GB2585875A - Thermoplastic prepregs and composites - Google Patents

Thermoplastic prepregs and composites Download PDF

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Publication number
GB2585875A
GB2585875A GB1910322.5A GB201910322A GB2585875A GB 2585875 A GB2585875 A GB 2585875A GB 201910322 A GB201910322 A GB 201910322A GB 2585875 A GB2585875 A GB 2585875A
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fibres
polyaryletherketone
prepreg
sulfonated
dispersion
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GB201910322D0 (en
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Tilbrook David
Mason Christopher
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Hexcel Composites Ltd
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Hexcel Composites Ltd
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Priority to GB1910322.5A priority Critical patent/GB2585875A/en
Publication of GB201910322D0 publication Critical patent/GB201910322D0/en
Publication of GB2585875A publication Critical patent/GB2585875A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

Preferably the dispersion comprises 0.25-5 wt.% sulfonated polyaryletherketone (PAEK) surface active agent and particles of the equivalent (but non-sulfonated) PAEK in water. Preferably the PAEK powder is PEK, PEEK or PEKK having number median diameter (D50) ≤ 50 µm. Preferably the surfactant has degree of sulphonation = 0.5-1.5. A prepreg is formed by passing fibres through a bath containing the dispersion. The sulphonate groups are preferably removed during drying or moulding of the prepreg. The preferred prepreg comprise yarns comprising 3000-48000 filaments measuring 6-10 µm. The preferred prepreg comprises 35-75 wt.% carbon fibre reinforcements (CFRP). Alternative fibers are glass, quartz, graphite, silica, steel, aluminium, boron, silicon carbide, boron carbide, aramid, polyethylene, polyester, poly(p-phenylene benzobisoxazole), hemp, linen or silk. The prepregs are used in aerospace, automotive, wind energy and sporting goods industries.

Description

THERMOPLASTIC PREPREGS AND COMPOSITES
The invention relates to prepregs having a thermoplastic matrix and in particular the invention relates to emulsions or suspensions of thermoplastic polymers and their use in the production of materials such as prepregs and composites. The term prepreg is used to describe fibrous reinforcement that is preimpregnated with a polymeric material usually a thermosetting polymeric material such as an epoxy or a polyester resins. However this invention is particularly concerned with the production of emulsions of polyaryletherketones and particularly polyetheretherketones (PEEK) and polyetherketone ketones (PEKK) which can be used in the production of thermoplastic prepregs. Polyaryletherketones are high melting thermoplastic materials that are used in the manufacture of components for many industries particularly the aerospace, automotive, wind energy and sporting goods industries.
The invention also relates to impregnating reinforcement fibres with such an emulsion or suspension and to the manufacture of a prepreg comprising fibres impregnated with such a thermoplastic matrix derived from the emulsion or suspension as well as the prepreg so produced. The term prepreg is used to describe a fibrous material embedded in a matrix of a polymer that may be shaped and solidified to form a composite material.
The invention further relates to a method for manufacturing a part comprising a composite material from such a prepreg. Composite material parts having a thermoplastic matrix reinforced by fibres usually unidirectional fibres known as "strengthening fibres" or "reinforcement fibres" (made of glass, carbon, aramid, boron, etc.) and they may be manufactured from prepregs.
The invention is particularly useful in the manufacture of parts or components for the aeronautical and space industries, notably for the manufacture of structural parts of large dimensions. However, it may also find uses in other fields in which composite material parts are manufactured such as the rail, shipping and automotive industries, the armaments industry, for example for the manufacture of missiles or missile-launch tubes, or in the field of sports and leisure, for example for the manufacture of articles intended for nautical sports and sliding sports such as skis.
Various processes are known for the manufacture of thermoplastic prepregs. The impregnation of reinforcement fibres with the thermoplastic matrix, may be carried out by different methods, for example by melting of the thermoplastic polymer intended to form the matrix (or "hot melt" method), alternatively a solvent route may be used, which consists in dissolving the thermoplastic polymer intended to form the matrix in a suitable solvent, typically an organic solvent and the choice of the solvent depends on the chemical nature of the polymer. However, this process suffers from the disadvantages that the solvent has to be removed during the impregnation process and also the organic solvents that are used present environmental problems.
