EP2115084A2

EP2115084A2 - Method for preparing polyhydroxy-urethanes

Info

Publication number: EP2115084A2
Application number: EP08761823A
Authority: EP
Inventors: Jean-Marie Bernard
Original assignee: Rhodia Operations SAS
Current assignee: Rhodia Operations SAS
Priority date: 2007-01-31
Filing date: 2008-01-31
Publication date: 2009-11-11
Also published as: US20090312502A1; WO2008107568A3; US8017719B2; US20110288230A1; CN101627094A; FR2911878B1; FR2911878A1; WO2008107568A2

Abstract

The invention relates to a method for preparing polyhydroxy-urethanes without using a compound having an isocyanate function, and from amino compounds and compounds carrying carbonate functions, in particular cyclic carbonate functions. The invention also relates to a method for preparing aqueous or hydro-organic formulations containing polyhydroxy-urethanes, and to the use of said polyhydroxy-urethanes and of said aqueous or hydro-organic formulations.

Description

PROCESS FOR THE PREPARATION OF POLYHYDROXYURETHANES

The present invention relates to novel routes of synthetic polyurethanes functional, without using isocyanate functions, aqueous formulations containing them, as well as obtaining coatings.

More particularly, the present invention relates to a novel route of access to functional polyurethane compounds bearing hydroxyl functions along the polymer chain, as well as the use of polyurethanes obtained in organic, aqueous and hydro formulations. -organic, for the preparation of coatings.

[0003] Polyurethanes occupy a privileged place in the polymer field, because of both their nature and their applications. They are usually formed from the reaction between a di-isocyanate and a compound having two functions with a mobile hydrogen, mainly hydroxyl groups, for example a diol. The choice of raw materials, both diisocyanate and diol, is very wide and allows a wide variety of combinations leading to products with different properties and applications, depending on whether they have hard or soft fragments, depending on whether they are expanded or compact and / or have high mechanical characteristics. A disadvantage of these polyurethanes is their mode of synthesis which involves the use of monomers with several toxic isocyanate functions. The production of polyurethanes therefore presents numerous chemical risks and is dangerous for the operators.

[0005] Many research studies have been carried out to implement less harmful formulations. In recent years, a new strategy for the synthesis of urethane function has been studied. It has been found that the reaction between a diamine and a molecule comprising at least two cyclic carbonate functions leads to the formation of polyurethane, without the use of isocyanate compounds. These are sometimes called NIPU ("non-isocyanate polyurethanes" or polyurethanes without isocyanate), or polyhydroxy-urethanes because of the formation of a hydroxyl group (-OH) in the β-position of the urethane function during the reaction. Other routes of synthesis of polyurethanes without using isocyanate compounds involve transcarbamoylation reactions, as for example described in the work of Rokicki and Piotrowska (Polymer, 43, (2002), 2927 -2935) . The polyhydroxy-urethanes are now commonly obtained by polyaddition reaction between a compound having two cyclic carbonate functions and a diamine. The reaction between the diamine and the cyclic carbonate functions leads, in a strictly organic medium, to the formation of a polyurethane bearing primary and / or secondary hydroxyl functions (Hidetoshi Tomita et al., Journal of Polymer Science, Part A: Polymer Chemistry , 39, (2001), 851-859). As another example of a process employing cyclic carbonate groups with a diamine, US Pat. No. 5,175,231 describes the formation of amino terminal amide oligonuclei from a diamine and a compound containing several diamines. cyclic carbonate groups, said cyclic carbonate groups being obtained from epoxy functions and carbon dioxide. The oligo-urethanes are then involved in various reactions to form polyurethanes (PU).

The application WO 2006/010408 also describes the reaction between a compound bearing at least two cyclic carbonate groups and a compound carrying at least two amino functions for producing a bicomponent adhesive.

It is therefore clear from the state of the art that current processes for preparing NIPU require a carrier compound of at least two cyclic carbonate groups, or cyclocarbonate. There is currently no process for the preparation of polyhydroxy-urethanes, without the use of isocyanate compounds, and using compounds carrying a single cyclic carbonate function, with a di-amine or a polyamine. Thus, a first object of the present invention is to provide a process for the preparation of polyhydroxy-urethanes, without the use of compounds. isocyanate, and using readily commercially available products, and having an economic advantage over known methods of the prior art.

Another object is to provide a process for the preparation of polyhydroxy-urethanes, without the use of isocyanate compounds, a wide variety.

Yet another object is to provide a process for the preparation of polyhydroxy-urethanes, without the use of isocyanate compounds, having one or more hydroxyl functions (-OH) located in position β and / or Y position of the urethane function.

As another object, the present invention provides a process for the preparation of polyhydroxy-urethanes, capable of reacting with other components to form crosslinked polymer compositions, useful as coatings, adhesives, and the like. Another object is to provide aqueous formulations of polyhydroxy-urethanes obtained without using isocyanate compounds, as well as the process for preparing said formulations and their uses, in particular for the preparation of coatings, adhesives and the like. . Another object of the present invention is to provide simple synthesis routes to polyfunctionalized compounds which can find applications such as surfactants and / or synthetic intermediates.

The present inventors have now discovered that these and other objects which will become apparent in the disclosure of the invention can be achieved in whole or in part by virtue of the present invention which is described hereinafter. Thus, the present invention firstly relates to a process for preparing a compound, an oligomer, or a polymer, (U), comprising at least one urethane group and at least one hydroxyl group ( -OH), said process employing: a) at least one compound (1) comprising a cyclic carbonate function and at least one hydroxyl function (-OH), the oxygen atom of at least one function hydroxyl being connected to the carbonyl carbon atom of said cyclic carbonate through 3 to 5, preferably 3 or 4 atoms; b) at least one compound (2) carrying at least one linear carbonate function; c) at least one compound (3) carrying at least one primary or secondary amine function, preferably carrying at least two primary and / or secondary amine functions; and d) optionally, at least one catalyst (4); the compounds (1), (2), (3) and optionally the catalyst (4) being engaged, simultaneously, sequentially or sequentially, in a reaction, optionally in the presence of a solvent, to obtain, after possible elimination of said solvent and / or co-products of the reaction, said compound, oligomer, or polymer, (U), comprising at least one urethane group and at least one hydroxyl group (-OH).

The method of the invention has many advantages, especially in terms of safety of people since it implements less toxic products than isocyanates. This method also provides access to a wide range of functional polyurethanes that can be used in the field of coatings or adhesives, and have an increased interest in obtaining aqueous polyhydroxy urethanes formulations.

The compound (1) is typically a cyclic carbonate bearing at least one hydroxyl function at the β or Y position of the carbonyl function. Such compounds are known to those skilled in the art and readily available commercially, or readily prepared using known procedures available in the literature, patents and patent applications, in the "Chemical Abstracts" or in the literature. 'Internet.

As compounds (1) that can be used in the process of the invention, mention may be made, for example, of polyol carbonates, such as glycerol carbonate, trimethylolpropane carbonate, pentaerythritol carbonate and the like, or sugars carbonates (carbohydrates). When the compound (1) has more than one hydroxyl function, it is preferred that the other hydroxyl function (s) are protected, for example in the form of carbamate, urethane, ester, in the form of dioxolane, or other.

Some compounds (1) are illustrated below:

where "alkyl" represents a linear or branched alkyl chain of 1 to 10 carbon atoms. Glycerol carbonate is a preferred compound (1) for the process of the present invention. According to a variant, which represents a preferred aspect of the process of the invention, the compound (1) may be present in the form of its precursor in the reaction medium. The precursors (1 ') of the compounds (1) are generally compounds comprising at least three hydroxyl functions, two of them being capable of forming the cyclic carbonate function of the compound (1) and a third being located in the β or γ position. of said carbonyl function capable of being formed.

The precursor (1 ') is converted to the compound (1), advantageously in situ, in the reaction medium, under the action of a compound bearing a cyclic or linear carbonate function. According to a preferred variant, the compound (2), which carries a linear or branched carbonate function, allows the conversion of the precursor (1 ') to compound (1).

The precursors (1 ') may be of any type known per se and mention may be made, for example, of rethane-1, 1, 2-triol (glycerol), 2,2- (dihydroxymethyl) butan-1-ol ( trimethylolpropane), propane-1,2,3-triol, 2,2- (dihydroxymethyl) propane-1,3-diol, and trishydroxymethylaminomethane derivatives (the amino function of which is optionally and advantageously protected in amide, urethane, salt, or other form), and others. As precursors (1 '), mention may also be made of sugars (carbohydrates) and polyethers or polyesters functionalized with hydroxyl functions (-OH). Mixtures of one or more compounds (1) and / or one or more compounds (1 ') may also be used.

The compound (2) carrying at least one linear carbonate function is also of any type known per se, and is easily accessible commercially or easily prepared using known procedures available in the literature, the patents and patent applications, in "Chemical Abstracts" or on the Internet. Compounds (2) whose boiling point (Eb) is between 80 ^° C. and 280 ^° C. at atmospheric pressure (760 mmHg, or 1013.25 hPa) are preferred. According to one embodiment, the compound (2) comprises at least one linear carbonate function corresponding to the following general formula (a):

_/ O. _/ O ^

R γ R '

O (a)

in which R and R ', which are identical or different, each represent a linear or branched alkyl radical comprising from 1 to 6 carbon atoms, preferably methyl or ethyl, each alkyl being able to be substituted by at least one cyclic carbonate, preferably by a cyclic carbonate.

By way of examples of compound (2) useful in the process of the invention, mention may be made of dimethyl carbonate (bp: 90 ° C.) and diethyl carbonate (bp: 126 ° -128 ° C.), alone or in mixtures.

It should be understood that one or more compounds (2) can be implemented in the process of the present invention.

