RU2795087C2 - Hybrid polyurethane-polyhydroxyurethane composition - Google Patents

Abstract

FIELD: hybrid polyurethane-polyhydroxyurethane composition.

SUBSTANCE: present invention relates to a hybrid polyurethane-polyhydroxyurethane (PU-PHU) composition used to produce thermoset or thermoplastic polymers with the possibility of further processing of the hybrid PU-PHU polymer at a later stage. The hybrid polyurethane-polyhydroxyurethane composition is prepared through a process comprising the following steps: (i) reacting at least one isocyanate-containing compound in a stoichiometric excess with at least one isocyanate-reactive compound to form at least one prepolymer; (ii) reacting at least one said prepolymer with a compound containing at least one cyclic carbonate functional group to form a cyclic carbonate-terminated prepolymer; (iii) ring-opening reaction of said cyclic carbonate-terminated prepolymer with at least one difunctional amine compound and at least one polyfunctional amine compound, resulting in the above PU-PHU hybrid composition. The ring-opening reaction step is carried out at a temperature above room temperature.

EFFECT: these hybrid polyurethane-polyhydroxyurethane compositions are obtained in a simpler and more economical way, which allows a certain freedom of action regarding the final properties of the product, in particular mechanical properties.

16 cl, 4 tbl, 10 ex

Description

The present invention relates to a hybrid polyurethane-polyhydroxyurethane (PU-PHU) composition and to a product containing such a hybrid PU-PHU composition.

Typically, polyurethane (PU) meshes can be either thermosets or thermoplastics, depending on the structure of the polymer contained. Thermoplastic polymers typically consist of linear polymer chains, while thermoset polymers consist of branched, cross-linked polymer chains.

More specifically, thermosets are cured thermoset polymers that upon curing become irreversibly cured. The curing reaction results in cross-linking of the polymer chains to form an infusible and insoluble polymer network. It is known that traditional covalent polymer networks, such as thermoset PU networks, cannot be easily recycled for useful applications. Irreversible cross-linking bonds can make them impossible to process. In contrast to thermosets, thermoplastic polymers have such an internal chemical structure that processing occurs without the need for any external force other than heat and shear.

In recent years, there has been a growing interest in developing solutions to obtain isocyanate-free systems while maintaining unchanged isocyanate reactivity. Two main strategies have been developed to achieve an isocyanate-free system.

The first strategy is based on the development of a system based on polyhydroxyurethane, obtaining it exclusively from the reaction of glycerol carbonate (GC) and amines.

The second strategy is based on adapting modern polyurethane networks made from isocyanate-terminated prepolymers, typically prepared by reacting an isocyanate-reactive compound with an isocyanate-containing compound. Such an isocyanate-terminated prepolymer can be functionalized with cyclic carbonate compounds, resulting in a carbonate-terminated prepolymer, which allows end-capping of the isocyanate-reactive end groups preferably located at the ends of the prepolymer discussed above. In this second strategy, amines can react with the carbonate-terminated prepolymer in curing reactions, resulting in cross-linking. This method offers a hybrid system because polyurethane and polyhydroxyurethane (PU-PHU) bonds are present in the final compound, commonly known as a thermoset.

The present invention relates to a second strategy which has several drawbacks in terms of the number of steps involved in the known manufacturing process. In addition, the viscosity of the carbonate-terminated prepolymer must be appropriate as this will determine the discretion the user will have regarding the applications of the finished product obtained after curing.

The difficulty lies in finding a compromise between the properties of a thermoplastic material and those of a thermoset material, taking into account the needs considered.

The fine adjustment of viscosity in current known manufacturing processes is the use of solvents. This makes the process expensive and inconvenient, since it involves the use of additional steps to remove solvents from the finished product. In addition, the process takes a long time to complete, which is a limiting factor for industrial applications. It is also believed that such methods do not guarantee the processability of the final cured product when thermosetting materials are produced.

In addition, the fine adjustment of the viscosity in the known methods is limited in such a way that the mechanical properties of the final products are unsatisfactory.

For the reasons discussed above, there is a need to obtain hybrid PU-PHU compositions that can be obtained using a simpler and more economical method, allowing the user to use the finished cured product in several applications.

The aim of the present invention is to overcome the disadvantages discussed above by obtaining hybrid PU-PHU compositions (thermoplastic materials or thermosetting materials), which are obtained using a simpler, less expensive method, which at the same time allows a certain freedom of action regarding the final properties of the product, in particular , in terms of mechanical properties.

In this regard, the present invention provides a hybrid polyurethane-polyhydroxyurethane (PU-PHU) composition obtained by a process comprising the following steps:

(i) reacting at least one isocyanate-containing compound, in a stoichiometric excess, with at least one isocyanate-reactive compound, resulting in the formation of at least one prepolymer,

(ii) reacting said at least one prepolymer with a compound containing at least one cyclic carbonate functional group, resulting in the formation of a prepolymer with cyclic carbonate end groups,

(iii) ring-opening reaction of said cyclic carbonate-terminated prepolymer with a compound containing at least one amine functional group, resulting in the above PU-PHU hybrid composition,

characterized in that the step of said ring-opening reaction is carried out at a temperature above room temperature, preferably above 20°C, more preferably above 25°C.

It is observed that the application of a temperature that is above room temperature (preferably above 20° C., more preferably above 25° C.) in step (iii) makes it possible to obtain a finished cured product with improved mechanical properties. As noted, some finished cured products have been observed to have high elongation at break (>2600%).

Said compound containing at least one amine functional group may preferably contain an amine functional group which has a functionality of at least 2. More preferably, said compound containing at least one amine functional group is an amine having a functionality of at least 2.

Said at least one isocyanate-containing compound is preferably a polyisocyanate-containing compound.

The hybrid composition obtained by the method of the present invention is particularly preferred as it ensures that the carbonate functionalities of the cyclic carbonate-terminated prepolymer are retained prior to polymerization with the amine. In other words, it is surprising to be able to polymerize a cyclic carbonate-terminated prepolymer in the presence of amines, without thermal degradation of the carbonate functionalities.

In addition, the use of a solvent in the system is no longer mandatory, which is more convenient for the user, and the viscosity can be finely tuned, giving discretion regarding the end uses of the product obtained using the method of the present invention.

