Use of n-carboxyanhydrides as blowing agent for polymer foam production

Abstract

The present invention relates to the use of N-carboxyanhydride compounds as blowing agent for the preparation of polymer foam materials. Said use comprises the reaction of a N-carboxyanhydride compound with a nucleophile to produce carbon dioxide and an amine compound, which can be incorporated into the polymer material. The invention also relates to a polymerizable composition and a kit comprising said composition, said composition comprising a N-carboxyanhydride compound and a nucleophile and a polymerizable mixture comprising a polyamine. The invention also relates to a process for the preparation of a foam material and to the product obtainable by said process.

Description

[0001] USE OF N-CARBOXYAN HYDRIDES AS BLOWING AGENT FOR POLYMER FOAM PRODUCTION

[0002] FIELD OF THE INVENTION

[0003]

[0001] The present invention relates to the use of N-carboxyanhydride compounds as a blowing agent for the preparation of polymer foam materials. Said use comprises the reaction of a N-carboxyanhydride compound with a nucleophile to produce carbon dioxide and an amine compound, which can be incorporated into the polymer material. The invention also relates to a polymerizable composition and a kit comprising said composition, said composition comprising a N-carboxyanhydride compound and a nucleophile and a polymerizable mixture comprising a polyamine. The invention also relates to a process for the preparation of a foam material and to the product obtainable by said process.

[0004] BACKGROUND

[0005]

[0002] Polymer foam materials are used worldwide in a broad range of applications, including insulation, sealants, packaging, safety, cushioning, etc. These materials comprise gas molecules entrapped within the network of polymer chains of the polymer material, thus forming a cellular structure. The preparation of foam materials thus usually requires the use of blowing agents in charge of generating the cellular structure of the foam material, said structure appearing during a transition of the material (phase transition or polymerization). The cellular structure in a polymer foam provides a material with low density, increased thermal and acoustic insulation, and increased relative stiffness with respect to the original polymer. Polyurethane foam materials are in particular very popular, as those are prepared easily by the polyaddition of polyisocyanates and macropolyols. The decarboxylation ability of isocyanates in the presence of water allows for the fabrication of polyurethane foams in a one-step process involving simultaneous reactions of polyurethane formation and gas generation. In this regard, such polyurethane foams are called self-blowing foams, as no external blowing agent needs to be added to promote the formation of the cellular structure of the foam material. However, the use of hazardous and toxic isocyanate compounds is of concern and there is a need for more sustainable alternative precursors of polymer foam materials.

[0003] As discussed by Jin F. and co-workers in “Recent Trends of Foaming in Polymer Processing: A Review.” Polymers 2019, 77(6), 953, several alternative polymeric matrices such as polystyrene (PS), poly(vinyl chloride) (PVC), and propylene (PP), can be foamed. However, to create cells inside those matrices, the addition of an external physical or chemical blowing agent is mandatory. Externally-blown foams cannot mimic the cell uniformity and properties of self-blowing foams, and the addition of external blowing agents increases the cost and complexity of the industrial production process. Therefore, the provision of novel self-foaming systems that allow avoiding the use of isocyanates leading to adverse impacts on human health and the environment, is of great interest.

[0006]

[0004] In an attempt to provide non-isocyanate based self-blown polyurethane foams, patent application WO 2021 / 004993 A1 discloses an isocyanate-free composition for the preparation of polyurethane foams comprising at least one multifunctional cyclic carbonate, at least one multifunctional amine (compound B), at least one multifunctional thiol (compound C) and a catalyst. The function of the thiol is to trigger the decarboxylation of the cyclic carbonate, such that gaseous CO2 evolves during the polymerization, providing a foam material. A similar approach to the one of WO 2021 / 004993 is disclosed in patent application WO 2023 / 104362 A1, but replacing the thiol with an amount of water. The disclosed systems may comprise a basic catalyst.

[0007]

[0005] Besides polyurethane foam materials, other foam materials are of interest. For instance, epoxy foams are widely used in lightweight structural composites, electrical insulation, and fire-resistant coatings, benefiting industries such as aerospace, automotive, and construction. Polyamine-based foams, often utilized as high-temperature insulators and impact-resistant materials, find applications in protective gear, coatings, and adhesives. Polyamide foams offer excellent chemical resistance and mechanical strength, making them suitable for filtration systems, vibration damping, and lightweight engineering components. Polyimide foams are particularly valued for their superior thermal stability and flame resistance, serving as insulation materials in aerospace, electronics, and high-performance soundproofing. Meanwhile, polyhydroxyurethane foams, known for their environmentally friendly properties and enhanced flexibility, are emerging as sustainable alternatives in biodegradable packaging, medical cushioning, and thermal insulation.

[0008]

[0006] Epoxy materials are highly valued for their thermal stability, mechanical strength, chemical resistance, low shrinkage upon curing, and strong adhesion to various substrates. However, the chemical of foaming epoxies is challenging. Chemical foaming typically involves a foaming agent that produces gases as byproducts of temperature-activated reactions. Common chemical blowing agents for epoxy foams known in the art include gases like hydrogen and carbon dioxide, generated through the reaction ofaluminum powder with NaOH or citric acid with NaHCO3. However, these agents often exhibit low compatibility with epoxy resins, which lead to poorly homogeneous structures. Furthermore, the presence of any residual blowing agent in the foamed material after processing may compromise or jeopardize the physical properties of the material.

[0009]

[0007] Recently, new chemical foaming agents for epoxy systems have been reported. For instance, Chang Y, et al. disclose in R. Soc. open sci. 2019 6: 182119 the use of polysilazane as a foaming agent to create low-density, high-strength epoxy foams. By adjusting the polysilazane content from 2.5% to 7.5%, foam densities between 0.321 and 0.151 g / cm3were achieved. In the foaming process, polysilazanes react with hydroxyl groups formed during the ring-opening of oxirane units, generating Si-NH2and Si-O-C groups that subsequently react with hydroxyl groups, releasing NH3gas. However, NH3can also react with epoxide groups, potentially impeding network formation. Additionally, ammonia is a highly toxic, corrosive, and flammable gas at room temperature and pressure, posing serious risks of exposure via inhalation or skin contact, with potential long-term effects. Hydrogen gas is also generated through reactions between Si-H groups in polysilazanes and NH2groups in triethylenetetramine, facilitating the formation of a porous foam structure. Although hydrogen is less toxic than ammonia, it is highly explosive, which is a concern for foams intended for insulation and construction applications.

[0010]

[0008] Wang, L. et al. disclosed in J. Mater. Sci. 53, 1540-1555 and in Adv. Mater. 30, 1703992 the use of 3,7-dinitroso-1,3,5,7-tetraazobicyclononane as foaming agent in the production of epoxy foams with small microcell sizes. The disclosed process requires high temperatures and long processing times (about 3 hours).

[0011]

[0009] US patent US 8,003,730 B1 discloses the use of a combination of an acidic anhydride, such as maleic anhydride, and a nucleophilic catalyst, such as imidazole to foam an epoxy resin, the reaction forming carbon dioxide as blowing agent.

[0012]

[0010] The use of carbamate compounds deriving from the absorption of carbon dioxide by polyamine compounds suitable for forming epoxy resin (such as diaminodicyclohexylmethane) has been suggested by Ren, Q. et al in Ind. Eng. Chem. Res. 2015, 54, 44, 11056-11064. Following a similar approach, Ruckdashel, H. and coworkers disclose in Polymer 2022, 254,125080 and in Ind. Eng. Chem. Res. 2021, 60, 19, 7065-7080 the formation of epoxy foams using isophorone diamine-carbamate as source of carbon dioxide and isophorone diamine which further reacts with the epoxy and incorporates in the foam material. The lack of thermal stability of the used diamine-carbamate source of carbon dioxide however hampers the broad adoption of this approach.

[0013]

[0011] Kanazawa et al. disclose in Polymer, Elsevier, 1992, vol. 33 (12), 2557-2566 the synthesis of high-molecular-weight polypeptides through the solid-state polymerizationof various N-carboxy-a-amino acid anhydrides (NCAs), including L-leucine, L-alanine, and y-benzyl-L-glutamate. The polymerization process occurs within the monomer crystals and involves the evolution of carbon dioxide gas as a byproduct. The escape of this gas from the crystal lattice results in the formation of a polymeric structure characterized by numerous internal voids and structural deformation. The disclosure does not describe or include any other types of foam or porous polymers.

[0014]

[0012] Onder et al. disclose in Macromolecules, ACS, 2021, vol. 54 (18), 8321-8330 a method for preparing macroporous, stimuli-responsive hydrogels using a High Internal Phase Emulsion (HIPE) templating technique. The process involves the ring-opening polymerization of amino acid NCAs within the continuous phase of an oil-in-oil emulsion to create a "polyHIPE" structure. Upon removal of the internal phase, a highly interconnected foam morphology is produced, featuring large voids and interconnecting windows with porosities exceeding 89%. The resulting foam polymer is a polypeptide (such as poly(L-glutamic acid) or its copolymers). The disclosure does not describe or include any other types of foam or porous polymers.

[0015]

[0013] Florent, M. et al. review in Material Science and Engineering: R: Reports, Elsevier, 2021, vol. 145 (16), 100628 self-blown polymers. The document does not disclose the use of NCAs as blowing agents.

[0016]

[0014] From what is disclosed in the art, it derives that there is still a need for further methods and compositions for the preparation of polymeric foam materials, such as epoxy foams.

[0017] SUMMARY OF THE INVENTION

[0018]

[0015] After exhaustive research, the inventors have found that N-carboxyanhydride compounds comprising at least one moiety of formula (I) and / or of formula (II)

[0019]

[0020] are suitable for acting as latent sources of carbon dioxide, the release of carbon dioxide being triggered by a nucleophilic attack, according to the following scheme:

[0021]

[0022] The release of carbon dioxide takes place concomitantly with the formation of an amine compound, which is suitable for reacting with a polymerizable mixture comprising acompound suitable for forming a polymer by reaction with an amine or a polyamine, such that the by-product of the formation of carbon dioxide is incorporated in the polymer material formed upon polymerization of said polymerizable mixture. The inventors have thus found that such compounds are particularly useful as blowing agents, i.e. sources of gas, for the formation of polymer foam materials obtainable by polymerization of a polymerizable mixture comprising a polyamine.

[0023]

[0016] Thus, a first aspect of the invention relates to the use of a compound A1 comprising at least one moiety of formula (I), such as from one to three moieties of formula (I), and / or at least one moiety of formula (II) , such as from one to three moieties of formula (II), in its molecular formula as blowing agent for the production of a polymeric foam material other than a poly(peptide)

[0024]

[0025] (I) (II)

[0026] wherein:

[0027] each n is an integer of from 1 to 3;

[0028] each wavy line represents the covalent bond through which the moiety of formula (I) or of formula (II) is attached to the remainder of the molecule;

[0029] each Ri is selected from the group consisting of hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl (C3-C8)cycloalkyl, and (Ce-C2o)aryl optionally substituted at any available position with a group selected from the group consisting of halo, cyano, nitro, (Ci-Ce)alkyl, (Ci-Ce)alkyloxy and (Ci-Ce)haloalkyl;

[0030] R2 is selected from the group consisting of hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl, (C3-C8)cycloalkyl, and (Ce-C2o)aryl optionally substituted at any available position with a group selected from the group consisting of halo, cyano, nitro, (Ci-Ce)alkyl, (C1-Ce)alkyloxy and (Ci-Ce)haloalkyl; and

[0031] R3 is selected from the group consisting of hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl, (C3-C8)cycloalkyl, and (Ce-C2o)aryl optionally substituted at any available position with a group selected from the group consisting of halo, cyano, nitro, (Ci-Ce)alkyl, (C1-Ce)alkyloxy and (Ci-Ce)haloalkyl;

[0032] and wherein said use preferably comprises forming carbon dioxide by reaction of the compound A1 with a nucleophilic compound A2.

[0033]

[0017] A polymerizable mixture suitable for forming a foam material comprising said compounds A1 and A2 also forms part of the invention. The second aspect of the invention thus relates to a composition for forming a polymer foam comprising:

[0034] (i) a source of carbon dioxide comprising:(i-1) a compound A1 comprising at least one moiety of formula (I) and / or at least one moiety of formula (II) in its molecular formula as defined in any one of claims 1 to 3;

[0035] (i-2) a compound A2 comprising in its molecular formula at least one functional group selected from the group consisting of amino, hydroxyl, thiol, or at least one of a negatively charged carbon atom, a negatively charged nitrogen atom, a negatively charged oxygen atom or a negatively charged sulfur atom;

[0036] (ii) a polymerizable mixture of compounds comprising one or more of:

[0037] (ii-1) a polyepoxide and a polyamine or a polyol;

[0038] (ii-2) a polycarboxylic acid chloride and a polyamine or a polyol;

[0039] (ii-3) a polyisocyanate and a polyamine or a polyol;

[0040] (ii-4) a compound comprising in its molecular formula at least one moiety, preferably a plurality of moieties, of formula (III) Q

[0041] o A o, ,

[0042] ^4^

[0043]

[0044] (III)

[0045] wherein m is 1 or 2 and each wavy line represents the position to which the moiety of formula (III) is attached to the remainder of the compound and a polyamine or a polyol; (ii-5) a compound comprising in its molecular formula a plurality of moieties, of formula (IV)

[0046]

[0047] (IV)

[0048] wherein p is 1 or 2 and each wavy line represents the position to which the moiety of formula (IV) is attached to the remainder of the compound and a polyamine or a polyol; (ii-6) a compound comprising in its molecular formula a plurality of moieties, of formula (IX)

[0049]

[0050] (IX)

[0051] wherein each wavy line represents the position to which the moiety of formula (III) is attached to the remainder of the compound and a polyamine;

[0052] (ii-7) a mixture of formaldehyde and one or more of urea and melamine;

[0053] (ii-8) a mixture of formaldehyde and a compound comprising at least one hydroxyl group attached to a carbon atom that is member of an aromatic ring

[0054] (ii-9) a polyepoxide and a polythiol; and(ii-10) a polyepoxide, a carboxylic acid anhydride and a polymerization initiator.

[0055]

[0018] Said composition may be provided as a kit of parts. A third aspect of the invention thus relates to a kit for forming a polymer foam comprising a plurality of parts comprising a composition according to the second aspect of the invention wherein the compound A1 is provided in a different part than the compound A2.

[0056]

[0019] A process for the preparation of a polymer foam comprising the use of the compound A1 as a blowing agent also forms part of the invention. The fourth aspect of the invention relates to a process for the preparation of a polymer foam comprising the steps of:

[0057] (i) providing a source of carbon dioxide comprising a compound A1 and a compound A2; (ii) providing a polymerizable composition;

[0058] (iii) causing the polymerizable composition to polymerize and the compound A2 to react with the compound A1 concomitantly;

[0059] wherein the compounds A1, A2, the polymerizable composition and the relative amounts thereof are as defined in the second aspect of the invention.

[0060]

[0020] The fifth aspect of the invention relates to a polymer foam obtainable according to the process of the fourth aspect of the invention.

[0061] BRIEF DESCRIPTION OF THE DRAWINGS

[0062]

[0021] Fig. 1 shows the composition of a polymerizable composition comprising a polyepoxide, a polyamine and oxazolidine-2, 5-dione, as well as the chemical reactions involved in the foaming of said composition. Fig. 1 (right) shows photographs and SEM pictures of the resulting foamed material resulting from the heating of said composition.

