• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    COMPOSITION, METHOD FOR FORMING AN INHIBITOR-TREATED AMINE, AND, POLYURETHANE PRODUCT In one embodiment, an amine oxidation inhibitor, such as a free radical remover and / or antioxidant, is added to an oxidation sensitive amine, such as an amine catalyst, to inhibit amine oxidation. The inhibitor-treated amine can then be used in an application such as polyurethane application to reduce the emission of unwanted polyurethane oxidation products.
    公开号:BR112012016114B1
    申请号:R112012016114-8
    申请日:2010-12-30
    公开日:2020-10-27
    发明作者:Bhajendra Narayan Barman；Robert A. Grigsby, Jr.
    申请人:Huntsman Petrochemical Llc；
    IPC主号:
    专利说明:

    Cross-reference to related order
    [1] This request claims priority for Ped. of Pat. U.S. Ser. N- 61 / 293,388, filed January 8, 2010, which is incorporated herein by reference. Technical field
    [2] This invention generally relates to preventing the formation of or decreasing the presence of oxidation degradation products in oxidation-sensitive amines, and more particularly to preventing the formation of or decreasing the presence of formaldehyde and / or dimethylformamide in amines. sensitive to oxidation. Foundations
    [3] Amines, such as amine catalysts that are useful in the polyurethane industry, can degrade over time or on exposure to air. As amines degrade, undesirable products such as formaldehyde and dimethylformamide (DMF), or both are produced. For example, formaldehyde can be formed by oxidative demethylation of an amine and DMF can be obtained from certain tertiary amines by a similar oxidation process as shown in Fig. 1. Formaldehyde and / or DMF of the amine can then be inadvertently incorporated into formulations polyurethane or polyisocyanurate and consequently in the formulation product. Such products include insulation for buildings and utensils; flexible foams for beds, other furniture, and automotive seats; elastomers such as shoe soles, skate wheels, medical elastomers, and the like; urethane and / or urea coatings; and high modulus urethane plastics such as foam for furniture, molded doors, and rigid insulation panels just to name a few final products.
    [4] Both formaldehyde and DMF are linked to human health risks. Formaldehyde is a common indoor pollutant and can be toxic. In addition, it can cause allergic reactions in people sensitive to formaldehyde and it can be a human carcinogen. DMF is a possible carcinogen and is believed to cause birth defects. Therefore, exposure to formaldehyde and DMF should be limited. Current short-term exposure limits, such as 15 minutes, for DMF and formaldehyde are 20 parts per million (ppm) and 2 ppm respectively and longer allowable exposure limits, such as eight hours, for DMF and formaldehyde are 10 ppm and 0.75 ppm respectively, as determined by the Occupational Safety and Health Administration (OSHA).
    [5] Depending on the age of an oxidation-sensitive amine, DMF and formaldehyde can be found in relatively high amounts. Thus, there is a need for reduced concentrations of DMF and / or formaldehyde in amines sensitive to oxidation. summary
    [6] In an embodiment of the present invention, an amine oxidation inhibitor such as a free radical scavenger and / or an antioxidant is added to an oxidation sensitive amine to inhibit amine oxidation. For example, when added to an oxidation sensitive amine, such as an amine catalyst, the amine oxidation inhibitor (s) can stop or reduce the formation of unwanted amine oxidation products. In one embodiment, the free radical remover 1-methyl-3H-imidazole-2-thione (methimazole) can be added to an amine catalyst to stop or reduce the formation of dimethylformamide and / or formaldehyde. In other embodiments, antioxidants and azoles (imidazole, substituted imidazoles, substituted benzothiazole and benzoxazole) can be used to obtain similar results. Brief Description of Drawings
    [7] FIG. 1 shows possible ways to form amine oxidation products such as dimethylformamide and formaldehyde;
    [8] FIG. 2 is a graph showing the time-dependent increase in dimethylformamide at room temperature (~ 25 ° C) in a sample of a tertiary amine catalyst;
    [9] FIG. 3 is a graph showing the effect of various concentrations of a free radical remover on the formation of dimethylformamide in samples that were incubated for up to 682 days at 25 ° C;
    [10] FIG. 4 is a graph showing the effect of various concentrations of a free radical remover on the formation of dimethylformamide in samples that were incubated for up to 39 days at 40 ° C;
    [11] FIG. 5 is a graph showing the effect of various concentrations of a free radical remover on the formation of dimethylformamide in samples that were incubated for up to 39 days at 70 ° C.
    [12] FIG. 6 is a graph showing the effects of two concentrations of various antioxidants on the formation of dimethylformamide in samples that were incubated for up to 368 days at 25 ° C;
    [13] FIG. 7 is a graph showing the effects of various antioxidants on the formation of formaldehyde in samples that were incubated for up to 368 days at 25 ° C;
    [14] FIG. 8 is a graph showing the effects of various antioxidants on the formation of dimethylformamide in samples that were incubated for up to 216 days at 40 ° C;
    [15] FIG. 9 is a graph showing the effects of various antioxidants on the formation of formaldehyde in samples that were incubated for 217 days at 40 ° C;
    [16] FIG. 10 is a graph showing the effects of two concentrations of various azoles on the formation of dimethylformamide in samples that were incubated for up to 140 days at 25 ° C;
    [17] FIG. 11 is a graph showing the effects of various azoles on the formation of formaldehyde in samples that were incubated for up to 140 days at 25 ° C; and
    [18] FIG. 12 is a graph showing the effects of various azoles on the formation of dimethylformamide in samples that were incubated for up to 93 days at 40 ° C. Detailed Description
    [19] Oxidation is a concern for some amine products. For example, oxidation of urethane catalysts can lead to the production of undesirable oxidation products, which can reduce the shelf life and usability of the catalyst. Referring to FIG. 2, an untreated urethane catalyst, bis- (2-dimethylaminoethyl ether) (JEFFCAT® ZF-20), is oxidized in the presence of air at room temperature such that there is a constant increase in the dimethylformamide oxidation product (DMF) with pass the time. For example, the DMF concentration increased from the initial concentration from 14 ppm to 1378 ppm in 136 days, to 2026 ppm in 369 days, and to 2350 ppm in 682 days. Because DMF is banned in at least some countries, its production can limit the product's life and usability.
