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CN-117203185-B - Diisocyanate stabilizer, use thereof and diisocyanate composition

CN117203185BCN 117203185 BCN117203185 BCN 117203185BCN-117203185-B

Abstract

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

Inventors

  • YUAN GUOLIANG
  • M. Ishak
  • JIN SHUNYING
  • K.WANG
  • ZHENG YIZHOU

Assignees

  • 巴斯夫欧洲公司

Dates

Publication Date
20260512
Application Date
20220328
Priority Date
20210426

Claims (20)

  1. 1. A diisocyanate stabilizer comprising a sterically hindered phenol other than butylated hydroxytoluene, a thioether and a phosphite other than triphenyl phosphite, Wherein the hindered phenol is selected from the group consisting of branched C 7 -C 9 alkyl 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionate, octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, branched C 13 -C 15 alkyl 3, 5-di (1, 1-dimethylethyl) -4-hydroxyphenylpropionate, methyl 3, 5-di-tert-butyl-4-hydroxybenzoate, methyl 1,3, 5-trimethyl-2, 4, 6-tri (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) isocyanurate, 1,3, 5-tris (2, 6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2, 6-di-tert-butyl-4-hydroxybenzyl) propionate, tris (3, 5 '-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris [3, 5' -di-tert-butyl-4-hydroxyphenyl ] phenol, 3 '-di-tert-butyl-4-hydroxyphenyl) propionate, tris [3, 3' -di-tert-butyl-4-hydroxyphenyl ] propionate At least one of 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 ], Wherein the thioether is at least one member selected from the group consisting of formula (III): Wherein the method comprises the steps of R 4 is selected from C 1 -C 20 alkylene, and R 5 is selected from the group consisting of C 1 -C 18 alkyl, Wherein the phosphite is at least one of 3, 9-diisodecyloxy-2, 4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane and formula (IV): P(OR 6 )(OR 7 )(OR 8 ) (IV) Wherein R 6 、R 7 and R 8 are each independently selected from C 1 -C 18 alkyl, And Wherein the sterically hindered phenol is present in an amount of from 35 to 85 weight percent, based on the total weight of the diisocyanate stabilizer.
  2. 2. The diisocyanate stabilizer according to claim 1, wherein the sterically hindered phenol is present in an amount of 40-80 wt%, the thioether is present in an amount of 5-55 wt% and the phosphite is present in an amount of 5-55 wt%, based on the total weight of the diisocyanate stabilizer.
  3. 3. The diisocyanate stabilizer according to claim 1 or 2, consisting of a sterically hindered phenol, a thioether and a phosphite.
  4. 4. The diisocyanate stabilizer according to claim 1 or 2, wherein the diisocyanate stabilizer has a melting point below 50 ℃.
  5. 5. The diisocyanate stabilizer according to claim 1 or 2, wherein the diisocyanate stabilizer has a melting point below 20 ℃.
  6. 6. The diisocyanate stabilizer according to claim 1 or 2, wherein the hindered phenol is at least one selected from the group consisting of branched C 7 -C 9 alkyl 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionate, octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, branched C 13 -C 15 alkyl 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionate, methyl 3, 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3- (3 ',5' -di-tert-butyl-4 '-hydroxyphenyl) propionate, octyl 3- (3', 5 '-di-tert-butyl-4' -hydroxyphenyl) propionate.
  7. 7. The diisocyanate stabilizer according to claim 1 or 2, wherein the hindered phenol is at least one selected from the group consisting of branched C 7 -C 9 alkyl 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid esters, octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and branched C 13 -C 15 alkyl 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid esters.
  8. 8. The diisocyanate stabilizer according to claim 1 or 2, wherein the thioether is at least one selected from the group consisting of formula (III): Wherein the method comprises the steps of R 4 is selected from the group consisting of methylene, 1, 2-ethylene, 1, 2-or 1, 3-propylene, 1,2-, 1, 3-or 1, 4-butylene, 1-dimethyl-1, 2-ethylene or 1, 2-dimethyl-1, 2-ethylene, 1, 6-hexylene, 1, 8-octylene and 1, 10-decylene, and R 5 is selected from C 1 -C 18 alkyl.
  9. 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 dimyristoyl thiodipropionate.
  10. 10. The diisocyanate stabilizer according to claim 1 or 2, wherein the phosphite is at least one selected from the group consisting of formula (IV): P(OR 6 )(OR 7 )(OR 8 ) (IV) Wherein the method comprises the steps of R 6 、R 7 and R 8 are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 2, 4-trimethylpentyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl.
  11. 11. The diisocyanate stabilizer according to claim 1 or 2, wherein the phosphite is at least one selected from the group consisting of tri-dodecyl phosphite and 3, 9-diisodecyloxy-2, 4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane.
  12. 12. The diisocyanate stabilizer according to claim 1 or 2, wherein the hindered phenol is at least one selected from the group consisting of branched C 7 -C 9 alkyl 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid esters, octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and branched C 13 -C 15 alkyl 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid 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 dimyristyl thiodipropionate, and the phosphite is at least one selected from the group consisting of tri-dodecyl phosphite and 3, 9-diisodecyloxy-2, 4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane.
  13. 13. Use of a diisocyanate stabilizer according to any of claims 1 to 12 for stabilizing diisocyanates.
  14. 14. A diisocyanate composition comprising: (A) Diisocyanate, and (B) The diisocyanate stabilizer according to any one of claims 1 to 12.
  15. 15. The diisocyanate composition according to claim 14, wherein the diisocyanate stabilizer is present in an amount of 0.08 to 0.5 wt% based on the total weight of the diisocyanate composition.
  16. 16. The diisocyanate composition according to claim 14, wherein the diisocyanate stabilizer is present in an amount of 0.1 to 0.4 wt% based on the total weight of the diisocyanate composition.
  17. 17. The diisocyanate composition according to claim 14, wherein the diisocyanate stabilizer is present in an amount of 0.15 to 0.35 wt% based on the total weight of the diisocyanate composition.
  18. 18. The diisocyanate composition according to any of claims 14-17, wherein said diisocyanate is an aromatic diisocyanate.
  19. 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 isomer mixtures thereof, m-or p-xylylene diisocyanate, 2,4' -or 4,4' -diisocyanato diphenylmethane and isomer mixtures thereof, 1, 3-or 1, 4-xylylene diisocyanate, 1-chlorobenzene-2, 4-diisocyanate, naphthalene-1, 5-diisocyanate, biphenyl-4, 4' -diisocyanate, 4' -diisocyanato-3, 3' -dimethylbiphenyl, 3-methyldiphenylmethane-4, 4' -diisocyanate, tetramethylxylylene diisocyanate, 1, 4-diisocyanatobenzene or 4,4' -diisocyanato diphenyl ether.
  20. 20. The diisocyanate composition according to claim 18, wherein said aromatic diisocyanate is at least one selected from the group consisting of toluene-2, 4-or 2, 6-diisocyanate and isomer mixtures thereof, m-or p-xylylene diisocyanate, 2,4 '-or 4,4' -diisocyanato diphenylmethane and isomer mixtures thereof.

