BROMINATED FLAME RETARDANT AND ITS APPLICATION IN POLYURETHANE FOAMS

Abstract

This invention provides polyurethane foams containing a brominated flame retardant. Also provided are formulations and methods for preparing polyurethane foams containing a brominated flame retardant.

Claims

1. A polyurethane foam formed from ingredients comprising 2,3-dibromoallyl alcohol.

2. The polyurethane foam of claim 1, which is a flexible polyurethane foam.

3. The polyurethane foam of claim 1, which is a rigid polyurethane foam.

4. The polyurethane foam of claim 1, further comprising a mixed ester of tetrabromophthalic anhydride with diethylene glycol and propylene glycol and/or tris(1-chloro-2-propyl) phosphate.

5. A polyurethane foam formed from ingredients comprising: 2,3-dibromoallyl alcohol; at least one polyol; at least one blowing agent; at least one catalyst; and at least one surfactant.

6. The polyurethane foam of claim 5, further comprising at least one polyisocyanate.

7. The polyurethane foam of claim 5, wherein the polyol is an aromatic polyester polyol and either a polyether polyol or at least one sucrose/glycerine polyol; wherein the blowing agent 1s water, trans-1-chloro-3,3,3-trifluoropropene, 1,2-bis(trifluoromethyl) ethene or a mixture of any two or more of these; wherein the catalyst is potassium octoate and/or dibutylbis(dodecylthio) stannane; wherein the surfactant is a silicone glycol; and/or wherein the polyisocyanate is diphenylmethane diisocyanate.

8. The polyurethane foam of claim 5, wherein the amount of 2,3-dibromoallyl alcohol is about 1.5 wt % to about 10 wt %; wherein the amount of polyol is about 25 wt % to about 35 wt %; wherein the amount of catalyst is about 0.5 wt % to about 4 wt %; and/or wherein the amount of surfactant is about 0.25 wt % to about 2.5 wt %, based on the total weight of the polyurethane foam.

9. The polyurethane foam of claim 7, wherein the aromatic polyester polyol has a functionality of about 1.75 to about 2.75 and a hydroxyl number in the range of about 200 to about 350.

10. The polyurethane foam of claim 5, wherein the polyurethane foam is a flexible polyurethane foam.

11. The polyurethane foam of claim 5, wherein the polyurethane foam is a rigid polyurethane foam.

12. The polyurethane foam of claim 5, further comprising a mixed ester of tetrabromophthalic anhydride with diethylene glycol and propylene glycol and/or tris(1-chloro-2-propyl)phosphate.

Description

EXAMPLESGENERAL

[0055] In the Examples, some of the substances used are referred to by their trade names. More specifically: [0056] DBAA: 2,3-dibromoallyl alcohol [0057] Saytex RB-79: a mixed ester of tetrabromophthalic anhydride with diethylene glycol and propylene glycol (Albemarle Corporation). [0058] TCPP: tris(1-chloro-2-propyl)phosphate. [0059] DE: diethylene glycol monoethyl ether. [0060] Voranol280: a polyether polyol with a functionality of about 7.0, a hydroxyl number of about 280, and an average molecular weight of about 1400; Voranol 370: a sucrose/glycerine polyether polyol with a functionality of 7.0; Voranol 490: a sucrose/glycerine polyether polyol with a functionality of 4.3 (all Voranol materials are products of Dow Chemical Company). [0061] Vorasurf 504 is a non-silicone organic surfactant (Dow Chemical Company). [0062] Terate HT 5503: an aromatic polyester polyol with a hydroxyl number in the range of 225 to 245, a functionality of 2, and an equivalent weight of 239; Terate HT 5349: an aromatic polyester polyol with a functionality of about 2.45, and a hydroxyl number of 295 to 315 (all Terate materials are products of Invista Corporation). [0063] Stepanpol PS-3152 is a diethylene glycol-phthalic anhydride polyester polyol with a functionality of 2 and a hydroxyl number of 315 (Stepan Chemical Company). [0064] Carpol GP-5171: glycerin-initiated polyether polyol with a functionality of about 3, a hydroxyl number of 35, and an average molecular weight of about 5000; Carpol GP-5015: glycerin-initiated polyether polyol with a functionality of 3, a hydroxyl number of 34, and an average molecular weight of about 5000; Carpol GP-1500: glycerin-initiated polyether polyol with a functionality of 3, a hydroxyl number of 112, and an average molecular weight of about 1500; Carpol GSP-280: sucrose polyether polyol based on glycerine, propylene oxide and ethylene oxide with a functionality of 7, a hydroxyl value of 280, and an average molecular weight of about 1400; Carpol GSP-355: glycerine/sucrose initiated polyether polyol with a functionality of 4.5, a hydroxyl value of 355; Carpol MX-470: mannich-based polyether polyol with a functionality of about 4, a hydroxyl number of 470, and an average molecular weight of 480; Carpol GP-700: glycerine and propylene oxide polyether polyol with a functionality of 3, a hydroxyl number of 240, and an average molecular weight of about 700 (all Carpol materials are products of Carpenter Company). [0065] Terol 250 is an aromatic polyester polyol with a functionality of 2 and a hydroxyl number in the range of 235 to 255 (Huntsman Corporation). [0066] Dabco DC193: silicone glycol surfactant; Dabco T: amine with hydroxyl groups; Dabco T-120: dibutylbis (dodecylthio) stannane; Dabco PM-300:2-butoxyethanol; Dabco DC 5598: silicone glycol copolymer surfactant; Dabco K-15: potassium octoate; Dabco TMR: 2-hydroxypropyltrimethylammonium formate (all Dabco materials are products of Air Products and Chemicals, Inc.). [0067] Polycat 204: amine catalyst (Air Products and Chemicals, Inc). [0068] Tomamine Q17-2 PG is an ether amine quaternary ammonia surfactant (75%) in isopropyl alcohol (Air Products and Chemicals, Inc.). [0069] Tegostab B 8871: polysiloxane copolymer; Tegostab B 8407: polyether polydimethylsiloxane copolymer (both are products of Evonik Industries AG, Essen, Germany). [0070] Jeffcat ZR-70 is 2-(2-dimethylaminoethoxy) ethanol, an ethanol amine catalyst; Jeffcat Z-110 is N,N,N-trimethylaminoethyl-ethanolamine; Jeffcat ZF-20 is bis-(2-dimethylaminoethyl) ether (all Jeffcat materials are products of Huntsman Corp., The Woodlands, TX). [0071] Pel-cat 9506 is a mixture of potassium octoate and potassium acetate; Pel-cat 9858-A is sodium hydroxy-nonylphenyl-N-methylglycinate (both are products of El Corporation). [0072] Solstice LBA: trans-1-chloro-3,3,3-trifluoropropene (Honeywell Inc.). [0073] Genetron 245fa: 1,1,1,3,3-pentafluoropropane (Honeywell Inc.). [0074] Opteon 1100:1,2-bis(trifluoromethyl)ethene; also called Formacel 1100 (The Chemours Company). [0075] Papi 27: polymeric diphenylmethane diisocyanate (MDI) with 31.4 wt % NCO, viscosity 150 to 225 cps at 25 C., and an isocyanate equivalent weight of 134 (Dow Chemical Company).

