Diisocyanate stabilizers, uses thereof, and diisocyanate compositions

Abstract

The present disclosure relates to a diisocyanate stabilizer, use of the diisocyanate stabilizer in stabilizing diisocyanate, and a diisocyanate composition comprising the stabilizer. The diisocyanate stabilizer comprises a sterically hindered phenol different from butylated hydroxytoluene, a thioether, and a phosphite different from triphenyl phosphite. The present disclosure aims to provide a diisocyanate stabilizer that can maintain diisocyanate stable during long-term storage and heating conditions.

Description

Technical Field

[0001] This disclosure relates to a diisocyanate stabilizer, the use of the diisocyanate stabilizer in stabilizing diisocyanates, and a diisocyanate composition comprising said stabilizer.

[0002] background

[0003] Diisocyanates are important intermediates in organic synthesis, such as in the preparation of polyurethane resins. However, due to the high reactivity of the isocyanate groups, diisocyanates tend to yellow and / or become cloudy due to self-polymerization during storage, thus affecting their application in downstream industries. To prevent yellowing and / or clouding, those skilled in the art typically add a certain amount of antioxidant to diisocyanates.

[0004] For example, US3555072 discloses a method for suppressing discoloration and turbidity formation in toluene diisocyanate (TDI), which includes adding a stabilizing amount of a sulfide compound thereto.

[0005] However, the TDI solution obtained according to US3555072 exhibits poor long-term thermal stability. To extend thermal stability, those skilled in the art could increase the amount of the sulfide, but this would introduce odor problems into the TDI, which is unacceptable.

[0006] Therefore, there remains a need in the art to provide a stabilizer for diisocyanates that enables them to remain colorless and transparent after long-term storage. Invention Overview

[0008] This disclosure provides a diisocyanate stabilizer that solves or at least partially solves the problems described above or other potential problems with stabilizing diisocyanates present in the prior art.

[0009] Specifically, in a first aspect, this disclosure provides a diisocyanate stabilizer comprising a hindered phenol, a thioether, and a phosphite, which is different from butylated hydroxytoluene.

[0010] In some embodiments, the hindered phenol is present in an amount of 10-90% by weight, the thioether in an amount of 5-80% by weight, and the phosphite in an amount of 5-80% by weight, based on the total weight of the stabilizer in each case.

[0011] In other embodiments, the diisocyanate stabilizer is composed of sterically hindered phenols, thioethers, and phosphites.

[0012] The inventors of this disclosure have surprisingly discovered that hindered phenols, thioethers, and phosphites can work synergistically to effectively prevent the self-polymerization of diisocyanates. By combining hindered phenols, thioethers, and phosphites, this disclosure provides a stabilizer that can prevent diisocyanates from yellowing and / or becoming cloudy during long-term storage and under heating conditions. The stabilizer of this disclosure effectively solves the problem of diisocyanates easily yellowing and / or becoming cloudy during long-term storage and under heating conditions.

[0013] In some preferred embodiments, the diisocyanate stabilizer has a melting point below 50°C, preferably below 20°C. For example, the diisocyanate stabilizer has melting points below 50°C, 45°C, 40°C, 35°C, 30°C, 25°C, 20°C, or 10°C. In these preferred embodiments, the diisocyanate stabilizer is liquid at the operating temperature (typically 45-50°C) to facilitate automated production, thereby improving production efficiency. Furthermore, when the diisocyanate stabilizer has a melting point below 20°C and is therefore liquid even below 20°C, it is additionally advantageous for transporting the diisocyanate stabilizer at low temperatures.

[0014] This disclosure provides, in a second aspect, the use of a stabilizer according to the first aspect of the invention in stabilizing diisocyanates.

[0015] This disclosure provides a composition in a third aspect comprising:

[0016] (A) diisocyanate, and

[0017] (B) A diisocyanate stabilizer according to the first aspect of the present invention.

[0018] The inventors of this disclosure have made a remarkable discovery that the resulting diisocyanate compositions can (substantially) remain transparent and colorless during long-term storage and under heating conditions, which significantly expands the application range of diisocyanates. Therefore, the diisocyanate compositions of this disclosure are suitable for applications with high requirements for color and transparency.

[0019] Compared with existing technologies, the diisocyanate stabilizer disclosed herein provides advantageous technical effects to diisocyanates during long-term storage and heating conditions (e.g., melting processes at approximately 100°C), including but not limited to:

[0020] (1) The diisocyanate composition has a light color;

[0021] (2) The diisocyanate composition has high transparency; and

[0022] (3) The diisocyanate composition maintains a light color and high transparency.

[0023] It should be understood that the overview portion of this invention is neither intended to define the key or essential features of this disclosure nor to limit its scope. Other features of this disclosure will become readily apparent from the following description. Invention Details

[0025] In the following description, reference is made to embodiments to further explain this disclosure to enable those skilled in the art to fully understand it. It should be understood that these embodiments are provided only for a better understanding of the subject matter of this disclosure and are not intended to limit the scope of protection, application, or embodiments set forth in these claims. It should be understood that those skilled in the art may omit, substitute, or add various technical features to the embodiments as needed, provided that this does not depart from the spirit of this disclosure. Furthermore, some technical features described in some embodiments may be combined with technical features described in other embodiments.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one skilled in the art to which this disclosure pertains.

[0027] In this disclosure, the terms “comprising,” “including,” and their various variations are to be understood as open-ended terms meaning “including but not limited to”; conversely, the terms “consisting of,” and their various variations exclude any component, step, or procedure not specifically listed; the term “one embodiment” is to be understood as “at least one embodiment”; and the term “another embodiment” is to be understood as “at least one other embodiment.” Unless expressly stated otherwise, other terms that may arise but are not mentioned herein should not be interpreted or limited in a manner contrary to the concept upon which embodiments of this disclosure are based.

[0028] The terms “a,” “an,” “the,” and “one or more” are used interchangeably throughout this disclosure and are intended to include both the plural and singular forms, unless explicitly stated herein or the context clearly indicates the singular form. The term “a” is generally used when used only in the singular form. The term “or” is generally intended to include the meaning of “and / or” unless the context explicitly states otherwise. The terms “preferred,” “ideal,” and “preferred” as used herein refer to embodiments of the present disclosure that may provide advantages in certain circumstances. However, other embodiments may also be preferred in the same circumstances. Furthermore, the listing of one or more preferred embodiments does not imply that other embodiments are unavailable and is not intended to exclude other embodiments from the scope of this disclosure.

[0029] Unless otherwise specified, all percentages, portions and ratios are by weight. Furthermore, the enumeration of values ​​within a range includes all values ​​falling within that range (e.g., 5-10 includes 5, 5.1, 5.2, 5.55, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10).

[0030] In this disclosure, a "diisocyanate stabilizer" refers to a mixture / composition capable of stabilizing diisocyanates against internal or external influencing factors. Regarding internal factors, as discussed above, diisocyanates tend to self-polymerize due to their highly reactive groups. Regarding external factors, diisocyanates are easily affected by heat, light, etc. This diisocyanate stabilizer is provided to stabilize diisocyanates in terms of color stability, transparency, etc. The diisocyanate stabilizer enables the diisocyanate to maintain its colorlessness and transparency during long-term storage and under heating conditions.

[0031] Throughout this disclosure, the terms “phosphite” and “phosphite class” are used interchangeably and are intended to include both the plural and singular forms, unless otherwise expressly stated herein or clearly indicated by the context.

[0032] The term "diol" refers to an aliphatic diol containing two hydroxyl groups (-OH groups) attached to different carbon atoms.

[0033] The term "color stability" refers to the fact that the color of the diisocyanate composition remains unchanged or changes only slightly during long-term storage, even under heating conditions. For example, the diisocyanate composition disclosed herein can maintain its colorless or pale yellow color during long-term storage and under heating conditions.

