IMPROVED POLYURETHANE FOAM USING HFO PROPELLANTS

Abstract

The invention pertains generally to a shelf-stable polyurethane HFO-blown two-component polyurethane foam composition which includes controlling the ratio of tin-containing catalyst(s) to potassium-containing catalyst(s).

Claims

1. A low-pressure two-component polyurethane foam composition formed by the reaction of an A-side reactant and at least one B-side reactant: the A-side comprising at least one diisocyanate and at least one hydrofluoroolefin propellant; the B-side comprising at least two polyols, at least one B-side plasticizer, at least one surfactant, at least two catalysts, at least 1.5 wt. % and less than 5 wt. % water, at least 1.5 wt. % and less than 5 wt. % glycerin and at least one HFO hydrofluoroolefin propellant; said at least two catalysts comprising an at least one organo-tin mercaptide tin-containing catalyst and an at least one potassium carboxylate potassium-containing catalyst; a weight ratio of the at least one organo-tin mercaptide tin-containing catalyst to the at least one potassium carboxylate potassium-containing catalyst being approximately equal to or greater than 0.5; the catalytic decay ratio of the polyurethane foam composition being approximately equal to or less than 2.5; the polyurethane foam composition having an initial density of at least approximately 1.6 pounds/ft.sup.3 (pcf) and not exceeding a deviation of 0.5 pcf after accelerated aging; the polyurethane foam composition having an initial R-value of at least approximatel 5.5 Ft.sup.2 h/BTU and not exceeding a deviation of ±1 Ft.sup.2 h/BTU after accelerated aging; the polyurethane foam composition having an initial closed cell content of at least approximately 85% and not exceeding a deviation of ±20% after accelerated aging; the polyurethane foam composition having a dimensional stability with no greater than approximately an 8% volume change after accelerated aging; and the polyurethane foam composition having an initial compression of at least approximately 10 psi.

2. The two-component polyurethane foam composition of claim 1 wherein the at least two polyols are selected from the group consisting of ##STR00021## n ranges from 1-30 inclusive; o ranges from 1 to 5 inclusive; and p ranges from 1 to 5 inclusive; and ##STR00022## n ranges from 1-30 inclusive; o ranges from 1 to 5 inclusive; and p ranges from 1 to 5 inclusive;

3. The two-component polyurethane foam composition of claim 1 wherein the at least two polyols are selected from the group consisting of an aromatic phthalic anhydride polyester polyol, an aromatic terephthalic anhydride polyester polyol and a polyamide polyester polyol.

4. The two-component polyurethane foam composition of claim 1 wherein the at least two polyols are selected from the group consisting of an aromatic polyester polyol and a saturated polyester polyol.

5. The two-component polyurethane foam composition of claim 1 wherein the at least two polyols are selected from the group consisting of a sucrose polyether polyol based on a sucrose-glycerol mixture with a functionality of ˜4.5 having a hydroxyl number of ˜360 and a polyether polyol having a hydroxyl number of ˜112 and a M.W. of ˜1000 and a viscosity @ 25° C. of ˜145 cP.

6. The two-component polyurethane foam composition of claim 1 wherein the at least two polyols are selected from the group consisting of a hybrid aromatic polyester polyol having a diethylene glycol/adipic acid polymer backbone and an aromatic polyester polyol.

7. (canceled)

8. (canceled)

9. The two-component polyurethane foam composition of claim 8 wherein a combined weight percent of the tin-containing catalyst and the potassium-containing catalyst is less than 3 weight percent.

10. (canceled)

11. The two-component polyurethane foam composition of claim 10 wherein a weight percent of added water is less than approximately 3 weight percent.

12. The two-component polyurethane foam composition of claim 1 wherein a weight percent of added water is less than or equal to approximately 2 weight percent.

13. (canceled)

14. The two-component polyurethane foam composition of claim 1 wherein a weight percent of added glycerin is less than approximately 3 weight percent.

15. The two-component polyurethane foam composition of claim 1 wherein a weight percent of added glycerin is less than approximately 2 weight percent.

16. (canceled)

17. A process for synthesizing a low-pressure two-component polyurethane foam composition formed by the reaction of an A-side reactant and at least one B-side reactant and controlling a shelf life of a low-pressure two-component polyurethane foam composition using a metric of a catalytic decay ratio from accelerated aging, the accelerated aging effected by storing a reactant combination and propellant at 50° C. for 12-48 days prior to reacting the A-side reactant and at least one B-side reactant and spraying the resultant polyurethane foam composition followed by measuring the catalytic decay ratio, the ratio derived from measuring an accelerated aging gel time to that of an initial gel time: the A-side comprising at least one diisocyanate and at least one HFO hydrofluoroolefin propellant; the B-side comprising at least two polyols, at least one plasticizer, at least one surfactant, at least two catalysts, at least 1.5 wt. % and less than 5 wt. % water, at least 1.5 wt. % and less than 5 wt. % glycerine and at least one hydrofluoroolefin propellant; said at least two catalysts comprising an at least one organotin mercaptide tin-containing catalyst and an at least one potassium carboxylate potassium-containing catalyst; a weight ratio of the at least one organo-tin mercaptide tin-containing catalyst to the at least one potassium carboxylate potassium-containing catalyst being approximately equal to or greater than 0.5; the catalytic decay ratio of the polyurethane foam composition being approximately equal to or less than 2.5; the polyurethane foam has an initial density of at least approximately 1.6 pounds/ft.sup.3 (pcf) and not exceeding a deviation of ±0.5 pcf after accelerated aging; the polyurethane foam having an initial R-value of at least approximately 5.5 Ft.sup.2 h/BTU and not exceeding a deviation of ±1 Ft.sup.2 h/BTU after accelerated aging; the polyurethane foam having an initial closed cell content of at least approximately 85% and not exceeding a deviation of ±20% after accelerated aging; the polyurethane foam having a dimensional stability with no greater than approximately an 8% volume change after accelerated aging; the polyurethane foam having an initial compression of at least approximately 10 psi; and the process comprising the step of adding the at least one tin-containing catalyst and at least one potassium catalyst in a weight ratio of approximately equal to or greater than 0.5 in addition to controlling the at least 1.5 wt. % and less than 5 wt. % water, and controlling the at least 1.5 wt. % and less than 5 wt. % glycerine.

18. The process of claim 17 wherein the step of adding the at least one tin-containing catalyst and the at least one potassium catalyst is in a weight ratio of approximately equal to or greater than 0.67.