Description

Diisocyanate stabilizer, use thereof and diisocyanate composition Technical Field The present disclosure relates to a diisocyanate stabilizer, the use of the diisocyanate stabilizer in stabilizing a diisocyanate, and a diisocyanate composition comprising the stabilizer. Background Diisocyanates are important intermediates in organic synthesis, for example in the preparation of polyurethane resins. However, due to the high reactivity of the isocyanate groups, diisocyanates tend to yellow and/or cloudy due to self-polymerization during storage, thereby affecting their use in downstream industries. To prevent the diisocyanate from yellowing and/or clouding, a person skilled in the art generally adds an amount of antioxidant to the diisocyanate. For example, US3555072 discloses a method of inhibiting discoloration and haze formation in Toluene Diisocyanate (TDI) comprising adding thereto a stabilizing amount of a thioether compound. However, the long-term thermal stability of the TDI solution obtained according to US3555072 is poor. To extend the thermal stability, the person skilled in the art can increase the amount of this thioether, which in turn will cause odor problems for TDI, which is also unacceptable. Accordingly, there remains a need in the art to provide a stabilizer for diisocyanates that is capable of maintaining the color and transparency of the diisocyanates after long term storage. Summary of The Invention The present disclosure provides a diisocyanate stabilizer that solves or at least partially solves the above-mentioned problems, or other potential problems in the prior art that stabilize diisocyanates. In particular, the present disclosure provides in a first aspect a diisocyanate stabilizer comprising a sterically hindered phenol other than butylated hydroxytoluene, a thioether, and a phosphite other than triphenyl phosphite. In some embodiments, the hindered phenol is present in an amount of 10 to 90 weight percent, the thioether is present in an amount of 5 to 80 weight percent and the phosphite is present in an amount of 5 to 80 weight percent, in each case based on the total weight of the stabilizer. In other embodiments, the diisocyanate stabilizer is comprised of a hindered phenol, a thioether, and a phosphite. The inventors of the present disclosure surprisingly found that hindered phenols, thioethers and phosphites can synergistically act to effectively prevent the self-polymerization of diisocyanates. By combining together the hindered phenol, thioether, and phosphite, the present disclosure provides a stabilizer that can prevent the diisocyanate from yellowing and/or clouding during long-term storage and heating conditions. The stabilizers of the present disclosure effectively solve the problem of the diisocyanate being prone to yellowing and/or cloudiness during long term storage and heating conditions. In some preferred embodiments, the diisocyanate stabilizer has a melting point of less than 50 ℃, preferably less than 20 ℃. For example, the diisocyanate stabilizer has a melting point below 50 ℃, 45 ℃, 40 ℃, 35 ℃, 30 ℃, 25 ℃, 20 ℃, or 10 ℃. In these preferred embodiments, the diisocyanate stabilizer is liquid at the operating temperature (typically at 45-50 ℃) to facilitate automated production, so that production efficiency may be improved. Furthermore, when the diisocyanate stabilizer has a melting point below 20 ℃ and is thus liquid even below 20 ℃, the transportation of the diisocyanate stabilizer at low temperatures is additionally facilitated. The present disclosure provides in a second aspect the use of a stabiliser according to the first aspect of the invention in stabilising a diisocyanate. The present disclosure provides in a third aspect a composition comprising: (A) Diisocyanate, and (B) The diisocyanate stabilizer according to the first aspect of the present invention. The inventors of the present disclosure surprisingly found that the resulting diisocyanate composition can be maintained (substantially) transparent and colorless during long term storage and heating conditions, which significantly widens the application area of the diisocyanate. Thus, the diisocyanate compositions of the present disclosure may be suitable for applications having high requirements in terms of color and transparency. The advantageous technical effects of the diisocyanate stabilizers of the present disclosure that bring about diisocyanates during long term storage and heating conditions (e.g., a melting process at a temperature of about 100 ℃) compared to the prior art include, but are not limited to: (1) The diisocyanate composition has a lighter color; (2) The diisocyanate composition has high transparency, and (3) The diisocyanate composition maintains a lighter color and a higher transparency. It should be understood that the summary of the invention is not intended to determine key or essential features of the disclosure nor is it intended to limit the scope of the disclosure. Oth