COMPOSITION MADE FROM POLY(ARYLENE-ETHER-KETONE) (PAEK) WHICH IS STABLE IN THE MOLTEN STATE AND METHOD FOR STABILIZING SUCH A COMPOSITION

Abstract

A composition based on poly(arylene ether ketone) (PAEK) which is stable in the molten state, characterized in that it includes a phosphate salt or a mixture of phosphate salts, a process for the stabilization of a composition based on PAEK incorporating said phosphate salts and objects manufactured using the composition.

Claims

1. A composition based on poly(arylene ether ketone) (PAEK) which is stable in the molten state, wherein the composition comprises a phosphate salt or a mixture of phosphate salts.

2. The composition as claimed in claim 1, wherein the phosphate salt(s) is (are) chosen from at least one of the following salts: one (or more) phosphate salt(s) of ammonium, of sodium, of calcium, of zinc, of potassium, of aluminum, of magnesium, of zirconium, of barium, of lithium, or of rare earths.

3. The composition as claimed in claim 1, wherein the phosphate salt(s) is (are) chosen from at least one of the salts of formula: ##STR00022## wherein R is or is not different from R′, R and R′ being formed by: a negative charge:⊖, an atom of hydrogen, or one or more aromatic groups which are substituted or unsubstituted by one or more groups having from 1 to 9 carbons, R and R′ possibly being directly linked to one another or separated by at least one group chosen from the following groups: —CH.sub.2—; —C(CH.sub.3).sub.2—; —C(CF.sub.3).sub.2—; —SO.sub.2—; —S—; —CO—; —O—, and M represents an element from Group IA or IIA of the Periodic Table.

4. The composition as claimed in claim 1, wherein the phosphate salt(s) is (are) non-organometallic phosphate salt(s).

5. The composition as claimed in claim 1, wherein the phosphate salt(s) is (are) more particularly chosen from at least one of the following compounds: anhydrous monosodium phosphate, monosodium phosphate monohydrate or monosodium phosphate dihydrate, anhydrous disodium phosphate, disodium phosphate dihydrate, disodium phosphate heptahydrate, disodium phosphate octahydrate or disodium phosphate dodecahydrate, anhydrous hexagonal trisodium phosphate, anhydrous cubic trisodium phosphate, trisodium phosphate hemihydrate, trisodium phosphate hexahydrate, trisodium phosphate octahydrate, trisodium phosphate dodecahydrate, or ammonium dihydrogen phosphate.

6. The composition as claimed in claim 1, wherein the proportions of phosphate salt(s) in the composition are between 10 ppm and 50,000 ppm.

7. The composition as claimed in claim 1, wherein the proportions of phosphate salt(s) in the composition are between 100 ppm and 5000 ppm.

8. The composition as claimed in claim 1, wherein the composition based on PAEK is more particularly a composition based on one of the following polymers: PEKK, PEEK, PEEKK, PEKEKK, PEEEK or PEDEK.

9. The composition as claimed in claim 1, wherein the composition based on PAEK is more particularly a poly(ether ketone ketone) (PEKK) composition.

10. The composition as claimed in claim 9, wherein the composition based on PAEK is more particularly a composition based on PEKK, and comprises, in addition to the PEKK, at least one of the following polymers: PEK, PEEKEK, PEEK, PEEKK, PEKEKK, PEEEK, PEDEK, with a content of less than 50% by weight of the composition, preferably less than or equal to 30% by weight of the composition.

11. The composition as claimed in claim 1, wherein the composition further comprises at least one filler and/or at least one other additive.

12. The composition as claimed claim 1, wherein the phosphate salt, or the mixture of phosphate salts, also acts as nucleating agent within said composition.

13. The composition as claimed in claim 1, wherein the percentage change in the viscosity, measured in a molten state, under air, with an oscillation frequency of 0.1 Hz, and with a strain amplitude of 0.5% is lower than the one of said composition without the phosphate salt or the mixture of phosphate salts.

14. The composition as claimed in claim 1, wherein the phosphate salt or the mixture of phosphate salts is water-soluble.

15. The composition as claimed in claim 14, wherein the phosphate salt(s) have been incorporated in the composition by wet impregnation of an aqueous solution thereof.

16. The composition as claimed in claim 1, wherein the phosphate salt or the mixture of phosphate salt(s) have been incorporated by compounding.

17. The composition as claimed in claim 1, wherein the mixture of phosphate salts is composed of monosodium phosphate and anhydrous disodium phosphate.

