POLYMER COMPOSITION WHICH CAN BE CURED AT ROOM TEMPERATURE AND WHICH IS MADE OF POLYALDEHYDE AND POLYCYANOACETATE

Abstract

A curable composition including a first component containing aldehyde group-containing compounds and a second component containing cyanoacetate group-containing compounds, wherein the average molecular weight Mn of the first and second components, with respect to the aldehyde or cyanoacetate group-containing compounds, ranges from 400 to 20,000 g/mol, and the average functionality of at least one of the two components, with respect to the aldehyde or the cyanoacetate group-containing compounds, is greater than 2.0. The composition is largely free of toxic ingredients and cures in ambient conditions using conventional catalysts quickly and in a trouble-free manner in order to form a non-tacky elastic polymer with a high degree of strength, elasticity, and resistance to tear propagation. The composition is particularly suitable for use as an elastic adhesive, sealant, or coating with a high degree of robustness during production, storage, and processing as well as a high degree of resistance after curing.

Claims

1. A curable composition comprising a first component containing compounds containing aldehyde groups, comprising at least one compound having two or more aldehyde groups, and a second component containing compounds containing cyanoacetate groups, comprising at least one compound having two or more cyanoacetate groups, where the average molecular weight M.sub.n of the first and second components in relation to the compounds containing aldehyde or cyanoacetate groups is in the range from 400 to 20 000 g/mol, and where the average functionality of at least one of the two components in relation to the compounds containing aldehyde or cyanoacetate groups is greater than 2.0.

2. The composition as claimed in claim 1, wherein less than 10% by weight, of water is present, based on the overall composition.

3. The composition as claimed in claim 1, wherein the compound having two or more aldehyde groups is liquid at room temperature.

4. The composition as claimed in claim 1, wherein the average molecular weight M.sub.n of the first component in relation to the compounds containing aldehyde groups is in the range from 1000 to 20 000 g/mol, measured by gel permeation chromatography (GPC) versus polystyrene as standard.

5. The composition as claimed in claim 1, wherein the compounds containing aldehyde groups comprise a polymer having a polymer backbone containing poly(oxyalkylene) units and/or polyester units.

6. The composition as claimed in claim 1, wherein the compound having two or more aldehyde groups additionally contains urethane groups.

7. The composition as claimed in claim 1, wherein the compounds containing aldehyde groups comprise a polymer containing urethane groups which is liquid at room temperature and has an average molecular weight M.sub.n of 1000 to 20 000 g/mol, and an average aldehyde functionality of 1.8 to 3.5.

8. The composition as claimed in claim 1, wherein the compound having two or more aldehyde groups is obtained from the reaction of at least one hydroxyaldehyde with at least one polymer containing isocyanate groups or at least one polyisocyanate.

9. The composition as claimed in claim 1, wherein the average functionality of the second component in relation to the compounds containing cyanoacetate groups is in the range from 1.6 to 4.

10. The composition as claimed in claim 1, wherein the average molecular weight M.sub.n of the second component in relation to the compounds containing cyanoacetate groups is in the range from 400 to 10 000 g/mol.

11. The composition as claimed in claim 1, wherein the compounds containing cyanoacetate groups comprise at least one cyanoacetate-functional polymer selected from propoxylated 1,1,1-trimethylolpropane tris(cyanoacetate) having average molecular weight M.sub.n of 500 to 2000 g/mol, poly(oxy-1,2-propylene)diol bis(cyanoacetate) having average molecular weight M.sub.n of 2000 to 10 000 g/mol, poly(oxy-1,2-propylene)triol tris(cyanoacetate) having average molecular weight M.sub.n of 2000 to 10 000 g/mol, poly(oxy-1,2-propylene)diol bis(cyanoacetate) containing ethylene oxide units and having average molecular weight M.sub.n of 2000 to 10 000 g/mol, poly(oxy-1,2-propylene)triol tris(cyanoacetate) containing ethylene oxide units and having average molecular weight M.sub.n of 2000 to 10 000 g/mol, dimer fatty acid-based polyesterdiol bis(cyanoacetate) having average molecular weight M.sub.n of 1000 to 4000 g/mol and trimer fatty acid-based polyestertriol tris(cyanoacetate) having average molecular weight M.sub.n of 1000 to 4000 g/mol.

