This invention relates to polymers, processes for manufacturing the polymers and uses of the polymers.
There is a wide range of thermoplastic polymeric materials available for use in industry, either alone or as part of composite materials. However, industry is constantly demanding materials with properties that are improved in at least some respect over existing materials.

Polyaryletherketones (PAEKs) such as polyetheretherketone (PEEK) are often used. PEEK is the material of choice for many commercial applications because it is highly crystalline and has outstanding chemical resistance properties. PAEKs, particularly including PEEK, can be manufactured by nucleophilic polycondensation of bisphenols with organic dihalide compounds in a suitable solvent in the presence of alkali metal carbonates and/or bicarbonates or alkaline earth metal carbonates and/or bicarbonates. Such processes are set out, for example, in EP0001879A, EP0182648A, EP0244167A and EP3049457A.

While PAEKs may exhibit mechanical properties that are acceptable in a number of applications, it would be beneficial to provide PAEKs that demonstrate improved mechanical properties such as fracture toughness. Fracture toughness testing measures the energy required to propagate a crack through a test bar until the bar breaks. The propagation of a crack requires less energy in brittle materials than in ductile/tough materials. A material with higher fracture toughness characteristics is better suited than a material with lower fracture toughness for use in thicker walled parts (e.g. stock shapes including rods, machined components, in extruded and injection moulded articles such as pipes and casings and in composites generally).

Furthermore, there is a need in a number of areas (for example in the electronics industry for components for mobile phones, tablets etc.) for thermoplastic polymeric materials that exhibit as light or as white a colour as possible, e.g. compositions that exhibit a higher lightness, L* (according to the 1976 CIE L* a* b* colour space). Components manufactured from such compositions are useful because they enable ease of colour matching with similarly white-coloured components. It is easier to adjust the colour and/or match (e.g. by addition of colourants) a lighter polymer compared to e.g. the light brown/beige colour of known PEEKs. Furthermore, in general, light or white polymers and lighter or whiter components made therefrom are desirable since whiteness implies higher purity and quality.

Additionally, it would be beneficial to provide a PAEK that exhibits a lower incidence of gel formation. PAEKs have a tendency to contain small amounts of very high molecular mass, branched and cross-linked material, which can cause visual defects, particularly evidenced in thin films and commonly known as fish-eyes. Such defects reduce the effective yield of good quality, defect-free polymer film, and hence increase the amount of material that must be

scrapped. Gels can also lead to processing, quality and yield issues in the manufacture of melt-spun fibres.

A conventional commercial route for the formation of PAEKs and particularly PEEK is by nucleophilic polycondensation of one or more bisphenols with one or more organic dihalide compounds, in the presence of alkali metal or alkali earth metal carbonates or bicarbonates, leading to the presence of organic dihalide compounds as residual impurities in the resulting polymer. Even after extensive washing of the polymer by solvents, residual levels of organic dihalide compounds in the resulting PAEK, particularly levels of 4,4' difluorobenzophenone in PEEK, when this monomer is used for PEEK polycondensation, may be undesirably high. If the PAEK or PEEK is intended for use in contact with foods or pharmaceutical compounds, it is desirable to reduce the levels of such residues and/or to facilitate their removal from the PAEK or PEEK.

Furthermore, the conventional nucleophilic polycondensation route may lead to residual polymerisation reaction solvent, typically residual diphenyl sulfone (DPS) being present in the PAEK or PEEK, even after extensive washing of the polymer with solvents intended to remove residual polymerisation reaction solvent. Such residual polymerisation solvent may lead to problems when the PAEK or PEEK is subsequently processed by melt-processing such as extrusion or injection moulding. For instance the polymerisation solvent may migrate to surfaces leading to formation of localised solvent droplets or particles in a product, potentially generating product defects. It is thus desirable to reduce the levels of such polymerization solvent residues, such as DPS residues, and/or to facilitate their removal from the PAEK or PEEK.

Accordingly there is a need for a polymeric PAEK, and particularly PEEK material that has one or more of the following: improved mechanical properties, lighter or whiter colour, reduced incidence of gel formation, reduced residual organic dihalide compounds, such as 4,4'-difluorobenzophenone, and reduced residual polymerisation solvent such as reduced DPS residues. There is also a need for an industrially applicable process for preparing such PAEK or PEEK.

Throughout this specification, the term "comprising" or "comprises" means including the component(s) specified but not to the exclusion of the presence of other components. The term "consisting essentially of or "consists essentially of means including the components specified but excluding other components except for materials present as impurities, unavoidable materials present as a result of processes used to provide the components, and components added for a purpose other than achieving the technical effect of the invention. Typically, when referring to compositions, a composition consisting essentially of a set of components will comprise less than 5% by weight, typically less than 3% by weight, more typically less than 1 % by weight of non-specified components.

The term "consisting of or "consists of means including the components specified but excluding other components.

Whenever appropriate, depending upon the context, the use of the term "comprises" or "comprising" may also be taken to include the meaning "consists essentially of" or "consisting essentially of, and also may also be taken to include the meaning "consists of or "consisting of.

All references to L*, a* and b* values in the present application are when measured in accordance with Example 6 and with reference to the 1976 CIE L* a* b* colour space.

As used herein, the term "nucleophilic condensation" is used to refer briefly to the process for preparation of PAEK, particularly PEEK, by nucleophilic polycondensation of bisphenols with organic dihalide compounds, in the presence of alkali and/or alkali earth metal carbonates and/or bicarbonates in the presence of a polymerisation solvent such as diphenyl sulfone (DPS). For PEEK, the bisphenol is preferably hydroquinone and the organic dihalide compound is preferably 4,4'-difluorobenzophenone.

References to the monomers, solvents and other additives of the nucleophilic condensation reaction are meant to refer to these compounds with their commercially available purities, without further special purification.