    [20] According to an embodiment of the present invention, an oxidation sensitive amine is treated with an amine oxidation inhibitor such as a free radical remover and / or an antioxidant to inhibit amine oxidation. As a result, amine oxidation products such as DMF and / or formaldehyde do not form or do not form as readily, which can increase the shelf life and usability of the inhibitor-treated amine.
    [21] In another embodiment, such an inhibitor-treated amine can be added to other oxidation-sensitive materials such as polyols, isocyanates, blowing agents, and combinations thereof. The inhibitor-treated amine, another material sensitive to oxidation, or combinations of these can then be used to compose a product. As an example, the inhibitor-treated amine can be a urethane catalyst for use in the production of a polyurethane product. Using the inhibitor-treated amine guarantees minimal amounts of DMF and / or formaldehyde in the urethane catalyst as well as in the urethane foam product or other urethane product.
    [22] The oxidation-sensitive amine can be any amine that is susceptible to oxidation. For example, the oxidation sensitive amine can be one or more amine-containing catalysts that are useful in the production of polyurethanes, including polyurethane elastomers, and / or polyisocyanurates. Such oxidation-sensitive amine catalysts include catalysts containing tertiary amine, amine catalysts that catalyze reactions of urethane or urea, or both. Exemplary amine catalysts include, without limitation, tertiary amine catalysts such as bis- (2-dimethylaminoethyl ether) (JEFFCAT® ZF-20 catalyst), N, N, N'-trimethyl-N'-hydroxyethyl bisaminoethyl ether (JEFFCAT® catalyst ZF-10), N- (3-dimethylaminopropyl) - N, N-diisopropanolamine (JEFFCAT® DP A catalyst), N, N-dimethylethanolamine (JEFFCAT® DMEA catalyst), Methylene diamine (JEFFCAT® TEDA catalyst), N combinations , N-dimethylethanolamine and triethylene diamine (such as JEFFCAT® TD-20 catalyst), N, N-dimethylcyclohexylamine (JEFFCAT® DMCHA catalyst), benzildimethylamine (JEFFCAT® BDMA catalyst), pentamethyldethylenetriamine (NED, CAT® catalyst) N ', N ”, N” -pentamethyldipropylenetriamine (JEFFCAT® ZR-40 catalyst), N, N-bis (3-dimethylaminopropyl) -N- isopropanolamine (JEFFCAT® ZR-50 catalyst), N- (3-dimethylaminopropyl) - N, N-diisopropanolamine (JEFFCAT® DPA catalyst), N '- (3- (dimethylamino) propyl-N, N-dimethyl-1,3-propanediamine (JEFFCAT® Z- catalyst 130), 2- (2-dimethylaminoethoxy) ethanol (JEFFCAT® ZR-70 catalyst), N, N, N'-trimethylaminoethyl-ethanolamine (JEFFCAT® Z- 110 catalyst), N-ethylmorpholine (JEFFCAT® NEM catalyst), N -methylmorpholine (JEFFCAT® NMM catalyst), 4-methoxyethylmorpholine, N, N'dimethylpiperzine (JEFFCAT® DMP catalyst), 2,2'dimorpholinethyl ether (JEFFCAT® DMDEE catalyst), 1,3,5-tris (3- (dimethylamino ) propyl) -hexahydro-s-triazine (JEFFCAT® TR-90 catalyst), 1-Propanamine, 3- (2- (dimethylamino) ethoxy), and combinations thereof. The previously mentioned JEFFCAT® catalysts are available from Huntsman Petrochemical LLC, The Woodlands, Texas.