It has also been found that the presence of reactive hydroxyl groups in the finished cured material allows the hydroxyurethane bonds to show reversibility under certain temperature and pressure conditions (see below). The PU-PHU products of the present invention can therefore be defined as processable thermosets when at least one component used to make the hybrid PU-PHU products of the present invention has a functionality of at least 2. Advantageously, said the at least one isocyanate-containing compound may be a polyisocyanate with a functionality of at least 2, or said at least one isocyanate-reactive compound has a functionality of at least 2, or said, a compound containing at least one cyclic carbonate functional group has a cyclic carbonate functional group with a functionality of at least 2, or said compound containing at least one amine functional group has an amine functionality of at least , 2. Other functional groups may also optionally be included in said compound containing at least one amine functional group.

More preferably, at least one isocyanate-containing compound is a polyisocyanate with a functionality of at least 2, or at least one isocyanate-reactive compound is a polyol or a mixture of polyols with a functionality of at least at least 2, or a compound containing at least one cyclic carbonate functional group is a glycerol carbonate with a functionality of at least 2, or said at least one amine functional group is an amine with a functionality, at least 2. Combinations are also possible.

When thermosetting polymers are produced by the process of the present invention, such materials can be recycled and this is unexpected in view of known thermosetting materials which are difficult to process, recycle or melt. The reversible behavior of the hydroxyurethane bonds allows the user to process the finished material several times, preferably up to at least 3 times, without adversely affecting the mechanical properties.

Depending on the compound used in the process of the present invention, thermosetting polymers or thermoplastic polymers can be obtained, with the possibility of further processing of the hybrid PU-PHU polymer at a later stage through at least one treatment (see below).

Advantageously, said compound containing at least one cyclic carbonate functional group contains at least one 4-membered cyclic carbonate, preferably at least one 5-membered cyclic carbonate, more preferably at least one 6-membered cyclic carbonate. Said at least one 5-membered cyclic carbonate may be preferred for reasons of sensitivity and reactivity.

More preferably, the amine of said compound containing at least one amine functional group has a functionality of at least 1.8.

According to a particular embodiment of the present invention, the temperature at which said step (iii) of the ring-opening reaction is carried out is between 25°C and 160°C, preferably between 40°C and 160°C, more preferably between 45° C and 140°C.

Stage (ii) basically gives one single phase, consisting of a prepolymer with cyclic carbonate end groups, ready to interact with amines.

The choice of temperature makes it possible to define ranges where thermal degradation of carbonate functionalities is limited, even eliminated. Hence, the use of a solvent is no longer the most important.

According to a preferred embodiment of the present invention, said isocyanate-reactive compound has a number average molecular weight equal to or greater than 62, preferably greater than 400, more preferably greater than 1000, even more preferably greater than 2000, most preferably greater than 3800.

Advantageously, said isocyanate-reactive compound is a mixture of isocyanate-reactive compounds, such as a mixture of polyols.

Preferably, the isocyanate-reactive compound has a number average molecular weight between 62 and 12,000.

Advantageously, it has been observed that the use of an isocyanate-reactive compound with a number average molecular weight greater than 3800, for example equal to 4000, allows the formation of a prepolymer with a lower viscosity (for example, compared to isocyanate-reactive compounds having a number average molecular weight lower than 2500), which also results in the formation of said cyclic carbonate-terminated prepolymer with reduced viscosity compared to compounds prepared using isocyanate-reactive compounds with a number average molecular weight below 3800, preferably below 2500.

This feature also contributes to the fine tuning of the viscosity, which is particularly advantageous.

In a specific embodiment of the present invention, step (ii) is carried out at a molar ratio of said at least one prepolymer to said compound containing at least one cyclic carbonate functional group, which is reactive with respect to the NCO groups of this at least at least one prepolymer (for example, NCO:OH, NCO:NH ₂ , NCO:NH and NCO:SH), in the range from 0.5 to 1.05, preferably from 0.8 to 1.

A compound containing a cyclic carbonate functional group may contain isocyanate-reactive groups such as OH, NH ₂ , NH or SH.

Preferably, step (i) is carried out at a molar ratio of said at least one isocyanate-containing compound to said at least one isocyanate-reactive compound (e.g., NCO:OH) ranging from 1.8 to 25, preferably 2 to 5.

According to the present invention, said at least one prepolymer preferably has an NCO number ranging from 0.8 to 25%, more preferably from 0.8 to 10%.

According to a preferred embodiment of the present invention, step (ii) is carried out at a temperature in the range of 50°C to 150°C, preferably 60°C to 130°C, more preferably 80°C to 125°C, most preferably , ranging from 95°C to 122°C.

In a particular embodiment of the present invention, step (ii) may be carried out under solvent-free conditions.

Advantageously, step (iii) can be carried out under solvent-free conditions.

More preferably, step (ii) and/or step (iii) may be carried out in the presence of a catalyst selected from the group consisting of organic bases, organic acids, organometallic compounds, in particular dibutyltin dilaurate (DBTDL), a cyclic carbonate, and combinations thereof.

Even more preferably, the catalyst of the present invention is selected from the group consisting of 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU ), triazabicyclodecene (TBD), triethylamine, potassium tert-butanoate, mixtures thereof, including any other suitable catalysts known to those skilled in the art.

Preferably, said compound containing at least one cyclic carbonate functional group is selected from the list containing glycerol carbonate, 4-(hydroxymethyl)-1,3-dioxolan-2-one, 4-(mercaptomethyl)-1, 3-dioxolan-2-one, 4-((methylamino)methyl)-1,3-dioxolan-2-one, 4-(aminomethyl)-1,3-dioxolan-2-one, 2-(2-oxo- 1,3-dioxolan-4-yl)acetic acid.

More preferably, step (iii) is carried out over a period of up to 24 hours, preferably 3 hours, more preferably 2 hours, even more preferably 1 hour.

According to one embodiment of the present invention, the conversion of the cyclic carbonate-terminated prepolymer of step (iii) is preferably at least 90%, preferably at least 95%.

In a specific embodiment of the present invention, the hybrid PU-PHU composition can be further processed after curing by applying mechanical pressure to the finished cured product at a given temperature, for processing (processing), melting or recycling, without adversely affecting the mechanical properties of the finished product. It has been found that the finished cured PU-PHU product obtained by the method of the present invention is particularly advantageous in terms of renewability. More specifically, the present invention provides a recyclable polymer network (recyclable hybrid PU-PHU composition) having self-healing properties that allow cross-linked polymers to be recycled with full recovery of mechanical properties resulting from the presence of cross-links. Such a PU-PHU composition contains enough dynamic links to reconfigure the mesh under appropriate conditions. This particular embodiment occurs when the thermoset polymers are produced by the process of the present invention or any other possible type of known methods providing thermoset hybrid PU-PHU polymers. Thermoset polymers obtained in the context of the present invention are highly preferred in terms of processability.

