CYCLOALIPHATIC ALDIMINE MIXTURE

Abstract

A mixture of isomeric aldimines of the formulae (Ia), (Ib) and (Ic) in which the ratio of the trans,trans isomer (Ia) to the sum of the cis,trans isomer (Ib) and the cis,cis isomer (Ic) is in the range of 5/95 to 30/70, and its use as latent hardener for moisture-curing isocyanate-functional polyurethane compositions. The inventive mixture of isomeric aldimines enables polyurethane compositions with very low content of monomeric isophorone diisocyanate and excellent stability under outdoor wheathering conditions and high UV load, which cure quickly to an elastic material of low surface tack and good mechanical properties, particularly in terms of high tensile strength and modulus of elasticity at high elongation. Such compositions are particularly suitable as elastic adhesives and/or sealants or elastic coatings, particularly for outdoor use such as on roofs, floors or ships.

Claims

1. Mixture of isomeric aldimines of the formulae (Ia), (Ib) and (Ic), ##STR00010## wherein each Y independently is a monovalent linear or branched C.sub.3 to C.sub.20 alkyl or cycloalkyl or arylalkyl group optionally containing ether, ester, tertiary amine, amide, urethane and/or urea groups, wherein the ratio of the trans,trans isomer (Ia) to the sum of the cis,trans isomer (Ib) and the cis,cis isomer (Ic) is in the range of 5/95 to 30/70.

2. Mixture of isomeric aldimines according to claim 1, wherein the ratio of the trans,trans isomer (Ia) to the sum of the cis,trans isomer (Ib) and the cis,cis isomer (Ic) is in the range of 15/85 to 25/75.

3. Mixture of isomeric aldimines according to claim 1, wherein Y is a branched C.sub.3 to C.sub.7 alkyl.

4. Mixture of isomeric aldimines according to claim 1, wherein Y is a moiety of the formula (II), ##STR00011## wherein R.sup.1 and R.sup.2 are the same or different C.sub.1 to C.sub.4 alkyls, or are joined together to form a C.sub.4 to C.sub.6 alkylene, and R.sup.5 is H or a C.sub.1 to C.sub.17 alkyl optionally containing one or more ether groups.

5. Mixture of isomeric aldimines according to any one of claim 1, wherein Y is a moiety of the formula (III), ##STR00012## wherein R.sup.1 and R.sup.2 are the same or different C.sub.1 to C.sub.4 alkyls, or are joined together to form a C.sub.4 to C.sub.6 alkylene, and R.sup.3 and R.sup.4 are the same or different C.sub.1 to C.sub.8 alkyls optionally containing ether oxygen, or are joined together to form a C.sub.4 to C.sub.6 alkylene optionally containing ether oxygen.

6. Mixture of isomeric aldimines according to claim 5, wherein R.sup.1 and R.sup.2 are both methyl and R.sup.3 and R.sup.4 are joined together to form a 3-oxa-1,5-pentylen group, which is part of a morpholine ring.

7. A latent hardener for moisture-curing polyurethane compositions comprising the mixture of isomeric aldimines according to claim 1.

8. The latent hardener according to claim 7, further comprising at least one further aldimine of the formula (VII), ##STR00013## wherein n is 2 or 3, A is the residue of a di- or triamine after the removal of the amine groups, wherein the di- or triamine is selected from the group consisting of hexane-1,6-diamine, 2-methylpentane-1,5-diamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 4(2)-methylcyclohexane-1,3diamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3bis(aminomethyl)benzene, 1,2-diaminocyclohexane, polyoxypropylene diamines with an average molecular weight M.sub.n in the range of 200 to 4,000 g/mol and polyoxypropylene triamines with an average molecular weight M.sub.n in the range of 380 to 5,000 g/mol, and Y is the same substituent in the formulae (Ia), (Ib) and (Ic) and in the formula (VII).