    [23] In other embodiments, the oxidation-sensitive amine may be one or more of a polyethylene, ethyleneamine, alkoxylated amine, and surfactant amine, although embodiments are not as limited. Suitable polyetheramines include monoamines such as JEFF AMINE® M-1000 amine, JEFF AMINE® M-2005 amine, and JEFF AMINE® M-2070 amine; diamines such as amine JEFF AMINE® D-230, amine JEFFAMINE® D-400, and amine JEFFAMINE® D-2000; polyether diamines such as amine JEFFAMINE® HK-511, amine JEFFAMINE® ED-600, amine JEFFAMINE® ED-900, and amine JEFFAMINE® ED-2003; unimpeded diamines such as amine JEFFAMINE® EDR-104, amine JEFFAMINE® EDR-148, and amine JEFFAMINE® EDR-176; triamines such as amine JEFFAMINE® T-403, amine JEFFAMINE® T-3000, and amine JEFFAMINE® T-5000; and mixtures of polyether monoamines and diamines such as amino triethylene glycol (e.g., JEFFAMINE® XTJ-512 amine), and the like; Suitable ethylene amines include ethylenediamine (EDA), diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylenepentamine (TEPA), aminoethylpiperzine (AEP), aminoethylethanolamine (AEEA), pentaethyleneexamine (PEHA), hexaethyleneeptamine (EHA), hematoethyleneeptamine (EHA), these; Suitable alkoxylated amines include 2- (2-aminoethoxy) ethanol (DGA® amine), diethanolamine (DEA), N-methyldiethanolamine (MDEA), triethanolamine (TEA), and the like; and suitable surfactant amines include hydrophobic polyether monoamines such as SURFONAMINE® B-100 amine and SURFONAMINE® B-200 amine, and hydrophilic polyether monoamines such as H23 such as SURFONAMINE® L-100 amine, SURFONAMINE® L-200 amine, SURFONAMINE® L- amine 207, SURFONAMINE® L-300 amine, and the like. JEFF AMINE® products, SURFONAMINE® products, and DGA® products are available from Huntsman Petrochemical LLC, The Woodlands, Texas.
    [24] The amine oxidation inhibitor can be any suitable inhibitor such as an antioxidant and / or free radical scavenger. Suitable amine oxidation inhibitors include those that are compatible with, and that can inhibit, the oxidation of, one or more amines such as amine catalysts, polyetheramines, ethylene amines, alkoxylated amines, and / or surfactant amines, although embodiments are not limited to these. In one embodiment the amine oxidation inhibitor can be one or more free radical scavengers such as methimazole, phenyl methimazole, and derivatives thereof; alupurinol, propyl thiouracil, glutamine, diaminobenzylamine, and nicotinamide to name a few. Other suitable amine oxidation inhibitors can be one or more antioxidants that are compatible with an oxidation sensitive amine, such as an amine catalyst, and that can suppress the formation of free radical-mediated DMF and / or formaldehyde. Antioxidants can be hindered phenols such as butylated toluene hydroxy, IRGASTAB® PUR 68 antioxidant, IRGANOX® 1010 antioxidant, IRGANOX® 1135 antioxidant, and IRGANOX® 1076 antioxidant; hindered aliphatic amines such as TINUVIN® 770 optical stabilizer; aromatic hindered amines such as antioxidant IRGASTAB® PUR 55, antioxidant IRGANOX® 5057, and antioxidant NAUGARD® 445; phenolics and mixed amines such as antioxidant IRGANOX® MD 1024 and IRGANOX® 565; antioxidants with triazole and phenolic groups such as antioxidant TINUVIN® P, antioxidant TINUVIN® 234, antioxidant TINUVIN® 327, and antioxidant TINUVIN® 328; proprietary antioxidants such as TINUVIN® 866 antioxidant; and natural antioxidants such as Vitamin C, Vitamin E and / or glutathione, although embodiments are not limited to these exemplary antioxidants. In addition, in some embodiments, the amine oxidation inhibitor may be a combination of one or more free radical inhibitors and antioxidants. IGASTAB®, IRGANOX®, and TINUVIN® products are available from Ciba Specialty Chemical Corporation, Tarrytown, New York, and NAUGARD® products are available from Chemtura Corporation, Middlebury, Connecticut.
    [25] Azoles such as substituted imidazoles, arylimidazoles have been discovered to show inhibitory activity for hydroxylation and N-demethylation. These inhibitors can be imidazole, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, triazole and substituted triazoles, although embodiments are not limited to these exemplary azoles.
    [26] The oxidation-sensitive amine can be treated with the amine oxidation inhibitor at any time. For example, in some embodiments the amine oxidation inhibitor can be added to the oxidation sensitive amine just before use or any other point where exposure to air is possible. Alternatively, the amine oxidation inhibitor can be added to the oxidation sensitive amine in production, for storage. In a particular embodiment, the container in which the inhibitor-treated amine is stored is filled with an inert gas. In a preferred embodiment, the free space of the container that holds an inhibitor-treated amine can be filled with nitrogen to improve stability. These examples are non-limiting and an amine oxidation inhibitor can be added to an oxidation sensitive amine at any time and in any way.
    [27] The amount of amine oxidation inhibitor added to an oxidation sensitive amine can be any effective amount. For example, in some embodiments, the oxidation sensitive amine can be treated with 5 ppm, 10 ppm, 100 ppm, 250 ppm, 1000 ppm, or 5000 ppm of an amine oxidation inhibitor, and all amounts in between. . In other embodiments, an amine oxidation inhibitor can be added to an oxidation sensitive amine to form a combination where the amount of amine oxidation inhibitor in the combination is 0.5% to 10% by weight of the total combination. . In one embodiment, the aforementioned combination can be used as a concentrate to allow customization to a desired inhibitor concentration level. For example, the concentrated combination can be mixed with an untreated oxidation sensitive amine to achieve a desired level of amine oxidation inhibitor. These examples are also non-limiting and the amount of amine oxidation inhibitor used to treat a particular oxidation sensitive amine can be adjusted according to factors such as the type of amine, estimated storage time, and application. The temperature and pressure at which the amine oxidation inhibitor is effective may depend on several factors including the amount of amine oxidation inhibitor used to treat the oxidation sensitive amine. Generally, the amine oxidation inhibitor can be effective at temperatures from 0 ° C to 150 ° C and at pressures up to 200 psi (pounds per square inch). In some embodiments, the amine oxidation inhibitor is especially effective at 25 ° C, 40 ° C, or 70 ° C and ranges between them.
