CA2451170A1

CA2451170A1 - In-situ preparation of polyaspartic ester mixtures

Info

Publication number: CA2451170A1
Application number: CA002451170A
Authority: CA
Inventors: Karsten Danielmeier; Catherine M. Britsch; Rolf Gertzmann; Michele E. Vargo; Terrell D. Wayt; Edward P. Squiller; Richard R. Roesler
Original assignee: Bayer AG; Bayer Polymers LLC
Current assignee: Bayer AG; Covestro LLC
Priority date: 2002-12-05
Filing date: 2003-11-26
Publication date: 2004-06-05
Anticipated expiration: 2023-11-26
Also published as: DE60318808T2; KR20040049265A; JP2004182992A; PT1426397E; CA2451170C; DK1426397T3; KR100981513B1; JP4435551B2; US6790925B2; EP1426397A1; ATE384755T1; DE60318808D1; EP1426397B1; MXPA03011210A; ES2299661T3; US20040110917A1

Abstract

The present invention relates to polyaspartate mixtures containing a) 5 to 50 equiv.%, based on the total equivalents of aspartate groups, of a polyoxypropylene polyaspartate corresponding to the formula wherein X1 represents the residue obtained by removing the amino groups from a polyoxypropylene polyamine having a functionality of n, R1 and R2 are identical or different and represent organic groups which are inert to isocyanate groups at a temperature of 100°C or less, R3 and R4 are identical or different and represent hydrogen or organic groups which are inert towards isocyanate groups at a temperature of 100°C or less and n is 2 to 4, and b) 50 to 95 equiv.%, based on the total equivalents of aspartate groups, of a polyether polyaspartate corresponding to the formula I
wherein X1 represents the residue obtained by removing the amino groups from a polyether polyamine having a functionality of n and a number average molecular weight of less than 5000, wherein the amino groups are attached to primary carbon atoms and the ether groups are separated by at least two carbon atoms.
The present invention also relates to a process for preparing these polyaspartate mixtures and to the polyureas prepared by reacting the polyaspartate mixtures and optionally other isocyanate-reactive compounds with polyisocyanates.

Claims

1. A polyaspartate mixture comprising to 50 equiv.%, based on the total equivalents of aspartate groups, of a polyoxypropylene polyaspartate corresponding to the formula wherein X1 represents the residue obtained by removing the amino groups from a polyoxypropylene polyamine having a functionality of n, R1 and R2 are identical or different and represent organic groups which are inert to isocyanate groups at a temperature of 100°C or less, R3 and R4 are identical or different and represent hydrogen or organic groups which are inert towards isocyanate groups at a temperature of 100°C or less and n is 2 to 4, and b) 50 to 95 equiv.%, based on the total equivalents of aspartate groups, of a polyether polyaspartate corresponding to the formula wherein X2 represents the residue obtained by removing the amino groups from a polyether polyamine having a functionality of n and a number average molecular weight of less than 5000, wherein the amino groups are attached to primary carbon atoms and the ether groups are separated by at least two carbon atoms.

2. The polyaspartate of Claim 1 wherein X2 represents the residue obtained by removing the amino groups from a polyether polyamine having a number average molecular weight of less than 600 and corresponding to the formula H2N - R6 - O - [R5 - O]x - R7 - NH2 (IV) wherein R5 represents the residue obtained by removing the hydroxyl groups from a linear or branched hydrocarbon radical having 2 to 10 carbon atoms, R6 and R7 may be the same of different and represent linear or branched hydrocarbon radicals containing 2 to 8 carbon atoms and x has a value of 1 to 10.

3. The polyaspartate of Claim 2 wherein R5 represents the residue obtained by removing the hydroxyl groups from a linear or branched hydrocarbon radical having 2 to 6 carbon atoms, R6 and R7 may be the same of different and represent linear or branched hydrocarbon radicals containing 2 to 4 carbon atoms and x has a value of 1 to 5.

