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    • 专利摘要:
    IMPROVED STABILITY OF POLYURETHANE AND POLYOL COMBINATIONS CONTAINING HALOGENATED OLEFIN BLOWING AGENTS. A polyol premix composition includes a blowing agent having a halogenated hydroolefin, a polyol, a catalyst composition, and an antioxidant. The antioxidant may be, for example, a benzenediol or a benzenetriol or other polyhydroxy substituted aromatic compound, which is optionally substituted by one or more substituents such as alkyl groups. A two-part system for producing a thermoset foam combination includes (a) a polyisocyanate and, optionally, one or more isocyanate-compatible raw materials; and (b) the polyol premix composition. A method for producing a thermoset foam blend includes blending: (a) a polyisocyanate; and (b) the polyol premix composition.
    公开号:BR112015006376B1
    申请号:R112015006376-4
    申请日:2013-09-19
    公开日:2022-01-25
    发明作者:Benjamin Bin Chen；Joseph S. Costa；Laurent Abbas；Sri R. Seshadri；Gary S. Smith
    申请人:Arkema Inc；
    IPC主号:
    专利说明:

    AREA OF THE INVENTION
    [0001] The present invention relates to a method for stabilizing thermoset foam blends that include halogenated olefinic blowing agent, such as hydrochlorofluoroolefin (HCFO) HCFO-1233zd. More particularly, the present invention relates to a method for stabilizing thermoset foam blends using a polyol premix composition that includes one or more antioxidants. The present invention further relates to the stable premix formulations and resulting polyurethane or polyisocyanurate foams. BACKGROUND OF THE RELATED TECHNIQUE
    [0002] The Montreal Protocol for the Protection of the Ozone Layer mandated the phasing out of the use of chlorofluorocarbons (CFCs). More ozone-friendly materials, such as hydrofluorocarbons (HFCs), eg HFC-134a, have replaced chlorofluorocarbons. These latter compounds proved to be greenhouse gases, causing global warming, and were regulated by the Kyoto Protocol on Climate Change. The emerging replacement materials, hydrofluoropropenes, were shown to be environmentally acceptable, i.e., they have zero ozone depletion potential (ODP) and an acceptable low global warming potential (GWP).
    [0003] Blowing agents currently used for thermosetting foams include HFC-134a, HFC-245fa, HFC-365mfc, which have a relatively high global warming potential, and hydrocarbons such as pentane isomers, which are flammable and have low energy efficiency. Therefore, new alternative blowing agents are being sought. Halogenated hydroolefin 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 desired ozone depleting properties.
    [0004] It is convenient in many applications to provide components for polyurethane or polyisocyanurate foams in pre-blended formulations. Most typically, the foam formulation is pre-blended into two components. The polyisocyanate and optional isocyanate compatible raw materials comprise the first component, commonly referred to as the A-side component. A polyol or mixture of polyols, surfactant, catalyst, blowing agent, and other reactive and non-reactive isocyanate components comprise the second component, commonly referred to as the B-side component. Accordingly, polyurethane or polyisocyanurate foams are readily prepared by placing the A and B-side components together or by hand mixing for small preparations and, preferably, machine mixing techniques to form blocks, slabs, laminates, cast-in-place panels and other items, spray applied foams, foams, and the like.
    [0005] Two-component systems, however, have been found to have reduced shelf life of the B-side composition, especially those systems that use certain hydrohaloolefins, such as, for example, HFO-1234ze and HCFO-1233zd. Normally, when a foam is produced by putting the A and B side components together, 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 foaming. The poor foam structure is attributed to the reaction of certain catalysts with certain hydrohaloolefins, including HFO-1234ze and HCFO-1233zd, which results in partial decomposition of the blowing agent and subsequently undesirable modification of the polymeric silicone surfactants.
    [0006] One way to overcome this problem, for example, is by separating the blowing agent, surfactant, and catalyst, and introducing them using a separate stream of the A or B side components. However, a preferred solution would not require such a solution. reformulation or process change. A more favorable method may be to stabilize the polyol premix composition to help prevent blowing agent decomposition. As certain catalysts are now known to have a deleterious effect on halogenated olefinic blowing agents, a stable polyol premix composition that will reduce or eliminate such deleterious interactions is desired. Additionally, a method for stabilizing thermoset foam blends, the resulting stable premix blend formulations, and environmentally friendly polyurethane or polyisocyanurate foams having good foam structure remains highly desirable. BRIEF SUMMARY OF THE INVENTION
    [0007] It has now been discovered that antioxidants can function to stabilize polyol premix compositions that contain catalysts and blowing agents. Specifically it has now been discovered that antioxidants can be favorably used to stabilize a B-side of polyol premix containing a halogenated hydroolefin blowing agent. The stabilization method has been found to prolong the shelf life of the premix and enhance the foam characteristics of the foam obtained by combining the polyol premix composition with a polyisocyanate.
    [0008] Accordingly, polyol premix compositions containing antioxidants are a favorable replacement for traditional polyol premixes which have been found to have negative interactions between the catalyst, such as an amine catalyst, and the halogenated hydroolefin. Without being bound by any theory it is believed that antioxidants prevent the halogenated hydroolefin from attacking the catalyst, such as an amine catalyst, and prevent the formation of an amine halogenated hydroolefin intermediate, which in turn forms a halogenated hydroolefin radical. of amine. Antioxidants can be used as a stabilizing component of a polyol premix blend, in the process for stabilizing thermoset foam blends, and in the resulting polyurethane or polyisocyanurate foams. The method of the present invention has been found to surprisingly stabilize the polyol premix composition, thereby providing longer shelf life. That is, the polyol premix compositions in accordance with the present invention are capable of being stored for long periods of time with little or no detrimental effect on their characteristics and properties. Foams produced by reacting the polyol premix compositions of the present invention with an A-side component containing polyisocyanate have been found to have enhanced foam characteristics and can be employed to meet the requirements of low or zero ozone depletion potential, lower global warming potential, low VOC content, and low toxicity, thus making them environmentally friendly.
    [0009] In one embodiment, the present invention provides a polyol premix composition that comprises a blowing agent, a polyol, a catalyst composition, and an antioxidant. The catalyst composition may comprise an amine catalyst, a non-amine catalyst, or a mixture thereof. The blowing agent may comprise a halogenated hydroolefin and, optionally, hydrofluorocarbons (HFCs), hydrofluoroethers (HFEs), hydrocarbons, alcohols, aldehydes, ketones, ethers/diethers, esters, or CO2 generating materials, or combinations thereof. In at least one embodiment, the hydrocarbons are selected from the group consisting of normal pentane, isopentane, cyclopentane, neopentane, and butane. The polyol premix composition may additionally comprise a surfactant, which may be a silicone or non-silicone surfactant. The polyol premix composition may additionally comprise a flame retardant or suppressant.