    [28] In another embodiment, an inhibitor-treated amine (for example, an amine that has been treated with a suitable amine oxidation inhibitor) can be added to other materials sensitive to oxidation. In a particular embodiment, an inhibitor-treated amine can be added to one or more components to make a polyurethane product, a polyisocyanurate product, or any other polyurethane products. Generally, a polyurethane product (or a polyisocyanurate product) can be formed by reacting an isocyanate component with a polyol component. One or more amines treated with an inhibitor such as an amine catalyst can be added to the isocyanate component, the polyol component, or both. In addition or alternatively, the inhibitor-treated amine can be added to one or more subcomponents, such as blowing agents, additives, or auxiliary agents, which can then be added to the polyol component and / or the isocyanate component. As such, the resulting polyurethane / polyisocyanurate products may contain reduced oxidation products such as DMF, formaldehyde, or both, which means that less of these oxidation products can be emitted from the product.
    [29] The isocyanate component can be any isocyanate or combinations of isocyanates known in the field of polyurethanes and / or polyisocyanurates. Examples of such isocyanates include, without limitation, toluenediisocyanate (TDI), methylenediphenyldiisocyanate (MDI), methylenediphenyldiisocyanates (poly MDI or pMDI) superior functional (greater than 2), and prepolymers / quasi-prepolymers of these isocyanates. In some embodiments, an inhibitor-treated amine such as an inhibitor-treated amine catalyst can be added to the isocyanate component. In a particular embodiment, the inhibitor-treated amine catalyst is an inhibitor-treated urethane catalyst.
    [30] The polyol component can include any polyol or combinations of polyols that are useful in the fields of polyurethanes / polyisocyanurates. For example, the polyol component can include polyether polyols, polyester polyols, any other polyol, and combinations of polyols. In addition, polyols can be manufactured from mono-, di-, tri-functional, or higher initiators and they can include alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and / or any combination of these or other oxides. An example of polyether polyols includes polyoxypropylene and / or polyoxyethylene polyols, and an example of polyester polyols includes aromatic polyester polyols and / or polyester aliphatic polyols. Particularly useful polyols include propylene glycol-initiated polyols such as polyol JEFFOL® PPG-2000, copolymers of propylene oxide-ethylene oxide such as polyol JEFFOL® G-31 -28 and polyol JEFFOL® PPG- 3706, polyether polyols such as polyol VORANOL® 4701 and VORANOL® 4702 polyol. JEFFOL® products can be obtained from Huntsman International LLC, The Woodlands, Texas; VORANOL® products can be obtained from Dow Chemical Company, Midland, Michigan.
    [31] The polyol component can also include one or more low molecular weight chain extenders, crosslinking agents, or mixtures of chain extenders and crosslinking agents. Chain extenders can include alkane diols, dialkylene glycols, polyalkylene polyols, and combinations thereof, and crosslinking agents can include ethanediols, butanediols, hexanediols, heptanediols, octanediols, nonanodiols, diethylene glycol, dipropylene glycol, polyoxyalkylene glycols, and combinations of these.
    [32] In some embodiments, an inhibitor-treated amine such as an inhibitor-treated amine catalyst can be added to one or more polyols of the composition. In a particular embodiment, the inhibitor-treated amine catalyst is an inhibitor-treated urethane catalyst.
    [33] In some embodiments, a blowing agent can be added to the isocyanate component or the polyol component. In addition, the blowing agent may or may not have an inhibitor-treated amine added to it. The blowing agent can be any blowing agent or combination of blowing agents useful in the polyurethane and / or polyisocyanurate technique. Generally, such blowing agents include water, physical blowing agents, and chemical blowing agents, which can be used alone or in combination. Exemplary blowing agents include, but are not limited to, water, pentane, cyclopentane, butane, FORANE® 141B agent, which is available from Arlcema Inc. (Philadelphia, PA), and HFC-245FA, which is available from Honeywell International Inc (Morristown, NJ).
    [34] Typically, the polyol component can include additives and / or auxiliary agents. Exemplary additives and / or auxiliary agents include film stabilizers, cell regulators, flame retardants, plasticizers, fillers, pigments, surfactants, and the like, or any combination thereof. To the extent that an additive or auxiliary agent is an oxidation sensitive amine, an amine oxidation inhibitor can be added to such an additive or auxiliary agent.
    [35] Polyurethanes or polyisocyanurates can be manufactured using any technique. For example, a polyurethane or polyisocyanurate can be formed by separately combining the components of the polyol component and the isocyanate component, either or both of which may include an inhibitor-treated catalyst and / or another inhibitor-treated amine. Once separately combined, the two components can be mixed by any means known in the art. For example, the polyol component and the isocyanate component can be mixed to facilitate the manufacture of a molded product or a product manufactured without a mold.