In the case where the compound (2) has the formula (a), R and R 'being as defined above, and R and / or R' includes (s) at least one cyclic carbonate group, the compound (2) then comprises at least one linear carbonate group and at least one cyclic carbonate group. In this case, the compound (2) plays both the role of the compound (1) and the compound (2) in the process of the invention, in other words, the presence of the compound (1) is optional in said method. Examples of such compounds (2) which can overcome the use of the compound (1), can be illustrated by the following structures, which have no limiting character:

A particularly interesting aspect of the present process is that the respective carbonate functions of the compounds (1) and (2) have different reactivities. This makes it possible to obtain block polyhydroxy urethanes by using a second or even a third compound (2) and / or a second or even a third compound (3). When the process is carried out with more than one compound (2), for example with a second or even a third compound (2), said second and / or third compound (2) may be a compound containing at least one cyclic carbonate functional group with 5 or 6 ring members, such as for example ethylene carbonate (b.p. 243 ° C at 740 mm Hg (98.66 kPa)) and propylene carbonate (b.p.: 24O ⁰ C ), alone or in mixtures.

The compounds (2) carrying only cyclic carbonate functions, and in particular carriers of at least two cyclic carbonate functions are not preferred, in order to avoid competition between the cyclic carbonate function (s) (s). ) of the compound (s) (1) and the cyclic carbonate functions of the compound (s) (2). In the process of the present invention, and whatever the implementation used (simultaneous, sequential or sequential), the total number of linear carbonate functions introduced into the reaction medium by the compound (s) (2) ) must always be at least equal to the total number of cyclic carbonate functions introduced into the reaction medium by the compound (s) (2) and / or the compound (s) (1). In other words, the method of the invention is implemented with a ratio (A) defined as follows:

. . . Total number of linear carbonate functions _> Total number of cyclic carbonate functions ^~

The compound (3) comprises at least one primary or secondary amine function, preferably at least two primary amine functions and / or secondary (s), preferably at least two primary amine functions. Compound (3) can be of any type known per se, commercially available or easily prepared from known procedures, available in the literature, patents and patent applications, "Chemical Abstracts" or on the Internet . Generally the molar mass of the compound (3) is between 60 and

5000, preferably between 80 and 3000. [0039] In the case of primary amine function (s), the primary amino functions that are not very congested, preferably those having a -CH ₂ - group in the α-position, are preferred. the primary amine function.

According to a preferred aspect, the compound (3) comprises one or more other groups, for example and in particular one or more functions ether, urethane, amide, hydroxyl, thiol, carboxyl, ionic function (such as for example carboxylate). , sulfonate, phosphate, phosphonate, quaternary ammonium) or a mixture of two or more of these groups.

As non-limiting examples of compound (3), there may be mentioned: primary or secondary monoamines, such as alkylamines, straight-chain, branched or cyclic, optionally comprising one or more unsaturations, and comprising 1 to 20 carbon atoms, for example butylamine, hexylamine, cyclohexylamine; primary or secondary monoamines, such as alkylamines, with a linear, branched or cyclic chain, optionally comprising one or more unsaturations, and comprising from 1 to 20 carbon atoms, and comprising one or more ionic functions, for example chosen from carboxylate, carbonate, Q

sulfonate, phosphate, phosphonate, quaternary ammonium, and / or comprising one or more functions selected from -OH, -SH and ether; polyether monoamines, especially amines with a polymer chain (s) (alkylene oxide such as ethylene oxide and / or propylene oxide and / or butylene oxide and / or tetramethylene) which may also comprise one or more ionic functions , for example selected from carboxylate, carbonate, sulfonate, phosphate, phosphonate, quaternary ammonium, and / or one or more functions selected from -OH, -SH; aliphatic or cycloaliphatic diamines such as, for example, bis (aminopropyl) piperazine (marketed by Hunstman), aliphatic or cycloaliphatic diamines, generally known as precursors of diisocyanates, such as hexamethylenediamine (HMDA), isophorone diamine (IPDA), bis- (4,4'-aminocyclohexyl) methane (H ₁₂ MDA), tricyclodecanediamine (or 3 (4), 8 (9) -bis- (aminomethyl) tricyclo [5.2.1.10] decane sold by Celanese); 2-methylpentane-1,5-diamine; aromatic diamines, generally known as diisocyanate precursors, and for example toluene diamine, but such aromatic diamines are not preferred; diamines with ionic function (s), such as, for example, lysine and its salts, in particular alkali, for example sodium, or quaternary ammonium salts; oligomers and polymers comprising at least two amino functions, the backbone of the polymer may be indifferently a polyamide, a polyether, a polyester, a polyurethane or copolymers thereof. According to one embodiment, the compound (3) is chosen from di-, tri- or tetra-functional polyetheralkines or polyoxyalkyleneamines, the linear or branched alkylene unit of which preferably comprises 2, 3 or 4 carbon atoms. carbon, and mixtures thereof. Such polyetheramines are, for example, those marketed by Hunstman under the generic names Jeffamine ™ and Elastamine ™.

The process preferably involves one or more compounds (3), each of them advantageously comprising at least 2 amine functions. However, the invention does not exclude the use of mono-amines as the compound (3) as described above. The monoamines may, like the di- or polyamines defined above, be of any type known per se, and in particular mono-amines of polymers or oligomers, polyamides, polyethers, polyesters, polyurethanes or copolymers of them. Monoamines of interest are, for example, polyethermonoamines, and in particular those of the type known under the generic name of Surfonamine ™, marketed by the Hunstman Company.

The reaction solvent of the process of the present invention is generally a solvent of the highly polar type, and by way of example there may be mentioned deo methoxypropyl acetate (AMP), N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO), or else an alcohol-type solvent, for example methanol or ethanol or else an acetal-type solvent such as tetramethoxyethane, also called Highlink W (sold by Clariant). Mixtures of one, two or more solvents may also be used. It should be understood that the compound (2) can serve as a solvent for the reaction, in which case the use of another solvent is not required, even though this is not excluded.

The process of the invention involves several successive reactions that can be performed in a direct process, in a single step ("one pot"), or in a process in successive steps or sequenced. This process may be carried out at atmospheric pressure or under pressure, especially if the compound (2) has a boiling point of less than 150 ^° C.

Thus, for example, the process of the invention may be carried out by bringing the compound (1) into contact with the compound (2), and then adding to the reaction medium compound (3) with, if appropriate, the catalyst. (4).

Alternatively, it may be envisaged to bring into contact the compounds (1), (2) and (3), then optionally adding the catalyst (4) and / or one or more compound (s) (2). ) and / or (3), identical and / or different from the previous one (s). According to another variant, the process is carried out in a single step by simultaneously bringing all the compounds (1), (2) and (3) into contact with the catalyst (4). In the different possibilities of implementing the method, as explained above, it should be understood that the compound (1) can be replaced by γ j

its precursor (1 '). Thus, the process of the invention can be implemented by contacting the precursor (1 ') with the compound (2), then adding to the reaction medium compound (3) with optionally the catalyst (4) and / or one or more compound (s) (2) and / or (3), identical and / or different from (the) previous (s), or it may be envisaged to contact the precursor (1 ') with the compounds (2) and (3), then optionally adding the catalyst (4), or even a single step by contacting simultaneously the precursor (1 ') with all the compounds (2) and ( 3) and catalyst (4).

In each of these possibilities, and as indicated above, the ratio (A) defined above must be such that (A)> 1.

In general, purely illustrative and not restrictive, the overall reaction scheme of the process of the invention can be schematized as follows:

or when the precursor (1 ') is used in place of the compound (1):

(1 ¹ ) (2) (3) (U)

where R ¹ R ² N- represents the residue of the compound (3) after removal of a hydrogen atom from an amine function.

The successive reactions involved in the process of the present invention are described below, in a purely illustrative and non-restrictive way: i) in the presence of the compound (2), the compound (1) reacts with the amine compound ( 3), to lead, by opening the carbonate ring, to a compound (B), or its isomer (B '), comprising at least one carbamate function and at least one hydroxyl function, and preferably carrying two hydroxyl functional groups spaced by an optionally substituted two or three carbon alkylene chain:

ii) the compound (B) (and / or (B ')) then reacts with the carbonate (2) present in the reaction medium or added again in the reaction medium (the same or different compound of the first), to conduct, by cyclisation in cyclic carbonate, compound (C) (and / or (C)) bearing at least one urethane function and at least one cyclic carbonate functional group with 5 or 6 carbon atoms:

iii) in a last reaction, the compound (C) (and / or (C)) may optionally react with the amine compound (3) present in the reaction medium or added again in the reaction medium (amino compound identical to or different from the first), to give, by opening the carbonate ring, the compound (U) (and / or its isomer (U ')) bearing a hydroxyl group (s):

The entities (U) and (U '), isomers of each other, will be designated jointly by (U) in the present application.

Compounds B and B 'comprising at least one carbamate function and at least one hydroxyl function, and an amine function have structures that are typically representative of surfactant structures; the present invention thus relates to an alternative method for synthesizing surfactant compounds of structures B or B '.

The compound, oligomer, or polymer, (U), obtained according to the process of the present invention comprises, as indicated above, at least one urethane function and at least one hydroxyl function, said at least one hydroxyl function of the compound, oligomer, or polymer, (U) is preferably predominantly located along the chain, in particular of the polymer chain, in the β or Y position of the said at least one urethane function, as indicated schematically below:

The molecular weight and the functionality of the final compound with urethane and hydroxyl functional groups ((U) and / or (U ')) depend on the ratios of the various amine and carbonate functions used in the process, and lie in a wide range and depend on the applications that one seeks to develop. Depending on the ratios of the compounds (1), (2) and (3), the compound (U) (and / or its isomer (U ')) will also carry hydroxyl functions and / or primary amines or secondary and / or carrying 5 and / or 6 carbon cyclic carbonates. The molar ratio of amine / cyclic carbonate functions is generally between 0.1 and 10.

Step i) is illustrated more precisely by following Example 1. Step ii) is further illustrated by Example 2 which follows. Step iii) is illustrated more precisely by virtue of example 15 which follows.

According to a variant mentioned above, the compound (1) can be prepared in situ, from its precursor (1 ') in the presence of the carbonate (2) according to the following scheme:

(1 ') (2) (1).

In the reaction above, two alcohol functions are consumed for the formation of the cyclic carbonate (1). When the starting polyol contains more than two alcohol functions, ie 2 + n alcohol functions, the cyclic carbonate (1) obtained then carries n alcohol functions. For example, in the diagram above, n is 1.