The temperature applied during the application of mechanical pressure is preferably at least 110°C.

The pressure is advantageously at least 10 kPa.

More preferably, the time during which the mechanical pressure is applied is at least 30 seconds.

Surprisingly, the PU-PHU composition of the present invention can be processed many times with full restoration of mechanical properties.

Other embodiments of the composition of the present invention are discussed in the appended claims.

The present invention also relates to a product containing the PU-PHU composition of the present invention.

The product may be an adhesive, coating, elastomer or foam.

Other embodiments of the product of the present invention are discussed in the appended claims.

The present invention also relates to a process for producing a processable hybrid PU-PHU composition comprising the following steps:

(i) reacting at least one isocyanate-containing compound in a stoichiometric excess with at least one isocyanate-reactive compound, resulting in the formation of at least one prepolymer,

(ii) reacting said at least one prepolymer with a compound containing at least one cyclic carbonate functional group, resulting in the formation of a prepolymer with cyclic carbonate end groups,

(iii) ring-opening reaction of said cyclic carbonate-terminated prepolymer with a compound containing at least one amine functional group, resulting in the above PU-PHU hybrid composition,

characterized in that step (iii) of said ring-opening reaction is carried out at a temperature above room temperature, preferably above 20°C, more preferably above 25°C.

All the above features of the composition obtained using the above method according to the present invention are also applicable to the method of obtaining a processed hybrid PU/PHU composition.

The present invention also relates to a process for processing a thermoset hybrid PU-PHU product as defined above.

Typically, thermoset products are difficult to process, melt, or recycle after curing due to their cross-linked structure, which prevents them from being processed by melting. Most of the time, the urethane bonds of these products are irreversible, meaning that they cannot re-form the cross-link bonds. The method of the present invention includes the following steps:

- obtaining a cured thermosetting hybrid PU-PHU product obtained using the method of the present invention, this product has an outer surface,

- treating said thermoset hybrid PU-PHU product by applying at least one action, preferably consisting of mechanical pressure, to said outer surface, at a given temperature and/or for a given period of time,

- obtaining a processed hybrid PU-PHU product, with a complete restoration of mechanical properties.

It is observed that applying an impact, preferably consisting of mechanical pressure, to the outer surface of said hybrid PU-PHU product at a given temperature allows the user to process (process) it in such a way that the mechanical properties can be fully restored. For example, it can be useful for "healing" a product that has a defect on its surface. The application of mechanical pressure at a given temperature allows the formation of new bonds in the material (through re-meshing) to restore a product with such a defect. Another example may also refer to combining several granules by applying mechanical pressure at a given temperature to obtain a product made from such granules. It is possible to reshape the product in a different way without loss of mechanical properties. Also surprising is the processing (processing) of the material at a given temperature, without thermal degradation of the product or the observation of side reactions. Such products contain a dynamic network of connections that can be reconfigured under the specific conditions proposed by the present invention, namely, with the help of the specified impact, which may consist of at least one mechanical pressure at a given temperature.

Advantageously, it is also possible to use the process of the present invention to recycle/improve the products used.

In a specific embodiment of the method of the present invention, said action consists of the application of mechanical pressure.

Preferably, said mechanical pressure is at least 10 kPa.

More preferably, said target temperature is at least 110°C.

Advantageously, said predetermined time period is at least 30 seconds.

Shorter processing times minimize thermal degradation of the material and allow at least 3 processing cycles without seeing a significant deterioration in mechanical properties.

Said cured hybrid PU-PHU product is obtained with a Tg ranging from 70°C to 160°C.

According to a particular embodiment of the method of the present invention, a PU-PHU product can be obtained by reacting the prepolymer with at least 4-membered cyclic carbonates (such as glycerol carbonate) to form a cyclic carbonate-terminated prepolymer which is then reacted with amines. . The formation of hybrid PU-PHU products makes it possible to obtain reversible hydroxyurethane bonds in the finished product, these reversible bonds can be used to process the material. It is also possible to recycle/recycle the PU-PHU product under the conditions described in the present invention.

All features associated with the hybrid PU-PHU composition and method of its preparation also apply to the PU-PHU product used in the process discussed above.

Suitable prepolymers are known in the art and are commercially available. Preferably, they are the reaction product of an isocyanate-containing compound with an isocyanate-reactive compound. Such prepolymers are typically prepared by reacting a molar excess of polymeric or pure aromatic isocyanate monomers with one or more polyols using reaction conditions known in the art. The polyols may include aminated polyols, imine or enamine modified polyols, polyether polyols, polyester polyols, polyamines such as alkanolamines, and diols and triols. The prepolymers of the present invention may be hard block prepolymers, soft block prepolymers, or mixtures thereof.

Suitable isocyanate-containing compounds for use in preparing the prepolymer may be aromatic, (cyclic) aliphatic or araliphatic organic isocyanates. Suitable aromatic isocyanates also include polyisocyanates.

Preferably, the isocyanate-containing compounds for use in preparing the prepolymer may be aromatic, (cyclic) aliphatic or araliphatic organic isocyanates, preferably having x end groups, all of which are NCO end groups.

Suitable polyisocyanates include polyisocyanates of the Ra-(NCO)x type, where x is at least 2 and Ra is an aromatic such as diphenylmethane or toluene or a similar polyisocyanate.

Non-limiting examples of suitable aromatic polyisocyanate monomers that can be used in the present invention can be any polyisocyanate compounds or a mixture of polyisocyanate compounds, preferably, where these compounds preferably contain at least two isocyanate groups.