18. The composition as claimed in claim 1, wherein composition does not comprise any phosphite and/or any phosphonate.

19. The composition as claimed in claim 1, wherein composition is stable at a temperature of greater than 350° C.

20. A process for the stabilization of a composition based on PAEK, said process comprising: incorporating a stabilizing agent which stabilizes with regard to the phenomena of thermal oxidation in a composition based on PAEK, wherein the stabilizing agent is a phosphate salt or a mixture of phosphate salts; and stabilizing the composition in a molten state.

21. An object manufactured by a technology chosen from laser sintering, fused deposition modeling, molding, injection molding, extrusion, thermoforming, rotational molding, compression molding, compounding or impregnation, using a composition as claimed in claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Other advantages and features of the invention will become apparent on reading the following description given by way of illustrative and non-limiting example, with reference to the appended figures, of which:

[0049] FIG. 1 represents a curve of the complex viscosity measured by an oscillating rheometer as a function of time of a non-stabilized reference product under nitrogen,

[0050] FIG. 2 represents a thermogravimetric curve as a function of temperature of a reference stabilizer used by way of comparison.

DETAILED DESCRIPTION

[0051] The poly(arylene ether ketone)s (PAEKs) used in the invention comprise units of the following formulae:

(—Ar—X—) and (—Ar.sub.1—Y—)

wherein:
Ar and Ar.sub.1 each denote a divalent aromatic radical;
Ar and Ar.sub.1 may preferably be chosen from 1,3-phenylene, 1,4-phenylene, 4,4′-biphenylene, 1,4-naphthylene, 1,5-naphthylene and 2,6-naphthylene;
X denotes an electron-withdrawing group; it may preferably be chosen 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 —CH.sub.2— and isopropylidene.

[0052] In these units X and Y, at least 50%, preferably at least 70% and more particularly at least 80% of the groups X are a carbonyl group, and at least 50%, preferably at least 70% and more particularly at least 80% of the groups Y represent an oxygen atom.

[0053] According to a preferred embodiment, 100% of the groups X denote a carbonyl group and 100% of the groups Y represent an oxygen atom.

[0054] More preferentially, the poly(arylene ether ketone) (PAEK) may be chosen from: [0055] a poly(ether ketone ketone), also referred to as PEKK, comprising units of formula I A, of formula I B, and the mixture thereof:

##STR00002## [0056] a poly(ether ether ketone), also referred to as PEEK, comprising units of formula IIA:

##STR00003##

[0057] Similarly, it is possible to introduce para sequences into these structures at the ethers and the ketones according to the formula IIB:

##STR00004##

[0058] The sequence may be totally para but it is also possible to introduce partially or totally meta sequences:

##STR00005##

or else:

##STR00006##

or ortho sequences according to the formula V:

##STR00007## [0059] a poly(ether ketone), also referred to as PEK, comprising units of formula VI:

##STR00008##

[0060] Similarly, the sequence may be totally para but it is also possible to introduce partially or totally meta sequences (formulae VII and VIII):

##STR00009## [0061] a poly(ether ether ketone ketone), also referred to as PEEKK, comprising units of formula IX:

##STR00010##

[0062] Similarly, it is possible to introduce meta sequences into these structures at the ethers and the ketones. [0063] a poly(ether ether ether ketone), also referred to as PEEEK, comprising units of formula X:

##STR00011##

[0064] Similarly, it is possible to introduce meta sequences into these structures at the ethers and the ketones, but also biphenol sequences according to the formula XI:

##STR00012##

[0065] Other arrangements of the carbonyl group and of the oxygen atom may also be possible.

[0066] The composition which is a subject of the invention is based on PAEK. More particularly, in some embodiments, the composition may be a composition based on poly(ether ketone ketone) (PEKK).

[0067] According to one variant embodiment, the composition based on PAEK may also be a composition based on one of the following polymers: PEEK, PEEKK, PEKEKK, PEEEK or PEDEK.

[0068] The composition based on PAEK may also be a composition based on a mixture of polymers of the PAEK family. Thus, the composition may be based on PEKK and comprise, in addition to the PEKK, at least one of the following polymers: PEK, PEEKEK, PEEK, PEEKK, PEKEKK, PEEEK, PEDEK, with a content of less than 50% by weight of the composition, preferably less than or equal to 30% by weight of the composition.

[0069] Advantageously, the PAEK composition according to the invention is stable in the molten state by virtue of the incorporation of a phosphate salt in the composition.