[0076] Cone calorimetry measurements were performed on a Fire Testing Technology Dual Cone calorimeter according to ASTM E-1354. For all of the Examples, an incident heat flux of 40 kW/m.sup.2 was used in the cone calorimetry tests for the Predicted Smoke Index calculations and an incident heat flux of 100 kW/m.sup.2 was used in the cone calorimetry tests for the Predicted Flame Spread Index calculations. The Peak Heat Release Rate (PHRR), the maximum value of the heat released during combustion of the sample in the cone calorimeter, was measured. Values for the Peak Heat Release Rate are preferably less than 250. The ASTM E-84 burn profiles for predicted Smoke Index calculations and for predicted Flame Spread Index calculations were calculated from the cone calorimetry results. Using mathematical equations that were previously derived from a cone calorimeter and ASTM E-84 correlation study, the cone calorimeter results were converted into predicted numbers in the ASTM E-84. The target value for the Flame Spread Index was less than 25, preferably less than 20, and the target value for the Smoke Density Index was less than 450, preferably less than 200. The term Smoke Index is short for smoke density developed, which is also referred to as Smoke Developed Index and Smoke Density Index.

[0077] For some samples, the dimensional stability was determined; preferred volume changes in dimensional stability are 15%. Some samples were subjected to a thermal conductivity test, and R values were calculated from the thermal conductivities. The R value (or R-value) is a measure of insulation efficiency or thermal resistance (the ability of a material to slow down heat transfer within itself), and is often used in the building and construction industry. The higher the R-value, the more a material prevents heat transfer. R-values for polyurethane foams are preferably about 6.5 or more.

Examples 1-22

[0078] The reported results in Examples 1-16 are an average of three lots with 5 samples per lot (a total of 15 samples for each test). The volume ratio of the A side to the B side in each run was 1:1, unless otherwise noted. The polyurethane foams of Examples 1-16 were prepared according to Procedure 1 below. The polyurethane foams of Examples 17-19 were prepared according to Procedure 2 below. The polyurethane foams of Examples 20-22 were prepared according to Procedure 1 below; the A side was Papi 27 in all runs of Examples 1-22. [0079] Procedure 1: To form the B side, DBAA, polyols, surfactants, flame retardant, blowing agent and catalyst were weighed into a 0.5 gallon (1.9 L) reclosable container, and blended with a bow-tie agitator at 2000 rpm for 60 seconds or until a homogenous mixture with no visible phase separation was obtained. At a 450-g scale (total of A and B sides), the required amount of the B side mixture was weighed and added to a one-liter paper cup.

[0080] The polymeric MDI was wet-tared by weighing about 10% of its required amount into a 250-mL paper cup, pouring out the polymeric MDI within 3 seconds, re-taring the wet 250-mL cup and adding the full amount of the polymeric MDI. The polymeric MDI was then poured within a 3-second time span into the one-liter cup containing the B-side mixture, and the contents of the one liter paper cup were immediately mixed for 5 seconds at 2000 rpm. By this process, the amount of MDI used is within 1% of the required amount.

[0081] While the foam was rising but before the foam reached the top of the one liter paper cup, the cup was inverted and held over a paper sheet. While the foam continued to rise, the cup was guided upwards without impeding the rising of the foam. Once the foam had sufficient strength to support itself and the cup, guiding of the cup was discontinued. After allowing the foam to sit for at least 24 hours, it was cut to generate specimens for cone calorimeter testing. Each specimen was weighed to determine the foam density. [0082] Procedure 2: To prepare each polyurethane foam, blends of the B-side components other than the catalyst(s) (DBAA, polyols, surfactants, flame retardant, and blowing agent) were made. The polyisocyanate and the B-side formulation were weighed into a 16 oz. (473 mL) paper cup and then mixed at 2000 rpm with a bow tie agitator for 15 seconds, at which point the catalyst(s) was injected into the mixture while the agitation continued. At the 20-second mark, the agitation was discontinued, and the reacting mixture was immediately poured into a 10-in10-in10-in (25.4 cm25.4 cm25.4 cm) wooden box mold that had been pre-lined with a polyethylene bag, and the box was closed. After 15 minutes, the cube-shaped foam encased in the polyethylene bag was removed from the mold. After allowing the foam to sit for at least 24 hours, it was cut to generate the specimens for cone calorimeter testing. Each specimen was weighed to determine the foam density. The catalyst was added after the A side and B side were brought into contact, which is related to handling and timing on the laboratory scale; at larger scales, the catalyst is included in the B side formulations.

