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    • 专利摘要:
    1) Particular polyurethane prepolymer (PP2) comprising at least two terminal (2-oxo-1,3-dioxolan-4-yl) methyl-carbamate low viscosity groups, its method of preparation and its use in the manufacture of a composition adhesive. 2) multicomponent system comprising as first component (A), a composition comprising at least one such polyurethane prepolymer and as second component (B), a composition comprising at least one hardener comprising at least two primary amine groups (-NH2) (B1 ). 3) Method of assembling materials using the polyurethane prepolymer (PP2) according to the invention.
    公开号:FR3018816A1
    申请号:FR1452276
    申请日:2014-03-19
    公开日:2015-09-25
    发明作者:Guillaume Michaud；Frederic Simon；Marjorie Pereira
    申请人:Bostik SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a cyclocarbonate-terminated polyurethane prepolymer ((2-oxo-1, 3-dioxolan-4-yl) methyl), and to its use in the manufacture of a multicomponent adhesive composition. carbamate)) (PP2) of low viscosity, its process of preparation, and its use in the manufacture of an adhesive composition. The invention also relates to a multicomponent system comprising at least: - as first component (denoted component A), a composition comprising at least one cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention and - as a second component (denoted as component B ), a composition comprising at least one hardener comprising at least two primary amino groups NH2 (B1). The invention also relates to a process for joining materials by bonding, using at least one polyurethane prepolymer with cyclocarbonate terminations (PP2) according to the invention.
    [0002] Adhesive (adhesive or mastic) compositions based on polyurethane have long been known, especially in the form of multicomponent systems (generally two-component systems) in which the (two) reactive components necessary for the synthesis of the polyurethane are stored separately, and mixed at the last moment before use of the adhesive composition.
    [0003] For such a system to be correctly implemented, the reactive components must have, on the one hand, sufficient reactivity for the reaction to take place and take place rapidly, and, on the other hand, a viscosity adapted to the mixing temperature for that it operates easily. Traditionally, polyurethane synthesis occurs through a polyaddition reaction between a polyol and a polyisocyanate. However, polyisocyanates are very sensitive compounds in the presence of atmospheric moisture and need to take appropriate measures to prevent their premature crosslinking, and therefore their loss of reactivity, during handling and storage (anhydrous conditions). In addition, some of these compounds, such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI) or diphenyl methane diisocyanate (MIDI), referred to as "diisocyanate monomer In the rest of the present application, are known to present toxicological risks for man and the environment, and may even generate toxic emissions for the most volatile. The use and storage of large quantities of such polyisocyanates should be avoided because it requires the implementation of complex and expensive security devices adapted to their use and storage. In particular, it is desired to avoid resorting to such compounds during the last stage of polyurethane synthesis, in order to make available to the public polyurethane adhesive compositions in the form of multicomponent systems, more respectful of the man and his environment and more stable storage.
    [0004] Patent application US 2007/0151666 discloses adhesive or putty compositions in the form of a two-component system, obtained by mixing a component A comprising at least two cyclocarbonate groups with a component B comprising at least two primary amine groups and / or secondary. Component A may be, inter alia, a prepolymer comprising ester or isocyanate groups functionalized with glycerol carbonate. In particular, the examples illustrate glue or putty compositions comprising a poly (hydroxyurethane-urethane) in which component A is a prepolymer or mixture of polyurethane prepolymers functionalized with glycerol carbonate. Although these compositions have the advantage of not using polyisocyanate when mixing components A and B, they have the disadvantage of using a component A very viscous or solid at low temperature, to be heated to a temperature of at least 125 ° C which may cause thermal degradation of the component, or be solubilized in a large amount of solvent (about 50% by weight of ethyl acetate in the examples) to be sufficiently liquid so that mix with the compound B. Otherwise, the mixture may mass and put out of production lines. The use of such operating conditions is however undesirable when it is desired to develop a process of economic preparation, quick to implement and respectful of man and the environment. A bad mixture of the compounds A and B can also lead to a product no longer having the desired properties and performance. In addition, when it is desired to formulate compositions in the form of a transportable kit that is practical, easy and quick to implement on demand ("Do It Yourself"), the mixture of the reagents must be able to be made as much as possible on volumes restricted and at low temperatures, especially at room temperature. Thus, glue or putty compositions in the form of an existing two-component system based on poly (hydroxyurethane-urethane) are not entirely satisfactory and remain to be improved. Therefore, there is a need to provide adhesive compositions based on polyurethane, not using, on the one hand, polyisocyanate as end-of-synthesis reagent polyurethane, including diisocyanate monomer potentially toxic to the last polyurethane synthesis step, and on the other hand, to overcome the disadvantages of the prior art, while maintaining satisfactory adhesive properties. There is also a need to formulate polyurethane compositions, available in the form of a multicomponent system and in particular two-component systems, which are easier to prepare compared to the prior art, for example at a mixing temperature of less than 95 ° C. preferably less than or equal to 80 ° C, more preferably less than or equal to 60 ° C, and more preferably close to room temperature (23 ° C). In particular, there is a need to find available compositions in the form of multicomponent systems, including transportable (kits), respectful of humans and the environment.
    [0005] In particular, there is a need to provide multicomponent systems, the implementation of which leads to adhesive compositions, especially adhesive or sealant compositions, having satisfactory adhesive properties. There is also a need to provide multicomponent systems, the implementation of which leads to adhesive compositions, especially adhesive or putty compositions, having mechanical performance (for example elongation and / or module) adapted to the use of the adhesive composition. There is also a need to develop a method for preparing such adhesive compositions, which is economical, quick to implement, and respectful of man and the environment. In particular, it is sought for a process for the preparation of such compositions that are inexpensive in energy and that do not use a large quantity of solvent in contrast to the existing preparation methods. Surprisingly, it has been found that the reaction of a particular NCO-terminated polyurethane prepolymer with glycerol carbonate, under particular conditions, makes it possible to obtain a polyurethane prepolymer with low viscosity low-temperature cyclocarbonate terminations, in particular at a temperature of less than 95 ° C, preferably less than or equal to 80 ° C, more preferably less than or equal to 60 ° C, and more preferably close to ambient temperature (ranging from 15 to 35 ° C), thus allowing to formulate easily under such conditions, especially without the aid of solvent, a composition having satisfactory adhesive properties, available in the form of a multicomponent system. The subject of the present invention is therefore, in the first place, a (2-oxo-1,3-dioxolan-4-yl) methyl-carbamate (PP 2) terminated polyurethane prepolymer obtainable by a preparation method according to the invention. invention, as defined in any one of the paragraphs below. It has been observed that the cyclocarbonate-terminated polyurethane prepolymer (PP2) thus obtained by complete functionalization of the NCO groups of an NCO-terminated polyurethane prepolymer (PP1), has a viscosity, measured at equal temperature, lower compared to the prepolymers of polyurethane functionalized with glycerol carbonate, disclosed in the prior art, thus making it possible to formulate easily and rapidly at a mixing temperature T3 of less than 95 ° C, preferably less than or equal to 80 ° C, more preferably less than or equal to at 60 ° C. and better still close to ambient temperature (ranging from 15 to 35 ° C.), a solvent-free adhesive composition, in the form of a multicomponent system. It has furthermore been observed that using the cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention, it is possible to manufacture solvent-free adhesive compositions having good wettability properties and good mechanical performance, suitable for surface coating. and satisfactory adhesive properties for adhesive bonding of at least two materials. The subject of the present invention is secondly a process for the preparation of such a (2-oxo-1,3-dioxolan-4-yl) methyl-carbamate-terminated polyurethane prepolymer comprising: in a first step (denoted El ), the preparation of an NCO-terminated polyurethane prepolymer (PP1) by a polyaddition reaction: (i) at least one diisocyanate selected from the following aliphatic or aromatic diisocyanates, and mixtures thereof: - isophorone diisocyanate ( IPDI), - 2,4-toluene diisocyanate (2,4-TDI), 2,4'-diisocyanate diphenylmethane (2,4'-MIDI), (ii) with at least one polyol selected from polyether polyols and polydiene polyols, at a reaction temperature Ti below 95 ° C, under anhydrous conditions, and in amounts of diisocyanate and polyol leading to a molar ratio NCO / OH, denoted r1, ranging from 1.6 to 1.9; then - in a second step (denoted E2), the reaction, under anhydrous conditions, at a reaction temperature T2 less than 95 ° C. of the product formed in the first step (E1) with at least one glycerol carbonate in a quantity such that all of the NCO groups present in the reaction medium at the end of step E1 react in the presence of glycerol carbonate. Preferably, a quantity of glycerol carbonate leading to an NCO / OH molar ratio, denoted r2, ranging from 0.9 to 1.0, preferably from 0.95 to 1.0, is used. The third subject of the present invention is a multicomponent system, preferably without a solvent, comprising: as the first component (denoted as component A), a composition comprising at least one cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention and as the second component (denoted as component B), a composition comprising at least one hardener comprising at least two primary amine groups NH 2 (denoted hardener amine (B 1)).
