• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to the use of a sulfonated polyaryletherketone as a dispersing agent for a polyaryletherketone resin powder in an aqueous solution, as well as a corresponding composition, and a process for preparing a semi-finished product comprising a polyaryletherketone resin and reinforcing fibers.
    公开号:FR3073523A1
    申请号:FR1760709
    申请日:2017-11-14
    公开日:2019-05-17
    发明作者:Guillaume Le；Fabien Sguerra；Julien Jouanneau
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    The present invention relates to the use of a sulfonated polyaryletherketone as a dispersing agent for polyaryletherketone resin powders, in particular in the manufacture of semi-finished products comprising a polyaryletherketone resin and reinforcing fibers.
    TECHNICAL BACKGROUND
    Due to their excellent mechanical properties at low weight, composite materials combining a thermoplastic resin with reinforcing fibers are of great interest in many fields, particularly in the aeronautics and space industry, but also in the automotive industry and sports equipment.
    These composite materials are generally manufactured by consolidation of semi-products made of reinforcing fibers coated with resin such as prepregs in the form of unidirectional sheets, wicks or woven fabrics.
    These semi-finished products can be obtained by impregnating the fibers with the resin. There are different processes in which the resin can be melted, dissolved in a solvent, or even in the form of a powder, either in a fluidized bed or dispersed in an aqueous solution. The impregnated fibers are then optionally freed from the solvent or the aqueous solution and then heated in order to melt the retained resin and form the semi-finished product.
    For polymers with a high melting point such as polyaryletherketones (PAEK), the impregnation by passing through an aqueous dispersion in a bath is advantageous from an economic and environmental point of view. With this technique, it is important to ensure a homogeneous distribution of the resin particles during the impregnation of the fibers.
    It is known to include dispersing agents or surfactants in the aqueous dispersion in order to allow dispersing and to promote this homogeneous distribution, whether with stirring or not. These agents are often composed of a hydrophobic part (fatty chain, aromatic group) and a hydrophilic part (ethoxylated chain or ionic group). The ethoxylated chains, like in particular the polyethylene glycol chains, have a low thermal stability.
    In the presence of oxygen, they oxidize and form radicals from 200-250 ° C. Under an inert atmosphere, they undergo thermolysis from 350-370 ° C. The radicals generated by these parasitic reactions lead to the degradation of the polymer (branching reactions, presence of insolubles, drop in the crystallization temperature ...), disrupting the following steps to manufacture the composite and inducing unsatisfactory properties.
    Furthermore, document US 2015 / 274588A describes the use of sulfonated PAEK for sizing fibers. The sulfonated PAEK is dissolved in hot water and then coated on fibers. The fibers are subjected to a heat treatment to be dried, then to desulfonate the PAEK.
    Document US 2004/0131910 describes methods of sulfonating polyether ketone ketone (PEKK) with hot-fuming sulfuric acid or with chlorosulfuric acid at room temperature.
    There is a need to provide homogeneous aqueous dispersions of PAEK for the impregnation of reinforcing fibers, while avoiding deteriorating the thermal stability of PAEK.
    SUMMARY OF THE INVENTION
    The invention relates firstly to the use of a sulfonated polyaryletherketone as a dispersing agent for a powder of polyaryletherketone resin in an aqueous solution.
    In certain embodiments, the polyaryletherketone is chosen from the group consisting of polyether ketones (PEK), polyether ether ketones (PEEK), polyether ether-ketone ketones (PEEKK), polyether -ketone-ketones (PEKK), poly-ether-ketone-ether-ketone-ketones (PEKEKK), poly-ether-ether-ketone-ether-ketones (PEEKEK), polyether-ether-ether-ketones (PEEEK) ), poly-ether-diphenyl-ether-ketone (PEDEK), their mixtures and copolymers comprising them, the polyaryletherketone preferably being a polyether ketone ketone (PEKK) or a polyether ether -ketone (PEEK).
    In certain embodiments, the sulfonated polyaryletherketone is chosen from the group consisting of sulfonated polyether ketones (PEK), sulfonated polyether ether ketones (PEEK), ketone polyether ether ketones (PEEKK) sulfonated, sulfonated poly-ether-ketone-ketones (PEKK), sulfonated poly-ether-ketone-ether-ketone-ketones (PEKEKK), sulfonated polyether-ether-ketone-ether-ketones (PEEKEK) sulfonated ether-etherether-ketones (PEEEK), sulfonated poly-ether-diphenyl-ether-ketone (PEDEK), mixtures thereof and copolymers comprising them.
    In certain embodiments, the sulfonated polyaryletherketone has a degree of sulfonation of 0.01 to 4, preferably 0.01 to 1 and more preferably 0.01 to 0.1.
    In certain embodiments, the sulfonated polyaryletherketone comprises sulfonated groups chosen from sulfonic acid groups and / or sulfonate groups, the molar proportion of sulfonate groups in the sulfonated polyaryletherketone relative to all of the sulfonated groups being preferably greater than or equal to 50%, preferably still greater than or equal to 80%.
    The invention also relates to a composition comprising a polyaryletherketone resin powder in suspension in an aqueous solution, the composition further comprising a sulfonated polyaryletherketone.
    In certain embodiments, the polyaryletherketone is chosen from the group consisting of polyether ketones (PEK), polyether ether ketones (PEEK), polyether ether-ketone ketones (PEEKK), polyether -ketone-ketones (PEKK), poly-ether-ketone-ether-ketone-ketones (PEKEKK), poly-ether-ether-ketone-ether-ketones (PEEKEK), polyether-ether-ether-ketones (PEEEK) ), poly-ether-diphenyl-ether-ketone (PEDEK), their mixtures and copolymers comprising them, the polyaryletherketone preferably being a polyether ketone ketone (PEKK) or a polyether ether -ketone (PEEK).
    In certain embodiments, the sulfonated polyaryletherketone is chosen from the group consisting of sulfonated polyether ketones (PEK), sulfonated polyether ether ketones (PEEK), ketone polyether ether ketones (PEEKK) sulfonated, sulfonated poly-ether-ketone-ketones (PEKK), sulfonated poly-ether-ketone-ether-ketone-ketones (PEKEKK), sulfonated polyether-ether-ketone-ether-ketones (PEEKEK) sulfonated ether-etherether-ketones (PEEEK), sulfonated poly-ether-diphenyl-ether-ketone (PEDEK), mixtures thereof and copolymers comprising them. The sulfonated poly-ether-ketone (PEKK) and sulfonated poly-ether-ketone (PEEK) are particularly preferred.