19. (canceled)

20. The process of claim 17 wherein the at least two B-side polyols are polyester polyols.

21. The process of claim 17 wherein the at least two B-side polyols are polyester polyols and selected from the group consisting of ##STR00023## n ranges from 1-30 inclusive; o ranges from 1 to 5 inclusive; and p ranges from 1 to 5 inclusive; and ##STR00024## n ranges from 1-30 inclusive; o ranges from 1 to 5 inclusive; and p ranges from 1 to 5 inclusive;

22. The process of claim 17 wherein the at least two B-side polyols are polyether polyols.

23. (canceled)

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0015] FIG. 1 is a graphical depiction of varying the weight catalyst ratio of tin-containing catalyst to potassium-containing catalyst and its impact on the catalytic decay ratio (“CDR”) for various polyurethane foams;

[0016] FIG. 2 is a graphical depiction of the impact of added glycerin compared to no added glycerin with various catalyst packages;

[0017] FIG. 3 is a graphical depiction of dimensional stability of the synthesized polyurethane foam vs. the weight ratio of Sn-containing catalyst/K-containing catalyst; and

[0018] FIG. 4 is a graphical depiction of closed cell content of various synthesized polyurethane foam over time.

DETAILED DESCRIPTION OF THE INVENTION

[0019] The best mode for carrying out the invention will now be described for the purposes of illustrating the best mode known to the applicant at the time of the filing of this invention. The examples and figures are illustrative only and not meant to limit the invention, as measured by the scope and spirit of the claims.

[0020] Unless the context clearly indicates otherwise: the word “and” indicates the conjunctive; the word “or” indicates the disjunctive; when the article is phrased in the disjunctive, followed by the words “or both” or “combinations thereof” both the conjunctive and disjunctive are intended.

[0021] As used in this application, the term “approximately” is within 10% of the stated value, except where noted.

[0022] As used in this application, the term “catalytic decay ratio” or “CDR” is defined as the ratio of accelerated aging gel time to that of initial gel time. This value was recorded in order to determine gel time shift over the age of the system. A low CDR would indicate greater catalytic stability over that of a high CDR. For long term stability, the CDR ratio should remain less than or equal to approximately 2.5, more preferably less than or equal to approximately 2.0.

[0023] As also used in this application, “shelf life” means a polyurethane foam which when subjected to accelerated aging, still results in a foam having physical properties such as foam height, gel time, density, etc., preferably within approximately 20% of those parameters prior to accelerated aging.

[0024] As further used in this application, “accelerated aging” means storing the reactant combination and propellant at 50° C. for 12-48 days prior to reacting the “A” and “B” cylinders and spraying the polyurethane foam. Using the Arrhenius equation, this equates to 3-12 months at room temperature.

[0025] As additionally used in this application, “low-pressure” means a pressure less than 250 psi at room temperature. Typically, the pressure in the full cylinders is between approximately 130-250 psi.

[0026] The literature would appear to teach that to achieve shelf life stability for an HFO propellant-based two-component polyurethane composition, there should preferably be at least one aromatic polyester polyol (in a major amount) and no more than approximately 10% aliphatic polyether polyol. The literature appears to highlight the benefits of polyester polyols, and more specifically aromatic polyester polyols, over those of aliphatic polyether polyols. This composition was believed to be counterintuitive, as one skilled in the art might expect the polyester polyols to be problematic due to the polyester polyols being greater nucleophiles and, therefore, more susceptible to attack. The prior art would appear to be teaching that polyether polyols seem to be significantly detrimental to the shelf life of the foam product. See United States Published Patent Application No. 2019/0092910.

[0027] In this application, a shelf-life stable formula blown with a gaseous hydrofluoroolefin (HFO) was selected in the following study to show differences between catalysts, particularly those with tin and potassium in their chemical composition, as related to accelerated shelf stability of the polyurethane formulation.

[0028] The invention will now be described by a series of examples and identification of various reactants used in the invention.

Polyols

[0029] As illustrated in a non-exhaustive, non-exclusive, exemplary list below, there are a myriad of polyols (both polyester polyols and polyether polyols) which are useful in effecting the reaction with a diisocyanate to form a foam having varying characteristics. The ability to add widely varying amounts of polyols and/or different polyol combinations could easily be affected via either supplementing existing amounts of “B-side” polyol(s) via the third stream or by essentially eliminating “B-side” polyol(s) and making their addition via the third stream. In one aspect of the invention, the polyol(s) are added by using a pumping mechanism from a “B-side” cylinder or other container, and the third stream is employed to add the blowing agent and/or pressurizing agent.

TABLE-US-00001 Polyester Polyol(s) PS 2352 [00001] Hydroxyl Number, mg KOH/g 230-250 Water, % by wt., max.  0.15 Acid Number, mg KOH/g, max. 0.6-1.0 Viscosity at 77° F. (25° C.), cP 2,000-4,500 Equivalent Weight (average) 234    Molecular Weight (average) 468    Color, Gardner 4   Density at 77° F. (25° C.), lb./U.S. gal 9.9 n  1-30 Specific Gravity at 77° F. (25° C.)  1.19 DEG/PA backbone [00002] n ranges from 1-30 inclusive; o ranges from 1 to 5 inclusive; and p ranges from 1 to 5 inclusive; TB-350 [00003] Hydroxyl Number, mg KOH/g 335-365 Water, % by wt., max.  0.15 Acid Number, mg KOH/g, max. 0.5-2.0 Viscosity at 77° F. (25° C.), cP 2,500-3,500 Color, Gardner 4-5 Specific Gravity at 77° F. (25° C.)  1.233 Functionality 2.2 n  1-25 DEG/TA backbone (diethylene glycol terephthalate anhydride) [00004] n ranges from 1-30 inclusive; o ranges from 1 to 5 inclusive; and p ranges from 1 to 5 inclusive; Stepanpol ® Aromatic diethylene glycol-phthalic anhydride polyester polyol (DEG/PA backbone)— PS-3152 avg. viscosity @ 25° C. ~2756 cP; Avg. ~350; and Hydroxyl Value (mgKOH/g) ~300-350 Isoexter 3061 Aromatic phthalic anhydride polyester polyol Stepanpol ® Saturated polyester polyol (DEG/AA backbone) wherein AA = adipic acid)—avg. PC 2011-225 viscosity @ 25° C. ~400-600 cP; Avg. MW ~500; and Hydroxyl Value (mgKOH/g) ~215-235 Stepanpol ® Hybrid phthalate anhydride polyester polyol (DEG/PA backbone)—avg. viscosity @ PDP-70 25° C. ~1900 cP; Avg. MW ~1600; and Hydroxyl Value (mgKOH/g) ~70 Stepanpol ® Aromatic polyester polyol PS-3422 Stepanpol ® Aromatic phthalic anhydride polyester polyol (DEG/PA backbone)—avg. viscosity @ PS-1752 25° C. ~3900 cP; Avg. MW ~640; and Hydroxyl Value (mgKOH/g) ~175 with some propylene carbonate (unspecified by the manufacturer)

[0030] Furthermore without being bound to any one theory or mode-of-operation, it is believed that the use of glycerin as a fluoride ion scavenger may beneficially increase the shelf life stability of this product. Note that it is now possible to have significant amounts of polyester polyols and polyether polyols in the composition, provided that at least some glycerin (synonymously “glycerol”) is also present, a simple triol. It is recognized that the fluoride ion scavenger will preferably have a functionality of ≥2.0, preferably ≥2.2.