    [0006] The fourth subject of the present invention is also the use of the cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention for the manufacture of an adhesive composition (glue or putty), in particular without solvent. The fifth subject of the present invention is a method for assembling materials by gluing using at least one cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention. Other objects and features of the present invention will appear more clearly on reading the description and examples. In the present application, in the absence of any indication to the contrary: the amounts expressed in the form of a percentage correspond to weight / weight percentages; the term "cyclocarbonate group" means the (2-oxo-1,3-dioxolan-4-yl) methyl-carbamate group, that is to say a monovalent group corresponding to the following formula: NH - the masses number-average molar, expressed in grams per mole (g / mol) are determined by calculation by analysis of the end-group content (NCO, OH and cyclocarbonate) expressed in milliequivalents per gram (meq / g) and the functionality ( number of NCO, OH or cycicocarbonate functions per mole) of the compound under consideration (NCO-terminated polyurethane prepolymer (PP1), polyol, glycerol carbonate or cyclocarbonate-terminated polyurethane prepolymer (PP2) respectively). "Polyurethane prepolymer" denotes an intermediate for the synthesis of a polyurethane, corresponding to a polymer comprising in its main chain at least two urethane groups and at least two reactive functions (for example isocyanate or cyclocarbonate) enabling it to undergo at least one polyaddition reaction. Such a polyurethane prepolymer can be obtained by polyaddition reaction of at least one polyol with at least one polyisocyanate. In particular, the term "NCO-terminated polyurethane prepolymer" means a polyurethane prepolymer comprising at least two isocyanate groups (NCO) allowing it to undergo a polyaddition reaction in the presence of a cyclocarbonate (glycerol carbonate). Such an NCO-terminated polyurethane prepolymer is obtainable by polyaddition reaction of at least one polyol with a stoichiometric excess of polyisocyanate (s). This stoichiometric excess can be expressed by an NCO / OH molar ratio strictly greater than 1, which corresponds to the molar ratio of the number of isocyanate groups (NCO) to the number of hydroxyl groups (OH) carried by the species carrying such functions present in the reaction medium of the preparation of the polyurethane. In the process for preparing the NCO-terminated polyurethane prepolymer (PP1) of this invention, this ratio is denoted as ri.
    [0007] In particular, the term "cyclocarbonate-terminated polyurethane prepolymer" denotes a polyurethane prepolymer comprising at least two cyclocarbonate groups, enabling it to undergo a polyaddition reaction in the presence of a polyamine. Such a cyclocarbonate-terminated polyurethane is obtained by complete functionalization of the isocyanate groups of a polyisocyanate with glycerol carbonate. The complete functionalization of the isocyanate groups with glycerol carbonate can be obtained by mixing the reactants in a stoichiometric amount or with a stoichiometric excess of glycerol carbonate. This results in an NCO / OH molar ratio of less than or equal to 1. In the process for preparing the cyclocarbonate-terminated polyurethane prepolymer (PP2) of the invention, this ratio is denoted r2. - By "aminated hardener (B1)" is meant the hardener comprising at least two primary amine groups N} 12 (Bi) used according to the invention - the molar ratio NCO / OH noted ri, corresponds to the molar ratio of the number of isocyanate groups on the number of hydroxyl groups carried respectively by all of the isocyanate (s) and alcohol (s) present in the reaction medium of step El. - the molar ratio NCO / OH noted r2, corresponds to the molar ratio of number of unreacted isocyanate groups at the end of the preceding step (E1) on the number of hydroxyl groups carried respectively by all the isocyanates and alcohol (s) present in the reaction medium of step E2 . the hydroxyl number of an alcoholic product (in particular a polyol or glycerol carbonate which may be pure or in the form of a mixture) represents the number of hydroxyl functions per gram of product, and is expressed in the text of the present application under the form the equivalent number of milligrams of potash (KOH) used in the determination of hydroxyl functions, per gram of product. the measurement of viscosity at 23 ° C. can be carried out using a Brookfield viscometer according to the ISO 2555 standard. Typically, the measurement carried out at 23 ° C. can be carried out using a Brookfield RVT viscometer, a needle adapted to the viscosity range and a rotation speed of 20 revolutions per minute (rpm). the measurement of viscosity at 60 ° C. can be carried out using a Brookfield RVT viscometer coupled with a Thermosel heating module of the Brookfield brand, a mobile adapted to the viscosity range and at a rotational speed 20 rpm. the different embodiments described in the present application can be combined with each other.
    [0008] The subject of the present invention is a process for the preparation of a (2-oxo-1,3-dioxolan-4-yl) methyl-carbamate (PP 2) terminated polyurethane prepolymer comprising: in a first step (denoted by E ), the preparation of an NCO-terminated polyurethane prepolymer (PP1) by a polyaddition reaction: (i) at least one diisocyanate selected from the following aliphatic or aromatic diisocyanates, and mixtures thereof: - isophorone diisocyanate ( IPDI) (the weight percentage of isocyanate group is about 38% by weight based on the weight of IPDI), 2,4-toluene diisocyanate (2,4-TDI) (the percentage by weight of isocyanate group is equal to about 48% by weight based on the weight of 2,4-TDI), 2,4'-MIDI diphenylmethane 2,4'-diisocyanate (the percentage by weight of isocyanate group is equal to about 34% by weight relative to the weight of 2,4'-MIDI), (ii) with at least one polyol selected from polyeth polyols and polydiene polyols, at a Ti reaction temperature below 95 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyol (s) resulting in a molar ratio NCO / OH, noted r1 ranging from 1.6 to 1.9; then - in a second step (denoted E2), the reaction under anhydrous conditions, at a reaction temperature T2 lower than 95 ° C., of the product formed in the first step E1 with at least one glycerol carbonate in a quantity of carbonate glycerol resulting in an NCO / OH molar ratio, denoted r2, ranging from 0.9 to 1.0, preferably from 0.95 to 1.0. At the end of step E1, the NCO-terminated polyurethane prepolymer (PP1) obtained is such that the content of NCO groups (also referred to as "NCO content" and noted as% NCO) present in the reaction medium of the Step E1 is preferably from 0.5 to 5.7%, more preferably from 0.7 to 3%, and more preferably from 1 to 2.5% relative to the weight of the reaction medium of step E1. "NCO group content" (also referred to as "NCO content", denoted% NCO) means the content of isocyanate groups carried by all the compounds present in the reaction medium, namely the NCO-terminated polyurethane prepolymer (PP1) formed and the other species bearing isocyanate group (s) present, such as unreacted diisocyanate monomers. This NCO group content is calculable in a manner well known to those skilled in the art and is expressed as a percentage by weight relative to the total weight of the reaction medium. At the end of step E2, the reaction medium is free of potentially toxic diisocyanate monomers (IPDI, TDI, MDI). The cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention therefore does not present any toxicological risks related to the presence of such monomers.