The invention provides a process for producing polyaryletherketone (PAEK), the process comprising:

a nucleophilic polycondensation of a bisphenol with an organic dihalide compound in a reaction mixture comprising sodium carbonate and potassium carbonate, in an aromatic sulfone solvent, at a reaction temperature rising to a temperature from 290°C to 320°C immediately prior to;

b addition of a salt to the reaction mixture, wherein the molar ratio of the salt to potassium carbonate is from 6.0 to 10.0;

c addition of further organic dihalide compound to the reaction mixture, simultaneously with or subsequent to step b, wherein the molar ratio of further organic dihalide compound to bisphenol is from 0.009 to 0.035;

d maintenance of the resulting reaction mixture's temperature at from 290°C to 320°C for from 20 to 180 minutes;

e cooling of the resulting reaction mixture and recovery of the PAEK resulting from steps a to d from the reaction mixture;

wherein in step a of the process:

i the molar ratio of sodium carbonate to bisphenol is from 0.95 to 1 .15;

ii the molar ratio of potassium carbonate to sodium carbonate is from 0.0025 to 0.0040; and

iii the molar ratio of organic dihalide compound to bisphenol is from 1 .005 to 1 .010.

In step a of the process, the reaction temperature may be maintained at a temperature from 290°C to 320°C until a desired molecular mass of the PAEK has been reached. This may be assessed by monitoring the measured torque of a stirrer motor driving a stirrer paddle in the reaction mixture which has been calibrated to correlate the measured torque with the molecular mass of PAEK reached by polycondensation. More preferably, the reaction temperature may be maintained at a temperature from 300°C to 312°C.

Once the desired molecular mass of the PAEK has been reached, the salt is added to the reactor to act as a reaction-stopping agent.

The salt may be an alkali metal salt or an alkaline earth metal salt. The salt may be selected from lithium chloride, calcium chloride, magnesium chloride, lithium bromide, lithium iodide and/or lithium sulphate. In one example, the salt is preferably lithium chloride. In another example the salt is preferably lithium sulphate. The molar equivalents of the salt (relative to the moles of potassium carbonate present in step a of the process) may be at least 1 .0 molar equivalents, preferably at least 4.0 molar equivalents, more preferably at least 6.0 molar equivalents, most preferably at least 7.0 molar equivalents. The molar equivalents of the salt may be less than 15.0 molar equivalents, preferably less than 12.0 molar equivalents, more preferably less than 10.0 molar equivalents, most preferably less than 9.0 molar equivalents.

The molar ratio of potassium carbonate may alternatively be defined as the molar ratio of potassium carbonate to bisphenol and may range from 0.0025 to 0.0046.

The further organic dihalide compound is added to the reaction mixture in step c, simultaneously with the addition of step b, or subsequent to completion of the addition of step b. For instance the addition of step c may commence part-way through the addition of step b and end after step b has been completed.

Preferably, the addition of step c is completed within 10 minutes of the commencement of step b, and more preferably, to prevent reduction in the PAEK molecular mass, step c does not

commence until after the completion of the addition of step b. Typically, the addition of step b will be over a period of 5 minutes or less, as will the addition of step c.

In step d, the resulting reaction mixture's temperature is maintained at from 290°C to 320°C for from 20 to 180 minutes. In this step, a preferred maintained temperature is from 300°C to 312°C. The temperature may be maintained at a temperature from 290 °C to 320 °C, preferably from 300°C to 312°C, more preferably 305°C to 308°C for from 20 to 180 minutes, preferably from 20 to 120 minutes, more preferably from 20 to 60 minutes, even more preferably from 30 to 60 minutes, prior to the cooling of step e.

In step e, the reaction mixture is typically cooled by discharging the reaction mixture onto a water-cooled surface.

Once cool, the PAEK may be recovered by processes known in the art. Typically, the crude cooled reaction product may be milled into a coarse powder, for instance with less than 2 mm maximum dimension. The powder may be washed in a separating column with an organic solvent, preferably a partially water-miscible solvent such as acetone, to remove organic impurities, specifically to remove aromatic sulfone solvent. Typically, acetone may be passed through the column until aromatic sulfone solvent, such as diphenylsulfone, is no longer precipitated out of organic wash on addition of water to the wash. The remaining product may then be washed with ambient temperature deionised water to remove the organic solvent, such as acetone, prior to further washing with hot (e.g. 90°C) deionised water to remove water-soluble residues such as sodium and potassium salts. This may be monitored by monitoring the conductivity of the wash water. Once this has reached a minimal level, the material remaining may be dried to yield the recovered PAEK.

Typically, the reaction mixture in step a will be formed with the reaction mixture at a temperature of 130°C or more, then heated to a target polymerisation range for the reaction mixture temperature from 290°C to 320°C. Typically, the reaction mixture may be gradually heated to the target polymerisation range over a period of 1 to 6 hours before a temperature in the target polymerisation range is reached, This may be achieved by continuous heating, or by heating to intermediate "hold" temperatures, with the reaction mix held at a "hold" temperature such as 200°C or 220°C for 20 to 60 minutes the reaction mixture temperature reaches the target polymerisation range, the reaction mixture may be held at a temperature within the target polymerisation range for a period from 20 to 360 minutes, preferably from 30 to 240 minutes, more preferably from 60 to 90 minutes, prior to commencement of step b.

In the process, sodium bicarbonate or a mixture of sodium bicarbonate and sodium carbonate may be considered as equivalent to sodium carbonate based upon providing the same molar equivalence of sodium ions to the reaction mixture.

In the process, potassium bicarbonate or a mixture of potassium bicarbonate and potassium carbonate may be considered as equivalent to potassium carbonate based upon providing the same molar equivalence of potassium ions to the reaction mixture.