9. Moisture-curing polyurethane composition comprising at least one polyisocyanate and/or isocyanate-functional polymer obtained from the reaction of at least one monomeric diisocyanate and at least one polyol, and a mixture of isomeric aldimines according to claim 1.

10. Composition according to claim 9, containing an isocyanate-functional polymer with an NCO-content in the range of 1 to 10 weight-% obtained from at least one polyether polyol.

11. Composition according to claim 9 containing an amount of monomeric diisocyanates of below 0.1 weight-% in relation to the total composition.

12. Cured composition, obtained from the composition according to claim 9 after its contact with moisture.

13. Elastic coating, adhesive or sealant containing the cured composition according to claim 12.

14. Primer, paint or varnish containing the cured composition according to claim 12.

15. Waterproofing and/or floor system, comprising optionally a primer undercoat, optionally an undercoat, and one or more than one layer of the composition according to claim 10, optionally in combination with a fibre reinforcement mesh or broadcasted with decorative flakes or quartz sand.

Description

EXAMPLES

[0193] The following examples illustrate the present invention without being limiting. “Normal climate” means a temperature of 23±1° C. and a relative atmospheric moisture of 50±5% and is abbreviated with “NC”.

[0194] Unless otherwise stated, chemicals were purchased from Sigma-Aldrich Chemie GmbH and used as received.

Used Amines:

[0195] Vestamine® PACM: 4,4′-methylene-bis(cyclohexylamine), mixture of isomers containing approx. 20% of the trans,trans isomer, liquid at room temperature, solidification at approx. 15° C. (from Evonik) [0196] Dicykan®: 4,4′-methylene-bis(cyclohexylamine), mixture of isomers containing approx. 50% of the trans,trans isomer, solid at room temperature, solidification at approx. 38° C. (from BASF) [0197] IPDA: 3-aminomethyl-3,5,5-trimethylcyclohexylamine (Vestamin® IPD from Evonik) [0198] Jeffamine® T-403: polyoxypropylene triamine of average molecular weight of about 440 g/mol (from Huntsman)

Preparation of Aldimines:

[0199] The amine content (total content of free amino and aldimino groups) of the prepared aldimines was determined by titration (with 0.1N HClO.sub.4 in acetic acid against cristal violet) and is given in mmol N/g.

[0200] The viscosity was measured with a thermostated cone-plate-viscometer Rheotec RC.sub.30 (cone diameter 50 mm, cone angle 1°, cone-plate-distance 0.05 mm, shear rate 10 s-1).

[0201] Aldimine A1: Mixture of Isomeric N,N′-Bis(2,2-Dimethyl-3-(N-Morpholino)Propylidene)-4,4′-Methylene-Bis(Cyclohexylamine) with a Ratio of the Trans,Trans Isomer to the Sum of the Cis,Trans Isomer and the Cis,Cis Isomer of Approx. 20/80 210.4 g (1 mol) Vestamine® PACM were placed in a round bottom flask under nitrogen atmosphere. Then 359.5 g (2.1 mol) 2,2-dimethyl-3-(N-morpholino)propanal were added under good stirring, followed by removing the volatile contents at 80° C. and 10 mbar vacuum. The product obtained was a clear yellow liquid with a viscosity of 13.9 Pa.Math.s at 20° C. and an amine content of 7.68 mmol N/g, corresponding to a calculated aldimine equivalent weight of approx. 267 g/Eq.

[0202] Aldimine A2: Mixture of Isomeric N, N′-Bis(Isobutylidene)-4,4′-Methylene-Bis(Cyclohexylamine) with a Ratio of The Trans,Trans Isomer to the Sum Of The Cis,Trans Isomer and the Cis,Cis Isomer of Approx. 20/80

[0203] 42.1 g (0.20 mol) Vestamine® PACM were placed in a round bottom flask under nitrogen atmosphere. Then 30.3 g (0.42 mol) isobutyraldehyde were slowly added with a dropping funnel under cooling with a water bath and good stirring, followed by removing the volatile contents at 80° C. and 10 mbar vacuum. The product obtained was a clear colorless liquid with a viscosity of 138 mPa.Math.s at 20° C. (83 mPa.Math.s at 25° C.) and an amine content of 6.13 mmol N/g, corresponding to a calculated aldimine equivalent weight of approx. 163 g/Eq.

