A CURABLE ORGANIC POLYMER COMPRISING AT LEAST ONE ACYLUREA UNIT, ITS PREPARATION AND USE

Abstract

The present invention suggests a curable organic polymer comprising at least one acylurea unit represented by structural formula (I):

##STR00001##

Moreover, the present invention suggests a process for the preparation of said polymer and the use of said curable organic polymer for the preparation of a cured composition and for the preparation of hydroxyurethanes.

Claims

1. A curable organic polymer comprising at least one acylurea unit represented by structural formula (I): ##STR00022##

2. The polymer of claim 1, comprising 3 to 12 acylurea units.

3. The polymer of claim 1, characterized in that the polymer is represented by structural formula (II): ##STR00023## with n=1 to 12 and wherein R.sup.1 is selected from straight-chain, branched or cyclic C.sub.1-12-alkyl groups, C.sub.6-10-aryl groups, C.sub.6-14-aralkyl groups, and C.sub.6-14-alkaryl groups and in that the polymer is terminated by terminal groups, which are, in each case independently of one another, selected from: ##STR00024## wherein R.sup.2, R.sup.3 and R.sup.4 are independently of one another selected from straight-chain, branched or cyclic C.sub.1-12-alkyl groups, C.sub.6-10-aryl groups, C.sub.6-12-aralkyl groups, C.sub.6-12-alkaryl groups, C.sub.1-4-alkoxy-C.sub.2-120-(poly)(oxyalkylene) groups, polyester groups and polycarbonate groups.

4. The polymer of claim 3, characterized in that R.sup.2 is an alkoxy-polyoxyethylene group with a molecular weight of 76 to 2000.

5. A process for the preparation of a curable organic polymer as defined in claim 1, characterized in that 2-oxo-1,3-dioxolane-4-carboxylic acid of formula (III): ##STR00025## is reacted with a polymer comprising at least one carbodiimide unit represented by structural formula (IV):
—N═C═N—  (IV).

6. The process of claim 5, characterized in that 0.5 to 2.0 equivalents of 2-oxo-1,3-dioxolane-4-carboxylic acid of formula (III) are used per carbodiimide unit of formula (IV).

7. The process of claim 5, characterized in that the reaction is performed at 20-100° C.

8. The process of claim 5, characterized in that the reaction is carried out in the presence of a solvent.

9. The process of claim 5, characterized in that the reaction is performed in the presence of a catalyst selected from tertiary amines, organometallic compounds, and mixtures thereof.

10. A process comprising utilizing the polymer as defined in claim 1 comprising curing the polymer for the preparation of a cured composition.

11. The process of claim 10, characterized in that the polymer is cured by reaction with an at least bifunctional amine.

12. A process comprising utilizing the polymer as defined in claim 1 for the preparation of hydroxyurethanes by crosslinking of the polymer at its bound cyclic carbonate group with an at least bifunctional amine, and/or reacting the amine at the polymer acylurea group.

13. A process for the preparation of a curable organic polymer as defined in claim 3, characterized in that 2-oxo-1,3-dioxolane-4-carboxylic acid of formula (III): ##STR00026## is reacted with a polymer comprising at least one carbodiimide unit represented by structural formula (IV):
—N═C═N—  (IV).

14. The process of claim 5, characterized in that the reaction is performed at 20-30° C.

15. The process of claim 5, characterized in that the reaction is carried out in the presence of a solvent selected from acetone, THF, toluene and dioxane.

16. The polymer of claim 1, comprising 4 to 8 acylurea units.

Description

EXAMPLES

Example 1: Preparation of a TDI-Carbodiimide and Subsequent Reaction with CYCA

[0045] ##STR00020##

[0046] 34.83 g TDI (0.2 mol) was dissolved in 66 ml hexane and 0.25 g DMPO (Phospholene oxide, Lubio Polykat® 1, Schäfer-Additivsysteme GmbH) was added. The reaction mixture was stirred at ambient temperature for 12 h, and a white precipitate formed. The solid product was filtered off, washed with petrol ether and recrystallized from hexane.

[0047] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.12-6.86 (m, 6H, Ar), 2.29 (s, 6H, CH.sub.3) ppm. IR (v, cm.sup.−1): 2361 (w), 2344 (w), 2273 (s, NCO), 2131 (s, diimide), 2098 (s, diimide), 1717 (w), 1600 (s), 1562 (m), 1512 (m), 1477 (s), 1287 (w), 1224 (w), 1196 (m), 1145 (w), 1073 (m), 993 (m), 917 (m), 887 (s), 823 (s), 751 (w), 718 (m), 591 (s), 548 (s).

[0048] 2.25 g of the obtained TDI-carbodiimide (7.4 mmol) was dissolved in 60 ml dry THF and 2.93 g (22.2 mmol) 2-oxo-1,3-dioxolane-4-carboxylic acid (CYCA) was added. The reaction mixture was stirred at ambient temperature until the carbodiimide was reacted completely (12 h, IR control). Afterwards, 0.04 g DMAP (4-dimethylamino pyridine, 0.3 mmol) were added and the reaction mixture was heated to 65° C. until the TDI-carbodiimide was completely reacted (12 h). During this period a white precipitate formed which was filtered off and dried in vacuo. The solid product was obtained as a white powder in quantitative yield.