One aspect of the process, which represents an object of the present invention, is characterized by an intermediate reaction (reaction ii) above) of closing a urethanediol ((B) or (B ')), in which two hydroxyl functions are separated by two or three atoms, into a cyclic urethane-carbonate ((C) or (C)), in the presence of a carbonate (2) and optionally a catalyst. It should be noted that this cyclic carbonate "closure" step leads to 5- or 6-membered rings.

The inventors have surprisingly discovered that the closure of the carbonate cycle can take place in shorter times, at lower temperatures, and generally without parasitic reaction with the urethane function, using various types. catalysts. The use of a catalyst is not mandatory, but has the advantage of accelerating the kinetics of the reaction and / or operating at a lower temperature. The use of a catalyst, especially as defined below, is preferred when the compound (2) corresponds to the formula (a) defined above and R and R 'are identical or different and each represents an alkyl radical, linear or branched, comprising from 1 to 6 carbon atoms, preferably methyl or ethyl, and do not contain a cyclic carbonate substituent.

Examples of suitable catalysts for the closure of the carbonate ring include oxides, alcoholates, or carboxylates of a metal selected from zinc, tin, zirconium, titanium and bismuth. Mention may also be made, as catalyst, of alkali and alkaline earth metals, hydroxides, carbonates, and alcoholates of alkali and alkaline earth metals, and their salts of tertiary amines and quaternary ammonium. There may be mentioned, more specifically by way of example zinc stearate, zinc acetate, zinc 2,4-pentanedionate, tin octoate, tin dibutyldilaurate, oxide. of dibutyltin, titanium isopropanolate, and titanium butanolate. As other types of catalysts, mention may also be made of Lewis acids, and advantageously among them, those which are stable in water, for example metal triflates such as triflate of bismuth, rare earths, or still strong non-ionic bases, such as tertiary amines and bases of phosphazene type.

According to a preferred embodiment, the ring closure reaction is very accelerated in the presence of phosphazene-type bases, even when they are used in catalytic proportions. In addition, the use of these phosphazene-type bases makes it possible to close the carbonate ring at a lower temperature, thus avoiding any degradation of the product formed.

Phosphazene bases are known as strong non-metallic, nonionic and non-nucleophilic bases. As examples of bases of phosphazene type which may be used, mention may be made, without limitation, of the following phosphazenes:

Phosphazene P ₁ -NBu ; molecular weight 312.43, CAS RN: 161118-67-8, purity 97%; Phosphazene P? -F-Bu (C ₁₄ H ₃₉ N ₇ P ₂ , molecular weight: 367.45, CAS RN: 111324-03-9, for example in 2 mol / L solution in tetrahydrofuran); Phosphazene P ₇ -Et: molecular weight: 339.40, CAS RN: 165535-45-5, purity 98%); Phosphazene BTPP: Phosphazene BEMP; Phosphazene Pi-f-Oct.

All these phosphazenes are commercially available (see for example http://www.sigmaaldrich.com). The Applicant has in fact surprisingly discovered that two hydroxyl functions separated by two or three atoms can be cyclized in cyclic carbonate function with 5 or 6 members respectively in the presence of a compound carrying at least one linear carbonate function. (For example a compound (2) as defined above) and a catalytic amount of at least one phosphazene base.

The use of a phosphazene-type base as a carbonate ring closure reaction catalyst in compounds carrying at least two hydroxyl functions, said at least two hydroxyl functions being separated by two or three atoms, is new and as such represents another aspect of the present invention.

The closure of a carbonate ring, in the presence of a catalytic amount of at least one phosphazene base, is particularly suitable for substrates bearing at least one carbamate (urethane) function and at least one two hydroxyl functions, said at least two hydroxyl functions being separated by two or three atoms and, in particular for substrates which are the compounds of type (B) or (B ') previously defined.

The compounds (U) (and (U ')) obtained according to the process of the present invention, and in particular the polyhydroxy-urethanes, find quite interesting applications in the form of compositions, in particular organic, aqueous or hydro-organic, preferably aqueous or hydro-organic, that is to say with at least one solvent and / or water, as components of coatings, adhesives, and others, optionally with one or several hardeners, especially polyurethane hardeners known to those skilled in the art, for example hardeners based on polyisocyanates.

As indicated above, the hydroxyl (-OH) functions of the polyhydroxy-urethanes obtained according to the process of the present invention are preferably mainly located along the polymer chain, in position β or γ urethane functions.

The organic formulations of the polyhydroxy-urethanes of the invention may also be used in combination with one or more conventional polyurethane (s) or conventional polyol (s), such as, for example, acrylic polyols or polyesters-polyols, for producing coatings with hardeners, for example of the polyisocyanate type.

According to another aspect, the present invention also relates to the process for preparing aqueous phase formulations of polyhydroxy-urethanes. By "aqueous phase formulations" is meant solutions, suspensions, dispersions, or emulsions, in which the solvent may be purely aqueous or hydro-organic.

The aqueous polyhydroxy-urethanes formulations according to the present invention can be obtained from compounds carrying at least one, preferably at least two carbonate functions, at least one of which is cyclic, such as for example those from the process of the invention, and noted compound (C) (and / or (C)) described above, and which are diurethane-dicarbonates. Alternatively, the aqueous formulations according to the invention can be obtained from compounds comprising at least one, preferably at least two carbonate functions, at least one of which is cyclic and which are obtained according to conventional methods known from the art. skilled person.

As examples of compounds carrying at least one, preferably at least two carbonate functions useful for the preparation of the aqueous formulations of the present invention, mention may be made of the following known compounds: diglycerol dicarbonate ; penta-erythritol dicarbonate; the di-ester of adipic acid and glycerol carbonate; and the adducts of a diisocyanate on glycerol carbonate; As examples of compounds bearing at least one, preferably at least two cyclic carbonate functional groups useful for the preparation of the aqueous formulations of the present invention, mention may be made of the following di-urethanes, obtained according to the process of the present invention: - isophorone diamine di-urethane (IPDA) and glycerol carbonate; the di-urethane of hexamethylenediamine (HDA) and glycerol carbonate; di-urethane of tricyclodecanediamine and glycerol carbonate; di-urethane of a polyetheramine, for example Jeffamine ™ XTJ 548, and glycerol carbonate; and di-urethane of bis- (4,4'-aminocyclohexyl) methane (Hi ₂ MDA) and glycerol carbonate.

Still other examples of compounds bearing at least one, preferably at least two cyclic carbonate functions useful for the preparation of the aqueous formulations of the present invention are those corresponding to the following formulas:

Thus, the process for preparing an aqueous phase formulation of polyhydroxy-urethane comprises the following steps:

1) the reaction of at least one compound bearing at least one, preferably at least two carbonate functions, at least one of which is cyclic, and optionally at least one carbamate (urethane) function, for example a compound ( 2) or a compound (C) bearing cyclic carbonate function (s), as defined above, with

2) at least one compound carrying at least two primary amine functions and / or secondary (s); and

3) optionally at least one compound carrying at least one primary amine function (s) and / or secondary (s);

4) mixing the reagents, or reaction product (s) in an aqueous phase, optionally containing an organic phase; and

5) obtaining an aqueous polyhydroxy-urethane formulation.

The compound comprising at least two primary amine functional groups and / or secondary functional groups, preferably at least two primary amine functional groups, may be of any type known per se, with a molecular weight of between 60 and 5000, preferably between 80 and 3000, and is commercially available or readily prepared from known procedures available in the literature, patents and patent applications, "Chemical Abstracts" or on the Internet. This compound is as previously described in the definition of compound (3) supra.

As non-limiting examples of compound comprising at least two amine functions, mention may be made of: aliphatic or cycloaliphatic diamines such as, for example, bis (aminopropyl) piperazine (marketed by Hunstman); aliphatic or cycloaliphatic diamines, generally known as precursors of diisocyanates, such as hexamethylenediamine (HMDA), isophorone diamine (IPDA), bis (4,4'-aminocyclohexyl) methane (Hi ₂ MDA); tricyclodecanediamine (or 3 (4), 8 (9) -bis- (aminomethyl) tricyclo [5.2.1.10] decane sold by Celanese); aromatic diamines, generally known as diisocyanate precursors, and for example toluene diamine, but such aromatic diamines are not preferred; diamines with ionic function (s), such as, for example, lysine and its salts, in particular alkali, for example sodium, or quaternary ammonium salts; oligomers and polymers comprising at least two amino functions, the backbone of the polymer may be indifferently a polyamide, a polyether, a polyester, a polyurethane or copolymers thereof.

According to one embodiment, the compound comprising at least two amine functional groups is chosen from di-, tri- or tetra-functional polyetheralkines or polyoxyalkyleneamines, the linear or branched alkylene unit of which comprises preferably 2, 3 or 4 carbon atoms, and mixtures thereof. Such polyetheramines are, for example, those marketed by Hunstman under the generic names Jeffamine ™ and Elastamine ™.

The process for the preparation of aqueous polyhydroxy-urethanes also preferably employs at least one compound carrying at least one primary and / or secondary amine function, preferably less a mono-amine, as for example those described in the definition of compound (3) supra. The monoamines may, like the di- or polyamines defined above, be of any type known per se, and in particular mono-amines of polymers or oligomers, polyamides, polyethers, polyesters, polyurethanes or copolymers thereof. this. By way of example, mention may be made of: primary or secondary monoamines, such as alkylamines, with a linear, branched or cyclic chain, optionally comprising one or more unsaturations, and comprising from 1 to 20 carbon atoms, by butylamine, hexylamine, cyclohexylamine; primary or secondary monoamines, such as alkylamines, with a linear, branched or cyclic chain, optionally comprising one or more unsaturations, and comprising from 1 to 20 carbon atoms, and comprising one or more ionic functions, for example chosen from carboxylate, carbonate, sulfonate, phosphate, phosphonate, quaternary ammonium, and / or comprising one or more functions selected from -OH, -SH and ether; and polyether monoamines, especially amines with a polymer chain (s) (alkylene oxide such as ethylene oxide and / or propylene oxide and / or butylene oxide and / or tetramethylene oxide) which may also comprise one or more functions ionic, for example selected from carboxylate, carbonate, sulfonate, phosphate, phosphonate, quaternary ammonium, and / or one or more functions selected from -OH, -SH. Mono-amines of interest are, for example polyether monoamines, and in particular those of the type known under the generic name Surfonamine ™, marketed by the Hunstman Company. The subject of the present invention is also the aqueous formulations of polyhydroxy-urethanes obtained according to the method described above, and in particular the aqueous polyhydroxy-urethanes formulations obtained by using a compound (2) defined above and having at least one cyclic carbonate function.

