Diisocyanate stabilizers, their use, and diisocyanate compositions

Abstract

The present disclosure relates to diisocyanate stabilizers, the use of the diisocyanate stabilizers to stabilize diisocyanates, and diisocyanate compositions containing the stabilizers. The diisocyanate stabilizers include sterically hindered phenols, thioethers, and phosphites. The present disclosure aims to provide a diisocyanate stabilizer that can keep diisocyanates stable under long-term storage and heating conditions.

Description

[Technical Field]

[0001] This disclosure relates to diisocyanate stabilizers, the use of diisocyanate stabilizers for stabilizing diisocyanates, and diisocyanate compositions comprising the stabilizers. [Background technology]

[0002] Diisocyanates are important intermediates in organic synthesis, such as in the preparation of polyurethane resins. However, due to the high reactivity of the isocyanate group, diisocyanates tend to yellow and / or become turbid during storage due to self-polymerization, which affects their applications in downstream industries. To prevent the yellowing and / or turbidity of diisocyanates, those skilled in the art typically add a certain amount of antioxidant to the diisocyanates.

[0003] For example, U.S. Patent No. 3,555,072 discloses a process for suppressing discoloration and turbidity of toluene diisocyanate (TDI), which includes adding a stabilizing amount of a thioether compound.

[0004] However, the long-term thermal stability of the TDI solution obtained according to U.S. Patent No. 3,555,072 is poor. To extend the thermal stability, those skilled in the art may increase the amount of thioether, but this causes an odor problem in the TDI, which is also unacceptable. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Therefore, in this field, there is still a need to provide stabilizers for diisocyanates that enable diisocyanates to remain colorless and transparent even after long-term storage. [Means for solving the problem]

[0006] This disclosure provides a diisocyanate stabilizer that solves, or at least partially solves, the above-mentioned problems or other potential problems for stabilizing diisocyanates present in the prior art.

[0007] Specifically, in the first embodiment, this disclosure is: Other than butylated hydroxytoluene Sterilely hindered phenols, thioethers and Other than triphenylphosphite The present invention provides a diisocyanate stabilizer containing a phosphite.

[0008] In some embodiments, in each case, based on the total weight of the stabilizers, sterically hindered phenol is present in an amount of 10 to 90% by weight, thioether is present in an amount of 5 to 80% by weight, and phosphite is present in an amount of 5 to 80% by weight.

[0009] In other embodiments, the diisocyanate stabilizer consists of sterically hindered phenols, thioethers, and phosphites.

[0010] The inventors of this disclosure have surprisingly found that sterically hindered phenols, thioethers, and phosphites work synergistically to effectively prevent the autopolymerization of diisocyanates. By combining sterically hindered phenols, thioethers, and phosphites, this disclosure provides a stabilizer that can prevent diisocyanates from yellowing and / or becoming turbid under long-term storage and heating conditions. The stabilizer of this disclosure effectively solves the problem that diisocyanates are prone to yellowing and / or becoming turbid under long-term storage and heating conditions.

[0011] In some preferred embodiments, the diisocyanate stabilizer has a melting point below 50°C, preferably below 20°C. For example, the diisocyanate stabilizer may have a melting point of 50°C, 45°C, 40°C, 35°C, 30°C, 25°C, 20°C, or below 10°C. In these preferred embodiments, the diisocyanate stabilizer is liquid at the operating temperature (typically 45°C to 50°C) to facilitate automated production, thereby improving production efficiency. Furthermore, if the diisocyanate stabilizer has a melting point below 20°C and is therefore liquid below 20°C, it further facilitates the transport of the diisocyanate stabilizer at low temperatures.

[0012] In a second embodiment, the Disclosure provides the use of a stabilizer according to the first embodiment of the Disclosure for stabilizing a diisocyanate.

[0013] In a third embodiment, this disclosure is, (A) Diisocyanate and (B) Diisocyanate stabilizers according to the first aspect of the present disclosure The present invention provides a composition containing the following:

[0014] The inventors of this disclosure have surprisingly found that the resulting diisocyanate compositions can maintain (substantially) transparency and colorlessness under long-term storage and heating conditions, thereby significantly expanding the range of applications for diisocyanates. Therefore, the diisocyanate compositions of this disclosure may be suitable for applications with high requirements in terms of color and transparency.

[0015] Compared to prior art, the advantageous technical effects that the diisocyanate stabilizers of this disclosure bring to diisocyanates during long-term storage and heating conditions (e.g., melting processes with a temperature of approximately 100°C) include, but are not limited to, the following: (1) The diisocyanate composition has a brighter color; (2) The diisocyanate composition has higher transparency; and (3) The diisocyanate composition maintains a brighter color and higher transparency.

[0016] It should be understood that the summary of the invention is not intended to determine any important or fundamental features of the disclosure, nor is it intended to limit the scope of the disclosure. Other features of the disclosure will be readily apparent from the following description. [Modes for carrying out the invention]

[0017] In the following description, the disclosure will be further illustrated with reference to embodiments to facilitate a thorough understanding for those skilled in the art. These embodiments are provided solely for the purpose of better understanding the subject matter of the disclosure and are not intended to impose any limitations on the scope, applicability, or embodiments described in the claims. Those skilled in the art will understand that, without departing from the spirit of the disclosure, various technical features may be omitted, substituted, or added to each embodiment on a case-by-case basis. Furthermore, technical features described in some embodiments may be combined with those described in other embodiments.

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which this disclosure pertains.

[0019] In this disclosure, the terms “comprise,” “comprisin,” and their various variations can be understood as open-ended terms meaning “comprise but not limited to.” In contrast, the terms “consisting of,” and their various variations exclude any components, steps, or procedures not specifically described. The term “one embodiment” can be understood as “at least one embodiment,” and the term “another embodiment” can be understood as “at least one other embodiment.” Other terms that may appear but are not explicitly mentioned herein should not be interpreted or limited in a manner contrary to the concepts on which the embodiments of this disclosure are based, unless expressly stated otherwise.

[0020] Throughout this disclosure, the expressions “a,” “an,” “the,” and “one or more” are used interchangeably and are intended to include both singular and plural forms unless the singular form is explicitly specified or clearly indicated in the context. Where only the singular form is intended, the term “one” is usually used. The term “or” is also intended to generally include the meaning of “and / or” unless the context clearly indicates otherwise. As used herein, “preferred,” “preferable,” and “preferably” refer to embodiments of the disclosure that may provide particular advantages under certain circumstances. However, other embodiments may also be preferred under the same circumstances. Furthermore, the description of one or more preferred embodiments does not mean that other embodiments are not useful and is not intended to exclude other embodiments from the scope of this disclosure.

[0021] All percentages, parts, and ratios are expressed by weight unless otherwise specified. Furthermore, numerical ranges with fractional values ​​include all values ​​within that range (for example, 5-10 includes 5, 5.1, 5.2, 5.55, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, and 10).

[0022] In this disclosure, "diisocyanate stabilizer" refers to a mixture / composition capable of stabilizing diisocyanate against internal or external influencing factors. Regarding internal factors, as described above, diisocyanate tends to self-polymerize due to its highly reactive groups. Regarding external factors, diisocyanate is susceptible to the effects of heat, light, etc. Diisocyanate stabilizers are provided to stabilize diisocyanate from the viewpoint of color stability, transparency, etc. The diisocyanate stabilizer makes it possible for diisocyanate to maintain its colorless and transparent state even under long-term storage and heating conditions.