Non-limiting examples of useful aromatic polyisocyanate monomers include diisocyanates, in particular aromatic diisocyanates and higher functionality isocyanates. Non-limiting examples of aromatic polyisocyanate monomers that can be used in the present invention include aromatic isocyanate monomers such as diphenylmethane diisocyanate (MDI) in the form of its 2,4'-, 2,2'- and 4,4'-isomers and mixtures thereof (also referred to as pure MDI), mixtures of diphenylmethane diisocyanates (MDI) and their oligomers (known in the art as "raw" or polymeric MDI), m- and p-phenylene diisocyanate, tolylene-2,4- and tolylene-2,6-diisocyanate ( also known as toluene diisocyanate and referred to as TDI such as 2,4 TDI and 2,6 TDI) in any usable isomeric mixture, chlorophenylene-2,4-diisocyanate, naphthylene-1,5-diisocyanate, diphenylene-4,4 '-diisocyanate, 4,4'-diisocyanate-3,3'-dimethylbiphenyl, 3-methyl-diphenylmethane-4,4'-diisocyanate and diphenylether diisocyanate; tetramethylxylene diisocyanate (TMXDI) and tolidine diisocyanate (TODI); any usable mixture of these polyisocyanates and any usable mixture of one or more of these polyisocyanates with MDI in the form of its 2,4'-, 2,2'- and 4,4'-isomers and mixtures thereof (also referred to as pure MDI ), mixtures of diphenylmethane diisocyanates (MDI) and their oligomers (known in the art as "raw" or polymeric MDI), and reaction products of polyisocyanates (eg, polyisocyanates as above, and preferably MDI-based polyisocyanates). Preferably, isocyanates of the diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI) type are used.

In some embodiments, said aromatic isocyanate monomer comprises polymeric methylene diphenyl diisocyanate. The polymeric methylene diphenyl diisocyanate may contain any mixture of pure MDI (2,4'-, 2,2'- and 4,4'-methylene diphenyl diisocyanate) and higher homologues of the following formula:

Wheren is an integer that can be 0, 1, or 2, and wheremrepresents an integer that can be between 0 and 10, or higher. The forked version may be preferred.

Preferably, the aromatic isocyanate monomer includes diphenylmethane diisocyanate (MDI), polymeric forms thereof and/or variants thereof (such as uretonimine-modified MDI).

The isocyanate-reactive compounds may be a component containing isocyanate-reactive groups. As used herein, the term “isocyanate-reactive groups” refers to chemical groups susceptible to the electrophilic attack of isocyanate groups.

Non-limiting examples of these groups may be OH, SH, NH ₂ , NH, acids, and other R-CH-R' groups. In some embodiments, said isocyanate-reactive compound contains at least one OH group. Examples of suitable isocyanate-reactive compounds containing isocyanate-reactive OH groups include polyols such as glycols or even relatively high molecular weight polyether polyols (e.g. above 1500, preferably above 3800) and polyester polyols, carboxylic acids such as polybasic acids.

In some preferred embodiments, the at least one isocyanate-reactive compound is selected from the group consisting of hydroxyl-terminated polyether (polyether polyols); polyols such as glycols; hydroxyl-terminated polyesters (polyether polyols) and mixtures thereof, all of which are well known to those skilled in the art.

Suitable hydroxyl-terminated polyethers are preferably polyether polyols derived from a diol or polyol having a total of 2 to 15 carbon atoms, preferably an alkyl diol or glycol which is reacted with an ether containing an alkylene oxide containing from 2 up to 6 carbon atoms, usually with ethylene oxide or propylene oxide, or mixtures thereof. For example, a hydroxy-functional polyether can be obtained by first reacting propylene glycol with propylene oxide, followed by reaction with ethylene oxide. Primary hydroxyl groups derived from ethylene oxide are more reactive than secondary hydroxyl groups and thus are preferred. Suitable commercial polyether polyols include poly(ethylene glycol) containing ethylene oxide reacted with ethylene glycol, poly(propylene glycol) containing propylene oxide reacted with propylene glycol, poly(tetramethyl glycol) (PTMG) containing water reacted with tetrahydrofuran (THF). In addition, polyether polyols include polyamide alkylene oxide adducts and may include, for example, ethylenediamine adduct containing the reaction product of ethylenediamine and propylene oxide, diethylenetriamine adduct containing the reaction product of diethylenetriamine and propylene oxide, and similar polyether polyols of the polyamide type. In the present invention copolyethers can also be used. Exemplary copolyethers include the reaction product of glycerol and ethylene oxide or glycerol and propylene oxide.

The isocyanate-reactive compound of the present invention has a number average molecular weight (MW) equal to or greater than 62, preferably greater than 400 g/mol, more preferably equal to or greater than 500 g/mol. Preferably, the polyols have a number average molecular weight equal to or greater than 62, preferably equal to or greater than 400 g/mol, preferably equal to or greater than 500 g/mol.

For an isocyanate-reactive compound having a number average molecular weight equal to or greater than 400 g/mol, more preferably equal to or greater than 500, the various polyethers may have a molecular weight (MW) of at least 500 to at most up to 20000 g/mol, preferably at least 600 at most up to 10000 g/mol, more preferably at least 1000 at most up to 12000 g/mol.

Molecular weight is determined by terminal functional group analysis and refers to the number average molecular weight.

The hydroxy-terminated polyester can be prepared by (1) an esterification reaction of one or more glycols with one or more dicarboxylic acids or anhydrides, or (2) a transesterification reaction, that is, the reaction of one or more glycols with dicarboxylic acid esters. Molar ratios, generally in excess of more than one mole of glycol relative to acid, are preferred to obtain linear chains having a predominance of terminal hydroxyl groups. Suitable polyesters also include various lactones, such as polycaprolactone, typically prepared from caprolactone and a bifunctional initiator such as diethylene glycol. The dicarboxylic acids of the desired polyester may be aliphatic, cycloaliphatic, aromatic, or combinations thereof. Suitable dicarboxylic acids, which may be used alone or in mixture, generally have 4 to 15 carbon atoms in total and include: succinic, glutaric, adipic, pimelic, subic, azelaic, sebacic, dodecanedioic, isophthalic, terephthalic, cyclohexanedicarboxylic , etc. It is also possible to use anhydrides of the dicarboxylic acids discussed above, such as phthalic anhydride, tetrahydrophthalic anhydride, or the like. Adipic acid is the preferred acid. Glycols which react to form the desired polyester intermediate may be aliphatic, aromatic, or combinations thereof and contain from 2 to 12 carbon atoms in total, and they include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexaniol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and the like, and their mixtures. 1,4-butanediol is the preferred glycol.

In some embodiments, the isocyanate-reactive compound may be reacted with at least one isocyanate, along with the chain extender glycol. Non-limiting examples of suitable chain extender glycols (i.e., chain extenders) include lower aliphatic or short chain glycols containing from about 2 to about 10 carbon atoms and include, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexaniol, 1,3-butanediol, 1,5-pentanediol, 1,4-cyclohexane dimethanol, hydroquinone di(hydroxyethyl) ether, neopentyl glycol, and the like.

