Method for producing polyurethanes without isocyanate

Abstract

The present invention concerns a method for producing a polyurethane without isocyanate. The invention also relates to the polyurethane obtained by such a method, and to the uses thereof, in particular as a coating, adhesive, mastic or foam. The invention also relates to a kit for carrying out said method.

Description

[0001] Process for preparing isocyanate-free polyurethanes TECHNICAL FIELD The present invention relates to a process for preparing an isocyanate-free polyurethane. It also relates to the polyurethane obtained by such a process, and its uses, in particular as a coating, adhesive, sealant, or foam. It further relates to a kit for implementing such a process. TECHNOLOGICAL BACKGROUND 10 Global consumption of polyurethanes has continued to increase in recent years. Given the strength and versatility of these polymers, they offer a greater number of applications than other products on the market. They are found, for example, in the form of flexible foams, in car seats, in the form of rigid foams, in ship hulls, or in the form of textile fibers, commonly called elastane fibers.More specifically, in the construction industry, polyurethanes are used as coatings, particularly to ensure the waterproofing of roofs, facades or balconies, as adhesives, or even as sealants. Polyurethane is typically a two-component system, obtained by the reaction of a polyisocyanate and a polyol. However, polyisocyanates are toxic molecules, which can cause asthma and dermatitis in the long term. Legislation is becoming increasingly strict regarding the use of these monomers, and in particular diisocyanates. The development of alternative processes for manufacturing polyurethanes, without using polyisocyanates, has therefore been an important subject of research in the field of polymers over the last twenty years.25 In particular, the reaction of a polycyclocarbonate and a polyamine has been studied, with the aim of obtaining polyhydroxyurethanes, which have a polyurethane structure and contain additional hydroxyl groups. However, the major problem with this system is its slow reactivity, which is significantly lower than the system involving a polyisocyanate and a polyol. In order to improve the performance of the reaction, and in particular to achieve high conversions, 30 the use of a catalyst and / or the use of heating is necessary. For example, Panchireddy et al. (Polymer Chemistry, 2018, 9, 2650-2659) describe adhesives based on polyhydroxyurethanes, prepared by mixing a diamine and soybean oil functionalized with cyclocarbonates, at 50°C, 70°C and then 100°C over several hours. The poor adhesion performance obtained at 25°C demonstrates the low reactivity of the system at this temperature.WO2013 / 060950 describes a process for preparing polyhydroxyurethanes by mixing a polycyclocarbonate with an amine, in the presence of an organometallic catalyst and a co-catalyst selected from Lewis bases or tetraalkyl ammonium salts. The reaction is carried out at room temperature, and a heating step at 100°C may optionally be carried out to complete the polymerization. In addition to a catalyst and / or heating, the synthesis of polyhydroxyurethanes is generally carried out in a solvent, in order to facilitate interactions between the monomers, which can be viscous. However, for many applications, in particular the building applications mentioned above, a practical and efficient system that can be carried out under "green" and mild conditions, in particular in the absence of catalyst and solvent, and at room temperature is required.Thus, there remains a need to provide a process for preparing isocyanate-free polyurethanes, achieving high conversion rates and / or low soluble rates, and capable of being implemented under "green" and mild conditions, in particular in the absence of catalyst and solvent, and at room temperature. SUMMARY OF THE INVENTION 20 In this context, the inventors have demonstrated that polycyclocarbonates having cyclocarbonates activated by a heteroatomic group, such as an oxygen (-O-), could be implemented in polymerization reactions with polyamines, in the absence of a catalyst and at room temperature. The inventors have also shown that it is possible to do without the solvent, which makes it possible to significantly limit the emissions of volatile organic compounds (VOCs).25 High conversion rates, generally greater than 85%, or even greater than 90%, have been obtained for polymerization reactions involving bi-functional monomers, and low soluble rates, generally less than 30%, or even less than 15%, have been obtained for reactions involving at least one tri- or tetra-functional monomer, in advantageously short times, typically of the order of a few minutes or a few hours.30 Thus, the present invention relates to a process for preparing an isocyanate-free polyurethane, comprising a step of bringing into contact at least one polycyclocarbonate and at least one polyamine comprising at least two -NH2 groups, in which each cyclocarbonate group of said at least one polycyclocarbonate is separated from a heteroatom by at most 2 carbon atoms, the contacting step being carried out at a temperature of between 5°C and 35°C, in the absence of a reaction catalyst between an amine function and a carbonate group, and in the absence of an organic solvent. 5 In certain embodiments, the average functionality of the mixture formed by said at least one polycyclocarbonate and said at least one polyamine is greater than 2.In some embodiments, the cyclocarbonate groups of said at least one polycyclocarbonate are linked together by an aliphatic chain comprising each heteroatom from which each cyclocarbonate group is separated by at most 2 carbon atoms, and optionally comprising one or more additional heteroatoms and / or one or more substituents. In some embodiments, the -NH2 groups of said at least one polyamine are linked together by an aliphatic chain optionally comprising one or more heteroatoms, preferably at least one oxygen. In some embodiments, each cyclocarbonate group of said at least one polycyclocarbonate is a 5- or 6-membered ring, preferably a 5-membered ring. In some embodiments, said at least one polycyclocarbonate has a cyclocarbonate equivalent weight of less than 500 g / eq, preferably less than 400 g / eq, more preferably less than 300 g / eq.In some embodiments, each cyclocarbonate group of said at least one polycyclocarbonate is separated from a heteroatom by 0 or 1 carbon atom. In some embodiments, each heteroatom from which each cyclocarbonate group is separated by at most 2 carbon atoms is selected from oxygen, nitrogen and sulfur. In some embodiments, said at least one polycyclocarbonate is: - of formula (I): [Chem 1] wherein: each X1 is an optionally substituted cyclocarbonate, each L1 is a single bond or a chain comprising at most 2 carbon atoms, each Het is a heteroatom, and L2 is a linker arm; or - of formula (II): [Chem 2]. wherein: n is 0 or 1, R1 is hydrogen or an optionally substituted hydrocarbon group, each X1 is an optionally substituted cyclocarbonate, each L1 is a single bond or a chain comprising at most 2 carbon atoms, each Het is a heteroatom, and each L2 is a linker arm. In certain embodiments, said at least one polycyclocarbonate is selected from the following compounds: [Chem 3] 20 [Chem 4]

