Two-component polyurethane or polyisocyanurate spray foam compositions containing hydrohaloolefin blowing agents

Abstract

Disclosed is a storage stable two-component polyurethane or polyisocyanurate spray foam composition comprising: (a) an A-side component comprising one or more polyisocyanates and one or more catalysts; and (b) a B-side component comprising one or more polyols; and further comprising one or more hydrohaloolefin blowing agents in either the A-side component, the B-side component, or both; wherein both the A-side component and the B-side component, separately, generate less than 600 ppm fluoride ions after 2 weeks aging at 50°C.

Description

[Technical field]

[0001] Described herein are two-component (A-side and B-side) polyurethane or polyisocyanurate spray foam compositions that include a hydrohaloolefin blowing agent in either the A-side component or the B-side component, or both, and that have improved shelf life by adding a catalyst to the A-side component formulation. Additionally described herein are methods for making and using these two-component compositions. The compositions disclosed herein can be utilized, for example, as expandable foams for air sealing and gap filling, or for insulation, and / or other household and industrial applications. [Background technology]

[0002] Two-component compositions are often used for reactive systems that cannot be stored and / or transported together in one mixed composition. Two-component compositions are particularly advantageous for reactive systems that either generate gas or an exothermic reaction can convert a low boiling point liquid component into a gas, and the product can form a foam, which hardens into a solid foam. This scenario allows for in-situ reactions and foam generation that can be utilized to fill spaces, including voids, in building structures. Two-component polyurethane or polyisocyanurate spray (2C-SPU) foam compositions find utility in such applications (air-tight and gap-filling) and are typically applied by simultaneously feeding an isocyanate component (A-side component) with a polyol component (B-side component) to produce a mixture and then spraying the mixture from a dispensing device (or achieving mixing during the spraying operation), where the A-side component typically includes a monomeric isocyanate, a polymeric isocyanate, or a blend of the two, and, optionally, a blowing agent; the B-side component typically includes one or more polyols, a blowing agent, a catalyst, a surfactant, and, optionally, a flame retardant.

[0003] 2C-SPU foam systems are generally divided into two classes: those containing a gaseous blowing agent (GBA) in one or both of the A and B components, and those without GBA in the A and B components ("GBA-Free 2C-SPU foam systems"). GBAs are blowing agents that have a vapor pressure of greater than 0.23 megapascals (MPa) at 25 degrees Celsius (°C). Typical conventional GBAs include lower alkanes such as butane, pentane; and many halogenated or partially halogenated lower alkanes (e.g., 1-6 carbon halogenated alkanes), such as trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1,1,2-tetrafluoroethane (HFC-134a). GBAs are not only useful as foaming aids in 2C-SPUs, but also act as propellants and to reduce the viscosity of the components in which they are found. Lower viscosity ingredients are easier to dispense because they require less pressure to flow through the flow passages of the dispensing device.

[0004] The GBA-Free 2C-SPU foam system requires the use of either a positive displacement pump device to meter the two components to the spray gun, or pressurized gas as a separate third supply that occurs simultaneously with the A and B components when dispensing the 2C-SPU foam system. The pressurized gas requirement means that the dispensing device requires at least three simultaneous supplies as opposed to two supplies for the GBA-containing 2C-SPU foam system.

[0005] GBA-Free 2C-SPU foam systems can be classified as either high pressure or low pressure systems. In high pressure systems, herein, which are systems requiring dispensing pressures of more than 4 megapascals (MPa), a positive displacement pump as described above can be used to enable metering, help shape the spray, and clean the dispensing spray head used to dispense the 2C-SPU. In low pressure systems, herein, which are systems capable of dispensing at pressures below 4 MPa (580 psig), typically below 2 MPa (290 psig), a third supply pressurized gas (e.g., nitrogen or air) is used as the motive and mixing force for the A and B components.

[0006] In general, dispensing operation is more convenient with low pressure 2C-SPU foam systems containing GBA because they are less complicated than low pressure systems without GBA and avoid the use of expensive and mechanically complicated dispensing hardware required for high pressure systems without GBA. However, due to the higher flammability of lower alkanes (butane, pentane, etc.) and increasing regulatory pressure on active blowing agents such as chlorofluorocarbons and hydrofluorocarbons (such as CFC-11, CFC-12, HFC-134 and HFC-134a) in the world market, hydrohaloolefins (HHO), such as hydrofluoroolefins (HFO), are now being considered as alternative blowing agents because they offer low global warming potential (GWP). Hydrohaloolefins include hydrochlorofluoroolefins, such as 1-chloro-3,3,3-trifluoropropene (1233zd(E)), and hydrofluoroolefins, such as trans-1,3,3,3-tetrafluoropropene (1234ze(E)), 2,3,3,3-tetrafluoroprop-1-ene (1234yf), and 1,1,1,4,4,4-hexafluorobut-2-ene (1336mzzm(Z)). Unfortunately, the development of polyurethane and polyisocyanurate formulations using hydrohaloolefin blowing agents, such as hydrofluoroolefins, is a major challenge due to shelf-life stability issues caused by side reactions between current catalysts and HHO (e.g., HFO) blowing agents (gaseous and / or liquid HHO blowing agents). Typical shelf-life stability for conventional HFC-containing formulations is at least 15 months, while the shelf-life stability of current HFO-containing formulations is generally less than 2 months. It is believed that commercial products should have a shelf life stability of at least 12 months.

[0007] Various approaches have been explored to circumvent this problem, such as the addition of hydrocarbons as blowing agents instead of hydrofluorocarbons, but this approach would appear to be limited, at least in terms of quantity, due to the high twistability of hydrocarbons. Another approach is seen in efforts to use non-amine catalysts in the B-side component (see, for example, U.S. Patent Application Publication No. 2018 / 0105633 A1), but to date this approach has not gained traction as most non-amine catalysts have the same problem of instability with HHO blowing agents, and no alternative catalysts have been identified that match the reactivity of the blowing chemistry in the low NCO index formulations obtained with amine catalysts. Similar approaches focus on minimizing or eliminating any amine content in the B-side component to such an extent that, for example, the nitrogen content in the B-side component is less than 1% nitrogen as a % of the B-side component formulation (see, for example, WO 2016 / 164671 A1).

[0008] Although there appears to be considerable interest in replacing hydrohalocarbons (such as hydrofluorocarbons) with hydrohaloolefins due to the much lower global warming potential of hydrohaloolefins, to date attempts to formulate low pressure two-component polyurethane or polyisocyanurate spray foam compositions have not met with success. Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, there is a need for two-component polyurethane or polyisocyanurate spray foam compositions containing hydrohaloolefin blowing agents which have improved shelf life and which are capable of producing stable foams comparable to those produced using current formulations (which employ hydrofluorocarbon blowing agents).The present invention is directed to these, as well as other important ends. [Means for solving the problem]

[0010] The present invention describes a dramatic improvement in the shelf life of formulations using gaseous hydrohaloolefin blowing agents for two-component polyurethane or polyisocyanurate low pressure spray foams. The "B" side components of the formulation include one or more polyols, a gelling catalyst that can be selected from metal complexes or nucleophilic organic compounds, and one or more B-side gaseous blowing agents that are or include gaseous hydrohaloolefin blowing agents. Optionally, the "B" side components of the formulation may further include one or more surfactants, one or more flame retardants, and / or one or more liquid blowing agents. The "A" side components of the formulation include one or more polyisocyanates, one or more blowing catalysts that can be selected from certain amine compounds, and optionally one or more surfactants and one or more A-side gaseous blowing agents that can be or include gaseous hydrohaloolefin blowing agents.

[0011] A catalyst capable of accelerating the reaction between polyols and isocyanates to form urethane bonds can be defined as a gelation catalyst (or gelling catalyst). Gelling catalysts in low pressure spray foam formulations can be metal complexes with nucleophilic ligands or potassium carboxylate salts. Potassium carboxylate salts are also used as trimerization catalysts to promote the condensation reaction of three isocyanate groups to produce isocyanurate moieties. Amine-based catalysts can accelerate the reaction between water and isocyanates to produce carbon dioxide and urea, and are known as blowing catalysts (while also contributing to the gelling reaction).

[0012] When either a metal catalyst (gelling catalyst) or an amine-based catalyst (blowing catalyst), or both, are in the presence of hydrohaloolefins, undesirable side reactions generally occur with the hydrohaloolefin blowing agent (e.g., hydrofluoroolefins, HFOs, blowing agents, etc.), resulting in slower reactivity times that deteriorate upon aging. In addition, fluoride ions may be released that can further react with formulation components such as silicone surfactants and / or catalysts, resulting in poor foaming properties.

[0013] In the novel approach of the present invention, a gelling catalyst (such as one or more metal complexes or nucleophilic organic compounds) is added to the B-side component (polyol formulation) in the presence of a gaseous hydrohaloolefin blowing agent (such as HFO); a blowing catalyst (such as one or more certain amine compounds) is added to the A-side component (isocyanate formulation), optionally in the presence of a gaseous hydrohaloolefin blowing agent. The shelf life of formulations using gaseous HHO (such as HFO) for low pressure two-component polyurethane or polyisocyanurate spray foams can be dramatically improved with this approach.