[0034] As used herein, the term "transmitted intensity" refers to the percentage of light that passes through an object. For example, in embodiments of this disclosure, it relates to the percentage of light that passes through a glass vial containing the diisocyanate composition.

[0035] As mentioned above, diisocyanates are important intermediates in many organic syntheses, such as for the preparation of polyurethane resins. However, diisocyanates have highly reactive groups, which makes them prone to self-polymerization and thus causes them to become cloudy during storage. These problems exist in various diisocyanates, including aliphatic, alicyclic, and aromatic diisocyanates.

[0036] I. Diisocyanate stabilizers

[0037] In view of the difficulties existing in stabilizing diisocyanates in the prior art, this disclosure provides a diisocyanate stabilizer in a first aspect, comprising a hindered phenol different from butylated hydroxytoluene, a thioether, and a phosphite different from triphenyl phosphite.

[0038] The inventors of this disclosure have surprisingly discovered that hindered phenols, thioethers, and phosphites can work synergistically to effectively prevent the self-polymerization of diisocyanates. By combining hindered phenols, thioethers, and phosphites, this disclosure provides a stabilizer that can prevent diisocyanates from yellowing and / or becoming cloudy during long-term storage and under heating conditions (e.g., melt processes at approximately 100°C). The stabilizer of this disclosure effectively solves the problem of diisocyanates easily yellowing and becoming cloudy during long-term storage and under heating conditions.

[0039] steric phenol

[0040] The sterically hindered phenols include phenols having one or more phenolic hydroxyl groups on an aromatic ring, preferably at the ortho position of the phenolic hydroxyl group, most preferably at the ortho and para positions, and preferably those with alkyl groups.

[0041] It should be understood that the above description is not intended to limit the scope of sterically hindered phenols suitable for this disclosure.

[0042] Examples of suitable phenols include alkylphenols, such as o-, m-, or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol or 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-oxobisphenol, 3,4-methylenedioxybisphenol (sesamol), 3,4-dimethylphenol, hydroquinone, tert-butylhydroquinone, 2,5-di-tert-butyl... Hydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, pyrocatechol (1,2-dihydroxybenzene), 2-(1'-methylcyclohexyl-1'-yl)-4,6-dimethylphenol, 2-or 4-(1'-phenylethyl-1'-yl)phenol, 2-tert-butyl-6-methylphenol, 2,4,6-tri-tert-butylphenol, 2,6-di-tert-butylphenol, nonylphenol [11066-49-2], octylphenol [140-66-9], 2,6-dimethylphenol, bisphenol A, bisphenol F, bisphenol B, bisphenol C, bisphenol S, 3,3',5,5'-tetrabromobisphenol A, from BASF AG Methyl 3,5-di-tert-butyl-4-hydroxybenzoate, 4-tert-butylpyrocatechol, 2-hydroxybenzyl alcohol, 2-methoxy-4-methylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 2-isopropylphenol, 4-isopropylphenol, 6-isopropyl-m-cresol, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl ester, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-propionyloxyethyl isocyanurate Tris(3,5-di-tert-butyl-4-hydroxyphenyl) ester, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate or pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 6-isobutyl-2,4-dinitrophenol, 6-sec-butyl-2,4-dinitrophenol, 2,6-di-tert-butyl-4-(4,6-di(octylthio)-1,3,5-triazin-2-ylamino)phenol, octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, hexadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 3-(3',5'-di-tert-butyl... Octyl 4'-hydroxyphenyl)propionate, 3-thia-1,5-pentanediol di[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol di[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol di[(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate], 1,9-nonanediol di[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 1,7-heptanediamine di[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 1,1-methanediamine di[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide] [amine], 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionylhydrazine, 3-(3',5'-dimethyl-4'-hydroxyphenyl)propionylhydrazine, di(3-tert-butyl-5-ethyl-2-hydroxyphenyl-1-yl)methane, di(3,5-di-tert-butyl-4-hydroxyphenyl-1-yl)methane, di[3-(1'-methylcyclohexyl-1'-yl)-5-methyl-2-hydroxyphenyl-1-yl]methane, di(3-tert-butyl-2-hydroxy-5-methylphenyl-1-yl)methane, 1,1-di(5-tert-butyl-4-hydroxy-2-methylphenyl-1-yl)ethane, di(5-tert-butyl-4-hydroxy-2-methylphenyl-1-yl) sulfide, di(3-tert-butyl-2-hydroxy-5-methylphenyl-1-yl) sulfide, 1,1-Di(3,4-dimethyl-2-hydroxyphenyl-1-yl)-2-methylpropane, 1,1-Di(5-tert-butyl-3-methyl-2-hydroxyphenyl-1-yl)butane, 1,3,5-tris[1'-(3”,5”-di-tert-butyl-4”-hydroxyphenyl-1”-yl)methyl-1'-yl]-2,4,6-trimethylbenzene, 1,1,4-tris(5'-tert-butyl-4'-hydroxy-2'-methylphenyl-1'-yl) Butane, aminophenols such as p-aminophenol and 3-diethylaminophenol, nitrosophenols such as p-nitrosophenol and p-nitroso-o-cresol, alkoxyphenols such as 2-methoxyphenol (guaiacol, pyrocatechol monomethyl ether), 4-methoxyphenol (hydroquinone monomethyl ether), 2-ethoxyphenol, 4-ethoxyphenol, 2-isopropoxyphenol, 4-butoxyphenol, mono- or di-tert-butyl-4-methoxyphenol, 3,5 - Di-tert-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2,5-dimethoxy-4-hydroxybenzyl alcohol (eugenol), 4-hydroxy-3-methoxybenzaldehyde (vanillin), 4-hydroxy-3-ethoxybenzaldehyde (ethyl vanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1-(4-hydroxy-3-methoxyphenyl) ethyl ketone (acetylvanillin), eugenol, dihydroeugenol, isobutyl Tocopherols, such as α-, β-, γ-, δ- and ε-tocopherols, magnolol, α-tocopherol hydroquinone, 4-methylpyrocatechol, 3-methylpyrocatechol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2,5-di-tert-pentylhydroquinone, 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumarin), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid, and its derivatives.

[0043] Corresponding sterically hindered phenol products, for example, by trade name (BASF), such as pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (e.g.) 1010), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)trione (e.g.) 3114), thiodiethylidene di[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate] (e.g.) 1035), 3,5-bis(1,1-dimethylethyl)-4-phenylpropionic acid branched C7-C9 alkyl esters (e.g. 1135), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g.) 1076), polyethylene glycol ether esters capped with phenol derivatives (e.g.) 2000), 4,6-bis(octylthiomethyl)-o-cresol (e.g.) 1520), 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid branched C 13 -C 15 Alkyl esters (e.g.) 1315) obtained.

[0044] It should be understood that the above examples of sterically hindered phenols are merely illustrative and are not intended to limit the scope of this disclosure. Any other suitable sterically hindered phenols are also applicable.

[0045] In some preferred embodiments, the hindered phenols include those with melting points below 55°C, such as those with melting points below 20°C, 25°C, 30°C, 40°C, 45°C, 50°C, or 55°C. These hindered phenols allow the stabilizer to remain liquid at operating temperatures (typically 45-50°C) and thus facilitate automated production.

[0046] In a preferred embodiment, the sterically hindered phenol is selected from branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-phenylpropionic acid (e.g. 1135), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g.) 1076), 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid branched C 13 -C 15 Alkyl esters (e.g.) 1315), polyethylene glycol ether esters capped with phenol derivatives (e.g.) 2000), 4,6-bis(octylthiomethyl)-o-cresol (e.g.) At least one of (1520). These preferred hindered phenols are harmless to humans and are therefore safer and more environmentally friendly.

