Light colored modified isocyanate mixture and preparation method thereof

Patent metadata

Field	Value
Publication number	US-11034651-B2
Application number	US-201816645612-A
Country	US
Kind code	B2
Filing date	Aug 2, 2018
Priority date	Oct 20, 2017
Publication date	Jun 15, 2021
Grant date	Jun 15, 2021

Abstract

Disclosed is a light colored modified isocyanate mixture and a preparation method thereof. The method comprises the following steps: a) reacting isocyanate groups of a raw material isocyanate under the action of a phospholenecatalyst, and finally obtaining a modified isocyanate reaction solution containing carbodiimide and/or uretonimine derivatives; and b) adding a compounded terminator of a halosilane organic and a sulfonic anhydride to the reaction solution obtained in step a so as to terminate the reaction of carbodiimidization. The modified isocyanate prepared by the method has the characteristics of a liquid state at room temperature, being stable in storage at room temperature and high temperature, and low color number.

First claim

The invention claimed is:

1. A preparation method of a light colored modified isocyanate mixture, the method includes the following steps:
a) subjecting the isocyanate group of a raw material isocyanate to carbodiimidization under the action of a phosphorus heterocyclic catalyst to obtain a reaction solution of modified isocyanate containing carbodiimide and/or uretonimine derivatives;
b) adding a compounded terminator to the reaction solution obtained in step a) to terminate the carbodiimidization;
the compounded terminator is a compound of a halosilane organic and a sulfonic anhydride substance.

2. The preparation method according to claim 1 , wherein, the reaction of step a) is carried out at a temperature of 40° C.-210° C.

3. The preparation method according to claim 1 , wherein, the halosilane organic has a chemical formula of the following formula (I):
R 1 X 3 Si or R 1 R 2 X 2 Si or R 1 R 2 R 3 X 1 Si   (I)

in the molecular formula (I), R 1 , R 2 and R 3 independently represent aliphatic, aromatic, araliphatic, cycloaliphatic groups optionally containing heteroatoms, wherein R 1 , R 2 and R 3 can be the same or different; and two groups of R 1 , R 2 and R 3 can be connected to each other to form a ring structure;
X represents the halogen element selected from the group consisting of fluorine, chlorine, bromine and iodine.

4. The preparation method according to claim 1 , wherein, the sulfonic anhydride substance has the following structural formula (II):

in the structural formula (II), R 4 and R 5 independently represent aliphatic, aromatic, araliphatic, or cycloaliphatic groups optionally contain heteroatoms and/or other functional groups, wherein R 4 and R 5 can be the same or different, the two groups R 4 and R 5 are optionally connected to each other to form a ring structure.

5. The preparation method according to claim 1 , wherein, the compounded terminator is a compound of diphenyldifluorosilane and p-toluenesulfonic anhydride.

6. The preparation method according to claim 1 , wherein, the temperature condition of adding the compounded terminator to terminate the carbodiimidation of step b) is 40-70° C.

7. The preparation method according to claim 1 , wherein, the amount of compounded terminator is based on the weight of the raw material isocyanate, the amount of halosilane organic is 50-2000 ppm; the amount of sulfonic anhydride substance is 10-200 ppm.

8. The preparation method according to claim 1 , wherein, the catalyst used for preparing the isocyanate containing carbodiimide and/or uretonimine derivatives is a phospholene catalyst and/or a phospholene oxide, the amount of the catalyst is 0.1-10 ppm, relative to the weight of the raw material isocyanate.

9. The preparation method according to claim 1 , wherein, the raw material isocyanate is one or more selected from the group consisting of aromatic, araliphatic, aliphatic, and cycloaliphatic diisocyanates.

10. The preparation method according to claim 1 , wherein, when the reaction time of the carbodiimidation reaches 10 min-24 h, the compounded terminator is added to terminate the reaction.

11. The preparation method according to claim 3 , wherein, in the molecular formula (I), R 1 , R 2 and R 3 independently represent C1-C10 hydrocarbyl, C6-C15 aromatic, C7-C15 araliphatic, or C3-C12 cycloaliphatic groups optionally containing heteroatoms.

12. The preparation method according to claim 11 , wherein in the molecular formula (I), R 1 , R 2 and R 3 independently represent phenyl, tolyl, ethylphenyl, phenmethyl or phenyethyl optionally containing heteroatoms.

13. The preparation method according to claim 3 , wherein, the halosilane organic is selected from the group consisting of diphenyldifluorosilane, diphenyldichlorosilane, tritylfluorosilane, tert-butyltrichlorosilane and combinations thereof.

14. The preparation method according to claim 4 , wherein, in the structural formula (II), R 4 and R 5 independently represent C1-C10 hydrocarbyl, C6-C15 aromatic, C7-C15 araliphatic, or C3-C12 cycloaliphatic groups optionally contain heteroatoms and/or other functional groups.

15. The preparation method according to claim 14 , wherein, in the structural formula (II), R 4 and R 5 independently represent phenyl, tolyl, ethylphenyl, phenmethyl, phenethyl, cyclopropyl, cyclobutyl, cyclohexyl or cyclopentyl optionally containing heteroatoms and/or other functional groups.

16. The preparation method according to claim 4 , wherein, the sulfonic anhydride substance is selected from the group consisting of p-toluenesulfonic anhydride, methanesulfonic anhydride, ethylsulfonic anhydride, trifluoromethanesulfonic anhydride and combinations thereof.

17. The preparation method according to claim 7 , wherein, the amount of compounded terminator is based on the weight of the raw material isocyanate, the amount of halosilane organic is 100-600 ppm; the amount of sulfonic anhydride substance is 10-100 ppm.

18. The preparation method according to claim 7 , wherein, the compounding mass ratio of the halosilane organic and the sulfonic anhydride substance is 2-6:1.

19. The preparation method according to claim 8 , wherein, the amount of the catalyst is 0.2-2 ppm relative to the weight of the raw material isocyanate.

20. The preparation method according to claim 9 , wherein, the raw material isocyanate is diphenylmethane diisocyanate.

Assignees

• Wanhua Chemical Group Co Ltd

Inventors

• Zhou Ye
• Wang Wenbo
• Xia Yilu
• Zhang Hongke
• Liu Xiaogao
• Niu Guiying
• Wang Huihui
• Liu Xueting

Classifications

• C08G18/10 Primary

  Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step · CPC title

• C07D229/00

  Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms · CPC title

• C07C265/14 Primary

  containing at least two isocyanate groups bound to the same carbon skeleton · CPC title

• C07C263/18 Primary

  Separation; Purification; Stabilisation; Use of additives · CPC title

• C07C267/00

  Carbodiimides · CPC title