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    • 专利摘要:
    The present invention relates to a solvent system comprising: - from 5 to 95% by weight of a composition (A) comprising dimethylsulfoxide (DMSO) relative to the total weight of the solvent system; and from 5 to 95% by weight of a composition (B) comprising at least one lactone relative to the total weight of the solvent system. The invention also relates to the uses of the solvent system for the manufacture of films, coatings, membranes, batteries, electronic circuits, for the protection of electrical cables.
    公开号:FR3041352A1
    申请号:FR1558878
    申请日:2015-09-21
    公开日:2017-03-24
    发明作者:Paul-Guillaume Schmitt
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    SOLVENT SYSTEM COMPRISING A MIXTURE OF DIMETHYLSULFOXIDE AND AT LEAST ONE LACTONE
    The present invention relates to the field of polymer solvents that can be used in particular for the production of films, membranes, artificial leathers, polymeric suede, polymer fibers, coatings, electronic circuits, batteries, in particular lithium-ion batteries (Li-ion). ion), or for the protection of electric cables by sheathing.
    The polymers concerned by these various applications are fluorinated polymers or polymers comprising at least one X = O double bond, X being chosen from sulfur atom, carbon atom, N-C group and O-C group. More specifically, the polymers concerned are polyurethanes (PU), polyethersulfones (PES), polysulfones (PSU), poly (vinylidene fluorides), cellulose acetates, polyesters, polyamides, polyamide-imides and polyesters. polyimides.
    These polymers are today widely used for example for their mechanical and chemical resistance properties or their extensible properties. Polymers are indeed increasingly used in many applications.
    Among these applications, the most common are those for which the polymers are in the form of films, membranes, coatings. In general, the polymers find applications quite interesting when they are in the form of films, supported or not, whose thickness varies from a few tens of nanometers to a few millimeters. Another possibility is to find these polymers in the form of hollow fibers.
    For such applications, the polymers must first be dissolved, more or less concentrated, the films then being obtained by removal of the solvent (s), for example by evaporation or by extraction with a third solvent. , or any other method known to those skilled in the art.
    More particularly, the production of these films requires many steps including: - the synthesis of the polymer in a solvent medium, - the dissolution of the polymer in a solvent in the case where the polymer resulting from the synthesis is in solid form, for example extrudates or beads, - obtaining a polymer solution, - making a film by a coating process of the polymer solution followed by drying to evaporate the solvent.
    This last step can also be substituted by a step of producing a film or a hollow fiber by a method of impregnating on a support or spinning the polymer solution followed by quenching in a third solvent to precipitate the polymer and migrate the solvent from the polymer solution to the third solvent.
    Nowadays, the solvents commonly used for the production of polymer films are polar aprotic solvents, such as N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF) or dimethylacetamide (DMAc). However, these solvents have many toxicological disadvantages because they are classified as CMR agent (Carcinogenic, Mutagenic or toxic for Reproduction).
    There is therefore an interest in substituting these solvents with solvents having a better toxicological profile.
    Dimethylsulfoxide (DMSO) is a polar aprotic solvent for solubilizing a number of polymers, including certain grades of polyvinylidene fluoride (PVDF), such as for example Kynar® and Kynar Flex® marketed by Arkema. or the Solef®, Hylar®, Halar® or Hyflon® marketed by the company Solvay. The use of DMSO makes it possible to obtain viscosity solutions comparable to those obtained with NMP. However, to allow this solubilization, the DMSO must be heated to a temperature of the order of 50 ° C, or even greater than 50 ° C.
    In addition, it has been observed that some solutions of PVDF in DMSO thus prepared are not stable over time. Indeed, a gelation or a disorder of the solution was observed after only 1 to 2 days. Users are therefore forced to implement the solution quickly, including applying it quickly to make the required films. These disadvantages are a brake on the substitution of NMP by DMSO. Indeed, it is known that PVDF is commonly solubilized in NMP.
    The patent application FR 2 285 227 describes a process for assembling PVDF parts by gluing, the glue being a dilute solution of PVDF in a solvent, said solvent possibly being chosen from DMF, DMAc and tetrahydrofuran (THF). , DMSO, cyclohexanone (CyHone), hexamethylphosphoramide (HMPA), butyrolactone, and mixtures thereof. An example actually shows that the PVDF can be solubilized in DMF, but at a temperature of 60 ° C.