[0083] In Examples 1-4, open-cell spray polyurethane foams were prepared. Examples 2 and 3 are comparative. Amounts of the components and process information are listed in Table 1; test results are summarized in Table 2. In Examples 1-4, water was the only blowing agent.

[0084] In Examples 5-10, closed-cell spray polyurethane foams were prepared. Examples 5, 6, 8, and 9 are comparative. In Example 9, the Saytex RB-79 flame retardant was added as a solution in 2-butoxyethanol. Amounts of the components and process information are listed in Table 3; test results are summarized in Table 4.

[0085] In Examples 11-16, closed-cell spray polyurethane foams were prepared. Examples 12-16 are comparative. Amounts of the components and process information are listed in Table 5; test results are summarized in Table 6.

[0086] In Examples 17-19, panel polyurethane foams were prepared. Examples 17 and 18 are comparative. Amounts of the components and process information are listed in Table 7; test results are summarized in Table 8.

[0087] In Examples 20-22, closed-cell spray polyurethane foams were prepared. Run 1 of Example 21 and runs 1 and 2 of Example 22 are comparative. Amounts of the components and process information for Examples 20-22 are listed in Tables 9A-B, 11A-B, and 13A-C; test results for Examples 20-22 are summarized in Tables 10A-B, 12A-B, and 14A-C.

TABLE-US-00001 TABLE 1 Example 1 2 3 4 B side DBAA 5.45 5.50 Saytex RB-79 8.67 TCPP 30.00 2-butoxyethanol 4.95 4.78 4.00 Sucrose in water (67%) 69.35 67.00 50.50 69.46 Carpol GP-5171 4.95 4.78 5.00 5.00 Jeffcat ZR-70 5.75 5.55 5.80 6.40 Tegostab B 8407 1.85 1.77 1.85 1.85 Tegostab B 8871 1.85 1.77 1.85 1.85 Tomamine Q17-2 PG 0.93 0.90 0.94 Water 4.95 4.78 5.00 5.00 A-Side Papi 27 100.00 100.00 100.00 100.00 Process A:B Weight Ratio 104.2:100 103.7:100 103.5:100 104.1:100 Isocyanate Index 27.3 28.0 35.1 27.2

TABLE-US-00002 TABLE 2 Example Foam properties 1 2 3 4 Density, lb/ft.sup.3 0.81 0.70 0.60 0.62 Density, kg/m.sup.3 13.0 11.2 9.6 9.9 Dimensional Stability* (% vol. 0.5 0.5 5.1 0.5 change) Predicted Flame Spread Index 24 24 23 24 Predicted Smoke Density Index 18 11 45 17 Predicted Fire Rating Class 1 Class 1 Class 1 Class 1 *Dimensional stability was measured at 70 C. for 14 days at 95% RH.

[0088] Tables 1 and 2 show that much lower amounts of DBAA can be used relative to TCPP and RB-79 in open cell foams to achieve a Class 1 flame retardant rating for the foam. The polyurethane foams containing DBAA had a much better dimensional stability than the foams containing TCPP or Saytex RB-79 flame retardant.

TABLE-US-00003 TABLE 3 Example 5 6 7 8 9 10 B-side DBAA 8.11 8.11 Saytex RB-79 6.76 13.33 6.76 TCPP 8.26 8.26 2-butoxyethanol Terate HT 5503 40.00 39.26 41.94 38.00 25.75 41.94 Voranol 490 28.47 30.01 32.06 30.52 12.00 32.08 Carpol GSP-355 22.00 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 Dabco T 3.00 3.00 3.00 3.00 3.00 3.00 Dabco PM-300 2.00 2.00 2.00 2.00 2.00 2.00 Water 2.07 1.90 1.80 2.02 1.85 1.76 Genetron 245fa 7.44 8.5 9.10 Solstice LBA 7.44 8.45 9.10 A-side Papi 27 100.00 100.00 100.00 100.00 100.00 100.00 Process A:B Weight Ratio 1.044:1 1.027:1 1.035:1 Isocyanate Index 110.1 105.9 106.2 109.9 110.1 106.6

TABLE-US-00004 TABLE 4 Example 5 6 7 8 9 10 Foam properties Density 1.57 1.64 1.80 1.68 1.75 1.99 (lb/ft.sup.3) Density 25.1 26.3 28.8 26.6 28.0 31.9 (kg/m.sup.3) Compressive 94.5 86.2 101.4 94.5 85.5 124.1 Strength (kPa) R-value (/inch) 6.34 6.35 6.74 6.8 6.7 7.1 R-value 1.117 1.118 1.187 1.98 1.80 1.250 (m.sup.2K/W) Predicted 21.4 23 24 27 27 31 Flame Spread Index Predicted 101 185 49 304 105 56 Smoke Density Index Predicted Class Class Class Fire Rating 1 1 1

[0089] Tables 3 and 4 show that much lower amounts of DBAA can be used relative to RB-79 alone or combinations of TCPP and RB-79 in closed cell foams to achieve a Class 1 flame retardant rating for the foam. The polyurethane foams containing DBAA had improved R-values as compared to the foams containing TCPP and/or Saytex RB-79 flame retardant.

