Self-blowing isocyanate-free polyurethane foams

Abstract

The present invention relates to a curable isocyanate-free formulation for preparing a polyurethane self-blowing foam comprising at least one multifunctional cyclic carbonate having at least two cyclic carbonate groups at the end of the chain (compound A), at least one multifunctional amine (compound B), water or/and a water source and optionally at least one catalyst (compound D), to a process for preparing said foams and to the thus obtained foams, to a process for recycling the obtained foams and to the thus recycled foams.

Claims

1. A curable isocyanate-free formulation for preparing a polyurethane self-blowing foam, said formulation comprising at least one multifunctional cyclic carbonate having at least two cyclic carbonate groups at the end of the chain (compound A), at least one multifunctional amine having at least 2 primary amine groups (compound B), water as such or/and a water source, and optionally at least one catalyst (compound D) and optionally at least one epoxide compound (compound I), wherein water as such and/or water source is present in the formulation in such amounts that the molar ratio of water including water provided by the water source towards the cyclic carbonate groups from compound A in the formulation is from 0.025 to 8 and wherein the molar ratio of compound B towards the cyclic carbonate groups from compound A and optionally the epoxide groups from compound I when present in the formulation is in the range 0.5 to 1.25.

2. The formulation according to claim 1 wherein the formulation comprises at least one epoxide compound (compound I) and wherein the molar ratio of epoxide groups from compound I in the formulation towards the cyclic carbonate groups from compound A in the formulation is in the range 0.05 up to 20, preferably in the range 0.2 up to 4.

3. The formulation according to claim 1 wherein the molar ratio of water including water provided by the water source towards the cyclic carbonate groups from compound A in the formulation is between 0.025 and 2, preferably between 0.25 and 2.0.

4. The formulation according to claim 1 wherein compound I corresponds to formula X ##STR00021## Wherein: j is an integer, in particular from 1 to 10, more particularly 2 or 3, R.sup.1 is a carbon bond between the epoxide rings when j is from 2, or is a linear or branched hydrocarbon chain, which may be unsubstituted or substituted and wherein one or several hydrocarbon groups of said hydrocarbon chain may be replaced by a heteroatom, a ketone, a cycloalkyl, a heterocycle, an aryl or a heteroaryl, each of which may be unsubstituted or substituted, said hydrocarbon chain having at least 2 carbon atoms, in particular from 3 to 60 carbon atoms.

5. The formulation according to claim 1 wherein compound I is selected from a compound comprising one epoxide group and/or a polyepoxide compound comprising more than one epoxide group, preferably compound I selected from a di-epoxide and/or tri-epoxide compound such as trimethylolethane triglycidyl ether (TMPTE), 1,4 butanediol diglycidyl ether (BDDE), Bisphenol A diglycidyl ether and combinations thereof.

6. The formulation according to claim 1 wherein the epoxide compound is selected from at least one linear epoxide compound, preferably the amount of linear epoxide compounds is at least 50 wt %, more preferably at least 60 wt %, most preferably at least 80 wt % based on the total weight of all epoxide compounds in the formulation.

7. The formulation according to claim 1 wherein the epoxide compound is selected from at least one aromatic epoxide compound, preferably the amount of aromatic epoxide compounds is at least 50 wt %, more preferably at least 60 wt %, most preferably at least 80 wt % based on the total weight of all epoxide compounds in the formulation.

8. The formulation according to claim 1 wherein compound A corresponds to formula I ##STR00022## wherein i is an integer higher than or equal to 2, in particular from 2 to 10, more particularly 2 or 3, R.sup.1 is a carbon bond between the cyclic carbonate rings or is a linear or branched hydrocarbon chain, which may be unsubstituted or substituted and wherein one or several hydrocarbon groups of said hydrocarbon chain may be replaced by a heteroatom, a ketone, a cycloalkyl, a heterocycle, an aryl or a heteroaryl, each of which may be unsubstituted or substituted, said hydrocarbon chain having at least 2 carbon atoms, in particular from 3 to 60 carbon atoms.

9. The formulation according to claim 1 wherein compound D is selected from the group consisting of an amine catalyst, an ionic salt or ionic liquid composed of a combination of a cation and an anion, organometallic catalyst and a phosphine-based catalyst and is preferably 1,8-diazabicyclo[5.4.0]undec-7-ene, tetrabutylammonium phenolate, tetrabutyl ammonium hydroxide, sodium or potassium hydroxide.

10. The formulation according to claim 1 wherein compound A is present in an amount of from 1 to 99 wt %, preferably 18 to 80 wt %, more preferably 40 to 80 wt %, most preferably from 50 to 80 wt %, the percentage being expressed relative to the total weight of the formulation.