[0204] Aldimine A3: Mixture Of Isomeric N,N′-Bis(2,2-Dimethyl-3-Acetoxypropylidene)-4,4′-Methylene-Bis(Cyclohexylamine) with a Ratio of the Trans,Trans Isomer to the Sum of the Cis,Trans Isomer and the Cis,Cis Isomer of Approx. 20/80

[0205] 42.1 g (0.20 mol) Vestamine® PACM were placed in a round bottom flask under nitrogen atmosphere. Then 60.6 g (0.42 mol) 2,2-dimethyl-3-acetoxypropanal were added under good stirring, followed by removing the volatile contents at 80° C. and mbar vacuum. The product obtained was a clear colorless liquid with a viscosity of 1.9 Pas at 20° C. and an amine content of 4.19 mmol N/g, corresponding to a calculated aldimine equivalent weight of approx. 239 g/Eq.

[0206] Aldimine A4: Mixture of Isomeric N,N′-Bis(2,2-Dimethyl-3-Lauroyloxypropylidene)-4,4′-Methylene-Bis(Cyclohexylamine) with a Ratio of the Trans,Trans Isomer to the Sum of the Cis,Trans Isomer and the Cis,Cis Isomer of Approx. 20/80

[0207] 42.1 g (0.20 mol) Vestamine® PACM were placed in a round bottom flask under nitrogen atmosphere. Then 119.5 g (0.42 mol) 2,2-dimethyl-3-lauroyloxypropanal were added under good stirring, followed by removing the volatile contents at 80° C. and 10 mbar vacuum. The product obtained was a clear yellowish liquid with a viscosity of 468 mPa.Math.s at 20° C. and an amine content of 2.59 mmol N/g, corresponding to a calculated aldimine equivalent weight of approx. 386 g/Eq.

[0208] Aldimine B1: Mixture of Isomeric N,N′-Bis(2,2-Dimethyl-3-(N-Morpholino)Propylidene)-4,4′-Methylene-Bis(Cyclohexylamine) with a Ratio of the Trans,Trans Isomer to the Sum of the Cis,Trans Isomer and the Cis,Cis Isomer of Approx. 50/50 210.4 g (1 mol) Dicykan® were melted at 60° C. and placed in a round bottom flask under nitrogen atmosphere. Then 359.5 g (2.1 mol) 2,2-dimethyl-3-(N-morpholino)propanal were added under good stirring, followed by removing the volatile contents at 80° C. and 10 mbar vacuum. The product obtained was a brownish liquid with a viscosity of 13.9 Pas at 20° C., which gradually solidified upon storage at room temperature, with an amine content of 7.68 mmol N/g, corresponding to a calculated aldimine equivalent weight of approx. 267 g/Eq.

[0209] Aldimine B2: Mixture of Isomeric N, N′-Bis(Isobutylidene)-4,4′-Methylene-Bis(Cyclohexylamine) with a Ratio of the Trans,Trans Isomer to the Sum of the Cis,Trans Isomer and the Cis,Cis Isomer of Approx. 50/50

[0210] 42.1 g (0.20 mol) Dicykan® were melted at 60° C. and placed in a round bottom flask under nitrogen atmosphere. Then 30.3 g (0.42 mol) isobutyraldehyde were added with a dropping funnel under cooling with a water bath and good stirring, followed by removing the volatile contents at 80° C. and 10 mbar vacuum. The product obtained was a clear brownish liquid with a viscosity of 150 mPa.Math.s at 20° C. (100 mPa.Math.s at 25° C.), which gradually solidified upon storage at room temperature, with an amine content of 6.13 mmol N/g, corresponding to a calculated aldimine equivalent weight of approx. 163 g/Eq.