12. The composition as claimed in claim 1, wherein at least one further constituent selected from plasticizers, fillers and catalysts is present.

13. The composition as claimed in claim 1, wherein less than 10% by weight of volatile organic solvents having a boiling point at standard pressure of less than 250 C. is present, based on the overall composition.

14. A cured composition obtained from the curable composition as claimed in claim 1 after the two components have been mixed, wherein the cured composition especially has a tear propagation resistance of at least 7 N/mm determined to DIN ISO 34-1 Method B at a strain rate of 500 mm/min.

15. An elastic adhesive, elastic sealant or elastic coating on a substrate, comprising the composition of claim 1 applied in a liquid state to at least one substrate, wherein the first and second and any further components of the composition present are mixed with one another before the mixed composition is applied to the at least one substrate.

Description

EXAMPLES

[0146] Working examples are adduced hereinafter, which are intended to further elucidate the invention described. It will be apparent that the invention is not limited to these described working examples.

[0147] Standard climatic conditions (SCC) refer to a temperature of 231 C. and a relative air humidity of 505%.

[0148] The chemicals used were from Sigma-Aldrich Chemie GmbH, unless otherwise stated.

Description of the Measurement Methods:

[0149] Viscosity was measured on a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 10 mm, cone angle 1, cone tip-plate distance 0.05 mm, shear rate s.sup.1). Viscosities of less than 1 Pa's were measured with a cone diameter of 50 mm.

[0150] Infrared spectra (FT-IR) were measured as undiluted films on a Nicolet iS5 FT-IR instrument from Thermo Scientific equipped with a horizontal ATR measurement unit with a diamond crystal. Absorption bands are reported in wavenumbers (cm-1).

Preparation of Polymers Containing Isocyanate Groups:

Polymer P-1:

[0151] 780 g of ethylene oxide-terminated polyoxypropylene triol (Desmophen 5031 BT, OH number 28.0 mg KOH/g, OH functionality about 2.3, from Covestro) and 303 g of isophorone diisocyanate (Vestanat IPDI, from Evonik) were converted at 80 C. by a known method to a reaction mixture having an NCO content of 9.1% by weight. Subsequently, the volatile constituents, in particular unconverted isophorone diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 160 C., pressure 0.1 to 0.005 mbar) to obtain a polymer having an NCO content of 1.84% by weight and a monomeric isophorone diisocyanate content of 0.02% by weight.

Polymer P-2:

[0152] 590 g of polyoxypropylene diol (Acclaim 4200, OH number 28 mg KOH/g, from Covestro), 1180 g of ethylene oxide-terminated polyoxypropylene triol (Caradol MD34-02, OH number 35 mg KOH/g, from Shell) and 230 g of isophorone diisocyanate (Vestanat IPDI, from Evonik) were converted at 80 C. by a known method to a polymer having an NCO content of 2.1% by weight.

Polymer P-3:

[0153] 725 g of ethylene oxide-terminated polyoxypropylene triol (Desmophen 5031 BT, OH number 28.0 mg KOH/g, OH functionality about 2.3, from Covestro) and 275 g of diphenylmethane 4,4-diisocyanate (Desmodur 44 MC L, from Covestro) were converted at 80 C. by a known method to a reaction mixture having an NCO content of 7.6% by weight. Subsequently, the volatile constituents, in particular unconverted diphenylmethane 4,4-diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 180 C., pressure 0.1 to 0.005 mbar, condensation temperature 47 C.) to obtain a polymer having an NCO content of 1.68% by weight and a monomeric diphenylmethane 4,4-diisocyanate content of 0.04% by weight.

Polymer P-4:

[0154] 513.3 g of polyoxypropylene diol (Acclaim 4200, OH number 28 mg KOH/g, from Covestro), 256.7 g of ethylene oxide-terminated polyoxypropylene triol (Caradol MD34-02, OH number 35 mg KOH/g, from Shell) and 64.2 g of toluene diisocyanate (Desmodur T 80 P, from Covestro) were converted at 80 C. by a known method to a polymer having an NCO content of 1.5% by weight.