[0047] In a more preferred embodiment, the sterically hindered phenol is selected from branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-phenylpropionic acid (e.g. 1135) and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g.) At least one of 1076). These more preferred sterically hindered phenols are liquids or solids with low melting points, which enables the stabilizer to be liquid at room temperature or at typical operating temperatures (e.g., 45°C).

[0048] Preferably, the hindered phenol does not include butylated hydroxytoluene (BHT) because BHT is highly volatile and therefore limited in many applications.

[0049] Sulfides

[0050] The thioethers used in this disclosure include compounds comprising at least one thioether group, i.e., sulfur atoms substituted by two identical or different organic substituents. It should be understood that the above description is not intended to limit the scope of the thioethers in this disclosure. This disclosure does not limit the scope of thioethers.

[0051] Suitable sulfides have the structure of formula (I):

[0052] R 1 -SR 2 (I)

[0053] in

[0054] R 1 and R 2 Each can be independently defined as C1-C 18 Alkyl groups, C2-C separated by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups. 18 Alkyl, C2-C 18 Alkenyl, C6-C 12 Aryl, C5-C 12 Cycloalkyl or a 5- or 6-membered heterocycle containing oxygen, nitrogen and / or sulfur, wherein said group is optionally substituted with hydroxyl, amino, aryl, alkyl, aryloxy, alkoxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom and / or heterocycle.

[0055] Here R 1 and R 2 Each of the following groups can be selected independently:

[0056] Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, diphenylmethyl, p- Tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolane-2-yl, 1,3-di Alkyl-2-yl, 2-methyl-1,3-dioxolane-2-yl, 4-methyl-1,3-dioxolane-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octoxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-amino Hexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl;

[0057] 5-Hydroxy-3-oxapentyl, 8-Hydroxy-3,6-dioxaoctyl, 11-Hydroxy-3,6,9-trioxaundecyl, 7-Hydroxy-4-oxaheptyl, 11-Hydroxy-4,8-dioxaundecyl, 15-Hydroxy-4,8,12-trioxapentadecanyl, 9-Hydroxy-5-oxanonyl, 14-Hydroxy-5,10-oxatetradecyl, 5-Methoxy-3-oxapentyl, 8-Methoxy-3,6-dioxaoctyl, 11-Methoxy-3,6,9-trioxaundecyl, 7-Methoxy-4-oxaheptyl, 11-Methoxy-4, 8-Dioxaundecyl, 15-methoxy-4,8,12-trioxapentadecanyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4,8,12-trioxapentadecanyl, 9-ethoxy-5-oxanonyl, or 14-ethoxy-5,10-oxatetradecyl;

[0058] Vinyl, 1-propenyl, allyl, methallyl, 1,1-dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, undecenyl, dodecenyl, octadecenyl, 2-phenylvinyl, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl, 2-ethoxyallyl, 3-ethoxyallyl or 1- or 2-chlorovinyl;

[0059] Phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-biphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexoxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl;

[0060] Cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, or saturated or unsaturated bicyclic systems such as norbornyl or norbornenyl; and furanyl, thiopheneyl, pyrroleyl, pyridylyl, indoleyl, benzo[] azole group, m-dioxacyclopentenyl group, di Dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridinyl, methylquinolinyl, dimethylpyrroleyl, methoxyfuranyl, dimethoxypyridinyl, difluoropyridinyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.

[0061] In some embodiments, the sulfide is selected from 2-methyl-1-propenyl tert-dodecyl sulfide, cyclohexene-methyl n-dodecyl sulfide, 3-cyclohexene-(1)-methylene-methyl n-octadecyl sulfide, 3-cyclohexene-(1)-methylene-methyl n-dodecyl sulfide, 3-cyclohexene-(1)-methylene-methyl n-octyl sulfide, 3-cyclohexene-(1)-methylene-methyl cyclohexyl sulfide, 3-methyl-(3)-cyclohexene-(1)-methylene-methyl n-dodecyl sulfide, 3-cyclohexene-(1)-methylene-methyl p-tolyl sulfide, 3-cyclohexene-(1)-methylene-methyl benzyl sulfide, preferably 3-cyclohexene-(1)-methylene-methyl n-dodecyl sulfide and 1-hexene-n-dodecyl sulfide.

[0062] In other embodiments, the sulfide is a compound having the structure of formula (II):

[0063]

[0064] in

[0065] R 3 and R 5 Each can be independently defined as C1-C 18 Alkyl groups, C2-C separated by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups. 18 Alkyl, C6-C 12 Aryl or C5-C 12 Cycloalkyl, wherein the group is optionally substituted with hydroxyl, amino, aryl, alkyl, aryloxy, alkoxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom and / or heterocyclic, and

[0066] R 4 It can be C1-C 20 Alkylene or C3-C 12 Cycloalkylene groups, wherein the groups are optionally substituted with hydroxyl, amino, aryl, alkyl, aryloxy, alkoxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom and / or heterocyclic groups.

[0067] Here R 3 and R 5 Each of the following groups can be selected independently:

[0068] Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, diphenylmethyl, p- Tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolane-2-yl, 1,3-di Alkyl-2-yl, 2-methyl-1,3-dioxolane-2-yl, 4-methyl-1,3-dioxolane-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octoxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-amino Hexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl;

[0069] 5-Hydroxy-3-oxapentyl, 8-Hydroxy-3,6-dioxaoctyl, 11-Hydroxy-3,6,9-trioxaundecyl, 7-Hydroxy-4-oxaheptyl, 11-Hydroxy-4,8-dioxaundecyl, 15-Hydroxy-4,8,12-trioxapentadecanyl, 9-Hydroxy-5-oxanonyl, 14-Hydroxy-5,10-oxatetradecyl, 5-Methoxy-3-oxapentyl, 8-Methoxy-3,6-dioxaoctyl, 11-Methoxy-3,6,9-trioxaundecyl, 7-Methoxy-4-oxaheptyl, 11-Methoxy-4, 8-Dioxaundecyl, 15-methoxy-4,8,12-trioxapentadecanyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4,8,12-trioxapentadecanyl, 9-ethoxy-5-oxanonyl, or 14-ethoxy-5,10-oxatetradecyl;

[0070] Phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-biphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexoxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl; and

[0071] Cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethiocyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, or saturated or unsaturated bicyclic systems such as norbornyl or norbornyl.

[0072] Here R 4 It can be selected from the following groups:

[0073] Methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,1-dimethyl-1,2-ethylene or 1,2-dimethyl-1,2-ethylene, 1,6-hexene, 1,8-octene, 1,10-decene, 1,12-dodecylene and 1,20-eicosylene, as well as cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene and cyclododecylene.

[0074] In some preferred embodiments, R 3 C6-C is arbitrarily replaced. 12 Aryl or C1-C 18 Alkyl groups, preferably optionally substituted C1-C 18 Alkyl groups, particularly unsubstituted C1-C, are preferred. 18 Alkyl; R 5 For the optional replacement of C1-C 18 Alkyl groups, preferably unsubstituted C1-C 18 Alkyl; and / or R 4 It is methylene, 1,2-ethylene, or 1,2-propylene, preferably 1,2-ethylene.

[0075] In some embodiments, compounds having the structure of formula (III) are particularly preferred:

[0076]

[0077] Where R 4 and R 5 As defined above.

[0078] In some preferred embodiments, the sulfide includes those with melting points below 50°C, such as sulfides with melting points below 20°C, 25°C, 30°C, 40°C, 45°C, or 50°C. This type of sulfide allows the stabilizer to be liquid at operating temperatures (typically 45-50°C) and thus facilitates automated production.

[0079] In a preferred embodiment, the sulfide is selected from thiodipropionates, such as dimethyl 3,3'-thiodipropionate and di-dodecyl 3,3'-thiodipropionate (DLTDP) (e.g., from BASF). PS 800), di-tetrazyl 3,3'-thiodipropionate (DTDTP) (e.g., from Songwon International AG) At least one of DTDTP, di-octadecyl 3,3'-thiodipropionate (DSTDP), dimyristyl thiodipropionate (DMTDP), and 2,2-bis[[3-dodecylthio-1-oxopropoxy]methyl]-1,3-propylene di[3-dodecylthiopropionate] (e.g., Seenox 412S).