    [0010] In another embodiment, the present invention provides a two-part system for producing a thermoset foam combination, wherein the system comprises: (a) as a first part, a polyisocyanate and, optionally, one or more isocyanate-compatible raw materials; and (b) as a second part, a polyol premix composition comprising a blowing agent, a polyol, a catalyst composition, and an antioxidant. The catalyst composition may comprise an amine catalyst, a non-amine catalyst, or a mixture thereof, and may also comprise a surfactant and/or a flame retardant or suppressor.
    [0011] In a further embodiment, the present invention is a method for producing a thermoset foam blend comprising blending: (a) a polyisocyanate and, optionally, one or more isocyanate-compatible raw materials; and (b) a polyol premix composition comprising a blowing agent, a polyol, a catalyst composition, and an antioxidant. The catalyst composition may comprise an amine catalyst, a non-amine catalyst, or a mixture thereof. The polyol premix composition may additionally comprise a surfactant, which may be a silicone or non-silicone surfactant. The polyol premix composition may also comprise a flame retardant or flame arrestor.
    [0012] In yet another embodiment, the present invention provides a blend suitable for providing a polyurethane or polyisocyanurate foam having uniform cell structure with little or no foam collapse, wherein the blend comprises: (a) a polyisocyanate and, optionally, one or more isocyanate compatible raw materials; and (b) a polyol premix composition comprising a blowing agent, a polyol, a catalyst composition, and an antioxidant. The catalyst composition may comprise an amine catalyst, a non-amine catalyst, or a mixture thereof. The polyol premix composition may additionally comprise a surfactant and/or a flame retardant or suppressor. Accordingly, polyurethane or polyisocyanurate foams are readily prepared by placing the A and B side components together or by hand mixing for small preparations and, preferably, machine mixing techniques to form blocks, slabs, laminates, cast-in-place panels and other items, spray applied foams, foams, and the like.
    [0013] It was unexpectedly discovered that antioxidants function to stabilize polyol premix compositions by compensating for the decomposition of hydrohaloolefins. The use of one or more antioxidants in a polyol premix blend composition surprisingly produces a thermoset blend composition that has increased shelf life stability. BRIEF DESCRIPTION OF THE DRAWINGS
    [0013] FIG. 1 shows solutions comprising a blowing agent and catalyst after aging and when freshly prepared.
    [0014] FIG. 2 shows the reactivity over time for the compositions shown in FIG. 1. DETAILED DESCRIPTION OF CERTAIN FORMS OF CARRYING OUT THE INVENTION
    [0015] The formation of polyurethane foams has been studied using halogenated olefins such as hydrochlorofluoroolefin 1-chloro-3,3,3-trifluoropropene, commonly referred to as HCFO-1233zd. Combinations for polyurethane foam include a polyol, a catalyst, a halogenated olefin blowing agent, and an antioxidant. It has now surprisingly been found that the antioxidant used in the present invention results in improved stability of the foam blends over time. Additionally, the resulting foams were surprisingly found to have a uniform cellular structure with little or no foam collapse.
    [0016] Without wishing to be bound by theory it is believed that the problem of decreased shelf life stability of two-component systems, especially those using HCFO-1233zd, is related to the reaction of the halogenated olefins with the catalyst, such as a catalyst of amine. The reaction produces an intermediate, which in turn forms an oxidizing radical. Subsequent reactions produce hydrofluoric acid (HF) which attacks the silicone surfactant in situ. This side reaction was confirmed by nuclear magnetic resonance (NMR) spectra of hydrogen, fluorine, and silicon and gas chromatography-mass spectrometry (GC-MS). This effect can be summarized as the nucleophilic attack of the catalyst, for example an amine catalyst, on the C1 of the halogenated olefin HCFO-1233zd. Accordingly, embodiments of the present invention reduce such harmful interaction by preventing the halogenated olefin from reacting with the catalyst. Without wishing to be bound by any theory it is believed that the reduction in olefin degradation caused by the catalyst is linked to primary antioxidants acting to protect the halogenated olefin blowing agent. This protective functionality of the primary antioxidants prevents the catalyst's harmful interaction with halogenated olefins, such as HCFO-1233zd, and the subsequent resulting HF production. Secondary antioxidants also work to break down peroxides. Antioxidants are also believed to provide at least some protection to the blowing agent even when a non-amine catalyst is used.
    [0017] Generally speaking, an amount of one or more antioxidants is used that is effective to improve the stability of the polyol premix composition relative to the stability observed in the same composition in the absence of any antioxidants and/or to improve the stability of the polyol premix composition. foam quality obtained by combining the polyol premix composition with an A-side comprised of polyisocyanate compared to the foam quality obtained in the absence of any antioxidants. Such amount may vary depending upon the details of a particular formulation, including, for example, the types and amounts of blowing agent, catalyst, and/or surfactant used as well as the particular antioxidant(s) selected. ), but can be readily determined by routine experimentation. Typically, however, an amount of primary antioxidant that is at least about 0.01% by weight based on the total weight of the polyol premix will be suitable. Generally speaking it is not necessary to employ a primary antioxidant content of more than about 20% by weight based on the total weight of the polyol premix. For example, the polyol premix composition can contain from about 0.01% by weight to about 20% by weight of primary antioxidant based on the total weight of the polyol premix.
    [0018] The present invention thus provides a polyol premix composition that comprises a blowing agent, a polyol, a catalyst composition, and an antioxidant. The polyol premix composition may additionally comprise a surfactant and/or a metal salt. The catalyst composition may comprise an amine catalyst, a non-amine catalyst, or a mixture thereof.
    [0019] In another embodiment, the present invention provides a stabilized thermoset foam combination comprising: (a) a polyisocyanate and, optionally, isocyanate compatible raw materials; and (b) a polyol premix composition comprising a blowing agent, a polyol, a catalyst composition, and an antioxidant. The polyol premix composition may additionally comprise a surfactant and/or a metal salt. The catalyst composition may comprise an amine catalyst, a non-amine catalyst, or a mixture thereof.
    [0020] In yet another embodiment, the present invention is a method for stabilizing thermoset foam blends comprising blending: (a) a polyisocyanate and, optionally, isocyanate-compatible raw materials; and (b) a polyol premix composition comprising a blowing agent, a polyol, a catalyst composition, and an antioxidant. The polyol premix composition may additionally comprise a surfactant and/or a metal salt. The catalyst composition may comprise an amine catalyst, a non-amine catalyst, or a mixture thereof. Mixing according to this method produces a stable foamable thermosetting composition which can be used to form polyurethane or polyisocyanurate foams.