[0031] While glycerin is one specific example of a triol with scavenging capabilities, the invention is not limited to such. In fact, lower molecular weight polyols, e.g., a triol or specifically a polyol (including diols) having a functionality ≥2, preferably ≥2.2 are believed to be useful in this invention. Molecular weight ranges of the polyol(s) are anticipated to range between ˜90 to 1500 g/mol are believed to be applicable to this invention.

TABLE-US-00002 Polyether Polyol(s) (actual and potential) Voranol 360 (SG-360) [00005] sucrose polyether polyol based on a sucrose-glycerol mixture with a functionality of ~4.5 having a hydroxyl number of ~360 wherein x ranges from 1 to 100 Multranol aromatic amine-initiated polyether polyol having a hydroxyl number of about 388 mg 8114 KOH/g and a functionality of 4 Poly-G ® 30-280 [00006] glycerin-based oxypropylated polyether polyol having a functionality greater than or equal to 3 and a molecular weight of about 600, an OH number of about 274, an acid number (max) of 0.05, an average pH of about 6.5 wherein n ranges from 2 to 50 Poly-G ® 30-168 [00007] 1,2,3-propanetriol, methyloxirane polymer wherein n ranges from 2 to 50 Poly-G ® Polyether triol having an average molecular weight of ~4,000, an OH number of about 30-42 40, an acid number (max) of ~0.03, an average pH of about 5.5 Jeffol ® 31-35 [00008] ethylene oxide triol, ethylene oxide capped, and glycerin initiated wherein the polyol has a hydroxyl number of ~35 and a M.W. of ~4800 and provides for chain entanglement and packing without distorting a profile wherein x ranges from 2 to 50. Carpol TEAP- 265 [00009] 3,3′,3″-[nitrilotris(ethane-2,1-diyloxy)]tripropan-1-ol Poly-G ® 70-600 [00010] Ethoxylatedtriethanolamine wherein n ranges from 1 to 50 Poly-G ® 55-28 [00011] Block copolymer of propylene oxide and polyethylethylene oxide having a nominal molecular weight of 4,000 and wherein n & m are integers ranging from 2 to 50. Poly-G Polyether polyol having a hydroxyl number of ~112 and a M.W. of ~1000 and a 20-112 viscosity @ 25° C. of ~145 cP Poly-G Ethanol, 2,2′ imino bis, polymer with 2-methyl oxirane, a polyether triol having a 37-600 hydroxyl number of ~600 and a M.W. of ~280 and a viscosity @ 25° C. of ~380 cP

Flame Retardants and/or Plasticizers

[0032] As illustrated in a non-exhaustive, non-exclusive, exemplary list below, there are a myriad of flame retardants and/or plasticizers which are useful in modifying the properties of the reaction of a polyol with a diisocyanate to form a foam having varying characteristics. The ability to add widely varying amounts of flame retardants/plasticizers and/or different flame retardant/plasticizer combinations could easily be effected via either supplementing existing amounts of “B-side” flame retardant(s/plasticizer(s) via the third stream or by essentially eliminating “B-side” flame retardant(s)/plasticizer(s) and making their addition via the third stream.

##STR00012##

Surfactants

[0033] As illustrated in a non-exhaustive, non-exclusive, exemplary list below, there are a myriad of surfactants which are useful in modifying the properties of the reaction of a polyol with a diisocyanate to form a foam having varying characteristics. The ability to add widely varying amounts of surfactants and/or different surfactant combinations could easily be affected via either supplementing existing amounts of “B-side” surfactant(s) via the third stream or by essentially eliminating “B-side” surfactant(s) and making their addition via the third stream.

TABLE-US-00003 Trade name Composition (if known) Tegostab ® B-8433 Polyether polydimethylsiloxane copolymer Tegostab ® B-8870 Polyether polydimethylsiloxane copolymer Dabco ® LK ®-443 Non-silicone organic surfactant Nonoxynol-9 [00013] the hydroxyl number is ~88 L12-8 ethoxylated alcohol (dodecyl alcohol ethoxylate) [00014] Tegostab ® B-8465 Polyether polydimethylsiloxane copolymer Surfonic N-95 ethylene oxide content of 65.5% & HLB value of 13.1

Catalysts

[0034] As illustrated in a non-exhaustive, non-exclusive, exemplary list below, there are a myriad of catalysts which are useful in effecting the reaction of a polyol with a diisocyanate to form a foam having varying characteristics. The ability to add widely varying amounts of catalysts and/or different catalyst combinations could easily be affected via either supplementing existing amounts of “B-side” catalyst(s) via the third stream or by essentially eliminating “B-side” catalyst(s) and making their addition via the third stream.

TABLE-US-00004 Trade name and/ or Chemical name Chemical structure Dabcoe ®K-15 (Potassium octoate/ DEG (diethylene glycol)) [00015] Dabco ® TMR-20 Proprietary K-carboxylate composition DABCO ® T-120/ (CH.sub.3(CH.sub.2).sub.3).sub.2—Sn—S(CH.sub.2).sub.11CH.sub.3 PC 3014 (dibutyl tin dilauryl mercaptide) Polycat ® 12 [00016] DMDEE (2,2′- dimorpholine- diethylether) [00017]

[0035] As better illustrated in FIG. 1, the desired CDR ratio under accelerated aging is only achieved when the weight ratio relationship between the weight of the catalyst containing tin (“Sn”) to the weight of the catalyst containing potassium (“K”) is greater than approximately 0.50, more preferably greater than approximately 0.67.

[0036] At same catalyst ratios (1:3, 2:3), the catalyst compositions with TMR-20 has greater stability. As ratio of T-120 (Sn-containing catalyst) to KC (potassium carboxylate, K-15 or TMR-20) reaches 1, resulting sprayed polyurethane foam stability is enhanced as measured using accelerated aging testing and quantifying the CDR ratio.

Other

[0037] Water can be both beneficial and deleterious to catalyst foams, depending on the blowing agent used or the end-use application. The ability to add widely varying amounts of water could easily be affected via either supplementing existing amounts of “B-side” water via the third stream or by essentially eliminating “B-side” water and making its addition via the third stream of a spray gun.

[0038] Glycerin has been found to be beneficial to the reactant mix and is one specific example of a triol with scavenging capabilities, the invention is not limited to such. In fact, lower molecular weight polyols, e.g., a triol or specifically a polyol (including diols) having a functionality 2, preferably 2.2 are believed to be useful in this invention. Molecular weight ranges of the polyol(s) are anticipated to range between ˜90 to ˜1500 g/mol are believed to be applicable to this invention.

[0039] As illustrated in FIG. 2, at the same catalyst ratios, glycerin improves aging stability.

Blowing Agents

[0040] As illustrated in a non-exhaustive, non-exclusive, exemplary list below, there are a myriad of blowing agents which are useful in effecting the reaction of a polyol with a diisocyanate to form a foam having varying characteristics. The ability to add widely varying amounts of blowing agents and/or different blowing agent combinations could easily be effected via either supplementing existing amounts of “A-side” and/or “B-side” blowing agent(s) via the third stream or by essentially eliminating blowing agent(s) and making their addition via the third stream.