    In certain embodiments, the sulfonated polyaryletherketone has a degree of sulfonation of 0.01 to 4, preferably 0.1 to 1 and more preferably 0.1 to 0.5.
    In certain embodiments, the sulfonated polyaryletherketone comprises sulfonated groups chosen from sulfonic acid groups and / or sulfonate groups, the molar proportion of sulfonate groups in the sulfonated polyaryletherketone relative to all of the sulfonated groups being preferably greater than or equal to 50%, preferably greater than or equal to 80%.
    In certain embodiments, the mass content of sulfonated polyaryletherketone relative to the polyaryletherketone resin powder is from 0.1 to 20%, advantageously from 0.2 to 10%, preferably from 0.5 to 5% and all particularly from 1 to 3%.
    The invention also relates to a process for the preparation of a semi-product comprising a polyaryletherketone resin and reinforcing fibers, comprising:
    - the supply of a composition as described above, and the impregnation of reinforcing fibers with this composition;
    - drying the impregnated reinforcing fibers;
    - Heating the impregnated reinforcing fibers so as to melt the polyaryletherketone; and
    - optionally, a calendering step.
    In some embodiments, the reinforcing fibers are carbon fibers.
    In certain embodiments, the semi-finished product is chosen from a prepreg or a tape.
    The invention also relates to a semi-finished product capable of being prepared according to the process described above.
    The invention also relates to the use of a semi-finished product as described above for the manufacture of composite materials.
    The present invention overcomes the drawbacks of the state of the art. It more particularly provides a means of dispersing (suspending) a PAEK powder in an aqueous solution in a homogeneous manner, while avoiding deteriorating the thermal stability of the PAEK.
    This is accomplished through the use of a sulfonated PAEK as a dispersing agent.
    The invention can make it possible to dispense with the use of conventional surfactants which are insufficiently thermally stable.
    The invention can be implemented with a relatively small amount of sulfonated compound, which makes it possible to limit the porosity problems inherent in this type of compound. Indeed, despite a high thermal stability, these compounds can be desulfonated under the conditions of implementation, which can generate volatiles and thereby increase the porosity.
    The invention can make it possible to avoid the use of a sizing of the fibers, the sulfonated PAEK making it possible to promote the bond between the reinforcing fibers and the PAEK matrix.
    DESCRIPTION OF EMBODIMENTS OF THE INVENTION
    The invention is now described in more detail and without limitation in the description which follows.
    The invention relates to the use of a sulfonated PAEK as a dispersing agent for a PAEK resin powder in an aqueous medium.
    PAEK resin
    By "resin" is meant a composition mainly comprising one or more polymers, if necessary, added with additives such as fillers and functional additives.
    By "PAEK" is meant polymers comprising units of formulas (-Ar-X-) as well as units of formula (-Ar’-Y-), in which:
    - Ar and Ar ’each denote a divalent aromatic radical;
    - Ar and Ar 'can be chosen, preferably, from 1,3phenylene, 1,4-phenylene, 4,4'-biphenylene, 1,4-naphthylene, 1,5-naphthylene and 2,6 -naphthylene, optionally substituted;
    - X denotes an electron-withdrawing group, which can be chosen, preferably, from the carbonyl group and the sulfonyl group;
    - Y denotes a group chosen from an oxygen atom, a sulfur atom, an alkylene group, such as in particular -CH2- and isopropylidene.
    Among the X units, at least 50 mol.%, Preferably at least 70 mol.% And more particularly, at least 80 mol.% Of the X units represent a carbonyl group. In certain embodiments, all the units X denote a carbonyl group.
    Among the Y units, at least 50 mol.%, Preferably at least 70 mol.% And more particularly at least 80 mol.% Of the Y units represent an oxygen atom. In some embodiments, all of the patterns Y denote an oxygen atom.
    Thus, in certain embodiments, the PAEK is a polymer comprising, or preferably consisting of, units of formulas (-Ar-CO-) as well as units of formula (-Ar'-O-), the units Ar and Ar 'being as defined above.
    In certain embodiments, the PAEK is a polyether ketone ketone (PEKK), comprising a succession of repeating units of type - (An-OAr2-CO-Ar3-CO) n-, each year, Ar2 and An representing independently a divalent aromatic radical, preferably a phenylene.
    In the above formula, as in all of the following formulas, n represents an integer.
    The links on either side of each motif An, An and An can be of the para, or meta, or ortho type (preferably of the para or meta type).
    In certain embodiments, the PEKK comprises a succession of repeating units of formula (IA) and / or of formula (IB) as follows:
    (IA) (IB)
    The units of formula (IA) are units derived from isophthalic acid (or units I), while the units of formula (IB) are units derived from terephthalic acid (or units T).
    In the PEKK used in the invention, the mass proportion of T units relative to the sum of the T and I units can vary from 0 to 5%; or from 5 to 10%; or from 10 to 15%; or from 15 to 20%; or from 15 to 20%; or from 20 to 25%; or from 25 to 30%; or from 30 to 35%; or from 35 to 40%; or from 40 to 45%; or from 45 to 50%; or from 50 to 55%; or from 55 to 60%; or from 60 to 65%; or from 65 to 70%; or from 70 to 75%; or from 75 to 80%; or from 80 to 85%; or from 85 to 90%; or from 90 to 95%; or from 95 to 100%.
    Ranges from 35 to 100%, in particular from 55 to 85% and more specifically still from 60 to 80%, are particularly suitable. In all the ranges set out in this request, the terminals are included unless otherwise stated.
    In certain embodiments, the PAEK is a polyether etherketone (PEEK), comprising a succession of repeated units of type - (An-OAr2-O-Ar3-CO) n-, each An, Ar2 and An representing independently a divalent aromatic radical, preferably a phenylene.
    The links on either side of each motif An, An and An can be of the para, or meta, or ortho type (preferably of the para or meta type).