[0070] In the present description, “polymer stable in the molten state” means a polymer, the structure of which barely changes when it is molten, so that the physicochemical properties thereof, especially the viscosity, only vary within a limited range. More specifically, a polymer will be considered to be stable in the molten state under nitrogen when the change in the viscosity thereof in the molten state in 30 minutes, measured by an oscillating rheometer under nitrogen and with an oscillation frequency of 1 Hz, at 380° C. or 20° C. above the melting point thereof when said melting point is greater than 370° C., is less than 100%, especially less than 50%, in particular less than 20%, and most particularly between −20% and +20%. Likewise, a polymer will be considered to be stable in the molten state under air when the change in the viscosity thereof in the molten state in 30 minutes, measured as indicated above but under air and with an oscillation frequency of 0.1 Hz, is less than 150%, especially less than 100%, in particular less than 50%, and most particularly between −20% and +50%.

[0071] According to one variant, the stabilizer incorporated into the composition may be a mixture of phosphate salts.

[0072] Indeed, it has been discovered that such a phosphate salt makes it possible to stabilize a PAEK composition in the molten state just as well under nitrogen as under air. This effect of stabilizing the PAEK in the molten state under air is very surprising, and it was not at all intuitive for those skilled in the art to choose to incorporate a phosphate salt to stabilize a PAEK in the molten state with regard to a phenomenon of thermal oxidation. Indeed, a phosphate salt has a maximum degree of oxidation, with the result that it is not known to be an antioxidant. Yet, in the presence of the oxygen in the air, it manages to stabilize the polymer in the molten state with regard to the phenomenon of thermal oxidation. Indeed, a more stable viscosity of the composition in the molten state is obtained compared to one and the same composition devoid of phosphate salt, which means that the phenomena of chain extension through phenomena of branching, inter alia, are more limited.

[0073] The phosphate salt is therefore present as an active agent stabilizing PAEK compositions in the molten state, even in the presence of air, with as great an effectiveness as an aromatic organophosphorus compound. Nonetheless, it also has a considerable advantage relative to an aromatic organophosphorus compound since it does not hydrolyze and does not generate any emission of volatile organic compounds. Only water may be generated in certain cases in which the phosphate salt is present in a hydrated form or when the phosphate salt dimerizes.

[0074] Advantageously, one or more phosphate salt(s) may be incorporated into the composition based on PAEK. The phosphate salt is advantageously chosen from one (or more) phosphate salt(s) of ammonium, of sodium, of calcium, of zinc, of aluminum, of potassium, of magnesium, of zirconium, of barium, of lithium or of rare earths. Preferably, the phosphate salt(s) is (are) one (or more) inorganic or organometallic phosphate salt(s).

[0075] According to some embodiments, the phosphate salt(s) used may have the following formula:

##STR00013##

wherein R is or is not different from R′, R and R′ being formed by: a negative charge:⊖, an atom of hydrogen, or one or more aromatic groups which are substituted or unsubstituted by one or more groups having from 1 to 9 carbons, R and R′ possibly being directly linked to one another or separated by at least one group chosen from the following groups: —CH.sub.2—; —C(CH.sub.3).sub.2—; —C(CF.sub.3).sub.2—; —SO.sub.2—; —S—; —CO—; —O—, and M represents an element from Group IA or IIA of the Periodic Table.

[0076] According to some embodiments, the phosphate salt(s) used may have the following formula:

##STR00014##

wherein R is or is not different from R′, R and R′ being formed by one or more aromatic groups which are substituted or unsubstituted by one or more groups having from 1 to 9 carbons, R and R′ possibly being directly linked to one another or separated by at least one group chosen from the following groups: —CH.sub.2—; —C(CH.sub.3).sub.2—; —C(CF.sub.3).sub.2—; —SO.sub.2; —S—; —CO—; —O—, and M represents an element from Group IA or IIA of the Periodic Table.

[0077] The phosphate salt(s) may be more particularly chosen from at least one of the following compounds: anhydrous monosodium phosphate, monosodium phosphate monohydrate or monosodium phosphate dihydrate, anhydrous disodium phosphate, disodium phosphate dihydrate, disodium phosphate heptahydrate, disodium phosphate octahydrate or disodium phosphate dodecahydrate, anhydrous hexagonal trisodium phosphate, anhydrous cubic trisodium phosphate, trisodium phosphate hemihydrate, trisodium phosphate hexahydrate, trisodium phosphate octahydrate, trisodium phosphate dodecahydrate, and/or ammonium dihydrogen phosphate.