The aromatic sulfone solvent used in the process may suitably be a solvent of formula

where W is a direct link, an oxygen atom or two hydrogen atoms (one attached to each benzene ring) and Z and Z', which may be the same or different, are hydrogen atoms or phenyl groups. A mixture of such solvents may be used. Examples of such aromatic sulfones include diphenylsulfone, dibenzothiophen dioxide, phenoxanthin dioxide and 4-phenylsulfonyl biphenyl. Diphenylsulfone is a preferred solvent. Step a of the process is preferably carried out in the presence of diphenylsulfone as solvent. References to diphenylsulfone as solvent mean that the solvent comprises at least 95% by weight of diphenylsulfone.

In step a of the process the molar ratio of potassium carbonate to sodium carbonate is from 0.0025 to 0.0040 preferably from 0.0030 to 0.0036, more preferably less than 0.0034. Preferably step a of the process is carried out in the presence of greater than 0.0025 molar ratio of potassium carbonate. These preferred ranges provide benefits in terms of increased speed of reaction whilst avoiding side reactions, in particular excessive chain branching that can occur if the rate of reaction is too low.

The molar ratio of sodium carbonate to bisphenol in step a is from 0.95 to 1 .15. The molar ratio may be greater than 0.95, preferably 1 .00 or more, preferably greater than 1 .00, more preferably greater than 1 .01 , most preferably greater than 1.02. The molar ratio may be less than 1 .15, preferably less than 1 .10, more preferably less than 1 .06, most preferably less than 1 .04.

The molar ratio of carbonates to bisphenol, for carbonates other than sodium carbonate and potassium carbonate (and their equivalents if bicarbonates are included), used in step a of the process is preferably less than 0.05, more preferably less than 0.01 .

Preferably, the only carbonates used in step a of the process are sodium carbonate and potassium carbonate (including their bicarbonate equivalents). Even more preferably, the bicarbonate equivalents are excluded.

In step b of the process the molar ratio of salt, for example, lithium chloride, to potassium carbonate is from 6.0 to 10.0, preferably from 7.0 to 9.0.

Step a of the process has the molar ratio of organic dihalide compound to bisphenol from 1 .005 to 1 .010. This is preferably from 1 .006 to 1 .008. The molar ratio of organic dihalide compound is defined as the number of moles of organic dihalide compound used in step a of the process divided by the total number of moles of bisphenol used in step a of the process.

The bisphenol may be or comprise hydroquinone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 1 ,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and 1 ,6-dihydroxynaphthalene, or mixtures thereof. Preferably, the one or more bisphenol may be or comprise hydroquinone, 4,4'-dihydroxybenzophenone and 4,4'-dihydroxybiphenyl, or mixtures thereof.

The organic dihalide compound may be or comprise 4,4'-dichlorobenzophenone, 4-chloro-4'-fluorobenzophenone, 4,4'-difluorobenzophenone, 1 ,4-bis(4'-fluorobenzoyl)benzene and 1 ,3-bis(4'-fluorobenzoyl)benzene or mixtures thereof. Preferably the organic dihalide compound is 4,4'-difluorobenzophenone, 1 ,4-bis(4'-fluorobenzoyl)benzene or mixtures thereof. Most preferably the organic dihalide compound is 4,4'-difluorobenzophenone.

Step a of the process is preferably carried out under substantially anhydrous conditions. Step a is preferably carried out with stirring. The temperature may increase in step a at a rate of greater than 0.25°C/min, more preferably greater than 0.50°C/min, even more preferably greater than 0.70°C/min, but preferably less than 1 .50°C/min, more preferably less than 1 .25°C/min, even more preferably less than 1 .10°C/min. Preferably, however, prior to reaching a maximum temperature, step a of the process may further comprise one or more periods of time during which the temperature is held to remain constant. For example, step a of the process may further comprise one or more periods of time (e.g. for at least 20 minutes) during which the temperature is constant, for instance at a temperature from 170°C to 210°C; and/or at a temperature from 210°C to 240°C.

In step a of the process the bisphenol and the organic dihalide compound are preferably brought into contact with each other prior to contacting with the sodium and potassium carbonates, preferably in the presence of a solvent, preferably diphenylsulfone, prior to the contacting with the carbonates.

Preferably in step a, after the maximum temperature is reached, the maximum temperature is maintained until a desired molecular mass of the PAEK has been reached. The desired molecular mass may be indicated by reaching a desired stirrer torque rise. A relationship can be obtained between the molecular mass of the polymer in solution and the torque experienced by a stirrer motor. This is for a defined mass, polymer concentration and temperature. Based on this relationship, a torque rise can be predicted for a desired molecular mass (number average or weight average molecular mass).

The further organic dihalide compound added in step c may be selected from one or more of 4,4'-difluorobenzophenone or 4,4'-dichlorodiphenylsulfone, 1 ,3-Bis(4-fluorobenzoyl)benzene, 4,4'-dichlorobenzophenone, and 1 ,3-bis(4-chlorobenzoyl)benzene. The end-capping agent is preferably 4,4'-difluorobenzophenone. As a result of the addition in step c, ends of the PAEK may be end-capped with halogen atoms, preferably fluorine atoms, which is understood to stabilise the PAEK. The molar ratio of further organic dihalide compound to bisphenol is greater than 0.008 to less than 0.036, more preferably from 0.009 to 0.035, preferably less than 0.030 molar ratio, even more preferably less than 0.025 molar ratio, most preferably less than 0.022 molar ratio. A preferred addition of further organic dihalide composition is from 0.010 to 0.020 molar ratio, such as 0.012 to 0.018.

In particular, the process of the invention is suitable for the preparation of PAEK wherein the PAEK comprises a repeat unit of formula:

wherein t1 and w1 independently represent 0 or 1 and v1 represents 0, 1 or 2.

Preferred PAEKs have a the repeat unit wherein t1 =1 , v1 =0 and w1 =0; t1 =0, v1 =0 and w1 =0; t1 =0, w1 =1 , v1 =2; or t1 =0, v1 =1 and w1 =0. More preferred have a repeat unit wherein t1 =1 , v1 =0 and w1 -0; or t1 =0, v1 =0 and w1 =0. The most preferred has a repeat unit wherein t1 =1 , v1 =0 and w1 =0.

