Stabilizing polyol premixes, kits, and foam compositions containing halogenated olefins

Abstract

A storage-stable polyol premix is disclosed comprising: a halogenated physical blowing agent comprising an HFO, an HFCO, or a combination thereof; one or more polyols; a catalyst system comprising (i) a non-oxygen-containing tertiary amine and (ii) an organometallic compound comprising at least one metal from Groups 13-15 of the Periodic Table of Elements; an epoxide acid scavenger containing an epoxy moiety; and optionally one or more additives. Foam compositions comprising the storage stable polyol premix and an isocyanate (source), as well as kits comprising the polyol premix and isocyanate components in separate vessels, is also described.

Description

Attorney Docket No. IR4671 WO-PCTSTABILIZING POLYOL PREMIXES, KITS, AND FOAM COMPOSITIONS CONTAINING HALOGENATED OLEFINSFIELD

[0001] The present invention relates to a method of improving the shelflife of polyol premixes (as well as foams made therefrom) that contain halogenated olefin blowing agents, including hydrofluoroolefin (HFO) blowing agents such as 1234ze, 1234yf, and / or 1336, as well as hydrochlorofluoroolefin (HCFO) blowing agents such as 1233zd.BACKGROUND

[0002] The Montreal Protocol for the protection of the ozone layer mandated the phase out of the use of chlorofluorocarbons (CFCs). Materials more “friendly” to the ozone layer, such as hydrofluorocarbons (HFCs), e.g., HFC-134a, replaced chlorofluorocarbons. The latter compounds have proven to be greenhouse gases, causing global warming and are subject to reduction that is coordinated by the United Nations Framework Convention on Climate Change (UNFCCC). The emerging replacement materials, hydrofluoropropenes, were shown to be environmentally acceptable as they have zero ozone depletion potential (ODP) and acceptable low global warming potential (GWP).

[0003] Currently used blowing agents for thermoset foams include HFC-134a, HFC-245fa, HFC-365mfc (that have relatively high global warming potential) and hydrocarbons such as pentane isomers (that are flammable and have low energy efficiency). Therefore, new alternative blowing agents are being sought. Halogenated hydroolefinic materials such as hydrofluoropropenes and / or hydrochlorofluoropropenes have generated interest as replacements for HFCs. The inherent chemical instability of these materials in the lower atmosphere provides for a low global warming potential and zero or near zero ozone depletion properties desired.

[0004] However, the preparation of satisfactory thermoset foams using such halogenated olefinic materials as blowing agents can be challenging, due to certain shelf-life issues. In commercial practice, blowing agents typically are combined with polyols and possibly other components such as surfactant and catalyst to form so-called “B-side” pre-mixes that are then stored for several days to several months prior to being combined with an “A-side” component containing a reactant such as isocyanate that is capable of reacting with the polyol to form a thermoset foam. Ideally, the characteristics of the thermoset foam thereby obtained should notAttorney Docket No. IR4671 WO-PCTbe significantly affected by the length of time the polyol pre-mix has aged prior to such use. Nonetheless, as disclosed by U. S. Patent Application Publication No. 2009 / 0099272, “[a] shortcoming of two-component systems, especially those using certain hydrohaloolefins, including, HFO-1234ze and HFCO-1233zd is the shelf-life of the B-side composition. Normally when a foam is produced by bringing together the A and B component, a good foam is obtained. However, if the polyol premix composition is aged, prior to treatment with the polyisocyanate, the foams are of lower quality and may even collapse during the formation of foam.”

[0005] U. S. Patent No. 12,098,260 approached the shelf-life improvement issue by focusing on apparent pH of the polyols in the premix. However, this is only one approach.

[0006] This disclosure focuses on a different approach - the combined stabilizing effects of the catalyst system and an epoxide acid scavenger.SUMMARY

[0007] The present disclosure describes storage-stable polyol premixes comprising: a halogenated physical blowing agent comprising an HFO, an HFCO, or a combination thereof; one or more polyols; a catalyst system comprising (i) a non-oxygen-containing tertiary amine and (ii) an organometallic compound comprising at least one metal from Groups 13-15 of the Periodic Table of Elements; an epoxide acid scavenger containing an epoxy moiety; and optionally one or more additives comprising flame retardants / suppressors, chemical blowing agents, surfactants / foam stabilizers, non-epoxide acid scavengers, radical scavengers, fillers, adhesion promoters, anti-static agents, antioxidants, hydrolysis agents, lubricants, anti-microbial agents, pigments / whiteners, viscosity modifiers, UV resistance agents, and combinations thereof.

[0008] In some embodiments, to test storage stability, the polyol premix can be aged at a temperature and for a time that is, or that correlates to, at least 4 months and optionally up to 24 months at room temperature (~17-23°C). When combined with a polyisocyanate component, the aged polyol premix can react to form a foam with closed cells within which the halogenated physical blowing agent can be disposed. Advantageously, the aged foam exhibits a yellowing index of 50 or below (or 45 or below) and / or an average density from 1.85 lb / ft3to 2.15 lb / ft3(from 29.6 kg / m3to 34.4 kg / m3). In some embodiments, the storage-stable polyol premix can be aged at ~50°C for a time from 9 to 55 days.

[0009] In various embodiments, the halogenated blowing agent can comprise an HFCO, e.g., 1-chloro-3,3,3-trifluoropropene, of which at least 70 wt% is trans-isomer.Attorney Docket No. IR4671 WO-PCT

[0010] In various embodiments of the catalyst system, the organometallic compound can comprise at least one metal from Groups 13-14 of the Periodic Table of Elements, e.g., tin. Additionally or alternatively, the organometallic compound can comprise a di-(Cl-C4-alkyl)tin di-(Cl-C18-hydrocarbyl) mercaptide, e.g., comprises or is dimethyltin di(lauryl sulfide). Further additionally or alternatively, the non-oxygen-containing tertiary amine can comprise a C1-C12 linear, branched, or cyclic hydrocarbyl-substituted poly(C2-C4 alkylene amine), a C1-C8 linear, branched, or cyclic hydrocarbyl-substituted C5-C7 nitrogen-containing heterocyclic ring moiety or a combination or mixture thereof. Yet further additionally or alternatively, the non-oxygen-containing tertiary amine can comprise a hydrocarbyl-substituted imidazole.

[0011] In various embodiments, the epoxide acid scavenger can comprise a cyclic moiety attached directly or indirectly to the epoxy moiety, wherein the cyclic moiety comprises: an aromatic ring, a ring comprising at least two unsaturations conjugated to each other, a ring comprising at least two unsaturations not conjugated to each other, a ring comprising one unsaturation, or a ring comprising no unsaturations. Additionally or alternatively, the epoxide acid scavenger can comprise at least one oxygen atom in addition to the epoxy moiety. Further additionally or alternatively, the epoxide acid scavenger can comprise a cyclohexane ring attached directly to two carbons of the epoxy moiety.

[0012] In various embodiments, the polyol premix can affirmatively comprise at least the following optional components: a flame retardant / suppressor, a chemical blowing agent comprising water, and a surfactant / foam stabilizer.

[0013] In various embodiments, the storage stability of the polyol premix can be tested in the following way. The storage-stable polyol premix can be aged by exposure to a temperature and for a time that is, or that correlates to, at least 4 months at room temperature (~17-23°C) to form an aged polyol premix, which, when thereafter combined with a first polyisocyanate component, can react to form an aged closed-cell polyurethane foam in cells of which the halogenated physical blowing agent is disposed, said aged foam having an aged gel time, an aged tack free time, and an aged rise time. Also, an unaged polyol premix can be made, which is identical to the storagestable polyol premix but is exposed to room temperature (~17-23°C) for no more than 2 days, and when combined with a second polyisocyanate component identical to the first polyisocyanate component, can react to form an unaged closed-cell polyurethane foam in cells of which the halogenated physical blowing agent is disposed, said unaged foam having an unaged gel time, anAttorney Docket No. IR4671 WO-PCTunaged tack free time, and an unaged rise time. As noted herein, an aged gel time difference is the aged gel time minus the unaged gel time, an aged tack free time difference is the aged tack free time minus the unaged tack free time, and an aged rise time difference is the aged rise time minus the unaged rise time. Also, for context, a comparative polyol premix can be made, which is identical to the storage-stable premix except that it contains 0.0 parts epoxide acid scavenger, and aged by exposure to a temperature and for a time that is, or that correlates to, at least 4 months at room temperature (~17-23°C) to form an aged comparative polyol premix, which, when thereafter combined with a third polyisocyanate component identical to said first and second polyisocyanate components, can react to form an aged comparative polyurethane foam in cells of which the halogenated physical blowing agent is disposed, said aged comparative foam having an aged comparative gel time, an aged comparative tack free time, and an aged comparative rise time. Further, an unaged comparative polyol premix can be made, which is identical to the comparative polyol premix but is exposed to room temperature (~17-23°C) for no more than 2 days, and when combined with a fourth polyisocyanate component identical to said first, second and third polyisocyanate components, can react to form an unaged comparative polyurethane foam in cells of which the halogenated physical blowing agent is disposed, said unaged comparative foam having an unaged comparative gel time, an unaged comparative tack free time, and an unaged comparative rise time. As noted herein, an aged comparative gel time difference is the aged comparative gel time minus the unaged comparative gel time, an aged comparative tack free time difference is the aged comparative tack free time minus the unaged comparative tack free time, and an aged comparative rise time difference is the aged comparative rise time minus the unaged comparative rise time. Also as noted herein, a normalized gel time delay is the aged comparative gel time difference minus the aged gel time difference, a normalized tack free time delay is the aged comparative tack free time difference minus the aged tack free time difference, and a normalized aged rise time delay is the aged comparative rise time difference minus the aged rise time difference. Similarly, a normalized gel time ratio is the aged gel time difference divided by the aged comparative gel time difference, a normalized tack free time ratio is the aged tack free time difference divided by the aged comparative tack free time difference, and a normalized rise time ratio is the aged rise time difference divided by the aged comparative rise time difference. With that lead-up, one, two, three, four, or five or more, or all six, of the following can be satisfied: the normalized gel time delay is at least 2 seconds, e.g., at least 3 seconds; the normalized tackAttorney Docket No. IR4671 WO-PCTfree time delay is at least 2 seconds, e.g., at least 3 seconds; the normalized rise time delay is at least 2 seconds, e.g., at least 3 seconds; the normalized gel time ratio is less than 75%, e.g., less than 60%; the normalized tack free time ratio is less than 75%, e.g., less than 60%; and the normalized rise time ratio is less than 75%, e.g., less than 60%.

[0014] As a related aspect, a foam composition according to the present disclosure can comprise a reaction product of the polyol premix according to the present disclosure with the polyisocyanate component, thereby forming a closed-cell foam in cells of which the halogenated physical blowing agent is disposed.