[0014] In one embodiment, the invention relates to a storage stable two-component polyurethane or polyisocyanurate spray foam composition comprising: (a) an A-side component comprising one or more polyisocyanates and one or more catalysts; and (b) a B-side component comprising one or more polyols; and further comprising one or more hydrohaloolefin blowing agents in either the A-side component or the B-side component, or both, wherein both the A-side component and the B-side component, separately, generate less than 600 ppm fluoride ion after aging at 50° C.

[0015] In some embodiments, one or more catalysts in the A-side component is a blowing catalyst.

[0016] In some embodiments, one or more catalysts in the A-side component are N-heterocyclic compounds. In some embodiments, one or more catalysts in the A-side component are N,X-heterocyclic compounds; in one such embodiment, one or more catalysts in the A-side component are morpholino compounds.

[0017] In some embodiments, the foams produced upon mixing the A-side and B-side components can be used in air sealing or gap filling applications, such as, for example, sealant or insulating foams. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention can be more readily understood by reference to the following detailed description, examples, and claims, as well as their preceding and following descriptions. However, it should be understood that the present invention is not limited to the specific compositions, articles, devices, systems, and / or methods disclosed, unless otherwise specified, and thus, of course, may vary. Although aspects of the present invention may be described and claimed in a particular legal classification, such as a composition legal classification, this is for convenience only, and one of ordinary skill in the art will understand that each aspect of the present invention may be described and claimed in any legal classification.

[0019] While the present invention can be embodied in various forms, the following description of some embodiments is made with the understanding that the present disclosure should be considered as an example of the present invention and is not intended to limit the present invention to the specific embodiments illustrated. Headings are provided for convenience only and should not be construed as limiting the present invention in any way. An embodiment illustrated under any heading or in any portion of this disclosure may be combined with an embodiment illustrated under the same or any other heading or portion of this disclosure.

[0020] Any combination of the elements described herein in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

[0021] Unless expressly stated otherwise, any method or aspect described herein is never intended to be construed as requiring that its steps be performed in a particular order. Thus, unless a method claim specifically recites in the claims or description that the steps are limited to a particular order, no order is intended to be inferred in any sense. This applies to all possible non-expressive bases for interpretation, including logical considerations regarding the arrangement or operational flow of steps, simple meaning derived from grammatical constructions or punctuation, or the number or type of embodiments described herein. It should be understood that both the general description above and the detailed description below are exemplary and explanatory only, and not restrictive.

[0022] All publications mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in connection with which the publications are cited.

[0023] It should be understood that the terminology used herein is merely for the purpose of describing certain aspects and is not intended to be limiting. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. In this specification and in the claims that follow, reference will be made to a number of terms defined herein.

[0024] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0025] As used herein, the term "and / or" means "and, or alternatively."

[0026] As used herein, the term "optional" or "optionally" means that a described event, condition, ingredient, or circumstance may or may not occur, and that the description includes instances in which said event, condition, ingredient, or circumstance occurs and instances in which said event, condition, ingredient, or circumstance does not occur.

[0027] As used herein, the phrase "sufficient for" (e.g., "conditions sufficient for") refers to a value or condition sufficient for such a function or property to be manifested. As noted below, the exact values ​​or specific conditions required may vary from embodiment to embodiment, depending on widely recognized variables such as the materials and / or processing conditions used.

[0028] The term "by weight," when used in conjunction with an ingredient, is based on the total weight of the formulation or composition in which the ingredient is included, unless otherwise specified. For example, if a particular element or ingredient in a composition or article is said to be present in an amount of 8% by weight (or 8 wt.%), it is understood that this percentage is relative to the overall composition percentage of 100%. In some examples, the weight percentage of an ingredient is based on the total weight of the composition on a "dry basis," which indicates the weight of the composition without water (e.g., less than about 1% by weight, less than about 0.5% by weight, less than about 0.1% by weight, less than about 0.05% by weight, or about 0% by weight water, based on the total weight of the composition). For elements or ingredients not expressed as a percentage, the parts by weight may or may not add up to 100 parts. They are simply listed as a number of parts with a relative amount compared to the total number of parts.

[0029] When numerical values ​​are disclosed herein, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc., the following sentence typically follows such numerical values: "Each of the foregoing numbers can be preceded by the term "about," "at least about," or "less than about," and any of the foregoing numbers can be used alone to describe an open-ended range, or in combination to describe a limited range." This sentence means that each of the foregoing numbers can be used alone (e.g., 4), can be preceded by the word "about" (e.g., about 8), can be preceded by the phrase "at least about" (e.g., at least about 2), can be preceded by the phrase "less than about" (e.g., less than about 7), or can be used in any combination with or without any of the preceding words or phrases to define a range (e.g., 2 to 9, about 1 to 4, 8 to about 9, about 1 to about 10, etc.). Furthermore, if a range is described as "about X or less," this phrase is equivalent to the range "about X" combined with "less than about X" instead. For example, "about 10 or less" is equivalent to "about 10, or less than about 10." Such interchangeable range descriptions are contemplated herein. Other range formats are disclosed herein, but the difference in format should not be construed to imply a difference in substance.

[0030] The use of numerical values ​​in the various quantitative values ​​set forth in this application is described as approximations, unless expressly indicated otherwise, as if the minimum and maximum values ​​in the stated ranges were both preceded by the word "about". In this manner, slight variations from the stated values ​​may be used to achieve substantially the same results as the stated values. The disclosure of ranges also contemplates a continuous range, including all values ​​between the minimum and maximum values ​​recited, and any ranges that may be formed by such values. Also disclosed herein are any and all ratios (and ranges of any such ratios) that may be formed by dividing a recited numerical value into any other recited numerical value. Thus, one of ordinary skill in the art will appreciate that many such ratios, ranges, and ranges of ratios thereof may be explicitly derived from the numerical values ​​presented herein, and in all instances, such ratios, ranges, and ranges of ratios thereof represent various embodiments of the present invention.

[0031] As used herein, the term "substantially free" means a composition having less than about 1% by weight, e.g., less than about 0.5% by weight, less than about 0.1% by weight, less than about 0.05% by weight, or less than about 0.01% by weight of the indicated substance, based on the total weight of the composition.

[0032] As used herein, the term "substantially" when used in reference to a composition means at least about 60% by weight, e.g., at least about 70% by weight, at least about 80% by weight, at least about 90% by weight, at least about 95% by weight, at least about 98% by weight, at least about 99% by weight, or about 100% by weight of a particular feature or component, based on the total weight of the composition.

[0033] Hydroxyl (OH) number is a measure of the amount of reactive hydroxyl groups available for reaction. OH number is measured by ASTM D 4274-88. The total equivalent weight of the polyols disclosed herein can be calculated using the OH number according to the formula:

number

[0034] %NCO is a measure of the amount of reactive isocyanate groups available for reaction. %NCO is measured by ASTM D 2575-97. The total equivalent weight of the pMDI disclosed herein can be calculated using %NCO according to the formula:

number

[0035] As used herein and in the art, the isocyanate (NCO) index of a polyurethane or polyisocyanurate foam formulation is the amount of (actual) isocyanate groups in the formulation divided by the amount of (theoretical) isocyanate groups required to react with the available polyol -OH groups in the formulation. This ratio is multiplied by 100, such that an index of 100 corresponds to a stoichiometric equivalent of -NCO and -OH (an index greater than 100 is equivalent to an excess of isocyanate). The formulation index can vary widely depending on the desired properties and end use of the foam. For example, flexible polyurethane foams can have a formulation index of 30 to 100, and rigid polyurethane foams can more typically have a formulation index of 100 to 250. The index for polyisocyanurate (rigid) foam formulations is usually much higher, usually greater than 250, such as about 250 to about 400.

[0036] Generally, polyurethanes are produced by reacting an isocyanate (R-(N=C=O)n), i.e., a polyisocyanate, containing two or more isocyanate groups per molecule, with a polyol (R'-(OH)n), containing an average of two or more hydroxyl groups per molecule; the polymerization reaction creates a polymer containing a urethane linkage -RNHCOOR'-. At room temperature, the reaction between the polyisocyanate and the polyol begins almost instantly, so the two components are not stored together prior to the desired foaming process. Typically, they are stored as an A-side component containing the polyisocyanate, and a B-side component containing the polyol. Typically, for the formation of free-standing or space-filling foams, a catalyst is used to optimize the balance between foam blowing and gelling. When formulating an NCO index greater than 200, a trimerization catalyst can be added to the B-side component. The catalyst may include, for example, one or more amines as blowing catalysts, such as tertiary amines, for example, N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, 4,4'-(oxydi-2,1-ethanediyl)-bismorpholine (DMDEE), 1,4-diazabicyclo[2.2.2]octane (DABCO) or 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) or N1-(2-(dimethylamino)ethyl)-N2,N2-dimethylethane-1,2-diamine, and one or more metal compounds or one or more carboxylate salts as gelation catalysts (or gelling catalysts), such as dibutyltin dilaurate or tin octoate (generally tin carboxylates or dialkyltin dicarboxylates) or bismuth octoate or potassium octoate or potassium pivalate. The potassium carboxylate salt also serves as a trimerization catalyst in the formulation, where the NCO index is desirably greater than 200. Since most catalysts react with or cause the polyisocyanate to react with itself, the catalyst is traditionally formulated with the polyol (included in the B-side component). For convenience, all other formulation ingredients are then usually included in the B-side component.As an exception, blowing agents are typically placed in both the A-side and B-side components. The A-side component is traditionally limited to only one or more polyisocyanates, optionally with one or more blowing agents and / or surfactants.

