC using ExxonMobil test method OMP STC 136 22
Significant reduction of stress whitening The addition of can effectively reduce stress whitening gives synergistic effect with LLDPE to reduce stress whitening more Vistamaxx polymers in ICP Vistamaxx polymers in ICP with LLDPE Color, ΔL Test based on ExxonMobil Method 14 12 10 8 6 4 2 0 ICP Vistamaxx 100 0 80 20 6202 3000 70 30 Color, ΔL Test based on ExxonMobil Method 14 12 10 8 6 4 2 0 ICP LLDPE Vistamaxx 100 0 0 70 30 0 85 7.5 7.5 70 15 15 60 30 10 6202 3000 55 22.5 22.5 Tests performed in Shanghai Technology Center (STC) following ExxonMobil test methods, some of which are based on certain versions of industry standards (ASTM/ISO). Color was tested in STC using ExxonMobil test method OMP STC 136
AFM study on compatibility Pure ICP EP polymer shows well dispersed distinguished phase in ICP LLDPE alone in ICP has lumps of polymers undispersed Adding Vistamaxx performance polymers in ICP with LLDPE, a more homogeneous phase is observed ICP + LLDPE ICP + LLDPE + Vistamaxx 10 x 10 µm scan size
Blend properties analysis Both Vistamaxx performance polymer grades show better stress whitening reduction and impact performance than LLDPE The synergistic effect of Vistamaxx polymers upgrade ICP/ LLDPE blend to achieve more balanced properties ICP Stress whitening, ΔL Test based on ExxonMobil Method 0 3 NI at -20 C, KJ/m 2 Hardness, Shore D Test based on ISO 180 15 Test based on TPE 0189 65 3 NI at 23 C, KJ/m 2 60 Test based on ISO 180 Elongation at yield, % Test based on ISO 572 Vistamaxx 6202 blend 22 15 0 1200 25 Tensile strength at yield, MPa Test based on ISO 572 Vistamaxx 3000 blend 90 1 HDT, C Test based on ISO 75 2 FM, MPa Test based on ISO 178 Stress whitening, ΔL Test based on ExxonMobil Method 0 3 Hardness, Shore D NI at -20 C, KJ/m 2 15 Test based on TPE 01 Test based on ISO 180 65 70% ICP + 30% LLDPE 70% ICP + 30% Vistamaxx polymers 3 NI at 23 C, KJ/m 2 60 Test based on ISO 180 15 0 1 HDT, C 90 Test based on ISO 75 70% ICP + 15% LLDPE + 15% Vistamaxx polymers 1 Heat Deflection Temperature, 2 Flexural Modulus (1% Secant), 3 Notched Izod Tests performed in Shanghai Technology Center (STC) following ExxonMobil test methods, some of which are based on certain versions of industry standards (ASTM/ISO). Color was tested in STC using ExxonMobil test method OMP STC 136 Elongation at yield, % Test based on ISO 572 22 25 Tensile strength at yield, MPa Test based on ISO 572 2 FM, MPa 1200 Test based on ISO 178
Case sharing: suitcase Vistamaxx performance polymers provide a reliable solution to stress whitening in PP ICP Customer requirements Develop a reliable solution for high end suitcase Compatible with PP ICP & PE Significant reduction of stress whitening Decrease scrap rate during production Easy to adopt, no additional process and cost Deliver required properties ExxonMobil solutions Improve impact performance when blended with polypropylene Excellent compatibility with PP ICP & LLDPE Provide a solution to stress whitening reduction Achieve lower scrap rate at production line Dry blending, no additional process Tailor made properties 26
Significant reduction of stress whitening Reduce stress whitening for better aesthetic parts and less defect ratio Improved toughness for higher durability and provide downgauge possibility Enable ICP with LLDPE to achieve more balanced cost and performance challenges Properties in ICP blend LLDPE Vistamaxx Vistamaxx + LLDPE Stress whitening reduction + ++ +++ Impact strength - ++ + Stiffness / hardness / HDT - --- -- Specific gravity - + Tailorable Compatibility - ++ ++ MFR No improvement Tailorable Tailorable
An innovation for the masterbatch industry
Higher filler loading and better processing in AFMB compounding 29
Better dispersion at higher filler loading LLDPE based Masterbatch Vistamaxx based Masterbatch Filler Particle PE Phase Agglomerated Particle Filler Particle 70% filler 80% filler Vistamaxx Phase Individual filler particles and agglomerates are clearly visible in both samples and easily distinguished from polymer phase Filler dispersion is more uniform in Vistamaxx performance polymer carrier than in LLDPE carrier 30
Lower processing temperature Low melt temperature of Vistamaxx performance polymer allows for lower mixing temperature during masterbatch compounding process Protect heat-sensitive additives in MB compound DSC melting scan Vistamaxx 6202 LLDPE hpp
