Amorphous polyesters on the basis of betulin

Abstract

The present invention relates to amorphous polyesters on the basis of betulin, a method for producing them and their use.

Claims

1. An amorphous polyester prepared from a reactive raw material mixture of: (a) betulin; (b) dicarboxylic acid; and (c) at least one compound selected from the group consisting of short-chain polyol, amine, and vegetable oil, characterized in that the amorphous polyester has a glass transition temperature T.sub.g in the range of ?50? C. to 80? C., as determined by means of DSC, and all or part of the reactive raw materials are produced from renewable materials, such that the amorphous polyester includes a proportion of renewable raw materials of 90 to 100 wt. %, based on the total weight of the amorphous polyester.

2. The amorphous polyester according to claim 1, characterized in that a proportion of betulin structural units in the amorphous polyester is 6 to 65 mol %.

3. The amorphous polyester according to claim 1, characterized in that the (a) betulin is produced from renewable raw materials; and at least one of the (b) dicarboxylic acid and the (c) at least one compound, is produced from renewable raw materials.

4. The amorphous polyester according to claim 1, characterized in that the (b) dicarboxylic acid is selected from the group consisting of aliphatic dicarboxylic acids with 4 to 24 carbon atoms, aromatic dicarboxylic acids and dimer acids.

5. The amorphous polyester according to claim 4, characterized in that the dimer acid is a dimer of a fatty acid and/or derivatives thereof of the general formula C.sub.nH.sub.2n+1COOH, where n is a whole number from 7 to 33.

6. The amorphous polyester according to claim 1, characterized in that the short-chain polyol contains 2 to 8 carbon atoms.

7. The amorphous polyester according to claim 1, characterized in that the vegetable oil is selected from the group consisting of soybean oil, linseed oil, sunflower oil, rapeseed oil, thistle oil, fish oil, castor oil, tall oil, coconut oil, palm oil, olive oil and mixtures thereof.

8. A composition comprising the amorphous polyester according to claim 1.

9. A method for producing the amorphous polyester according to claim 1, comprising the following steps: providing a reactive raw material mixture of: the (a) betulin, the (b) dicarboxylic acid, and the (c) at least one compound selected from the group consisting of short-chain polyol, amine, and vegetable oil; and heating the mixture to a temperature of 200 to 250? C. to form the amorphous polyester.

10. The method according to claim 9, characterized in that the (a) betulin is soluble in the mixture.

11. The method according to claim 9, characterized in that the mixture further contains a catalyst, in an amount of 0.01 to 0.05 wt. %, based on the total weight of the mixture.

12. A method for producing a polymeric material, comprising the following steps: providing the amorphous polyester according to claim 1, characterized in that the amorphous polyester has terminal hydroxyl groups; and chemically modifying the terminal hydroxyl groups of the amorphous polyester by addition with organic compounds containing at least one epoxide and/or isocyanate group.

13. A polymeric material prepared by the method according to claim 12.

14. A composition comprising the polymeric material of claim 13.

15. The composition of claim 14, which is an adhesive or a sealant.

16. The composition of claim 14, which is a deformation or extrusion aid.

Description

EXAMPLES

(1) Generally, the polyesters according to the invention can be produced by mixing the individual components and heating the mixture to 220? C. in the nitrogen stream. Exemplary compositions are summarized in Table 1.

(2) The samples are analyzed by means of GPC (gel permeation chromatography). The chromatography with an IR detector after calibration by means of a polystyrene standard occurred at a column oven temperature of 40? C. and a temperature in the detector of likewise 40? C. The relative and the numerical average and weight average molecular weight values can be calculated from the molecular weight distribution curve, and the polydispersity can be determined from that.

(3) The polyesters thereby produced were measured by differential scanning calorimetry, wherein a sample was first heated to 150? C. in order to then be brought to ?90? C. at a cooling rate of 10 Kelvin per minute. After 10 minutes at ?90? C., the sample was brought to 150? C. at a heating rate of 10 Kelvin per minute and the DSC diagram was recorded. The glass transition temperature of the sample was determined with the aid of the DSC diagram.

(4) TABLE-US-00001 TABLE 1 Acid OH value value Viscosity Glass in mg in mg Brookfield transition KOH/g KOH/g Mn in Example Composition at 140? C. temperature sample sample g/mol Polydispersity 1 131.6 g 4500 mPas 29? C. 4.0 56 2453 2.1 betulin (25 mol %), 25.5 g butanediol (31.6 mol %, 87.8 g sebacic acid (43.4 mol %) 2 110.68 g 30,000 mPas 19? C. 3.2 27 5326 2.3 betulin (25 mol %), 24.06 g 1,2-propanediol (31.6 mol %, 90.75 g azelaic acid (43.4 mol %) 3 110.68 g 310,000 mPas 59? C. 2.4 34 3872 2.1 betulin (25 mol %), 24.05 g 1,2-propanediol (31.6 mol %, 64.07 g adipic acid (43.4 mol %) 4 131.63 g 1550 mPas 12? C. 2.6 80 1933 2.1 betulin (25 mol %), 25.55 g butanediol (31.6 mol %, 87.8 g sebacic acid (43.4 mol %) 5 110.68 g 1500 mPas ?1? C. 3.0 61 2472 2.3 betulin (25 mol %), 28.48 g butanediol (31.6 mol %, 89.65 g azelaic acid (43.4 mol %) 6 110.65 g 7500 mPas 29? C. 2.8 59 2207 2.1 betulin (25 mol %), 28.51 g butanediol (31.6 mol %, 63.44 g adipic acid (43.4 mol %) 7 110.68 g 185,000 mPas 63? C. 1.1 58 2356 2 betulin (25 mol %), 28.49 g butanediol (31.6 mol %, 51.25 g succinic acid (43.4 mol %) 8 64.78 g 160 mPas ?35? C. 1.8 71 2508 2.3 betulin (30.5 mol %), 135.16 g castor oil (30.5 mol %) 22.08 g succinic acid (39 mol %) 9 110.67 g 25,100 mPas 42? C. 1.3 53 2552 2 betulin (25 mol%), 32.93 g 2,2-dimethyl- 1,3-propanediol (31.6 mol %), 63.42 g adipic acid (43.4 mol %) 10 103.18 g 6800 mPas 22? C. 2.0 29 2368 2.5 betulin (46.6 mol %), 4.51 g butanediol (10 mol %), 125.43 g dimer acid Pripol 1013 (43.4 mol %)