    [36] Embodiments however are not limited to polyurethanes and / or polyisocyanurates; the inhibitor-treated amine can be used in any application where free radical-mediated oxidation can occur. In addition, there is no restriction on when the inhibitor-treated amine can be added to another oxidation-sensitive material; however, it may be beneficial to add the inhibitor-treated amine before storing the other oxidation-sensitive material or just before use. Likewise, there can be a wide range of temperatures in which an inhibitor is effective such as temperatures from 0 ° C to 150 ° C, and pressures can be up to 200 psi (1.38MPa). Examples
    [37] The following non-limiting examples are provided to further illustrate the embodiments described here. The examples, however, are not intended to be fully inclusive and are not intended to limit the scope of the embodiments described here. Example 1
    [38] In Examples 1 to 1c, concentrations of DMF and formaldehyde were screened in samples of a tertiary amine mixed with methimazole (MM). Generally, 50 ml of each of the 10, 100, 250, and 1000 ppm solutions of methimazole (an amine oxidation inhibitor) were prepared with bis- (2-dimethylaminoethyl) ether (JEFFCAT® ZF-20 amine catalyst, available from Huntsman Petrochemical LLC, The Woodlands, Texas). Metimazole is available from Sigma-Aldrich Corp., St. Louis, MO.
    [39] An 8 ml aliquot of each of the preceding preparations was poured into a corresponding 20 ml vial, and an 8 ml aliquot of untreated JEFFCAT® ZF-20 amine catalyst was poured into a separate 20 ml vial. . Thus, there were five 20 ml bottles in a set; at least one sample per set had 0, 10, 100, 250, or 1000 ppm methimazole. Sample sets were incubated at 25 ° C, 40 ° C, or 70 ° C. Periodically, a portion of each sample (about 0.4 ml) was removed to determine the concentration of DMF and / or formaldehyde formed in this sample. DMF and formaldehyde concentrations were determined by high performance liquid chromatography with a UV detector Example la
    [40] In this example, concentrations of DMF and formaldehyde were screened in a set of samples that were incubated at room temperature (about 25 ° C) for up to 680 days. Sample la (pure ZF-20) was a control sample having no methimazole, and samples 2a, 3a, 4a, and 5a were test samples, which included 10, 100, 250, and 1000 ppm of methimazole, respectively . Before incubation, DMF and reference formaldehyde concentrations were determined. Subsequently, for each sample in the set, concentrations of DMF and formaldehyde were periodically determined.
    [41] Referring to FIG. 3, DMF concentrations (ppm) at different points in time are shown for samples 1 to 5a. After about 1 day (18 hours) of incubation, the samples do not show an appreciable difference in the accumulation of DMF. Subsequently, however, the DMF concentration in the la sample began to rise compared to the test samples, and for 12 days and thereafter the difference in the DMF concentration between the control sample la and the test samples was very dramatic. This is especially true for the difference in DMF concentrations between sample la and samples 4a and 5a.
    [42] Referring to Table 1 below, DMF concentrations (in ppm) for samples la, 4a, and 5a are shown. The initial DMF content for these samples was 14 ppm. After incubating at 25 ° C for 39 days, however, the DMF concentration in the sample la rose to 812 ppm, and for samples 4a and 5a the DMF concentrations were less than 100 ppm and less than 25 ppm, respectively . Thus, at this point in time much less DMF was formed in test samples 4a and 5a when compared to control sample la. Similarly, after incubating for 136 days the DMF content in the sample increased to 1378 ppm (about 100 times the initial concentration) whereas it was only 337 ppm and 35 ppm in samples 4a and 5a respectively. Similarly, after 232 days, the DMF contents of samples 4a and 5a were 588 ppm and 184 ppm, respectively, compared to 1940 ppm for the control sample la. Thus, at 25 ° C, which is around room temperature, samples with methimazole, especially those with 250 and 1000 ppm of methimazole, had lower DMF concentrations compared to the control sample with no methimazole. Referring to Table 1 and FIG 3, this trend continued for all time points up to 682 days. However, the DMF concentration of samples 5a was found to approximate that of sample 4a in 521 days and eventually, DMF concentrations were higher for sample 5a compared to sample 4a at 597 days and 682 days.
    Table 1
    [43] Referring to Table 2 below, it was observed that the free radical remover methimazole also prevented the increase of formaldehyde in samples 4a and 5a (compared to the control sample la). For example, the initial formaldehyde content in samples la, 4a, and 5a was 50 ppm. After incubating at 25 ° C for 521 days, however, the control sample la had 772 ppm formaldehyde and test samples 4a and 5a had 538 ppm and 580 ppm formaldehyde, respectively. After being incubated for 682 days at 25 ° C, the concentration of formaldehyde for samples 4a increased to 548 ppm, but still well below the concentration of formaldehyde in the control sample at 851 ppm. However, the formaldehyde concentration of 782 ppm for sample 5a was close to that of the control sample at this point in time.
    Table 2
    [44] The amounts of methimazole remaining in the samples after being incubated for 136 days, 232 days, 368 days and 682 days at 25 ° C have also been determined. Similar to DMF, methimazole was determined by high performance liquid chromatography with UV detection. Referring to Table 3, samples 2a and 3a, which initially included 10 and 100 ppm of methimazole respectively, were both free of methimazole after 136 days. In contrast, samples 4a and 5a had 30 ppm and 760 ppm of methimazole, respectively remaining after 136 days. Additional methimazole losses from samples 4a and 5a were observed after 232 days. After 682 days, sample 5a was left with only 70 ppm of methimazole below 1000 ppm.
    Example 1b
    [45] In this example, a set of samples was analyzed for the presence of DMF after being incubated in an oven at 40 ° C for a total of 39 days. Sample 1b was a control sample having no methimazole and samples 2b, 3b, 4b, and 5b were test samples, which included 10, 100, 250, and 1000 ppm of methimazole, respectively.
