RENEWABLE RESOURCE BIO-BASED URETHANES. Northstar Polymers, LLC U.S.S.C.

Size: px

Start display at page:

Download "RENEWABLE RESOURCE BIO-BASED URETHANES. Northstar Polymers, LLC U.S.S.C."

Dale Ellis
6 years ago
Views:

1 RENEWABLE RESOURCE BIO-BASED URETHANES n David Tweet Eric Geiger Northstar Polymers, LLC U.S.S.C.

2 Introduction In the late 1950 s vegetable oil modified urethane oils and alkyds were developed and commercialized. These urethane oils are still used today as the binders in high quality paints and varnishes. These were the systems developed at Cargill, Inc. The basic formulas are based on transesterifying a vegetable oil like soybean, sunflower, safflower or linseed using polyols like Glycerin, Trimethyol Propane or Pentaerythritol. The transesterfied oil was then polymerized with Toluene diisocyanate. The finished polymer cures by air oxidation. The chemical makeup is shown on slide 1.

3 What did the Isocyanate Contribute to the Cured Film? 1. Greater flexibility. 2. Greater abrasion resistance. 3. Greater durability.

4 Objectives I. Believe that viable Bio-Based Urethane Systems are available for several markets. II. Believe that Bio-Based Systems are not difficult to work with. III. Believe that the cost advantage of Bio-Based Systems is likely to remain.

5 Urethane Modified Vegetable Oil Oil (Triglyceride) + Polyol (Like Trimethyol Propane heat + cat. Hydroxyl terminated oil + Toluene Diisocyante heat + cat Urethane oil polymer in aliphatic solvent etc. Vegetable oil: unsaturated Trigylcerides + Low MW Polyol 1. Soybean 1. Glycerin 2. Linseed 2. Trimethyol Propane 3. Sunflower 3. Pentaery Thritol 4. Safflower

6 Glycerin OH + TMP OH Fatty acid OH Transesterify cat OH + TMP OH OH Add TDI, MDI, H12MDI, IPDI cat TDI OH TMP TMP OH OH TDI OH Solvent Urethane modified oil

7 Research aimed at making useful polyols from vegetable oil This research led to the development of acceptable and reproducible polyols*: 1. A 2000 MW diol 2. A 1000 MW triol

8 Rigid Foam System Comparison Rigid Foam Systems ½ lb. Foam Bio- based 100% Petroleum-based *SoyTherm 50 RM Cost :USSC Lower +25% Insulating Equal Equal Fire Retardant Equal Equal Processing Better, wider? window for both application and surface temperature. Not as good Physicals Equal Equal 2 lb. Foam RM Cost Lower +10% Insulating Equal Equal Fire Retardant Equal Equal Moldability Equal Equal Physicals Equal Equal 6 lb. Foam RMC Lower +10% Pourability Equal Equal Physicals Equal Equal Adhesion/wetting Superior Deficient

9 Bio Based Rigid Foam System 0.5 pcf Rigid Spray Foam System Mannich Polyol 6 Soy-based 25 Polyol Chain Extenders 4.6 Amine Catalyst Amine Catalyst Silicon 2.5 Surfactant Fire Retardant 1 35 Fire Retardant Water 15 2 pcf Rigid Pour-in-Place Foam System Polyether 55 Polyol Soy-based 35 Polyol Amine Catalyst Amine Catalyst Metal Catalyst 1 Silicone 0.5 Surfactant Chain Extender 4.5 Water 4 6 pcf Rigid Pour-in-Place Foam System Polyether 55 Polyol Soy-based 30 Polyol Amine Catalyst 1 1 Amine Catalyst Metal Catalyst 0.5 Silicone 1 Surfactant Chain Extender 8 Water 1.25