As indicated above, the hydroxyl (-OH) functions of the polyhydroxy-urethanes are preferably predominantly located along the polymer chain, in the β-position and / or in the urethane functional groups. [0091] Very interesting and diverse applications can be envisaged with aqueous formulations of polyhydroxy-urethanes, especially the aqueous formulations of the present invention, advantageously as formulations for coatings, adhesives, and others.

In particular, aqueous formulations of polyhydroxy-urethanes obtained according to the process of the present invention find applications as coatings, especially when the hardeners of said polyhydroxy-urethanes are hydrophilic and / or water-dispersible polyisocyanates, such as, for example those known under the generic name of Rhodocoat® ^®, marketed by the applicant, or those known under the generic name of Bayhydur ^®, marketed by Bayer. The aqueous polyhydroxy-urethanes formulations of the invention may also be used in combination with conventional polyurethanes or conventional polyols, such as, for example, acrylic polyols or polyester-polyols, or with aminoplast resins, for example. example melamine resins, for the development of coatings. Such associations are of very interesting interest when they are used in aqueous phase, or even hydro-organic, especially in the field of cosmetics. Indeed, the polyhydroxy-urethanes having been prepared without using isocyanate functional compounds, they do not exhibit the toxicity related to conventional polyurethanes prepared from isocyanates.

Depending on the type of amine (di-amine or mono-amine) used, the polyhydroxy-urethanes obtained may comprise one or more functions. pendent cyclic carbonate type generally located in position β and / or Y urethane functions.

The various types of polyhydroxy urethanes described above may carry terminal functions, these being, for example, cyclic carbonate units, and / or hydroxyl functions (-OH) and / or primary amine functional groups or secondary or tertiary and / or carboxylic and / or sulfonic acid and / or phosphoric or phosphonic acid functions; these functions may be in acid form or in salified form and / or comprise polyether monoalkyl ether chains, preferably with the proviso that the primary and secondary amine functions do not coexist with compounds with cyclic carbonate units.

The following examples are given purely by way of illustration and do not show any limiting nature of the field of protection conferred by the claims appended to the present description.

Examples

The phosphazene catalysts are supplied by the company Fluka. The polyether amines used are provided by Hunstman. Jeffamine ™ XTJ 542 is a polyether diamine containing a polytetramethylene glycol segment and whose amino functions are linked to this segment by a short chain of propylene glycol ether. The structure is as follows: NH 2 - [CH- (CH 3) -CH ₂ -O] n - [(CH ₂ ) ₄ -O] _m - [CH 2 -CH (CH 3) -O] p-CH 2 -CH (CH ₃ ) -NH2, with n = 3, m = 9 and p = 2. The average molecular weight is about 1000 g.

Jeffamine ™ XTJ 548 (also noted HT 1700) is a mixture composed of polyether diamines containing a polytetramethylene glycol segment and whose amino functions are linked to this segment by a short tetramethylene chain and polyether triamines containing two polytetramethylene glycol segments connected by a secondary amino function and whose primary amino functions are linked to the polytetramethylene segments by a short tetramethylene chain. The structure is as follows: NH ₂ - (CH ₂ ) ₄ -O - [(CH ₂ ) ₄ -O] _m - (CH ₂ ) ₄ -NH ₂ + NH ₂ - (CH ₂ ) ₄ -O - [(CH ₂ ) ₄ -O ] _m - (CH ₂ ) 4-NH- (CH ₂ ) ₄ -

O - [(CH ₂ ) ₄ -O] _m - (CH ₂ ) ₄ -NH ₂ , with m = 12 approximately.

The average molecular weight is about 1700 g.

EXAMPLE 1 Preparation of a mixture of glycerol / N-octylcarbamate In a three-necked reactor equipped with a condenser and an addition funnel, 354 g of methoxypropyl acetate are introduced successively under nitrogen. g (2 moles) of glycerol carbonate (Jeffsol GC from Hunstman, CAS RN: 931-40-8, molecular weight: 118.09). The mixture is stirred at 230 rpm and heated to 70 ^° C. Then 262.5 g (2.03 moles) of n-octylamine (CAS RN: 11-86-4, molecular weight: 129.25) are added in 15 minutes to the reaction medium. The reaction is strongly exothermic and the temperature of the reaction medium reaches about 88 ° C. The analysis of the reaction medium by infra-red analysis immediately after the addition of the amine shows a sharp decrease in the cyclic carbonate function (1780 cm ^-1 ) with appearance of the carbamate band around 1730 cm ^-1 . After 3 hours of reaction, the reaction mixture is cooled, the infrared analysis shows the absence of a cyclic carbonate function (1790 cm ^-1 ) and the formation of characteristic bands of the urethane functions (-NH at 3346 cm ^-1 C. = 0 to 1684 cm ^-1 , -CONH at 1535 cm ^-1 and hydroxyl (3400 cm ^-1 ).

The reaction mixture contains the mixture of the two carbamates Λ-n-octylcarbamate 1,3-dihydroxypropan-2-ol (C ₈ H ₁₇ NH-C (= O) -O-CH- (CH ₂ OH) ₂ ) (32% by weight, given by NMR analysis) and β-N-octylcarbamate of 2,3-dihydroxypropan-1-ol (C ₈ H ₁₇ NH-C (= O) -O-CH ₂ -CHOH- CH ₂ OH) (68% by weight by NMR analysis). The concentration of the carbamate diols in the mixture is 58.5% by weight. The molecular weight of these carbamate diols is 247.3. The NMR analysis of the proton and carbon 13 in CDCl ₃ medium confirms the structure of the compounds obtained. - Carbamate functions:

Proton NMR: -NH at 5.35 and 5.2 ppm, -CH ₂ N at 3.05 ppm. ¹³ C NMR: 2 types of C = O carbamates at 157.0 ppm and 156.7 ppm. - Confirmation of the absence of carbonate functions: no signal at 155- 154 ppm. The CHO and CH ₂ O signals of the glycerol group of the two carbamate species are confirmed in CO 2 by NMR:

1 -3-di-hydroxypropan-2-ol (C ₈ H ₁₇ NH-C (= O) -O-CH- (CH ₂ OH) ₂ ) n-octylcarbamate. o CHO: 4.7 ppm ( ¹ H NMR) and 75.7 ppm ( ¹³ C NMR); o CH ₂ O: 3.7 ppm ( ¹ H NMR) and 63.1 ppm ( ¹³ C NMR).

Α-N-octylcarbamate of 2,3-di-hydroxypropan-1-ol (C ₈ H ₇ NH-C (= O) -O-CH ₂ -CHOH-CH ₂ OH). o -CH ₂ OC (= O): 4.05 ppm ( ¹ H NMR) and 62.2 ppm ( ¹³ C NMR); o -CHOH: 3.75 ppm ( ¹ H NMR) and 70.5 ppm ( ¹³ C NMR); o -CH ₂ OH: 3.5 ppm ( ¹ H NMR) and 65.6 ppm ( ¹³ C NMR).

EXAMPLE 2 Cyclization of Octyl Urethanes Diols to N-Octylurethanes Bearing Cyclic Carbonate Functions [0102] 50.2 g of the composition of Example 1 are placed in a stirred reactor.

(ie 29.4 g of N-octylurethanediol or 0.119 mol). 8.5 g of methoxypropyl acetate (AMP) are added and the reaction mixture is stirred.

10.7 g of dimethyl carbonate (0.118 mol, CAS RN 616-38-6, molecular weight: 90.08) are added. After stirring, 0.31 g (0.001 moles) pure phosphazene P-pf-Bu (CAS RN: 81675-81-2) are added. The reaction mixture is brought to 100 ⁰ C for 4 hours of reaction, then the methanol is removed by distillation.

This synthesis was carried out with a molar ratio [basic phosphazene catalyst / urethane diol function] of 8.4 × 10 ³ . The infrared analysis of the reaction medium shows the presence:

cyclic carbonate functions at 1785-1800 cm ^-1 ; and

carbamate functions: NH at 3335 cm ^-1 , -CONH at 1540 cm ^-1 . The NMR analysis confirms:

the presence of the carbamate functions: NH at 5.1 ppm; CH ₂ N at 3.05; CH ₂ -O at 4.2; CHO at 4.8;

- presence of 6 C = O in ¹³ C NMR between 157 and 154 ppm, attesting the formation of cyclic carbonate functions and carbamates; and

the presence of the ester functions of the solvent C = O at 170.6 ppm. Examples 3 to 5

The synthesis of Example 2 is repeated using dilute solutions of catalysts based on phosphazene in hexane. Catalyst solutions of 2% by weight of phosphazene base in hexane are prepared from pure phosphazenes catalysts or 2M solutions in tetrahydrofuran supplied by Fluka.

The catalyst solutions are then added to the reaction medium in place of the basic pure phosphazene catalyst of Example 2. The results are shown in Table 1 below.

- Table 1 -

After 4 hours of reaction, carbamates diols give the carbamates bearing cyclic carbonate functions with methanol release.

The infrared spectra and the NMR analysis confirm the presence of the urethane and cyclic carbonates functions.

The carbylates of octyl and glycerol carbonate are also confirmed by comparison with a sample prepared by reaction of an equivalent of octylisocyanate with an equivalent of glycerol carbonate (see Example 6); this pathway through an isocyanate is not part of the invention. EXAMPLE 6 (Comparative / Not Part of the Invention) Synthesis of octyl carbamate and glycerol carbonate according to an isocyanate route In a reactor, 11 g of octylisocyanate, 9.6 g, are successively introduced. of glycerol carbonate (Jeffsol GC from Huntsman), and 40 g of methoxypropyl acetate and 0.01 g of tin dibutyldilaurate. The reaction mixture is heated at 70 ^° C.