Suitable amine compounds that can be used in the present invention include, without limitation, difunctional amines, polyfunctional amines, mixtures of amines, in particular amines including difunctional amines, or combinations thereof. For example, primary amines, secondary amines, or combinations thereof can be used as the amine compound of the present invention. Preferably, primary amines are used. Most preferred is a primary amine that is not hindered on the alpha carbon of the amine. Examples of such amines include, without limitation, compounds selected from the group consisting of 1,2-ethanediamine, N,N′-bis(3-aminopropyl)methylamine, N,N′-dimethylethylenediamine, neopentanediamine, 4,4′-diaminodiphenylmethane and 2-methylpentamethylenediamine (such as DYTEK A available from Invista, Wilmington, Del., U.S.A.). In addition, polyetheramines (such as JEFFAMINE polyetheramines available from Huntsman Corporation, The Woodlands, Tex., U.S.A.), (such as ELASTAMINE HT1100, ECA-29, EDR 148) and combinations thereof can be used in the present invention.

Preferably, the compound containing at least one amine functional group used in step (iii) of the present invention has a functionality of at least 2. This functionality is determined according to the amine functional groups, which are composed of primary amines. The compound containing at least one amine functional group preferably contains at least 2 amine-based functional groups consisting of primary amines.

According to a preferred embodiment, the carbonate ring/-NH ₂ molar ratio is 1:1.

Non-limiting examples of suitable ring-closing reaction catalysts include 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU), triazabicyclodecene (TBD), triethylamine and potassium tert-butanol.

Suitable catalysts that can be used in the present invention include, without limitation, tertiary amines, tin compounds, any standard urethane catalyst known in the polyurethane art such as triethylenediamine (TEDA), dibutyltin dilaurate (DBTDL), titanium containing compounds. or zirconium (eg TYZOR available from DuPont), or combinations thereof. Preferably, the catalyst is present in an amount of at least 10 ppm, preferably at least 0.01% by weight, preferably at least 0.05% by weight, with the % by weight referring to the total weight of the prepolymer .

In a preferred embodiment, steps (ii) and (iii) are carried out under solvent-free conditions.

Non-limiting examples of (isocyanate-reactive) compounds containing a cyclic carbonate functional group are listed below:

4-(гидроксиметил)-1,3-диоксолан-2-он

4-(hydroxymethyl)-1,3-dioxolan-2-one

4-(меркаптометил)-1,3-диоксолан-2-он

4-(mercaptomethyl)-1,3-dioxolan-2-one

4-((метиламино)метил)-1,3-диоксолан-2-он

4-((methylamino)methyl)-1,3-dioxolan-2-one

4-(аминометил)-1,3-диоксолан-2-он

4-(aminomethyl)-1,3-dioxolan-2-one

2-(2-оксо-1,3-диоксолан-4-ил)уксусная кислота

2-(2-oxo-1,3-dioxolan-4-yl)acetic acid

Glycerol carbonate is preferred.

As used herein, the term "isocyanate-containing compound" refers to a compound that contains at least one isocyanate group (-N=C=O), wherein the isocyanate group may be an end group. Preferably, the isocyanate group is an end group.

The isocyanate content (NCOv) (also referred to as percent NCO or NCO content) of the prepolymers, given in % by weight, is measured by conventional NCO titration following the standard method ASTM D5155, preferably with the Metrohm Titrino Plus. Briefly, the isocyanate reacts with an excess of di-n-butylamine to form urea. The unreacted amine is then titrated with standard nitric acid until the bromocresol green indicator changes color or to the potentiometric endpoint. The NCO percentage or NCO number is defined as the percentage by weight of NCO groups present in the product.

In the context of the present invention, the expression "NCO number" corresponds to the isocyanate number, which is the percentage by weight of reactive isocyanate (NCO) groups in an isocyanate-containing compound or prepolymer and is determined using the following equation, where the molecular weight of the NCO group is 42:

Infrared (IR) spectroscopy is performed on a Perkin Elmer Spectrum 100 FT-IR (Fourier Transform Infrared) spectrometer. ^-1 and with 16 scans. The spectra obtained are normalized to a peak at 1090 cm ^-1 corresponding to the bending of CO bonds present in isocyanate-reactive compounds (eg polyol).

The number average molecular weight, in particular of the polyol, and its distribution are analyzed by gel permeation chromatography (GPC) by dissolving the sample in THF (at a concentration of 5 wt %) and analyzing with a refractive index detector. Detection is based on retention time and is performed using a UV detector. The Agilent G1310B instrument is equipped with 5 µm 2xPLgel columns (flow rate 30 mL/min). As a result, the % peak area distribution of the prepolymer is obtained. The resulting chromatogram is compared with a calibration curve for a polystyrene standard.

Young's modulus (kPa), elongation at break (%), stress at break (kPa) are measured according to ISO DIN53504. A sample, "dog bone" hybrid PU-PHU compound having a cross section of 4×2 mm, is deformed at 100 mm/min using an Instron machine.

In the context of the present invention, viscosity can be measured with a Rheometrics (Brookfield R/S-CPS-P2 Rheometer equipped with a C25-2 conical spindle at 350 Pa using a cone and plate geometry (CONE SST 20 mm X 0.5) using the speed shear 100-300 rpm, and gap at truncation 250-450 microns Viscosity can be measured at ambient temperature (ie, 25°C), 50°C or 75°C.

The viscosity of at least one prepolymer, said cyclic carbonate-terminated prepolymer, and/or said PU-PHU hybrid composition is preferably non-Newtonian.

The expression "conversion of the cyclic carbonate-terminated prepolymer" is to be understood as corresponding to step (iii) of the present invention, during which the addition of said amine-functional compound results in ring-opening of said cyclic carbonate-terminated prepolymer. In practice, conversion can be defined as one hundred times the ratio of the area of the carbonyl carbonate peak in the FT-IR spectrum of cured PU-PHU to the area of the same peak in the FT-IR spectrum of the GC prepolymer before it is cured with amines.

Tg can be measured using differential scanning calorimeter (DSC) analysis, which is carried out using a TAQ2000 DSC device. The thermal protocol may consist of gradual linear heating from -90°C to +200°C, followed by gradual linear cooling down to -90°C, at a heating rate of 10°C/minute.

The terms "processable/processable/processability/processability" used in the present invention refer to processability at a certain pressure and at a given temperature when thermosetting polymers are produced using the method of the present invention, or refer to natural processability when thermoplastic polymers are produced in the context of of the present invention, without the need for any external influence to carry out the processing of this polymer.