TABLE-US-00005 TABLE 5 Example 11 12 13 14 15 16 B-side DBAA 8.11 2.3-dibromo-2-butene- 9.23 4.44 9.23 1.4-diol Saytex RB-79 12.00 6.75 TCPP 8.57 8.25 Terol 250 46.60 45.93 32.21 42.21 43.58 43.58 Carpol GSP-280 9.79 Carpol MX-470 14.38 Carpol GP-700 15.27 19.05 5.00 Voranol 370 17.42 36.83 Voranol 490 16.07 24.77 28.07 Diethylene glycol 1.7 Dabco PM-300 2.00 2.00 2.30 2.00 3.00 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 Diglycolamine 2.96 6.15 Dabco T 2.00 2.00 3.00 2.00 2.00 2.00 Water 1.66 1.67 1.69 1.67 1.65 1.65 Solstice LBA 5.83 5.83 6.00 5.90 6.00 6.00 A-side Papi 27 100.00 100.00 100.00 100.00 100.00 100.00 Process A:B Weight Ratio 102:100 103:100 104.5:100 104.1:100 102.6:100 102.5:100 Isocyanate Index 109.9 109.9 111.6 107 110 110

TABLE-US-00006 TABLE 6 Example 11 12 13 14 15 16 Foam Properties Density 2.06 1.98 2.01 2.33 1.82 1.82 (lb/ft.sup.3) Density 33.0 31.7 32.2 37.3 29.2 29.2 (kg/m.sup.3) Compressive 117.2 109.6 84.8 66.9 91.0 Strength (kPa) R-value 6.45 6.50 6.62 6.84 (/inch) R-value 1.136 1.145 1.662 1.205 (m.sup.2K/W) Predicted 21.9 22.4 17.5 19.2 22.2 20.4 Flame Spread Index Predicted 33 31 123 47 15 55 Smoke Density Index Predicted Class Class Class Class Class Class Fire 1 1 1 1 1 1 Rating

TABLE-US-00007 TABLE 7 Example 17 18 19 B-side DBAA 15.02 Saytex RB-79 8.56 TCPP 14.96 DE 0.95 Stepanpol PS-3152 62.67 36.72 Carpol GSP-280 66.21 Voranol 370 34.42 Dabco DC 5598 1.25 1.27 1.23 Dabco K-15 1.14 1.86 1.81 Pel-cat 9506 1.96 Pel-cat 9858-A 0.89 Jeffcat Z-110 0.21 Jeffcat ZF-20 0.37 Dabco TMR-2 1.24 1.21 Dabco T 0.65 0.62 Water 0.17 0.94 0.91 N-Pentane/isopentane (50/50) 16.38 13.40 13.00 A-side Papi 27 100.00 100.00 100.00 Process A:B Volume Ratio 131.1:100 145.8:100 142.4:100 A:B Weight Ratio 153.4:100 169.1:100 164:100 Isocyanate Index 297.8 208.9 232.7

TABLE-US-00008 TABLE 8 Example Foam Properties 17 18 19 Density (lb/ft.sup.3) 1.90 2.0 1.95 Density (kg/m.sup.3) 30.4 32.0 31.2 Compressive Strength (kPa) 187 314 214 R-value (/inch) 6.2 6.8 5.25 R-value (m.sup.2K/W) 1.092 1.198 0.925 Predicted Flame Spread Index 21 22 22.5 Predicted Smoke Density Index 25 48 439 Predicted Fire Rating Class 1 Class 1 Class 1

[0090] Tables 7 and 8 show that using DBAA in panel foams achieves a Class 1 flame retardant rating for the foam.

TABLE-US-00009 TABLE 9A Example 20 - Run 1 2 3 4 5 6 7 8 9 10 B side Viscosity 255 410 250 170 200 245 1325 1440 1050 180 (cPs; at 25 C.) DBAA 0.69 0.69 5.45 7.32 7.32 7.32 7.63 7.63 7.95 9.41 Terate HT 5349 51.61 51.61 51.61 47.36 47.36 47.36 51.61 51.61 48.04 42.88 Voranol 370 0.14 0.14 1.09 1.46 1.46 1.46 0.80 0.80 1.58 1.88 Carpol GSP-280 26.21 26.21 21.45 23.83 23.83 23.83 25.53 25.53 26.21 26.21 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Dabco K-15 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Dabco T-120 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Polycat 204 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Water 0.08 0.08 0.08 0.08 0.08 0.08 0.86 0.86 0.60 0.08 Genetron 245fa 15.00 15.00 15.00 15.00 15.00 15.00 8.74 8.74 11.31 15.00 Process A:B vol. ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Isocyanate Index 1.335 1.335 1.313 1.314 1.315 1.315 1.086 1.086 1.171 1.314

TABLE-US-00010 TABLE 9B Example 20 - Run 11 12 13 14 15 16 17 18 19 20 B side Viscosity 865 925 190 1290 930 65 920 965 1450 1540 (cPs; at 25 C.) DBAA 7.79 8.87 9.18 9.39 11.09 11.82 12.00 12.00 12.00 12.00 Terate HT 5349 51.26 44.79 46.02 48.71 47.96 42.30 43.69 43.69 48.30 51.61 Voranol 370 1.95 2.22 2.29 2.35 2.77 2.95 3.00 3.00 3.00 3.00 Carpol GSP-280 21.45 26.21 21.45 25.36 21.45 21.45 24.28 24.28 26.21 22.90 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Dabco K-15 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Dabco T-120 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Polycat 204 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Water 0.62 0.57 0.00 1.08 0.72 0.08 0.67 0.67 1.59 1.59 Genetron 245fa 11.06 11.41 14.57 7.71 10.24 15.00 10.54 10.54 4.00 4.00 Process A:B vol. ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Isocyanate Index 1.148 1.167 1.307 1.048 1.111 1.292 1.124 1.124 0.947 0.941