    [46] Referring to FIG. 4, DMF concentrations in samples 1b to 5b are shown. As with the control sample la, control sample 1b showed a constant increase in the concentration of DMF during the 39 days. In contrast, samples 2b to 5b had reduced DMF formation over time compared to control 1b. The most effective concentration of methimazole at 40 ° C was 1000 ppm. Increasingly, sample 4b, which included 250 ppm of methimazole, did not appear to be as effective at 40 ° C on or after 18 days of incubation as sample 3b, which included 100 ppm of methimazole. Example 1c
    [47] In this example, a set of catalyst samples was analyzed for the presence of DMF after being incubated in an oven at 70 ° C for a total of 39 days. Sample 1c was a control catalyst sample having no methimazole and samples of catalyst 2c, 3c, 4c, and 5c were test catalyst samples, which, in addition to the amine catalyst, included 10, 100, 250, and 1000 ppm of methimazole, respectively.
    [48] Referring to FIG. 5, concentrations of DMF in catalyst samples 1c to 5c are shown. As with the other control samples, the control sample 1c showed a steady increase in the formation of DMF during the 39-day incubation period. Methimazole in samples 2c and 3c did not affect the formation of DMF at this temperature. In fact, the formation of DMF in sample 3c, which included 100 ppm methimazole, was greater than the control (1c) at most points in time. The formation of DMF in sample 4c (250 ppm of methimazole), however, was usually less than the control sample at various points in time. As with other temperatures, the sample containing 1000 ppm methimazole (5c) showed the greatest reduction in the formation of DMF during the entire incubation period when compared to the 1c control.
    [49] It should be noted that the data obtained for examples 1b it had a higher level of uncertainty, which was believed to be due to the loss of evaporation from some DMF. Evaporation loss was measured by weighing the sample before placing the sample in the oven and after removing it from the oven and cooling it. Typical evaporation losses have been found to be 0.2% and 0.4% at 40 ° C and 70 ° C, respectively. Example 2
    [50] In this example, aldehyde emissions from flexible foams were determined. Generally, a control foam and a test foam were manufactured using the same formula:

    Table 4 in which the catalyst used in the control foam was free of methimazole and the catalyst used in the test foam contained 1000 ppm of methimazole. In the above formulation, the JEFFCAT® ZF-10 catalyst and the JEFFCAT® DPA catalyst are tertiary amines, and serve as reactive catalysts. These are available from Huntsman Petrochemical LLC, The Woodlands, Texas.
    [51] Before use in the foam formulation, catalysts for the test foam were prepared by adding enough methimazole to each of the JEFFCAT® ZF-10 catalyst and the JEFFCAT® DPA catalyst to provide 1000 ppm of methimazole per catalyst. The concentrations of aldehydes and ketone in the JEFFCAT® ZF-10 catalyst before adding methimazole were as follows: 46 ppm formaldehyde, 41 ppm acetaldehyde, 0.1 ppm acetone, 1.1 ppm propionaldehyde, and 0 ppm butyraldehyde . The corresponding concentrations for the JEFFCAT® DPA catalyst were as follows: formaldehyde at 12 ppm, acetaldehyde at 9.3 ppm, acetone at 6.0 ppm, propionaldehyde at 22 ppm, and butyraldehyde at 0 ppm. Catalysts for the control foam were from the same catalyst batches as those of the test foam, but without having any free radical scavengers added to it.
    [52] Foams were generally manufactured by mixing the polyol, water, respective catalysts, silicone surfactant, and stabilizer in a mixing cup for 24 seconds. Subsequently, the isocyanate was added to the polyol mixture, which was then stirred for 6 seconds and poured into a 65 cm x 60 cm x 10 cm block mold. The foams were allowed to cure for 3 minutes at 60 ° C.
    [53] The foam blocks were then tested for aldehyde emission in a manner similar to ASTM D-5116-06. For this, a VCE 1000 model instrument from Votsch Industrietechnik (Germany) was used for testing in an environmental chamber. The chamber size was 1000 liters. The sample size was a 65 cm x 60 cm x 10 cm piece of foam block. The chamber temperature was maintained at 65 ° C and the humidity was maintained at 50%. The zero air exchange rate was 400 L / h. Volatile aldehydes emitted by the foam were removed at the exhaust flow outlet through a silica gel cartridge coated with 2,4-dinitrophenylhydrazine (DNPH) using a sampling pump for 5 hours. After sample collection, aldehydes were eluted from each DNPH cartridge with 5 ml of acetonitrile and determined by HPLC-UV detection.
    [54] Referring to Table 5 below, the presence of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde was assessed in both control and test foam samples. When compared to the control foam, the concentration of each gas was lower in the test foam. Thus, the free radical remover added to the catalyst samples also has a beneficial effect on the foams manufactured from such catalysts.
    Table 5 Example 3
    [55] In Examples 3a to 3b, concentrations of DMF and formaldehyde were screened in samples of a tertiary amine, JEFFCAT® ZF-20 mixed with antioxidants. Generally, 25 ml of each 200 ppm antioxidant solutions, and 1000 ppm were prepared with JEFFCAT® ZF-20 amine catalyst. JEFFCAT® ZF-20 untreated (pure ZF-20) was used as the control sample. As antioxidants, IRGANOX® 1010 (Irg 1010), IRGANOX® MD 1024 (MD 1024), TINUVIN® 866 (Tin 866), TINUVIN® 328 (Tin 328), and TINUVIN® 770 (Tin 770). These were available from Sigma-Aldrich Corp., St. Louis, MO. In Figures 6 to 9, these antioxidants are referred to by abbreviations shown in parentheses.