    [0009] At the end of step E2, the cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention preferably has from 0.1 to 1.5 milliequivalents of cyclocarbonate groups per gram of said prepolymer (PP2), more preferably from 0.15 to 1 milliequivalent of cyclocarbonate groups per gram of said prepolymer (PP2) and more preferably 0.2 to 0.8 milliequivalent of cyclocarbonate groups per gram of said prepolymer (PP2). The diisocyanate (s) i) usable (s) to prepare the NCO-terminated polyurethane prepolymer used according to the invention is (are) preferably chosen from among the following diisocyanates, and their mixture: al) l) isophorone diisocyanate (IPDI), a2) 2,4-toluene diisocyanate (2,4-TDI). The diisocyanate (s) i) usable (s) according to the invention (cited in a2 and a3 above) can be implemented in the form of a mixture containing essentially (s) said diisocyanate (s) and a low content of residual diisocyanate compound (s) resulting from the synthesis of said diisocyanate (s). The content of the residual diisocyanate compound (s) tolerated (corresponding to the isomers of 2,4-TDI and 2,4'-MDI respectively) is such that the use of said mixture in the preparation of the NCO-terminated polyurethane prepolymer used according to the invention has no impact on the final properties of said polyurethane prepolymer.
    [0010] For example, the diisocyanate (s) i) usable (s) according to the invention (cited in a2 and a3 above) can be implemented in the form of a mixture containing at least 99% by weight of diisocyanate (s) and less than 1% by weight of residual diisocyanate compound (s), preferably in the form of a mixture containing at least 99.5% by weight of diisocyanate (s) and less than 0.5% by weight of residual diisocyanate compound (s), more preferably in the form of a mixture containing at least 99.8% by weight of diisocyanate (s) and less than 0.2% by weight of residual diisocyanate compound (s), relative to the weight of said mixture. Preferably, the content of the residual diisocyanate compound (s) is such that the weight content of isocyanate group in said mixture remains approximately equal to that indicated above relative to the weight of the diisocyanate a2) and a3) alone. Thus, 2,4-TDI as mentioned in a2) can be implemented in the form of a commercially available technical TDI, corresponding to a composition whose 2,4-TDI content is at least 99 % by weight, and preferably at least 99.5% by weight, based on the weight of said composition. The 2,4'-MIDI as mentioned in a3) can be implemented in the form of a commercially available technical MDI, corresponding to a composition whose content of 2,4'-MIDI is at least 99% by weight, and preferably at least 99.5% by weight, relative to the weight of said composition. The diisocyanate (s) i) usable (s) to prepare the polyurethane used according to the invention are widely available commercially. By way of example, mention may be made of the "Scuranatee T100" marketed by the company Vencorex, corresponding to a 2,4-TDI of purity greater than 99% by weight, the "Desmodure I" marketed by Bayer, corresponding to an IPDI. The polyol (s) ii) that can be used to prepare the NCO-terminated polyurethane prepolymer used according to the invention can be chosen from those whose number-average molar mass ranges from 200. at 20000 g / mol, preferably from 250 to 18 000 g / mol, and more preferably from 2000 to 12000 g / mol. Preferably, their hydroxyl functionality is from 2 to 3. The hydroxyl functionality is the average number of hydroxyl groups per mole of polyol. Preferably, the polyol (s) which can be used according to the invention has (nt) a hydroxyl (IOH) ranging from 9 to 105 mg KOH / g, and preferably from 13 to 90 mg KOH / g, more preferably 25 to 70 mg KOH / g, and more preferably 40 to 65 mg KOH / g polyol. The polyether polyol (s) ii) that can be used according to the invention is (are) preferably chosen from polyoxyalkylene polyol, the linear or branched alkylene portion of which comprises from 1 to 4 atoms. carbon, preferably 2 to 3 carbon atoms. More preferably, the polyether polyol (s) (ii) which can be used according to the invention is (are) preferably chosen from polyoxyalkylene diols or polyoxyalkylene triols, and more preferably polyoxyalkylene diols, of which the alkylene portion, linear or branched, comprises from 1 to 4 carbon atoms, preferably from 2 to 3 carbon atoms, and whose average molar mass ranges from 200 to 20000 g / mol, and preferably from 2000 to 12000 g / mol. By way of example of polyoxyalkylene diols or triols that can be used according to the invention, mention may be made of: polyoxypropylene diol or triol (also referred to as polypropylene glycols (PPG) diol or triol) having an average molar mass ranging from 400 to 18 000 g / mol and preferably ranging from 400 to 4000 g / mol; polyoxyethylene diol or triol (also known as polyethylene glycols (PEG) diol or triol) having an average molar mass ranging from 400 to 18,000 g / mol and preferably ranging from 400 to 4000 g / mol; copolymers of PPG / PEG diol or triol having an average molar mass ranging from 400 to 18,000 g / mol and preferably ranging from 400 to 4000 g / mol; polytetrahydrofuran (PolyTHF) diol or triol having an average molar mass ranging from 250 to 4000 g / mol; - and their mixtures. Preferably, the polyether polyol (s) that can be used is (are) chosen from polyoxypropylene diols or triols with a polydispersity index ranging from 1 to 1.4, in particular ranging from 1 to 1. 3. This index corresponds to the ratio of the weight average molar mass to the number average molecular weight of the polyether polyol (Ip = Mw / Mn) determined by GPC. The aforementioned polyether polyols are prepared conventionally and are widely available commercially. They can be obtained by polymerization of the corresponding alkylene oxide in the presence of a catalyst based on a double metal-cyanide complex. As examples of polyether diols, mention may be made of the polyoxypropylene diols sold under the name "Acclaime" by Bayer, such as "Acclaim® 12200" with an average molecular weight in the region of 11335 g / mol and the hydroxyl number ranges from 9 to 11 mg KOH / g, the "Acclaime 8200" of average molecular weight in the region of 8057 g / mol and the hydroxyl number of which ranges from 13 to 15 mg KOH / g, and "Acclaimer 4200" of average molar mass in number of about 4020 g / mol, and whose hydroxyl number ranges from 26.5 to 29.5 mg KOH / g, or the polyoxypropylene diol sold under the name "Voranol P2000" By the company Dow with a molar mass average number of about 2004 g / mol and whose hydroxyl number is about 56 mg KOH / g. By way of examples of polyether triol, mention may be made of the polyoxypropylene triol marketed under the name "Voranol CP3355" by the Dow Company, with an average molecular weight in the vicinity of 3554 g / mol and a hydroxyl number of 40 at 50 mg KOH / g.
    [0011] The polydiene (s) polyol (s) ii) usable (s) according to the invention is (are) chosen (s) preferably from polydienes containing terminal hydroxyl groups, and their corresponding hydrogenated or epoxidized derivatives. More preferably, the polydiene (s) polyol (s) ii) used (s) according to the invention is (are) chosen from polybutadienes having terminal hydroxyl groups, optionally hydrogenated or epoxidized. More preferably, the polydiene polyol (s) ii) used (s) according to the invention is (are) chosen from homopolymers of butadiene having terminal hydroxyl groups, optionally hydrogenated or epoxidized.
    [0012] By terminals, it is meant that the hydroxyl groups are located at the ends of the main chain of the polydiene polyol. The above-mentioned hydrogenated derivatives can be obtained by total or partial hydrogenation of the double bonds of a polydiene containing terminal hydroxyl groups, and are therefore saturated or unsaturated.
    [0013] The above-mentioned epoxidized derivatives can be obtained by chemoselective epoxidation of the double bonds of the main chain of a polydiene containing terminal hydroxyl groups, and therefore comprise at least one epoxy group in its main chain. As examples of polybutadiene polyols, mention may be made of saturated or unsaturated butadiene homopolymers comprising terminal hydroxyl groups, optionally epoxidized groups, as sold under the name poly bde or krasole by the company Cray Valley. The amount of diisocyanate (s) and polyol (s) used in step E1 is such that the molar ratio NCO / OH, denoted r1, ranges from 1.6 to 1.9, and preferably from 1.65 at 1.85.
