Tertiary amines as hydrofluoroolefin stable polyurethane catalyst

Abstract

The present invention discloses a tertiary amine comprising cycloalkyl moiety catalyst system useful in the production of polyurethane and / or polyisocyanurate foams using hydrohaloolefin blowing agents and a catalyst system. In particular, disclosed is a polyol premix composition comprising the catalyst system, a polyol, and a hydrohaloolefin blowing agent, wherein the polyol premix may be used to produce a polyurethane and / or polyisocyanurate foam by combining the polyol premix with an isocyanate.

Description

TERTIARY AMINES AS HYDROFLUOROOLEFIN STABLE POLYURETHANE CATALYST CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application Serial Number 63 / 673,843 filed July 22, 2024. The noted Application(s) are incorporated herein by reference. FIELD

[0002] The present disclosure generally relates to a catalyst system useful in the production of polyurethane and / or polyisocyanurate foams using hydrohaloolefin blowing agents. In particular, the present disclosure relates to a polyol premix composition comprising the catalyst system, a polyol, and a hydrohaloolefin blowing agent. The presently disclosed polyol premix may be used to produce a polyurethane and / or polyisocyanurate foam by combining the polyol premix with an isocyanate. BACKGROUND

[0003] Polyurethane and polyisocyanurate foams have utility in numerous insulation applications including roofing systems, building panels, building envelope insulation, spray applied foams, one and two component froth foams, insulation for refrigerators and freezers, and in the automotive and aerospace industry.

[0004] Polyurethane foams are typically prepared by reacting an isocyanate and a premix which consists of isocyanate-reactive components such as a polyol, and optionally other components such as blowing agents, catalysts, flame retardants, water, foam-stabilizing surfactants. Typically, the components for such polyurethane or polyisocyanurate foams are in pre-blended formulations referred to as an “A side” and a “B side”. The A side comprises one or more polyisocyanates and, optionally, one or more isocyanate-compatible ingredients. The “B side” generally comprises: (i) one or more polyols, (ii) one or more catalysts, (iii) one or more blowing agent, and, optionally, (iv) one or more auxiliary components such as, for example, surfactants, flame retardants, colorants, compatibilizers, and solubilizers. The B side is also often referred to as a “polyol premix”.

[0005] Polyurethane and polyisocyanurate foams are prepared by bringing the A and B sides together by either hand mixing (for small preparations) and / or using machine mixing techniques to form, e.g., blocks, slabs, laminates, spray applied foams, froths, and pour-in- place panels and other items. Optional ingredients such as fire retardants, colorants, auxiliaryblowing agents, and other polyols can be added when mixing rather than being premixed into the A side or B side.

[0006] Historically, liquid blowing agents such as chlorofluorocarbons (CFCs) and hydrofluorocarbons (HFCs) have been used to make polyurethane and polyisocyanurate foams due to their ease of use and ability to produce foams with beneficial mechanical and thermal insulation properties. However, due to a concern that CFCs and HFCs are bad for the environment, a new generation of halogenated hydroolefinic blowing agents (also referred to as “hydrohaloolefins”) have been developed to replaced CFCs and HFCs. Without intending to be bound to a specific theory, it is generally thought that such hydrohaloolefins have an inherent chemical instability in the lower atmosphere resulting in a low global warming potential (GWP) and zero or near zero ozone depletion potential (ODP), thereby rendering hydrohaloolefins better for the environment than CFCs and HFCs.

[0007] Among the category of hydrohaloolefin blowing agents are certain hydrofluoroolefins (HFOs) of particular interest, including, for example, trans-1,3,3,3-tetrafluoropropene (1234ze(E)) and 1,1,1,4,4,4-hexafluorobut-2-ene (1336mzzm(Z)). Among the category of hydrohaloolefin blowing agents are certain hydrochlorofluoroolefins (HCFOs) of particular interest, which include, for example, 1-chloro-3,3,3-trifluoropropene (1233zd) (including both cis and trans isomers and combinations thereof). Processes for the manufacture of trans-1,3,3,3- tetrafluoropropene are disclosed in U.S. Pat. Nos.7,230,146 and 7,189,884, which are hereby incorporated by reference in their entirety (to the extent that they do not contradict the instant disclosure). Processes for the manufacture of trans-1-chloro-3,3,3-trifluoropropene are disclosed in U.S. Pat. Nos. 6,844,475 and 6,403,847, which are hereby incorporated by reference in their entirety (to the extent that they do not contradict the instant disclosure).

[0008] The use of HFOs and HFCOs in polyol premixes for polyurethane and polyisocyanurate foams has been described in numerous applications such as U.S. Patent Publication Nos. 2012 / 0220677, 2015 / 0197614, and 2016 / 0376397, which are hereby incorporated by reference in their entirety (to the extent that they do not contradict the instant disclosure). However, it has been found that when polyol premixes (i.e., B sides) containing a hydrohaloolefin blowing agent and a typical amine catalyst are aged prior to mixing and reacting with a polyisocyanate (i.e., an A side), deleterious effects can occur. For instance, it has been found that such formulations, when aged, can produce a foamable composition which has an undesirable increase in reactivity time (i.e., a delay in reaction completion) and / or undesirable properties.