Polymer P-5:

[0155] 818 g of polyoxypropylene diol (Acclaim 4200, OH number 28.5 mg KOH/g, from Covestro) and 227 g of isophorone diisocyanate (Vestanat IPDI, from Evonik) were converted at 80 C. by a known method to a reaction mixture having an NCO content of 6.6% by weight. Subsequently, the volatile constituents, in particular unconverted isophorone diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 160 C., pressure 0.1 to 0.005 mbar) to obtain a polymer having an NCO content of 1.91% by weight and a monomeric isophorone diisocyanate content of 0.03% by weight.

Polymer P-6:

[0156] 600 g of polyoxypropylene diol (Voranol 1010 L, OH number 112 mg KOH/g, from Dow) and 533.3 g of isophorone diisocyanate (Vestanat IPDI, from Evonik) were converted at 80 C. by a known method to a reaction mixture having an NCO content of 15.6% by weight. Subsequently, the volatile constituents, in particular unconverted isophorone diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 160 C., pressure 0.1 to 0.005 mbar) to obtain a polymer having an NCO content of 5.18% by weight and a monomeric isophorone diisocyanate content of 0.03% by weight.

Preparation of Compounds Having Two or More Aldehyde Groups:

Compounds A-1 to A-7:

[0157] For each of the compounds, the amounts specified in table 1 (in parts by weight) of the corresponding polymer containing isocyanate groups were reacted, in the presence of 0.02% by weight of dibutyltin dilaurate, with exclusion of moisture at 110 C., with the specified amount (in parts by weight) of the corresponding hydroxy-functional aldehyde until no isocyanate groups were detectable any longer by IR spectroscopy. In the case of the polymers having aromatic isocyanate groups P-3 and P-4, reaction was effected without dibutyltin dilaurate and at 80 C. What was obtained in each case was a clear colorless liquid.

[0158] The properties of compounds A-1 to A-7 are reported in table 1.

TABLE-US-00001 TABLE 1 Preparation and properties of compounds A-1 to A-8. Compound A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 Polymer P-1 500.0 500.0 500.0 Polymer P-2 500.0 Polymer P-3 500.0 Polymer P-4 500.0 Polymer P-5 500.0 Polymer P-6 250.0 5- 27.7 31.5 25.5 23.8 28.9 38.9 Hydroxymethylfurfural 2-(2-Hydroxyethoxy)- 37.4 benzaldehyde Vanillin-dialdehyde .sup.1 78.9 Viscosity (20 C.) 63.7 138.3 111.7 187.1 138.4 33.2 438.0 1050 [Pa .Math. s] Average aldehyde 2.3 2.3 >2 2.3 >2 2.0 2.0 4.6 functionality Equivalent weight 2381 2381 2128 2632 2857 2326 935 1322 [g/eq] .sup.1 4,4-(2-hydroxypropane-1,3-diyl)bis(oxy)bis(3-methoxybenzaldehyde), prepared from 2 mol of vanillin and 1 mol of epichlorohydrin

[0159] The average molecular weight M.sub.n of compound A-1 was additionally determined by gel permeation chromatography (GPC) versus polystyrene (474 to 2 520 000 g/mol) as standard with tetrahydrofuran as mobile phase and refractive index detector. The average molecular weight M.sub.n was 6100 g/mol.

Preparation of Compounds Having Two or More Cyanoacetate Groups:

Compounds C-1 to C-9:

[0160] For each of the compounds, the amount specified in table 2 (in parts by weight) of the particular polyfunctional alcohol was admixed with the specified amount (in parts by weight) of ethyl cyanoacetate and 0.1% by weight of tetra-n-butyl titanate (Tyzor TnBT, from Dorf Ketal), and the mixture was converted at a temperature of 80 to 140 C. under reduced pressure and with removal of the volatile constituents. What was obtained in each case was a clear colorless liquid, with the exception of compound C-9.

