Closed cell polyurethane foam spray additives for improving adhesion under low temperature conditions

Abstract

A spray polyurethane foam composition comprising the contact product of at least one polyisocyanate, at least one active hydrogen-containing compound, at least one blowing agent, and a catalyst composition.

Description

CLOSED CELL POLYURETHANE FOAM SPRAY ADDITIVES FOR IMPROVING ADHESION UNDER LOW TEMPERATURE CONDITIONSFIELD OF THE INVENTION

[0001] The field of invention is the composition and application of polyurethane additives useful for the production of insulating polyurethane spray foam produced with blowing agents containing a halogen and that improve adhesion of the polyurethane foam under low temperature conditions.BACKGROUND OF THE INVENTION

[0002] Polyurethane foam compositions are typically prepared by reacting an isocyanate and a premix which consists of isocyanate-reactive components such as a polyol. The premix optionally also contains other components such as water, flame retardants, blowing agents, foam-stabilizing surfactants, and catalysts to promote the reactions of isocyanate with polyol to make urethane, with water to make CO2and urea, and with excess isocyanate to make isocyanurate (trimer).

[0003] The blowing agent in the premix is usually a liquid or gas with a boiling point sufficiently low to be vaporized by the heat released during the polymerization reaction. Examples of blowing agents useful in the production of insulating polyurethane foam include but are not limited to hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), hydrofluorochloroolefins (HFCOs), hydrochlorofluorocarbons (HCFCs), formates, ketones such as acetone and hydrocarbons.

[0004] Unlike simple hydrocarbons, such as pentane, halogen containing molecules such as chrolofluorocarbons (CFOs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) are far less flammable and safer to use in foam production. However, they either harm the ozone layer or contribute to global warming in other ways. In contrast, HFOs are very efficient and environmentally friendly blowing agents with a much lower global warming potential (GWP). However, decomposition of HFO can happen in a polyol premix formulation having an amine catalyst. Considering the wide use of amine catalysts in polyurethane foam production, this has limited the use of HFOs.

[0005] The proper selection and combination of the components in the polyol premix and the isocyanate can be useful for the production of polyurethane spray foam and used in applications such as refrigerators, freezers, insulation panels, garage doors, entry doors, and other various applications where insulation is desired.

[0006] For some of these applications, the premix is stored for one day up to one year before being reacted with isocyanate to generate polyurethane foam. This is common in sprayfoam applications, where drums of polyol premix and isocyanate are shipped to field locations for on-site application.

[0007] Adhesion plays a critical role in spray polyurethane foam (SPF) as it determines the material's capacity to establish a robust and long-lasting bond with the substrate. The insulation system's overall performance and longevity greatly rely on proper adhesion. Several factors contribute to SPF adhesion, including the substrate type, surface preparation, and the quality of the SPF application.

[0008] A thorough understanding of adhesion principles and how to optimize the adhesion of SPF is crucial for contractors and builders aiming to achieve a successful insulation system that meets performance, safety, and environmental standards. Adhesion plays a significant role in determining the insulation value and overall energy efficiency of the building envelope. The efficiency of adhesion is influenced by the use of a blow-based catalyst composition. The amine catalyst composition can impact the adhesion of SPF to different substrates.

[0009] Common amine catalysts useful for the production of polyurethane foam include tertiary amines, such as N,N,N’,N”,N”-pentamethyldiethylenetriamine (available from Evonik as Polycat®-5) or 1 ,4-diazabicyclo[2.2.2]octane (available in solution from Evonik as Dabco®33LV) which are known to accelerate the urethane reaction promoting the formation of polyurethane polymers. However, tertiary amines are also known to react with halogen containing organic compounds causing deactivation of the tertiary amine catalysts resulting in a net decrease in the kinetics of the polymerization process.Reaction between tertiary amine and halogen containing organic compounds occurs more rapidly when the halogen atom is bound to an olefinic carbon because halogensubstituted olefins are susceptible to nucleophillic attack by tertiary amines. This results in a fast deactivation of the tertiary amine catalysts rendering the premix not active enough for reaction with the isocyanate. Deactivation of tertiary amine by reaction with halogen containing compounds can also occur in halogen containing aliphatic compounds via formation of a quaternary ammonium salt or dehydrohalogenation, bothpathways resulting in tertiary amine deactivation. One way to minimize the deactivation of the amine catalysts is by selecting tertiary amines with bulky substituents to minimize the nucleophillic character of the amine center reducing the kinetics of these decomposition processes. However, the limitation of this approach is that sterically hindered amines are also poor catalysts for the urethane reaction requiring high use levels of tertiary amines and in many instances large use levels of amines are not sufficient to achieve the desired reaction speed. Another common way to mitigate the deactivation of tertiary amine by these processes is by combining the tertiary amine catalyst with an organic carboxylic acid to produce a tertiary ammonium carboxylate salt. The disadvantage of this approach is that the salt is substantially less active than the free tertiary amine resulting in slow reaction rates that can impact both productivity and product quality. Thus, the present invention is directed tocompositions able to produce a spray polyurethane foam with improved adhesion.

[0010] US9000061 discloses a method to make pour in place polyurethane foam as well as polyol premixes comprising 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd) with one or more co-blowing agents. Some of the useful catalysts listed in the specification structurally related to the catalyst of the invention included N, N, N’, N”, N”- pentamethyltriethylenediamine and N, N, N’, N”, N”-pentaethyltriethylenediamine. The compound N, N, N’, N”, N”-pentamethyltriethylenediamine is commercially known as Polycat®-5 and as shown in Example 11 , excessive deterioration of the hydrofluoroolefin leads to deactivation of the catalyst and causes sagging of the polyurethane mass in spraying systems that have been aged for two weeks or more. The compound N, N, N’, N”, N”-pentamethyltriethylenediamine is considered a sterically hindered blowing catalyst. To solve the problem of catalyst deactivation observed when using Polycat®-5, full substitution of Me-groups for Ethyl-groups is suggested. However, this approach brings excessive steric hindrance and deactivation of the catalysts rendering it essentially ineffective even at high use levels. This is in part by the introduction of a relatively large alkyl group at the central nitrogen atom of the diethylene triamine backbone. Thus, on a related matter N, N”-diisopropyl-N, N’, N”- trimethyldiethylenetriamine is presented as an effective catalyst of this invention while the ethyl substituted analogue N, N”-diisopropyl-N, N’, N”-triethyldiethylenetriamine was completely ineffective as shown in Example 14. Furthermore, the reference is silent as it relates to adhesion properties of the preferred formulations.

[0011] US9453115 discloses polyurethane and polyisocyanurate foams as well as their preparation methods which included the use of polyol-based foaming mixtures containing hydrohaloolefin blowing agents in the presence of a catalyst which is an adduct of an amine and an organic acid. The inventive polyol premix composition contains a catalyst which is an adduct between an amine and an organic acid. Multiple examples of tertiary amines are considered but particularly important are the sterically hindered amine adducts with organic acids including carboxylic acids, dicarboxylic acids, phosphinic acids, phosphonic acids, sulfonic acids, etc. The stabilization of the polyol premix containing the hydrohaloolefin is given by virtue of reducing the overall alkalinity of the premix with an acid. The limitation of this approach is that the use of acids in the presence of tertiary amine catalysts substantially reduces their ability to promote the polymerization process. Also, tertiary amine salts are typically insoluble or have tendency to precipitate from liquid mixtures making the process of foam making more difficult. In addition, many of the acids utilized are corrosive and can induce damage of mechanical equipment. Furthermore, the reference is silent as it relates to adhesion properties of the preferred formulations.

[0012] US9051442 discloses a method to make polyurethane foam and in particular closed cell rigid polyurethane foam made with a polyol premix which comprises a combination of a hydrohaloolefin physical blowing agent, a polyol, a silicone surfactant and a non-amine catalyst used alone or in combination with an amine catalyst. The foam is characterized by a fine and uniform cell structure and little or no foam collapse. The disclosure teaches that amines that are relatively stable with hydrohaloolefins are generally not sufficiently active to provide the necessary foam reactivity. The disclosure also teaches that there is a large number of amine catalysts that can be identified as sufficiently active to produce acceptable foam reactivity but that these catalysts are not suitable for use with hydrohaloolefins due to the formation of fluoride ion. Because of this limitation a catalyst system comprising at least a first metal and at least a second metal and at least one amine catalyst with a pKa of no less than ten is suggested as a plausible solution to this problem, where the at least first metal and the at least second metal are typically bismuth nitrate, lead 2-ethylhexanoate, lead benzoate, lead naphthanate, ferric chloride, antimony trichloride, antimony glycolate, tin salts of carboxylic acids, dialkyl tin salts of carboxylic acids, potassium acetate, potassium octoate, potassium 2-ethylhexanoate, potassium salts of carboxylic acids, zinc salts of carboxylic acids, zinc 2-ethylhexanoate, glycine salts, dibutyltin dilaureate, sodium N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate, tin(ll) 2-ethylhexanoate and combinations thereof. The limitation in this approach is the introduction of heavy metals many of which are toxic or hydrolytically unstable or in the case of the alkali metal salts of carboxylic acid induction of other reactions such as trimerization to form polyisocyanurates makes the processing aspect more difficult because there is not an easy way to balance the gelling and blowing reaction processes thereby compromising the final properties of the polyurethane product. Furthermore, the reference is silent as it relates to adhesion properties of the preferred formulations.

[0013] US9133306 discloses a polymeric amine composition having a multiplicity of tertiary amine groups and a method to make the composition. The composition is used as an amine-epoxy curing agent or alternatively as a chain extender or catalyst in polyurethane applications. The disclosure does not teach and does not show how any particular combination within the genus of the disclosure could be used in hydrohaloolefins-polyol premixes and systems. Furthermore, the preferred compositions having primary and secondary amine groups are expected to react very rapidly with hydrohaloolefins. Furthermore, the reference is silent as it relates to adhesion properties of the preferred formulations.