Improved tape toughness and processing efficiency, cost savings 32
Vistamaxx polymer-based AFMB enhances performance Compared with PP-based masterbatch, Vistamaxx polymerbased masterbatch can: Improve tenacity and elongation of raffia tape at same MB level Reduce tape breakage during tape making and weaving process Tenacity (g/d) 6 5 4 3 Tenacity (g/d) Elongation at Break (%) Elongation at Break (%) 20 15 10 5 0 AFMB with Vistamaxx and hpp blend as carrier resin provides balanced cost and performance Tape Reference 80% hpp/ 20% hpp-based MB Vistamaxx polymerbased Masterbatch 80% hpp/ 20% Vistamaxx polymerbased MB MB 85% CaCO 3 / 15% hpp 85% CaCO 3 / 7.5% hpp/ 7.5% Vistamaxx 6202 33
Higher AFMB level for cost saving Compared with PP-based masterbatch, Vistamaxx-based masterbatch can: Allow higher AFMB let down and maintain tape properties, hence achieve cost saving Tenacity (g/d) 5 4 Elongation at Break (%) 20 15 10 5 Reduce tape breakage during tape making and weaving process 3 Tenacity (g/d) Elongation at Break (%) 0 AFMB with Vistamaxx and hpp blend as carrier resin provides balanced cost and performance Tape MB Reference 80% hpp/ 20% hpp-based MB 85% CaCO 3 / 15% hpp Vistamaxx-based Masterbatch 70% hpp/ 30% Vistamaxx-based MB 85% CaCO 3 / 7.5% hpp/ 7.5% Vistamaxx 6202 34 34
HDPE shopper bags and garbage bags Trends Cost reduction, flat growth Increased in filler and recycle material Limited down gauging options New legislation on the usage of plastic carry bags Drivers Lower margins, stiff competition Ban on plastics bags in some states / countries 35
Vistamaxx performance polymer-based MB in HDPE Shopper & Garbage bags MD Elmendorf Tear, g Test based on ASTM D-1922-06a Puncture Break Energy, mj/µm Test based on ASTM D-5748 30 6 Avg. Tensile Strength, MPa *** Test based on ASTM D-882 50 180 400 Dart Impact, g ** Test based on ASTM D-1709 Avg. Elongation at Break, % *** Test based on ASTM D-882 Avg.1% Secant modulus, MPa *** 800 Test based on ASTM D-882 15µm, HDPE (77%) + C4LL (13%) + LL MB (10%) 15µm, HDPE (69%) + C4LL (11%) + Vistamaxx based MB (20%) Significantly increase CaCO 3 loading via Vistamaxx based MB Significantly increase toughness via Vistamaxx based MB Source: ExxonMobil Data All masterbatches used contain 80% CaCO 3, ** dart impact measured 48g *** shown as average of MD/TD Puncture, ASTM D-5748; dart impact, ASTM D-1709, tensile strength/elongation, ASTM D-882; FM, ASTM D- 790A; MD Elmendorf tear, ASTM D-1922-06a ** dart impact measured 48g *** shown as average of MD/TD 36
Vistamaxx performance polymer-based MB in HDPE S&G bags Increase CaCO 3 content Increase recycle content Test based on ASTM D1709 Test based on ASTM D1709 ExxonMobil Data, films produced on commercial line, 20 µm nominal thickness, all MB used contain 80% CaCO 3 Vistamaxx polymer based MB enhances the property profile at a lower cost Vistamaxx polymer based MB solutions allow increased filler loading 37
Summary Vistamaxx performance polymers as a resin carrier for masterbatch offer improved compound processing to compounders Vistamaxx based masterbatch improves the properties of PP raffia tape in addition to the benefit of resin carrier for the filler Vistamaxx performance polymer-based masterbatch optimizes cost and performance of HDPE shopper bag and garbage bag producers
Introduction of Vistamaxx performance polymers
The next generation of products building on ExxonMobil s history of providing technically advanced solutions to the market. 40
Vistamaxx performance polymers Based on ExxonMobil Chemical s proprietary metallocene technology Semi-crystalline polymer with tunable amorphous content Compatible with other polyolefinic materials, e.g., PE & PP Produced in the Singapore facility with a 300,000 ton per year capacity Microcrystalline regions Amorphous regions Amorphous Content Crystallinity Density Hardness Flex Modulus Vicat Softening Point
Enable customers to bring innovative, cost-effective solutions to market. 42