[0015] Also as a related aspect, a foam kit according to the present disclosure can comprise the foam composition according to the present disclosure, wherein the polyol premix can be disposed in a first vessel and the polyisocyanate component can be stored in a second vessel separate from but capable of being in fluid communication with said first vessel. The fluid communication between said first and second vessels can be removably blocked, such that the polyol premix and the polyisocyanate component can be prevented from reacting before formation of a foam is desired.DETAILED DESCRIPTION OF THE EMBODIMENTS

[0016] The present disclosure relates to polyol pre-mixes having improved stability / shelf life. That is, the pre-mixes, which contain halogenated olefin physical blowing agent(s), polyol(s), a catalyst system, and one or more additives, are capable of being stored at ambient conditions for extended periods of time with no or only minor changes in their performance, when combined with polyisocyanate components to form (polyurethane) foams.Physical Blowing Agents

[0017] The physical blowing agent in the storage-stable premixes of the present disclosure can comprise one or more halogenated olefins such as hydrofluoroolefins (HFOs), hydrochloroolefins (HCOs), and / or hydrochlorofluoroolefins (HCFOs), optionally in combination with one or more other types of physical blowing agents such as hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs), hydrochlorofluorocarbons (HCFCs), hydrofluoroethers (HFEs), hydrocarbons, carbon dioxide, or the like, or combinations or reaction products thereof. In particular, the physical blowing agent can comprise an HCFO such as 1233zd and / or an HFO such as 1234ze, 1234yf, and / or 1336.Attorney Docket No. IR4671 WO-PCT

[0018] Non-limiting examples of HFOs can include, but are not necessarily limited to, those containing from 2 to 6 carbons, e.g., trifluoroethylenes (e.g., 1123); difluoroethylenes (e.g., 1132, 1132a); vinyl fluoride (1141); pentafluoropropenes (e.g., 1225ye); tetrafluoropropenes such as 1.3.3.3-tetrafluoropropene (1234ze, E and Z isomers), 2,3,3,3-tetrafluoropropene (1234yf), 1.2.3.3-tetrafluoropropene (1234ye); trifluoropropenes such as 3,3,3-trifluoropropene (1243zf); difluoropropenes e.g., 1252zc); pentafluoro- 1,3 -butadienes; tetrafluoro- 1,3 -butadienes; trifluoro- 1,3 -butadienes; difluoro-l,3-butadienes; fluorobutenes; difluorobutenes;tri fluorobutenes; tetrafluorobutenes (e.g., 1345); pentafluorobutenes such as 1354 (e.g., 1354cfz); hexafluorobutenes such as 1336 (e.g., 1336mzz); heptafluorobutene isomers such as 1327 (e.g., 1327myz); pentafluorocyclobutenes; tetrafluorocyclobutenes; trifluorocyclobutenes; difluorocyclobutenes; fluorocyclobutenes; tetrafluorobutenes; heptafluoropentene isomers such as 1447 (e.g., 1447myfz); octafluoropentene isomers such as 1438 (e.g., 1438mzz); nonafluoropentene isomers such as 1429 (e.g., 1429mzy, 1429fz); hexafluoropentenes; pentafluoropentenes; tetrafluoropentenes; trifluoropentenes; difluoropentenes; heptafluorocyclopentenes (e.g., cl427yz); hexafluorocyclopentenes (e.g., cl436zz); pentafluorocyclopentenes (e.g., cl445yfz); tetrafluorocyclopentenes; trifluorocyclopentene; difluorocyclopentenes; fluorocyclopentenes; and the like; and combinations thereof.

[0019] Non-limiting examples of HCFOs can include, but are not necessarily limited to, fluorodichloroethylene, chlorodifluoroethylene (1122, 1122a), chlorofluoroethylene (1131, 1131a), l-chloro-3,3,3-trifluoropropene (1233zd), 2-chloro-3,3,3-trifluoropropene (1233xf), 1223, l,2-dichloro-l,2-difluoroethene (E andZ isomers), 3,3-dichloro-3-fluoropropene, 2-chloro-l,l,l,4,4,4-hexafluorobutene-2 (E andZ isomers), 2-chloro-l,l,l,3,4,4,4-heptafluorobutene-2 (E and Z isomers), and the like, and combinations thereof.

[0020] Non-limiting examples of HCOs can include, but are not necessarily limited to, trichloroethylenes (e.g., trans- 1,2-dichloroethylene, 1120), vinyl chloride (1140), and the like, and combinations thereof. In particular, the physical blowing agent can comprise, consist essentially of, or be 1233zd, in which case at least 70 wt%, at least 85 wt%, at least 90 wt%, at least 97 wt%, or at least 99 wt% (and optionally up to 100 wt%) of the 1233zd can be in the form of the trans- (E-) isomer, while the remainder (if any) can be in the form of the cis- (Z-) isomer.

[0021] Particularly advantageous physical blowing agents can comprise unsaturated halogenated hydroolefins with normal boiling points of about 60°C or less.Attorney Docket No. IR4671 WO-PCT

[0022] When present, non-limiting examples of HFCs can include, but are not necessarily limited to, difluoromethane (32); 1,1,1,2,2-pentafluoroethane (125); 1,1,1 -trifluoroethane (143a); 1,1,2,2-tetrafluoroethane (134); 1,1,1,2-tetrafluoroethane (134a); 1,1 -difluoroethane (152a);1,1,1,2,3,3,3-heptafluoropropane (227ea); 1,1,1,3,3-pentafluoropropane (245fa); 1,1,1,3,3-pentafluorobutane (365mfc), 1,1,1,2,2,3,4,5,5,5-decafluoropentane (4310mee), and the like, and combinations thereof.

[0023] When present, non-limiting examples of HCFCs can include, but are not necessarily limited to, chlorodifluoromethane (22), l-chloro-1,1 difluoroethane (142b), 1,1-Dichloro-1-fluoroethane (141b), 1,1 dichloro-2-fluoroethane (141a), 2,2,-Dichloro-l,l,l-trifluoroethane (123), di chlorofluoromethane (21), chlorofluoromethane (31), 1-chloro-1,2,2,2-tetrafluoroethane (124), 3-chloro-l,l,l-trifluoropropane (253fb), 1-chloro-1,1,2,2-trifluoropropane, chlorotrifluoropropane(253), dichlorodifluoropropane (252), and the like, and combinations thereof.

[0024] When present, non-limiting examples of HCCs can include, but are not necessarily limited to, dichloromethane (30), 1,1 -di chloroethane (150a), trans-l,2-di chloroethylene (1130E), trichloroethylene (1120), 1,1 -di chloroethane (150a), chloroethane (160) and the like, and combinations thereof.

[0025] When present, non-limiting examples of HFEs can include, but are not necessarily limited to, difluoro-(trifluoromethoxy)ethene, fluoro-(trifluoromethoxy)ethene, trifluoromethoxyethene, difluoromethoxyethene, fluoromethoxyethene, trifluoromethyl tetrafluoropropenyl ether, C4F9OCH3 (HFE-7100), C4F9OC2H5 (HFE-7200), CF3CF2OCH3 (HFE-245cb2), CF3CH2CHF2 (HFE-245fa), CF3CH2OCF3 (HFE-236fa), C3F7OCH3 (HFE-7000), 2-trifluoromethyl-3-ethoxydodecofluorohexane (HFE-7500), l,l,l,2,3-hexafluoro-4-(l,l,2,3,3,3-hexafluoropropoxy)-pentane (HFE-7600), l,l,l,2,2,3,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane (HFE-7300), ethyl nonafluoroisobutyl ether / ethyl nonafluorobutyl ether (HFE-8200), CHF2OCHF2, CHF2OCH2F, CH2FOCH2F, CH2FOCH3, cyclo-CF2CH2CF2O, cyclo-CF2CF2CH2O, CHF2CF2CHF2, CF3CF2OCH2F, CHF2OCHFCF3, CHF2OCF2CHF2, CH2FOCF2CHF2, CF3OCF2CH3, CHF2CHFOCHF2, CF3OCHFCH2F, CF3CHFOCH2F, CF3OCH2CHF2, CHF2OCH2CF3, CH2FCF2OCH2F, CHF2OCF2CH3, CHF2CF2OCH3 (HFE254 pc), CH2FOCHFCH2F, CHF2CHFOCH2F, CF3OCHFCH3, CF3CHFOCH3, CHF2OCH2CHF2, CF3OCH2CH2F, CF3CH2OCH2F, CF2HCF2CF2OCH3, CF3CHFCF2OCH3, CHF2CF2CF2OCH3,Attorney Docket No. IR4671 WO-PCTCHF2CF2CH2OCHF2, CF3CF2CH2OCH3, CHF2CF2OCH2CH3, (CF3)2CFOCH3, (CF3)2CHOCHF2, (CF3)2CHOCH3, and the like, and combinations thereof.

[0026] When present, non-limiting examples of hydrocarbon physical blowing agents can include, but are not necessarily limited to, isopentane, neopentane, n-pentane, cyclopentane, isobutane, cyclobutene, n-butane, and the like, and combinations thereof.

[0027] Physical blowing agent mixtures can contain components in various amounts relative to each other, which are typically chosen based on performance relative to the particular foam application. In any event, whether one or more physical blowing agents are included, the total amount of physical blowing agent can advantageously include from ~0.5 parts per hundred polyol (pphp) to -60 pphp (e.g., from -1 pphp to -50 pphp, from -5 pphp to -40 pphp, or from -10 pphp to - 35 pphp), or additionally or alternatively from -0.3 wt% to -40 wt% (e.g., from -0.7 wt% to -33 wt%, from -3 wt% to -27 wt%, or from -7 wt% to -23 wt%), based on a total weight of the B-side (non-isocyanate / non-A-side) composition.Polyol Component

[0028] As used herein, the term “polyol” (singular or plural) should be understood to refer to a compound or component containing at least two (typically at least three and optionally up to six or more) moieties that may be hydroxyl (-OH) and / or thiol / mercaptyl (-SH) groups.

[0029] Although, generally speaking, any type of polyol or combination of different types of polyols may be utilized in the polyol premixes of the present disclosure, in various embodiments the one or more polyols can comprise polyether polyols, polyester polyols, poly ether / ester polyols, polycarbonate polyols, and the like, and combinations thereof. In some embodiments, the stability of the polyol premixes of the present disclosure may be advantageously improved when one or more polyols may exhibit, or may be included in the polyol premix under conditions designed to create, an apparent pH from 3 to 11.4 (e.g., from 4 to 10 or from 4 to 9). For details of how to measure and / or control apparent pH in polyol components, see, for example, U. S Patent No. 12,098,260, the relevant contents of which are hereby incorporated by reference.

[0030] Polyether polyols are well known in the art and may, for example, be prepared by reacting an active hydrogen-containing initiator compound (or mixture of such compounds) with one or more alkylene oxides such as ethylene oxide and / or propylene oxide. Typically, base catalysis is employed for such purpose, with the base subsequently being removed or neutralized prior to use of the polyether polyol Suitable initiator compounds can contain two or more activeAttorney Docket No. IR4671 WO-PCThydrogens per molecule, such as may be provided by hydroxyl (-OH) groups or primary or secondary amino (-NH2 or -NHR) groups. The alkylene oxide(s) react with the initiator compound so as to add oxyalkylene groups onto the hydroxyl or amino groups, with additional alkylene oxide then reacting with the alkoxylated initiator compound to form polyether chains originating from what originally had been the position of the active hydrogen-containing functional group(s). Suitable initiator compounds may, in various embodiments of the invention, contain two to eight, two to seven or two to six active hydrogens per molecule, which will generally yield polyether polyols having functionalities corresponding approximately to the number of active hydrogens in the initiator compound. As used herein, the term “functionality” (e.g., as used to refer to a polyether polyol having a functionality of 3) means the average number of isocyanate- and / or isocyanurate- reactive functional groups (e.g., hydroxyl groups) per molecule. In some embodiments, the at least one polyol can exhibit an average functionality greater than 2 by comprising a polyol having a functionality or 2 or greater and a polyol having a functionality of 3 or greater. Examples of suitable initiator compounds include, but are not limited to, glycerin, trimethylolpropane, aminoalcohols such as ethanolamine, diethanolamine and triethanolamine, pentaerythritol, dipentaerythritol, α-methyl glucoside, xylitol, sugars (such as sucrose), sugar alcohols (such as sorbitol), mono- and oligomeric glycols such as ethylene glycol, propylene glycol, di ethylene glycol, dipropylene glycol and the like, polyamines (such as ethylene diamine, toluene diamine, diethylene triamine, di aminodiphenylmethane and polymethylene polyphenylene diamine), aromatic amines, Mannich bases, Novolacs (phenol¬ formaldehyde resins), and combinations thereof (such as a mixture of sucrose and glycerin or a mixture of sorbitol and glycerin).

