Rigid Panel Foams with Unique Properties from CO 2 -based Polyols

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1 Rigid Panel Foams with Unique Properties from CO 2 -based Polyols Anna Cherian, Chris Fordice, Kimberly Jaskula, Mike Nagridge, Simon Waddington, Wayne Willkomm UTECH North America June 2014 Charlotte, NC

2 Novomer stechnology: Direct conversion of waste CO 2 to useful products 2

3 Polycarbonate Polyols from CO 2 O + CO 2 Unique characteristics of the new polyol technology Distinctive performance from the high density carbonate backbone Economically attractivedue to the use of inexpensive & readily available CO 2 Strong sustainability story due to direct sequestering of CO 2 in backbone 3

backbone Economically attractivedue to the use of inexpensive & readily

4 A wide range of starting molecules can be used Examples of starters used to create PPC polyols Fn= 2 H O OH n HO OH Fn> 2 HO O O O HO O O O O OH HO OH 4

5 Polycarbonate Polyol Polycarbonate polyols are clear, amorphous, viscous liquids. Hydroxyl termination reacts in equivalent manner to any commercial polyol. Polyurethanes containing polycarbonate polyols have excellent chemical, UV, oxidative and hydrolytic resistance. 5

Hydroxyl termination reacts in equivalent manner to any commercial

6 These precise polycarbonate polyolsenhance the strength of polyurethane products Characteristics of Novomer polyols 100% polycarbonate backbone: perfectly alternating CO 2 / epoxide units yielding 100% carbonate and zero ether linkages Perfect -OH functionality: diolsare 2.0 functional & triolsare 3.0 functional at any molecular weight; no unsaturation Tensile strength of TPUs based on Novomer and other polyols Psi (thousands) Precise control of molecular weight: any Mw from ~500 g/molto 10,000+ g/mol, all with a polydispersityindex (PDI) of ~ PPC Polyol Exist. PCDs Ester Polyol 6

7 The convergence of Performance, Cost, and Sustainability : This is a 1,000 Mw diol from propylene oxide and CO 2, OH# = 112, 39% mass from CO : This is a 2,000 Mw diol from propylene oxide and CO 2, OH# = 56, 41% mass from CO 2 Commercial quantities available in mid-june

CO 2 212-20: This is a 2,000 Mw diol from propylene oxide and CO 2, OH#

8 Rigid Foam Formulations B-side EW Parts PPC 1000 Mw diol Stepanpol PS Water Fyrol PCF E-AF E Pentane Polycat Polycat Dabco SI Lupranate M Index

4 0.4 0.4 0.4 0.4 Fyrol PCF - 10 0 10 0 0 0 E-AF084-0 0 0 0 10 0 E06-16 187 0 0 0 0 0 10 Pentane - 14 14

9 Rigid Foam Blocks PPC/PS 2352 PS 2352 (controls) PPC/PS 2352 PCF no FR PCF no FR E-AF084 E06-16 Density: Rigid foams made with PPC have shown significantly lower density than control foams 9

10 2.1 Blowing Efficiency 2 Density (pcf) Pentanes (parts) Control foams yield 2.5 pcfat 14 parts pentane This can be valuable for high performance blowing agents such as HFC 245fa 10

11 Dimensional Stability 1 Wk: Dimensional Stability (%) Δ Wt Δ L (Sides 1 & 3) Δ W (Sides 2 & 4) Δ L&W (All 4 Sides) Δ H Dimensional Stability for 1 week at 200 F Dimensional Stability is acceptable for controls and PPC samples 2 (with FyrolPCF) and 5 (experimental FR), despite very low density of 1.64 and 1.48, respectively 11

12 Cone Calorimeter - Controls HRR (kw/m 2 ) HRR-3A HRR-3B HRR-3C Time (seconds) 3 replicates of control formulation, 100% Stepanpol, with 10% Fyrol PCF 12