[0014] US2015 / 0197614A1 discloses a polyol premix composition which includes a blowing agent having a halogenated hydrohalolefin, a polyol, a catalyst composition and an antioxidant. The role of the antioxidant is to stabilize the hydrohaloolefin when present in the system together with amine catalyst. The presence of the antioxidant helps enable to some extent the use of tertiary amine catalysts that otherwise would lead to system deactivation. This approach nevertheless requires a substantial amount of antioxidant which does not play any other functional role in the polyurethane process. This approach also requires substantial amounts of antioxidants to have a positive impact on foam kinetics after ageing and it does not address the question regarding the structural requirements that a catalyst needs to meet to function in these haloolefin containing premixes. Furthermore, the reference is silent as it relates to adhesion properties of the preferred formulations.

[0015] US2016 / 0130416A1 discloses a stable polyol premix composition comprising hydrohaloolefin blowing agent, a polyol, a surfactant, and a catalyst composition comprising a substituted imidazole having a C2or greater substitution at the N1 nitrogen atom. The reference is silent as it relates to adhesion properties of the preferred compositions.

[0016] JP2014105288 discloses a composition for polyurethane foam manufacturing including tertiary amine catalysts comprising an amine compound represented by the general formula RiR2N-(CH2)m-[X-(CH2)n-]-Z where Ri and R2are each independently an alkyl or hydroxyalkyl group having 2 to 8 carbon atoms and where Z represents -OH or - NR3R4 and X is -O- or -NR5- where R3and R4represents an alkyl or hydroxyalkyl group having 2-8 carbon atoms where R5represents an alkyl or hydroxyalkyl having 2 to 8 carbon atoms. Because the smallest substituent in this composition is essentially an ethyl group, the steric hindrance around the nitrogen atoms is too excessive to provide sufficient catalytic activity to make these compounds useful in foam applications. Thus, these compounds can provide stable hydrohaloolefin-polyol stable systems but the catalytic activity will be insufficient even at very high use levels as illustrated in example 14 in the experimental section. Furthermore, the reference is silent as it relates to adhesion properties of the preferred formulations.

[0017] Thus, there is a need in the art for making polyurethane foam using low GWP blowing agents such as hydrohaloolefins with catalysts that are able to provide sufficient adhesion. The compositions presented in this invention can offer the right balance for making foam even in applications where high foam speed rise is needed (spray foam, for example) without sacrificing the adhesion of the foam.BRIEF SUMMARY OF THE INVENTION

[0018] The instant invention can solve problems associated with conventional insulating polyurethane spray foam produced with blowing agents containing a halogen by allowing the use of the inventive catalyst composition thereby improving adhesion of the polyurethane foam under low temperature conditions.

[0019] In one preferred embodiment, the spray polyurethane foam composition comprises a catalyst composition comprising at least one compound selected from the group consisting of N, N”-diethyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dipropyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-diisopropyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-dibutyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”- diisobutyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-disecbutyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-ditertbutyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dipentyl-N, N’, NMrimethyl(diethylenetriamine); N, N”-diisopentyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-ditertpentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dineopentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-disecpentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-di(3-pentyl)-N, N’, N”-trimethyl(diethylenetriamine); N, N”-disecisopentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dihexyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-diisohexyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dineohexyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”’-diethyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dipropyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisopropyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dibutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisobutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecbutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-ditertbutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dipentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-ditertpentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dineopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecpentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-di(3-pentyl)-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecisopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dihexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisohexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dineohexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”-diethyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dipropyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisopropyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-dibutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisobutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecbutyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-ditertbutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dipentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisopentyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-ditertpentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dineopentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecpentyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-di(3-pentyl)-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecisopentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dihexyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-diisohexyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dineohexyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”’-diethyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dipropyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisopropyl-N, N’, N”,N”’-tetramethyl(tripropylenetetraamine); N, N”’-dibutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisobutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecbutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-ditertbutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dipentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-ditertpentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dineopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecpentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-di(3-pentyl)-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecisopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dihexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisohexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); and N, N”’-dineohexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine), in combination with at least one tertiary amine catalyst component selected from the group consisting of diazobicyclooctane (triethylenediamine), 1 ,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, 2, 2'- dimorpholinodiethyl ether, N-methylimidazole, 1 ,2-dimethylimidazole, 1 -ethylimidazole, N-methylmorpholine, N-ethylmorpholine, and N-cetylmorpholine.

[0020] In another preferred embodiment, the spray polyurethane foam composition comprises a catalyst composition comprising at least one compound selected from the group consisting of N, N’-diethyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dipropyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-diisopropyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dibutyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-diisobutyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-disecbutyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’- ditertbutyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dipentyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-dibutyl-N, N’-diisopentyl-bis(aminoethyl)ether; N, N’- ditertpentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dineopentyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-disecpentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-di(3- pentyl)-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-disecisopentyl -N, N’-dimethyl- bis(aminoethyl)ether; N, N’-dihexyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-diisohexyl- N, N’-dimethyl-bis(aminoethyl)ether; and N, N’-dineohexyl-N, N’-dimethyl- bis(aminoethyl)ether, in combination with at least one tertiary amine catalyst componentselected from the group consisting of diazobicyclooctane (triethylenediamine), 1 ,8- diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, 2, 2'- dimorpholinodiethyl ether, N-methylimidazole, 1 ,2-dimethylimidazole, 1 -ethylimidazole, N-methylmorpholine, N-ethylmorpholine, and N-cetylmorpholine.

[0021] Other features and advantages of the present invention will be apparent from the following more detailed description of the preferred embodiment.BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Fig. 1 shows the reactivity for the samples in example 1 .

[0023] Fig. 2 shows the reactivity for the samples in example 7.

[0024] Fig. 3 shows the three test substrates of example 7- OSB wood, steel, and cement.

[0025] Fig. 4 shows the adhesion testing on the OSB-wood substrate.

[0026] Fig. 5 shows the reactivity for the samples in example 9.

[0027] Fig. 6 shows the foam samples of example 10 over a four week period.

[0028] Fig. 7 shows the reactivity for the samples in example 10.DEFINITIONS

[0029] The following definitions are provided in order to aid those skilled in the art in understanding the detailed description of the present invention.PUR - Polyurethane.Isocyanate Index - The actual amount of polyisocyanate used divided by the theoretically required stoichiometric amount of polyisocyanate required to react with all the active hydrogen in the reaction mixture, multiplied by 100. Also known as (Eq NCO / Eq of active hydrogen)x100. pphp - parts by weight per hundred weight parts polyol.Polycat®-5 - A commercial catalyst supplied by Evonik Corporation with a chemical name pentamethyldiethylenetriamine HFO - hydrofluoroolefinDETAILED DESCRIPTION OF THE INVENTION

[0030] The present invention is directed to a spray polyurethane foam composition comprising the contact product of at least one polyisocyanate, at least one active hydrogen-containing compound, at least one blowing agent, and a catalyst composition.

[0031] In one preferred embodiment, the spray polyurethane foam composition comprises a catalyst composition comprising at least one compound selected from the group consisting of N, N”-diethyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dipropyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-diisopropyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-dibutyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”- diisobutyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-disecbutyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-ditertbutyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dipentyl-N, N’, NMrimethyl(diethylenetriamine); N, N”-diisopentyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-ditertpentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dineopentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-disecpentyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-di(3-pentyl)-N, N’, N”-trimethyl(diethylenetriamine); N, N”-disecisopentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dihexyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-diisohexyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dineohexyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”’-diethyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dipropyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisopropyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dibutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisobutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecbutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-ditertbutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dipentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-ditertpentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dineopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecpentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-di(3-pentyl)-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecisopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dihexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisohexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dineohexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”-diethyl-N, N’, N”-trimethyl(dipropylenetriamine);N, N”-dipropyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisopropyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-dibutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisobutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecbutyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-ditertbutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dipentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisopentyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-ditertpentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dineopentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecpentyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-di(3-pentyl)-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecisopentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dihexyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-diisohexyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dineohexyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”’-diethyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dipropyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisopropyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dibutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisobutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecbutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-ditertbutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dipentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-ditertpentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dineopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecpentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-di(3-pentyl)-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecisopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dihexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisohexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); and N, N”’-dineohexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine), in combination with at least one tertiary amine catalyst component selected from the group consisting of diazobicyclooctane (triethylenediamine), 1 ,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, 2, 2'- dimorpholinodiethyl ether, N-methylimidazole, 1 ,2-dimethylimidazole, 1 -ethylimidazole, N-methylmorpholine, N-ethylmorpholine, and N-cetylmorpholine.

[0032] In a preferred embodiment of the spray polyurethane foam composition, the catalyst composition comprises N, N”-diisopropyl-N, N’, N”-trimethyl(diethylenetriamine) and 1 ,2-dimethylimidazole.

[0033] In another preferred embodiment, the spray polyurethane foam composition comprises a catalyst composition comprising at least one compound selected from the group consisting of N, N’-diethyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dipropyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-diisopropyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dibutyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-diisobutyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-disecbutyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’- ditertbutyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dipentyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-dibutyl-N, N’-diisopentyl-bis(aminoethyl)ether; N, N’- ditertpentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dineopentyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-disecpentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-di(3- pentyl)-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-disecisopentyl -N, N’-dimethyl- bis(aminoethyl)ether; N, N’-dihexyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-diisohexyl- N, N’-dimethyl-bis(aminoethyl)ether; and N, N’-dineohexyl-N, N’-dimethyl- bis(aminoethyl)ether, in combination with at least one tertiary amine catalyst component selected from the group consisting of diazobicyclooctane (triethylenediamine), 1 ,8- diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, 2, 2'- dimorpholinodiethyl ether, N-methylimidazole, 1 ,2-dimethylimidazole, 1 -ethylimidazole, N-methylmorpholine, N-ethylmorpholine, and N-cetylmorpholine.