[0031] Ethylene oxide (EO) can be used in conjunction with propylene oxide (PO) to produce a variety of copolymer polyol structures: as an end-cap (or tip), as a block in the polymer chain, as a “random copolymer” formed by polymerizing ethylene oxide and propylene oxide together, and as a combination of two or more of these types of structures. In certain embodiments, the at least one polyol can comprise a polyether polyol that is an ethylene oxide homopolymer, a propylene oxide homopolymer, or an ethylene oxide / propylene oxide copolymer (e.g, block, gradient, random, alternating, or other types of copolymer), e.g., in which the weight ratio of EO: PO may be from 1:99 to 99: 1.Attorney Docket No. IR4671 WO-PCT

[0032] In various embodiments, for example, a polyether EO / PO copolymer polyol containing two or more hydroxyl-terminated polyether chains extending from a residue of an initiator compound can be used, wherein the polyether chains each can contain an inner block and an outer block, said inner block of each of said polyether chains can have a molecular weight of from about 150 to 350 and / or can contain from 10 to 35 wt% of oxy propylene (PO) units and from 65 to 90% by weight of oxyethylene (EO) units, and said outer block of each of said polyether chains can contain from 95 to 100wt % oxypropylene (PO) units and from 0 to 5 wt% oxyethylene (EO) units, and further wherein the PO / EO copolymer can have a hydroxyl equivalent weight of from 800 to 2000 and a total oxyethylene (EO) content from 5 to 18 wt%. Such polyether polyols are described, for example, in U. S. Patent No. 9,156,936, the relevant contents of which are hereby incorporated by reference

[0033] When a polyether polyol is included in the at least one polyol, according to advantageous embodiments of the present disclosure, its hydroxyl number may be selected in accordance with the desired properties of the foam to be obtained by reacting the at least one polyol with a polyisocyanate component. For example, the polyether polyol(s) may each exhibit or may collectively exhibit an average hydroxyl number from -200 to 850 mg KOH / g.

[0034] Non-limiting examples of polyether polyols can include, but are not necessarily limited to, sucrose / glycerin-initiated poly ether polyols having hydroxyl numbers of -300-600 mg KOH / g and functionalities of -4-7, Mannich-base initiated polyether polyols having hydroxyl numbers of -400-500 mg KOH / g and functionalities of -3.1-3.8, aliphatic amine-initiated polyether polyols having hydroxyl numbers of -500-850 mg KOH / g and functionalities of -3-4, sucrose / diethylene glycol -initiated polyether polyols having hydroxyl numbers of -390-490 mg KOH / g and functionalities of ~4-47, sorbitol-initiated polyether polyols having hydroxyl numbers of -440-540 mg KOH / g and functionalities of -4.4-5.8, sucrose / amine-initiated polyether polyols having hydroxyl numbers of from 440 to 550 mg KOH / g and functionalities of -4-7, aromatic amine-initiated (e.g., based on o-toluene diamine (TDA) and / or methylene diphenylene diamine (MDA )) polyether polyols having hydroxyl numbers of -275-550 mg KOH / g and functionalities of -3.2-4.0, and the like, and combinations or reaction products thereof

[0035] Non-limiting examples of commercially available polyether polyols can include, but are not necessarily limited to, products sold under the following trade names: Jeffol® SG-360Attorney Docket No. IR4671 WO-PCT(Huntsman), Voranol® 490 (Dow Chemical), Jeffol® R-470X (Huntsman), Jeffol® R-425X (Huntsman), Jeffol® AD-310 (Huntsman), Jeffol® AD-500 (Huntsman), Jeffol® SD-441 (Huntsman), Jeffol® S-490 (Huntsman), Jeffol® SA-499 (Huntsman), Pluracol® 1578 (BASF) Carpol® EDAP 800 (Carpenter Chemicals), and the like, and combinations thereof.

[0036] Polyester polyols are well known in the art and can be characterized by having polyester-containing chains and hydroxyl end groups, optionally with any and / or all of the oxygen atoms in the ester and / or hydroxyl moieties being substituted with sulfur atoms.Polyester polyol s are typically produced by condensation of a polyacid (e.g., a compound having a functionality of (carboxylic) acid of at least 2) with (generally a molar excess of polyalcohol (e.g., a compound having a hydroxyl and / or thiol functionality of at least 2). The (poly)condensation may be carried out in the presence of a catalyst, such as a metal-containing catalyst. To produce polyester polyols with branched structures and / or functionalities greater than 2, some amount of polyacid and / or polyalcohol having a functionality greater than 2 may be employed. While any type of polyester polyol may be utilized in the present disclosure, when present, aromatic polyester polyols may be especially advantageous. Aromatic polyester polyols may be prepared, for example, by utilizing aromatic polyacids as reactants (e.g., phthalic acids). In certain embodiments, an aromatic polyester polyol can have a hydroxyl number of -200-450 mg KOH / and a functionality of -2-3. If a polyester polyol is utilized in the polyol premixes according to the present disclosure, it can generally be advantageous that it have a relatively low level of certain Lewis acid catalysts e.g., Sb, Ti and Mn-containing catalysts), which are sometimes employed in the manufacture of such polyols but which can, in some circumstances, have a tendency to decrease premix stability. In particular, when employed, a polyester polyol can desirably contain: (i) less than 60 wppm (e.g., less than 40 wppm or less than 20 wppm) Sb; (ii) less than 150 wppm (e.g, less than 120 wppm or less than 75 wppm) Ti; (iii) less than 6000 wppm (e.g., less than 4000 wppm or less than 2000 wppm) Mn; or (iv) a combination of two or more of (i), (ii), and (iii).

[0037] Non-limiting examples of commercially available polyester poly ols can include, but are not necessarily limited to, products sold under the following trade names: Terate® 3510 (Invista), Terate® HT 5100 (Invista), Terate® 20 1 (Invista), Terate® HT 5349 (the Stepan Company), Terol® XO 12009 (Huntsman), Terol® 305 (Huntsman), Stepanpol® PS 2520 (the Stepan Company), Stepanpol® PS 3021 (the Stepan Company), Stepanpol® PS 3422 (the StepanAttorney Docket No. IR4671 WO-PCTCompany), Stepanpol® PS 3524 (the Stepan Company), Stepanpol® PS 2352 (the Stepan Company), and the like, and combinations thereof.

[0038] Polyether / ester polyols can be (typically block) copolymers containing both oxyalkylene and ester-containing repeating units. Non-limiting examples of polyether / ester polyols can include, but are not necessarily limited to, aromatic polyether / ester polyols having hydroxyl numbers of ~275-575 mgKOH / g and functionalities of ~2.8-3.5, and the like.

[0039] When one or more polyether, polyester, and / or polyether / ester polyols are included in the at least one polyol, according to advantageous embodiments of the present disclosure, its number average molecular weight may be from 250 to 6500 Daltons, or, if more than one polyol is used, they can have similar or different number average molecular weights, either each being within the disclosed range or together being averaged to fall collectively within the disclosed range Additionally or alternatively, the vi scosity of each polyol or ail polyols collectively may be from 400 to 21,000 cps at ~25°C.

[0040] Although any amount of the at least one polyol can be used, typically the amount of polyol(s) (collectively) used can be (or can add to) — 100 parts. As the amounts of virtually all other components can generally be expressed in pphp ( / .<?., parts per hundred polyol), if the collective amount of polyols adding together to represent the at least one polyol component is less than or greater than 100 parts, the amounts of the other components (if expressed in relative / “pphp” terms) can be adjusted to account for that.Catalyst System

[0041] Polyol premixes according to the present disclosure typically also contain a catalyst system, which can advantageously facilitate curing of the foam on an expedited timescale necessary to lock in the condensed (polyurethane) foam structure, typically so as to achieve a relatively mechanically strong and insulative closed-cell foam, generally with physical blowing agent retained within some / all of the cells of said foam.

[0042] Although some foaming catalyst systems may contain a single catalytic component, it is often more popular that there be two or more catalyst system components. For example, a multicomponent catalyst system can advantageously comprise (i) a non-oxygen-containing (advantageously tertiary) amine catalyst component and (ii) an organometallic component, which can comprise at least one metal from Groups 1-15 (in particular, from Groups 13-15, from Groups 13-14, or from Group 13) of the Periodic Table of Elements. Additionally orAttorney Docket No. IR4671 WO-PCTalternatively, (iii) an oxygen-containing amine catalyst component may optionally be included along with component (i) or with the combination of components (i) and (ii), but that is not always desired and can, in some embodiments, lead to decreased stability, particularly in combination with certain HFO and / or HFCO physical blowing agents (e.g., such as 1233zd, 1234ze, 1234yf, and / or 1336, individually or in combination).

[0043] Non-limiting examples of non-oxygen-containing amine catalyst components (i) can include, but are not necessarily limited to: N, N-dimethylcyclohexylamine (DMCHA), N, N, N', N', N"-pentamethyldi ethylenetriamine (PMDETA), N, N', N''-tris(3-dimethylamino-propyl)hexahydrotriazine, N. N-dimethylbenzylamine, N, N, N', N", N"-pentaamethyldipropylenetriamine, N, N'-diethylpiperazine, di cyclohexylmethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylisopropylamine, methylisopropylbenzylamine, methylcyclopentylbenzylamine, isopropyl-sec-butyl-trifluoroethylamine, diethyl-a-phenyethyl)amine, tri-n-propylamine, dicyclohexylamine, t-butylisopropylamine, di -t-butyl amine, cyclohexyl-t-butylamine, de-sec-butylamine,di cyclopentylamine, di-a-trifluoromethylethyl)amine, di-(a-phenylethyl)amine, triphenylmethylamine, 1,1,-diethyl-n-propylamine, N, N, N', N', N"-pentamethyldi ethylenetriamine, N, N, N', N', N''-pentaethyldiethylenetriamine, N, N, N', N', N"-pentam ethyldipropylenetriamine, imidazoles, n-m ethylimidazole, 1,2-dimethylimidazole, quaternary ammonium salts of organic (carboxylic) acids such as quaternary ammonium formates, quaternary ammonium acetate, quaternary ammonium acetyl acet onate, quaternary ammonium citrates, quaternary ammonium oxalates, and the like, and mixtures thereof, guanidines including pentamethyl guanidine and cyclic guanidines, guanidine derivatives / salts including cyanoguanidine, guanidine hydrochloride salt, guanidine phosphate salts, guanidine sulfate salts, 1 -acetylguanidine, nitroguanidine, l-(o-tolyl)biguanidine, and mixtures thereof, as well as tetraalkyl guanidines of the formula: RnRi2N-C(=NH)-NRi3Ri4, where Rn, R12, R13, and R14 are independently Cl -CIO alkyl groups (with an exemplary tetraalkyl guanidine being tetramethyl guanidine), PolyCat® 201 (Air Products), PolyCat® 204 (Air Products), Polycat® 5 (Air Products), Polycat® 8 (Air Products), and the like, and combinations thereof.

[0044] The organometallic compound catalyst component (ii) can contain one or more metals selected from the group consisting of bismuth, lead, tin, cadmium, cobalt, iron, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, zirconium,Attorney Docket No. IR4671 WO-PCTmagnesium, calcium, sodium, potassium, lithium, and combinations thereof; in particular, bismuth, lead, tin, aluminum, or a combination thereof (in various embodiments, containing tin). Non-limiting examples of the organometallic compound catalyst component (ii) can include, but is not necessarily limited to, stannous octoate, dibutyltin dilaurate (DBTDL), dibutyltin mercaptide, dimethyl tin mercaptides such as dimethyl tin dilaurate (DMTDL), phenylmercuric propionate, lead octoate, potassium acetate / octoate, magnesium acetate, titanyl oxalate, potassium titanyl oxalate, ferric acetylacetonate, a bismuth carboxylate, and combinations thereof; in particular a di-(Cl-C4-alkyl)tin di-(Cl-C18-hydrocarbyl) mercaptide, a di-(Cl-C3-alkyl)tin di-(Cl-C18-hydrocarbyl) mercaptide, a di-(Cl-C4-alkyl)tin di-(C8-C18-hydrocarbyl) mercaptide, or a di-(Cl-C3-alkyl)tin di-(C8-C18-hydrocarbyl) mercaptide (such as dimethyl tin di laurate).