[0041] In one aspect of the invention, blowing agents having up to four carbon atoms in their backbone and which are useful in this invention fall within the general formula (I) illustrated below:

[CV.sub.a].sub.m-A-[CX.sub.b].sub.n-B-[CY.sub.c].sub.o-D-[CZ.sub.d].sub.p

[0042] wherein [0043] C is a carbon atom; [0044] V, X, Y & Z are independently selected from the group consisting of H, F and Cl; [0045] a & d are independently selected from the integral values ranging from 0 to 3 inclusive; [0046] b & c are independently selected from the integral values ranging from 0 to 2 inclusive; [0047] o, p & n are equal to 1; [0048] m is selected from the integral values ranging from 0 to 1 inclusive; [0049] A, B & D are covalent bonds sufficient to satisfy the available bonding sites of adjacent carbon atoms, if such carbon atoms are present; and [0050] the blowing agent, including miscible blends and azeotropes thereof, having a boiling point between approximately −5° C.-50° C., and an ozone depletion potential of essentially zero; and [0051] in a preferred embodiment, the blowing agent is non-flammable, recognizing that co-blowing agents may be flammable, although in a more preferred embodiment, the co-blowing agent will be added in such an amount as to render the combination non-flammable either as a blend or as an azeotrope.

[0052] In another aspect of the invention, and listed more generically, the blowing agents having up to six carbon atoms in their backbone and which are useful in this invention fall within the general formula (II) illustrated below:

[CU.sub.e].sub.q-E-[CW.sub.f].sub.r-F-[CV.sub.a].sub.m-A-[CX.sub.b].sub.n-B-[CY.sub.c].sub.o-D-[CZ.sub.d].sub.p

[0053] wherein [0054] C is a carbon atom; [0055] U, W, V, X, Y and Z are independently selected from the group consisting of H, F and CI; [0056] d & e are independently selected from the integral values ranging from 0 to 3 inclusive; [0057] a, b, c & f are independently selected from the integral values ranging from 0 to 2 inclusive; [0058] o, p & n are equal to 1; [0059] m, q & r are independently selected from the integral values ranging from 0 to 1 inclusive; [0060] A, B, D, E and F are covalent bonds sufficient to satisfy the available bonding sites of adjacent carbon atoms, if such carbon atoms are present; [0061] the blowing agent having a boiling point between approximately −5° C.-50° C., and an ozone depletion potential of not greater than 0.05; and [0062] in a preferred embodiment, the blowing agent is non-flammable, recognizing that co-blowing agents may be flammable, although in a more preferred embodiment, the co-blowing agent will be added in such an amount as to render the combination non-flammable either as a blend or as an azeotrope.

[0063] As illustrated in a non-exhaustive, non-exclusive, exemplary list below, there are a myriad of blowing agents which are useful in effecting the reaction of a polyol with a diisocyanate to form a foam having varying characteristics. The ability to add widely varying amounts of blowing agents and/or different blowing agent combinations could easily be effected via either supplementing existing amounts of “A-side” and/or “B-side” blowing agent(s) via the third stream or by essentially eliminating blowing agent(s) and making their addition via the third stream.

TABLE-US-00005 HFO 1234-ze (1,3,3,3-tetrafluoropropene) [00018] HFC-245fa (1,1,1,3,3 pentafluoropentane) [00019] Opteon 1100 (1,1,1,4,4,4 hexafluoro-2-butene) [00020]

[0064] As used in this application, a non-limiting definition for the term “blowing agent” which includes miscible mixtures and azeotropes of blowing agents, means a propellant or solvent which are useful and provide efficacy to various applications in the form of performance, pressure performance, or solubility, without deleterious effect due to molar gas volume, flammability migration, or GWP reduction, yet which have a vapor pressure within defined limits as defined herein. Exemplary and non-limiting blowing agents include HFC-245fa (Honeywell Intl.), namely 1,1,1,3,3 pentafluoropentane or HFO-1336mzz or sold under the trade name Opteon® 1100 (Chemours), namely 1,1,1,4,4,4 hexafluoro-2-butene.

[0065] And while the above identified blowing agents are preferred from an ozone depletion potential (ODP) perspective as well as a global warming potential (GWP) perspective, the third stream within the spray gun offers the ability to use a myriad of blowing agents, alone or in combination with others, the combination in one aspect including all non-flammable blowing agents, while in another aspect including a combination of non-flammable and flammable blowing agents. A non-limiting list of other blowing agents includes, but is not limited to air, C.sub.1 to C.sub.6 hydrocarbons, C.sub.1 to C.sub.8 alcohols, ethers, diethers, aldehydes, ketones, hydrofluoroethers, C.sub.1 to C.sub.4 chlorocarbons, methyl formate, water, carbon dioxide, C.sub.3 to C.sub.4 hydrofluoroolefins, and C.sub.3 to C.sub.4 hydrochlorofluoroolefins. Examples of these non-exclusively include one or more of difluoromethane, trans-1,2-dichloroethylene, difluoroethane, 1,1,1,2,2-pentafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1-trifluoroethane, 1,1-difluoroethane, fluoroethane, hexafluoropropane isomers, including HFC-236fa, pentafluoropropane isomers of HFC-245fa, heptafluoropropane isomers, including HFC-227ea, hexafluorobutane isomers, and pentafluorobutane isomers including HFC-365mfc, tetrafluoropropane isomers, and trifluoropropene isomers (HFO-1243). Specifically included are all molecules and isomers of HFO-1234, including 1,1,1,2-tetrafluoropropene (HFO-1234yf), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)) sold under the trade name Solstice LBP by Honeywell and cis- and trans-1,2,3,3-tetrafluoropropene (HFO-1234ye), HFC-1233zd, and HFC-1225ye. The blowing agents may be used in combination with at least one co-blowing agent which non-exclusively include: hydrocarbons, methyl formate, halogen containing compounds, especially fluorine containing compounds and chlorine containing compounds such as halocarbons, fluorocarbons, chlorocarbons, fluorochlorocarbons, halogenated hydrocarbons such as hydrofluorocarbons, hydrochlorocarbons, hydrofluorochlorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, CO.sub.2, CO.sub.2 generating materials such as water, and organic acids that produce CO.sub.2 such as formic acid. Examples non-exclusively include low-boiling, aliphatic hydrocarbons such as ethane, propane(s), i.e. normal pentane, isopropane, isopentane and cyclopentane; butanes(s), i.e. normal butane and isobutane; ethers and halogenated ethers; trans 1,2-dichloroethylene, pentafluorobutane; pentafluoropropane; hexafluoropropane; and heptafluoropropane; 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124); and 1,1-dichloro-1-fluoroethane (HCFC-141b) as well as 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1,2-tetrafluoroethane (HFC-134a); 1-chloro 1,1-difluoroethane (HCFC-142b); 1,1,1,3,3-pentafluorobutane (HFC-365mfc); 1,1,1,2,3,3,3-heptafluoropropane (HCF-227ea); trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12); 1,1,1,3,3,3-hexafluoropropane (HFC-236fa); 1,1,1,2,3,3-hexafluoropropane (HFC-236ea); difluoromethane (HFC-32); difluoroethane (HFC-152a); trifluoropropenes, pentafluoropropenes, chlorotrifluoropropenes, tetrafluoropropenes including 1,1,1,2-tetrafluoropropene (HFO-1234yf), 1,1,1,2,3-pentafluoropropene (HFO-1225ye), and 1-chloro-3,3,3-trifluoropropene (HCFC-1233zd). Combinations of any of the aforementioned are useful including blends and azeotropes thereof. The relative amount of any of the above noted additional co-blowing agents, as well as any additional components included in present compositions, can vary widely within the general broad scope of the present invention according to the particular application for the composition, and all such relative amounts are considered to be within the scope hereof.