[0078] According to some embodiments, the phosphate salt(s) may be more an organometallic phosphate salt. It may preferably be sodium 2,2′-methylenebis(4,6-di-tert-butylphenyl) phosphate.

[0079] Preferably, the phosphate salt, or the mixture of phosphate salts, may be incorporated into the composition based on PAEK in proportions of between 10 ppm and 50,000 ppm, and even more preferably between 100 and 5000 ppm.

[0080] Another surprising effect linked to the incorporation of the phosphate salt into the composition based on PAEK lies in the fact that it makes it possible to act as a nucleating agent. Increasing the crystallization kinetics to make a crystallizable product therefrom under standard transformation conditions, or for example in laser sintering, and thus to have a semicrystalline PEKK, is advantageous for certain properties such as chemical resistance. Moreover, such a nucleating agent makes it possible to control the crystalline morphology of the polymer, and especially the size of the crystalline zones (or spherulites), in order to ensure a consistency in the mechanical properties of the polymer, regardless of the processing conditions of the polymer.

[0081] The invention also relates to a process for the stabilization, in the molten state, of a composition based on PAEK, said process comprising a step of incorporating an agent which stabilizes with regard to the phenomena of thermal oxidation, said process being characterized in that the stabilizing agent incorporated is a phosphate salt or a mixture of phosphate salts.

[0082] The phosphate salt may be incorporated into the composition based on PAEK by one of the following techniques: dry blending, compounding, wet impregnation or during the process for synthesizing the PAEK polymer.

[0083] The process for synthesizing a PAEK generally consists of a polycondensation. The synthesis may be carried out according to two routes: a nucleophilic route, according to which ether bonds form during the polymerization step, or an electrophilic route, according to which carbonyl bridges form during the polymerization step. PEKK, for example, results from a Friedel-Crafts polycondensation reaction between DPE (diphenyl ether) and a terephthaloyl chloride and/or an isophthaloyl chloride, for example.

[0084] When the stabilized composition based on PAEK is obtained by impregnation of PAEK during the process for obtaining same, this impregnation of the PAEK by a solution of phosphate salt(s) is carried out after the polymerization of the PAEK and before the drying thereof. The solvent is chosen so that it is able to dissolve the metallic phosphate salt(s) while being also soluble with the solvent phase constituting at least 50% of the PAEK grain. This impregnation is advantageously carried out with stirring to promote homogenization. Advantageously, a PAEK wet with water and an aqueous solution of metallic phosphate salt(s) are chosen.

[0085] Advantageously, the stabilized composition based on PAEK may be obtained in the form of granules by compounding on a device known to those skilled in the art, such as a twin-screw extruder, a co-kneader or an internal mixer.

[0086] The composition prepared in this way may then be transformed for a use or a subsequent transformation known to those skilled in the art by means of devices such as an injection-molding machine, an extruder, laser sintering equipment, etc.

[0087] The process for preparing the composition according to the invention may also use a twin-screw extruder feeding, without intermediate granulation, an injection-molding machine or an extruder according to a processing device known to those skilled in the art.

[0088] The stabilized composition based on PAEK may also be obtained in powder form, by dry blending, for example. Thus, the PAEK is mixed with the phosphate salt(s) and then this mixture is heated above the melting point of the PAEK with stirring in a suitable apparatus, such as an extruder.

[0089] The stabilized composition based on PAEK may also be obtained by wet blending. For this purpose, the dried PAEK is impregnated with a solution of the metallic phosphate salt(s). This solution is preferably aqueous if the phosphate salt(s) is (are) water-soluble. Mixing is preferably carried out with stirring to promote homogenization. The mixture is then dried and the solvent is thus removed.

[0090] Using the composition obtained, which may either be in the form of granules or in the form of a powder, it is possible to manufacture various objects by a technique of laser sintering, injection molding or extrusion, thermoforming, rotational molding, compression molding or else impregnation, for example.

[0091] Wet impregnation, for example, for manufacturing pre-impregnated composite strips, also referred to as tape, consists in depositing an aqueous dispersion of a PAEK powder and of phosphate salt(s) on carbon or glass fibers, for example. More particularly, the dispersion may for example comprise a PEKK powder and phosphate salt(s) and a surfactant in aqueous solution. The fibers thus covered with the aqueous dispersion are then passed into an oven to evaporate the water. They are then passed into a die at high temperature, typically of greater than 370° C., in order to be able to melt the stabilized PEKK polymer and for it to be able to correctly coat the fibers. After cooling, tapes or pre-impregnated strips are obtained which are then used by assembling and/or superimposing them, to remelt them and form composite objects.