[0023] Throughout this disclosure, the terms “phosphite” and “phosphate” are used interchangeably and are intended to include both the plural and singular forms unless the singular form is explicitly specified or clearly indicated by the context.

[0024] The term "glycol" refers to an aliphatic diol containing two hydroxyl groups (-OH groups) bonded to different carbon atoms.

[0025] The term "color stability" means that the color of the diisocyanate composition does not change, or changes only slightly, during long-term storage, even under heating conditions. For example, the diisocyanate compositions of this disclosure can maintain their colorless or pale yellow state during long-term storage and under heating conditions.

[0026] As used herein, the term “transmission intensity” refers to the proportion of light transmitted through an object. For example, in embodiments of this disclosure, it refers to the proportion of light transmitted through a glass vial containing a diisocyanate composition.

[0027] As mentioned above, diisocyanates are important intermediates in many organic synthesis processes, for example, they are intermediates for the preparation of polyurethane resins. However, because diisocyanates have highly reactive groups, they readily undergo self-polymerization and are therefore prone to turbidity during storage. This problem exists for various diisocyanates, including aliphatic, alicyclic, and aromatic diisocyanates.

[0028] I. Diisocyanate stabilizers In light of the existing difficulties in stabilizing diisocyanates in the prior art, in a first embodiment, this disclosure provides: Other than butylated hydroxytoluene Sterilely hindered phenols, thioethers and Other than triphenylphosphite The present invention provides a diisocyanate stabilizer containing a phosphite.

[0029] The inventors of this disclosure have surprisingly found that sterically hindered phenols, thioethers, and phosphites work synergistically to effectively prevent the autopolymerization of diisocyanates. By combining sterically hindered phenols, thioethers, and phosphites, this disclosure provides a stabilizer that can prevent diisocyanates from yellowing and / or becoming turbid under long-term storage and heating conditions (e.g., a melting process at a temperature of about 100°C). The stabilizer of this disclosure effectively solves the problem that diisocyanates are prone to yellowing and becoming turbid under long-term storage and heating conditions.

[0030] Steriohed phenol Examples of sterically hindered phenols include phenols having one or more phenolic hydroxyl groups on an aromatic ring, preferably those having substituents at the ortho position, most preferably at the ortho and para positions relative to the phenolic hydroxyl group, and preferably alkyl groups.

[0031] Please understand that the above description is not intended to limit the range of sterically hindrance phenols that are appropriate for this disclosure. 。

[0032] Suitable phenols include alkylphenols, e.g., 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'-oxydiphenol, 3,4-methylenedioxydiphenol (sesamol), 3,4-dimethylphenol, hydroquinone, tert-butylhydroquinone, 2,5- Di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, pyrocatechol (1,2-dihydroxybenzene), 2-(1'-methylcyclohexe-1'-yl)-4,6-dimethylphenol, 2-or-4-(1'-phenylethe-1'-yl)phenol, 2-tert-butyl-6-methylphenol, 2,4,6-tris-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, BASF Koresin (registered trademark) from 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, n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,46-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 or pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxybenzyl) [Droxyphenyl)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-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, hexadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate Phenyl)propionate, octyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 3-thia-1,5-pentanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3'-tert-butyl-4'-hydroxy-5'-methyl [3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 1,9-nonanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 1,7-heptanediamine bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 1,1-methanediamine bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionoic hydrazide, 3-(3',5'-dimethyl-4'-hydroxyphenyl)propionoic hydrazide, bis(3-tert-butyl-5-ethyl-2-hydroxyphen-1-yl)methane, bis(3,5-di-tert-butyl-4-hydroxyphen-1-yl)methane, bis[3-(1'-methylcyclohexe-1'-yl)-5-methyl-2-hydroxyphen-1-yl]methane, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl)methane, 1,1-bis( 5-tert-butyl-4-hydroxy-2-methylphen-1-yl)ethane, bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl) sulfide, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl) sulfide, 1,1-bis(3,4-dimethyl-2-hydroxyphen-1-yl)-2-methylpropane, 1,1-bis(5-tert-butyl-3-methyl-2-hydroxyphen-1-yl)butane, 1,3, 5-Tris[1'-(3'',5''-di-tert-butyl-4''-hydroxyphen-1''-yl)-methyl-1'-yl]-2,4,6-trimethylbenzene, 1,1,4-Tris(5'-tert-butyl-4'-hydroxy-2'-methylphen-1'-yl)butane, aminophenols, e.g., para-aminophenol, 3-diethylaminophenol, nitrosophenols, e.g., para-nitrosophenol, p-nitroso-o-cresol, alkoxyphenols, e.g., 2-methoxyphenol (guajacol, 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 (syringa alcohol), 4-hydroxy-3-methoxybenzaldehyde (vanillin), 4-hydroxy-3-ethoxybenzaldehyde (ethyl vanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1-(4-hydroxy-3-methoxyphenyl)ethanone (acetovanillone), eugenol, dihydroeugenol, isoeugenol, tocopherol, e.g., α-, β-, γ-, δ- and ε-tocopherol, toco Examples include α-tocopherol hydroquinone, 4-methylpyrocatechol, 3-methylpyrocatechol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2,5-di-tert-amylhydroquinone, 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumaran), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox®) and their derivatives.

[0033] Corresponding sterically hindered phenol products include, for example, trade names Irganox® (BASF), such as pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (e.g., Irganox® 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., Irganox® 3114), and thiodiethylene bis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate] (e.g., Irganox® 10 35) 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, branched C7-C9 alkyl ester (e.g., Irganox® 1135), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g., Irganox® 1076), ester of polyglycol ethers terminated with phenol derivatives (e.g., Irganox® 2000), 4,6-bis(octylthiomethyl)-o-cresol (e.g., Irganox® 1520); 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, branched C 13 ~C 15 -Available as alkyl esters (e.g., Anox® 1315).

[0034] The above examples of sterically hindrance phenols are for illustrative purposes only and should not be used to limit the scope of protection of this disclosure. Any other suitable sterically hindrance phenols are also applicable.

[0035] In some preferred embodiments, sterically hindered phenols include those having a melting point below 55°C, such as sterically hindered phenols having melting points of 20°C, 25°C, 30°C, 40°C, 45°C, 50°C, or below 55°C. Such sterically hindered phenols allow the stabilizer to be liquid at the operating temperature (typically 45°C to 50°C), thereby facilitating automated production.

[0036] In preferred embodiments, the sterically hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, branched C7-C9 alkyl ester (e.g., Irganox® 1135), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g., Irganox® 1076), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid, branched C 13 ~C 15 The phenol is selected from the group consisting of alkyl esters (e.g., Anox® 1315), esters of polyglycol ethers terminated with phenol derivatives (e.g., Irganox® 2000), and 4,6-bis(octylthiomethyl)-o-cresol (e.g., Irganox® 1520). These preferred sterically hindered phenols are harmless to the human body and are therefore safer and more environmentally friendly.

[0037] In a more preferred embodiment, the sterically hindered phenol is at least one selected from the group consisting of 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, branched C7-C9 alkyl esters (e.g., Irganox® 1135), and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g., Irganox® 1076). These more preferred sterically hindered phenols are liquids or solids having a low melting point, which allows the stabilizer to be liquid at room temperature or a typical operating temperature (e.g., 45°C).

[0038] Preferably, the sterically hindered phenol does not contain butylated hydroxytoluene (BHT) because BHT is highly volatile and therefore limited in many applications.

[0039] thioether The thioethers used in accordance with the present disclosure include compounds containing at least one thioether group, i.e., a sulfur atom 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 of the present disclosure. In the present disclosure, the thioethers are not limited.