Another method is a dispersion method, where the thermoplastic polymer intended to form the thermoplastic matrix is dispersed as particles such as a powder in a liquid medium from which the polymer is deposited on the fibres. Here the preferred liquid medium is water. It is known from, for example, United States patent publication 2018/119333 that thermoplastic prepregs can be produced by passing continuous fibres such as carbon fibre rovings and glass fibres through a bath of an aqueous suspension or a dispersion of polyaryletherketones whereby the polymer is deposited on the fibres following which the polymer coated fibres are dried and heated to melt the polymer so that the polymer encases the fibre.
In a preferred embodiment US2018/119333 provides a dispersion useful in the dispersion method. The preferred dispersion method comprises circulating the reinforcement fibres in an impregnation bath comprising the thermoplastic polymer dispersed in the liquid medium; the impregnated fibres are taken out of the impregnation bath, the liquid medium is removed by drying the fibres; followed by heating the impregnated fibres and drying to a temperature above the melting temperature of the polymer to enhance the adherence of the polymer to the fibres and to confer cohesion to the material. Finally the coated fibres may be calendered to produce the prepreg of the desired shape and dimensions.
An example of this method is described in the US Pat. No. 5,888,580.
However given the hydrophobic nature of polyaryletherketones, it is necessary to add surfactants to the impregnation bath usually in low quantity to stabilise the dispersion of the polyaryletherketones in the aqueous phase. The surfactant that is used to stabilise an aqueous impregnation bath will be deposited on the fibres along with the polyaryletherketone as the polyaryletherketone is deposited on the fibres during the impregnation process. The surfactant that is deposited on the fibres will be subjected to the conditions to which the impregnated fibres are subjected such as drying, heating to the melting temperature of the polymer matrix, and calendering. This means that the surfactant, perhaps in degraded form, is present as a contaminant in the prepreg and in the composite material components produced from the prepreg.
Examples of surfactants that have been proposed for such purposes include ethoxylated long chain alcohols such as the commercially available Cremophor and Brij materials which are described in United States patent publication 2018/119333. Other surfactants which are proposed in PCT publication WO 2019/053379 include Brij S100 and Lanphos P35 and a neutralised version of Lanphos P35. Other surfactants that have been proposed include naphthalene sulfonic acid formaldehyde polymers. Whichever surfactant is used there remains a surfactant residue in the prepreg which can be undesirable in terms of the quality and properties of the prepreg and composites made therefrom.
It is known that polyaryletherketones can be sulfonated by the action of a mixture of fuming sulfuric acid and fresh sulfuric acid thereon. The production of such sulfonated materials and their use in membranes is described in United States patent 6,984,713.
The invention aims to overcome one or more of the aforesaid problems and/or to provide improvements generally.
According to the invention there is provided a use, a dispersion, a method, a prepreg and a moulding as defined in any one or more of the accompanying claims.
We have now found that these sulfonated polyaryletherketones are useful emulsifiers for unsulfonated polyaryletherketones in an aqueous environment. We have also found that an aqueous emulsion of a polyaryletherketone employing a sulfonated polyaryletherketone as an emulsifier may be used to deposit the polyaryletherketone on reinforcing fibres such as in a bath of the aqueous emulsion through which the reinforcing fibre passes.
Furthermore we have found that during the formation of a prepreg from the coated fibres so produced and during the production of moulded articles from the prepreg the sulfonate groups on the sulfonated polyaryletherketone can be liberated so that the sulfonated polyaryletherketone reverts or substantially reverts to the unsulfonated material and the prepreg or the article produced therefrom can be substantially free of surfactant residues such as sulfur.
In a preferred embodiment this allows the production of a prepreg based on a polyaryletherketone to be substantially free from surfactant contamination since the residue of the surfactant remaining in the prepreg is also a polyaryletherketone which in a preferred embodiment is the same as the unsulfonated polyaryletherketone that has been deposited on the reinforcing fibre.
Accordingly the present invention provides the use of a sulfonated polyaryletherketone as a surfactant in aqueous polymer dispersions particularly when the polymer in the dispersion is a polyaryletherketone.