[0002] In some embodiments, said at least one polyamine has an amine equivalent weight of less than 300 g / eq, preferably less than 200 g / eq. 5 In some embodiments, said at least one polyamine is selected from the group consisting of ethylene diamine, 1,5-pentanediamine, tetraethylene pentamine, 1,8-diamino-3,6-dioxaoctane, 1,13-diamino-4,7,10-trioxatridecane, 4,9-dioxa-1,12-dodecanediamine, isophorone diamine, and m-xylylene diamine, preferably 1,13-diamino-4,7,10-trioxatridecane. 10 In some embodiments, the molar ratio of cyclocarbonate groups of the polycyclocarbonate to -NH2 groups of the polyamine is between 0.5:1 and 3:1, preferably between 0.8:1 and 1.2:1. 15 In some embodiments, the contacting step is carried out at a temperature between 15°C and 30°C. Preferably, the method according to the invention is carried out in the absence of polythiol.Preferably, the method according to the invention is carried out in the absence of polyol, acrylate, methacrylate, and epoxy. The present invention also relates to a polyurethane obtained by a method as defined in the present application. The present invention also relates to a coating, adhesive or sealant comprising such a polyurethane, and optionally one or more additives and / or fillers. Another object of the present invention is a use of such a polyurethane as a coating, adhesive, sealant, or foam.Another subject of the present invention is a kit for implementing a method as defined in the present application, comprising: - a first component comprising at least one polycyclocarbonate, wherein each cyclocarbonate group of said at least one polycyclocarbonate is separated from a heteroatom by at most 2 carbon atoms, and - a second component comprising at least one polyamine comprising at least two -NH2 groups, wherein - neither of the first component nor of the second component comprises a reaction catalyst between an amine function and a carbonate group, nor an organic solvent, and - the first component and the second component being in separate compartments. In some embodiments, at least one of the first and second components further comprises at least one filler and / or at least one additive. In some embodiments, at least one of the first and second components further comprises at least one reactive diluent.DETAILED DESCRIPTION Definitions: The groups mentioned in the present application with a Cx-Cy prefix, where x and y are integers, have from x to y carbon atoms. If, for example, the term C1-C6 is used, this means that the corresponding group can comprise from 1 to 6 carbon atoms, in particular 1, 2, 3, 4, 5 or 6 carbon atoms. By "aliphatic" is meant a non-cyclic, saturated or unsaturated, linear or branched hydrocarbon group or chain. In a particular embodiment, an aliphatic chain is an alkyl chain. By "alkyl" is meant a saturated, linear or branched hydrocarbon group or chain. Examples of alkyl (or C1-C6 alkyl) are in particular methyl, ethyl, propyl, isopropyl, butyl, pentyl, or hexyl. By "carbocyclic" is meant a hydrocarbon group or chain, mono- or polycyclic, non-aromatic (i.e. saturated or unsaturated alicyclic) or aromatic.In a particular embodiment, a carbocyclic group is a cycloalkyl group or an aromatic group. By "cycloalkyl" is meant a saturated, mono- or polycyclic hydrocarbon group or chain. Examples of cycloalkyl (or C3-C. 12cycloalkyl) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, or cyclododecyl. "Oxo" means a group of formula =O. When bonded to a carbon atom, an oxo group forms a carbonyl with the latter. 5 "A chain (e.g., aliphatic or alkyl) comprising a heteroatom" means a chain (e.g., aliphatic or alkyl) interrupted by, or comprising at one or other of its ends, a heteroatom. An aliphatic chain comprising one or more heteroatoms may also be referred to as "heteroaliphatic." An alkyl chain comprising one or more heteroatoms may also be referred to as "heteroalkyl." 10 By “a chain (e.g. aliphatic or alkyl) comprising a carbocyclic group” is meant a chain (e.g. aliphatic or alkyl) interrupted by, or comprising at its ends, a carbocyclic group.In the present application, the expression "at least one" may be used equivalently to "one or more". In the present application, a range defined with the expression "between (X) and (Y)" includes the lower (X) and upper (Y) limits. The present invention relates to a process for forming polyurethanes, without the use of isocyanates (i.e. without mono- or polyisocyanate as monomers), which is simple and efficient, and which can be carried out under mild conditions. More particularly, the process involves one or more polycyclocarbonates and one or more polyamines. The expression "process for manufacturing an isocyanate-free polyurethane" means that said process uses monomers devoid of isocyanate functions, in particular does not use polyisocyanate, and furthermore that said monomers used in the process (i.e.25 polycyclocarbonate(s) and polyamine(s)) are themselves not obtained from isocyanates or polyisocyanates. Thus, the monomers used in the process (i.e. polycyclocarbonate(s) and polyamine(s)) do not comprise isocyanate functions (-NCO) and, preferably, do not comprise urethane functions (-NH-C(O)-O-). 30 Preferably, the process according to the invention does not use monomers other than the polycyclocarbonate(s) and the polyamine(s). In particular, it is preferable that the process does not use polythiol. By "polythiol" is meant a chemical compound comprising at least two thiol functions (-SH). 35 In particular, it is preferable that the process does not use polyol. By "polyol" is meant a chemical compound comprising at least two hydroxyl functions (-OH). In particular, it is preferable that the process does not use acrylate or methacrylate.In particular, it is preferable that the method does not use epoxide. 5 By "acrylate" is meant any organic compound comprising one or more acrylate groups. By "methacrylate" is meant any organic compound comprising one or more methacrylate groups. By "epoxide" is meant any organic compound comprising one or more epoxide groups. 10 By "polycyclocarbonate" is meant a chemical compound comprising at least two cyclocarbonate groups, for example two, three or four cyclocarbonate groups. The cyclocarbonates of a polycyclocarbonate may be the same or different from each other, preferably they are identical. A cyclocarbonate group (or equivalently "cyclic carbonate") is a cyclic hydrocarbon chain comprising a carbonate unit -OC(O)-O- within its ring.Each cyclocarbonate group of a polycyclocarbonate used in the process of the invention may in particular be a 5-, 6-, 7- or 8-membered ring, preferably 5- or 6-membered, better still 5-membered. Each cyclocarbonate group may optionally be substituted by one or more (in particular, a single) substituents. An example of substituents is in particular a C1-C6alkyl group. In a particular embodiment, the cyclocarbonate group is a 5-membered ring. More particularly, the cyclocarbonate group is a 1,3-dioxolan-2-onyl group, which may be represented as follows: [Chem 5]. In another particular embodiment, the cyclocarbonate group is a 6-membered ring. More particularly, the cyclocarbonate group is a 1,3-dioxan-2-onyl group, which can be represented as follows: [Chem 6] Each cyclocarbonate group of said at least one polycyclocarbonate used in the method of the invention is separated from a heteroatom by at most 2 carbon atoms (or equivalently “linked to a heteroatom via at most 2 carbon atoms”), i.e. 0, 1 or 2 carbon atoms. Preferably, each cyclocarbonate group is separated from a heteroatom by 0 or 1 carbon atoms. It is understood that a cyclocarbonate group separated from a heteroatom by 0 carbon atoms (or “linked to a heteroatom via 0 carbon atoms”) is in fact directly linked to the heteroatom, via a covalent bond (typically a single bond). It is also understood that the heteroatom is distinct from the cyclocarbonate, i.e. the heteroatom is not included in the structure of the cyclocarbonate.The heteroatom may be adjacent to another chemical group (such as a carbonyl), and thus form with the latter a chemical function (such as an ester, an amide, or a thioester). Preferably, the heteroatom is an oxygen, a nitrogen or a sulfur, more preferably an oxygen. In a particular embodiment, the heteroatom is an oxygen and is adjacent to a carbonyl, thus forming an ester function (-C(O)-O- or -OC(O)-). The cyclocarbonate groups of said at least one polycyclocarbonate may be linked together by any type of hydrocarbon chain. This hydrocarbon chain may for example be an aliphatic chain (e.g. an alkyl chain), a carbocyclic chain (e.g. a cycloalkyl or aromatic chain), or a combination thereof, and may comprise one or more heteroatoms (e.g. O, N, S) and / or one or more substituents (e.g., an oxo group).Preferably, each heteroatom linked to a cyclocarbonate via at most 2 carbon atoms is included in this hydrocarbon chain. It is understood that, in this case, said at most 2 carbon atoms are part of the hydrocarbon chain. 25 For example, in the compound represented below, the two cyclocarbonates X1 are each linked to a heteroatom -O- via 2 carbon atoms, and are linked together by an alkyl chain with 10 carbon atoms comprising two additional heteroatoms -S-: X1-CH2-CH2-O-CH2-CH2-S-CH2-CH2-S-CH2-CH2-O-CH2-CH2-X1. 30 In a particular embodiment, the cyclocarbonate groups of said at least one polycyclocarbonate are linked together by an aliphatic chain, preferably comprising each heteroatom from which each cyclocarbonate group is separated by at most 2 carbon atoms (preferably 0 or 1 carbon atom).In this embodiment, the aliphatic chain may further comprise one or more additional heteroatoms (e.g., one or more sulfur or oxygen atoms) and / or one or more substituents (e.g., one or more oxo groups). In this embodiment, the aliphatic chain may, for example, comprise from 4 to 50 carbon atoms, or even from 10 to 40 carbon atoms. In a more particular embodiment, the cyclocarbonate groups of said at least one polycyclocarbonate are linked together by an alkyl chain, preferably comprising each heteroatom from which each cyclocarbonate group is separated by at most 2 carbon atoms (preferably 0 or 1 carbon atom). In this embodiment, the alkyl chain may further comprise one or more additional heteroatoms (e.g., one or more sulfur or oxygen atoms) and / or one or more substituents (e.g., one or more oxo groups).In this embodiment, the alkyl chain may for example comprise from 4 to 50 carbon atoms, or even from 10 to 40 carbon atoms. In another particular embodiment, the cyclocarbonate groups of said at least one polycyclocarbonate are linked together by an aliphatic chain comprising at least one carbocyclic group (e.g. a C3-C12 cycloalkyl or a phenyl), and preferably comprising each heteroatom from which each cyclocarbonate group is separated by at most 2 carbon atoms (preferably 0 or 1 carbon atom). In this embodiment, the aliphatic chain may further comprise one or more additional heteroatoms (e.g. one or more sulfur or oxygen atoms) and / or one or more substituents (e.g. one or more oxo groups).In certain particular embodiments, said at least one polycyclocarbonate is represented by the following formula (I): [Chem 7] 25 in which: each X1 is an optionally substituted cyclocarbonate, each L1 is a single bond or a chain comprising at most 2 carbon atoms, each Het is a heteroatom, and 30 L2 is a linker arm. In certain particular embodiments, said at least one polycyclocarbonate is represented by the following formula (II): [Chem 8] in which: n is 0 or 1, 5 R1 is a hydrogen or an optionally substituted hydrocarbon group, each X1 is an optionally substituted cyclocarbonate, each L1 is a single bond or a chain comprising at most 2 carbon atoms, each Het is a heteroatom, and each L2 is a linker arm. 10 In formulas (I) and (II), each X1 preferably represents a 5- or 6-membered cyclocarbonate, optionally substituted by a C1-C6alkyl (such as a methyl or ethyl group).In a particular mode, each X1 is chosen from: [Chem 9]. 15 Preferably, the X1s within a polycyclocarbonate of formula (I) or (II) are identical. In formulas (I) and (II), each L1 is preferably chosen from a single bond, -CH2, -C(O)-, 20 and -CH2-CH2-, better -CH2- or -C(O)-. Preferably, the L1s within a polycyclocarbonate of formula (I) or (II) are identical. In formulas (I) and (II), each Het is preferably -O-, -NH-, or -S-, better -O-. Preferably, the Hets within a polycyclocarbonate of formula (I) or (II) are identical. 25 In formulas (I) and (II), the linker arms L2 may in particular be any type of hydrocarbon chain. L2 may for example comprise from 2 to 30 carbon atoms, or even from 4 to 20 carbon atoms.L2 may more particularly be an aliphatic chain, which may comprise: - one or more carbocyclic groups, - one or more heteroatoms (for example, one or more sulfur, nitrogen or oxygen atoms), and / or - one or more substituents (for example, one or more oxo groups). 5 Preferably, L2 is an alkyl chain, which may comprise one or more heteroatoms (preferably chosen from sulfur, nitrogen and oxygen) and / or one or more substituents (preferably, one or more oxo groups). More preferably, L2 is a C4-C20 alkyl chain, optionally comprising 2 to 6 heteroatoms each chosen from sulfur, nitrogen and oxygen, and optionally 1 to 4 oxo substituents. In formula (II), the 3 (if n = 1) or 4 (if n = 0) [L2-Het-L1-X1] fragments are preferably identical. 15 In a particular embodiment, R1 is C1-C6 alkyl, such as methyl or ethyl.Preferably, said at least one polycyclocarbonate has a cyclocarbonate equivalent weight of less than 1000 g / eq, or even less than 500 g / eq, preferably less than 400 g / eq, more preferably less than 300 g / eq. The cyclocarbonate equivalent weight of said at least one polycyclocarbonate is furthermore preferably greater than 100 g / eq, more preferably greater than 150 g / eq, better still greater than 200 g / eq. The term "cyclocarbonate equivalent weight" of a polycyclocarbonate means the molar mass of the polycyclocarbonate divided by the number of cyclocarbonate groups it comprises. In a particular embodiment, said at least one polycyclocarbonate is chosen from the following compounds: [Chem 10].