[0080] In a more preferred embodiment, the sulfide is at least one selected from di-dodecyl thiodipropionate (DLTDP) and di-tetrazyl thiodipropionate (DTDTP). These more preferred sulfides are liquids or solids with low melting points, which allows the stabilizer to be liquid at typical operating temperatures (e.g., 45-50°C).

[0081] Phosphite

[0082] Suitable phosphites according to this disclosure include, but are not limited to, monophosphites and polymeric phosphites.

[0083] Examples of suitable monophosphites according to this disclosure include compounds having the structure of formula (IV):

[0084] P(OR 6 (OR) 7 (OR) 8 (IV)

[0085] in

[0086] R 6 R 7 and R 8 Each can be independently defined as C1-C 18Alkyl, C6-C 12 Aryl or C5-C 12 Cycloalkyl, wherein the group is optionally substituted with hydroxyl, amino, aryl, alkyl, aryloxy, alkoxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom and / or heterocyclic.

[0087] Here R 6 R 7 and R 8 Each of the following groups can be selected independently:

[0088] Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, diphenylmethyl, p- Tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolane-2-yl, 1,3-di Alkyl-2-yl, 2-methyl-1,3-dioxolane-2-yl, 4-methyl-1,3-dioxolane-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octoxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-amino Hexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl;

[0089] Phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-biphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexoxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl; and

[0090] Cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethiocyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, or saturated or unsaturated bicyclic systems such as norbornyl or norbornyl.

[0091] Examples of suitable polymeric phosphites according to this disclosure include those having a structure of formula (V):

[0092]

[0093] in

[0094] R 9 R 10 R 11 and R 12 Each can be the same or different and is independently selected from C. 1-20 Alkyl, C 3-22 Alkenyl, C 6-40 cycloalkyl, C 7-40 Cycloalkylene, C 1-20 Methoxyalkyl glycol ethers, C 1-20 Alkyl glycol ethers and / or Y-OH (used as end-capping structural moiety);

[0095] Y is selected from C 2-40 Alkylene, C 2-40 Alkyl lactones (e.g., ethylidene, propyleneide, octyl lactone), -R 13 -N(R 14 )-R 15 -(e.g., C) 2-40 Alkyldiamine and C 2-40 Alkyltriamine),

[0096] Where R 13 R 14 and R 15Independently selected from the preceding R 9 R 10 R 11 and R 12 The defined groups now further include H;

[0097] m is an integer value in the range of 2-100; and

[0098] x is an integer value in the range of 1 to 1,000.

[0099] In some implementations, alkyl, alkenyl, and cycloalkyl groups can be separated by oxygen, sulfur, or nitrogen.

[0100] In some preferred embodiments, the polymeric phosphite is polyalkylene glycol phenyl phosphite. More preferably, the polyalkylene glycol phenyl phosphite is poly(dipropylene glycol) phenyl phosphite (CAS: 116265-68-0), poly(propylene glycol) phenyl phosphite, or poly(ethylene glycol) phenyl phosphite.

[0101] In other preferred embodiments, the polymeric phosphite is a polymeric diphosphite having the structure of formula (VI):

[0102]

[0103] in

[0104] R 9 R 10 R 11 and R 12 Each as defined above;

[0105] Y is as defined above; and

[0106] m is as defined above.

[0107] Preferably, the phosphites according to this disclosure are selected from tri-dodecyl phosphite (e.g., CCP STAB 3012T), mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyltriesters of phosphite (CAS: 939402-02-5; e.g., Weston 705), 3,9-diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (e.g., CCP STAB 508T), 4,4'-butylene di(3-methyl-6-tert-butylphenylalkyl)phosphite (C 13 ) esters (e.g., CCPSTAB AS-4500) and poly(dipropylene glycol) phenyl phosphite (CAS: 116265-68-0). These preferred phosphites exhibit excellent color stability for diisocyanates during melt processing.

[0108] More preferably, the phosphite is selected from tri-dodecyl phosphite (e.g., CCP STAB 3012T), a mixture of 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyltriesters (CAS: 939402-02-5; e.g., Weston 705), 3,9-diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (e.g., CCPSTAB 508T) and poly(dipropylene glycol) phenyl phosphite (CAS: 116265-68-0).

[0109] Preferably, the phosphites according to this disclosure do not include triphenyl phosphite (TPP), as TPP is limited in many applications due to its high volatility and toxicity.

[0110] In some embodiments, the diisocyanate stabilizer has a melting point below 50°C, preferably below 20°C. For example, the diisocyanate stabilizer has melting points below 50°C, 45°C, 40°C, 35°C, 30°C, 25°C, 20°C, or 10°C. In some embodiments, the diisocyanate stabilizer is solid at room temperature but liquid at 45-50°C. When the diisocyanate stabilizer is liquid at the operating temperature (e.g., 45-50°C), it facilitates automated production, which can effectively improve production efficiency. Furthermore, when the diisocyanate stabilizer has a melting point below 20°C and is therefore liquid even below 20°C, it is additionally advantageous for transporting the diisocyanate stabilizer at low temperatures.

[0111] Those skilled in the art can obtain liquid stabilizers with melting points below 50°C by selecting suitable hindered phenols, thioethers, and / or phosphites based on their melting points and / or by selecting appropriate amounts of each component. This disclosure makes no limitation on those suitable hindered phenols, thioethers, phosphites, or their corresponding amounts in the stabilizer.

[0112] For example, in some embodiments, the sterically hindered phenol is selected from branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-phenylpropionate, octadecyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate. 13 -C 15Alkyl esters, polyethylene glycol ether esters capped with phenol derivatives, 2,4-dimethyl-6-(1-methylpentadecanyl)phenol, and 4,6-bis(octylthiomethyl)-o-cresol; the sulfide is selected from at least one of di-dodecyl 3,3'-thiodipropionate, di-octadecyl 3,3'-thiodipropionate, di-tetrazyl 3,3'-thiodipropionate, dimyristyl thiodipropionate, and 2,2-bis[[3-dodecylthio-1-oxopropoxy]methyl]-1,3-methyl At least one of propyl di[3-dodecylthiopropionate]; and the phosphite is selected from tri-dodecyl phosphite, a mixture of 2,4-di(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyltriesters (CAS: 939402-02-5), 3,9-diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 4,4'-butylene di(3-methyl-6-tert-butylphenylalkyl)phosphite. 13 At least one of esters and poly(dipropylene glycol) phenyl phosphite (CAS: 116265-68-0). In another embodiment, the hindered phenol comprises branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-phenylpropionate and octadecyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; the thioether comprises di-dodecyl ester of 3,3'-thiodipropionate and di-tetrazyl ester of 3,3'-thiodipropionate; and the phosphite comprises tri-dodecyl phosphite, a mixture of 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyltriesters (CAS: 939402-02-5), 3,9-diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and poly(dipropylene glycol) phenyl phosphite (CAS: 116265-68-0).

[0113] In the above embodiments, the hindered phenol and thioether are liquids or solids with low melting points, which enables the diisocyanate stabilizer to be liquid at the operating temperature (typically 45-50°C).

[0114] As discussed above, this disclosure does not limit the amount of the hindered phenol, thioether, or phosphite. Those skilled in the art can select the appropriate amount according to actual needs.

[0115] For example, in some embodiments, the hindered phenol is present in an amount of 10-90% by weight, the thioether is present in an amount of 5-80% by weight, and the phosphite is present in an amount of 5-80% by weight, based on the total weight of the stabilizer in each case.