Grade slate Typical values Grade MFR 230 C/2.16 kg EMCC method g/10 min Density 1 23 C ASTM D1505, g/cm 3 Hardness 15 sec ASTM D2240, Shore D/A Tensile Stress 1 @ Break ASTM D638, MPa (psi) Elongation 1 @ Break ASTM D638, % Flex Mod 1,2 1% Secant ASTM D790 MPa (psi) Tear Strength 1 Die C ASTM D624, kn/m (lbf/in) Vicat Softening Point 200g EMCC Method, C ( F) 3000 8 0.873 33D 17.1 (2480) 1898 59.3 (8610) 62.3 (356) 65.6 (150) 3020FL ** 3 0.874 34D 17.0 (2460) 1756 59.7 (8650) 64.3 (367) 68.3 (155) 3980FL ** 8 0.878 40D 17.2 (2500) 1682 110 (16000) 81.3 (464) 76.7 (170) 6102/6102FL ** 3 0.862 66A >6.90 (>1000) >2000 12.3 (1790) 34.3 (196) 52.2 (126) 6202/6202FL ** 20 0.863 66A >5.50 (>798) >2000 12.3 (1790) 33.3 (190) 47.2 (117) 6502 48 0.865 71A >9.65 (>1400) >1900 20.5 (2980) 38.4 (220) 51.5 (125) **FL grades pass ExxonMobil Chemical s test for film appearance with regard to gels, as needed for performance film applications ( A rating) 1. All physical properties were measured on specimens cut from compression molded plaques per ASTM D4703, Procedure A, Type I and conditioned at 23ºC for a minimum of 40 hours per ASTM D618 prior to testing. 2. 1% secant @ break. 43
New possibilities in compounding Polymer modification and compounding Stationary files Soft PP grips Ice cream containers Cosmetic Bottles Food containers Thermoformed trays Filler masterbatch HDPE shopper & garbage bags Nonwoven packaging Raffia bag Storage boxes DVD cases Shopper & garbage bag Buckets 44
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Test methods (PP modification) Testing ExxonMobil Test Method based on Hardness ASTM D2240 Ultimate Tensile Strength ASTM D638 Elongation at Break ASTM D638 Tensile Strength at Yield ASTM D638 Flexural modulus (1% Secant Modulus) ASTM D790 Notched IZOD Impact energy ASTM D256 Instrumented impact test ASTM D3763 Haze ASTM D1003 Tests performed in STC follow ExxonMobil test methods, some of which are based on certain versions of industry standards (ASTM/ISO). 48
Testing method (Stress whitening) Testing ExxonMobil Test Method based on Stress whitening EMCC method Notched IZOD Impact energy ISO 180 Flexural Modulus (1% Secant) ISO 178 Hardness TPE 0189 Tensile Strength @ yield ISO 572 Elongation @ yield ISO 572 HDT (Heat deflection temperature) ISO 175 49
Materials (masterbatch) Manufacturer Grade MFR 230ºC/2.16 kg ASTM D1238 g/10 min MI 190ºC/2.16 kg ASTM D1238 g/10 min Density D23ºC ASTM D1505 modified g/cm³ Pour Density ASTM D1513 kg/m³ Bulk Density ASTM C110 lbs/ft³ ExxonMobil Chemical Vistamaxx 6202 20 0.861 Sunoco Chemicals ExxonMobil Chemical ExxonMobil Chemical Huber Engineered Materials Cabot Corporation F180A homopolymer polypropylene (hpp) ExxonMobil LLDPE LL 6201RQ resin ExxonMobil PP4712E1 polypropylene homopolymer resin Hubercarb M4 Calcium Carbonate (CaCO 3 ) Vulcan 9A32 carbon black (CB) 17 -- -- -- 50 0.926 2.8 -- 0.9 mean particle size 4.5 µm -- -- 40 less than or equal to 19 nm particle size -- 352 Note: Values obtained from product data sheet for each material. 50
Test methods (masterbatch) Test method ExxonMobil Test Method based on MFR (230 ⁰C/2.16 kg) ISO 1133 MI (190 ⁰C/2.16 kg) ISO 1133 Differential Scanning Calorimeter (DSC) ASTM D3418 Tests performed in STC follow ExxonMobil test methods, some of which are based on certain versions of industry standards (ASTM/ISO). 51
Materials (blown film study) Manufacturer Grade MFR 230ºC/2.16 kg ASTM D1238 (g/10 min) MI 190ºC/2.16 kg ASTM D1238 (g/10 min) Density D23ºC ASTM D1505 modified (g/cm³) Pour Density ASTM D1513 (kg/m³) ExxonMobil Chemical Vistamaxx 6202 20 0.861 -- Sunoco Chemicals ExxonMobil Chemical ExxonMobil Chemical Cabot Corporation ExxonMobil Chemical F180A homopolymer polypropylene (hpp) ExxonMobil LLDPE LL 6201RQ resin ExxonMobil PP4712E1 polypropylene homopolymer resin Vulcan 9A32 carbon black (CB) ExxonMobil HDPE HTA 001 HD 17 -- -- -- -- 50 0.926 -- 2.8 -- 0.9 -- less than or equal to 19nm particle size -- 9.0 (190ºC/21.6 kg) -- 352 0.952 Note: Values obtained from product data sheet, for each material. Tests performed in STC follow ExxonMobil test methods, some of which are based on certain versions of industry standards (ASTM/ISO). 52
Test methods (blown film study) Test method ExxonMobil Test Method based on Differential Scanning Calorimeter (DSC) ExxonMobil Method Elmendorf tear strength ASTM D 1922-06a Impact resistance by free-falling dart: Method A (Dart impact) ASTM D 1709 Optical microscopy ISO 18553 Puncture resistance ASTM D 5748 Tensile properties on film ASTM D 882 Tests performed in STC follow ExxonMobil test methods, some of which are based on certain versions of industry standards (ASTM/ISO). 53
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