    In certain embodiments, the PEEK comprises a succession of repeating units of formula (II):
    and / or a succession of repeated patterns of formula (III):
    and / or a succession of repeated patterns of formula (IV):
    and / or a succession of repeated patterns of formula (V):

    In certain embodiments, the PAEK is a polyether ketone (PEK), comprising a succession of repeated units of type - (An-O-AnCO) n-, each An and An independently representing a divalent aromatic radical , preferably phenylene.
    The links on either side of each motif An and ΑΓ2 can be of the para, or meta, or ortho type (preferably of the para or meta type).
    In certain embodiments, the PEK comprises a succession of repeating units of formula (VI):
    In certain embodiments, the PEK comprises a succession of repeating units of formula (VII):
    (VII) L
    In this formula, as in the following formulas, x and y represent whole numbers.
    In certain embodiments, the PEK comprises a succession of repeating units of formula (VIII):

    In certain embodiments, the PAEK is a poly-ether-etherketone-ketone (PEEKK), comprising a succession of repeated patterns of type - (ΑΓι-Ο-ΑΓ2-Ο-ΑΓ3-ΟΟ-ΑΓ4-ΟΟ) η-, each An, ΑΓ2, An and An independently representing a divalent aromatic radical, preferably a phenylene.
    The links on either side of each motif An, An, An and An can be of the para, or meta, or ortho type (preferably of the para or meta type).
    In certain embodiments, the PEEKK comprises a succession of repeated units of formula (IX):
    In certain embodiments, the PAEK is a poly-ether-ether ether-ketone (PEEEK), comprising a succession of repeated units of type - (Ar-iO-Ar2-O-Ar3-O-Ar4-CO) n-, each year, ΑΓ2, Au and Au independently representing a divalent aromatic radical, preferably a phenylene.
    The links on either side of each motif Ar-ι, Au, Au and Au can be of the para, or meta, or ortho type (preferably of the para or meta type).
    In certain embodiments, the PEEEK comprises a succession of repeating units of formula (X):
    In certain embodiments, the PAEK is a poly-ether-ketoneether-ketone-ketone (PEKEKK), comprising a succession of repeating units of type - (Ar-iO-Au-CO-Au-O-Au-CO-Au -COjn-, each Au, Au, Au, Au and Au independently representing a divalent aromatic radical, preferably a phenylene.
    The links on either side of each motif Au, Au, Au, Au and Au can be of the para, or meta, or ortho type (preferably of the para or meta type).
    In certain embodiments, the PAEK is a poly-ether-ketone-ether-ketone (PEEKEK), comprising a succession of repeating units of type - (Ar-iO-Au-O-Au-CO-Au-O-Au -COjn-, each Ar-ι, Au, Au, Au and Au independently representing a divalent aromatic radical, preferably a phenylene.
    The links on either side of each motif Au, Au, Au, Au and Au can be of the para, or meta, or ortho type (preferably of the para or meta type).
    In certain embodiments, the PAEK is according to the most general formula indicated below, in which certain Ar and / or Ar ’units represent a divalent radical derived from diphenyl or biphenol.
    In certain embodiments, the PAEK is a poly-etherdiphenyl-ether-ketone (PEDEK), comprising a succession of repeating units of type - (Ar-iODO-Ar2-CO) n-, each year and ΑΓ2 representing independently a divalent aromatic radical, preferably a phenylene, and D representing a divalent radical derived from diphenyl.
    The links on either side of each motif An and ΑΓ2 can be of the para, or meta, or ortho type (preferably of the para or meta type).
    In certain embodiments, the PEDEK comprises a succession of repeated patterns of formula (XI):
    Mixtures of the previous PAEKs can also be used, as well as copolymers of the previous PAEKs.
    PEEK and PEKK as well as their mixtures are particularly preferred.
    The PAEK resin may comprise one or more additional polymers not belonging to the PAEK family.
    Preferably, the mass content of PAEK in the PAEK resin is greater than or equal to 50%, preferably to 60%, more preferably to 70%, more preferably to 80% and more preferably to 90%.
    In some embodiments, the PAEK resin consists essentially of one or more PAEKs.
    In certain embodiments, the PAEK resin comprises PEKK, the mass content of PEKK in the PAEK resin being greater than or equal to 50%, preferably to 60%, more preferably to 70%, more preferably to 80 % and more preferably 90%.
    In some embodiments, the PAEK resin consists essentially of PEKK.
    The resin may include one or more phosphates or phosphate salts, to improve the stability of PAEK in the molten state.
    The resin may include additives such as fillers and functional additives. It is also possible to dispense with fillers and / or dispense with functional additives.
    PAEK sulfonated
    By “sulfonated”, it is meant that the PAEK comprises as substituent (s) at least one group which is designated here “sulfonated group”, that is to say a sulfonic acid group of formula -SO3H or a sulfonate group of formula SO3M where M + represents a monovalent cation. Preferably, M represents the sodium cation (Na) or the potassium cation (K).
    The whole description of the PAEKs given above concerning the resin applies in the same way to the sulfonated PAEK.
    In particular embodiments, the sulfonated PAEK can be a sulfonated PEEK (as described above) or a sulfonated PEKK (as described above).
    The sulfonated PAEK comprises a number of repeating units greater than or equal to 2, preferably greater than or equal to 10, more preferably greater than or equal to 100.
    The number average molecular weight of the sulfonated PAEK is preferably from 1500 to 30,000 g / mol, more preferably from 5,000 to 20,000 g / mol, and more preferably from 10,000 to 20,000 g / mol. The fact of using a polymer with a target molar mass makes it possible to modulate the viscosity of the dispersion in order to limit, for example, sedimentation or facilitate the entrainment of the powder by the fibers.
    In sulfonated PAEK, sulfonated groups may be present as substituents of hydrogen atoms at any position in the molecule.
    In particular, the sulfonated groups can be present as substituents of hydrogen atoms on one or more Aret Ar ’units as described above.
    Preferably, the sulfonated groups are present on one or more units Ar and Ar ’linked to an ether unit -O-.
    An example of sulfonated PAEK is the sulfonated PEKK of generic formula (XIII):
    (XIII)
    a b c
    wherein a, b and c each independently represent 0 or an integer. It is understood that, in the above formula, the sulfonic acid groups can also be replaced in whole or in part by sulfonate groups.
