CURABLE COMPOSITION COMPRISING AN ACETAL PLASTICIZER

Abstract

Curable compositions include at least one organic polymer which contains silane groups and/or isocyanate groups, at least one compound which contains acetal groups and has a molecular weight of at least 280 g/mol, and at least one basic catalyst. The composition is particularly storage-stable and can be readily processed. Using moisture the composition cures rapidly, and with very little residual tackiness, to form a resilient material that has good adhesive and mechanical properties, in particular a high level of malleability and elasticity, is heat resistant and exhibits hardly any odour formation or migration effects. In particular, the composition has very consistent product properties during storage in respect of viscosity, curing rate and odour.

Claims

1. A curable composition comprising at least one organic polymer containing silane groups and/or isocyanate groups, at least one compound containing acetal groups and having a molecular weight of at least 280 g/mol, and at least one basic catalyst.

2. The composition as claimed in claim 1, wherein the organic polymer has an average molecular weight, determined by means of GPC against polystyrene as standard, in the range from 1000 to 30,000 g/mol.

3. The composition as claimed in claim 1, wherein the organic polymer is free of isocyanate groups.

4. The composition as claimed in claim 3, wherein the organic polymer is a polyether containing silane groups.

5. The composition as claimed in claim 1, wherein the organic polymer contains isocyanate groups and the composition has a total content of free isocyanate groups in the range from 0.2% to 2% by weight.

6. The composition as claimed in claim 1, wherein the compound containing acetal groups has a molecular weight in the range from 280 to 10,000 g/mol.

7. The composition as claimed in claim 1, wherein the compound containing acetal groups is a compound of the formula (I) ##STR00011## where R.sup.1 and R.sup.2 are each independently H or an alkyl, cycloalkyl, aralkyl or aryl radical having 1 to 7 carbon atoms, R.sup.3 is an alkyl, cycloalkyl or aralkyl radical optionally having ether groups and having 1 to 30 carbon atoms, or is a monovalent polyoxyalkylene radical having an average molecular weight in the range from 300 to 2,000 g/mol, R.sup.4 is an n-valent alkyl, cycloalkyl or aralkyl radical optionally having ether groups and having 4 to 30 carbon atoms, or is an n-valent polyoxyalkylene radical having an average molecular weight in the range from 300 to 4,000 g/mol, and n is 1 or 2 or 3, where R.sup.1 and R.sup.2 may also together be an unbranched or branched alkylene radical having 4 to 12 carbon atoms and R.sup.2 and R.sup.3 may also together be an unbranched or branched alkylene radical having 3 to 8 carbon atoms, and wherein the compound of the formula (I) has a molecular weight of at least 280 g/mol.

8. The composition as claimed in claim 7, wherein n is 1, R.sup.1 and R.sup.2 are each H, and R.sup.3 and R.sup.4 are each identical radicals.

9. The composition as claimed in claim 7, wherein n is 1, R.sup.1 is H, R.sup.4 is a 1-butanol-started polyoxypropylene radical having an average molecular weight in the range from 650 to 2,000 g/mol, and either R.sup.2 and R.sup.3 together are 1,3-propylene or 1,4-butylene or R.sup.2 is methyl and R.sup.3 is methyl, ethyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, allyl, cyclohexyl, benzyl or phenyl.

10. The composition as claimed in claim 7, wherein n is 2, R.sup.1 is H, R.sup.4 is a polyoxypropylene radical having an average molecular weight in the range from 650 to 4,000 g/mol, and either R.sup.2 and R.sup.3 together are 1,3-propylene or 1,4-butylene or R.sup.2 is methyl and R.sup.3 is methyl, ethyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, allyl, cyclohexyl, benzyl or phenyl.

11. The composition as claimed in claim 1, wherein the basic catalyst is a nitrogen or phosphorus compound having a pK.sub.a of the conjugate acid of at least 9.