[0092] One major advantage of phosphate salts lies in the fact that, even heated to a very high temperature, greater than or equal to 350° C. for example, they do not generate the emission of volatile organic compounds but they simply lose water in the form of vapor. Consequently, phosphate salts do not present any risk for the environment and/or health and they do not create porosities liable to hinder the coating of the fibers and/or to generate the appearance of defects in the final manufactured object, liable to then lead to a deterioration in the mechanical properties.

[0093] The composition based on PAEK and on phosphate salt(s) as defined above may be prepared by any known method making it possible to obtain a homogeneous mixture containing the composition according to the invention and optionally other additives, fillers or other polymers. Such a method may be chosen from techniques of dry blending (using, for example, a roll mill), of melt extrusion, of compounding or else of wet impregnation or during the process for synthesizing the polymer.

[0094] More particularly, the composition according to the invention may be prepared by melt blending all the components thereof, especially in a “direct” process.

[0095] Compounding, for example, is a process which makes it possible to mix, by melting, plastic materials and/or additives and/or fillers. In order to manufacture the composition, the starting materials, present in the form of granules, are placed in a co-rotating twin-screw extruder.

[0096] The following examples nonlimitingly illustrate the scope of the invention:

Example 1: Measurements of Viscosity Under Nitrogen

[0097] Several compositions based on PEKK were prepared. A control composition C.sub.T of PEKK comprising no stabilizer was prepared by a conventional synthesis process by a polycondensation reaction.

[0098] A second composition based on PEKK, with the reference C1, was prepared by wet impregnation, wherein PEP-Q (tetrakis(2,4-di-tert-butylphenyl) [1,1′-biphenyl]-4,4′-diyl bisphosphonite), of formula (1) below, was incorporated at an amount of 1000 ppm. This phosphonite is used as comparative example for stabilizing the PEKK composition.

##STR00015##

[0099] A third composition based on PEKK, with the reference C2, was prepared by aqueous impregnation, wherein anhydrous monosodium phosphate (NaH.sub.2PO.sub.4), also referred to as sodium dihydrogen phosphate, of formula (2) below, was incorporated at an amount of 1000 ppm.

##STR00016##

[0100] A fourth composition based on PEKK, with the reference C3, was prepared in the same manner as the second and third compositions, by aqueous impregnation, wherein sodium trimetaphosphate (Na.sub.3P.sub.3O.sub.9), also referred to as anhydrous trisodium phosphate, of formula (3) below, was incorporated at an amount of 1000 ppm.

##STR00017##

[0101] A fifth composition based on PEKK, with the reference C4, was prepared in the same manner as the preceding compositions, by impregnation with acetone, wherein an organic phosphate, and more particularly triphenyl phosphate, of formula (4) below, was incorporated at an amount of 1000 ppm.

##STR00018##

[0102] The melt viscosity of these compositions C.sub.T to C4 was then measured with an oscillating rheometer as a function of time, at 380° C., under nitrogen, with an oscillation frequency, also referred to as stress, of 1 Hz, and with a strain amplitude of 0.5%.

[0103] The curve of FIG. 1 represents the viscosity of the control composition C.sub.T of PEKK, measured in this way. From the initial viscosity and the viscosity after a duration of 30 minutes, the stability of the polymer over time is then calculated, expressed as percentage change in the viscosity (EV %), at 380° C. The stability of the polymer is then calculated according to the following formula:

% EV=(viscosity at 30 min-initial viscosity)/initial viscosity*100

[0104] It emerges from the curve of FIG. 1 that the stability, expressed as percentage change in the viscosity EV, of the control composition C.sub.T based on PEKK-based polymer, under nitrogen with a 1 Hz stress, is equal to 160%.

[0105] Table I below brings together the data on stability (EV %) under nitrogen of the different compositions C.sub.T to C4 obtained by wet impregnation, with or without stabilizer.