[0037] Polyisocyanurate foams are produced from starting materials and formulation components similar to those used to make polyurethane foams, except that the percentage of isocyanate is higher. However, the resulting chemical structure of polyisocyanurates is significantly different, with the isocyanate groups trimerizing to form six-membered (alternating -CN-) isocyanurate ring structures with N-pendant polyol groups further linking the isocyanurate groups.

[0038] In both cases (polyurethane foam and polyisocyanurate foam), the A-side and B-side components are contained and stored in separate containers or stored in separate compartments within the same container. The A-side component formulation and the B-side component formulation are usually kept separate and delivered through separate lines to a dispensing unit, which typically accomplishes the mixing and dispensing of the two combined components in the form of a spray.

[0039] Herein, a heterocyclic amine is a compound that contains at least one heterocyclic ring, which by definition has at least two atoms of different elements in the cyclic backbone of the ring structure, and at least one amine group.Generally, heteroatom refers to an atom that is neither carbon nor hydrogen, although in the art, most ring compounds contain carbon in the cyclic backbone of the heterocyclic ring, and thus the most common meaning of the term "heteroatom" (when describing cyclic ring structures, and especially in relation to the cyclic backbone of the heterocyclic ring) is an atom that is not carbon.

[0040] As used herein, the term "N-heterocyclic amine" refers to a compound containing at least one heterocycle containing at least two different elements, at least one of which is a nitrogen atom, and at least one amine group. Thus, an "N-heterocyclic amine" has at least one heteroatom in the cyclic backbone of the (at least one) heterocycle, at least one of which is a nitrogen atom. It may have more than one nitrogen atom in the heterocycle, and / or it may also contain one or more other heteroatoms (such as oxygen or sulfur) in the heterocycle structure. As used herein, "N,N-heterocyclic amine" and "N,X-heterocyclic amine" are subsets within the term "N-heterocyclic amine". For the avoidance of doubt, heteroatoms present on pendant groups attached to the backbone of the cyclic ring structure are not included in the count of heteroatoms in the cyclic backbone of the heterocycle.

[0041] As used herein, "N,N-heterocyclic amine" means a heterocyclic amine that contains at least two nitrogen atoms in the cyclic backbone of the cyclic ring structure.

[0042] As used herein, "N,X-heterocyclic amine" refers to a heterocyclic amine as described above, where X is a heteroatom other than nitrogen; for example, X could be oxygen (O) or sulfur (S). Thus, an "N,X-heterocyclic amine" has at least two heteroatoms in the cyclic backbone of the heterocycle, at least one of which is a nitrogen atom, and at least one of which is a heteroatom other than nitrogen. It may have two or more nitrogen atoms in the heterocycle, and / or it may also have two or more other heteroatoms (such as oxygen or sulfur) in the heterocycle structure.

[0043] The problem addressed herein is the poor shelf life stability of polyurethane or polyisocyanurate foam formulations when using HHO (including HFO) blowing agents. The halide ion, X-, is a by-product of an unwanted side reaction between the catalyst and the HHO blowing agent during storage (the fluoride ion, F-, is a by-product of an unwanted side reaction between the catalyst and the HFO blowing agent during storage). The amount of halide ion (fluoride ion) generated is evaluated using an accelerated aging study heated at 50°C. (Aging at 50°C for one week is approximately equivalent to aging at room temperature (25°C) for one to three months).

[0044] Herein, in some embodiments, a two-component polyurethane or polyisocyanurate spray foam composition is considered to be "storage stable" when both the A-side and B-side components, separately, generate less than 600 ppm of halide ions (fluoride ions) after 2 weeks of aging at 50° C.; or, in some embodiments, such a composition is considered to be "storage stable" when both the A-side and B-side components, separately, generate less than 200 ppm of halide ions (fluoride ions) after 2 weeks of aging at 50° C. Further, in some embodiments, a two-component polyurethane or polyisocyanurate spray foam composition is considered to be "storage stable" when both the A-side and B-side components, separately, are stable with respect to gelling into a solid or gel over a two month period, and both the A-side and B-side components, separately, generate less than 600 ppm (or, in some embodiments, 200 ppm) of halide ions (fluoride ions) after 2 weeks of aging at 50° C.

[0045] As used herein, the term "gel" is used in its ordinary sense in chemistry. The general definition given by the International Union of Pure and Applied Chemistry (IUPAC) describes a gel as "a non-fluid colloidal or polymeric network that is expanded throughout its entire volume by a fluid" (Aleman et al., 2007). As used herein, a gel may not be easily sprayable.

[0046] In general, suitable polyisocyanates for the synthesis of polyurethanes include aliphatic, cycloaliphatic, arylaliphatic and aromatic polyisocyanates. The polyisocyanates can be polymeric isocyanates, monomeric isocyanates, or blends of monomeric and polymeric isocyanates. Examples of suitable polyisocyanates include alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene portion (e.g., 1,12-dodecane diisocyanate; 2-methylpentamethylene 1,5-diisocyanate; tetramethylene 1,4-diisocyanate; and hexamethylene 1,6-diisocyanate (HDI)), cycloaliphatic diisocyanates (e.g., cyclohexane 1,3- and 1,4-diisocyanate (CHDI); 5-isocyanato-1-( isocyanatomethyl)-1,3,3-trimethyl-cyclohexane (also known as isophorone diisocyanate, or IPDI); 2,4- and 2,6-hexahydrotoluene diisocyanate and the corresponding isomeric mixtures; 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate (H12MDI) and the corresponding isomeric mixtures), and aromatic diisocyanates and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate. isocyanate and its corresponding isomeric mixtures; 4,4'-, 2,4'-, and 2,2'-diphenylmethane diisocyanate and their corresponding isomeric mixtures; and polymethylene polyphenylisocyanate (polymeric MDI or p(MDI). In some embodiments of the present invention, the polyurethane or polyisocyanurate foam is formed from one or more polyisocyanates that may include or consist of a polymeric polyisocyanate compound, such as p(MDI). In some embodiments, the composition may include p(MDI) having an equivalent weight in the range of 100 to 10,000, desirably 100 to 5,000, or 100 to 2,500. In some embodiments of the present invention, the polyurethane polymer is formed from one or more aliphatic or cycloaliphatic polyisocyanate compounds. In some embodiments, the one or more aliphatic or cycloaliphatic polyisocyanates include isophorone diisocyanate.In some embodiments, the one or more aliphatic or cycloaliphatic polyisocyanates are isophorone diisocyanate. In some embodiments, the polyurethane or polyisocyanurate spray foam of the present invention is free of toluene diisocyanate and reaction products of toluene diisocyanate to avoid concerns about possible health problems associated with toluene diisocyanate. In some embodiments, the polyurethane or polyisocyanurate spray foam of the present invention is substantially free of monomeric aromatic polyisocyanates and reaction products of monomeric aromatic polyisocyanates to avoid concerns about possible health problems associated with monomeric aromatic polyisocyanates. Commercially available polyisocyanates include, but are not limited to, Lupranate® M20S (BASF Corp., Ludwigshafen, Germany), Mondur® MR (Covestro, Leverkusen, Germany), and PAPI™ 27 (Dow Chemical Co., Midland, MI, USA).

[0047] The polyol component is generally one or more polymeric polyols, characterized as having an average hydroxyl functionality of 2.0 or greater, typically in the range of 2.0 to 7.0. The average hydroxyl functionality for the polymeric polyol component can be measured according to ASTM D4274-11 (Method D). The hydroxyl functionality of the polyols in the polymeric polyol component can be any value, but should be selected such that the average hydroxyl functionality of the overall polymeric polyol component is in the desired range, such as, but not limited to, 2.0 to 7.0.

[0048] Suitable polymeric polyol components for polyurethane synthesis include polyether polyols, polyester polyols, and polycarbonate polyols, as well as polycaprolactone polyols, polyacrylate polyols, polybutadiene polyols, and polysulfide polyols. These can be used individually or in any desired mixture with each other. Polyisocyanurate foams generally use polyester polyols.