12. The composition as claimed in claim 1, wherein it has a content of fillers in the range from 10 to 60% by weight.

13. The composition as claimed in claim 1, wherein it is a one-component composition.

14. The composition as claimed in claim 1, wherein it is an elastic adhesive or a sealant or an elastic coating.

15. A cured composition obtained from the curing of the composition as claimed in claim 1 with water.

Description

EXAMPLES

[0207] Working examples are adduced hereinafter, which are intended to further elucidate the invention described. Of course, the invention is not limited to these described working examples.

[0208] “Standard climatic conditions” refer to a temperature of 23±1° C. and a relative air humidity of 50±5%.

[0209] Unless stated otherwise, the chemicals used were from Sigma-Aldrich.

[0210] 1.) Preparation of Compounds Containing Acetal Groups:

[0211] The viscosity was measured with a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s.sup.−1).

[0212] 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. The absorption bands are reported in wavenumbers (cm.sup.−1).

[0213] Compound V-1: Butanol-started polypropylene glycol with 1-(isobutoxy)epoxy end group and average molecular weight of about 850 g/mol 300.00 g of butanol-started polyoxypropylenemonool with average molecular weight 750 g/mol (Synalox® 100-20B, from DowDuPont) and 0.17 g of methanesulfonic acid (anhydrous) were initially charged in a round-bottom flask under nitrogen atmosphere. Then 41.16 g of isobutyl vinyl ether (stabilized with 0.1% potassium hydroxide) was slowly added dropwise while stirring, such that the temperature of the reaction mixture did not rise above 70° C., and then the mixture was stirred at 70° C. under a nitrogen atmosphere until no hydroxyl groups were detectable any longer by means of IR and GC spectrometry. Subsequently, 0.07 g of sodium methoxide was added and stirred in, followed by 0.06 g of acetic acid. Then the volatile constituents were removed from the reaction mixture, first at 80° C. and a reduced pressure of 5 mbar and then at 100° C. and 2 mbar. A clear, yellowish liquid having a viscosity of 97 mPa.Math.s at 20° C. was obtained.

[0214] FT-IR: 2969, 2931, 2868, 1455, 1372, 1343, 1296, 1257, 1099, 1012, 924, 905, 867, 831.

[0215] Compound V-2: Butanol-started polypropylene glycol with tetrahydropyran-2-oxy end group and average molecular weight of about 840 g/mol Compound V-2 was prepared as described for compound V-1, except that 34.57 g of 3,4-dihydro-2H-pyran was used rather than 41.16 g of isobutyl vinyl ether. A clear, colorless liquid having a viscosity of 77 mPa.Math.s at 20° C. was obtained.

[0216] FT-IR: 2967, 2931, 2867, 1454, 1372, 1343, 1297, 1260, 1099, 1021, 997, 925, 906, 869, 814.

[0217] Compound V-3: Butanol-started polypropylene glycol with tetrahydrofuran-2-oxy end group and average molecular weight of about 830 g/mol Compound V-3 was prepared as described for compound V-1, except that 28.81 g of 2,3-dihydrofuran was used rather than 41.16 g of isobutyl vinyl ether. A clear, colorless liquid having a viscosity of 64 mPa.Math.s at 20° C. was obtained. FT-IR: 2969, 2931, 2867, 1455, 1372, 1343, 1296, 1258, 1099, 1035, 1010, 919, 865, 836.

[0218] Compound V-4: Butanol-started polypropylene glycol with 1-(isobutoxy)ethoxy end group and average molecular weight of about 1′200 g/mol 300.00 g of butanol-started polyoxypropylenemonool with average molecular weight 1′100 g/mol (Synalox® 100-40B, from DowDuPont) and 28.16 g of isobutyl vinyl ether (stabilized with 0.1% potassium hydroxide) were converted using 0.08 g of sodium methoxide as described for compound V-1. A clear, yellowish liquid having a viscosity of 207 mPa.Math.s at 20° C. was obtained. FT-IR: 2969, 2931, 2868, 1455, 1372, 1344, 1296, 1257, 1099, 1012, 924, 906, 867, 831.