[0211] Aldimine B3: Mixture of Isomeric N,N′-Bis(2,2-Dimethyl-3-Acetoxypropylidene)-4,4′-Methylene-Bis(Cyclohexylamine) with a Ratio of the Trans,Trans Isomer to the Sum of the Cis,Trans Isomer and the Cis,Cis Isomer of Approx. 50/50 42.1 g (0.20 mol) Dicykan® were melted at 60° C. and placed in a round bottom flask under nitrogen atmosphere. Then 60.6 g (0.42 mol) 2,2-dimethyl-3-acetoxypropanal were added under good stirring, followed by removing the volatile contents at 80° C. and 10 mbar vacuum. The product obtained was a clear brownish liquid with a viscosity of 2.7 Pa.Math.s at 20° C. and an amine content of 4.26 mmol N/g, corresponding to a calculated aldimine equivalent weight of approx. 235 g/Eq.

[0212] Aldimine B4: Mixture of Isomeric N,N′-Bis(2,2-Dimethyl-3-Lauroyloxypropylidene)-4,4′-Methylene-Bis(Cyclohexylamine) with a Ratio of the Trans,Trans Isomer to the Sum of the Cis,Trans Isomer and the Cis,Cis Isomer of Approx. 50/50 42.1 g (0.20 mol) Dicykan® were melted at 60° C. and placed in a round bottom flask under nitrogen atmosphere. Then 119.5 g (0.42 mol) 2,2-dimethyl-3-lauroyloxypropanal were added under good stirring, followed by removing the volatile contents at 80° C. and 10 mbar vacuum. The product obtained was a clear brownish liquid with a viscosity of 518 mPa.Math.s at 20° C. and an amine content of 2.59 mmol N/g, corresponding to a calculated aldimine equivalent weight of approx. 386 g/Eq.

[0213] Aldimine B5: Mixture of Isomeric N,N′-Bis(Benzylidene)-4,4′-Methylene-Bis(Cyclohexylamine) with a Ratio of the Trans,Trans Isomer to the Sum Of The Cis,Trans Isomer and the Cis,Cis Isomer of Approx. 20/80

[0214] 42.1 g (0.20 mol) Vestamine® PACM were placed in a round bottom flask under nitrogen atmosphere. Then 44.6 g (0.42 mol) benzaldehyde were added under good stirring, followed by removing the volatile contents at 80° C. and 10 mbar vacuum. The product obtained was a yellowish solid with an amine content of 5.02 mmol N/g, corresponding to a calculated aldimine equivalent weight of approx. 199 g/Eq. The solid product had a melting point above 80° C.

[0215] Aldimine B6: Mixture of Isomeric N,N′-Bis(Benzylidene)-4,4′-Methylene-Bis(Cyclohexylamine) with a Ratio of the Trans,Trans Isomer to the Sum Of The Cis,Trans Isomer and the Cis,Cis Isomer of Approx. 50/50

[0216] 42.1 g (0.20 mol) Dicykan® were melted at 60° C. and placed in a round bottom flask under nitrogen atmosphere. Then 44.6 g (0.42 mol) benzaldehyde were added under good stirring, followed by removing the volatile contents at 80° C. and 10 mbar vacuum. The product obtained was a yellowish solid with an amine content of 5.03 mmol N/g, corresponding to a calculated aldimine equivalent weight of approx. 199 g/Eq. The solid product had a melting point above 100° C.