4. The polyaspartate of Claim 2 wherein polyoxypropylene polyaspartate a) is present in an amount of 5 to 40 equiv.%, based on the total equivalents of aspartate groups, and polyether polyaspartate b) is present in an amount of 60 to 95 equiv.%, based on the total equivalents of aspartate groups.

5. The polyaspartate of Claim 1 wherein R1 and R2 are identical or different and represent alkyl groups having 1 to 9 carbon atoms and R3 and R4 represent hydrogen.

6. The polyaspartate of Claim 2 wherein R1 and R2 are identical or different and represent alkyl groups having 1 to 9 carbon atoms and R3 and R4 represent hydrogen.

7. The polyaspartate of Claim 3 wherein R1 and R2 are identical or different and represent alkyl groups having 1 to 9 carbon atoms and R3 and R4 represent hydrogen.

8. The polyaspartate of Claim 4 wherein R1 and R2 are identical or different and represent alkyl groups having 1 to 9 carbon atoms and R3 and R4 represent hydrogen.

9. The polyaspartate of Claim 1 wherein R1 and R2 are identical or different and represent alkyl groups having 1 to 4 carbon atoms, R3 and R4 represent hydrogen and n is 2.

10. The polyaspartate of Claim 2 wherein R1 and R2 are identical or different and represent alkyl groups having 1 to 4 carbon atoms, R3 and R4 represent hydrogen and n is 2.

11. The polyaspartate of Claim 3 wherein R1 and R2 are identical or different and represent alkyl groups having 1 to 4 carbon atoms, R3 and R4 represent hydrogen and n is 2.

12. The polyaspartate of Claim 4 wherein R1 and R2 are identical or different and represent alkyl groups having 1 to 4 carbon atoms, R3 and R4 represent hydrogen and n is 2.

13. The polyaspartate of Claim 10 wherein X represents the residue obtained by removing the amino groups from 3-[2-(3-aminopropoxy) ethoxy]propylamine.

14. The polyaspartate of Claim 12 wherein X represents the residue obtained by removing the amino groups from 3-[2-(3-aminopropoxy) ethoxy]propylamine.

15. A process for preparing the polyaspartate mixture of Claim 1 which comprises a) reacting one equivalent of unsaturated groups from a maleic or fumaric acid ester corresponding to the formula R1OOC-CR3=CR4-COOR2 (III) with 5 to 50 equiv.% of a polyoxypropylene polyamine corresponding to the formula X1-(-NH2)n (IV) to form a reaction mixture containing a polyoxypropylene polyaspartate a) and excess maleic or fumaric acid ester (III) and b) reacting the excess maleic or fumaric ester (III) with a substantially equivalent amount of a polyether polyamine corresponding to the formula X2-(-NH2)n (V) to form a mixture of polyoxypropylene polyaspartate a) and polyether polyaspartate b).

16. The process of Claim 15 wherein X2 represents the residue obtained by removing the amino groups from a polyether polyamine corresponding to the formula H2N - R6 - O - [R5 - O]x - R7 - NH2 (IV) wherein R5 represents the residue obtained by removing the hydroxyl groups from a linear or branched hydrocarbon radical having 2 to 10 carbon atoms, R6 and R7 may be the same of different and represent linear or branched hydrocarbon radicals containing 2 to 8 carbon atoms and x has a value of 1 to 10.

17. The process of Claim 15 wherein R1 and R2 are identical or different and represent alkyl groups having 1 to 4 carbon atoms, R3 and R4 represent hydrogen and n is 2.

18. The process of Claim 16 wherein R1 and R2 are identical or different and represent alkyl groups having 1 to 4 carbon atoms, R3 and R4 represent hydrogen and n is 2.

19. A polyurea which comprises the reaction product of a polyisocyanate with an isocyanate-reactive component comprising the polyaspartate mixture of Claim 1.

20. The polyurea of Claim 19 wherein the isocyanate-reactive component additionally contains a polyol.