[0034] In a preferred embodiment of the spray polyurethane foam composition, the catalyst composition comprises N, N’-diisopropyl-N, N’-dimethyl-bis(aminoethyl)ether and 1 ,2-dimethylimidazole.

[0035] Also, the present invention in one embodiment provides a method for preparing a spray polyurethane foam which comprises contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of at least one blowing agent, and a catalyst composition.

[0036] In one preferred embodiment of the method, the catalyst composition comprises at least one compound selected from the group consisting of N, N”-diethyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-dipropyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-diisopropyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dibutyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-diisobutyl-N, N’, N”-trimethyl(diethylenetriamine); N,N”-disecbutyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-ditertbutyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-dipentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-diisopentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-ditertpentyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-dineopentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-disecpentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-di(3-pentyl)-N, N’, N”- trimethyl(diethylenetriamine); N, N”-disecisopentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dihexyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-diisohexyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-dineohexyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”’-diethyl-N, N’, N”,N”’-tetramethyl(triethylenetetraamine); N, N”’-dipropyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisopropyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dibutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisobutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecbutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-ditertbutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dipentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-ditertpentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dineopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecpentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-di(3-pentyl)-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecisopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dihexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisohexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dineohexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”-diethyl-N, N’, N”-trimethyl(dipropylenetriamine);N, N”-dipropyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisopropyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-dibutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisobutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecbutyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-ditertbutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dipentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisopentyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-ditertpentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dineopentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecpentyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-di(3-pentyl)-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecisopentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dihexyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisohexyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dineohexyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”’-diethyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dipropyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisopropyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dibutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisobutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecbutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-ditertbutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dipentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-ditertpentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dineopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecpentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-di(3-pentyl)-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecisopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dihexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisohexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); and N, N”’-dineohexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine), in combination with at least one tertiary amine catalyst component selected from the group consisting of diazobicyclooctane (triethylenediamine), 1 ,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, 2, 2'- dimorpholinodiethyl ether, N-methylimidazole, 1 ,2-dimethylimidazole, 1 -ethylimidazole, N-methylmorpholine, N-ethylmorpholine, and N-cetylmorpholine.

[0037] In a preferred embodiment of the method, the catalyst composition comprises N, N”-diisopropyl-N, N’, N”-trimethyl(diethylenetriamine) and 1 ,2-dimethylimidazole.

[0038] In another preferred embodiment of the method, the catalyst composition comprises at least one compound selected from the group consisting of N, N’-diethyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dipropyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-diisopropyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dibutyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-diisobutyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’- disecbutyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-ditertbutyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-dipentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dibutyl-N, N’-diisopentyl-bis(aminoethyl)ether; N, N’-ditertpentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dineopentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’- disecpentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-di(3-pentyl)-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-disecisoopentyl -N, N’-dimethyl-bis(aminoethyl)ether; N, N’- dihexyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-diisohexyl-N, N’-dimethyl- bis(aminoethyl)ether; and N, N’-dineohexyl-N, N’-dimethyl-bis(aminoethyl)ether, in combination with at least one tertiary amine catalyst component selected from the group consisting of diazobicyclooctane (triethylenediamine), 1 ,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, 2, 2'-dimorpholinodiethyl ether, N- methylimidazole, 1 ,2-dimethylimidazole, 1 -ethylimidazole, N-methylmorpholine, N- ethylmorpholine, and N-cetylmorpholine.

[0039] In a preferred embodiment of the method, the catalyst composition comprises N’-diisopropyl-N, N’-dimethyl-bis(aminoethyl)ether and 1 ,2-dimethylimidazole.

[0040] Several types of ranges are disclosed in the present invention. These include, but are not limited to, a range of temperatures; a range of number of atoms; a range of foam density; a range of Isocyanate Index; and a range of pphp for the blowing agent, water, surfactant, flame retardant, and catalyst composition. Each possible number that such a range could reasonably encompass, as well as any sub-ranges and combinations of sub-ranges encompassed therein are the subject of the present invention.

[0041] For example, the parts by weight of the catalyst composition per hundred weight parts of the at least one active hydrogen-containing compound in a composition or a foam formulation. If the at least one active hydrogen-containing compound is an at least one polyol, the parts by weight per hundred weight parts polyol is abbreviated as pphp. Hence, by the disclosure that the catalyst composition is present in an amount from about 0.05 to about 10 pphp, for example, the pphp can be selected from about 0.05, about 0.06, about 0.07, about 0.08, about 0.09, about 0.1 , about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1 , about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10. Likewise, all other ranges disclosed herein should be interpreted in a manner similar to this example.

[0042] Any individual members of any such group, including any sub-ranges or combinations of sub-ranges within the group may be excluded. Further, any individual substituents, analogs, compounds, ligands, structures, or groups thereof, or any members of a claimed group may be excluded.

[0043] The catalyst compositions can be used to make close celled spray foam having desirable physical properties including dimensional stability, adhesion, friability, thermal insulation and compression strengths. In a further aspect, the catalyst compositions can be used to make spray foams having a density of about 0.5 lb / ft3to about 5 lb / ft3, about 1 lb / ft3to about 4 lb / ft3and in some cases about 2 lb / ft3to about 3 lb / ft3. Density can be measured in accordance with ASTM D3574 Test A.

[0044] In another preferred embodiment, the tertiary amine catalyst component further comprises a volatile blowing catalyst selected from the group consisting of bisdimethylaminoethyl ether, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine and related compositions, higher permethylated polyamines, 2-[N-(dimethylaminoethoxyethyl)-N- methylamino]ethanol and related structures, alkoxylated polyamines, imidazole-boron compositions, amino propyl-bis(amino-ethyl) ether compositions, or combinations thereof.

[0045] In another preferred embodiment, the catalyst composition can also preferably be acid blocked with an acid including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic), sulfonic acids or any other organic or inorganic acid. Examples of preferable carboxylic acids include mono-acids, di-acids or poly-acids with or without isocyanate reactive groups. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, salicylic acid and the like. An acid blocked catalyst can be obtained by known methods using conventional equipment.

[0046] In another preferred embodiment, the tertiary amine catalyst component is used in conjunction with a metal catalyst. For example, in one embodiment, the tertiary amine catalyst component is preferably used with an organotin compound, tin(ll) carboxylate salts, bismuth(lll) carboxylate salts, or combinations thereof. Examples of preferable transition metal catalysts such as organotin compounds or bismuth carboxylates can comprise at least one member selected from the group consisting of dibutylin dilaureate,dimethyltin dilaureate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilaurylmercaptide, dibutyltin dilaurylmercaptide, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin bi(2-ethylhexyl mercaptacetate), dibutyltin bi(2-ethylhexyl mercaptacetate), stannous octate, other suitable organotin catalysts, or a combination thereof. Other metals can also be included, such as, for example, bismuth (Bi). Suitable bismuth carboxylate salts preferably include salts of pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, and other suitable carboxylic acids. Other metal salts of of lead (Pb), iron (Fe), zinc (Zn) with pentanoic acid, neopentanoic acid, hexanoic acid, 2- ethylhexyl carboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids may also be included.

[0047] The catalyst composition can be produced, for example, by following these steps; Step 1 : reacting a mixture of polyalkylene polyamine with a corresponding ketone in a stainless steel reactor equipped with mechanical stirrer, heating mantle and cooling coil in the presence of 5% Pt / C that are charged into a stainless steel reactor. Next, the steel reactor is sealed and purged with nitrogen gas for three times followed by purging with hydrogen gas for three times while stirring. Then the reactor is heated to 120°C and the pressure of hydrogen gas is set at 800 psi until the hydrogen uptake finished and kept for an additional hour. The reactor is vented after cooling to room temperature. All volatiles are removed on a rotary evaporator under reduced pressure, and the product is collected as a mixture of material containing, in one aspect of the invention, di-alkylated polyalkylene polyamine; Step 2: placing the di-alkylated polyalkylene polyamine in a stainless steel reactor equipped with mechanical stirrer, heating mantle and cooling coil in the presence of 5% Pd / C that are charged into a stainless steel reactor. Formaldehyde 37 wt. % aqueous solution is charged into the high pressure syringe pump.Formaldehyde solution is fed from the pump into the reactor for about 2-3 hours until the methylation is completed. The reactor is vented after cooling to room temperature. All volatiles are removed on rotary evaporator under reduced pressure, and the product is collected as a mixture of material containing, in one aspect of the invention, di-alkylated permethylated polyalkylene polyamine.

[0048] In another preferred embodiment, the catalyst system or compositions of the present invention can further comprise other catalytic materials such as carboxylate salts in any amount. Preferably, the other catalytic materials are selected from alkali metal salts, alkaline earth metal salts, and quaternary ammonium carboxylate salts including, but are not limited to, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonante, potassium stearate, sodium octoate, lithium stearate, sodium caprioate, lithium octoate, 2- hydroxypropyltrimethylammonium octoate solution, and the like, or any combination thereof.

[0049] Preferably, the amount of the other catalytic materials and salts can range from about 0 pphp to about 20 pphp, about 0.1 pphp to about 15 pphp and in some cases about 0.5 pphp to about 10 pphp.

[0050] The term “contact product” is used herein to describe compositions wherein the components are contacted together in any order, in any manner, and for any length of time. For example, the components can be contacted by blending or mixing. Further, contacting of any component can occur in the presence or absence of any other component of the compositions or foam formulations described herein. Combining additional catalyst components can be done by any method known to one of skill in the art. For example, in one aspect of the present invention, catalyst compositions can be prepared by combining or contacting the catalyst composition as defined in Formula I with at least one tertiary amine having or not at least one isocyanate reactive group and optionally with an alkali metal carboxylate salt. This typically occurs in solution form.