[0219] Compound V-5: Butanol-started polypropylene glycol with 1-(isobutoxy)ethoxy end group and average molecular weight of about 1′900 g/mol 300.00 g of butanol-started polyoxypropylenemonool with average molecular weight 1′800 g/mol (Synalox® 100-85B, from DowDuPont) and 17.33 g of isobutyl vinyl ether (stabilized with 0.1% potassium hydroxide) were converted using 0.09 g of sodium methoxide as described for compound V-1. A clear, yellowish liquid having a viscosity of 533 mPa.Math.s at 20° C. was obtained. FT-IR: 2969, 2930, 2867, 1455, 1372, 1344, 1296, 1257, 1099, 1012, 924, 867, 832.

[0220] Compound V-6: Butanol-started polypropylene glycol with tetrahydropyran-2-oxy end group and average molecular weight of about 1′890 g/mol 300.00 g of butanol-started polyoxypropylenemonool with average molecular weight 1′800 g/mol (Synalox® 100-85B, from DowDuPont) and 14.55 g of 3,4-dihydro-2H-pyran rather than isobutyl vinyl ether were converted using 0.11 g of sodium methoxide as described for compound V-1. A clear, yellowish liquid having a viscosity of 412 mPa.Math.s at 20° C. was obtained.

[0221] FT-IR: 2969, 2931, 2867, 1454, 1372, 1344, 1296, 1259, 1097, 1020, 925, 908, 869, 834.

[0222] Compound V-7: Butanol-started polypropylene glycol with tetrahydrofuran-2-oxy end group and average molecular weight of about 1′880 g/mol 300.00 g of butanol-started polyoxypropylenemonool with average molecular weight 1′800 g/mol (Synalox® 100-85B, from DowDuPont) and 12.13 g of 2,3-dihydro-2H-furan rather than isobutyl vinyl ether were converted using 0.11 g of sodium methoxide as described for compound V-1, except that the temperature of the reaction mixture in the course of addition of 2,3-dihydro-2H-furan was kept below 50° C. and then the mixture was stirred at 50 rather than 70° C. A clear, yellowish liquid having a viscosity of 347 mPa.Math.s at 20° C. was obtained. FT-IR: 2969, 2930, 2867, 1455, 1372, 1344, 1296, 1257, 1097, 1011, 922, 866, 834.

[0223] Compound V-8: Polypropylene glycol with two 1-(isobutoxy)ethoxy end groups and average molecular weight of about 1′200 g/mol 300.00 g of polyoxypropylenediol with average molecular weight 1′000 g/mol (Voranol® P 1010, from DowDuPont) and 61.90 g of isobutyl vinyl ether (stabilized with 0.1% potassium hydroxide) were converted using 0.07 g of sodium methoxide as described for compound V-1. A clear, yellowish liquid having a viscosity of 711 mPa.Math.s at 20° C. was obtained.

[0224] FT-IR: 2970, 2931, 2869, 1454, 1372, 1343, 1296, 1257, 1099, 1013, 984, 924, 903, 867, 830.

[0225] Compound V-9: Polypropylene glycol with two 1-(isobutoxy)ethoxy end groups and average molecular weight of about 2′200 g/mol 300.00 g of polyoxypropylenediol with average molecular weight 2′000 g/mol (Voranol® 2000 L, from DowDuPont) and 39.95 g of isobutyl vinyl ether (stabilized with 0.1% potassium hydroxide) were converted using 0.08 g of sodium methoxide as described for compound V-1. A clear, yellowish liquid having a viscosity of 1149 mPa.Math.s at 20° C. was obtained.

[0226] FT-IR: 2970, 2930, 2868, 1454, 1372, 1343, 1296, 1257, 1099, 1012, 924, 906, 867, 831.