TABLE-US-00001 TABLE I EV (%) Reference Composition (under N.sub.2, 1 Hz) C.sub.T Reference PEKK 160% C1 1000 ppm PEP-Q  50% C2 1000 ppm of anhydrous monosodium  50% phosphate C3 1000 ppm of anhydrous trisodium  50% phosphate C4 1000 ppm of triphenyl phosphate 110%

[0106] It emerges from the results presented in table I that the presence of a phosphate salt in a composition based on PEKK makes it possible to obtain a composition in the molten state which has a more stable viscosity over time, unlike the control composition C.sub.T, the viscosity of which increases rapidly with time, indicating chain extensions and therefore significant changes in the characteristics of the polymer.

[0107] While the organic phosphate (in composition C4) has a lesser effect compared to the phosphate salts, it also makes it possible to obtain a composition in the molten state having a more stable viscosity than the control composition C.sub.T of PEKK.

Example 2: Measurements of Viscosity Under Nitrogen and Under Air

[0108] Several compounds based on PEKK were prepared by the compounding technique. The different compounds are produced with an extruder from several compositions based on PEKK. The behavior of the different compositions at 380° C. under nitrogen and under air was compared.

[0109] A first control composition C.sub.T′ of PEKK in the form of granules and not comprising any stabilizer was prepared.

[0110] A second composition based on PEKK, with the reference C5, was prepared by the compounding technique, wherein monosodium phosphate (NaH.sub.2PO.sub.4), of formula (1) above, was incorporated at an amount of 1000 ppm.

[0111] A third composition based on PEKK, with the reference C6, was prepared by the compounding technique, wherein trisodium phosphate (Na.sub.3P.sub.3O.sub.9), of formula (3) above, was incorporated at an amount of 1000 ppm.

[0112] A fourth composition based on PEKK, with the reference C7, was prepared by the compounding technique, wherein ADK STAB NA-11UH (sodium 2,2′-methylene-bis(4,6-di-tert-butylphenyl) phosphate), of formula (5) below, was incorporated at an amount of 1000 ppm.

##STR00019##

[0113] The melt viscosity of these compositions C.sub.T′, C5, C6 and C7 was then measured with an oscillating rheometer as a function of time, at 380° C., under nitrogen then under air, with an oscillation frequency, also referred to as stress, respectively of 1 Hz and of 0.1 Hz, and with a strain amplitude of 0.5%.

[0114] Table II below brings together the data on stability (EV %) under nitrogen and under air of these different compositions obtained by compounding, with or without stabilizer.

TABLE-US-00002 TABLE II EV (%) EV (%) Refer- (under N.sub.2, (under air, ence Composition 1 Hz) 0.1 Hz) C.sub.T′ Granulated PEKK 230% 390% C5 1000 ppm of anhydrous monosodium  30% 115% phosphate C6 1000 ppm of anhydrous trisodium  45% 115% phosphate C7 1000 ppm of sodium 2,2′-methylene-  15%  2% bis(4,6-di-tert-butylphenyl) phosphate

[0115] It emerges from the results of table II that the phosphate salts are good stabilizers of the PEKK, equally well under nitrogen as under air. The most surprising phenomenon of stabilization lies in the fact that, even under air, the viscosity measured in the molten state remains relatively stable. The phosphate salts are therefore stabilizing agents which are highly effective with regard to the phenomenon of thermal oxidation, even in the presence of air.

Example 3: Influence of the Ratio of Phosphate Salt Incorporated

[0116] Several compositions based on PEKK were prepared. A control composition C.sub.T of PEKK comprising no stabilizer was prepared by a conventional synthesis process by a polycondensation reaction. The other compositions are based on PEKK and each comprise anhydrous trisodium phosphate at different contents.

[0117] The compositions compared are prepared by aqueous impregnation.

[0118] The composition with the reference C8 in table III below comprises 500 ppm of anhydrous trisodium phosphate, while the composition with the reference C9 comprises 1000 ppm thereof and the composition with the reference C10 comprises 3000 ppm thereof.

[0119] The melt viscosity of these compositions C.sub.T, C8, C9 and C10 was then measured with an oscillating rheometer as a function of time, at 380° C., under nitrogen, with a stress of 1 Hz and with a strain amplitude of 0.5%.

[0120] Table III below brings together the data on stability (EV %) under nitrogen of these different compositions.

TABLE-US-00003 TABLE III Refer- EV (%) ence Composition (under N.sub.2, 1 Hz) C.sub.T Reference PEKK 160% C8  500 ppm of anhydrous trisodium phosphate  50% C9 1000 ppm of anhydrous trisodium phosphate  45% C10 3000 ppm of anhydrous trisodium phosphate  10%

[0121] It emerges from this table III that the stability over time of the viscosity of the composition in the molten state increases with the content of phosphate salt.