    EP 0 639 106 B1 teaches the preparation of membranes using solvent / co-solvent mixtures for dissolving PVDF at all temperatures. Although many possible mixtures are proposed, it is clear from this teaching that only mixtures based on NMP and DMF or n-butyl acetate are effective and are the only ones to be exemplified.
    Patent Application EP 0 223 709 A2 also describes a process for preparing porous membranes by dissolving a fluoropolymer in a solvent. Suitable solvents for this process are selected from ketones, ethers, amides and sulfoxides, and mixtures thereof. The best solvent is indicated to be the acetone / DMF mixture, which is confirmed by the examples which illustrate only this single solvent mixture. In addition, these examples teach that the dissolution must be carried out hot and that the polymer solution must be used immediately.
    EP 0 574 957 B1 describes acrylonitrile-PVDF composite membranes that can be used in separation operations. The constituent polymers of the membranes may be solubilized in a solvent chosen from NMP, DMF, DMSO, HMPA, DMAc, dioxane, and mixtures thereof, optionally in the presence of cosolvents chosen from acetone, methanol, methanol and the like. ethanol, formamide, water or methyl ethyl ketone. The examples presented only show polyacrylonitrile membranes (PAN) and their good resistance to attack by solvents such as NMP, DMF, DMSO, toluene, methyl ethyl ketone or acetone.
    EP 1725703 describes the manufacture of polymer fibers in a solvent chosen from a number of solvents, including DMSO and γ-butyrolactone. This document does not suggest an advantage in using a mixture of DMSO or lactone
    Patent KR100868536 describes the manufacture of polyurethane textile suede from a DMSO-based polymer solution.
    JP1266811 discloses the manufacture of hollow fiber polyethersulfone membranes from polymer solutions containing DMSO.
    The patent WO2012 / 173938 describes the manufacture of polyols that can be used to produce polyurethanes or polyurethane prepolymers that still contain polyols. To use these prepolymers, it is indicated that the addition of a solvent is possible. DMSO and some lactones are among others mentioned. This document does not suggest an advantage to use a mixture of DMSO or lactone.
    EP1578521 discloses the manufacture of hollow fiber membranes based on hydrophobic (such as polyethersulfone) and hydrophilic (such as polyvinylpyrrolidone) polymers. DMSO and butyrolactone, alone or as a mixture, are cited as potential solvents for polymers. This document does not suggest an advantage to use a mixture of DMSO or lactone.
    Moreover, it is known that DMSO alone or butyrolactone alone makes it possible to dissolve numerous polymers such as certain polyurethanes, polyethersulfones or polysulfones by heating these solutions at 50 ° C. for several hours, but the polymer solutions obtained gell very quickly after a return to working temperatures (from 0 to 20 ° C). However, no prior art document seems to show any advantages in using mixtures comprising DMSO and one or more lactones.
    Thus, among these techniques known today of the prior art, none of them is satisfactory, because none of them can be imposed as a technique for which the solvent systems of fluoropolymers or polymers comprising at least one double bond X = 0, X being selected from sulfur, carbon, NC and OC may advantageously replace the reference solvents NMP, DMF and DMAc.
    The techniques of the prior art teach that the solutions obtained are not stable over time. Indeed, they tend to gel either at room temperature or at the shaping temperature of the polymer solution. This problem of stability of the polymer solutions implies that it is very difficult to implement an industrial process without significant adaptation of said process.
    Thus, one of the objectives of the present invention is to provide a solvent system, which does not have the aforementioned drawbacks and encountered in the prior art.
    More specifically, a first objective of the present invention is to provide a solvent system that is less toxic than NMP, DMF and DMAc, in particular of low toxicity or even non-toxicity.
    Yet another object is to provide a fluoropolymer or polymer solvent system comprising at least one X = O double bond, X being selected from sulfur atom, carbon atom, NC group and OC group, leading to stable solutions over time, that is to say solutions whose stability over time is sufficient to allow industrial use, that is to say over several weeks, or similar to that obtained with solutions in NMP, DMF and DMAc and generally more stable than with the known solvents of the prior art, such as NMP, DMSO, ketones or DMAC.
    It has now been discovered that the aforementioned objectives can be achieved, in whole or at least in part, by the solvent system of the present invention. The subject of the invention is therefore a solvent system comprising: from 5% to 95% by weight of a composition (A) comprising dimethylsulfoxide (DMSO) relative to the total weight of the solvent system; and from 5 to 95% by weight of a composition (B) comprising at least one lactone relative to the total weight of the solvent system.