[0116] In other embodiments, the hindered phenol is present in amounts of 10-90% by weight, for example 15-85% by weight, 20-80% by weight, 25-75% by weight, 30-70% by weight, 35-65% by weight, 40-60% by weight, or 45-55% by weight. For example, the amount of hindered phenol is 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight, or any value or range therebetween.

[0117] In other embodiments, the sulfide is present in amounts of 5-80% by weight, for example, 10-75% by weight, 15-70% by weight, 20-65% by weight, 25-60% by weight, 30-55% by weight, 35-50% by weight, or 40-45% by weight. For example, the amount of sulfide is 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, or any value or range therebetween.

[0118] In other embodiments, the phosphite is present in amounts of 5-80% by weight, such as 10-75% by weight, 15-70% by weight, 20-65% by weight, 25-60% by weight, 30-55% by weight, 35-50% by weight, or 40-45% by weight. For example, the amount of phosphite is 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, or any value or range therebetween.

[0119] In some preferred embodiments, the diisocyanate stabilizer comprises a hindered phenol, a thioether, and a phosphite, wherein the hindered phenol includes branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-phenylpropionate, octadecyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate. 13 -C 15Alkyl esters, polyethylene glycol ether esters capped with phenol derivatives, 2,4-dimethyl-6-(1-methylpentadecanyl)phenol, and 4,6-bis(octylthiomethyl)-o-cresol; thioethers include di-dodecyl 3,3'-thiodipropionate, di-octadecyl 3,3'-thiodipropionate, di-tetrazyl 3,3'-thiodipropionate, dimyristyl thiodipropionate, and 2,2-bis[[3-dodecylthio-1-oxopropoxy]methyl]-1,3-methyl Propyl di[3-dodecylthiopropionate]; and phosphites including tri-dodecyl phosphite, a mixture of 2,4-di(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyltriesters (CAS: 939402-02-5), 3,9-diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 4,4'-butylene di(3-methyl-6-tert-butylphenylalkyl)phosphite (C 13 ) ester and poly(dipropylene glycol) phenyl phosphite (CAS: 116265-68-0); hindered phenols are present in an amount of 10-90% by weight, thioethers are present in an amount of 5-80% by weight and phosphite are present in an amount of 5-80% by weight, in each case based on the total weight of the diisocyanate stabilizer.

[0120] In a more preferred embodiment, the diisocyanate stabilizer comprises a hindered phenol, a thioether, and a phosphite, wherein the hindered phenol comprises branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-phenylpropionate and octadecyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; the thioether comprises di-dodecyl ester of 3,3'-thiodipropionate and di-tetrazyl ester of 3,3'-thiodipropionate; and the phosphite comprises tri-dodecyl phosphite and a mixture of 2,4-bis(1,1-dimethyl)phosphite. (1,1-Dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyltriester (CAS: 939402-02-5), poly(dipropylene glycol) phenyl phosphite (CAS: 116265-68-0) and 3,9-diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; the amount of hindered phenol is 10-90% by weight, the amount of thioether is 5-80% by weight and the amount of phosphite is 5-80% by weight, based on the total weight of the diisocyanate stabilizer in each case.

[0121] The following are some examples of preparing the diisocyanate stabilizers of this disclosure. However, it should be understood that these examples are for illustrative purposes only. The diisocyanate stabilizers of this disclosure can be prepared by known methods well known to those skilled in the art. For example, suitable amounts of a suitable hindered phenol, thioether, and phosphite can be added sequentially or simultaneously, and then the composition can be heated and mixed at a certain temperature for a certain period of time. There is nothing special about the mixing process, and conventional mixing techniques and equipment can be used.

[0122] II. Uses of this isocyanate stabilizer

[0123] This disclosure also provides, in a second aspect, the use of the diisocyanate stabilizer according to the first aspect of this disclosure in stabilizing diisocyanates.

[0124] III. Diisocyanate Compositions

[0125] This disclosure provides a diisocyanate composition comprising, in a third aspect, a diisocyanate composition:

[0126] (A) diisocyanate, and

[0127] (B) A diisocyanate stabilizer according to the first aspect of this disclosure.

[0128] In some embodiments, this disclosure provides a diisocyanate composition comprising:

[0129] (A) diisocyanate, and

[0130] (B) A diisocyanate stabilizer comprising a hindered phenol, a thioether, and a phosphite.

[0131] diisocyanate

[0132] Examples of suitable diisocyanates include aliphatic, alicyclic, and aromatic diisocyanates.

[0133] Examples of suitable aliphatic diisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate, or tetramethylhexane diisocyanate.

[0134] Examples of suitable alicyclic diisocyanates include 1,2-, 1,3- or 1,4-diisocyanate-cyclohexane, 2,4'- or 4,4'-di(isocyanate-cyclohexyl)methane, 1-isocyanate-3,3,5-trimethyl-5-(isocyanate-cyclohexane) (isophorone diisocyanate), 1,3- or 1,4-di(isocyanate-methyl)cyclohexane, or 2,4- or 2,6-diisocyanate-1-methylcyclohexane.

[0135] Examples of suitable aromatic diisocyanates include toluene-2,4- or 2,6-diisocyanate and mixtures of its isomers, meta- or terephthalimide diisocyanate, 2,4'- or 4,4'-diisocyanate diphenylmethane (MDI) and mixtures of its isomers, 1,3- or 1,4-phenyl diisocyanate, 1-chlorobenzene-2,4-diisocyanate, naphthalene-1,5-diisocyanate, biphenyl-4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethylbiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, tetramethylphenylmethylene diisocyanate, 1,4-diisocyanate-benzene, or 4,4'-diisocyanate-diphenyl ether.

[0136] The diisocyanate stabilizers disclosed herein are particularly suitable for stabilizing toluene-2,4- or 2,6-diisocyanate and mixtures thereof, meta- or terephthalimide diisocyanate, 2,4'- or 4,4'-diisocyanate-based diphenylmethane and mixtures thereof, with 2,4'- or 4,4'-diisocyanate-based diphenylmethane being particularly preferred due to its specific structure, which is more prone to yellowing.

[0137] Mixtures of the diisocyanates are also suitable. For example, isophorone diisocyanates are typically in the form of mixtures, specifically mixtures of cis and trans isomers, in a typical ratio of about 60:40-80:20 (w / w), a preferred ratio of about 70:30-75:25, and a more preferred ratio of about 75:25. Dicyclohexylmethane-4,4'-diisocyanate can also be used in the form of mixtures of different cis and trans isomers.

[0138] For the purposes of this disclosure, diisocyanates can generally be obtained by phosgenating the corresponding amine or by a phosgen-free method without the use of phosgene.

[0139] The diisocyanate that can be used preferably has an isocyanate group content (calculated as NCO, molecular weight = 42) of 30-50% by weight based on the diisocyanate.

[0140] Regarding the hindered phenols, thioethers, and phosphites in this diisocyanate stabilizer, it should be understood that suitable hindered phenols, thioethers, and phosphites, and their amounts in the stabilizer, are the same as those described in the first aspect of this disclosure. Therefore, suitable hindered phenols, thioethers, and phosphites, and their amounts in the stabilizer, will not be repeated here. Only some exemplary hindered phenols, thioethers, and phosphites suitable for the diisocyanate compositions of this disclosure, and their amounts in the diisocyanate stabilizer, are provided below.

[0141] In some embodiments, the steric phenol is present in an amount of 10-90% by weight, the thioether in an amount of 5-80% by weight, and the phosphite in an amount of 5-80% by weight, based on the total weight of the diisocyanate stabilizer.

[0142] In some embodiments, the diisocyanate stabilizer is composed of sterically hindered phenols, thioethers, and phosphites.

[0143] In some embodiments, the diisocyanate stabilizer has a melting point below 50°C, preferably below 20°C.