Example 4: Influence of the Cation

[0122] Several compositions based on PEKK were prepared. A control composition C.sub.T of PEKK comprising no stabilizer was prepared by a conventional synthesis process by a polycondensation reaction. The other compositions are based on PEKK and each comprise a dihydrogen phosphate with a different counter-anion.

[0123] The composition with the reference C11 in table IV below comprises 1000 ppm of anhydrous sodium dihydrogen phosphate (of formula (1) above), while the composition with the reference C12 comprises 1000 ppm of ammonium dihydrogen phosphate.

[0124] The melt viscosity of these compositions C.sub.T, C11 and C12 was then measured with an oscillating rheometer as a function of time, at 380° C., under nitrogen, with a stress of 1 Hz and with a strain amplitude of 0.5%.

[0125] Table IV below brings together the data on stability (EV %) under nitrogen of these different compositions.

TABLE-US-00004 TABLE IV Reference Composition EV (%) (under N.sub.2, 1 Hz) C.sub.T Reference PEKK 160% C11 1000 ppm of anhydrous  50% sodium dihydrogen phosphate C12 1000 ppm of ammonium  55% dihydrogen phosphate

[0126] It emerges from this table IV that the presence of ammonium dihydrogen phosphate or of anhydrous sodium dihydrogen phosphate in a composition based on PEKK makes it possible to obtain a composition in the molten state which has a more stable viscosity over time, unlike the control composition C.sub.T, the viscosity of which increases rapidly with time, indicating chain extensions and therefore significant changes in the characteristics of the polymer.

Example 5: Phosphate Salt Mixture

[0127] A composition based on PEKK, with the reference C13, was prepared by aqueous impregnation, wherein anhydrous monosodium phosphate (NaH.sub.2PO.sub.4), was incorporated at an amount of 2500 ppm.

[0128] A composition based on PEKK, with the reference C14, was prepared by aqueous impregnation, wherein a (1.5:1) (wt:wt) mixture of anhydrous monosodium phosphate and anhydrous disodium phosphate (Na.sub.2HPO.sub.4), of formula (6) below, was incorporated at an amount of 2500 ppm.

##STR00020##

[0129] The melt viscosity of these compositions was then measured with an oscillating rheometer as a function of time, at 380° C., under nitrogen, with an oscillation frequency, also referred to as stress, of 1 Hz, and with a strain amplitude of 0.5%.

[0130] From the initial viscosity and the viscosity after a duration of 60 minutes, the stability of the polymer over time is then calculated, expressed as percentage change in the viscosity (EV′ %), at 380° C., according to the following formula:

% EV′=(viscosity at 60 min-initial viscosity)/initial viscosity*100

[0131] Table V below brings together the data on stability (EV′%) under nitrogen of the different compositions C.sub.T C13 and C14.

TABLE-US-00005 TABLE V EV′ (%) (60 minutes, Reference Composition under N.sub.2, 1 Hz) C13 2500 ppm of NaH.sub.2PO.sub.4 15 C14 2500 ppm of a mixture (1.5:1)(wt:wt) 22 (NaH.sub.2PO.sub.4:Na.sub.2HPO.sub.4)
It emerges from this table V that the mixture of (NaH.sub.2PO.sub.4: Na.sub.2HPO.sub.4) may bring a relatively similar stabilization than NaH.sub.2PO.sub.4 alone.

Example 6: Thermal Stability

[0132] The phosphate salts incorporated into the composition based on PAEK are moreover highly stable thermally. Indeed, for the phosphate salts, the losses of weight measured correspond to losses of water. The phenomenon which is then occurring, for example with monosodium phosphate, is a dehydration and a dimerization in accordance with the following equation (A):

##STR00021##

[0133] For its part, PEP-Q begins to degrade and to emit organic compounds at a temperature of the order of 200° C.

[0134] The thermogravimetric (TG) curves as a function of temperature T (° C.) presented in the graph of FIG. 2 make it possible to demonstrate a loss of weight of the phosphate salts due to a loss of water, whereas the phosphonite PEP-Q degrades rapidly from 200° C., emitting volatile organic compounds.

[0135] The phosphate salts therefore have a high thermal stability combined with a high stability with regard to phenomena of thermal oxidation.

Example 7: Effect of Additional Nucleation of the Phosphate Salts

[0136] A study of crystallization was performed on different samples, with the references E1 to E4, of different compositions and listed in table V below.