[0227] 2.) Commercial Substances Used and Abbreviations Thereof: [0228] DPEF: di(2-phenoxyethyl) formal (Desavin®, from Covestro) [0229] DIDP: diisodecyl phthalate (Palatinol® 10-P, from BASF) [0230] DINP: diisononyl phthalate (Palatinol® N, from BASF) [0231] DINCH: diisononyl cyclohexane-1,2-dicarboxylate (Hexamoll® DINCH, from BASF) [0232] DOA: di(2-ethylhexyl) adipate (Adimoll® DO, from Lanxess) [0233] TXIB: 1-isopropyl-2,2-dimethyltrimethylene diisobutyrate (Eastman TXIB™, from Eastman Chemical) [0234] IsoSDE: isosorbide diester (Polysorb® ID-37, from Roquette Freres) [0235] DPGDB: dipropylene glycol dibenzoate (Benzoflex® 9-88, from Eastman Chemical) [0236] PAS: phenyl C.sub.10-C.sub.21-alkylsulfonate (Mesamoll®, from Lanxess) [0237] TOF: tris(2-ethylhexyl) phosphate (Disflamoll® TOF, from Lanxess) [0238] DPO: 2-ethylhexyl diphenylphosphate (Disflamoll® DPO, from Lanxess) [0239] BBSA: N-butylbenzenesulfonamide (Proviplast® 024, from Proviron) [0240] ESBO: epoxidized soybean oil (Merginat® ESBO, from HOBUM Oleochemicals) [0241] PPG400: polypropylene glycol with average molecular weight about 400 g/mol (Voranol® P 400, from DowDuPont) [0242] Castor oil: castor oil (Alberdingk® castor oil DIN quality, from Alberdingk Boley) [0243] DME500: polyethylene glycol dimethyl ether with average molecular weight about 500 g/mol (Polyglycol DME 500, from Clariant) [0244] IBAY: bis(ethylacetoacetato)diisobutoxytitanium(IV) (Tyzor® IBAY, from Dorf Ketal) [0245] DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene (Lupragen® N 700, from BASF) [0246] AMMO 3-aminopropyltrimethoxysilane (Silquest® A-1110, from Momentive) [0247] DAMO 3-(2-aminoethyl)aminopropyltrimethoxysilane (Silquest® A-1120, from Momentive) [0248] Chalk: Omyacarb® 5-GU (from Omya) [0249] Carbon Monarch® 570 (from Cabot) black: [0250] Silica: fumed silica (Aerosil® R 972, from Evonik)

[0251] 3.) Preparation of Organic Polymers Containing Silane Groups and/or Isocyanate Groups:

[0252] Polymer P1: (Polyether Containing Silane Groups)

[0253] With exclusion of moisture, 1000 g of Acclaim® 12200 polyol (polyoxypropylenediol having a low level of unsaturation, from Covestro; OH number 11.0 mg KOH/g), 43.6 g of isophorone diisocyanate (IPDI; Vestanat® IPDI, from Evonik) and 0.1 g of bismuth tris(neodecanoate) (10% by weight in diisodecyl phthalate) were heated up to 90° C. while stirring constantly and left at this temperature until the content of free isocyanate groups determined by titrimetry had reached a stable value of 0.7% by weight. Subsequently, 63.0 g of diethyl N-(3-trimethoxysilylpropyl)aminosuccinate (adduct of 3-aminopropyltrimethoxysilane and diethyl maleate; prepared as per U.S. Pat. No. 5,364,955) was mixed in and the mixture was stirred at 90° C. until it was no longer possible to detect any free isocyanate by FT-IR spectroscopy. The polyether containing trimethoxysilane groups obtained in this way was cooled down to room temperature and stored with exclusion of moisture.

[0254] Polymer P2: (Polyether Containing Silane Groups)

[0255] With exclusion of moisture, 720.0 g of Acclaim® 12200, 34.5 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik), 80.0 g of diisononyl cyclohexane-1,2-dicarboxylate (Hexamoll® DINCH, from BASF) and 0.5 g of bismuth tris(neodecanoate) solution (10% by weight in diisononyl cyclohexane-1,2-dicarboxylate) were heated up to 90° C. while stirring constantly and left at this temperature until the content of free isocyanate groups determined by titrimetry had reached a stable value of 0.73% by weight. Subsequently, 49.1 g of N-(3-triethoxysilylpropyl)-2-hydroxypropanamide, prepared as described below, was added and the mixture was stirred under a nitrogen atmosphere at 80° C. until no isocyanate groups were detectable any longer by means of IR spectroscopy (about 2 hours). The polyether containing triethoxysilane groups obtained in this way was cooled down to room temperature and stored with exclusion of moisture.