    The sulfonated PAEK can be prepared by sulfonation of the corresponding PAEK or by polymerization of sulfonated monomers, or of mixtures of sulfonated and non-sulfonated monomers. The PAEK sulfonation reaction can be carried out, for example, by placing the PAEK in the presence of fuming sulfuric acid (H2SO4 + SO3). The temperature for carrying out the reaction can in particular be from 20 to 90 ° C., preferably from 20 to 60 ° C. The duration of the reaction can in particular be from 0.5 to 24 h, preferably from 1 to 8 h. The concentration of PAEK in the acid is preferably from 1 to 40%, more preferably from 5 to 35%, and more preferably from 10 to 30% (mass).
    Alternatively, the sulfonation reaction can be carried out under milder conditions, by reacting PAEK in chlorosulfuric acid (CISO3H). The temperature for carrying out the reaction can in particular be from 0 ° C to 50 ° C, preferably from 10 to 25 ° C. The reaction time can in particular be from 1 hour to 12 hours, preferably from 2 hours to 10 hours. The concentration of PAEK in the acid is preferably from 1 to 40%, more preferably from 5 to 35%, and more preferably from 10 to 30% (mass).
    After the sulfonation reaction, the product of interest can be collected, for example by pouring it into cold water so as to cause it to precipitate. It can be washed in cold water to remove excess acid and dried.
    The above reactions make it possible to graft sulfonic acid groups on the molecules.
    It is then possible to convert all or part of these sulfonic acid groups to sulfonate groups, by contacting with a base, such as sodium or potassium hydroxide (neutralization reaction).
    The temperature for carrying out the neutralization reaction can in particular be from 5 to 95 ° C., preferably from 50 to 80 ° C. The reaction time can in particular be from 1 to 50 h, preferably from 1 to 8 h. The concentration of sulfonated PAEK in the basic solution can be in particular from 5 to 50% by weight, and preferably from 10 to 30% by weight.
    The sulfonated PAEK can be characterized by its degree of sulfonation. The degree of sulfonation corresponds to the average number of sulfonated groups per repeat unit in the polymer. The higher the degree of sulfonation, the more water-soluble the PAEK sulfonated. The solubility also depends on the nature of the PAEK, its molar mass and its crystallinity in particular. It is generally desirable to use the minimum degree of sulphonation which makes it possible to dissolve the sulphonated PAEK in water.
    Depending on the nature of the PAEK and the degree of sulfonation, some sulfonated PAEKs are soluble in water at room temperature, others only at higher temperatures, for example 30, or 40 or 50 ° C.
    Preferably, the sulfonated PAEK is soluble in water at ambient temperature (20 ° C.), which facilitates the management of the impregnation bath and avoids a loss of water inducing a variation in viscosity of the bath.
    The degree of sulfonation can be controlled by acting on the conditions of the sulfonation reaction, in particular the duration of the reaction, the temperature and the concentration of sulfonate ions.
    The articles Sulfonated Poly (aryl ether ketone) s by Ulrich and Rafler in Die Angewandte Makromolekulare Chemie 263: 71-78 (1998) and Sulfonated Poly (ether ketone ketone) lonomers as Proton Exchange Membranes, by Swier et al. in Polymer Engineering and Science, DOI 10.1002 / pen.20361 (2005) describe examples of PAEK sulfonation as well as possible adjustment of reaction conditions.
    The degree of sulfonation can be determined by acid-base titration, for example with sodium hydroxide. For example, one can take a test sample of 1 to 2 g of sulfonated PAEK, dissolve it in 60 ml of pure water (for example of HPLC quality) by stirring for for example 15 minutes, then carry out a 0.01 N soda dosage
    The degree of sulfonation of the sulfonated PAEK can in particular be from 0.01 to 0.05; or from 0.05 to 0.1; or from 0.1 to 0.2; or from 0.2 to 0.5; or from 0.5 to 1; or from 1 to 2; or from 2 to 3; or from 3 to 4. Ranges of 0.1 to 1 and 0.1 to 0.5 may be particularly suitable.
    The rate of neutralization of the sulfonated groups corresponds to the molar proportion of sulfonate groups relative to all of the sulfonated groups.
    The neutralization rate can be controlled by acting on the amount of base brought into contact with the sulfonated PAEK. Preferably, an amount of stoichiometric base, or slightly lower (0.98 equivalent), is used compared to the sulfonated groups.
    The neutralization rate can be determined by titration by measuring the residual acidity with sodium hydroxide.
    Preferably, the degree of neutralization of the sulfonated PAEK is from 50% to 100%, more preferably from 75% to 100% and more preferably from 95% to 100%.
    Neutralization makes it possible to limit the degradation of the PAEK resin by the sulfonated PAEK.
    The mixtures of different sulfonated PAEKs are considered in the present description as a sulfonated PAEK.
    The present inventors have furthermore discovered that the sulfonation of the PAEKs described above can be applied in exactly the same way to a non-polymeric aryletherketone. It is in particular possible to thus manufacture sulfonated 1,4-bis (4-phenoxybenzoylbenzene).
    By way of example, this 1,4-bis (4-phenoxybenzoylbenzene) sulfonated can correspond to the following formula (XII):
    wherein each X independently represents a hydrogen atom or a sulfonated group, at least one of the two X represents a sulfonated group.
    Preferably, each X represents a sulfonated group.
    Resin powder suspension
    According to the invention, a composition is prepared by adding the PAEK resin powder to an aqueous solution so as to form a suspension or dispersion.
    The term "suspension" or "dispersion" means a heterogeneous composition comprising a liquid phase and a solid phase. The liquid phase is aqueous and contains the sulfonated PAEK as well as other additives, if necessary. The solid phase essentially comprises or consists of PAEK resin powder.
    In order to ensure optimal homogeneity of the suspension, and good subsequent impregnation of the fibers, it is preferred that the resin powder be finely divided. More specifically, it is preferred that the PAEK resin powder has a median diameter Dv50 ranging from 1 to 300 μm, preferably from 5 to 100 μm and very particularly from 10 to 50 μm, as measured according to standard ISO 13 320 .
    Preferably, the content of PAEK resin powder in this composition is from 1 to 50%, preferably from 10 to 40% and very particularly from 25 to 35% by weight (relative to the weight of the total composition).