TABLE-US-00002 TABLE 2 Preparation and properties of compounds C-1 to C-9. Compound C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 PPG triol 300 .sup.1 50.0 PPG triol 440 .sup.2 50.0 PPG triol 700 .sup.3 100.0 EO-castor oil .sup.4 100.0 PEster 1700 .sup.5 100.0 EO-PPG triol 6000.sup.6 100.0 Dimer diol .sup.7 100.0 PPG diol 400 .sup.8 50.0 1,4-butanediol 20.0 Ethyl 61.0 42.7 52.8 25.5 15.5 6.2 44.8 27.8 55.2 cyanoacetate Viscosity (20 C.) 1.72 2.37 2.91 2.04 18.1 2.40 1.35 0.4 solid [Pa .Math. s] Average 3.0 3.0 3.0 2.7 2.2 2.3 2.0 2.0 2.0 cyanoacetate functionality Equivalent 169 212 303 568 857 2083 344.8 281 112.1 weight [g/eq] .sup.1 trimethylolpropane-started polyoxypropylene triol (Desmophen 4011 T, OH number 550 mg KOH/g, from Covestro) .sup.2 trimethylolpropane-started polyoxypropylene triol (Desmophen 1381 BT, OH number 385 mg KOH/g, from Covestro) .sup.3 polyoxypropylene triol (Desmophen 28HS98, OH number 233 mg KOH/g, from Covestro) .sup.4 ethoxylated castor oil (Etocas 10, OH number 115 mg KOH/g, from Croda) .sup.5 amorphous, dimer fatty acid-based polyester diol (Priplast 3186, OH number 71 mg KOH/g, from Croda) .sup.6ethylene oxide-terminated polyoxypropylene triol (Desmophen 5031 BT, OH number 28 mg KOH/g, from Covestro) .sup.7 dimer fatty acid diol (Pripol 2043, OH number 202 mg KOH/g, from Croda) .sup.8 polyoxypropylene diol (Voranol P400, OH number 263 mg KOH/g, from Dow)

Preparation of a Compound Having Acetoacetate Groups (as Comparison);

Compound R-1:

[0161] To 50 g of trimethylolpropane-started polyoxypropylene triol (Desmophen 4011 T, OH number 550 mg KOH/g, from Covestro) were added 67 g of ethyl acetoacetate and 0.12 of tetra-n-butyl titanate (Tyzor TnBT, from Dorf Ketal), and the mixture was converted at a temperature of 140 C. under reduced pressure and with removal of the volatile constituents. What was obtained was a clear, colorless liquid having a viscosity at 20 C. of 0.8 Pa.Math.s, an average acetoacetate functionality of 3 and an acetoacetate equivalent weight of 186 g/eq.

Production of Curable Compositions

Examples E-1 to E-33

[0162] For each example, the ingredients of the first component (K1) that are specified in tables 3 to 8 were mixed with one another in the specified amounts (in parts by weight) using a centrifugal mixer (SpeedMixer DAC 150, FlackTek Inc.) and stored in a closed container.

[0163] The ingredients of the second component (K2) that are specified in tables 3 to 8 were likewise processed and stored.

[0164] The precipitated CaCO.sub.3 used was Socal U1S2 (from Imerys), a precipitated and stearate-coated calcium carbonate.

[0165] The carbon black used was Monarch 570 (from Cabot).

[0166] Subsequently, the two components of each composition were then processed using the centrifugal mixer to give a homogeneous paste, which was tested as described below. In the case of E-33 (Ref.), component K2 consisting of compound C-9 was heated up to 60 C. and melted prior to mixing.

[0167] Gel time was determined by stirring a freshly mixed amount of about 3 g under standard climatic conditions with a spatula at regular intervals until this was no longer possible as a result of gelation of the mass.

[0168] Mechanical properties were determined by applying the mixed composition to a silicone-coated release paper to give a film of thickness 2 mm, leaving the film to cure under standard climatic conditions for 7 days, punching a few dumbbell-shaped test specimens having a length of 75 mm with a bar length of 30 mm and a bar width of 4 mm out of the film and testing these in accordance with DIN EN 53504 at a strain rate of 200 mm/min for Tensile strength, Elongation at break, MoE 5% (at 0.5%-5% elongation) and MoE 50% (at 0.5%-50% elongation). Furthermore, a number of test specimens were punched out for determination of Tear propagation resistance and were tested in accordance with DIN ISO 34-1, Method B (angular test specimens) at a strain rate of 500 mm/min.