TABLE-US-00011 TABLE 10A Example 20 - Run 1 2 3 4 5 6 7 8 9 10 Density, lb/ft.sup.3 2.12 2.22 2.12 2.13 2.28 2.05 1.96 1.95 2.04 2.1 Density, kg/m.sup.3 34.0 35.6 34.0 34.1 36.5 32.8 31.4 31.2 32.7 33.6 Dimensional 7.29 5.55 3.75 5.58 7.49 4.44 2.27 3.04 4.00 5.69 stability.sup.1 (vol. change) Compressive 21.2 25.8 22.2 20.3 22.5 20.9 26.1 18.9 19.7 19.6 Strength, psi Compressive 146.2 177.9 153.1 140.0 155.1 144.1 180.0 130.3 135.8 135.1 Strength, kPa R-value,/in. 7.42 7.23 7.64 7.27 7.84 7.44 4.54 6.82 7.07 7.19 R-value, m.sup.2K/W 1.307 1.273 1.345 1.280 1.381 1.310 0.800 1.201 1.245 1.266 Peak Heat 288 276 238 234 224 235 235 245 242 226 Release Rate Predicted Flame 25.4 23.0 22.3 21.2 21.9 20.8 21.3 23.0 23.9 21.3 Spread Index Predicted 153 89 47 19 28 52 28 24 30 35 Smoke Index .sup.1Dimensional stability was measured at 70 C. for 14 days at 95% RH.

TABLE-US-00012 TABLE 10B Example 20 - Run 11 12 13 14 15 16 17 18 19 20 Density, lb/ft.sup.3 2.02 1.96 2.1 1.87 1.89 1.94 1.93 1.95 1.92 1.89 Density, kg/m.sup.3 32.4 31.4 33.6 30.0 30.3 31.1 30.9 31.2 30.8 30.3 Dimensional 1.00 1.10 6.37 0.12 2.47 7.20 0.26 2.74 0.41 2.33 stability.sup.1 (vol. change) Compressive 20.1 17.0 17.9 24.4 17.9 16.4 16.6 17.9 21.2 22.0 Strength, psi Compressive 138.6 117.2 123.4 168.2 123.4 113.1 114.5 123.4 146.2 151.7 Strength, kPa R-value,/in. 7.4 7.03 7.43 4.8 7.06 7.39 7.09 6.98 4.86 4.75 R-value, m.sup.2K/W 1.303 1.238 1.308 0.845 1.243 1.301 1.249 1.229 0.856 0.837 Peak Heat 247 231 211 226 226 229 203 200 222 231 Release Rate Predicted Flame 22.2 21.1 20.7 22.1 22.9 22.7 20.2 21.5 19.1 21.2 Spread Index Predicted 48 18 22 27 18 29 17 21 28 37 Smoke Index .sup.1Dimensional stability was measured at 70 C. for 14 days at 95% RH.

TABLE-US-00013 TABLE 11A Example 21 - Run 1.sup.1 2 3 4 5 6 7 B side Viscosity 1715 1350 1265 1275 1115 1125 965 (cPs; at 25 C.) DBAA 0 4.52 4.55 6.92 7.03 7.03 8.38 Terate HT 5349 40.69 51.22 51.61 50.32 51.61 51.61 47.31 Voranol 280 26.01 26.21 26.21 23.11 23.11 25.72 Voranol 370 23.91 1.13 1.14 1.73 1.76 1.76 2.10 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Dabco T-120 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Dabco K-15 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Polycat 204 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Water 1.00 0.76 0.80 1.05 0.80 0.80 0.80 Solstice LBA 10.00 10.00 10.00 8.32 10.00 10.00 10.00 Process A:B vol. ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Isocyanate Index 1.078 1.139 1.164 1.098 1.144 1.144 1.147 Example 21 - Run 8 9 10 11 12.sup.2 13 B side Viscosity 1010 1610 1590 1165 1265 1395 (cPs; at 25 C.) DBAA 8.38 8.54 8.54 9.57 9.57 9.43 Terate HT 5349 47.31 51.61 51.61 46.92 46.92 48.69 Voranol 280 25.72 25.75 25.75 26.21 Voranol 370 2.10 2.13 2.13 26.22 26.22 2.43 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 Dabco T-120 0.25 0.25 0.25 0.25 0.25 0.25 Dabco K-15 0.25 0.25 0.25 0.25 0.25 0.25 Polycat 204 4.00 4.00 4.00 4.00 4.00 4.00 Water 0.80 1.43 1.43 0.80 0.80 1.29 Solstice LBA 10.00 5.48 5.48 10.00 10.00 6.45 Process A:B vol. ratio 1:1 1:1 1:1 1:1 1:1 1:1 Isocyanate Index 1.147 1.015 1.015 1.049 1.052 1.04 .sup.1Comparative run. .sup.2Contains 9% of a mixed ester of tetrabromophthalic anhydride with diethylene glycol and propylene glycol (Saytex RB-79 flame retardant) and 6% tris(1-chloro-2-propyl)phosphate (TCPP).

