POLYAMIDE DISPERSION IN POLYOL AND PREPARATION THEREOF

Abstract

The invention relates to a process for preparing a polyamide dispersion in polyol, the polyamide dispersion in polyol thus obtained, the use of a polyether amine in the preparation of the polyamide dispersion in polyol, the use of the polyamide dispersion in polyol for preparing a polyurethane, a respective process and the polyurethane.

Claims

1-14. (canceled)

15. A process for preparing a polyamide dispersion in polyol, comprising reacting diamine and dicarboxylic acid components in a molar ratio of from 1.1:0.9 to 0.9:1.1 in a polyol component in a reactor, the diamine component comprising 10 to 100 wt % of at least one polyetheramine which is a difunctional primary amine with a number average molecular weight (M.sub.n) of from 500 to 5,000 g/mol, the polyol component having a number average molecular weight (M.sub.n) of from 2,000 to 8,000 g/mol, wherein at most 80 wt % of the diamine component is provided in the reactor at the start of the reaction and at least 20 wt % of the diamine component is added stepwise or continuously to the reactor in the course of the reaction.

16. The process of claim 15, wherein the diamine component comprises 20 to 80 wt % of the at least one polyetheramine and 20 to 80 wt % of one or more diamines different therefrom, at least part of which are added to the reactor after the at least one polyetheramine.

17. The process of claim 15, wherein the amount of the polyol component is 20 to 80 wt %, based on the sum of diamine and diacid components and polyol components.

18. The process of claim 15, wherein the polyetheramine comprises repeating oxyethylene and/or oxypropylene units in the backbone, and terminal primary amino groups.

19. The process of claim 15, wherein the polyol is a polyetherol prepared from at least one starter molecule comprising 2 to 8 reactive hydrogen atoms and one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene radical.

20. The process of claim 15, wherein the dicarboxylic acid component is provided in the reactor at the start of the reaction.

21. A polyamide dispersion in a polyol, obtained by the process of claim 1.

22. A polyamide dispersion in a polyol, wherein the polyamide is based on diamine and dicarboxylic acid components is a molar ratio of from 1.1:0.9 to 0.9:1.1, 10 to 100 wt % of the diamine component being at least one polyetheramine with a number average molecular weight (M.sub.n) of from 500 to 5,000 g/mol.

23. The polyamide dispersion of claim 22, wherein the polyol component has a number average molecular weight (M.sub.n) of from 2,000 to 8,000 g/mol.

24. The polyamide dispersion of claim 21, wherein the amount of polyol component is 20 to 80 wt. %, based on the sum of diamine and diacid components and polyol component.

25. A method comprising using a polyetheramine which is a difunctional primary amine with a number average molecular weight (M.sub.n) of from 500 to 5,000 g/mol, as a reactive stabilizer for polyamides in the in situ polycondensation of dicarboxylic acids and diamines in a polyol.

26. The method of claim 25, for preparing a polyurethane.

27. A process for preparing a polyurethane, comprising mixing a polyamide dispersion in polyol prepared by the process of claim 1 with polyisocyanates and, optionally, one or more further compounds having hydrogen atoms which are reactive towards isocyanates, chain extenders and/or crosslinkers, catalysts, blowing agents and further additives, and reacting the mixture to form the polyurethane.

28. The process of claim 27, wherein the polyurethane is a polyurethane foam and the mixture comprises blowing agents.

29. A polyurethane, obtained by the process of claim 27.

Description

EXAMPLES

Example 1

Amine Added Dropwise and Stoichiometric

[0129] 6.9 g (47 mmol) adipic acid and 400 g of a trifunctional highly active polyether polyol having primary hydroxyl end groups based on glycerine and PO/EO blocks with 14 wt % EO blocks (Lupranol of BASF SE) were provided in a 2.5 I glass reactor. After purging the reactor with nitrogen, the contents were heated to 240 C. under stirring and a constant nitrogen flow. After reaching the reaction temperature, 93 g (47 mmol) of a polyetheramine (difunctional primary amine) having a number average molecular weight of approximately 2,000 g/mol (Baxxodur EC 303 of BASF SE) were added via a dropping funnel. After ending the addition of Baxxodur EC 303, the reaction mixture was maintained at 240 C. for additional 15 minutes. Subsequently, the reaction mixture was cooled to 80 C. A clear solution was obtained which remained homogeneous after weeks of storage.