[0009] W.O. Pat. Appl. No.2019050970A1 (the contents of which are incorporated herein by reference) by Huntsman describes a catalyst system comprising 2,2'- dimorpholinodiethyl ether, Ν,Ν-dimethylcyclohexylamine, and a hydroxyl-containing compound selected from a diol (e.g., ethylene glycol) and / or an alkanolamine (e.g., methyldiethanolamine) is capable of stabilizing a polyol premix containing a hydrohaloolefin blowing agent while improving the front-end reactivity of the polyol premix over comparable catalysts / polyol premixes when contacted with an isocyanate. Although the catalyst stability is better than those previously available, there is still room for improvement in catalyst stability.

[0010] EP 4253442 A2 (the contents of which are incorporated herein by reference) by Evonik also describes an amine composition useful for making polyurethane foam systems. The foam systems described by this document have some stability in HFOs.

[0011] U.S. Pat. Appl. No.20120313035A1, which is hereby incorporated by reference in its entirety, describes a foamable composition comprising a hydrohaloolefin blowing agent and an amine catalyst that produce a stable polyol premix. The method includes the use of 1,2- dimethylimidazole, N-methylmorpholine, and other hindered tertiary amines such as diisopropylethylamine catalysts. These catalysts suffer from the drawback that they do not contain isocyanate-reactive groups and thus are emissive from the final polyurethane foam. Additionally, it is demonstrated that reactive amine catalysts such as dimethylaminoethoxyethanol and 2-[N-(dimethylaminoethoxyethyl)]-N-methylamino)ethanol result in an unstable polyol premix in the presence of a hydrohaloolefin.

[0012] U.S. Pat. Appl. No. 2013019415A1 describes a foamable composition comprising a non-emissive catalyst and a tetraalkyl guanidine catalyst. Specifically, the non-emissive catalyst can include 2-[N-(dimethylaminoethoxyethyl)]-N-methylamino]ethanol and dimethylaminoethoxyethanol, and the tetraalkyl guanidine can be tetramethylguanidine. The drawback being that the blowing agent composition is water, and will not produce a closed- cell insulating foam with the same insulation value as a foamable composition utilizing a halogenated blowing agent containing a hydrohaloolefin.

[0013] W.O. Pat. Appl. No.2013116416A1, which is hereby incorporated by reference in its entirety, describes a foamable composition comprising an encapsulated amine catalyst and a hydrohaloolefin blowing agent. The drawback being that the amine catalyst is encapsulated in a solid thermoplastic polymer which must be dispersed in the polyol premix.

[0014] There is therefore a need to provide a catalyst that is capable of catalyzing the formation of a polyurethane or polyisocyanurate foam and is stable in the presence of a HFO blowing agent.DETAILED DESCRIPTION

[0015] It is to be understood that the present disclosure is not limited in its application to the details of construction and the arrangement of components or steps or methodologies set forth in the following description. The present disclosure is capable of other embodiments or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.

[0016] Unless otherwise defined herein, technical terms used in connection with the present disclosure shall have the meanings that are commonly understood by those having ordinary skill in the art. Further, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.

[0017] All patents, published patent applications, and non-patent publications mentioned in the specification are indicative of the level of skill of those skilled in the art to which the present disclosure pertains. All patents, published patent applications, and non-patent publications referenced in any portion of this application are herein expressly incorporated by reference in their entirety to the same extent as if each individual patent or publication was specifically and individually indicated to be incorporated by reference to the extent that they do not contradict the instant disclosure.

[0018] All of the compositions and / or methods disclosed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of the present disclosure have been described in terms of preferred embodiments, it will be apparent to those having ordinary skill in the art that variations may be applied to the compositions and / or methods and in the steps or sequences of steps of the methods described herein without departing from the concept, spirit, and scope of the present disclosure. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the present disclosure.

[0019] As utilized in accordance with the present disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings.

[0020] The use of the word “a” or “an”, when used in conjunction with the term “comprising”, “including”, “having”, or “containing” (or variations of such terms) may mean “one”, but it is also consistent with the meaning of “one or more”, “at least one”, and “one or more than one”.

[0021] The use of the term “or” is used to mean “and / or” unless clearly indicated to refer solely to alternatives and only if the alternatives are mutually exclusive.

[0022] Throughout this disclosure, the term “about” is used to indicate that a value includes the inherent variation of error for the quantifying device, mechanism, or method, or the inherent variation that exists among the subject(s) to be measured. For example, but not by way of limitation, when the term “about” is used, the designated value to which it refers may vary by plus or minus ten percent, or nine percent, or eight percent, or seven percent, or six percent, or five percent, or four percent, or three percent, or two percent, or one percent, or one or more fractions therebetween.

[0023] The use of “at least one” will be understood to include one as well as any quantity more than one, including but not limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term “at least one” may extend up to 100 or 1000 or more depending on the term to which it refers. In addition, the quantities of 100 / 1000 are not to be considered as limiting since lower or higher limits may also produce satisfactory results.

[0024] In addition, the phrase “at least one of X, Y, and Z” will be understood to include X alone, Y alone, and Z alone, as well as any combination of X, Y, and Z. Likewise, the phrase “at least one of X and Y” will be understood to include X alone, Y alone, as well as any combination of X and Y. Additionally, it is to be understood that the phrase “at least one of” can be used with any number of components and have the similar meanings as set forth above.