According to a preferred embodiment of the present invention, the glycerol-carbonate-terminated prepolymer (GC-terminated prepolymer) can be reacted with a primary amine at a carbonate ring/-NH ₂ molar ratio of 1:1, preferably in the presence of 0.5% by weight of the selected catalyst . The reaction mixture is purged with dry nitrogen, agitated with a mechanical stirrer, and the internal temperature of the reaction mixture is monitored with a stream of nitrogen. The selected GC-terminated prepolymer is weighed into a disposable glass flask, the catalyst is added, and the mixture is heated in an oil bath at 100° C. (unless otherwise indicated) with vigorous mechanical agitation. When the reaction temperature is reached, the amine is added through the filling funnel. When two different amines are used, the less reactive one is preferably added first to react for 15 minutes, the second amine can be added later. The mixing time is adapted depending on the reactivity of the amine(s) used and consequently on the resulting increase in viscosity. The reaction is followed by ATR FT-IR observing the disappearance of the carbonate carbonyl peak at 1810 cm ^-1 and the simultaneous growth of the urethane peaks at about 1704 cm ^-1 . To obtain thin films, the mixture is homogenized by stirring at high speed and immediately transferred to a closed mold for molding, heated to 100°C for curing.

The following examples illustrate some embodiments of the present invention.

Examples of chemicals

Products Trade name Description Provider Isocyanates SUPRASEC® 1306 4,4'-MDI Huntsman Polyols Acclaim 4200
Acclaim 2200 PPG, Mw 2000 g/mol, f=1.98
PPG, Mw 4000 g/mol, f=1.98 Covestro Carbonates JEFFSOL® GC Glycerol carbonate Huntsman Amines JEFFAMINE® EDR 148
ECA 29
Tris(2-aminoethyl)amine 3,6-dioxaoctamethylenediamine
Epoxy curing agent, mixture of polyamines
trifunctional amine Huntsman
Huntsman
Sigma Aldrich Catalysts DABCO Triethylenediamine Sigma Aldrich TBD 1,5,7-Triazobicyclo[4,4,0]dec-5-ene DBU 1,8-Diazabicyclo[5,4,0]undec-7-ene Sigma Aldrich

EXAMPLES

Example 1 Synthesis of NCO-terminated prepolymers

NCO-terminated prepolymers are prepared by reacting an isocyanate and a polyol at an NCO/OH molar ratio of 2:1 (or higher).

400.24 g of 4,4'-MDI (SUPRASEC®1306; 3.19 mol -NCO, NCOv=33.52%) are weighed into a 4-necked lid reactor equipped with a mechanical stirrer , filling funnel, digital thermocouple and nitrogen flow . 4,4'-MDI is heated to 80° C. under nitrogen flow. When the reaction temperature is reached, 1593.72 g PPG (functionality=1.98, OHv=56.2 mg KOH) (1.60 mol -OH) are added dropwise while the mixture is mechanically stirred under nitrogen atmosphere. Isocyanate conversion is monitored by potentiometric NCO titration until the target NCOv (3.37±0.05%) is reached and kept constant over time. The resulting NCO-terminated prepolymers having a non-Newtonian viscosity of 30 Pa.s at ambient temperature (25° C.) can be stored in a sealed metal flask under a nitrogen atmosphere.

Example 2 Functionalization of Prepolymers with Glycerol Carbonate (GC)

In this example, functionalization is carried out using the same setup as used for the synthesis of the prepolymer obtained in example 1. GC (JEFFSOL®) and isocyanates interact at an equimolar ratio. The reaction is carried out under conditions without a catalyst. 250.11 g of the prepolymer (0.2 mol -NCO) from example 1 is heated at 70° C. under nitrogen. When the prepolymer reaches the reaction temperature, 23.67 g of GC (0.2 mol -OH) are added dropwise using a filling funnel. The reaction is highly exothermic and the mixture turns from clear to cloudy white. The reaction is monitored with an ATR FT-IR and monitored by observing the disappearance of the peak at 2270 cm ^-1 corresponding to unreacted isocyanates, while observing an increase in the urethane peak at 1726 cm ^-1 . When the reaction is complete, the product is stored at room temperature under nitrogen.

The GC terminated prepolymer has a non-Newtonian viscosity of 1333 Pa·s at ambient temperature (25°C).

Preferably, a DABCO catalyst can be used on occasion, up to 0.05 wt%, to reduce the reaction time.

Example 3 Synthesis of NCO-Terminated Prepolymers

NCO terminated prepolymers are prepared by reacting an isocyanate and a polyol with MW 4000 at an NCO/OH molar ratio of 2:1 (or higher).

200.09 g of 4,4'-MDI (SUPRASEC®1306; 1.6 mol -NCO, NCOv=33.48%) are weighed into a 4-necked lid reactor equipped with a mechanical stirrer, filling funnel, digital thermocouple and nitrogen flow . 4,4'-MDI is heated to 80° C. under nitrogen flow. When the reaction temperature is reached, 1597.94 g of PPG (functionality = 1.98, OHv = 28.2 mg KOH) (0.8 mol -OH) are added dropwise while the mixture is mechanically stirred under a nitrogen atmosphere. Isocyanate conversion is monitored by potentiometric NCO titration until the target NCOv (1.85±0.05%) is reached and kept constant over time. The resulting NCO-terminated prepolymers having a non-Newtonian viscosity of 25 Pa·s at ambient temperature (25° C.) can be stored in a sealed metal flask under a nitrogen atmosphere.

Example 4 Functionalization of Prepolymers with Glycerol Carbonate (GC)

In this example, the functionalization is carried out in the same setup as used for the synthesis of the prepolymer obtained in example 3. GC and isocyanates interact at an equimolar ratio. The reaction is carried out under conditions without a catalyst. 750 g of the prepolymer (0.33 mol -NCO) from example 3 is heated at 70° C. under nitrogen. When the prepolymer reaches the reaction temperature, 40.93 g of GC (0.35 mol -OH) are added dropwise using a filling funnel. The reaction is highly exothermic and the mixture turns from clear to cloudy white. The reaction is followed by ATR FT-IR and monitored by observing the disappearance of the peak at 2270 cm ^-1 corresponding to unreacted isocyanates, and at the same time observing the increase in the peak of urethane at 1726 cm ^-1 . When the reaction is complete, the product is stored at room temperature under nitrogen.