    [0021] In at least one embodiment, the antioxidant is a primary antioxidant that limits the reaction between the blowing agent and the catalyst. In at least one embodiment, the primary antioxidant is a monohydroxy-substituted aromatic compound or a polyhydroxy-substituted aromatic compound, ie, a compound containing at least one aromatic ring in which hydrogen atoms in the aromatic ring are replaced by two or more hydroxyl groups, and optionally one or more non-hydroxy substituents. According to at least one embodiment, the primary antioxidant is chosen from benzenediols and triols. Benzenediols and triols may be substituted (i.e., the aromatic ring may be substituted by one or more groups other than hydrogen and hydroxyl) or unsubstituted (i.e., the aromatic ring does not carry any substituents other than hydrogen and hydroxyl). Substitutions can include, for example, alkyl groups (both straight-chain and branched as well as cycloalkyl) such as methyl, ethyl, propyl, and butyl groups (e.g., n-butyl, sec-butyl, tert-butyl ), as well as other types of substituents such as aryl, aryloxy, substituted carbonyl, alkaryl, halogen, alkoxy, or cyano groups or the like.
    [0022] According to at least one embodiment, the primary antioxidant is chosen from 1,2-benzenediols, 1,3-benzenediols, substituted or unsubstituted 1,4-benzenediols, and mixtures thereof. In at least one embodiment, the primary antioxidant is chosen from substituted or unsubstituted 1,2-benzenediols and 1,4-benzenediols. In at least one further embodiment, the primary antioxidant comprises a substituted or unsubstituted 1,2-benzenediol.
    [0023] In at least one embodiment, the primary antioxidant is chosen from benzenetriols, which may optionally be substituted by at least one alkyl group. According to at least one embodiment, the benzenetriols can be chosen from substituted or unsubstituted 1,2,4-benzenetriol, 1,2,3-benzenetriol, and 1,3,5-benzenetriol compounds.
    [0024] Examples of illustrative polyhydroxy substituted aromatic compounds suitable for use in the present invention include, but are not limited to, 1,2-benzenediol (catechol), 1,4-benzenediol (hydroquinone), 1,3-benzenediol (resorcinol ), naphthohydroquinones, anthrohydroquinones, catechins, alkyl substituted phenols, and the like.
    [0025] In at least one embodiment, the polyol premix comprises 0.01% by weight to 20% by weight of primary antioxidant based on the total weight of the polyol premix. In other embodiments, the polyol premix comprises at least 0.01% by weight of primary antioxidant based on the total weight of the polyol premix, such as at least 0.1% by weight, at least 0 .5% by weight, at least 1% by weight, or at least 2% by weight of primary antioxidant based on the total weight of the polyol premix. In certain embodiments, the polyol premix comprises not more than 20% by weight of primary antioxidant based on the total weight of the polyol premix, such as not more than 15% by weight, not more than than 10% by weight, not more than 8% by weight, not more than 7% by weight, not more than 6% by weight, or not more than 5% by weight of primary antioxidant based on total weight of the polyol premix.
    [0026] In at least one embodiment, the polyol premix may comprise a total amount of antioxidant ranging from 0.01% by weight to about 40% by weight based on the total weight of the polyol premix. . In at least one further embodiment, the polyol premix comprises at least 0.01% by weight of total antioxidant based on the total weight of the polyol premix, such as at least 0.1% by weight, at least 0.5% by weight, at least 1% by weight, or at least 2% by weight of total antioxidant based on the total weight of the polyol premix. In certain embodiments, the polyol premix comprises not more than 20% by weight of total antioxidant based on the total weight of the polyol premix, such as not more than 15% by weight, not more than than 10% by weight, not more than 8% by weight, not more than 7% by weight, not more than 6% by weight, or not more than 5% by weight of total antioxidant based on total weight of the polyol premix.
    [0027] The polyol premix according to the present invention may additionally comprise a secondary antioxidant. The secondary antioxidant can decompose peroxides in the composition. Non-limiting examples of secondary antioxidants that can be used in accordance with the present invention include: furan, furfuryl alcohol, furfurylamine, 2,5-dimethylfuran, N-methylfurfurylamine, mono-tert-butyl malonate, N,N-diethylacetamide, N,N-diethylacetamide, ethylene glycol dimethyl ether, N,N-diethylhydroxylamine, N,N-diethylhydroxylamine, N,N-diethylhydroxylamine, sodium sulfite, triethylphosphite, triphenylphosphite, ethylenesulfite, α-methylstyrene, carbohydrazide, tris(2 -chloroethyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, dimethylglyoxime, time (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl, 4-hydroxy-time, DMDO (1,8 -dimercapto-3,6-dioxaoctane), tert-butanol, 2-(tert-butylamino)ethanol, dimethyl sulfite, trimethylphosphite, triphenylphosphine, diphenyl sulfite, phenyl ethyl sulfite, butyl sulfite, dioctyl sulfite, acid boric acid, triisopropyl borate, triethyl borate, trimethoxyboroxine, isopropylboronic acid, 1,2-thiodiethanol, DMSO (dime sulfoxide) thyl), tributylphosphine, phenylboronic acid, N-propyl gallate, N,N,N',N'-tetramethyl-p-phenylenediamine, N,N,N',N'-tetramethyl-1,3-phenylenediamine, 1, 3-phenylenediamine, N,N-dimethyl-p-phenylenediamine, gallic acid, N-methyl-1,2-phenylenediamine, nitrosobenzene, P-phenylenediamine, 2-methyl-2-nitrosopropane, lauryl gallate, octyl gallate. In at least one embodiment, the secondary antioxidant is chosen from phenylenediamine, phosphites, sulfides, sulfites, and mercaptides.
    [0028] In at least one embodiment, the polyol premix comprises 0.01% by weight to 20% by weight of secondary antioxidant based on the total weight of the polyol premix. In other embodiments, the polyol premix comprises at least 0.01% by weight of secondary antioxidant based on the total weight of the polyol premix, such as at least 0.1% by weight, at least 0 .5% by weight, at least 1% by weight, or at least 2% by weight of secondary antioxidant based on the total weight of the polyol premix. In certain embodiments, the polyol premix comprises not more than 20% by weight of secondary antioxidant based on the total weight of the polyol premix, such as not more than 15% by weight, not more than than 10% by weight, not more than 8% by weight, not more than 7% by weight, not more than 6% by weight, or not more than 5% by weight of secondary antioxidant based on total weight of the polyol premix.
    [0029] In at least one embodiment of the present invention, the polyol premix comprises at least one primary and secondary antioxidant. In at least one further embodiment, the polyol premix comprises at least one primary antioxidant, but no secondary antioxidant.
    [0030] The antioxidant can be added directly to the polyol blends, or it can be dissolved in a solvent such as water, an alcohol, a polyetherpolyol, an ester, a polyesterpolyol, an ether, a ketone, a hydrocarbon such as iso, normal , cyclo, and neopentane, butane, a blowing agent, a silicone and/or non-silicone surfactant, a tertiary amine catalyst, a metal catalyst, and a flame retardant or suppressor, then formulated into b-side combinations. In at least one embodiment, the antioxidant is dissolved in a solvent chosen from ethylene glycol, di or triethylene glycol, pentanes, HFO-1233zd, and polyols.
