Process for the solvent-free, continuous preparation of polyureas

• US 20030212238A1
• Filed: 11/29/2002
• Published: 11/13/2003
• Est. Priority Date: 05/10/2002
• Status: Active Grant

• Current Assignee: Degussa AG (Rag-Stiftung)
• Original Assignee: Degussa AG (Rag-Stiftung)
• Inventors: Weihrauch, Thomas, Herda, Silvia, Grenda, Werner, Behrendt, Klaus, Weiss, Joern Volker
• Granted Patent: US 7,129,313 B2
• Time in Patent Office: Days
• US Class Current: 528/65
• CPC Class Codes: C08G 18/0895 Manufacture of polymers by continuous processes C08G18/0838 takes precedence
• CPC Class Codes: C08G 18/3234 cycloaliphatic
• CPC Class Codes: C08G 18/755 and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates

Abstract

The invention relates to a process for the solvent-free, continuous preparation of polyureas by reacting at least one isocyanate and/or isocyanurate having at least two NCO groups with at least one diamine and/or polyamine in an extruder, intensive kneader, intensive mixer or static mixer by thorough mixing and rapid reaction by briefly heating and subsequent cooling to isolate the end product.

Claims

1. A process for the solvent-free, continuous preparation of polyureas comprising:

reacting at least one compound selected from the group consisting of isocyanate(s) having at least two NCO groups and isocyanurate(s) having at least two NCO groups, and mixtures thereof, with at least one compound selected from the group consisting of diamine(s) and polyamine(s), and mixtures thereof, in an extruder, intensive kneader, intensive mixer or static mixer by thorough mixing and rapid reaction by briefly heating and subsequent cooling to isolate the end product.

2. The process as claimed in claim 1, wherein the isocyanate(s) and isocyanurate(s) is/are selected from the group consisting of aliphatic, cycloaliphatic, araliphatic and aromatic, isocyanates and isocyanurates, and mixtures thereof.

3. The process as claimed in claim 1, wherein the diamine(s) and polyamine(s) is/are selected from the group consisting of cyclohexane diisocyanates, methylcyclohexane diisocyanates, ethylcyclohexane diisocyanates, propylcyclohexane diisocyanates, methyldiethylcyclohexane diisocyanates, phenylene diisocyanates, tolylene diisocyanates, bis(isocyanatophenyl)methane, propane diisocyanates, butane diisocyanates, pentane diisocyanates, hexane diisocyanates, such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanates, octane diisocyanates, nonane diisocyanates, such as 1,6-diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), nonane triisocyanates, such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane di- and triisocyanates, undecane di- and triisocyanates, dodecane di- and triisocyanates, isophorone diisocyanate (IPDI), bis(isocyanatomethyl-cyclohexyl)methane (H₁₂MDI), isocyanatomethyl-methylcyclohexyl isocyanates, 2,5(2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (NBDI), 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H₆-XDI) or 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H₆-XDI), and the isocyanurates thereof, and mixtures thereof.

4. The process as claimed in claim 1, wherein the isocyanate(s) and isocyanurate(s) is/are selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), the isocyanurates thereof, and mixtures thereof.

5. The process as claimed in claim 1, wherein the diamine(s) is/are an aliphatic, a cycloaliphatic, an araliphatic or aromatic diamine(s), or mixtures thereof.

6. The process as claimed in claim 1, wherein the diamine(s) is/are 1,2-ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2-butylenediamine, 1,3-butylenediamine, 1,4-butylenediamine, 2-(ethylamino)ethylamine, 3-(methylamino)propylamine, 3-(cyclohexylamino)propylamine, 4,4′

-diaminodicyclohexylmethane, isophoronediamine, 4,7-dioxadecane-1,10-diamine, N-(2-aminoethyl)-1,2-ethanediamine, N-(3-aminopropyl)-1,3-propanediamine, N,N″

-1,2-ethanediylbis(1,3-propanediamine) and hexamethylenediamines, which may be substituted by one or more C₁-C₄-alkyl radicals, or mixtures thereof.

