DOW ECOLIBRIUM Bio-Based Plasticizers - Greening of PVC with Renewably Sourced Plasticizers Bharat I. Chaudhary R. Eaton, B. Sczekalla, C. Laufer, B. Neese, A. Ghosh-Dastidar The Dow Chemical Company
Outline Introduction to DOW ECOLIBRIUM Bio- Based Plasticizers Plasticizer Properties Properties of PVC Compounds & Wire Commercial Status Closing Remarks 2
What are DOW ECOLIBRIUM Bio-Based Plasticizers? A new family of phthalate-free plasticizers made from renewable feedstocks. Particularly of interest for flexible PVC applications, with initial thrust in wire insulation & jacket. Can help cable-makers and original equipment manufacturers (OEMs) reduce greenhouse gas emissions if used instead of traditional PVC plasticizers. Developed to meet growing demand for more sustainable options in personal electronics & appliance wires, communications & data cables, residential & commercial building wires, and automotive wires. Maintain the same look, feel, performance and processability of incumbent flexible PVC compounds. 3
Classification of DOW ECOLIBRIUM Bio-Based Plasticizers LPLAS-1100 Series Developmental Grades Low Viscosity Liquid Medium Volatility Medium Solution Temperature Suitable for Test Temperatures < 113 C Compatible with PVC, CPE, TPU, nitrile rubber, etc LPLAS-HT Series Medium Viscosity Liquid Low Volatility High Solution Temperature Suitable for Test Temperatures < 136 C Compatible with PVC, CPE, TPU, nitrile rubber, etc 4
DOW ECOLIBRIUM Bio-Based Plasticizers: Features and Benefits - Derived from Renewable Reduced Greenhouse Gas Feedstocks Feature Benefit Emissions - Good Solubility in Polymers Compatible from Low to High Temperature - Low to Medium Viscosity Readily Absorbed in Polymers (Powders) - Medium to Low Volatility High Upper Service Temperatures of Compounds 5
Life Cycle Analysis of DOW ECOLIBRIUM Bio-Based Plasticizers The use of 1 ton of PVC compound plasticized with LPLAS 1101 EXP1 will help the industry to reduce CO 2 equivalent emissions by 0.7 ton. This environmental benefit is equal to saving the use of 302 liters of petrol (gasoline) or the use of 266 liters of diesel*. 2.0 1.5 1.0 GWP [CO2 eq kg / kg product] Δ 0.7kg Cradle-to-gate analysis with independent third party critical review Reviewer: Dr.-Ing. Constantin Herrmann, PE International End of Life assumption retain the net benefit 0.5 0.0 US soybean PVC phthalate free PVC conv GWP 1.0 1.7 comparison -41% 0 LCA white paper to be available soon on http://www.dow.com/wire/. *Carbon Trust, 2008, Energy and Carbon Conversions 2008 update
Typical Properties of DOW ECOLIBRIUM Bio-Based Plasticizers Specific Gravity, 20 C (g/cm 3 ) Moisture Content (ppm) Viscosity @ 25 C (cp) Color (APHA) DC Resistivity, 500V, 25 C (Ohm m) Dielectric Constant, 60 Hz, 25 C Dissipation Factor, 60 Hz, 25 C Test Method ASTM D 1298 ASTM E203 ASTM D445 ASTM D 1209 ASTM D 1169 ASTM D924 ASTM D924 LPLAS- 1101 EXP 1 LPLAS-HT EXP 3 0.975 0.974 < 1000 ppm < 1000 ppm 78 340 < 150 < 200 1.0E+08 2.8E+09 5.6 4.8 0.56 0.03 7
DC Resistivity of DOW ECOLIBRIUM Bio-Based Plasticizers 1.0E+10 Resistivity (Ohm m) 1.0E+09 1.0E+08 TOTM 1.0E+07 8
TGA of DOW ECOLIBRIUM Bio-Based Plasticizers 100 95 90 Weight (%) 85 80 75 70 TOTM 65 60 30 130 230 330 430 Temperature ( C) 9
Solution Temperatures of DOW ECOLIBRIUM Bio- Based Plasticizers in PVC 180 DOP 170 160 TOTM 150 140 Ultramoll III (Lanxess, adipic polyester) 130 120 10