    [0031] The antioxidant of the present invention can be employed in polyol premix compositions containing various amine catalysts. Traditional amine catalysts have been tertiary amines such as triethylenediamine (TEDA), dimethylcyclohexylamine (DMCHA), and dimethylethanolamine (DMEA). Amine catalysts are generally selected based on whether they drive the gelling reaction or the blowing reaction. In the gelation reaction, polyfunctional isocyanates react with polyols to form polyurethane. In the blowing reaction, isocyanate reacts with water to form polyurea and carbon dioxide. Amine catalysts can also drive the isocyanate trimerization reaction. These reactions take place at different rates; reaction rates are dependent on temperature, catalyst level, catalyst type and a variety of other factors. However, to produce high quality foam, the rates of competing gelling and blowing reactions must be properly balanced. If the blowing reaction occurs faster than the gelling reaction, the gas generated by the reaction can expand before the polymer is strong enough to contain it and internal splitting or foam collapse can occur. In contrast, if gelation occurs faster than the blowing reaction, the foam cells will remain closed, causing the foam to shrink as it cools. The molecular structure gives some clues regarding the strength and selectivity of the catalyst. Blowing catalysts generally have a two-carbon ether bond from the tertiary nitrogen. Strong gel catalysts may contain alkyl-substituted nitrogens, while weaker gel catalysts may contain ring-substituted nitrogens. Trimerization catalysts may contain the triazine structure, and are quaternary ammonium salts. Catalysts which contain a hydroxyl group or an active amino hydrogen can also be employed.
    [0032] Amine catalysts are generally selected based on whether they direct: the gel catalysis (or polymerization) reaction, in which polyfunctional isocyanates react with polyols to form polyurethane, or the blow catalysis (or hydrogen-producing) reaction. gas), in which isocyanate reacts with water to form polyurea and carbon dioxide. Amine catalysts can also drive the isocyanate trimerization reaction. Since some amine catalysts will drive all three reactions to some extent, they are often selected based on how much they favor one reaction over another. As described above, catalysts function to control and balance the gelling and blowing reactions. Tertiary amine catalysts have their own specific catalytic characteristics such as gelling, blowing, and crosslinking activity. As would be appreciated by one of ordinary skill in the art, these catalytic activities bear a strong relationship to the growth profile, blow efficiency, moldability, productivity, and other properties of the resulting foam. Accordingly, the polyol premix compositions of the present invention include an antioxidant in addition to a variety of amine catalysts to balance the blow, gel, and trimerization catalysis reactions and produce a foam having the desired properties. For example, the polyol premix composition of the present invention may contain one or more antioxidants in combination with one or more oxygen-containing amine catalysts. The polyol premix composition of the present invention may alternatively, or additionally, include one or more amine catalysts and/or non-amine catalysts containing no oxygen.
    [0033] Oxygen-containing amine catalysts that can be used in the present invention include those amines containing an ether and/or hydroxyl group. For example, the oxygen-containing amine catalyst may be an alkanolamine, etheramine, or a morpholine group-containing catalyst such as an N-alkyl substituted morpholine. The catalyst may contain one, two, three or more nitrogen atoms in the form of amine functional groups. The catalyst, in one embodiment, may contain two, three or more oxygen atoms; these oxygen atoms may be present in the form of ether groups, hydroxyl groups or both ether and hydroxyl groups. Suitable oxygen-containing amine catalysts include compounds corresponding to the following chemical structure: R1R2N(CH2)2X wherein R1 and R2 are the same or different and are each a C1-C6 alkyl group, such as methyl, and/or an alkanol group , such as -CH2CH2OH or CH2CH(CH3)OH; X is O(CH2)2Y, OH, or NR3(CH2)2Y, where R3 is a C1-C6 alkyl group, such as methyl or an alkanol group, such as -CH2CH2OH or CH2CH(CH3)OH; and Y is OH or NR4R5, where R4 and R5 are the same or different and are each a C1-C6 alkyl group, such as methyl, and/or an alkanol group such as -CH2CH2OH or CH2CH(CH3)OH; subject to the proviso that the compound contains at least one ether and/or hydroxyl group.
    [0034] Exemplary oxygen-containing amine catalysts include: bis-(2-dimethylaminoethyl)ether; N,N-dimethylethanolamine; N-ethylmorpholine; N-methylmorpholine; N,N,N'-Trimethyl-N'-hydroxyethyl-bisaminoethylether; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine; 2-(2-dimethylaminoethoxy)ethanol; N,N,N'-trimethylaminoethyl-ethanolamine; and 2,2'-dimorpholinodiethyl ether, and mixtures thereof.
    [0035] Exemplary non-oxygen containing amine catalysts include: 1,3-propanediamine, N'-(3-dimethylamino)propyl-N,N-dimethyl-, triethylenediamine, 1,2-dimethylimidazole, N,N,N'N '-Tetramethylhexanediamine, N,N',N”-trimethylaminoethylpiperazine, N,N,N',N'-tetramethylethylenediamine, N,N-dimethylcyclohexylamine (DMCHA), 1,4-diazadicyclo[2,2,2]octane ( DABCO), N,N',N''-tris(3-dimethylamino-propyl)hexahydrotriazine, N,N-dimethylbenzylamine, N,N,N',N”,N”-pentamethyldipropylenetriamine, N,N'-diethylpiperazine, dicyclohexylmethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylisopropylamine, methylisopropylbenzylamine, methylcyclopentylbenzylamine, isopropyl-sec-butyl-trifluoroethylamine, diethyl-(α-phenylethyl)amine, tri-n-propylamine, dicyclohexylamine, t-butylisopropylamine, di-t-butylamine, t-cyclohexylamine - butylamine, di-sec-butylamine, dicyclopentylamine, di-(α-trifluoromethylethyl)amine, di-(α-phenylethyl)amine, triphenylmethylamine, pentamethyldiethylenetriamine (PMDETA) and 1,1-diethyl-n-propyl blade.
    [0036] Exemplary non-amine catalysts include organometallic compounds containing bismuth, lead, tin, antimony, cadmium, cobalt, iron, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, titanium, vanadium, copper, manganese, zirconium, magnesium, calcium, sodium, potassium, lithium or a combination thereof such as stannous octoate, dibutyltin dilaurate (DBTDL), dibutyltin mercaptide, phenylmercuric propionate, copper octoate, potassium acetate/octoate, magnesium acetate, titanyl oxalate, oxalate of potassium titanyl, quaternary ammonium formates, and ferric acetylacetonate, and combinations thereof.
    [0037] Bismuth and zinc carboxylates may be favorably employed over mercury and lead based catalysts due to toxicity and the need to dispose of mercury and lead catalysts and catalyzed material as hazardous waste in the United States, however they may have deficiencies in working time and in certain environmental conditions or applications. Alkyl tin carboxylates, oxides and mercaptides are used in all types of polyurethane applications. Organometallic catalysts are useful in two-system polyurethane systems. These catalysts are designed to be highly selective in the direction of the isocyanate-hydroxyl reaction as opposed to the isocyanate-water reaction, thus preventing the generation of bubbles at low humidity levels.