TABLE-US-00014 TABLE 11B Example 21 - Run 14 15 16 17 18 19 20 B side Viscosity 1080 1655 1660 1085 1145 900 2070 (cPs; at 25 C.) DBAA 10.51 10.72 10.77 11.07 11.07 11.24 12.00 Terate HT 5349 47.61 50.33 48.28 49.75 49.75 45.02 51.61 Voranol 280 24.11 26.21 25.23 21.45 21.45 26.21 26.21 Voranol 370 2.63 2.68 2.69 2.77 2.77 2.81 3.00 Carpol GSP-280 Carpol GP-5015 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Dabco T-120 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Dabco K-15 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Polycat 204 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Water 0.96 1.70 1.40 0.98 0.97 1.02 2.10 Solstice LBA 8.65 3.56 5.24 8.48 8.48 8.23 0.69 Process A:B vol. ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Isocyanate Index 1.096 0.962 0.983 1.081 1.083 1.086 0.897 Example 21 - Run 21 22 23 24 25 26 B side Viscosity 1605 1590 1355 1075 820 1395 (cPs; at 25 C.) DBAA 12.00 12.00 12.00 12.00 12.00 10.92 Terate HT 5349 51.61 51.61 47.17 45.22 42.30 48.96 Voranol 280 23.25 23.25 25.69 23.29 26.21 Voranol 370 3.00 3.00 3.00 3.00 3.00 Carpol GSP-280 16.95 Carpol GP-5015 10.00 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 Dabco T-120 0.25 0.25 0.25 0.25 0.25 0.25 Dabco K-15 0.25 0.25 0.25 0.25 0.25 0.25 Polycat 204 4.00 4.00 4.00 4.00 4.00 4.00 Water 1.65 1.65 1.38 0.76 0.77 1.36 Solstice LBA 3.65 3.65 5.64 10.00 10.00 5.31 Process A:B vol. ratio 1:1 1:1 1:1 1:1 1:1 1:1 Isocyanate Index 0.957 0.956 1.01 1.132 1.14 1.059

TABLE-US-00015 TABLE 12A Example 21 - Run 1.sup.1 2 3 4 5 6 7 8 9 10 11 12 13 Density, lb/ft.sup.3 1.95 2.07 2.02 1.98 1.94 2.01 2.05 1.95 1.94 2.04 1.81 1.91 1.99 Density, kg/m.sup.3 31.2 33.2 32.4 31.7 31.1 32.2 32.8 31.2 31.1 32.7 29.0 30.6 31.9 Dimensional 11.8 0.64 1.07 +3.67 1.09 1.11 0.74 2.93 19.04 16.27 0.15 14.24 stability.sup.2 (vol. change) Compressive 26.0 20.1 18.63 18.13 17.50 18.27 19.40 19.63 17.93 19.63 24.7 18.10 Strength, psi Compressive 179.3 138.6 128.4 125.0 120.7 126.0 133.8 135.3 123.6 135.3 170.3 124.8 Strength, kPa R-value,/in. 7.29 7.07 7.27 7.35 7.3 7.37 7.17 7.67 6.89 7.03 4.78 7.92 6.99 R-value, m.sup.2K/W 1.284 1.245 1.280 1.294 1.286 1.298 1.263 1.351 1.213 1.238 0.842 1.395 1.231 Peak Heat 184 240 226 212 198 248 198 215 233 221 228 214 219 Release Rate Predicted Flame 19.8 21.4 22.1 21.9 21.1 23.3 20.9 19.6 24.0 21.0 19.9 18.6 22.9 Spread Index Predicted 15 22 19 27 18 22 29 36 21 25 88 13 16 Smoke Index .sup.1Comparative run. .sup.2Dimensional stability was measured at 70 C. for 14 days at 95% RH.

TABLE-US-00016 TABLE 12B Example 21 - Run 14 15 16 17 18 19 20 21 22 23 24 25 26 Density, lb/ft.sup.3 1.98 1.86 1.89 1.75 1.94 1.93 1.92 1.89 2.02 1.99 1.86 1.96 1.90 Density, kg/m.sup.3 31.7 29.8 30.3 28.0 31.1 30.9 30.8 30.3 32.4 31.9 29.8 31.4 30.4 Dimensional 4.52 43.42 1.62 3.36 0.33 4.74 69.19 14.89 24.33 2.12 0.07 0.22 39.22 stability.sup.1 (vol. change) Compressive 16.37 17.37 22.2 23.37 17.03 19.23 16.67 19.00 15.23 26.50 22.90 17.43 9.5 Strength, psi Compressive 112.9 119.8 153.1 161.1 117.4 132.6 114.9 131.0 105.0 182.7 157.9 99.5 65.5 Strength, kPa R-value,/in. 7.53 6.72 4.52 5.05 7.15 4.98 6.22 5.55 6.35 4.99 7.18 7.25 6.50 R-value, m.sup.2K/W 1.326 1.183 0.796 0.889 1.259 0.877 1.095 0.977 1.118 0.879 1.264 1.277 1.145 Peak Heat 214 210 238 197 210 192 197 197 204 201 193 187 453 Release Rate Predicted Flame 19.8 21.4 20.1 19.0 19.1 19.0 21.5 19.3 20.1 17.5 18.1 18.7 21.6 Spread Index Predicted 17 48 109 38 42 43 58 32 50 56 76 49 1074 Smoke Index .sup.1Dimensional stability was measured at 70 C. for 14 days at 95% RH.