[0144] In some embodiments, the sterically hindered phenol is selected from alkylphenols, bisphenol A, bisphenol F, bisphenol B, bisphenol C, bisphenol S, 3,3',5,5'-tetrabromobisphenol A, methyl 3,5-di-tert-butyl-4-hydroxybenzoate, 4-tert-butylpyrocatechol, 2-hydroxybenzyl alcohol, 2-methoxy-4-methylphenol, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl ester, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)propionyloxyethyl isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)propionyloxyethyl isocyanurate, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)propionyloxyethyl isocyanurate. 5-Di-tert-butyl-4-hydroxyphenyl) ester, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) ester or pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 6-isobutyl-2,4-dinitrophenol, 6-sec-butyl-2,4-dinitrophenol, 2,6-di-tert-butyl-4-(4,6-di(octylthio)-1,3,5-triazin-2-ylamino)phenol, octadecyl ester of 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, hexadecyl ester of 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate Octyl 3'-hydroxyphenyl)propionate, 3-thia-1,5-pentanediol di[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol di[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol di[(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate], 1,9-nonanediol di[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 1,7-heptanediamine di[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 1,1-methanediamine di[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide] 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionylhydrazine, 3-(3',5'-dimethyl-4'-hydroxyphenyl)propionylhydrazine, di(3-tert-butyl-5-ethyl-2-hydroxyphenyl-1-yl)methane, di(3,5-di-tert-butyl-4-hydroxyphenyl-1-yl)methane, di[3-(1'-methylcyclohexyl-1'-yl)-5-methyl-2-hydroxyphenyl-1-yl]methane, di(3-tert-butyl-2-hydroxy-5-methylphenyl-1-yl)methane, 1,1-di(5-tert-butyl-4-hydroxy-2-methylphenyl-1-yl)ethane, di(5-tert-butyl-4-hydroxy-2-methylphenyl-1-yl) sulfide, di(3-tert-butyl-2-hydroxy-5-methylphenyl-1-yl) sulfide, 1,1-Di(3,4-dimethyl-2-hydroxyphenyl-1-yl)-2-methylpropane, 1,1-Di(5-tert-butyl-3-methyl-2-hydroxyphenyl-1-yl)butane, 1,3,5-tris[1'-(3”,5”-di-tert-butyl-4”-hydroxyphenyl-1”-yl)methyl-1'-yl]-2,4,6-trimethylbenzene, 1,1,4-tris(5'-tert-butyl-4'-hydroxy-2'-methylphenyl-1'-yl)butane, aminophenols, nitrosophenols, alkoxyphenols, eugenol, dihydroeugenol, isoeugenol The following are included: at least one of the following: tocopherols, magnolol, α-tocopherol hydroquinone, 4-methylpyrocatechol, 3-methylpyrocatechol, hydroquinone monobenzyl ether, p-phenoxyphenol, hydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, 2,5-di-tert-pentylhydroquinone, 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumarin), 6-hydroxy-2,5,7,8-tetramethylchromo-2-carboxylic acid, and their derivatives.

[0145] In some embodiments, the sterically hindered phenol is selected from branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-phenylpropionate, octadecyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate. 13 -C 15 At least one of alkyl esters, polyethylene glycol ether esters capped with phenol derivatives, 2,4-dimethyl-6-(1-methylpentadecanyl)phenol, and 4,6-bis(octylthiomethyl)-o-cresol.

[0146] In some embodiments, the sulfide is at least one selected from formula (III):

[0147]

[0148] in

[0149] R 4 Selected from C1-C 20 Alkylene or C3-C 12 Cycloalkylene groups, optionally substituted with hydroxyl, amino, aryl, alkyl, aryloxy, alkoxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom and / or heterocyclic groups, and

[0150] R 5 Selected from C1-C 18 C2-C spaced by alkyl groups, and interposed by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups. 18 Alkyl, C6-C 12 Aryl or C5-C 12Cycloalkyl groups, optionally substituted with hydroxyl, amino, aryl, alkyl, aryloxy, alkoxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom and / or heterocyclic groups.

[0151] In some embodiments, the thioether is at least one selected from di-dodecyl thiodipropionate, di-octadecyl thiodipropionate, di-tetrazyl thiodipropionate, dimyristyl thiodipropionate, and 2,2-bis[[3-dodecylthio-1-oxopropoxy]methyl]-1,3-propylene di[3-dodecylthiopropionate].

[0152] In some embodiments, the phosphite is at least one selected from formula (IV):

[0153] P(OR 6 (OR) 7 (OR) 8 (IV)

[0154] in

[0155] R 6 R 7 and R 8 Each is independently selected from C1-C 18 Alkyl, C6-C 12 Aryl or C5-C 12 Cycloalkyl groups, optionally substituted with hydroxyl, amino, aryl, alkyl, aryloxy, alkoxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom and / or heterocyclic groups.

[0156] In some embodiments, the phosphite is a polymeric phosphite having the structure of formula (V):

[0157]

[0158] in

[0159] R 9 R 10 R 11 and R 12 Each can be the same or different and is independently selected from C. 1-20 Alkyl, C 3-22 Alkenyl, C 6-40 cycloalkyl, C 7-40 Cycloalkylene, C 1-20 Methoxyalkyl glycol ethers, C 1-20 Alkyl glycol ethers and / or Y-OH (used as end-capping structural moiety);

[0160] Y is selected from C 2-40 Alkylene, C 2-40Alkyl lactones (e.g., ethylidene, propyleneide, octyl lactone), -R 13 -N(R 14 )-R 15 -(e.g., C) 2-40 Alkyldiamine and C 2-40 Alkyltriamine),

[0161] Where R 13 R 14 and R 15 Independently selected from the preceding R 9 R 10 R 11 and R 12 The defined groups now further include H;

[0162] m is an integer value in the range of 2-100; and

[0163] x is an integer value in the range of 1 to 1,000.

[0164] In some embodiments, the polymeric phosphite is a polymeric diphosphite having the structure of formula (VI):

[0165]

[0166] in

[0167] R 9 R 10 R 11 and R 12 Each as defined above;

[0168] Y is as defined above; and

[0169] m is as defined above.

[0170] In some embodiments, the phosphite is selected from tri-dodecyl phosphite, a mixture of 2,4-di(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyltriesters (CAS: 939402-02-5), 3,9-diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 4,4'-butylene di(3-methyl-6-tert-butylphenylalkyl)phosphite, and C 13 At least one of esters and poly(dipropylene glycol) phenyl phosphite (CAS: 116265-68-0).

[0171] In some embodiments, the diisocyanate stabilizer comprises a hindered phenol, a thioether, and a phosphite, wherein the hindered phenol includes branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-phenylpropionate, octadecyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate. 13 -C 15 Alkyl esters, polyethylene glycol ether esters capped with phenol derivatives, 2,4-dimethyl-6-(1-methylpentadecanyl)phenol, and 4,6-di(octylthiomethyl)-o-cresol; the sulfides include di-dodecyl 3,3'-thiodipropionate, di-octadecyl 3,3'-thiodipropionate, di-tetrazyl 3,3′-thiodipropionate, dimyristyl thiodipropionate, and 2,2-di[[3-dodecylthio-1-oxopropoxy]methyl]-1,3-propylene di[3-dodecylthiopropionate] ; and phosphites include tri-dodecyl phosphite, a mixture of 2,4-di(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyltriesters of phosphite (CAS: 939402-02-5), poly(dipropylene glycol) phenyl phosphite (CAS: 116265-68-0), 3,9-diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and 4,4'-butylene di(3-methyl-6-tert-butylphenylalkyl)phosphite (C 13 Ester; hindered phenols are present in an amount of 10-90% by weight, thioethers are present in an amount of 5-80% by weight and phosphites are present in an amount of 5-80% by weight, in each case based on the total weight of the diisocyanate stabilizer.