    The sulfonated PAEK is used as a dispersing agent, or surfactant, in the composition. It is present in the aqueous phase of the composition.
    In certain embodiments, the mass proportion of the sulfonated PAEK, relative to the sum of the sulfonated PAEK and of the PAEK resin, is 0.1 to 0.2%; or from 0.2 to 0.5%; or from 0.5 to 1%; or from 1 to 2%; or from 1 to 5%; or from 5 to 10%. A range of 0.5 to 5% is particularly suitable.
    The optimal mass proportion can be chosen as a function of the quantity of powder to be dispersed, its particle size and its surface appearance.
    The sulfonated PAEK can be of the same nature or not as the PAEK of the resin.
    The aqueous phase of the composition can optionally comprise one or more other surfactants different from the sulfonated PAEK. It is however preferred that no other surfactant is present to ensure the dispersion function.
    By "use as a dispersing agent" is meant that the sulfonated PAEK makes it possible to improve the dispersion of the PAEK resin powder in the aqueous solution, and more particularly to reduce the dispersion time. Thus, when an aqueous solution of sulfonated PAEK of 25 ° C. is introduced, an amount of 20% by weight relative to the weight of the finished dispersion of PAEK powder having an average Dv50 of 20 μm and that one disperses this powder in the solution with moderate stirring, the presence of the sulfonated PAEK makes it possible to obtain a homogeneous dispersion in a time of less than 3 h, preferably less than 2 h, whereas, under the same conditions but in the absence of PAEK sulfonated, no homogeneous dispersion is obtained.
    The aqueous phase of the dispersion can, if necessary, include other additives such as thickening agents, anti-foaming agents, biocidal agents. Preferably, in order to limit the presence of additives in the semi-finished products and the associated potential problems, the total amount of other additives does not exceed 4% by weight, in particular 3% and very particularly 2% by weight or even 1 % by weight of the total composition.
    More preferably, the aqueous phase of the dispersion does not contain other additives, and in particular no thickening agents.
    The aqueous phase of the dispersion consists mainly of water. The aqueous phase of the dispersion comprises at least 60%, preferably 70%, more preferably at least 80% and very particularly at least 90% by weight of water. The water used to prepare the dispersion is preferably demineralized water.
    The dispersion and more particularly its aqueous phase may also contain one or more volatile organic compounds.
    The term “volatile organic compound” means a compound containing at least the carbon element and one or more of the elements chosen from hydrogen, halogens, oxygen, sulfur, phosphorus, silicon and nitrogen, with the exception of carbon oxides and carbonates and bicarbonates, the compound having a boiling point at atmospheric pressure of less than 200 ° C, and preferably less than 150 ° C, more preferably less than 120 ° C and all particularly below 100 ° C.
    These volatile organic compounds, soluble in water under the conditions of use, can be chosen in particular from the families of alcohols, ketones, aldehydes, esters of carboxylic acids, glycols and ethers.
    In certain embodiments, as volatile organic compound, an alcohol chosen from ethanol, isopropanol, n-propanol, nbutanol, 2-butanol, te / ï-butanol, 1-methoxy is used. -2-propanol, 1-ethoxy-2propanol and their mixtures, a glycol chosen from ethylene glycol, propylene glycol and their mixtures, a chosen ketone such as acetone, an ether or a carboxylic acid ester chosen from methyl acetate, ethyl acetate and propyl acetate and their mixtures.
    Particularly preferred are the volatile organic compounds forming an azeotrope with water facilitating their elimination such as ethanol, methyl acetate, propyl acetate and their mixtures.
    Adding such volatile organic compounds to the aqueous phase can reduce the surfactant content required to stabilize the PAEK resin in the dispersion and / or increase the viscosity of the dispersion by ensuring better wetting of the dispersed particles. Their volatility ensures that they do not remain in the resin, unlike usual non-volatile additives which may then be broken down into reactive species when the resin melts.
    The aqueous phase of the dispersion may preferably comprise from 0 to 50%, more preferably from 1 to 40%, or from 5 to 30%, or from 10 to 25% by weight of one or more volatile compounds. The content of these compounds is adjusted to avoid precipitating the surfactant.
    The dispersion obtained preferably has a dynamic viscosity, as measured at 25 ° C under shear stress of 6.8 s 1 on a Brookfield DVT2T Extra viscometer, from 0.1 Pa s to 20 Pa s, in particular from 0.1 to 5 Pa s, in particular from 0.3 to 3 Pa s and very particularly from 0.5 to 2 Pa s.
    The dispersion can be carried out in a manner known per se. It can for example be prepared by introducing into a container of suitable volume and provided with an appropriate stirring device the quantity of water required, then then adding the dispersing agent as well as the other additive (s), if necessary. . If necessary, the mixture is stirred until a homogeneous solution is obtained. The PAEK resin powder is then introduced into the aqueous solution, followed by stirring until a stable dispersion is obtained.
    The additions and mixtures to prepare the dispersion can be carried out in particular at a temperature of 10 to 95 ° C, preferably from 20 to 60 ° C. The choice of a suitable temperature can be made in particular as a function of the solubility of the sulfonated PAEK in water. It is preferable to use a relatively high temperature if the sulfonated PAEK is relatively poorly soluble in water, whereas a lower temperature and in particular the ambient temperature may be suitable if the solubility of the sulfonated PAEK in water is high.
    Process for preparing a semi-finished product
    The term “semi-finished product” means a product comprising a resin and reinforcing fibers, which is used as an intermediate product in the manufacture of composite materials. The semi-finished products can in particular be prepregs in the form of unidirectional sheets of wicks, woven fabrics, or even fiber-matrix mixtures.
    The reinforcing fibers used for the manufacture of semi-finished products can be chosen from all the fibers capable of being used as reinforcement in the manufacture of parts made of composite materials.
    Thus, it may in particular be glass fibers, quartz fibers, carbon fibers, graphite fibers, silica fibers, metallic fibers such as steel fibers, aluminum fibers or boron fibers, ceramic fibers such as silicon carbide or boron carbide fibers, synthetic organic fibers such as aramid fibers or poly (p-phenylene benzobisoxazole) fibers, better known under the acronym PBO, or PAEK fibers, or mixtures of such fibers.
    Preferably, these are carbon fibers or glass fibers, and more particularly carbon fibers.
