Polyisocyanates which contain carbodiimide groups and which are stable in storage

• US 4,294,719 A
• Filed: 08/08/1977
• Issued: 10/13/1981
• Est. Priority Date: 02/01/1975
• Status: Expired due to Term

• Current Assignee: Bayer AG
• Original Assignee: Bayer AG
• Inventors: Block, Hans-Dieter, Schafer, Walter, Wagner, Kuno
• Primary Examiner(s): Padgett, Benjamin R.
• Assistant Examiner(s): Gluck, Irwin
• Application Number:
  US05/822,489
• Time in Patent Office: 1,527 Days
• Field of Search: 252/182, 528/67, 528/44
• US Class Current: 252/182.22
• CPC Class Codes: C07C 263/18 Separation; Purification; Stabilisation; Use of additives
• CPC Class Codes: C07C 265/12 having isocyanate groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07C 267/00 Carbodiimides
• CPC Class Codes: C07D 229/00 Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms
• CPC Class Codes: C07D 251/30 Only oxygen atoms
• CPC Class Codes: C07D 251/54 Three nitrogen atoms
• CPC Class Codes: C07D 303/04 containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
• CPC Class Codes: C07F 9/65685 the ring phosphorus atom being part of a phosphine oxide or thioxide
• CPC Class Codes: C08G 18/3228 acyclic
• CPC Class Codes: C08G 18/3275 containing two hydroxy groups
• CPC Class Codes: C08G 18/3893 containing silicon
• CPC Class Codes: C08G 18/4018 Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• CPC Class Codes: C08G 18/4238 derived from dicarboxylic acids and dialcohols
• CPC Class Codes: C08G 18/4825 Polyethers containing two hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/4829 Polyethers containing at least three hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/7831 containing biuret groups
• CPC Class Codes: C08G 18/797 containing carbodiimide and/or uretone-imine groups
• CPC Class Codes: C08G 18/836 by phosphorus containing compounds
• CPC Class Codes: C08G 2110/005 < 50kg/m3
• CPC Class Codes: C08G 2110/0083 prepared using water as the sole blowing agent
• CPC Class Codes: C08G 77/54 : Nitrogen-containing linkages C08G77/485 takes precedence

Abstract

The present invention relates to stable equilibrium mixtures of carbodiimides, uretone imines and organic isocyanates and to stable solutions of carbodiimides and uretone imines in polyisocyanates which are free from carbodiimide groups. Either the carbodiimide, or the uretone imine, or both, may contain isocyanate groups. The present invention also relates to a process for the preparation of such products by "heterogeneous catalysis" and the use thereof for the production of polyurethane resins. According to one embodiment of the process according to the instant invention, individual isocyanates in a mixture of various isocyanates may be carbodiimidized selectively.

Claims

1. A composition of matter comprising a storage-stable, catalyst-free, equilibrium mixture of an organic carbodiimide, an organic uretone imine, and an organic isocyanate produced by the process comprising:

(a) contacting an organic mono- and/or polyisocyanate, optionally dissolved in an inert solvent, with a high molecular weight, insoluble catalyst, said catalyst comprising a high molecular weight, insoluble inorganic or organic matrix and a low molecular weight carbodiimidization catalyst linked to said matrix via ionic bonds, and

(b) removing said insoluble catalyst when the desired degree of carbodiimidization has been reached.

2. The composition of claim 1, wherein at least one of said carbodiimide or said uretone imine contains isocyanate groups.

3. The composition of claim 2, wherein said isocyanate is a mono and/or polyisocyanate free from carbodiimide and uretone imine groups.

4. The composition of claim 1, wherein said isocyanate is a mono and/or polyisocyanate free from carbodiimide and uretone imine groups.

5. The composition of claim 4 comprising

(A) an equilibrium mixture of (i) the diisocyanatocarbodiimide of tolylene diisocyanate, and (ii) the corresponding triisocyanato uretone imine, and

(B) an isocyanate selected from the group consisting of 4,4'"'"'-diisocyanatodiphenylmethane, naphthylene-1,5-diisocyanate, and mixtures thereof.

6. The composition of claim 5 wherein component (A) comprises from about 5 to about 80 parts, by weight, and component (B) comprises about 100 parts by weight.

7. The composition of claim 4 comprising:

(A) an equilibrium mixture of the carbodiimide and uretone imine of a member selected from the group consisting of phenyl isocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, cyclohexyl isocyanate and tolyl isocyanate, and

(B) an isocyanate selected from the group consisting of 4,4'"'"'-diisocyanatodiphenylmethane, naphthylene-1,5-diisocyanate, and mixtures thereof.

8. The composition of claim 7, wherein component (A) comprises from about 10 to about 30 parts by weight and component (B) comprises about 100 parts by weight.

9. The composition of claim 4 comprising:

(A) an equilibrium mixture of the carbodiimide and uretone imine of a member selected from the group consisting of phenyl isocyanate and tolyl isocyanate, and

(B) tolylene diisocyanate.

10. The composition of claim 9, wherein component (A) comprises from about 5 to about 30 parts by weight, and component (B) comprises about 100 parts by weight.

11. The composition of claim 4 comprising:

(A) an equilibrium mixture of the carbodiimide and uretone imines of tolylene diisocyanate, and

(B) a modified tolylene diisocyanate containing from about 10 to about 40 percent by weight of biuret, allophanate, urethane or isocyanurate polyisocyanates based on tolylene diisocyanate.

12. The composition of claim 11, wherein component (A) comprises from about 10 to about 20 parts by weight, and component (B) comprises about 100 parts by weight.

13. The composition of claim 4 comprising:

(A) an equilibrium mixture of the carbodiimide and uretone imines of hexamethylene diisocyanate, and

(B) the biuret polyisocyanates of hexamethylene diisocyanates.

14. The composition of claim 13, wherein component (A) comprises from about 10 to about 30 parts by weight, and component (B) comprises about 100 parts by weight.

15. The composition of claim 4 comprising:

(A) an equilibrium mixture of the carbodiimide and uretone imines of a member selected from the group consisting of phenyl isocyanate, tolyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and tolylene diisocyanate; and

(B) α

, ω

-diisocyanato prepolymers derived from 1 mol of α

,ω

-dihydroxy polyesters or polyethers having molecular weights of from about 400 to about 10,000, and from about 1.4 to about 2.5 mole of an isocyanate selected from the groupconsisting of tolylene diisocyanate, diisocyanatodiphenylmethane, and hexamethylene diisocyanate.

16. The composition of claim 15, wherein component (A) comprises from about 5 to about 30 parts by weight, and component (B) comprises about 100 parts by weight.

17. The composition of claim 1, wherein the process further comprises the step of:

adding a mono- or polyisocyanate which is free from carbodiimide and uretone imide groups to the equilibrium mixture.

18. A process for preparing a storage stable, catalyst-free, equilibrium mixture of an organic carbodiimide, an organic uretone imine, and an organic isocyanate comprising the steps:

(A) contacting an organic mono and/or polyisocyanate, optionally dissolved in an inert solvent, with a high molecular weight, insoluble catalyst, said catalyst comprising a high molecular weight, insoluble, inorganic or organic matrix and a low molecular weight carbodiimidization catalyst linked to said matrix via ionic bonds, and

(B) removing said insoluble catalyst when the desired degree of carbodiimidization has been reached.

19. The process of claim 18, further comprising the step of

(C) adding a mono and/or polyisocyanate which is free from carbodiimide and uretone imine groups to the equilibrium mixture.