    Surprisingly, it has been discovered that the solvent system according to the invention makes it possible to obtain solutions of fluorinated polymers or polymers comprising at least one X = O double bond, X being chosen from the sulfur atom. , the carbon atom, an NC group and an OC group, especially polyurethanes, polyethersulfones and polysulfones, stable over time. Surprisingly, the polymer solutions obtained with the solvent system according to the invention are much more stable than the polymer solutions obtained with DMSO alone or a lactone alone. The subject of the invention is also the use of the solvent system as defined above for the solubilization of fluorinated polymers or of polymers comprising at least one X = O double bond, X being chosen from the sulfur atom, the carbon, an NC group and an OC group, in particular polyurethanes, polyethersulfones and polysulfones.
    Another subject of the invention is a process for solubilizing a polymer such as those mentioned above. The invention also relates to a solution comprising at least one polymer such as those mentioned above and at least one solvent system as defined above.
    Finally, the invention relates to the use of the solvent system according to the invention or of the solution according to the invention for the production of films, artificial leathers, polymeric suede, polymer fibers, coatings, membranes, batteries , of electronic circuits, for the protection of electric cables. Other advantages and features of the invention will emerge more clearly from the detailed description.
    It is furthermore specified that the expressions "between ... and ..." and "from ... to ..." used in the present description must be understood as including each of the mentioned terminals.
    The solvent system of the present invention comprises from 5 to 95% by weight of a composition (A) comprising DMSO, based on the total weight of the solvent system.
    According to a particular embodiment, the composition (A) comprises DMSO alone.
    By DMSO alone, or more simply DMSO, it is meant that the composition (A) comprises more than 80% by weight, preferably more than 90% by weight, more preferably more than 95% by weight of DMSO, relative to the weight total of the composition, the remainder may be impurities inherent in the manufacture of DMSO, after optional purification (as described in WO 1997/019047, EP 0 878 454, EP 0 878 466), and / or odorants (as described in WO 2011/012820), and / or any other additives known to those skilled in the art, such as, for example and without limitation, stabilizers, dyes, anti-UV agents, preservatives or biocides.
    The solvent system according to the invention comprises from 5 to 95% by weight of a composition (B) comprising at least one lactone, relative to the total weight of the solvent system.
    Preferably, the lactone comprises from 4 to 12 carbon atoms, said lactone being saturated or not, and optionally substituted with one or more C 1 -C 10 alkyl chains.
    Preferably, the lactone is chosen from γ-butyrolactone, γ-pentalactone, γ-hexalactone, γ-octalactone, δ-octalactone, γ-decalactone, δ-decalactone, γ-dodecalactone, δ -dodecalactone, 6-amyl-a-pyrone, δ-valerolactone, γ-valerolactone, ε-caprolactone, coumarin, ascorbic acid, and mixtures of two or more of them in all proportions.
    The lactone, or the mixture of lactones, preferably has a boiling point between 150 and 250 ° C.
    Preferably, said lactone is soluble in water.
    For the purposes of the present invention, the term "lactone" is meant to be soluble in water when at least 30 g, preferably 50 g, more preferably 100 g of lactone (s) are dissolved in one liter of water at 20 ° C. ° C and at atmospheric pressure, that is to say that a homogeneous solution (that is to say a single liquid phase) is obtained after 30 minutes of stirring. Most preferably, the lactone is selected from γ-butyrolactone (GBL) and γ-valerolactone (GVL).
    Preferably, the solvent system according to the invention comprises from 5 to 80% by weight of a composition (A) comprising DMSO, more preferably from 30 to 80% by weight, still more preferably from 30 to 65% by weight, relative to the total weight of the solvent system.
    Preferably, the solvent system according to the invention comprises from 20 to 95% by weight of a composition (B) comprising at least one lactone, more preferably from 20 to 70% by weight, even more preferably from 35 to 70% by weight. weight, based on the total weight of the solvent system.
    Advantageously, when the solvent system according to the invention comprises from 5 to 80% by weight of a composition (A) comprising DMSO, relative to the total weight of the solvent system, then said system comprises from 20 to 95% by weight. weight of a composition (B) comprising at least one lactone, relative to the total weight of the solvent system.
    Preferably, when the solvent system according to the invention comprises from 30 to 80% by weight of a composition (A) comprising DMSO, relative to the total weight of the solvent system, then said system comprises from 20 to 70% by weight. weight of a composition (B) comprising at least one lactone, relative to the total weight of the solvent system.