[0025] The use of ordinal number terminology (i.e., “first”, “second”, “third”, “fourth”, etc.) is solely for the purpose of differentiating between two or more items and, unless otherwise stated, is not meant to imply any sequence or order or importance to one item over another or any order of addition.

[0026] As used herein, the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0027] The phrases “or combinations thereof” and “and combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC and, if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more items or terms such as BB, AAA, CC, AABB, AACC, ABCCCC, CBBAAA, CABBB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from thecontext. In the same light, the term “and combinations thereof” when used with the phrase “selected from the group consisting of” refers to all permutations and combinations of the listed items preceding the phrase.

[0028] The phrases “in one embodiment”, “in an embodiment”, “according to one embodiment”, and the like generally mean the particular feature, structure, or characteristic following the phrase is included in at least one embodiment of the present disclosure, and may be included in more than one embodiment of the present disclosure. Importantly, such phrases are non-limiting and do not necessarily refer to the same embodiment but, of course, can refer to one or more preceding and / or succeeding embodiments. For example, in the appended claims, any of the claimed embodiments can be used in any combination.

[0029] As used herein, the terms “% by weight”, “wt %”, “weight percentage”, or “percentage by weight” are used interchangeably.

[0030] The phrase “substantially free” shall be used herein to mean present in an amount less than 1 weight percent, or less than 0.1 weight percent, or less than 0.01 weight percent, or alternatively less than 0.001 weight percent, based on the total weight of the referenced composition.

[0031] As used herein, the term “alkyl” refers to a hydrocarbon of the formula -CnH2n+1. Example alkyls may be branched or straight chain.

[0032] As used herein, the term “cycloalkyl” means a mono or bicyclic carbocyclic ring functional group including, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, bicyclo[2.2.1]heptanyl, bicyclo[3.2.1]octanyl, and bicyclo[5.2.0]nonanyl. Unless otherwise indicated, the term “(C3-C8)cycloalkyl” refers to a cycloalkyl group containing from 3 to 8 carbons. Thus, the term “(C3-C8)cycloalkyl” encompasses a monocyclic cycloalkyl group containing from 3 to 8 carbons and a bicyclic cycloalkyl group containing from 6 to 8 carbons. Examples of substituted cycloalkyl groups include, but are not limited to, 2-methyl-cyclohexyl, 3-methyl-cyclohexyl, and 4-methyl- cyclohexyl.

[0033] As used herein, the term “ambient temperature” refers to the temperature of the surrounding work environment (e.g., the temperature of the area, building or room where the curable composition is used), exclusive of any temperature changes that occur as a result of the direct application of heat to the curable composition to facilitate curing. The ambient temperature is typically between about 10 °C (about 50 °F) and about 30 °C (about 85 °F), more specifically about 15 °C (about 60 °F) and about 25 °C (about 75°F).

[0034] The phrase “front-end reactivity” is defined as the start of the reaction process to produce a polyurethane or polyisocyanurate foam. In particular, spray foam formulations need a very fast front-end reactivity on the reaction profile such that the foam does not sag or run when it is sprayed. It must set up quickly to prevent the foam from running down a sprayed surface or drip down from a sprayed ceiling. The “front-end reactivity” can be assessed by measuring the cream time and top of cup time of the polyurethane or polyisocyanurate foam after mixing a polyol premix and isocyanate.

[0035] It was unexpectedly found that a catalyst comprising an amine of the formula (I) as described below is capable of stabilizing a polyol premix containing a hydrohaloolefin blowing agent while improving the front-end reactivity of the polyol premix over comparable catalysts / polyol premixes when contacted with an isocyanate.

[0036] According to one aspect, is described a catalyst of formula (I):(I); wherein A is O or N-R3, R3is a C1to C6straight or branched alkyl; n and m is an integer independently selected from 2, 3, 4, 5 or 6; x is an integer selected from 0, 1, 2, 3, 4, 5, or 6; and R1and R2are independently selected from a C4to C7cycloalkyl.

[0037] It has been surprisingly found that a catalyst such as that described above is highly stable in HFO and demonstrates high reactivity.

[0038] In at least one embodiment, A is O.

[0039] In at least one embodiment, R1and R2are independently selected from a C5or a C6cycloalkyl.

[0040] In some embodiments, the catalyst is a compound of formula (II):

[0042] In some embodiments, the catalyst is a compound of formula (IV):

[0043] In some embodiments, the catalyst is a compound of formula (V):

[0044] In some embodiments, the catalyst is a compound of formula (VI):

[0045] In some embodiments, the catalyst is a compound of formula (VII):

[0046] According to one aspect, the present disclosure is directed to a catalyst system comprising a catalyst of formula (I):(I): wherein A is O or N-R3, R3is C1to C6straight or branched alkyl; n and m is an integer independently selected from 2, 3, 4, 5, or 6; x is an integer selected from 0, 1, 2, 3, 4, 5, or 6; and R1and R2are independently selected from a C4to C7cycloalkyl.

[0047] It has been surprisingly found that a catalyst system such as that described above is highly stable and demonstrates high reactivity.

[0048] In at least one embodiment, A is O.