    [0014] When the diisocyanate used is in the form of a composition or mixture as described above, the calculation of the ratio r2 takes into account, on the one hand, the NCO groups carried by the diisocyanate and the residual diisocyanate compounds resulting from the synthesis of said diisocyanate (s) optionally present in a mixture, and on the other hand OH groups carried by the polyether polyol (s) and polydiene polyol (s)) present in the reaction medium of step El. The polyaddition reaction of the Step E1 may be carried out in the presence or absence of at least one reaction catalyst.
    [0015] The reaction catalyst (s) that may be used during the polyaddition reaction of step E may be any catalyst known to a person skilled in the art for catalyzing the formation of polyurethane by reacting the reaction mixture. at least one diisocyanate with at least one polyol selected from polyether polyols and polydiene polyols.
    [0016] An amount of up to 0.3% by weight of catalyst (s) relative to the weight of the reaction medium of step E1 can be used. In particular, it is preferred to use from 0.02 to 0.2% by weight of catalyst (s) relative to the weight of the reaction medium of step E1. Preferably, the NCO-terminated polyurethane prepolymer (PP1) is obtained by polyaddition of one or two aromatic or aliphatic diisocyanates chosen from those mentioned in al), a2) and a3) as described in any one of the preceding paragraphs, with one or two polyols chosen from polyether polyols and polydiene polyols in the presence of at least one reaction catalyst, at a reaction temperature Ti of less than 95 ° C and preferably from 65 ° C to 80 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether polyol (s) resulting in an NCO / OH molar ratio, r1, ranging from 1.6 to 1.9, preferably from 1.65 to 1.85. More preferably, the NCO-terminated polyurethane prepolymer (PP1) is obtained by polyaddition of 2,4-TDI, with a polyol chosen from polyether diols or triols, and preferably with a polyether diol, in the presence of minus a reaction catalyst, at a reaction temperature Ti of less than 95 ° C and preferably from 65 ° C to 80 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether diol (s); ) or triol (s) leading to a molar ratio NCO / OH, denoted 1-1, ranging from 1.6 to 1.9, preferably from 1.65 to 1.85. The glycerol carbonate ii) that can be used according to the invention can be used either pure or in the form of a mixture or a composition of glycerol carbonate containing at least 96% by weight of glycerol carbonate and at most 3% by weight of residual polyol compound (s) (glycerol) resulting from the synthesis of said glycerol carbonate. In the latter case, the content of residual polyol compound (s) (glycerin) resulting from the synthesis of said glycerol carbonate is such that the average hydroxyl number of said glycerol carbonate composition is from 475 to 510 mg KOH / g of composition.
    [0017] Such compositions are commercially available as Jeffsole Glycerine Carbonate from Huntsman Corporation. The amount of glycerol carbonate used during step E2 is such that the molar ratio NCO / OH, denoted r2, ranges from 0.9 to 1, and preferably from 0.95 to 1.0.
    [0018] When the glycerol carbonate used is in the form of a composition or mixture as described above, the calculation of the ratio r 2 takes into account, on the one hand, the NCO groups carried by all the isocyanates present in the reaction medium of the step E2 (NCO-terminated polyurethane prepolymer (PP1) and optionally the unreacted diisocyanates used for its synthesis) and on the other hand OH groups carried by the glycerol carbonate, but also the compound (s) residual polyol (s) (glycerine) optionally mixed with the glycerol carbonate. According to a preferred embodiment of the process for preparing the cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention, the process does not comprise a step of purifying the intermediate reaction products, or of a solvent elimination step. . More preferably, said method does not include a step of adding one or more solvent (s) and / or plasticizer (s). Such a preparation method can thus be implemented without interruption, with very high production line speeds on an industrial scale. According to a more preferred embodiment of the process for the preparation of a (2-oxo-1,3-dioxolan-4-yl) methyl-carbamate (PP 2) -terminated polyurethane prepolymer according to the invention, this consists of in a first step E1 and in a second step E2, as defined in any one of the preceding paragraphs.
    [0019] The subject of the present invention is also a (2-oxo-1,3-dioxolan-4-yl) methyl-carbamate (2-oxo-1,3-dioxolan-4-yl) methyl-carbamate-terminated polyurethane prepolymer (PP2) obtainable by a preparation process according to the invention, as described in any of the preceding paragraphs. According to a first embodiment of the cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention, it preferably has a viscosity measured at room temperature (23 ° C.) of less than or equal to 1500 Pa · s, more preferably less than or equal to 600 Pa.s., and more preferably less than or equal to 400 Pa.s., for easy formulation, an adhesive composition according to the invention, especially without adding solvent.
    [0020] According to a second embodiment of the cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention, it preferably has a viscosity measured at 60 ° C. of less than or equal to 50 Pa · s, more preferably less than or equal to 40 Pa.s., and more preferably less than or equal to 30 Pa.s., to formulate easily, an adhesive composition according to the invention, especially without adding solvent. According to a preferred variant of these embodiments, the cyclocarbonate-terminated polyurethane prepolymer (PP2) has a viscosity measured at room temperature (23 ° C.) of less than or equal to 600 Pa.s. and a viscosity measured at 60 ° C. of less than or equal to 40 Pa.s. The subject of the present invention is also a multicomponent system, preferably without a solvent, comprising: as the first component (component A), a composition comprising at least one cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention and as a second component (component B), a composition comprising at least one hardener having at least two primary amine groups (-NH2) (denoted hardener amine (B1)). The components of the multicomponent system are generally stored separately and are mixed at the time of use at a blending temperature T3 to form an adhesive composition for application to the surface of a material. The adhesive composition according to the invention thus obtained comprises at least one poly (hydroxyurethaneurethane) comprising at least two primary amine groups, said poly (hydroxyurethaneurethane) comprising at least two primary amine groups resulting from the reaction of the polyurethane prepolymer (PP2) and the Amino hardener (B1). The components of the multicomponent system, and in particular components A and B, can be mixed under anhydrous conditions. Preferably, the amounts of cyclocarbonate-terminated polyurethane (PP2) prepolymer (s) and amino-hardener (s) (B1) present in the multicomponent system according to the invention lead to a molar ratio of the number of cyclocarbonate groups. the number of primary amine groups noted r3, ranging from 0.5 to 1. The molar ratio noted r3 throughout the present application corresponds to the molar ratio of the total number of cyclocarbonate groups present in the multicomponent system, the number of total of total primary amine groups present in the multicomponent system. The use of such a ratio r3 makes it possible to obtain, by a polyaddition reaction between the cyclocarbonate-terminated polyurethane prepolymer (PP2) and the amine curative (s) (B1), an adhesive composition comprising at least one poly (hydroxyurethane-urethane) having at least two or three primary amine groups according to the invention and having improved mechanical performance. The amine curative (s) (B1) used according to the invention preferably have a viscosity adapted to the mixing temperature T3. The amine curative (s) (B1) used according to the invention preferably has a primary alkalinity ranging from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / ml. g of amine hardener. The primary alkalinity is the number of primary amine functions NH 2 per gram of amino hardener (B 1), said number being expressed in the form of milliequivalents HCl (or milliequivalents of NH 2) used in the determination of the amine functions, determined in a well-known manner. by titrimetry. The amine curative (s) (B1) used according to the invention can be monomeric compounds or polymers. The amine curative (s) (B1) used according to the invention may be chosen from linear, branched, cyclic or acyclic, saturated or unsaturated hydrocarbon compounds and comprising at least two primary amine -NH 2 groups, the hydrocarbon chain between the -NH 2 or -CH 2 -NH 2 functions being optionally interrupted by one or more heteroatoms chosen from O, N, S and / or optionally interrupted by one or more divalent groups - NH- (secondary amine), -000- (ester), -CONH- (amide), -NHCO- (carbamate), -C = N- (imine), -CO- (carbonyl) and -SO- (sulfoxide) and having a primary alkalinity of from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g of amine hardener. By way of example of such compounds, there may be mentioned for example: alkylene polyamines containing at least two primary amine groups -NH 2 -cycloalkylene polyamines containing at least two primary amine groups NH 2 -polyamines comprising both alkyl groups and cycloalkyls and having at least two primary amine groups -NH2 - polyether polyamines having at least two primary amine groups -N1-12 - polyethylene imines comprising at least two primary amine groups -N1-12 - polypropylene imines comprising at least two primary amine groups -N1-12 - polyamidoamines containing at least two primary amine groups -N1-12 Preferably, the amine curative (s) (B1) used (s) according to the invention has (nt ) two or three primary amine groups.