    The fibers are preferably not sized. When they are sized, the size is preferably adapted to the matrix, in particular in that it does not cause degradation products harmful to the matrix.
    The reinforcing fibers used are generally continuous.
    Preferably, they are in the form of unidirectional fibers, for example in the form of threads grouping together several thousand elementary filaments (typically from 3000 to 48000) measuring, for example, from 6 to 10 μm in diameter for carbon fibers. This type of fiber is known under the name of wick (in English: "rovings").
    The fibers can nevertheless also be organized in a different way, for example in the form of a mat, or else of textiles obtained by weaving wicks.
    The semi-products according to the invention can be manufactured in a conventional manner, by implementing the dispersion as described above.
    More specifically, they can be obtained by introduction and circulation of the reinforcing fibers in a dispersion bath as described above. The fibers impregnated with PAEK resin powder are then removed from the bath and freed from water, for example by drying in an infrared oven. The dried impregnated fibers are then heated until the resin melts, in order to allow the fibers to be coated with the PAEK resin. The coated fibers obtained are then optionally shaped, for example by calendering. This step can texturize and ensure the sizing of the semi-finished product.
    Preferably, the semi-products according to the invention comprise from 1 to 99% by weight, preferably from 30 to 90%, in particular from 50 to 80% by weight, and in particular from 60 to 70% by weight of fibers. reinforcement.
    The semi-products obtained according to this can be used in particular for the manufacture of composite parts.
    Composite parts are obtained, for example, by first manufacturing a preform, in particular by placing or draping pre-impregnated semi-products in a mold. The composite part is then obtained by consolidation, a step during which the preform is heated, generally under pressure in an autoclave, so as to assemble the semi-finished products by fusion. Preferably, the semi-products produced according to the invention can be consolidated outside of an autoclave, for example under a vacuum cover placed in an oven.
    The semi-finished products produced according to the process of the invention are characterized in particular by a resin whose viscosity changes little despite the high temperatures required for their manufacture in order to melt the resin.
    In the processes for manufacturing composite parts, the semi-products are subjected to different thermal cycles under pressure or under vacuum in order to assemble them together to form the composite part and / or to shape it.
    The composite products manufactured according to the process of the invention are characterized in particular by a resin whose viscosity has changed little despite the high temperatures required for their manufacture.
    During these steps, it is important that the viscosity of the matrix is not too high, in order to ensure that the semi-finished products conform to the shapes of the mold. The viscosity of the matrix also ensures good flow during consolidation and thus avoids surface defects such as wrinkling.
    The semi-finished products can then be assembled, for example by manual or automated draping or by robotic depositing, and shaped by consolidation, for the manufacture of composite parts. The composite parts thus produced can be further processed, in order to obtain assemblies of complex composite parts. Thus, it is possible to co-consolidate composite parts, a process generally carried out in an autoclave by means of a new thermal cycle, or to weld parts to one another by local heating.
    EXAMPLES
    The following examples illustrate the invention without limiting it.
    Example 1 - Preparation of a non-neutralized S-PEKK
    A PEKK produced by Arkema, reference Kepstan® 6004 PF (10 g), having an MVI (melt volume index) of 23.4cm 3 / 10min (at 380 ° C under a load of 1kg), as well as CISO3H (38, 8 g) are brought together at 0 ° C. The mixture is then vigorously stirred and heated at 50 ° C for 6 hours. The mixture is then cooled to 0 ° C and dichloromethane (50 mL) is added to thin the mixture. Then the excess acid is quenched with water (100 ml_). A solid forms, it is filtered and washed thoroughly with water to remove the residual acid. Finally the solid is dried in an oven under vacuum for 2 hours at 120 ° C.
    By acid-base determination with sodium hydroxide, a degree of sulfonation of 0.38 is determined.
    Example 2 - Preparation of a non-neutralized S-oPEKK
    A PEKK oligomer (10 g) with a molecular mass of 2600 g / mol is sulfonated according to the conditions of Example 1.
    By dosing with sodium hydroxide, a degree of sulfonation of 0.21 is determined.
    The same protocol can be used with 1,4-bis (4phenoxybenzoylbenzene). Note that at room temperature, 1,4-bis (4phenoxybenzoylbenzene) sulfonated with a degree of sulfonation of 2 is not soluble in water but is dispersible in water with stirring.
    Example 3 Preparation of a neutralized sulfonated oligomer S-oPEKK-Na
    From the product of Example 2, the degree of sulfonation is determined by acid-base determination, and the neutralized sulfonated PEKK is prepared by reacting the sulfonated oligomer with an equivalent of sodium hydroxide with respect to the sulfonic functions in water at reflux.
    Example 4 - Preparation of a non-neutralized S-PEEK
    A PEEK produced by Victrex (grade 150G, 10 g), having an MVI (melt volume index) of 49cm 3 / 10min (at 380 ° C under a load of 5kg), as well as CISO3H (38.8 g) are put in the presence at 0 ° C. The mixture is then vigorously stirred and heated at 50 ° C for 6 hours. The mixture is then cooled to 0 ° C and dichloromethane (50 mL) is added to thin the mixture. Then the excess acid is quenched with water (100 mL). A solid forms, it is filtered and washed thoroughly with water to remove the residual acid. Finally the solid is dried in an oven under vacuum for 2 hours at 120 ° C.
    By acid-base determination with sodium hydroxide, a degree of sulfonation of 1.13 is determined.
    Example 5 - Preparation of a neutralized S-PEEK
    From the product of Example 4, the degree of sulfonation is determined by acid-base determination, and the neutralized sulfonated PEEK is prepared by reacting it with an equivalent of sodium hydroxide with respect to the sulfonic functions in water at reflux. .
    Example 6 Dispersion Properties and Thermal Stability
    PEKK powder dispersions were prepared. The PEKK used is supplied by Arkema under the reference 7002 PT. The Dv50 of the powder is approximately 20 μm.
    The following mixtures were thus prepared and then heated to reflux:
    - A (comparison): PEKK 7002PT (1 g) + water (9 g).
    - B (comparison): Brij® S100 surfactant from Sigma Aldrich (0.01 g) + PEKK 7002PT (0.99 g) + water (9 g).
    - C: S-oPEKK (0.01 g) + PEKK 7002PT (0.99 g) + water (9 g).