[0217] Aldimine D1: N,N′-Bis(2,2-Dimethyl-3-(N-Morpholino)Propylidene)-3-Aminomethyl-3,5,5-Trimethylcyclohexylamine

[0218] 170.3 g (1 mol) IPDA were placed in a round bottom flask under nitrogen atmosphere. Then 359.5 g (2.1 mol) 2,2-dimethyl-3-(N-morpholino)propanal were added under good stirring, followed by removing the volatile contents at 80° C. and 10 mbar vacuum. The product obtained was a nearly colourless liquid with an amine content of 8.25 mmol N/g, corresponding to a calculated aldimine equivalent weight of approx. 247 g/Eq.

[0219] Aldimine D2: N,N′,N″-tris(2,2-Dimethyl-3-(N-Morpholino)Propylidene) Polyoxypropylene Triamine 157.1 g (1 mol N) Jeffamine® T-403 were placed in a round bottom flask under nitrogen atmosphere. Then 179.8 g (1.05 mol) 2,2-dimethyl-3-(N-morpholino)propanal were added under good stirring, followed by removing the volatile contents at 80° C. and 10 mbar vacuum. The product obtained was a nearly colourless liquid with an amine content of 6.44 mmol N/g, corresponding to a calculated aldimine equivalent weight of approx. 320 g/Eq.

[0220] The Aldimines A1 to A4 are mixtures of isomeric aldimines according to the invention. The Aldimines B1 to B6 and D1 and D2 are for reference.

TABLE-US-00001 TABLE 1 Overview of the aldimines A1 to B6 B1 B2 B3 B4 B5 B6 Aldimine A1 (Ref.) A2 (Ref.) A3 (Ref.) A4 (Ref.) (Ref.) (Ref.) aldehyd 2,2-dimethyl-3- isobutyr- 2,2-dimethyl- 2,2-dimethyl- benz- base (N-morpho- aldehyde 3-acetoxy- 3-lauroyloxy- aldehyde lino)propanal propanal propanal content of the 20% 50% 20% 50% 20% 50% 20% 50% 20% 50% trans, trans isomer approx. viscosity 13.9 (13.3) 0.138 (0.150) 1.9 2.7 0.468 0.518 — — 20° C. [Pa .Math. s] solid solid solid solid
Preparation of Isocyanate-Functional Polyurethane Polymers: The content of monomeric diisocyanates was determined with HPLC (detection by photodiode array; 0.04 M sodium acetate/acetonitrile mobile phase) after derivatization with N-propyl-4-nitrobenzylamine.

[0221] The viscosity was measured with a thermostated cone-plate-viscometer Rheotec RC.sub.30 (cone diameter 25 mm, cone angle 1°, cone-plate-distance 0.05 mm, shear rate 10 s.sup.−1).

[0222] Polymer P1

[0223] 590 g polyoxypropylene diol (Acclaim® 4200, OH-number 28.5 mg KOH/g, from Covestro), 1180 g ethyleneoxide-capped polyoxypropylene triol (Caradol® MD34-02, OH-number 35.0 mg KOH/g, from Shell) and 230 g isophorone diisocyanate (Vestanat® IPDI, from Evonik) were reacted at 80° C. according to known procedures. The polymer obtained had an NCO-content of 2.1 weight-%, a viscosity of 22.5 Pa.Math.s at 20° C. and a content of monomeric isophorone diisocyanate of approx. 2 weight-%.

Polymer P2

[0224] 780 g ethyleneoxide-capped polyoxypropylene triol (Desmophen® 5031 BT, OH-number 28.0 mg KOH/g, from Covestro) and 220 g isophorone diisocyanate (Vestanat® IPDI, from Evonik) were reacted at 80° C. according to known procedures to form a mixture with an NCO-content of 6.4 weight-% and a content of monomeric isophorone diisocyanate of approximately 12 weight-%. The volatile contents, particularly most of the monomeric isophorone diisocyanate, were then removed from the mixture in a short path evaporator by distillation (jacket temperature 160° C., 0.1 to 0.005 mbar). The polymer obtained had an NCO-content of 1.9 weight-%, a viscosity of 10 Pa.Math.s at 20° C. and a content of monomeric isophorone diisocyanate of 0.02 weight-%.

