Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
  • C08G71/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group

Definitions

• the present invention relates to novel routes of synthetic polyurethanes functional, without using isocyanate functions, aqueous formulations containing them, as well as obtaining coatings.
• 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.
• 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.
• a di-isocyanate 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.
• 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.
• 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 ⁇ and / or Y position of the urethane function.
• 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 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
• 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 ⁇ 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.
• 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).
• polyol carbonates such as glycerol carbonate, trimethylolpropane carbonate, pentaerythritol carbonate and the like
• sugars carbonates carbahydrates
• the other hydroxyl function (s) are protected, for example in the form of carbamate, urethane, ester, in the form of dioxolane, or other.
• 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.
• 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 ⁇ or ⁇ 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.
• 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.
• 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.
• the compound (2) comprises at least one linear carbonate function corresponding to the following general formula (a):
• 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.
• 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.
• 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).
• 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).
• 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).
• the method of the invention is implemented with a ratio (A) defined as follows:
• 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
• the primary amino functions that are not very congested preferably those having a -CH 2 - group in the ⁇ -position, are preferred. the primary amine function.
• 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.
• 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
• 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
• HMDA hexamethylenediamine
• 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.
• polyetheramines are, for example, those marketed by Hunstman under the generic names Jeffamine TM and Elastamine TM.
• the process preferably involves one or more compounds (3), each of them advantageously comprising at least 2 amine functions.
• 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 TM, 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.
• AMP deo methoxypropyl acetate
• NMP N-methylpyrrolidone
• DMSO dimethylsulfoxide
• an alcohol-type solvent for example methanol or ethanol or else an acetal-type solvent such as tetramethoxyethane, also called Highlink W (sold
• 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.
• 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).
• 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).
• the compound (1) can be replaced by ⁇ j
• 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).
• R 1 R 2 N- represents the residue of the compound (3) after removal of a hydrogen atom from an amine function.
• 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:
• 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):
• 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 ⁇ 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 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.
• 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.
• the compound (1) can be prepared in situ, from its precursor (1 ') in the presence of the carbonate (2) according to the following scheme:
• n 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.
• reaction ii) above
• reaction ii) of closing a urethanediol
• C cyclic urethane-carbonate
• carbonate (2) optionally a catalyst
• 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.
• 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.
• catalysts examples include 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.
• the ring closure reaction is very accelerated in the presence of phosphazene-type bases, even when they are used in catalytic proportions.
• 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.
• 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.
• 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.
• 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 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 ⁇ or ⁇ 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.
• conventional polyurethane s
• conventional polyol s
• acrylic polyols acrylic polyols or polyesters-polyols
• hardeners for example of the polyisocyanate type.
• the present invention also relates to the process for preparing aqueous phase formulations of polyhydroxy-urethanes.
• 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.
• 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.
• 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;
• 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
• 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:
• the process for preparing an aqueous phase formulation of polyhydroxy-urethane comprises the following steps:
• 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.
• 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
• 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.
• polyetheramines are, for example, those marketed by Hunstman under the generic names Jeffamine TM and Elastamine TM.
• 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.
• 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 /
• Mono-amines of interest are, for example polyether monoamines, and in particular those of the type known under the generic name Surfonamine TM, 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.
• the hydroxyl (-OH) functions of the polyhydroxy-urethanes are preferably predominantly located along the polymer chain, in the ⁇ -position and / or in the urethane functional groups.
• 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.
• 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.
• the polyhydroxy-urethanes obtained may comprise one or more functions.
• pendent cyclic carbonate type generally located in position ⁇ and / or Y urethane functions.
• 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.
• 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
• the phosphazene catalysts are supplied by the company Fluka.
• the polyether amines used are provided by Hunstman.
• Jeffamine TM 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 average molecular weight is about 1000 g.
• Jeffamine TM 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 -
• the average molecular weight is about 1700 g.
• EXAMPLE 1 Preparation of a mixture of glycerol / N-octylcarbamate
• 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.
• 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 .
• 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:
• Example 2 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.
• 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
• 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.
• 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.
• 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
• 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.
• Example 9 (comparative / not part of the invention): Synthesis of isophorone diamine diurethane and glycerol carbonate by an isocyanate route.
• 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
• HMDA 1, ie 0.5 mol hexamethylenediamine
• 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.
• 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
• Example 10 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 10 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.
• the mixture thus contains 1. 145 moles of carbonate functions. 74 g of Highlink W
• Example 16 Preparation of an aqueous lysine formulation [0138] An aqueous solution of sodium salt of lysine is prepared as follows.
• 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
• 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.
• Example 16 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.
• Example 17 The procedure is as for Example 17, except that hexamethylenediamine is added to the reaction medium immediately after introducing the lysine solution.
• 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 formulations 20 and 21 give after drying opaque polyurethane films.
• Formulation 22 gives a transparent film.
• Example 24 (according to the invention): Synthesis Example of an aqueous suspension of polyhydroxy-urethane
• 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.
• Surfonamine L 100 primary alkyl amine-polyether primary sold by Huntsman
• the molar ratio ⁇ amine functions / carbonate functions ⁇ is 0.33. After one night at room temperature, the solvent is evaporated under vacuum.
• 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:
• the ratio ⁇ amine functions / carbonate functions ⁇ is equal to 1.
• 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:
• Example 15-1 102 g of formulation of Example 15-1 of isophorone diamine di-urethane and glycerol carbonate, prepared according to the procedure described in Example 7;
• HMDA hexamethylenediamine
• the molar ratio ⁇ primary amine functions / carbonate functions ⁇ is 1, 32.
• the ratio ⁇ primary amines HMDA / primary amines lysine ⁇ is 1.
• 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%.
• Example 27 (according to the invention): Example of preparation of a coating from an aqueous formulation containing a polyhydroxy-urethane bearing sulphonate functional groups
• the formulation is then applied to a glass plate (wet film thickness: 200 ⁇ m).
• 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.
• 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
• 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.
• DMSO dimethylsulfoxide
• the hydroxyl function titer is 0.144 moles per 100 g.
• Example 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 ⁇ m). The film is then dried for 1 hour at 60 ° C. and is left at room temperature.
• HDT LV2 low viscosity polyisocyanate
• a precursor compound of a cyclic carbonate is used to prepare a polyhydroxy-urethane composition.
• reaction medium 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.
• IR infrared spectroscopy
• NMR proton nuclear magnetic resonance
• 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.
• 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.
• 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.
• 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.
• 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.
• Example 31 B 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 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 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
• 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.
• 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.
• 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.
• HDI hexamethylene diisocyanate
• hydroxypyvalyl hydroxypivalate also known as hydroxypivalate
• the NCO content of the starting reaction mixture is 1 08 moles of NCO per 100 g representing 45.4% by weight.
• 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)
• 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.
• reaction medium 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.
• Example 33 (according to the invention): Preparation of a hydroorganic formulation of a polyhydroxy-urethane-amide with pendant hydroxyl functions and salified carboxylate functions
• Example 32 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.
• Example 30.1 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.

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