[0051] While compositions and methods are described in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components or steps.POLYISOCYANATES

[0052] Polyisocyanates that are useful in the PIR / PUR foam formation process preferably include, but are not limited to, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyante, toluene diisocyanate (TDI), diphenyl methane diisocyanate isomers (MDI), hydrated MDI and 1 ,5-naphthalene diisocyanate. For example, 2,4-TDI, 2,6-TDI, and mixtures thereof, can be readily employed in the presentinvention. Other suitable mixtures of diisocyanates include, but are not limited to, those known in the art as crude MDI, or PAPI, which contain 4,4’-diphenylmethane diisocyanate along with other isomeric and analogous higher polyisocyanates. In another aspect of this invention, prepolymers of polyisocyanates comprising a partially pre-reacted mixture of polyisocyanates and polyether or polyester polyol are suitable. In still another aspect, the polyisocyanate comprises MDI, or consists essentially of MDI or mixtures of MDI’s.

[0053] This composition is useful, for example, in the formation of foam products for rigid and flame retardant applications, which usually require a high Isocyanate Index. As defined previously, Isocyanate Index is the actual amount of polyisocyanate used divided by the theoretically required stoichiometric amount of polyisocyanate required to react with all the active hydrogen in the reaction mixture, multiplied by 100. For purposes of the present invention, Isocyanate Index is represented by the equation: Isocyanate Index = (Eq NCO / Eq of active hydrogen)x100, wherein Eq NCO is the number of NCO functional groups in the polyisocyanate, and Eq of active hydrogen is the number of equivalent active hydrogen atoms.

[0054] Foam products which are produced with an Isocyanate Index from about 10 to about 800 are within the scope of this invention. In accordance with other aspects of the present invention, the Isocyanate Index ranges from about 20 to about 700, from about 30 to about 650, from about 50 to about 600, or from about 70 to about 500.POLYOLS

[0055] Active hydrogen-containing compounds for use with the foregoing polyisocyanates in forming the polyisocyanurate / polyurethane foams of this invention can be any of those organic compounds having at least two hydroxyl groups such as, for example, polyols. Polyols that are typically used in PIR / PUR foam formation processes include polyalkylene ether and polyester polyols. The polyalkylene ether polyol includes the poly(alkyleneoxide) polymers such as poly(ethyleneoxide) and poly(propyleneoxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols. These preferably include, but are not limited to, ethylene glycol, propylene glycol, 1 ,3-butane diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane, cyclohexane diol, and sugars such as sucrose and like low molecular weight polyols.

[0056] Amine polyether polyols can be used in the present invention. These can be prepared when an amine such as, for example, ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine, or triethanolamine is reacted with ethylene oxide or propylene oxide.

[0057] In another aspect of the present invention, a single high molecular weight polyether polyol, or a mixture of high molecular weight polyether polyols, such as mixtures of different multifunctional materials and / or different molecular weight or different chemical composition materials can be used.

[0058] In yet another aspect of the present invention, polyester polyols can be used, including those produced when a dicarboxylic acid is reacted with an excess of a diol. Non-limiting examples include adipic acid or phathalic acid or phthalic anhydride reacting with ethylene glycol or butanediol. Polyols useful in the present invention can be produced by reacting a lactone with an excess of a diol, for example, caprolactone reacted with propylene glycol. In a further aspect, active hydrogen-containing compounds such as polyester polyols and polyether polyols, and combinations thereof, are useful in the present invention.

[0059] The polyol can have an OH number of about 5 to about 600, about 100 to about 600 and in some cases about 50 to about 100. and a functionality of about 2 to about 8, about 3 to about 6 and in some cases about 4 to about 6.

[0060] The amount of each type of polyol can range from about 0 pphp to about 100 pphp about 10 pphp to about 90 pphp and in some cases about 20 pphp to about 80 PPhp.BLOWING AGENTS

[0061] In accordance with the compositions, foam formulations, and methods of producing PIR / PUR foam within the scope of the present invention, suitable blowing agents that can be used alone or in combination preferably include, but are not limited to, water, methylene chloride, acetone, hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs), hydrofluoroolefins (HFOs), chlorofluoroolefins (CFOs), hydrochloroolefins (HCOs), hydrofluorochloroolefins (HFCOs), hydrochlorofluorocarbons (HCFCs), chloroolefins, formates and hydrocarbons. Examples of HFCs include, but are not limited to, HFC-245fa, HFC-134a, and HFC-365; illustrative examples of HCFCs include, but are not limited to, HCFC-141 b, HCFC-22, and HCFC-123. Exemplary hydrocarbons include, but are not limited to, n-pentane, iso-pentane, cyclopentane, and the like, or anycombination thereof. In one aspect of the present invention, the blowing agent or mixture of blowing agents comprises at least one hydrocarbon. In another aspect, the blowing agent comprises n-pentane. Yet, in another aspect of the present invention, the blowing agent consists essentially of n-pentane or mixtures of n-pentane with one or more blowing agents. Examples of hydrohaloolefin blowing agents are HFO-1234ze (trans-1 ,3,3,3-Tetrafluoroprop-1-ene), HFO-1234yf (2,3,3, 3-Tetrafluoropropene) and HFCO-1233zd (1 -Propene, 1-chloro-3, 3, 3-trifluoro), among other HFOs.

[0062] The blowing agent component comprises a hydrohaloolefin, preferably comprising at least one of trans-HFO-1234ze and HFCO-1233zd., and optionally a hydrocarbon, fluorocarbon, chlorocarbon, fluorochlorocarbon, halogenated hydrocarbon, ether, fluorinated ether, ester, aldehyde, ketone, carbon dioxide generating material, or combinations thereof. The hydrohaloolefin preferably comprises at least one halooalkene such as a fluoroalkene or chloroalkene containing from 3 to 4 carbon atoms and at least one carbon-carbon double bond. Preferred hydrohaloolefins non-exclusively include trifluoropropenes, tetrafluoropropenes such as (HFO-1234), pentafluoropropenes such as (HFO-1225), chlorotrifloropropenes such as (HFO-1233), chlorodifluoro propenes, chlorotrifluoropropenes, chlorotetrafluoropropenes, and combinations of these. Other preferred blowing agents comprise the tetrafluoropropene, pentafluoropropene, and chlorotrifloropropene compounds in which the unsaturated terminal carbon has not more than one fluorine or chlorine substituent. Included are 1 ,3, 3, 3- tetrafluoropropene (HFO- 1234ze); 1 ,1 ,3,3-tetrafluoropropene; 1 ,2,3,3, 3-pentafluoropropene (HFO-1225ye); 1 ,1 ,1- trifluoropropene; 1 ,1 , 1 ,3, 3-pentafluoropropene (HFO 1225zc); 1 ,1 ,1 ,3,3,3-hexafluorobut- 2-ene, 1 ,1 , 2, 3, 3- pentafluoropropene (HFO-1225yc); 1 ,1 , 1 ,2, 3- pentafluoropropene (HFO-1225yez); 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd); 1 , 1 ,1 , 4,4,4- hexafluorobut-2-ene or combinations thereof, and any and all structural isomers, geometric isomers, or stereoisomers of each of these. Preferred optional blowing agents non-exclusively include water, formic acid, organic acids that produce carbon dioxide when they react with an isocyanate, hydrocarbons; ethers, halogenated ethers; pentafluorobutane; pentafluoropropane; hexafluoropropane; heptafluoropropane; trans- 1 ,2 dichloro-ethylene; methyl formate; 1 -chloro-1 ,2,2,2-tetrafluoroethane; 1 , 1 -dichloro-1 - fluoroethane; 1 ,1 ,1 ,2-tetrafluoroethane; 1 ,1 ,2,2-tetrafluoroethane; 1 -chloro-1 , 1- difluoroethane; 1 ,1 ,1 ,3,3-pentafluorobutane; 1 ,1 ,1 ,2,3,3,3-heptafluoropropane; trichlorofluoromethane; dichlorodifluoromethane; 1 ,1 , 1 ,3, 3, 3-hexafluoropropane; 1 ,1 ,1 ,2,3,3-hexafluoropropane; difluoromethane; difluoroethane; 1 ,1 ,1 ,3,3-pentafluoropropane; 1 ,1 -difluoroethane; isobutane; normal pentane; isopentane; cyclopentane, or combinations thereof. The blowing agent component is usually present in the polyol premix composition in an amount of from about 1 wt.% to about 30 wt.%, preferably from about 3 wt.% to about 25 wt.%, and more preferably from about 5 wt.% to about 25 wt.%, by weight of the polyol premix composition. When both a hydrohaloolefin and an optional blowing agent are present, the hydrohaloolefin component is usually present in the blowing agent component in an amount of from about 5 wt.% to about 90 wt.%, preferably from about 7 wt.% to about 80 wt.%, and more preferably from about 10 wt.% to about 70 wt.%, by weight of the blowing agent component; and the optional blowing agent is usually present in the blowing agent component in an amount of from about 95 wt. % to about 10 wt.%, preferably from about 93 wt.% to about 20 wt.%, and more preferably from about 90 wt.% to about 30 wt.%, by weight of the blowing agent component.

[0063] Due to the discovery that chlorofluorocarbons (CFCs) can deplete ozone in the stratosphere, this class of blowing agents is not desirable for use. A chlorofluorocarbon (CFC) is an alkane in which all hydrogen atoms are substituted with chlorine and fluorine atoms. Examples of CFCs include trichlorofluoromethane and dichlorodifluoromethane.