[0066] As used herein, a non-limiting definition for the term “co-blowing agent” which includes mixtures or miscible blends and/or azeotropes of blowing agents, means a one or more co-blowing agents, co-propellants, or co-solvents which are useful and provide efficacy to various applications in the form of performance, pressure performance, or solubility, without deleterious effect due to molar gas volume, flammability mitigation, or GWP reduction. These co-agents include but are not limited to those described previously.

[0067] Characteristics of the various synthesized additives may be characterized at least in part by the following Examples and Tables. It is noted that the catalyst ratio is important when considering that all tin catalysts are very aggressive gelation catalysts that drive the urethane reaction while the K-15 and TMR-20 catalysts are slower reaction trimerization catalysts. The relatively “softer” polyurethane reaction is being driven faster than the more “rigid” polyisocyanurate reaction. It is therefore, not particularly surprising that high ratios of tin catalyst in comparison to the trimerization catalysts would result in cured foams having poor dimensional stability.

[0068] The use of T-120 by itself produces poor dimensional stability results (even though it passes CDR). Therefore, it is not possible to simply use TMR-20 (or even K15), i.e., the potassium containing catalyst, as it is too slow and does not facilitate passing insulation properties (even though it passes CDR). What has been learned through experimentation is that it is important to combine the speed of T-120, Sn-containing catalyst, with the dimensional stability of the potassium-containing catalyst. This has to be done at certain ratios: if the tin to potassium catalyst is too low, it fails CDR. If that same ratio is too high, and it tends to fail on dimensional stability.

[0069] And yet when looking at the broader picture, and without being held to any theory or mode of operation, glycerin imparts greater reactivity stability over time. If glycerin is taken out of the reactants, reactivity stability suffers. We then attempted to expand on the types of polyols we could use in this system. Experimentation which included keeping the hydroxyl numbers of the blends relatively constant, it was determined that all systems passed reactivity stability, i.e., passing CDR criteria, but some maintained physical properties, others faded and failed.

[0070] Unlike the Prior Art, these polyurethane reactant systems can now utilize systems with pure polyether and unlike previous systems, can include an aggressive catalyst package to make insulation spray foam (as opposed to just an adhesive).

[0071] All experiments in this application employed the following recognizing that the exact percentages can vary and still produce acceptable polyurethane foam. Each can was pressurized to between 130-250 psi (typically using an inert gas, e.g., nitrogen):

TABLE-US-00006 All Cans* A-side B-side PMDI 93% Respective blend 86% 1234ze  7% 14% 100%  100%  Optimal A/B Ratio ~ 1:1

TABLE-US-00007 TABLE #1 KB-1 YB-1 KB-2 YB-2 YB-3 OH # % % % % % Polyol(s) PS-2352/Isoexter 4404 240 17.00 17.00 17.00 17.00 16.70 TB-350 350 32.60 32.60 32.10 32.10 32.00 Plasticizer TCPP 0 36.60 36.60 36.60 36.60 36.60 Flame Retardant PHT4-Diol 218 5.00 5.00 5.00 5.00 5.00 Surfactant(s) B8870 60 3.00 3.00 3.00 3.00 3.00 L-31 103 — — — — — Catalyst(s) Dabco ® K-15 271 1.50 — 1.50 — — Dabco ® T-120/PC3014 0 0.50 0.50 1.00 1.00 3.00 Dabco ® TMR-20 850 — 1.50 — 1.50 — Other Additive(s) Water 6233 2.00 2.00 2.00 2.00 1.80 Glycerin 1829 1.80 1.80 1.80 1.80 1.90 Compares directly to: — KB-1 KB-1 KB-2 — T-120:PC ratio 1:3 1:3 2:3 2:3 T-120 CDR (6 months) 2.12 1.96 1.95 1.41 0.91 CDR (12 months) 2.85 3.00 2.42 1.83 0.96 Reactivity Assessment Fail Fail Borderline Pass Pass (Pass/Fail)* Phys. Property Assessment Fail Fail Borderline Pass Fail (Pass/Fail)** Maximum Dimensional 3.64 4.33 4.76 4.27 37.42 Stability Value YB-4 NB-1 A-5 A-2 A-1 OH # % % % % % Polyol(s) PS-2352/Isoexter 4404 240 16.70 19.30 15.90 15.20 15.30 TB-350 350 32.00 35.30 34.70 35.40 35.50 Plasticizer TCPP 0 36.60 36.60 36.60 36.60 36.60 Flame Retardant PHT4-Diol 218 5.00 — 5.00 5.00 5.00 Surfactant(s) B8870 60 3.00 3.00 3.00 2.00 2.00 L-31 103 — — — 1.00 1.00 Catalyst(s) Dabco ® K-15 271 — — — — Dabco ® T-120/PC3014 0 — 0.90 0.50 0.80 0.80 Dabco ® TMR-20 850 3.00 1.35 1.00 1.00 0.80 Other Additive(s) Water 6233 1.80 1.80 1.50 1.50 1.50 Glycerin 1829 1.90 1.80 1.80 1.50 1.50 Compares directly to: — YB-2 YB-2 YB-2 YB-2 T-120:PC ratio TMR-20 2:3 1:2 4:5 1:1 CDR (6 months) 0.97 1.54 1.44 1.67 1.50 CDR (12 months) 1.29 1.94 2.08 1.50 1.40 Reactivity Assessment Pass Pass Borderline Pass Pass (Pass/Fail)* Phys. Property Assessment Fail Pass Borderline Pass Fail (Pass/Fail)** Maximum Dimensional 2.09 2.33 2.49 6.93 8.94 Stability Value Minor changes impact properties --> formulation sensitivity (lack of robustness). *CDR < 2 - Pass; 2 < CDR < 2.5 - Borderline; CDR > 2.5 - Fail **To pass, density cannot exceed past +/−0.5 pcf of initial, R-value must be above 5.5, closed cell content > 85%, compression > 10 psi, dimensional stability < +/−7%

