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JP-7855015-B2 - Diisocyanate stabilizers, their use, and diisocyanate compositions

JP7855015B2JP 7855015 B2JP7855015 B2JP 7855015B2JP-7855015-B2

Inventors

  • ユエン，グオ リアン
  • イシャケ，マイケル
  • ジン，シュン イン
  • ワン，コー
  • ジョン，イー ジョウ

Assignees

  • ビーエーエスエフ ソシエタス・ヨーロピア

Dates

Publication Date
20260507
Application Date
20220328
Priority Date
20210426

Claims (20)

  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-butylphenyl) [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-dioxa-1,11-undecanediolbis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediolbis[( [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, 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 At least one selected from the group consisting of -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(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) (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 , 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-dioxa-1,11-undecanediol bis[(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 , bis (3,5-di-tert-butyl-4-hydroxyphenyl-1-yl)methane , 1 The diisocyanate stabilizer according to claim 1 or 2 , which is at least one selected from the group consisting of ,3,5-tris[1'-(3'',5''-di-tert-butyl-4''-hydroxyphen-1''-yl) -meth -1'-yl]-2,4,6-trimethylbenzene.
  7. The diisocyanate stabilizer according to claim 1 or 2, wherein the sterically hindered phenol is at least one selected from the group consisting of 3,5-bis(1,1-dimethylethyl)-4 - hydroxybenzenepropanoic acid, branched C7 - C9 alkyl esters, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, and branched C13 - C15 alkyl esters .
  8. The thioether is of formula (III) (In the formula, R4 is selected from C1 to C20 - alkylenes , and R5 is selected from C1 to C18 - alkyls . 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( OR6 )( OR7 )( OR8 )(IV) (In the formula, R6 , R7 , and R8 are each independently selected from C1 - C18 -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 phenols include 3,5-bis(1,1-dimethylethyl)-4 - hydroxybenzenepropanoic acid, branched C7 - C9 alkyl esters, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)-4- hydroxybenzenepropanoic acid, and branched C13 - C15 - 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 composition comprising (A) a diisocyanate and (B) a diisocyanate stabilizer according to any one of claims 1 to 12 .
  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.

Description

This disclosure relates to diisocyanate stabilizers, the use of diisocyanate stabilizers for stabilizing diisocyanates, and diisocyanate compositions comprising the stabilizers. 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 yellowing and/or turbidity of diisocyanates, those skilled in the art typically add a certain amount of antioxidant to the diisocyanate. 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. However, the long-term thermal stability of the TDI solution obtained according to U.S. Patent No. 3,555,072 is low. Those skilled in the art may increase the amount of thioether to extend thermal stability, but this introduces an odor problem to the TDI, which is also unacceptable. The following description further illustrates the disclosure 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 practical basis. Furthermore, technical features described in some embodiments may be combined with those described in other embodiments. 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. In this disclosure, the terms “comprise,” “comprisin,” and their various variations can be understood as open-ended terms meaning “includes 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. 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 typically used. Furthermore, the term “or” is generally intended to include the meaning of “and/or” unless explicitly indicated by the context. As used herein, “preferred,” “preferable,” and “preferably” refer to embodiments of the disclosure that may provide particular advantages under specific circumstances. However, other embodiments may also be preferred under the same circumstances. Moreover, the description of one or more preferred embodiments does not imply that other embodiments are unhelpful, nor is it intended to exclude other embodiments from the scope of this disclosure. 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). 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. The diisocyanate stabilizer is provided to stabilize diisocyanate from the viewpoint of color stability, transparency, etc. The diisocyanate stabilizer enables diisocyanate to maintain its colorless and transparent state even under long-term storage and heating conditions. Throughout this disclosure, the terms “phosphite” and “phosphate” are used interchangeably and are intended to include both the plural and singular forms unless explicitly specified or clearly indicated by the context. The term "glycol" refers to an aliphatic diol containing two hydroxyl groups (-OH groups) bonded to different carbon atoms. The term "color stability" means that the color of the diisocyanate composition does not change, o