[0045] When present, non-limiting examples of oxygen-containing amine catalyst components (iii) can include, but are not necessarily limited to, N, N-dimethylethanolamine (DMEA), bis(N, N-dimethylaminoethyl)ether (BDMAFE), l,4-diazadicyclo[2,2,2]octane (DABCO), 2-(2-dimethylaminoethoxy)-ethanol (DMAFE), 2-((2-dimethylaminoethoxy)-ethyl methyl-amino)ethanol, l-(bis(3-dimethylamino)-propyl)amino-2-propanol, dimorpholinodi ethylether (DMDEE), morpholinesdimorpholinodiethylether, N-ethylmorpholine, N-methylmorpholine, bis(dimethylaminoethyl)ether, dimorpholinodimethylether, bis(diethylaminoethyl)ether, bis(dimethylaminopropyl)ether, and the like, and combinations thereof.

[0046] In particular embodiments, the catalyst system can comprise (i) a non-oxygen-containing tertiary amine comprising, consisting essentially of, or being a C1-C12 linear, branched, or cyclic hydrocarbyl-substituted poly(C2-C4 alkylene amine), a C1-C8 linear, branched, or cyclic hydrocarbyl-substituted C5-C7 nitrogen-containing heterocyclic ring moiety or a combination or mixture thereof, and (ii) an organometallic compound comprising, consisting essentially of, or being at least one metal from Groups 13-14 of the Periodic Table of Elements (e.., containing tin).

[0047] When the non-oxygen-containing tertiary amine component of the catalyst system contains a substituted C5-C7 nitrogen-containing heterocyclic ring moiety, it should be understood that the compound comprising that heterocyclic ring moiety may, in addition to the substitution, contain one or more other ring moieties attached at one or more carbons and / or nitrogens (typically at least two carbons and / or nitrogens) of the heterocyclic ring. For example,Attorney Docket No. IR4671 WO-PCTa substituted carbazole contains two phenyl rings each attached to two carbons of the 6-membered central heterocyclic ring and thus should be understood by the ordinary skilled artisan to be included as a compound satisfying the description of a “substituted C5-C7 nitrogencontaining heterocyclic ring moiety” herein.

[0048] Additionally or alternatively, in particular, the non-oxygen-containing tertiary amine can comprise a hydrocarbyl -substituted imidazole.

[0049] Further additionally or alternatively, in particular, a di-(Cl-C4-alkyl)tin di-(Cl-C18-hydrocarbyl) mercaptide, a di-(C 1 -C3-alkyl)tin di-(Cl-C18-hydrocarbyl) mercaptide, a di-(C 1 -C4-alkyl)tin di-(C8-C18-hydrocarbyl) mercaptide, or a di-(Cl-C3-alkyl)tin di-(C8-C18-hydrocarbyl) mercaptide (such as dimethyl tin dilaurate).

[0050] Although relative amounts of the multiple components of the catalyst system can vary with respect to each other, the total amount of catalyst components can be from -0.00007 parts per hundred polyol (pphp) to -10 pphp (e.g., from -0.0007 pphp to -9.0 pphp, from -0.003 pphp to -7.5 pphp, or from -0.007 pphp to -6.8 pphp), or additionally or alternatively from -0.1 wppm to -7.0 wt% (e.g., from -1 wppm to -6.0 wt%, from -5 wppm to -5.0 wt%, or from -10 wppm to -4.5 wt%), based on a total weight of the B-side (non-isocyanate / non-A-side) composition.Epoxide Acid Scavenger

[0051] Storage-stable polyol premixes according to the present disclosure can advantageously include an epoxide acid scavenger, which is a compound that contains an epoxy moiety. Without being bound by theory, it is believed that this epoxide acid scavenger can help (e.g., work in tandem with the catalyst system) to mitigate, prevent, cure, or at least delay storage stability issues, particularly in polyol premixes containing certain HFO and / or HFCO physical blowing agents (e.g., such as 1233zd, 1234ze, 1234yf, and / or 1336, individually or in combination).

[0052] In particular embodiments, the epoxide acid scavenger can comprise a cyclic moiety attached directly or indirectly to the epoxy moiety. In such embodiments, the cyclic moiety can comprise: an aromatic ring, a ring comprising at least two unsaturations conjugated to each other, a ring comprising at least two unsaturations not conjugated to each other, a ring comprising one unsaturation, or a ring comprising no unsaturations. Additionally or alternatively, in particular, the epoxide acid scavenger can comprise at least one oxygen atom inAttorney Docket No. IR4671 WO-PCTaddition to the epoxy moiety. Further additionally or alternatively, the epoxide acid scavenger can comprise a cyclohexane ring attached directly to two carbons of the epoxy moiety.

[0053] Non-limiting examples of epoxide acid scavengers useful in the present disclosure can include, but are not necessarily limited to, 1,2-epoxycyclohexane oxide, 1,2-epoxy cyclopentane, 1,2-epoxy cycloheptane, 1,2-4,5-diepoxycyclohexane, 2 -m ethylhexyl- 1 -(3, 4-epoxy cyclohexane carboxylate), 3, 4-epoxy cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, limonene oxide, and the like, and combinations thereof.

[0054] In advantageous embodiments, the amount of epoxide acid scavenger in the storagestable polyol premixes according to the present disclosure can generally be sufficient to impart storage stability improvement. However, exemplary ranges of epoxide acid scavenger can include from -0.01 parts per hundred polyol (pphp) to -10 pphp (e.g., from -0.05 pphp to -9.0 pphp, from -0.1 pphp to -7.5 pphp, or from -0.5 pphp to -6.8 pphp), or additionally or alternatively from -0.007 wt% to -7.0 wt% (e.g., from -0.03 wt% to -6.0 wt%, from -0.07 wt% to -5.0 wt%, or from -0.3 wt% to -4.5 wt%), based on a total weight of the B-side (non-i socy anate / non- A- si de) compositi on.Optional Additives

[0055] Additionally or alternatively, the curable compositions of the present disclosure may optionally additionally comprise one or more additives, as desired, as necessary for short- or long- term stability, and / or as desired / necessary for its application. Such additives, when present, may include but are not necessarily limited to, flame retardants / suppressors, chemical blowing agents, surfactants / foam stabilizers, non-epoxide acid scavengers, radical scavengers, fillers, adhesion promoters, anti-static agents, antioxidants, hydrolysis agents, lubricants, antimicrobial agents, pigments / whiteners, viscosity modifiers, UV resistance agents, and the like, and combinations thereof.

[0056] Non-limiting examples of flame retardants / suppressors can include, but are not necessarily limited to, tri chloropropyl phosphate (TCPP), triethyl phosphate (TEP), diethyl ethyl phosphate (DEEP), diethyl bis(2-hydroxyethyl)amino methyl phosphonate, brominated anhydride based ester, dibromoneopentyl glycol, brominated polyether polyol, melamine, ammonium polyphosphate, aluminum trihydrate (ATH), tris(l,3-dichloroisopropyl)phosphate, tri)-2-chloroethyl)phosphate, tri(2-chloroisopropyl)phosphate, chloroalkyl phosphate / oligomeric phosphonate, oligomeric chloroalkyl phosphate, brominated flame retardants based onAttorney Docket No. IR4671 WO-PCTpentabromo diphenyl ether, dimethyl methyl phosphonate, diethyl N, N bis(2-hydroxyethyl)amino methyl phosphonate, oligomeric phosphonate, and the like, and derivatives and / or combinations thereof.

[0057] As used herein and as understood by the ordinary skilled artisan, chemical blowing agents encompass compounds that are reactive with isocyanate and / or polyol moieties themselves (or the reactive moieties involved in foams of other chemistries) or can react / degrade into such reactive compounds. Non-limiting examples of chemical blowing agents regarding foams that can be made from the polyol premixes of the present disclosure can include, but are not necessarily limited to, water, hydrazine, sodium bicarbonate, carbonic acid, monoalcohols / monothiols, aldehydes, ketones, ammonia, (non-quatemary) ammonium hydroxides, other hygroscopic materials that can release water under reactive conditions, and the like, and combinations thereof.

[0058] Non-limiting examples of silicone-type surfactants can include, but are not necessarily limited to, polysiloxane polyoxyalkylene block co-polymers such as B8404, B8407, B8409, B8462 and B8465 commercially available from Goldschmidt; DC-193, DC-197, DC-5582, and DC-5598 commercially available from Air Products; L-5130, L5180, L-5340, L-5440, L-6100, L-6900, L-6980, and L6988 commercially available from Momentive; and the like; and combinations thereof. Non-limiting examples of non-silicone-type surfactants can include, but are not necessarily limited to, salts of sulfonic acid, alkali metal salts of fatty acids, ammonium salts of fatty acids, oleic acid, stearic acid, dodecylbenzenedisulfonic acid, dinaphthylmethanedisulfonic acid, ricinoleic acid, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil esters, ricinoleic acid ester, Turkey red oil, groundnut oils, paraffin fatty alcohols, and the like, and combinations thereof. When used, exemplary ranges of the total amount of surfactants can include from -0.07 pphp to -9.0 pphp (e.g., from -0.15 pphp to -6.8 pphp or from -0.3 pphp to -4.5 pphp), or additionally or alternatively from -0.1 wt% to -6 wt% of the polyol premix (e.g., from -0.2 wt% to -4.5 wt% or from -0.4 wt% to -3 wt%), based on a total weight of the B-side (non-isocyanate / non-A-side) composition.

[0059] Non-limiting examples of fillers can include, but are not necessarily limited to, glass particles, quartz, graphite powder, carbon black, alumina powder, silicas, aluminosilicates, carbon nanotubes, non-elastomeric fibers, calcium carbonate, barium sulfonate, microspheres, and the like, and combinations thereof.Attorney Docket No. IR4671 WO-PCT

[0060] Non-limiting examples of other additives can include, but are not necessarily limited to, cyclic-terpenes such as dl-limonene, 1 -limonene and d-limonene; nitromethane; di ethylhydroxyl amine; alpha methylstyrene; isoprene; p-methoxyphenol; m-methoxyphenol; hydrazines; 2,6-di-t-butyl phenol; hydroquinone; organic acids such as carboxylic acid, dicarboxylic acid, phosphonic acid, sulfonic acid, sulfamic acid, hydroxamic acid, formic acid, acetic acid, propionic acid, butyric acid, caproic acid, isocaprotic acid, 2-ethylhexanoic acid, caprylic acid, cyanoacetic acid, pyruvic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, trifluoroacetic acid, methanesulfonic acid, or benzenesulfonic acid; esters, including esters of the aforementioned acids, such as methyl formate, ethyl formate, methyl acetate, isopropyl formate, isobutyl formate, isoamyl formate, methyl benzoate, benzyl formate or ethyl acetate; sterically hindered phenols; diphenylamines; benzofuranone derivatives; butylated hydroxytoluene (BHT); melamine; waxes and soaps; titanium dioxide; chromium oxide; iron oxide; glycol ethers such as dimethoxymethane; dimethyl AGS esters; propylene carbonate; benzophenone; benzotriazole compounds; and the like; and combinations thereof.Foam Compositions / Foam Characteristics

[0061] The preparation of foam compositions (c.., polyurethane, polyurethaneurea, or polyisocyanurate) using the storage-stable polyol premixes described herein may follow any of the methods well known in the art can be employed, e.g.. see Saunders and Frisch, Volumes I and II Polyurethanes Chemistry and technology, 1962, John Wiley and Sons, New York, N. Y. or Gum, Reese, Ulrich, Reaction Polymers, 1992, Oxford University Press, New York, N. Y. or Klempner and Sendijarevic, Polymeric Foams and Foam Technology, 2004, Hanser Gardner Publications, Cincinnati, Ohio. In general, polyurethane or polyisocyanurate foams are prepared by combining an isocyanate component (typically a polyisocyanate, an isocyanurate, or the like, or any compound that has or is a source of an isocyanate moiety), the polyol pre-mix composition, and optionally other materials (which may be described herein as being part of the polyol premix component, whether actually disposed within that component or not). As used herein, a polyisocyanate can have or can be a source of at least two isocyanate (-N=C=O) and / or thioisocyanate (-N=C=S) functionalities / moieties. Foams formed by reaction with isocyanate can be rigid, flexible, or semi-rigid, and can have a closed cell structure, an open cell structure, or a mixture of open and closed cells. Although desired structure can be adapted to the foam application, in many embodiments herein the foam cell structure can be at least partially closed,Attorney Docket No. IR4671 WO-PCTsuch that at least a portion (typically a relatively large portion) of the physical blowing agent(s) can be disposed within those closed cells (advantageously being retained within the foam and not released to the environment).