    [0038] As would be appreciated by one of ordinary skill in the art, the catalysts of the present invention can be selected based on various factors such as temperature, to produce balanced gelling and blowing reaction rates. Balancing the two competing reactions will produce a high quality foam structure. One of ordinary skill in the art would further appreciate that the catalysts of the present invention can be employed alone, or in combination with organometallic catalysts, to achieve the desired functional properties and characteristics of the resulting foam structure. This includes, but is not limited to, other catalysts that have gelling or blowing reaction functionality.
    [0039] The blowing agent in the thermoset foam combinations in one embodiment of the present invention includes an unsaturated halogenated hydroolefin such as a hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO), or mixtures thereof, and, optionally, one or more hydrofluorocarbons. (HFCs), hydrofluoroethers (HFEs), hydrocarbons, alcohols, aldehydes, ketones, ethers/diethers or carbon dioxide generating materials. The preferred blowing agent in the thermoset foam combination of the present invention is a hydrofluoroolefin (HFO) or a hydrochlorofluoroolefin (HCFO), alone or in a combination. Preferred hydrofluoroolefin (HFO) blowing agents contain 3, 4, 5, or 6 carbons, and include but are not limited to pentafluoropropenes, such as 1,2,3,3,3-pentafluoropropene (HFO-1225ye); tetrafluoropropenes, such as 1,3,3,3-tetrafluoropropene (HFO-1234ze, E and Z isomers), 2,3,3,3-tetrafluoropropene (HFO-1234yf), and 1,2,3,3-tetrafluoropropene ( HFO-1234ye); trifluoropropenes such as 3,3,3-trifluoropropene (HFO-1243zf); tetrafluorobutenes such as (HFO-1345); pentafluorobutene isomers such as (HFO-1354); hexafluorobutene isomers such as (HFO-1336); heptafluorobutene isomers such as (HFO-1327); heptafluoropentene isomers such as (HFO-1447); octafluoropentene isomer such as (HFO-1438); nonafluoropentene isomers such as (HFO-1429); and hydrochlorofluoroolefins, such as 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) (E and Z isomers), 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), and 2-chloro-1,1,1,3,4,4,4-heptafluorobutene-2 (E and Z isomers). Preferred blowing agents in the thermoset foam combinations of the present invention include unsaturated halogenated hydroolefins with normal melting points less than 60°C. Preferred hydrochlorofluoroolefin and hydrofluoroolefin blowing agents include, but are not limited to, 1-chloro-3,3,3-trifluoropropene; HCFO-1233zd E and/or Z; 1,3,3,3-tetrafluoropropene; HFO-1234ze E and/or Z; and HFO-1336, both cis and trans isomers.
    [0040] In at least one embodiment, the blowing agent is chosen from all isomers of HFO-1233, HFO-1234, HFO-1354, and HFO-1336.
    [0041] The halogenated olefinic blowing agents in the thermosetting foam combination of the present invention can be used alone or in combination with other blowing agents, including but not limited to: (a) hydrofluorocarbons including but not limited to difluoromethane (HFC32 ); 1,1,1,2,2-pentafluoroethane (HFC125); 1,1,1-trifluoroethane (HFC143a); 1,1,2,2-tetrafluoroethane (HFC134); 1,1,1,2-tetrafluoroethane (HFC134a); 1,1-difluoroethane (HFC152a); 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea); 1,1,1,3,3-pentafluopropane (HFC245fa); 1,1,1,3,3-pentafluorobutane (HFC365mfc) and 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee), (b) hydrocarbons including, but not limited to a, pentane isomers and butane isomers; (c) hydrofluoroethers (HFE) such as 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), nonafluoroisobutyl ethyl ether/nonafluorobutyl ethyl ether (HFE 8200 ), CHF2OCHF2, CHF2-OCH2F, CH2F-OCH2F, CH2F-O-CH3, cyclo-CF2CH2CF2-O, cyclo-CF2CF2CH2-O, CHF2-CF2CHF2, CF3CF2-OCH2F, CHF2-O-CHFCF3, CHF2-OCF2CHF2, CH2F- O-CF2CHF2, CF3-O-CF2CH3, CHF2CHF-O-CHF2, CF3-O-CHFCH2F, CF3CHF-O-CH2F, CF3-O-CH2CHF2, CHF2-O-CH2CF3, CH2FCF2-O-CH2F, CHF2-O- CF2CH3, CHF2CF2-O-CH3 (HFE254pc), CH2F-O-CHFCH2F, CHF2-CHF-O-CH2F, CF3-O-CHFCH3, CF3CHF-O-CH3, CHF2-O-CH2CHF2, CF3-O-CH2CH2F, CF3CH2 -O-CH2F, CF2HCF2CF2-O-CH3, CF3CHFCF2-O-CH3, CHF2CF2CF2-O-CH3, CHF2CF2CH2-OCHF2, CF3CF2CH2-O-CH3, CHF2CF2-O-CH2CH3, (CF3)2CF -O-CH3, (CF3)2CH-O-CHF2, and (CF3)2CH-O-CH3, and mixtures thereof; and (d) C1 to C5 alcohols, C1 to C4 aldehydes, C1 to C4 ketones, C1 to C4 ethers and diethers, and carbon dioxide generating materials.
    [0042] The thermoset foam combinations of the present invention include one or more foam capable components having a generally cellular structure and blowing agent(s). Examples of thermosetting compositions include polyurethane and polyisocyanurate foam compositions, preferably low density, flexible or rigid foams.
    [0043] The invention also relates to foam, and preferably closed-cell foam, prepared from a thermoset foam formulation to which a stabilizing amount of an ester has been added. When an ester is employed, the order and manner in which the blowing agent and ester combination of the present invention is formed and/or added to the foamable composition does not generally affect the operability of the present invention. For example, in the case of polyurethane foams it is possible that the various components of the blowing agent and ester combination are not mixed prior to introduction into the foaming equipment, or even that the components are not added at the same location in the foaming equipment. foam formation. Therefore, in certain embodiments it may be desired to introduce one or more components of the blowing agent and ester combination in such a way that the components will be in the foaming equipment. Nevertheless, in certain embodiments, the components of the blowing agent and ester combination are pre-combined and introduced together into the foamable composition, either directly or as part of a premix which is then additionally added to other parts of the composition. foamable.
    [0044] In certain embodiments in the preparation of polyurethane polyol foams, the B-side polyol premix composition may include polyols, silicone or non-silicone based surfactants, catalysts, flame retardants or arresters, scavengers of acids, radical scavengers, fillers, metal salts, and other stabilizers or inhibitors.
