Azetidine Derivatives, Method for Producing Said Derivatives and Use Thereof

Abstract

A description is given of azetidine derivatives and methods for producing them, and of their use as a latent curing component for resins having functional groups which are reactive toward amino groups. The particular advantages of the curing component proposed in accordance with the invention, such as effective producibility, high environmental friendliness, and excellent storage stability of the resin/curing agent mixtures, make these azetidine derivatives outstandingly suitable for one-component, moisture-hardening polymer compositions, which are of special interest in particular for the production of (floor) coatings, sealants, and adhesives.

Description

EXAMPLES

All examples were produced with air exclusion in a nitrogen atmosphere.

Example 1 A

Preparation of a Bis-Azetidine Based on Jeffamin D-230

In a reaction vessel with water separator 30 g (0.306 mol) of mesityl oxide, 33.48 g (0.146 mol) of Jeffamin D-230 (Huntsman), and 0.1 g of p-toluenesulfonic acid are dissolved in 150 g of absolute toluene and the solution is heated to boiling. The reaction mixture is held at boiling temperature until water can no longer be removed via the water separator (theoretical: 5.24 g of water). Subsequently the toluene is removed completely. This gives a slightly orange-colored, oily product.

Example 1 B

Production of an NCO-containing Prepolymer with the Bisazetidine Curing Agent Derivative from Example 1A

In a reaction vessel 250 g (0.125 mol) of polypropylene glycol Dow Voranol P2000 (from Dow) are held with 55.55 g (0.25 mol) of isophorone diisocyanate and 0.1 g of T12-DBTL at 85° C. until the theoretical NCO content of 3.44% by weight is reached.

Subsequently 48.0 g (0.123 mol) of bisazetidine derivative from Example 1A are stirred into 300.0 g of the NCO-containing prepolymer at room temperature.

The product obtained is resinous, is transparently clear, and possesses a weak orange coloration. Drawn down on a glass plate, it cures right through within a short time without any unpleasant odor nuisance. Even in a high-build application, curing takes place right through.

Example 1 C

Production of an NCO-containing Prepolymer with the Bisazetidine Curing Agent Derivative from Example 1A

In a reaction vessel 250 g (0.125 mol) of polypropylene glycol Dow Voranol P2000 (from Dow) are held with 43.54 g (0.25 mol) of toluene diisocyanate and 0.1 g of T12-DBTL at 85° C. until the theoretical NCO content of 3.58% by weight is reached.

Subsequently 40.0 g (0.102 mol) of bisazetidine derivative from Example 1A are stirred into 250.0 g of the NCO-containing prepolymer at room temperature.

The product obtained is resinous, is transparently clear, and possesses a weak orange coloration. Drawn down on a glass plate, it cures right through without any unpleasant odor nuisance. Even in a high-build application, curing takes place right through.

Example 2 A

Preparation of a Bis-Azetidine Based on 1,6-hexamethylenediamine

In a reaction vessel with water separator 30 g (0.306 mol) of mesityl oxide, 16.91 g (0.146 mol) of 1,6-hexamethylenediamine, and 0.1 g of p-toluenesulfonic acid are dissolved in 150 g of absolute toluene and the solution is heated to boiling. The reaction mixture is held at boiling temperature until water can no longer be removed via the water separator (theoretical: 5.24 g of water). Subsequently the toluene is removed completely.

Example 2 B

Production of an NCO-Containing Prepolymer with the Bisazetidine Curing Agent Derivative from Example 2A

In a reaction vessel 250 g (0.125 mol) of polypropylene glycol Dow Voranol P2000 (from Dow) are held with 42.05 g (0.25 mol) of hexamethylene 1,6-diisocyanate and 0.1 g of T12-DBTL at 85° C. until the theoretical NCO content of 3.60% by weight is reached.

Subsequently 28.33 g (0.102 mol) of bisazetidine derivative from Example 2A are stirred into 250 g of the NCO-containing prepolymer at room temperature.