[0064] The amount of blowing agent used can vary based on, for example, the intended use and application of the foam product and the desired foam stiffness and density. In the compositions, foam formulations and methods for preparing a polyisocyanurate / polyurethane foam of the present invention, the blowing agent is present in amounts from about 5 to about 80 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound. In another aspect, the blowing agent is present in amounts from about 10 to about 60, from about 15 to about 50, or from about 20 to about 40, parts by weight per hundred weight parts of the at least one active hydrogen-containing compound. If the at least one active hydrogen-containing compound is an at least one polyol, the blowing agent is present in amounts from about 5 to about 80 parts by weight per hundred weight parts polyol (pphp), from about 10 to about 60 pphp, from about 15 to about 50 pphp, or from about 20 to about 40 pphp.

[0065] If water is present in the formulation, for use as a blowing agent or otherwise, water is present in amounts up to about 60 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound. Likewise, if the at least one active hydrogen-containing compound is an at least one polyol, water can range from 0to about 15 pphp. In another aspect, water can range from 0 to about 10 pphp, from 0 to about 8 pphp, from 0 to about 6 pphp, or from 0 to about 4 pphp.URETHANE CATALYST

[0066] In one preferred embodiment, conventional urethane catalysts having no isocyanate reactive group can preferably be employed to accelerate the reaction to form polyurethanes, and can be used as a further component of the catalyst systems and compositions of the present invention to produce polyisocyanurate / polyurethane foam. Urethane catalysts suitable for use herein preferably include, but are not limited to, metal salt catalysts, such as organotins, and amine compounds, such as triethylenediamine (TEDA), N-methylimidazole, 1 ,2-dimethyl-imidazole, N-methylmorpholine (commercially available as the DABCO® NMM catalyst), N-ethylmorpholine (commercially available as the DABCO® NEM catalyst), triethylamine (commercially available as the DABCO® TETN catalyst), N,N’-dimethylpiperazine, 1 ,3,5-tris(dimethylaminopropyl)hexahydrotriazine (commercially available as the Polycat® 41 catalyst), 2,4,6- tris(dimethylaminomethyl)phenol (commercially available as the DABCO TMR® 30 catalyst), N-methyldicyclohexylamine (commercially available as the Polycat® 12 catalyst), pentamethyldipropylene triamine (commercially available as the Polycat® 77 catalyst), N-methyl-N’-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyldiethylenetriamine (commercially available as the Polycat® 5 catalyst), hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexylamine (commercially available as the Polycat® 8 catalyst), pentamethyldipropylenetriamine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl)ether (commercially available as the DABCO® BL19 catalyst), tris(3-dimethylamino)- propylamine (commercially available as the Polycat® 9 catalyst), 1 ,8-diazabicyclo[5.4.0] undecene (commercially available as the DABCO® DBU catalyst) or its acid blocked derivatives, and the like, as well as any mixture thereof.

[0067] In another preferred embodiment, the present invention can be used with tertiary amine catalysts having isocyanate reactive groups. Preferably, the isocyanate reactive groups present in the tertiary amine gelling co-catalyst consist essentially of primary amine, secondary amine, secondary-hydroxyl group, amide and urea. Examples of gelling catalysts preferably include N,N-bis(3-dimethylamino-propyl)-N-(2- hydroxypropyl) amine; N,N-dimethyl-N’,N’-bis(2-hydroxypropyl)-1 ,3-propylenediamine; dimethylaminopropylamine (DMAPA); N-methyl-N-2-hydroxypropyl-piperazine,bis(dimethylaminopropyl)amine (POLYCAT® 15), dimethylaminopropylurea and N,N’- bis(3-dimethylaminopropyl) urea (DABCO® NE1060, DABCO® NE1070, DABCO® NE1080 and DABCO® NE1082), 1 ,3-bis(dimethylamino)-2-propanol, 6-dimethylamino- 1 -hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole, N,N’-bis(2- hydroxypropyl) piperazine, N-(2-hydroxypropyl)-morpholine, N-(2-hydroxyethylimidazole). Examples of blowing co-catalysts containing isocyanate reactive groups that can be used with the above mentioned gelling catalysts preferably include 2-[N- (dimethylaminoethoxyethyl)-N-methylamino]ethanol (DABCO® NE200), N,N,N’-trimethyl- N’-3-aminopropyl-bis(aminoethyl) ether (DABCO® NE300).

[0068] Suitable urethane catalysts that can be used in combination with the inventive catalyst preferably also include acid blocked tertiary amines with acids including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic), sulfonic acids or any other organic or inorganic acid. Examples of carboxylic acids preferably include mono-acids, di-acids or poly-acids with or without isocyanate reactive groups. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, salicylic acid and the like. An acid blocked catalyst can be obtained by known methods using conventional equipment.

[0069] In another preferred embodiment, the tertiary amine catalyst component can also be used in conjunction with a metal catalyst. For example, in one embodiment, the tertiary amine catalyst component is preferably used with an organotin compound, tin(ll) carboxylate salts, bismuth(lll) carboxylate salts, or combinations thereof. Preferable examples of transition metal catalysts such as organotin compounds or bismuth carboxylates can comprise at least one member selected from the group consisting of dibutylin dilaureate, dimethyltin dilaureate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilaurylmercaptide, dibutyltin dilaurylmercaptide, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin bi(2-ethylhexyl mercaptacetate), dibutyltin bi(2-ethylhexyl mercaptacetate), stannous octate, othersuitable organotin catalysts, or a combination thereof. Other metals can also be included, such as, for example, bismuth (Bi). Suitable bismuth carboxylate salts preferably include salts of pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, and other suitable carboxylic acids. Other salts of transition metals of lead (Pb), iron (Fe), zinc (Zn) with pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids may also be included.

[0070] In another preferred embodiment, the present invention can further comprise other catalytic materials such as carboxylate salts in any amount. Preferable examples of alkali metal, alkaline earth metal, and quaternary ammonium carboxylate salts include, but are not limited to, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonante, potassium stearate, sodium octoate, lithium stearate, sodium caprioate, lithium octoate, 2- hydroxypropyltrimethylammonium octoate solution, tetramethylammonium carboxylates, tetralkylammonium carboxylates such as tetramethylammonium pivalate (supplied by Evonik Corporation as DABCO®TMR7) and the like, or any combination thereof.

[0071] For preparing a polyisocyanurate / polyurethane foam of the present invention, the urethane catalyst can be present in the formulation from 0 to about 10 pphp, from 0 to about 8 pphp, from 0 to about 6 pphp, from 0 to about 4 pphp, from 0 to about 2 pphp, or from 0 to about 1 pphp. In another aspect, the urethane catalyst is present from 0 to about 0.8 pphp, from 0 to about 0.6 pphp, from 0 to about 0.4 pphp, or from 0 to about 0.2 pphp.MISCELLANEOUS ADDITIVES

[0072] Depending on the requirements during foam manufacturing or for the end-use application of the foam product, various additives can preferably be employed in the PIR / PUR foam formulation to tailor specific properties. These additives preferably include, but are not limited to, cell stabilizers, flame retardants, chain extenders, epoxy resins, acrylic resins, fillers, pigments, or any combination thereof. It is understood thatother mixtures or materials that are known in the art can be included in the foam formulations and are within the scope of the present invention.

[0073] Cell stabilizers include surfactants such as organopolysiloxanes. Silicon surfactants can be present in the foam formulation in amounts from about 0.5 to about 10 pphp, about 0.6 to about 9 pphp, about 0.7 to about 8 pphp, about 0.8 to about 7 pphp, about 0.9 to about 6 pphp, about 1 to about 5 pphp, or about 1 .1 to about 4 pphp. Useful flame retardants include halogenated organophosphorous compounds and nonhalogenated compounds. A non-limiting example of a halogenated flame retardant is trichloropropylphosphate (TCPP). For example, triethylphosphate ester (TEP) and DMMP are non-halogenated flame retardants. Depending on the end-use foam application, flame retardants can be present in the foam formulation in amounts from 0 to about 50 pphp, from 0 to about 40 pphp, from 0 to about 30 pphp, or from 0 to about 20 pphp. In another aspect, the flame retardant is present from 0 to about 15 pphp, 0 to about 10 pphp, 0 to about 7 pphp, or 0 to about 5 pphp. Chain extenders such as ethylene glycol and butane diol can also be employed in the present invention. Ethylene glycol, for instance, can also be present in the formulation as a diluent or solvent for the carboxylate salt catalysts of the present invention.

[0074] In another preferred embodiment, the composition can further comprise at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.METHOD OF PREPARING POLYURETHANE SPRAY FOAM

[0075] The present invention provides a method for preparing a polyurethane foam as well as a polyisocyanurate / polyurethane (PIR / PUR) foam which comprises contacting at least one polyisocyanate with at least one active hydrogen-containing compound, in the presence of at least one blowing agent and an effective amount of catalyst composition. In accordance with the method of the present invention, PUR as well as PIR / PUR foams can be produced having a density from about 16 Kg / m3to about 250 Kg / m3(about 0.5 Ib / ft3to about 15.5 lb / ft3), or from about 24 Kg / m3to about 60 Kg / m3(about 1 .5 lb / ft3to about 3.75 lb / ft3).

[0076] The instant invention can be used in a wide range of methods for making any kind of rigid closed-cell foam. Examples of suitable methods comprise spraying, amongother rigid foam production methods. The inventive foam can be laminated to a wide range of substrates including wood, steel, and concrete.

[0077] The catalyst composition as defined above should be present in the foam formulation in a catalytically effective amount. In PUR as well as in PIR / PUR foam formulations of the present invention, the catalyst composition is present in amounts from about 0.05 to about 20 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound, excluding the weight contribution of the catalyst system diluent. In another aspect, the catalyst composition is present in amounts from about 0.4 to about 10 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound, or from about 0.8 to about 8 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound. If the at least one active hydrogen-containing compound is an at least one polyol, the catalyst composition is present in amounts from about 0.05 to about 10 parts by weight per hundred weight parts polyol (pphp). In another aspect, the catalyst composition is present in amounts from about 0.2 to about 9.5 pphp, about 0.4 to about 9 pphp, about 0.6 to about 8.5 pphp, or about 0.8 to about 8 pphp.