After 5 hours of reaction, the isocyanate function has practically disappeared. The reaction medium is cooled to room temperature. The product is analyzed by infrared and proton NMR and ¹³ C NMR after evaporation of the solvent on a rotary evaporator. After evaporation of the solvent, the product crystallizes. The infrared analysis confirms:

the absence of isocyanate functions;

the presence of carbonate functions (1781 cm ^-1 ) and the presence of carbamate functions: NH at 3319 cm ^-1 , C = 0 at 1684 cm ^-1 ,

CONH at 1540 cm ^-1 Proton NMR analysis confirms:

the presence of C = O carbonate functions at 154.9 ppm ( ¹³ C NMR);

- the presence of carbamate functions: o ¹ H NMR: NH at 5.1 ppm and 4.85 ppm; CH ₂ -N at 3.05 ppm; ¹³ C NMR: -C = O at 155.6 and 155.4 ppm; and

the glycerol units: o ¹ H NMR: CH ₂ -O at 4.2 ppm; CHO at 4.8 ppm; ¹³ C NMR: CHO: 74.4 ppm; CH ₂ O of the cycle 63.2 ppm; and -CH ₂ O bound to the carbamate function: 65.9 ppm.

EXAMPLE 7 Synthesis of a Mixture of Di-urethanes of Isophorone Diamine and of a Molecule Carrying Cyclic Carbonate Functions by a Non-Isocyanate Route In a three-necked reactor, 27.7 is introduced successively under an inert atmosphere. g (0.235 moles) of glycerol carbonate (Jeffsol GC from Huntsman), and 52.9 g of dimethyl carbonate. This mixture is stirred and heated to 50 ^° C. 20.4 g (0.12 mol) of isophorone diamine (CAS RN: 2855-13-2, molecular weight: 170.3) are added in 30 minutes. The temperature of the reaction medium is then maintained at about 85 ° C. for 24 hours. By infra-red analysis, the transformation of the cyclic carbonate function of glycerol carbonate and the formation of the carbamate of isophorone diamine and glycerol are monitored.

0.243 g (7.8 × 10 ^-4 mol) of basic phosphazene catalyst Pif-Bu is then added to the reaction medium in order to convert the carbamate diol formed into a carbamate carbonate The molar ratio of catalyst to glycerol carbonate is 3.3 ^{10 -3.} the weight ratio catalyst / glycerol carbonate ratio is 0.88%. the reaction mixture is maintained at temperature of 85 ° C for 2 hours under reflux of the methyl carbonate. the methanol formed and part of the carbonate The reaction mixture is then left at ambient temperature (20 ^° C.) for 20 hours.

The Infra red analysis carried out on the reaction medium shows the presence of the cyclic carbonate band at 1792 cm ^{-1, the} methanol and the excess of dimethyl carbonate are then evaporated under vacuum on a rotary evaporator. mixture of carbamates of isophorone diamine and glycerol carbonate are then recovered The product is analyzed by the various ¹ H and ¹³ C NMR techniques, and by infrared spectroscopy, which confirm the formation of the functions well. urethanes and cyclic carbonates.

The urethane of isophorone diamine and 4-hydroxymethyl-1,3-dioxolan-2-one is also confirmed by comparison with a sample obtained by reacting 1 equivalent of isophorone diisocyanate with 2 equivalents. glycerol carbonate (Jeffsol GC from Huntsman) in methoxypropyl acetate (Comparative Example 9).

Example 8 (according to the invention): Synthesis of a mixture of di-urethanes of isophorone diamine and of a molecule carrying non-isocyanate cyclic carbonate functional groups

In a reactor is successively added under nitrogen 80 g of methoxypropyl acetate, 46.5 g of glycerol carbonate and 32.5 g (0.19 mol) of isophorone diamine. The temperature of the mixture is brought to 70 ° C. and the reaction is left with stirring at 70 ^° C. The disappearance of the carbonate functions is monitored by infrared analysis (1790 cm ^-1 ).

After stirring for 24 hours at 70 ^° C., 171 g (1.9 moles) of dimethyl carbonate and 31.2 g of a basic phosphazene P _r catalyst solution are added to the reaction medium under nitrogen. 2% by weight in hexane, ie 0.624 g of pure phosphazene PK-Bu catalyst, or 2 × ³ mole of pure catalyst. The molar ratio [catalyst / urethane diol function] is therefore 5.25 × 10 ^-3 . The temperature of the reaction medium is increased to 100 ^° C. until the dimethyl carbonate is under reflux. Hexane, catalyst solvent, is distilled off The methanol formed during the reaction is distilled off with a portion of the methyl carbonate (methanol-methyl carbonate azeotrope).

The formation of carbonate rings is followed by infrared spectroscopy at about 1780 cm ^-1 (appearance of the cyclic carbonate functions) After stirring for 8 hours at this temperature of 100 ^° C., the reaction is stopped by decreasing the temperature. at room temperature.

The structure of the products formed is confirmed by NMR analysis directly on the reaction medium. The urethanes of isophorone diamine and 4-hydroxymethyl-1,3-dioxolan-2-one and 5-hydroxy-1,3-dioxan-2-one are present in the reaction mixture.

The urethane of isophorone diamine and 4-hydroxymethyl-1,3-dioxolan-2-one is also confirmed by comparison with a sample obtained by reaction of 1 equivalent of isophorone diisocyanate with 2 equivalents. glycerol carbonate (Jeffsol GC from Huntsman) in methoxypropyl acetate (Comparative Example 9).

Example 9 (comparative / not part of the invention): Synthesis of isophorone diamine diurethane and glycerol carbonate by an isocyanate route.

In a reactor, are added successively 30 g of Highsolv P (Clariant solvent containing tetramethoxyethane), 17.5 g of glycerol carbonate (Jeffsol GC from Huntsman), 12.5 g of IPDI (isophorone di-isocyanate). ) and 0.015 g of tin dibutyldilaurate. The reaction mixture is heated at 100 ^° C. for 7 hours. The product obtained is used to confirm the presence of this glycerol carbamate carbonate in the mixture of Examples 7 and 8.

Example 10 (According to the Invention) Synthesis of a Hexamethylenediamine Di-urethane Carrying Cyclic Carbonate Functions Obtained According to the Invention by a Non-Isocyanate Route

In a three-necked reactor equipped with agitation and a reflux column, is introduced, under nitrogen, successively 118 g (1 mole) of glycerol carbonate.

(Jeffsol GC) and 360 g (4 moles) of methyl carbonate. 100 g of a methanolic solution containing 58% by weight of hexamethylenediamine (HMDA _1, ie 0.5 mol) are added to the reaction medium in 30 minutes. The reaction is exothermic. The temperature of the reaction medium is maintained at 85 ° C. throughout the reaction time.

After 2 hours of reaction, 10 g of a basic phosphazene catalyst solution P _r f-Bu at 20% by weight in hexane, ie 2 g of pure phosphazene Prf-Bu catalyst, or 6, are added. 4 ^{10 -3} mol of pure catalyst. The catalyst / diol carbamate molar ratio is 6.4 × 10 ^-3 .

The temperature of the reaction medium is raised to 100-110 ⁰ C, such that the hexane, the methanol formed during the reaction, and a portion of the methyl carbonate are removed by distillation.

After 8 hours of reaction, the reaction is stopped.

Example 11 (according to the invention): Preparation of a mixture of hexamethylenediamine di-urethane and of a molecule carrying cyclic carbonate functions, obtained according to the invention by non-isocyanate route

The procedure is as for Example 10, except that 236 g (2 moles) of diethyl carbonate are used in place of the methyl carbonate and that the temperature of the reaction medium after addition of the catalyst is brought to 120 ^° C.

Example 12 to 14 (according to the invention)

The procedure is as for Example 10, with the difference that the amines used are those shown in Table 2 below, that the amounts of the The reagents used for Example 13 are divided by 10 and the reaction time before catalyst addition is 8 hours at 85 ° C.

- Table 2 -

Example 15 (According to the Invention) Synthesis of Polyhydroxy-urethane with Cyclic Carbonate Terminal Functions

15-1: Preparation of a formulation containing 50% by weight of isophorone diamine di-urethane and glycerol carbonate

302 g of Highlink W (solvent sold by Clariant) are introduced into a stirred reactor of 1 liter. 305 g of isophorone diamine di-urethane and glycerol carbonate, prepared according to the procedure described in Example 7, are added to prepare 607 g of a 50% by weight solution of di-urethane.

15-2: Preparation of the polyhydroxy urethane end cyclic carbonates functions.

381, 7 g of 50% by weight formulation of di-urethane isophorone diamine and glycerol carbonate (obtained under 15-1) are introduced into a reactor of 1 liter.

The mixture thus contains 1. 145 moles of carbonate functions. 74 g of Highlink W

(Celanese) are added. 25.4 g of hexamethylenediamine (0.214 mol) are added over 30 minutes to the reaction mixture. The molar ratio {primary amine / carbonate function} is 0.37. The reaction is exothermic. The temperature of the reaction medium is maintained at 70 ^° C. for 8 hours.

Example 16: Preparation of an aqueous lysine formulation [0138] An aqueous solution of sodium salt of lysine is prepared as follows.

In a stirred reactor, 140 g of 1M sodium hydroxide are introduced. 20 g of lysine are then added with stirring. After complete dissolution of the lysine, obtain a solution of sodium salt of lysine which is used for the preparation of the aqueous polyhydroxy-urethane formulation.

This lysine solution will be used for the preparation of aqueous polyhydroxy-urethane formulations.

Example 17 (according to the invention) Synthesis of an aqueous polyhydroxy-urethane formulation

In a reactor, 50 g of formulation of Example 15-1 of isophorone diamine diurethane and glycerol carbonate, prepared according to the procedure described in Example 7, are introduced. The number of moles Carbonate functions in the formulation is 0.11.

64 g of lysine solution of Example 16 (ie 0.11 moles of amine functions) are then added at room temperature. The molar ratio primary amino functions / cyclic carbonates functions is 1. The reaction mixture is then heated to 85 ° C. and left stirring for 6 hours. Analytical monitoring by infrared shows the disappearance of carbonate functions.

An aqueous polyhydroxy-urethane formulation carrying sodium carboxylate functions is obtained.