[0049] In some embodiments, the catalyst is a compound of formula (II):

[0051] In some embodiments, the catalyst is a compound of formula (IV):

[0052] In some embodiments, the catalyst is a compound of formula (V):

[0053] In some embodiments, the catalyst is a compound of formula (VI):

[0054] In some embodiments, the catalyst is a compound of formula (VII):

[0055] In another embodiment, the catalyst system further comprises one or more additional catalysts. Non-limiting examples of such catalysts include sterically hindered primary, secondary or tertiary amines; for example, dicyclohexylmethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylisopropylamine, methylisopropylbenzylamine, methylcyclopentylbenzylamine, isopropyl-sec-butyl-trifluoroethylamine, diethyl-α- phenyethyl)amine, tri-n-propylamine, dicyclohexylamine, t-butylisopropylamine, di-t- butylamine, cyclohexyl-t-butylamine, de-sec-butylamine, dicyclopentylamine, di-α- trifluoromethylethyl)amine, di-(α-phenylethyl)amine, triphenylmethylamine, and 1,1,-diethyl- n-propylamine. Other sterically hindered amines include morpholines, imidazoles, ether containing compounds such as dimorpholinodiethylether (JEFFCAT® DMDEE), N- ethylmorpholine (JEFFCAT® NEM catalyst), N-methylmorpholine (JEFFCAT® NMM catalyst), 4-methoxyethylmorpholine, bis(dimethylaminoethyl)ether, imidazole, n- methylimidazole, 1,2-dimethylimidazole, dimorpholinodimethylether, N,N,N’,N’,N’’- pentaethyldiethylenetriamine, N,N,N’,N’,N’’-pentamethyl-dipropylenetriamine, bis(diethylaminoethyl)ether, and bis(dimethylaminopropyl)ether. The aforementioned JEFFCAT® catalysts are available from Huntsman Petrochemical LLC or an affiliate thereof (The Woodlands, TX).

[0056] According to another aspect, the present disclosure is directed to a polyol premix comprising (i) at least one hydrohaloolefin blowing agent, (ii) at least one polyol, and (iii) a catalyst or catalyst system as described above.

[0057] In one embodiment, the at least one hydrohaloolefin blowing agent is a hydrofluoroolefin, hydrochlorofluoroolefin, or a combination thereof.

[0058] Non-limiting examples of the at least one hydrohaloolefin blowing agent include hydrofluoroolefin (HFO) blowing agents containing 3, 4, 5, or 6 carbons, and further include, for example but without limitation, pentafluoropropenes; tetrafluoropropenes such as 1,3,3,3-tetrafluoropropene (HFO 1234ze, E and Z isomers), 2,3,3,3-tetrafluoropropene (HFO 1234yf), 1,2,3,3-tetrafluoropropene (HFO 1234ye); trifluoropropenes such as 3,3,3- trifluoropropene (1243zf); tetrafluorobutenes such as HFO 1345; pentafluorobutene isomers such as HFO1354; hexafluorobutene isomers such as HFO 1336 (e.g. z-1336mzz); heptafluorobutene isomers such as HFO 1327; heptafluoropentene isomers such as HFO1447; octafluoropentene isomers such as HFO 1438; nonafluoropentene isomers such as HFO 1429; hydrochlorofluoroolefin (HCFO) blowing agents such as 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO 1233xf), HCFO 1223, 1,2-dichloro- 1,2-difluoroethene (E and Z isomers), 3,3-dichloro-3-fluoropropene, 2-chloro-1,1,1,4,4,4- hexafluorobutene-2 (E and Z isomers), and 2-chloro-1,1,1,3,4,4,4-heptafluorobutene-2 (E and Z isomers).

[0059] The at least one hydrohaloolefin blowing agent in the polyol premix can be used alone or in combination with other blowing agents including, but not limited to: (a) hydrofluorocarbons including, for example, difluoromethane (HFC-32); 1,1,1,2,2- pentafluoroethane (HFC-125); 1,1,1-trifluoroethane (HFC143a); 1,1,2,2-tetrafluorothane (HFC-134); 1,1,1,2-tetrafluoroethane (HFC-134a); 1,1-difluoroethane (HFC-152a); 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea); 1,1,1,3,3-pentafluopropane (HFC-245fa); 1,1,1,3,3-pentafluobutane (HFC-365mfc) and 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC- 4310mee); (b) hydrocarbons including, for example, pentane isomers (iso-pentane, n-pentane, cyclo-pentane) and butane isomers; (c) hydrofluoroethers (HFE), including, for example, C4F9OCH3(HFE-7100), C4F9OC2H5(HFE-7200), CF3CF2OCH3(HFE-245cb2), CF3CH2CHF2(HFE-245fa), CF3CH2OCF3(HFE-236fa), C3F7OCH3(HFE-7000), 2-trifluoromethyl-3- ethoxydodecofluorohexane (HFE-7500), 1,1,1,2,3-hexafluoro-4-(1,1,2,3,3,3- hexafluoropropoxy)-pentane (HFE-7600), 1,1,1,2,2,3,5,5,5-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, CHF2CF2CH2OCHF2, CF3CF2CH2OCH3, CHF2CF2OCH2CH3, (CF3)2CFOCH3, (CF3)2CHOCHF2, (CF3)2CHOCH3, and mixture thereof; (d) C1to C5alcohols, C1to C4aldehydes, C1to C4ketones, C1to C4ethers and diethers, C1to C6hydrocarbons, e.g. iso-, normal, cyclo-pentane; (e) water, (f) carbon dioxide; (g) trans-1,2- dichloroethylene; and (h) methylformate, methylacetate, ethyl formate, and dimethoxymethane.