In preferred embodiments, the PAEK is selected from polyetheretherketone, polyetherketone, polyetherketoneetherketoneketone and/or polyetherketoneketone, and/or a copolymer including polyetheretherketone and polyetherdiphenyletherketone. In a more preferred embodiment, the PAEK is selected from polyetherketone and/or polyetheretherketone, and/or a copolymer including polyetheretherketone and polyetherdiphenyletherketone. In an especially preferred embodiment, the PAEK is selected from polyetheretherketone, and/or a copolymer including polyetheretherketone and polyetherdiphenyletherketone.

The PAEK suitably includes at least 50 mol%, (e.g. 50-99.8 mol%), preferably at least 60 mol% (e.g. 60-100 mol%), more preferably at least 68 mol% (e.g. 68 to 100 mol%), of repeat units of formula I, especially such units where t1 =1 , v1 =0 and w1 =0. In an especially preferred

embodiment, the PAEK includes at least 90 mol%, preferably at least 95 mol%, more preferably at least 98 mol%, especially at least 99 mol% of repeat units of formula I, especially repeat units of formula I wherein t1 =1 , v1 =0 and w1 =0. Other repeat units in the PAEK may be different repeat units of formula I or may include -Ph-Ph- moieties where Ph represents an unsubstituted phenylene moiety (especially wherein both -Ph- moieties are linked to each other and to adjacent repeat units at the 4,4' positions-). Other repeat units may include Ph moieties bonded to two moieties selected from carbonyl moieties and ether moieties and -Ph-Ph- moieties bonded to two ether moieties.

The PAEK formed in the process may be a copolymer which comprises a first moiety of formula I and a second moiety which includes -Ph-Ph- moieties where Ph represents an unsubstituted phenylene moiety (which suitably includes 4,4' bonds to adjacent moieties).

In one embodiment, the PAEK may be selected from: a polymer comprising at least 98 mol% of a repeat unit of formula I, especially such units wherein t1 =1 , v1 =0 and w1 =0; and a copolymer which includes a repeat unit of formula

-O-Ph-O-Ph-CO-Ph- II

and a repeat unit of formula

-O-Ph-Ph-O-Ph-CO-Ph- III

wherein Ph represents a phenylene moiety. Preferably the repeat units of the copolymer consist essentially of the repeat units II and III.

In a preferred embodiment, the PAEK is homopolymer polyetheretherketone, PEEK, with repeat units consisting of formula II:

-O-Ph-O-Ph-CO-Ph- II

or is a copolymerwith repeat units consisting repeat units of formula II and repeat units of formula III:

-O-Ph-Ph-O-Ph-CO-Ph- III.

The ends of the polymer may be provided by the same monomers as the monomers making up the repeat units or may be provided by other compounds specifically added to provide end-capping.

Preferably the PAEK is homopolymer PEEK. More preferably, the ends of the polymer are provided by the same monomers as those used to form the repeat units.

The PAEK may preferably comprise at least 98 mole% (e.g. 98 to 99.9 mole%) of a repeat unit of formula I or a copolymer which includes repeat units of formulae II and III.

In the copolymer, the repeat units II and III are preferably in the relative molar proportions VI:VII of from 50:50 to 95:5, more preferably from 60:40 to 95:5, even more preferably from 65:35 to 95:5.

The phenylene moieties (Ph) in each repeat unit II and III may independently have 1 ,4- para linkages to atoms to which they are bonded or 1 ,3- meta linkages. Where a phenylene moiety includes 1 ,3- linkages, the moiety will be in the amorphous phase of the polymer. Crystalline phases will include phenylene moieties with 1 ,4- linkages. It is generally preferred for the PAEK or PEEK to be crystalline , for instance having a crystallinity of about 25 to 35% and, accordingly, the PAEK or PEEK preferably includes high levels of phenylene moieties with 1 ,4- linkages.

In a preferred embodiment, at least 95%, preferably at least 99%, of the number of phenylene moieties (Ph) in the repeat unit of formula II have 1 ,4-linkages to moieties to which they are bonded. It is especially preferred that each phenylene moiety in the repeat unit of formula II has 1 ,4-linkages to moieties to which it is bonded.

In a preferred embodiment, at least 95%, preferably at least 99%, of the number of phenylene moieties (Ph) in the repeat unit of formula III have 1 ,4-linkages to moieties to which they are bonded. It is especially preferred that each phenylene moiety in the repeat unit of formula III has 1 ,4- linkages to moieties to which it is bonded.

Preferably, the phenylene moieties in the repeat unit of formula II are unsubstituted. Preferably, the phenylene moieties in the repeat unit of formula III are unsubstituted.

The repeat unit of formula II preferably has the structure:

The repeat unit of formula III preferably has the structure:

The copolymer may include at least 50 mol%, preferably at least 60 mol% of repeat units of formula IV. Particular advantageous copolymers may include at least 62mol%, or, especially, at least 64 mol% of repeat units of formula IV. The copolymer may include less than 90 mol%, suitably 82mol% or less of repeat units of formula IV. The copolymer may include 58 to 82 mol%, preferably 60 to 80 mol%, more preferably 62 to 77 mol% of units of formula IV.

The copolymer may include at least 10 mol%, preferably at least 18 mol%, of repeat units of formula V. The copolymer may include less than 42 mol%, preferably less than 39 mol% of repeat units of formula V. Particularly advantageous copolymers may include 38 mol% or less; or 36 mol% or less of repeat units of formula V. The copolymer may include 18 to 42 mol%, preferably 20 to 40 mol%, more preferably 23 to 38 mol% of units of formula V.

The sum of the mol% of units of formula IV and V in the copolymer is suitably at least 95 mol%, is preferably at least 98 mol%, is more preferably at least 99 mol%.