[0063]

[0022] Fig. 2 shows a SEM picture (bar scale represents 2 mm) of the foam material of Example 1.

[0064]

[0023] Fig. 3 shows a SEM picture (bar scale represents 2 mm) of the foam material of Example 4.

[0065]

[0024] Fig. 4 shows a SEM picture (bar scale represents 2 mm) of the foam material of Example 5.

[0066]

[0025] Fig. 5 shows a SEM picture (bar scale represents 2 mm) of the foam material of Example 6.

[0067]

[0026] Fig. 6 shows a SEM picture (bar scale represents 2 mm) of the foam material of Example 1.

[0068]

[0027] Fig. 7 shows a SEM picture (bar scale represents 2 mm) of the foam material of Example 4.

[0069]

[0028] Fig. 8 shows a SEM picture (bar scale represents 2 mm) of the foam material of Example 5.

[0029] Fig. 9 shows a SEM picture (bar scale represents 2 mm) of the foam material of Example 6.

[0070] DETAILED DESCRIPTION

[0071]

[0030] All terms as used herein in this application, unless otherwise stated, shall be understood in their ordinary meaning as known in the art. Other more specific definitions for certain terms as used in the present application are as set forth below and are intended to apply uniformly throughout the specification and claims unless an otherwise expressly set out definition provides a broader definition.

[0072]

[0031] For the purposes of the invention, any ranges given include both the lower and the upper end-points of the range. Ranges given, such as temperatures, times, molar ratio, volume ratio and the like, should be considered approximate (i.e. with a 5% margin of variation around indicated point), unless specifically stated.

[0073]

[0032] In the context of the invention, the term “diradical” refers to a molecular fragment having two attachment points to the remainder part of a molecule. Thus, a diradical is divalent. In the context of the invention, a diradical is said to “derive” from a monovalent group (that is, a group having one attachment point to the remainder part of a molecule) when the second attachment point of said diradical is the result of the abstraction of a hydrogen atom comprised in said monovalent group.

[0074]

[0033] In the context of the invention, the term “triradical” refers to a molecular fragment having 3 attachment points to the remainder part of a molecule. Thus, a triradical is trivalent. In the context of the invention, a triradical is said to “derive” from a monovalent group (that is, a group having one attachment point to the remainder part of a molecule) when each of the second and third attachment points of said triradical is the result of the abstraction of a hydrogen atom comprised in said monovalent group.

[0075]

[0034] In the context of the invention, the term “alkyl” refers to an aliphatic saturated hydrocarbon chain that is linear or branched and having the number of carbon atoms defined in the claims and the description. Non-limiting examples of alkyl groups include, for instance, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, neo-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecanyl and dodecanyl.

[0076]

[0035] In the context of the invention, the term “alkyl” refers to an aliphatic saturated hydrocarbon chain that is linear or branched and having the number of carbon atoms defined in the claims and the description and wherein at least one hydrogen atom is replaced by a halogen atom.

[0077]

[0036] In the context of the invention, the term “cycloalkyl” refers to an aliphatic saturated cyclic hydrocarbon and having the number of carbon atoms defined in the claims and the description. Non-limiting examples of cycloalkyl groups include, for instance, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0037] In the context of the invention, the term “alkenyl” refers to an aliphatic unsaturated hydrocarbon chain that is linear or branched and having the number of carbon atoms defined in the claims and the description wherein at least two carbon atoms are linked through a double carbon-carbon bond. Non-limiting examples of alkenyl groups include, among others, vinyl, methylvinyl, propen-1 -yl, propen-2-yl, butenyl, and iso-butenyl.

[0078]

[0038] In the context of the invention, the term “alkylcarbonyl” refers to a saturated linear or branched aliphatic hydrocarbon group having the number of carbon atoms indicated in the description or in the claims which is attached to the remainder of the molecular formula through a carbonyl group (C=O).

[0079]

[0039] In the context of the invention, the term “alkylcarbonyloxy” refers to a saturated linear or branched aliphatic hydrocarbon group having the number of carbon atoms indicated in the description or in the claims which is attached to the remainder of the molecular formula through a carboxyl group (-COO-) and wherein the alkyl chain is attached to the carbon atom of the carboxyl group.

[0080]

[0040] In the context of the invention, the term “alkyloxycarbonyl” refers to a saturated linear or branched aliphatic hydrocarbon group having the number of carbon atoms indicated in the description or in the claims which is attached to the remainder of the molecular formula through a carboxyl group (-OOC-) and wherein the alkyl chain is attached to the non-carbonyl oxygen atom of the carboxyl group.

[0081]

[0041] In the context of the invention, the term “alkyloxy” refers to a saturated linear or branched aliphatic hydrocarbon group having the number of carbon atoms indicated in the description or in the claims which is attached to the remainder of the molecular formula through an oxy group (-O-).

[0082]

[0042] In the context of the invention, the term “alkylthio” refers to a saturated linear or branched aliphatic hydrocarbon group having the number of carbon atoms indicated in the description or in the claims which is attached to the remainder of the molecular formula through a thioxy group (-S-).

[0083]

[0043] In the context of the invention, the term “alkylamino” refers to a saturated linear or branched aliphatic hydrocarbon group having the number of carbon atoms indicated in the description or in the claims which is attached to the remainder of the molecular formula through an amino group (-NR-), being R a hydrogen or a (Ci-Ce)alkyl.

[0084]

[0044] In the context of the invention, the term “alkylcarbonylamino” refers to a saturated linear or branched aliphatic hydrocarbon group having the number of carbon atoms indicated in the description or in the claims which is attached to the remainder of the molecular formula through a carboxamyl group (-CONH-) and wherein the alkyl chain is attached to the carbon atom of the carboxamyl group.

[0085]

[0045] In the context of the invention, the term “alkylaminocarbonyl” refers to a saturated linear or branched aliphatic hydrocarbon group having the number of carbon atomsindicated in the description or in the claims which is attached to the remainder of the molecular formula through a carboxamyl group (-NHOC-) and wherein the alkyl chain is attached to the nitrogen atom of the carboxamyl group.

[0086]

[0046] In the context of the invention, the term “viscosity” and “complex viscosity” refers to a measure of the total resistance to flow as a function of angular frequency (co) and is given by the quotient of the maximum stress amplitude and maximum strain rate amplitude in a small amplitude oscillatory rheological testing.

[0087]

[0047] In the context of the invention, two rings are said to be “isolated” when their respective cyclic structure do not share a common atom; for instance when two rings are connected by a covalent bond formed between an atom of a first ring and a different atom of a second ring other than the first ring.

[0088]

[0048] In the context of the invention, two rings are said to be “fused” when their respective cyclic structure share two adjacent atoms.

[0089]

[0049] In the context of the invention, two rings are said to be “bridged” when their respective cyclic structure share two non-adjacent atoms.

[0090]

[0050] In the context of the invention, a carbon atom is said to be saturated when it is in the sp3hybridization state, such as a carbon atom being attached to four substituents by the means of single covalent bonds.

[0091]

[0051] In the context of the invention, the term “blowing agent” relates to a substance suitable for providing a gas, e.g. by the means of a chemical reaction, concomitantly with a polymerization reaction, thus promoting the formation of a cellular or partially cellular structured polymer material. In the context of the invention, said gas is carbon dioxide.

[0092]

[0052] In the context of the invention, the term “polymer foam” refers to a material comprising a matrix, such as an organic polymeric material, and a dispersed phase of gas within said matrix, so as to form a partially cellular structured material.

[0093]

[0053] In the context of the invention, a molar ratio of a compound A to a compound B expressed as x:y in a composition refers to the fact that the composition comprises x moles of A for each y moles of B.

[0094]

[0054] In the context of the invention, the term “polyepoxide” refers to a compound comprising a plurality of epoxy groups, i.e. moieties of formula ,

[0095]

[0096] in its molecular formula, wherein each wavy line represents an attachment

[0097] to the remainder of the compound.

[0098]

[0055] In the context of the invention, the term “epoxy weight equivalent” of a polyepoxide compound refers to the weight amount of said polyepoxide compound containing one mole of an epoxy group. This term is also referred to herein as “WPE” or “weight per epoxide” and is expressed in grams (of polyepoxide) per equivalent (ofepoxide). This parameter is calculated as the ratio of the molecular weight of the polyepoxide compound to the number of epoxy groups in said polyepoxide.

[0099]

[0056] In the context of the invention, the term “polyamine” refers to a compound comprising at least two amino groups, preferably -NH2 groups, in its molecular formula. Polyamine compounds may further be characterized by their Amine Hydrogen Equivalent Weight or "“AHEW’, which is a parameter that is expressed in grams of polyamine per equivalent of amino groups and is calculated as the ratio of the molecular weight of the polyamine compound to the number of hydrogen atoms in amino groups in said polyamine.

[0100]

[0057] In the context of the invention, the term “polycarboxylic acid chloride” refers to a compound comprising at least two carboxylic acid chloride moieties of formula -COCI in its molecular formula.

[0101]

[0058] In the context of the invention, the term “polyisocyanate” refers to a compound comprising at least two isocyanate moieties of formula -NCO in its molecular formula.

[0102]

[0059] In the context of the invention, the term “polyol” refers to a compound comprising at least two hydroxyl groups of formula -OH in its molecular formula.

[0103]

[0060] In the context of the invention, the term “poly(peptide)” refers to a polymer comprising amino acid residues and having one or more repeating unit of formula

[0104]

[0105] whereby the * represent the attachment point of a repeating unit to an adjacent repeating unit and the wavy line represents the attachment point to the side chain of the amino acid(s) forming the poly(peptide). More particularly, the term “poly(peptide)” also refers to the polymer obtained by polymerization or cross-polymerization of the moieties of formula (I) and (II) in compound A1 disclosed herein.

[0106]

[0061] As defined above, a first aspect of the invention relates to the use of a compound A1 comprising at least one moiety of formula (I), such as from one to three moieties of formula (I), and / or at least one moiety of formula (II) , such as from one to three moieties of formula (II), in its molecular formula as blowing agent for the production of a polymeric foam material other than a poly(peptide)

[0107]

[0108] (I) (H)wherein:

[0109] each n is an integer of from 1 to 3;

[0110] each wavy line represents the covalent bond through which the moiety of formula (I) or of formula (II) is attached to the remainder of the molecule;

[0111] each Ri is selected from the group consisting of hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl (C3-C8)cycloalkyl, and (Ce-C2o)aryl optionally substituted at any available position with a group selected from the group consisting of halo, cyano, nitro, (Ci-Ce)alkyl, (Ci-Ce)alkyloxy and (Ci-Ce)haloalkyl;

[0112] R2 is selected from the group consisting of hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl (C3-C8)cycloalkyl, and (Ce-C2o)aryl optionally substituted at any available position with a group selected from the group consisting of halo, cyano, nitro, (Ci-Ce)alkyl, (C1-Ce)alkyloxy and (Ci-Ce)haloalkyl; and

[0113] R3 is selected from the group consisting of hydrogen, hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl (C3-C8)cycloalkyl, and (Ce-C2o)aryl optionally substituted at any available position with a group selected from the group consisting of halo, cyano, nitro, (C1-Ce)alkyl, (Ci-Ce)alkyloxy and (Ci-Ce)haloalkyl;

[0114]

[0062] and wherein said use preferably comprises forming carbon dioxide by reaction of the compound A1 with a nucleophilic compound A2. In a preferred embodiment, the first aspect of the invention relates to the use of a compound A1 comprising at least one moiety of formula (I), such as from one to three moieties of formula (I), and, optionally at least one moiety of formula (II) , such as from one to three moieties of formula (II), in its molecular formula as blowing agent for the production of a polymeric foam material other than a poly(peptide).

[0115]

[0063] In a preferred embodiment, the first aspect of the invention relates to the use of a compound A1 comprising from one to three moieties of formula (I) and / or (II). When the compound of formula A1 comprises a plurality of moieties of formula (I) and / or (II), the formation of the blowing agent produces a polyamine that is suitable for taking part in the polymerization, such that the propagation of the polymerization is not ended by the incorporation of the amine by-product of the formation of the carbon dioxide.

[0116]

[0064] In an embodiment of the first aspect of the invention, the compound A1 is one wherein each n is 1 in the moieties of formula (I) and (II).

[0117]

[0065] In an embodiment of the first aspect of the invention, the compound A1 is one wherein R1 is selected from hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl and (C3-C8)cycloalkyl.

[0118]

[0066] In a preferred embodiment of the first aspect of the invention, the compound A1 is one wherein R1 is selected from hydrogen and (Ci-Ce)alkyl. Preferably, R1 is selected from hydrogen, isopropyl and methyl in the moieties of formula (I) and (II). More preferably, R1 is hydrogen.

[0067] In an embodiment of the first aspect of the invention, the compound A1 is one wherein R2 is selected from hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl and (C3-C8)cycloalkyl. Preferably, R2 is selected from hydrogen and methyl in the moieties of formula (I). More preferably, R2 is hydrogen.

[0119]

[0068] In an embodiment of the first aspect of the invention, the compound A1 is one wherein R3 is selected from hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl and (C3-C8)cycloalkyl. Preferably, R3 is selected from hydrogen and methyl in the moieties of formula (I) and (II). More preferably, R3 is hydrogen.

[0120]

[0069] In an embodiment of the first aspect of the invention, the compound A1 is one which comprises at least one moiety of formula (I).

[0121]

[0070] In an embodiment of the first aspect of the invention, the compound A1 is one which comprises at least one moiety of formula (I) wherein each of R1 and R2 is hydrogen.

[0122]

[0071] In an embodiment of the first aspect of the invention, the compound A1 is one which comprises at least one moiety of formula (I) wherein n is 1.

[0123]

[0072] In an embodiment of the first aspect of the invention, the compound A1 is one which comprises at least one moiety of formula (I) wherein n is 1, and each of R1 and R2 is hydrogen.

[0124]

[0073] In an embodiment of the first aspect of the invention, the compound A1 is one which comprises at least one moiety of formula (I) wherein R1 is a methyl group and R2 is hydrogen.

[0125]

[0074] In an embodiment of the first aspect of the invention, the compound A1 is one which comprises at least one moiety of formula (I) wherein n is 1, R1 is a methyl group and R2 is hydrogen.

[0126]

[0075] In an embodiment of the first aspect of the invention, the compound A1 is one which comprises at least one moiety of formula (II).

[0127]

[0076] In an embodiment of the first aspect of the invention, the compound A1 is one which comprises at least one moiety of formula (II) wherein R3 is hydrogen.

[0128]

[0077] In an embodiment of the first aspect of the invention, the compound A1 is one which comprises at least one moiety of formula (II) wherein n is 1 and R3 is hydrogen.

[0129]

[0078] In an embodiment of the first aspect of the invention, the compound A1 is one which comprises at least one moiety of formula (II) wherein n is 1, and each of R1 and R3 is hydrogen.

[0130]

[0079] In an embodiment of the first aspect of the invention, the compound A1 is one which comprises at least one moiety of formula (II) wherein n is 1, R1 is a methyl group and R3 is hydrogen.