Examples 18 and 19 (according to the invention): Examples of syntheses of aqueous polyhydroxy-urethane formulations

The procedure is as for Example 17, except that hexamethylenediamine is added to the reaction medium immediately after introducing the lysine solution.

The characteristics of each of the formulations are summarized in Table 3 below.

- Table 3 -

These examples show that aqueous formulations of polyhydroxy-urethane are obtained by conducting the reaction in a hydro-organic medium.

These formulations are used for the preparation of polyurethane films.

Examples 20 to 23: Examples of preparations of polyurethane compositions for coatings

[0149] Aqueous formulations polyhydroxy urethanes of Examples 17, 18 and 19 are formulated with polyisocyanate curing agents based on hexamethylene diisocyanate Rhodocoat ^® brand dispersible. Rhodocoat ^® XWT 2104 is used as a polyisocyanate hardener. For example 22 the dry extract of the final formulation is adjusted by adding water. The formulations obtained are applied to glass plates and left to dry at ambient temperature for 30 minutes and then for 2 hours at 60 ^° C.

The characteristics of the formulations obtained are summarized in the following Table 4:

- Table 4 -

* adding 5 ml of water

The formulations 20 and 21 give after drying opaque polyurethane films. Formulation 22 gives a transparent film. These examples show that the aqueous polyhydroxy-urethane formulations give polyurethane networks by crosslinking with water-dispersible polyisocyanates.

An optimization of the formulations makes it possible to adjust the properties to the required specifications.

Example 24 (according to the invention): Synthesis Example of an aqueous suspension of polyhydroxy-urethane

26 g of formulation of Example 15-1 of isophorone diamine diurethane and glycerol carbonate, prepared according to the procedure described in Example 7, are introduced into a reactor. 40 g of ethanol are added to the reaction medium and then 3.7 g of Surfonamine L 100 (primary alkyl amine-polyether primary sold by Huntsman) are added to the reaction medium. The molar ratio {amine functions / carbonate functions} is 0.33. After one night at room temperature, the solvent is evaporated under vacuum.

After adding 30 g of water to the reaction medium, a suspension of polyhydroxy-urethane is obtained.

Example 25 (according to the invention) Synthesis of an aqueous polyhydroxy urethane formulation with sulfonate functions

A first aqueous solution of triethylamine N-cyclohexylaminopropane sulphonate salt is prepared as follows: a) In a reactor, the following are successively added with stirring:

40.5 g of distilled water; 10 g of triethylamine;

21.8 g of N-cyclohexylaminopropanesulphonic acid; The solution obtained is homogeneous.

b) In a reactor, is added successively: 4.2 g of formulation 15-1 of isophorone diamine diurethane and glycerol carbonate, prepared according to the procedure described in Example 7;

0.6 g of hexamethylenediamine; 3.6 g of isopropanol;

4.3 g of aqueous solution of triethylamine N-cyclohexylaminopropanesulfonate salt prepared as above.

The ratio {amine functions / carbonate functions} is equal to 1.

The reaction is stirred at 70 ⁰ C for 18 hours. The absence of carbonate functions is confirmed by infrared analysis. The reaction medium is allowed to cool to 20 ^° C. to give a homogeneous hydro-organic solution of polyhydroxy urethane containing triethylamine sulfonate functional groups.

EXAMPLE 26 (According to the Invention) Synthesis of an aqueous polyhydroxy urethane formulation containing a polyhydroxy urethane having terminal primary amine functional groups [0158] In a stirred reactor, the following are successively introduced:

102 g of formulation of Example 15-1 of isophorone diamine di-urethane and glycerol carbonate, prepared according to the procedure described in Example 7;

8.5 g of hexamethylenediamine (HMDA); 86.6 g of solution of sodium salt of lysine (prepared from 11.77 g of lysine and 83.9 g of 1M sodium hydroxide).

The molar ratio {primary amine functions / carbonate functions} is 1, 32. The ratio {primary amines HMDA / primary amines lysine} is 1. [0106] The temperature of the reaction medium is brought to 70 ^° C. The reaction mixture is left stirring for 4 hours. The disappearance of the carbonate functions is followed by analysis by infrared spectroscopy. A homogeneous final polyhydroxy-urethane formulation is obtained, the solids content of which is 35.6%.

Polyvinyl urethane solubility test:

[0161] 3.1 g of formulation are taken and introduced into a 20 ml glass tube. A solution of 0.1 N HCl is added to neutralize the carboxylate functions. After addition of 1.5 ml of HCl solution, the appearance of a precipitate is observed. 14 g of the formulation obtained are then rapidly mixed with 4.95 g of Rhodocoat ^® WT 2102 (water-dispersible polyisocyanate based on HDI isocyanurate sold by the company Rhodia) and then rapidly applied to a glass plate to give a polyurethane coating.

Example 27 (according to the invention): Example of preparation of a coating from an aqueous formulation containing a polyhydroxy-urethane bearing sulphonate functional groups

27-1: Preparation of a hydro organic solution of the tetraethylamine salt of N-cyclohexylaminopropane sulfonic acid.

In a reactor is successively introduced 346 g of Highlink W (solvent sold by Clariant), 610 g of distilled water, 105 g of N-cyclohexylaminopropane sulfonic acid and 48 g of triethylamine. It is left stirring for 30 minutes at room temperature. 27-2: Preparation of a hydro-organic formulation of polyhydroxy urethane with pendant sulfonate functions.

105 g of a 55% solids solution of isophorone diamine diurethane and glycerol carbonate in Highlink W prepared as described in Example 15-1 are introduced into a reactor. 20.2 g of Highlink W, 9 g of HMDA are added successively. The primary amine molar ratio of HMDA / carbonate functions is 0.5. The temperature of the reaction medium is brought to 60 ° C. It is left stirring for 3 hours. The measurement of the hydroxyl function ratio of the polyhydroxy-urethane thus formed is 1, 0815 moles of OH / kg dry. 365 g of hydro-organic solution of the triethylamine salt of N-cyclohexylaminopropanesulfonic acid are added and stirred for 3 hours at 70 ^° C. and 16 hours at room temperature.

27-3: Preparation of a polyurethane coating from the hydroorganic formulation of Example 27.2. 173 g of polyhydroxy-urethane formulation of Example 27.2 and 21.6 g of Rhodocoat XEZM 501 (water-dispersible polyisocyanate from Rhodia of NCO titre of 0.514 mol / 100 g, ie 21, are added successively to a reactor, 58% by weight). The ratio NCO / OH is of the order of 1, 1. The mixture is slowly stirred manually with a glass rod to give a fluid formulation at 32% solids.

The formulation is then applied to a glass plate (wet film thickness: 200 μm). The film thus formed is then dried in an oven at 60 ⁰ C for 2 hours and then left at room temperature for 24 hours.

We obtain a PU film, matte appearance and 165 persoz hardness after 7 days.

Example 28: Example of preparation of a coating from a solvent-containing formulation containing a polyhydroxy-urethane composition of the invention and an isocyanurate polyisocyanate of HDI

This example is intended to demonstrate that the solvent formulations (organic solvent medium) of polyhydroxy-urethanes of the invention can give polyurethane coatings by reaction with polyisocyanate hardeners. 28-7: Preparation of the polyhydroxy-urethane formulation [0170] 105 g of the formulation of Example 15-1 (50% diurethane formulation) are introduced into a 250 ml reactor equipped with stirring. isophorone diamine and glycerol carbonate in the Highlink W). The number of moles of carbonate functional groups in the reaction medium is 0.23. The temperature of the reaction medium is brought to 35 ° C. 13.3 g of HMDA (0.115 mol) are then added over 10 minutes. The molar ratio NH ₂ functions / cyclic carbonate functions is 1. The temperature of the reaction medium is brought to 70 ⁰ C and the mixture is stirred for 5 hours.

The formulation is then stored at room temperature. 39.4 g of dimethylsulfoxide (DMSO) are added to bring the dry extract of the formulation to 42% and to reduce the viscosity of the reaction medium. The hydroxyl function titer is 0.144 moles per 100 g.

28-2: Obtaining an Organic Polyurethane Coating [0172] 7.34 g of the polyhydroxy-urethane formulation of Example 28-1 are mixed with 2.05 g of Tolonate HDT LV2 (low viscosity polyisocyanate). Rhodia based on isocyanurate of HDI and isocyanate-functional title of 23% by weight) and 1.98 g of DMSO. The coating formulation thus prepared is then applied to a glass plate (wet film thickness: 200 μm). The film is then dried for 1 hour at 60 ^° C. and is left at room temperature.

We obtain a transparent and smooth polyurethane coating (for which it is not possible to measure Persoz hardness, the pendulum slides).

Example 29 Preparation of a Polyhydroxy-Urethane Composition of the Invention

A precursor compound of a cyclic carbonate is used to prepare a polyhydroxy-urethane composition.

In a closed reactor of 50 ml, 8.35 g of glycerol (0.0906 mol), 16.35 g of methyl carbonate (0.182 mol), 0.13 g of phosphazene base catalyst Prf- Bu (4 × 10 ^-4 mol) and 2.59 g of hexamethylenediamine (HMDA, 0.045 mol) are left stirring at 100 ^° C. and the progress of the reaction is monitored by infrared analysis.

After one night of reaction, the temperature of the reaction medium is brought to room temperature. The reaction medium is analyzed by infrared spectroscopy (IR) and proton nuclear magnetic resonance (NMR). These analyzes confirm the formation of urethane and cyclic carbonate functions and the presence of hydroxy-urethane functions.

This gives a composition containing hexamethylenediamine diurethane and glycerol carbonate, polyhydroxy urethanes hexamethylenediamine and glycerol carbonate and whose terminal functions are urethanes of cyclic carbonates, carbonate of methyl and methanol.

Example 30 (According to the Invention) Preparation of a Hydroorganic Formulation of a Polyhydroxy-Urethane with Hanging Hydroxyl Functions and Bearing Amino Functions

The object of this example is to show the possibility of obtaining polyhydroxy-urethane formulations having preferably secondary amine functions, a portion of which is salified with a strong acid to obtain a solution or a dispersion in aqueous or hydroorganic phase. , using the selectivity of the reaction of opening of cyclic carbonates functions by primary amines relative to secondary amines.