11. The formulation according to claim 1 wherein compound B is present in an amount of from 10 to 80 wt %, in particular from 10 to 70 wt %, more in particular from 10 to 50 wt %, the percentage being expressed relative to the total weight of the formulation.

12. The formulation according to claim 1 wherein compound B is selected from at least one polyamine having at least 2 primary amine groups and at least one polyamine having at least 3 primary amine groups wherein the amount of polyamine having at least 2 primary amine groups is preferably at least 50 wt %, more preferably at least 60 wt %, most preferably at least 80 wt % based on the total weight of all multifunctional amine compounds in the formulation.

13. The formulation according to claim 1 wherein compound B is selected from at least one polyamine having at least 2 primary amine groups, preferably selected from xylylenediamine (XDA), 1,3-Cyclohexanebis(methylamine) and or triethyleneglycoldiamine and optionally at least one polyamine having at least 3 primary amine groups, preferably selected from diethylenetriamine (DETA) and/or Tris(2-aminoethyl)amine (TREN).

14. The formulation according to claim 1 wherein the total amount of water including water provided by the water source is of from 0.5 to 20 wt %, the percentage being expressed relative to the total weight of the formulation.

15. The formulation according to claim 1 wherein the water source is a hydrate and wherein the hydrate is present in an amount of from 0.05 to 50 wt %, in particular from 0.1 to 20 wt %, more in particular from 1 to 15 wt %.

16. The formulation according to claim 1 wherein compound D is present in an amount of from 0.1 to 50 wt %, in particular from 0.5 to 25 wt %, more in particular from 0.5 to 10 wt %, the percentage being expressed relative to the total weight of the formulation.

17. The formulation according to claim 1 further comprising a multifunctional thiol (compound H), preferably in an amount of from 1 to 50 wt %, in particular from 2 to 20 wt %, more in particular from 2 to 15 wt %, the percentage being expressed relative to the total weight of the formulation, said multifunctional thiol preferably corresponding to formula XII ##STR00023## Wherein: r is an integer higher than or equal to 2, in particular from 2 to 6, R.sup.26 is a linear or branched hydrocarbon chain, which may be unsubstituted or substituted, and wherein one or several hydrocarbon groups of said hydrocarbon chain may be replaced by a heteroatom, a ketone, a cycloalkyl or a heterocycle, each of which may be unsubstituted or substituted, said hydrocarbon chain having at least 2 carbon atoms, in particular from 2 to 60 carbon atoms, more particularly from 2 to 20 carbon atoms, even more particularly from 2 to 15 carbon atoms, or R.sup.26 is a linear or branched polymeric group.

18. The formulation according to claim 1 further comprising a masked thiol precursor (compound C), wherein compound C is present in an amount of from 1 to 60 wt %, in particular from 2 to 40 wt %, more in particular from 5 to 20 wt %, the percentage being expressed relative to the total weight of the formulation.

19. A process for preparing a polyurethane self-blowing foam comprising the steps of providing a formulation as defined in claim 1 and allowing said formulation to expand to form a non-isocyanate polyurethane foam.

20. The process according to claim 18 wherein the foaming takes place at room temperature and without further heating said formulation to achieve an appropriate foaming temperature.

21. A process for preparing a polyurethane foam which comprises the steps of (i) mixing compounds A, B, water and/or a water source and optionally compound C, D, H and/or I wherein the molar ratio of epoxide groups from compound I in the formulation towards the cyclic carbonate groups from compound A in the formulation is in the range 0.05 up to 20, preferably from 0.2 to 4, and the molar ratio of water including water provided by the water source towards the cyclic carbonate groups from compound A in the formulation is from 0.025 to 8, preferably from 0.025 to 2, and the molar ratio of compound B towards the cyclic carbonate groups from compound A and optionally the epoxide groups from compound I when present in the formulation in the range 0.5 to 1.25 so as to form a viscous mixture, (ii) allowing said mixture obtained in step (i) to foam so as to form a non-isocyanate polyurethane foam, wherein compounds A, B, C, D, I and H are as defined in claim 18.

22. The process for preparing a polyurethane foam according to claim 19 by reactive injection molding.

23. The process for preparing a polyurethane foam according to claim 19 by reactive extrusion foaming.

24. Polyurethane foam obtainable by the process as defined in claim 19.

25. The process for recycling a polyurethane foam as defined in claim 24 by compression molding or extrusion.

26. Recycled polyurethane foam obtainable by the process as defined in claim 25 processed as a film, coating, adhesive, fiber or as bulk material.