[0003] 5 In a more particular embodiment, said at least one polycyclocarbonate is chosen from the following compounds: 10 [Chem 12]

[0004] In some embodiments, said at least one polycyclocarbonate is a polycyclocarbonate comprising at least three cyclocarbonate groups (e.g., three or four cyclocarbonate groups), wherein each cyclocarbonate group is separated from a heteroatom by at most 2 carbon atoms. In some embodiments, said at least one polycyclocarbonate is a mixture of polycyclocarbonates (wherein each cyclocarbonate group of these polycyclocarbonates is separated from a heteroatom by at most 2 carbon atoms), wherein at least one of the polycyclocarbonates comprises at least three cyclocarbonate groups (e.g., three or four cyclocarbonate groups). More particularly, the method according to the invention can implement a polycyclocarbonate comprising three cyclocarbonate groups (wherein each cyclocarbonate group is separated from a heteroatom by at most 2 carbon atoms),and a polycyclocarbonate comprising four cyclocarbonate groups (wherein each cyclocarbonate group of said at least one polycyclocarbonate is separated from a heteroatom by at most 2 carbon atoms). 15 A polycyclocarbonate comprising three cyclocarbonate groups is in particular a compound of formula (II) as defined above, in which n is 1. A polycyclocarbonate comprising four cyclocarbonate groups is in particular a compound of formula (II) as defined above, in which n is 0. 20 The polyamine used in the process according to the invention comprises at least two -NH2 groups, for example two, three or four -NH2 groups. Preferably, the polyamine comprises two or three -NH2 groups. The polyamine may further optionally comprise one or more (for example, from 2 to 5) -NH- groups. 25 In a particular embodiment, the polyamine is chosen from aliphatic polyamines, cycloaliphatic polyamines,arylaliphatic polyamines, aromatic polyamines, heteroaliphatic polyamines (e.g., those containing at least one ether group), polyamidoamines, phenalkamines, fatty amines, adducts of these polyamines with epoxy resins, and a combination thereof. Aliphatic polyamines are in particular chosen from 2,2-dimethyl-1,3-propanediamine, 1,3-pentanediamine, 1,5-pentanediamine, 1,5-diamino-2-methylpentane, 2-butyl-2-ethyl-1,5-pentanediamine, 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2,4- and 2,4,4- trimethylhexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-10 nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 3-(2-aminoethyl)-aminopropylamine, bis-(hexamethylene)-triamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine,pentaethylenehexamine and other homologs of linear polyethylene amines having 5 or more ethylene amine units. Preferred examples of aliphatic polyamines include 2-methylpentane-1,5-diamine, 1,5-pentanediamine, 15-tetraethylene pentamine, 1,8-diamino-3,6-dioxaoctane and 1,13-diamino-4,7,10-trioxatridecane. The cycloaliphatic polyamines are in particular chosen from 1,2-, 1,3- and 1,4-diaminocyclohexane, bis-(4-aminocyclohexyl)-methane, bis-(4-amino-3-methylcyclohexyl)-methane, bis-(4-amino-3-ethylcyclohexyl)-methane, bis-(4-amino-3,5-dimethylcyclohexyl)-methane, bis-(4-amino-3-ethyl-5-methylcyclohexyl)-methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane(isophoronediamine), 2- and 4-methyl-1,3-diaminocyclohexane, 1,3- and 1,4-bis-(aminomethyl)-cyclohexane, 1,4-diamino-2,2,6-trimethylcyclohexane. Arylaliphatic polyamines include 1,3- and 1,4- bis-(aminomethyl)-benzene. Polyamines containing at least one ether group are known in particular under the trade name Jeffamine® (Huntsman) or Polyetheramine (BASF) or PC Amine® (Nitroil). In particular, polyalkylene diamines such as 4,9-Dioxa-1,12-dodecanediamine, 1,13-diamino-4,7,10-trioxatridecane (Ancamine 1922A), 1,11-Diamino-3,6,9-trioxaundecane, poly(propylene glycol) bis(2-aminopropyl ether) (Jeffamine D-230®, Jeffamine® D-400, Jeffamine® D-2000), 2-aminoethyl ether (Jeffamine® EDR-104), 2,2′-(Ethylenedioxy)bis(ethylamine) (Jeffamine® EDR-148) and Ethylene Glycol Bis(3-aminopropyl) Ether (Jeffamine® EDR-176) and the corresponding polyamines from BASF and Nitroil, as well as polyalkylene triamines such as Trimethylolpropane tris[poly(propylene glycol), amine terminated] ether (Jeffamine® T403, Jeffamine® T-3000,Jeffamine® T-5000) and the corresponding polyamines from BASF and Nitroil. The aromatic polyamines are in particular chosen from m-phenylenediamine, p-phenylenediamine, 4,4', 2,4' and 2,2'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,4- and 2,6-toluenediamine, mixtures of 3,5-dimethylthio-2,4- and 2,6-toluylenediamine (marketed under the reference Ethacure® 300 by the company Albemarle), mixtures of 3,5-diethyl-2,4- and -2,6-toluylenediamine, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-2,2'-dichloro-4,4'-diaminodiphenylmethane, 3,3'- diisopropyl 5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraisopropyl-4,4'- diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4-amino-N-(4-aminophenyl)-benzenesulfonamide, 5,5'-methylenedianthranilic acid, dimethyl-(5,5'-10 methylenedianthranilate), 1,3-propylene-bis-(4-aminobenzoate), 1,4-butylene-bis-(4-aminobenzoate),polytetramethyleneoxide-bis-(4-aminobenzoate) (marketed under the reference Versalink® by the company Evonik), 1,2-bis (2-aminophenylthio)-ethane, 2-methylpropyl-(4-chloro-3,5-diaminobenzoate) and tert-butyl-(4-chloro-3,5-diaminobenzoate). The polyamidoamines are preferably reaction products of a monofunctional or polyfunctional carboxylic acid or their esters or anhydrides, in particular fatty acids, with an aliphatic, cycloaliphatic, arylaliphatic or aromatic polyamine (in particular a polyalkyleneamine such as diethylenetriamine or triethylenetetramine) used in stoichiometric excess. These products are in particular commercially available under the name polyamidoamines Versamid® 100, 125, 140 and 150 (Cognis), Aradur R 223, 250 and 848 (Huntsman), 20 Euretek® 3607 and 530 (from Huntsman) and Beckopox®, EH 651, EH 654, EH 655, EH 661 and EH 663 (Cytec). Phenalkamines, also known as Mannich bases,are the products of the reaction of phenol derivatives with aldehydes, in particular formaldehyde, and polyamines. Particular mention may be made of the Mannich bases commercially available under the name Cardolite® NC-541, NC-557, NC-558, NC-566, Lite 2001 and Lite 2002 (Cardolite), Aradur R. 3440, 3441, 3442 and 3460 (Huntsman) and Beckopox ®, EH 614, EH 621, EH 624, EH 628 and EH 629 (Cytec). The fatty amines are preferably N-cocoalkyl-1,3-propanediamine and the products of a Michael-type reaction of primary amines with acrylonitrile, maleic, fumaric, citraconic diesters, acrylic and methacrylic esters, acrylic and methacrylic amides and itaconic diesters, reacted with a molar ratio of 1:1. 30 Adducts of the above-mentioned polyamines with epoxy resins are in particular the adducts with diepoxides in a molar ratio of about 2:1,adducts with monoepoxides with a molar ratio of at least 1 / 1 and reaction products of polyamines with epichlorohydrin known for example as Gaskamine® 328 (MGC). In some embodiments, the polyamine is an aliphatic polyamine (preferably alkyl chain). In this embodiment, the -NH2 groups of the polyamine are typically linked together by an aliphatic chain (preferably alkyl chain). In some embodiments, the polyamine is a heteroaliphatic polyamine (preferably heteroalkyl chain). In this embodiment, the -NH2 groups of the polyamine are typically linked together by a heteroaliphatic chain (preferably heteroalkyl chain). In some embodiments, the polyamine comprises two or three NH2 groups, and the -NH2 groups are linked together by an aliphatic chain (preferably alkyl chain). In some embodiments, the polyamine comprises two or three NH2 groups,and the -NH2 groups are linked together by a heteroaliphatic chain (preferably heteroalkyl chain). A preferred polyamine is a polyethereal polyamine, in particular a polyethereal diamine (or "polyetherdiamine"). The polyethereal polyamine is a typically aliphatic polyamine comprising several ether functions (-O-). For example, the polyethereal polyamine may be 2-aminoethyl ether, 4,9-dioxa-1,12-dodecanediamine, 1,13-diamino-4,7,10-trioxatridecane or 1,8-diamino-3,6-dioxaoctane, ethylene glycol bis(3-aminopropyl) ether, 2,2′-(ethylenedioxy)bis(ethylamine), poly(propylene