    Advantageously, when the solvent system according to the invention comprises from 30 to 65% by weight of a composition (A) comprising DMSO, relative to the total weight of the solvent system, then said system comprises from 35 to 70% by weight of a composition (B) comprising at least one lactone relative to the total weight of the solvent system.
    Very surprisingly, the combination of DMSO and at least one lactone in a specific proportion leads to better results than those observed during the dissolution, in particular of polyurethanes, polyethersulfones or polysulfones in DMSO alone or in a lactone alone. , said results being understood in terms of stability over time.
    In one embodiment of the invention, a lactone, or a mixture of lactones, having a boiling point close to that of DMSO, more precisely close to that of composition (A), is preferred.
    In another embodiment, a lactone or a mixture of lactones forming an azeotrope with DMSO or with composition (A) is preferred.
    In these two preferred embodiments, removal of the solvent system from the polymer in which it is dissolved will be facilitated, whereby the composition (A) and the composition (B) can be removed simultaneously by heating, evaporation or any other means. known to those skilled in the art.
    Another advantage related to the neighboring or identical boiling points of the composition (A) and of the composition (B) or again related to the formation of an azeotrope between the composition (A) and the composition (B) is their ease purification and their recyclability much easier.
    In another embodiment of the invention, a lactone, or a mixture of lactones, soluble in water is preferred.
    In this preferred embodiment, the removal of the solvent system from the polymer, in which it is dissolved, will be facilitated, whereby composition (A) and composition (B) can be removed simultaneously by quenching in a water bath or any other coagulation technique or phase inversion known to those skilled in the art.
    According to one embodiment of the invention, the solvent system comprises from 0 to 20% by weight of one or more additional solvents, relative to the total weight of the solvent system, chosen from water; ketones, preferably chosen from acetone, methyl ethyl ketone, methyl isobutyl ketone, hexanone, cyclohexanone, ethyl amyl ketone, isophorone, trimethylcyclohexanone, and diacetone alcohol; the amines, preferably chosen from monoethanolamine, diethanolamine, propanolamine, butyl-isopropanolamine, iso-propanolamine, 2- [2- (3-aminopropoxy) ethoxy] ethanol, N-2 hydroxyethyl diethylenetriamine, (3-methoxy) -propylamine, 3-isopropoxypropylamine, monoethylamine, diethylamine, diethylaminopropylamine, triethylamine; nitriles, for example acetonitrile; alcohols, preferably selected from ethanol, methanol, propanol, isopropanol, glycerol, butanol, methyl isobutyl carbinol, hexylene glycol, and benzyl alcohol; ethers, preferably selected from tetrahydrofuran, methylfuran, methyltetrahydrofuran, tetrahydropyran, and glycoldialkyl ether; the esters, preferably chosen from dibasic esters, dimethyl glutarate, dimethyl succinate, dimethyl adipate, butyl acetate, ethyl acetate, diethyl carbonate and dimethyl carbonate, propylene carbonate, ethyl and methyl carbonate, glycerol carbonate, dimethyl-2-methylglutarate, dimethyl-2-methyladipate, dimethyl-2-methylsuccinate, N-butyl propionate, benzyl, and ethylethoxypropionate; sulphones, preferably chosen from dimethylsulfone and sulpholane; aromatic solvents selected from toluene and xylene; acetals, preferably selected from methylal, ethylal, butylal, dioxolane, and 2,5,7,10-tetraoxaundecane (TOU); N-butylpyrrolidone; N-isobutylpyrrolidone; N-t-butylpyrrolidone; N-n-pentylpyrrolidone; N- (methyl-substituted butyl) pyrrolidone; N-propyl- or N-butyl-pyrrolidone whose ring is methyl-substituted or N- (methoxypropyl) pyrrolidone; dipropylene glycol dimethyl ether; polyglyme; ethyl diglyme; 1,3-dioxolane; and methyl-5 (dimethylamino) -2-methyl-5-oxopentanoate.
    Advantageously, the additional solvents have a boiling point close to that of DMSO, more precisely close to that of composition (A), or close to that of the solvent system according to the invention. The additional solvents may preferentially form an azeotrope with the solvent system according to the invention.
    In this preferred embodiment, removal of the solvent system from the polymer in which it is dissolved will be facilitated as discussed above. The presence of the additional solvent does not change the method of removing the solvent system.