Polymer P3:

[0225] 818 g polyoxypropylene diol (Acclaim® 4200, OH-number 28.5 mg KOH/g, from Covestro) and 182 g isophorone diisocyanate (Vestanat® IPDI, from Evonik) were reacted at 80° C. according to known procedures to form a mixture with an NCO-content of 5.1 weight-% and a content of monomeric isophorone diisocyanate of approximately 9 weight-%. The volatile contents, particularly most of the monomeric isophorone diisocyanate, were then removed from the mixture in a short path evaporator by distillation (jacket temperature 160° C., 0.1 to 0.005 mbar). The polymer obtained had an NCO-content of 1.9 weight-%, a viscosity of 6.5 Pa.Math.s at 20° C. and a content of monomeric isophorone diisocyanate of 0.03 weight-%.

Polymer P4:

[0226] 600 g polyoxypropylene diol (Voranol® 1010 L, OH-number 112 mg KOH/g, from Dow) and 400 g isophorone diisocyanate (Vestanat® IPDI, from Evonik) were reacted at 80° C. according to known procedures to form a mixture with an NCO-content of 10 weight-% and a content of monomeric isophorone diisocyanate of approximately 13 weight-%. The volatile contents, particularly most of the monomeric isophorone diisocyanate, were then removed from the mixture in a short path evaporator by distillation (jacket temperature 160° C., 0.1 to 0.005 mbar). The polymer obtained had an NCO-content of 5.5 weight-%, a viscosity of 21.8 Pa.Math.s at 20° C. and a content of monomeric isophorone diisocyanate of 0.03 weight-%.

Moisture-Curing Polyurethane Compositions:

Compositions C1 to C.SUB.10:

[0227] Each composition was prepared by mixing the ingredients given in Table 2 in the given amounts (weight parts) in a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) under exclusion of moisture, and stored in a moisture-tight container. Solid Aldimines were melted at 60° C. before use.

[0228] The compositions were tested as follows:

[0229] The viscosity was measured with a thermostated cone-plate-viscometer Rheotec RC.sub.30 (cone diameter 25 mm, cone angle 1° , cone-plate-distance 0.05 mm, shear rate 10 s-1) at 20° C. after storing the moisture-tight container in normal climate for one day (“1 d NC”) and again after storing the moisture-tight container in an oven at 60° C. for 7 days (“7d 60° C”). A small increase is an indication for a good storage stability.

[0230] The skinning time (skin formation time) was determined in normal climate by applying a few grams of the composition in a layer thickness of approx. 2 mm on cardboard and gently touching its surface with an LDPE pipette from time to time, until the touching did not leave any polymer residues on the pipette.

[0231] The Shore A hardness was determined according to DIN 53505 with cylindrical samples of 20 mm diameter and a thickness of 5 mm which had been stored in normal climate for 7 days.

[0232] To determine the mechanical properties, the composition was poured onto a PTFE coated foil in a layer thickness of approx. 2 mm and stored in normal climate for 7 days, followed by punching dumbell shaped samples out of the cured film with a length of 75 mm at a bridge length of 30 mm and a bridge width of 4 mm. With the so prepared samples, the tensile strength, the elongation (at break) and the E-modulus 5% (from 0.5 to 5% elongation) were determined according to DIN EN 53504 at a crosshead speed of 200 mm/min. The cured films of all the compositions were homogeneous and bubble-free.

[0233] The test results are given in Table 2.

[0234] Reference examples are marked with “(Ref.)”.