100 120 140 160 180 Time (seconds) 3 replicates of

13 Cone Calorimeter - PPC HRR (kw/m 2 ) HRR-1A HRR-1B HRR-1C Time (seconds) 3 replicates of formulation with 50% PPC:50% Stepanpol and 10% Fyrol PCF PPC enables faster extinguishing and less total heat release 13

14 Cone Calorimeter Summary Total Heat (MJ/m2) Peak HRR (kw/m2) Total Smoke (m2/m2) Mass Loss (wt%) PPC Control s PPC w/experimental FR 14

(m2/m2) Mass Loss (wt%) 300 200 100 0 1 2 3

15 Total Heat Release Total Heat (MJ/m2) Mass Loss (wt%) PPC Controls PPC w/experimental FR 15

16 Formulation Summary B-side OH # Parts PPC 1000 Mw diol PS Fyrol PCF E-AF E Aromatic Content 40% 41% 45% 46% 40% 41% Density (pcf) PPC containing Rigid foams have similar flammability results, with lower density and lower aromatic content 16

Aromatic Content 40% 41% 45% 46% 40% 41% Density (pcf) 1.50 1.64 2.58 2.56 1.48 1.

17 Novomer Polyols have lower Heat of Combustion 35 Heat of Combustion (MJ/kg) Up to 50% lower Fuel Value 10 Rigid polyether Flexible polyether Mannich polyol Aromatic polyester Lower heat of combustion -one of the carbons is already fully oxidized. This is a fundamental characteristic of Novomer polycarbonate polyols. 17 Polypropylene carbonate Polyethylene carbonate n

Lower heat of combustion -one of the carbons is already fully oxidized.

18 Cannon Machine Trials Cannon has 3 stream, high pressure, multipurpose machine This machine was used to prepare flexible and rigid foams, and aliphatic polyurethane clear coats One stream is heated, allowing the use of higher viscosity components A blend of 70% PPC and 30% StepanpolPS 2352 was used to deliver the PPC polyol 18

polyurethane clear coats One stream is heated, allowing the use of higher

19 Reduced Viscosity Blends Viscosity (cp) DBE-3 Diexter G Propylene Carbonate PPG 425 Stepanpol PS 2352 TCPP Voranol 270 A number of different components can be used to blend with PPC and reduce the viscosity Weight % PPC 19

Stepanpol PS 2352 TCPP Voranol 270 A number of different components can be used to

20 Cannon Trial Foam w/25% PPC Average cell size is 143 microns (per ASTM D3576) High closed cell content was not achieved, so k factor was greater than expected. 20

21 Cannon Trial Foam w/50% PPC Average cell size is 169 microns (per ASTM D3576) 50% PPC foam was run hotter, and had some scorching 21

22 Commercial Benchmark Commercial benchmark has average cell size of 241 microns (per ASTM D3576) and measured by the same laboratory 22

23 Conclusions Rigid polyisocyanurate foams can readily be made with PPC polyol. Rigid foams using PPC have demonstrated better blowing efficiency and smaller cell sizes. Blends can be used to produce a workable viscosity. PPC polyols have a lower heat of combustion which can translate to reduced flame retardant requirements. 23

24 Future Work Optimize the polyisocyanurate formulation to take advantage of the features that the CONVERGE polyols offer Fully characterize the foam systems with respect to: k factor Dimensional stability Polymer rigidity Closed cell content Reduced moisture uptake Reduced heat of combustion 24

FLAME RETARDANT USAGE AND OTHER FACTORS AFFECTING BURN CHARACTERISTICS OF POLYURETHANE RIGID FOAMS

Blowing Agents & Foaming Processes 2014 13-14 May 2014 Vienna, Austria FLAME RETARDANT USAGE AND OTHER FACTORS AFFECTING BURN CHARACTERISTICS OF POLYURETHANE RIGID FOAMS David Modray Foam Supplies, Inc.