[0172] In some embodiments, the diisocyanate stabilizer comprises a hindered phenol, a thioether, and a phosphite, wherein the hindered phenol comprises branched C7-C9 alkyl esters of 3,5-bis(1,1-dimethylethyl)-4-phenylpropionate and octadecyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; the thioether comprises di-dodecyl ester of 3,3'-thiodipropionate and di-tetrazyl ester of 3,3'-thiodipropionate; and the phosphite comprises tri-dodecyl phosphite and a mixture of 2,4-bis(1,1-dimethyl)phosphite. Propyl)phenyl and 4-(1,1-dimethylpropyl)phenyltriester (CAS: 939402-02-5), poly(dipropylene glycol) phenyl phosphite (CAS: 116265-68-0) and 3,9-diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; the amount of hindered phenol is 10-90% by weight, the amount of thioether is 5-80% by weight and the amount of phosphite is 5-80% by weight, based on the total weight of the diisocyanate stabilizer in each case.

[0173] In some embodiments, the diisocyanate stabilizer is present in an amount of 0.08-0.5% by weight based on the total weight of the diisocyanate composition. In some preferred embodiments, the diisocyanate stabilizer is present in an amount of 0.1-0.4% by weight, more preferably 0.15-0.35% by weight based on the total weight of the diisocyanate composition.

[0174] Using the preferred dosage range described above, this diisocyanate stabilizer can economically impart sufficient stability to the diisocyanate without adversely affecting its appearance.

[0175] This diisocyanate composition can be prepared using conventional methods in the art. For example, a diisocyanate stabilizer according to the first aspect of this disclosure can be prepared in advance, added to the diisocyanate in an appropriate dose, and then mixed for a certain period of time. Alternatively, a certain amount of hindered phenol, thioether, and phosphite can be added directly to the diisocyanate sequentially or simultaneously, and then mixed for a certain period of time. The resulting diisocyanate composition can be stored for a long time and under heating conditions without affecting its color and transparency.

[0176] This disclosure is further illustrated by the following embodiments. Example

[0177] Material

[0178] Diisocyanate: Monomer MDI (4,4'-diisocyanate diphenylmethane) ME, BASF)

[0179] Stabilizer: Steric hindered phenol:

[0180] 3,5-Bis(1,1-dimethylethyl)-4-phenylpropionic acid branched C7-C9 alkyl esters (from BASF) 1135)

[0181] 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl ester (from BASF SE) 1076)

[0182] 2,6-Di-tert-butyl-4-methylphenol (BHT, SCRC)

[0183] Sulfides:

[0184] Di-dodecyl 3,3'-thiodipropionate (DLTDP, from BASF) PS 800)

[0185] Di-tetrazyl 3,3′-thiodipropionate (DTDTP, from Songwon International AG) DTDTP)

[0186] Phosphite:

[0187] Tri-dodecyl phosphite (CCP STAB 3012T, CCP)

[0188] 3,9-Diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane (CCP STAB 508T, CCP)

[0189] Test methods

[0190] Transmission intensity is measured according to the following standards or procedures:

[0191] Prepare samples according to the following embodiments and store the resulting samples in transparent glass vials;

[0192] Images of each sample were captured by a charge-coupled device (CCD) camera; and

[0193] The light transmission intensity value of each sample is calculated based on the electron charge measured by a CCD camera.

[0194] A charge-coupled device (CCD) is an integrated circuit containing an array of connected or coupled capacitors. A CCD camera allows incident photons to be converted into electronic charges. The value of the electronic charge depends on the intensity of the light incident on the CCD. Therefore, the light transmission intensity of each sample can be calculated from the electronic charge measured by the CCD camera.

[0195] Examples of preparation of diisocyanate stabilizers (Examples 1-7)

[0196] Example 1:

[0197] 1) Take 90g (90% by weight) 1135g and 5g (5% by weight) of CCP STAB 3012T were added to a beaker and mixed thoroughly at room temperature;

[0198] 2) Add 5g (5% by weight) of DLTDP to the liquid mixture above; and

[0199] 3) Heat to 45°C, maintain this temperature and stir for 30 minutes to obtain a diisocyanate stabilizer that is liquid at room temperature (e.g., 20-25°C).

[0200] Example 2:

[0201] 1) Take 10g (10% by weight) 1135g and 80g (80% by weight) of CCP STAB 3012T were added to a beaker and mixed thoroughly at room temperature;

[0202] 2) Add 10g (10% by weight) of DLTDP to the liquid mixture above; and

[0203] 3) Heat to 45°C, maintain this temperature and stir for 30 minutes to obtain a diisocyanate stabilizer that is liquid at 45°C.

[0204] Example 3:

[0205] 1) Take 25g (25% by weight) 1135g and 25g (25% by weight) of CCP STAB 3012T were added to a beaker and mixed thoroughly at room temperature;

[0206] 2) Add 50g (50% by weight) of DLTDP to the liquid mixture above; and

[0207] 3) Heat to 45°C, maintain this temperature and stir for 30 minutes to obtain a diisocyanate stabilizer that is liquid at 45°C.

[0208] Example 4:

[0209] 1) Take 90g (90% by weight) 1076 and 5g (5% by weight) of CCP STAB 3012T were added to a beaker and mixed thoroughly at room temperature;

[0210] 2) Add 5g (5% by weight) of DLTDP to the liquid mixture above; and

[0211] 3) Heat to 45°C, maintain this temperature and stir for 30 minutes to obtain a diisocyanate stabilizer that is liquid at 50°C.

[0212] Example 5:

[0213] 1) Take 50g (50% by weight) 1135g and 30g (30% by weight) of CCP STAB 508T were added to a beaker and mixed thoroughly at room temperature;

[0214] 2) Add 20g (20% by weight) of DLTDP to the liquid mixture above; and

[0215] 3) Heat to 45°C, maintain this temperature and stir for 30 minutes to obtain a diisocyanate stabilizer that is liquid at 45°C.

[0216] Example 6:

[0217] 1) Take 10g (10% by weight) 1135 and 10g (10% by weight) of CCP STAB 3012T were added to a beaker and mixed thoroughly at room temperature; and

[0218] 2) Add 80g (80% by weight) of DTDTP to the liquid mixture above and stir for 30 minutes to obtain a diisocyanate stabilizer that is liquid at room temperature.

[0219] Example 7:

[0220] 1) Take 10g (10% by weight) 1135 and 30g (30% by weight) of CCP STAB 3012T were added to a beaker and mixed thoroughly at room temperature; and

[0221] 2) Add 60g (60% by weight) of DTDTP to the liquid mixture above and stir for 30 minutes to obtain a diisocyanate stabilizer that is liquid at room temperature.

[0222] Examples of preparation of diisocyanate compositions (Ex. ag and Ex. a'-g'):

[0223] The diisocyanate stabilizers prepared according to Examples 1-7 were added to monomeric MDI at 45°C and mixed thoroughly to obtain diisocyanate compositions ag (containing 0.3% by weight of diisocyanate stabilizer based on the total weight of the diisocyanate composition) and a'-g' (containing 0.1% by weight of diisocyanate stabilizer based on the total weight of the diisocyanate composition).

[0224] Comparison of diisocyanate compositions (Comp.Ex.h and i):

[0225] For comparative purposes, BHT and DLTDP were added to monomeric MDI at 45°C and mixed thoroughly to obtain diisocyanate compositions. Specifically, the diisocyanate composition of Comparative Example h contained BHT; and the diisocyanate composition of Comparative Example i contained DLTDP.

[0226] The dosage of the diisocyanate stabilizer in each diisocyanate composition, as well as the transmittance and appearance of each diisocyanate composition, are shown in Tables 1-3.

[0227] The higher the transmission intensity, the higher the transparency and the lower the yellowness.

[0228] The appearance of the diisocyanate compositions was evaluated on a scale of 1 to 5, where 1 indicates colorless and transparent, and 5 indicates cloudy and strong yellow. The lower the value, the higher the transparency and the less yellow.