glycol) bis(2-aminopropyl ether) (Jeffamine D-203), 1,11-Diamino-3,6,9-trioxaundecane. In another particular embodiment, the -NH2 groups of said at least one polyamine are linked together by an aliphatic chain comprising at least one carbocyclic group (for example, a C3-C12 cycloalkyl group or a phenyl). In this embodiment,the aliphatic chain may further comprise one or more additional heteroatoms (for example, one or more nitrogen, sulfur or oxygen atoms) and / or one or more substituents. Examples of such polyamines include isophorone diamine, or m-xylylene diamine. Mention may also be made of priamine 1075. Preferably, said at least one polyamine has an amine equivalent weight of less than 300 g / eq, preferably less than 200 g / eq. The amine equivalent weight of said at least one polyamine is typically greater than 15 g / eq (for example, greater than 25 g / eq, or even greater than 30 g / eq, or even greater than 40 g / eq). The term "amine equivalent weight" of a polyamine means the molar mass of the polyamine divided by the number of -NH2 groups it comprises. For example, the amine equivalent weight of ethylene diamine (H2N-CH2-CH2-NH2) is 60 / 2 = 30 g / eq. In some embodiments,said at least one polyamine is a polyamine comprising at least three -NH2 groups (for example three or four -NH2 groups). In a particular embodiment, the cyclocarbonate groups of said at least one polycyclocarbonate are linked together by an aliphatic chain preferably comprising each heteroatom from which each cyclocarbonate group is separated by at most 2 carbon atoms, and optionally comprising one or more additional heteroatoms and / or one or more substituents, and the -NH2 groups of said at least one polyamine are linked together by an aliphatic chain, in which the aliphatic chain of said at least one polyamine preferably comprises at least one heteroatom, for example at least one oxygen. In another particular embodiment, the cyclocarbonate groups of said at least one polycyclocarbonate are linked together by an aliphatic chain comprising at least one carbocyclic (eg aromatic) group,said aliphatic chain preferably comprising each heteroatom from which each cyclocarbonate group is separated by at most 2 carbon atoms, and optionally comprising one or more additional heteroatoms and / or one or more substituents, and the -NH2 groups of said at least one polyamine are linked together by an aliphatic chain comprising at least one carbocyclic (e.g. aromatic) group. In a particular embodiment, the method of the invention uses at least one polycyclocarbonate having two cyclocarbonate groups and at least one polyamine having two -NH2 groups. In such an embodiment, it is preferred that: - the two cyclocarbonate groups are linked together by an alkyl chain, comprising each heteroatom from which each cyclocarbonate group is separated by at most 2 carbon atoms, and optionally one or more additional heteroatoms (for example, chosen from oxygen,nitrogen and sulfur) and / or one or more substituents (for example, one or more oxo groups), and - the two -NH2 groups are linked together by an alkyl chain, optionally comprising one or more heteroatoms (eg chosen from oxygen, nitrogen and sulfur). In this embodiment, the alkyl chain of the polyamine may further optionally comprise a carbocyclic group such as a C3-C12 cycloalkyl or a phenyl. A polycyclocarbonate comprising two cyclocarbonate groups is in particular a compound of formula (I) as defined above. In a more particular embodiment, the method of the invention uses one or more polycyclocarbonates and one or more polyamines comprising at least two -NH2 (for example two or three -NH2 groups), including at least one polycyclocarbonate comprising at least three cyclocarbonate groups, for example three or four cyclocarbonate groups. In a preferred embodiment,the method of the invention uses at least one polycyclocarbonate having three or four cyclocarbonate groups (for example, a mixture of a polycyclocarbonate having three cyclocarbonate groups and a polycyclocarbonate having four cyclocarbonate groups), and at least one polyamine having two -NH2 groups. In such an embodiment, it is preferred that: - the three or four cyclocarbonate groups are linked together by an alkyl chain, comprising each heteroatom from which each cyclocarbonate group is separated by at most 2 carbon atoms linked to a cyclocarbonate via at most 2 carbon atoms, and optionally one or more additional heteroatoms (for example, chosen from oxygen, nitrogen and sulfur) and / or one or more substituents (for example, one or more oxo groups), and - the two -NH2 groups are linked together by an alkyl chain, optionally comprising one or more heteroatoms (eg chosen from oxygen,nitrogen and sulfur). A polycyclocarbonate comprising three cyclocarbonate groups is in particular a compound of formula (II) as defined above, in which n is 1. A polycyclocarbonate comprising four cyclocarbonate groups is in particular a compound of formula (II) as defined above, in which n is 0. In a preferred embodiment, the process of the invention uses the following reagents: - one or more polycyclocarbonates chosen from: [Chem 13], and - a polyamine comprising two -NH2 groups, in which the two -NH2 groups are linked together by an alkyl chain, optionally comprising one or more heteroatoms (eg chosen from oxygen, nitrogen and sulfur, preferably one or more oxygens), preferably aminoethyl ether, 4,9-dioxa-1,12-dodecanediamine, 1,13-diamino-4,7,10-trioxatridecane, 1,8-diamino-3,6-dioxaoctane, ethylene glycol bis(3-aminopropyl) ether, 2,2′-(ethylenedioxy)bis(ethylamine), poly(propylene glycol) bis(2-aminopropyl ether) (Jeffamine D-203), 1,11-diamino-3,6,9- trioxaundecane, better still 1,13-diamino-4,7,10-trioxatridecane. In another preferred embodiment, the process of the invention uses the following reagents: 5 - one or more polycyclocarbonates chosen from: [Chem 14] - a polyamine comprising two -NH2 groups, in which the two -NH2 groups are linked together by an alkyl chain, optionally comprising one or more heteroatoms (e.g. chosen from oxygen, nitrogen and sulfur, preferably one or more nitrogens), preferably tetraethylenepentamine. In a particular embodiment, the average functionality of the mixture formed by said at least one polycyclocarbonate and said at least one polyamine is greater than 2, for example greater than or equal to 2.25, or greater than or equal to 2.5, or greater than or equal to 3. Preferably, the functionality is less than or equal to 5, or even less than or equal to 4. The average functionality of a mixture is defined by the following equation (1): [Math 1] 20 where xi is the number of initial moles for each monomer i participating in the polymerization and fi is its functionality. The functionality of a polycyclocarbonate is the number of cyclocarbonate functions it contains, and the functionality of a polyamine is the number of -NH2 functions it contains. For example, a mixture of one mole of a polyamine having two -NH2 groups (i.e. polyamine of functionality 2) and one mole of tricyclocarbonate (i.e. polycyclocarbonate of functionality 3) has an average functionality of 2.5. 5 In a particular embodiment, the molar ratio of cyclocarbonate groups to -NH2 groups is between 0.5:1 and 3:1, preferably between 0.5:1 and 2:1, or even between 0.8:1 and 1.2:1, more preferably between 0.9:1 and 1.1:1. In a particular embodiment, the initial content of said at least one polycyclocarbonate, in which each cyclocarbonate group is separated from a heteroatom by at most 2 carbon atoms,in the mixture formed in the contacting step, represents 5 to 90% by weight relative to the total weight of the mixture. In a particular embodiment, the initial content of said at least one polyamine comprising at least two -NH2, in the mixture formed in the contacting step, represents 5 to 90% by weight relative to the total weight of the mixture. The contacting step of the process of the invention is carried out at a temperature between 5°C and 35°C, preferably between 15°C and 30°C, better still between 20°C and 25°C. Preferably, the polycyclocarbonate(s) and the polyamine(s) are liquid at the contacting temperature. The contacting step of the process of the invention is preferably carried out in air. The relative humidity of the air is not limiting, and can be between 0.1 and 100%, for example between 20% and 70%,or even between 40 and 60%. The contacting step of the process of the invention is preferably carried out for a duration 25 (or equivalently “reaction time”) of between 10 seconds and 7 days, for example between 5 minutes and 48 hours, between 5 minutes and 1 hour, or between 10 minutes and 2 hours, or between 1 hour and 5 hours, or between 10 minutes and 12 hours, or between 6 hours and 36 hours, or between 1 hour and 48 hours. 