7. The process as claimed in claim 1, comprising IPDI and isophoronediamine (IPD).

8. The process as claimed in claim 1, comprising an isocyanurate of IPDI and IPD.

9. The process as claimed in claim 1, comprising a mixture of IPDI and IPDI-isocyanurate and IPD.

10. The process as claimed in claim 1, comprising HDI and IPD.

11. The process as claimed in claim 1, comprising an isocyanurate of HDI and IPD.

12. The process as claimed in claim 1, comprising a mixture of HDI and HDI-isocyanurate and IPD.

13. The process as claimed in claim 1, comprising a mixture of IPDI- and HDI-isocyanurate and IPD.

14. The process as claimed in claim 1, wherein the reaction is carried out with an NCO/NH₂ ratio of 0.8 to 1.2:

1.

15. The process as claimed in claim 1, wherein the reaction is carried out in a single-screw, twin-screw or multiscrew extruder, annular extruder or planetary roller extruder.

16. The process as claimed in claim 1, wherein the reaction is carried out in a twin-screw extruder.

17. The process as claimed in claim 1, wherein the reaction is carried out in an intensive mixer or intensive kneader.

18. The process as claimed in claim 1, wherein the reaction is carried out in a static mixer.

19. The process as claimed in claim 1, wherein the reaction is carried out in an extruder, intensive kneader, intensive mixer or static mixer having a plurality of identical or different housings which can be thermally controlled independently of one another.

20. The process as claimed in claim 1, wherein the temperature in the extruder, intensive kneader, intensive mixer or static mixer is from 10 to 325°

C.

21. The process as claimed in claim 1, wherein, by appropriate equipment in the mixing chambers and design of the screw geometry, the extruder or intensive kneader firstly gives rapid, thorough mixing and rapid reaction with simultaneous intense heat exchange and, secondly, produces uniform flow in the longitudinal direction with a uniform residence time.

22. The process as claimed in claim 1, wherein the reaction is carried out in the presence of catalyst(s) and/or additive(s).

23. The process as claimed in claim 1, wherein starting materials and/or catalyst(s) and/or additive(s) are fed together or in separate reaction streams, in liquid or solid form, to the extruder, intensive kneader, intensive mixer or static mixer.

24. The process as claimed in claim 23, wherein additive(s) are combined with starting materials to give one reactant stream.

25. The process as claimed in claim 23, wherein, if there are more than two reactant streams, these are combined before being fed in.

26. The process as claimed in claim 23, wherein one or both reactant streams are divided.

27. The process as claimed in claim 23, wherein catalyst(s) is/are combined with one of the reactant streams, or is initially introduced in solution in one of the streams.

28. The process as claimed in claim 23, wherein additive(s) is/are combined with one of the reactant streams, or is initially introduced in solution in one of the streams.

29. The process as claimed in claim 23, wherein the entry points of the reactant streams in the sequence can be varied and can be offset timewise.

30. The process as claimed in claim 1, wherein a post-reaction is carried out.

31. The process as claimed in claim 30, wherein the post-reaction is carried out in a continuously operated system.

32. The process as claimed in claim 1, wherein a compounding is first initiated after further cooling to a temperature sufficient for subsequent filling/silo storage, depending on the viscosity of the product leaving the extruder, intensive kneader, intensive mixer or static mixer and/or a post-reaction zone.

33. The process as claimed in claim 1, wherein a residence time of reactant materials is from 3 seconds to 15 minutes.

34. The process as claimed in claim 1, wherein the reaction takes place at temperatures of from 25 to 325°

C.

36. The process as claimed in claim 30, wherein the post-reaction is carried out in a tubular reactor, a stirred or unstirred dwell tank or a tube bundle.

37. The process as claimed in claim 1, wherein a residence time of reactant materials is from 3 seconds to 5 minutes.

38. The process as claimed in claim 1, wherein a residence time of reactant materials is from 5 to 180 seconds.

39. The process as claimed in claim 1, wherein the reaction takes place at temperatures from 50 to 250°

C.

40. The process as claimed in claim 1, wherein the reaction takes place at temperatures from 70 to 220°

C.

35. A polyurea obtained by solvent-free, continuous reaction of at least one isocyanate and/or isocyanurate having at least two NCO groups with at least one diamine and/or polyamine in an extruder, intensive kneader, intensive mixer or static mixer by thorough mixing and rapid reaction by briefly heating and subsequent cooling to isolate the end product.