[0049] Polyether polyols include those obtained using conventional synthetic means by reacting an epoxide (an alkylene oxide, such as one selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, or a combination thereof) with an initiator having two active hydrogen atoms (for a diol), or an initiator having three active hydrogen atoms (for a triol), or an initiator having more than three active hydrogen atoms (for a polyol with more than three hydroxyl functional groups). Examples of suitable initiators include cycloaliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, glycerol, trimethylolpropane, ethylenediamine, triethanolamine, sucrose, and aromatic initiators, or mixtures thereof. The preferred polyols are those obtained using ethylene oxide, or propylene oxide, or a combination of ethylene oxide and propylene oxide (i.e., poly(ethylene oxide-propylene oxide)). Another commonly used polyether polyol is polytetramethylene glycol polyol. Polyether polyols are commercially available, such as, but not limited to, Voranol™ 360, Voranol™ 370, or Voranol™ RN482 (The Dow Chemical Co., Midland, MI, USA); or JEFFOL® SG-360 or JEFFOL® SG-522 (Huntsman Corp., The Woodlands, TX, USA); or Carpol® SP-477, Carpol® GSP-280, or Carpol® GSP-355 (Carpenter Co., Richmond, VA, USA).

[0050] Polyester polyols include those obtained by conventional synthesis means using polycarboxylic acids and polyfunctional alcohols, such as those having 2 to 12 carbon atoms. Examples of suitable polycarboxylic acids include glutaric acid, succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid. Examples of suitable polyfunctional alcohols that can be combined with any of these polycarboxylic acids include ethylene glycol, propanediol (such as propylene glycol), butanediol, hexanediol, and neopentyl glycol. For example, poly(neopentyl glycol adipate) can be synthesized using neopentyl glycol and adipic acid. Polyester polyols are commercially available, for example, but not limited to, Terol® 350 or Terol® 352 (Huntsman Corp., The Woodlands, TX, USA); or STEPANPOL® PS-2352 or STEPANPOL® PS-2412 (Stepan Company, Northfield, IL, USA); or Terate® 3512 or Terate® 3512A (INVISTA, Wichita, KS, USA).

[0051] Polycarbonate polyols include those obtained from the reaction of polyfunctional alcohols (e.g., diols, including those disclosed above) with carbon acid derivatives, such as diphenyl carbonate, dimethyl carbonate, ethylene carbonate, or phosgene. For example, polyhexamethylene carbonate can be synthesized by transesterification polycondensation of ethylene carbonate (or dimethyl carbonate) with 1,6-hexanediol. Polycarbonate polyols are commercially available, such as, but not limited to, DESMOPHEN® C 2100 (Covestro AG, Leverkusen, Germany).

[0052] In some embodiments, the composition can include one or more polymeric polyether polyols, polyester polyols, polycarbonate polyols, or combinations thereof, having an equivalent weight (g / eq) in the range of 30 to 10,000, more preferably 30 to 5,000, and most preferably 30 to 2,500.

[0053] The amounts of isocyanate and polyol in the present invention are generally such as to provide a formulation index for the polyurethane foam formulation of about 30 to 300. In certain embodiments, the polyurethane foam formulation index (the ratio of isocyanate-NCO groups to polyol-OH groups multiplied by 100) is 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, or 300. Each of the foregoing numbers can be preceded by the word "about," "at least about," or "less than about," and any of the foregoing numbers can be used alone to describe an open-ended range, or in combination to describe a limited range. In an embodiment designed for rigid foams, the index for the polyurethane foam formulation is 100-300, desirably 100-250, or 100-200. In another embodiment designed for flexible foams, the index for the foam formulation is 30-100, desirably 35-95, or 40-80.

[0054] The index for polyisocyanurate foam formulations is usually much higher, usually greater than 150, such as from about 150 to about 400. In certain embodiments, the index for polyisocyanurate foam formulations (100 times the ratio of isocyanate-NCO groups to polyol-OH groups) is 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, or 400. Each of the foregoing numbers can be preceded by the word "about," "at least about," or "less than about," and any of the foregoing numbers can be used alone to describe an open-ended range, or in combination to describe a limited range. In one embodiment, the index for the polyisocyanurate foam formulation is 180-400, desirably 200-350, or 250-350.

[0055] To facilitate the production of fine wet foams and, optionally, to provide enhanced properties for specific applications for the cured foam, the combined components of the A-side component and the B-side component can be blended to provide a foamable pre-urethane or pre-cyanurate composition upon spraying and combining the two pack components. For example, for dispensing from a pressurized container, the blend can include one or more propellants, such as liquefied soluble blowing gases (blowing agents) as known in the art. Blowing agents are often referred to in the art as gaseous or liquid blowing agents, depending on the state of the blowing agent at ambient temperature and pressure (e.g., at 25°C and 1 atm). The A-side component and, separately, the B-side component can include one or more gaseous blowing agents, or one or more liquid blowing agents, or both one or more gaseous and one or more liquid blowing agents.

[0056] Optionally, other known blowing agents can function as co-blowing agents, but desirably the first blowing agent is one or more hydrohaloolefins because they have a lower global warming potential. Suitable hydrohaloolefins include fluoroalkenes or chlorofluoroalkenes containing 3 to 4 carbon atoms and at least one C-C double bond.

[0057] Suitable gaseous hydrohaloolefin blowing agents in either the A-side component or the B-side component, or both, include, but are not limited to, hydrofluoroolefins, such as 3,3,3-trifluoropropene (HFO); 1,3,3,3-tetrafluoropropene (HFO1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO1234yf); 1,2,3,3,3-pentafluoropropene (HFO1225ye); 1,1,1,3,3-pentafluoropropene (HFO1225zc); 1,1,2,3,3-pentafluoropropene (HFO1225yc); (Z)-1,1,1,2,3-pentafluoropropene (HFO1225yez(Z)); or combinations thereof.

[0058] Suitable liquid hydrohaloolefin blowing agents in either the A-side component or the B-side component, or both, include, but are not limited to, hydrofluoroolefins, such as (Z)-1,1,1,4,4,4-hexafluorobut-2-ene (HFO 1336mzzm(Z)); and hydrochlorofluoroolefins, such as, for example, (E)-1-chloro-3,3,3-trifluoropropene (HFO 1233zd(E)).

[0059] In some embodiments, the preferred hydrohaloolefin is selected from one or more of (E)-1-chloro-3,3,3-trifluoropropene (1233zd(E)), (E)-1,3,3,3-tetrafluoropropene (1234ze(E)), and (Z)-1,1,1,4,4,4-hexafluorobut-2-ene (1336mzzm(Z)), and combinations thereof. Desirably, the hydrohaloolefin in either the A-side component or the B-side component, or both, comprises 1,3,3,3-tetrafluoropropene (HFO 1234ze). The total blowing agent content can be 1-40% by weight of the combined A-side and B-side component formulation, or more typically 3-30%, or 3-25%, or 10-20% by weight of the total weight of the foamable pre-urethane or pre-socianurate components. The blowing agent is more typically included in the B-side (polyol) component, but may optionally be present in both the A-side and B-side components (the weight percent of the blowing agent in the A-side and B-side components may be equal or unequal). For example, excluding water, the blowing agent content may be 1-45 weight percent of the B-side component formulation, or more typically 5-40 weight percent, or 10-35 weight percent of the B-side component formulation; and excluding water, the blowing agent content may be 0-30 weight percent of the A-side component formulation, or more typically 0-20 weight percent, or 5-20 weight percent, or 5-15 weight percent of the A-side component formulation. Desirably, at least 50 weight percent, or at least 75 weight percent of the total blowing agent content (combined A-side and B-side components) is HHO; in some embodiments, at least 90 weight percent of the total blowing agent content, or in some embodiments, all of the blowing agent is HHO. In some embodiments, at least 50% by weight, or at least 75% by weight, of the total blowing agent content (combined A-side and B-side components) is an HFO; in some embodiments, at least 90% by weight of the total blowing agent content, or in some embodiments, all of the blowing agent is an HFO.

[0060] The optional co-blowing agent, as known in the art, is not particularly limited in type and may include, for example, chlorofluorocarbons (CFCs) and / or hydrofluorocarbons (HFCs), such as, for example, propane, butane, isobutane, pentane, hexane, dimethyl ether, diethyl ether, acetone, methyl ethyl ketone, etc., and / or hydrofluorocarbons (HFCs), such as, for example, trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), and 1,1-difluoroethane (HFC-152a), etc., which may be used alone or in combination. Other auxiliary gases, such as carbon dioxide, nitrogen, argon, etc., may also be used.

[0061] Optionally, water may be incorporated into these compositions, for example in an amount of 0-10% by weight of the total composition, since it reacts with the isocyanate to produce carbon dioxide which in turn acts as a co-blowing agent. As used herein, the terms "blowing agent" and "co-blowing agent" do not include water, even though it may have a similar effect.

[0062] Traditionally, polyurethane and polyisocyanurate foams are produced using one or more of three types of catalysts, e.g., blowing catalysts, gelling catalysts, and trimerization catalysts. Traditional gelling catalysts include various metal complexes, e.g., tin carboxylates, bismuth carboxylates, zinc carboxylates, zirconium carboxylates, and nickel carboxylates. Examples include stannous octoate (stannous (II) 2-ethylhexanoate), tin mercaptides, and dibutyltin dilaurate (generally dialkyltin dicarboxylates). Traditional blowing catalysts more commonly include various tertiary amines, e.g., trimethylamine, triethylamine, dimethylethanolamine, or 1,4-diazabicyclo[2.2.2]octane (DABCO). Traditional trimerization catalysts in formulations with an NCO index greater than 200 include potassium carboxylate salts, e.g., potassium octoate or potassium pivalate. Such catalysts are usually effective in amounts of 0.25% to 3.0% by weight, although higher or lower amounts may be used. Traditionally, for example, when using HFC and CFC blowing agents, the B-side component is the fully formulated component, including the catalyst and all other additives, while the A-side component is simply one or more isocyanate components, optionally with a blowing agent to aid in dispensing the isocyanate and mixing with the B-side formulation components as the A-side component is dispensed. Commonly used catalysts cannot be added to the A-side components, as they will either react with the isocyanate or cause the isocyanate to react with itself, resulting in the container contents completely solidifying within a few days. This approach has been considered unhelpful.