TABLE-US-00002 TABLE 2 Composition (in weight parts) and test results of the Compositions C1 to C10. C2 C4 C6 Composition C1 (Ref.) C3 (Ref.) C5 (Ref.) Polymer P1 80.00 80.00 — — — — Polymer P2 — — 80.00 80.00 80.00 80.00 Aldimine A1 B1 A1 B1 A2 B2 7.48 7.48 6.41 6.41 3.86 3.86 SA-solution.sup.1 1.50 1.50 1.50 1.50 1.50 1.50 DBTDL-solution.sup.2 0.50 0.50 0.50 0.50 0.50 0.50 viscosity 1 d NC 17.2 17.3 12.5 12.3 85.0 112.0 [Pa .Math. s] 7 d 60° C. 23.0 21.5 17.2 15.6 cured cured skinning time [min] 25 21 18 18 7 7 tensile strength [MPa] 2.37 1.53 2.12 1.40 1.89 1.43 elongation [%] 305 190 350 239 322 259 E-modulus 5% [MPa] 1.87 1.89 1.45 1.49 1.41 1.38 Shore A n.d. n.d. 39 40 n.d. n.d. C8 C10 Composition C7 (Ref.) C9 (Ref.) Polymer P1 — — — — Polymer P2 80.00 80.00 80.00 80.00 Aldimine A3 B3 A4 B4 5.71 5.71 9.26 9.26 SA-solution.sup.1 1.50 1.50 1.50 1.50 DBTDL-solution.sup.2 0.50 0.50 0.50 0.50 viscosity 1 d NC 11.1 11.2 9.3 9.4 [Pa .Math. s] 7 d 60° C. 12.8 12.3 11.7 11.5 skinning time [min] 44 44 39 39 tensile strength [MPa] 1.57 1.57 1.75 1.62 elongation [%] 237 236 304 291 E-modulus 5% [MPa] 1.82 1.77 1.36 1.35 Shore A 43 43 38 38 “(Ref.)” means “reference example” “n.d.” means “not determined” .sup.15 weight-% salicylic acid in dioctyl phthalate .sup.25 weight-% dibutyltindilaurate in diisodecylphthalate

[0235] Moisture-Curing Polyurethane Adhesives:

Compositions C.sub.11 to C.sub.14:

[0236] Each composition was prepared by mixing the ingredients given in Table 3 in the given amounts (weight parts) with a planetary mixer under vacuum and exclusion of moisture, followed by storing it in a moisture-tight container. The solid Aldimine B1 was melted at 60° C. before adding.

[0237] The thickening paste was prepared by placing 300 g diisodecyl phthalate and 48 g 4,4′-diphenylmethane diisocyanate (Desmodur® 44 MC L, from Covestro) in a vacuum mixer, heating the mixture to 40° C., followed by adding 27 g monobutyl amine dropwise under vigorous stirring. The resulting paste was further stirred under vacuum and cooling for one hour.

[0238] The compositions were tested as follows:

[0239] The skinning time (skin formation time) and the Shore A hardness were determined as described for composition C.sub.1.

[0240] To determine the mechanical properties, each composition was pressed between two wax-coated transfer printing papers to form a film of 2 mm thickness and stored in normal climate. After removing the wax-coated papers, dumbell shaped samples were punched from the cured film and tested for tensile strength, elongation and the E-modulus 5% as described for composition C.sub.1. The cured films of all the adhesives were homogeneous and bubble-free.

[0241] The test results are given in Table 3.

[0242] Reference examples are marked with “(Ref.)”.