[0137] The crystallization study is performed by differential scanning calorimetry, denoted DSC. DSC is a thermal analysis technique which makes it possible to measure the differences in the exchanges of heat between a sample to be analyzed and a reference.

[0138] In order to perform this crystallization study, the apparatus Q 2000 from TA Instruments was used. The study was performed in anisothermal and isothermal crystallization.

[0139] The samples studied are in the form of granules. A control sample based on PEKK, with the reference E1, is compared to samples E2 and E3 based on PEKK and on a phosphate salt in the same proportions. The different samples are more particularly described in table V below.

Anisothermal Crystallization

[0140] The protocol for DSC under anisothermal conditions on the different samples E1 to E3 first consists in stabilizing the temperature at 20° C. The temperature is then gradually increased according to a gradient of 20° C. per minute up to 380° C., then it is gradually decreased again down to 20° C. according to a reverse gradient of 20° C. per minute.

[0141] The crystallization is studied during the cooling step. The heat flow is measured as a function of temperature, and a curve representing the change in the heat flow as a function of temperature is obtained for each sample studied. The crystallization temperature, denoted T.sub.c and expressed in degrees Celsius, is then determined for each sample, by projecting the maximum of the corresponding curve onto the axis of the abscissae. This determination is carried out directly by the DSC apparatus used. The crystallization temperature T.sub.c measured for each sample E1 to E3 is given in table V below.

Isothermal Crystallization

[0142] A DSC analysis under isothermal conditions was also performed on the samples E1 to E3 to measure the crystallization half-time. For this purpose, the isothermal DSC protocol comprises the following three steps: a first step consists in first stabilizing the temperature at 20° C., a second step then consists in gradually increasing the temperature according to a gradient of 20° C. per minute up to 380° C. Finally, the temperature is reduced from 380° C. down to 315° C., according to a gradient of 20° C. per minute, then it is stabilized at 315° C. for one hour.

TABLE-US-00006 TABLE VI Reference T.sub.c Crystallization half- samples Description (° C.) time at 315° C. (min) E1 Control PEKK granules 292 3.1 E2 (Control PEKK + 1000 ppm 296 2.2 NaH.sub.2PO.sub.4) granules E3 (PEKK + 1000 ppm Na.sub.3P.sub.3O.sub.9) 301 1.2 granules

[0143] It emerges from table VI of results obtained that the crystallization half-time is approximately 3.1 minutes for the sample E1 of control PEKK granules. The crystallization half-time of a polymer is the time required for crystallization of 50% of this polymer.

[0144] The crystallization half-time of the samples E2 and E3, the composition of which comprises phosphate salts, is reduced while the crystallization temperature increases. This phenomenon is due to the nucleation effect of the phosphate salts. Thus, for large bars obtained with such a composition, the nucleation effect makes it possible to avoid the appearance of large crystallized zones and to obtain good mechanical properties.

[0145] Regarding the granules intended to be used in injection molding or in extrusion, the accelerated crystallization makes it possible to control the crystalline morphology and especially the size of the spherulites, and to thereby ensure specific mechanical properties and consistency of the latter.

[0146] Regarding the granules intended to be used by the aqueous impregnation route, hydrated phosphate salts may be used in the composition. Anhydrous phosphate salts are, however, preferred since water may be released during the subsequent processing of the composition, which may lead to a possible negative effect on the physical properties of the composition.

[0147] Phosphate salts are thus good stabilizers of PAEKs and more particularly, but not exclusively, of PEKKs. These phosphate salts also combine several very advantageous effects. Indeed, they provide temperature stability in the absence or in the presence of air, and they are stable with regard to hydrolysis, unlike other phosphorus-based stabilizers such as phosphites or phosphonites such as PEP-Q, and do not generate volatile organic compounds but simply steam. They also combine all the positive effects of a stabilizer for transformation: they make it possible to limit changes in color during transformation, they make it possible to improve the stability of the structure in the molten state, significantly reducing the change in the polymer chains and thereby making it possible to retain the crystalline and mechanical properties of the material. Finally, they act as a nucleating agent and a regulator of residual acids (buffer effect), with the result that they may also help protect equipment from corrosion.

[0148] Phosphate salts may also be readily incorporated into the PAEK polymer, either by impregnation in aqueous solution or by dry blending or else by compounding.

[0149] They may finally be used in synergy with other additives such as other stabilizers and/or nucleating agents for example, and in the presence of continuous or dispersed filler(s), and of plasticizers.