    [0021] More preferably, the amine curative (s) (B1) used according to the invention is (are) chosen from hydrocarbon compounds, linear, branched, cyclic or acyclic, saturated and comprising two or three primary amine groups -NH2, said compounds being optionally interrupted by one or more heteroatoms chosen from an oxygen atom -O- and a nitrogen atom -N- and / or one or more divalent secondary amine -NH groups -,), and having a primary alkalinity ranging from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g of amine hardener. By way of example of such compounds, mention may be made, for example, of: alkylene diamines and alkylene triamines, comprising respectively two or three primary amine groups -NH 2 -cycloalkylenediamines and triamines, respectively comprising two or three primary amine groups -NH 2 diamines and triamines comprising both alkyl and cycloalkyl groups, comprising respectively two or three primary amine groups -NH 2 -polyether diamines and polyether triamines, respectively comprising two or three primary amine groups -NH 2 -polyethylene imines comprising two or three three primary amine groups -NH 2 - polypropylene imines containing two or three primary amine groups -NH 2 - polyamidoamines containing two or three primary amine groups -NH 2 More particularly, mention may be made of: - ethylene diamine (EDA) having a primary alkalinity 33.28 meq / g: NI-12 NI-12 - diethylenetriamine (DETA) with alkalinity primary content of 19.39 meq / g: I-12N NH NI-12 - tris (2-aminoethyl) amine (TAEA) having a primary alkalinity of 20.52 meq / g: NI-12 NH (N1-12 - the polyethylene imines corresponding to the formulas below: ## STR2 ## wherein x is a number integer such that the primary alkalinity is from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g; the polypropylene imines corresponding to the formulas below: H 2 N- (CH 2 -CH 2 -CH 2 -NH) x -CH 2 -CH 2 -CH 2 -NH 2 N [- (CH 2 -CH 2 -CH 2 -NH) x -CH 2 -CH 2 -CH 2 -NH2] 3 wherein x is an integer such that the primary alkalinity is from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g; the poly (ethylene-propylene) imines corresponding to the formulas below: H 2 N- (CH 2 -CH 2 -NH) x- (CH 2 -CH 2 -CH 2 -NH) y H N [- (CH 2 -CH 2 -NH) x- ( In which x and y are integers such that the primary alkalinity ranges from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g; hexamethylenediamine (HMDA) having a primary alkalinity of 17.11 meq / g NH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -NH 2; isophorone diamine (IPDA) having a primary alkalinity of 11.73 meq / g NI-12 NI-12 - polyether diamines having a primary alkalinity ranging from 7.58 to 19.23 meq / g and corresponding to the formula below: H2N- (CH2) y-O- [- CH2-CH (R4) -O-] .- (CH2) y-NE12 wherein y = 2 or 3, R4 is a hydrogen atom or a alkyl group of 1 to 2 carbon atoms, and n is an integer ranging from 0 to 3 such that the primary alkalinity ranges from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g; such polyether diamines are marketed for example under the name JEFFAMINES EDR-148 and EDR-176 by Huntsman and have respective primary alkalites of 13.51 and 11.36 meq / g; dimeric and trimeric fatty amines comprising two or three primary primary alkali amine groups ranging from 3.39 meq / g to 3.60 meq / g. These dimeric and trimeric fatty amines can be obtained from corresponding dimerized and trimerized fatty acids. By way of example of such dimeric fatty amines, mention may be made of those having the following formulas: ## STR2 ## The dimeric and trimeric fatty acids used to prepare the above-mentioned fatty amines are obtained by polymerization at high temperature and at atmospheric pressure. monocarboxylic unsaturated fatty acids (monomeric acid), comprising from 6 to 22 carbon atoms, preferably from 12 to 20 carbon atoms, and come from plant or animal sources. Examples of such unsaturated fatty acids are C18 acids having one or two double bonds (respectively oleic or linoleic acid) obtained from tall oil which is N H2 N H2 N H2 NI-12 a by-product. the manufacture of paper pulp. After polymerization of these unsaturated fatty acids, a technical mixture is obtained containing on average 30-35% by weight of monocarboxylic fatty acids which are often isomerized with respect to the starting monocarboxylic unsaturated fatty acids, 60-65% by weight of dicarboxylic acids ( dimer acids) comprising twice the number of carbon relative to the starting unsaturated monocarboxylic fatty acids and 5-10% by weight of tricarboxylic acids (trimer acids) having three times the number of carbon relative to the starting unsaturated monocarboxylic fatty acids . Purification of this mixture gives the different commercial grades of dimer acids, monomers or trimers. These dimeric and trimeric fatty acids are then subjected to a reducing ammoniation reaction (NH 3 / H 2) in the presence of a catalyst, making it possible to obtain the dimerized fatty amines. Advantageously, the primary amino groups -NH 2 of the amine hardeners (B1) usable according to the invention mentioned in the preceding paragraphs are methylene amine groups (-CH 2 -NH 2).
    [0022] When the multicomponent system according to the invention comprises at least two amine hardeners (B1), these can be included in two different components, for example a component (B) and a component (C). The components (A), (B) and (C) are then stored separately before mixing at the time of use of said system, at a mixing temperature T3, to form an adhesive composition intended to be applied to the surface of a material. The multicomponent system according to the invention may comprise at least one crosslinking catalyst. The crosslinking catalyst (s) can be any catalyst usually used to accelerate the ring-opening reaction of a compound having a cyclocarbonate group (2-0x0-1, 3-dioxolan-4-yl) methyl carbamate with a primary amine. As an example of a crosslinking catalyst that may be used according to the invention, mention may be made of: alcoholates, such as potassium tert-butoxide or sodium methanolate; strong bases chosen from: phosphazenes such as 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphoride (BMEP), guanidines such as: 1.5 7-Triazabicyclo [4.4.0] dec-5-ene (TBD) N-methyl triazabicyclodecene (Me-TBD) N-tertiary amines such as: 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) NN 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) NN diethyl ether-2,2'-morpholine (DMDEE) / o 1,4 diazabicyclo [2.2.2] octane (DABCO) An amount ranging from 0.05 to 1% by weight of crosslinking catalyst (s) relative to the total weight of the multicomponent system according to the invention may be used.
    [0023] The crosslinking catalyst (s) may be distributed in one or more of the components forming the multicomponent system according to the invention. Advantageously, the multicomponent system according to the invention may comprise at least one mineral filler.