30 When the average functionality of the mixture formed by said at least one polycyclocarbonate and said at least one polyamine is greater than 2, the gel point is advantageously reached in a time of between 5 minutes and 48 hours, between 5 minutes and 1 hour, or between 10 minutes and 2 hours, or between 1 hour and 5 hours, or between 10 minutes and 12 hours, or between 6 hours and 36 hours,or between 1 hour and 48 hours. The gel point is typically determined by rheology in oscillation mode at a frequency of 1 rad / s. The method according to the invention is carried out in the absence of a catalyst. The term "catalyst" means any chemical entity (or combination of chemical entities) which accelerates the reaction between a carbonate group and an amine function (e.g. primary or secondary amine function), more particularly between a cyclocarbonate group and an amine function, and in particular the polymerization reaction between a polycyclocarbonate and a polyamine. Examples of such catalysts include: - Lewis acids, in particular organometallic complexes or metal salts, in particular based on an alkali, alkaline-earth, or transition metal (in particular chosen from groups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIIA, VIIB and VIII of the periodic table),for example: - titanium-based such as tetrabutyl titanate or tetraisopropyl titanate, tin-based such as dibutyltin dilaurate, tin 2-ethylhexanoate, tin dioctoate, or monobutylstannic acid, zinc-based such as zinc acetate, antimony-based, magnesium-based such as magnesium bromide (MgBr2), calcium-based such as calcium carbonate, iron-based such as iron(III) triflate or iron(III) chloride, chromium-based such as tris(2,4-pentanedione)chromium(III), bismuth-based such as bismuth triflate, ytterbium-based such as ytterbium triflate, lithium-based such as lithium triflate, lithium tetrafluoroborate, lithium hexafluoroantimonate, lithium hexafluorophosphate, lithium chloride, or lithium acetate, or 20 - based on an alkali, alkaline earth, or transition metal and comprising beta-diketonate ligands; - modified clays,- Bronsted or Lewis bases, including: - aliphatic or alicyclic tertiary amines, such as triethylamine, tributylamine, 25 or 1,4-diazobicyclo-[2.2.2]-octane (DABCO), - amidines, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), - guanidines, such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5.7-triazabicyclo-[4.4.0]dec-5-ene (MTBD); - imidazolines, 30 - aromatic heterocyclic amines such as pyridine, 2-hydroxypyridine, 4-dimethylaminopyridine (DMAP), or N-methyl imidazole; - phosphines, in particular trialkylphosphines such as triethylphosphine or butylphosphine; triarylphosphines such as triphenylphosphine or tri(o-toly)phosphine; monoalkylbiarylphosphines such as methyldiphenylphosphine; - phosphites, in particular trialkylphosphites such as trimethylphosphite, triethylphosphite, triisopropylphosphite,tri-n-butylphosphite; or triarylphosphites such as triphenylphosphite. - quaternary ammonium salts: tetrabutylammonium bromide and 5-tetrabutylammonium chloride, betaine, tetraethylammonium hydroxide, tetraethylammonium tetrafluoroborate, tetramethylammonium bromide, - phosphazenes such as 2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro- 1,3,2-diazaphosphorine (BEMP), tert-Butylimino-tris(dimethylamino)phosphorane (P1-tBu), 1- tert-Butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ, 5 ,4λ 5-catenadiphosphazene (P2-tBu) 10 - ureas such as dicyclohexyl urea, diphenyl urea, cyclohexylphenyl urea, butylphenyl urea, cyclohexyl(3,5-bis(trifluoromethyl)phenyl) urea, butyl(3,5-bis(trifluoromethyl)phenyl) urea, phenyl(3,5-bis(trifluoromethyl)phenyl) urea, di(3,5-bis(trifluoromethyl)phenyl) urea, di(3-trifluoromethylphenyl) urea; - thioureas such as dicyclohexyl thiourea, diphenyl thiourea, cyclohexylphenyl thiourea, butylphenyl thiourea, cyclohexyl(3,5-bis(trifluoromethyl)phenyl) thiourea, butyl(3,5-bis(trifluoromethyl)phenyl) thiourea, phenyl(3,5-bis(trifluoromethyl)phenyl) thiourea, di(3,5-bis(trifluoromethyl)phenyl) thiourea, di(3-trifluoromethylphenyl) thiourea; - salts (egalkali, alkaline earth or ammonium salts) including hydroxide, methoxide, ethoxide, t-butoxide, trifluoroethoxide, benzyloxide, triphenylmethoxide anions, N,N-bis(trimethylsily)-amide anion, N-alkylamide anion, malononitrile, alkyl acetoacetate, methylene disulfone anion, diethyl malonate, N-methyl ethylcarbamatemethoxide, alkyl or aryl ketone anion, diphenylamine anion, amidoindole, benzimidazole, or squaramide, such as those described in application WO2020 / 141046, 25 or a combination thereof. The process according to the invention is also carried out in the absence of organic solvent, or even in the absence of any solvent. The term “solvent” means any chemical substance, liquid under the conditions of implementation of the process, distinct from the monomers (i.e.polycyclocarbonate(s) and polyamine(s)) and any reactive diluents used in the process, inert with respect to said monomers (i.e. it does not react with said monomers, it does not form covalent bonds with said monomers), and used in a quantity sufficient to solubilize these monomers, said sufficient quantity typically being between 0.1 and 100 mass equivalents relative to the monomers and any reactive diluents. An “organic” solvent is a solvent as defined above, which is carbon-based.Examples of solvents (in particular organic) include: - aliphatic hydrocarbon solvents, such as halogenated or non-halogenated alkanes (for example cyclohexane, chloroform, or dichloromethane), - aromatic hydrocarbon solvents, such as benzene, toluene, or xylene, 5 - oxygenated solvents, such as alcohols (for example methanol, ethanol, isopropanol, butanol, ethylene glycol), ketones (for example acetone, or methyl isobutyl ketone), acids (for example acetic acid), esters (for example, ethyl acetate), ethers (for example, diethyl ether, or tetrahydrofuran (THF)), - nitrogenous solvents, such as aliphatic or aromatic tertiary amines (for example, triethylamine or pyridine), amides (e.g. dimethylacetamide (DMA), dimethylformamide (DMF), or N-methyl-pyrrolidone (NMP)), or acetonitrile, - dimethyl sulfoxide (DMSO), or a combination thereof.In the present invention, the “reactive diluent” and the “solvent” are distinct in that the “solvent” within the meaning of the invention is inert with respect to the monomers (i.e. polycyclocarbonate(s) and polyamine(s)), i.e. it does not react with said monomers, does not form covalent bonds with said monomers, whereas the “reactive diluent” reacts, forms covalent bonds, with the monomers during the polymerization process. The “reactive diluent” is not considered to be a monomer in the process according to the invention. The process according to the invention can be carried out in the presence of additives and / or fillers, in particular mineral fillers. Mineral fillers make it possible in particular to reduce the cost of the formulation and possibly to improve certain properties, such as abrasion resistance.Examples of such fillers include expanded glass, talc, dolomite, mica, silica sand, basalt ground material, organic pigments, mineral pigments, colored sands, and kaolin, particularly calcined kaolin. Examples of additives that may be mentioned are dispersing agents, surfactants (especially non-ionic surfactants), defoaming agents, or thickening agents (preferably chosen from water-soluble organic polymers), rheology agents (especially thickening or thixotropic agents), dispersing agents, leveling agents, wetting agents, expansion agents, adhesion promoters, stabilizing agents against oxidation, heat or UV radiation, flame retardants (especially halogenated or phosphorus derivatives), or a mixture of these compounds.In a particular embodiment, the process according to the invention is carried out in the presence of one or more reactive diluents. The