[0256] N-(3-Triethoxysilylpropyl)-2-hydroxypropanamide was prepared by mixing 20.00 g of 3-aminopropyltriethoxysilane and 6.71 g (46.6 mmol) of L-lactide and stirring under a nitrogen atmosphere at 80° C. for 3 h until no further reaction progress was detected by means of IR spectroscopy, and the crude product was then aftertreated at 60° C. and about 10 mbar for 15 min. A colorless liquid product was obtained.

[0257] Polymer P3: (Polymer Containing Isocyanate Groups)

[0258] With exclusion of moisture, 590 g of Acclaim® 4200 (polyoxypropylenediol, from Covestro; OH number 28.5 mg KOH/g), 1180 g of Caradol® MD34-02 (polyoxypropylenepolyoxyethylenetriol, from Shell; OH number 35.0 mg KOH/g) and 230 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were reacted by a known method at 80° C. to give an NCO-terminated polyurethane polymer which was liquid at room temperature and had a content of free isocyanate groups of 2.10% by weight.

[0259] 4. Production of Curable Compositions:

[0260] Compositions Z1 to Z16: (SMP Compositions)

[0261] For each composition, the ingredients specified in table 1 were mixed in the amounts specified (in parts by weight) by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) with exclusion of moisture at 3000 rpm for one minute and stored with exclusion of moisture.

[0262] Each composition was tested for skin time and viscosity, in fresh form (one hour after production) and after a storage time of 7 days in a closed container in an air circulation oven heated to 60° C. The skin time constitutes a measure of the curing rate, and a low viscosity enables good application properties.

[0263] The skin time (ST) was determined by applying a few grams of the composition to cardboard in a layer thickness of about 2 mm and, under standard climatic conditions, determining the time until, when the surface of the composition was gently tapped by means of an LDPE pipette, there were for the first time no residues remaining any longer on the pipette. The skin time was determined in the fresh state and in the stored state. A change of less than 25% was rated as “good”, of 25% to 100% as “average”, and of more than 100% as “poor”. Viscosity was measured as described above at 20° C. in the fresh state and in the stored state. A change of less than 100% was rated as “good”, of 100% to 200% as “average”, and of more than 200% as “poor”.

[0264] The results are reported in table 1.

[0265] The compositions labeled with (Ref) are comparative examples.

TABLE-US-00001 TABLE 1 Composition (in parts by weight) and properties of Z1 to Z16. Z2 Z3 Z4 Z5 Z6 Composition Z1 (Ref.) (Ref.) (Ref.) (Ref.) (Ref.) Polymer P1 90.00  90.00  90.00  90.00  90.00  90.00  Plasticizer DPEF — DIDP DINCH DOA TXIB 10.00  10.00  10.00  10.00  10.00  IBAY 1.50 1.50 1.50 1.50 1.50 1.50 DBU 0.15 0.15 0.15 0.15 0.15 0.15 DAMO 1.00 1.00 1.00 — — 1.00 AMMO — — — 1.00 1.00 — ST fresh 17′    15′    17′    24′    11′    15′    stored 14′    13′    28′    15′    73′    17′    Change good good average average poor good Viscosity fresh 75    114    80    72    60    67    [Pa .Math. s] stored 127    141    100    132    82    280    Change good good good good good poor Z7 Z8 Z9 Z10 Z11 Z12 Composition (Ref.) (Ref.) (Ref.) (Ref.) (Ref.) (Ref.) Polymer P1 90.00  90.00  90.00  90.00  90.00  90.00  Plasticizer IsoSDE DPGDB PAS TOF DPO BBSA 10.00  10.00  10.00  10.00  10.00  10.00  IBAY 1.50 1.50 1.50 1.50 1.50 1.50 DBU 0.15 0.15 0.15 0.15 0.15 0.15 DAMO 1.00 1.00 — — — 1.00 AMMO — — 1.00 1.00 1.00 — ST fresh 20′    16′    11′    10′    14′    17′    stored 9′  13′    40′    17′    >12 h 20′    Change average good poor average poor good Viscosity fresh 96    109    74    57    59    114    [Pa .Math. s] stored 279    330    138    138    99    315    Change average poor good average good average Z13 Z14 Z15 Z16 Composition (Ref.) (Ref.) (Ref.) (Ref.) Polymer P1 90.00  90.00  90.00  90.00  Plasticizer ESBO PPG400 Castor oil DME500 10.00  10.00  10.00  10.00  IBAY 1.50 1.50 1.50 1.50 DBU 0.15 0.15 0.15 0.15 DAMO 1.00 1.00 1.00 1.00 AMMO — — — — ST fresh 15′    22′    15′    15′    stored 49′    13′    80′    20′    Change poor average poor average Viscosity fresh 96    128    90    75    [Pa .Math. s] stored 139    405    292    93    Change good poor poor good