[0060] In one particular embodiment, the at least one hydrohaloolefin blowing agent is selected from trans-1-chloro-,3,3,3-tetrafluoropropene (HFCO 1233zd), trans-1,3,3,3- tetrafluoropropene (HFO 1234ze), or a combination thereof.

[0061] The at least one hydrohaloolefin blowing agent is present in the polyol premix in an amount ranging from about 1 to about 35 wt%, or from about 2 to about 30 wt%, or from about 3 to about 25 wt%, or from about 4 to about 20 wt%, or from about 5 to about 15 wt%, or from about 7 to about 15 wt% based on the weight of the polyol premix.

[0062] The polyol can be one or more polyols which react in a known fashion with an isocyanate in the preparation of a polyurethane and / or polyisocyanurate foam. In one embodiment, the polyol component includes polyols typically used for making rigid PIR / PUR (polyisocyanurate and / or polyurethane) foam.

[0063] In one embodiment, the polyol comprises one or more polyether polyols. Non-limiting examples of the polyether polyols include poly(alkylene oxide) polymers, such as, poly(ethylene oxide), poly(propylene oxide), with terminal hydroxyl groups derived from polyhydric compounds (for example, diols, triols, tetraols, pentaols, and the like); polyhydroxy-terminated acetal resin; hydroxy-terminated amine; hydroxyl-terminated polyamine; or combinations thereof.

[0064] In another embodiment, the polyol component includes amine polyether polyols that can be prepared when an amine, such as ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine, triethanolamine, or the like, is reacted with ethylene oxide or propylene oxide.

[0065] In yet another embodiment, the polyol component includes a polyester polyol produced when a dicarboxylic acid is reacted with an excess of a diol, for example, terephtalic acid,adipic acid, phathalic acid, phthalic anhydride with ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol or butanediol, or when a lactone is reacted with an excess of a diol, such as, caprolactone with propylene glycol.

[0066] In another embodiment, the polyol is, or includes, polyalkylene carbonate-based polyols, phosphate-based polyols, or combinations thereof.

[0067] In still another embodiment, the polyol is or includes a natural oil polyol. The natural oil polyol includes triglycerides of saturated and / or unsaturated acids having a carbon chain length between about 12 and about 24. The saturated acids are lauric acid, myristic acid, palmitic acid, steric acid, arachidic acid, lignoceric acid, or a combination thereof. The unsaturated acids are mono-unsaturated (for example, palmitoleic acid, oleic acid, or a combination thereof) and / or poly-unsaturated (for example, linoleic acid, linolenic acid, arachidonic acid, or a combination thereof).

[0068] The polyol is present in the polyol premix in an amount ranging from about 20 to about 95 wt%, or from about 25 to about 95 wt%, or from about 30 to about 95 wt%, or from about 35 to about 95 wt%, or from about 40 to about 95 wt%, or from about 45 to about 95 wt%, or from about 50 to about 90 wt%, or from about 60 to about 90 wt%, or from about 70 to about 90 wt% based on the weight of the polyol premix.

[0069] The amount of the catalyst system present in the polyol premix can range from about 0.1 to about 20 wt%, or from about 0.1 to about 15 wt%, or from about 0.2 to about 15 wt%, or from 0.3 to about 10 wt%, or from about 0.5 to about 7 wt% based on the weight of the polyol premix.

[0070] In one embodiment, the polyol premix can further comprise additional component such as, for example but without limitation, fire retardants, dyes, fillers, pigments, dispersing agents, and cell stabilizers.

[0071] According to another aspect, the present disclosure is directed to a method of forming the above-described polyol premix comprising combining the at least one hydrohaloolefin blowing agent, the polyol, and the catalyst system.

[0072] In yet another aspect, the present disclosure is directed to a method of forming a polyurethane or polyisocyanurate foam, comprising contacting the above-described polyol premix with at least one isocyanate.

[0073] Any polyisocyanate can be employed as the at least one isocyanate, inclusive of aliphatic and aromatic polyisocyanates. Suitable organic polyisocyanates include aliphatic,cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanates which are well known in the field of polyurethane chemistry.

[0074] Non-limiting examples of the polyisocyanates that can be used as the at least one isocyanate include those represented by the formula Q(NCO)awhere a is a number from 2-5, preferably 2-3 and Q is an aliphatic hydrocarbon group containing 2-18 carbon atoms, a cycloaliphatic hydrocarbon group containing 5-10 carbon atoms, an araliphatic hydrocarbon group containing 8-13 carbon atoms, or an aromatic hydrocarbon group containing 6-15 carbon atoms.

[0075] Additional examples of polyisocyanates include, but are not limited to, ethylene diisocyanate; 1,4-tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; 1,12- dodecane diisocyanate; cyclobutane-1,3-diiso cyanate; cyclohexane-1,3- and -1,4-diisocyanate, and mixtures of these isomers; isophorone diisocyanate; 2,4- and 2,6-hexahydrotoluene diisocyanate and mixtures of these isomers; dicyclohexylmethane-4,4’-diisocyanate (hydrogenated MDI, or HMDI); 1,3- and 1,4-phenylene diisocyanate; 2,4- and 2,6-toluene diisocyanate and mixtures of these isomers (TDI); diphenylmethane-2,4’- and / or -4,4’- diisocyanate (MDI); naphthylene-1,5-diisocyanate; triphenylmethane-4,4’,4’’-triisocyanate; polyphenyl-polymethylene-polyisocyanates of the type which may be obtained by condensing aniline with formaldehyde, followed by phosgenation (crude MDI); norbornane diisocyanates; m- and p-isocyanatophenyl sulfonylisocyanates; perchlorinated aryl polyisocyanates; modified polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups, or biuret groups; polyisocyanates obtained by telomerization reactions; polyisocyanates containing ester groups; and polyisocyanates containing polymeric fatty acid groups. Those skilled in the art will recognize that it is also possible to use mixtures of the polyisocyanates described above.