[0063] As alluded to above, HFC and CFC blowing agents will soon be regulated and will no longer be available for use in such two-component polyurethane or polyisocyanurate spray foam compositions. HFO blowing agents appear to be a suitable alternative, at least in view of having a much lower global warming potential, except that the formulations are not as storage stable and foams made from stored formulations are of poor and unsatisfactory quality.

[0064] Quite unexpectedly, applicants have discovered that certain amines are, in fact, storage stable with isocyanates. For example, N-heterocyclic amines, such as 4-(2-hydroxyethyl)morpholine, dimorpholinodiethyl ether, 4-(2-chloroethyl)morpholine, 4-ethylmorpholine, or 4-(2-aminoethyl)morpholine, are found to be storage stable when mixed with isocyanates. The inclusion of a gelling catalyst in the B-side component of the formulation and an N-heterocyclic amine in the A-side component of the formulation provides a storage stable two-component polyurethane or polyisocyanurate spray foam composition with one or more HFO blowing agents in either the A-side or the B-side or both, which storage stable compositions produce fully satisfactory (but more environmentally friendly) foams equivalent in quality to those produced from conventional processes using HFC and CFC blowing agents.

[0065] Other optional additives as known in the art include, but are not limited to, viscosity modifiers (thickeners), surfactants, flame retardants, antifreeze agents, preservatives, co-solvents, cell stabilizers, colorants, fillers, pigments, biocides, fungicides, algaecides, etc. Such additives may constitute 5-30% of the total foamable pre-urethane or pre-socianurate component.

[0066] In some embodiments, the total foamable A-side and B-side components contain 10% or less by weight of an ionic surfactant, soap, or wax, e.g., 0.1-10% by weight based on the total foamable A-side and B-side components. In some embodiments, the foamable A-side and B-side components contain less than 0.3% by weight of an ionic surfactant, soap, or wax, based on the total foamable A-side and B-side components. Such ionic surfactants, soaps, or waxes, if used, are typically added to the B-side component of the formulation. In some embodiments, the foamable A-side and B-side components are free of ionic surfactants, soaps, or waxes.

[0067] Other surfactants as known in the art, such as silicone surfactants, may also or alternatively be used. In some embodiments, the silicone surfactant is a polysiloxane-polyoxyalkylene block copolymer. Alternatively, or in addition, non-silicone non-ionic surfactants may be used. Such surfactants may be added to either or both of the A-side and B-side components of the formulation (in a total amount of 0.25-5.0 wt%, preferably 1.0 wt%-4.0 wt% of the total A-side and B-side component formulation weight), but are usually added to the B-side component of the formulation in an amount of 0.25-5.0 wt%, preferably 1.0 wt%-4.0 wt% of the B-side component formulation weight.

[0068] Polyurethane and polyisocyanurate foams find utility in many building and construction applications, and so the fully formulated compositions may (and often do) optionally incorporate a flame retardant (in a total amount of 0-30% by weight, preferably 1.0%-10% by weight of the combined A-side and B-side component formulation weight). Suitable flame retardants, as known in the art, include (but are not limited to) alkyl phosphates, haloalkyl phosphates, alkyl phosphonates, haloalkyl phosphonates, or halogenated polyols, such as, for example, triethyl phosphate, tris(chloropropyl)phosphate, tris(2-chloroethyl)phosphate, tris(2,3-dibromopropyl)phosphate, diethylethylphosphonate, diethyl(bromodifluoromethyl)-phosphonate, tetrabromophthalate diol, and the like.

[0069] In certain embodiments, both the formulation A-side components and the formulation B-side components described herein can separately exhibit a fluoride ion concentration range of 0 ppm to 600 ppm after heating for 2 weeks at 50° C. The fluoride ion concentration (in ppm) of either or both of the A-side components and B-side components after heating for 2 weeks at 50° C. can be 0, 0.1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 150, 160, 180, 200, 220, 240, 250, 260, 280, 300, 320, 340, 350, 360, 380, 400, 450, 500, 550, or 600. Each of the foregoing numbers can be preceded by the word "about," "at least about," or "less than about," and any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a limited range. For example, in some embodiments, the fluoride ion concentration after heating at 50° C. for 2 weeks can be less than about 600 ppm, e.g., 0.1 ppm to 600 ppm, and desirably less than 300 ppm, or less than 250 ppm, or less than 200 ppm. Desirably, the fluoride ion concentration after heating at 50° C. for 2 weeks is zero or near zero, e.g., less than 150 ppm, e.g., 0.1 ppm to 150 ppm, less than 100 ppm, e.g., 0.1 ppm to 100 ppm, or less than 50 ppm, e.g., 0.1 ppm to 50 ppm, or less than 30 ppm, e.g., 0.1 ppm to 30 ppm.

[0070] Formulation shelf life instability affects characteristic polyurethane / polyisocyanurate reaction parameters. For spray applications, short gel and tack-free times are essential even after at least 6 months shelf life. The acceptable range of reactivity change after 4 weeks aging at 50° C. is less than a 30% increase in gel or tack-free time compared to a fresh sample of the same formulation. In some embodiments, the combination of A-side components with B-side components results in gel and tack-free times that change by less than 30% when the components are aged at 50° C. for 4 weeks compared to the gel and tack-free times that occur for the freshly prepared and combined components. Desirably, the combination of A-side components with B-side components results in gel and tack-free times that change by less than 20% when the components are aged at 50° C. for 4 weeks compared to the gel and tack-free times that occur for the freshly prepared and combined components.

[0071] Furthermore, foams derived from aged formulations should demonstrate the same or similar properties as foams derived from fresh formulations. Measurement of the open cell content of foams is a good analytical tool for evaluating foam quality. Desirably, the open cell content of sprayed foams derived from sprayed two-component foam compositions is preferably 25% or less, desirably 20% or less.

[0072] In some embodiments, there is provided a method of providing a space-filling layer or volume near a surface, the method comprising, consisting of, or consisting essentially of the steps of applying a foamed or pre-foamed mixture of foamable A-side and B-side component components of the present invention to said surface; and curing the foamed sample of the foamable components to provide a stable foam. For example, disclosed herein is a method of providing a space-filling layer or volume near a surface, the method comprising, consisting of, or consisting essentially of the steps of: (a) providing a foamable composition comprising: (i) an A-side component comprising one or more polyisocyanates and one or more catalysts, and, optionally, one or more hydrohaloolefin blowing agents; and (ii) a B-side component comprising one or more polyols and one or more hydrohaloolefin blowing agents, where both the A-side and B-side components, separately, generate less than 600 ppm fluoride ion after aging at 50° C. for 2 weeks; (b) applying a foamed or pre-foamed sample of the foamable composition to said surface; and (c) curing the foamed sample of the foamable composition to a foam having a density of less than 48 kg / m3. In some embodiments, the step of applying the foamed or pre-foamed sample of the foamable composition is performed by dispensing the foamable composition from a pressurized container.

[0073] In some embodiments, foams are provided that are made from the foamable compositions of the present invention. In some embodiments, the foam is dispensed from a pressurized container and dried to form the foam. The physical properties of the foam can be adjusted to some extent depending on the desired application. For example, the foam can be flexible, rigid, or semi-rigid and can have a closed cell structure, an open cell structure, or a mixture of open and closed cells. Dry flexible polyurethane foams can have a density of about 4.8 to about 24.0 kg / m3, desirably about 6.4 to about 16.0 kg / m3, and dry rigid polyurethane foams can have a density of about 16.0 to about 48.0 g / m3, desirably about 24.0 to about 40.0 kg / m3. Dry rigid polyisocyanurate foams can have a density of about 16.0 to about 48.0 kg / m3, desirably about 24.0 to about 40.0 kg / m3. Foams may be used in many fields and applications, such as, without limitation, packaging, building and construction materials, and many more. In building and construction, foams may be used to fill the space between two surfaces or portions of two surfaces, to prevent air transmission through gaps in the building envelope, to provide thermal and / or acoustic insulation, to prevent unwanted movement of surfaces, or to prevent wear or rattle due to moving surfaces. Flexible foams are also utilized as caulking materials, sealants, or gaskets.

[0074] Some embodiments disclosed herein are set forth in the following clauses, and any combination of these clauses (or portions thereof) may be made to clarify the embodiments. For example, if a composition described in an embodiment may vary according to additional features or claim elements, it should be understood that other compositions described in other embodiments may also vary according to the same additional features or claim elements. Furthermore, methods described herein that utilize the compositions may also vary according to such compositional variations.