The product obtained is resinous, is transparently clear, and possesses a weak yellowish coloration. Drawn down on a glass plate, it cures right through without any unpleasant odor nuisance. Even in a high-build application, curing takes place right through.

Example 2 C

Production of an NCO-Containing Prepolymer with the Bisazetidine Curing Agent Derivative from Example 2A

In a reaction vessel 250 g (0.125 mol) of polypropylene glycol Dow Voranol P2000 (from Dow) are held with 65.59 g (0.25 mol) of H12MDI and 0.1 g of T12-DBTL at 85° C. until the theoretical NCO content of 3.33% by weight is reached.

Subsequently 35.78 g (0.129 mol) of bisazetidine derivative from Example 2A are stirred into the NCO-containing prepolymer at room temperature.

The product obtained is resinous, is transparently clear, and possesses a weak yellowish coloration. Drawn down on a glass plate, it cures right through without any unpleasant odor nuisance. Even in a high-build application, curing takes place right through.

Example 2 D

Formulation of an Epoxy-Functional Resin with the Bisazetidine Curing Agent Derivative from Example 2A

At 40° C. 203.2 g (0.735 mol) of bisazetidine derivative from Example 2A are stirred homogeneously into 250 g (0.735 mol) of bisphenol A diglycidyl ether.

The product obtained is viscous, is transparently clear, and possesses a weak yellowish coloration. Drawn down on a glass plate, it cures right through without any unpleasant odor nuisance.

Example 3 A

Preparation of a Tris-Azetidine Based on Jeffamin T-403

In a reaction vessel with water separator 30 g (0.306 mol) of mesityl oxide, 45.85 g (0.102 mol) of Jeffamin T-403 (Huntsman), and 0.1 g of p-toluene-sulfonic acid are dissolved in 150 g of absolute toluene and the solution is heated to boiling. The reaction mixture is held at boiling temperature until water can no longer be removed via the water separator (theoretical: 5.50 g of water). Subsequently the toluene is removed completely. This gives a slightly orange-colored, resinous oil.

Example 3 B

Production of an NCO-Containing Prepolymer with the Trisazetidine Curing Agent Derivative from Example 3A

In a reaction vessel 250 g (0.125 mol) of polypropylene glycol Dow Voranol P2000 (from Dow) are held with 42.05 g (0.25 mol) of hexamethylene 1,6-diisocyanate and 0.1 g of T12-DBTL at 85° C. until the theoretical NCO content of 3.60% by weight is reached.

Subsequently 57.66 g (0.0835 mol) of trisazetidine derivative from Example 3A are stirred into the NCO-containing prepolymer at room temperature.

The product obtained is resinous, is transparently clear, and possesses a weak orange coloration. Drawn down on a glass plate, it cures right through without any unpleasant odor nuisance. Even in a high-build application, curing takes place right through.

Example 3 C

Formulation of an Epoxy-Functional Resin with the Trisazetidine Curing Agent Derivative from Example 3A

At 40° C. 338.26 g (0.490 mol) of trisazetidine derivative from Example 3A are stirred homogeneously into 250 g (0.735 mol) of bisphenol A diglycidyl ether. The product obtained is viscous, is transparently clear, and possesses a weak yellowish coloration. Drawn down on a glass plate, it cures right through without any unpleasant odor nuisance.

Example 4 A

Preparation of a Tris-Azetidine Based on Jeffamin T-403

In a reaction vessel with water separator 30 g (0.357 mol) of 3-methylcrotonaldehyde, 53.50 g (0.119 mol) of Jeffamin T-403 (Huntsman), and 0.1 g of p-toluenesulfonic acid are dissolved in 200 g of absolute toluene and the solution is heated to boiling. The reaction mixture is held at boiling temperature until water can no longer be removed via the water separator (theoretical: 6.42 g of water). Subsequently the toluene is removed completely. This gives a slightly orange-colored, resinous oil.