    The additional solvents preferably have a boiling point between 150 and 250 ° C.
    Advantageously, said additional solvent is soluble in water.
    For the purposes of the present invention, an additional solvent is understood to be water-soluble when at least 30 g, preferably 50 g, more preferably 100 g of this additional solvent is dissolved in one liter of water at 20 g. ° C and at atmospheric pressure, that is to say that a homogeneous solution (that is to say a single liquid phase) is obtained after 30 minutes of stirring.
    According to another aspect, the invention relates to the use of at least one solvent system as defined above, for the solubilization of fluorinated polymers or polymers comprising at least one X = O double bond, X being chosen from the atom sulfur, the carbon atom, an NC group and an OC group, in particular polyurethanes, polyethersulfones and polysulfones.
    Preferably, the polymers are chosen from polyurethanes, polyethersulfones, polysulfones, polyvinylidene fluorides, cellulose acetates, polyesters, polyamides, polyamide-imides and polyimides.
    More preferentially, the polymers are chosen from polyurethanes, polyethersulfones and polysulfones.
    According to yet another aspect, the present invention relates to the process for solubilizing a fluorinated polymer or a polymer comprising at least one X = O double bond, X being chosen from the sulfur atom, the carbon atom, an NC group and an OC group, in particular polyurethanes, polyethersulfones and polysulfones, comprising at least one step of bringing said polymer into contact with at least one solvent system as defined above.
    This contacting is preferably carried out with stirring, at room temperature or at a temperature between room temperature and 90 ° C., preferably between room temperature and 80 ° C., more preferably between room temperature and 70 ° C. . The polymer can be contacted with at least one solvent system according to the invention in any form, but for reasons of rapid dissolution, it is preferred that said polymer is in the form of powder or granules.
    The solvent system according to the present invention is entirely suitable for the solubilization of fluorinated polymers or polymers comprising at least one X = O double bond, X being chosen from the sulfur atom, the carbon atom and an NC group. and an OC group, especially polyurethanes, polyethersulfones and polysulfones. In other words, the solvent system of the invention makes it possible to obtain polymer solutions which are clear and stable over time.
    The amount of polymer (s), which can be dissolved, in the solvent system of the invention varies in large proportions, depending on the nature of the polymer and the nature of the solvent system, and is generally between 1% and 50% by weight, preferably between 1% and 40% by weight, more preferably between 1% and 25% by weight, for example about 15% by weight, of fluoropolymers or of polymers comprising at least one X = 0 double bond, X being chosen from the sulfur atom, the carbon atom, an NC group and an OC group, in particular polyurethanes, polyethersulfones and polysulfones, relative to the total weight of the final solution comprising said polymer and the system solvent.
    According to another aspect of the invention, the present invention relates to a solution comprising: from 1 to 50% by weight, preferably from 1 to 40% by weight, more preferably from 1 to 25% by weight of at least a fluorinated polymer or a polymer comprising at least one X = O double bond, X being chosen from the sulfur atom, the carbon atom, an NC group and an OC group, in particular polyurethanes, polyethersulfones and polysulfones. , relative to the total weight of the solution, and from 50 to 99% by weight, preferably from 60 to 99% by weight, more preferably from 75 to 99% by weight, relative to the total weight of the solution, at least one solvent system as defined above.
    As indicated above, polyurethanes, polyethersulfones and polysulfones are well known today for their good mechanical properties and excellent stability over time. All these qualities make them the materials of choice for their use as membranes for filtration and ultrafiltration, manufacture of batteries, artificial leathers or textile suede to name only some of their applications.
    Polyurethanes, polyethersulfones, polysulfones, polyvinylidene fluorides, cellulose acetates, polyesters, polyamides, polyamide-imides and polyimides, because of their solubility in the solvent system of the present invention, can thus easily be shaped by molding in a solvent medium by the method of phase inversion or coagulation ("solvent casting" in English or "wet process" according to the skilled person), or be prepared under form of leaflets, fibers, hollow fibers or tubes. The invention also relates to the use of the solvent system as defined above, or the solution as defined above for the production of films, artificial leathers, polymeric suede, polymer fibers, coatings, membranes, for the protection of electric cables, and in the manufacture of batteries and electronic circuits.
    For the preparation of batteries, the solvent system according to the invention may comprise any type of additives and charges usually employed for the synthesis of said batteries, and in particular carbon, whether in the form of charcoal, activated carbon or under form of carbon nanotubes (CNTs). Other advantages and details of the invention will emerge more clearly from the examples given below solely by way of illustration and having no limiting character.