    [56] An 8 ml aliquot of each of the preceding preparations was poured into a corresponding 20 ml vial and an 8 ml aliquot of untreated JEFFCAT® ZF-20 amine catalyst was poured into a separate 20 ml vial. Thus, there were two 20 ml bottles for each antioxidant; for example, Irg 1010, 200 ppm and Irg 1010, 1000 ppm are two solutions with 200 ppm and 1000 ppm of antioxidant IRGANOX® 1010, respectively. Thus, there were eleven sample solutions in each sample set. Sample sets were incubated at 25 ° C and 40 ° C. Periodically, a portion of each sample (about 0.4 ml) was removed to determine the concentration of DMF and / or formaldehyde formed in this sample. Concentrations of DMF and formaldehyde were determined by high performance liquid chromatography with a UV detector. Example 3a
    [57] Referring to FIG. 6, DMF concentrations at different points in time and at 25 ° C are shown for a set of eleven sample solutions. The initial concentration of DMF in JEFFCAT® ZF-20 was 18.9 ppm. The DMF concentrations in the samples of pure ZF-20, Tin 770, 200 ppm and Tin 770, 1000 ppm began to rise faster than other test samples after 4 days. Subsequently, the difference in DMF concentration between the control sample and the test samples was very significant. At almost all points in time, the lowest concentrations of DMF were observed in samples with 1000 ppm of IRGANOX® MD 1024, followed by 1000 ppm of IRGANOX® 1010 and 200 ppm of IRGANOX® 1010. However, this study for 368 days suggests that all solutions, except two TINUVIN® 770 solutions, produced lower amounts of DMF compared to the control sample.
    [58] Referring to FIG. 7, a study with antioxidants over a period of 368 days, showed that two antioxidants IRGANOX® 1010 and IRGANOX® MD 1024 can provide reduced formaldehyde increase compared to the control sample. Both antioxidants at 1000 ppm, and Irg 1010 at 200 ppm have been found to be effective. Example 3b
    [59] Referring to FIG. 8, the second set of samples was analyzed for the presence of DMF after being incubated in a greenhouse at 40 ° C for a total of 216 days. Here, DMF concentrations remain relatively low at 163 ppm or less for an 18-day period. Subsequently, as with the control sample, all samples showed a constant increase in the concentration of DMF. However, the Irg 1010, 1000 ppm and MD 1024, 1000 ppm samples had reduced DMF formation over time compared to the control sample.
    [60] Referring to FIG. 9, formaldehyde concentrations were measured for all samples incubated in a greenhouse for 217 days. Formaldehyde concentrations in JEFFCAT® ZF-20 at the end of the incubation period showed that Irg 1010, 1000 ppm and MD 1024, 1000 ppm were effective in reducing formaldehyde formation in the amine catalyst. Example 4
    [61] In Examples 4a and 4b, concentrations of DMF and formaldehyde were screened in samples of a tertiary amine, JEFFCAT® ZF-20, mixed with azoles. Generally, 25 ml of each 200 ppm azole solutions, and 1000 ppm were prepared with JEFFCAT® ZF-20 amine catalyst. JEFFCAT® ZF-20 untreated (pure ZF-20) was used as the control sample. The following azoles were studied: 2-mercaptoimidazole (2-MCIZ), 2-mercaptobenzimidazole (2-MCBIZ), 2-mercaptobenzothiazole (2-MCBTZ), 2-mercaptobenzoxazole (2-MCBOZ) and imidazole (IMIDAZ). These are available from Sigma-Aldrich Corp., St. Louis, MO. In Figures 10 to 12, these azoles are referred to by abbreviations shown in parentheses.
    [62] An 8 ml aliquot of each of the azole preparations was poured into a corresponding 20 ml vial and an 8 ml aliquot of untreated JEFFCAT® ZF-20 amine catalyst was poured into a separate 20 ml vial . Thus, there were two 20 ml bottles for each azole. For example, 2-MCIZ, 200 ppm and 2-MCIZ, 1000 ppm are two solutions with 200 ppm and 1000 ppm of 2-mercaptoimidazole, respectively. Thus, there were eleven sample solutions in each sample set. Sample sets were incubated at 25 ° C and 40 ° C. Periodically, a portion of each sample (about 0.4 ml) was removed to determine the concentration of DMF and / or formaldehyde formed in this sample. Concentrations of DMF and formaldehyde were determined by high performance liquid chromatography with a UV detector. Example 4a
    [63] Referring to FIG. 10, concentrations of DMF at different points in time up to 140 days and at 25 ° C are shown for a set of eleven sample solutions. The initial concentration of DMF in JEFFCAT® ZF-20 was 18.1 ppm. Compared to the control sample solution (pure ZF-20), solutions of 2-mercaptoimidazole, 2-mercaptobezoxazole and imidazole showed reduced amounts of DMF. Both 2-mercaptobenzimidazole and 2-mercaptobenzothiazole provided comparable or higher amounts of DMF when compared to the control sample at almost all points in time.
