T E C H N O L O G Y Form No. 746-03801
MATERIAL CLASSIFICATION AND APPLICATIONS OF NEW PROPYLENE-ETHYLENE COPOLYMERS K. W. Swogger 2, B. Poon 1, C. H. Stephens 1, P. Ansems 2, S. Chum 2, A. Hiltner 1, and E. Baer 1 1 Center for Applied Polymer Research (CAPRI) and Department of Macromolecular Science and Engineering Case Western Reserve University, Cleveland, OH 44106 2 Polyolefins and Elastomers R&D The Dow Chemical Company Freeport, TX 77541 Form No. 746-03801
New Families of Propylene-Based Elastomers & Plastomers Based on INSITE* Technology With a New Catalyst Design Catalyst Structure Will Be Presented at the Global Homogeneous Catalyst Conference by Dr. Jim Stevens, June, 2003, Italy New Polymer Families Are Propylene/Alpha-Olefins Copolymers With Semi-Crystalline Isotactic Propylene Blocks Comonomers: Most Alpha-olefins Including Ethylene, Butene, Pentene, 4-Methyl-1-Pentene, Hexene, Heptene, Octene, Nonene. First Generation Products Described in This Paper Are Mostly Propylene-Ethylene Copolymers INSITE* is a Trademark of The Dow Chemical Company
Basic Molecular Structure of New Propylene-Based Elastomers & Plastomers Narrow Molecular Weight Distribution Mw/Mn < 3 High Molecular Weight Capability MFR From 1 to >100 Unique Comonomer Distributions Different From Z/N Copolymer Different From Metallocene Copolymers Unique Stereo- and Regio-Defects Along the Semi- Crystalline Isotactic Propylene Blocks NMR Investigations of Stereo- and Regio-Defect Structure to Be Presented at the Global Catalyst Conference by Dr. Jim Stevens in June, 2003, Italy
Samples of New Propylene-Ethylene (P/E) Copolymers for Property Evaluation Ethylene Content Mw Material (mol %) (Kg/mol) Mw/Mn MFR P/E0.0 0.0 316 2.5 2.5 P/E4.4 4.4 329 2.2 2.1 P/E8.2 8.2 296 2.2 2.2 P/E13.6 13.6 285 2.1 2.3 P/E15.7 15.7 262 2.2 2.0 P/E19.4 19.4 263 2.4 2.0
Molecular Weight Distribution of Dow s New Polypropylene (PP) vs. Z/N PP vs Metallocene PP Z/N PP Copolymer Dow s New PP Copolymer Metallocene PP Copolymer 3 4 5 6 7 Log Molecular Weight (g/mole)
Comparison of Comonomer Distribution Using TREF New P/E vs Metallocene P/E Copolymers
Comparison of Comonomer Distribution Using TREF New P/E vs Ziegler-Natta P/E Copolymers
High Molecular Weight Capability of Dow s New PP Copolymer Catalyst Comparison of Melt Flow Rates for Catalyst Types for Co-polymerization of Propylene and Ethylene (under constant H2 reactor conditions) 120 100 MFR (g/10min) 80 60 40 Standard Metallocene Catalyst 20 0 New DOW PP Catalyst 0 2 4 6 8 10 12 14 16 Mole % Ethylene
General Properties of New Propylene- Based Elastomers and Plastomers Thermal Properties Crystallinity
Melting Behavior of New P/E Copolymers DSC Melting Behavior of Dow s New Propylene/Ethylene Copolymers 3.0 2.5 7-12 Days Aging Heating Rate: 10 C min -1 1st Heating Heat Flow (W/g) 2.0 1.5 1.0 0.5 P/E (0.0%E; 316K Mw) P/E (4.4%E, 329K Mw) P/E (8.2%E, 296K Mw) P/E (13.6%E, 285K Mw) P/E(15.7%E, 262K Mw) P/E (19.4%E, 263K Mw) 0.0-25 0 25 50 75 100 125 150 175 Temperature ( C) With increasing comonomer content, P/E melts at lower temperature and becomes less crystalline
Effect of Ethylene Content on Crystallinity (Measured by DSC Technique) 70 60 7-12 Days Aging New P/E m-p/e DSC Crystallinity (wt %) 50 40 30 20 10 Plastomer Elastomer 0 0 5 10 15 20 25 Ethylene Content (mole %)
Classification of New Propylene-Ethylene Copolymer Families Mol.% Comonomer Content [wt.%] Crystallinity(wt.%) Tg ( C) Tm ( C) Type IV Type III Type II Type I 0 [0] 3 [2] 7 [5] 15 [10] 21 [14] 60 48 33 18 5 13 7 0-10 -20 144 ~110 ~90 ~70 ~60 Bulk Morphology Spherulites Sheaflike spherulites+ crosshatched web Embryonic axialites + crosshatched web Radial lamellae + random lamellae Crystal type Mostly α α, some γ α & increasing γ α & γ Mechanical Properties Thermoplastic Plastomer Elasto-plastomer Elastomer
Material Performance Properties Related to Applications Elastic Recovery Optical Properties Heat Seal
Experimental for Measuring Recovery ε applied l + l o Stress Loading Open Grips ε applied l o ' ε set l o l o l o Time Strain ε applied ε set Instantaneous Recovery ε applied = Strain applied during experiment ε set = Non-recoverable strain after load is released Delayed Recovery ε applied - ε set Time % Recovery = ε applied