30-1: Preparation of a polyhydroxy-urethane with pendant hydroxyl functional groups and terminal amine functions, [0180] Initially, a polyhydroxyurethane with pendant hydroxyl functions and having amine functional groups which are preferably secondary in the structure and terminal amines are prepared. .

A solution containing 84% by weight of the product of Example 7 (25.4 g /

0.055 moles) in the HighSolv ™ Solvent Clariant containing tetramethoxyethane (4.7g).

30.24 g of this solution are added to a 250 ml flask, then 7.4 g (0.034 mole) of bis (6-amino-hexamethylene) imine from Fluka (MW = 215) are successively added thereto. ) and 37.6 g of jeffamine HT1100 ™ (about 0.034 mole). The molar ratio of cyclic carbonate functions / primary amine functions is about 81%. The secondary amines / primary amines molar ratio is 29%. 25 g of HighSolvP are added. The mixture is stirred at approximately 50 ^° C.

After 8 hours of reaction, the disappearance of the carbonate band (1798 cm -1) is observed by infrared.

Potentiometric analysis of amino functions by triflic acid in acetic acid medium gives a total basicity (sum of primary and secondary amines) of 0.54 milliequivalents per gram for an expected theoretical value of 0.57 meq. /boy Wut. The quantity of hydroxyl functions obtained by assay gives a total amount of 0.95 meq / g for a theoretical expected value of 1.05. The determination of the hydroxyl functions is carried out by difference of the total of the acetylatable functions (amine and hydroxyl functions) and of the amino functions obtained by potentiometric assay (see above). The method of assaying the acetylatable functions is identical to the method for assaying hydroxyl functions of polyols well known to those skilled in the art. 30-2: Preparation of hydroorganic formulations of polyhydroxyurethane, part of the amine functions are salified.

B1 to B4 / Neutralization of amine functions by hydrochloric acid. In a 50 ml reactor, 5 g of formulation obtained in step 31.1, 1.5 ml of a solution of 1N HCl in isopropanol and 2.13 g of water are successively added. The reaction medium is strongly stirred. A milky solution of polyhydroxy-urethane hydrochloride is obtained.

The following examples show that the increasing salification of the amine functions makes it possible to obtain solutions of polyhydroxy-urethane hydrochloride.

B5 to B7 / Neutralization of amino functions by acetic acid.

Example 31 (According to the Invention): Preparation of Coatings from the Formulations of Example 30 A polyurethane coating was made from hydroorganic formulations obtained according to Example 30 and a hydrophobic or hydrophilic polyisocyanate hardener.

Example 31A:

The hydrophobic polyisocyanate hardener used is Tolonate HDT LV2 which is a low viscosity polyisocyanate (about 700 mPa.s at 25 ° C.) based on hexamethylene diisocyanate and having isocyanurate and uretidine dione functions, sold by the company Rhodia. The isocyanate titer of this polyisocyanate hardener is about 23% by weight. In a beaker is introduced 5.5 g of a formulation of Example 30.1, a solution of 1 N HCl in isopropanol (2.2 ml) and 0.2 ml of acetic acid is added. then 4 ml of water and 2 ml of HighsolvP. The mixture is mixed and then 0.68 g of tolonate HDT LV2 is added. The molar ratio NCO functions / OH functions is 1.9. The mixture is rapidly stirred vigorously to homogenize and the formulation is rapidly applied to a glass plate. The pot life of the formulation is very short (10 minutes) and it is important to quickly apply the formulation on the support. It is allowed to crosslink under a controlled atmosphere in humidity and at room temperature. The resulting film dries quickly (dry to the touch after 1 hour). The film obtained after drying has good properties. Example 31 B:

The hydrophilic polyisocyanate hardener used is RHODOCOAT EZ M 502, which is a polyisocyanate with a viscosity of about 3600 mPa.s at 25 ° C., based on hexamethylene diisocyanate and having isocyanurate and uretidine dione functions, sold by the company Rhodia. The isocyanate titer of this polyisocyanate hardener is about 18.4% by weight.

In a beaker is introduced to 9 g of a formulation of Example 30.1, 3 ml of Highsolv P then 9 g of water and 3 ml of acetic acid. A solution of polyhydroxy-urethane is obtained to which 1 g of RHODOCOAT EZM 502 is added. The molar ratio of NCO functions / OH functions is 1, 5. The mixture is rapidly stirred vigorously to homogenize and the formulation is rapidly applied to a glass plate

It is allowed to crosslink in a controlled atmosphere in moisture and at room temperature. An opaque film is obtained which dries rapidly.

Example 32 (according to the invention): Preparation of a hydroorganic formulation of a polyhydroxy-urethane with pendant hydroxyl functional groups and with pendant salified carboxylate functions. The object of this example is to show the possibility of obtaining a hydroorganic polyhydroxyurethane formulation by reacting a part of the pendant hydroxyl functions with a cyclic carboxylic anhydride which after reaction gives acidic ester functions which are salified by an amine. tertiary. The formulation thus obtained makes it possible to obtain polyhydroxyurethane formulations dispersible in water or in a hydroorganic medium. The cyclic carboxylic anhydride is succinic acid.

32.1: Preparation of polyhydroxyurethane bearing pendant hydroxyl functions. A terminal glycerol carbonate functional diurethane is prepared as follows. In a 1-liter jacketed reactor equipped with stirring and a condenser, 830 g of hexamethylene diisocyanate (HDI), 83 g of hydroxypyvalyl hydroxypivalate (also known as hydroxypivalate) are successively added under a stream of nitrogen. 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropionate (product sold by Eastmann Chemical, RN CAS 1115-20-4) The reaction medium is then stirred and the temperature of the reaction medium is set to 100 ⁰ C. the NCO content of the starting reaction mixture is 1 08 moles of NCO per 100 g representing 45.4% by weight. After 4 hours of reaction, the reaction mixture is distilled under vacuum on a wire evaporator scraping at the temperature of 160 ° C. and under vacuum (0.2 mm Hg) After removal of the excess HDI monomer, the amount of diurethane recovered is 197 g, 190 g of this diurethane are then added under a current of 100.degree. nitrogen in a jacketed 500 ml reactor and reacted with g of glycerol carbonate.

The temperature of the reaction medium is brought to 100 ⁰ C and the reaction medium is left stirring for 5 hours. A complete disappearance of the isocyanate functions is observed. 274 g of terminal glycerol carbonate-functional diurethane are obtained.

30 g of this mixture are taken and are introduced under nitrogen into a 250 ml reactor. 3 g of hexamethylenediamine and 22 g of polyamide ester CAPA 606036 from SOLVAY (polycaprolactone with terminal primary amine functions) are added to the reaction mixture and stirred at 80 ^° C. for 4 hours. The molar ratio of the primary amine functions on cyclic carbonate functions is 1. 52 g of polymer are obtained.

32.2: Preparation of a polyhydroxyurethane formulation carrying pendant hydroxyl functional groups and with pendant salified carboxylate functions

18.6 g of polymer of Example 32.1 are introduced into a 100 ml reactor. The temperature of the reaction medium is brought to 100 ° C. and 0.85 g of succinic anhydride are added. After 1 hour of reaction, 33% of the hydroxyl functions are thus converted into acidic ester functions. 1,11 g of N, N-dimethylcyclohexylamine are added to the reaction medium in order to salify the carboxylic functions pending. The product is recovered under heat and then allowed to cool to give a solid product at room temperature.

[0200] 10 g of solid product are introduced into a beaker and 10 g of N methylpyrrolidone are added to dissolve the polymer. The temperature of the mixture is brought to 50 ^° C. to promote dissolution. After complete dissolution, it is allowed to cool to room temperature and 4 ml of water are added to the reaction medium to give a hydroorganic solution of hydroxy-functional polyhydroxy urethane and pendant salified carboxylic functions.

Example 33 (according to the invention): Preparation of a hydroorganic formulation of a polyhydroxy-urethane-amide with pendant hydroxyl functions and salified carboxylate functions

Using a starting polyhydroxyurethane bearing secondary amine functions in the backbone and pendant hydroxyl functions, as described in Example 30.1.

[0202] With the difference of Example 32, the amine functional groups react with cyclic anhydride preferentially with pendant hydroxyl functions, and acidic amide functions are thus obtained, which can then be salified with tertiary amines and lead to polyhydroxy-urethanes. dispersible amides in water or in a hydroorganic solvent.

50 g of a polyhydroxy-urethane prepared as described in Example 30.1 are introduced into a 100 ml jacketed reactor equipped with stirring. The temperature of the reaction medium is brought to 80 ^° C. and 2.5 g of succinic anhydride are added. After 1 hour of reaction, the temperature of the reaction medium is allowed to return to room temperature and 3 g of N ₁ N -dimethylcyclohexylamine are added to salify the carboxylic acid functions. To 10 g of the mixture obtained are then added 5 ml of N-methylpyrrolidone and 2.5 ml of water to give a hydroorganic formulation of polyhydoxyurethane with pendant hydroxyl functions and pendant saline acid amide functional groups.

Claims

A process for the preparation of a compound, an oligomer, or a polymer, comprising at least one urethane group and at least one hydroxyl function, said process employing: a) at least one compound (1) comprising a cyclic carbonate function and at least one hydroxyl function (-OH), the oxygen atom of which is connected to the carbonyl carbon atom of said cyclic carbonate via 3 to 5, o preferably 3 or 4 atoms; b) at least one compound (2) carrying at least one linear carbonate function; c) at least one compound (3) carrying at least one primary or secondary amine function, preferably carrying at least two primary and / or secondary amine functions; and d) optionally, at least one catalyst (4); the compounds (1), (2), (3) and optionally the catalyst (4) being engaged, simultaneously, sequentially or sequentially, in a reaction, optionally in the presence of a solvent, to obtain, after possible elimination of said solvent and / or co-products of the reaction, said compound, oligomer, or polymer, (U). 0

2. Method according to claim 1, wherein said at least one hydroxyl function of said compound, oligomer, or polymer, (U), is located in position β or γ of said at least one urethane function.