Example 4 B

Production of an NCO-Containing Prepolymer with the Trisazetidine Curing Agent Derivative from Example 4A

In a reaction vessel 250 g (0.125 mol) of polypropylene glycol Dow Voranol P3000 (from Dow) are held with 28.03 g (0.167 mol) of hexamethylene 1,6-diisocyanate and 0.1 g of T12-DBTL at 85° C. until the theoretical NCO content of 2.52% by weight is reached.

Subsequently 36.03 g (0.0556 mol) of trisazetidine derivative from Example 4A are stirred into the NCO-containing prepolymer at room temperature.

The product obtained is resinous, is transparently clear, and possesses a weak orange coloration. Drawn down on a glass plate, it cures right through without any unpleasant odor nuisance. Even in a high-build application, curing takes place right through.

Example 5 A

Preparation of a Bis-Azetidine Based on Jeffamin D-230

In a reaction vessel with water separator 30 g (0.357 mol) of 3-methylcrotonaldehyde, 41.00 g (0.178 mol) of Jeffamin D-230 (Huntsman), and 0.1 g of p-toluenesulfonic acid are dissolved in 150 g of absolute toluene and the solution is heated to boiling. The reaction mixture is held at boiling temperature until water can no longer be removed via the water separator (theoretical: 6.42 g of water). Subsequently the toluene is removed completely. This gives a slightly orange-colored oil.

Example 5 B

Formulation of an Epoxy-Functional Resin with the Bisazetidine Curing Agent Derivative from Example 5A

At 40° C. 266.25 g (0.735 mol) of bisazetidine derivative from Example 5A are stirred homogeneously into 250 g (0.735 mol) of bisphenol A diglycidyl ether.

The product obtained is viscous, is transparently clear, and possesses a weak yellowish coloration. Drawn down on a glass plate, it cures right through without any unpleasant odor nuisance.

Example 6

Storage Stability Test

The mixtures of prepolymers and latent curing agents produced in accordance with Examples 1 to 5 are subjected to storage in closed vessels at room temperature (20-25° C.), the results obtained being as follows:

After a storage time of 12 months at a temperature between 20-25° C. in lightfast and airtight vessels, no notable change in color was found for any of the examples. The increase in viscosity over this period was very low (increase by a factor in the range of 1.1-1.3 relative to the initial viscosity) and exhibited no effect at all on the curing or the processing properties.

Claims

1. An azetidine derivative of the general

2. (canceled)

3. (canceled)

4. A method for producing an azetidine derivative of claim 1, wherein a polyamine of the formula NH2-Z′-NH2 is reacted with an α,β-unsaturated aldehyde of the formula R1R2—C═CR3CHO or with an α,β-unsaturated ketone of the formula R1R2C═CR3—COR4 in the temperature range from 20 to 150° C., where Z′ is C2-C25 alkylidene, C5-C25 cycloalkylidene, C6-C24 arylene, and

5. The method of claim 4, wherein the reaction is carried out in the presence of an organic solvent, especially toluene.

6. The use of an azetidine derivative of claim 1 as a latent curing component for resins having functional groups which are reactive toward amino groups.

7. The use of claim 6, wherein the azetidine derivative of the formula (II) and/or (III) is mixed with the resin to be cured, the azetidine ring is hydrolytically opened by moisture exposure, and the secondary amine formed is caused to react with the reactive functional groups of the resin to be cured.

8. The use of claim 6, wherein polyurethanes or polyepoxides and also mixtures thereof are used as resin to be cured.

9. The use of claim 6 wherein the curing component is used an amount of 0.01% to 150% by weight, in particular 0.1% to 20% by weight, based on the amount of the resin to be cured.

10. The use of claim 6 wherein the mixture consisting of curing component and resin is cured at a temperature of 5 to 80° C. and optionally in the presence of a suitable catalyst.

11. The use of claim 6 wherein the curing component is used in the production of (floor) coatings, sealants, and adhesives.