The skilled person would have no difficulty in selecting suitable monomer combinations for use in the process of the invention in order to arrive at the PAEKs described above. For instance, the bisphenol may be one or more of hydroquinone, 4,4'-dihydroxybenzophenone and 4,4'-dihydroxybiphenyl. The organic dihalide compound of step a may be 4,4'-difluorobenzophenone. The further organic dihalide compound of step c may also be 4,4'-difluorobenzophenone.

In a most preferred process according to the invention, the process is for the preparation of a polyetheretherketone PEEK polymer in which the polymer comprises at least 90 mol% of repeat units of formula II, preferably is a homopolymer consisting or consisting essentially of a polymer of repeat units of formula II with corresponding end groups from the monomers used to generate the repeat units. For this embodiment of the process, the bisphenol is preferably hydroquinone and the organic dihalide compound is preferably 4,4'-difluorobenzophenone, with diphenylsulfone as the solvent. The further organic dihalide compound added in step c is also preferably 4,4'-difluorobenzophenone.

Such polymers which comprise at least 90 mol% of repeat units of formula II, preferably consisting or consisting essentially of a polymer of repeat units of formula II with corresponding end groups from the monomers used to generate the repeat units, as referred to herein as PEEK polymers.

Hence, in a preferred embodiment of the process of the invention, there is provided a process for producing homopolymer polyetheretherketone (PEEK), the process comprising:

a nucleophilic polycondensation of hydroquinone with 4,4'-difluorobenzophenone in a reaction mixture comprising sodium carbonate and potassium carbonate, in an aromatic sulfone solvent, preferably diphenylsulfone, at a reaction temperature rising to a temperature from 290°C to 320°C immediately prior to;

b addition of a salt to the reaction mixture, wherein the molar ratio of the salt to potassium carbonate is from 6.0 to 10.0;

c addition of 4,4'-difluorobenzophenone to the reaction mixture, simultaneously with, or subsequent to, step b, wherein the molar ratio of 4,4'-difluorobenzophenone to hydroquinone is from 0.009 to 0.035;

d maintenance of the resulting reaction mixture's temperature at from 290°C to 320°C for from 20 to 180 minutes;

e cooling of the resulting reaction mixture and recovery of the PEEK resulting from steps a to d from the reaction mixture;

wherein in step a of the process:

i the molar ratio of sodium carbonate to hydroquinone is from 0.95 to 1 .15;

ii the molar ratio of potassium carbonate to sodium carbonate is from 0.0025 to 0.0040; and

iii the molar ratio of 4,4'-difluorobenzophenone to hydroquinone is from 1 .005 to 1 .010.

The optional preferred features for this process for PEEK formation are as set out above in relation to the process for PAEK formation described above.

The salt may be an alkali metal salt or an alkaline earth metal salt. The salt may be selected from lithium chloride, calcium chloride, magnesium chloride, lithium bromide, lithium iodide and/or lithium sulphate. In one example, the salt is preferably lithium chloride. In another example the salt is preferably lithium sulphate. The molar equivalents of the salt (relative to the moles of potassium carbonate present in step a of the process) may be at least 1 .0 molar equivalents, preferably at least 4.0 molar equivalents, more preferably at least 6.0 molar equivalents, most preferably at least 7.0 molar equivalents. The molar equivalents of the salt may be less than 15.0 molar equivalents, preferably less than 12.0 molar equivalents, more preferably less than 10.0 molar equivalents, most preferably less than 9.0 molar equivalents.

The molar ratio of potassium carbonate may alternatively be defined as the molar ratio of potassium carbonate to hydroquinone and may range from 0.0025 to 0.0046.

The process of the invention results in the formation of a PAEK or PEEK polymer comprising residual impurities of aromatic sulfone solvent, sodium salt and organic dihalide monomer from its formation by nucleophilic polycondensation. At the time of writing, it had not proved possible to remove all of these residual impurities when recovering PAEK or PEEK on an industrial scale from commercially viable reaction mixtures in which the PAEK or PEEK was formed by nucleophilic polycondensation. This is thought to be due to trapping of the residual impurities in the solidified PAEK or PEEK so that not all impurities are accessible for removal by solvent extraction.

When the process is specifically for making a PEEK polymer as described above, the PEEK polymer may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer, particularly 4,4'-difluourobenzophenone, from its formation by nucleophilic polycondensation.

However, it has been found that the process of the invention surprisingly results in greater ease of extraction of the residual impurities, particularly the residual impurities of aromatic sulfone solvent and organic dihalide monomer, so that the levels of these impurities may be reduced to previously unattainably low values. Wthout wishing to be bound by any theory, it is thought that the process of the invention leads to the formation of a PAEK or PEEK with unusually low levels of branching compared to PAEK or PEEK formed in prior art nucleophilic polycondensation processes.

For instance, a typical prior art PEEK prepared by nucleophilic polycondensation in DPS as solvent in the presence of sodium carbonate, with 4,4'-difluourobenzophenone as the organic dihalide monomer, will comprise at least at least 0.064 wt.% of DPS even after extensive solvent/water washing to extract reaction by-products. Furthermore, the PEEK may be prone to release residual 4,4'-difluourobenzophenone in certain environments such that the PEEK is not suitable for use in materials that come into contact with food, even after extensive solvent/water washing to extract reaction by-products.

Hence, according to an aspect of the present invention there is provided a polyaryletherketone (PAEK), wherein when the PAEK is dissolved in concentrated sulfuric acid, for instance having a concentration of 95-98% by weight sulfuric acid, specific gravity of 1 .84 g/ml at 25°C, to prepare a resultant solution with 1 g of the PAEK per 100ml of the resulting solution, the resultant solution has an absorbance from the PAEK of less than 0.20 at a wavelength of light of 550nm.

The PAEK may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer from its formation by nucleophilic polycondensation.

In particular, the PAEK may be a PEEK polymer as described above. The PEEK polymer may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer, particularly 4,4'-difluorobenzophenone, from its formation by nucleophilic polycondensation.