10 Petro Based Rigid Foam Systems 3 lbs. Rigid Pour-in-Place Foam System MPN-R03A 3lbs. Rigid Foam % Polymeric MDI % Polyol % Water % Surfactant % Amine Catalyst 7 lbs. Rigid Pour in-place Foam System MPN-R07A 7lbs. Rigid Foam % Polymeric MDI % Polyol % Water % Surfactant % Amine Catalyst Physical Property ASTM# Typical Value Durometer Hardness: D A Free Rise Density: 2.5 lbs./ft³. Packing Density: 3 lbs./ft³ Packing Factor: 1.12 Cell size (99% are less than): 0.5 mm (theoretically 95% closed cells) Physical Property ASTM# Typical Value Durometer Hardness: D A Free Rise Density: 6.5 lbs./ft³. Packing Density: 7 lbs./ft³ Packing Factor: Cell size (99% are less than): 0.5 mm (theoretically 95% closed cells)

11 Flexible Foam *Flexible Foam Systems 3 lb. Foam **Bio based (MDI) 100% Petroleum-based RMC Lower 10% Higher Pourability Equal Equal Physicals Equal Equal 4 lb. Foam (Instrument Panel) RMC Lower 10% Higher Pourability Better mold fill Equal Physicals Equal Equal 6 lb. Foam RMC Lower 10% Higher Pourability Equal Equal Physicals Superior

12 Flexible Foam, Cont. 6 pcf Flexible Pour-in-Place Foam System Polyether Polyol 1 50 Polyether Polyol 2 30 Soy-based Polyol 20 Amine Catalyst Amine Catalyst Amine Catalyst Silicone Surfactant 2 Chine Extender 2 Water lbs. Flexible Pour-in-Place Foam System MPS-F06A 6 LBS Flexible Foam % Pure MDI % Modified MDI % Polyol % Polyol % Foam Stabilizer % Water % Amine Catalyst % Catalyst Typical Bio-Based Flexible Foam Formula Typical Petroleum-Based Flexible Foam Formula

13 Microcellular Foam Microcellular Foams RMC Pourability Physicals RMC Pourability Physicals RMC Pourability Physicals Bio-based 20 lb. Foam 30 lb. Foam 100% Petroleum-based Low to High Very Easy Excellent Low to High Very Easy Excellent Low to High Very Easy Excellent

14 Cast Elastomers, Room Temperature Cure Cast Urethane Elastomers Room Temperature Cure Shore A-40 Bio based 100% Petroleum (PPGbased) RMC Lower 20% higher Molding Characteristics Equal Equal Physicals Equal Equal Shore A-60 RMC Lower 20% higher Moldability Equal Equal Physicals Equal Equal Shore A-80 RMC Lower 20% higher Moldability Equal Equal Physicals Equal Equal

15 Cast Elastomer Comparison, Bio vs Petroleum Based Typical Bio-Based Cast Elastomers- Room Temp. Cure Shore A-80 Cast Elastomer System Polyether Poloyol 1 40 Polyether Polyol 2 10 Soy-based Polyol 40 Amine Catalyst 0.1 Chain Extender 10 Bio-Base RTC 60A Php MDI 23 Polyol 1 26 Polyol 2 22 Polyol 3 22 Polyol Molecular Siv. Paste 1.4 Chain Extender 1.1 Catalyst Catalyst Defoamer 0.05 Typical Petroleum-Based Cast Elastomers -Room Temp. Cure MPP-A80E 80A RTC % Modified MDI % Polyol % Polyol % Chain Extender % Amine Catalyst % Silicone Defoamer MPP-A90A 90A RTC % Modified MDI % Polyol % Polyol % Chain Extender % Amine Catalyst % Tin Catalyst % Silicone Defoamer

16 Typical Petroleum-Based Cast Elastomers Room Temperature Cure MPP-A65A 65A RTC % Modified MDI % Polyol % Polyol % Chain Extender % Amine Catalyst % Silicone Defoamer Property ASTM# Typical Value Durometer Hardness: D2240 A65 Modulus (psi): 100% Elongation D Tensile Strength (psi): D Ultimate Elongation (%) D Tear Resistance (pli) Die C: D Split: D Taber Abrasion (mg loss) D Bashore Rebound (%) D

17 Typical Petroleum-Based Cast Elastomers Room Temperature Cure MPA-A50A 50A RTC % Modified MDI % Polyol % Polyol % Chain Extender % Amine Catalyst % Silicone Defoamer Property ASTM# Typical Value Durometer Hardness: D2240 Shore A50 Modulus (psi): 100% Elongation: D Tensile Strength (psi): D Ultimate Elongation (%) D Tear Resistance (pli) Die C: D Split: D Taber Abrasion (mg loss): D