Description

DESCRIPTION OF FIGURES

[0168] FIG. 1 is a micrography by Scanning Electron Microscopy (SEM) of the foam obtained in example 1, sample c.

[0169] FIG. 2 is a SEM image of the foam obtained in example 2.

[0170] FIG. 3 is a SEM image of the foam obtained in example 3.

[0171] FIG. 4 is a SEM image of the foam obtained in example 4.

[0172] FIG. 5 is a SEM image of the foam obtained in example 5.

[0173] FIG. 6 is a SEM image of the foam obtained in example 6.

[0174] FIG. 7 is a SEM image of the film obtained after foam reprocessing in example 16.

[0175] FIG. 8 is a graph representing the foam density and the gel content as a function of water amount in the formulation.

[0176] FIG. 9 shows the influence of epoxide compounds (compound I) on the core temperature of the foam over the foaming time.

EXAMPLES

[0177] The following examples illustrate the formation of self-blowing NIPU foams induced by water from the following precursors:

##STR00019## ##STR00020##

[0178] In the following examples, 5CC states for a cyclic carbonate group, NH.sub.2 for a primary amine group and eq for equivalent.

[0179] Example 1: The following example illustrates the use of different catalysts (compound D) for foaming. A mixture of compounds A (trimethylolpropane triscarbonate TMPTC 0.8 g, 57.8 wt % and isocyanurate-triCC 0.2 g and 14.5 wt %, 5CC=6.9 mmol, 1 eq), compound B (m-x Dia, 0.350 g, NH.sub.2=5.15 mmol, 0.75 eq), compound D selected from Na.sub.3PO.sub.4 or K.sub.2CO.sub.3 or LiCl or DBU (0.05 eq) and water (0.031 g. 1.7 mmol. 0.25 eq) was placed in a silicon mold and stirred at room temperature for 1 minute. The reactive mixture was cured 3 h at 100 C. A rigid foam was obtained. Density of the different foams was measured by cutting the foam in a cube of 10 mm10 mm10 mm and weighing such cube. Results are presented in the table below. An image of sample c obtained by Scanning Electron Micrography (SEM) is presented in FIG. 1.

TABLE-US-00001 Sample Compound D Mass (g) Density (kg/m3) a Na3PO4 0.057 243 b K2CO3 0.048 283 C LiCI 0.015 260 d KOH 0.018 378 e DBU 0.051 164 Table 1: Compounds D used in Example 1.

[0180] Example 2: A mixture of compound A (TMPTC, 1 g, 69.7 wt %, 5CC=6.9 mmol, 1 eq), compound B (m-x Dia, 0.350 g, 24.4 wt %, NH.sub.2=5.15 mmol, 0.75 eq), compound D (DBU, 0.052 g, 3.6 wt %, 0.34 mmol, 0.05 eq) and water (0.031 g, 2.2 wt %, 1.72 mmol, 0.25 eq) was placed in a silicon mold and stirred at room temperature for 1 minute. The reactive mixture was placed in an oven at 100 C. for 3 h. A rigid foam was obtained with a density of 265 Kg/m.sup.3. A SEM image is presented in FIG. 2.

[0181] Example 3: Example 2 was reproduced with a curing temperature of 80 C. during 3 h. A rigid foam was obtained with a density of 309 Kg/m.sup.3. A SEM image is presented in FIG. 3.

[0182] Example 4: Example 2 was reproduced with a curing temperature of 25 C. during 3 h and 100 C. during 3 h. A rigid foam was obtained with a density of 170 Kg/m.sup.3. A SEM image is presented in FIG. 4.

[0183] Example 5: A mixture of compounds A (TMPTC 0.8 g, 55.8 wt % and isocyanurate-triCC 0.2 g, 14 wt %, 5CC total=6.9 mmol, 1 eq), compound B (m-x Dia 0.350 g 24.4 wt %, NH.sub.2=5.15 mmol, 0.75 eq), compound D (DBU, 0.052 g, 3.6 wt %, 0.34 mmol, 0.05 eq) and water (0.031 g, 2.1 wt %, 1.72 mmol, 0.25 eq) was placed in a silicon mold and stirred at room temperature for 1 minute. The mixture was placed in an oven at 100 C. for 3 h. A rigid foam was obtained with a density of 177 Kg/m.sup.3 (FIG. 5). A SEM image is presented in FIG. 5.