    [0045] The polyol component, which may include blends of polyols, may be any polyol which reacts in a known manner with an isocyanate in the preparation of a polyurethane or polyisocyanurate foam. Exemplary polyols include: glycerin-based polyether polyols such as Carpol® GP-700, GP-725, GP-4000, GP-4520; amine-based polyether polyols such as Carpol® TEAP-265 and EDAP-770, Jeffol® AD-310; sucrose-based polyether polyols, such as Jeffol® SD-360, SG-361, and SD-522, Voranol® 490, and Carpol® SPA-357; Mannich-based polyether polyols such as Jeffol® R-425X and R-470X; sorbitol-based polyether polyols such as Jeffol® S-490; and aromatic polyester polyols such as Terate® 2541 and 3510, Stepanpol® PS-2352, and Terol® TR-925.
    [0046] The polyol premix composition may also contain a surfactant. The surfactant is used to form a foam from the mixture as well as control the bubble size of the foam such that a foam of a desired cellular structure is obtained. Preferably a foam with small bubbles or cells therein of uniform size is desired as it has the most desirable physical properties such as compressive strength and thermal conductivity. It is equally critical to have a foam with stable cells that do not collapse prior to foaming or during foam lift. Silicone surfactants for use in preparing polyurethane or polyisocyanurate foams are available under a number of registered names known to those skilled in the art. Such materials have been found to be applicable over a wide range of formulations allowing uniform cell formation and maximum gas entrapment to achieve very low density foam structures.
    [0047] Exemplary silicone surfactants include polysiloxane and polyoxyalkylene block copolymers such as B8404, B8407, B8409, B8462 and B8465 available from Goldschmidt; DC-193, DC-197, DC-5582, and DC-5598 available from Air Products; and L-5130, L5180, L-5340, L-5440, L-6100, L-6900, L-6980, and L6988 available from Momentive. Exemplary non-silicone surfactants include sulfonic acid salts, alkali metal salts of fatty acids, ammonium salts of fatty acids, oleic acid, stearic acid, dodecylbenzenedisulfonic acid, dinaphthylmethanedisulfonic acid, ricinoleic acid, an oxyethylated alkylphenol, an oxyethylated fatty alcohol, a paraffin oil, a castor oil ester, a ricinoleic acid ester, turkey red oil, peanut oil, a paraffin fatty alcohol, or combinations thereof. Typical usage levels of surfactants are from about 0.4 to 6% by weight of polyol premix, preferably from about 0.8 to 4.5% by weight, and more preferably from about 1 to 3% by weight. by weight.
    [0048] Exemplary flame retardants include trichloropropyl phosphate (TCPP), triethyl phosphate (TEP), diethyl ethyl phosphate (DEEP), diethyl methyl bis(2-hydroxyethyl)amino phosphonate, anhydride-based ester brominated, dibromonepentyl glycol, brominated polyether polyol, melamine, ammonium polyphosphate, aluminum trihydrate (ATH), tris(1,3-dichloroisopropyl)phosphate, tri(2-chloroethyl)phosphate, tri(2-chloroisopropyl)phosphate, chloroalkyl phosphate /oligomeric phosphonate, oligomeric chloroalkyl phosphate, brominated flame retardant based on pentabromine diphenyl ether, dimethyl methyl phosphonate, diethyl methyl N,N-bis(2-hydroxyethyl)amino phosphonate, oligomeric phosphonate, and its derivatives.
    [0049] In at least one embodiment, the polyol premix comprises at least one metal salt, such as metal carboxylates, metal acetylacetonates, metal alcoholates, metal amidinates, such as those disclosed in the US Patent. USA At the. 7,485,729, incorporated herein by reference, for example, alkaline earth carboxylates, acetylacetonates and alkaline earth alcoholates, alkali carboxylates, acetylacetonates and alkali alcoholates, and carboxylates, acetylacetonates and alcoholates of zinc (Zn), cobalt (Co), tin (Sn), cerium ( Ce), lanthanum (La), aluminum (Al), vanadium (V), manganese (Mn), copper (Cu), nickel (Ni), iron (Fe), titanium (Ti), zirconium (Zr), chromium ( Cr), scandium (Sc), calcium (Ca), magnesium (Mg), strontium (Sr), and barium (Ba), bismuth (Bi). For example metal carboxylates having one or more carboxyl functional groups may be employed. The metal carboxylate may comprise a metal salt of a C1-C21 carboxylic acid. For example, the metal carboxylate may comprise a metal salt of a C1-C21 straight chain or branched aliphatic monocarboxylic acid. Similarly, a metal alcoholate such as, for example, a metal alcoholate comprising a metal salt of a C1-C21 alcohol may be employed. The metal alcoholate may comprise a metal salt of a C1-C21 straight or branched chain aliphatic alcohol. Suitable carboxylic acids include, but are not limited to, formic acid, octanoic acid, 2-ethylhexanoic acid and the like. Suitable alcohols include methanol, ethanol, isopropanol, and the like. In one embodiment, the metal carboxylate comprises a carboxylate of a metal selected from the group consisting of Zn, Co, Ca, Mg, Bi, K, and Sn. Suitable metal carboxylates may include, for example, magnesium formate, magnesium benzoate, magnesium octoate, calcium formate, calcium octoate, zinc octoate, cobalt octoate, stannous octoate, bismuth octoate, potassium octoate, acetylacetonate zinc, cobalt acetylacetonate, magnesium acetylacetonate, bismuth acetylacetonate, potassium acetylacetonate, tin acetylacetonate, and calcium acetylacetonate.
    [0050] In certain embodiments, acid scavengers, radical scavengers, and/or other stabilizers/inhibitors are included in the premix. Exemplary stabilizers/inhibitors include 1,2-epoxy butane; glycidyl methyl ether; cyclic terpenes such as dl-limonene, l-limonene, d-limonene; 1,2-epoxy-2,2-methylpropane; nitromethane; diethylhydroxylamine; alpha-methylstyrene; isoprene; p-methoxyphenol; m-methoxyphenol; dl-limonene oxide; 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, benzenesulfonic acid, and combinations thereof. Other additives such as adhesion promoters, antistatic agents, antioxidants, fillers, hydrolysis agents, lubricants, antimicrobial agents, pigments, viscosity modifiers, UV resistant agents may also be included. Examples of these additives include: sterically hindered phenols; diphenylamines; benzofuranone derivatives; butylated hydroxytoluene (BHT); calcium carbonate; barium sulphate; glass fibers; carbon fibers; microspheres; silicas; melamine; carbon black; waxes and soaps; organometallic derivatives of antimony, copper, and arsenic; titanium dioxide; chromium oxide; iron oxide; glycol ethers; dimethyl AGS esters; propylene carbonate; and benzophenone and benzotriazole compounds.