Preferably the resultant solution may exhibit an absorbance from the dissolved PAEK of less than 0.18, more preferably less than 0.16, even more preferably less than 0.14, most preferably less than 0.12, at a wavelength of light of 550nm. The resultant solution may exhibit an absorbance of greater than 0.02, such as greater than 0.04, for instance greater than 0.06, at a wavelength of light of 550nm.

Without wishing to be bound by any theory, it is thought that the absorbance at 550nm in the specified solution is an indicator of the presence of branching in the PAEK, so that low absorbance is thought to correspond to a low degree of branching in the PAEK.

It has surprisingly been found that the PAEK of the first aspect of the invention has enhanced mechanical properties, has light colour and has a lower incidence of gels compared to PAEK made by prior art nucleophilic condensation. It has also been found that such PAEKs, when treated by solvent washing to remove residual impurities from the nucleophilic condensation, can be purified to a greater extent than was achievable by solvent washing of prior art PAEKs, such that the residual levels of organic dihalide compounds and of aromatic sulfone polymerisation solvent, particularly of DPS when DPS is used as polymerisation solvent, are lower than was previously attainable.

The absorbance that a resultant solution, obtained by dissolving PAEK in concentrated sulfuric acid at the specified levels explained above, is thought to correspond to the level of carbonyl branching of the PAEK, i.e. branching that has occurred via reaction at a carbonyl carbon to form a branch point, e.g. a triaryl carbinol. Such branch points are converted to stable carbonium ions in the presence of sulfuric acid which gives rise to the absorbance of light at a wavelength of 550nm exhibited by the resultant solutions of PAEKs comprising such branch points. The PAEK of the first aspect comprises lower levels of carbonyl branching than known PAEKs as indicated by the absorbance measurement.

The invention also provides a polyaryletherketone (PAEK), wherein the PAEK has a molecular mass dispersity, also referred to as a polydispersity index (PDI), of less than 2.6. The molecular mass dispersity, or polydispersity index, PDI, may suitably be measured in accordance with Example 4.

The PAEK with this molecular weight dispersity may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer from its formation by nucleophilic polycondensation.

In particular, the PAEK may be a PEEK polymer as described above. The PEEK polymer with the specified molecular mass dispersity may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer, particularly 4,4'-difluorobenzophenone, from its formation by nucleophilic polycondensation.

The molecular mass (also referred to as molecular weight) dispersity was formerly also referred to by the term "polydispersity index" or PDI, and corresponds to the value:

PDI = Mw / Mn

where Mw = weight average molecular mass and Mn = number average molecular mass.

PDI has a value equal to or greater than 1 , with the value approaching 1 if all polymer chains in a sample are of uniform chain length.

For some addition polymerization, dispersity can be as high as 10 or more. However, for typical step growth polymerization of linear polymers carried out in batch reactors, most probable values of dispersity are around 2.6. Carothers' equation limits dispersity/PDI for linear polymers formed by step-growth from 2 monomers to minimum value of 2.

However, for branched polymers, the modified Carothers' equation leads to values in excess of 2, and in practice, for PAEKs formed by nucleophilic polycondensation, typical value considerably in excess of 2 are found in the prior art, indicating that conventional nucleophilic polycondensation leads to branching of the PAEK or PEEK formed.

Surprisingly, the process of the present invention has been found to generate PAEK polymers with low degrees of branching in which the molecular mass dispersity (PDI) approaches the minimum theoretical value of 2 for the polymer generated by the process.

The PAEK may have a PDI of less than 2.6, preferably less than 2.5, more preferably less than 2.4, even more preferably less than 2.3, most preferably less than 2.2.

The PAEK has a PDI of 2.0 or more.

The PAEK of low PDI may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer from its formation by nucleophilic polycondensation.

In particular, the PAEK may be a PEEK polymer as described above. The PEEK polymer of low PDI may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer, particularly 4,4'-difluorobenzophenone, from its formation by nucleophilic polycondensation.

The invention also provides a PEEK, wherein the PEEK comprises an extractable concentration of 0.05 mg/kg or less of 4,4'-difluorobenzophenone, for instance 0.04 mg/kg or less when the PEEK is submersed in a fatty food simulant at 175°C for six hours. The level of 4,4'-difluorobenzophenone is expressed as the amount of extractable 4,4'-difluorobenzophenone per kg of PEEK including the 4,4'-difluorobenzophenone when the PEEK is submersed in a fatty food simulant at 175°C for six hours. The level of extractable 4,4'-difluorobenzophenone in the PEEK may be measured by extraction into Miglyol 812. As such, the PEEK of the present invention is suitable for use with materials that come into contact with food. Details of the measurement of the level of the extractable 4,4'-difluorobenzophenone in the PEEK are as set out in the Example below.

Hence, the invention further provides the use of a PAEK or PEEK according to the invention in a component intended to contact food. The invention also provides components machined, formed, or moulded from, or coated with, a composition comprising or consisting of the PAEK or PEEK of the invention intended to contact food. The composition may comprise from 30 to 100% of the PAEK or PEEK of the invention with from 0 to 70% by weight of other components such as filler, for instance fibrous filler, colourants and the like. Preferably the composition comprises no other PAEK or PEEK, more preferably no other polymer.

In particular, the PEEK may be a PEEK polymer as described above and may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and 4,4'-difluorobenzophenone, from its formation by nucleophilic polycondensation. In particular, the PEEK may be a PEEK formed by nucleophilic polycondensation from hydroquinone and 4,4'-difluorobenzophenone in DPS as a polymerisation solvent. The PEEK may be a PEEK formed in a process according to the invention.

The invention also provides a PAEK, wherein the PAEK comprises residual diphenylsulfone (DPS) present as 0.063% or less by weight (expressed as weight percent of the PAEK including the DPS). More preferably, the DPS is present as 0.060% by weight or less. The DPS may be 0.055% by weight or less, for instance, 0.052% by weight or less. However, there will typically be at least 0.01 % by weight of DPS present.