    - D: S-oPEKK (0.05 g) + PEKK 7002PT (0.95 g) + water (9 g).
    - E: S-oPEKK Na (0.05 g) + PEKK 7002PT (0.95 g) + water (9 g).
    - F: S-PEEK (0.05 g) + PEKK 7002PT (0.95 g) + water (9 g).
    - G: S-PEEK Na (0.05 g) + PEKK 7002PT (0.95 g) + water (9 g).
    The quality of the dispersions was studied visually, in a pill box. A dispersion is considered to be good if the mixture is fluid, and little or no PEKK powder is fixed to the walls of the pill box (except liquid phase) after stirring. It is considered fair if the mixture is fluid but a significant amount of PEKK powder is attached to the walls of the pill box (except liquid phase) after shaking. No dispersion is considered to be obtained if the mixture is thick, and a demixing is observed, with the presence of residues of non-wet PEKK. It is noted that the dispersion time is less than 2 h when the aqueous solution contains 1% by weight of sulfonated PAEK and less than 1 h when it contains 5% by weight of sulfonated PAEK.
    Then, the water of the samples was evaporated on a rotary evaporator and the solids obtained dried under vacuum at 120 ° C for 2 hours. The crystallization temperature of each material after 30 minutes at 380 ° C was then measured. This is indeed impacted by the structural changes in PEKK.
    A decrease in this temperature is explained either by significant chemical modifications of the polymer or by chain extension reactions associated for example with branching phenomena.
    The results are summarized in the table below:
    Sample Quality of the dispersion Crystallization temperature AT No dispersion 269 ° C B Good dispersion 250 ° C VS Fair dispersion 270 ° C. D Good dispersion 259 ° C E Good dispersion 268 ° C F Good dispersion amorphous G Good dispersion 263 ° C
    It is also found that a PEKK impregnated by means of a dispersion comprising one of the sulfonated PAEKs prepared as a dispersing agent exhibits a thermal stability greater than that of PEKK 5 impregnated with 1% of commercial surfactant.
    权利要求:
    Claims (16)
    [1" id="c-fr-0001]
    1. Use of a sulfonated polyaryletherketone as a dispersing agent for a powder of polyaryletherketone resin in an aqueous solution.
    [2" id="c-fr-0002]
    2. Use according to claim 1, in which the polyaryletherketone is chosen from the group consisting of polyether ketones (PEK), polyether ether-ketones (PEEK), polyether-ether-ketone-ketones (PEEKK ), polyether ketone ketones (PEKK), polyether ketone-ether-ketone-ketones (PEKEKK), poly-ether-ketone-ether-ketone (PEEKEK), poly-ether-ether-ether -ketones (PEEEK), poly-ether-diphenyl-ether-ketone (PEDEK), mixtures thereof and copolymers comprising these, the polyaryletherketone preferably being a polyether ketone ketone (PEKK).
    [3" id="c-fr-0003]
    3. Use according to claim 1 or 2, in which the sulphonated polyaryletherketone is chosen from the group consisting of sulphonated polyether ketones (PEK), sulphonated polyether etherketones (PEEK), polyether ether- sulfonated ketone-ketones (PEEKK), sulfonated poly-ketone-ketones (PEKK), sulfonated poly-ether-ketone-ether-ketone-ketones (PEKEKK), poly-ether-ether-ketone-ether-ketones (PEEKEK) sulfonated, poly-ether-ether-ether-ketone (PEEEK) sulfonated, poly-ether-diphenyl-ether-ketone (PEDEK) sulfonated, mixtures thereof and copolymers comprising them.
    [4" id="c-fr-0004]
    4. Use according to one of claims 1 to 3, in which the sulfonated polyaryletherketone comprises a degree of sulfonation of 0.01 to 4, preferably 0.1 to 1 and more preferably 0.1 to 0.5 .
    [5" id="c-fr-0005]
    5. Use according to one of claims 1 to 4, in which the sulfonated polyaryletherketone comprises sulfonated groups chosen from sulfonic acid groups and / or sulfonate groups, the molar proportion of sulfonate groups in the sulfonated polyaryletherketone relative to the all of the sulfonated groups preferably being greater than or equal to 50%, more preferably still greater than or equal to 80%.
    [6" id="c-fr-0006]
    6. Composition comprising a polyaryletherketone resin powder in suspension in an aqueous solution, the composition further comprising a sulfonated polyaryletherketone.
    [7" id="c-fr-0007]
    7. Composition according to claim 6, in which the polyaryletherketone is chosen from the group consisting of polyether ketones (PEK), polyether ether-ketones (PEEK), polyether-ether-ketone-ketones (PEEKK ), polyether ketone ketones (PEKK), polyether ketone-ether-ketone-ketones (PEKEKK), poly-ether-ketone-ether-ketone (PEEKEK), poly-ether-ether-ether -ketones (PEEEK), poly-ether-diphenyl-ether-ketone (PEDEK), mixtures thereof and copolymers comprising these, the polyaryletherketone preferably being a polyether ketone ketone (PEKK).
    [8" id="c-fr-0008]
    8. Composition according to claim 6 or 7, in which the sulphonated polyaryletherketone is chosen from the group consisting of sulphonated poly-ether ketones (PEK), sulphonated poly-ether ketones (PEEK), poly-ether-ether- sulfonated ketone-ketones (PEEKK), sulfonated poly-ketone-ketones (PEKK), sulfonated poly-ether-ketone-ether-ketone-ketones (PEKEKK), poly-ether-ether-ketone-ether-ketones (PEEKEK) sulfonated, poly-ether-ether-ether-ketone (PEEEK) sulfonated, poly-ether-diphenyl-ether-ketone (PEDEK) sulfonated, mixtures thereof and copolymers comprising them.
    [9" id="c-fr-0009]
    9. Composition according to one of claims 6 to 8, in which the sulfonated polyaryletherketone comprises a degree of sulfonation of 0.01 to 4, preferably of 0.01 to 1 and more preferably of 0.1 to 0.5 .
    [10" id="c-fr-0010]
    10. Composition according to one of claims 6 to 9, in which the sulfonated polyaryletherketone comprises sulfonated groups chosen from sulfonic acid groups and / or sulfonate groups, the molar proportion of sulfonate groups in the sulfonated polyaryletherketone relative to the all of the sulfonated groups preferably being greater than or equal to 50%, preferably greater than or equal to 80%.