[0184] Example 6: A mixture of compound A (TMPTC, 1 g, 64.5 wt %, 5CC total=6.9 mmol, 1 eq), compound B (m-x Dia 0.350 g, 22.5 wt %, NH.sub.2=5.15 mmol, 0.75 eq), compound D (DBU, 0.052 g, 3.4 wt %, 0.34 mmol, 0.05 eq), water (0.031 g, 2 wt %, 1.72 mmol, 0.25 eq) and Laponite S482 (0.120 g and 7.7 wt %) was placed in a silicon mold and stirred at room temperature for 1 minute. The reactive mixture was placed in an oven at 100 C. for 3 h. A rigid foam was obtained with a density of 186 Kg/m.sup.3. A SEM image is presented in FIG. 6.

[0185] Example 7: A mixture of compound A (TMPTC 1 g, 72.4 wt %, 5CC=6.9 mmol, 1 eq), compound B (m-x Dia 0.350 g, 25.3 wt %, NH.sub.2=5.15 mmol, 0.75 eq), and water (0.031 g, 2.2 wt %, 1.72 mmol, 0.25 eq) was placed in a silicon mold and stirred at room temperature for 1 minute. No compound D was added in this case. The reactive mixture was cured 3 h at room temperature and then placed in an oven at 100 C. for 3 h. A foam was obtained with a density of 465 Kg/m.sup.3.

[0186] The following examples present the use of a mineral base as compound D. KOH has been grinded into fine powder to facilitate incorporation into the monomer mixture.

[0187] Example 8: A mixture of compound A (TMPTC, 1 g, 68 wt %, 5CC=6.9 mmol, 1 eq), compound B (m-x Dia 0.350 g, 23.8 wt %, NH.sub.2=5.15 mmol, 0.75 eq), compound D (KOH powder 0.09 g, 6.1 wt %, 1.6 mmol, 0.23 eq) and water (0.031 g, 2.1 wt %, 1.72 mmol, 0.25 eq) was placed in a silicon mold and stirred at room temperature for 1 minute. The reactive mixture was placed in an oven at 100 C. for 3 h. A rigid foam was obtained with a density of 218 Kg/m.sup.3.

[0188] Example 9: A mixture of compound A (TMPTC, 5 g, 64.1 wt %, 5CC=34.5 mmol, 1 eq), compound B (m-x Dia 1.750 g, 22.4 wt %, NH.sub.2=25.8 mmol, 0.75 eq), compound D (KOH powder 0.450 g, 5.7 wt %, 8.0 mmol, 0.23 eq) and water (0.600 g, 7.6 wt %, 8.6 mmol, 0.25 eq) was placed in a silicon mold and stirred at room temperature for 1 minute. The reactive mixture was placed in an oven at 80 C. for 5 h. A rigid foam was obtained with a density of 338 Kg/m.

[0189] Example 10: A mixture of compound A (TMPTC 0.8 g, 54.4 wt % and isocyanurate-triCC 0.2 g, 13.6 wt %, 5CC=6.9 mmol, 1 eq), compound B (m-x Dia 0.350 g, 23.8 wt %, NH.sub.2=5.15 mmol, 0.75 eq), compound D (KOH 0.09 g, 6.1 wt %, 1.6 mmol, 0.23 eq) and water (0.031 g, 2.1 wt %, 1.72 mmol, 0.25 eq) was placed in a silicon mold and stirred at room temperature for 1 minute. The reactive mixture was placed in an oven at 100 C. for 3 h. A rigid foam was obtained with a density of 170 Kg/m.sup.3.

[0190] The following examples deal with the use of a hydrated inorganic salt as catalyst that also provides water for foaming.

[0191] Example 11: A mixture of compound A (TMPTC 1 g, 65.1 wt %, 5CC=6.9 mmol, 1 eq), compound B (m-x Dia 0.350 g, 22.8 wt %, NH.sub.2=5.15 mmol, 0.75 eq), a hydrated inorganic salt (Na.sub.2B.sub.4O.sub.7.Math.10H.sub.2O 0.131 g, 8.5 wt %, H.sub.2O=3.4 mmol, 0.5 eq), compound D (DBU 0.052 g, 3.4 wt %, 0.34 mmol, 0.05 eq) was placed in a silicon mold and stirred at room temperature for 1 minute. No further water was added; water was provided by the dehydratation of Na.sub.2B.sub.4O.sub.7.Math.10H.sub.2O upon heating. The reactive mixture was placed in an oven at 100 C. for 3 h. A rigid foam was obtained with a density of 216 Kg/m.sup.3.

