PROCESS FOR THE PREPARATION OF DI- OR POLYFORMAMIDES

Abstract

The invention relates to a process for preparing at least one di- or polyformamide comprising at least two NHCHO groups by reacting at least one primary di- or polyamine with carbon dioxide in the presence of hydrogen and at least one catalyst selected from the group consisting of heterogeneous and homogeneous catalysts or mixtures thereof. The invention further relates to a di- or polyformamide and their use for different purposes as well as a two-component-system comprising the di- or polyformamide.

Claims

1. A process for preparing at least one di- or polyformamide comprising at least two NHCHO groups, the process comprising reacting at least one primary di- or polyamine with carbon dioxide in the presence of hydrogen and at least one catalyst selected from the group consisting of heterogeneous catalysts, homogeneous catalysts and mixtures thereof.

2. The process according to claim 1, wherein the primary di- or polyamine is a primary diamine.

3. The process according to claim 1, wherein the primary di- or polyamine is selected from the group consisting of 1,5-diaminopentane, 1,6-diaminohexane, 2,4-hexahydrotoluenediamine, 2,6-hexahydrotoluenediamine, 2,4-diaminodicyclohexylmethane, 4,4diaminodicyclohexylmethane, 3,3,5-trimethyl-5-aminomethyl-cyclohexane, and mixtures thereof.

4. The process according to claim 1, wherein the primary di- or polyamine is one or more of 1,5-diaminopentane and 1,6-diaminohexane.

5. The process according to claim 1, wherein the catalyst is a heterogeneous catalyst containing one or more transition metals.

6. The process according to claim 1, wherein the catalyst is a homogeneous catalyst containing one or more transition metals.

7. The process according to claim 6, wherein the homogeneous catalyst comprises one or more transition metal complexes comprising ligands bearing one donor atom selected from the group consisting of phosphorous, nitrogen, carbon and sulfur and mixtures thereof.

8. The process according to claim 7, wherein at least one ligand is a pincer type ligand selected from the group consisting of PCP, PNP, NCN and SCS.

9. The process according to claim 6, wherein the homogenous catalyst is selected from the group consisting of [IrCl(CO)(PPh.sub.3).sub.2], [RuCl.sub.2(PMe.sub.3).sub.4], Fe(BF.sub.4).sub.2*6 H.sub.2O/P(CH.sub.2CH.sub.2PPh.sub.2).sub.2, [RuCl.sub.2{PMe.sub.2(CH.sub.2).sub.2]Si(OEt).sub.3}.sub.3, [RuCl(H)CO(MeN(CH.sub.2CH.sub.2PPh.sub.2).sub.2)], [RuCl.sub.2(tris[(2-diphenylphosphino)phenyl]phosphine)(NHC)], [RuCl.sub.2(1,2-bis(diphenylphosphino)ethan).sub.2] and mixtures thereof, wherein NHC is an n-heterocyclic carbene.

10. The process according to claim 1, wherein the reaction is carried out in the presence of a solvent.

11. A di- or polyformamide, obtained by the process according to claim 1.

12. A binder in a polyurethane or polyurea formulation comprising the di- or polyformamide according to the process of claim 11.

13. In a process for the production of an NCO-terminated prepolymer, the improvement comprising including the di- or polyformamide according to the process of claim 11.

14. A starting material in a phosgene free process for the production of isocyanates, wherein the starting material comprises the di- or polyformamide according to the process of claim 11.

15. A two-component-system, containing a binder component A), comprising at least one di- or polyformamide according to claim 11, and a crosslinker component B), comprising at least one polyisocyanate.

Description

EXAMPLES

[0042] The following examples can be carried out in an autoclave. This autoclave is made from stainless steel and suitable to withstand pressures up to 200 bar and has a heating mantle to allow isothermal reaction conditions up to 200 C. The autoclave is equipped with a pressure meter and a means for stirring the reaction mixture. The top lid of the autoclave contains 2 feed lines for the gaseous reactants.

Example 1

[0043] Hexamethylene diamine is added to an autoclave together with a heterogeneous catalyst (1% Au on TiO.sub.2 support). The autoclave is closed and heated to 125 C. before pressurization to 140 bar by addition of CO.sub.2 and H.sub.2 (p(CO.sub.2):p(H.sub.2)=2:1). The autoclave is stirred for 12 h and hexamethylene diformamide is obtained in good yields.

Example 2

[0044] Hexamethylene diamine is added to an autoclave together with the homogeneous catalyst RuCl.sub.2(dppe).sub.2 where the ligand dppe refers to 1,2-bis(diphenylphosphino)ethane. The autoclave is closed and heated to 100 C. before pressurization to 160 bar by addition of CO.sub.2 and H.sub.2 (p(CO.sub.2):p(H.sub.2)=2.5:1). The autoclave is stirred for 10 h and hexamethylene diformamide is obtained in good yields.

Example 3

[0045] Isophorone diamine is added to an autoclave together with a homogeneous catalyst [RuCl(H)CO(MeN(CH.sub.2CH.sub.2PPh.sub.2).sub.2)]. The autoclave is closed and heated to 120 C. before pressurization to 150 bar by addition of CO.sub.2 and H.sub.2 (p(CO.sub.2):p(H.sub.2)=1:1). The autoclave is stirred for 20 h and isophorone diformamide is obtained in good yields.

Example 4

[0046] Pentamethylene diamine is added to an autoclave together with the homogeneous catalyst RuCl.sub.2(PMe.sub.3).sub.4. The autoclave is closed and heated to 110 C. before pressurization to 100 bar by addition of CO.sub.2 and H.sub.2 (p(CO.sub.2):p(H.sub.2)=1.5:1). The autoclave is stirred for 17 h and pentamethylene diformamide is obtained in good yields.

Example 5

[0047] Hexamethylene diamine is added to an autoclave together with a heterogeneous catalyst (1% Au on TiO.sub.2 support) and THF. The autoclave is closed and heated to 125 C. before pressurization to 140 bar by addition of CO.sub.2 and H.sub.2 (p(CO.sub.2):p(H.sub.2)=2:1). The autoclave is stirred for 12 h and hexamethylene diformamide is obtained in good yields.

Example 6

[0048] Isophorone diamine is added to an autoclave together with a homogeneous catalyst [RuCl(H)CO(MeN(CH.sub.2CH.sub.2PPh.sub.2).sub.2)] and DMSO. The autoclave is closed and heated to 120 C. before pressurization to 150 bar by addition of CO.sub.2 and H.sub.2 (p(CO.sub.2):p(H.sub.2)=1:1). The autoclave is stirred for 20 h and isophorone diformamide is obtained in good yields.