[0131]

[0080] In an embodiment of the first aspect of the invention, the compound A1 is selected from the group consisting of the compounds of formula A1 a, A1b and mixtures thereof

[0132]

[0133] 0

[0134] A1a A1b

[0135] wherein each Y represents a hydrogen atom or a moiety of formula (VI) or (VII)

[0136]

[0137] (VI) (VII)

[0138] wherein each wavy line represents the covalent bond through which the moiety of formula (VI) or of formula (VII) is attached to the remainder of the molecule, and wherein each L’ represents a diradical deriving from the abstraction of one hydrogen atom from a group selected from the group consisting of (Ci-Ce)alkyl, (Ci-Ce)alkyloxy, (Ci-Ce)alkylamino, (Ci-C6)alkyloxycarbonyl, (Ci-C6)alkylaminocarbonyl, (Ci-C6)alkylcarbonylamino, (Ci-C6)alkylcarbonyloxy, (Ci-Ce)alkylthio, (C2-Ce)alkenyl, a group of formula (Ci-C6)alkyl-O-(Ci-Ce)alkyl, a radical of formula (Ci-Ce)alkyl-S-(Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-NRi3-(Ci-C6)alkyl wherein R13 is hydrogen or (Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-CONRi3-(Ci-C6)alkyl wherein R13 is hydrogen or (Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-NRi3CO-(Ci-C6)alkyl wherein R13 is hydrogen or (Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-OCO-(Ci-C6)alkyl, a group of formula (Ci-C6)alkyl-COO-(Ci-C6)alkyl, a group of formula (Ci-Ce)alkyl-(O-(Ci-Ce)alkyl)x-0 wherein x is an integer of from 1 to 10, a group of formula G, a group of formula (Ci-Ce)alkyl-G, a group of formula (Ci-C6)alkyl-G-(Ci-C6)alkyl, wherein G is a ring system comprising from 1 to 3 rings, each ring being saturated, unsaturated or aromatic, said rings being isolated, bridged or fused and comprising from 3 to 8 members selected from the group consisting of O, C, CH, CH2, N, NH, S, C=O, S=O and -SO2-, the members of the rings being optionally substituted where chemically possible with one or more groups selected from halo, (Ci-Ce)alkyl, (Ci-Ce)haloalkyl, (Ci-Ce)alkyloxy, (Ci-Ce)alkylamino, (Ci-C6)alkyloxycarbonyl, (C1-C6)alkylaminocarbonyl, cyano and nitro.

[0139]

[0081] In an embodiment of the first aspect of the invention, the compound A1 is selected from the group consisting of the compounds of formula A1 a, A1b and mixtures thereof wherein Y is hydrogen.

[0082] In an embodiment of the first aspect of the invention, the compound A1 is selected from the group consisting of oxazolidine-2, 5-dione, 3-methyloxazolidine-2, 5-dione, 4-isopropyloxazolidine-2, 5-dione and 4-methyloxazolidine-2, 5-dione.

[0140]

[0083] In an embodiment of the first aspect of the invention, said use comprises forming carbon dioxide by reaction of the compound A1 with a compound A2 comprising in its molecular formula at least one functional group selected from the group consisting of amino, hydroxyl and thiol.

[0141]

[0084] In a preferred embodiment, the nucleophilic compound A2 is not a compound comprising at least one moiety of formula (I), such as from one to three moieties of formula (I), and / or at least one moiety of formula (II) , such as from one to three moieties of formula (II), in its molecular formula.

[0142]

[0085] In an embodiment of the first aspect of the invention, said compound A2 comprises in its molecular formula at least one functional group selected from the group consisting of amino, hydroxyl, thiol, or at least one of a negatively charged carbon atom, a negatively charged nitrogen atom, a negatively charged oxygen atom or a negatively charged sulfur atom.

[0143]

[0086] Preferably, said compound A2 comprises in its molecular formula at least one functional group selected from the group consisting of amino, hydroxyl, thiol; more particularly, a plurality of amino groups, i.e. compound A2 is a polyamine. More particularly, it is preferred that said compound A2 comprises in its molecular formula two or more amino groups which are connected to a saturated carbon atom.

[0144]

[0087] In a more particular embodiment of the first aspect, compound A2 is a polyamine having an Amine Hydrogen Equivalent Weight of between 5 grams per equivalent and 120 grams per equivalent. Such amines include, for instance, tris(2-aminoethyl)amine, xylylenediamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, isophorone diamine, Hexamethylenediamine, N-Aminoethylpiperazine, 1,3-Bis(aminomethyl)cyclohexane, 1,2-Diaminocyclohexane, 2- Methylpentamethylenediamine, 4,4'-diaminodicyclohexylmethane, Bis(hexamethylene)triamine, Polyetheramine D230, Polyetheramine D400, Jeffamine T403, 4,4'-Methylenebis(cyclohexylamine), m-Phenylenediamine, p-Phenylenediamine , 1,4-Diaminobutane, Jeffamine® D-230, Jeffamine® D-400, Isophorone diamine, 4,4'-methylenedianiline, furfuryldiamine, cyclohexane-1,3-diyldimethanamine, N,N-bis(2-aminoethyl)ethane-1,2-diamine and 1,5-Diaminopentane.

[0145]

[0088] In a more particular embodiment of the first aspect, compound A2 is a polyamine having an Amine Hydrogen Equivalent Weight of between 10 grams per equivalent and 60 grams per equivalent. Such amines include, for instance, tris(2-aminoethyl)amine, xylylenediamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, isophorone diamine, Hexamethylenediamine, N-Aminoethylpiperazine, 1,3-Bis(aminomethyl)cyclohexane, 1,2-Diaminocyclohexane, 2- Methylpentamethylenediamine, Jeffamine® D-230, Jeffamine® D-400, Isophorone diamine, 4,4'-methylenedianiline and 4,4'-diaminodicyclohexylmethane. Even more preferably, said compound A2 is selected from the group consisting of tris(2-aminoethyl)amine, xylylenediamine, Jeffamine® D-230, furfuryldiamine, cyclohexane-1,3-diyldimethanamine, N,N-bis(2-aminoethyl)ethane-1,2-diamine , Jeffamine® D-400, Isophorone diamine, 4,4'-methylenedianiline and 4,4'-diaminodicyclohexylmethane.

[0146]

[0089] The terms “Jeffamine® D-230” and “Jeffamine® D-400” refer to polypropylene oxide polyetheramines terminated with an amino group and with an average molecular weight of 230 and 400 g / mol respectively.

[0147]

[0090] In a further embodiment of the first aspect of the invention, in said reaction of the compound A1 with A2, compound A2 is in an amount such that the number of amino, hydroxy or thiol groups is from 0.5 to 1.5 times the amount of moieties of formula (I) and / or (II) in the compound A1. Preferably, in said reaction of the compound A1 with A2, compound A2 is in an amount such that the number of amino, hydroxy or thiol groups is substantially the same as the amount of moieties of formula (I) and / or (II) in the compound A1.

[0148]

[0091] As mentioned above, said use of the compound A1 is particularly useful for forming polymer foam materials.

[0149]

[0092] In particular embodiments of the first aspect of the invention, compound A1 is used as blowing agent during processing of a thermoplastic, such as extrusion, injection molding, blow molding, thermoforming, rotational molding (rotomolding), compression molding, calendering, foam molding, filament winding, and additive manufacturing (3D printing).

[0150]

[0093] A second aspect of the invention thus relates to a composition for forming a polymer foam comprising:

[0151] (i) a source of carbon dioxide comprising:

[0152] (i-1) a compound A1 comprising at least one moiety of formula (I) and / or at least one moiety of formula (II) in its molecular formula as defined in any one of claims 1 to 3;

[0153] (i-2) a compound A2 comprising in its molecular formula at least one functional group selected from the group consisting of amino, hydroxyl, thiol, or at least one of a negatively charged carbon atom, a negatively charged nitrogen atom, a negatively charged oxygen atom or a negatively charged sulfur atom;

[0154] (ii) a polymerizable mixture of compounds comprising one or more of:

[0155] (ii-1) a polyepoxide and a polyamine or a polyol;

[0156] (ii-2) a polycarboxylic acid chloride and a polyamine or a polyol;

[0157] (ii-3) a polyisocyanate and a polyamine or a polyol;(II-4) a compound comprising in its molecular formula at least one moiety, preferably a plurality of moieties, of formula (III) Q

[0158]

[0159] (HI)

[0160] wherein m is 1 or 2 and each wavy line represents the position to which the moiety of formula (III) is attached to the remainder of the compound and a polyamine or a polyol; (ii-5) a compound comprising in its molecular formula at least one moiety, preferably a plurality of moieties, of formula (IV)

[0161]

[0162] (IV)

[0163] wherein p is 1 or 2 and each wavy line represents the position to which the moiety of formula (IV) is attached to the remainder of the compound and a polyamine or a polyol; (ii-6) a compound comprising in its molecular formula a plurality of moieties, of formula

[0164]

[0165] (IX)

[0166] wherein each wavy line represents the position to which the moiety of formula (III) is attached to the remainder of the compound and a polyamine;

[0167] (ii-7) a mixture of formaldehyde and one or more of urea and melamine;

[0168] (ii-8) a mixture of formaldehyde and a compound comprising at least one hydroxyl group attached to a carbon atom that is member of an aromatic ring;

[0169] (ii-9) a polyepoxide and a polythiol; and

[0170] (ii-10) a polyepoxide, a carboxylic acid anhydride and a polymerization initiator.

[0171]

[0094] In an embodiment, the composition of the second aspect of the invention is one wherein the compound A1 is as defined in any embodiment of the first aspect of the invention defining this compound.

[0172]

[0095] In an embodiment, the composition of the second aspect of the invention is one wherein the compound A2 is as defined in any embodiment of the first aspect of the invention defining this compound.

[0173]

[0096] In a further embodiment, the composition of the second aspect of the invention is one wherein the compound A2 is the same compound as the polyamine comprised in the polymerizable mixture. In said embodiment, and as the skilled person will appreciate,the amount of compound A2 is such that the molar amount of amino groups in compound A2 is larger than the molar amount of moieties of formula (I) and / or (II) in the compound A1.

[0174]

[0097] In an embodiment, the composition of the second aspect of the invention is one wherein the polymerizable mixture comprises a polyepoxide and a polyamine. Such composition is suitable for forming epoxy foam materials.

[0175]

[0098] In an embodiment, the polymerizable mixture of the composition of the second aspect of the comprises a polyepoxide having an Epoxide Equivalent Weight of between 60 grams per equivalent and 1000 grams per equivalent. Such polyepoxides include, in a non-limiting manner, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, resorcinol diglycidyl ether, hydrogenated diglycidyl ether of bisphenol a, tetraglycidyl methylene dianiline, triglycidyl p-aminophenol, novolac epoxy resin, epoxidized soybean oil, dicyclopentadiene epoxy resin, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, 1,3-bis(2,3-epoxypropoxy)benzene, trimethylolpropane triglycidyl ether, glycerol epoxide, polyglycerol epoxide, sorbitol epoxide, diglycidyl ether of bisphenol, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, epoxidized linseed oil, and diglycidyl 1 ,2-cyclohexanedicarboxylate.

[0176]

[0099] In an embodiment, the polymerizable mixture of the composition of the second aspect of the comprises a polyepoxide having an Epoxide Equivalent Weight of between 100 grams per equivalent and 300 grams per equivalent. Such polyepoxides include, in a non-limiting manner, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, resorcinol diglycidyl ether, hydrogenated diglycidyl ether of bisphenol a, trimethylolpropane triglycidyl ether, glycerol epoxide, polyglycerol epoxide, sorbitol epoxide, diglycidyl ether of bisphenol, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,3-bis(2,3-epoxypropoxy)benzene, epoxidized soybean oil, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, diglycidyl 1,2-cyclohexanedicarboxylate, hydrogenated bisphenol diglycidyl ether, dicyclopentadiene epoxy resin, epoxidized linseed oil, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl p-aminophenol, and tetraglycidyl methylene dianiline.

[0177]

[0100] In an embodiment, the polymerizable mixture of the composition of the second aspect of the comprises a polyepoxide selected from the group consisting of trimethylolpropane triglycidyl ether, glycerol epoxide, sorbitol epoxide, diglycidyl ether of bisphenol, hydrogenated bisphenol diglycidyl ether and polyglycerol epoxide.

[0178]

[0101] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises a polyamine. Said polyamine is preferably the sameas the compound A2 having a plurality of amino groups as defined above in any embodiments of the first aspect of the invention defining said compound.

[0179]

[0102] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises a polyol. Said polyol is preferably a compound having a Hydroxyl Weight Equivalent of between 200 and 2500 grams per mole. In certain embodiments, said polyol may be polypropylene glycol (PPG), polytetramethylene ether glycol (PTMEG), polyethylene glycol (PEG), polyether polyols, polycaprolactone polyols, polyadipate polyols, phthalate-based polyester polyols, polycarbonate polyols, castor oilbased polyols, acrylate polyols.

[0180]

[0103] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a polyepoxide and a polyamine, the polyepoxide being in amount such that the molar amount of epoxy groups in said composition is from 0.5 to 1.5 times the molar amount of amino groups in the polyamine and the compound A2. Preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polyepoxide and a polyamine, the polyepoxide is in an amount such that the molar amount of epoxy groups in said composition is from 0.8 to 1.2 times the molar amount of amino groups in the polyamine and the compound A2. More preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polyepoxide and a polyamine, the polyepoxide is in an amount such that the molar amount of epoxy groups in said composition is substantially the same as the molar amount of amino groups in the polyamine and the compound A2.

[0181]

[0104] In an embodiment, the composition of the second aspect of the invention is one wherein the polymerizable mixture comprises a polyepoxide and a polyol. Such composition is suitable for forming polyether foam materials.

[0182]

[0105] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a polyepoxide and a polyol, the polyepoxide being in amount such that the molar amount of epoxy groups in said composition is from 0.5 to 1.5 times the molar amount of OH groups in the polyol and the compound A2. Preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polyepoxide and a polyol, the polyepoxide is in an amount such that the molar amount of epoxy groups in said composition is from 0.8 to 1.2 times the molar amount of OH groups in the polyol and the compound A2. More preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polyepoxide and a polyol, the polyepoxide is in an amount such that the molar amount of epoxy groups in said composition is substantially the same as the molar amount of OH groups in the polyol and the compound A2.

[0106] In an embodiment, the composition of the second aspect of the invention is one wherein the polymerizable mixture comprises a polycarboxylic acid chloride and a polyamine. Such composition is suitable for forming polyamide foam materials.

[0183]

[0107] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises a polycarboxylic acid chloride. Suitable polycarboxylic acid chlorides for forming polyamide foam materials are known in the art and will become apparent to the skilled person on the basis of common general knowledge. Those include, for instance, adipoyl chloride, sebacoyl chloride, isophthaloyl chloride, terephthaloyl chloride, glutaroyl chloride, suberoyl chloride, azelaoyl chloride, aromatic acid chlorides such as a benzene ring substituted with from 2 to 6 -COCI groups such as 1,3,5-benzenetricarbonyl chloride (trimesoyl chloride), cyclohexane-1,4-dicarbonyl chloride, pyridine-2,6-dicarbonyl chloride, malonyl chloride, succinyl chloride, fumaroyl chloride, maleoyl chloride, malonyl chloride, phthaloyl chloride, naphthalene-1,4-dicarbonyl chloride, biphenyl-4,4'-dicarbonyl chloride, trimellitic trichloride, ethylenedioxydiethyl dicarbonyl chloride, and 4,4'-sulfonylbis(benzoyl chloride).

[0184]

[0108] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises a polycarboxylic acid chloride selected from the group consisting of aliphatic acid chlorides, such as adipoyl chloride, sebacoyl chloride and malonyl chloride, aromatic acid chlorides such as a benzene ring substituted with from 2 to 6 -COCI groups such as 1,3,5-benzenetricarbonyl chloride (trimesoyl chloride). Preferably said polycarboxylic acid chloride is 1,3,5-benzenetricarbonyl chloride.