[0078] In accordance with one aspect of the method of the present invention, the components of the foam formulation are contacted substantially contemporaneously. For example, at least one polyisocyanate, at least one active hydrogen-containing compound, at least one blowing agent and an effective amount of catalyst composition, are contacted together. Given the number of components involved in PUR and PIR / PUR formulations, there are many different orders of combining the components, and one of skill in the art would realize that varying the order of addition of the components falls within the scope of the present invention. As well, for each of the different orders of combining the aforementioned components of the foam formulation, the foam formulation of the present invention can further comprise at least one urethane catalyst. In addition, the method of producing PIR / PUR foams can preferably further comprise the presence of at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof. In one aspect of the present invention, all of the components, including optional components, are contacted substantially contemporaneously.

[0079] In another aspect of the present invention, a premix of ingredients other than the at least one polyisocyanate are contacted first, followed by the addition of the at leastone polyisocyanate. For example, the at least one active hydrogen-containing compound, the at least one blowing agent, and the catalyst composition of the present invention are contacted initially to form a premix. The premix is then contacted with the at least one polyisocyanate to produce PUR or PIR / PUR foams in accordance with the method of the present invention. In a further aspect of the present invention, the same method can be employed, wherein the premix preferably further comprises at least one urethane catalyst. Likewise, the premix can preferably further comprise at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.COMPOSITES

[0080] In another aspect of the present invention, the spray polyurethane foam composition is used to create a polyurethane composite interface with a surface substrate. In a preferred embodiment of the invention, a polyurethane composite interface comprises the spray polyurethane foam composition and a surface substrate selected from the group consisting of wood, concrete, and steel. The wood substrate can be any type of wood, plywood or oriented strand board (OSB) that is used in construction, preferably OSB. The concrete substrate can be any type of concrete that is used in construction. The steel substrate can be any type of steel that is used in construction.

[0081] In another aspect of the present invention, a spray polyurethane foam composite composition comprising the contact product of at least one polyisocyanate, at least one active hydrogen-containing compound, at least one blowing agent, a catalyst composition, and a surface substrate selected from the group consisting of wood, concrete, and steel.EXAMPLES