[0040] Suitable thioethers are of formula (I) R 1 -S-R 2 (I) (wherein R 1 and R 2 are each independently of the other, C1-C 18 -alkyl, C2-C interrupted by one or more oxygen atoms 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, and the above groups may be optionally substituted by hydroxy, amino, aryl, alkyl, aryloxy, alkyloxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocycle, heteroatom and / or heterocycle).

[0041] Here, R 1 and R 2 can each independently of the other be selected from the group consisting of the following groups: 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-heptadecyl, n-octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, benzaldehyde L, p-tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxolan-2-yl Xollan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 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 Pill, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 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; 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-Trioxapentadecyl, 9-Hydroxy-5-Oxanonyl, 14-Hydroxy-5,10-Oxatetradecyl, 5-Hydroxy-3-oxapentyl, 8-Hydroxy-3,6-Dioxaoctyl, 11-Hydroxy-3,6,9-Trioxaundecyl, 7-Hydroxy-4-Oxaheptyl, 1 1-Methoxy-4,8-dioxaundecyl, 15-Methoxy-4,8,12-trioxapentadecyl, 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-trioxapentadecyl, 9-Ethoxy-5-oxanonyl, or 14-Ethoxy-5,10-oxatetradecyl; 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; Phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, 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; 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 Furyl, thiophenyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl, or tert-butylthiophenyl.

[0042] In some embodiments, the thioether is 2-methyl-1-propenyl tert-dodecyl thioether, cyclohexylidene methyl-n-dodecyl thioether, 3-cyclohexene-(1)-ylidene methyl-n-octadecyl thioether, 3-cyclohexene-(1)-ylidene methyl-n-dodecyl thioether, 3-cyclohexene-(1)-ylidene methyl-n-octyl thioether, 3-cyclohexene-(1)-ylide The following are selected from the group consisting of n-methylcyclohexylthioether, 3-methyl-(3)-cyclohexen-(1)-ylidenemethyl-n-dodecylthioether, 3-cyclohexen-(1)-ylidenemethyl-p-tolylthioether, 3-cyclohexen-(1)-ylidenemethylbenzylthioether, preferably 3-cyclohexen-(1)-ylidenemethyl-n-dodecylthioether and 1-hexenyl-n-dodecylthioether.

[0043] In other embodiments, the thioether is given by formula (II) [ka] (In the formula, R 3 and R 5 These are, C1~C, which are independent of each other. 18 -C2-C2 suspended by alkyl, one or more oxygen atoms and / or sulfur atoms, and / or one or more substituted or unsubstituted imino groups 18 -alkyl, C6~C 12 - Aryl or C5~C 12 -It can be cycloalkyl, and the above group is optionally substituted with hydroxy, amino, aryl, alkyl, aryloxy, alkyloxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom and / or heterocyclic, and R 4 C1~C 20 -Alkylene or C3~C 12-It can be a cycloalkylene, and the above group has a structure in which it is optionally substituted with hydroxy, amino, aryl, alkyl, aryloxy, alkyloxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom and / or heterocyclic groups.

[0044] Here, R 3 and R 5 Each of these can be independently selected from the following group of elements: 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-heptadecyl, n-octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, benzaldehyde L, p-tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxolan-2-yl Xollan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 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 Pill, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 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; 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-Trioxapentadecyl, 9-Hydroxy-5-Oxanonyl, 14-Hydroxy-5,10-Oxatetradecyl, 5-Hydroxy-3-oxapentyl, 8-Hydroxy-3,6-Dioxaoctyl, 11-Hydroxy-3,6,9-Trioxaundecyl, 7-Hydroxy-4-Oxaheptyl, 1 1-Methoxy-4,8-dioxaundecyl, 15-Methoxy-4,8,12-trioxapentadecyl, 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-trioxapentadecyl, 9-Ethoxy-5-oxanonyl, or 14-Ethoxy-5,10-oxatetradecyl; Phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, 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 Cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, or saturated or unsaturated bicyclic compounds, such as norbornyl or norbornenyl.

[0045] Here, R 4 The group can be selected from the following groups: 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, 1,10-decylene, 1,12-dodecylene and 1,20-eicosilene, and Cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene, and cyclododecylene.

[0046] In some preferred embodiments, R 3 C6~C is an arbitrarily substituted C6~C12 - Aryl or C1~C 18 -alkyl, preferably optionally substituted C1-C 18 -alkyl, particularly preferably unsubstituted C1-C 18 -It is alkyl; R 5 C1~C are optionally substituted. 18 -alkyl, preferably unsubstituted C1-C 18 - is alkyl; and / or R 4 This is methylene, 1,2-ethylene, or 1,2-propylene, preferably 1,2-ethylene.

[0047] In some embodiments, formula (III) [ka] (In the formula, R 4 and R 5 Compounds having the structure (as defined above) are particularly preferred.

[0048] In some preferred embodiments, the thioethers include those having a melting point below 50°C, such as thioethers with melting points of 20°C, 25°C, 30°C, 40°C, 45°C, or below 50°C. Such thioethers allow the stabilizer to be liquid at the operating temperature (typically 45°C to 50°C), thereby facilitating automated production.

[0049] In a preferred embodiment, the thioether is at least one selected from the group consisting of thiodipropionates, e.g., dimethyl 3,3'-thiodipropionate, didodecyl 3,3'-thiodipropionate (DLTDP) (e.g., Irganox® PS800 from BASF), ditridecyl 3,3'-thiodipropionate (DTDTP) (e.g., Songnox® DTDTP from Songwon International AG), dioctadecyl 3,3'-thiodipropionate (DSTDP), dimyristylthiodipropionate (DMTDP), and 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]propane-1,3-diylbis[3-(dodecylthio)propionate] (e.g., Seenox 412S).

[0050] In a more preferred embodiment, the thioether is at least one selected from the group consisting of didodecyl 3,3'-thiodipropionate (DLTDP) and ditridecyl 3,3'-thiodipropionate (DTDTP). These more preferred thioethers are liquids or solids having a low melting point, which allows the stabilizer to be liquid at typical operating temperatures (e.g., 45°C to 50°C).

[0051] Phosphite Book Appropriate phosphites disclosed include, but are not limited to, monophosphites and polymeric phosphites.

[0052] Examples of suitable monophosphites in this disclosure include formula (IV) P(OR 6 )(OR 7 )(OR 8 ) (IV) (In the formula, R 6 , R 7 and R 8 These are, C1~C, which are independent of each other. 18 -alkyl, C6~C 12 - Aryl or C5~C 12-The compound may be cycloalkyl, and the above group may be optionally substituted with hydroxy, amino, aryl, alkyl, aryloxy, alkyloxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom and / or heterocyclic groups.

[0053] Here, R 6 , R 7 and R 8 Each of these can be independently selected from the following group of elements: 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-heptadecyl, n-octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, benzaldehyde L, p-tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxolan-2-yl Xollan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 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 Pill, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 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; Phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, 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 Cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, or saturated or unsaturated bicyclic compounds, such as norbornyl or norbornenyl.

[0054] Examples of suitable polymeric phosphites according to this disclosure include formula (V) [ka] (In the formula, Each R 9 , R 10 , R 11 and R 12These may be the same or different, and are independently selected from the group consisting of C1-20 alkyl, C3-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene, C1-20 methoxyalkyl glycol ether, C1-20 alkyl glycol ether, and / or Y-OH (which functions as a terminal capping moiety); Y is C2-40 alkylene, C2-40 alkyl lactone (e.g., ethylene, propylene, caprylactone), -R 13 -N(R 14 )-R 15 -Selected from the group consisting of (for example, C2-40 alkyldiamines and C2-40 alkyltriamines), Here, R 13 , R 14 , and R 15 R 9 , R 10 , R 11 , and R 12 It is selected independently from the group defined above, but here it further includes H; m is an integer value in the range of 2 to 100, and This includes structures where x is an integer value in the range of 1 to 1,000.