reactive diluents are typically chosen from a mono-cyclocarbonate and a monoamine (i.e. primary monoamine or secondary monoamine). Examples of monoamines are bis(2-ethylhexyl)amine, benzylamine, nonylamine. The process according to the invention advantageously makes it possible to achieve: - a conversion into cyclocarbonates greater than or equal to 70%, in particular greater than or equal to 80%, preferably greater than or equal to 85%, better still greater than or equal to 90%, or even greater than or equal to 95%, and / or - a solubles content less than or equal to 40%, in particular less than or equal to 30%, preferably less than or equal to 20%, better still less than or equal to 10%, or even less than or equal to 5%. The conversion into cyclocarbonates is typically measured by infrared spectroscopy.The soluble content is defined as the fraction of a polymer sample obtained by the process of the invention which dissolves when the latter is immersed in a “good organic solvent”, i.e. a suitable organic solvent allowing the polymer chains to swell (e.g. THF). The soluble content is typically measured after immersing the sample in the organic solvent for a time sufficient to reach a stationary state (generally several days, for example 3 days) then drying the solid residue (e.g. under vacuum at 40°C). It is understood that a soluble content is only relevant for samples for which at least one of the monomers used in the process has a functionality greater than 2 (i.e. at least one polycyclocarbonate having at least 3 cyclocarbonates or at least one polyamine having at least 3 -NH2 groups).A solubles content of a polymer sample obtained from monomers of functionality 2 will generally have a solubles content of 100%. Another subject of the present invention is a polyurethane obtained by a process as defined in the present application. The process according to the invention can be implemented in particular to form a coating (for example a floor covering, a wall covering, a roof covering, more particularly an adhesion layer, a mass layer, a finishing or wear layer), an adhesive, a sealant (for example, to form a seal) or a foam (for example, to form a seal or an adhesive foam), preferably a coating, an adhesive or a sealant. Thus, another subject of the present invention is the use of a polyurethane obtained by the process of the invention, as a coating, adhesive, sealant or foam, preferably as a coating, adhesive or sealant.The present invention also relates to a coating comprising a polyurethane according to the invention. Such a coating is typically in the form of a film preferably having a thickness of 0.1 to 2.0 mm, in particular 0.2 to 1.5 mm. The weight content of polyurethane according to the invention (in dry extract) in the coating is generally 10 to 99.9%, preferably 20 to 99%, or even 60 to 98%, relative to the total dry weight of the coating. The coating according to the invention may further comprise additives and / or fillers, such as those mentioned above. The weight content of additives and / or fillers (in dry extract) in the coating is generally 0.1 to 90%, preferably 1 to 80%, or even 2 to 40%, relative to the total dry weight of the coating. The present invention also relates to an adhesive comprising a polyurethane according to the invention.The weight content of polyurethane according to the invention (in dry extract) in the adhesive is generally from 5 to 95%, preferably from 15 to 90%, relative to the total dry weight of the adhesive. The adhesive according to the invention may further comprise additives and / or fillers, such as those mentioned above. The weight content of additives and / or fillers (in dry extract) in the adhesive is generally from 5 to 95%, preferably from 10 to 85%, relative to the total dry weight of the adhesive. The present invention also relates to a sealant comprising a polyurethane according to the invention. The weight content of polyurethane according to the invention (in dry extract) in the sealant is generally from 5 to 90%, preferably from 20 to 80%, relative to the total dry weight of the sealant. The sealant according to the invention may further comprise additives and / or fillers, such as those mentioned above.The weight content of additives and / or fillers (in dry extract) in the mastic is generally from 10 to 95%, preferably from 20 to 80%, relative to the total dry weight of the mastic. The mastic may in particular comprise one or more plasticizers. When present, the weight content of plasticizer (in dry extract) in the mastic is for example from 5 to 25%, preferably from 10 to 20%, relative to the total dry weight of mastic. The mastic may in particular comprise one or more adhesion promoters. When present, the weight content of adhesion promoter (in dry extract) in the mastic is for example from 0.01 to 10%, preferably from 0.1 to 5%, relative to the total dry weight of mastic. The present invention also relates to a foam comprising a polyurethane according to the invention.The weight content of polyurethane according to the invention (in dry extract) in the foam is generally from 30 to 99.9%, preferably from 50 to 90%, relative to the total dry weight of foam. The foam according to the invention may further comprise additives and / or fillers, such as those mentioned above. The weight content of additives and / or fillers (in dry extract) in the foam 5 is generally from 0.1 to 70%, preferably from 10 to 50%, relative to the total dry weight of foam. The foam according to the invention may in particular comprise one or more blowing agents. When there are any, the weight content of blowing agent (in dry extract) in the foam is for example from 0.1 to 50%, preferably from 0.1 to 20%, relative to the total dry weight of foam.10 The present invention also relates to a kit for implementing the method according to the invention, comprising: - a first component comprising at least one polycyclocarbonate in which each cyclocarbonate group of said at least one polycyclocarbonate is separated from a heteroatom by at most 2 carbon atoms, said at least one polycyclocarbonate being as defined above, and 15 - a second component comprising at least one polyamine comprising at least two - NH2 groups, said polyamine being as defined above, in which - neither of the first nor the second component comprises a catalyst as defined above nor an organic solvent as defined above, and 20 - the first component and the second component being in separate compartments. It is understood that the first component does not contain a polyamine and that the second component does not contain a polycyclocarbonate.Preferably, the kit according to the invention (in particular, none of its components) does not comprise any monomers other than the polycyclocarbonate(s) and the polyamine(s). In particular, it is preferable that the kit (in particular, none of its components) does not comprise polythiol. In particular, it is preferable that the kit (in particular, none of its components) does not comprise polyol, acrylate, methacrylate, and epoxide. According to a particular embodiment, the first component and / or the second component comprises at least one mineral filler, additive and / or reactive diluent, as defined above. In a particular embodiment, the first component comprises at least one mineral filler and / or additive. In this case, the second component may not comprise a mineral filler and / or additive, or may comprise one or more, identical to or different from that (or those) of the first component.In a particular embodiment, the first component further comprises at least one monocyclocarbonate, as a reactive diluent. In a particular embodiment, the second component comprises at least one mineral filler and / or additive. In this case, the first component may not comprise a mineral filler and / or additive, or may comprise one or more, identical to or different from that (or those) of the second component. In a particular embodiment, the second component comprises at least one monoamine, as a reactive diluent. Typically, the first component does not comprise a monoamine and the second component does not comprise a monocyclocarbonate. When the kit contains mineral fillers, additives and / or reactive diluents, the mass proportion of mineral fillers, additives and / or reactive diluents in the kit is preferably within a range from 20 to 90%, in particular from 30 to 80%.15 The mixing of the first component and the second component of the kit is carried out under the conditions of the method of the invention described above. The two components of the kit can be mixed to form a coating (for example a floor covering, a wall covering, a roof covering, more particularly an adhesion layer, a mass layer, a finishing or wear layer), an adhesive, a sealant (for example, to form a joint), or a foam (for example, to form a joint or an adhesive foam). In particular, the two components can be mixed to form a coating for waterproofing roofs, facades or balconies. The two components can be mixed to form a joint between tiled tiles or between facade plates, or to bond the tiled tiles or facade plates to a support.Depending on the application, the mixture can be applied using a brush, roller, paintbrush, spatula, smoother, trowel, trowel, or by spraying. In the case of a foam, the two components can be mixed with the addition of gas (e.g., air or nitrogen), generally under pressure. 