[0062] It is convenient in many applications to provide the components for polyurethane or polyisocyanurate foams in a foam kit, which, though described herein as existing in essentially two components, can be separated into more than two components. The (poyl)isocyanate and optionally other isocyanate-Zisocyanurate- compatible raw materials can comprise a first component, commonly referred to as the “A-” side component -- that component can be stored in a first vessel The storage-stable polyol mixture composition, including polyol, catalyst system, physical blowing agent(s), epoxide acid scavenger, and optional other polyol-compatible ingredients comprise a second component, commonly referred to as the “B-” side component Accordingly, polyurethane or polyisocyanurate foams are readily prepared by bringing together the A- and B-side components either by hand mix for small preparations and, preferably, machine mix techniques to form blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, froths, and the like. Thus, for non-hand mix applications, the first vessel and second vessel, whether actually two separate vessels or separate compartments within a single vessel, should be capable of being in fluid communication with each other, but the fluid communication between said first and second vessels (and any optional additional vessels or portions of the single vessel in which any remaining foam composition components might be held) can be removably blocked, e.g., such that the polyol premix and the (poly)isocyanate component can be prevented from reacting before formation of a foam is desired. Removing the removably blocked fluid communication between the vessels can thus enable contact, which promotes foam formation.

[0063] Non-limiting examples of the polyisocyanate (A-side) compositions contemplated herein can include, but are not necessarily limited to, aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, crude toluene diisocyanate, methylene diphenyl diisocyanate (MDI), which can exist as different isomers such as 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI, with the 4,4' isomer being most widely used; crude methylene diphenyl diisocyanate and the like; aromatic triisocyanates such as 4,4',4"-triphenylmethane triisocyanate, 2,4,6-toluene triisocyanates; aromatic tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, and the like; arylalkyl polyisocyanatesAttorney Docket No. IR4671 WO-PCTsuch as xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene-1,6- diisocyanate, lysine diisocyanate methyl ester, and the like; polyrnethylene polyphenylisocyanate; hydrogenated methylene diphenylisocyanate; m-phenylene diisocyanate; naphthylene- 1,5-diisocyanate; l-methoxyphenylene-2,4-diisocyanate; 4, 4 '-biphenylene diisocyanate; 3,3'-dimethoxy-4,4'-biphenyl diisocyanate; 3, 3'-dimethyl-4, 4 '-biphenyl diisocyanate; 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; alkylene diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and the like; aromatic polyisocyanates such as m-, and p-phenylene disocyanate, polymethylene polyphenyl isocyanate, 2.4- and 2,6-toluenediisocyanate, dianisidine diisocyanate, bitolylene isocyanate, naphthylene 1.4-diisocyanate, bi s(4-isocyanatophenyl)m ethene, bis(2-metbyl-4-isocyanatophenyl)methane, and the like; and combinations thereof, isocyanurate (trimeric) versions thereof, and derivatives thereof (in particular, comprising polyrnethylene polyphenyl isocyanate, methylenebis(phenyl isocyanate), toluene di isocyanates, or combinations thereof). In foam compositions and / or foam kits according to the present disclosure, the polyisocyanate and the polyol components may be employed in amounts which will yield, when combined, an NCO / OH stoichiometric ratio of -0.9 to -5.0, e.g., -1.00 or more and -3.50 or less, such as from -1.05 to -3.00.

[0064] In various embodiments, the storage-stable polyol premix can be tested for its stability by aging at a temperature and for a time that is, or that correlates to, at least 4 months e.g., at least 6 months or at least 8 months; optionally also or alternatively up to -24 months, e.g., up to -18 months or up to -12 months) at room temperature (~17-23°C). After storage / aging, hopefully in a stable manner, the storage-stable polyol can react with the (first) (poly)isocyanate component to form a foam having at least some closed cells, in which closed cells the halogenated physical blowing agent can advantageously disposed. For example, in one evaluation, the storage-stable polyol premix can be aged at ~50°C for a time from 9 to 55 days (without being bound by theory, which is believed to correspond roughly to from -4-24 months at room temperature) or from -14-28 days (without being bound by theory, which is believed to correspond roughly to from -6-12 months at room temperature).

[0065] In general, an aged foam can exhibit an aged gel time, an aged tack free time, and an aged rise time, among other characteristics. As used herein, “gel time” means the time from the beginning of mixing to the point at which the first string forms using a standard tongue depressorAttorney Docket No. IR4671 WO-PCTto pull upward or resistance of foam forming is felt from under the foam surface. Typically, it can be desirable for the gel time of such systems to be relatively brief, e.g., from -1-300 seconds or more typically from -5-60 seconds. As used herein, “tack free time” means the time from the beginning of mixing to the point that the outer skin of the foam loses its stickiness. As used herein, “rise time” means the time from the beginning of mixing to the point at which the foam stops gaining height. Such characteristics and their measurement parameters are described, e.g., in ASTM D7484-18.

[0066] Sometimes, characteristic parameters of aged foams can only / best be judged in terms of stability with reference to unaged foams. Therefore, an unaged polyol premix that is identical to the storage-stable polyol premix but is exposed to room temperature (~17-23°C; and not at all to any correlative higher temperature) for no more than 2 days, typically for no more than 1 day or no more than 16 hours / overnight, can be reacted with a second (poly)isocyanate component identical to the (first) (poly)isocyanate component to form an unaged foam having at least some closed cells, in which closed cells the halogenated physical blowing agent can advantageously disposed. Like aged foams, unaged foams can exhibit an unaged gel time, an unaged tack free time, and an unaged rise time, among other characteristics.

[0067] As used herein, an “aged gel time difference” is defined as the aged gel time minus the unaged gel time, an “aged tack free time difference” is defined as the aged tack free time minus the unaged tack free time, and an “aged rise time difference” is defined as the aged rise time minus the unaged rise time.

[0068] Sometimes even comparisons of stable systems to themselves don’t fully elucidate the benefit and / or improvement offered by comparison of storage-stable systems to systems that don’t fully address instabilities. In one such situation, a foam composition whose polyol premix contains an epoxide acid scavenger can be compared to a foam composition whose polyol premix specifically contains substantially no (e.g, no intentionally added and / or less than 0.1 wppm in any case) epoxide acid scavenger. Thus, a comparative polyol premix (identical to the storage-stable premix except that it contains -0.0 parts epoxide acid scavenger) can be aged by exposure to a temperature and for a time that is, or that correlates to, at least 4 months (e.g., at least 6 months or at least 8 months; optionally also or alternatively up to -24 months, e.g., up to -18 months or up to -12 months) at room temperature (~17-23°C), thereby forming an aged comparative polyol premix. Whatever time / temperature to which the aged polyol premix wasAttorney Docket No. IR4671 WO-PCTexposed, the aged comparative polyol premix can be identically aged. After storage / aging, the comparative polyol premix can react with a third (poly)isocyanate component (identical to the first) to form a comparative aged foam having at least some closed cells, in which closed cells the halogenated physical blowing agent can advantageously disposed. That aged comparative foam can exhibit an aged comparative gel time, an aged comparative tack free time, and an aged comparative rise time, among other characteristics.

[0069] As with the storage-stable premix, an unaged comparative polyol premix that is identical to the storage-stable polyol premix but is exposed to room temperature (~17-23°C; and not at all to any correlative higher temperature) for no more than 2 days, typically for no more than 1 day or no more than 16 hours / overnight (and identically as in the storage- stable case), can be reacted with a fourth (poly)isocyanate component identical to the third (poly)isocyanate component to form an unaged comparative foam having at least some closed cells, in which closed cells the halogenated physical blowing agent can advantageously disposed.Correspondingly, the unaged comparative foams can exhibit an unaged comparative gel time, an unaged comparative tack free time, and a comparative unaged rise time, among other characteristics.

[0070] As used herein, an “aged comparative gel time difference” is defined as the aged comparative gel time minus the unaged comparative gel time, an “aged comparative tack free time difference” is defined as the aged comparative tack free time minus the unaged comparative tack free time, and an “aged comparative rise time difference” is defined as the aged comparative rise time minus the unaged comparative rise time. Also as used herein, a “normalized gel time delay” is defined as the aged comparative gel time difference minus the aged gel time difference, a “normalized tack free time delay” is defined as the aged comparative tack free time difference minus the aged tack free time difference, and a “normalized aged rise time delay” is defined as the aged comparative rise time difference minus the aged rise time difference. As further used herein, a “normalized gel time ratio” is defined as the aged gel time difference divided by the aged comparative gel time difference, a “normalized tack free time ratio” is defined as the aged tack free time difference divided by the aged comparative tack free time difference, and a “normalized rise time ratio” is defined as the aged rise time difference divided by the aged comparative rise time difference.Attorney Docket No. IR4671 WO-PCT

[0071] Thus, the various storage-stable and comparative polyol premixes can yield foams that satisfy one, two, three, four, five, or all of the following: the normalized gel time delay can at least 2 seconds, in particular at least 3 seconds; the normalized tack free time delay is at least 2 seconds, in particular at least 3 seconds; the normalized rise time delay is at least 2 seconds, in particular at least 3 seconds; the normalized gel time ratio is less than 75%, in particular less than 60%; the normalized tack free time ratio is less than 75%, in particular less than 60%; and the normalized rise time ratio is less than 75%, in particular less than 60%.

[0072] Further additionally or alternatively, in particular the storage-stable polyol premix can be formulated such that the aged (closed-cell) foam formed from its reaction can exhibit: a yellowness index of 50 or below (e.g., 47 or below, 45 or below, 43 or below, or 41 or below), as measured using a Datacolor Spectro™ 750 spectrophotometer (e.g., based on an average of -6 measurements, with one measurement per side of each hand-mix cup foam cube - see below), and / or an average density from 1.85 lb / ft3to 2.15 lb / ft3(e.g., from 1.87 lb / ft3to 2.10 lb / ft3or from 1.89 lb / ft3to 2.08 lb / ft3), as measured according to the following procedure. In “cgs” units, these density ranges convert to from 29.6 kg / m3to 34.4 kg / m3(e.g., from 30.0 kg / m3to 33.6 kg / m3or from 30.3 kg / m3to 33.3 kg / m3). From each hand-mix cup foam (made according to ASTM D-7487-18), a -2” x -2” x -2” (~5.1 cm x ~5.1 cm x ~5.1 cm) cube can be cut from the crown (the “muffin-top,” or the part of the foam above located above the top of the cup). The length, width, and thickness of the -2” x -2” x -2” cube can each be measured at both edges of the foam and in the center of the foam, resulting in three length, three width, and three thickness measurements. An average of the three measurements can be taken to obtain one length, one width, and one thickness measurement. The weight of the -2” x -2” x -2” cube can also be recorded. The free rise density can then be calculated by dividing the weight of the -2” x -2” x -2” cube in pounds by the average volume (the average length multiplied by the average width multiplied by the average thickness) in cubic feet. If weights are in grams and dimensions (length / width / height) are in millimeters, for example, they can be converted from g / mm³ to lb / ft³ by multiplying by ~62428.Additional Embodiments

[0073] Additionally or alternatively, the present disclosure can include one or more of the following embodiments.Attorney Docket No. IR4671 WO-PCT

[0074] Embodiment 1. A storage-stable polyol premix comprising: a halogenated physical blowing agent comprising an HFO, an HFCO, or a combination thereof; one or more polyols; a catalyst system comprising (i) a non-oxygen-containing tertiary amine and (ii) an organometallic compound comprising at least one metal from Groups 13-15 of the Periodic Table of Elements; an epoxide acid scavenger containing an epoxy moiety; and optionally one or more additives comprising flame retardants / suppressors, chemical blowing agents, surfactants / foam stabilizers, non-epoxide acid scavengers, radical scavengers, fillers, adhesion promoters, anti-static agents, antioxidants, hydrolysis agents, lubricants, anti-microbial agents, pigments / whiteners, viscosity modifiers, UV resistance agents, and combinations thereof.