[0076] The polyol premix and at least one isocyanate may be contacted by mixing a stream of the at least one isocyanate (A side) and a stream of the polyol premix (B side). The mixing can be carried out by in a spray apparatus, a mixhead with or without a static mixer for combining the polyol component and blowing agent, or a vessel, and then spraying or otherwise depositing the reacting mixture onto a substrate. This substrate may be, for example, a rigid or flexible facing sheet made of foil or another material, including another layer of similar or dissimilar polyurethane which is conveyed, continuously or discontinuously, along a production line, or directly onto a conveyor belt.

[0077] Alternatively, the at least one isocyanate and the polyol premix may be contacted by being mixed and poured into an open mold or distributed via laydown equipment into an openmold or simply deposited at or into a location for which it is desired, i.e., a pour-in-place application, such as between the interior and exterior walls of a structure. In the case of deposition on a facing sheet, a second sheet may be applied on top of the deposited mixture. In other embodiments, the polyol premix and at least one isocyanate may be mixed and injected into a closed mold, with or without vacuum assistance for cavity-filling. If a mold is employed, it is most typically heated.

[0078] In general, such applications may be accomplished using the known one-shot, prepolymer or semi-prepolymer techniques used together with conventional mixing methods. The mixture, on reacting, takes the shape of the mold or adheres to the substrate to produce a polyurethane polymer or a more-or-less predefined structure, which is then allowed to cure in place or in the mold, either partially or fully. Optimum cure conditions will depend upon the particular components, including catalysts and quantities used in preparing the polymer and also the size and shape of the article manufactured.

[0079] The result may be a rigid foam in the form of slabstock, a molding, a filled cavity, including but not limited to a pipe or insulated wall or hull structure, a sprayed foam, a frothed foam, or a continuously- or discontinuously-manufactured laminate product, including but not limited to a laminate or laminated product formed with other materials such as hardboard, plasterboard, plastics, paper, metal, or a combination thereof. EXAMPLES

[0080] Examples are provided below. However, the present disclosure is to be understood to not be limited in its application to the specific experiments, results, and laboratory procedures disclosed herein below. Rather, the Examples are simply provided as one of various embodiments and are meant to be exemplary and not exhaustive.

[0081] From the above description, it is clear that the present disclosure is well adapted to carry out the object and to attain the advantages mentioned herein as well as those inherent in the present disclosure. The synthesis of a few exemplary catalysts is provided below, while exemplary embodiments of the present disclosure have been described for the purposes of the disclosure, it will be understood that numerous changes may be made which will readily suggest themselves to those skilled in the art which can be accomplished without departing from the sprit and scope of the present disclosure and the appended claims.

[0082] Example 1 – Synthesis of N,N’-dicyclopentyl-N,N’-dimethyl-bis (aminoethyl) ether

[0083] In a reaction vessel, bis(aminoethyl)ether (BAEE) was dissolved into a minimal amount of methanol and co-fed into a high-pressure hydrogenation reactor along with 1.5 moles of cyclopentanone per amine group and hydrogen gas at 150-190 °C (about 300 to 375 °F) and a pressure of 2000 psig, using a Pd / C catalyst for the reduction. The resulting product was fed back into the same reactor, this time with an excess of formaldehyde and hydrogen gas at 100- 140 °C (about 210 to 285 °F) and 2000 psig, over a supported polymetallic catalyst. The resulting crude mixture was distilled to yield the following compound of formula (VI) below, in greater than 98% purity.N,N’-dicyclopentyl-N,N’-dimethyl-bis (aminoethyl) ether

[0084] Example 2 – Synthesis of N,N’-dicyclohexyl-N,N’-dimethyl-bis (aminoethyl) ether

[0085] In a reaction vessel, bis(aminoethyl)ether (BAEE) was dissolved into a minimal amount of methanol and co-fed into a high-pressure hydrogenation reactor along with 1.5 moles of cyclohexanone per amine group and hydrogen gas at 150-190 °C (about 300 to 375 °F) and a pressure of 2000 psig, using a Pd / C catalyst for the reduction. The resulting product was fed back into the same reactor, this time with an excess of formaldehyde and hydrogen gas at 100- 140 °C (about 210 to 285 °F) and 2000 psig, over a supported polymetallic catalyst. The resulting crude mixture was distilled to yield the following compound of formula (VII) below, in greater than 98% purity.N,N’-dicyclohexyl-N,N’-dimethyl-bis (aminoethyl) ether

[0086] Example 3 – Catalyst stability testing

[0087] The stability of Example catalyst 1 and Example catalyst 2 was tested and compared with three commercially available reference catalysts, JEFFCAT® ZF-20 (Huntsman - bis-(2- dimethylaminoethyl)ether catalyst), Polycat® 204, and Polycat® 206 (Polyurethane foam catalysts available from Evonik). All 5 catalysts were tested using the same procedure and same formulation in parallel.