30 EXAMPLES Example 1. Synthesis of polycyclocarbonates Stoichiometric amounts of a cyclocarbonate compound and a polythiol are mixed with DMPA (2,2-dimethoxy-2-phenylacetophenone) (0.5 mol %) and THF in an open reactor ([cyclocarbonate group] = [SH groups] = 0.8 mol.L. -1 ). The mixture is then irradiated at λ = 365 nm (intensity 15000 w / m²) at room temperature until complete conversion of the C=C double bonds (NMR monitoring 1 H). The THF is then evaporated using a rotary evaporator and the synthesized monomer stored in a refrigerator at 5°C. [Chem 15] Polycyclocarbonates préparés : [Chem 16] RMN 1 H (THF-d8, 25 °C, 400 MHz) δ (ppm) : 0,88 (t, 6H), 1,24-1,42 (m, 8H), 1,46 (q, 4H), 1,54 (quint, 4H), 1,79 (quint, 4H), 2,47 (t, 4H), 2,53 (t, 4H), 3,38 (s, 4H), 3,49 (t, 4H), 4,09-4,28 (dd, 8H) MS (ESI): M + H + = 579,3 [Chem 17] RMN 1 H (THF-d8, 25 °C, 400 MHz) δ (ppm) : 1,25-1,42 (m, 8H), 1,55 (q, 4H), 1,79 (q, 4H), 2,47 (t, 4H), 2,53 (t, 4H), 3,53-3,68 (superposition qd et triplet, 8H), 4,23-4,49 (dt, 4H), 4,79 (m, 2H) MS (ESI): M + H + = 495,4 [Chem 18] RMN 1 H (THF-d8, 25 °C, 400 MHz) δ (ppm) : 1,24 (s, 6H), 1,28-1,45 (m, 8H), 1,57 (quint, 4H), 1,90 (quint, 4H), 2,49 (t, 4H), 2,56 (t, 2H), 4,25 (t, 4H), 4,17-4,60 (dd, 4H) MS (ESI): M + H + = 579,2 [Chem 19] RMN 1H (THF-d8, 25 °C, 400 MHz) δ (ppm) : 0,88 (t, 3H), 1,49 (q, 2H), 1,80 (quint, 6H), 2,58 (q, 12H), 2,72 (t, 6H), 3,57 (t, 6H), 3,54-3,69 (qd, 6H), 4,04 (s, 6H), 4,25-4,50 (dt, 6H), 4,82 (m, 3H) MS (ESI): M + Na + = 895,4 [Chem 20] RMN 1 H (THF-d8, 25 °C, 400 MHz) δ (ppm) : 1,82 (quint, 8H), 2,60 (q, 16H), 2,74 (t, 8H), 3,5-3,68 (plusieurs signaux), 4,18 (s, 8H), 4,23-4,48 (dt, 8H), 4,78 (m, 4H) MS (ESI): M + K + = 1159,4 [Chem 21] RMN 1 H (THF-d8, 25 °C, 400 MHz) δ (ppm) : 0,89 (t, 12H), 1,47 (q, 8H), 1,80 (quint, 6H), 2,59 (quint, 12H), 2,72 (t, 6H), 3,30 (s, 6H), 3,50 (t, 6H), 4,04 (s, 6H), 4,10-4,28 MS (ESI): M + K + = 1037,5 [Chem 22] RMN 1 H (THF-d8, 25 °C, 400 MHz) δ (ppm) : 0,88 (t, 3H), 1,24 (s, 9H), 1,50 (q, 2H), 1,91 (quint, 6H), 2,60 (quint, 12H), 2,74 (t, 6H), 4,05 (s, 6H), 4,28 (t, 6H), 4,20-4,64 (dd, 12H) [Chem 23] RMN 1H (THF-d8, 25 °C, 400 MHz) δ (ppm) : 0,89 (t, 12H), 1,48 (q, 8H), 1,80 (q, 8H), 2,59 (q, 16H), 2,73 (t, 8H), 3,40 (s, 8H), 3,5 (t, 8H), 4,15 (s, 8H), 4,09-4,29 (dd, 16H) MS (ESI): M + Na + = 1311 [Chem 24] RMN 1 H (THF-d8, 25 °C, 400 MHz) δ (ppm) : 1,25 (s, 3H), 1,92 (quint, 8H), 2,61 (quint, 16H), 2,75 (t, 8H), 4,17 (s, 8H), 4,25 (t, 8H), 4,24-4,66 (dd, 16H) MS (ESI): M + Na += 1311 Table 1 Polycyclocarbonate Mn (g / mol) Cyclocarbonate equivalent weight (g / eq) Bis-6CC2 578 289 Bis-5CC2 494 247 Bis-6CC3 578 289 Tri-5CC2 872 291 Tetra-5CC2 1120 280 Example 2. Kinetic studies of reactions between polycyclocarbonate and polyamine The polymerization reactions between a polycyclocarbonate chosen from Bis-6CC3, Bis-6CC2 and Bis-5CC2 and a polyamine chosen from 1,13-diamino-4,7,10-trioxatridecane (tDA) and isophorone diamine (IPDA) were carried out at 23°C, without solvent and without catalyst, and the kinetics of such polymerizations were followed by spectroscopy infrared (“FTIR”) in ATR mode.Table 2 Conversion Bis-6CC3 Bis-6CC2 Bis-5CC2 Cyclocarbonate 49%, t=11 min tDA 100%, t=11min 100%, t=15min & >90%, t=8h 66%, t=70 min 26%, t=70 min IPDA 100%, t=70min 88%, t=9 days* 87%, t=9 days* 10 * time not optimized Table 2 shows that high conversions, between 87% and 100%, were achieved when a di-cyclocarbonate, in which the cyclocarbonates are activated by a heteroatom, and a diamine were mixed in the absence of catalyst and solvent, at room temperature. 15 Example 3. Synthesis and characterization of isocyanate-free polyurethane thermosets Polyfunctional monomers, i.e. polycyclocarbonates and polyamines, are mixed by hand and cast into a silicone mold, in stoichiometric amounts of functions ([cyclocarbonate groups] = [NH2 groups]). The conversion of cyclocarbonate groups (CC) is measured by infrared spectroscopy (“FTIR”) in ATR mode at 25°C.The gel point is determined by rheology in oscillation mode at a frequency of 1 rad / s. The soluble fraction and swelling rate in THF are determined by immersing a sample of cured material in THF for ~7 days. The glass transition temperature (Tg) is determined by DSC using a heating rate of 10°C / min. The tensile test is performed at a rate of 5 mm / min. Finally, the thermal degradation is determined by thermogravimetric analysis (“TGA”) by heating a cured material at a rate of 10 °C / min under a N2 atmosphere. In Tables 3, and 4 below, the different polycyclocarbonates were reacted with 1,13-Diamino-4,7,10-trioxatridecane (tDA) at 25°C and 50% relative humidity (“RH”). In Table 5 below, the different polycyclocarbonates were reacted with tetraethylenepentamine (TEPA) at 25°C and 50% relative humidity (“RH”). Table 3 α. Carbona Polycyclocarbonate 24h T Tetra-5CC2 ( r m i-5 o C L % C ) 2 ( mol%) Solid P14 100 0 slightly 90 83 5.8 83 136 11 yellow P16 75 25 Yellow solid 99 81 2.6 90 157 14 P17 50 50 Yellow solid 98 79 2.4 90 114 7 P18 25 75 Orange solid 99 77 1.2 86 109 8 P19 0 100 Orange solid 96 75 1.3 76 90 5 a: Physical state of the polymer after 24 h of crosslinking at room temperature (“Tamb”); b: conversion of cyclic carbonates measured by relative integration of the νC=O, 5CC absorption band in infrared spectroscopy after 24 h of crosslinking at T amb; c: Theoretical conversion at gel point; d: Crosslinking time to reach gel point measured by rheological monitoring; e: Conversion of cyclic carbonate functions at gel point measured by relative integration of the νC=O, 5CC absorption band in infrared spectroscopy after tgel at Tamb; f: Swelling rate measured after ~3 days of immersion in THF; g: Soluble fraction measured after ~3 days of immersion in THF and drying of the PHU for 4 h under vacuum at 40 °C Table 4 P olycyclocarbonate T Tetra-5CC2 ( r m i- o 5C L % C ) 2 ( mol%)P14 100 0 291 -16 0.48 ± 0.12 0.26 ± 0.049 148 ± 18 P16 75 25 276 -15 1.53 ± 0.13 0.39± 0.027 37 ± 7 P17 50 50 280 -13 1.19 ± 0.088 0.34± 0.058 40 ± 17 P18 25 75 281 -12 1.78 ± 0.34 0.56 ± 0.072 42 ± 5 P19 0 100 298 -12 1.99 ± 0.20 0.46 ± 0.023 34 ± 5 ​​a: Degradation onset temperature measured by TGA; b: Glass transition temperature measured during the second DSC analysis cycle; c: Young's modulus, d: Stress at break and e: Elongation at break measured during tensile strength tests with v = 5 mm.min -1 (average of 4 specimens and standard deviation) Table 5 Polycyclocarbonate αCarbonate, Q wsol Tonset Tg 24h (%) b (%) c (%) d (°C) e (°C) f g Solid P12 Tri-5CC2 slightly 34 84 30 218 0 yellow P13 Tri-6CC2 hYellow solid / 130 26 286 -6 a: Physical state of the polymer after 24 h of crosslinking at Tamb; b: conversion to cyclic carbonate measured by relative integration of the νC=O, 5CC absorption band in infrared spectroscopy after 24 h of crosslinking at Tamb; c: Swelling rate measured after ~3 days of immersion in THF; d: soluble fraction measured after ~3 days of immersion in THF and drying of the PHU for 4 h under vacuum at 40 °C; e: Degradation onset temperature, measured by TGA; f: Glass transition temperature measured by DSC during the second analysis cycle; g: [CC] = [NH2]; h: [CC] = 2.5*[NH2] Example 4. Comparative tests with and without catalyst