[0192] Example 12: A mixture of compound A (TMPTC 1 g, 67.5 wt %, 5CC=6.9 mmol, 1 eq), compound B (m-x Dia 0.350 g, 23.6 wt %, NH.sub.2=5.15 mmol, 0.75 eq), a hydrated inorganic salt (Na.sub.2B.sub.4O.sub.7.Math.10H.sub.2O 0.131 g, 8.8 wt %) was placed in a silicon mold and stirred at room temperature for 1 minute. No further water was added; water was provided by the dehydratation of Na.sub.2B.sub.4O.sub.7.Math.10H.sub.2O upon heating. The reactive mixture was placed in an oven at 100 C. for 3 h. A rigid foam was obtained with a density of 315 Kg/m.sup.3. This example shows that Na.sub.2B.sub.4O.sub.7.Math.10H.sub.2O is able to catalyze the reaction and to generate water needed for the blowing, even in the absence of DBU.

[0193] The following examples deal with the use of both water and thiol (compound H) as foaming agent.

[0194] Example 13: A mixture of compound A (TMPTC 1 g, 62.9 wt %, 5CC=6.9 mmol, 1 eq), compound B (m-x Dia 0.350 g, 22 wt %, NH.sub.2=5.15 mmol, 0.75 eq), compound H (diTh, 0.156 g, 9.8 wt %, SH=1.72 mmol, 0.25 eq), water (0.031 g, 1.9 wt %, 1.72 mmol, 0.25 eq) and compound D (DBU 0.052 g, 3.3 wt %, 0.34 mmol, 0.05 eq) was placed in a silicon mold and stirred at room temperature for 1 minute. The reactive mixture was placed in an oven at 100 C. for 3 h. A rigid foam was obtained with a density of 207 Kg/m.sup.3.

[0195] The following examples deal with the use of a hydrated inorganic filler as the catalyst for foaming, either without any further compound D, either with DBU as compound D.

[0196] Example 14: A mixture of compound A (TMPTC 1 g, 58.2 wt %, 5CC=6.9 mmol, 1 eq), compound B (m-x Dia 0.350 g, 20.3 wt %, NH.sub.2=5.15 mmol, 0.75 eq), water (0.150 g, 14.4 wt %, 1.72 mmol, 0.25 eq) and hydrotalcite (Mg.sub.6Al.sub.2(CO.sub.3)(OH).sub.16.Math.4H.sub.2O, 0.120 g, 7.0 wt %) was placed in a silicon mold and stirred at room temperature for 1 minute. The reactive mixture was placed in an oven at 80 C. for 3 h. A rigid foam was obtained with a density of 262 Kg/m.sup.3.

[0197] Example 15: A mixture of compound A (TMPTC 1 g, 56.4 wt %, 5CC=6.9 mmol, 1 eq), compound B (m-x Dia 0.350 g, 19.8 wt %, NH.sub.2=5.15 mmol, 0.75 eq), water (0.150 g, 14.0 wt %, 1.72 mmol, 0.25 eq), compound D (DBU, 0.052 g, 2.9 wt %, 0.34 mmol, 0.05 eq) and hydrotalcite (Mg.sub.6Al.sub.2(CO.sub.3)(OH).sub.16.Math.4H.sub.2O, 0.120 g, 6.8 wt %) was placed in a silicon mold and stirred at room temperature for 1 minute. The reactive mixture was placed in an oven for 3 h at 80 C. or for 24 h at 60 C. Rigid foams were obtained with a density of 215 Kg/m.sup.3 and 395 Kg/m.sup.3 respectively. The same formulation using another compound B (Cyh Dia, 0.310 g, NH.sub.2=5.15 mmol, 0.75 eq) leads to a rigid foam with a density of 171 Kg/m.sup.3 after 3 h of foaming at 80 C. and a rigid foam with a density of 322 Kg/m.sup.3 after 24 h at 60 C.

[0198] The following examples illustrate the influence of the water content on the density and gel content of the foam.

[0199] Example 16: A mixture of compound A (TMPTC 5 g, 5CC=1 eq) and hydrotalcite (0.6 g) was stirred at room temperature in a silicon mold until reaching a viscous formulation. A mixture of compound B (m-x Dia, 1.75 g, NH.sub.2=0.75 eq), compound D (DBU, 0.260 g, 0.05 eq) and different amounts of water was added to the TMPTC/hydrotalcite mixture and stirred until homogenization. Hydrotalcite was used as a filler. Although being sometimes considered as a hydrate, hydrotalcite only generates a very small amount of water under the curing conditions used. Such amount of water was therefore neglected in this example.