[0169] The measure used for the strength of an adhesive bond of a number of compositions was lap shear strength on glass. For this purpose, composite specimens were produced by bonding two glass plates that had been degreased with isopropanol and pretreated with Sika Aktivator-205 (from Sika Schweiz) in such a way that the overlapping adhesive bond had dimensions of 1225 mm and a thickness of 4 mm and the glass plates protruded at the top ends. After the composite specimens had been stored under standard climatic conditions for 7 d, lap shear strength was tested to DIN EN 1465 at a strain rate of 20 mm/min. Subsequently, the Fracture profile was assessed for AF (adhesive failure) or CF (cohesive failure). Without further data, the fracture profile specified in the table was assessed for 90% to 100% of the fracture area.

[0170] Shore A hardness was determined to DIN 53505 on test specimens cured under standard climatic conditions for 7 days. These results are given the addition 7 d SCC. Resistance to heat and water was determined by storing further Shore A test specimens, after curing under standard climatic conditions for 7 days, either additionally in an air circulation oven at 100 C. for 7 days or additionally at 70 C. and 100% relative humidity for 7 days, cooling them down to room temperature and then determining Shore A hardness as described in each case. These results are given the addition +7 d 100 C. or +7 d 70/100.

[0171] The curing of the inventive examples in each case gave a nontacky, elastic material. The examples labeled (Ref.) are noninventive comparative examples. The results are reported in tables 3 to 8.

TABLE-US-00003 TABLE 3 Composition and properties of E-1 to E-8. Example E-7 E-8 E-1 E-2 E-3 E-4 E-5 E-6 (Ref.) (Ref.) Component K1: Compound A-1 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 Diisodecyl phthalate 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Precipitated CaCO.sub.3 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 Carbon black 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 DAEE .sup.1 0.6 0.6 0.6 0.6 0.6 0.6 DBU .sup.2 0.3 0.3 Component K2: Compound C-1 C-2 C-3 C-4 C-5 C-7 R-1 R-1 3.01 3.91 4.14 7.59 11.88 4.71 2.26 3.62 Gel time [min] 10 5 3 5 5 8 15 15 Tensile strength [MPa] 5.9 6.4 4.6 5.6 5.2 6.3 2.4 3.3 Elongation at break [%] 609 633 373 617 744 754 208 157 MoE 5% [MPa] 2.10 2.09 3.96 1.95 0.87 1.05 1.9 3.9 MoE 50% [MPa] 1.22 1.28 2.23 1.22 0.56 0.70 1.15 2.2 Tear propagation 16.5 14.8 7.6 13.6 14.3 19.1 3.6 3.5 resistance [N/mm] Shore A (7 d SCC) 40 45 58 44 29 32 4 54 (+7 d 100 C.) 56 61 62 55 43 47 63 59 (+7 d 70/100) 42 40 47 30 26 30 42 53 .sup.1 2,2-bis(dimethylamino)diethyl ether .sup.2 1,8-diazabicyclo[5.4.0]undec-7-ene (Lupragen N700, from BASF)

[0172] Comparison of example E-1 with comparative examples E-7 (Ref.) and E-8 (Ref.) shows that compound C-1 having cyanoacetate groups enables much better mechanical values than compound R-1 having acetoacetate groups, especially in relation to high tensile strength, high elongation and high tear propagation resistance. For comparative examples E-7 (Ref.) and E-8 (Ref.), DBU was used as catalyst in order to achieve a similarly rapid gel time.