[0185]

[0109] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises a polycarboxylic acid chloride and a polyamine. Said polyamine is preferably the same as the compound A2 having a plurality of amino groups as defined above in any embodiments of the first aspect of the invention defining said compound.

[0186]

[0110] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a polycarboxylic acid chloride and a polyamine, the polycarboxylic acid chloride being in amount such that the molar amount of acyl chloride (-COCI) groups in said composition is from 0.5 to 1.5 times the molar amount of amino groups in the polyamine and the compound A2. Preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polycarboxylic acid chloride and a polyamine, the polycarboxylic acid chloride is in an amount such that the molar amount of acyl chloride (-COCI) groups in said composition is from 0.8 to 1.2 times the molar amount of amino groups in the polyamine and the compound A2. More preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polycarboxylic acid chloride and a polyamine, the polycarboxylic acid chloride is in an amount such that the molaramount of acyl chloride (-COCI) groups in said composition is substantially the same as the molar amount of amino groups in the polyamine and the compound A2.

[0187]

[0111] In an embodiment, the composition of the second aspect of the invention is one wherein the polymerizable mixture comprises a polycarboxylic acid chloride and a polyol. Such composition is suitable for forming polyether foam materials.

[0188]

[0112] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a polycarboxylic acid chloride and a polyol, the polycarboxylic acid chloride being in amount such that the molar amount of -COCI groups in said composition is from 0.5 to 1.5 times the molar amount of OH groups in the polyol and the compound A2. Preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polycarboxylic acid chloride and a polyol, the polycarboxylic acid chloride is in an amount such that the molar amount of -COCI groups in said composition is from 0.8 to 1.2 times the molar amount of OH groups in the polyol and the compound A2. More preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polycarboxylic acid chloride and a polyol, the polycarboxylic acid chloride is in an amount such that the molar amount of -COCI groups in said composition is substantially the same as the molar amount of OH groups in the polyol and the compound A2.

[0189]

[0113] In an embodiment, the composition of the second aspect of the invention is one wherein the polymerizable mixture comprises a polyisocyanate and a polyamine. Such composition is suitable for forming polyurea foam materials.

[0190]

[0114] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises a polyisocyanate. Suitable polyisocyanates for forming polyurea foam materials are known in the art and will become apparent to the skilled person on the basis of common general knowledge. Those include, for instance, toluene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), xylylene diisocyanate, 1 ,6-hexamethylene diisocyanate, 4,4'-diisocyanatodiphenylmethane, 2,4,4'-triisocyanatodiphenylmethane, 1,3-diphenylmethane diisocyanate, 1,3,5-benzenetriisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 1,3,5-cyclohexanetricarbonyl triisocyanate, 4,4’-methylenebis(phenyl isocyanate) or a polymer thereof, aliphatic polyisocyanates, such as hexamethylene diisocyanate, isophorone diisocyanate or hydrogenated 4,4’-methylenebis(phenyl isocyanate), and cycloaliphatic polyisocyanates, such as 1 ,4-cyclohexane diisocyanate and 4,4’-dicyclohexylmethane diisocyanate.

[0115] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises a polyisocyanate and a polyamine. Said polyamine is preferably the same as the compound A2 having a plurality of amino groups as defined above in any embodiments of the first aspect of the invention defining said compound.

[0191]

[0116] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a polyisocyanate and a polyamine, the polyisocyanate being in amount such that the molar amount of isocyanate (-NCO) groups in said composition is from 0.5 to 1.5 times the molar amount of amino groups in the polyamine and the compound A2. Preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polyisocyanate and a polyamine, the polyisocyanate is in an amount such that the molar amount of isocyanate (-NCO) groups in said composition is from 0.8 to 1.2 times the molar amount of amino groups in the polyamine and the compound A2. More preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polyisocyanate and a polyamine, the polyisocyanate is in an amount such that the molar amount of isocyanate (-NCO) groups in said composition is substantially the same as the molar amount of amino groups in the polyamine and the compound A2.

[0192]

[0117] In an embodiment, the composition of the second aspect of the invention is one wherein the polymerizable mixture comprises a polyisocyanate and a polyol. Such composition is suitable for forming polycarbamate foam materials.

[0193]

[0118] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a polyisocyanate and a polyol, the polyisocyanate being in amount such that the molar amount of -NCO groups in said composition is from 0.5 to 1.5 times the molar amount of OH groups in the polyol and the compound A2. Preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polyisocyanate and a polyol, the polyisocyanate is in an amount such that the molar amount of -NCO groups in said composition is from 0.8 to 1.2 times the molar amount of OH groups in the polyol and the compound A2. More preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polyisocyanate and a polyol, the polyisocyanate is in an amount such that the molar amount of -NCO groups in said composition is substantially the same as the molar amount of OH groups in the polyol and the compound A2.

[0194]

[0119] In an embodiment, the composition of the second aspect of the invention is one wherein the polymerizable mixture comprises a compound of formula (V) and a polyamine. Such composition is suitable for forming polyhydroxyurethane foam materials.

[0120] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises a compound comprising a plurality of moieties of formula (III) that is a compound of formula (V) and a polyamine. Said polyamine is preferably the same as the compound A2 having a plurality of amino groups as defined above in any embodiments of the first aspect of the invention defining said compound.

[0195]

[0121] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a compound comprising a plurality of moieties of formula (III) that is a compound of formula (V) and a polyamine, the compound of formula (V) being in amount such that the molar amount of carbonate (-O(CO)O)-) groups in said composition is from 0.5 to 1.5 times the molar amount of amino groups in the polyamine and the compound A2. Preferably, when the composition of the second aspect of the invention comprises or consists essentially of a compound of formula (V) and a polyamine, the compound of formula (V) is in an amount such that the molar amount of carbonate (-O(CO)O)-) groups in said composition is from 0.8 to 1.2 times the molar amount of amino groups in the polyamine and the compound A2. More preferably, when the composition of the second aspect of the invention comprises or consists essentially of a compound of formula (V) and a polyamine, the compound of formula (V) is in an amount such that the molar amount of carbonate (-O(CO)O)-) groups in said composition is substantially the same as the molar amount of amino groups in the polyamine and the compound A2.

[0196]

[0122] In an embodiment, the composition of the second aspect of the invention is one wherein the polymerizable mixture comprises a compound comprising a plurality of moieties of formula (III) and a polyol. Such composition is suitable for forming polycarbonate foam materials.

[0197]

[0123] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a compound comprising a plurality of moieties of formula (III) and a polyol, the compound comprising a plurality of moieties of formula (III) being in amount such that the molar amount of moieties of formula (III) groups in said composition is from 0.5 to 1.5 times the molar amount of OH groups in the polyol and the compound A2. Preferably, when the composition of the second aspect of the invention comprises or consists essentially of a compound comprising a plurality of moieties of formula (III) and a polyol, the compound comprising a plurality of moieties of formula (III) is in an amount such that the molar amount of moieties of formula (III) groups in said composition is from 0.8 to 1.2 times the molar amount of OH groups in the polyol and the compound A2. More preferably, when the composition of the second aspect of the invention comprises or consists essentially of a compound comprising a plurality of moieties of formula (III) and a polyol, the compound comprising a plurality of moieties of formula (III) is in an amount such that themolar amount of moieties of formula (III) groups in said composition is substantially the same as the molar amount of OH groups in the polyol and the compound A2.

[0198]

[0124] In a further preferred embodiment of the second aspect of the invention, the compound of formula (V) of the polymerizable composition is

[0199]

[0200] (V)

[0201] wherein,

[0202] each q is independently 1 or 2;

[0203] each one of R4, Rs, Re, R7, Rs, R9, R10, R11 and R12 is independently selected from the group consisting of hydrogen, halo, (Ci-Cs)alkyl, (C2-Cs)alkenyl and (C3- C8)cycloalkyl; the dashed bond represents the presence or the absence of a covalent bond;

[0204] when the dashed bond represents the absence of a covalent bond, L is a diradical deriving from the abstraction of one hydrogen atom from a group selected from the group consisting of (Ci-Cs)alkyl, (Ci-Cs)alkyloxy, (Ci-Cs)alkylamino, (C1- Cs)alkyloxycarbonyl, (Ci-Cs)alkylaminocarbonyl, (Ci-Cs)alkylcarbonylamino, (Ci-Cs)alkylcarbonyloxy, (Ci-Cs)alkylthio, (C2-Cs)alkenyl, a group of formula (C1- Cs)alkyl-O-(Ci-C6)alkyl, a radical of formula (Ci-C6)alkyl-S-(Ci-Cs)alkyl, a group of formula (Ci-C6)alkyl-NRi3-(Ci-Cs)alkyl wherein R13 is hydrogen or (Ci-Cs)alkyl, a group of formula (Ci-C6)alkyl-CONRi3-(Ci-Cs)alkyl wherein R13 is hydrogen or (Ci-Cs)alkyl, a group of formula (Ci-C6)alkyl-NRi3CO-(Ci-Cs)alkyl wherein R13 is hydrogen or (Ci-Cs)alkyl, a group of formula (Ci-C6)alkyl-OCO-(Ci-Cs)alkyl, a group of formula (Ci-C6)alkyl-COO-(Ci-Cs)alkyl, a group of formula (Ci-Cs)alkyl- (0-(Ci-Cs)alkyl)x-0 wherein x is an integer of from 1 to 10, a group of formula G, a group of formula (Ci-Cs)alkyl-G, a group of formula (Ci-C6)alkyl-G-(Ci-C6)alkyl, wherein G is a ring system comprising from 1 to 3 rings, each ring being saturated, unsaturated or aromatic, said rings being isolated, bridged or fused and comprising from 3 to 8 members selected from the group consisting of O, C, CH, CH2, N, NH, S, C=O, S=O and -SO2-, the members of the rings being optionally substituted where chemically possible with one or more groupsselected from halo, (Ci-Ce)alkyl, (Ci-Ce)haloalkyl, (Ci-Ce)alkyloxy, (Ci- C6)alkylamino, (Ci-C6)alkyloxycarbonyl, (Ci-C6)alkylaminocarbonyl, cyano and nitro;

[0205] or, alternatively,

[0206] when the dashed bond represents the presence of a covalent bond; L is a triradical deriving from the abstraction of three hydrogen atoms from each X2 group in a compound comprising three groups of formula -(X1-X2), being each one of said group of formula -(X1-X2) attached to a carbon atom comprised in a triradical of formula G’, wherein

[0207] G’ is a triradical deriving from the abstraction of two hydrogen atoms from a group selected from (Ci-Ci2)alkyl, N[(Ci-Ci2)alkyl]3, (C2-Ce)alkenyl, a group of formula (Ci-C6)alkyl-O-(Ci-C6)alkyl, a radical of formula (Ci-Ce)alkyl-S-(Ci- Ce)alkyl, a group of formula (Ci-C6)alkyl-NRio-(Ci-C6)alkyl wherein R10 is hydrogen or (Ci-C6)alkyl, a group of formula (Ci-C6)alkyl-CONRi3-(Ci-C6)alkyl wherein R13 is hydrogen or (Ci-C6)alkyl, a group of formula (Ci-Ce)alkyl-NRi3CO- (Ci-C6)alkyl wherein R13 is hydrogen or (Ci-C6)alkyl, a group of formula (C1- C6)alkyl-OCO-(Ci-C6)alkyl, a group of formula (Ci-C6)alkyl-COO-(Ci-C6)alkyl, a group of formula (Ci-C6)alkyl-(O-(Ci-C6)alkyl)x- wherein x is an integer of from 1 to 10 and a ring system comprising from 1 to 3 rings, each ring being saturated, unsaturated or aromatic, said rings being isolated, bridged or fused and comprising from 3 to 8 members selected from the group consisting of O, C, CH, CH2, N, NH, S, C=O, S=O and -SO2-, the members of the rings being optionally substituted where chemically possible with one or more groups selected from halo, (Ci-Ce)alkyl, (Ci-Ce)haloalkyl, (Ci-Ce)alkyloxy, (Ci-Ce)alkylamino, (C1- C6)alkyloxycarbonyl, (Ci-C6)alkylaminocarbonyl, cyano and nitro;

[0208] Xi is selected from the group consisting of a covalent bond, -O-, -S-, - COO-, -OCO-, -SO-, -SO2-, -SO2NH-, -NHCO- and -CONH-; and

[0209] X2 is selected from the group consisting of (Ci-Ci2)alkyl, (C2-Ce)alkenyl, a group of formula (Ci-C6)alkyl-O-(Ci-Ce)alkyl, a radical of formula (Ci-C6)alkyl-S-(Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-NRi3-(Ci-C6)alkyl wherein R13 is hydrogen or (Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-CONRi3-(Ci-C6)alkyl wherein R13 is hydrogen or (C1-Ce)alkyl, a group of formula (Ci-C6)alkyl-NRi3CO-(Ci-C6)alkyl wherein R13 is hydrogen or (Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-OCO-(Ci-C6)alkyl, a group of formula (C1-C6)alkyl-COO-(Ci-C6)alkyl, a group of formula (Ci-C6)alkyl-(O-(Ci-C6)alkyl)x- wherein x is an integer of from 1 to 10.

[0210]

[0125] In a further preferred embodiment of the second aspect of the invention, the compound of formula (V) of the polymerizable composition is one wherein the dashedbond represents the presence of a covalent bond. In said embodiment, the compound of formula (V) is preferably a compound of formula (Va)

[0211]

[0212] wherein each one of R4, Rs, Re, R7, Rs, R9, R10, R11 and R12 is independently selected from the group consisting of hydrogen, halo, and (Ci-Cs)alkyl, and

[0213] Li is a triradical deriving from the abstraction of three hydrogen atoms from each X2 group in a compound of formula G’-(XI-X2)3, wherein each group of formula - (X1-X2) is attached to the same carbon atom of the group G’, and wherein G’ is a radical selected from the group consisting of (Ci-Ci2)alkyl, N[(Ci- Ci2)alkyl]3, (C2-Cs)alkenyl, a group of formula (Ci-C6)alkyl-O-(Ci-C6)alkyl, and a group of formula (Ci-C6)alkyl-(O-(Ci-C6)alkyl)x- wherein x is an integer of from 1 to 10;

[0214] Xi is selected from the group consisting of a covalent bond, -O-, -S-, -COO-, - OCO-, -SO-, -SO2-, -SO2NH-, -NHCO- and -CONH-; and

[0215] X2 is selected from the group consisting of (Ci-Ci2)alkyl, (C2-Cs)alkenyl, a group of formula (Ci-C6)alkyl-O-(Ci-Cs)alkyl and a group of formula (Ci-Cs)alkyl-(O-(Ci-Cs)alkyl)x- wherein x is an integer of from 1 to 10.