[0200] The reactive mixture was placed in an oven at 100 C. for 3 h. Results are presented graphically in FIG. 8. This example shows that the gel content lowers when the amount of water is increased. This is explained by the fact that there is more hydrolysis taking place, thereby loosing potential cyclic carbonate function that can form the crosslinking nodes of the structure. It induces a decrease of potential reticulation nods. If the amount of water is too high, no network (crosslinked structure) can be formed and no foaming occurs. An upper limit was found for the tested formulation with 8 equivalent of water versus the cyclic carbonate group. With that content, a foam can still be obtained, with a density of 783 kg/m.sup.3 (density about 75% of the bulk material). Regarding the lower limit, we observed that a foam can be obtained for the tested formulation with 0.025 equivalent of water versus the cyclic carbonate group. To obtain a foam with a lower density, it is preferred to use an amount of water from 0.05 eq, more preferred from 0.1 eq, even more preferred from 0.25 eq and preferably up to 5.0 eq, more preferably up to 4.0 eq, even more preferably up to 2 eq.

TABLE-US-00002 Water (eq vs cyclic Water (wt%) Density(kg/m3) Gel content (%) carbonate) 0 eq 0 963 NA 0.025 eq 0.2 750 98 0.05 eq 0.4 693 95 0.25 eq 2 154 94 1 eq 7.5 119 82 2 eq 13 130 84 4 eq 24 327 79 8 eq 40 783 31 Table 2: water amounts used in Example 16.

[0201] The following examples present the procedure to obtained flexible foam.

[0202] Example 17: A mixture of compounds A (TMPTC 0.8 g, 57.8 wt % and isocyanurate-triCC 0.2 g and 14.5 wt %, 5CC=6.9 mmol, 1 eq), compound B (Hm Dia 0.300 g, 21.7 wt %, NH.sub.2=5.15 mmol, 0.75 eq), compound D (DBU 0.052 g 3.8 wt %, 0.34 mmol, 0.05 eq) and water (0.031 g, 2.2 wt %, 1.72 mmol, 0.25 eq) was placed in a silicon mold and stirred at room temperature for 1 minute. The reactive mixture was cured 3 h at room temperature and then placed in an oven at 100 C. for 3 h. A flexible foam was obtained with a density of 153 Kg/m.sup.3.

[0203] Example 18: A mixture of compound A (TMPTC 5 g, 59.8 wt %, 5CC=34.5 mmol, 1 eq) and hydrotalcite (Mg.sub.6Al.sub.2(CO.sub.3)(OH).sub.16.Math.4H.sub.2O, 0.6 g, 7.2 wt %) was stirred in a silicon mold until reaching a viscous formulation. Compound B (EDR 148, 1.9 g, 22.7 wt %, NH.sub.2=25.7 mmol, 0.75 eq), compound D (DBU, 0.260 g 3.1 wt %, 1.7 mmol, 0.05 eq) and water (0.600 g 7.2 wt %, 33 mmol, 0.95 eq), were added to the TMPTC/hydrotalcite mixture and stirred until homogenization. The reactive mixture was placed in an oven at 80 C. for 5 h. A flexible foam with a density of 335 Kg/m.sup.3 was obtained.

[0204] Example 19: Example 18 was reproduced without the addition of hydrotalcite leading to a flexible foam with a density of 429 Kg/m.sup.3.

[0205] Example 20: A mixture of compound A (TMPTC 5 g, 62.3 wt %, 5CC=34.5 mmol, 1 eq) and hydrotalcite (Mg.sub.6Al.sub.2(CO.sub.3)(OH).sub.16.Math.4H.sub.2O, 0.6 g, 7.5 wt %) was stirred in a silicon mold until obtention of viscous formulation. Compound B (hm Dia, 1.55 g, 19.3 wt %, NH.sub.2=25.7 mmol, 0.75 eq), compound D (DBU, 0.260 g 3.2 wt %, 1.7 mmol, 0.05 eq) and water (0.600 g 7.5 wt %, 33 mmol, 0.95 eq), were added to the TMPTC mixture and stirred until homogenization. The reactive mixture was placed in an oven at 80 C. for 5 h. A flexible foam with a glass transition of 0.6 C. and a density of 255 Kg/m.sup.3 was obtained.

[0206] The following examples illustrate some conditions to obtain flexible or rigid foam in a short period of time of 0.5 h at 120 C. or 100 C.

[0207] Example 21: A mixture of compound A (TMPTC 5 g, 64 wt %, 5CC=34.5 mmol, 1 eq) and hydrotalcite (Mg.sub.6Al.sub.2(CO.sub.3)(OH).sub.16.Math.4H.sub.2O, 0.6 g, 7.7 wt %) was stirred in a silicon mold until reaching a viscous formulation and preheated at 120 C. A mixture of compound B (m-x Dia, 1.75 g, 23 wt %, NH.sub.2=25.7 mmol, 0.75 eq), compound D (DBU, 0.260 g, 3.3 wt %, 1.7 mmol, 0.05 eq) and water (0.155 g 2 wt %, 8.7 mmol, 0.25 eq), was preheated for 5 min at 120 C., and was then added to the TMPTC mixture and stirred until homogeneisation at 120 C. The reactive mixture was placed in an oven at 120 C. for 0.5 h. A rigid foam was obtained with a density of 161 Kg/m.sup.3.