TABLE-US-00008 TABLE #2 (glycerin vs. no glycerin) Glycerin No Glycerin A-5 NB-1 A-1 NG-1 NG-2 NG-3 OH # % % % % % % Polyol(s) PS-2352/Isoexter 4404 240 15.90 15.20 15.30 15.90 20.20 16.00 TB-350 350 34.70 35.40 35.50 36.50 36.30 36.20 Plasticizer TCPP 0 36.60 36.60 36.60 36.60 36.60 36.60 Flame Retardant PHT4-Diol 218 5.00 5.00 5.00 5.00 — 5.00 Surfactant(s) B8870 60 3.00 2.00 2.00 2.00 3.00 2.00 L-31 103 — 1.00 1.00 1.0 — 1.0 Catalyst(s) Dabco ® T-120/PC3014 0 0.50 0.80 0.80 0.50 0.90 0.80 Dabco ® TMR-20 850 1.00 1.00 0.80 1.00 1.35 0.80 Other Additive(s) Water 6233 1.50 1.50 1.50 1.50 1.65 1.60 Glycerin 1829 1.80 1.50 1.50 — — — Compares directly to: YB-2 YB-2 YB-2 A-5 NB-1 A-1 T-120:PC ratio 1:2 4:5 1:1 1:2 2:3 1:1 CDR (6 months) 1.44 1.67 1.50 2.12 2.11 2.39 CDR (12 months) 2.08 1.50 1.40 2.76 2.67 1.83 Reactivity Assessment (Pass/Fail)* Borderline Pass Pass Fail Fail Borderline Phys. Property Assessment (Pass/Fail)** Borderline Pass Fail Fail Fail Borderline Maximum Dimensional Stability Value 2.49 6.93 8.94 2.49 2.31 — Minor changes impact properties --> formulation sensitivity (lack of robustness). *CDR < 2 - Pass; 2 < CDR < 2.5 - Borderline; CDR > 2.5 - Fail **To pass, density cannot exceed past +/−0.5 pcf of initial, R-value must be above 5.5, closed cell content > 85%, compression > 10 psi, dimensional stability < +/−7%

TABLE-US-00009 TABLE #3 (Expanded Polyol Testing) Polyol Swap A-4 PI-1 PI-2 PI-3 PI-4 PI-5 PI-6 F-1 OH # % % % % % % % % Polyol(s) PS-2352/COIM 4404 240 35.50 — — — — — — — TB-350 350 15.30 — — — — — — — PS-1752 240 — 16.00 — 16.50 — — — — PS-3152 321 — 38.50 — — — — — — Isoexter 3061-US 315 — — 37.80 38.00 — — — — Stepanpol ® PC 2011-225 225 — — 11.50 — — — 24.50 — Stepanpol ® PDP-70 70 — — 5.00 — — — — — SG-360 360 — — — — 38.00 — — 42.20 Poly-G 20-112 112 — — — — 16.50 17.00 — 24.50 Poly-G 30-168 168 — — — — — 23.30 — — Poly-G 37-600 600 — — — — — 14.30 — — PS-3422 350 — — — — — — 29.80 — Plasticizer TCPP 0 36.60 36.60 36.60 36.60 3.60 36.60 36.60 21.00 Flame Retardant PHT4-Diol 218 5.00 — — — — — — — Surfactant(s) B8870 60 2.00 3.00 3.00 3.00 3.00 3.00 3.00 — L-31 103 1.0 — — — — — — — B8465 0 — — — — — — — — Surfonic N-95 88 — — — — — — — — Catalyst(s) Dabco ® K-15 (KC) 271 — — — — — — — — Dabco ® T-120/PC3014 0 0.80 0.90 0.90 0.90 0.90 0.80 0.90 0.10 Dabco ® TMR-20 (KC) 850 0.80 1.35 1.35 1.35 1.35 1.20 1.35 0.15 Other Additive(s) Water 6233 1.50 1.80 1.80 1.80 1.80 1.80 1.80 2.0 Glycerin 1829 1.50 1.85 2.05 1.85 1.85 2.05 2.05 4.0 Compares directly to: A-1 NB-1 NB-1 NB-1 NB-1 NB-1 NB-1 P-4 T-120:PC ratio 1:1 2:3 2:3 2:3 2:3 2:3 2:3 2:3 CDR (6 months) 1.90 1.57 1.28 0.88 0.84 1.09 1.23 1.20 CDR (12 months) 1.38 1.78 1.33 1.04 1.13 1.13 1.53 N/A Reactivity Assessment (Pass/Fail)* Pass Pass Pass Pass Pass Pass Pass Pass Phys. Property Assessment (Pass/Fail)** Pass Pass Fail Fail Pass Fail Pass Pass Maximum Dimensional Stability Value 4.56 2.15 −2.14 1.02 0.87 −4.52 1.76 — E17-1 E17-3 E31-3 OH # % % % Polyol(s) PS-2352/COIM 4404 240 — — — TB-350 350 37.00 37.70 — PS-1752 240 14.50 14.25 12.05 PS-3152 321 — — — Isoexter 3061-US 315 — — 39.00 Stepanpol ® PC 2011-225 225 — — — Stepanpol ® PDP-70 70 — — — SG-360 360 — — — Poly-G 20-112 112 — — — Poly-G 30-168 168 — — — Poly-G 37-600 600 — — — PS-3422 350 — — — Plasticizer TCPP 0 40.50 40.50 40.50 Flame Retardant PHT4-Diol 218 3.00 3.00 3.00 Surfactant(s) B8870 60 2.00 3.00 3.00 L-31 103 — — — B8465 0 — — — Surfonic N-95 88 — — — Catalyst(s) Dabco ® K-15 (KC) 271 — — — Dabco ® T-120/PC3014 0 0.60 0.45 0.60 Dabco ® TMR-20 (KC) 850 0.90 0.60 0.90 Polycat ® 12 0 0.10 0.10 0.10 Other Additive(s) Water 6233 1.55 1.55 1.55 Glycerin 1829 1.85 1.85 2.30 Compares directly to: T-1 E17-1 PI-3 T-120:PC ratio 0.67 0.75 0.67 CDR (6 months) 1.40 1.46 1.27 CDR (12 months) 1.85 1.67 1.69 Reactivity Assessment (Pass/Fail)* Pass Pass Pass Phys. Property Assessment (Pass/Fail)** Pass Pass Pass Maximum Dimensional Stability Value 4.81 3.14 4.76 Tertiary Amine Addition T-1 T-2 T-3 T-4 T-5 T-6 T-7 OH # % % % % % % % Polyol(s) PS-2352/COIM 4404 240 19.60 19.50 19.50 19.50 19.30 19.30 — TB-350 350 35.10 35.20 35.20 35.20 35.20 35.00 — SG-360 360 36.00 Poly-G 20-112 112 13.85 Poly-G 30-168 168 — — — — — — — Poly-G 37-600 600 — — — — — — — PS-3422 350 — — — — — — — Plasticizer TCPP 0 36.60 36.60 36.60 36.60 36.60 36.60 36.60 Flame Retardant PHT4-Diol 218 — — — — — — 5.00 Surfactant(s) B8870 60 3.00 3.00 3.00 3.00 3.00 3.00 33.00 L-31 103 — — — — — — — B8465 0 — — — — — — — Surfonic N-95 88 — — — — — — — Catalyst(s) Dabco ® K-15 (KC) 271 — — — — — — — Dabco ® T-120/PC3014 0 0.85 0.80 0.70 0.50 0.85 0.80 0.90 Dabco ® TMR-20 (KC) 850 1.20 1.20 1.05 0.75 1.25 1.20 1.20 Polycat ® 12 0 0.10 0.25 0.50 1.00 — — 0.10 DMDEE 0 — — — — 0.35 0.70 — Other Additive(s) Water 6233 1.65 1.65 1.65 1.65 1.65 1.65 1.50 Glycerin 1829 1.80 1.80 1.80 1.80 1.80 1.80 1.85 Compares directly to: NB-1 NB-1 NB-1 NB-1 NB-1 NB-1 P-4 T-120:PC ratio 0.71 0.67 0.67 0.67 0.68 0.67 0.75 CDR (6 months) 1.53 2.23 — 2.25 — 2.26 1.54 CDR (12 months) 1.88 3.00 3.38 — 2.61 4.21 N/A Reactivity Assessment (Pass/Fail)* Pass Pass Pass Borderline Fail Fail Pass Phys. Property Assessment (Pass/Fail)** Pass Fail Fail Fail Fail Fail Pass Maximum Dimensional Stability Value 4.85 1.23 4.45 6.41 — — −0.75 *CDR < 2 - Pass; 2 < CDR < 2.5 - Borderline; CDR > 2.5 - Fail **To pass, density cannot exceed past +/−0.5 pcf of initial, R-value must be above 5.5, closed cell content > 85%, compression > 10 psi, dimensional stability < +/−7%