The level of DPS in the PAEK may be measured by a test method as set out in the Example below.

In particular, the PAEK may be a PAEK polymer as described above and may comprise residual impurities of diphenylsulfone, sodium salt and organic dihalide monomer, such as 4,4'-

difluorobenzophenone, from its formation by nucleophilic polycondensation in DPS as the aromatic sulfone polymerisation solvent.

In particular, the PAEK may be a PEEK polymer as described above and may comprise residual impurities of diphenylsulfone, sodium salt and 4,4'-difluorobenzophenone, from its formation by nucleophilic polycondensation in diphenylsulfone as aromatic sulfone polymerisation solvent. In particular, the PEEK may be a PEEK formed by nucleophilic polycondensation from hydroquinone and 4,4'-difluorobenzophenone in DPS as a polymerisation solvent. The PEEK may be formed in a process according to the invention.

The invention also provides polyaryletherketone (PAEK), wherein when the polymeric material is in the form of melt-filtered granules having a maximum dimension from 1 to 10mm, preferably from 2 to 5mm, the PAEK has a lightness L* of greater than 56.0, an a* coordinate of greater than 1 .3 but less than 5.0, and a b* coordinate of greater than 6.5 but less than 10.0 with reference to the 1976 CIE L* a* b* colour space.

The PAEK of light colour may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer from its formation by nucleophilic polycondensation.

In particular, the PAEK may be a PEEK polymer as described above. The PEEK polymer of light colour may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer, particularly 4,4'-difluorobenzophenone, from its formation by nucleophilic polycondensation.

It has surprisingly been found that the PAEK or PEEK of the present invention is lighter and consequently appears whiter than known PAEKs or PEEKs. As detailed above, lighter/whiter PAEKs and PEEKs are useful because they enable ease of colour matching with similarly coloured components and their colour can be more easily adjusted.

Preferably the PAEK or PEEK in the form of melt-filtered granules having a maximum dimension from 1 to 10mm has a lightness L* of greater than 58.0, more preferably greater than 59.0, even more preferably greater than 60.0, most preferably greater than 61 .0.

Preferably the PAEK or PEEK in the form of melt-filtered granules having a maximum dimension from 1 to 10mm has an a* coordinate of greater than 1 .5 but less than 3.5, more preferably greater than 1 .8 but less than 3.0, even more preferably greater than 2.0 but less than 2.5, most preferably greater than 2.1 but less than 2.4.

Preferably the PAEK in the form of melt-filtered granules having a maximum dimension from 1 to 10mm has a b* coordinate of greater than 6.7 but less than 9.0, more preferably greater than 7.0 but less than 8.7, even more preferably greater than 7.2 but less than 8.5, most preferably greater than 7.4 but less than 8.4.

In a preferred embodiment the PAEK or PEEK in the form of melt-filtered granules having a maximum dimension from 1 to 5mm has a lightness L* of greater than 60.0, an a* coordinate of greater than 2.0 but less than 2.5, and a b* coordinate of greater than 7.2 but less than 8.5. In a more preferred embodiment the PAEK or PEEK has a lightness L* of greater than 61 .0, an a* coordinate of greater than 2.1 but less than 2.4, and a b* coordinate of greater than 7.4 but less than 8.4.

The invention also provides a device or article formed, moulded, machined from, or coated with, a composition comprising or consisting of a PAEK or a homopolymer PEEK according to the invention. The composition may consist of the PAEK or PEEK of the invention, or may include say 30 to 100% by weight of the PAEK or PEEK, with from 0 to 70% by weight of other ingredients, for instance filler, such as fibrous filler, colourants and the like. Preferably no other PAEK and more preferably no other polymer is present in the composition

The PAEK of the device or article may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer from its formation by nucleophilic polycondensation.

In particular, the PAEK may be a PEEK polymer as described above. The PEEK polymer of the formed, moulded or machined device or article may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer, particularly 4,4'-difluorobenzophenone, from its formation by nucleophilic polycondensation.

The PAEK of the invention, when injection moulded, for instance as a disc, tablet, plaque or otherform of sample, to provide planar surface from a powder ofthe PAEK, may have a lightness L* of greater than 65.0, an a* coordinate of greater than 0.2 but less than 5.0, and a b* coordinate of greater than 5.0 but less than 12.0, with reference to the 1976 CIE L* a* b* colour space. The method of colour measurement may suitably be as set out in Example 6.

The PAEK in planar surface form may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer from its formation by nucleophilic polycondensation.

In particular, the PAEK may be a PEEK polymer as described above. The PEEK in planar surface form may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer, particularly 4,4'-difluorobenzophenone, from its formation by nucleophilic polycondensation.

Preferably the PAEK or PEEK in planar surface form has a lightness L* of greater than 67.0, more preferably greater than 69.0, even more preferably greater than 70.0, most preferably greater than 71 .0.

Preferably the PAEK or PEEK in planar surface form has an a* coordinate of greater than 0.5 but less than 4.5, more preferably greater than 0.8 but less than 4.0, even more preferably greater than 1 .0 but less than 3.5, most preferably greater than 1 .1 but less than 3.2.

Preferably the PAEK or PEEK in planar surface form has a b* coordinate of greater than 5.5 but less than 1 1 .0, more preferably greater than 6.0 but less than 10.5, even more preferably greater than 6.5 but less than 10.0, most preferably greater than 7.0 but less than 9.7.

In a preferred embodiment the PAEK or PEEK in planar surface form has a lightness L* of greater than 70.0, an a* coordinate of greater than 1 .0 but less than 3.5, and a b* coordinate of greater than 6.5 but less than 10.0. In a more preferred embodiment the PAEK or PEEK in planar surface form has a lightness L* of greater than 71 .0, an a* coordinate of greater than 1.1 but less than 3.2, and a b* coordinate of greater than 7.0 but less than 9.7.