    EXAMPLES
    Example 1: Solution Comprising Polyurethane and a DMSO / GBL Solvent System a) Solubility test at T = 70 ° C. and at room temperature T 12.5% by weight of Desmoderm® KB2H polyurethane are introduced into various solvent systems comprising DMSO and γ-butyrolactone (GBL), based on the total weight of the solution formed by the polymer and the solvent system.
    The mixture is heated to 70 ° C with gentle stirring. The solubility of the tested solutions is evaluated.
    The solutions are cooled to room temperature and the appearance of the tested solutions is evaluated.
    The results are shown in Table 1:
    Table 1
    After a few hours, the polymer is completely dissolved, except in the case of solution D. Fluid solutions are obtained for solutions A to C.
    It is also found that solutions A to C have a fluid appearance after they have been cooled to room temperature.
    b) Solubility test at T = -2 ° C
    The solutions are then stored at low temperature (-2 ° C) for several days to observe their stability over time.
    The results are shown in Table 2:
    Table 2
    Thus, it is found that solution A has a solid appearance only two hours after it has been stored at a temperature of -2 ° C. Indeed, the solution gels very quickly.
    On the other hand, solutions B and C always have a fluid appearance after 6 days of storage at this temperature. The solution is stable for at least 6 days.
    Thus, the solvent system according to the invention has an improvement in the stability of the polymer solution, thus showing a surprising advantage in using these two solvents as a mixture.
    Example 2: Solution Comprising Polyurethane and a DMSO / GVL Solvent System a) Solubility test at T = 70 ° C. and at room temperature T 12.5% by weight of Desmoderm® KB2H polyurethane are introduced into various solvent systems comprising DMSO and γ-valerolactone (GVL), based on the total weight of the solution formed by the polymer and the solvent system.
    The mixture is heated to 70 ° C with gentle stirring. The solubility of the tested solutions is evaluated.
    The solutions are cooled to room temperature and the appearance of the tested solutions is evaluated.
    The results are shown in Table 3:
    Table 3
    After a few hours, the polymer is completely dissolved, except in the case of solution H. Fluid solutions are obtained for solutions E to G.
    It is also found that solutions E to G have a fluid appearance after they have cooled to room temperature.
    b) Solubility test at T = -2 ° C
    The solutions are then stored at low temperature (-2 ° C) for several days to observe their stability over time. _The results are shown in Table 4:
    Table 4
    Thus, it is found that the solution E has a frozen appearance only a week after it has been stored at a temperature of -2 ° C.
    On the other hand, solutions F and G remain stable, after storage at a temperature of -2 ° C.
    Thus, the solvent system according to the invention has an improvement in the stability of the polymer solution, thus showing a surprising advantage in using these two solvents as a mixture.
    Example 3: Solution Comprising Polyvinylidene Fluoride and a Solvent System DMSO / GVL a) Solubility Test at T = 70 ° C and Ambient T 10% by weight of Kynar K761 polyvinylidene fluoride are introduced into various solvent systems including DMSO and γ-valerolactone (GVL), based on the total weight of the solution formed by the polymer and the solvent system.
    The mixture is heated to 70 ° C with gentle stirring. The solubility of the tested solutions is evaluated.
    The solutions are cooled to room temperature and the appearance of the tested solutions is evaluated.
    The results are shown in Table 5:
    Table 5
    After a few hours, the polymer is completely dissolved, except in the case of the solution L. Fluid solutions are obtained for solutions I to K.
    It is also found that the solutions I to K have a fluid appearance after they have been cooled to room temperature. b) Solubility test at ambient T over time
    The solutions are then stored at room temperature for several days to observe their stability over time.
    The results are shown in Table 6:
    Table 6
    Thus, it is found that solution I has a troubled appearance only a week after it has been stored at room temperature.
    In contrast, solution K has a slightly disturbed appearance two weeks after it has been stored at room temperature.
    Finally, the solution J always has a colorless and transparent appearance after two weeks of storage.
    Thus, the solvent system according to the invention has an improvement in the stability of the polymer solution, thus showing a surprising advantage in using these two solvents as a mixture.
    Example 4: Solution Comprising a Polyethersulfone and a DMSO / GBL Solvent System a) Solubility test at T = 70 ° C. and at ambient T 15% by weight of polyethersulfone Ultrason® E3010 are introduced into various solvent systems comprising DMSO and γ-butyrolactone (GBL), based on the total weight of the solution formed by the polymer and the solvent system.