The invention further provides an aqueous dispersion of a polyaryletherketone wherein the polyaryletherketone is dispersed in the aqueous medium by a surfactant comprising a sulfonated polyaryletherketone.
In a further embodiment the invention provides a method for the impregnation of fibres with a polyaryletherketone comprising passing the fibres through a bath containing an aqueous dispersion of a polyaryletherketone wherein the polyaryletherketone is dispersed in the aqueous medium by a surfactant comprising a sulfonated polyaryletherketone.
In a further embodiment the method further comprises drying the impregnated fibres to form a prepreg and moulding the prepreg to produce a finished article wherein in this further embodiment the conditions are such that the sulfonate groups of the sulfonated polyaryletherketone are removed.
In a further embodiment the invention provides a moulding from a prepreg comprising a fibre reinforced polyaryletherketone containing no surfactant residue other than a polyaryletherketone.
In all the embodiments it is preferred that the polyaryletherketone that is sulfonated has the same basic chemical structure as the unsulfonated polyaryletherketone that is dispersed in the aqueous medium.
The sulfonated polyaryletherketone surfactant is, preferably, present in the emulsion or dispersion of the polyaryletherketone in a proportion by weight ranging from 0.25% to 5% and, preferably from 0.50% to 1.5% with respect to the polyaryletherketone which is typically present in the emulsion or dispersion in a proportion by weight ranging from 10% to 50% and, preferably from 25% to 35% with respect to the weight of the emulsion or dispersion. Using these proportions we have found that aqueous dispersions of the polyaryletherketone are produced which remain stable for a period of time to enable fibre impregnation at a preferred rate to provide a prepreg having the desirable weight content of fibres.
The polyaryletherketone may be a PAEK, a polyetherketone (or PEK), a polyetheretherketone (or PEEK) or a polyetherketoneketone (or PEKK), but it is preferably a PEKK. The polyaryletherketone that is sulfonated to produce the surfactant may be the same or different from the polyaryletherketone that is emulsified or dispersed in the aqueous medium, but preferably it is the same.
The polyaryletherketone is preferably present in the impregnation bath in a micronized form, that is to say in the form of particles of which the number median diameter (D50) is at the most 50 micrometres, or 40 micrometres, or more preferably 30 micrometres or 20 micrometres.
The reinforcement fibres used in the invention may be selected from all fibres capable of being used as reinforcement in the manufacture of composite material parts. They may be glass fibres, quartz fibres, carbon fibres, graphite fibres, silica fibres, metal fibres such as steel fibres, aluminum fibres or boron fibres, ceramic fibres such as silicon carbide or boron carbide fibres, synthetic organic fibres such as aramid fibres, polyethylene fibres, polyester fibres or fibres of poly(p-phenylene benzobisoxazole), better known by the acronym PBO, natural organic fibres such as hemp fibres, linen fibres or silk fibres.
These fibres are, preferably, in the form of yarns grouping together several thousand elementary filaments (typically 3,000 to 48,000) measuring, for example, 6 to 10 pm diameter in the case of carbon fibres. Said fibres are known as "rovings" or "tapes".
In a preferred embodiment, the reinforcement fibres are carbon fibres, and the weight content of reinforcement fibres in the prepreg of this invention ranges from 35% to 75% preferably 25 from 57% to 72% with respect to the total weight of reinforcement fibres and polyaryletherketone.
In another preferred embodiment, the reinforcement fibres are glass or silica fibres, in which case the preferred weight content of reinforcement fibres ranges from 45% to 82% and, preferably from 66% to 78% with respect to the total weight of reinforcement fibres and polyaryletherketone.
The impregnation of the reinforcement fibres may be carried out by the process described in United States Patent publication 2018/119333 by circulation and guiding of fibres in a bath filled with the emulsion or dispersion of this invention with agitation to maintain bath homogenous and provided with drive means making it possible to ensure the circulation and the guiding of the reinforcement fibres.