Effect of Comonomer Content on Recovery Behavior of New P/E Copolymers 100 80 10s "Instantaneous" Recovery 1 Hour Delayed Recovery Applied Strain: 300% Temperature: 22 C % Recovery 60 40 20 0 Thermoplastics/Plastomers Elastomers 0 5 10 15 20 25 Ethylene Content (mol %)
Comparison of Haze of 2 mil Blown Film New P/E VS Metallocene VS Ziegler-Natta Copolymers % Haze 40 35 30 25 20 15 10 5 0 Haze for Selected Films New Dow P/E Copolymers ZN-P/E Copolymers Metallocene P/E Copolymer* 0 2 4 6 8 10 % of Ethylene * Cast Film
Comparison of Heat Seal Performance New P/E vs Other Competitive Materials 1200 Heat Seal Strength (gr/in)) 1000 800 600 400 200 0 80 90 100 110 120 130 140 150 Test Temperature ( C) New Propylene-Ethylene Sealant Competitive Material-II (6 MFR Propylene/Ethylene/Butene Terpolymer with 6%E and 15%B) Competitive Material-I (7 MFR Propylene/Ethylene/Butene Terpolymer with 12%E and 7%B)
Applications of New Propylene Based Elastomers & Plastomers Polymer Properties Broad Melting Point, Good Processability Excellent Clarity and Gloss Softness with Grip Hot Tack Over Broad Temp. Range Heat Seal Over Broad Temp. Range Compatibility with PP Systems Compatibility as Impact Modifier (ICP) Improved Elongation, Elasticity Fabrication /Application Fibers, Blown Film Food & Specialty Packaging (F&SP) Soft Touch, Dual Durometer F&SP BOPP, Cast Sealants, F&SP Sealants, F&SP, Flexible Materials Extrusion Blow Molding, Thermoforming Extensible and Elastic Fibers, Carpet Fiber
Stream-Line Application Development Cap Liners Carpet Fibers Cast/Calendared Sheets - Artificial Leather - Stationary - Consumer Products - Medical Packaging Footwear Roofing Membrane BOPP Sealants Today F&SP Films - Lamination - Produce Packaging - Food Wrap Film - Shrink Film - Candy Bags BM Bottles Soft TPO/TPEs - Overmolding - W&C - Automotive Hygiene Applications - Extensible NW - Elastic NW - Elastic Films - Backsheet Films - Binder Fibers Low MW Polymers - Hot Melt Adhesives - Bitumen Modification - Melt Blown Fibers Modifier for Tire formulations Future
Application Development Opportunities Validate Value and Applications Using Speed Base Development Approach Using Molecular Architecture Concept
Integration of Science and Technology for Customer Successes Chemistry Molecular Modelling Mass + Energy Balance Process Research Manufacturing Wisdom, Luck Or Outside Dow Sources Catalyst Design Chemistry Kinetics Reactor Design Reactor Conditions Plant Design Comonomer Choice Molecular Structure Start Inside/Out Rheology Fabrication Conditions Molecular Modelling Materials Science Physical Property Melt Properties Morphology Product Design Materials Science Marketing Start Outside/In Customer or Market Idea Performance Requirements Development Marketing Comonomers = Vinyl Containing, Inexpensive & Ethylene, Propylene, Styrene-Based (In General) Implementation At Customer Sales Technical Service
Speed Based Development Philosophy Create a Vision Choose the Right People Using Prior Experience to Avoid Mistakes Make Commitments Look for You Can t Do That or That Is Impossible Emphasize Decision Making Use Collaborative Partnerships to Lead Development Use Outside Experts or Consultants Use Flexible Allocation of Resources
Speed Based Speed Based Development Philosophy Development Philosophy Continue to Learn Align With Business Strategy Probe the Market Early and Use Marketing to Position the Product Involve the Customer Early Use Good Science Build and Manage Intellectual Assets Use Time Driven Measurements Use Net Present Value (NPV) to Measure Project Value
Summary Dow Is Developing New Families of Propylene Based Elastomers and Plastomers Based on Its INSITE* Technology With a New Catalyst These Polymers Have a Broad Range of Properties Suitable for Many Value Added Applications Excellent Optics Good Heat Seal Performance High Elastic Properties Excellent Processability: Blown Film, Cast Film, Injection Molding, Blow Molding. We Will Continue to Update You on the Progress of this Development Global Catalyst Conference, Italy, June 2003 National ACS Meeting, NYC, September 2003