    The mixture is heated to 70 ° C with gentle stirring. The solubility of the tested solutions is evaluated.
    The solutions are cooled to room temperature and the appearance of the tested solutions is evaluated.
    The results are shown in Table 7:
    Table 7
    After a few hours, the polymer is completely dissolved and a fluid solution is obtained for all the solutions M to P.
    It has also been found that the M to O solutions exhibit a fluid appearance after they have been cooled to room temperature for several weeks. In contrast, solution P has a solid appearance at room temperature after one week.
    b) Solubility test at T = -2 ° C
    The solutions are then stored at low temperature (-2 ° C) for several days to observe their stability over time.
    The results are shown in Table 8:
    Table 8
    Thus, it can be seen that solution M has a solid appearance only two hours after it has been stored at a temperature of -2 ° C. Indeed, the solution gels very quickly.
    Moreover, the solution P has a solid appearance at room temperature very rapidly.
    On the other hand, solution O has an appearance that is still liquid one week after it has been stored at a temperature of -2 ° C.
    Finally, solution N still has a liquid appearance three weeks after it has been stored at a temperature of -2 ° C.
    Thus, the solvent system according to the invention has an improvement in the stability of the polymer solution, thus showing a surprising advantage in using these two solvents as a mixture.
    Example 5: Solution Comprising a Polysulfone and a DMSO / GVL Solvent System a) Solubility test at T = 70 ° C. and at room temperature T 10% by weight of polysulfone (PSU) Solvay Udel® P-3500 are introduced into various solvent systems comprising DMSO and γ-valerolactone (GVL), based on the total weight of the solution formed by the polymer and the solvent system.
    The mixture is heated to 70 ° C with gentle stirring. The solubility of the tested solutions is evaluated.
    The solutions are cooled to room temperature and the appearance of the tested solutions is evaluated.
    The results are shown in Table 9:
    Table 9
    After a few hours, the polymer is completely dissolved and a fluid solution is obtained for all solutions Q to T.
    It has also been found that the R to T solutions have a fluid appearance after being cooled to room temperature except for the Q solution which has a gelled appearance
    b) Solubility test at T = -2 ° C
    The solutions are then stored at low temperature (-2 ° C) for several days to observe their stability over time.
    The results are shown in Table 10:
    Table 10
    Thus, it is found that the solution T has a frozen appearance only a week after it has been stored at a temperature of -2 ° C.
    In contrast, solution R has a viscous appearance one week after it has been stored at a temperature of -2 ° C.
    Finally, the solution S still has a fluid appearance one week after it has been stored at a temperature of -2 ° C, this fluid aspect can also still be observed after three weeks of storage.
    Thus, the solvent system according to the invention has an improvement in the stability of the polymer solution, thus showing a surprising advantage in using these two solvents as a mixture.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    A solvent system comprising: from 5 to 95% by weight of a composition (A) comprising dimethylsulfoxide (DMSO) based on the total weight of the solvent system; and from 5 to 95% by weight of a composition (B) comprising at least one lactone relative to the total weight of the solvent system.
    [2" id="c-fr-0002]
    2. Solvent system according to claim 1, wherein said lactone comprises from 4 to 12 carbon atoms, said lactone being saturated or not, and optionally substituted with one or more C 1 -C 10 alkyl chains.
    [3" id="c-fr-0003]
    3. Solvent system according to claim 1 or 2, wherein said lactone is selected from γ-butyrolactone, γ-pentalactone, γ-hexalactone, γ-octalactone, δ-octalactone, γ-decalactone, δ decalactone, γ-dodecalactone, δ-dodecalactone, 6-amyl-α-pyrone, δ-valerolactone, γ-valerolactone, ε-caprolactone, coumarin and ascorbic acid, preferably chosen from γ-butyrolactone and γ-valerolactone and their mixture.
    [4" id="c-fr-0004]
    4. Solvent system according to any one of the preceding claims, wherein said lactone or the mixture of lactones has a boiling point between 150 and 250 ° C.
    [5" id="c-fr-0005]
    The solvent system of any preceding claim, wherein said lactone is water soluble.
    [6" id="c-fr-0006]
    A solvent system according to any one of the preceding claims, wherein said solvent system comprises from 5 to 80% by weight of a composition (A) comprising DMSO, preferably from 30 to 80% by weight, more preferably from 30 to 65% by weight, based on the total weight of the solvent system.