[0208] Example 22: A mixture of compound A (TMPTC 5 g, 63.2 wt %, 5CC=34.5 mmol, 1 eq) and hydrotalcite (Mg.sub.6Al.sub.2(CO.sub.3)(OH).sub.16.Math.4H.sub.2O, 0.6 g, 7.5 wt %) was stirred in a silicon mold until reaching a viscous formulation and preheated at 100 C. A mixture of compound B (EDR 148, 1.9 g, 24 wt %, NH.sub.2=25.7 mmol, 0.75 eq), compound D (DBU, 0.260 g, 3.2 wt %, 8.7 mmol, 0.25 eq) and water (0.155 g, 2 wt %, 8.7 mmol, 0.25 eq), was preheated for 5 min at 100 C., and was then added to the TMPTC mixture and stirred until homogeneisation at 100 C. The reactive mixture was placed in an oven at 100 C. for 0.5 h. A flexible foam was obtained with a density of 301 Kg/m.sup.3.

[0209] The following example illustrates the foaming in a closed mold.

[0210] Example 23: A mixture of compound A (TMPTC 5 g, 64 wt %, 5CC=34.5 mmol, 1 eq) and hydrotalcite (0.6 g, 7.7 wt %) was stirred until reaching a viscous formulation. Compound B (m-x Dia, 1.75 g, 23 wt %, NH.sub.2=25.7 mmol, 0.75 eq), compound D (DBU, 0.260 g 3.3 wt %, 0.05 eq) and water (0.155 g 2 wt %, 8.7 mmol, 0.25 eq) were added to the formulation and stirred until homogeneisation. The formulation was directly added in a preheated cylindrical metallic mold (V=34 cm.sup.3) at 100 C. with a syringe and let to react for 3 h at 100 C. A rigid foam was obtained with a density of 208 Kg/m.sup.3. The same example was reproduced with a curing time of 24 h at 80 C. and a rigid foam was obtained with a density of 252 Kg/m.sup.3

[0211] The following examples deal with the reprocessability of the foams of the invention (PHU) by compression molding under thermal treatment to form films, coatings, adhesives.

[0212] Example 24: Foam synthesized in example 2 was pressed on a Teflon film at a pressure of 1,000,000 kg and 160 C. for 2 h. A cracks-free PHU film was obtained. A SEM image in presented in FIG. 7.

[0213] Example 25: Foam synthesized in example 5 was pressed on a Teflon film at a pressure of 1,000,000 kg and 160 C. for 2 h. A cracks-free PHU film was also obtained.

[0214] The following examples illustrate formulations to obtain flexible or rigid foam at room temperature in less than 15 minutes.

[0215] Example 26: A mixture of compound A (TMPTC) 25 g, 48 wt %, 5CC=173 mmol, 1 eq), compound I (trimethylolethane triglycidyl ether (=TMPTE) 8.7 g, 16.7 wt %, epoxide=86 mmol, 0.5 eq), Hydrotalcite (3 g, 5.7 wt %) was placed in a plastic mold and stirred at room temperature for 2 minutes until homogeneous mixture was obtained. Compound B (XDA 10.3 g, 19.8 wt % NH.sub.2=151 mmol, 0.87 eq and TREN 3.17 g, 6.1 wt %, NH.sub.2=65 mmol, 0.37 eq) was added to the mixture. Compound D (KOH 1.125 g, 2.1 wt % 20 mmol, 0.115 eq) was solubilized in compound E (water, 0.775 g, 1.5 wt % 43 mmol, 0.25 eq), and then added to the mixture. The reactive mixture was stirred for 2 min and let at room temperature. Foam started to expand between 1 and 3 minutes after mixing and full expansion of the foam was reached within 5 min. After cooling to room temperature, a rigid foam with a density of 258 kg/m.sup.3 was obtained.

[0216] Example 27: The same formulation as in Example 26 was used but without Hydrotalcite. This formulation did lead to a rigid foam with a density of 388 kg/m.sup.3

[0217] The following examples illustrate formulations to obtain flexible or rigid foams at room temperature in less than 15 minutes thereby using different diamines (compound B) compared to Example 26.