    [64] Referring to FIG. 11, a study with azole solutions over a period of 140 days, suggests that formaldehyde data are dispersed. However, 2-mercaptoimidazole, 2-mercaptobezoxazole and imidazole showed some advantages compared to the control sample Example 4b
    [65] Referring to FIG. 12, the second set of samples was analyzed for the presence of DMF after being incubated in a greenhouse at 40 ° C for a total of 93 days. Here, concentrations of DMF constantly increased in all solutions. However, 2-MCBOZ, 200 ppm and IMIDAZ 1000 ppm samples provided reduced amounts of DMF compared to the control sample at all points in time. Example 5
    [66] In Example 5, a tertiary amine, JEFFCAT® ZF- sample in a 20 mE flask was stored for a period of 370 days at room temperature in a nitrogen box after covering with nitrogen. DMF and formaldehyde concentrations were measured at the beginning and at the end of the experiment. The initial concentration of DMF was 18.9 ppm and that after 370 days was 36 ppm. The corresponding amounts of formaldehyde are 60 ppm and 221 ppm, respectively.
    [67] The subject disclosed above is to be considered illustrative, not restrictive, and the appended claims are intended to cover all such modifications, enhancements, and other embodiments, which fall within the true scope of the present invention. Thus, to the maximum extent permitted by law, the scope of the present invention must be determined by the broadest permissible interpretation of the following claims and their equivalents, and must not be restricted or limited by the foregoing detailed description.
    权利要求:
    Claims (8)
    [0001]
    1. Method for forming an inhibitor-treated amine, characterized by the fact that it comprises combining: (i) an oxidation sensitive amine selected from one or more of an alkoxylated amine, a tertiary amine catalyst, a polyetheramine, an ethyleneamine, an amine surfactant and an amine selected from 2- (2-aminoethoxy) ethanol, diethanolamine, N-methyldiethanolamine and triethanolamine, with (ii) an amine oxidation inhibitor, where the amine oxidation inhibitor is a free radical remover selected from one or more among alupurinol, propyl thiouracil, glutamine, diaminobenzylamine, nicotinamide, methimazole, phenyl methimazole and methimazole or phenyl methimazole derivatives, in which the amount of amine oxidation inhibitor added to the oxidation-sensitive amine is in an amount varying from 5 ppm to 100,000 ppm.
    [0002]
    2. Method according to claim 1, characterized by the fact that it also includes storing the inhibitor-treated amine in a container filled with an inert gas.
    [0003]
    3. Method according to claim 1, characterized by the fact that it also includes incubating the inhibitor-treated amine at a temperature of 0 ° C to 150 ° C.
    [0004]
    4. Method according to claim 1, characterized by the fact that it also includes adding the inhibitor-treated amine to another material sensitive to oxidation selected from one or more of an isocyanate, a polyol, a prepolymer, a quasi prepolymer , and a blowing agent.
    [0005]
    5. Method according to claim 1, characterized by the fact that the oxidation sensitive amine is a tertiary amine catalyst selected from one or more of bis- (2-dimethylaminoethyl) ether, N, N, N'- ether trimethyl-N'-hydroxyethylbisaminoethyl, N- (3-dimethylaminopropyl) - N, N- diisopropanolamine, N, N-dimethylethanolamine, triethylene diamine, N, N-dimethylcyclohexylamine, benzildimethylamine, pentamethyldiethylenetriamine, N, N, ', , N ”-pentamethyldipropylenetriamine, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, N- (3-dimethylaminopropyl) -N, N- diisopropanolamine, N '- (3- (dimethylamino) propyl-N, N- dimethyl-dimethyl-1,3-propanediamine, 2- (2-dimethylaminoethoxy) ethanol, N, N, N'-trimethylaminoethyl-ethanolamine, N-ethylmorpholine, N-methylmorpholine, 4-methoxyethylmorpholine, N, N'dimethylpiperzine, ether 2 , 2'dimorpholinodiethyl, 1,3,5-tris (3- (dimethylamino) propyl) -hexahydro-s-triazine and 3- (2- (dimethylamino) ethoxy) propylamine.
    [0006]
    Method according to claim 1, characterized by the fact that the oxidation sensitive amine is a polyetheramine selected from one or more of a monoamine, a diamine, a polyether diamine, an unimpeded diamine, and a triamine.
    [0007]
    Method according to claim 1, characterized in that the oxidation sensitive amine is an ethyleneamine selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoethylpiperzine, aminoethylethanolamine, pentaethyleneexamine, hexaethyleneeptamine, and mixtures of these.
    [0008]
    Method according to claim 1, characterized in that the oxidation sensitive amine is a surfactant amine selected from one or more of a monoamine polyether, a hydrophobic monoamine and a hydrophilic monoamine polyether.
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    BR112012016114A2|2016-05-31|
    CN102741310B|2016-04-27|
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    JP2013516539A|2013-05-13|
    WO2011084865A8|2012-07-05|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-07-16| B06T| Formal requirements before examination|
    2019-10-01| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-01-21| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-06-30| B09A| Decision: intention to grant|
    2020-10-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    2020-11-24| B16C| Correction of notification of the grant|Free format text: REF. RPI 2599 DE 27/10/2020 QUANTO AOS DESENHOS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US29338810P| true| 2010-01-08|2010-01-08|
    US61/293388|2010-01-08|
    PCT/US2010/062476|WO2011084865A1|2010-01-08|2010-12-30|Inhibition of amine oxidation|
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