TABLE-US-00003 TABLE 3 Composition (in weight parts) and test results of the Compositions C11 to C14. Composition C13 C14 C11 C12 (Ref.) (Ref.) Polymer P2 27.5 27.5 27.5  27.5  IPDI-isocyanurate.sup.1 0.5 0.5 0.5 0.5 diisodecyl phthalate 4.0 4.0 4.0 4.0 Aldimine A1 2.9 A1 0.6 B1 2.9 D1 2.8 D1 2.2 thickening paste 25.0 25.0 25.0  25.0  chalk.sup.2 33.6 33.7 33.6  33.7  titanium dioxide 6.0 6.0 6.0 6.0 SA-solution.sup.3 0.50 0.50  0.50  0.50 skinning time n.d..sup.4 n.d..sup.4 40′  55′  tensile strength [MPa] 3.2 3.2 2.6 2.8 elongation [%] 640 675 585    780% E-modulus 5% [MPa] 4.9 3.6 3.0 2.2 Shore A 41 39 41   37   “(Ref.)” means “reference example” .sup.1Vestanate ® T1890/100 (from Evonik), NCO-content 17.3 weight-% .sup.2Omya ® BLH (from Omya) .sup.35 weight-% dibutyltin dilaurate in diisodecyl phthalate .sup.4not determined

Moisture-Curing Polyurethane Coatings:

[0243] Compositions C.sub.15 to C.sub.17:

[0244] Each composition was prepared by mixing the ingredients given in Table 4 in the given amounts (weight parts) in the centrifugal mixer under exclusion of moisture and stored in a moisture-tight container. Prior to use, the solid Aldimine B1 was melted at 60° C., while salicylic acid was dissolved in 1-methoxy-2-propylacetate.

[0245] The compositions were tested as follows:

[0246] The viscosity was measured at a temperature of 20° C. with a Rotothinner type viscometer with the spherical spindle DV2011 at 500 rpm, a first time after storing the moisture-tight container in normal climate for one day (“1d NC”), and again after storing the moisture-tight container in an oven at 40° C. for 21 days (“21d 40° C.”

[0247] Cure speed (“BK drying time”) was determined at 20° C./45% relative humidity using a Beck-Koller drying time recorder according to ASTM D5895.

[0248] To determine the mechanical properties, a two-layer cured film was prepared for each coating. To prepare the film, a first layer of 800 pm thickness was applied with a draw down bar and left curing in normal climate (NC) for 24 h; then a second layer of 400 μm thickness was applied thereon at an angle of 90° and again left curing in NC for 24 h; the two-layer film was then placed in an oven at 60° C. for 72 h. After an additional 24 h in NC, bar shaped test items with a length of 100 mm and a width of 25 mm were punched from the film and the tensile strength, the elongation at break and Young's modulus were determined according to BS EN ISO 527-3 at a crosshead speed of 180 mm/min. The cured films of all the coatings were homogeneous and bubble-free.

[0249] The results are given in Table 4.

[0250] Reference examples are marked with “(Ref.)”.

TABLE-US-00004 TABLE 4 Composition (in weight parts) and test results of the Compositions C15 to C17. Composition C16 C17 C15 (Ref.) (Ref.) Polymer P3 21.72 21.72 21.72 Polymer P4 10.86 10.86 10.86 IPDI-isocyanurate solution.sup.1 3.35 3.35 3.35 Aldimine A1 2.26 B1 2.26 D1 4.40 D1 2.26 D1 2.26 D2 3.01 D2 3.01 D2 3.01 1-methoxy-2-propyl acetate 21.05 21.05 21.05 aluminium trihydroxide filler 21.63 21.79 21.91 titanium dioxide 4.93 4.93 4.93 barytes 2.80 2.80 2.80 fumed silica 2.02 2.02 2.02 additives 3.87 3.87 3.87 salicylic acid 0.08 0.08 0.08 viscosity 1 d NC 14 14 n.d..sup.3 [Poise] 21 d 40° C. 21 22 BK drying time: gel-time 2 2 1.75 [h] skinning-time 5 5 7.5 dry-time 12 12 72 tensile strength [MPa] 7.6 6.6 5.8 elongation at break [%] 600 575 620 Young's modulus [MPa] 25.2 19.2 19.2 “(Ref.)” means “reference example” .sup.1Desmodur ® Z 4470SN (70 weight-% in solventnaphtha 100, NCO-content 12.0 weight-%, from Covestro) .sup.2 aluminium trihydroxide powder .sup.3not determined