[0266] Compositions Z17 to Z24: (SMP Compositions)

[0267] For each composition, 25.1 parts by weight (PW) of polymer P1, 25.1 PW of the plasticizer specified in table 2, 1.0 PW of vinyltrimethoxysilane, 12.4 PW of precipitated, stearate-coated chalk, 35.1 PW of chalk, 1.0 PW of DAMO, 0.2 PW of DBU and 0.05 PW of IBAY were mixed as described for composition Z1 and stored with exclusion of moisture.

[0268] Each composition was tested for skin time and viscosity as described for composition Z1. For the change in viscosity, a change of less than 50% was rated as “good”, of 50% to 100% as “average”, and of more than 100% as “poor”.

[0269] The odor of the uncured material was tested in the fresh state and after storage in a closed container at 60° C. for 7 days by smelling by nose at a distance of 10 cm. It is reported as “weak”, “average” or “strong”.

[0270] To determine the mechanical properties, each composition was applied to a PTFE-coated film to give a film of thickness 2 mm and stored under standard climatic conditions for 7 days, and a few dumbbells having a length of 75 mm with a bar length of 30 mm and a bar width of 4 mm were punched out of the film and these were tested in accordance with DIN EN 53504 at a strain rate of 200 mm/min for tensile strength (breaking force), elongation at break, and 50% modulus of elasticity (at 0.5-50% elongation). These results are reported as “SCC”.

[0271] Resistance to heat in the cured state was tested by storing films of thickness 2 mm that had been cured under standard climatic conditions for 7 days, produced as described above, in an air circulation oven at 60° C. or at 100° C. for 7 days, and then determining tensile strength, elongation at break and 50% modulus of elasticity as described above. These results are reported as “7 d 60° C.” and “7 d 100° C.” respectively.

[0272] In addition, the appearance of these films before and after storage at 60° C. was assessed visually, identified as “SCC” and “7 d 60° C.” respectively. “Nice” was used to describe an even film with a nontacky surface without blisters. “Greasy” was used to describe a film on the surface of which an oily film had formed as a result of plasticizer migration.

[0273] The results are reported in table 2.

[0274] The compositions labeled with (Ref) are comparative examples.