[0049] IR (v, cm.sup.−1): 3356 (bw), 2975 (m), 2870 (m), 2275 (w), 1817 (s, cyclocarbonate), 1704 (s), 1592 (m), 1536 (s), 1451 (m), 1413 (w), 1385 (w), 1220 (m), 1155 (s), 1058 (s), 899 (m), 815 (w), 766 (w), 656 (m), 532 (w).

Example 2: Reaction of TMXDI-Carbodiimides with CYCA

[0050] ##STR00021##

[0051] a) 12.5 g Elastostab® H02 (NCO-terminated TMXDI-carbodiimide of BASF, 7% Isocyanate, 14% Carbodiimide) was dissolved in 80 g dry acetone and 8.53 g (0.065 mol, excess) 2-oxo-1,3-dioxolane-4-carboxylic acid (CYCA) was added. The reaction mixture was stirred at ambient temperature until the carbodiimide was completely reacted (12 h, IR control). Afterwards 0.16 g DMAP (1.3 mmol) was added, and the reaction mixture was heated to 65° C. until the TMXDI-carbodiimide was completely reacted (12 h). The solvent was evaporated and the product was obtained as white powder in quantitative yield.

[0052] b) 277 g Elastostab® H01 (polyether-terminated TMXDI-carbodiimide of BASF, 7% Carbodiimide) was dissolved in 1 l dry acetone and 64 g (0.49 mol) 2-oxo-1,3-dioxolane-4-carboxylic acid (CYCA) was added. The reaction mixture was stirred at ambient temperature until the carbodiimide was completely reacted (12 h, IR control). The solvent was evaporated, and the product was obtained as white powder in quantitative yield.

[0053] IR (v, cm.sup.−1): 3310 (bw), 2974 (m), 2862 (m), 1822 (m, cyclocarbonate), 1710 (m), 1693 (m), 1521 (w), 1460 (w), 1386 (w), 1252 (m), 1149 (m), 1065 (s), 907 (s), 799 (w), 766 (w), 708 (w), 655 (w), 499 (w).

Example 3: Reaction of IPDI-Carbodiimide with CYCA

[0054] 28.39 g IPDI-carbodiimide (of BASF, 6.8% diimide content, 60% solution in Proglyde® DMM,) was dissolved in 100 ml dry THF, and 3.74 g (0.18 mol) 2-oxo-1,3-dioxolane-4-carboxylic acid (CYCA) was added. The reaction mixture was stirred at ambient temperature until the carbodiimide was completely reacted (12 h, IR control). The solvent was evaporated and the product was obtained as a viscous yellow oil in quantitative yield.

[0055] IR (v, cm.sup.−1): 2973 (m), 2862 (m), 2122 (w), 1823 (m, cyclocarbonate), 1692 (m), 1539 (w), 1460 (m), 1366 (w), 1245 (w), 1066 (s), 907 (m), 766 (w), 655 (w).

Example 4: Curing of Acylurea-Based Cyclocarbonate Binders

[0056] The reaction products of Examples 2a and 2b were cured with different bi/tri-functional amine hardeners. The respective reaction products, amine hardeners, amounts (mol), cyclocarbonate (“Cyc”): amine ratio, and the curing behavior are given in Table 1 hereinbelow.

TABLE-US-00001 TABLE 1 Binder/Amine Amount “Cyc”:Amine Curing Behavior 1 Ex. 2a, 60% solution in THF 0.005 1:1 Exothermic, fast curing, potlife IPDA 0.005 10 min, brittle, tack-free 2 Ex. 2a, 60% solution in THF 0.005 1:1 Very exothermic, fast curing, DYTEK ® EP diamin 0.005 potlife 10 min, brittle, tack-free 3 Ex. 2a, 60% solution in THF 0.005 1:1 Exothermic, fast curing, potlife 1,3-Diamino-2,2- 0.005 10 min, brittle, tack-free dimethylpropan 4 Ex. 2a, 60% solution in THF 0.005 1:1 Exothermic, fast curing, potlife Diethylentriamin 0.005 10 min, brittle, tack-free 5 Ex. 2a, 60% solution in THF 0.005 1:1 Gelling, no complete curing Jeffamin D 400 0.005 6 Ex. 2a, 60% solution in THF 0.005 1:1 Potlife 5 min, tacky Polyetheramin T 403 0.005 7 Ex. 2a, 60% solution in THF 0.005 1:1 Exothermic, fast curing, potlife 1,3-Cyclohexanbis(methylamin) 0.005 10 min, brittle, tack-free 8 Ex. 2b, 70% solution in H.sub.2O 0.005 1:1 Tacky, soft and elastic IPDA 0.005 9 Ex. 2b, 70% solution in H.sub.2O 0.005 1:2 Hard and brittle, tack-free, IPDA 0.010 completely cured 10 Ex. 2b, 70% solution in H.sub.2O 0.008 1:2 Cured, tacky TMD 0.016 11 Ex. 2b, 70% solution in H.sub.2O 0.003 — No curing Without Amine —

[0057] Curing of acylurea-based cyclocarbonate binders can be observed with various amines. Best results, i.e. tack-free, stable and hard films with good mechanical properties were obtained with the modified Elastostab® H01 system (i.e. Ex. 2a) with an excess of IPDA.