[0082] These Examples are provided to demonstrate certain aspects of the invention and shall not limit the scope of the claims appended hereto.Example 1This example describes the preparation of Sample 1In a 5-gallon pail, polyester polyol, polyether polyol, Mannich polyol and TCPP were combined and mixed until a homogeneous solution formed. The following polyester polyol, polyether polyol, and Mannich polyol were used: (a) polyester polyol (MW= 5000- 6000, fn= 2.2), (b) polyether polyol (MW= 700, fn= 4), (c) Mannich polyol (fn= 3.3). Tetrabromophthalate diol was then added to this solution and stirred well before adding silicon surfactant TEGOSTAB B 84402 and solubility enhancer DABCO PM301. Dabco® PM301 was added as a performance enhancer that enables the solubility of HFO in the resin system. After approximately 5 minutes of stirring, water was added, followed by N,N”-diisopropyl-N, N’, N”-trimethyldiethylenetriamine, 1 ,2-dimethylimidazole, and gelling catalyst DABCO MB20. Water was added based on the formula % Water = 3.706 / (p)1 126which results approximate 2.3% to achieve 2 pcf density. Once a homogeneous solution was achieved, blowing agent Solstice® 1233zd(E) was carefully added to the solution in small portions to avoid any boil-off situations. After 10 minutes of stirring at room temperature, the pail was sealed and left overnight for spraying.Example 2This example describes the preparation of the polyurethane formulations as well as the adhesion evaluation of the resulting polyurethane foamsThe following formulations (Table 1 and Table 2) were used for making hand-mixed and spray polyurethane foam. A combination of blow-based and gel-based catalyst packages were used to evaluate the system's performance. The performance of N,N”-diisopropyl- N, N’, N”-trimethyldiethylenetriamine was evaluated against commonly used industry standards, i.e., TMG / SA (tetramethylguanidine in combination with succinic acid), TMG / SA / GA (tetramethylguanidine in combination with succinic acid and glutaric acid), and N,N,N',N",N"-pentamethyldiethylenetriamine. N,N,N',N",N"- pentamethyldiethylenetriamine and TMG / SA were used as commercial catalysts for reference to compare the performance of N,N”-diisopropyl-N, N’, N”- trimethyldiethylenetriamine. Polymeric MDI was used to make spray polyurethane foam samples (Index 112).Table 1. Conventional Formulation1silicone surfactant obtained from Evonik Industires.2HFO solubility enhancer obtained from Evonik Industires.3gelling catalyst obtained from Evonik Industires.4tetramethylguanidine in combination with succinic acid.5tetramethylguanidine in combination with succinic acid and glutaric acid.6blowing agent obtained from Honeywell.Table 2. Conventional FormulationExample 3This example describes the adhesion performance of N,N”-diisopropyl-N, N’, N”- trimethyldiethylenetriamine in comparison with various commonly used industry standard amine catalystsThe adhesion studies were conducted at a temperature of 20 °F, following ambient spray machine parameters (125 °F temperature and 1000-1100 psi pressure). A substrate sizeof 1 square foot was maintained consistently for all substrates (OSB board, concrete, and steel). Prior to spraying, all substrates were conditioned at 20 °F overnight. Subsequently, the sprayed substrates were kept at 20 °F for 5-6 hours before being brought to room temperature.To evaluate adhesion and tensile stress, the samples were meticulously cut and affixed onto the steel coupons, following the ASTM D-1623-03 test procedure. The summarized results can be found in Table 3 and Table 4. Table 3. Summary of tensile stress and maximum load as a function of adhesion of various amine catalysts based on formulation of Table 1.Table 4. Adhesion profiles of N,N”-diisopropyl-N, N’, N”-trimethyldiethylenetriamine, TMG / SA, TMG / SA / GA, and N,N,N',N",N"-pentamethyldiethylenetriamine on various substrate ( / .e. OSB board, concrete and steel) based on formulation mentioned in Table 2.The results obtained from ASTM D-1623-03 test indicate that N,N”-diisopropyl-N, N’, N”- trimethyldiethylenetriamine shows an improved adhesion on OSB board, concrete and steel substrates compared to TMG / SA, TMG / SA / GA, and N,N,N',N",N"- pentamethyldiethylenetriamine.Example 4A homogenous solution of samples 1-8 containing polyol, flame retardant, surfactant, water, catalyst and HFO was placed in a 32 ounce paper cup. MDI was added into it and mixed for 3 seconds at 12,000 RPM using a Laboratory Dispensator made by Premier Mill Corp. Immediately after mixing, the paper cup was placed under the Foamat® machine (FOMAT Messtechnik GmbH) sonar and software equipment was used to obtain foam rise profiles, and measure the ROR profile for 60 seconds. The ROR (Rate Of Rise) profile was monitored at room temperature and the summary of the observations is listed in the following table 5 and the graphs in Fig. 1.Table 5Example 5Synthesis of Bis(2-aminoethyl)etherSulfuric acid (ACS reagent, 434 g, 4.20 mol) was charged into the 3-neck reaction flask (1 L) equipped with an addition funnel, mechanical stirrer, nitrogen inlet, and water / ice bath. Ethanolamine (EOA, 244 g) was dispensed slowly in one portion where the starting temperature was <15°C and the addition rate with mechanical mixing was used to keepthe temperature of the flask at or below 60°C. The mixture was allowed to cool to room temperature becoming a milky slurry. Distillation was carried out at atmospheric pressure under nitrogen where solids started to dissolve at 130°C, and a clear very pale yellow solution was observed when 160°C was reached. Water began to distill from the reactor at 160°C at a steady rate with an overhead temperature of 91 °C. The reaction temperature was increased up to 215°C and the total distillate was 56 g. The reaction temperature was maintained at 215°C for at least 90 min before heating was stopped. Cold water (290 g) was added to the dark colored reaction mixture once the temperature reached 110°C to give a black sludge with a crystalline solid. A filtration was performed using a Millipore pressure filtration apparatus equipped with a Durapore membrane to remove the settled solid. The reaction flask and solid was rinsed with water to ensure quantitative transfer. An off white crystalline solid was obtained in the pressure filter. The filter cake was rinsed with IPA (120 g), and it was dried under a stream of nitrogen for at least 90 min. The solid was isolated from the pressure filter to give 156 g of a free flowing crystalline powder. The FTIR spectrum matched 2-aminoethyl hydrogen sulfate (AEHS, 27 % yield), and the minimum ethanolamine conversion to AEHS was 27.7%. An aliquot of the very dark liquid filtrate was titrated with 50% NaOH solution until pH 12 minimum to determine the g NaOH sln / g of sample with values about 0.4-0.6 g NaOH sln / g of sample. Next, the required amount of 50% NaOH solution was calculated for the remainder of the filtrate. However, a portion of the water was removed first from the filtrate via distillation. The required amount of 50% NaOH solution was added to the concentrated filtrate to give a dark slurry with pH ~12 and then IPA was added. A filtration was performed using a Millipore pressure filtration apparatus equipped with a Durapore membrane to remove the insoluble solid. IPA and water were removed from the cola colored filtrate via distillation which resulted in additional solid to precipitate. The solid was removed via filtration as described before. The GC chromatogram of the product mixture showed that bis(2-aminoethyl)ether (BAEE, 69.7 area%) and ethanolamine (29.9 area%) were the largest components with other minor impurities. Distillation of the product mixture was carried out under vacuum to yield a mixture of bis(aminoethyl)ether and ethanolamine with a composition about 67% BAEE and 37% EGA.Example 6Synthesis of N, N’-bis(isopropyl)-N, N’-dimethyl-bis(2-aminoethyl)ether (BIP-DMAEE)Procedure 1 : A 1 liter stainless steel reactor was charged with 74.92 g of bis(2- aminoethyl)ether (BAEE) supplied by ChemScene LLC and 6.19 g of 15 % Pd / C catalyst (50 % suspension in water), 100.3 g isopropanol and the reactor was purged with nitrogen followed by a hydrogen gas purge. The reactor was heated up to 100°C and then the hydrogen pressure was increased to 800 psig. The cooling system was turned on and 109.9 mL acetone was fed into the reactor over a period of 3 hours. The temperature was held at 100°C for an additional 1.5 hours. The reactor was then fed with112.7 mL formalin solution ( 37 % formaldehyde in methanol and water ) over a period of ~ 2.5 hours and held at temperature for an additional hour until the hydrogen consumption was completed. The reactor was cooled to room temperature and the contents filtered to remove the Pd / C catalyst. The filter was rinsed with additional 15 mL of isopropanol and the crude filtered product (386.1 g) was transferred to a rotary evaporator to remove solvents yielding 92 % BIP-DMAEE based on GC analysis and confirmed by GCMS.Procedure 2: A 1 liter stainless steel reactor was charged with 74.96 g of bis(2- aminoethyl)ether (BAEE) purchased from ChemScene LLC and 7.95 g of 15 % Pd / C catalyst (50 % suspension in water), 98.5 g isopropanol and the reactor was purged with nitrogen followed by a hydrogen gas purge. The reactor was heated up to 110°C and then the hydrogen pressure was increased to 800 psig. The cooling system was turned on and 109.9 mL acetone was fed into the reactor over a period of 3 hours. The temperature was held at 100°C for an additional 1.5 hours. The reactor was then fed with110.8 mL formalin solution (37 % formaldehyde in methanol and water) over a period of ~ 2.5 hours and held at temperature for an additional 10 minutes. The reactor wascooled to room temperature and the contents filtered to remove the Pd / C catalyst. The filter was rinsed with additional 15 mL of isopropanol and the crude filtered product (369.2 g) was transferred to a rotary evaporator to remove solvents yielding 98 % BIP- DMAEE based on GC analysis and confirmed by GCMS and NMR spectroscopy.N,N’-bis(isopropyl)-N,N’-dimethyl-bis(2-aminoethyl)ether isEXAMPLE 7This example shows the performance of N,N”-diisopropyl-N, N’, N”- trimethyldiethylenetriamine and N, N‘-diisopropyl-N, N’-dimethyl-bis(2-aminoethyl) ether under foam spraying conditions on various substrates including OSB wood (Oriented Strand Board), cement and steel at cold temperatures (2CPF; -6.7°C)The formulations shown in Table 6 were used for making equivalent hand-mixed and spray polyurethane materials.Table 6. Conventional Formulation1silicone surfactant obtained from Evonik Industires. 2HFO solubility enhancer obtained from Evonik Industires. 3gelling catalyst obtained from Evonik Industires. 4 blowing agent obtained from Honeywell.The formulations shown in Table 6 were used for making equivalent hand-mixed and spray polyurethane materials as shown in Table 7 where indicators show no significant difference in foam kinetic data. The hand-mix reactivity of samples 9 and 10 are shown in Fig. 2.Table 7Test substrates, shown in Fig. 3, were conditoned overnight at 20°F (-6.7°C) in a spray foam testing chamber at 20 °F I -6.7°C.The substrates were then individually sprayed with rigid closed-cell polyurethane foam according to the formulations described for sample 9 and sample 10.Post spray, the specimens were allowed to condition for 4 hours at 20°F before being placed into a CHT room (CHT = control humidity and temperature room) at 23°C and 50 % humidity. The adhesion testing was performed one week later by meticulously trimming and cutting the excess foam and affixing the resulting sample onto the steel coupons according to ASTM D-1623-03 guidelines as shown in Fig. 4 for an OSB-wood specimen.Measurements were done 24 hours after glueing the steel coupons on the surface of the spray foam samples. The summarized results can be found in Table 7 and Table 8.Table 8These results demonstrate that while maintaining all the other formulation components constants, adhesion to various substrates is improved when using N,N”-diisopropyl-N, N’, N”-trimethyldiethylenetriamine. Thus, the overall performance for adhesion to substrates improves according to the following trend:EXAMPLE 8This example shows the emissive characteristics of selected catalysts using a microchamber emission test methodThe emissiveness of amine catalysts from foam were determined using the microchamber method following ASTM D8142-17. Tenax TD tubes were used to collect the emissions after a 2 hours and 24 hours period. The organic compounds collected were desorbed and their contents analyzed using thermal desorption GC / MS.The microchamber parameters used during the thermal desorption method as well as the emissions results are summarized below in Table 9 showing much lower emissions for N,N”-diisopropyl-N, N’, N”-trimethyldiethylenetriamine.Table 9Temperature 34.2°CFlow Rate 50+ 2 ml / minEquilibration Time 2 hours Sample Area: 0.003018 m2Chamber HeadspaceVolume: 9.65 x 10-6m3Loading Factor: 333 m2 / m3Air Change Rate: 187 h -1 (N)EXAMPLE 9Synthesis of N, N’-bis(sec-butyl)-N, N’-dimethyl-bis(2-aminoethylether) (BSB-DMAEE) from bis(2-aminoethyl)ether described in example 5A 1 liter stainless reactor was charged with 133.3 g of a mixture having 64.5 % bis(aminoethyl)ether (BAEE) and 35.5 % ethanolamine (EOA) obtained from example 5 along with 14.8 g of 15 % Pd I C catalyst (50 % suspension in water), 100 g isopropanol and the reactor was purged with nitrogen followed by a hydrogen gas purge. The reactor was heated up to 120°C and then the hydrogen pressure was increased to 800 psig. The cooling system was turned on and 232.9 mL 2-butanone was fed into the reactor over a period of 2.25 hours. Temperature was held at 120°C for an additional 4 hours. The reactor was then fed with 238.92 mL formalin solution ( 37 % formaldehyde in methanol and water ) over a period of ~ 3 hours and held at temperature for an additional hour until the hydrogen consumption was completed. The reactor was cooled to room temperature and the contents filtered to remove the Pd I C catalyst. The filter was rinsed with additional 20 g of isopropanol and the crude filtered product (605.8 g) was transferred to a rotary evaporator to remove solvents yielding 72.3 % BSB-DMAEE and 25.9 % g of N- sec-butyl-N-methyl-ethanolamine based on GC analysis and confirmed by GCMS. The crude product (262.4 g) was distilled via fractional vacuum distillation to separate BSB- DMAEE from N-sec-butyl-N-methyl-ethanolamine. The appropriate fractions were combined yielding 149.9 g of 99.8 % BSB-DMAEE and 59.0 g of 96.9 % N-sec-butyl-N- methyl-ethanolamine based on GC analyses. Mixed fractions were collected that contained both components totaling 32.9 g.BSB-DMAEE product was evaluated and compared with DIPTM-DETA in a HFO foam formulation having the following components shown in Table 10:Table 10xTerol®305 is a polyester polyol and2Jeffol® R-470X is a polyether polyol obtained from Huntsman. 3Flame retardant: TCPP obtained from ICL-IP.4Surfactant: Tegostab® obtained from Evonik Industries.5DABCO®MB20 is a bismuth metal carboxylate salt catalyst commercially available from Evonik Corporation6HFO solubility enhancer: DABCO®PM301 commercially available from Evonik 7HFO-LBA: Solstice® LBA obtained from HoneywellThe summary of the kinetic foam data is listed in the following Table 11 and the graph inFig. 5.Table 11EXAMPLE 10Performance of N,N’-bis(isopropyl)-N,N’-dimethyl-bis(2-aminoethyl)ether (BIP-DMAEE) as Catalyst in the Preparation of HFO-Blown Spray Rigid Foam Used in Residential InsulationThe performance and the shelf life stability of N,N’-bis(isopropyl)-N,N’-dimethyl- bis(aminoethylether) (BIP-DMAEE) was carried out using the foam formulation shown below. The evaluation of the catalyst reactivity in a spray polyurethane system was conducted using free-rise cup foam sample with a FOAMAT sonar Rate-Of-Rise (ROR) device.The shelf life study of the following formulation was tested at 50 °C for four weeks in hot air oven. The rate of rise properties were monitored using FOAMAT sonar and the kinetic parameters cream time, gel time and rise time were determined experimentally together with the final height and pH. The polyurethane formulations in parts per hundred polyol is shown in Table 12.Table 12. HFO-Blown Spray Foam Rigid Formulation:Table 13 below shows the ageing performance of formulation I at 50°C over a period of 4 weeks. The data shows a moderate but acceptable increase in gel time (from 19.7 to 27.6 seconds) and rise time (from 33.7 to 45.7 seconds). On the other hand, a moderate loss in foam height (from 193.8 to 170.9 mm) is consistent with a moderate loss in catalytic activity as reflected by the moderate decrease in pH from 9.55 to 8.9 over the same period. Table 14 shows these changes as percentage. Fig. 6 shows the resuting foam samples consistent with the experimental measurements. Thus, although a decrease in catalytic activity and performance is observed over a period of four weeks, the foam samples produced are of much higher quality than conventional catalysts.Table 13. Ageing Performance of BIP-DMAEETable 14. % Change vs. InitialHence, these results are very similar to the results disclosed for the analogous chemical structure N, N”-diisopropyl-N,N’N”-trimethyldipropylenetriamine showing a substantial improvement when compared with traditional blowing catalysts such as pentamethyldiethylenetriamine (Polycat®5). Fig. 7 shows that N, N”-diisopropyl-N,N’N”- trimethyldipropylenetriamine is about 20 % more active than N,N’-bis(isopropyl)-N,N’- dimethyl-bis(aminoethylether) for similar foam kinetics (2.0 pphp vs. 2.4 pphp respectively).