[0075] Embodiment 2. The polyol premix of embodiment 1, wherein the storage-stable polyol premix is aged at a temperature and for a time that is, or that correlates to, at least 4 months and optionally up to 24 months at room temperature (~17-23°C) and, when combined with a polyisocyanate component, reacts to form a closed-cell foam in cells of which the halogenated physical blowing agent is disposed, wherein the aged closed-cell foam exhibits a yellowing index of 45 or below and an average density from 1.85 lb / ft3to 2.15 lb / ft3(from 29.6 kg / m3to 34.4 kg / m3).

[0076] Embodiment 3. The polyol premix of embodiment 1 or embodiment 2, wherein the storage-stable polyol premix is aged at ~50°C for a time from 9 to 55 days.

[0077] Embodiment 4. The polyol premix of any of embodiments 1-3, wherein the halogenated blowing agent comprises an HFCO, e.g., l-chloro-3,3,3-trifluoropropene, of which at least 70 wt% is trans-isomer.

[0078] Embodiment 5. The polyol premix of any one of embodiments 1-4, wherein the organometallic compound comprises at least one metal from Groups 13-14 of the Periodic Table of Elements, e.g., tin.

[0079] Embodiment 6. The polyol premix of any one of embodiments 1-5, wherein the organometallic compound comprises a di-(Cl-C4-alkyl)tin di-(Cl-C18-hydrocarbyl) mercaptide, e.g., comprises or is dimethyltin di(lauryl sulfide).

[0080] Embodiment 7. The polyol premix of any one of embodiments 1-6, wherein the non-oxygen-containing tertiary amine comprises a C1-C12 linear, branched, or cyclic hydrocarbyl-substituted poly(C2-C4 alkylene amine), a C1-C8 linear, branched, or cyclic hydrocarbyl-Attorney Docket No. IR4671 WO-PCTsubstituted C5-C7 nitrogen-containing heterocyclic ring moiety or a combination or mixture thereof.

[0081] Embodiment 8. The polyol premix of any one of embodiments 1-7, wherein the non-oxygen-containing tertiary amine comprises a hydrocarbyl-substituted imidazole.

[0082] Embodiment 9. The polyol premix of any one of embodiments 1-8, wherein the epoxide acid scavenger comprises a cyclic moiety attached directly or indirectly to the epoxy moiety, wherein the cyclic moiety comprises: an aromatic ring, a ring comprising at least two unsaturations conjugated to each other, a ring comprising at least two unsaturations not conjugated to each other, a ring comprising one unsaturation, or a ring comprising no unsaturations.

[0083] Embodiment 10. The polyol premix of any one of embodiments 1-9, wherein the epoxide acid scavenger comprises at least one oxygen atom in addition to the epoxy moiety.

[0084] Embodiment 11. The polyol premix of any one of embodiments 1-10, wherein the epoxide acid scavenger comprises a cyclohexane ring attached directly to two carbons of the epoxy moiety.

[0085] Embodiment 12. The polyol premix of any one of embodiments 1-11, further comprising a flame retardant / suppressor, a chemical blowing agent comprising water, a surfactant / foam stabilizer, or a combination thereof.

[0086] Embodiment 13. The polyol premix of any one of embodiments 1-12, wherein: the storage-stable polyol premix is aged by exposure to a temperature and for a time that is, or that correlates to, at least 4 months at room temperature (~17-23°C) to form an aged polyol premix, which, when thereafter combined with a first polyisocyanate component, reacts to form an aged closed-cell polyurethane foam in cells of which the halogenated physical blowing agent is disposed, said aged foam having an aged gel time, an aged tack free time, and an aged rise time; an unaged polyol premix, which is identical to the storage-stable polyol premix but is exposed to room temperature (~17-23°C) for no more than 2 days, when combined with a second polyisocyanate component identical to the first polyisocyanate component, reacts to form an unaged closed-cell polyurethane foam in cells of which the halogenated physical blowing agent is disposed, said unaged foam having an unaged gel time, an unaged tack free time, and an unaged rise time; an aged gel time difference is the aged gel time minus the unaged gel time, an aged tack free time difference is the aged tack free time minus the unaged tack free time, and an aged rise time difference is the aged rise time minus the unaged rise time; a comparative polyol premix,Attorney Docket No. IR4671 WO-PCTwhich is identical to the storage- stable premix except that it contains 0.0 parts epoxide acid scavenger, is aged by exposure to a temperature and for a time that is, or that correlates to, at least 4 months at room temperature (~17-23°C) to form an aged comparative polyol premix, which, when thereafter combined with a third polyisocyanate component identical to said first and second polyisocyanate components, reacts to form an aged comparative polyurethane foam in cells of which the halogenated physical blowing agent is disposed, said aged comparative foam having an aged comparative gel time, an aged comparative tack free time, and an aged comparative rise time; an unaged comparative polyol premix, which is identical to the comparative polyol premix but is exposed to room temperature (~17-23°C) for no more than 2 days, when combined with a fourth polyisocyanate component identical to said first, second and third polyisocyanate components, reacts to form an unaged comparative polyurethane foam in cells of which the halogenated physical blowing agent is disposed, said unaged comparative foam having an unaged comparative gel time, an unaged comparative tack free time, and an unaged comparative rise time; an aged comparative gel time difference is the aged comparative gel time minus the unaged comparative gel time, an aged comparative tack free time difference is the aged comparative tack free time minus the unaged comparative tack free time, and an aged comparative rise time difference is the aged comparative rise time minus the unaged comparative rise time; a normalized gel time delay is the aged comparative gel time difference minus the aged gel time difference, a normalized tack free time delay is the aged comparative tack free time difference minus the aged tack free time difference, and a normalized aged rise time delay is the aged comparative rise time difference minus the aged rise time difference; a normalized gel time ratio is the aged gel time difference divided by the aged comparative gel time difference, a normalized tack free time ratio is the aged tack free time difference divided by the aged comparative tack free time difference, and a normalized rise time ratio is the aged rise time difference divided by the aged comparative rise time difference; and two, three, four, or five or more, or all six, of the following are satisfied: the normalized gel time delay is at least 2 seconds, e.g., at least 3 seconds; the normalized tack free time delay is at least 2 seconds, e.g., at least 3 seconds; the normalized rise time delay is at least 2 seconds, e.g., at least 3 seconds; the normalized gel time ratio is less than 75%, e.g., less than 60%; the normalized tack free time ratio is less than 75%, e.g., less than 60%; and the normalized rise time ratio is less than 75%, e.g., less than 60%.Attorney Docket No. IR4671 WO-PCT

[0087] Embodiment 14. A foam composition comprising a reaction product of the polyol premix according to any one of embodiments 1-12 with a first and / or second polyisocyanate component, or alternatively according to embodiment 13 with the first / second polyisocyanate component, thereby forming a closed-cell foam in cells of which the halogenated physical blowing agent is disposed.

[0088] Embodiment 15. A foam kit comprising the foam composition of embodiment 14, wherein the polyol premix is disposed in a first vessel and the first / second polyisocyanate component is stored in a second vessel separate from but capable of being in fluid communication with said first vessel, wherein the fluid communication between said first and second vessels is removably blocked such that the polyol premix and the polyisocyanate component are prevented from reacting before formation of a foam is desired.

[0089] Within this specification, embodiments have been described in a way which enables a clear and concise specification to be written, but it is intended and should be appreciated that embodiments may be variously combined or separated without departing from the teachings herein. For example, unless specifically noted to the contrary, it should be appreciated that any preferred and / or optional features described herein can be applicable to all aspects of the disclosure.

[0090] The following Examples are intended to support and / or exemplify, but not necessarily limit, the scope of the invention, as recited in the claims. In this disclosure, the roots of the inclusive words “comprising,” “containing,” and “including” (inter alia) can alternatively include exclusionary or semi-exclusionary terms, such as variations of “consisting of’ and / or “consisting essentially of’, respectively, the latter of which should be understood to be given the meaning provided by United States case law. Indeed, the invention(s) herein can be construed as excluding any element or process step that does not materially affect the basic and novel characteristics of the composition or process, which is specifically encompassed by the phrase “consisting essentially of’ herein. Additionally or alternatively, in various embodiments, the disclosure can be implicitly construed as excluding any element or process step that is not affirmatively specified herein.

[0091] Although the disclosure is illustrated and described herein with reference to specific embodiments, it is not necessarily intended to be limited to the details shown. Rather, variousAttorney Docket No. IR4671 WO-PCTmodifications may be made in the details within the scope and range of equivalents of the claims and without departing from the spirit of the disclosure.EXAMPLESComparative Examples 1-2 and Examples 3-6

[0092] In Comparative Examples 1-2 and Examples 3-6, foams were made by a hand mix method according to ASTM method D7484-18. B-side mixtures (comprising polyols, surfactant, catalyst, blowing agents, and additives) were pre-blended and mixed thoroughly. The B-side mixtures were charged into containers suitable for pressure up to ~100 psig and were then placed in a gravity convection oven (from VWR) with its temperature controlled at ~50°C (~122°F) for various lengths of time. Samples that were aged at ~50°C were weighed after they were removed from the oven to confirm that the loss of component in the B-side was negligible. The A-side (isocyanate) and B-side were placed in an orbital shaker (from Thermo Scientific) set to ~15.6°C (~60°F) at ~60 rpm the night before making the foams.Comparative Example 1

[0093] Comparative Example 1 formulation is shown in Table 1 below. Elastospray® 8000A is a polymeric methylene diphenyl diisocyanate (MDI) commercially available from BASF. Jeffol® SG-360 and Jeffol® R-470X are polyols commercially available from Huntsman.Terate® HT 5349 a polyol commercially available from Stepan. PMDETA and DMCHA, Poly cat® 5 and Poly cat® 8 respectively, and Dabco® T-120 are catalysts commercially available from Evonik. Tegostab® B 8466 a surfactant commercially available from Evonik. TCPP (Tris(2-chloro-1-methylethyl) phosphate) is a commercially available flame retardant from ICL-IP America. Forane® FBA 1233zd is a commercially available blowing agent from Arkema. The isocyanate used was an aromatic polyisocyanate. Total blowing agent level for this formulation (and all formulations described in these Examples) was ~22 ml / g.Attorney Docket No. IR4671 WO-PCTTable 1.FormulationB-Side PPHP Wt% B-Side Jeffol® SG-360 22.50 14.91Jeffol® R-470X 22.50 14.91Terate® HT 5349 55.00 36.43 PMDETA 0.30 0.20 DMCHA 4.22 2.80 Dabco® T-120 0.30 0.20 Tegostab® B 8466 1.48 0.98TCPP 24.30 16.10 Added Water 2.94 1.94Forane® FBA 1233zd 17.42 11.54Epoxy containing additive 0.00 0.00Total B Side: 150.96 100ROH Index 123Isocyanate 157.2B / A 0.960Total Blowing, ml / g 21.55Comparative Example 2