[0088] For testing, a pre-blended masterbatch with the formulation shown in Table 1 was prepared without water or catalyst. A certain amount of pre-blended masterbatch was added to a 4oz jar with appropriate amount of water and testing catalysts. The resultant mixture was then mixed on a sample roller for 20 minutes.Table 1 Masterbatch formulation.

[0089] After mixing, the resin mixtures were placed into a 22ºC (about 72°F) water-bath for 30 minutes. Then 50 g of a above resin mixture was poured into a 32 oz cup followed by adding 50 g of isocyanate (Polymeric MDI). The two components were then immediately mixed using a high shear mixer for 5 seconds and then measure and record the string gel reactivity.

[0090] To obtain a similar string gel in all catalyst tests, the masterbatch amount and the catalyst load was adjusted. Since Polycat® 204 contains some water the added water amount was adjusted to ensure that the resin side of each formulation had a total of 1.8% water. The final compositions of each sample tested is shown in Table 2 below.* DABCO 2040 (Evonik) is a blend of 1,2-dimethylimidazole in ethylene glycol. Table 2 Resin side compositions of all 4 tests String gel reactivity comparison

[0091] For the initial reactivity and stability testing, 930g of each resin mixture was prepared in a one-liter glass jar using the compositions above. The samples were placed on the sample roller and mixed for 30 minutes before placing into a 22ºC (about 72°F) water bath to equilibrate for 30 minutes and then tested. The initial reactivity was tested on day 0 before heating and foaming. The day 0 string reactivities are shown in Table 3 below:Table 3 Initial string gel reactivity comparison.

[0092] As indicated in Table 3, the initial reactivity string gel formation time for each of the tested samples was very similar. Catalyst stability comparison

[0093] Once the initial string gel reactivity testing was completed, the samples were sealed well with electrical tape, to limit HFO loss, and then placed into the oven maintained at a constant temperature of 50ºC (about 120°F) for six weeks.

[0094] After six weeks, the samples were removed from the oven and shaken thoroughly to remix the contents. They were then allowed to sit at room temperature for five hours, beforeplacing them into the 22ºC (about 72°F) water bath and allowed to equilibrate for 30 minutes before testing the stability. The final reactivity at the end of the 6 weeks is shown in Table 4 below.Table 4

[0095] The stability of a sample is a measure of the reactivity drift observed over the duration of the testing. As shown, the string gel time of Example Catalyst 1 and Example Catalyst 2 are significantly shorter than that of the comparative catalysts. Table 5 shows the percentage of loss of string gel time after the 6 weeks.Table 5 String Gel Drift After 6 weeks at 50C (%).

[0096] As indicated in Table 5, the conventional catalysts (JEFFCAT® ZF-20, POLYCAT® 204, POLYCAT® 206) showed significant loss in catalytic activity, when aged with HFO blowing agent in the polyol premix. Example Catalyst 1 and Example Catalyst 2 retained the catalytic activity better than those of the prior art after aging at an elevated temperature when it mixes with HFO blowing agent in the polyol premix.

[0097] Example 4 – Single Catalyst stability testing

[0098] The single catalyst stability of Example catalyst 1 and Example catalyst 2 were compared with two commercially available reference catalysts Polycat® 204 and Polycat® 206 (Polyurethane foam catalysts available from Evonik). All 4 catalysts were tested using the same procedure and same formulation in parallel.

[0099] For all the tests, a pre-blended masterbatch with the formulation shown in Table 1, above, was prepared without water or catalyst. A certain amount of pre-blended masterbatch was added to a 4oz jar with appropriate amount of water and testing catalyst. The resultant mixture was then mixed on a sample roller for 20 minutes.

[0100] After mixing, the resin mixtures were placed into a 22ºC (about 72°F) water-bath for 30 minutes. Then 50 g of a above resin mixture was poured into a 32 oz cup followed by adding 50 g of isocyanate (Polymeric MDI). The two components were then immediately mixed using a high shear mixer for 5 seconds and then measure and record the string gel reactivity.

[0101] To obtain a similar string gel in all catalyst tests, the masterbatch amount and the catalyst load was adjusted. Polycat® 204 was adjusted for water as described above. The final compositions of each sample tested is shown in Table 6, below.Table 6 Resin side compositions of single catalyst tests String gel reactivity comparison

[0102] The same methods as described in Example 3 were used for the initial reactivity and stability testing. The day 0 string reactivities are shown in Table 7 below:Table 7 Initial string gel reactivity comparison of single catalyst

[0103] The results in Table 7 shows similar string gel formation time.

[0104] Once the initial string gel reactivity testing was completed, the samples were sealed well with electrical tape, to limit HFO loss, and then placed into the oven maintained at a constant temperature of 50ºC (about 120°F) for six weeks.

[0105] After six weeks, the samples were removed from the oven and shaken thoroughly to remix the contents. They were then allowed to sit at room temperature for five hours, before placing them into the 22ºC (about 72°F) water bath and allowed to equilibrate for 30 minutes before testing the stability. The final reactivity at the end of the 6 weeks is shown in Table 8 below.Table 8

[0106] The stability of a sample is a measure of the reactivity drift observed over the duration of the testing. Table 9 shows the percentage of loss of string gel time after the 6 weeks.Table 9 String Gel Drift After 6 weeks at 50C (%).