Claims

CLAIMS1 . A spray polyurethane foam composition comprising the contact product of at least one polyisocyanate, at least one active hydrogen-containing compound, at least one blowing agent, and a catalyst composition.

2. The spray polyurethane foam composition of claim 1 , wherein the catalyst composition comprises at least one compound selected from the group consisting of N, N”-diethyl-N, N’, NMrimethyl(diethylenetriamine); N, N”-dipropyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-diisopropyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dibutyl-N, N’, NMrimethyl(diethylenetriamine); N, N”-diisobutyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-disecbutyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-ditertbutyl-N, N’, NMrimethyl(diethylenetriamine); N, N”-dipentyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-diisopentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-ditertpentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dineopentyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-disecpentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-di(3-pentyl)-N, N’, N”-trimethyl(diethylenetriamine); N, N”-disecisopentyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-dihexyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”- diisohexyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-dineohexyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”’-diethyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dipropyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisopropyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dibutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisobutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecbutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-ditertbutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dipentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-ditertpentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dineopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecpentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-di(3-pentyl)-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecisopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dihexyl-N, N’, N”,N”’-tetramethyl(triethylenetetraamine); N, N”’-diisohexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dineohexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”-diethyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dipropyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisopropyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-dibutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisobutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecbutyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-ditertbutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dipentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisopentyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-ditertpentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dineopentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecpentyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-di(3-pentyl)-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecisopentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dihexyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-diisohexyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dineohexyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”’-diethyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dipropyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisopropyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dibutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisobutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecbutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-ditertbutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dipentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-ditertpentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dineopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecpentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-di(3-pentyl)-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecisopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dihexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisohexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); and N, N”’-dineohexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine), in combination with at least one tertiary amine catalyst component selected from the group consisting of diazobicyclooctane (triethylenediamine), 1 ,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, 2, 2'-dimorpholinodiethyl ether, N-methylimidazole, 1 ,2-dimethylimidazole, 1 -ethylimidazole, N-methylmorpholine, N-ethylmorpholine, and N-cetylmorpholine.

3. The spray polyurethane foam composition of claim 2, wherein the catalyst composition comprises N, N”-diisopropyl-N, N’, N”-trimethyl(diethylenetriamine) and 1 ,2- dimethylimidazole.

4. The spray polyurethane foam composition of claim 1 , wherein the catalyst composition comprises at least one compound selected from the group consisting of N, N’-diethyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dipropyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-diisopropyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dibutyl- N, N’-dimethyl-bis(aminoethyl)ether; N, N’-diisobutyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-disecbutyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-ditertbutyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-dipentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dibutyl-N, N’-diisopentyl-bis(aminoethyl)ether; N, N’-ditertpentyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-dineopentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’- disecpentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-di(3-pentyl)-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-disecisopentyl -N, N’-dimethyl-bis(aminoethyl)ether; N, N’- dihexyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-diisohexyl-N, N’-dimethyl- bis(aminoethyl)ether; and N, N’-dineohexyl-N, N’-dimethyl-bis(aminoethyl)ether, in combination with at least one tertiary amine catalyst component selected from the group consisting of diazobicyclooctane (triethylenediamine), 1 ,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, 2, 2'-dimorpholinodiethyl ether, N- methylimidazole, 1 ,2-dimethylimidazole, 1 -ethylimidazole, N-methylmorpholine, N- ethylmorpholine, and N-cetylmorpholine.

5. The spray polyurethane foam composition of claim 4, wherein the catalyst composition comprises N, N’-diisopropyl-N, N’-dimethyl-bis(aminoethyl)ether and 1 ,2- dimethylimidazole.

6. The spray polyurethane foam composition of any of claims 1 -5 wherein the catalyst composition is acid blocked with a carboxylic or sulfonic acid.

7. The spray polyurethane foam composition of claim 6 wherein the catalyst composition is acid blocked with an acid selected from the group consisting of formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, and salicylic acid.

8. The spray polyurethane foam composition of any of claims 1 -7 wherein the catalyst composition further comprises catalytic materials.

9. The spray polyurethane foam composition of claim 8 wherein the catalytic materials are selected from the group consisting of potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonante, potassium stearate, sodium octoate, lithium stearate, sodium caprioate, lithium octoate, 2-hydroxypropyltrimethylammonium octoate solution, or any combination thereof.

10. The spray polyurethane foam composition of any of claims 1-9, further comprising at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.11 . A method for preparing a spray polyurethane foam comprising contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of at least one blowing agent, and a catalyst composition.

12. The method of claim 11 wherein the catalyst composition comprises at least one compound selected from the group consisting of N, N”-diethyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-dipropyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-diisopropyl-N, N’, NMrimethyl(diethylenetriamine); N, N”-dibutyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-diisobutyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-disecbutyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-ditertbutyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-dipentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-diisopentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-ditertpentyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-dineopentyl-N, N’, N”-trimethyl(diethylenetriamine);N, N”-disecpentyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-di(3-pentyl)-N, N’, N”- trimethyl(diethylenetriamine); N, N”-disecisopentyl-N, N’, N”-trimethyl(diethylenetriamine);N, N”-dihexyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”-diisohexyl-N, N’, N”- trimethyl(diethylenetriamine); N, N”-dineohexyl-N, N’, N”-trimethyl(diethylenetriamine); N, N”’-diethyl-N, N’, N”,N”’-tetramethyl(triethylenetetraamine); N, N”’-dipropyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisopropyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dibutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisobutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecbutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-ditertbutyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dipentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-ditertpentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dineopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecpentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-di(3-pentyl)-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-disecisopentyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dihexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-diisohexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”’-dineohexyl-N, N’, N”,N”’- tetramethyl(triethylenetetraamine); N, N”-diethyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dipropyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisopropyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-dibutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisobutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecbutyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-ditertbutyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dipentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-diisopentyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-ditertpentyl-N, N’, N”-trimethyl(dipropylenetriamine);N, N”-dineopentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-disecpentyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-di(3-pentyl)-N, N’, N”-trimethyl(dipropylenetriamine);N, N”-disecisopentyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dihexyl-N, N’, N”- trimethyl(dipropylenetriamine); N, N”-diisohexyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”-dineohexyl-N, N’, N”-trimethyl(dipropylenetriamine); N, N”’-diethyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dipropyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisopropyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dibutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisobutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecbutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-ditertbutyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dipentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-ditertpentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dineopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecpentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-di(3-pentyl)-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-disecisopentyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-dihexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); N, N”’-diisohexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine); and N, N”’-dineohexyl-N, N’, N”,N”’- tetramethyl(tripropylenetetraamine), in combination with a tertiary amine having no isocyanate reactive groups selected from the group consisting of diazobicyclooctane (triethylenediamine), 1 ,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, 2, 2'- dimorpholinodiethyl ether, N-methylimidazole, 1 ,2-dimethylimidazole, 1 -ethylimidazole, N-methylmorpholine, N-ethylmorpholine, and N-cetylmorpholine, in combination with at least one tertiary amine catalyst component selected from the group consisting of diazobicyclooctane (triethylenediamine), 1 ,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, 2, 2'-dimorpholinodiethyl ether, N- methylimidazole, 1 ,2-dimethylimidazole, 1 -ethylimidazole, N-methylmorpholine, N- ethylmorpholine, and N-cetylmorpholine.

13. The method of claim 12, wherein the catalyst composition comprises N, N”- diisopropyl-N, N’, N”-trimethyl(diethylenetriamine) and 1 ,2-dimethylimidazole.

14. The method of claim 11 wherein the catalyst composition comprises at least one compound selected from the group consisting of N, N’-diethyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-dipropyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’- diisopropyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dibutyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-diisobutyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’- disecbutyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-ditertbutyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-dipentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-dibutyl-N, N’-diisopentyl-bis(aminoethyl)ether; N, N’-ditertpentyl-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-dineopentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’- disecpentyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-di(3-pentyl)-N, N’-dimethyl- bis(aminoethyl)ether; N, N’-disecisopentyl -N, N’-dimethyl-bis(aminoethyl)ether; N, N’- dihexyl-N, N’-dimethyl-bis(aminoethyl)ether; N, N’-diisohexyl-N, N’-dimethyl- bis(aminoethyl)ether; and N, N’-dineohexyl-N, N’-dimethyl-bis(aminoethyl)ether, in combination with at least one tertiary amine catalyst component selected from the group consisting of diazobicyclooctane (triethylenediamine), 1 ,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, 2, 2'-dimorpholinodiethyl ether, N- methylimidazole, 1 ,2-dimethylimidazole, 1 -ethylimidazole, N-methylmorpholine, N- ethylmorpholine, and N-cetylmorpholine.

15. The method of claim 14, wherein the catalyst composition comprises N, N’- diisopropyl-N, N’-dimethyl-bis(aminoethyl)ether and 1 ,2-dimethylimidazole.

16. The method of any of claims 11-15 wherein the catalyst composition is acid blocked with a carboxylic or sulfonic acid.

17. The method of claim 16 wherein the catalyst composition is acid blocked with an acid selected from the group consisting of formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, and salicylic acid.

18. The method of any of claims 11-15 wherein the catalyst composition further comprises catalytic materials.

19. The method of claim 18 wherein the catalytic materials are selected from the group consisting of potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonante, potassium stearate, sodium octoate, lithium stearate, sodium caprioate, lithium octoate, 2- hydroxypropyltrimethylammonium octoate solution, or any combination thereof.

20. The method of any of claims 11-15, further comprising contacting at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.21 . A polyurethane composite interface comprising the spray polyurethane foam composition of any of claims 1-10 and a surface substrate selected from the group consisting of wood, concrete, and steel.

22. A spray polyurethane foam composite composition comprising the contact product of at least one polyisocyanate, at least one active hydrogen-containing compound, at least one blowing agent, a catalyst composition, and a surface substrate selected from the group consisting of wood, concrete, and steel.

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