[0094] Comparative Example 2 formulation is shown in Table 2 below. Dabco® 2040 and Polycat® 206 are catalysts commercially available from Evonik. Fomrez® UL-22 is a catalyst available from Galata Chemicals. All remaining components were sourced same as described in Comparative Example 1 above.Table 2.FormulationB-Side PPHP Wt % B-Side Jeffol® SG-360 22.50 14.88Jeffol® R-470X 22.50 14.88Terate® HT 5349 55.00 36.38Dabco® 2040 2.00 1.32Polycat® 206 2.21 1.46Fomrez® UL-22 0.90 0.60 Tegostab® B 8466 1.47 0.97TCPP 24.27 16.05 Added Water 2.93 1.94Forane® FBA 1233zd 17.41 11.52Epoxy containing additive 0.00 0.00Total B Side: 151.19 100ROH Index 120Isocyanate 156.9B / A 0.964Total Blowing, ml / g 21.55Attorney Docket No. IR4671 WO-PCTExamples 3-6

[0095] The formulation for Example 3 was the same as for Comparative Example 2, except that Vikolox® 68 (a cyclic epoxide acid scavenger) was added at -0.50 pphp (-0.33 wt%). Vikolox® 68 was previously commercially available from Arkema (currently commercially available from Cargill). The remainder of the B-side component amounts were adjusted accordingly so the total B side remained at 100 wt%. The formulations for Examples 4, 5, and 6 were each the same as for Example 3, except that the epoxide acid scavenger was added at -1.00 pphp (-0.65 wt%), -1.90 pphp (-1.23 wt%), and -3.00 pphp (-1.93 wt%), respectively. B-side component amounts were each adjusted to sum to 100 wt%.

[0096] For these Examples, the A- and B- sides were dispensed into a container and mixed with a hand mixer at ~4000 rpm for ~3 seconds, to ensure the mixing was thorough and foam quality was consistently good, to form a free rise foam. Reactivity times (gel time, tack free time, and rise time) as defined within ASTM D7484-18 were measured at the initial time (no accelerated aging, abbreviated as 0*) and then at -14, -21, and -28 days after aging at ~50°C. Each formula was repeated at least once, and reactivity times were the average of triplicates with standard deviations typically -1 sec (unless otherwise noted). The formulations tested all had an Iso Index around 120 (unitless).Table 3.Reactivity at 0*, ~14, ~21, and ~28 day aged at ~50°CGel Time Tack Free Time Rise Time _...,,, „.....,,.,, Density (lb / ft³) Yellowness Ex. (days / secs) (days / secs) (days / secs)0*714 / 21 / 28 0* / 14 / 21 / 28 0* / 14 / 21 / 28 0* / 14 / 21 / 28 0* / 14 / 21 / 28 Comp. 1 10 / 22 / 26 / 30 11 / 26 / 36 / 39 22 / 46 / 54 / 58 1.99 / 1.92 / 1.95 / 2.24 26.9 / 49.1 / 39.6 / 40.0 Comp. 2 11 / 15 / 16 / 18 14 / 18 / 18 / 20 28 / 34 / 37 / 37 1.98 / 1.97 / 2.01 / 2.00 34.6 / 36.0 / 38.3 / 40.1 3 12 / 15 / 16 / 17 15 / 19 / 19 / 19 29 / 33 / 34 / 36 1.94 / 2.00 / 2.00 / 2.00 34.1 / 35.2 / 35.6 / 39.6 4 13 / 15 / 16 / 17 16 / 18 / 19 / 20 31 / 33 / 33 / 36 1.99 / 2.01 / 2.04 / 1.91 33.2 / 34.4 / 35.9 / 41.0 5 12 / 15 / 15 / 16 15 / 18 / 19 / 19 30 / 33 / 35 / 35 1.89 / 2.00 / 2.00 / 2.05 32.6 / 34.9 / 35.3 / 42.2 6 13 / 15 / 15 / 15 17 / 18 / 19 / 19 29 / 33 / 34 / 34 1.89 / 1.99 / 1.96 / 2.01 34.0 / 34.9 / 35.9 / 37.9 *Foamed ~1 day after formulation blended to equilibrate at room temp in orbital shaker, not subject to heat aging.

[0097] Table 3 shows that reactivity appeared to decrease as the time of aging increased, as indicated by the longer gel, tack free, and rise times. It can be desired that the reactivity, particularly the gel time, change after -14 days of aging at ~50°C be less than -7 seconds, which can be equivalent to ~6 months of stability under ambient conditions. It is even more desirable that the gel time change after ~28 days of aging at ~50°C be less than ~7 seconds, which can be equivalent to ~1 year of stability under ambient conditions. Typically, industrial foam producersAttorney Docket No. IR4671 WO-PCTcan require ~ 6 months of storage stability for fully blended B-side. The Comparative Example 1 formula doesn’t appear to have acceptable ~6-month stability as indicated by the -12 second gel time difference between the -0* and -14 day aging. Also, the ~28 day aged foam had an anomalous density, larger than -2.15 lb / ft3(-34.4 kg / m3). The Comparative Example 2 formula appears to exhibit -1 year stability as indicated by the -7 second gel time difference between the -0 and -28 day aging. Examples 3-6 appear to exhibit a decrease in the gel time difference of -5 seconds to -2 seconds between the -0 and -28 day aging, as the amount of cyclic epoxide acid scavenger is increased from -0.5 to - 3 pphp. Comparative Examples 1 and 2 and Examples 3-6 yielded what appeared to be “good quality” foam with a regular cell structure.Comparative Examples 1-2 and Examples 7-10

[0098] With Comparative Examples 1-2 identical to above, the formulation for Example 7 was the same as for Comparative Example 2, except that Vikolox® 16 (a linear, not cyclic, epoxide acid scavenger) was added at -0.50 pphp (-0.33 wt%). Vikolox® 16 was previously commercially available from Arkema (currently commercially available from Cargill). The remainder of the B-side component amounts were adjusted accordingly so the total B side remained at 100 wt%. The formulations for Examples 8, 9, and 10 were each the same as for Example 7, except that the epoxide acid scavenger was added at -1.00 pphp (-0.65 wt%), -1.90 pphp (-1.23 wt%), and -2.99 pphp (-1.92 wt%), respectively. B-side component amounts were each adjusted to sum to 100 wt%. Foam characteristics are shown in Table 4 below.Table 4.Reactivity at 0*, -14. -21, and -28 day aged at ~50°CGel Time Tack Free Time Rise Time Density (lb / ft³) YellownessEx. (days / secs) (days / secs) (days / secs)0* / 14 / 21 / 28 0*714 / 21 / 28 0*714 / 21 / 28 0*714 / 21 / 28 0*714 / 21 / 28 Comp. 1 10 / 22 / 26 / 30 11 / 26 / 36 / 39 22 / 46 / 54 / 58 1.99 / 1.92 / 1.95 / 2.24 26.9 / 49.1 / 39.6 / 40.0 Comp. 2 11 / 15 / 16 / 18 14 / 18 / 18 / 20 28 / 34 / 37 / 37 1.98 / 1.97 / 2.01 / 2.00 34.6 / 36.0 / 38.3 / 40.1 7 11 / 14 / 16 / 17 15 / 18 / 18 / 19 28 / 30 / 27 / 36 2.09 / 2.04 / 2.06 / 2.08 34.8 / 37.6 / 41.7 / 44.6 8 12 / 14 / 15 / 17 15 / 19 / 19 / 20 29 / 30 / 27 / 34 2.01 / 2.00 / 2.03 / 2.08 35.3 / 37.6 / 44.4 / 50.8 9 12 / 14 / 15 / 17 15 / 17 / 19 / 20 27 / 28 / 27 / 30 2.00 / 2.03 / 2.10 / 2.53 35.6 / 37.0 / 44.0 / 57.7 10 12 / 14 / 15 / 17 15 / 19 / 18 / 19 31 / 28 / 26 / 21 1.95 / 2.03 / 2.02 / 2.88 37.9 / 39.2 / 44.3 / 67.3 *Foamed -1 day after formulation blended to equilibrate at room temp in orbital shaker, not subject to heat aging.

[0099] Table 4 shows that reactivity appeared to decrease as the time of aging increased, as indicated by the longer gel and tack free times. In these Examples, the decrease in rise times as the time of aging increased appeared to reflect a breakdown in foam quality. The Comparative Example 2 formula exhibits some stability at -1 year accelerated aging, but any positive effect isAttorney Docket No. IR4671 WO-PCTcountered by Examples 7-10 exhibiting a decrease in the gel time difference of -6 seconds to -5 seconds between the -0 and -28 day aging as the amount of linear epoxide acid scavenger is increased from ~0.5 to - 3 pphp. If the linear epoxide acid scavenger has any effect in these systems, it could be at higher content. In addition, Examples 7-10 yielded poorer foam quality, with significant cell collapse and yellowing observed upon heat aging for -28 days.Comparative Examples 1 and 3 and Examples 11-12Comparative Example 3

[0100] Comparative Example 3 formulation is shown in Table 5 below. All components were sourced same as described in Comparative Examples 1-2 above.Table 5.FormulationB-Side PPHP Wt % B-Side Jeffol® SG-360 22.50 14.88Jeffol® R-470X 22.50 14.88Terate® HT 5349 55.00 36.38Dabco® 2040 2.00 1.32Polycat® 206 2.21 1.46 Dabco® T-120 0.90 0.60 Tegostab® B 8466 1.47 0.97TCPP 24.27 16.05 Added Water 2.93 1.94Forane® FBA 1233zd 17.41 11.52Epoxy containing additive 0.00 0.00Total B Side: 151.19 100ROH Index 120Isocyanate 156.9B / A 0.964Total Blowing, ml / g 21.55Examples 11-12

[0101] The formulation for Example 11 was the same as for Comparative Example 1, except that 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (aka “3,4-Epoxy”; a cycloaliphatic epoxide acid scavenger) was added at -2.00 pphp (-1.30 wt%). 3,4-Epoxy is commercially available from Sigma-Aldrich. The remainder of the B-side component amounts were adjusted accordingly so the total B side remained at 100 wt%. The formulation for Example 12 was the same as for Comparative Example 3, except that the 3,4-Epoxy acid scavenger was added at -2.00 pphp (-1.30 wt%). Again, B-side component amounts were eachAttorney Docket No. IR4671 WO-PCTadjusted to sum to 100 wt%. Foam characteristics, this time for initial (0*), -7 days, and -14 days aged at ~50°C, are shown in Table 6 below (yellowness data not available).Table 6.Reactivity at 0*, -7, and -14 day aged at ~50°CGel Time Tack Free Time Rise Time Density (lb / ft3) Ex. (days / secs) (days / secs) (days / secs) Density (lb / ft³)0* / 7 / 14 0* / 7 / 14 0* / 7 / 14 0* / 7 / 14Comp. 1 10 / 16 / 22 11 / 20 / 26 22 / 33 / 46 1.99 / 1.87 / 1.92 Comp. 3 13 / 15 / 20 16 / 22 / 26 27 / 32 / 38 1.89 / 1.89 / 2.03 11 11 / 16 / 20 15 / 29 / 33 26 / 38 / 46 1.89 / 1.97 / 2.0312 12 / 15 / 17 17 / 20 / 23 28 / 30 / 36 1.89 / 1.92 / 2.01 *Foamed ~1 day after formulation blended to equilibrate at room temp in orbital shaker, not subject to heat aging.