    [0051] In some embodiments of the present invention an ester may be added to a thermoset foam blend. It has surprisingly been found that the addition of an ester further improves the stability of the blend over time, such as extending the shelf life of the premix, and enhancing the properties of the resulting foam. Esters useful in the present invention may have the formula RC(O)-O-R', where R and R' may be CaHc-bGb, where G is a halogen such as F, Cl, Br, I, a = 0 to 15 , b = 0 to 31, and c = 1 to 31, and include esters which are the products obtained by esterification of dicarboxylic acid, phosphinic acid, phosphonic acid, sulfonic acid, sulfamic acid, hydroxamic acid or combinations thereof. Preferred esters are the products obtained by esterification using an alcohol such as methanol, ethanol, ethylene glycol, diethylene glycol, propanol, isopropanol, butanol, iso-butanol, pentanol, iso-pentanol and mixtures thereof; and an acid such as formic, acetic, propionic, butyric, caproic, isocaprotic, 2-ethylhexanoic, caprylic, cyanoacetic, pyruvic, benzoic, oxalic, trifluoroacetic, oxalic, malonic, succinic, adipic, azelaic, trifluoroacetic, methanesulfonic, benzenesulfonic acid and your mixture. The most preferred esters are allyl hexanoate, benzyl acetate, benzyl formate, bornyl acetate, butyl butyrate, ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl cinnamate, ethyl formate, ethyl heptanoate, isovalerate of ethyl, ethyl lactate, ethyl nonanoate, ethyl pentanoate, geranyl acetate, geranyl butyrate, geranyl pentanoate, isobutyl acetate, isobutyl formate, isoamyl acetate, isopropyl acetate, linalyl acetate, linalyl butyrate , linalyl formate, methyl acetate, methyl anthranilate, methyl benzoate, methyl butyrate, methyl cinnamate, methyl formate, methyl pentanoate, methyl propanoate, methyl phenylacetate, methyl salicylate, nonyl caprylate, acetate of octyl, octyl butyrate, amyl acetate/pentyl acetate, pentyl butyrate/amyl butyrate, pentyl hexanoate/amyl caproate, pentyl pentanoate/amyl valerate, propyl ethanoate, ions propyl obutyrate, terphenyl butyrate and mixtures thereof. Most preferred esters are methyl formate, ethyl formate, methyl acetate, and methyl acetate, and mixtures thereof.
    [0052] The ester may be added in combination with the blowing agent, or may be added separately from the blowing agent to the thermoset foam combination by various means known in the art. The typical amount of an ester is from about 0.1% by weight to 10% by weight of the thermoset foam blend, the preferred amount of an ester is from about 0.2% by weight to 7% by weight of the blend. of thermoset foam, and the most preferred amount of an ester is from about 0.3% by weight to 5% by weight of the thermoset foam blend.
    [0053] The preparation of polyurethane and polyisocyanurate foams using the compositions described herein may follow any of the methods well known in the art may be employed, see Saunders and Frisch, Volumes I and II Polyurethanes Chemistry and technology, 1962, John Wiley and Sons , New York, NY or Gum, Reese, Ulrich, Reaction Polymers, 1992, Oxford University Press, New York, N.I. 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, the polyol premix composition, and other materials such as flame retardants, dyes, or other additional additives. These foams may be rigid, flexible, or semi-rigid, and may have a closed cell structure, an open cell structure, or a mixture of open and closed cells.
    [0054] It is convenient in many applications to provide the components for polyurethane or polyisocyanurate foams in pre-blended formulations. Most typically, the foam formulation is pre-blended into two components. The isocyanate and optionally other isocyanate compatible raw materials comprise the first component, commonly referred to as the A-side component. The polyol blend composition, including catalysts, blowing agents, antioxidants, and optionally other ingredients comprise the second component, commonly referred to as the B-side component. In any given application, the B-side component may not contain all of the components listed above, for example some formulations omit the flame retardant if that characteristic is not a required foam property. Accordingly, polyurethane or polyisocyanurate foams are readily prepared by placing the components together on sides A and B or by hand mixing for small preparations and, preferably, machine mixing techniques to form blocks, slabs, laminates, cast-in-place panels and the like. items, spray applied foams, foams, and the like. Optionally, other ingredients such as flame retardants, dyes, auxiliary blowing agents, water, and even other polyols can be added as a stream to the mixer head or reaction site. Most conveniently, however, they can be incorporated into a B-side component as described above. In some circumstances, sides A and B can be formulated and blended into a component in which water is removed. Polymerization occurs when a one-component mixture is discharged and exposed to air. This is typical, for example, for a spray foam bottle containing a one-component foam mixture for easy application.
    [0055] A foamable composition suitable for forming a polyurethane or polyisocyanurate foam can be formed by reacting an organic polyisocyanate and the polyol premix composition described above. Any organic polyisocyanate may be employed in the synthesis of polyurethane or polyisocyanate foam including aliphatic and aromatic polyisocyanates. Suitable organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanates which are well known in the art of polyurethane chemistry. EXAMPLES
    [0056] The invention is further illustrated by reference to the following Examples. The Examples show the improved stability conferred by the use of an antioxidant, such as 1,2-benzenediol, which imparts stability to the polyol premix composition.
    [0057] Tables 1A-1F list the compositions of Comparative Example and Examples 1-5. Comparative Example and Example 1 comprised PolyCat® 5 (available from Air Products and Chemicals, Inc.), which contains pentamethyldiethylenetriamine. PolyCat® 5 does not comprise at least one ether and/or at least one hydroxyl group.
    [0058] Examples 2-5 comprised JEFFCAT® amine catalysts, which are available from Huntsman Corp. JEFFCAT® Z-110 comprises N,N,N'-trimethylaminoethylethanolamine. JEFFCAT® ZR-70 comprises 2-(2-dimethylaminoethoxy)ethanol. JEFFCAT® ZF-10 comprises N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether. JEFFCAT® ZF-20 comprises bis(2-dimethylaminoethyl)ether. Table 1A. Composition of the Comparative Example
    Table 1B. Composition of Example 1
    Table 1C. Composition of Example 2

    Table 1D. Composition of Example 3
    Table 1E. Composition of Example 4
    Table 1F. Composition of Example 5
    Initial Stabilization
    [0059] Table 2 shows the cream time, gel time, and tack free time ("TFT") for each of the exemplary compositions immediately after the compositions were prepared. Table 2. Reaction Times Immediately After Preparation.

    [0060] As can be seen in Table 2, the presence of the antioxidant stabilized the catalyst even when the composition was used immediately after preparation. Aged 3 Days
    [0061] Table 3 shows the cream time, gel time, and tack free time ("TFT") for each of the compositions after the compositions have aged for 3 days. Table 3. Reaction Times After Aging for 3 Days.

    [0062] As seen in Table 3, the compositions comprising antioxidants according to the present invention exhibited less increase in reaction times when compared to the Comparative Example, which did not contain an antioxidant. Aged 7 Days
    [0063] Table 4 shows the cream time, gel time, and tack free time ("TFT") for each of the compositions after the compositions have aged for 7 days. Table 4. Reaction Times After Aging for 7 Days.


    [0064] After aging the composition for 7 days, the compositions containing an antioxidant according to the present invention continued to exhibit improved reaction times compared to the composition that did not comprise an antioxidant. Color Analysis
    [0065] The stabilizing effect of the antioxidant was also observed visually. A control comprising a catalyst and blowing agent was prepared and placed in a flask. A second vial similar to the first vial was prepared with the addition of acetic acid. A third vial similar to the first vial was prepared with the addition of 1,2-benzenediol.