[0055] In some embodiments, alkyl, alkenyl, and cycloalkyl groups may be interrupted by oxygen, sulfur, or nitrogen.

[0056] In some preferred embodiments, the polymeric phosphite is poly(alkylene glycol)phenyl phosphite. More preferably, the poly(alkylene glycol)phenyl phosphite is poly(dipropylene glycol)phenyl phosphite (CAS: 116265-68-0), poly(propylene glycol)phenyl phosphite, or poly(ethylene glycol)phenyl phosphite.

[0057] In yet another preferred embodiment, the polymeric phosphite is of formula (VI) [ka] (In the formula, Each R 9 , R 10 , R 11 and R 12 This is as defined above; Y is as defined above; and It is a polymeric diphosphite having the structure m as defined above.

[0058] Preferably, the phosphites according to this disclosure are toridodecyl phosphite (e.g., CCP STAB 3012T), phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester (CAS: 939402-02-5; e.g., Weston 705), 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (e.g., CCP STAB 508T), 4,4'-butylidene-bis(3-methyl6-tert-butylphenyl)alkyl (C 13 The phosphites are selected from the group consisting of )-phosphites (e.g., CCP STAB AS-4500) and poly(dipropylene glycol)phenyl phosphite (CAS: 116265-68-0). These preferred phosphites are excellent for stabilizing the color of diisocyanates during the melting process.

[0059] More preferably, the phosphite is selected from the group consisting of toridodecyl phosphite (e.g., CCP STAB 3012T), phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester (CAS: 939402-02-5; e.g., Weston 705), 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (e.g., CCP STAB 508T), and poly(dipropylene glycol)phenyl phosphite (CAS: 116265-68-0).

[0060] Preferably, the phosphites according to this disclosure do not contain triphenyl phosphite (TPP), as TPP is restricted in many applications due to its high volatility and toxicity.

[0061] In some embodiments, the diisocyanate stabilizer has a melting point below 50°C, preferably below 20°C. For example, the diisocyanate stabilizer may have a melting point of 50°C, 45°C, 40°C, 35°C, 30°C, 25°C, 20°C, or below 10°C. In some embodiments, the diisocyanate stabilizer is solid at room temperature but liquid at 45°C to 50°C. If the diisocyanate stabilizer is liquid at the operating temperature (e.g., 45°C to 50°C), automated production is facilitated, and production efficiency can be effectively improved. Furthermore, if the diisocyanate stabilizer has a melting point below 20°C and is therefore liquid at temperatures below 20°C, the transport of the diisocyanate stabilizer at low temperatures is further facilitated.

[0062] Those skilled in the art can obtain liquid stabilizers having a melting point below 50°C by selecting appropriate sterically hindered phenols, thioethers, and / or phosphites according to their melting points, and / or by selecting appropriate amounts of each component. This disclosure does not impose any limitations on the amounts of these appropriate sterically hindered phenols, thioethers, phosphites, or stabilizers.

[0063] For example, in some embodiments, the sterically hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, branched C7-C9 alkyl ester, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid, branched C 13 ~C 15- At least one selected from the group consisting of alkyl esters, esters of polyglycol ethers terminated with phenol derivatives, 2,4-dimethyl-6-(1-methylpentadecyl)-phenol and 4,6-bis(octylthiomethyl)-o-cresol; the thioether is either didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, dimyristylthiodipropionate and 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]propyl The phosphite is at least one selected from the group consisting of ropane-1,3-diylbis[3-(dodecylthio)propionate]; the phosphite is toridodecyl phosphite, phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester (CAS: 939402-02-5), 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 4,4'-butylidene-bis(3-methyl6-tert-butylphenyl)alkyl(C 13 It is at least one selected from the group consisting of )-phosphite and poly(dipropylene glycol)phenylphosphite (CAS: 116265-68-0). In another embodiment, sterically hindered phenols include 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, branched C7-C9 alkyl esters, and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; thioethers include didodecyl 3,3'-thiodipropionate and ditridecyl 3,3'-thiodipropionate; phosphites include toridodecyl phosphite, phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester (CAS: 939402-02-5), as well as 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane and poly(dipropylene glycol)phenyl phosphite (CAS: 116265-68-0).

[0064] In the embodiments described above, the sterically hindered phenol and thioether are liquids or solids with low melting points, thereby allowing the diisocyanate stabilizer to be liquid at the operating temperature (typically 45°C to 50°C).

[0065] As stated above, the amount of sterically hindered phenol, thioether, or phosphite is not limited in this disclosure. Those skilled in the art can select an appropriate amount according to their actual needs.

[0066] For example, in some embodiments, in each case, based on the total weight of the stabilizers, sterically hindered phenol is present in an amount of 10 to 90% by weight, thioether is present in an amount of 5 to 80% by weight, and phosphite is present in an amount of 5 to 80% by weight.

[0067] In other embodiments, the sterically hindered phenol is present in amounts of 10 to 90% by weight, for example, 15 to 85%, 20 to 80%, 25 to 75%, 30 to 70%, 35 to 65%, 40 to 60%, or 45 to 55% by weight. For example, the amount of sterically hindered phenol may be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or any value or range in between.

[0068] In yet another embodiment, the thioether is present in an amount of 5 to 80% by weight, for example, 10 to 75% by weight, or 15 to 70% by weight, or 20 to 65% by weight, or 25 to 60% by weight, or 30 to 55% by weight, or 35 to 50% by weight, or 40 to 45% by weight. For example, the amount of thioether 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 in between.

[0069] In yet another embodiment, the phosphite is present in an amount of 5 to 80% by weight, for example, 10 to 75% by weight, or 15 to 70% by weight, or 20 to 65% by weight, or 25 to 60% by weight, or 30 to 55% by weight, or 35 to 50% by weight, or 40 to 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 in between.

[0070] In some preferred embodiments, the diisocyanate stabilizer comprises a sterically hindered phenol, a thioether, and a phosphite, where the sterically hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, a branched C7-C9 alkyl ester, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid, and a branched C 13 ~C 15 Examples include alkyl esters, esters of polyglycol ethers terminated with phenol derivatives, 2,4-dimethyl-6-(1-methylpentadecyl)-phenol and 4,6-bis(octylthiomethyl)-o-cresol; as thioethers, examples include didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, dimyristylthiodipropionate and 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]propyl Examples of phosphites include ropane-1,3-diylbis[3-(dodecylthio)propionate]; and to name a phosphite, toridodecyl phosphite, phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester (CAS: 939402-02-5), 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and 4,4'-butylidene-bis(3-methyl6-tert-butylphenyl)alkyl(C 13Examples include )-phosphites and poly(dipropylene glycol)phenyl phosphites (CAS: 116265-68-0); in each case, based on the total weight of the diisocyanate stabilizers, the sterically 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.

[0071] In a more preferred embodiment, the diisocyanate stabilizer comprises a sterically hindered phenol, a thioether, and a phosphite. Examples of sterically hindered phenols include 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, branched C7-C9 alkyl esters, and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; examples of thioethers include didodecyl 3,3'-thiodipropionate and ditridecyl 3,3'-thiodipropionate; and examples of phosphites include toridodecyl phosphite, phosphorous acid, and mixed 2,4- Examples include bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triesters (CAS: 939402-02-5), poly(dipropylene glycol)phenyl phosphite (CAS: 116265-68-0), and 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; in each case, based on the total weight of the diisocyanate stabilizer, the amount of sterically 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.