TABLE-US-00017 TABLE 13A Example 22 - Run 1* 2* 3 4 5 6 7 8 B side Viscosity 4010 1560 1775 1635 2435 1645 2895 2750 (cPs; at 25 C.) DBAA 0.00 0.00 1.23 2.80 5.37 6.60 8.00 8.00 Terate HT 5349 64.74 52.75 64.74 64.35 62.72 48.93 60.00 60.00 Voranol 280 Voranol 370 0.31 0.70 1.34 1.65 2.00 2.00 Carpol GSP-280 29.95 29.95 16.43 16.43 22.84 29.95 7.14 Carpol GP-5015 16.05 8.92 Carpol GP-700 Vorasurf 504 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Dabco T-120 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Dabco K-15 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Polycat 204 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Water 2.26 0.89 0.86 1.04 1.94 1.36 1.45 1.44 Opteon 1100 0.01 12.00 12.00 10.43 2.43 7.56 6.00 6.00 Process A:B vol. ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Isocyanate Index 0.899 1.156 1.128 1.082 0.917 1.026 1.083 1.031 Example 22 - Run 9 10 11 12 13 14 15 16 B side Viscosity 2455 1620 1575 1585 1625 1425 955 1625 (cPs; at 25 C.) DBAA 8.00 8.61 8.61 8.61 8.61 9.83 9.85 9.85 Terate HT 5349 40.01 54.66 54.66 54.66 54.66 57.98 47.87 47.87 Voranol 280 10.00 15.00 Voranol 370 2.00 2.15 2.15 2.15 2.15 2.46 2.46 2.46 Carpol GSP-280 16.00 22.59 22.59 22.59 22.59 16.43 Carpol GP-5015 20.00 Carpol GP-700 14.52 Vorasurf 504 9.52 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Dabco T-120 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Dabco K-15 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Polycat 204 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Water 1.49 1.43 1.43 1.43 1.43 1.26 1.25 1.25 Opteon 1100 6.00 6.69 6.69 6.69 6.69 8.00 8.00 8.00 Process A:B vol. ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Isocyanate Index 1.149 0.991 0.991 0.991 0.991 1.007 1.058 1.119 *Comparative run.

TABLE-US-00018 TABLE 13B Example 22 - Run 17 18 19 20 21 22 23 24 B side Viscosity 695 470 890 1200 1955 1285 1395 (cPs; at 25 C.) DBAA 9.85 12.31 12.42 12.43 12.47 12.86 12.90 13.44 Terate HT 5349 47.87 47.87 48.72 41.01 56.81 59.66 58.38 58.84 Voranol 280 10.00 2.46 2.48 2.49 2.49 2.57 2.58 Voranol 370 12.46 Carpol GSP-280 29.26 16.43 16.43 16.43 16.43 Carpol GP-1500 14.52 14.52 24.74 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Dabco T-120 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Dabco K-15 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Polycat 204 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Water 1.25 1.25 1.50 0.85 1.15 1.52 1.38 1.48 Opteon 1100 8.00 8.00 6.00 12.00 9.00 5.77 7.00 6.00 Process A:B vol. ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Isocyanate Index 1.075 1.111 1.097 1.122 1.028 0.957 0.982 0.963 Example 22 - Run 25 26 27 28 29 30 B side Viscosity 2220 2420 2240 890 1010 1570 (cPs; at 25 C.) DBAA 13.44 13.54 15.28 16.11 17.23 20.57 Terate HT 5349 61.34 64.74 49.47 36.64 49.21 55.50 Voranol 280 2.69 2.69 2.71 3.06 3.22 3.45 Voranol 370 Carpol GSP-280 16.43 16.43 29.95 29.95 17.00 16.43 Carpol GP-1500 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 Dabco T-120 0.25 0.25 0.25 0.25 0.25 0.25 Dabco K-15 0.25 0.25 0.25 0.25 0.25 0.25 Polycat 204 4.00 4.00 4.00 4.00 4.00 4.00 Water 1.78 2.17 2.19 0.81 0.87 1.88 Opteon 1100 3.50 0.00 0.00 12.00 11.26 2.21 Process A:B vol. ratio 1:1 1:1 1:1 1:1 1:1 1:1 Isocyanate Index 0.913 0.856 0.868 1.12 1.074 0.877

TABLE-US-00019 TABLE 13C Example 22 - Run 31 32 33 34 35 36 37 B side Viscosity 600 1570 1630 1115 1035 575 650 (cPs; at 25 C.) DBAA 16.75 20.00 20.00 20.00 20.00 20.00 17.16 Terate HT 5349 35.51 47.10 47.10 35.51 35.51 41.28 43.05 Voranol 370 4.19 5.00 5.00 5.00 5.00 5.00 Carpol GSP-280 26.25 22.60 22.60 29.95 29.95 16.43 21.47 Dabco DC193 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Dabco T-120 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Dabco K-15 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Polycat 204 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Water 0.78 2.12 2.13 1.66 1.65 0.74 0.73 Opteon 1100 12.00 0.00 0.00 4.24 4.24 12.00 12.00 Process A:B vol. ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Isocyanate Index 1.103 0.840 0.840 0.921 0.922 1.076 1.100