    [7" id="c-fr-0007]
    The solvent system according to any one of the preceding claims, wherein said system comprises from 20 to 95% by weight of a composition (B) comprising at least one lactone, preferably from 20 to 70% by weight, preferably still 35 to 70% by weight, based on the total weight of the solvent system.
    [8" id="c-fr-0008]
    8. Solvent system according to any one of the preceding claims, wherein said system comprises from 0 to 20% by weight of one or more additional solvent (s), relative to the total weight of the solvent system.
    [9" id="c-fr-0009]
    9. Solvent system according to claim 8, wherein said additional solvent has a boiling point of between 150 and 250 ° C.
    [10" id="c-fr-0010]
    The solvent system of claim 8 or 9, wherein said additional solvent is water soluble.
    [11" id="c-fr-0011]
    11. Use of the solvent system as defined in any one of the preceding claims for the solubilization of fluoropolymers or polymers comprising at least one double bond X = 0, X being chosen from the sulfur atom, the atom of carbon, an NC group and an OC group.
    [12" id="c-fr-0012]
    12. Use according to claim 11, wherein the polymers are chosen from polyurethanes, polyethersulfones, polysulfones, polyvinylidene fluorides, cellulose acetates, polyesters, polyamides, polyamide imides and polyimides. preferably selected from polyurethanes, polyethersulfones and polysulfones.
    [13" id="c-fr-0013]
    13. Process for solubilizing a fluoropolymer or a polymer comprising at least one X = O double bond, X being chosen from the sulfur atom, the carbon atom, an NC group and an OC group, comprising at least one step of contacting said polymer with at least one solvent system as defined in any one of claims 1 to 10.
    [14" id="c-fr-0014]
    A solution comprising: from 1 to 50% by weight, preferably from 1 to 40% by weight, more preferably from 1 to 25% by weight of at least one fluorinated polymer or a polymer comprising at least one double bond X = 0, X being chosen from the sulfur atom, the carbon atom, an NC group and an OC group, relative to the total weight of the solution, and from 50 to 99% by weight, preferably from 60 to 99% by weight, more preferably 75 to 99% by weight, relative to the total weight of the solution, of at least one solvent system as defined in any one of claims 1 to 10.
    [15" id="c-fr-0015]
    15. Use of the solvent system as defined in any one of claims 1 to 10, or the solution as defined in the preceding claim, for the manufacture of films, artificial leathers, polymeric suede, polymer fibers, coatings, membranes, for the protection of electric cables, and in the manufacture of batteries and electronic circuits.
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    同族专利:
    公开号 | 公开日
    KR20180051589A|2018-05-16|
    US20180251627A1|2018-09-06|
    JP2018534384A|2018-11-22|
    EP3353237A1|2018-08-01|
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    JP6698827B2|2020-05-27|
    FR3041352B1|2019-12-13|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1558878A|FR3041352B1|2015-09-21|2015-09-21|SOLVENT SYSTEM COMPRISING A MIXTURE OF DIMETHYLSULFOXIDE AND AT LEAST ONE LACTONE|
    FR1558878|2015-09-21|FR1558878A| FR3041352B1|2015-09-21|2015-09-21|SOLVENT SYSTEM COMPRISING A MIXTURE OF DIMETHYLSULFOXIDE AND AT LEAST ONE LACTONE|
    KR1020187009900A| KR20180051589A|2015-09-21|2016-09-20|A solvent system comprising a mixture of dimethylsulfoxide and at least one lactone|
    US15/756,680| US20180251627A1|2015-09-21|2016-09-20|Solvent system comprising a mixture of dimethyl sulfoxide and at least one lactone|
    PCT/FR2016/052376| WO2017051107A1|2015-09-21|2016-09-20|Solvent system comprising a mixture of dimethyl sulfoxide and at least one lactone|
    CN201680054636.1A| CN108026323A|2015-09-21|2016-09-20|The dicyandiamide solution of mixture comprising dimethyl sulfoxideand at least one lactone|
    JP2018514966A| JP6698827B2|2015-09-21|2016-09-20|Solvent system containing a mixture of dimethyl sulfoxide and at least one lactone|
    EP16781513.3A| EP3353237A1|2015-09-21|2016-09-20|Solvent system comprising a mixture of dimethyl sulfoxide and at least one lactone|
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