NOVEL BIOBASED AMINES

Abstract

The present invention relates to a process for preparing an amidoamine by reacting a triacid derivative (I) with at least one amine (A), the at least one amine (A) being selected from the group consisting of diethylenetriamine and a diamine (II). The molar ratio of the triacid derivative (I) to the at least one amine (A) is in the range from 1:2 to 1:<3. The present invention further relates to the amidoamine as such and also to the use of the amidoamine of the invention as a crosslinker.

Claims

1.-13. (canceled)

14. A process for preparing an amidoamine comprising reacting a triacid derivative of the general formula (I) ##STR00002## in which X.sup.1 is selected from the group consisting of Cl, Br, I, and OR.sup.1; X.sup.2 is selected from the group consisting of Cl, Br, I, and OR.sup.2; X.sup.3 is selected from the group consisting of Cl, Br, I, and OR.sup.3, where R.sup.1, R.sup.2, and R.sup.3 independently of one another are selected from the group consisting of hydrogen and unsubstituted or at least monosubstituted. C.sub.1-C.sub.20 alkyl, where the substituents are selected from the group consisting of F, Cl, Br, OH, CN, and C.sub.1-C.sub.20 alkyl; R is selected from the group consisting of hydrogen and C(O)R.sup.4, where R.sup.4 is an unsubstituted or at least monosubstituted C.sub.1-C.sub.20 alkyl, where the substituents are selected from the group consisting of F, Cl, Br, OH, CN, and C.sub.1-C.sub.10 alkyl; with at least one amine (A) selected from the group consisting of diethylenetriamine and a diamine of the general formula (II)
H.sub.2NR.sup.5NH.sub.2 (II) in which R.sup.5 is a branched C.sub.3-C.sub.31 alkyl or an unbranched C.sub.n alkyl, where n is an odd integer in the range from 3 to 31, wherein the molar ratio of the triacid derivative (I) to the at least one amine (A) is in the range from 1:2 to 1:<3.

15. The process according to claim 14, wherein the reaction of the triacid derivative (I) with the at least one amine (A) takes place at a temperature T in the range from 20 to 200 C.

16. The process according to claim 14, wherein the molar ratio of the triacid derivative (I) to the at least one amine (A) is in the range from 1:2.4 to 1:2.8.

17. The process according to claim 14, wherein the triacid derivative (I) is selected from the group consisting of citric acid, trimethyl citrate, and triethyl citrate.

18. The process according to claim 14, wherein the amine (A) is a diamine of the general formula (II) in which R.sup.5 is a branched C.sub.3-C.sub.13 alkyl or an unbranched C.sub.n alkyl, where n is an odd integer in the range from 3 to 13.

19. The process according to claim 14, wherein the at least one amine (A) is selected from the group consisting of diethylenetriamine, 1,2-diaminopropane, 1,3-diaminopropane, 2,2-dimethyl-1,3-propanediamine, 1,5-diaminopentane, 1,5-diamine-2-methylpentane, 1,7-diaminoheptane, 2-butyl-2-ethyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, and 2,4,4-trirnethyl-1,6-hexanediamine.

20. The process according to claim 14, wherein the amidoamine has a number-average molecular weight M.sub.n in the range from 500 to 30 000 g/mol.

21. The process according to claim 14, wherein the amidoamine has a viscosity in the range from 1000 to 1 000 000 mPas as measured at 60 C. using an Anton Paar Physica MCR 301 rheometer with plate/plate geometry, shear rate 1/s, 6 sec/data point, 20 data points, 1 mm gap width.

22. The process according to claim 14, wherein the amidoamine has a glass transition temperature T.sub.g in the range from 40 to 20 C.

23. An amidoamine obtained by the process according to claim 14.

24. The use of the amidoamine according to claim 23 as a crosslinker.

25. A thermosettingly curable resin system comprising the amidoamine according to claim 23 as a crosslinker.

26. The thermosettingly curable resin system according to claim 25, wherein the thermosettingly curable resin system is selected from the group consisting of thermosettingly curable isocyanate resin systems, thermosettingly curable urethane resin systems, thermosettingly curable epoxy resin systems, thermosettingly curable polyester resin systems, thermosettingly curable polyamide resin systems, and thermosettingly curable carbonate resin systems.