The GC terminated prepolymer has a non-Newtonian viscosity of 852 Pa·s at ambient temperature (25°C).

Preferably, a DABCO catalyst is used on occasion, up to 0.05% by weight, to reduce the reaction time.

Example 5 - Viscosity measurements

Table 1

Prepolymers Viscosity at 25°C (Pa s) Viscosity at 50°C (Pa s) Viscosity at 75°C (Pa s) SUPRASEC®1306/PPG2000 (NCOv=3.36%) - Example 1 thirty 4.9 1.3 SUPRASEC®1306/PPG4000 (NCOv=1.86%) - Example 3 25 3.8 1.1 GC-terminated prepolymers GC-SUPRASEC®1306/PPG2000 - example 2 1333 100 15 GC-SUPRASEC®1306/PPG4000 - example 4 852 71 9

Example 6 - Polymerization of the GC-terminated prepolymer from Example 2

The synthesized GC-functionalized prepolymer from Example 2 is reacted with JEFFAMINE® EDR 148, a difunctional primary amine, at a 1:1 carbonate ring/-NH ₂ stoichiometric ratio, in the presence of 0.5 wt % DABCO. The reaction is carried out using dry nitrogen and a mechanical stirrer, and the internal temperature of the reaction is monitored using a digital thermocouple.

74.81 g of GC-terminated prepolymer (0.027 mol) was weighed into a disposable glass flask, DABCO (0.5 wt %) was added, and the mixture was heated in an oil bath at 100° C., with vigorous mechanical stirring. When the reaction temperature is reached, 4.053 g of JEFFAMINE® EDR 148 (0.0274 mol) are added using a filling funnel.

The reaction is followed by ATR FT-IR, observing the disappearance of the carbonyl peak at 1810 cm ^-1 and the simultaneous appearance of urethane carbonyl peaks at 1704 cm ^-1 . The reaction is then stopped after 2 hours, when no further changes in the infrared spectra are observed. The end product is cloudy and white.

Preferably, when two different amines are used, the less reactive chemical is added first and reacted for 15 minutes, and after a while the second amine is added. In this case, the mixing time is adapted depending on the reactivity of the amine(s) used and the resulting increase in viscosity as a consequence.

The carbonate ring opening conversion is 91% as measured by FT-IR.

Example 7 - Polymerization of the GC-terminated prepolymer from Example 4

The same procedure was used as detailed for Example 6, except that the GC-terminated prepolymer from Example 4 was used.

In this example, the carbonate ring opening conversion is 94% as measured by FT-IR.

Example 8 - Combination of amines

Table 2 illustrates two embodiments of Example 8. PU-PHU products are prepared by reacting the GC-terminated prepolymer from Example 2 (NCOv from 3.37% wt-S1306/PPG2000) with a mixture of ECA-29 and JEFFAMNE® EDR 148 at various proportions amines (i.e., 50 wt% and 100 wt%, respectively, for samples 1 and 2). In the present example, curing is carried out by reacting first 69.55 g of GC-terminated prepolymer (0.0254 mol) with 1.88 g of difunctional JEFFAMNE® EDR 148 (0.0127 mol) and after 15 minutes 3.46 g ECA-29 (0.0128 mol) to complete curing.

It has been found that when only 25% by weight of ECA-29 is used, the material becomes soluble in warm DMSO and heat treatable. When at least 50% by weight of ECA 29 is used, the resulting polymers are thermoset, indicating a significant degree of crosslinking.

Mechanical properties are also illustrated in Table 2

table 2

PU-PHU JEFFAMINE® EDR 148 (% mol) ECA-29
(% mol) Elongation at break (%) Breaking stress (kPa) Young's modulus (kPa) 1 50 50 2214 4104 1322 2 0 100 893 3261 1757

The mol % referred to in the above table is expressed relative to the total moles of the GC prepolymer.

Example 9 - trifunctional amine

Table 3 illustrates two embodiments of Example 9. PU-PHU products are prepared by reacting the GC terminated prepolymer from Example 2 (NCOv from 3.37 wt% S1306/PPG2000) and Example 4 (NCOv from 1.85 wt% S1306/PPG4000 ) with tris(2-aminoethyl)amine (a trifunctional amine).

The same protocol as described above is used, which gives a GC-terminated prepolymer conversion of 93% after one hour.

The mechanical properties of polyhydroxyurethanes prepared with tris(2-aminoethyl)amine are illustrated in Table 3 below.

Table 3

PU-PHU Amine Elongation at break (%) Breaking stress (kPa) Young's modulus (kPa) NCOv 3.37% mass - S1306/PPG2000 tris(2-aminoethyl)amine 555 2895 1919 NCOv 1.85% mass - S1306/PPG4000 tris(2-aminoethyl)amine 1056 1384 763

Example 10

A dry hybrid PU/PHU thermoset polymer prepared from a GC prepolymer as illustrated in Example 2 (Suprasec 1306+PPG 2000 NCOv=3.37%) and tris(2-aminoethyl)amine was cut into small pieces having approximate dimensions ( length, width, thickness) 3×4×2 mm.

The balls are placed on a sheet of non-stick paper forming a circle having a diameter of 6 cm. The sample is then placed on the bottom plate of a Servitec Polystat 200T hydraulic press preheated to 140°C and a mechanical pressure of 11 MPa is applied to obtain a thickness of 1 mm. After 30 minutes, the sample is removed from the press and allowed to cool to room temperature. As a result of the processing procedure, small pieces merge into one film. At least one "dog bone" of the tensile test specimen is cut from the processed film. The remainder is cut again into small pieces and processed following the same procedure up to a total of three times.

Sample Young's modulus (MPa) Deformation at break (%) Breaking stress (MPa) PU-PHU polymer 1.73 358 2.57 Recycled PU-PHU
1st cycle 1.81 345 4.37 Recycled PU-PHU
2nd cycle 1.63 249 2.85 Recycled PU-PHU
3rd cycle 1.64 295 3.61

Tensile properties are determined using a Zwick ProLine Z020 testing device. The following parameters are used: strain rate 200 mm/min, preload 0.5 N, Young's modulus is calculated at a strain between 5% and 10%.

Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the present invention. Thus, the appearance of the phrases "in one embodiment" or "in some embodiment" in different places in the present description does not necessarily always refer to the same embodiment, although it may be. In addition, specific features, structures, or characteristics may be combined in any usable manner, as will be apparent to those skilled in the art from the present disclosure, in one or more embodiments. In addition, while some of the embodiments described herein include some and not other features included in other embodiments, combinations of features of different embodiments are considered to be within the scope of the present invention and form different embodiments, as will understood by those skilled in the art. For example, in the appended claims, any of the claimed embodiments may be used in any combination.