[0072] The following are some examples for 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 processes well known to those skilled in the art. For example, appropriate amounts of appropriate sterically hindered phenols, thioethers, and phosphites can be added sequentially or simultaneously, and then the composition can be heated and mixed at a constant temperature for a certain period of time. There is nothing special about the mixing process, and conventional mixing techniques and apparatus can be used.

[0073] II. Use of diisocyanate stabilizers In a second aspect, the disclosure also provides the use of a diisocyanate stabilizer according to the first aspect of the disclosure for stabilizing a diisocyanate.

[0074] III. Diisocyanate Compositions In a third embodiment, this disclosure is, (A) Diisocyanate and (B) Diisocyanate stabilizers according to the first aspect of the present disclosure A diisocyanate composition containing [the specified substance] is provided.

[0075] In some embodiments, this disclosure is, (A) Diisocyanate and (B) Diisocyanate stabilizers containing sterically hindered phenols, thioethers, and phosphites A diisocyanate composition containing [the specified substance] is provided.

[0076] Diisocyanate Suitable examples of diisocyanates include aliphatic, alicyclic, and aromatic diisocyanates.

[0077] 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.

[0078] Suitable examples of alicyclic diisocyanates include 1,2-, 1,3- or 1,4-diisocyanatocyclohexane, 2,4'- or 4,4'-di(isocyanatocyclohexyl)methane, 1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethylcyclohexane) (isophorone diisocyanate), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, or 2,4- or 2,6-diisocyanato-1-methylcyclohexane.

[0079] Examples of suitable aromatic diisocyanates include toluene 2,4- or 2,6-diisocyanate and mixtures thereof, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane (MDI) and mixtures thereof, phenylene 1,3- or 1,4-diisocyanate, 1-chlorophenylene 2,4-diisocyanate, naphthylene 1,5-diisocyanate, biphenylene 4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 3-methyl-diphenylmethane 4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene, or 4,4'-diisocyanatodiphenyl ether.

[0080] The diisocyanate stabilizers of this disclosure are particularly suitable for stabilizing toluene 2,4- or 2,6-diisocyanates and mixtures thereof, m- or p-xylene diisocyanates, 2,4'- or 4,4'-diisocyanatodiphenylmethane and mixtures thereof, and are especially suitable for stabilizing 2,4'- or 4,4'-diisocyanatodiphenylmethane, which is prone to yellowing due to its unique structure.

[0081] Mixtures of the aforementioned diisocyanates are also suitable. For example, isophorone diisocyanate is usually in the form of a mixture, specifically a mixture of cis and trans isomers in a ratio of about 60:40 to 80:20 (w / w), preferably about 70:30 to 75:25, and more preferably about 75:25. Dicyclohexylmethane 4,4'-diisocyanate may similarly be in the form of a mixture of different cis and trans isomers.

[0082] In this disclosure, diisocyanates can be conventionally obtained by phosgenating the corresponding amine or by a process that does not use phosgene, i.e., a process that does not use phosgene.

[0083] The diisocyanates that can be used preferably have a content of 30-50% by weight of isocyanate groups (calculated as NCO, molecular weight = 42) based on the diisocyanate.

[0084] With respect to sterically hindered phenols, thioethers, and phosphates in diisocyanate stabilizers, it should be understood that suitable sterically hindered phenols, thioethers, and phosphates, as well as their amounts in the stabilizer, are the same as those described in the first aspect of this disclosure. Therefore, suitable sterically hindered phenols, thioethers, and phosphates, as well as their amounts in the stabilizer, will not be described again here. Hereafter, only some exemplary sterically hindered phenols, thioethers, and phosphates, as well as their amounts in the diisocyanate stabilizer, suitable for the diisocyanate compositions of this disclosure are provided.

[0085] In some embodiments, based on the total weight of the diisocyanate stabilizer, sterically hindered phenol is present in an amount of 10-90% by weight, thioether is present in an amount of 5-80% by weight, and phosphite is present in an amount of 5-80% by weight.

[0086] In some embodiments, the diisocyanate stabilizer consists of sterically hindered phenols, thioethers, and phosphites.

[0087] In some embodiments, the diisocyanate stabilizer has a melting point of less than 50°C, preferably less than 20°C.

[0088] In some embodiments, the sterically hindered phenols are 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, n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 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-hydroxyphenyl)propionyloxyethyl isocyanurate, 1,3,5-tris-(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl (L) Isocyanurate or Pentaerythritol Tetrakis[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-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, Octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) phenyl)propionate, hexadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, octyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 3-thia-1,5-pentanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-Undecanediol bis[(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate], 1,9-nonanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 1,7-heptanediamine bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 1,1-methanediamine bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 3-(3',5'-di-tert-butyl-4'- Hydroxyphenyl)propionoic hydrazide, 3-(3',5'-dimethyl-4'-hydroxyphenyl)propionoic hydrazide, bis(3-tert-butyl-5-ethyl-2-hydroxyphen-1-yl)methane, bis(3,5-di-tert-butyl-4-hydroxyphen-1-yl)methane, bis[3-(1'-methylcyclohexe-1'-yl)-5-methyl-2-hydroxyphen-1-yl]methane, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl)methane, 1,1-bis(5-tert- Butyl-4-hydroxy-2-methylphen-1-yl)ethane, bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl) sulfide, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl) sulfide, 1,1-bis(3,4-dimethyl-2-hydroxyphen-1-yl)-2-methylpropane, 1,1-bis(5-tert-butyl-3-methyl-2-hydroxyphen-1-yl)butane, 1,3,5-tris[1'-(3'',5''-di-tert-butyl-4''-hydroxyphen-1' '-yl)-methyl-1'-yl]-2,4,6-trimethylbenzene, 1,1,4-tris(5'-tert-butyl-4'-hydroxy-2'-methylphen-1'-yl)butane, aminophenol, nitrosophenol, alkoxyphenol, eugenol, dihydroeugenol, isoeugenol, tocopherol, tocol, α-tocopherolhydroquinone, 4-methylpyrocatechol, 3-methylpyrocatechol, hydroquinone monobenzyl ether, p-phenoxyphenol, hydroquinone, tert-butylhydroquinone, 2,It is at least one selected from the group consisting of 5-di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumaran), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid and their derivatives.

[0089] In some embodiments, the sterically hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, branched C7-C9 alkyl ester, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, branched C 13 ~C 15 - At least one selected from the group consisting of alkyl esters, esters of polyglycol ethers terminated with phenol derivatives, 2,4-dimethyl-6-(1-methylpentadecyl)-phenol, and 4,6-bis(octylthiomethyl)-o-cresol.

[0090] In some embodiments, the thioether is of formula (III) [ka] (In the formula, R 4 C1-C1 are optionally substituted with hydroxy, amino, aryl, alkyl, aryloxy, alkyloxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom and / or heterocyclic elements. 20 -Alkylene or C3~C 12 - Selected from cycloalkylenes, R 5 C1~C 18 -Alkyl, one or more oxygen atoms and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupting C2-C18 - alkyl, C6 - C 12 - aryl or C5 - C 12 - cycloalkyl, optionally substituted by hydroxy, amino, aryl, alkyl, aryloxy, alkyloxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic ring, heteroatom and / or heterocyclic ring), and is at least one selected from the group consisting of).