[0107] As shown in Table 9, the conventional catalysts (POLYCAT® 204 and POYCAT® 206) showed significant catalytic activity loss when aged with HFO blowing agent in the polyol premix. On the contrary, Example catalyst 1 and Example Catalyst 2 retain their catalytic activity after aging.

Claims

What is claimed is:

1. A catalyst of formula (I);(I); wherein A is O, or N-R3, R3is C1to C6straight or branched alkyl; n and m is an integer independently selected from 2, 3, 4, 5, or 6; x is an integer selected from 0, 1, 2, 3, 4, 5, or 6; and R1and R2are independently selected from a C4to C7cycloalkyl.

2. The catalyst of claim 1, wherein A is O.

3. The catalyst of claim 1 or claim 2, wherein R1and R2are independently selected from a C5or a C6cycloalkyl.

4. The catalyst of claim 1, wherein the catalyst is a compound of formula (II)5. The catalyst of claim 1, wherein the catalyst is a compound of formula (III):

6. The catalyst of claim 1, wherein the catalyst is a compound of formula (IV):

7. The catalyst of claim 1, wherein the catalyst is a compound of formula (V):

8. The catalyst of claim 1, wherein the catalyst is a compound of formula (VI):

9. The catalyst of claim 1, wherein the catalyst is a compound of formula (VII):

10. A catalyst system comprising: a catalyst of formula (I):(I); wherein A is O or N-R3, R3is C1to C6straight or branched alkyl; n and m is an integer independently selected from 2, 3, 4, 5, or 6; x is an integer selected from 0, 1, 2, 3, 4, 5, or 6; and R1and R2are independently selected from a C4to C7cycloalkyl.

11. The catalyst system according to claim 10, wherein A is O.

12. The catalyst system according to claim 10 or claim 11, wherein the catalyst is a compound of formula (II):

13. The catalyst system according to claim 10 or claim 11, wherein the catalyst is a compound of formula (III):

14. The catalyst system according to claim 10 or claim 11, wherein the catalyst is a15. The catalyst system according to claim 10 or claim 11, wherein the catalyst is a compound of formula (V):

16. The catalyst system according to claim 10 or claim 11, wherein the catalyst is a compound of formula (VI):

17. The catalyst system according to claim 10 or claim 11, wherein the catalyst is a compound of formula (VII):

18. The catalyst system of any one of claims 10 to 17, wherein the catalyst system further comprises one or more additional catalysts.

19. A polyol premix comprising: (i) at least one hydrohaloolefin blowing agent; (ii) at least one polyol; and (iii) the catalyst of any one of claims 1 to 9.

20. The polyol premix of claim 19, wherein the at least one hydrohaloolefin blowing agent is a hydrofluoroolefin, hydrochlorofluoroolefin, or a combination thereof, preferably selected from trans-1-chloro-,3,3,3-tetrafluoropropene (HFCO 1233zd), trans-1,3,3,3- tetrafluoropropene (HFO 1234ze), or a combination thereof.

21. The polyol premix of claim 19 or claim 20, wherein the at least one hydrohaloolefin blowing agent is present in the polyol premix in an amount ranging from about 1 to about 35 wt%, or from about 2 to about 30 wt%, or from about 3 to about 25 wt%, or from about 4 to about 20 wt%, or from about 5 to about 15 wt%, or from about 7 to about 15 wt% based on the weight of the polyol premix.

22. The polyol premix of any one of claims 19 to 21, wherein the amount of the catalyst system present in the polyol premix can range from about 0.1 to about 20 wt%, or from about 0.1 to about 15 wt%, or from about 0.2 to about 15 wt%, or from 0.3 to about 10 wt%, or from about 0.5 to about 7 wt% based on the weight of the polyol premix.

23. A method of forming the polyol premix of any one of claims 19 to 22 comprising combining the at least one hydrohaloolefin blowing agent, the polyol, and the catalyst system.

24. A method of forming a polyurethane or polyisocyanurate foam, comprising contacting the polyol premix of any one of claims 19 to 23 with at least one isocyanate.

25. The method of claim 24, wherein the at least one isocyanate, is selected from the group consisting of aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanates, preferably ethylene diisocyanate; 1,4-tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; 1,12-dodecane diisocyanate; cyclobutane-1,3-diiso cyanate; cyclohexane-1,3- and -1,4-diisocyanate, and mixtures of these isomers; isophorone diisocyanate; 2,4- and 2,6- hexahydrotoluene diisocyanate and mixtures of these isomers; dicyclohexylmethane-4,4’- diisocyanate (hydrogenated MDI, or HMDI); 1,3- and 1,4-phenylene diisocyanate; 2,4- and 2,6-toluene diisocyanate and mixtures of these isomers (TDI); diphenylmethane-2,4’- and / or - 4,4’-diisocyanate (MDI); naphthylene-1,5-diisocyanate; triphenylmethane-4,4’,4’’- triisocyanate; norbornane diisocyanates; m- and p-isocyanatophenyl sulfonylisocyanates; perchlorinated aryl polyisocyanates; modified polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups, or biuet groups; polyisocyanates obtained by telomerization reactions; polyisocyanates containing ester groups; and polyisocyanates containing polymeric fatty acid groups.

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