    [0024] The (or) mineral charge (s) usable (s) is (are) chosen so as to improve the mechanical performance of the composition according to the invention in the crosslinked state. As an example of filler (s) usable (s), include but not limited to calcium carbonate, kaolin, silica, gypsum, microspheres and clays. Preferably, the mineral filler (s) have (s) a maximum particle size, in particular an external diameter, less than 100 μm and preferably less than 1.1 μm. . Such fillers may be selected in a manner well known to those skilled in the art using appropriate mesh screens. Preferably, the total filler content (s) possibly present in the multicomponent system according to the invention does not exceed 70% by weight of the total weight of said system. The charge (s) can be distributed in one or more of the components forming the multicomponent system according to the invention. The multicomponent system according to the invention may include less than 2% by weight of one or more additives suitably selected not to deteriorate the properties of the adhesive composition according to the invention in the crosslinked state. Usable additives include antioxidants or UV stabilizers (ultraviolet), pigments, and dyes. These additives are preferably chosen from those usually used in adhesive compositions. The additive (s) may be distributed in one or more of the components forming the multicomponent system according to the invention. Due to the low viscosity of the cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention, the multicomponent system according to the invention can be used directly by mixing its various components, without the addition of solvent and / or plasticizer. , viscosity reducers, in component (A) and / or without heating said component to temperatures above 95 ° C. Preferably, the cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention has a viscosity measured at 23 ° C. of less than or equal to 600 Pa.s. and a viscosity measured at 60 ° C. of less than or equal to 40 Pa.s, allowing the multicomponent system according to the invention to be advantageously used without the addition of a solvent and / or a plasticizer in component (A) comprising said prepolymer (PP2), and / or without heating said component. The multicomponent system according to the invention thus advantageously comprises: as the first component (A), a composition comprising at least one cyclocarbonate-terminated polyurethane prepolymer (s) (PP2) according to the invention and as the second component (B), a composition comprising at least one or two amine hardener (s) as described in one of the preceding paragraphs (B1), and - does not include a solvent and / or plasticizer.
    [0025] The multicomponent system according to the invention may be a two-component system, that is to say a system consisting of two components (A) and (B), said components (A) and (B) being as described in one embodiment. previous paragraphs. In each of the preceding paragraphs, the distribution and the total content of crosslinking catalyst (s), mineral filler (s), and / or additive (s) possibly present (s) in the multicomponent system, are chosen so not to affect the mixing conditions of the different components of said system. Preferably, component (A) comprises at least 97% by weight, and more preferably at least 98% by weight of cyclocarbonate-terminated polyurethane prepolymer (s) (PP2) according to the invention.
    [0026] The invention also relates to the use of a cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention, for the manufacture of an adhesive composition (glue or putty), preferably without a solvent, in particular in the form of a multicomponent system. In particular, the cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention is reacted with at least one amine curative (B1) as described above to form, by a polyaddition reaction, a composition comprising at least one poly (hydroxyurethane urethane) comprising at least two, preferably two or three, primary amine groups. The amounts of cyclocarbonate-terminated polyurethane prepolymer (PP2) and amine hardener (B1) used to obtain such poly (hydroxyurethane-urethane) are such that the mole ratio r3 is preferably from 0.5 to 1.
    [0027] Preferably, the manufacture of the adhesive composition is carried out without adding a compound intended to lower the viscosity of said composition, such as a solvent (aqueous, organic), a reactive diluent and / or a plasticizer. Preferably, the components of the multicomponent system according to the invention comprising the cyclocarbonate-terminated polyurethane prepolymer (s) (PP1) according to the invention and the amine curative (s) (B1) according to the invention. the invention are mixed at a temperature T3 as defined above. Preferably, the adhesive composition according to the invention is manufactured by the implementation of the multicomponent system according to the invention, that is to say the mixture of the various components constituting it, at a mixing temperature T3. The subject of the invention is also a process for assembling materials using the cyclocarbonate-terminated polyurethane prepolymer (PP2) according to the invention, in particular by means of the implementation of the multicomponent system according to the invention comprising the following steps: - the mixture of at least one cyclocarbonate-terminated polyurethane prepolymer (PP2) as described above and at least one amine hardener (B1), and then - the coating of said mixture on the surface of a first material, then - the laminating of the surface of a second material on said coated surface, and - the crosslinking of said mixture. The step of mixing at least one cyclocarbonate-terminated polyurethane prepolymer (PP2) as described above and of at least one amine hardener (B1) as described above can be carried out in particular by implementing the system. multicomponent according to the invention, namely by mixing the components respectively comprising the (s) polycarbonate prepolymer (s) terminated with cyclocarbonate (PP2) (component (A)) and the (s) hardener (s) amine (s) (s) (s) ( component (B)), as defined above. This mixing step can be carried out at room temperature or hot, before coating.
    [0028] Preferably, the mixing is carried out at a temperature below the degradation temperature of the ingredients included in one or other of the components (A) and (B). In particular, the mixing is carried out at a temperature T3 of less than 95 ° C, preferably ranging from 15 to 80 ° C, in order to avoid any thermal degradation.
    [0029] Preferably, the cyclocarbonate-terminated polyurethane prepolymer (PP2) and the amine curative (s) (B 1) are mixed in such amounts that the molar ratio of the number of cyclocarbonate groups to the number of primary amine groups present in the mixture, denoted r3, ranges from 0.5 to 1.
    [0030] In each of these variants, the coating of said mixture can be carried out on all or part of the surface of a material. In particular, the coating of said mixture can be carried out in the form of a thickness layer ranging from 0.002 to 5 mm. Optionally, the crosslinking of said mixture on the surface of the material can be accelerated by heating the (s) material (s) coated (s) at a temperature less than or equal to 120 ° C. The time required to complete this crosslinking reaction and thus ensure the required level of cohesion is generally of the order of 0.5 to 24 hours. The coating and lamination of the second material are generally carried out in a time interval compatible with the coating process, as is well known to those skilled in the art, that is to say before the coating layer. Adhesive loses its ability to bond the two materials. Suitable materials are, for example, inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals) as well as metals and composites possibly coated with paint (as in the automotive field); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, epoxy resins and polyesters. The mechanical performance and the adhesive strength of the adhesive compositions according to the invention can be measured according to the tests described in the examples which follow. The adhesive compositions according to the invention are suitable for a wide range of applications such as food processing, cosmetics, hygiene, transport, housing, textiles, packaging. In particular, the adhesive compositions according to the invention have an intrinsic breaking elongation force ranging from 0.3 to 10 MPa. The following examples are given purely by way of illustration of the invention and can not be interpreted to limit its scope.
    [0031] A - Synthesis of the Cyclocarbonate Terminated Polyurethane Prepolymer (PP2) (Component A) The components (A) of Examples 1 to 4 according to the invention are prepared using the reagents indicated in Table 1 and according to the procedure described in US Pat. the following pages.
    [0032] The quantities indicated in Table 1 are expressed in grams of commercial products. Table 1 Ingredients 1 2 3 4 PPG diol 81.4 - - - PPG triol - 83.6 83.6 83.6 2,4-TDI 11.9 10.4 10.4 10.4 Reaction catalyst 0.1 0.1 0.1 0.1 NCO / OH ratio, r 1.68 1.78 1.78 1.78 Glycerol carbonate 6.6 5.9 5.9 5.9 NCO / OH molar ratio, r 2 0 In Table 1, the following is used as: PPG diol, the commercial product sold under the name Voranole P2000 by the company Dow, corresponding to polypropylene glycol diol, having an index of hydroxyl approximately equal to 56 mg KOH / g of PPG diol, - PPG triol, the commercial product sold under the name Voranol® CP3355 by the company Dow, corresponding to polypropylene glycol triol, having a hydroxyl value of approximately 10 equal to 45 mg KOH / g of PPG triol, 2,4-TDI, the commercial product sold under the name Scuranatee T100 by the company Vencorex, corresponding to a composition of TDI at 99% by weight of 2,4-TDI, -catalyst of reaction, the commercial product sold under the name B orchikate 315 by the company OM Group, a reaction catalyst of bismuth neodecanoate, 15-glycerol carbonate, the commercial product sold under the name Jeffsole GC by the company Huntsman, corresponding to a composition containing at least 96% by weight of glycerol carbonate and 3% by weight maximum of glycerine, having a hydroxyl value of approximately 505 mg KOH / g of composition. Step E1: Synthesis of the NCO-terminated Polyurethane Prepolymer (PP1) In a reactor placed under a nitrogen atmosphere, the diisocyanate is heated to 50 ° C., then a mixture of polyol and catalyst is introduced with constant stirring. reaction by controlling the reaction temperature Ti so that it does not exceed 80 ° C, in accordance with the amounts indicated in Table 1. This mixture is kept under constant stirring at 80 ° C, under nitrogen, up to 25 ° C. complete reaction of the NCO functions of the diisocyanate.