TABLE-US-00004 TABLE 4 Composition and properties of E-1 and E-9 to E-15. Example E-14 E-15 E-1 E-9 E-10 E-11 E-12 E-13 MD-704 MD-377 Component K1: Compound A-1 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 Diisodecyl phthalate 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Precipitated CaCO.sub.3 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 Carbon black 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 DAEE .sup.1 0.6 0.1 DMDEE .sup.2 0.9 0.9 K54 .sup.3 0.6 DABCO .sup.4 0.6 Triethanolamine 0.6 Potassium acetate 0.2 solution .sup.4 Water 1.6 Component K2: Compound C-1 3.01 3.01 3.01 3.01 3.01 3.01 3.01 3.01 Gel time [min] 10 60 20 8 3 5 20 20 Tensile strength [MPa] 5.9 6.7 6.7 7.1 6.8 6.5 6.9 6.3 Elongation at break [%] 609 688 686 610 643 611 526 572 MoE 5% [MPa] 2.10 2.37 2.11 2.21 2.14 2.62 2.17 2.56 MoE 50% [MPa] 1.22 1.38 1.25 1.47 1.34 1.40 1.49 1.54 Tear propagation resistance 16.5 14.5 16.2 13.0 15.5 15.6 12.2 12.5 [N/mm] Shore A (7 d SCC) 40 47 43 50 46 50 48 48 (+7 d 100 C.) 56 61 59 63 56 63 55 n.d. (+7 d 70/100) 42 44 43 46 41 43 36 n.d. .sup.1 2,2-bis(dimethylamino)diethyl ether .sup.2 2,2-dimorpholinodiethyl ether .sup.3 2,4,6-tris(dimethylaminomethyl)phenol .sup.4 DABCO 33-LV (from Evonik) .sup.5 potassium acetate, 25% by weight in water n.d. stands for not determined

TABLE-US-00005 TABLE 5 Composition and properties of E-10 and E-16 to E-20. Example E-10 E-16 E-17 E-18 E-19 E-20 Component K1: Compound A-1 A-1 A-1 A-1 A-1 A-1 30.0 30.0 30.0 30.0 30.0 30.0 Diisodecyl phthalate 20.0 20.0 20.0 20.0 20.0 20.0 Precipitated CaCO.sub.3 30.0 30.0 30.0 30.0 30.0 30.0 Carbon black 10.0 10.0 10.0 10.0 10.0 10.0 DAEE .sup.1 0.1 0.1 0.1 0.1 0.1 0.1 DMDEE .sup.2 0.9 0.9 0.9 0.9 0.9 0.9 Epoxysilane .sup.3 1.6 1.6 Mercaptosilane .sup.4 1.3 Component K2: Compound C-1 C-1 C-1 C-1 C-6 C-6 3.01 2.67 3.01 3.01 28.46 28.46 Diisodecyl phthalate 20.0 Precipitated CaCO.sub.3 30.0 Carbon black 10.0 Epoxysilane .sup.3 3.2 Gel time [min] 20 20 20 35 150 105 Tensile strength [MPa] 6.7 6.1 6.6 7.4 5.9 6.0 Elongation at break [%] 686 770 494 704 632 575 MoE 5% [MPa] 2.11 1.52 2.74 1.91 1.25 2.0 MoE 50% [MPa] 1.25 1.18 1.56 1.25 0.77 1.1 Tear propagation 16.5 17.5 14.9 14.1 10.0 29.3 resistance [N/mm] Lap shear strength 0.65 n.d. 3.75 2.96 4.01 2.97 (glass) [MPa] Fracture pattern AF CF CF CF AF/CF.sup.5 Shore A (7 d SCC) 43 43 50 45 34 45 (+7 d 100 C.) 59 60 71 64 49 60 (+7 d 70/100) 43 44 46 48 25 31 n.d. stands for not determined .sup.1 2,2-bis(dimethylamino)diethyl ether .sup.2 2,2-dimorpholinodiethyl ether .sup.3 3-glycidoxypropyltrimethoxysilane .sup.4 3-mercaptopropyltrimethoxysilane .sup.575% AF/25% CF