    [0066] The fresh solutions were all substantially colorless. After aging, the first bottle darkened significantly. The second vial, containing the acetic acid, also darkened, but not to the degree of the first vial. The third vial, which contained the antioxidant, showed little to no discoloration after aging. FIG. 1 shows the bottles in their fresh and aged states. Reactivity Over Time
    [0067] FIG. 2 shows the reactivity over time for the solutions shown in FIG. 1. It is evident that the control degraded significantly more over time than the antioxidant stabilized solution. Aging at 50°C increased catalyst degradation.
    [0068] While the invention is illustrated and described herein with reference to specific embodiments, it is not intended that the invention be limited to the details shown. Rather, various modifications may be made to the details within the scope and range of equivalents of the claims and without departing from the invention.
    权利要求:
    Claims (20)
    [0001]
    1. B-side polyol foam premix composition comprising a blowing agent comprising a halogenated hydroolefin, a polyol, a catalyst composition comprising an amine catalyst, a non-amine catalyst, or catalyst mixture thereof, and a primary antioxidant selected from the group consisting of substituted and unsubstituted 1,2-benzenediols, substituted and unsubstituted 1,3-benzenediols and mixtures thereof, wherein said B-side polyol foam premix forms a thermosetting foam when mixed with an A-side polyol foam premix.
    [0002]
    2. B-side polyol foam premix composition according to claim 1, characterized in that the primary antioxidant is present in an amount ranging from 0.01% by weight to 20% by weight of antioxidant based on in the total weight of the polyol premix.
    [0003]
    The B-side polyol foam premix composition of claim 1, further comprising a secondary antioxidant selected from the group consisting of phenylenediamine, phosphites, sulfides, sulfites, and mercaptides and mixtures thereof.
    [0004]
    4. B-side polyol foam premix composition according to claim 1, characterized in that the catalyst composition comprises an oxygen-containing amine catalyst.
    [0005]
    5. B-side polyol foam premix composition according to claim 4, characterized in that the oxygen-containing amine catalyst is an alkanolamine, ether-amine, or a morpholine group-containing catalyst.
    [0006]
    6. B-side polyol foam premix composition, according to claim 4, characterized in that the oxygen-containing amine catalyst is a compound having the chemical structure: R1R2N(CH2)2X where: R1 and R2 are the same or different and are each a C1-C6 alkyl group and/or an alkanol group, X is O(CH2)2Y, OH, or NR3(CH2)2Y, where R3 is a C1-C6 alkyl group or an alkanol group, and Y is OH or NR4R5, where R4 and R5 are the same or different and are each a C1-C6 alkyl group or an alkanol group, subject to the proviso that the compound contains at least one group ether and/or hydroxyl.
    [0007]
    7. A B-side polyol foam premix composition according to claim 1, characterized in that the catalyst composition comprises an oxygen-free amine catalyst.
    [0008]
    A B-side polyol foam premix composition according to claim 1, characterized in that the catalyst composition further comprises a non-amine catalyst.
    [0009]
    9. B-side polyol foam premix composition, according to claim 8, characterized in that the non-amine catalyst comprises an organometallic salt of tin (Sn) or lead (Pb) or mixtures thereof.
    [0010]
    10. B-side polyol foam premix composition according to claim 1, characterized in that the blowing agent further comprises one or more hydrofluorocarbons (HFCs), hydrofluoroethers (HFEs), hydrocarbons, alcohols, aldehydes, ketones, ethers/diethers, or CO2 generating materials, or combinations thereof.
    [0011]
    11. B-side polyol foam premix composition according to claim 1, characterized in that the blowing agent comprises a halogenated hydroolefin selected from the group consisting of hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), and their mixtures, and, optionally, one or more hydrofluorocarbons (HFCs), hydrofluoroethers (HFEs), hydrocarbons, alcohols, aldehydes, ketones, ethers/diethers, esters, or carbon dioxide generating materials.
    [0012]
    12. B-side polyol foam premix composition according to claim 11, characterized in that said hydrocarbons are selected from the group consisting of normal pentane, isopentane, cyclopentane, neopentane and butane.
    [0013]
    A B-side polyol foam premix composition according to claim 1, further comprising a surfactant.
    [0014]
    14. B-side polyol foam premix composition, according to claim 13, characterized in that the surfactant comprises a polysiloxane and polyoxyalkylene block copolymer silicone surfactant.
    [0015]
    A B-side polyol foam premix composition according to claim 1, further comprising a metal salt.
    [0016]
    A B-side polyol foam premix composition according to claim 15, wherein the metal salt comprises a carboxylate, alcoholate, and/or amidinate of a metal selected from the group consisting of Zn, Co , Ca, Mg, Bi, K and Sn.
    [0017]
    17. B-side polyol foam premix composition according to claim 15, characterized in that the metal salt comprises a carboxylate, alcoholate, and/or amidinate of a carboxylic acid or C1-C21 alcohol.
    [0018]
    18. B-side polyol foam premix composition according to claim 15, characterized in that the metal salt comprises a carboxylate, alcoholate, and/or amidinate of a straight-chain aliphatic monocarboxylic acid or monoalcohol or branched C1-C21.
    [0019]
    19. B-side polyol foam premix composition according to claim 15, characterized in that the metal salt is selected from the group consisting of magnesium formate, zinc octoate, calcium octoate, cobalt octoate , magnesium octoate, bismuth octoate, potassium octoate, and stannous octoate, magnesium acetylacetonate, zinc acetylacetonate, calcium acetylacetonate, cobalt acetylacetonate, bismuth acetylacetonate, potassium acetylacetonate, tin acetylacetonate and mixtures thereof.
    [0020]
    A B-side polyol foam premix composition according to claim 1, further comprising at least one flame retardant or flame arrestor.
    类似技术:
    公开号 | 公开日 | 专利标题
    US20190233605A1|2019-08-01|Stability of polyurethane polyol blends containing halogenated olefin blowing agent
    US10961339B2|2021-03-30|Stability of polyurethane polyol blends containing halogenated olefin blowing agents
    CA2829347C|2019-08-06|Improved stability of polyurethane polyol blends containing halogenated olefin blowing agent
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    CA2913764C|2021-05-11|Stabilized polyurethane polyol blends containing halogenated olefin blowing agent
    同族专利:
    公开号 | 公开日
    IN2015DN02388A|2015-09-04|
    EP2898038A4|2016-04-27|
    CA2885423A1|2014-03-27|
    CA2885423C|2020-09-22|
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    法律状态:
    2021-06-15| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-11-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-25| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261704626P| true| 2012-09-24|2012-09-24|
    US61/704,626|2012-09-24|
    PCT/US2013/060510|WO2014047230A1|2012-09-24|2013-09-19|Improved stability of polyurethane polyol blends containing halogenated olefin blowing agent|
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