After the step of immersing the reinforcement fibres in the impregnation bath, the coated fibres are dried and heated to a temperature above the melting temperature of the polyaryletherketone and calendered the reinforcement fibres thereby being coated with the polyaryletherketone. The manufacturing method may comprise in addition to the production of the prepreg the use formation of a preform from the prepreg and the consolidation of the preform to a final composite part. In a preferred embodiment the consolidation is performed at a pressure less than or equal to 5 bars and, preferably, without pressurisation.
The invention further relates to a component made from a prepreg according to this invention.
The degree of sulfonation of the sulfonated polyaryletherketone that is used as the surfactant in this invention is the number of sulfonate groups present per repeat unit of the polyaryletherketone and can be varied according to the nature of the polyaryletherketone that is to be dispersed.
As indicated in the article Sulfonated poly(ether ketone ketone) ionomers as proton exchange membranes, Swier etal, Journal of Polymer Eng and Sci, Volume 45, Issue 8, pp 1081-1091, 2005, the degree of sulfonation can be controlled by the length of time to which the polyaryletherketone is subjected to the suflonation conditions.
We have found that sulfonated polymers with a degree of sulfonation from 0.5 to 1.5 are particularly suitable as surfactants according to this invention. We prefer to use from 0.5 to 5 wt % of the sulfonated polyaryletherketone material based on the weight of the unsulfonated polyaryletherketone in the dispersion.
The invention is illustrated by the following Examples in which the degree of settling of a dispersion of a polyetherketone ketone (PEKK) in 9.5 grams of water was assessed visually in a 10 ml measuring cylinder.
The following aqueous dispersions containing various materials as surfactants were prepared Experiment Surfactant Surfactant PEKK (g) Water (g) mass (g) 1 n/a n/a 0.505 9.469 2 SPEKK Xs = 0.87 0.049 0.500 9.450 3 SPEKK Xs = 1.16 0.050 0.497 9.503 4 SPEKK Xs = 1.16 0.050 0.501 9.470 SPEKK Xs = 1.16 0.098 0.502 9.504 6 SPEKK Xs = 1.16 0.100 0.499 9.447 7 Oparyl DT120 0.049 0.501 9.463 8 Agrosurf DIS145 0.050 0.500 9.447
Table 1
In Table 1, the term SPEKK designates a sulfonated polyetherketone ketone and the numbers indicate the degree of sulfonation. The degree of separation of the PEKK within the aqueous phase overtime was observed with the following results.
In Experiment 1 a sediment of 2.6 ml was found at the bottom of the flask and a PEKK layer formed on the top of the water within 100 seconds. In Experiment 2 effective dispersion was achieved for up to 10 minutes with about 4 mi of sediment and no surface layer was formed after 92 minutes. In Experiments 3 to 6 the first sediment formed after 4 days was about 3.1 ml and there was little if any PEKK deposited on the surface of the water.
By comparison, in comparative Experiments 7 and 8 most of the PEKK was deposited from the suspension within 5 minutes.

Claims (17)

  1. CLAIMS1. The use of a sulfonated polyaryletherketone as a surfactant in aqueous polymer dispersions.
  2. 2. The use according to Claim 1 in which the polymer in the dispersion is a polyaryletherketone.
  3. 3. The use according to Claim 1 or Claims 2 in which the polyaryletherketone that is sulfonated is chemically the same as the dispersed polyaryletherketone.
  4. 4. An aqueous dispersion of a polyaryletherketone wherein the polyaryletherketone is dispersed in the aqueous medium by a surfactant comprising a sulfonated polyaryletherketone.
  5. 5. An aqueous dispersion according to Claim 4 in which the polyaryletherketone that is sulfonated is chemically the same as the dispersed polyaryletherketone.
  6. 6. A dispersion according to Claim 4 or Claim 5 in which the sulfonated polyaryletherketone surfactant is present in the emulsion or dispersion of the polyaryletherketone in a proportion by weight ranging from 0.25% to 5% of the polyaryletherketone.
  7. 7. A dispersion according to any of Claims 4 to 6 in which the polyaryletherketone is present in the emulsion or dispersion in a proportion by weight ranging from 10% to 50%.