[0075] Clause 1: A storage stable two-component polyurethane or polyisocyanurate spray foam composition comprising: (a) an A-side component comprising one or more polyisocyanates and one or more catalysts, such as one or more blowing catalysts; (b) a B-side component comprising one or more polyols; and further comprising one or more hydrohaloolefin blowing agents in either the A-side component or the B-side component, or both; wherein both the A-side component and the B-side component, separately, generate less than 600 ppm, or less than 300 ppm, of fluoride ions after 2 weeks aging at 50° C. In some embodiments, the one or more hydrohaloolefin blowing agents in either the A-side component or the B-side component, or both, are gaseous hydroxyhexanophenone blowing agents or comprise gaseous hydrohaloolefin blowing agents.

[0076] Clause 2: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of clause 1, wherein the one or more catalysts in the A-side component are or include a blowing agent.

[0077] Clause 3: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of clause 1, wherein the one or more catalysts in the A-side component is or includes an amine.

[0078] Clause 4: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of clause 1, wherein the one or more catalysts in the A-side component is or includes a tertiary amine.

[0079] Clause 5: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of clause 1, wherein the one or more catalysts in the A-side component are or include an N-heterocyclic compound.

[0080] Clause 6: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of clause 1, wherein the one or more catalysts in the A-side component are or include an N-heterocyclic compound selected from pyrrolidines, pyrrolidones, imidazolidines, pyrazolidines, oxazolidines, isoxazolidines, thiazolidines, isothiazolidines, piperidines, piperazines, morpholines, thiomorpholines, morpholinones, and morpholinediones.

[0081] Clause 7: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of any one of Clauses 1 to 6, wherein the one or more catalysts in the A-side component are or include an N,X-heterocyclic compound.

[0082] Clause 8: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of any one of clauses 1-7, wherein the one or more catalysts in the A-side component is or comprises a morpholino compound.

[0083] Clause 9. The storage stable two-component polyurethane or polyisocyanurate spray foam composition of clause 8, wherein the morpholino compound is 4-(2-hydroxyethyl)morpholine, dimorpholinodiethyl ether, 4-(2-chloroethyl)morpholine, 4-ethylmorpholine, or 4-(2-aminoethyl)morpholine, or a combination thereof.

[0084] Clause 10: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of clause 8, wherein the morpholino compound is 4-(2-hydroxyethyl)morpholine.

[0085] Clause 11: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of clause 8, wherein the morpholino compound is dimorpholino diethyl ether.

[0086] Clause 12: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of any one of clauses 1-11, wherein a hydrohaloolefin blowing agent is present in the A-side component. In some embodiments, the hydrohaloolefin blowing agent is or comprises a gaseous hydrohaloolefin blowing agent.

[0087] Clause 13: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of any one of clauses 1-11, wherein a hydrohaloolefin blowing agent is present in the B-side component. In some embodiments, the hydrohaloolefin blowing agent is or comprises a gaseous hydrohaloolefin blowing agent.

[0088] Clause 14: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of any one of clauses 1-11, wherein a hydrohaloolefin blowing agent is present in both the A-side component and the B-side component. In some embodiments, the hydrohaloolefin blowing agent is or comprises a gaseous hydrohaloolefin blowing agent.

[0089] Clause 15: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of any one of clauses 1-11, wherein the one or more hydrohaloolefin blowing agents is a hydrofluoroolefin blowing agent. In some embodiments, the hydrofluoroolefin blowing agent is or comprises a gaseous hydrofluoroolefin blowing agent.

[0090] Clause 16: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of any one of clauses 12-14, wherein the one or more hydrohaloolefin blowing agents are hydrofluoroolefin blowing agents. In some embodiments, the hydrofluoroolefin blowing agent is or comprises a gaseous hydrofluoroolefin blowing agent.

[0091] Clause 17: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of any one of clauses 15 or 16, wherein the hydrofluoroolefin blowing agent is selected from 3,3,3-trifluoropropene (HFO); 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,1,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-pentafluoropropene (HFO 1225yc); (Z)-1,1,1,2,3-pentafluoropropene (HFO1225yez(Z)); or combinations thereof.

[0092] Clause 18: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of any one of clauses 1 to 17, having a Foam Formulation Index of 100 to 400.

[0093] Clause 19: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of any one of clauses 1-18, wherein both the A-side component and the B-side component, separately, generate less than 200 ppm fluoride ion after 2 weeks aging at 50° C. In some embodiments, both the A-side component and the B-side component, separately, generate less than 150 ppm, or less than 100 ppm fluoride ion after 2 weeks aging at 50° C.

[0094] Clause 20: A storage-stable two-component polyurethane or polyisocyanurate spray foam composition comprising: (a) The following: (i) one or more polyisocyanates, (ii) one or more blowing agents, (iii optionally one or more hydrohaloolefin A-side blowing agents, and (iv) optionally one or more surfactants; and (b) The following: (i) one or more polyols, (ii) one or more gelling catalysts, (iii) one or more hydrohaloolefin B-side blowing agents, (iv) optionally, one or more flame retardants, and (v) optionally, one or more surfactants. B-side components including A composition comprising:

[0095] Clause 21: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of clause 20, wherein at least one of the one or more hydrohaloolefin A-side blowing agents or the one or more hydrohaloolefin B-side blowing agents, or both the A-side blowing agents and the B-side blowing agents, is a gaseous hydrohaloolefin blowing agent. In some embodiments, at least one of the one or more hydrohaloolefin A-side blowing agents or the one or more hydrohaloolefin B-side blowing agents, or both the A-side blowing agents and the B-side blowing agents, is a hydrofluoroolefin blowing agent. In some embodiments, at least one of the one or more hydrohaloolefin A-side blowing agents or the one or more hydrohaloolefin B-side blowing agents, or both the A-side blowing agents and the B-side blowing agents, is a gaseous hydrofluoroolefin blowing agent.

[0096] Clause 22: The storage stable two-component polyurethane or polyisocyanurate spray foam composition of clauses 20 or 21, wherein the one or more blowing catalysts in the A-side component are or include a morpholino compound.

[0097] Clause 23. The storage stable two-component polyurethane or polyisocyanurate spray foam composition of clause 22, wherein the morpholino compound is 4-(2-hydroxyethyl)morpholine, dimorpholinodiethyl ether, 4-(2-chloroethyl)morpholine, 4-ethylphenyl)morpholine, or 4-(2-aminoethyl)morpholine, or a combination thereof.

[0098] Clause 24: A method for providing a space-filling layer or volume in the vicinity of a surface, the method comprising: (a) The following: (i) an A-side component comprising one or more polyisocyanates and one or more catalysts, e.g., blowing catalysts, and, optionally, one or more hydrohaloolefin blowing agents; and (ii) a B-side component comprising one or more polyols and one or more hydrohaloolefin blowing agents; providing a foamable composition comprising (wherein both the A-side component and the B-side component separately generate less than 600 ppm, or less than 300 ppm, of fluoride ion after aging for 2 weeks at 50° C.); (b) applying a foamed or pre-foamed sample of a foamable composition to the surface; (c) curing a foamed sample of the foamable composition into a foam having a density of less than 48 kg / m3; The process comprises, consists of, or consists essentially of the steps. In some embodiments, at least one of the one or more hydrohaloolefin A-side blowing agents or one or more hydrohaloolefin B-side blowing agents, or both the A-side and B-side blowing agents, is a gaseous hydrohaloolefin blowing agent. In some embodiments, at least one of the one or more hydrohaloolefin A-side blowing agents or one or more hydrohaloolefin B-side blowing agents, or both the A-side and B-side blowing agents, is a hydrofluoroolefin blowing agent. In some embodiments, at least one of the one or more hydrohaloolefin A-side blowing agents or one or more hydrohaloolefin B-side blowing agents, or both the A-side and B-side blowing agents, is a gaseous hydrofluoroolefin blowing agent.

[0099] Clause 25: The process of clause 24, wherein the one or more catalysts in the A-side component is or comprises a morpholino compound.

[0100] Clause 26: The method of clause 25, wherein the morpholino compound is 4-(2-hydroxyethyl)morpholine, dimorpholinodiethyl ether, 4-(2-chloroethyl)morpholine, 4-ethylmorpholine, or 4-(2-aminoethyl)morpholine, or a combination thereof.

[0101] Clause 27: The method of any one of clauses 24-26, wherein both the A-side component and the B-side component, separately, generate less than 200 ppm, or less than 100 ppm, of fluoride ion after aging at 50° C. for 2 weeks.

[0102] As used herein, any embodiment, clause, or claim that includes use of the phrases "comprises" (or "comprising"), "consists of" (or "consisting of" or "consist essentially of" (or "consisting essentially of"), or similar language, also includes embodiments, clauses, or claims in which any of these alternatives exist.