As used herein, the singular forms include both singular and plural references unless the context clearly indicates otherwise. By way of example, "isocyanate group" means one isocyanate group or several isocyanate groups.

The terms "comprising", "comprises" and "composed of" as used herein are synonymous with "including", "includes" or "having", "has" and are inclusive or open-ended and do not exclude additional details not mentioned. elements or steps of the method. It will be appreciated that the terms "comprising", "comprises" and "consisting of", as used herein, include the terms "consisting of", "consists" and "consists of". This means that, preferably, the terms discussed above, such as “comprising”, “comprises”, “consisting of”, “having”, “has”, “composed of”, can be replaced by “consisting”, “consisting of”, "consists of".

In this application, the term "about" is used to indicate that the value includes the standard deviation for the error of the device or method used to determine the value.

As used herein, the terms “wt %”, “wt %”, “wt %” or “wt %” are used interchangeably.

References to numerical ranges using endpoints include all integers and, where possible, fractions within that range (for example, 1-5 may include 1, 2, 3, 4, when referring to, for example, the number of elements, and may also include 1.5, 2, 2.75 and 3, 3.80 when referring to measurements, for example). Reference to endpoints also includes the endpoint values themselves (for example, 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range referred to herein is intended to include all subranges within it.

All references cited herein are hereby incorporated by reference in their entirety. In particular, the disclosures of all references herein are specifically referred to as being incorporated by reference.

Unless otherwise defined, all terms used in the description of the present invention, including technical and scientific terms, have the meanings as commonly understood by experts in the field to which the invention pertains. As a further explanation, definitions of terms are included to better describe the concept of the present invention.

In the present application, various aspects of the present invention are defined in detail. Each aspect thus defined may be combined with any other aspect or aspects, unless expressly stated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous. While the preferred embodiments of the present invention have been described for illustrative purposes, it will be apparent to those skilled in the art that various modifications, additions, or substitutions are made without departing from the scope and spirit of the present invention as described in the appended claims.

Claims (23)

1. A hybrid polyurethane-polyhydroxyurethane (PU-PHU) composition suitable for producing thermoset polymers or thermoplastic polymers with the possibility of further processing of the hybrid PU-PHU polymer at a later stage, obtained using a method comprising the following stages: (i) reacting at least one isocyanate-containing compound in a stoichiometric excess with at least one isocyanate-reactive compound to form at least one prepolymer, (ii) reacting said at least one prepolymer with a compound containing at least one cyclic carbonate functional group, resulting in the formation of a prepolymer with cyclic carbonate end groups, (iii) ring-opening reaction of said cyclic carbonate-terminated prepolymer with at least one difunctional amine compound and at least one polyfunctional amine compound, resulting in the above PU-PHU hybrid composition, wherein the step of said ring-opening reaction is carried out at a temperature above room temperature. 2. The hybrid PU-PHU composition according to claim 1, wherein said compound containing at least one cyclic carbonate functional group comprises at least one 4-membered cyclic carbonate, preferably at least one 5- a cyclic carbonate, more preferably at least one 6-membered cyclic carbonate. 3. A PU-PHU hybrid composition according to claim 1 or 2, wherein said at least one polyfunctional amine compound has a functionality of at least 3, preferably said polyfunctional amine compound is a trifunctional amine compound. 4. Hybrid PU-PHU composition according to claim 1 or 2, wherein said ring-opening reaction step is carried out at a temperature above 20°C, preferably above 25°C. 5. Hybrid PU-PHU composition according to claim 1 or 2, wherein the temperature at which said ring-opening reaction step is carried out is between 25°C and 160°C, preferably between 40°C and 160°C, more preferably between 45°C and 140°C. 6. The hybrid PU-PHU composition according to claim 1 or 2, wherein said at least one isocyanate-reactive compound has a number average molecular weight equal to or greater than 62, preferably equal to or greater than 400, more preferably greater than 1000, even more preferably greater than 2000, most preferably greater than 3800. 7. A hybrid PU-PHU composition according to claim 1 or 2, wherein step (ii) is carried out at a molar ratio of said at least one prepolymer to said compound containing at least one cyclic carbonate functional group (NCO:OH ) ranging from 0.5 to 1.05, preferably from 0.8 to 1. 8. A PU-PHU hybrid composition according to claim 1 or 2, wherein said at least one prepolymer has an NCO number ranging from 0.8 to 25%, more preferably from 0.8 to 10%. 9. Hybrid PU-PHU composition according to claim 1 or 2, where step (ii) is carried out at a temperature in the range from 50°C to 150°C, preferably from 60°C to 130°C, more preferably from 80° C to 125°C, most preferably in the range from 95°C to 122°C. 10. A hybrid PU-PHU composition according to claim 1 or 2, wherein step (ii) is carried out under solvent-free conditions. 11. Hybrid PU-PHU composition according to claim 1 or 2, wherein step (ii) and/or step (iii) is carried out in the presence of a catalyst selected from the group consisting of 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo(5,4,0)undec-7-ene (DBU), triazabicyclodecene (TBD), triethylamine and potassium tert-butanoate, as well as mixtures thereof. 12. A PU-PHU hybrid composition according to claim 1 or 2, wherein said compound containing at least one cyclic carbonate functional group is a glycerol carbonate. 13. A hybrid PU-PHU composition according to claim 1 or 2, wherein step (iii) is carried out over a period of up to 3 hours, preferably 2 hours, more preferably 1 hour. 14. The hybrid PU-PHU composition according to claim 1 or 2, wherein the conversion of the cyclic carbonate-terminated prepolymer from step (iii) is at least 90%, preferably at least 95%. 15. An adhesive, coating, elastomer or foam product, wherein the product contains a PU-PHU composition according to any one of the preceding claims. 16. A method for processing a thermoset hybrid PU-PHU product, wherein the method includes the following steps: - obtaining a cured thermoset hybrid PU-PHU product obtained using a hybrid PU-PHU composition according to any one of claims 1 to 14, and this product has an outer surface, - treating said cured thermoset hybrid PU-PHU product by applying at least one impact, preferably consisting of mechanical pressure, to said outer surface, at a given temperature and/or for a given period of time, - obtaining a processed hybrid PU-PHU product.