[0216]

[0126] In a further preferred embodiment of the second aspect of the invention, the compound of formula (V) of the polymerizable composition is (Va1)

[0217]

[0218]

[0127] In a further embodiment of the second aspect of the invention, the compound of formula (V) is one wherein the dashed bond represents the absence of a covalent bond.In said embodiment, the compound of formula (V) is preferably a compound of formula (Vb)

[0219] Rc- R-io

[0220] Rs Rg

[0221]

[0222] (Vb)

[0223] wherein each one of R7, Rs, R9, R10, R11, R12, Ra, Rb, Rcand Rd is independently selected from the group consisting of hydrogen, halo, and (Ci-Ce)alkyl and

[0224] Li is a diradical deriving from a group selected from the group consisting of ((Ci-Ce)alkyl, (Ci-Ce)alkyloxy, (Ci-C6)alkyloxycarbonyl, (Ci-C6)alkylcarbonyloxy, a group of formula (Ci-C6)alkyl-O-(Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-OCO-(Ci-C6)alkyl, and a group of formula (Ci-C6)alkyl-COO-(Ci-C6)alkyl; more preferably, the compound of formula (V) is a compound of formula (Vb1)

[0225] Vo. .oV

[0226]

[0227] (Vb1)

[0228]

[0128] In an embodiment, the composition of the second aspect of the invention is one wherein the polymerizable mixture comprises a compound comprising a plurality of moieties of formula (IV) and a polyamine. Such composition is suitable for forming polyimide foam materials.

[0229]

[0129] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises a compound comprising a plurality of moieties of formula (IV). Suitable compounds comprising a plurality of moieties of formula (IV) for forming polyimide foam materials are known in the art and will become apparent to the skilled person on the basis of common general knowledge. Those include, for instance, pyromellitic dianhydride (PMDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (ODPA), hexafluoroisopropylidene diphthalic anhydride (6FDA), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), trimellitic anhydride (TMA), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTDA), 3, 3', 4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 3, 3', 4,4'-diphenylmethanetetracarboxylic dianhydride (DMTDA), ethylenetetraacetic dianhydride (ETDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), perfluorobutane-1, 2,3,4-tetracarboxylic dianhydride (PFBDA), 4,4'-thiodiphthalic anhydride (TDA), tetrahydrofuran tetracarboxylic dianhydride, cyclohexane-1 ,2,3,4-tetracarboxylic dianhydride, isopropylidenediphthalic anhydride, and 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride. Preferably, the compound comprising a plurality of moieties of formula (IV) is selected from aromatic anhydrides, such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, or hexafluoroisopropylidene diphthalic anhydride, and aliphatic anhydrides, such as succinic anhydride and glutaric anhydride.

[0230]

[0130] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises a compound comprising a plurality of moieties of formula (IV) and a polyamine. Said polyamine is preferably the same as the compound A2 having a plurality of amino groups as defined above in any embodiments of the first aspect of the invention defining said compound.

[0231]

[0131] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a compound comprising a plurality of moieties of formula (IV) and a polyamine, the compound comprising a plurality of moieties of formula (IV) being in amount such that the molar amount of moieties of formula (IV) in said composition is from 0.5 to 1.5 times the molar amount of amino groups in the polyamine and the compound A2. Preferably, when the composition of the second aspect of the invention comprises or consists essentially of a compound comprising a plurality of moieties of formula (IV) and a polyamine, the compound comprising a plurality of moieties of formula (IV) I s in an amount such that the molar amount of moieties of formula (IV) in said composition is from 0.8 to 1.2 times the molar amount of amino groups in the polyamine and the compound A2. More preferably, when the composition of the second aspect of the invention comprises or consists essentially of a compound comprising a plurality of moieties of formula (IV) and a polyamine, the compound comprising a plurality of moieties of formula (IV) is in an amount such that the molar amount of moieties of formula (IV) in said composition is substantially the same as the molar amount of amino groups in the polyamine and the compound A2.

[0232]

[0132] In an embodiment, the composition of the second aspect of the invention is one wherein the polymerizable mixture comprises a compound comprising a plurality of moieties of formula (IV) and a polyol. Such composition is suitable for forming polyester foam materials.

[0233]

[0133] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a compound comprising a plurality of moieties of formula (IV) and a polyol, the compound comprising a plurality of moieties of formula (IV) being in amount such that the molar amount ofmoieties of formula (IV) groups in said composition is from 0.5 to 1.5 times the molar amount of OH groups in the polyol and the compound A2. Preferably, when the composition of the second aspect of the invention comprises or consists essentially of a compound comprising a plurality of moieties of formula (IV) and a polyol, the compound comprising a plurality of moieties of formula (IV) is in an amount such that the molar amount of moieties of formula (IV) groups in said composition is from 0.8 to 1.2 times the molar amount of OH groups in the polyol and the compound A2. More preferably, when the composition of the second aspect of the invention comprises or consists essentially of a compound comprising a plurality of moieties of formula (IV) and a polyol, the compound comprising a plurality of moieties of formula (IV) is in an amount such that the molar amount of moieties of formula (IV) groups in said composition is substantially the same as the molar amount of OH groups in the polyol and the compound A2.

[0234]

[0134] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a compound comprising in its molecular formula a plurality of moieties of formula (IX) as defined above and a polyamine. Such composition is particularly suitable for forming a polyamide foam material.

[0235]

[0135] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a compound comprising in its molecular formula a plurality of moieties of formula (IX) as defined above and a polyamine, the compound comprising a plurality of moieties of formula (IX) being in amount such that the molar amount of moieties of formula (IX) in said composition is from 0.5 to 1.5 times the molar amount of amino groups in the polyamine and the compound A2. Preferably, when the composition of the second aspect of the invention comprises or consists essentially of a compound comprising a plurality of moieties of formula (IX) and a polyamine, the compound comprising a plurality of moieties of formula (IX) is in an amount such that the molar amount of moieties of formula (IX) in said composition is from 0.8 to 1.2 times the molar amount of amino groups in the polyamine and the compound A2. More preferably, when the composition of the second aspect of the invention comprises or consists essentially of a compound comprising a plurality of moieties of formula (IX) and a polyamine, the compound comprising a plurality of moieties of formula (IX) is in an amount such that the molar amount of moieties of formula (IX) in said composition is substantially the same as the molar amount of amino groups in the polyol and the compound A2.

[0236]

[0136] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a mixture of formaldehyde and one or more of urea and melamine. In such compositions the molar amount of formaldehyde is preferably from 0.5 to 1.5 times the molar amount of aminogroups in the melamine and / or urea; more preferably of from 0.8 to 1.2 times the molar amount of amino groups in the melamine and / or urea. Even more preferably, the molar amount of formaldehyde is substantially the same as the molar amount of amino groups in the melamine and / or urea. In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a mixture of formaldehyde and a compound comprising at least one hydroxyl group attached to a carbon atom that is member of an aromatic ring. In such compositions the molar amount of formaldehyde is preferably from 0.5 to 1.5 times the molar amount of hydroxyl groups attached to a carbon atom that is member of an aromatic ring in the mixture; more preferably of from 0.8 to 1.2 times the molar amount of hydroxyl groups attached to a carbon atom that is member of an aromatic ring in the mixture. Even more preferably, the molar amount of formaldehyde is substantially the same as the molar amount of hydroxyl groups attached to a carbon atom that is member of an aromatic ring in the mixture.

[0237]

[0137] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of, a polyepoxide and a polythiol, the polyepoxide being in amount such that the molar amount of epoxy groups in said composition is from 0.5 to 1.5 times the molar amount of SH groups in the polythiol and the compound A2. Preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polyepoxide and a polythiol, the polyepoxide is in an amount such that the molar amount of epoxy groups in said composition is from 0.8 to 1.2 times the molar amount of SH groups in the polyol and the compound A2. More preferably, when the composition of the second aspect of the invention comprises or consists essentially of a polyepoxide and a polythiol, the polyepoxide is in an amount such that the molar amount of epoxy groups in said composition is substantially the same as the molar amount of SH groups in the polythiol and the compound A2.

[0238]

[0138] Suitable polyepoxide compounds are as defined herein. Suitable polythiol compounds for forming polymers with epoxide are well known in the art and will become apparent to the skilled person on the basis of common general knowledge upon reduction to practice of the invention. In an embodiment, the sulfhydryl equivalent weight (SHEW) of suitable polythiols may fall within a broad range of about 20 g / eq to about 1000 g / eq. In more specific embodiments, the SHEW may be narrowed to about 50 g / eq to about 200 g / eq. Exemplary polythiols suitable for use in thiol-epoxy polymer formation include pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), pentaerythritol tetrakis(3-mercaptobutyrate), di pentaerythritol hexakis(3-mercaptopropionate) (DPETMP), trimethylolpropane tris(3-mercaptopropionate) (TMP-3MP), trimethylolpropane tris(3-mercaptobutyrate), polyethylene glycol di (mercaptoacetate),polypropylene glycol di (mercaptoacetate), thiol-terminated polyether dithiols, urethane-linked polythiols derived from diisocyanates and hydroxy-functional thiols, thiol-terminated urethane prepolymers, glycerol tris(mercaptopropionate), neopentyl glycol bis(mercaptopropionate) (NPG-diMP), thiol-terminated hyperbranched polymers, thiol-ether-modified polythiols, and blocked or protected thiols capable of deblocking under cure conditions.

[0239]

[0139] The inventors have found that the polymerization of a polyepoxide with a polythiol in the presence of the compound A1 advantageously takes place at room termperature, such that no heating is required to trigger the polymerization.

[0240]

[0140] In an embodiment, the polymerizable mixture of the composition of the second aspect of the invention comprises, such as consists essentially of a polyepoxide, a carboxylic acid anhydride and a polymerization initiator.

[0241]

[0141] Suitable polyepoxide compounds are as defined herein. Suitable carboxylic acid anhydride compounds are known in the art and will become apparent to the skilled person upon reduction to practice of the invention on the basis of common general knowledge. In an embodiment, the carboxylic acid anhydride is selected from wide range of cyclic, aromatic, aliphatic, cycloaliphatic, polyfunctional, bio-based, or specialty anhydrides. Suitable cyclic and aromatic anhydrides include phthalic anhydride, trimellitic anhydride (TMA), tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA), nadic methyl anhydride (NMA), methyl tetrahydrophthalic anhydride (MTHPA), methylnadic anhydride (MNA), maleic anhydride, pyromellitic dianhydride (PMDA), and benzophenonetetracarboxylic dianhydride (BTDA), which provide improved thermal stability and chemical resistance. Suitable aliphatic and cycloaliphatic anhydrides include succinic anhydride, glutaric anhydride, adipic anhydride, dodecenyl succinic anhydride (DDSA), octenyl succinic anhydride (OSA), cyclopentadiene-based anhydrides such as hydrogenated nadic-type derivatives, and alkenyl succinic anhydrides (ASA) of varying chain length, which may offer lower viscosity, extended pot life, and reduced color development. Polyfunctional anhydrides useful for increasing crosslink density include polymaleic anhydride, polycycloaliphatic anhydrides derived from hydrogenated dicarboxylic acids, polyester-anhydride adducts prepared from polyols and excess anhydrides, and anhydride-terminated oligomers such as maleated polybutadiene or maleated polyesters. Bio-based and specialty anhydrides that may also be employed include itaconic anhydride, citraconic anhydride, camphoric anhydride, isobornyl succinic anhydride (IBSA), and bio-derived alkenyl succinic anhydrides. The polyepoxide may be in amount such that the molar amount of epoxy groups in said composition is from 0.5 to 1.5 times the molar amount of anhydride groups.

[0242]

[0142] In a further preferred embodiment of the second aspect of the invention, the composition further comprises at least one additive. Such additive may be a texturizingagent, a stabilizer, a thickening agent, a flame retardant, an adhesion promoter, a foam hardener, a surfactant, a curing promoter (e.g. DMP-30, TMG), an inorganic filler or a cross-linking agent such as epoxy containing compounds.

[0243]

[0143] In a further preferred embodiment of the second aspect of the invention, the composition further comprising an additive that is selected from the group consisting of (nano)clays, hydrotalcite, graphene, carbon nanotube and nano fibers, organic / inorganic particles, iron oxide, silica, wood flour, (nano)cellulose, (nano)chitin, chitosan, fluorescent nano / microparticles.

[0244]

[0144] In a further preferred embodiment of the second aspect of the invention, the composition further comprising an additive that is selected from the group consisting of inorganic fillers, such as nanoclays or hydrotalcite.

[0245]

[0145] In a further preferred embodiment of the second aspect of the invention, the composition has a viscosity of between 0.05 Pa s and 500 Pa.s when measured after a time of 540 seconds of heating said composition at 70 °C; more preferably of between 0.5 and 100 Pa.s. Suitable methods for measuring viscosity are disclosed in Mezger, T. G. The Rheology Handbook: 4th Edition; Vincentz Network, 2019, chapter 8.2.3, incorporated herein by reference.

[0246]

[0146] In a further embodiment, when the polymerizable mixture of the composition of the second aspect of the invention comprises a compound comprising a plurality of moieties of formula (III), said composition may further comprise a cross-linking agent that is suitable for reacting with the pendent OH group resulting from the opening of the moiety of formula (III) by the polyamine. Such cross-linking agent is preferably one comprising in its molecular formula one or more moieties of formula -O-CH=CH2 or of formula or of formula -CHO.

[0247]

[0147] Preferably, the cross-linking agent is one which comprises in its molecular formula a plurality of moieties of formula -O-CH=CH2; preferably from 2 to 3 moieties of formula -O-CH=CH2.

[0248]

[0148] Preferably, said cross-linking agent is a compound of formula (VIII)

[0249]

[0250] (VIII)

[0251] wherein L2 is a diradical deriving from the abstraction of one hydrogen atom from a group selected from the group consisting of (Ci-C6)alkyl, (Ci-C6)alkyloxy, (Ci-C6)alkylamino, (Ci-C6)alkyloxycarbonyl, (Ci-C6)alkylaminocarbonyl, (Ci-C6)alkylcarbonylamino, (C1-C6)alkylcarbonyloxy, (Ci-Ce)alkylthio, (C2-Ce)alkenyl, a group of formula (Ci-C6)alkyl-O-(Ci-C6)alkyl, a radical of formula (Ci-C6)alkyl-S-(Ci-C6)alkyl, a group of formula (C1-C6)alkyl-NRi3-(Ci-C6)alkyl wherein R13 is hydrogen or (Ci-C6)alkyl, a group of formula (Ci-C6)alkyl-CONRi3-(Ci-C6)alkyl wherein R13 is hydrogen or (Ci-C6)alkyl, a group offormula (Ci-C6)alkyl-NRi3CO-(Ci-Ce)alkyl wherein R13 is hydrogen or (Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-OCO-(Ci-C6)alkyl, a group of formula (Ci-Ce)alkyl-COO-(Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-(O-(Ci-C6)alkyl)m-O wherein m is an integer of from 1 to 10, a group of formula G”, a group of formula (Ci-Ce)alkyl-G”, a group of formula (Ci-C6)alkyl-G”-(Ci-C6)alkyl, wherein G” is a ring system comprising from 1 to 3 rings, each ring being saturated, unsaturated or aromatic, said rings being isolated, bridged or fused and comprising from 3 to 8 members selected from the group consisting of O, C, CH, CH2, N, NH, S, C=O, S=O and -SO2-, the members of the rings being optionally substituted where chemically possible with one or more groups selected from halo, (Ci-Ce)alkyl, (Ci-Ce)haloalkyl, (Ci-Ce)alkyloxy, (Ci-Ce)alkylamino, (C1-C6)alkyloxycarbonyl, (Ci-C6)alkylaminocarbonyl, cyano and nitro.