Example Flexible PVC Formulations Building Wire Insulation (THHN/THWN) PVC Plasticizer Calcined Clay (Filler) Calcium/Zinc Metal Soap (Heat Stabilizer) Antioxidant Flame Retardant (FR) Representative Plasticizers: Diisodecyl Phthalate () Trioctyl Trimellitate (TOTM) Insulation and jacket formulations have also been made with calcium carbonate (& mixtures with calcined clay) and without FR. 11
Experimental Procedures - Flexible PVC Dry blends were made using: Low intensity mixer (with sigma blades) at 90 C & 40 rpm; or High intensity mixer @ 80-100 C & 1800 rpm Melt blending was conducted using: Low intensity mixer (with cam rotors) at 180 C & 40 rpm; or A conical twin screw extruder (25:1 L/D) at 45 rpm and ~ 185 C. Flexible PVC compound was: Compression molded into plaques at 180 C; or Fabricated into wire by extruding onto a 0.064 inch (14 AWG) solid copper conductor at ~ 185 C. The outside diameter of the insulated conductor was 0.094 inch (i.e., 0.015 inch thick wall). 12
Dry Blend Times of Flexible PVC Formulations Made with DOW ECOLIBRIUM Bio-Based Plasticizers 6 Dry Blend Time (Minutes) 5 4 3 2 1 TOTM 0 13
Hardness of Flexible PVC Compounds Made with DOW ECOLIBRIUM Bio-Based Plasticizers 39.0 37.0 Shore D 35.0 33.0 31.0 29.0 27.0 25.0 TOTM 14
Tensile Strength of Flexible PVC Compounds Made with DOW ECOLIBRIUM Bio-Based Plasticizers 4000 3500 3000 Pass Peak Stress (psi) 2500 2000 1500 TOTM 1000 500 0 15
Tensile Strength Retention of Flexible PVC Made with DOW ECOLIBRIUM Bio-Based Plasticizers @ 113 C 140 Peak Stress Retention after 7 Days @ 113 C (%) 120 100 80 60 40 20 Pass TOTM 0 16
Tensile Strength Retention of Flexible PVC Made with DOW ECOLIBRIUM Bio-Based Plasticizers @ 136 C 270 Peak Stress Retention after 7 Days @ 136 C (%) 240 210 180 150 120 90 60 30 Pass TOTM 0 17
Tensile Elongation of Flexible PVC Compounds Made with DOW ECOLIBRIUM Bio-Based Plasticizers 350 300 Pass Strain @ Break (%) 250 200 150 100 TOTM 50 0 18
Tensile Elongation Retention of Flexible PVC Made with DOW ECOLIBRIUM Bio-Based Plasticizers @ 113 C 120 Strain @ Break Retention after 7 Days @ 113 C (%) 100 80 60 40 20 0 Pass TOTM 19
Tensile Elongation Retention of Flexible PVC Made with DOW ECOLIBRIUM Bio-Based Plasticizers @ 136 C 100 Strain @ Break Retention after 7 Days @ 136 C (%) 90 80 70 60 50 40 30 20 10 0 Pass TOTM 20
Weight Loss of Flexible PVC Made with DOW ECOLIBRIUM Bio-Based Plasticizers @ 136 C 100 98 Weight Retained (%) at 136 C 96 94 92 90 88 86 84 82 TOTM 80 0 1 2 3 4 5 6 7 Time (Days) 21
Limiting Oxygen Index of Flexible PVC Compounds Made with DOW ECOLIBRIUM Bio-Based Plasticizers 32 30 Limiting Oxygen Index (LOI), % 28 26 24 22 + Flame Retardant 20 22
Wet Insulation Resistance of Flexible PVC Made with DOW ECOLIBRIUM Bio-Based Plasticizers 1 Insulation Resistance (Megaohms/1000 ft) Minimum for THWN (75 C) 0.1 0 10 20 30 Weeks in 75 C Water 23
Commercial Status: DOW ECOLIBRIUM Bio-Based Plasticizers Developmental quantities of the following grades are available Application test temperatures < 113 C Application test temperatures < 136 C 24
Closing Remarks: DOW ECOLIBRIUM Bio-Based Plasticizers DOW ECOLIBRIUM Bio-Based Plasticizers are a new family of phthalate-free plasticizers made from renewable feedstocks that have been developed to meet the growing demand for more sustainable plasticizers. These plasticizers are suitable for modification of polymers such as PVC, CPE, TPU, nitrile rubber, etc. Performance attributes have been validated in flexible PVC for wire and cable applications. 25