    [0033] The monitoring of the reaction is carried out by measuring the evolution of the NCO content in the mixture, for example by a dibutylamine assay in return, using hydrochloric acid according to NF T52-132. The reaction is stopped when the "NCO level" (/ 0NCO) measured is approximately equal to the desired NCO level. Characterization of the polyurethane prepolymer with NCO terminations (PP1) 1 2 3 4 ANCO calculated in the reaction medium of step E1 (in% by weight of the weight of the reaction medium) 2.5 2.3 2.3 2.3 Step E2: Synthesis of the Cyclocarbonated Terminated Polyurethane Prepolymer (PP2) (Component A) Once the reaction of step E1 completed, the glycerol carbonate is introduced into the reactor in the proportions indicated in Table 1, with stirring and under nitrogen, ensuring that the reaction temperature T2 does not exceed 80 ° C. The NCO-terminated polyurethane prepolymer (PP1) -glycerol carbonate mixture is kept under constant stirring at 80 ° C., under nitrogen, until complete disappearance of the visible NCO infra-red (IR) functions (approximately 2250 cm-1). Viscosity measurement: The viscosity of the component (A) obtained is measured 24 hours after the end of the reaction (D + 1) at 23 ° C. and 60 ° C. and expressed in Pascal seconds (Pa.s $). The set of measured values for Examples 1 to 4 are grouped in the following Table 2. The viscosity measurement at 23 ° C. is carried out using a Brookfield RVT viscometer, with a needle adapted to the viscosity range and at a rotation speed of 20 revolutions per minute (rpm).
    [0034] The viscosity measurement at 60 ° C. is carried out using a Brookfield RVT viscometer coupled with a Thermosel heating module of the Brookfield brand, with a mobile adapted to the viscosity range and at a rotation speed of 20 turns. per minute. Table 2 Characterization of Cyclocarbonate Termination Polyurethane Prepolymer (PP2) Viscosity at D + 1 at 23 ° C (Pa.s.) 365 1250 1250 1250 Viscosity at D + 1 at 60 ° C (Pa.s. ) 11.4 47.7 47.7 47.7 Content calculated as a cyclocarbonate group in the prepolymer (PP2) (meq / g of prepolymer (PP2)) 0.68 0.70 0.70 0.58 B - Preparation of adhesive compositions according to the invention by mixing the components (A) and (B) The adhesive compositions 1 'to 4' according to the invention are prepared by mixing the various ingredients indicated in the following Table 3, following the procedure described herein. -after. The amounts shown in Table 3 are in grams. Table 3 2 '3' 4 'Component A of Example 1 100 - - - Component A of Example 2 - 100 - - Component A of Example 3 - Component A of Example 4 - - - 100 TAEA 4.25 0.5 0.5 - HMDA - 3.8 3.8 5.3 Calcium carbonate 50 - 50 50 Molar ratio r3 0.7 0.7 0.7 0.6 Table 3 uses: - tris (2-aminoethyl) amine (TAEA) of primary alkalinity = 20.52 meq / g of TAEA, - hexamethylenediamine (HMDA) of primary alkalinity = 17.21 meq / g of HMDA, calcium carbonate of maximum particle size = 104m. In a polypropylene reactor placed under a nitrogen atmosphere, the component (A) is heated to between 65 and 80 ° C., and the component (B) consisting of (or) hardener (s) containing amine (s) (B1) is then added. and optionally charge, with stirring. The mixture is carried out hot at the temperature T3 of between 65 and 80 ° C. and is kept under constant stirring for 2 minutes under vacuum (for debulking). Then, the mixture is allowed to stir until complete disappearance of the cyclocarbonate functions visible in InfraRed (signal at 1800cm-1). Measurement of the mechanical performances: resistance and elongation at break of the compositions according to the invention in the crosslinked state Once crosslinked, the tensile strength and elongation at break are measured by tensile test of the adhesive composition according to the protocol described below. The principle of the measurement consists in stretching in a tensile machine, whose moving jaw moves at a constant speed equal to 100 mm / minute, a standard specimen consisting of the crosslinked adhesive composition; and to record, at the moment when the test piece breaks, the tensile stress applied (in MPa) as well as the elongation of the test piece (in%). The standard test piece is dumbbell-shaped, as shown in International Standard ISO 37. The narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 500 μm. To prepare the dumbbell, the composition packaged as described above is heated to 95 ° C., then the amount necessary to form a film having a thickness of 500 μm which is left 7 days at 23 ° C and 50% relative humidity for crosslinking. The dumbbell is then obtained by simply cutting in the crosslinked film using a punch. The tensile strength test is repeated twice and gives the same results. The recorded applied tensile stress is expressed in megapascal (MPa, ie 106 Pa) and elongation at break in% relative to the initial length of the specimen. The values are summarized in Table 4 below.
    [0035] Table 4 2 '3' 4 'Tensile stress applied (MPa) 2.3 0.7 2.1 2.1 Elongation at break (%) 1825 100 420 640 Adhesive power: Measurement of shear force under stress (English Lap Shear) Adhesive compositions 1 ', 3' and 4 'according to the invention were further subjected to bonding tests of two strips of powdered aluminum (each size 100 mm x 25 mm) previously cleaned with a solvent (isopropanol). One of the surfaces of one of the slats is applied with a spatula, in a space delimited by a window of 12.5 mm × 25 mm in teflon. The other slat is applied over the glued surface by pressing the two slats against each other. After crosslinking for seven days at 23 ° C. and 50% relative humidity, the shearing force at break as well as the failure facies are measured. Table 5 The 3 '4' Breaking Strength (MPa) 1.7 0.8 0.6 Type of Breaking RA RA RA We note "RA" for adhesive failure, meaning that we observe that the totality adhesive seal remained stuck on one side of laminated lamellae.
    [0036] Thus, the adhesive compositions according to the invention can be formulated easily by means of a process of preparation which is inexpensive in energy and respectful of man and his environment, not using solvents or plasticisers. . In addition, the adhesive compositions according to the invention thus obtained lead to high performance adhesives in terms of mechanical properties and / or adhesion strength, suitable for a wide range of applications.
    权利要求:
    Claims (12)
    [0001]
    REVENDICATIONS1. A process for the preparation of a (2-oxo-1,3-dioxolan-4-yl) methyl-carbamate-terminated polyurethane prepolymer (PP2) comprising: in a first step (denoted by E1), the preparation of a NCO-terminated polyurethane prepolymer (PP1) by a polyaddition reaction: (i) at least one diisocyanate selected from the following aliphatic or aromatic diisocyanates, and mixtures thereof: - isophorone diisocyanate (IPDI), - 2, 4-toluene diisocyanate (2,4-TDI), 2,4'-diisocyanate diphenylmethane (2,4'-MDI), (ii) with at least one polyol selected from polyether polyols and polydiene polyols, a Ti reaction temperature of less than 95 ° C under anhydrous conditions and in amounts of diisocyanate (s) and polyol (s) resulting in a molar ratio of NCO / OH, denoted r1, ranging from 1.6 to 1; , 9; then - in a second step (denoted E2), the reaction under anhydrous conditions, at a reaction temperature T2 lower than 95 ° C. of the product formed in the first step E1 with at least one glycerol carbonate in a quantity of carbonate glycerol leading to an NCO / OH molar ratio, denoted r2, ranging from 0.9 to 1.0.
    [0002]
    2. Preparation process according to claim 1, characterized in that the (s) polyol (s) is (are) chosen from polyoxyalkylene polyols, the alkylene portion, linear or branched, comprises from 1 to 4 atoms carbon, and polybutadienes having terminal hydroxyl groups optionally hydrogenated or epoxidized.
    [0003]
    3. Preparation process according to claim 1, characterized in that the NCO-terminated polyurethane prepolymer (PP1) is obtained by a polyaddition reaction of 2,4-TDI with a polyol chosen from polyether diols or triols, at a concentration of Ti reaction temperature below 95 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether diol (s) or triol (s) resulting in a molar ratio NCO / OH (ri) ranging from 1.6 to 1.9.