[0091] In some embodiments, the thioether is at least one selected from the group consisting of didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, dimyristyl thiodipropionate, and 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]propane-1,3-diyl bis[3-(dodecylthio)propionate].

[0092] In some embodiments, the phosphite is of formula (IV) P(OR 6 )(OR 7 )(OR 8 )(IV) (wherein R 6 、R 7 and R 8 are each independently selected from C1 - C 18 - alkyl, C6 - C 12 - aryl or C5 - C 12 - cycloalkyl, and the above groups are optionally substituted by hydroxy, amino, aryl, alkyl, aryloxy, alkyloxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic ring, heteroatom and / or heterocyclic ring), and is at least one selected from the group consisting of).

[0093] In some embodiments, the phosphite is of formula (V)

Chemical formula

Chemical formula

[0095] In some embodiments, the phosphite is toridodecyl phosphite, phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester (CAS: 939402-02-5), 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 4,4'-butylidene-bis(3-methyl6-tert-butylphenyl)alkyl(C 13 It is at least one selected from the group consisting of )-phosphite and poly(dipropylene glycol)phenylphosphite (CAS: 116265-68-0).

[0096] In some embodiments, the diisocyanate stabilizer comprises a sterically hindered phenol, a thioether, and a phosphite, where the sterically hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, a branched C7-C9 alkyl ester, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid, and a branched C 13 ~C 15Examples include alkyl esters, esters of polyglycol ethers terminated with phenol derivatives, 2,4-dimethyl-6-(1-methylpentadecyl)-phenol and 4,6-bis(octylthiomethyl)-o-cresol; as thioethers, examples include didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, dimyristylthiodipropionate and 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]propane-1,3-diylbis[3-(dodecyl Examples include thiopropionates; phosphites include toridodecyl phosphite, phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester (CAS: 939402-02-5), poly(dipropylene glycol)phenyl phosphite (CAS: 116265-68-0), 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and 4,4'-butylidene-bis(3-methyl6-tert-butylphenyl)alkyl(C 13 )-Phosphites are examples; in each case, based on the total weight of the diisocyanate stabilizers, sterically hindered phenols are present in amounts of 10-90% by weight, thioethers in amounts of 5-80% by weight, and phosphites in amounts of 5-80% by weight.

[0097] In some embodiments, the diisocyanate stabilizer comprises a sterically hindered phenol, a thioether, and a phosphite. Examples of sterically hindered phenols include 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, branched C7-C9 alkyl esters, and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; examples of thioethers include didodecyl 3,3'-thiodipropionate and ditridecyl 3,3'-thiodipropionate; and examples of phosphites include toridodecyl phosphite, phosphorous acid, and mixed 2,4-hydroxyphenyl Examples include s(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester (CAS: 939402-02-5), poly(dipropylene glycol)phenyl phosphite (CAS: 116265-68-0), and 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; in each case, based on the total weight of the diisocyanate stabilizer, the amount of sterically 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.

[0098] In some embodiments, the diisocyanate stabilizer is present in an amount of 0.08 to 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 to 0.4% by weight, more preferably 0.15 to 0.35% by weight, based on the total weight of the diisocyanate composition.

[0099] Within the preferred quantity range described above, diisocyanate stabilizers can economically provide sufficient stability to diisocyanate without adversely affecting its appearance.

[0100] Diisocyanate compositions can be prepared by methods common 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 sterically 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 under heating conditions for a long period of time without affecting its color and transparency.

[0101] This disclosure is further illustrated by the following embodiments. [Examples]

[0102] material Diisocyanates: Monomerized MDI: (4,4'-Diisocyanatodiphenylmethane, Lupranate® ME, BASF) Stabilizer: Sterile hindrance phenol: 3,5-Bis(1,1-dimethylethyl)-4-benzenepropanoic acid, branched C7-C9 alkyl ester (Irganox® 1135 from BASF) Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 1076 from BASF SE) 2,6-di-tert-butyl-4-methylphenol (BHT, SCRC) Thioether: Zidodecyl 3,3'-thiodipropionate (DLTDP, Irganox® PS 800 from BASF) Ditridecyl 3,3'-thiodipropionate (DTDTP, Songnox® DTDTP from Songwon International AG) Phosphite: Toridodecyl phosphite (CCP STAB 3012T, CCP) 3,9-Bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (CCP STAB 508T, CCP).

[0103] Test method The transmission intensity is measured according to the following criteria or procedure: Prepare the sample according to the following example, and store the obtained sample in a clear glass vial. Images of each sample are captured using a charge-coupled device (CCD) camera. The light transmission intensity value of each sample is calculated based on the charge measured by the CCD camera.

[0104] A charge-coupled device (CCD) is an integrated circuit containing an array of coupled or connected capacitors. A CCD camera can convert incident photons into electric charge. The value of the charge depends on the intensity of light incident on the CCD. Therefore, the light transmission intensity of each sample can be calculated from the charge measured by the CCD camera.

[0105] Preparation of diisocyanate stabilizers (Examples 1-7) Example 1: 1) Add 90 g (90% by weight) of Irganox® 1135 and 5 g (5% by weight) of CCP STAB 3012T to a beaker and mix well at room temperature; 2) Add 5 g (5% by weight) of DLTDP to the above liquid mixture; and 3) Heat to 45°C, stir for 30 minutes while maintaining this temperature, and obtain a liquid diisocyanate stabilizer at room temperature (e.g., 20°C to 25°C).

[0106] Example 2: 1) Add 10 g (10% by weight) of Irganox® 1135 and 80 g (80% by weight) of CCP STAB 3012T to a beaker and mix well at room temperature; 2) Add 10 g (10% by weight) of DLTDP to the above liquid mixture; and 3) Heat to 45°C, stir for 30 minutes while maintaining this temperature, and obtain a liquid diisocyanate stabilizer at 45°C.

[0107] Example 3: 1) Add 25 g (25% by weight) of Irganox® 1135 and 25 g (25% by weight) of CCP STAB 3012T to a beaker and mix well at room temperature; 2) Add 50 g (50% by weight) of DLTDP to the above liquid mixture; and 3) Heat to 45°C, stir for 30 minutes while maintaining this temperature, and obtain a liquid diisocyanate stabilizer at 45°C.

[0108] Example 4: 1) Add 90 g (90% by weight) of Irganox® 1076 and 5 g (5% by weight) of CCP STAB 3012T to a beaker and mix well at room temperature; 2) Add 5 g (5% by weight) of DLTDP to the above liquid mixture; and 3) Heat to 45°C, stir for 30 minutes while maintaining this temperature, and obtain a liquid diisocyanate stabilizer at 50°C.

[0109] Example 5: 1) Add 50 g (50% by weight) of Irganox® 1135 and 30 g (30% by weight) of CCP STAB 508T to a beaker and mix well at room temperature; 2) Add 20 g (20% by weight) of DLTDP to the above liquid mixture; and 3) Heat to 45°C, stir for 30 minutes while maintaining this temperature, and obtain a liquid diisocyanate stabilizer at 45°C.

[0110] Example 6: 1) Add 10 g (10% by weight) of Irganox® 1135 and 10 g (10% by weight) of CCP STAB 3012T to a beaker and mix well at room temperature; and 2) Add 80 g (80% by weight) of DTDTP to the above liquid mixture and stir for 30 minutes to obtain a liquid diisocyanate stabilizer at room temperature.