    [11" id="c-fr-0011]
    11. Composition according to one of claims 6 to 10, in which the mass content of sulfonated polyaryletherketone relative to the polyaryletherketone resin powder is 0.1 to 20%, preferably 0.5 to 5%.
    [12" id="c-fr-0012]
    12. Process for the preparation of a semi-finished product comprising a polyaryletherketone resin and reinforcing fibers, comprising:
    - the supply of a composition according to one of claims 6 to 11, and the impregnation of reinforcing fibers with this composition;
    - drying the impregnated reinforcing fibers;
    - Heating the impregnated reinforcing fibers so as to melt the polyaryletherketone; and
    - optionally, a calendering step.
    [13" id="c-fr-0013]
    13. The preparation method according to claim 12, wherein the reinforcing fibers are carbon fibers.
    [14" id="c-fr-0014]
    14. The preparation method according to claim 12 or 13, in which the semi-finished product is chosen from a prepreg or a tape.
    [15" id="c-fr-0015]
    15. Semi-finished product capable of being prepared according to the process of one of claims 12 to 14.
    [16" id="c-fr-0016]
    16. Use of a semi-finished product according to claim 15 for the manufacture of composite materials.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3710517B1|2021-09-08|Use of asulfonated poly| or of a sulfonated non-polymeric aryl ether ketone as a dispersant
    WO2018185440A1|2018-10-11|Method for impregnating reinforcing fibres with polyaryletherketones and semi-products obtained therefrom
    EP0241815B1|1993-09-08|Method of producing poly| compositions and articles made therefrom
    EP3325535B1|2020-10-14|Melt stable polyaryl-ether-ketone | based composition
    EP2758449B1|2019-01-16|Thermoplastic |polyimides and synthesis methods
    US5357040A|1994-10-18|Fine powders of ketone-containing aromatic polymers and process of manufacture
    JP6508194B2|2019-05-08|Composite separation membrane
    EP3408179B1|2020-09-16|Curable resin as a substitute for phenolic resins and the applications thereof
    FR2959995A1|2011-11-18|COMPOSITE POLYAMIDE ARTICLE
    JP4311246B2|2009-08-12|Synthetic fiber treatment oil
    EP0176378B1|1989-11-08|Phenolic-resin compositions
    CA3075681A1|2019-03-21|Method for impregnating reinforcing fibres with polyaryletherketones and semi-finished products obtained in this way
    KR20170099847A|2017-09-01|Polyimide-forming compositions, methods of manufacture, and articles prepared therefrom
    FR3107060A1|2021-08-13|Polyamide powder and method of preparation thereof
    EP3770150A1|2021-01-27|Method for manufacturing chromenes by copper salt catalysis intended for the preparation of heat-setting resins
    FR3112782A1|2022-01-28|PROCESS FOR THE POLYMERIZATION OF CHROMINES BY CATIONIC WAY
    EP3938181A1|2022-01-19|Method for producing a partially recycled polyaryletherketone powder by sintering
    BE617110A|
    BE537123A|
    BE539559A|
    同族专利:
    公开号 | 公开日
    JP2021503024A|2021-02-04|
    US20210363346A1|2021-11-25|
    EP3710517B1|2021-09-08|
    KR20200079324A|2020-07-02|
    FR3073523B1|2019-11-08|
    WO2019097148A1|2019-05-23|
    CN111356721A|2020-06-30|
    EP3710517A1|2020-09-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP2911807A1|2012-10-25|2015-09-02|Oxford Performance Materials, Inc.|Method of sizing of fibers and articles manufactured from the same|
    WO2016156325A1|2015-03-31|2016-10-06|Airbus Defence And Space Sas|Aqueous impregnation bath for reinforcement fibres and uses thereof|
    DE10116391A1|2001-03-28|2002-10-10|Fuma Tech Gmbh|Sulfonated polyether ketone ketone|GB2585875A|2019-07-18|2021-01-27|Hexcel Composites Ltd|Thermoplastic prepregs and composites|
    FR3112307A1|2020-07-10|2022-01-14|Arkema France|Method for analyzing semi-finished products comprising a thermoplastic resin|
    CN113430831A|2021-07-14|2021-09-24|上海交通大学|High-temperature-resistant universal sizing agent for water-based carbon fibers, and preparation method and application thereof|
    法律状态:
    2018-10-11| PLFP| Fee payment|Year of fee payment: 2 |
    2019-05-17| PLSC| Publication of the preliminary search report|Effective date: 20190517 |
    2019-10-14| PLFP| Fee payment|Year of fee payment: 3 |
    2020-10-13| PLFP| Fee payment|Year of fee payment: 4 |
    2021-10-18| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1760709|2017-11-14|
    FR1760709A|FR3073523B1|2017-11-14|2017-11-14|USE OF A POLYARYLETHERCETONE SULFONE AS A DISPERSING AGENT|FR1760709A| FR3073523B1|2017-11-14|2017-11-14|USE OF A POLYARYLETHERCETONE SULFONE AS A DISPERSING AGENT|
    US16/763,725| US20210363346A1|2017-11-14|2018-11-12|Use of a sulfonated polyaryl ether ketone or of a sulfonated non-polymeric aryl ether ketone as a dispersant|
    KR1020207016527A| KR20200079324A|2017-11-14|2018-11-12|Use of sulfonated poly or sulfonated non-polymeric aryl ether ketone as dispersant|
    EP18825743.0A| EP3710517B1|2017-11-14|2018-11-12|Use of asulfonated poly or of a sulfonated non-polymeric aryl ether ketone as a dispersant|
    CN201880073826.7A| CN111356721A|2017-11-14|2018-11-12|Use of sulfonated polyor sulfonated non-polymeric aryl ether ketones as dispersants|
    PCT/FR2018/052806| WO2019097148A1|2017-11-14|2018-11-12|Use of a sulfonated poly or of a sulfonated non-polymeric aryl ether ketone as a dispersant|
    JP2020526533A| JP2021503024A|2017-11-14|2018-11-12|Use of sulfonated polyaryletherketones or sulfonated non-polymeric aryletherketones as dispersants|
    [返回顶部]