  8. 8. A dispersion according to any of Claims 4 to 7 in which the polyaryletherketone is a polyaryletherketone (or PAEK) a polyetherketone (or PEK), a polyetheretherketone (or PEEK) or a polyetherketoneketone (or PEKK).
  9. 9. A dispersion according to any of Claims 4 to 8 in which the polyaryletherketone is present in the form of particles of which the number median diameter (D50) is at the most 50 micrometres.
  10. 10. An aqueous dispersion according to any of Claims 4 to 9 in which the degree of sulfonation of the sulfonated polyaryletherketone is from 0.5 to 1.5.
  11. 11. A method for the impregnation of fibres with a polyaryletherketone comprising passing the fibres through a bath containing an aqueous dispersion of a polyaryletherketone wherein the polyaryletherketone is dispersed in the aqueous medium by a surfactant comprising a sulfonated polyaryletherketone.
  12. 12. A method according to Claim 11 further comprising drying the impregnated fibres to form a prepreg and moulding the prepreg to produce a finished article wherein the drying and/or moulding conditions are such that the sulfonate groups of the sulfonated polyaryletherketone are removed.
  13. 13. A prepreg comprising reinforcing fibres in a matrix of a polyaryletherketone prepared by a process according to Claim 11 or Claim 12.
  14. 14. A prepreg according to Claim 13 in which the reinforcement fibres are selected from glass fibres, quartz fibres, carbon fibres, graphite fibres, silica fibres, metal fibres such as steel fibres, aluminum fibres or boron fibres, ceramic fibres such as silicon carbide or boron carbide fibres, synthetic organic fibres such as aramid fibres, polyethylene fibres, polyester fibres or fibres of poly(p-phenylene benzobisoxazole), natural organic fibres such as hemp fibres, linen fibres or silk fibres.
  15. 15. A prepreg according to Claim 14 in which the fibres are in the form of yarns grouping together 3,000 to 48,000 elementary filaments measuring, 6 to 10 pm diameter.
  16. 16. A prepreg according to Claim 14 or Claim 15 in which the reinforcement fibres are carbon fibres, and the weight content of reinforcement fibres in the prepreg ranges from 35% to 75% with respect to the total weight of reinforcement fibres and polyaryletherketone.
  17. 17. A moulding formed from a prepreg according to any of Claims 13 to 16 comprising a fibre reinforced polyaryletherketone containing no surfactant residue other than a polyaryletherketone.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10251621A (en) * 1997-03-07 1998-09-22 Dainippon Printing Co Ltd Polymeric antistatic agent
CN106752830A (en) * 2017-01-10 2017-05-31 滁州职业技术学院 One kind is for electric armour clamp corrosion-resistant high-strength composite organic silicon modified polyurethane water paint and preparation method thereof
CN107652829A (en) * 2017-08-24 2018-02-02 张家港市友成高新材料有限公司 Glass fiber reinforcement PEEK coating and preparation method thereof and film-forming process
US20180119333A1 (en) * 2015-03-31 2018-05-03 Arianegroup Sas Aqueous impregnation bath for reinforcement fibres and uses thereof
WO2019097148A1 (en) * 2017-11-14 2019-05-23 Arkema France Use of a sulfonated poly(aryl ether ketone) or of a sulfonated non-polymeric aryl ether ketone as a dispersant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10251621A (en) * 1997-03-07 1998-09-22 Dainippon Printing Co Ltd Polymeric antistatic agent
US20180119333A1 (en) * 2015-03-31 2018-05-03 Arianegroup Sas Aqueous impregnation bath for reinforcement fibres and uses thereof
CN106752830A (en) * 2017-01-10 2017-05-31 滁州职业技术学院 One kind is for electric armour clamp corrosion-resistant high-strength composite organic silicon modified polyurethane water paint and preparation method thereof
CN107652829A (en) * 2017-08-24 2018-02-02 张家港市友成高新材料有限公司 Glass fiber reinforcement PEEK coating and preparation method thereof and film-forming process
WO2019097148A1 (en) * 2017-11-14 2019-05-23 Arkema France Use of a sulfonated poly(aryl ether ketone) or of a sulfonated non-polymeric aryl ether ketone as a dispersant

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