[0229] Table 1. Transmission intensity of various diisocyanate compositions containing 0.3% by weight of diisocyanate stabilizer

[0230]

[0231] Table 2. Appearance of each diisocyanate composition containing 0.3% by weight of diisocyanate stabilizer

[0232]

[0233]

[0234] Table 3. Appearance of each diisocyanate composition containing 0.1% by weight of diisocyanate stabilizer

[0235]

[0236] As can be seen from Tables 1-3, compared with comparative examples h and i, the diisocyanate compositions (Ex. ag and Ex. a'-g') containing the diisocyanate stabilizer according to the present disclosure exhibit excellent stability in terms of both color and transparency. Specifically, the diisocyanate compositions containing the diisocyanate stabilizer according to the present disclosure can remain colorless (pale yellow in some examples) and transparent (with very little deposition in some examples) after long-term storage (45°C, 14 days) and heating conditions (100°C, 24 hours).

[0237] Although embodiments and examples of this disclosure have been described above, those skilled in the art should understand that they are for illustrative purposes only and are not intended to limit the scope of this disclosure. The scope of this disclosure is defined by the appended claims. Those skilled in the art can make various modifications, equivalent substitutions, or improvements to these embodiments without departing from the scope and spirit of this disclosure, but such modifications, equivalent substitutions, or improvements fall within the scope of this disclosure.

Claims

1. A diisocyanate stabilizer comprising a hindered phenol (different from butylated hydroxytoluene), a thioether, and a phosphite (different from triphenyl phosphite). The sterically hindered phenol is selected from branched C7-C9 alkyl esters of 3,5-di(1,1-dimethylethyl)-4-hydroxyphenylpropionate, octadecyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and branched C7-C9 alkyl esters of 3,5-di(1,1-dimethylethyl)-4-hydroxyphenylpropionate. 13 -C 15 Alkyl esters, methyl 3,5-di-tert-butyl-4-hydroxybenzoate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl isocyanurate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-(4,6-di(octylthio)-1,3,5-triazine-2-ylamino) At least one of the following: phenol, hexadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, octyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, thiodiethylenedi[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], 4,8-dioxa-1,11-undecanediol di[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol di[(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate], and 1,9-nonanediol di[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]. The sulfide thereon is at least one selected from formula (III): in R 4 Selected from C1-C 20 Alkylene, and R 5 Selected from C1-C 18 alkyl, The phosphite thereon is at least one of 3,9-diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane and formula (IV): P(OR 6 )(OR 7 )(OR 8 ) (IV) Where R 6 R 7 and R 8 Each is independently selected from C1-C 18 alkyl, and The steric phenol is present in an amount of 35-85% by weight, based on the total weight of the diisocyanate stabilizer.

2. The diisocyanate stabilizer according to claim 1, wherein, based on the total weight of the diisocyanate stabilizer, the hindered phenol is present in an amount of 40-80% by weight, the thioether is present in an amount of 5-55% by weight, and the phosphite is present in an amount of 5-55% by weight.

3. The diisocyanate stabilizer according to claim 1 or 2, comprising a hindered phenol, a thioether, and a phosphite.

4. The diisocyanate stabilizer according to claim 1 or 2, wherein the diisocyanate stabilizer has a melting point below 50°C.

5. The diisocyanate stabilizer according to claim 1 or 2, wherein the diisocyanate stabilizer has a melting point below 20°C.

6. The diisocyanate stabilizer according to claim 1 or 2, wherein the sterically hindered phenol is selected from branched C7-C9 alkyl esters of 3,5-di(1,1-dimethylethyl)-4-hydroxyphenylpropionate, octadecyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and branched C7-C9 alkyl esters of 3,5-di(1,1-dimethylethyl)-4-hydroxyphenylpropionate. 13 -C 15 At least one of the following: alkyl ester, methyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, and octyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate.

7. The diisocyanate stabilizer according to claim 1 or 2, wherein the hindered phenol is selected from branched C7-C9 alkyl esters of 3,5-di(1,1-dimethylethyl)-4-hydroxyphenylpropionate, octadecyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and branched C7-C9 alkyl esters of 3,5-di(1,1-dimethylethyl)-4-hydroxyphenylpropionate. 13 -C 15 At least one of alkyl esters.

8. The diisocyanate stabilizer according to claim 1 or 2, wherein the thioether is at least one selected from formula (III): in R 4 Selected from methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,1-dimethyl-1,2-ethylene or 1,2-dimethyl-1,2-ethylene, 1,6-hexylene, 1,8-octylene and 1,10-decylene, and R 5 Selected from C1-C 18 alkyl.

9. The diisocyanate stabilizer according to claim 1 or 2, wherein the thioether is at least one selected from di-dodecyl 3,3'-thiodipropionate, di-octadecyl 3,3'-thiodipropionate, di-tetrazyl 3,3'-thiodipropionate, and dimyristyl 3,3'-thiodipropionate.

10. The diisocyanate stabilizer according to claim 1 or 2, wherein the phosphite is at least one selected from formula (IV): P(OR 6 )(OR 7 )(OR 8 ) (IV) in R 6 R 7 and R 8 Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl.

11. The diisocyanate stabilizer according to claim 1 or 2, wherein the phosphite is at least one selected from tri-dodecyl phosphite and 3,9-diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane.

12. The diisocyanate stabilizer according to claim 1 or 2, wherein the hindered phenol is selected from branched C7-C9 alkyl esters of 3,5-di(1,1-dimethylethyl)-4-hydroxyphenylpropionate, octadecyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and branched C7-C9 alkyl esters of 3,5-di(1,1-dimethylethyl)-4-hydroxyphenylpropionate. 13 -C 15 At least one of the alkyl esters; the thioether is selected from at least one of di-dodecyl thiodipropionate, di-octadecyl thiodipropionate, di-tetrazyl thiodipropionate, and dimyristyl thiodipropionate; and the phosphite is selected from at least one of tri-dodecyl phosphite and 3,9-diisodecoxy-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane.

13. Use of the diisocyanate stabilizer according to any one of claims 1-12 in stabilizing diisocyanates.

14. A diisocyanate composition comprising: (A) diisocyanate, and (B) A diisocyanate stabilizer according to any one of claims 1-12.

15. The diisocyanate composition of claim 14, wherein the diisocyanate stabilizer is present in an amount of 0.08-0.5% by weight based on the total weight of the diisocyanate composition.

16. The diisocyanate composition of claim 14, wherein the diisocyanate stabilizer is present in an amount of 0.1-0.4% by weight based on the total weight of the diisocyanate composition.

17. The diisocyanate composition of claim 14, wherein the diisocyanate stabilizer is present in an amount of 0.15-0.35% by weight based on the total weight of the diisocyanate composition.

18. The diisocyanate composition according to any one of claims 14-17, wherein the diisocyanate is an aromatic diisocyanate.

19. The diisocyanate composition according to claim 18, wherein the aromatic diisocyanate is selected from at least one of toluene-2,4- or 2,6-diisocyanate and mixtures of its isomers, meta- or terephthalimide diisocyanate, 2,4'- or 4,4'-diisocyanate-diphenylmethane and mixtures of its isomers, 1,3- or 1,4-phenyl diisocyanate, 1-chlorobenzene-2,4-diisocyanate, naphthalene-1,5-diisocyanate, biphenyl-4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethylbiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, tetramethylphenylmethylene diisocyanate, 1,4-diisocyanate-benzene, or 4,4'-diisocyanate-diphenyl ether.

20. The diisocyanate composition of claim 18, wherein the aromatic diisocyanate is at least one selected from toluene-2,4- or 2,6-diisocyanate and mixtures of its isomers, meta- or terephthalimide diisocyanate, 2,4'- or 4,4'-diisocyanate-based diphenylmethane and mixtures of its isomers.

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