18 Sprayable Comparison Bio vs Petro Based High Pressure Sprayable Hybrid Polyurethane/Polyurea Bio-Based Petroleum-Based *Bio-Tuff RMC Lower 15% Higher Cure Pattern Equal Equal Physicals Similar Similar Application 30 mils per pass More mils per pass 20 mils per pass More passes needed *The improved wet-out of the soy-based system generates better adhesion

19 Bio-Based Sprayable High Pressure Spray Elastomer System Polyether Polyol 1 20 Polyether Polyol 2 25 Soy-based Polyol 35 Catalyst 1 Chain Extender 15

20 Pultrusion Techniques Pultruded Technique Bio-based *Soy Matrix USSC technology 100% Petroleum RMC Lower 20% higher Cure spray/ pattern Better Slower-more waste Physicals Similar Similar *Soy Matrix resins have been shown to offer improved wet-out of rovings used in the pultrusion process. This system has also shown increased line speeds relative to all petroleum formulations. Another advantage has been the decreased down time/turn over time which has resulted in a drastic decrease in waste generated.

21 Concrete Pattern Systems Concrete Pattern System Bio-based 100% Petroleum (PPG) Pattern Superior Inferior RMC Lower 10% higher Moldability Equal Equal Physicals Equal Equal Pattern Definition Better Inferior

22 High Performance Petro Based Liquid Quasi Systems 1,4BD Cured Shore A-80 PTMEG-based Ester-based Tensile PSI >5000 >6000 Elongation % Graves Tear PLI Split Tear PLI Tabor A (mg. Wt. Loss)* 8 15 *1000g. wt., 1000 revolution High performance systems (heat cured) (These systems are intended for extreme abrasion and cutting resistance) Bio-based systems are not yet capable of matching these properties

23 APPLICATIONS FOR BIO- BASED SYSTEMS 1. Ridgid Foams 1.1 Low -density rigid spray foams for wall insulation. 1.2 Higher density, water blown systems for molding and trim applications 2. Sprayable elastomer systems. 2.1 Bed liners. 2.2 Sizing screen frames. 2.3 Liners where corrosion resistance is needed. 2.4 Liners where moderate abrasion resistance is needed. 2.5 Areas where moisture barriers are desired. 2.6 Roof Coatings.

24 APPLICATIONS FOR BIO- BASED SYSTEMS, Cont. 3. Concrete molds/patterns 3.1 Stamping pads Bio-based systems give excellent pattern definition. 3.2 Thin brick forms for precast brick walls. 3.3 Large mold for precast wall systems 4. Energy absorbing backing systems 4.1 Holding ceramic tiles in place. 4.2 Matrix for stone chips, including ceramic

25 APPLICATIONS FOR BIO- BASED SYSTEMS, Cont. 5. Flexible Foams 5.1 Automotive seating. 5.2 Furniture seating. 5.3 Automotive interior applications. 6 Composites 6.1 Pultrusion. 6.2 Filament winding. 6.3 Hand/spray lay-up.

26 APPLICATIONS FOR BIO- BASED SYSTEMS, Cont. 7. Carpet 7.1 Pre-coat adhesive. 7.2 Carpet Pad 8. Adhesives 8.1 One component, moisture cure. 8.2 Two component reactive hot melt.

27 R & D Direction 1. Many agricultural companies involved. a. The initial successes will generate more R & D and more successes 2. Higher MW diols 3. Higher MW triols 4. Higher functionality polyols 5. Higher hydroxyl contents 6. Making specialty polyols by new pathways to oxidation

28 Objectives I. Believe that viable Bio-Based Urethane Systems are available for several markets. II. Believe that Bio-Based Systems are not difficult to work with. III. Believe that the cost advantage of Bio-Based Systems is likely to remain.

29 Questions??

TDI-terminated polyester based prepolymer

PRODUCT DATA VIBRATHANE 8080 TDI-terminated polyester based prepolymer Urethane Prepolymers VIBRATHANE 8080 VIBRATHANE 8080 is a TDI-terminated polyester based prepolymer which yields an 80 Shore A hardness