TABLE-US-00020 TABLE 14A Example 22 - Run 1* 2* 3 4 5 6 7 Density, lb/ft.sup.3 2.17 2.18 2.10 1.98 2.13 1.99 2.19 Density, kg/m.sup.3 34.8 34.9 33.6 31.7 34.1 31.9 35.1 Dimensional 66.50 0.14 0.32 3.21 56.61 1.21 1.37 stability.sup.1 (vol. change) Compressive 19.4 24.8 24.7 22.3 18.1 27.2 17.7 Strength, psi Compressive 133.8 171.0 170.3 153.8 124.8 187.5 122.0 Strength, kPa R-value,/in. 6.33 7.68 7.95 7.11 6.76 4.93 4.62 R-value, m.sup.2K/W 1.115 1.353 1.400 1.252 1.191 0.868 8.41 Peak Heat 280 275 241 233 227 235 656 Release Rate Predicted Flame 26.0 23.7 23.7 22.9 22.1 21.4 21.6 Spread Index Predicted 43 109 35 13 19 64 1060 Smoke Index Example 22 - Run 8 9 10 11 12 13 14 Density, lb/ft.sup.3 1.95 1.91 1.85 1.90 1.84 1.92 1.88 Density, kg/m.sup.3 31.2 30.6 29.6 30.4 29.5 30.8 30.1 Dimensional 1.99 0.74 0.03 1.30 0.44 0.20 1.25 stability.sup.1 (vol. change) Compressive 16.1 15.0 24.1 24.3 23.7 23.5 22.2 Strength, psi Compressive 111.0 103.4 166.2 167.5 163.4 162.0 153.1 Strength, kPa R-value,/in. 4.86 5.64 4.56 4.79 4.93 4.93 4.63 R-value, m.sup.2K/W 0.856 0.993 0.803 0.844 0.868 0.868 0.815 Peak Heat 507 435 215 199 225 219 208 Release Rate Predicted Flame 22.2 22.2 18.9 19.9 18.9 20.0 20.0 Spread Index Predicted 629 781 57 34 47 37 48 Smoke Index *Comparative run. .sup.1Dimensional stability was measured at 70 C. for 14 days at 95% RH.

TABLE-US-00021 TABLE 14B Example 22 - Run 15 16 17 18 19 20 21 22 23 24 25 26 27 Density, lb/ft.sup.3 1.93 1.97 1.94 1.93 1.87 1.81 1.97 1.95 1.93 1.91 1.93 2.19 2.08 Density, kg/m.sup.3 30.9 31.6 31.1 30.9 30.0 29.0 31.6 31.2 30.9 30.6 30.9 35.1 33.3 Dimensional stability.sup.1 9.36 11.57 27.1 35.73 4.72 2.01 41.59 0.68 1.32 57.31 62.93 47.63 (vol. change) Compressive 21.9 11.1 11.2 11.4 7.5 18.3 26.3 15.4 23.4 23.0 12.6 13.6 12.9 Strength, psi Compressive 151.0 76.5 77.2 78.6 51.7 126.2 181.3 106.2 161.3 158.6 86.9 93.8 88.9 Strength, kPa R-value,/in. 6.37 6.70 6.92 7.06 6.40 7.73 4.76 7.04 4.81 4.81 7.01 6.24 6.58 R-value, m.sup.2K/W 1.122 1.18 1.219 1.243 1.127 1.361 0.838 1.24 0.847 0.847 1.235 1.099 1.159 Peak Heat 220 518 431 404 479 222 219 221 233 236 214 201 219 Release Rate Predicted Flame 21.3 21.9 19.9 21.6 22.5 19.9 20.6 20.2 21.0 20.3 21.6 22.4 21.5 Spread Index Predicted 35 1003 1055 906 479 26 36 48 44 61 56 28 116 Smoke Index .sup.1Dimensional stability was measured at 70 C. for 14 days at 95% RH.

TABLE-US-00022 TABLE 14C Example 22 - Run 28 29 30 31 32 33 34 35 36 37 Density, lb/ft.sup.3 1.82 1.96 1.90 1.83 1.93 2.17 1.99 1.88 1.67 1.85 Density, kg/m.sup.3 29.1 31.4 30.4 29.3 30.9 34.8 31.9 30.1 26.8 29.6 Dimensional 1.18 2.71 1.04 16.55 47.57 80.89 39.23 57.00 23.00 17.5 stability.sup.1 (vol. change) Compressive 16.5 16.7 22.2 15.6 10.0 14.5 11.5 12.6 13.3 14.6 Strength, psi Compressive 113.8 115.1 153.1 107.6 68.9 100.0 79.3 86.9 91.7 100.7 Strength, kPa R-value,/in. 7.67 7.24 4.97 7.66 5.69 6.89 6.97 7.01 7.85 7.21 R-value, m.sup.2K/W 1.351 1.275 0.875 1.349 1.002 1.213 1.227 1.235 1.382 1.270 Peak Heat 192 200 204 193 190 213 197 207 187 172 Release Rate Predicted Flame 20.3 19.0 16.9 18.1 17.7 18.3 17.6 18.2 16.8 18.1 Spread Index Predicted 51 40 54 48 39 56 79 95 41 43 Smoke Index .sup.1Dimensional stability was measured at 70 C. for 14 days at 95% RH.

[0091] Components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another component, a solvent, or etc.). It matters not what chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution as such changes, transformations, and/or reactions are the natural result of bringing the specified components together under the conditions called for pursuant to this disclosure. Thus the components are identified as ingredients to be brought together in connection with performing a desired operation or in forming a desired composition. Also, even though the claims hereinafter may refer to substances, components and/or ingredients in the present tense (comprises, is, etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure. The fact that a substance, component or ingredient may have lost its original identity through a chemical reaction or transformation during the course of contacting, blending or mixing operations, if conducted in accordance with this disclosure and with ordinary skill of a chemist, is thus of no practical concern.

[0092] The invention described and claimed herein is not to be limited in scope by the specific examples and embodiments herein disclosed, since these examples and embodiments are intended as illustrations of several aspects of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fail within the scope of the appended claims.