[0252]

[0149] More preferably, the cross-linking agent is a compound of formula (VIII) wherein L3 is a diradical deriving from the abstraction of one hydrogen atom from a group selected from the group consisting of (Ci-Ce)alkyl, (Ci-Ce)alkyloxy, a group of formula (C1-C6)alkyl-O-(Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-(O-(Ci-C6)alkyl)m-O wherein m is an integer of from 1 to 10, a group of formula G”, wherein G” is a ring system comprising from 1 to 3 rings, each ring being saturated, unsaturated or aromatic, said rings being isolated, bridged or fused and comprising from 3 to 8 members selected from the group consisting of O, C, CH, CH2, N, NH, S, C=O, S=O and -SO2-, the members of the rings being optionally substituted where chemically possible with one or more groups selected from halo, (Ci-Ce)alkyl, (Ci-Ce)haloalkyl, (Ci-Ce)alkyloxy, (Ci-Ce)alkylamino, (C1-C6)alkyloxycarbonyl, (Ci-C6)alkylaminocarbonyl, cyano and nitro.

[0253]

[0150] Even more preferably, the cross-linking agent is a compound of formula (VIII) wherein L3 is a diradical deriving from the abstraction of one hydrogen atom from a group of formula G”, wherein G” is a ring system comprising from 1 to 3 rings, each ring being saturated, unsaturated or aromatic, said rings being isolated, bridged or fused and comprising from 3 to 8 members selected from the group consisting of O, C, CH, CH2, N, NH, S, C=O, S=O and -SO2-, the members of the rings being optionally substituted where chemically possible with one or more groups selected from halo, (Ci-Ce)alkyl, (C1-Ce)haloalkyl, (Ci-Ce)alkyloxy, cyano and nitro.

[0254]

[0151] Even more preferably, the cross-linking agent is a compound of formula (VIII) wherein L3 is a diradical deriving from the abstraction of one hydrogen atom from a group of formula G”, wherein G” is a ring system comprising one saturated ring comprising from 3 to 8 members selected from the group consisting of O, C, CH, CH2, N, NH, S, C=O, S=O and -SO2-, the members of the rings being optionally substituted where chemically possible with one or more groups selected from halo, (Ci-Ce)alkyl, (C1-Ce)haloalkyl, (Ci-Ce)alkyloxy, cyano and nitro.

[0255]

[0152] Even more preferably, the cross-linking agent is a compound of formula (Villa)

[0256]

[0257] (Villa)

[0258] wherein the * represents that said vinyl ether group may be attached to any carbon atom comprised in the ring of compound (Villa).

[0259]

[0153] The cross-linking agent is preferably in an amount such that the molar ratio of functional groups suitable for reacting with the -OH group in the cross-linking agent to the moieties of formula (III) in the polymerizable mixture is comprised from 1:4 to 1:10.

[0260]

[0154] In a further embodiment, the composition of the second aspect of the invention is one wherein the polymerizable mixture is selected from:

[0261] (ii-1) a polyepoxide and a polyamine;

[0262] (ii-2) a polycarboxylic acid chloride and a polyamine;

[0263] (ii-3) a polyisocyanate and a polyamine;

[0264] (ii-4) a compound comprising in its molecular formula at least one moiety, preferably a plurality of moieties, of formula (III) Q

[0265] o A o, ,

[0266] ^4^

[0267]

[0268] (III)

[0269] wherein m is 1 or 2 and each wavy line represents the position to which the moiety of formula (III) is attached to the remainder of the compound and a polyamine; and (ii-5) a compound comprising in its molecular formula at least one moiety, preferably a plurality of moieties, of formula (IV)

[0270] A

[0271] (IV)

[0272] wherein p is 1 or 2 and each wavy line represents the position to which the moiety of formula (IV) is attached to the remainder of the compound and a polyamine.

[0273]

[0155] In a further embodiment, the composition of the second aspect of the invention is one wherein the compound A1 represents from 0.1% in weight to 25% in weight of the composition; preferably from 0.5% in weight to 5% in weight of the composition.

[0274]

[0156] In a further embodiment, the composition of the second aspect of the invention is one wherein the compound A1 represents from 0.1% in weight to 25% in weight of the composition; preferably from 0.5% in weight to 5% in weight of the composition, and wherein the compound A2 is the same compound as the polyamine comprised in the polymerizable mixture.

[0157] In a further embodiment, the composition of the second aspect of the invention is one wherein the molar fraction of the compound A1 in said composition is from 1% to 10%, i.e. from 0.01 to 0.1.

[0275]

[0158] As mentioned above, a third aspect of the invention relates to a kit for forming a polymer foam comprising a plurality of parts comprising a composition according to the second aspect of the invention wherein the compound A1 is provided in a different part than the compound A2. It is further preferred that the polyamine of the polymerizable mixture is provided in a different part than the compound A1.

[0276]

[0159] As will be obvious, when the polyamine or polyol of the polymerizable mixture of the composition of the second aspect of the invention is the same compound as the compound A2, said polyamine or polyol is provided in a different part than the compound A1.

[0277]

[0160] The kit of parts of the third aspect of the invention may comprise a composition as defined in any of the embodiments described above defining the components and amount of said composition.

[0278]

[0161] In a further embodiment, the third aspect of the invention relates to a kit of parts wherein the polyamine or polyol of the polymerizable mixture is provided in a different part than the polyepoxide, the polycarboxylic acid chloride, the polyisocyanate, the compound comprising in its molecular formula at least one moiety of formula (III) and / or the compound comprising in its molecular formula at least one moiety of formula (IV).

[0279]

[0162] As mentioned above, the fourth aspect of the invention relates to a process for the preparation of a polymer foam comprising the steps of:

[0280] (i) providing a source of carbon dioxide comprising a compound A1 and a compound A2; (ii) providing a polymerizable composition;

[0281] (iii) causing the polymerizable composition to polymerize and the compound A2 to react with the compound A1 concomitantly;

[0282] wherein the compounds A1, A2, the polymerizable composition and the relative amounts thereof are as defined in the second aspect of the invention.

[0283]

[0163] In preferred embodiments of the fourth aspect, compound A1 provided in step (i) is as defined in the second aspect of the invention, that is compound A1 provided in step (i) is also as defined in the first aspect of the invention.

[0284]

[0164] In preferred embodiments of the fourth aspect, compound A2 provided in step (i) is as defined in the second aspect of the invention, that is compound A2 provided in step (i) is also as defined in the first aspect of the invention.

[0285]

[0165] In preferred embodiments of the fourth aspect, the relative amounts of compounds A1 and A2 are as defined in the first or second aspect of the invention.

[0166] In preferred embodiments of the fourth aspect, the polymerizable composition provided in step (ii) is as defined in any of the embodiments of the second aspect of the invention defining the components of said composition and their relative amount.

[0286]

[0167] In preferred embodiments of the fourth aspect, step (iii) comprises mixing the carbon dioxide source and the polymerizable composition.

[0287]

[0168] In preferred embodiments of the fourth aspect, step (iii) comprises heating the polymerizable composition in the presence of the source of carbon dioxide.

[0288]

[0169] In preferred embodiments of the fourth aspect, step (iii) comprises heating a mixture of the polymerizable composition and of the source of carbon dioxide. Said heating is preferably carried out at a temperature of between 25 °C and 200 °C; preferably of between 40 °C and 150 °C; more preferably of between 60 °C and 120 °C. Suitable temperature for carrying out step (iii) can readily be identified by the skilled person, as the initiation of the polymerization and generation of carbon dioxide can be recognized by simple observation of the sample. Step (iii) is preferably carried out for a period of time of between 1 minute to 10 hours.

[0289]

[0170] When the polyamine or polyol of the polymerizable composition is used as compound A2 in the source of carbon dioxide, step (i) comprises providing a compound A1. Said compound may be mixed with the polymerizable mixture by addition of a solution of the compound A1 in an organic solvent having a boiling point below the temperature at which step (iii) is carried out.

[0290]

[0171] As mentioned above, the fifth aspect of the invention relates to a polymer foam obtainable by the process of the fourth aspect of the invention.

[0291]

[0172] Preferred embodiments of the fifth aspect of the invention relate to a polymer foam obtainable by the process according to any of the embodiments of the fourth aspect of the invention.

[0292]

[0173] In a further aspect, the invention relates to the use of a compound A1 comprising at least one moiety of formula (I), such as from one to three moieties of formula (I), and / or at least one moiety of formula (II), such as from one to three moieties of formula (II), in its molecular formula as blowing agent for the production of a polymeric foam material

[0293]

[0294] (I) (H)

[0295] wherein:

[0296] each n is an integer of from 1 to 3;

[0297] each wavy line represents the covalent bond through which the moiety of formula (I) or of formula (II) is attached to the remainder of the molecule;each Ri is selected from the group consisting of hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl (C3-C8)cycloalkyl, and (Ce-C2o)aryl optionally substituted at any available position with a group selected from the group consisting of halo, cyano, nitro, (Ci-Ce)alkyl, (Ci-Ce)alkyloxy and (Ci-Ce)haloalkyl;

[0298] R2 is selected from the group consisting of hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl (C3-C8)cycloalkyl, and (Ce-C2o)aryl optionally substituted at any available position with a group selected from the group consisting of halo, cyano, nitro, (Ci-Ce)alkyl, (C1-Ce)alkyloxy and (Ci-Ce)haloalkyl; and

[0299] R3 is selected from the group consisting of hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl (C3-C8)cycloalkyl, and (Ce-C2o)aryl optionally substituted at any available position with a group selected from the group consisting of halo, cyano, nitro, (Ci-Ce)alkyl, (C1-Ce)alkyloxy and (Ci-Ce)haloalkyl;

[0300] and wherein said use preferably comprises forming carbon dioxide by reaction of the compound A1 with a nucleophilic compound A2.

[0301]

[0174] In said aspect, the compounds A1 and A2 may be preferably as defined in the first aspect of the invention.

[0302]

[0175] In a preferred embodiment of said further aspect, the compound A1 comprises at least one moiety of formula (I), such as from one to three moieties of formula (I), and, optionally, at least one moiety of formula (II), such as from one to three moieties of formula (II), in its molecular formula.

[0303]

[0176] Throughout the description and claims the word “comprises" and variations of the word, are not intended to exclude other technical features, additives, components or steps. Furthermore, the word “comprise” encompasses the cases of “consist of” and “consists essentially of’. Additional objects, advantages and features of the invention will become apparent to those skilled in the art upon examination of the description or may be learned by practice of the invention. The following examples are provided by way of illustration, and they are not intended to be limiting of the present invention.

[0304] EXAMPLES

[0305] Abbreviations

[0306] NCA: amino acid N-carboxyanhydride (Glycine NCA is oxazolidine-2, 5-dione, which is the N-carboxyanhydride derived from glycine)

[0307] SEM: Scanning Electron Microscopy

[0308] TMPTE: Trimethylolpropane triglycidyl ether

[0309] GE: Glycerol Epoxide

[0310] DGEBA: Diglycidyl Ether of Bisphenol A

[0311] HDGEBA: Hydrogenated Diglycidyl Ether of Bisphenol A

[0312] PGE: Polyglycerol Epoxide

[0313] SE: Sorbitol Epoxide

[0314] TMPTC: Trimethylolpropane TricarbonateCVE: Cyclic Vinyl Ether IIIPAC name: 1,4-bis((vinyloxy)methyl)cyclohexane

[0315] XDA: m-Xylylenediamine

[0316] PACM : 4,4'-Diaminodicyclohexylmethane

[0317] AHEW: Amine Hydrogen Equivalent Weight

[0318] WPE: Weight Per Epoxide, also referred to herein as EEW (epoxyde equivalent weight) Cloisite Na: Sodium-modified Montmorillonite

[0319] MSA: Methanesulfonic Acid

[0320] Example 1

[0321]

[0177] Glycine NCA (348 mg, 3.4 mmol, 3 wt.% relative to total weight) was partially dissolved in 300 pL of ethanol at room temperature. TMPTGE (with a WPE of 145 g / eq, 10 g, providing 69 mmol of epoxy groups) and PACM (3.6 g, AHEW = 52.6 g / eq, providing 69 mmol of NH groups) were placed into a silicone mold and mixed. The ethanolic solution of glycine NCA was then added to the epoxy and amine mixture, and the components were blended until fully homogenized. The mixture was subsequently cured at 110°C for 15 minutes. See FIG. 2.

[0322] Example 2

[0323]

[0178] Glycine NCA (460 mg, 3.4 mmol, 3 wt.% relative to total weight) was partially dissolved in 300 pL of ethanol at room temperature. DGEBA (with a WPE of 170 g / eq, 11.73 g, providing 69 mmol of epoxy groups) and PACM (3.63 g, AHEW = 52.6 g / eq, providing 69 mmol of NH groups) were placed into a silicone mold and mixed. The ethanolic solution of glycine NCA was then added to the epoxy and amine mixture, and the components were blended until fully homogenized. The mixture was subsequently cured at 140°C for 3 hours.

[0324] Example 3

[0325]

[0179] Glycine NCA (550 mg, 3.4 mmol, 3 wt.% relative to total weight) was partially dissolved in 300 pL of ethanol at room temperature. HDGEBA (with a WPE of 213 g / eq, 14.70 g, providing 69 mmol of epoxy groups) and PACM (3.63 g, AHEW = 52.6 g / eq, providing 69 mmol of NH groups) were placed into a silicone mold and mixed. The ethanolic solution of glycine NCA was then added to the epoxy and amine mixture, and the components were blended until fully homogenized. The mixture was subsequently cured at 150°C for 2 hours.

[0326] Example 4

[0327]

[0180] Glycine NCA (401 mg, 3.4 mmol, 3 wt.% relative to total weight) was partially dissolved in 300 pL of ethanol at room temperature. GE (with a WPE of 141 g / eq, 9.73g, providing 69 mmol of epoxy groups) and PACM (3.63 g, AHEW = 52.6 g / eq, providing 69 mmol of NH groups) were placed into a silicone mold and mixed. The ethanolic solution of glycine NCA was then added to the epoxy and amine mixture, and the components were blended until fully homogenized. The mixture was subsequently cured at 110°C for 15 minutes. See FIG. 3.

[0328] Example 5

[0329]

[0181] Glycine NCA (457 mg, 3.4 mmol, 3 wt.% relative to total weight) was partially dissolved in 300 pL of ethanol at room temperature. PGE (with a WPE of 168 g / eq, 11.59 g, providing 69 mmol of epoxy groups) and PACM (3.63 g, AHEW = 52.6 g / eq, providing 69 mmol of NH groups) were placed into a silicone mold and mixed. The ethanolic solution of glycine NCA was then added to the epoxy and amine mixture, and the components were blended until fully homogenized. The mixture was subsequently cured at 110°C for 15 minutes. See FIG. 4.

[0330] Example 6

[0331]

[0182] Glycine NCA (504 mg, 3.4 mmol, 3 wt.% relative to total weight) was partially dissolved in 300 pL of ethanol at room temperature. SE (with a WPE of 191 g / eq, 13.18 g, providing 69 mmol of epoxy groups) and PACM (3.63 g, AHEW = 52.6 g / eq, providing 69 mmol of NH groups) were placed into a silicone mold and mixed. The ethanolic solution of glycine NCA was then added to the epoxy and amine mixture, and the components were blended until fully homogenized. The mixture was subsequently cured at 80°C for 15 minutes. See FIG. 5.

[0332] Example 7

[0333]

[0183] TMPTC (5 g, 5CC = 34.5 mmol), glycine NCA (87 mg, 1 wt.% relative to the combined weight of cyclic carbonate and amine), and Cloisite Na (600 mg) were mixed together in a square silicone mold (surface area = 16 cm2) until a yellowish homogeneous mixture formed. The mold was then placed in an oven at 60°C until the mixture reached this temperature. Subsequently, XDA (2.35 g, NH2= 34.5 mmol) was preheated to 100°C for 5 minutes in a closed vial, then added to the mold with the other components. The polymerizable mixture was stirred and cured at 110°C for 10 minutes.