[0103] The present invention will be further defined in the following examples, in which all parts and percentages are by weight unless otherwise specified. It should be understood that these examples, while showing preferred embodiments of the present invention, are given for illustrative purposes only and should not be construed as limiting in any way. From the above discussion and these examples, those skilled in the art can ascertain the essential features of the present invention, and can make various changes and modifications of the present invention to adapt it to various usages and conditions without departing from the spirit and scope thereof. EXAMPLES

[0104] Due to the formation of fluoride ions after side reactions between catalysts and HFOs, fluoride ion measurements can be a useful approach to evaluate the shelf life of formulations containing HFOs. To evaluate shelf life, sample formulations were heated at 50°C for 2 hours as accelerated conditions. Two weeks of heating at 50°C is roughly equivalent to aging at room temperature for 2-6 months. Prior to fluoride ion measurements, volatiles (blowing agents) were removed from the samples by stirring the mixture in an open container until bubbling ceased.

[0105] To measure the concentration of fluoride ions in the B-side samples, 1.0 mL of B-side sample was added to a 20 mL glass centirlation vial and 9.0 mL of DI water was added using a 10 mL pipette. The mixture was shaken vigorously to bring all of the contents into the aqueous phase. The built-in pressure was released by twisting the cap open. The samples were left in the open container for 24 hours.

[0106] As a pretreatment, prior to measuring the fluoride ion concentration of the A-side samples, 0.15 g of the A-side components were weighed into a clean, tared, 20 mL glass vial and combined with 1 gram of acetone / MeOH (80 / 20 weight ratio). Using a 10 mL pipette, 9.0 mL of DI water was added to 1 mL of the A-side sample mixture to make a 1:10 dilution. The mixture was shaken vigorously to bring all contents into the aqueous phase. The built-up pressure was released by twisting the cap open.

[0107] A 10% by volume aqueous solution of the experimental material was left undistributed for 5 minutes to allow any water insoluble material to separate. If necessary, the aqueous phase was decanted by pipette into a clean vial to avoid contamination of the equipment with insoluble material.

[0108] For the measurement of free fluoride ions in the experimental samples, 1.0 mL of dilute aqueous solutions prepared as described above were diluted with 1.0 mL of TISAB II buffer (with or without 1,2-cyclohexanedinitrilotetraacetic acid - CDTA, Fisher Scientific). Fluoride ion concentrations were quantified in the experimental solutions according to the instrument instructions using a benchtop instrument (Orion Versa Star Pro or Orion Dual Star, Thermo Scientific) equipped with a fluoride ion-selective electrode (Orion model 9609BNWP, Thermo Scientific). To extrapolate the concentration of fluoride ions in the experimental samples before dilution, the measured fluoride ion concentrations were multiplied by the dilution factor of the dilute aqueous samples relative to the experimental samples (66.7 in this case). Prior to use, the instrument was calibrated according to the instrument instructions using fluoride ion standards with 10 to 10,000 ppm fluoride ions diluted with equal parts TISAB II buffer. Therefore, dilution of the sample with TISAB II buffer is not taken into account when calculating the fluoride levels in experimental samples. Furthermore, within the calibration range of the instrument from 10 to 10,000 ppm, the instrument precision is considered to be ±1%.

[0109] To calculate the actual free fluoride ion concentrations from the experimental samples, the measurements were multiplied by the dilution factor (×10 for B-side samples and ×66.7 for A-side samples).

[0110] Example 1 This example evaluates the feasibility of a direct drop-in substitution of a lower global warming potential HFO blowing agent in place of a conventional high global warming potential HFC blowing agent in a commercial formulation. Typically, the HFC blowing agent and blowing catalyst are introduced in the B-side component formulation (shown as a control in Table 1). The comparison in Table 1 uses the same formulation but substitutes an HFO blowing agent for the HFC blowing agent in the B-side component. Table 1 shows the effect of aging the A-side and B-side formulations prior to mixing and foam formation on the foam formulation reaction parameters. In general, aging an A-side or B-side formulation component for one week at 50° C. is considered to be approximately equivalent to aging that formulation component for one to three months under ambient conditions (approximately 25° C.).

[0111] [Table 1]

[0112] The control formulation (Comparative Example 1A: HFC blowing agent and catalyst in the B-side formulation) shows reasonable shelf-life stability, and foams are still of good quality when the formulation is produced after aging for 7 weeks at 50°C. Unfortunately, straight drop-in substitution of HFO for HFC in the same formulation cannot reproduce the same shelf-life stability (Comparative Example 1B). The formulation reactivity is much reduced after similar aging (7 weeks at 50°C), as indicated by the significantly slower reaction parameters (gel time, rise time and tack-free time), and the foams derived from the aged formulation are of unacceptable quality (they are unstable with respect to collapse or partial collapse, have high open cell content, and suffer from discoloration / yellowing). Changing the HFO gaseous blowing agent does not solve this problem.

[0113] Example 2 Traditionally, no blowing catalyst is used in the A-side component formulation because all known blowing catalysts either react with the isocyanate in the A-side component or cause the isocyanate to react with itself. This effect can be quite drastic; for example, a tertiary amine will completely cure the A-side component as a solid or gel (semi-solid) within 2-3 days. When this happens, the A-side component cannot be used for its desired purpose of spraying to form a foam. Comparative 1B in Example 1 shows poor stability due to the catalyst in the B-side component in the presence of the HFO blowing agent, and there seems to be no chance that an amine blowing catalyst can function in the A-side component of the formulation in the presence of the HFO blowing agent. This example explores the latter quite unlikely possibility. Tables 2 and 3 show the A-side and B-side formulations, respectively, for this example.

[0114] [Table 2]

[0115] [Table 3]

[0116] Foams were prepared from the formulations as follows: Into an appropriately sized plastic container with a lid, all of the B-side ingredients (which may include, but are not limited to, polyols, surfactants, colorants, catalysts, flame retardants) were weighed according to the recipe. An appropriately sized aerosol can and valve were assembled and a tare weight was obtained. Into the aerosol can, the B-side mixture and any volatile but liquid blowing agents (e.g., HFC-245fa, HFO-1233zd) were weighed according to the recipe (so that the can was approximately 75% full by volume). The valve was then crimped using a can crimper and another tare weight was obtained. The specified gaseous blowing agent (e.g., HFC-134a, HFO-1234ze) was then added volumetrically via a glass burette equipped with a fill valve and a transfer valve. The actual weight of the blowing agent was recorded and additional blowing agent was added if necessary to reach the target. The cans were then shaken for 60 shakes before being pressurized with nitrogen or stored briefly (not to exceed 24 hours for fresh analysis or longer for aged or accelerated aged studies). The A-side components were similarly prepared in separate cans using the A-side formulation. The cans were then pressurized with nitrogen before testing. The cans were sprayed using a dispensing system designed for FROTH-PAK™ 12 Sealant Foam Insulation Kits (commercially available) and reaction parameters (rise time, gel time, tack-free time, etc.) and foam properties were measured.

[0117] Table 4 shows the effect of aging the A-side and B-side formulations prior to mixing and foam formation on the foam formulation reaction parameters.

[0118] [Table 4]

[0119] When an HFO blowing agent is used and an amine blowing catalyst (dimorpholinodiethyl ether, DMDEE) is present in the B-side component of a conventional formulation (Control, Comparative Example 2A, Table 2), foam formation exhibits slower reaction parameters (gel time, rise time and tack-free time) after aging of the formulation A-side and B-side components, and foams produced after the formulation components are aged at 50° C. for 4 weeks exhibit unsatisfactory shelf life: the foams suffer from discoloration (yellowing) and partial foam collapse; they also have an open cell content of greater than 90%. Analysis of the B-side component formulation after aging shows very high fluoride ion concentrations (1535 ppm in Comparative Example 2A above) due to side reactions of the amine blowing agent with the HFO. On the other hand, in Example 2A, when HFO blowing agent is used and the same amine blowing agent (dimorpholino diethyl ether, DMDEE) is present in the formulation A-side component instead of in the B-side component (Table 3), the reaction parameters do not slow down after aging of the formulation A-side and B-side components, and the foams produced after the formulation components are aged at 50° C. for 4 weeks show satisfactory shelf life; contrary to all conventional beliefs, they produce good quality foams (open cell content less than 25%) with no discoloration and no foam collapse. The fluoride ion concentration in the A-side component formulation is negligible (7 ppm), and the fluoride ion concentration in the B-side component formulation is also very low (28 ppm). Even though HFO blowing agent is used in both the A-side and B-side component formulations, no undesirable side reactions occur in the A-side component.

[0120] The lower reactivity and slower reaction time correlate with side reactions of the catalyst with the HFO blowing agent that release fluoride ions. Similar side reactions do not occur with HFC blowing agents, although HFC blowing agents are being phased out due to their higher global warming potential. The release and increase of fluoride ions in the component blends upon aging is a convenient way to measure the relative shelf-life stability of various component blends. In general, it has been found that a fluoride ion content of more than about 600 ppm equates to a blend lacking sufficient shelf-life stability to be considered a commercial candidate. Preferably, both the A-side and B-side components, separately, generate less than 600 ppm of fluoride ions after aging for two weeks at 50° C., or in some embodiments, generate less than 200 ppm of fluoride ions after aging for two weeks at 50° C.