[0218] Example 28: A mixture of compound A (TMPTC 25 g, 47.8 wt %, 5CC=173 mmol, 1 eq), compound I (TMPTE 8.7 g, 16.6 wt %, epoxide=86 mmol, 0.5 eq), hydrotalcite (3 g, 5.7 wt %) was placed in a plastic mold and stirred at room temperature for 2 minutes until homogeneous mixture was obtained. Compound B (m-x Dia 10.55 g, 20.2 wt %, NH.sub.2=151 mmol, 0.87 eq and TREN 3.17 g, 6.1 wt %, NH.sub.2=65 mmol, 0.37 eq) was added to the mixture. Compound D (KOH 1.125 g, 2.1 wt %, mmol, 0.115 eq) was solubilized in water (0.775 g, 1.5 wt %, 43 mmol, 0.25 eq) and added to the mixture. The reactive mixture was stirred for 2 min and let at room temperature. Foam started to expand between 1 and 3 minutes after mixing and full expansion of the foam was reached within 5 min. After cooling to room temperature, a rigid foam with a density of 242 kg/m.sup.3 was obtained.

[0219] Example 29: A mixture of compound A (TMPTC 25 g, 47.3 wt %, 5CC=173 mmol, 1 eq), compound I (TMPTE 8.7 g, 16.5 wt %, epoxide=86 mmol, 0.5 eq), hydrotalcite (3 g, 5.7 wt %) was placed in a plastic mold and stirred at room temperature for 2 minutes until homogeneous mixture was obtained. Compound B (EDR 148 11 g, 20.8 wt %, NH.sub.2=149 mmol, 0.87 eq and TREN 3.17 g, 6 wt %, NH.sub.2=65 mmol, 0.37 eq) was added to the mixture. Compound D (KOH 1.125 g, 2.13 wt %, mmol, 0.115 eq) was solubilized in water (0.775 g, 1.5 wt %, 43 mmol, 0.25 eq) and added to the mixture. The reactive mixture was stirred for 2 min and let at room temperature. Foam started to expand between 1 and 3 minutes after mixing and full expansion of the foam was reached within 5 min. After cooling to room temperature, a rigid foam with a density of 360 kg/m.sup.3 was obtained.

[0220] The following examples illustrate formulations to obtain flexible or rigid foams at room temperature in less than 15 minutes thereby using different epoxides (compound I) compared to Example 26.

[0221] Example 30: A mixture of compound A (TMPTC 25 g, 43.2 wt %, 5CC=173 mmol, 1 eq), compound I (DER 332, 14.7 g, 25.4 wt %, epoxide=87 mmol, 0.5 eq), hydrotalcite (3 g, 5.2 wt %) was placed in a plastic mold and stirred at room temperature for 2 minutes until homogeneous mixture was obtained. Compound B (m-x Dia 10.1 g, 17.4 wt %, NH.sub.2=149 mmol, 0.87 eq and TREN 3.17 g, 5.5 wt %, NH.sub.2=65 mmol, 0.37 eq) was added to the mixture. Compound D (KOH 1.125 g, 1.94 wt %, mmol, 0.115 eq) was solubilized in water (0.775 g, 1.3 wt %, 43 mmol, 0.25 eq) and added to the mixture. The reactive mixture was stirred for 2 min and let at room temperature. Foam started to expand between 1 and 3 minutes after mixing and full expansion of the foam was reached within 5 min. After cooling to room temperature, a rigid foam with a density of 260 kg/m.sup.3 was obtained.

[0222] Example 31: A mixture of compound A (TMPTC 25 g, 48.1 wt %, 5CC=173 mmol, 1 eq), compound I (1,4 butanediol diglycidyl ether (=BDDE), 8.76 g, 16.8 wt %, epoxide=87 mmol, 0.5 eq), hydrotalcite (3 g, 5.8 wt %) was placed in a plastic mold and stirred at room temperature for 2 minutes until homogeneous mixture was obtained. Compound B (m-x Dia 10.1 g, 19.5 wt %, NH.sub.2=149 mmol, 0.87 eq and TREN 3.17 g, 6.1 wt %, NH.sub.2=65 mmol, 0.37 eq) was added to the mixture. Compound D (KOH 1.125 g, 2.2 wt %, 20 mmol, 0.115 eq) was solubilized in water (0.775 g, 1.5 wt %, 43 mmol, 0.25 eq) and added to the mixture. The reactive mixture was stirred for 2 min and let at room temperature. Foam started to expand between 1 and 3 minutes after mixing and full expansion of the foam was reached within 5 min. After cooling to room temperature, a rigid foam with a density of 197 kg/m.sup.3 was obtained.