Description

EXAMPLES

[0150] Triacid derivative (I) used with triethyl citrate (citric acid triethyl ester, 99%, FCC, Sigma Aldrich).

[0151] Amines used as amine (A) were as follows: [0152] 1,5-diaminopentane (pentamethylenediamine, PMDA) [0153] 1,3-diaminopropane (trimethylenediamine, TMDA) [0154] diethylenetriamine (DETA) [0155] 2,2 ,4-trimethyl-1,6-hexanediamine (TMHDA)

[0156] In examples C1 and 2 to 7, the triacid derivative (I) was prepared with the amine (A) indicated in Table 1a, in the molar ratio indicated in Table 1a (triacid derivative (I) to amine (A)), in a glass flask equipped with stirrer and reflux condenser, and this mixture was heated to the temperature specified in Table 1a, and held at this temperature for the reaction time indicated in Table 1a. Thereafter the reaction mixture obtained was transferred while still hot into a single-neck flask, where it was freed from ethanol formed in the reaction and optionally from residual monomeric amine (A) on a rotary evaporator at 55 C. under a pressure of 1 mbar for a period of 30 minutes.

[0157] In example 8, the triacid derivative (I) was prepared with the amine (A) indicated in Table 1a, in the molar ratio indicated in Table 1a (triacid derivative (I) to amine (A)), in a glass flask equipped with stirrer, descending condenser, and catch vessel, and this mixture was heated to the temperature indicated in Table 1a and held at this temperature for the reaction time indicated in Table 1a. Ethanol formed during the reaction was removed continuously from the reaction mixture. After the end of the reaction, the mixture was transferred while still hot into a single-neck flask, where residual ethanol and any remaining monomeric amine (A) were removed on a rotary evaporator at 55 C. under a pressure of 1 mbar over a time of 30 minutes.

[0158] In Tables 1a and 1b, the following parameters and results for the examples are indicated: [0159] Molar ratio: Molar ratio of triacid derivative (I) to amine (A). [0160] Temperature: Temperature at which the reaction was carried out. [0161] Reaction time: Time for which the reaction was carried out [0162] Viscosity of the resulting amidoamine, determined at 60 C. using an Anton Paar Physica MCR 301 rheometer with plate/plate geometry, shear rate 1/s, 6 s/data point, 20 data points, 1 mm gap width. [0163] M.sub.w and M.sub.n: Weight-average and number-average molecular weight, determined by gel permeation chromatography (GPC) using a Waters Alliance 2695 separation module with Shodex OHpak SB-804HQ, SB-802.5HQ (3008.0 mm) column and 0.3 mol/L sodium acetate, pH 4.5 (adjusted using acetic acid) as eluent. (Flow rate: 0.5 mL/min; injection: 50 L, detector: Waters Refractive Index (RI) 2410, calibration: PEG/PEO). [0164] T.sub.g: The glass transition temperatures (T.sub.g) were measured using a DSC-7 heat flow calorimeter from Perkin-Elmer. For this purpose, 5 to 7 mg of the sample were weighed out into an aluminum crucible, and measurement took place in a temperature range from 100 to +100 C. with a heating and cooling rate of 10 K min.sup.1. The glass transition temperatures (T.sub.g (I) and T.sub.g (II)) were determined from the first and second heating curves, respectively.

TABLE-US-00001 TABLE 1a Reaction time Temperature Example Amine (A) Molar ratio [h] [ C.] C1.sup. PMDA 1:3.0 4 90 2 PMDA 1:2.8 4 90 3 PMDA 1:2.6 4 90 4 PMDA 1:2.3 4 80 5 TMHDA 1:2.6 5.5 90 6 DETA 1:2.6 6 80 7 TMDA 1:2.6 5 80 8 PMDA 1:2.8 2 100

TABLE-US-00002 TABLE 1b M.sub.n M.sub.w T.sub.g (I) T.sub.g (II) Example [g/mol] [g/mol] [mPas] [ C.] [ C.] C1.sup. 1200 3600 102 600 14 8 2 11 400 33 500 22 300 35 4 3 14 200 88 200 46 800 29 1 4 12 300 102 000 53 700 23 2 5 14 900 37 200 79 800 44 25 6 6400 14 200 20 800 43 7 7 9700 34 600 48 400 26 5 8 12 300 36 800 23 200 32 6