[0102] Table 6 shows that reactivity appeared to decrease as the time of aging increased, as indicated by the longer gel, tack free, and rise times. Comparative Example 1 didn’t appear to exhibit ideal ~6-month stability as indicated by the -12 seconds gel time difference between the -0* and -14 day aging. Comparative Example 3 appeared to exhibit acceptable ~6-month stability as indicated by the -7 second gel time difference between the -0* and -14 day aging. Examples 11 and 12 appeared to exhibit a decrease in the gel time difference of -9 seconds and -5 seconds, respectively, between the -0* and -14 day aging, due to the presence of the cyclic epoxide acid scavenger at - 2 pphp. Comparative Examples 1 and 3 and Examples 11-12 each yielded what appeared to be “good quality” foam with a regular cell structure.Examples 13-16

[0103] The formulations for Examples 13-16 are shown generically in Table 7 below. Jeffcat® Z-110 and Jeffcat ZF-10 are catalysts commercially available from Huntsman. K-Kat™ XK-651 is a catalyst commercially available from King Industries. Although each of the Example 13-16 formulations contains an epoxide acid scavenger at -2.00 pphp, they are each different -Vikoflex® 7170 (a linear epoxide ester acid scavenger, previously commercially available from Arkema but currently commercially available from Cargill), Vikoflex® 7190 (a linear epoxide ester acid scavenger, previously commercially available from Arkema but currently commercially available from Cargill), Vikoflex® 16, and Vikoflex® 68, respectively. Foam characteristics, this time for initial (0*), -7 days, and -14 days aged at ~50°C, are shown in Table 8 below (yellowness data not available).Attorney Docket No. IR4671 WO-PCTTable 7.FormulationB-Side PPHP Wt % B-Side Jeffol® SG-360 22.50 14.71Jeffol® R-470X 22.50 14.71Terate® HT 5349 55.00 35.96Jeffcat® Z-110 4.02 2.63Jeffcat® ZF-10 0.30 0.20K-Kat™ XK-651 0.30 0.20 Tegostab® B 8466 1.48 0.97TCPP 24.40 15.95 Added Water 2.95 1.93Forane® FBA 1233zd 17.49 11.43Epoxy containing additive 2.00 1.31Total B Side: 152.94 100ROH Index 118Isocyanate 156.58B / A 0.977Total Blowing, ml / g 21.55Table 8.Reactivity at 0*, ~7, and ~14 day aged at ~50°CGel Time Tack Free Time Rise Time Density (lb / ft3)Ex. (days / secs) (days / secs) (days / secs) Density (lb / ft³)0* / 7 / 14 0* / 7 / 14 0* / 7 / 14 0* / 7 / 1413 13 / 30 / 41 15 / 42 / 55 28 / 60 / 76 1.37 / 1.45 / 1.7314 13 / 29 / 40 15 / 40 / 53 26 / 58 / 75 1.39 / 1.41 / 1.6915 11 / 29 / 37 14 / 39 / 48 25 / 55 / 74 1.32 / 1.46 / 1.5316 12 / 29 / 33 15 / 39 / 42 28 / 56 / 62 1.39 / 1.41 / 1.50 *Foamed ~1 day after formulation blended to equilibrate at room temp in orbital shaker, not subject to heat aging.

[0104] It is noted that, despite the much lower density in comparison to the foams with other catalyst systems, there are no Comparative Examples with 0.0 pphp epoxide acid scavenger content here, and so there are no exact comparative foams directly available - closest are those of Comparative Examples 1-2, but the catalyst system differences make drawing conclusions difficult. In any event, it was noted that all initial (0*) foams appeared to be of relatively good quality, as were the ~7-day aged foams with the exception of the Vikolox® 16 foam (Example 15). It was also noted that all ~14-day aged foams appeared to be of relatively poor quality, which is why none of these premixes were tested for storage stability for ~21 days or ~28 days.

Claims

Attorney Docket No. IR4671 WO-PCTCLAIMSWhat is claimed is:

1. A storage-stable polyol premix comprising:a halogenated physical blowing agent comprising an HFO, an HFCO, or a combination thereof;one or more polyols;a catalyst system comprising (i) a non-oxygen-containing tertiary amine and (ii) an organometallic compound comprising at least one metal from Groups 13-15 of the Periodic Table of Elements;an epoxide acid scavenger containing an epoxy moiety;and optionally one or more additives comprising flame retardants / suppressors, chemical blowing agents, surfactants / foam stabilizers, non-epoxide acid scavengers, radical scavengers, fillers, adhesion promoters, anti-static agents, antioxidants, hydrolysis agents, lubricants, antimicrobial agents, pigments / whiteners, viscosity modifiers, UV resistance agents, and combinations thereof.

2. The polyol premix of claim 1, wherein the storage-stable polyol premix is aged at a temperature and for a time that is, or that correlates to, at least 4 months at room temperature (~17-23°C) and, when combined with a polyisocyanate component, reacts to form a closed-cell foam in cells of which the halogenated physical blowing agent is disposed, wherein the aged closed-cell foam exhibits a yellowing index of 45 or below and an average density from 1.85 lb / ft3to 2.15 lb / ft3(from 29.6 kg / m3to 34.4 kg / m3).

3. The polyol premix of claim 2, wherein the storage-stable polyol premix is aged at a temperature and for a time that is, or that correlates to, up to 24 months at room temperature (~17-23°C).

4. The polyol premix of any of claims 1-3, wherein the storage-stable polyol premix is aged at ~50°C for a time from 9 to 55 days.

5. The polyol premix of any of claims 1-4, wherein the halogenated blowing agent comprises an HFCO.Attorney Docket No. IR4671 WO-PCT6. The polyol premix of any of claims 1-5, wherein the halogenated blowing agent comprises l-chloro-3,3,3-trifluoropropene, of which at least 70 wt% is trans-isomer.

7. The polyol premix of any of claims 1-6, wherein the organometallic compound comprises at least one metal from Groups 13-14 of the Periodic Table of Elements, e.g., tin.

8. The polyol premix of any of claims 1-7, wherein the organometallic compound comprises a di-(Cl-C4-alkyl)tin di-(Cl-C18-hydrocarbyl) mercaptide.

9. The polyol premix of claim 8, wherein the organometallic compound comprises or is dimethyltin di(lauryl sulfide).

10. The polyol premix of any of claims 1-9, wherein the non-oxygen-containing tertiary amine comprises a C1-C12 linear, branched, or cyclic hydrocarbyl-substituted poly(C2-C4 alkylene amine), a C1-C8 linear, branched, or cyclic hydrocarbyl-substituted C5-C7 nitrogencontaining heterocyclic ring moiety or a combination or mixture thereof.

11. The polyol premix of any of claims 1-10, wherein the non-oxygen-containing tertiary amine comprises a hydrocarbyl-substituted imidazole.

12. The polyol premix of any of claims 1-11, wherein the epoxide acid scavenger comprises a cyclic moiety attached directly or indirectly to the epoxy moiety, wherein the cyclic moiety comprises: an aromatic ring, a ring comprising at least two unsaturations conjugated to each other, a ring comprising at least two unsaturations not conjugated to each other, a ring comprising one unsaturation, or a ring comprising no unsaturations.

13. The polyol premix of any of claims 1-12, wherein the epoxide acid scavenger comprises at least one oxygen atom in addition to the epoxy moiety.

14. The polyol premix of any of claims 1-13, wherein the epoxide acid scavenger comprises a cyclohexane ring attached directly to two carbons of the epoxy moiety.

15. The polyol premix of any of claims 1-14, further comprising a flame retardant / suppressor, a chemical blowing agent comprising water, a surfactant / foam stabilizer, or a combination thereof.

16. The polyol premix of any of claims 1-15, wherein:Attorney Docket No. IR4671 WO-PCTthe storage-stable polyol premix is aged by exposure to a temperature and for a time that is, or that correlates to, at least 4 months at room temperature (~17-23°C) to form an aged polyol premix, which, when thereafter combined with a first polyisocyanate component, reacts to form an aged closed-cell polyurethane foam in cells of which the halogenated physical blowing agent is disposed, said aged foam having an aged gel time, an aged tack free time, and an aged rise time;an unaged polyol premix, which is identical to the storage-stable polyol premix but is exposed to room temperature (~17-23°C) for no more than 2 days, when combined with a second polyisocyanate component identical to the first polyisocyanate component, reacts to form an unaged closed-cell polyurethane foam in cells of which the halogenated physical blowing agent is disposed, said unaged foam having an unaged gel time, an unaged tack free time, and an unaged rise time;an aged gel time difference is the aged gel time minus the unaged gel time, an aged tack free time difference is the aged tack free time minus the unaged tack free time, and an aged rise time difference is the aged rise time minus the unaged rise time;a comparative polyol premix, which is identical to the storage-stable premix except that it contains 0.0 parts epoxide acid scavenger, is aged by exposure to a temperature and for a time that is, or that correlates to, at least 4 months at room temperature (~17-23°C) to form an aged comparative polyol premix, which, when thereafter combined with a third poly isocyanate component identical to said first and second polyisocyanate components, reacts to form an aged comparative polyurethane foam in cells of which the halogenated physical blowing agent is disposed, said aged comparative foam having an aged comparative gel time, an aged comparative tack free time, and an aged comparative rise time;an unaged comparative polyol premix, which is identical to the comparative polyol premix but is exposed to room temperature (~17-23°C) for no more than 2 days, when combined with a fourth polyisocyanate component identical to said first, second and third polyisocyanate components, reacts to form an unaged comparative polyurethane foam in cells of which the halogenated physical blowing agent is disposed, said unaged comparative foam having an unaged comparative gel time, an unaged comparative tack free time, and an unaged comparative rise time;Attorney Docket No. IR4671 WO-PCTan aged comparative gel time difference is the aged comparative gel time minus the unaged comparative gel time, an aged comparative tack free time difference is the aged comparative tack free time minus the unaged comparative tack free time, and an aged comparative rise time difference is the aged comparative rise time minus the unaged comparative rise time;a normalized gel time delay is the aged comparative gel time difference minus the aged gel time difference, a normalized tack free time delay is the aged comparative tack free time difference minus the aged tack free time difference, and a normalized aged rise time delay is the aged comparative rise time difference minus the aged rise time difference;a normalized gel time ratio is the aged gel time difference divided by the aged comparative gel time difference, a normalized tack free time ratio is the aged tack free time difference divided by the aged comparative tack free time difference, and a normalized rise time ratio is the aged rise time difference divided by the aged comparative rise time difference; and two or more of the following are satisfied:the normalized gel time delay is at least 2 seconds;the normalized tack free time delay is at least 2 seconds;the normalized rise time delay is at least 2 seconds;the normalized gel time ratio is less than 75%;the normalized tack free time ratio is less than 75%; andthe normalized rise time ratio is less than 75%.

17. The polyol premix of claim 16, wherein three or more of the following are satisfied: the normalized gel time delay is at least 3 seconds;the normalized tack free time delay is at least 3 seconds;the normalized rise time delay is at least 3 seconds;the normalized gel time ratio is less than 60%;the normalized tack free time ratio is less than 60%; andthe normalized rise time ratio is less than 60%.

18. A foam composition comprising a reaction product of the polyol premix according to any of claims 1-15 with a first and / or second polyisocyanate component, thereby forming a closedcell foam in cells of which the halogenated physical blowing agent is disposed.Attorney Docket No. IR4671 WO-PCT19. A foam composition comprising a reaction product of the polyol premix according to any claim 16 or claim 17 with the first / second polyisocyanate component, thereby forming a closedcell foam in cells of which the halogenated physical blowing agent is disposed.

20. A foam kit comprising the foam composition of claim 18 or claim 19, wherein the polyol premix is disposed in a first vessel and the first / second polyisocyanate component is stored in a second vessel separate from but capable of being in fluid communication with said first vessel, wherein the fluid communication between said first and second vessels is removably blocked such that the polyol premix and the first / second polyisocyanate component are prevented from reacting before formation of a foam is desired.

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