[0111] Example 7: 1) Add 10 g (10% by weight) of Irganox® 1135 and 30 g (30% by weight) of CCP STAB 3012T to a beaker and mix well at room temperature; and 2) Add 60 g (60% by weight) of DTDTP to the above liquid mixture and stir for 30 minutes to obtain a liquid diisocyanate stabilizer at room temperature.

[0112] Examples of preparation of diisocyanate compositions (Ex. a~g and Ex. a'~g'): The diisocyanate stabilizers prepared according to Examples 1 to 7 were each added to monomeric MDI at 45°C and thoroughly mixed to obtain diisocyanate compositions a to g (containing 0.3% by weight of diisocyanate stabilizer based on the total weight of the diisocyanate composition) and a' to g' (containing 0.1% by weight of diisocyanate stabilizer based on the total weight of the diisocyanate composition).

[0113] Comparative diisocyanate compositions (Comp.Ex.h and i): For comparison, BHT and DLTDP were each added to monomeric MDI at 45°C and thoroughly mixed to obtain diisocyanate compositions. Specifically, the diisocyanate composition of comparative example h contained BHT; the diisocyanate composition of comparative example i contained DLTDP.

[0114] Tables 1-3 show the dosage of the diisocyanate stabilizer in each diisocyanate composition, as well as the permeation intensity and appearance of each diisocyanate composition.

[0115] The higher the transmission intensity, the higher the transparency and the lower the yellowness.

[0116] The appearance of the diisocyanate composition is evaluated on a scale of 1 to 5, where 1 represents colorless and transparent, and 5 represents a strong cloudy yellow color. Lower numbers indicate higher transparency and lower yellowness.

[0117] [Table 1]

[0118] [Table 2]

[0119] [Table 3]

[0120] As can be seen from Tables 1 to 3, the diisocyanate compositions containing the diisocyanate stabilizer according to this disclosure (Ex. a to g, and Ex. a' to g') exhibit superior stability in both color and transparency compared to comparative examples h and i. Specifically, the diisocyanate compositions containing the diisocyanate stabilizer according to this disclosure can maintain their colorless (pale yellow in some examples) and transparency (with minimal sedimentation in some examples) even after long-term storage (45°C, 14 days) and heating conditions (100°C, 24 hours).

[0121] While embodiments and examples of the present disclosure have been described above, those skilled in the art should understand that these are illustrative and not intended to limit the scope of the disclosure. The scope of the 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 the disclosure, but such modifications, equivalent substitutions or improvements will fall within the scope of the disclosure. The following are examples of the forms of this disclosure: [1] Diisocyanate stabilizers containing sterically hindered phenols, thioethers, and phosphites. [2] The diisocyanate stabilizer according to embodiment 1, wherein, based on the total weight of the diisocyanate stabilizer, the sterically hindered phenol is present in an amount of 10 to 90% by weight, the thioether is present in an amount of 5 to 80% by weight, and the phosphite is present in an amount of 5 to 80% by weight. [3] A diisocyanate stabilizer according to embodiment 1 or 2, comprising a sterically hindered phenol, a thioether, and a phosphite. [4] The diisocyanate stabilizer according to embodiment 1 or 2, wherein the diisocyanate stabilizer has a melting point of less than 50°C, preferably less than 20°C. [5] The sterically hindered phenol is alkylphenol, 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, n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 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-hydroxyphenyl)propionyloxyethyl isocyanurate, 1,3,5-tris-(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl )Isocyanurate or pentaerythritol tetrakis[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-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) droxyphenyl)propionate, hexadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, octyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, thiodiethylenebis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], 4,8-dioxa-1,11-undecanediolbis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-Undecanediol bis[(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate], 1,9-nonanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 1,7-heptanediamine bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 1,1-methanediamine bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 3-(3',5'-di-tert-butyl-4'- Hydroxyphenyl)propionoic hydrazide, 3-(3',5'-dimethyl-4'-hydroxyphenyl)propionoic hydrazide, bis(3-tert-butyl-5-ethyl-2-hydroxyphen-1-yl)methane, bis(3,5-di-tert-butyl-4-hydroxyphen-1-yl)methane, bis[3-(1'-methylcyclohexe-1'-yl)-5-methyl-2-hydroxyphen-1-yl]methane, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl)methane, 1,1-bis(5-tert- Butyl-4-hydroxy-2-methylphen-1-yl)ethane, bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl) sulfide, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl) sulfide, 1,1-bis(3,4-dimethyl-2-hydroxyphen-1-yl)-2-methylpropane, 1,1-bis(5-tert-butyl-3-methyl-2-hydroxyphen-1-yl)butane, 1,3,5-tris[1'-(3'',5''-di-tert-butyl-4''-hydroxyphen-1' '-yl)-methyl-1'-yl]-2,4,6-trimethylbenzene, 1,1,4-tris(5'-tert-butyl-4'-hydroxy-2'-methylphen-1'-yl)butane, aminophenol, nitrosophenol, alkoxyphenol, eugenol, dihydroeugenol, isoeugenol, tocopherol, tocol, α-tocopherolhydroquinone, 4-methylpyrocatechol, 3-methylpyrocatechol, hydroquinone monobenzyl ether, p-phenoxyphenol, hydroquinone, tert-butylhydroquinone, 2,A diisocyanate stabilizer according to embodiment 1 or 2, which is at least one selected from the group consisting of 5-di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumaran), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid and derivatives thereof. [6] The sterically hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, branched C 7 ~C 9 -Alkyl ester, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, branched C 13 ~C 15 A diisocyanate stabilizer according to embodiment 1 or 2, which is at least one selected from the group consisting of alkyl esters, esters of polyglycol ethers terminated with phenol derivatives, 2,4-dimethyl-6-(1-methylpentadecyl)-phenol, and 4,6-bis(octylthiomethyl)-o-cresol. [7] The thioether is of formula (III)

change

[10] The phosphite is given by formula (V)

change

[11] The polymeric phosphite is of formula (VI)

change

[12] The phosphite is toridodecyl phosphite, phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester (CAS: 939402-02-5), 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 4,4'-butylidene-bis(3-methyl6-tert-butylphenyl)alkyl(C 13 A diisocyanate stabilizer according to embodiment 1 or 2, which is at least one selected from the group consisting of )-phosphite and poly(dipropylene glycol)phenylphosphite (CAS: 116265-68-0).

[13] The sterically hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-benzenepropanoic acid, branched C 7 ~C 9 -Alkyl ester, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, branched C 13 ~C 15 - At least one selected from the group consisting of alkyl esters, esters of polyglycol ethers terminated with phenol derivatives, 2,4-dimethyl-6-(1-methylpentadecyl)-phenol and 4,6-bis(octylthiomethyl)-o-cresol; the thioether is said to be didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, dimyristylthiodipropionate and 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]propyl The phosphite is at least one selected from the group consisting of ropane-1,3-diylbis[3-(dodecylthio)propionate]; and the phosphite is toridodecyl phosphite, phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester (CAS: 939402-02-5), 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 4,4'-butylidene-bis(3-methyl6-tert-butylphenyl)alkyl(C 13 A diisocyanate stabilizer according to embodiment 1 or 2, which is at least one selected from the group consisting of )-phosphite and poly(dipropylene glycol)phenylphosphite.

[14] Use of a diisocyanate stabilizer according to any one of embodiments 1 to 13 for stabilizing a diisocyanate.

[15] (A) diisocyanate and (B) A diisocyanate stabilizer according to any one of embodiments 1 to 13 A diisocyanate composition containing [a specific compound].