[0334] Example 8

[0335]

[0184] TMPTC (5 g, 5CC = 34.5 mmol), glycine NCA (87 mg, 1 wt.% relative to the combined weight of cyclic carbonate and amine), CVE (1.7 g, 8.7 mmol), and Cloisite Na (600 mg) were combined in a square silicone mold (surface area = 16 cm2) and mixed until a yellowish, homogeneous mixture was achieved. The mold was then placed in anoven at 60°C until the mixture reached this temperature. Meanwhile, XDA (2.35 g, NH2= 34.5 mmol) and MSA (0.166 g, 1.7 mmol) were preheated to 100°C for 5 minutes in a closed vial before being added to the mold with the other ingredients. The polymerizable mixture was stirred thoroughly and cured at 110°C for 10 minutes.

[0336] Example 9

[0337]

[0185] Glycine NCA (504 mg, 3.4 mmol, 3 wt.% relative to total weight) was partially dissolved in 300 pL of dichloromethane at room temperature. 1,3,5-Benzenetricarbonyl chloride (BC) (with MW 265.47, 10 g, providing 113 mmol of COCI) and PACM (12 g, providing 113 mmol of NH2 groups) were placed into a silicone mold and mixed. The dichloromethane solution of glycine NCA was then added to the BC and amine mixture, and the components were blended until fully homogenized. The mixture was then cured following a temperature ramp: 3 hours at 100°C, followed by 5 hours at 160°C. The formulation resulted in yellowish rigid foams.

[0338] Example 10

[0339]

[0186] Glycine NCA (504 mg, 3.4 mmol, 3 wt.% relative to total weight) was partially dissolved in 300 pL of dichloromethane at room temperature. Pyromellitic dianhydride (PMDA) (with MW 218.12, 10 g, providing 92 mmol of anhydride moieties) and tris(2- aminoethyl)amine (TREN) (4.5 g, providing 92 mmol of NH2 groups) were placed into a silicone mold and mixed. The dichloromethane solution of glycine NCA was then added to the BC and amine mixture, and the components were blended until fully homogenized. The mixture was then cured following a temperature ramp: 3 hours at 100°C, followed by 2 hours at 130°C. The formulation resulted in polyamide yellowish rigid foams.

[0340] Example 11

[0341]

[0187] Glycine NCA (504 mg, 3.4 mmol, 3 wt.% relative to total weight) was partially dissolved in 300 pL of dichloromethane at room temperature. Pyromellitic dianhydride (PMDA) (with MW 218.12, 10 g, providing 92 mmol of anhydride moieties) and tris(2- aminoethyl)amine (TREN) (4.5 g, providing 92 mmol of NH2 groups) were placed into a silicone mold and mixed. The dichloromethane solution of glycine NCA was then added to the BC and amine mixture, and the components were blended until fully homogenized. The mixture was then cured following a temperature ramp: 2 hours at 100°C, followed by 2 hours at 130°C, and 3 hours at 180°C. The formulation resulted in polyimide brownish rigid foams.

[0342]

[0343] 12

[0188] Methyloxazolidine-2, 5-dione (Alanine NCA)(348 mg, 3 mmol, 3 wt.% relative to total weight) was melted at 90°C. TMPTGE (with a WPE of 145 g / eq, 10 g, providing 69 mmol of epoxy groups) and PACM (3.6 g, AHEW = 52.6 g / eq, providing 69 mmol of NH groups) were placed into a silicone mould and mixed. The melted Alanine NCA was subsequently added to the epoxy and amine blend, and the mixture was stirred until completely homogeneous. Once the three components were combined, the polymerizable mixture began to foam and cure as a result of the exothermic epoxide ring-opening reaction. The resulting foam was then post-cured in an oven at 120°C for 5 minutes to ensure full conversion of the epoxide groups.

[0344] Example 13

[0345]

[0189] Glycine NCA (401 mg, 3.4 mmol, 3 wt.% relative to total weight), and sulfur (S8) (2.2g, 8.625 mmol) were dispersed in GE (with a WPE of 141 g / eq, 9.73 g, providing 69 mmol of epoxy groups). Then, PACM (0.145 g, AHEW= 52.6 g / eq, providing 0.69 mmol of NH groups) were placed into a silicone mold and mixed. The mixture was subsequently cured at 120°C for 5 hours.

[0346] Example 14

[0347]

[0190] Alanine-NCA (4-methyloxazolidine-2, 5-dione, 278 mg, 3 wt.% relative to total weight) was dispersed in PGE epoxy resin (WPE = 168 g / eq, 5 g, providing 29.8 mmol of epoxy groups). MHHPA (methyl hexahydrophthalic anhydride, Carboxylate equivalent weight = 143 g / eq, 4.25 g, providing 25.3 mmol of anhydride groups), TMG (tetramethylguanidinde, 146 mg, 5 mol% relative to MHHPA), and Benzyldimethylamine (185 mg, 2 wt.% relative to total weight) were then added to the Epoxy-NCA dispersion and blended until fully homogenized. The resulting mixture was subsequently cured at 150°C for 10 minutes.

[0348] Example 15

[0349]

[0191] Alanine-NCA (600 mg, 6 wt.% relative to epoxy resin) was pestled with Cloisite (1200 mg, 12 wt.% relative to epoxy resin) and dispersed in PGE epoxy resin (polyglycerol epoxy WPE = 168 g / eq, 10 g, providing 59.6 mmol of epoxy groups). A mixture of PETMP (pentaerythritol tetrakis(3-mercaptopropionate - SHEW = 122.1 g / eq, 7.25 g, providing 59.6 mmol of SH groups), TMG (171 mg, 10 mol% relative to PETMP), DMP-30 (600 mg, 6 wt.% relative to epoxy resin), and Tegostab (120 mg, 1.2 wt.% relative to epoxy resin) was then added to the Epoxy-NCA dispersion and mixed until fully homogenized. The resulting mixture was subsequently cured at room temperature.

[0350] Example 16

[0351]

[0192] Alanine-NCA (596 mg, 5 wt.% relative to total weight) was pestled with Cloisite (1200 mg, 12 wt.% relative to epoxy resin) and dispersed in PGE epoxy resin (WPE =168 g / eq, 10 g, providing 59.6 mmol of epoxy groups). A mixture of 1,3-BAC (1,3-cyclohexanedimethylamine - AHEW = 35.56 g / eq, 1.48 g, providing 41.7 mmol of NH groups), TREN (tris(2-aminoethyl)amine - AHEW = 24.37 g / eq, 0.435 g, providing 17.9 mmol of NH2 groups), and DMP-30 (2,4,6-tris(dimethylaminomethyl)phenol - 0.6 g, 5 wt.% relative to total weight) was then added to the Epoxy-NCA dispersion and mixed until homogenized. The resulting mixture was subsequently cured at room temperature.

[0352] Example 17

[0353]

[0193] Alanine-NCA (178 mg, 1.55 mmol, 3 wt.% relative to total weight) was pestled with Na+ Cloisite (600 mg, 12 wt.% relative to epoxy resin) and dispersed in PGE epoxy resin (WPE = 168 g / eq, 5 g, providing 29.8 mmol of epoxy groups). Furfuryldiamine (AHEW = 31.54 g / eq, 0.939 g, providing 29.8 mmol of NH2 groups) was then added to the Epoxy-NCA dispersion and mixed for 30 s. The resulting mixture was subsequently cured at 75°C for 5 min.

Claims

43CLAIMS1. Use of a compound A1 comprising at least one moiety of formula (I), such as from one to three moieties of formula (I), and / or at least one moiety of formula (II), such as from one to three moieties of formula (II), in its molecular formula as blowing agent for the production of a polymeric foam material other than a poly(peptide)R3O(I) (II)wherein:each n is an integer of from 1 to 3;each wavy line represents the covalent bond through which the moiety of formula (I) or of formula (II) is attached to the remainder of the molecule;each Ri is selected from the group consisting of hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl (C3-C8)cycloalkyl, and (Ce-C2o)aryl optionally substituted at any available position with a group selected from the group consisting of halo, cyano, nitro, (Ci-Ce)alkyl, (Ci-Ce)alkyloxy and (Ci-Ce)haloalkyl;R2 is selected from the group consisting of hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl (C3-C8)cycloalkyl, and (Ce-C2o)aryl optionally substituted at any available position with a group selected from the group consisting of halo, cyano, nitro, (Ci-Ce)alkyl, (C1-Ce)alkyloxy and (Ci-Ce)haloalkyl; andR3 is selected from the group consisting of hydrogen, (Ci-Ce)alkyl, (C2-Ce)alkenyl (C3-C8)cycloalkyl, and (Ce-C2o)aryl optionally substituted at any available position with a group selected from the group consisting of halo, cyano, nitro, (Ci-Ce)alkyl, (C1-Ce)alkyloxy and (Ci-Ce)haloalkyl;and wherein said use preferably comprises forming carbon dioxide by reaction of the compound A1 with a nucleophilic compound A2.

2. Use according to claim 1 wherein:each n is 1 ; and / oreach R1 is hydrogen; and / orR2 is hydrogen in the moiety of formula (I); and / orR3 is hydrogen in the moiety of formula (II).

443. Use according to any one of claims 1 or 2 wherein the compound A1 is selected from the group consisting of oxazolidine-2, 5-dione, 3-methyloxazolidine-2, 5-dione and 4-methyloxazolidine-2, 5-dione.

4. A composition for forming a polymer foam comprising:(i) a source of carbon dioxide comprising:(i-1) a compound A1 comprising at least one moiety of formula (I) and / or at least one moiety of formula (II) in its molecular formula as defined in any one of claims 1 to 3;(i-2) a compound A2 comprising in its molecular formula at least one functional group selected from the group consisting of amino, hydroxyl, thiol, or at least one of a negatively charged carbon atom, a negatively charged nitrogen atom, a negatively charged oxygen atom or a negatively charged sulfur atom;(ii) a polymerizable mixture of compounds comprising one or more of:(ii-1) a polyepoxide and a polyamine or a polyol;(ii-2) a polycarboxylic acid chloride and a polyamine or a polyol;(ii-3) a polyisocyanate and a polyamine or a polyol;(ii-4) a compound comprising in its molecular formula at least one moiety, preferably a plurality of moieties, of formula (III)OA o o, ,(HI)wherein m is 1 or 2 and each wavy line represents the position to which the moiety of formula (III) is attached to the remainder of the compound and a polyamine or a polyol;(ii-5) a compound comprising in its molecular formula at least one moiety, preferably a plurality of moieties, of formula (IV)oA oA(IV)wherein p is 1 or 2 and each wavy line represents the position to which the moiety of formula (IV) is attached to the remainder of the compound and a polyamine or a polyol;45(ii-6) a compound comprising in its molecular formula a plurality of moieties, of formula (IX) JWVI(IX)wherein each wavy line represents the position to which the moiety of formula (III) is attached to the remainder of the compound and a polyamine;(ii-7) a mixture of formaldehyde and one or more of urea and melamine;(ii-8) a mixture of formaldehyde and a compound comprising at least one hydroxyl group attached to a carbon atom that is member of an aromatic ring(ii-9) a polyepoxide and a polythiol; and(ii-10) a polyepoxide, a carboxylic acid anhydride and a polymerization initiator.

5. The composition according to claim 4 wherein the compound A1 is selected from oxazolidine-2, 5-dione, 3-methyloxazolidine-2, 5-dione and 4-methyloxazolidine-2,5-dione; preferably, it is oxazolidine-2, 5-dione.

6. The composition according to any one of claims 4 to 5 wherein the compound A2 is a compound comprising in its molecular formula two or more amino groups which are connected to a saturated carbon atom; preferably, said compound A2 is a compound comprising in its molecular formula two or more amino groups which are connected to a saturated carbon atom and having an Amine Hydrogen Equivalent Weight of between 5 grams per equivalent and 120 grams per equivalent; more preferably, said compound A2 is a compound comprising in its molecular formula two or more amino groups which are connected to a saturated carbon atom and having an Amine Hydrogen Equivalent Weight of between 10 grams per equivalent and 60 grams per equivalent; even more preferably, said compound A2 is selected from the group consisting of tris(2-aminoethyl)amine, xylylenediamine, Jeffamine® D-230, Jeffamine® D-400, Isophorone diamine, 4,4'-methylenedianiline, furfuryldiamine, cyclohexane-1,3-diyldimethanamine, N,N-bis(2-aminoethyl)ethane-1,2-diamine, and 4,4'-diaminodicyclohexylmethane.