    [0004]
    4. Preparation process according to any one of claims 1 to 3, characterized in that it does not include a step of adding one or more solvent (s) and / or plasticizer (s).
    [0005]
    5. A polyurethane prepolymer with (2-oxo-1,3-dioxolan-4-yl) methylcarbamate (PP2) terminations obtainable by the preparation process as defined in any one of claims 1 to 4.
    [0006]
    A multicomponent system comprising: as a first component (denoted as component (A)), a composition comprising at least one (2-oxo-1,3-dioxolan-4-yl) methyl carbamate (PP 2) terminated polyurethane prepolymer as defined in claim 5 and - as the second component (denoted component (B)), a composition comprising at least one hardener having at least two primary amine groups (-NH2) (B1).
    [0007]
    7. multicomponent system according to claim 6, characterized in that (s) says (s) hardener (s) (B1) have a primary alkalinity ranging from 0.4 to 34 meq / g of hardener. 15
    [0008]
    8. multicomponent system according to claim 6 or 7, characterized in that the primary amine groups of said (said) hardener (s) (B1) are primary methylene amine groups (--CH 2 -NH 2).
    [0009]
    9. multicomponent system according to any one of claims 6 to 8, characterized in that the amounts of polyurethane prepolymer (s) endings (2-oxo-1,3-dioxolan-4-yl) methyl-carbamate ( PP2) and hardener (s) (B1) as defined in claim 7 or 8 present in the multicomponent system, lead to a molar ratio of the number of cyclocarbonate groups to the number of primary amine group, denoted r3, ranging from 0.5 to 1.
    [0010]
    10. multicomponent system according to any one of claims 6 to 9, characterized in that it comprises at least one inorganic filler.
    [0011]
    11. Process for assembling materials using the (2-oxo-1,3-dioxolan-4-yl) methyl-carbamate (PP2) -terminated polyurethane prepolymer as defined in claim 5, comprising the following steps the mixture of at least one (2-0x0-1,330 dioxolan-4-yl) methyl-carbamate-terminated polyurethane prepolymer (PP2) as defined in claim 5 and at least one hardener having at least two primary amine groups (-NH2) (B1) as defined in claim 6 to 8, and then - coating said mixture on the surface of a first material, then-laminating the surface of a second material to said coated surface, then - the crosslinking of said mixture.
    [0012]
    12. Use of a (2-oxo-1,3-dioxolan-4-yl) methyl-carbamate (PP2) -terminated polyurethane prepolymer as defined in claim 5, obtainable by the method of preparation as defined in any one of claims 1 to 4 for the manufacture of an adhesive composition. 10
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    同族专利:
    公开号 | 公开日
    US10472453B2|2019-11-12|
    EP3119835B1|2020-04-22|
    FR3018816B1|2017-07-28|
    CN106459356A|2017-02-22|
    ES2805007T3|2021-02-10|
    WO2015140458A1|2015-09-24|
    EP3119835A1|2017-01-25|
    US20170088661A1|2017-03-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20070151666A1|2004-07-22|2007-07-05|Thomas Moeller|Two-component bonding agent|
    JP2008001789A|2006-06-22|2008-01-10|Konishi Co Ltd|Curable resin composition and room temperature-curable adhesive composition|
    JP2008285538A|2007-05-16|2008-11-27|Konishi Co Ltd|Curable resin composition and adhesive composition using the same|
    JP2008285539A|2007-05-16|2008-11-27|Konishi Co Ltd|Curable resin composition|
    JP2008291143A|2007-05-25|2008-12-04|Mitsui Chemicals Polyurethanes Inc|Aqueous urethane resin|
    JP2009155407A|2007-12-26|2009-07-16|Konishi Co Ltd|Curable resin composition and adhesive composition|
    JP2009173919A|2007-12-26|2009-08-06|Konishi Co Ltd|Curable resin composition, and ambient temperature-curable adhesive composition|
    JP2010126565A|2008-11-26|2010-06-10|Nitto Boseki Co Ltd|Coating composition|
    US7226523B2|2001-05-15|2007-06-05|Sika Technology Ag|Polyurethane adhesive for windshield applications|
    DE102006055974A1|2006-11-24|2008-05-29|Henkel Kgaa|reactive adhesive|FR3015510B1|2013-12-19|2017-05-12|Bostik Sa|POLYURETHANE-BASED HUMIDITY AND HEAT-ADHESIVE COMPOSITION COMPRISING LOW ISOMYANATE MONOMER CONTENT|
    FR3053977B1|2016-07-12|2018-08-03|Bostik Sa|TWO-COMPONENT ADHESIVE COMPOSITION BASED ON POLYURETHANE|
    FR3073849B1|2017-11-22|2019-10-18|Bostik Sa|TERMINATED POLYURETHANE |
    FR3073856B1|2017-11-22|2019-10-18|Bostik Sa|COMPOSITION BASED ON POLYURETHANE|
    FR3075213B1|2017-12-20|2020-08-28|Bostik Sa|PROCESS FOR PREPARING A COMPOSITION CONTAINING A POLYURETHANE WITH NCO TERMINATIONS|
    CN108949088A|2018-05-29|2018-12-07|无锡海特新材料研究院有限公司|A kind of high-performance dual-component polyurethane pressure sensitive adhesive, preparation method and application|
    FR3089514B1|2018-12-05|2021-07-30|Arkema France|Terminated polyurethane |
    KR102234276B1|2019-02-01|2021-04-01|한국타이어앤테크놀로지 주식회사|Adhesive composition and method for manufacturing non-pneumatic tire by using the same|
    CN110437790A|2019-08-16|2019-11-12|浙江金石包装有限公司|A kind of preparation method of solventless adhesive, composite soft packaging material and composite soft packaging material|
    WO2021222192A1|2020-04-29|2021-11-04|Presidium Usa, Inc.|Polyurethane compositions|
    法律状态:
    2016-02-08| PLFP| Fee payment|Year of fee payment: 3 |
    2017-02-13| PLFP| Fee payment|Year of fee payment: 4 |
    2018-02-23| PLFP| Fee payment|Year of fee payment: 5 |
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    2021-02-10| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1452276A|FR3018816B1|2014-03-19|2014-03-19|POLYURETHANE PREPOLYMER WITH LOW VISCOSITY CYCLOCARBONATE TERMINATIONS AND USE THEREOF IN THE MANUFACTURE OF A MULTICOMPONENT ADHESIVE COMPOSITION|FR1452276A| FR3018816B1|2014-03-19|2014-03-19|POLYURETHANE PREPOLYMER WITH LOW VISCOSITY CYCLOCARBONATE TERMINATIONS AND USE THEREOF IN THE MANUFACTURE OF A MULTICOMPONENT ADHESIVE COMPOSITION|
    CN201580014699.XA| CN106459356A|2014-03-19|2015-03-17|Low-viscosity polyurethane prepolymer with cyclic carbonate end groups and the use thereof in the production of a multi-component adhesive composition|
    US15/126,911| US10472453B2|2014-03-19|2015-03-17|Low-viscosity polyurethane prepolymer with cyclic carbonate end groups and the use thereof in the production of a multi-component adhesive composition|
    EP15719772.4A| EP3119835B1|2014-03-19|2015-03-17|Low-viscosity polyurethane prepolymer with cyclic carbonate end groups and the use thereof in the production of a multi-component adhesive composition|
    PCT/FR2015/050638| WO2015140458A1|2014-03-19|2015-03-17|Low-viscosity polyurethane prepolymer with cyclic carbonate end groups and the use thereof in the production of a multi-component adhesive composition|
    ES15719772T| ES2805007T3|2014-03-19|2015-03-17|Polyurethane prepolymer with low viscosity cyclocarbonate endings and its use in the manufacture of a multi-component adhesive composition|
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