TABLE-US-00006 TABLE 6 Composition and properties of E-1 and E-21 to E-27. Example E-26 E-27 E-1 E-21 E-22 E-23 E-24 E-25 HC-110 HC-115 Component K1: Compound A-1 A-2 A-2 A-3 A-4 A-5 A-7 A-8 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 Diisodecyl phthalate 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Precipitated CaCO.sub.3 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 Carbon black 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 DAEE .sup.1 0.6 0.6 0.1 0.6 0.6 0.6 0.1 0.1 DMDEE .sup.2 0.9 0.9 0.9 Component K2: Compound C-1 3.01 3.01 3.01 3.41 2.79 2.31 6.80 5.29 Gel time [min] 10 5 25 2 1 5 20 25 Tensile strength [MPa] 5.9 6.1 6.7 5.9 4.6 6.6 3.1 6.2 Elongation at break [%] 609 563 605 536 418 641 536 146 MoE 5% [MPa] 2.10 2.10 1.66 2.76 2.66 2.13 1.3 7.5 MoE 50% [MPa] 1.22 1.39 1.24 1.62 1.66 1.32 0.6 6.2 Tear propagation resistance 16.5 n.d. n.d. 13.4 14.9 16.9 7.9 5.3 [N/mm] Shore A (7 d SCC) 40 43 46 50 50 41 29 68 (+7 d 100 C.) 56 49 53 64 64 49 62 73 (+7 d 70/100) 42 30 41 44 43 30 34 54 n.d. stands for not determined .sup.1 2,2-bis(dimethylamino)diethyl ether .sup.2 2,2-dimorpholinodiethyl ether

TABLE-US-00007 TABLE 7 Composition and properties of E-28 to E-30. Example E-28 E-29 E-30 Component K1: Compound A-6 30.5 10.2 Compound A-7 12.3 C9 dialdehyde .sup.1 1.4 Component K2: Compound C-6 30.0 30.0 30.0 Diisodecyl phthalate 20.0 20.0 20.0 Precipitated CaCO.sub.3 30.0 30.0 30.0 Carbon black 10.0 10.0 10.0 DAEE .sup.2 0.1 0.1 0.1 DMDEE .sup.3 0.9 0.9 0.9 Epoxysilane .sup.4 1.6 1.6 1.6 Gel time [min] 240 40 180 Tensile strength [MPa] 1.7 2.8 2.4 Elongation at break [%] 633 107 590 MoE 5% [MPa] 0.6 4.5 0.7 MoE 50% [MPa] 0.2 3.0 0.3 Tear propagation resistance 7.5 3.0 8.9 [N/mm] Lap shear strength 1.0 1.8 1.4 (glass) [MPa] CF CF AF/CF .sup.5 Fracture pattern Shore A(7 d SCC) 15 59 19 (+7 d 100 C.) 45 57 55 (+7 d 70/100) 12 30 19 .sup.1 mixture of nonane-1,9-dial and 2-methyloctane-1,8-dial (NL/MOL, 78.1 g/eq of aldehyde, from Kuraray) .sup.2 2,2-dimorpholinodiethyl ether .sup.3 2,2-bis(dimethylamino)diethyl ether .sup.4 3-glycidoxypropyltrimethoxysilane .sup.5 25% AF/75% CF

TABLE-US-00008 TABLE 8 Composition and properties of E-31 to E-33. E-32 E-33 Example E-31 (Ref.) (Ref.) Component K1: Compound A-6 30.0 30.0 30.0 Diisodecyl phthalate 20.0 20.0 20.0 Precipitated CaCO.sub.3 30.0 30.0 30.0 Carbon black 10.0 10.0 10.0 DAEE .sup.1 0.1 0.1 0.1 DMDEE .sup.2 0.9 0.9 0.9 Compound C-1 C-8 C-9 Component K2: 2.84 3.83 1.45 Gel time [min] 80 >240 100 Tensile strength [MPa] 1.6 n.m. .sup.3 n.m. .sup.3 Elongation at break [%] 720 MoE 5% [MPa] 0.78 MoE 50% [MPa] 0.31 Shore A(7 d SCC) 15 n.m. .sup.3 n.m. .sup.3 (+7 d 100 C.) 58 n.d. n.d. (+7 d 70/100) 25 n.d. n.d. n.d. stands for not determined .sup.1 2,2-bis(dimethylamino)diethyl ether .sup.2 2,2-dimorpholinodiethyl ether .sup.3 not measurable (not properly cured, soft and tacky)

[0173] Examples E-32 (Ref.) and E-33 (Ref.) are comparative examples in which the first and second components each have only an average functionality in relation to the compounds having aldehyde groups or cyanoacetate groups of 2.0. Such a composition based on linear reactive compounds does not cure in each case to give a solid elastic material, whereas inventive example E-31 having a second component having an average cyanoacetate functionality of 3.0 cured to give an elastic material.