3. Process according to claim 1 or claim 2, wherein said compound, oligomer, or polymer, (U), comprising at least one urethane group and at least one hydroxyl function is a polyhydroxy-urethane.

4. Process according to any one of the preceding claims, in which the compound (1) is chosen from polyol carbonates, such as glycerol carbonate, trimethylolpropane carbonate, pentaerythritol carbonate, sugars carbonates (hydrates carbon), and others.

5. Method according to any one of the preceding claims, wherein the compound (1) is present in the form of its precursor (1 ') having at least three hydroxyl functions, two of them being capable of forming the carbonate function. cyclic of the compound (1) and a third being located in the β or γ position of said carbonyl function capable of being formed.

6. Process according to any one of the preceding claims, in which the compound (1 ') is chosen from ethane-1, 1, 2-triol (glycerol), 2,2- (dihydroxymethyl) butan-i- ol (trimethylolpropane), propane-1,2,3-triol, 2,2-o (dihydroxymethyl) propane-1,3-diol, derivatives of trishydroxymethylaminomethane (whose amine function is optionally and advantageously protected in amide form urethane, salt, or other), sugars (carbohydrates) and polyethers or polyesters functionalized by hydroxyl functions (-OH). 5

7. Process according to any one of the preceding claims, in which the boiling point of the compound (2) is between 80 ^° C. and 280 ^° C. at atmospheric pressure (1013.25 hPa).

The process according to any one of the preceding claims, wherein the compound (2) has the following general formula (a):

The process according to any one of the preceding claims, wherein the compound (2) has the general formula (a):

in which R and R ', which are identical or different, each represent an alkyl radical, linear or branched, comprising 1 to 6 carbon atoms, preferably methyl or ethyl, and R and / or R 'comprises (s) at least one cyclic carbonate group.

The method of claim 9, wherein the compound (2) plays both the role of the compound (1) and the compound (2).

11. Process according to any one of the preceding claims, in which the compound (2) is chosen from dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate and the like, preferably dimethyl carbonate and diethyl carbonate, alone or in mixtures.

12. Process according to any one of the preceding claims, in which the compound (3) comprises one or more other groups, for example and in particular one or more functions ether, urethane, amide, hydroxyl, thiol, carboxyl, ionic function. (such as, for example, carboxylate, sulfonate, phosphate, phosphonate, quaternary ammonium) or a mixture of two or more of these groups.

13. Process according to any one of the preceding claims, in which the compound (3) is chosen from: primary or secondary monoamines, such as alkylamines, with a linear, branched or cyclic chain, optionally comprising one or more unsaturations, and having from 1 to 20 carbon atoms, for example butylamine, hexylamine, cyclohexylamine; the primary or secondary monoamines, such as alkylamines, with a linear, branched or cyclic chain, optionally comprising one or more unsaturations, and comprising from 1 to 20 carbon atoms, and comprising one or more ionic functions, for example chosen from carboxylate; carbonate, sulfonate, phosphate, phosphonate, quaternary ammonium, and / or having one or more functions selected from -OH, -SH and ether; polyether monoamines, especially amines with polymer chain (s) (alkylene oxide such as ethylene oxide and / or propylene oxide and / or butylene oxide and / or tetramethylene) may also include one or more ionic functions, for example selected from carboxylate, carbonate, sulfonate, phosphate, phosphonate, quaternary ammonium, and / or one or more functions selected from -OH, -SH; aliphatic or cycloaliphatic diamines such as, for example, bis (aminopropyl) piperazine (marketed by Hunstman), aliphatic or cycloaliphatic diamines, generally known as precursors of diisocyanates, such as hexamethylenediamine (HMDA), isophorone diamine (IPDA), bis- (4,4'-aminocyclohexyl) methane (Hi ₂ MDA), tricyclodecanediamine (or 3 (4), 8 (9) -bis- (aminomethyl) tricyclo [5.2.1.10] decane sold by Celanese); 2-methylpentane-1,5-diamine; aromatic diamines, generally known as diisocyanate precursors, and for example toluene diamine, but such aromatic diamines are not preferred; diamines with ionic function (s), such as, for example, lysine and its salts, in particular alkali, for example sodium, or quaternary ammonium salts; oligomers and polymers comprising at least two amino functions, the backbone of the polymer may be indifferently a polyamide, a polyether, a polyester, a polyurethane or copolymers thereof.

14. Process according to any one of the preceding claims, in which the compound (3) is chosen from di-, tri- or tetra-functional polyetheralkines or polyoxyalkyleneamines, the linear or branched alkylene unit of which preferably comprises 2, 3 to 5, preferably 3 or 4 carbon atoms, and mixtures thereof

15. Process according to any one of the preceding claims, in which the reaction solvent of the process of the present invention is a solvent of the highly polar type, for example chosen from methoxypropyl acetate (MPA) and N-methylpyrrolidone. (NMP), dimethylsulfoxide (DMSO), an alcohol solvent, for example methanol or ethanol, and an acetal solvent.

16. Process according to any one of the preceding claims, in which the catalyst (4) is chosen from oxides, alkoxides and carboxylates of a metal chosen from zinc, tin, zirconium, titanium and bismuth; among the alkali metals and alkaline earth metals, alkali and alkaline earth metal hydroxides, carbonates, and alkoxides, and their tertiary amine and quaternary ammonium salts; among the Lewis acids, advantageously those which are stable in water; and among the phosphazene type bases.

17. Use of a phosphazene-type base as a carbonate ring closure reaction catalyst in a compound carrying at least two hydroxyl functions, said at least two hydroxyl functions being separated by two or three atoms.

18. Use according to claim 17, wherein the compound carrying at least two hydroxyl functions also has at least one carbamate (urethane) function.

19. Use according to claim 17 or claim 18, wherein the ring closure reaction is carried out in the presence of a compound carrying at least one linear carbonate function.

20. Use according to claim 19, wherein the compound carrying a linear, branched or cyclic carbonate function has the formula:

21. Composition comprising at least one compound obtained according to any one of Claims 1 to 16.

22. Composition according to claim 21 which is an organic, aqueous or hydro-organic formulation.

23. Use of a composition according to claim 21 or claim 22 as a coating component, adhesive, in combination with one or more conventional polyurethane (s) or conventional polyol (s) and optionally with one or more hardeners, especially polyisocyanate hardeners.

24. A process for preparing an aqueous phase formulation of polyhydroxy-urethane comprising the following steps:

1) the reaction of at least one compound carrying at least one, preferably at least two carbonate functions, at least one of which is cyclic, with 2) at least one compound comprising at least two primary amine functions ( ) and / or secondary (s); and

4) mixing the reactants or reaction product (s) in an aqueous phase, optionally containing an organic phase; and

5) obtaining an aqueous polyhydroxy-urethane formulation.

25. The method of claim 24, wherein the compound bearing at least one, preferably at least two carbonate functions, at least one of which is cyclic, also has at least one carbamate (urethane) function.

26. Method according to one of claims 24 or 25, wherein the carrier compound of at least one, preferably at least two carbonate functions, has at least two cyclic carbonate functions and is selected from: - dicarbonate de diglycerol; penta-erythritol dicarbonate; the di-ester of adipic acid and glycerol carbonate; adducts of a di-isocyanate on glycerol carbonate; the di-urethane of isophorone diamine and glycerol carbonate; the di-urethane of hexamethylenediamine and glycerol carbonate; di-urethane of tricyclodecanediamine and glycerol carbonate; the di-urethane of a polyetheramine and glycerol carbonate; and di-urethane of bis- (4,4'-aminocyclohexyl) methane and glycerol carbonate;

27. The method of claim 24, wherein the compound bearing at least one, preferably at least two cyclic carbonate functions is selected from the following compounds:

28. Process according to any one of claims 24 to 27, in which the compound comprising at least two primary amine functional groups and / or secondary functional groups, preferably at least two primary amine functions, has a molar mass of between 60 and 5000, preferably between 80 and 3000.

29. Process according to any one of claims 24 to 28, wherein the compound comprising at least two amine functions is chosen from: aliphatic or cycloaliphatic diamines; aliphatic or cycloaliphatic diamines, generally known as precursors of diisocyanates, such as hexamethylenediamine, isophorone diamine, bis (4,4'-aminocyclohexyl) methane, tricyclodecanediamine (or 3 (4 ), 8 (9) -bis- (aminomethyl) tricyclo [5.2.1.10] decane); aromatic diamines, generally known as diisocyanate precursors, and for example toluene diamine; diamines with ionic function (s), such as, for example, lysine and its salts, in particular alkali, for example sodium, or quaternary ammonium salts; and oligomers and polymers comprising at least two amine functions, the polymer backbone may be either a polyamide, a polyether, a polyester, a polyurethane or copolymers thereof.

30. Process according to any one of claims 24 to 29, in which the compound carrying at least one primary and / or secondary amine function (s) is a mono-amine chosen from polymer mono-amines. or oligomers, polyamides, polyethers, polyesters, polyurethanes or copolymers thereof, and is in particular chosen from: primary or secondary monoamines, such as alkylamines, straight chain, branched or cyclic, optionally comprising a or more unsaturations, and having from 1 to 20 carbon atoms, for example butylamine, hexylamine, cyclohexylamine; primary or secondary monoamines, such as alkylamines, with a linear, branched or cyclic chain, optionally comprising one or more unsaturations, and comprising from 1 to 20 carbon atoms, and comprising one or more ionic functions, for example chosen from carboxylate, carbonate, sulfonate, phosphate, phosphonate, quaternary ammonium, and / or having one or more functions selected from -OH, -SH and ether; and polyether monoamines, especially amines with a polymer chain (s) (alkylene oxide such as ethylene oxide and / or propylene oxide and / or butylene oxide and / or tetramethylene oxide) which may also comprise one or more ionic functions, for example selected from carboxylate, carbonate, sulfonate, phosphate, phosphonate, quaternary ammonium, and / or one or more functions selected from -OH, -SH.

31. Use of an aqueous phase formulation of polyhydroxy-urethane for the production of coatings, adhesives or in the field of cosmetics.

The use of claim 31, wherein the polyhydroxy urethane is obtained by the process of any one of claims 24 to 30.