TABLE-US-00002 TABLE 2 Composition and properties of Z17 to Z24. Z18 Z19 Z20 Composition Z17 (Ref.) (Ref.) (Ref.) Plasticizer DPEF DINP DINCH DOA ST fresh 23′    22′    25′    23′    stored 20′    28′    32′    32′    Change good average average average Viscosity fresh 40    30    27    12    [Pa .Math. s] stored 39    42    25    12    Change good good good good Odor fresh weak weak weak weak stored weak strong average strong Tensile SCC 1.61 1.63 1.47 1.65 strength [MPa] 7 d 60° C. 1.32 1.37 1.18 1.31 7 d 100° C. 1.19 1.13 1.05 1.07 Elongation at SCC 244    236    219    202    break [%] 7 d 60° C. 240    245    187    204    7 d 100° C. 162    155    149    147    Modulus of SCC 0.75 0.73 0.71 0.73 elasticity 7 d 60° C. 0.78 0.76 0.73 0.69 50% [MPa] 7 d 100° C. 0.64 0.58 0.56 0.57 Appearance SCC nice nice nice nice 7 d 60° C. nice nice greasy nice Z21 Z22 Z23 Z24 Composition (Ref.) (Ref.) (Ref.) (Ref.) Plasticizer PAS BBSA PPG400 DME500 ST fresh 21′    38′    107′    21′    stored 70′    27′    143′    13′    Change poor average average average Viscosity fresh 41    96    40    54    [Pa .Math. s] stored 50    179    82    67    Change good average poor good Odor fresh weak weak weak weak stored average average stark weak Tensile SCC 1.63 1.60 1.56 1.41 strength [MPa] 7 d 60° C. 1.35 1.48 1.22 1.19 7 d 100° C. n.m..sup.1 n.m..sup.1 n.m..sup.1 n.m..sup.1 Elongation at SCC 249    409    407    178    break [%] 7 d 60° C. 300    415    435    222    7 d 100° C. n.m..sup.1 n.m..sup.1 n.m..sup.1 n.m..sup.1 Modulus of SCC 0.75 0.56 0.52 1.31 elasticity 7 d 60° C. 0.72 1.19 0.39 1.19 50% [MPa] 7 d 100° C. n.m..sup.1 n.m..sup.1 n.m..sup.1 n.m..sup.1 Appearance SCC nice nice nice greasy 7 d 60° C. nice nice greasy greasy .sup.1not measurable, depolymerized

[0275] Compositions Z25 to Z33: (SMP Compositions)

[0276] For each composition, the ingredients specified in table 3 were mixed in the amounts specified (in parts by weight) by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) with exclusion of moisture at 3000 rpm for one minute and stored with exclusion of moisture.

[0277] Each composition was tested as follows:

[0278] As a measure of the curing rate, the skin time (ST) was determined. For this purpose, a few grams of the composition were applied to cardboard in a layer thickness of about 2 mm and, under standard climatic conditions, the time until, when the surface of the composition was gently tapped by means of an LDPE pipette, there were for the first time no residues remaining any longer on the pipette was determined.

[0279] To determine the mechanical properties, each composition was applied to a PTFE-coated film to give a film of thickness 2 mm, stored under standard climatic conditions for 7 days, and then, as described for composition Z17, tested for tensile strength (breaking force), elongation at break, 5% modulus of elasticity (at 0.5-5% elongation), and 50% modulus of elasticity (at 0.5-50% elongation).

[0280] The odor of the uncured material was tested in the fresh state and after storage in a closed container at 60° C. for 7 days by smelling by nose at a distance of 10 cm. It is reported as “weak”, “average” or “strong”.

[0281] Appearance was assessed visually on the films produced. “Nice” was used to describe an even film with a nontacky surface without blisters.

[0282] As a measure of plasticizer migration, horizontal staining on cardboard was determined. For this purpose, each composition was applied to a piece of cardboard such that it had a round base area of diameter 15 mm and a height of 4 mm, and then stored under standard climatic conditions for 7 days and subsequently in an air circulation oven at 100° C. for 12 hours. Around each composition, thereafter, a dark oval stain had formed on the cardboard. The dimensions thereof (height and width) were measured and reported as migration (horizontal).

[0283] The results are reported in table 3.

[0284] The compositions labeled with (Ref.) are comparative examples.