7. The composition according to any one of claims 4 to 6 wherein the polymerizable mixture of (ii) is selected from the group consisting of one or more of:(ii-1) a polyepoxide having an Epoxide Equivalent Weight of between 60 grams per equivalent and 1000 grams per equivalent; preferably having an Epoxide EquivalentWeight of between 100 grams per equivalent and 300 grams per equivalent; more preferably, the polyepoxide is selected from the group consisting of trimethylolpropane triglycidyl ether, glycerol epoxide, diglycidyl ether of bisphenol, hydrogenated diglycidyl ether of bisphenol a, polyglycerol epoxide and sorbitol epoxide; and a polyamine having an Amine Hydrogen Equivalent Weight of between 5 grams per equivalent and 120 grams per equivalent; more preferably, said polyamine has an Amine Hydrogen Equivalent Weight of between 10 grams per equivalent and 60 grams per equivalent; even more preferably, said polyamine is selected from the group consisting of tris(2-aminoethyl)amine, xylylenediamine, furfuryldiamine, cyclohexane- 1,3-diyldimethanamine, N,N-bis(2-aminoethyl)ethane-1,2-diamine , and 4,4'-diaminodicyclohexylmethane;(ii-2) a polycarboxylic acid chloride selected from the group consisting of aliphatic acid chlorides, such as adipoyl chloride, sebacoyl chloride and malonyl chloride, aromatic acid chlorides such as a benzene ring substituted with from 2 to 6 -COCI groups, and a polyamine having an Amine Hydrogen Equivalent Weight of between 5 grams per equivalent and 120 grams per equivalent; more preferably, said polyamine has an Amine Hydrogen Equivalent Weight of between 10 grams per equivalent and 60 grams per equivalent; even more preferably, said polyamine is selected from the group consisting of tris(2-aminoethyl)amine, xylylenediamine, furfuryldiamine, cyclohexane-1,3-diyldimethanamine, N,N-bis(2-aminoethyl)ethane-1,2-diamine , and 4,4'-diaminodicyclohexylmethane;(ii-3) a polyisocyanate selected from the group consisting of aromatic polyisocyanates, such as 4,4’-methylenebis(phenyl isocyanate) or a polymer thereof and toluene diisocyanate, aliphatic polyisocyanates, such as hexamethylene diisocyanate, isophorone diisocyanate or hydrogenated 4,4’-methylenebis(phenyl isocyanate), and cycloaliphatic polyisocyanates, such as 1,4-cyclohexane diisocyanate and 4,4’-dicyclohexylmethane diisocyanate, and a polyamine having an Amine Hydrogen Equivalent Weight of between 5 grams per equivalent and 120 grams per equivalent; more preferably, said polyamine has an Amine Hydrogen Equivalent Weight of between 10 grams per equivalent and 60 grams per equivalent; even more preferably, said polyamine is selected from the group consisting of tris(2-aminoethyl)amine, xylylenediamine, furfuryldiamine, cyclohexane-1,3-diyldimethanamine, N,N-bis(2-aminoethyl)ethane-1,2-diamine , and 4,4'-diaminodicyclohexylmethane;(ii-4) a compound of formula (V)(V)wherein in the compound of formula (V),each q is independently 1 or 2;each one of R4, Rs, Re, R7, Rs, R9, R10, R11 and R12 is independently selected from the group consisting of hydrogen, halo, (Ci-Cs)alkyl, (C2-Cs)alkenyl and (C3-C8)cycloalkyl; the dashed bond represents the presence or the absence of a covalent bond;when the dashed bond represents the absence of a covalent bond, L is a diradical deriving from the abstraction of one hydrogen atom from a group selected from the group consisting of (Ci-Cs)alkyl, (Ci-Cs)alkyloxy, (Ci-Cs)alkylamino, (C1-Cs)alkyloxycarbonyl, (Ci-Cs)alkylaminocarbonyl, (Ci-Cs)alkylcarbonylamino, (Ci-Cs)alkylcarbonyloxy, (Ci-Cs)alkylthio, (C2-Cs)alkenyl, a group of formula (C1-Cs)alkyl-O-(Ci-C6)alkyl, a radical of formula (Ci-C6)alkyl-S-(Ci-Cs)alkyl, a group of formula (Ci-C6)alkyl-NRi3-(Ci-Cs)alkyl wherein R13 is hydrogen or (Ci-Cs)alkyl, a group of formula (Ci-C6)alkyl-CONRi3-(Ci-Cs)alkyl wherein R13 is hydrogen or (Ci-Cs)alkyl, a group of formula (Ci-C6)alkyl-NRi3CO-(Ci-Cs)alkyl wherein R13 is hydrogen or (Ci-Cs)alkyl, a group of formula (Ci-C6)alkyl-OCO-(Ci-Cs)alkyl, a group of formula (Ci-C6)alkyl-COO-(Ci-Cs)alkyl, a group of formula (Ci-Cs)alkyl-(0-(Ci-Cs)alkyl)x-0 wherein x is an integer of from 1 to 10, a group of formula G, a group of formula (Ci-Cs)alkyl-G, a group of formula (Ci-C6)alkyl-G-(Ci-C6)alkyl, wherein G is a ring system comprising from 1 to 3 rings, each ring being saturated, unsaturated or aromatic, said rings being isolated, bridged or fused and comprising from 3 to 8 members selected from the group consisting of O, C, CH, CH2, N, NH, S, C=O, S=O and -SO2-, the members of the rings being optionally substituted where chemically possible with one or more groups selected from halo, (Ci-Ce)alkyl, (Ci-Ce)haloalkyl, (Ci-Ce)alkyloxy, (C1-Ce)alkylamino, (Ci-C6)alkyloxycarbonyl, (Ci-C6)alkylaminocarbonyl, cyano and nitro;or, alternatively,48when the dashed bond represents the presence of a covalent bond; L is a triradical deriving from the abstraction of three hydrogen atoms from each X2 group in a compound comprising three groups of formula -(X1-X2), being each one of said group of formula -(X1-X2) attached to a carbon atom comprised in a triradical of formula G’, whereinG’ is a triradical deriving from the abstraction of two hydrogen atoms from a group selected from (Ci-Ci2)alkyl, N[(Ci-Ci2)alkyl]3, (C2-Ce)alkenyl, a group of formula (Ci-C6)alkyl-O-(Ci-C6)alkyl, a radical of formula (Ci-Ce)alkyl-S-(Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-NRio-(Ci-C6)alkyl wherein R10 is hydrogen or (Ci-C6)alkyl, a group of formula (Ci-C6)alkyl-CONRi3-(Ci-C6)alkyl wherein R13 is hydrogen or (Ci-C6)alkyl, a group of formula (Ci-Ce)alkyl-NRi3CO-(Ci-C6)alkyl wherein R13 is hydrogen or (Ci-C6)alkyl, a group of formula (C1-C6)alkyl-OCO-(Ci-C6)alkyl, a group of formula (Ci-C6)alkyl-COO-(Ci-C6)alkyl, a group of formula (Ci-C6)alkyl-(O-(Ci-C6)alkyl)x- wherein x is an integer of from 1 to 10 and a ring system comprising from 1 to 3 rings, each ring being saturated, unsaturated or aromatic, said rings being isolated, bridged or fused and comprising from 3 to 8 members selected from the group consisting of O, C, CH, CH2, N, NH, S, C=O, S=O and -SO2-, the members of the rings being optionally substituted where chemically possible with one or more groups selected from halo, (Ci-Ce)alkyl, (Ci-Ce)haloalkyl, (Ci-Ce)alkyloxy, (Ci-Ce)alkylamino, (C1-C6)alkyloxycarbonyl, (Ci-C6)alkylaminocarbonyl, cyano and nitro;Xi is selected from the group consisting of a covalent bond, -O-, -S-, -COO-, -OCO-, -SO-, -SO2-, -SO2NH-, -NHCO- and -CONH-; andX2 is selected from the group consisting of (Ci-Ci2)alkyl, (C2-Ce)alkenyl, a group of formula (Ci-C6)alkyl-O-(Ci-Ce)alkyl, a radical of formula (Ci-Ce)alkyl-S-(Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-NRi3-(Ci-C6)alkyl wherein R13 is hydrogen or (Ci-Ce)alkyl, a group of formula (Ci-C6)alkyl-CONRi3-(Ci-C6)alkyl wherein R13 is hydrogen or (Ci-Ce)alkyl, a group of formula (Ci-Ce)alkyl-NRi3CO-(Ci-Ce)alkyl wherein R13 is hydrogen or (Ci-Ce)alkyl, a group of formula (C1-C6)alkyl-OCO-(Ci-C6)alkyl, a group of formula (Ci-C6)alkyl-COO-(Ci-C6)alkyl, a group of formula (Ci-C6)alkyl-(O-(Ci-C6)alkyl)x- wherein x is an integer of from 1 to 10;preferably, the compound of formula (V) is a compound of formula (Va)49(Va)wherein each one of R4, Rs, Re, R7, Rs, R9, R10, R11 and R12 is independently selected from the group consisting of hydrogen, halo, and (Ci-Cs)alkyl, and Li is a triradical deriving from the abstraction of three hydrogen atoms from each X2 group in a compound of formula G’-(XI-X2)3, wherein each group of formula -(X1-X2) is attached to the same carbon atom of the group G’, and wherein G’ is a radical selected from the group consisting of (Ci-Ci2)alkyl, N[(Ci-Ci2)alkyl]3, (C2-Cs)alkenyl, a group of formula (Ci-C6)alkyl-O-(Ci-C6)alkyl, and a group of formula (Ci-C6)alkyl-(O-(Ci-C6)alkyl)x- wherein x is an integer of from 1 to 10;Xi is selected from the group consisting of a covalent bond, -O-, -S-, -COO-, -OCO-, -SO-, -SO2-, -SO2NH-, -NHCO- and -CONH-; andX2 is selected from the group consisting of (Ci-Ci2)alkyl, (C2-Cs)alkenyl, a group of formula (Ci-C6)alkyl-O-(Ci-Cs)alkyl and a group of formula (Ci-Cs)alkyl-(O-(Ci-Cs)alkyl)x- wherein x is an integer of from 1 to 10;more preferably, the compound of formula (V) is a compound of formula (Vb)and a polyamine having an Amine Hydrogen Equivalent Weight of between 5 grams per equivalent and 120 grams per equivalent; more preferably, said polyamine has an Amine Hydrogen Equivalent Weight of between 10 grams per50equivalent and 60 grams per equivalent; even more preferably, said polyamine is selected from the group consisting of tris(2-aminoethyl)amine, xylylenediamine, furfuryldiamine, cyclohexane-1,3-diyldimethanamine, N,N-bis(2-aminoethyl)ethane-1,2-diamine , and 4,4'-diaminodicyclohexylmethane; and (ii-5) a compound comprising in its molecular formula a plurality of moieties of formula (IV) that is selected from the group consisting of aromatic anhydrides, such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, or hexafluoroisopropylidene diphthalic anhydride, and aliphatic anhydrides, such as succinic anhydride and glutaric anhydride, and a polyamine having an Amine Hydrogen Equivalent Weight of between 5 grams per equivalent and 120 grams per equivalent; more preferably, said polyamine has an Amine Hydrogen Equivalent Weight of between 10 grams per equivalent and 60 grams per equivalent; even more preferably, said polyamine is selected from the group consisting of tris(2-aminoethyl)amine, xylylenediamine, furfuryldiamine, cyclohexane-1,3-diyldimethanamine, N,N-bis(2-aminoethyl)ethane-1,2-diamine , and 4,4'-diaminodicyclohexylmethane;(ii-5) a polyepoxide having an Epoxide Equivalent Weight of between 60 grams per equivalent and 1000 grams per equivalent; preferably having an Epoxide Equivalent Weight of between 100 grams per equivalent and 300 grams per equivalent; more preferably, the polyepoxide is selected from the group consisting of trimethylolpropane triglycidyl ether, glycerol epoxide, diglycidyl ether of bisphenol, hydrogenated diglycidyl ether of bisphenol a, polyglycerol epoxide and sorbitol epoxide; and a polythiol having a sulfhydryl equivalent weight (SHEW) of from about 20 g / eq to about 1000 g / eq.; preferably of from about 50 g / eq to about 200 g / eq; even more preferably, said polythiol is selected from the group consisting ofpentaerythritol tetrakis(3-mercaptopropionate) (PETMP), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate) (DPETMP), trimethylolpropane tris(3-mercaptopropionate) (TMP-3MP), trimethylolpropane tris(3-mercaptobutyrate), polyethylene glycol di (mercaptoacetate), polypropylene glycol di(mercaptoacetate), thiol-terminated polyether dithiols, urethane-linked polythiols derived from diisocyanates and hydroxy-functional thiols, thiol-terminated urethane prepolymers, glycerol tris(mercaptopropionate), neopentyl glycol bis(mercaptopropionate) (NPG-diMP), thiol-terminated hyperbranched polymers, thiol-ether-modified polythiols, and blocked or protected thiols capable of deblocking under cure conditions; and(ii-6) a polyepoxide having an Epoxide Equivalent Weight of between 60 grams per equivalent and 1000 grams per equivalent; preferably having an Epoxide51Equivalent Weight of between 100 grams per equivalent and 300 grams per equivalent; more preferably, the polyepoxide is selected from the group consisting of trimethylolpropane triglycidyl ether, glycerol epoxide, diglycidyl ether of bisphenol, hydrogenated diglycidyl ether of bisphenol a, polyglycerol epoxide and sorbitol epoxide; a carboxylic acid anhydride selected from the group consisting of phthalic anhydride, trimellitic anhydride (TMA), tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA), nadic methyl anhydride (NMA), methyl tetrahydrophthalic anhydride (MTHPA), methylnadic anhydride (MNA), maleic anhydride, pyromellitic dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), succinic anhydride, glutaric anhydride, adipic anhydride, dodecenyl succinic anhydride (DDSA), octenyl succinic anhydride (OSA), cyclopentadiene-based anhydrides (incluyendo versiones hidrogenadas de anhidridos tipo nadic), alkenyl succinic anhydrides (ASA), polymaleic anhydride, polycycloaliphatic anhydrides derivados de acidos dicarboxilicos hidrogenados, polyester-anhydride adducts, anhydride-terminated oligomers (incluyendo maleated polybutadiene y maleated polyesters), itaconic anhydride, citraconic anhydride, camphoric anhydride, isobornyl succinic anhydride (IBSA), bio-derived alkenyl succinic anhydrides; and a polymerization initiator.

8. The composition according to any one of claims 4 to 7 which further comprises an additive that is an organic or inorganic filler, such as a (nano)clays, hydrotalcite, graphene, carbon nanotube, and nanofibers, organic / inorganic particles, iron oxide, silica, wood flour, (nano)cellulose, (nano)chitin, chitosan, fluorescent nano / microparticles.

9. The composition according to any one of claims 4 to 8 which, when the polymerizable composition comprises a polyamine and a compound comprising in its molecular formula at least one moiety, preferably a plurality of moieties, of formula (III), further comprises a cross-linking agent that preferably comprises in its molecular formula one or more moieties of formula -O-CH=CH2 or of formula A or of formula -CHO.

10. The composition according to any one of claims 4 to 9 wherein the compound A1 represents from 0.1% in weight to 25% in weight of the composition; preferably from 0.5% in weight to 5% in weight of the composition.

11. The composition according to any one of claims 4 to 10 wherein:52(i) the compound A2 and the polyamine of the polymerizable mixture are the same; and / or(ii) - when the polymerizable mixture comprises, such as consists essentially of, a polyepoxide and a polyamine, the polymerizable mixture comprises a number of epoxide groups that is from 0.5 to 1.5 times the number of amine groups; preferably from 0.8 to 1.2 times the number of amine groups; more preferably, the number of epoxide groups is substantially the same as the number of amine groups; or, alternatively,- when the polymerizable mixture comprises, such as consists essentially of, a polycarboxylic acid chloride and a polyamine, the polymerizable mixture comprises a number of groups of formula -COCI that is from 0.5 to 1.5 times the number of amine groups; preferably from 0.8 to 1.2 times the number of amine groups; more preferably, the number of groups of formula -COCI is substantially the same as the number of amine groups; or, alternatively,- when the polymerizable mixture comprises, such as consists essentially of a polyisocyanate and a polyamine, the polymerizable mixture comprises a number of groups of formula -NCO that is from 0.5 to 1.5 times the number of amine groups; preferably from 0.8 to 1.2 times the number of amine groups; more preferably, the number of groups of formula -NCO is substantially the same as the number of amine groups; or, alternatively,- when the polymerizable mixture comprises, such as consists essentially of a compound comprising in its molecular formula at least one moiety of formula (III) and a polyamine, the polymerizable mixture comprises a number of moieties of formula (III) that is from 0.8 to 2 times the number of amine groups; preferably from 1 to 1.5 times the number of amine groups; or, alternatively,- when the polymerizable mixture comprises, such as consists essentially of a compound comprising in its molecular formula at least one moiety of formula (IV) and a polyamine, the polymerizable mixture comprises a number of moieties of formula (IV) that is from 0.5 to 1.5 times the number of amine groups; preferably from 0.8 to 1.2 times the number of amine groups; more preferably, the number of groups of moieties of formula (IV) is substantially the same as the number of amine groups.

12. A kit for forming a polymer foam comprising a plurality of parts comprising a composition according to any one of claims 4 to 11 wherein the compound A1 is provided in a different part than the compound A2.

13. The kit of parts according to claim 12 wherein the polyamine or polyol of the polymerizable mixture is provided in a different part than the polyepoxide, the polycarboxylic acid chloride, the polyisocyanate, the compound comprising in its molecular formula at least one moiety of formula (III) and / or the compound comprising in its molecular formula at least one moiety of formula (IV).

14. A process for the preparation of a polymer foam comprising the steps of:(i) providing a source of carbon dioxide comprising a compound A1 and a compound A2; (ii) providing a polymerizable composition;(iii) causing the polymerizable composition to polymerize and the compound A2 to react with the compound A1 concomitantly;wherein the compounds A1, A2, the polymerizable composition and the relative amounts thereof are as defined in any one of claims 4 to 11.

15. A polymer foam obtainable by the process of claim 14.

Images