[0072] As illustrated in the table, minor changes impact properties which is indicative of formulation sensitivity (lack of robustness).

[0073] As illustrated in FIG. 3, higher ratios of T-120 work to the detriment of dimensional stability.

[0074] As seen in FIG. 4, All formulas PI-1 through PI-6 pass reactivity stability (CDR<2.0).

[0075] Higher ratios of T-120:potassium-containing catalyst harms dimensional stability. Using only a T-120 catalyst merits obscene dimensional stability results. Using only TMR-20 as the system catalyst does not yield passing insulation properties, nor does it come close to desired reactivity rates (though it does pass dimensional stability).

[0076] This is an extremely sensitive catalyst package: decreasing the ratio of tin catalyst (T-120) to potassium catalyst (K-15, TMR-20) increases CDR and reduces reactivity stability. The selection of potassium catalyst can and does affect CDR. For these formulas, TMR-20 seems to be more stable than K-15 at similar catalyst ratios.

[0077] Glycerine seems to enhance formula reactivity stability over time. Polyol ratios are important, noting that PS-2352 contains some amine, for instance. The selection of polyols can and do significantly change physical properties, physical property drift, and reaction mechanics.

[0078] A series of physical properties for the polyurethanes using the various combination of catalysts above will now be summarized.

TABLE-US-00010 TABLE #4 Physical Properties Characterization 6 9 12 Initial 3 months months months months Δ KB-1 Gel 26 40 55 — 74 48 Tack 40 70 105 — 186 146 A/B 1.17 1.14 1.11 — 1.09 0.08 Pcf 1.94 2.05 2.17 — 2.15 0.23 R 6.64 6.37 6.33 — 5.8 0.84 II comp. 16.43 18.47 16.99 — 16.91 2.04 % CCC 95.17 95.02 93.01 — — 2.16 Dim Stab. 3.64 2.69 — — — CDR 1.00 1.53 2.12 — 2.85 YB-1 Gel 23 — 45 — 69 46 Tack 32 — 71 — 95 63 A/B 1.04 — 1.23 — 0.87 0.36 pcf 2.06 — 2.15 — 2.11 0.09 R 6.93 — 6.39 — — 0.54 II comp. 19.88 — 22.85 — — 2.97 % CCC 94.51 — 96.01 — — 1.5 Dim Stab. 4.33 — — — — CDR 1.00 — 1.96 — 3.00 KB-2 Gel 19 25 37 45 46 27 Tack 30 32 54 67 66 37 A/B 1.12 1.1 1.06 1.03 1.03 0.09 pcf 1.85 2.01 2.14 2.08 2.15 0.3 R 6.73 6.61 6.60 6.45 6.15 0.58 II comp. 11.38 17.01 16.83 17.91 16.7 6.53 % CCC 96.8 97.09 95.69 94.21 95.89 2.88 Dim Stab. 4.07 3.20 4.76 — 4.50 CDR 1.00 1.32 1.95 2.37 2.42 YB-2 Gel 18 — 22 — 33 15 Tack 23 — 29 — 43 20 A/B 1.04 — 1.08 — 1.03 0.05 pcf 1.84 — 2.12 — 2.14 0.3 R 6.92 — 6.51 — 6.41 0.51 II comp. 10.15 — 13.51 — 11.93 3.36 % CCC 94.96 — 94.93 — 94.21 0.75 Dim Stab. 3.24 — 2.16 — 4.27 CDR 1.00 — 1.22 — 1.83 YB-3 Gel 23 21 21 19 22 4 Tack 30 30 29 24 40 16 A/B 0.9 0.93 0.99 0.96 0.92 0.09 pcf 2.14 2.5 2.55 2.63 — 0.49 R 6.72 7.12 7.18 6.81 — 0.46 II comp. 8.39 9.18 12.82 11.27 — 4.43 % CCC 81.08 91.81 90.16 91.36 — 10.73 Dim Stab. — — — 37.42 — CDR 1.00 0.70 0.70 0.63 0.73 YB-4 Gel 108 120 105 105 140 35 Tack 125 138 130 135 160 35 A/B 1.23 0.95 1.01 1.12 1.06 0.28 pcf 1.63 1.89 1.8 1.72 1.82 0.26 R 4.32 4.58 4.22 4.43 4.21 0.37 II comp. 14.74 10.8 14.42 13.87 14.78 3.98 % CCC 23.77 11.38 14.57 21.12 31.17 19.79 Dim Stab. −1.01 2.09 — — — CDR 1.00 1.11 0.97 0.97 1.30 NB-1 Gel 18 23 27 34 17 Tack 22 30 38 50 28 A/B 1.09 1.09 1.04 0.96 0.14 pcf 1.83 2.07 2.03 2.19 0.37 R 6.56 6.64 6.51 6.35 0.29 II comp. 17.6 21.0 15.9 16.0 5.10 % CCC 94.3 99.4 93.3 93.6 6.13 Dim Stab. 2.53 1.92 5.37 6.10 CDR 1.00 1.31 1.54 1.94 A-5 Gel 25 36 46 — 52 27 Tack 30 72 92 — 123 93 A/B 1.16 1.1 1.24 — 1.13 0.14 pcf 2.15 2.47 2.49 — 2.49 0.34 R 6.67 6.29 6.13 — 6.02 0.65 II comp. 15.12 18.1 21.3 — — 6.18 % CCC 92.98 89.42 92.5 — 90.7 3.56 Dim Stab. 1.93 1.71 −1.51 — 2.49 CDR 1.00 1.44 1.84 — 2.08 A-2 Gel 18 22 30 30 27 12 Tack 23 35 44 47 36 24 A/B 1.07 1.26 1.08 1.10 0.94 0.32 pcf 2.02 2.32 2.33 2.44 2.27 0.42 R 6.68 6.62 6.23 6.08 5.91 0.77 II comp. 13.67 22.74 15.44 16.64 15.01 9.07 % CCC 93.18 94.16 93.60 92.47 97.30 4.83 Dim Stab. 5.17 3.05 6.93 5.63 — CDR 1.00 