[0121] Example 3 Known blowing catalysts are incompatible with A-side component formulations because they either react with isocyanates or cause isocyanates to react with themselves. This example explores a range of blowing catalysts that are compatible with A-side component formulations and cause only minimal release of fluoride ions. Table 5 shows the fluoride ion concentration in the A-side component formulation after aging for various blowing catalysts.

[0122] [Table 5]

[0123] Conventional blowing catalysts, such as normal tertiary amines, are incompatible in A-side component formulations and cause the formulation to solidify in the vessel. This includes Comparative Examples 3A-3F: triethylamine, DABCO (1,4-diazabicyclo[2.2.2]octane), DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), N,N-dimethyl-cyclohexylamine, N-methyl-dicyclohexylamine, N1-(2-(dimethylamino)ethyl)-N2,N2-dimethylethane-1,2-diamine blowing catalysts, as well as some gelling catalysts such as dimethyltin-dilauryl mercaptide (Comparative Example 3H). They cannot be used in A-side component formulations. Only N,X-heterocyclic amines are found to be compatible with A-side component formulations, and these compounds cause minimal side reactions with the HFO blowing agents as indicated by negligible fluoride ion release and accumulation in the A-side component formulations. Those catalysts that are compatible in the A-side components do not provide stability to the system, which is unstable (e.g., as shown by the combination of dimethyltin-dilauryl mercaptide and DMDEE, which is compatible and does not cause any significant fluoride ion release; this combination, Comparative Example 3I, is unstable). Exemplary amine blowing catalysts include Examples 3A-3E: 4-(2-hydroxyethyl)morpholine, dimorpholinodiethyl ether, 4-(2-chloroethyl)morpholine, 4-ethylmorpholine, and b4-(2-aminoethyl)morpholine (Table 5).

[0124] When ranges are used herein for physical properties, such as temperature ranges and pressure ranges, or chemical properties, such as chemical formulas, all combinations and subcombinations of ranges and specific embodiments therein are intended to be encompassed.

[0125] The disclosures of each patent, patent application, and publication cited or described in this document are hereby incorporated by reference in their entirety.

[0126] Those skilled in the art will appreciate that many changes and modifications to the preferred embodiments of the present invention may be made, and that such changes and modifications may be made without departing from the spirit of the present invention. It is therefore intended that the appended claims cover all such equivalent variations as come within the spirit and scope of the present invention. (Aspect) (Aspect 1) 1. A storage stable two-component polyurethane or polyisocyanurate spray foam composition comprising: a) an A-side component comprising one or more polyisocyanates and one or more catalysts; b) a B-side component comprising one or more polyols; Including, further comprising one or more hydrohaloolefin blowing agents in either the A-side component or the B-side component, or both; wherein both the A-side component and the B-side component separately generate less than 600 ppm fluoride ion after aging at 50° C. for 2 weeks. composition. (Aspect 2) 2. The storage stable two-component polyurethane or polyisocyanurate spray foam composition of claim 1, wherein the one or more catalysts in the A-side component are or include a blowing catalyst. (Aspect 3) 2. The storage stable two-component polyurethane or polyisocyanurate spray foam composition of embodiment 1, wherein the one or more catalysts in the A-side component are or include an amine. (Aspect 4) 2. The storage stable two-component polyurethane or polyisocyanurate spray foam composition of claim 1, wherein the one or more catalysts in the A-side component are or include an N-heterocyclic compound. (Aspect 5) 2. The storage stable two-component polyurethane or polyisocyanurate spray foam composition of claim 1, wherein the one or more catalysts in the A-side component are or include an N,X-heterocyclic compound. (Aspect 6) 2. The storage stable two-component polyurethane or polyisocyanurate spray foam composition of claim 1, wherein the one or more catalysts in the A-side component are or include a morpholino compound. (Aspect 7) 7. The storage-stable two-component polyurethane or polyisocyanurate spray foam composition of claim 6, wherein the morpholino compound is 4-(2-hydroxyethyl)morpholine, dimorpholino diethyl ether, 4-(2-chloroethyl)morpholine, 4-ethylmorpholine, or 4-(2-aminoethyl)morpholine, or a combination thereof. (Aspect 8) 2. The storage stable two-component polyurethane or polyisocyanurate spray foam composition of embodiment 1, wherein the one or more hydrohaloolefin blowing agents is a hydrofluoroolefin blowing agent. (Aspect 9) 9. The storage stable two-component polyurethane or polyisocyanurate spray foam composition of embodiment 8, wherein the hydrofluoroolefin blowing agent is selected from 3,3,3-trifluoropropene (HFO); 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,1,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-pentafluoropropene (HFO 1225yc); (Z)-1,1,1,2,3-pentafluoropropene (HFO 1225yez(Z)); or combinations thereof. (Aspect 10) 1. A two-component polyurethane or polyisocyanurate spray foam composition comprising: a)Below: i) one or more polyisocyanates, ii) one or more blowing catalysts; (iii) optionally, one or more hydrohaloolefin blowing agents, and iv) optionally, one or more surfactants; and an A-side component comprising: b)Below: i) one or more polyols; ii) one or more gelling catalysts; iii) one or more hydrohaloolefin blowing agents; iv) optionally, one or more flame retardants, and v) optionally, one or more surfactants B-side components including A composition comprising: (Aspect 11) 11. The two-component polyurethane or polyisocyanurate spray foam composition according to embodiment 10, wherein the one or more blowing catalysts are or include morpholino compounds. (Aspect 12) 12. The two-component polyurethane or polyisocyanurate spray foam composition of claim 11, wherein the morpholino compound is 4-(2-hydroxyethyl)morpholine, dimorpholino diethyl ether, 4-(2-chloroethyl)morpholine, 4-ethylmorpholine, or 4-(2-aminoethyl)morpholine, or a combination thereof. (Aspect 13) 1. A method for providing a space-filling layer or volume near a surface, the method comprising: (a) The following: (i) an A-side component comprising one or more polyisocyanates and one or more catalysts, and, optionally, one or more hydrohaloolefin blowing agents; (ii) a B-side component comprising one or more polyols and one or more hydrohaloolefin blowing agents; providing a foamable composition comprising (wherein both the A-side component and the B-side component separately generate less than 600 ppm fluoride ion after aging for 2 weeks at 50° C.); (b) applying a foamed or pre-foamed sample of the foamable composition to the surface; (c) curing the foamed sample of the foamable composition to a foam density of less than 48 kg / m3; The method includes: (Aspect 14) The method of embodiment 13, wherein the one or more catalysts in the A-side component is or comprises a morpholino compound. (Aspect 15) The method of claim 14, wherein the morpholino compound is 4-(2-hydroxyethyl)morpholine, dimorpholino diethyl ether, 4-(2-chloroethyl)morpholine, 4-ethylmorpholine, or 4-(2-aminoethyl)morpholine, or a combination thereof.

Claims

1. 1. A two-component polyurethane or polyisocyanurate spray foam composition comprising: a) an A-side component comprising one or more polyisocyanates and one or more catalysts comprising a morpholino compound that is 4-(2-hydroxyethyl)morpholine, dimorpholinodiethyl ether, 4-(2-chloroethyl)morpholine, 4-ethylmorpholine, 4-(2-aminoethyl)morpholine, or a combination thereof; b) a B-side component comprising one or more polyols; Including, further comprising one or more hydrohaloolefin blowing agents in either the A-side component or the B-side component, or both; wherein both the A-side component and the B-side component separately generate less than 600 ppm fluoride ions after aging at 50° C. for 2 weeks. composition.

2. 10. The two-component polyurethane or polyisocyanurate spray foam composition of claim 1, wherein the one or more hydrohaloolefin blowing agents is a hydrofluoroolefin blowing agent.

3. 3. The two-component polyurethane or polyisocyanurate spray foam composition of claim 2, wherein the hydrofluoroolefin blowing agent is selected from 3,3,3-trifluoropropene (HFO); 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,1,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-pentafluoropropene (HFO 1225yc); (Z)-1,1,1,2,3-pentafluoropropene (HFO 1225yez(Z)); or combinations thereof.

4. A two-component polyurethane or polyisocyanurate spray foam composition according to any one of claims 1 to 3, comprising a) the following: i) one or more surfactants An A-side component further comprising and / or b) the following: i) one or more gelling catalysts; or i) one or more gelling catalysts, and ii) one or more flame retardants, and / or iii) one or more surfactants A B-side component further comprising A composition comprising:

5. 1. A method for providing a space-filling layer or volume near a surface, the method comprising: (a) the following: (i) the A-side component comprising one or more polyisocyanates, one or more catalysts comprising said morpholino compounds, and one or more hydrohaloolefin blowing agents, or comprising one or more polyisocyanates and one or more catalysts comprising said morpholino compounds; (ii) said B-side component comprising one or more polyols and one or more hydrohaloolefin blowing agents; providing a foam composition according to any one of claims 1 to 3, wherein both the A-side component and the B-side component separately generate less than 600 ppm fluoride ion after aging for 2 weeks at 50° C.; (b) applying a foamed or pre-foamed sample of the foam composition to the surface; (c) subjecting the foamed sample of the foam composition to a pressure of 48 kg / m ３ and curing the foam to a foam density of less than 0.05%. The method includes:

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