Example 2

Baxxodur and Hexamethylenediamine as Amino Components

[0130] 12.1 g (83 mmol) adipic acid, 83.0 g (41 mmol) Baxxodur EC 303 and 400 g Lupranol were provided in a 2.5 I glass reactor. After purging the reactor with nitrogen, the contents were heated to 180 C. with stirring and a constant nitrogen flow. After reaching the reaction temperature, 4.8 g (41 mmol) hexamethylenediamine were added dropwise with a dropping funnel. After adding the hexamethylenediamine, the reaction mixture was maintained for additional 30 minutes at 180 C. Subsequently, the reaction mixture was cooled to 80 C. The product was stable over weeks.

Comparative Example 3

All Reactants were Provided in the Reactor

[0131] 6.9 g (47 mmol) adipic acid, 93 g (47 mmol) Baxxodur EC 303 and 400 g Lupranol were provided in a 2.5 I glass reactor. After purging the reactor with nitrogen, the reactor ingredients were heated to 240 C. under stirring and a constant nitrogen flow. After reaching the reaction temperature, the mixture was maintained for additional 30 minutes at 240 C. Subsequently, the reaction mixture was cooled to 80 C. A solution was obtained which showed a phase separation after several days. The product had a viscosity of 1,398 mPa.Math.s (25 C.).

Comparative Example 4

Non-Stoichiometric

[0132] 6.6 g (45 mmol) adipic acid and 400 g Lupranol were provided in a 2.5 I glass reactor. After purging the reactor with nitrogen, the mixture was heated to 240 C. with stirring and a constant nitrogen flow. After reaching the reaction temperature, a mixture of 2.64 g (23 mmol) hexamethylenediamine and 91 g (45 mmol) Baxxodur EC 303 were added slowly and dropwise with a dropping funnel. Afterwards, the reaction mixture was maintained at 240 C. for additional 15 minutes. Subsequently, the reaction mixture was cooled to 80 C. A solution was obtained which showed phase separation after several days. The product had a viscosity of 1,206 mPa.Math.s (25 C.).

[0133] Testing in Flexible Foams

[0134] A polyol component was prepared by mixing various amount of the polyol from Example 1 with other polyols, catalysts and additives as indicated in the following table (parts by weight). The polyol component was manually mixed with the appropriate amount of a MDI blend (NCO value of 32.8%) to achieve an isocyanate index of 95 and poured into a mold where it cured to form a flexible foam.

[0135] The density was measured according to DIN EN ISO 845, the compressive strength according to DIN EN ISO 3386-1.

TABLE-US-00001 Type Hydroxyl number Comp. Example Example A Example B Component Polyol Ex. 1 See above 25 40 Polyol A Polyether 28 mg KOH/g 95 70 55 Polyol B Polyether 41 mg KOH/g 3.0 3.0 3.0 Catalyst 1 Amine catalyst 0.2 0.2 0.2 Catalyst 2 Amine catalyst 0.65 0.65 0.65 Stabilizer 1 0.5 0.5 0.5 Stabilizer 2 0.1 0.2 0.1 Water 3.0 3.0 3.0 Properties Start time/s 14 14 14 Density/g/L 49.4 50.4 48.9 Compressive 4.3 6.7 8.2 Strength/kPa

[0136] Catalyst 1 is a 33 wt % solution of triethylene diamine in dipropylene glycol.

[0137] Catalyst 2 is N,N,N-trimethyl-N-hydroxyethyl bisaminoethyl ether.

[0138] Stabilizer 1 is a silicone surfactant.

[0139] Stabilizer 2 is a silicone stabilizer.