[0005] The difunctional amine 1,3-Bis(aminomethyl)cyclohexane (cycloDA) was mixed with the tetracarbonate shown above and the reaction was carried out at room temperature. Two further room temperature polymerizations, involving the same reagents, were carried out this time with 2 wt% of 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) or 2,4,6-Tris-(dimethylaminomethyl)phenol (DMP-30) catalyst. Film-like polyurethanes were obtained. The α conversion of the carbonate functions was measured by infrared spectroscopy, the glass transition temperature Tg by DSC and the stress σ and the elongation ε at break by tensile strength test. 10 Table 6 Table 6 shows that the properties of the polyurethane from the uncatalyzed reaction are very different from the polyurethane from the catalyzed reaction.It should be noted in particular that its water-soluble fraction is twice as low and its breaking stress is higher. A reduction in the water-soluble fraction limits the release of potential monomers or oligomers into the environment. The increase in elongation means that the polymer is more flexible, and therefore particularly suitable for coating applications. 20.

Claims

CLAIMS 1. Process for preparing an isocyanate-free polyurethane, comprising a step of bringing into contact at least one polycyclocarbonate and at least one polyamine comprising at least two -NH2 groups, in which each cyclocarbonate group of said at least one polycyclocarbonate is separated from a heteroatom by at most 2 carbon atoms, the contacting step being carried out at a temperature of between 5°C and 35°C, in the absence of a reaction catalyst between an amine function and a carbonate group, and in the absence of an organic solvent.

2. Process according to claim 1, in which the average functionality of the mixture formed by said at least one polycyclocarbonate and said at least one polyamine is greater than 2. 3.A method according to claim 1 or 2, wherein the cyclocarbonate groups of said at least one polycyclocarbonate are linked together by an aliphatic chain comprising each heteroatom from which each cyclocarbonate group is separated by at most 2 carbon atoms, and optionally comprising one or more additional heteroatoms and / or one or more substituents.

4. A method according to one of claims 1 to 3, wherein the -NH2 groups of said at least one polyamine are linked together by an aliphatic chain optionally comprising one or more heteroatoms, preferably at least one oxygen.

5. A method according to one of claims 1 to 4, wherein each cyclocarbonate group of said at least one polycyclocarbonate is a 5- or 6-membered ring, preferably a 5-membered ring. 6.Method according to one of claims 1 to 5, wherein said at least one polycyclocarbonate has a cyclocarbonate equivalent weight of less than 500 g / eq, preferably less than 400 g / eq, more preferably less than 300 g / eq, and / or said at least one polyamine has an amine equivalent weight of less than 300 g / eq, preferably less than 200 g / eq.

7. Method according to one of claims 1 to 6, wherein each cyclocarbonate group of said at least one polycyclocarbonate is separated from a heteroatom by 0 or 1 carbon atom.

8. Method according to one of claims 1 to 7, wherein each heteroatom from which each cyclocarbonate group is separated by at most 2 carbon atoms is chosen from oxygen, nitrogen and sulfur. 5 9. Method according to one of claims 1 to 8, wherein said at least one polycyclocarbonate is: - of formula (I): [Chem 25] in which: each X1 is an optionally substituted cyclocarbonate, each L1 is a single bond or a chain comprising at most 2 carbon atoms, each Het is a heteroatom, and L2 is a linker arm; or - of formula (II): [Chem 26] in which: n is 0 or 1, R1 is hydrogen or an optionally substituted hydrocarbon group, each X1 is an optionally substituted cyclocarbonate, each L1 is a single bond or a chain comprising at most 2 carbon atoms, each Het is a heteroatom, and each L2 is a linker arm. 10.Method according to one of claims 1 to 9, in which said at least one polycyclocarbonate is chosen from the following compounds: [Chem 27].

11. The method of any one of claims 1 to 10, wherein said at least one polyamine is selected from the group consisting of ethylene diamine, 1,5-pentanediamine, tetraethylene pentamine, 1,8-diamino-3,6-dioxaoctane, 1,13-diamino-4,7,10-trioxatridecane, 4,9-dioxa-1,12-dodecanediamine, isophorone diamine, and m-xylylene diamine, preferably 1,13-diamino-4,7,10-trioxatridecane.

12. The method of any one of claims 1 to 11, wherein the molar ratio of cyclocarbonate groups of the polycyclocarbonate to -NH2 groups of the polyamine is between 0.5:1 and 3:1, preferably between 0.8:1 and 1.2:

1.

13. Method according to one of claims 1 to 12, in which the contacting step is carried out at a temperature between 15°C and 30°C.

14. Method according to one of claims 1 to 13, in which the method is carried out in the absence of polythiol.

15. Method according to one of claims 1 to 14, in which the method is carried out in the absence of polyol, acrylate, methacrylate, and epoxide. 16.Kit for implementing a method as defined in one of claims 1 to 15, comprising: - a first component comprising at least one polycyclocarbonate, wherein each cyclocarbonate group of said at least one polycyclocarbonate is separated from a heteroatom by at most 2 carbon atoms, and - a second component comprising at least one polyamine comprising at least two -NH2 groups, wherein neither of the first component nor of the second component comprises a reaction catalyst between an amine function and a carbonate group, nor an organic solvent, the first component and the second component being in separate compartments, and preferably at least one of the first and second components further comprising at least one filler and / or at least one additive.

17. Polyurethane obtained by a method as defined in any one of claims 1 to 15. 18.Use of a polyurethane as defined in claim 17, as a coating, adhesive, sealant or foam.

19. Coating, adhesive, or sealant comprising a polyurethane as defined in claim 17, and optionally one or more additives and / or fillers.

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