[16] The diisocyanate composition according to embodiment 15, wherein the diisocyanate stabilizer is present in an amount of 0.08 to 0.5% by weight, preferably 0.1 to 0.4% by weight, and more preferably 0.15 to 0.35% by weight, based on the total weight of the diisocyanate composition.

[17] The diisocyanate composition according to embodiment 15 or 16, wherein the diisocyanate is an aromatic diisocyanate.

[18] The aromatic diisocyanates include toluene 2,4- or 2,6-diisocyanate and mixtures thereof, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and mixtures thereof, phenylene 1,3- or 1,4-diisocyanate, 1-chlorophenylene 2,4-diisocyanate, naphthylene 1,5-diisocyanate, biphenylene 4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and 3-methyl -Diphenylmethane 4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene or 4,4'-diisocyanatodiphenyl ether; preferably, at least one selected from the group consisting of toluene 2,4- or 2,6-diisocyanate and mixtures thereof, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and mixtures thereof, according to embodiment 17.

Claims

1. A diisocyanate stabilizer comprising sterically hindered phenols other than butylated hydroxytoluene, thioethers, and phosphates other than triphenyl phosphite, The sterically hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, branched C7-C9 alkyl ester, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, branched C13-C15 alkyl ester, methyl 3,5-di-tert-butyl-4-hydroxybenzoate, 4-tert-butylpyrocatechol, 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-hydroxyphenyl)propionyloxyethyl isocyanurate, 1,3,5-Tris-(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2 ,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, hexadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, octyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, thiodiethylenebis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], 4,8-di Oxa-1,11-undecanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate], 1,9-nonanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 1,7-heptanediamine bis[3-(3',[5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 1,1-methanediaminebis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionoic hydrazide, bis(3-tert-butyl-5-ethyl-2-hydroxyphen-1-yl)methane, bis(3,5-di-tert-butyl-4-hydroxyphen-1-yl)methane, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl)methane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphen At least one selected from the group consisting of (n-1-yl)ethane, bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl) sulfide, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl) sulfide, 1,1-bis(5-tert-butyl-3-methyl-2-hydroxyphen-1-yl)butane, 1,3,5-tris[1'-(3'',5''-di-tert-butyl-4''-hydroxyphen-1''-yl)-meth-1'-yl]-2,4,6-trimethylbenzene, and 1,1,4-tris(5'-tert-butyl-4'-hydroxy-2'-methylphen-1'-yl)butane, The thioether is of formula (III) 【Chemistry 1】 (In the formula, R4 is selected from C1 to C20-alkylenes, and R5 is selected from C1-C18 alkyl groups, and C2-C18 alkyl groups interrupted by one or more oxygen atoms and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups. At least one selected from, The phosphite is a mixture of phosphorous acid = tris[4-(1,1-dimethylpropyl)phenyl], phosphorous acid = 2,4-bis(1,1-dimethylpropyl)phenyl = bis[4-(1,1-dimethylpropyl)phenyl], and phosphorous acid = bis[2,4-bis(1,1-dimethylpropyl)phenyl] = 4-(1,1-dimethylpropyl)phenyl, 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 4,4'-butylidene-bis(3-methyl6-tert-butylphenyl)C13-alkyl-phosphite, poly(dipropylene glycol)phenyl phosphite, and formula (IV) P(OR6)(OR7)(OR8)(IV) (In the formula, R6, R7, and R8 are each independently selected from C1-C18-alkyl or C5-C12-cycloalkyl groups, and the above groups are optionally substituted with hydroxy, amino, aryl, alkyl, aryloxy, alkyloxy, alkylthio, alkoxycarbonyl, nitro, acyl, carbocyclic, heteroatom, and / or heterocyclic groups. A diisocyanate stabilizer, which is at least one selected from the group consisting of the following.

2. The diisocyanate stabilizer according to claim 1, wherein, based on the total weight of the diisocyanate stabilizer, the sterically hindered phenol is present in an amount of 10 to 90% by weight, the thioether is present in an amount of 5 to 80% by weight, and the phosphite is present in an amount of 5 to 80% by weight.

3. The diisocyanate stabilizer according to claim 1 or 2, comprising a sterically hindered phenol other than butylated hydroxytoluene, a thioether, and a phosphite other than triphenyl phosphite.

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

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

6. The sterically hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, branched C7-C9 alkyl ester, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, branched C13-C15 alkyl ester, 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, pentae Lythritol tetrakiss [β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, hexadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, octyl 3-(3',5'-di-te rt-butyl-4'-hydroxyphenyl)propionate, thiodiethylenebis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], 4,8-dioxa-1,11-undecanediolbis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 1,9-nonanediolbis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 1,7-heptanediol Minbis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 1,1-methanediaminebis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionoic hydrazide, bis(3,5-di-tert-butyl-4-hydroxyphenyl-1-yl)methane, 1,3,5-tris[1'-(3'',The diisocyanate stabilizer according to claim 1 or 2, which is at least one selected from the group consisting of 5''-di-tert-butyl-4''-hydroxyphen-1''-yl)-meth-1'-yl]-2,4,6-trimethylbenzene.

7. The sterically hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, branched C ７ ~C ９ - Alkyl esters, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, and branched C １３ ~C １５ - The diisocyanate stabilizer according to claim 1 or 2, which is at least one selected from the group consisting of alkyl esters.

8. The thioether is of formula (III) 【Chemistry 2】 (In the formula, R ４ C １ ~C ２０ - Selected from alkylenes, and R ５ is selected from C １ to C １８ -alkyl) A diisocyanate stabilizer according to claim 1 or 2, which is at least one selected from the following.

9. The diisocyanate stabilizer according to claim 1 or 2, wherein the thioether is at least one selected from the group consisting of didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, and dimyristylthiodipropionate.

10. The phosphite is given by formula (IV) P(OR ６ )(OR ７ )(OR ８ ) (IV) (In the formula, R ６ , R ７ and R ８ Each of them is independent of the others, C １ ~C １８ (Selected from alkyl groups) A diisocyanate stabilizer according to claim 1 or 2, which is at least one selected from the following.

11. The diisocyanate stabilizer according to claim 1 or 2, wherein the phosphite is at least one selected from the group consisting of toridodecyl phosphite and 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

12. The sterically hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, branched C ７ ~C ９ - Alkyl esters, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, and branched C １３ ~C １５ - The diisocyanate stabilizer according to claim 1 or 2, wherein the thioether is at least one selected from the group consisting of alkyl esters; the thioether is at least one selected from the group consisting of didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, and dimyristylthiodipropionate; and the phosphite is at least one selected from the group consisting of toridodecyl phosphite and 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

13. Use of a diisocyanate stabilizer according to any one of claims 1 to 12 for stabilizing a diisocyanate.

14. (A) Diisocyanate and (B) The diisocyanate stabilizer according to any one of claims 1 to 12 A diisocyanate composition containing [a specific compound].

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

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

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

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

19. The diisocyanate composition according to claim 18, wherein the aromatic diisocyanate is at least one selected from the group consisting of toluene 2,4- or 2,6-diisocyanate and mixtures thereof, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and mixtures thereof, phenylene 1,3- or 1,4-diisocyanate, 1-chlorophenylene 2,4-diisocyanate, naphthylene 1,5-diisocyanate, biphenylene 4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 3-methyl-diphenylmethane 4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene, or 4,4'-diisocyanatodiphenyl ether.

20. The diisocyanate composition according to claim 18, wherein the aromatic diisocyanate is at least one selected from the group consisting of toluene 2,4- or 2,6-diisocyanate and mixtures thereof, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and mixtures thereof.

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