1.22 1.67 1.67 1.50 A-1 Gel 20 21 30 30 28 10 Tack 26 30 45 46 40 20 A/B 1.08 1.11 1.10 1.12 1.01 0.11 pcf 2.09 2.22 2.35 2.41 2.39 0.32 R 6.53 6.64 6.40 6.41 6.14 0.5 II comp. 13.57 17.38 15.31 17.08 15.89 3.81 % CCC 92.99 94.48 92.33 94.12 93.82 2.15 Dim Stab. 5.66 8.94 6.06 5.74 — CDR 1.00 1.05 1.50 1.50 1.40 A-4 Gel 21 28 40 33 29 19 Tack 48 60 98 78 54 50 A/B 1.19 1.26 1.28 1.19 1.30 0.11 pcf 2.13 2.43 2.61 2.50 2.60 0.48 R 6.66 6.42 6.35 6.19 5.79 0.87 II comp. 24.75 24.08 24.29 26.14 24.49 2.06 % CCC 93.32 95.24 94.97 94.66 92.87 2.37 Dim Stab. 3.14 4.56 2.43 1.78 — CDR 1.00 1.33 1.90 1.57 1.38 T-1 Gel 17 22 26 — 32 15 Tack 23 31 32 — 43 20 A/B 1.08 0.97 0.97 — 0.92 0.16 pcf 1.85 2.06 2.09 — 2.19 0.34 R 6.43 6.86 6.61 — 6.65 0.43 II comp. 13.93 14.09 14.3 — 12.37 1.93 % CCC 97.65 94.12 97.77 — 97.26 3.65 Dim Stab. — — 4.85 — 4.25 CDR 1.00 1.29 1.53 — 1.88 T-2 Gel 13 20 29 40 39 27 Tack 18 27 39 65 55 47 A/B 1.13 0.7 1.05 1.08 1.07 0.43 pcf 1.99 — 2.07 2.00 2.09 0.1 R 6.67 — 6.6 — — 0.07 II comp. 16.29 — 22.8 — — 6.51 % CCC 96.82 — 96.38 — — 0.44 Dim Stab. 1.23 — — — — CDR 1.00 1.54 2.23 3.08 3 T-3 Gel 13 25 — 40 44 31 Tack 19 44 — 63 62 44 A/B 1.25 1.18 — 1.16 1.00 0.25 pcf 2.06 1.94 — 2.07 2.22 0.28 R 6.58 6.47 — — — 0.11 II comp. 17.51 23.34 — — — 5.83 % CCC 95.62 92.29 — — — 3.33 Dim Stab. 2 4.45 — — — 2.45 CDR 1.00 1.92 — 3.08 3.38 T-5 Gel 18 24 — — 47 29 Tack 25 28 — — 84 59 A/B 1.14 0.98 — — 1.08 0.16 pcf 1.9 1.99 — — 2.20 0.3 R 6.7 5.3 — — — 1.4 II comp. 19.33 19.82 — — 13.54 6.28 % CCC 98.05 97.51 — — 90.24 7.81 Dim Stab. — — — — — CDR 1.00 1.33 — — 2.61 T-6 Gel 19 26 43 — 80 61 Tack 28 35 57 — 145 117 A/B 1.13 1.09 1.01 — 0.97 0.16 pcf 1.97 2.06 2.09 — 2.41 0.44 R 6.7 4.94 — — — 1.76 II comp. 18.86 24.89 — — 15.08 9.81 % CCC 98.03 99.07 — — 92.63 6.44 Dim Stab. — — — — — CDR 1.00 1.37 2.26 — 4.21 E17-1 Gel 20 25 28 34 37 17 Tack 25 32 38 45 52 27 A/B 1.01 0.95 0.96 1.03 0.81 0.22 pcf 2 2.18 2.2 2.23 2.44 0.44 R 6.72 6.6 6.45 6.22 6.65 0.5 II comp. 20.11 15.01 21.49 23.9 15.69 8.89 % CCC 96.29 96.1 97.65 96.3 90.08 7.57 Dim Stab. — 4.81 — — 4.1 CDR 1.00 1.25 1.40 1.70 1.85 E17-3 Gel 24 33 35 41 40 17 Tack 31 60 47 66 56 35 A/B 1 1.05 0.79 1.1 0.91 0.31 pcf 2.16 2.32 2.38 2.45 2.32 0.29 R 6.65 6.35 — 6.29 6.37 0.36 II comp. 23.46 22.59 16.75 33.06 23.35 16.31 % CCC 96.11 94.32 93.96 94.15 95.24 2.15 Dim Stab. — 3.14 — — — CDR .00 1.38 1.46 1.71 1.67 E31-3 Gel 26 29 33 35 44 18 Tack 40 37 43 49 57 20 A/B 1.15 1.1 1.17 1.01 0.9 0.26 pcf 1.99 2.08 2.12 2.14 2.48 0.49 R 6.47 6.39 6.39 6.67 6.51 0.28 II comp. 26.07 22.53 28.47 17.4 16.75 11.72 % CCC 96.48 95.93 97.33 94.47 92.62 4.71 Dim Stab. — 4.76 — — — CDR 1.00 1.12 1.27 1.35 1.69

[0079] Formulation F-1 is an all polyether polyol based polyurethane slow cure formulation as noted by the gel and tack times. As used in this application, slow cure means: a polyurethane foam which has an initial gel time of at least 50 seconds, more preferably of at least 60 seconds, and most preferably of at least 70 seconds; and an initial tack of at least 60 seconds, more preferably of at least 80 seconds, and most preferably of at least 100 seconds.

[0080] The addition of amine catalysts is within the scope of this invention as evidenced by formulations T-1 through T-7. However, the ratio of the catalysts still plays a role in whether the synthesized polyurethane will meet the targeted characteristics.

[0081] The best mode for carrying out the invention has been described for purposes of illustrating the best mode known to the applicant at the time. The examples are illustrative only and not meant to limit the invention, as measured by the scope and merit of the claims. The invention has been described with reference to preferred and alternate embodiments. Obviously, modifications and alterations will occur to others upon the reading and understanding of the specification. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.