TABLE-US-00003 TABLE 3 Composition (in parts by weight) and properties of Z-25 to Z-33. Z-33 Composition Z-25 Z-26 Z-27 Z-28 Z-29 Z-30 Z-31 Z-32 (ref.) Polymer P2 30.3 30.3 30.3 30.3 30.3 30.3 30.3 30.3 30.3 Compound V-2 V-3 V-4 V-5 V-6 V-7 V-8 V-9 DIDP 34.1 34.1 34.1 34.1 34.1 34.1 34.1 34.1 34.1 Chalk 30.3 30.3 30.3 30.3 30.3 30.3 30.3 30.3 30.3 Silica 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Vinyltriethoxysilane 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 IBAY 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 DAMO 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 ST 35 45 40 35 45 40 35 35 50 Tensile strength 0.81 0.81 0.75 0.77 0.83 0.83 0.81 0.76 0.90 [MPa] Elongation at 134 132 128 133 147 141 137 129 149 break [%] Modulus of 0.28 0.29 0.24 0.26 0.24 0.27 0.27 0.25 0.34 elasticity 5% [MPa] Modulus of 0.38 0.38 0.37 0.36 0.35 0.36 0.37 0.37 0.39 elasticity 50% Appearance nice nice nice nice nice nice nice nice nice Odor fresh weak weak weak weak weak weak weak weak weak stored weak weak weak weak weak weak weak weak average Migration Height 1 1 3 3 1 1 4 2 2 (horizontal) Width 2 2 2 2 2 2 3 3 3 [mm]

[0285] Compositions Z34 to Z40: (Polyurethane compositions)

[0286] For each composition, the ingredients specified in table 4 were mixed in the amounts specified (in parts by weight) by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) with exclusion of moisture at 3000 rpm for one minute and stored with exclusion of moisture.

[0287] Each composition was tested as follows:

[0288] Skin time (ST), tensile strength, elongation at break, 5% modulus of elasticity, 50% modulus of elasticity, appearance and odor were tested as described for composition Z-25.

[0289] As a measure of plasticizer migration, vertical staining on paper was determined. For this purpose, 30 g of the composition was introduced into a round vessel of diameter 45 mm that was open at the top (fill height about 17 mm) and then a piece of printer paper that had been rolled into a cylinder with a diameter of 26 mm and a height of 100 mm was placed into the fresh composition by the round side such that the rolled paper touched the base of the vessel and projected out of the composition at the top. This arrangement was stored under standard climatic conditions and observations were made after 3, 7 and 14 days as to whether staining had arisen as a result of liquid absorbed into the paper. The height of the ring-shaped stain was measured and reported as migration (vertical).

[0290] The results are reported in table 4.

[0291] The compositions labeled with (Ref.) are comparative examples.

TABLE-US-00004 TABLE 4 Composition (in parts by weight) and properties of Z-34 to Z-40. Z-40 Composition Z-34 Z-35 Z-36 Z-37 Z-38 Z-39 (ref.) Polymer P3 30.4 30.4 30.4 30.4 30.4 30.4 30.4 Compound V-1 V-2 V-3 V-5 V-6 V-7 DIDP 35.2 35.2 35.2 35.2 35.2 35.2 35.2 Chalk 30.4 30.4 30.4 30.4 30.4 30.4 30.4 Silica 3.8 3.8 3.8 3.8 3.8 3.8 3.8 Amidine catalyst.sup.1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 ST [min] 35 35 35 35 35 35 35 Tensile strength 0.65 0.69 0.65 0.58 0.66 0.62 0.57 [MPa] Elongation at 331 334 324 234 366 300 269 break [%] Modulus of elasticity 0.43 0.30 0.33 0.49 0.39 0.44 0.36 [MPa] 5% 50% 0.30 0.27 0.26 0.31 0.27 0.29 0.28 Appearance nice nice nice nice nice nice nice Odor fresh weak weak weak weak weak weak weak stored weak weak weak weak weak weak strong Migration 3 d 5 6 6 5 3 4 6 (vertical) 7 d 5 6 6 8 3 7 6 [mm] 14 d 5 6 6 10 3 9 6 .sup.11-(3-dimethylaminopropyl)-2-methyl-1,4,5,6-tetrahydropyrimidine (prepared like amidine A3 in WO 2016/166336), 25% by weight in xylene