Preferably the PAEK of the invention comprises a repeat unit of formula:

wherein t1 and w1 independently represent 0 or 1 and v1 represents 0, 1 or 2.

Preferred PAEKs have a the repeat unit wherein t1 =1 , v1 =0 and w1 =0; t1 =0, v1 =0 and w1 =0; t1 =0, w1 =1 , v1 =2; or t1 =0, v1 =1 and w1 =0. More preferred have a repeat unit wherein t1 =1 , v1 =0 and w1 -0; or t1 =0, v1 =0 and w1 =0. The most preferred has a repeat unit wherein t1 =1 , v1 =0 and w1 =0.

In preferred embodiments, the PAEK is selected from polyetheretherketone, polyetherketone, polyetherketoneetherketoneketone and/or polyetherketoneketone, and/or a copolymer including polyetheretherketone and polyetherdiphenyletherketone. In a more preferred embodiment, the PAEK is selected from polyetherketone and/or polyetheretherketone, and/or a copolymer including polyetheretherketone and polyetherdiphenyletherketone. In an especially preferred embodiment, the PAEK is selected from polyetheretherketone, and/or a copolymer including polyetheretherketone and polyetherdiphenyletherketone.

The PAEK suitably includes at least 50 mol%, (e.g. 50-99.8 mol%), preferably at least 60 mol% (e.g. 60-100 mol%), more preferably at least 68 mol% (e.g. 68 to 100 mol%), of repeat units of formula I, especially such units where t1 =1 , v1 =0 and w1 =0. In an especially preferred embodiment, the PAEK includes at least 90 mol%, preferably at least 95 mol%, more preferably at least 98 mol%, especially at least 99 mol% of repeat units of formula I, especially repeat units of formula I wherein t1 =1 , v1 =0 and w1 =0. Other repeat units in the PAEK may be of formula I; or may include -Ph-Ph- moieties where Ph suitably represents an unsubstituted phenylene moiety (especially wherein both -Ph- moieties are 4,4'-substituted). Other repeat units may include Ph moieties bonded to two moieties selected from carbonyl moieties and ether moieties; and-Ph-Ph- moieties bonded to two ether moieties.

The PAEK may be a copolymer which comprises a first moiety of formula I and a second moiety which includes -Ph-Ph- moieties where Ph represents an unsubstituted phenylene moiety (which suitably includes 4,4'-bonds to adjacent moieties).

In one embodiment, the PAEK may be selected from: a polymer comprising at least 98 mol% of a repeat unit of formula I, especially such units wherein t1 =1 , v1 =0 and w1 =0; and a copolymer which includes a repeat unit of formula

-O-Ph-O-Ph-CO-Ph-

and a repeat unit of formula

-O-Ph-Ph-O-Ph-CO-Ph- III

wherein Ph represents a phenylene moiety.

The PAEK preferably comprises at least 98 mol% (e.g. 98 to 99.9 mol%) of a repeat unit of formula I or a copolymer which includes repeat units of formulae II and III.

In a preferred embodiment, the PAEK is homopolymer polyetheretherketone, PEEK, with repeat units consisting of formula II:

-O-Ph-O-Ph-CO-Ph- II

or is a copolymerwith repeat units consisting repeat units of formula II and repeat units of formula III:

-O-Ph-Ph-O-Ph-CO-Ph- III.

The ends of the polymer may be provided by the same monomers as the monomers making up the repeat units or may be provided by other compounds specifically added to provide end-capping.

Preferably the PAEK is homopolymer PEEK. More preferably, the ends of the polymer are provided by the same monomers as those used to form the repeat units

In the copolymer, the repeat units II and III are preferably in the relative molar proportions VI:VII of from 50:50 to 95:5, more preferably from 60:40 to 95:5, even more preferably from 65:35 to 95:5.

The phenylene moieties (Ph) in each repeat unit II and III may independently have 1 ,4- para linkages to atoms to which they are bonded or 1 ,3- meta linkages. Where a phenylene moiety includes 1 ,3- linkages, the moiety will be in the amorphous phase of the polymer. Crystalline phases will include phenylene moieties with 1 ,4- linkages. It is generally preferred for the PAEK to be highly crystalline and, accordingly, the PAEK preferably includes high levels of phenylene moieties with 1 ,4- linkages.

In a preferred embodiment, at least 95%, preferably at least 99%, of the number of phenylene moieties (Ph) in the repeat unit of formula II have 1 ,4-linkages to moieties to which they are bonded. It is especially preferred that each phenylene moiety in the repeat unit of formula II has 1 ,4- linkages to moieties to which it is bonded.

In a preferred embodiment, at least 95%, preferably at least 99%, of the number of phenylene moieties (Ph) in the repeat unit of formula III have 1 ,4-linkages to moieties to which they are bonded. It is especially preferred that each phenylene moiety in the repeat unit of formula III has 1 ,4- linkages to moieties to which it is bonded.

Preferably, the phenylene moieties in the repeat unit of formula II are unsubstituted. Preferably, the phenylene moieties in the repeat unit of formula III are unsubstituted.

The repeat unit of formula II suitably has the structure:

The repeat unit of formula III suitably has the structure:

The copolymer may include at least 50 mol%, preferably at least 60 mol% of repeat units of formula IV. Particular advantageous copolymers may include at least 62mol%, or, especially, at least 64 mol% of repeat units of formula IV. The copolymer may include less than 90 mol%, suitably 82mol% or less of repeat units of formula IV. The copolymer may include 58 to 82 mol%, preferably 60 to 80 mol%, more preferably 62 to 77 mol% of units of formula IV.

The copolymer may include at least 10 mol%, preferably at least 18 mol%, of repeat units of formula V. The copolymer may include less than 42 mol%, preferably less than 39 mol% of repeat units of formula V. Particularly advantageous copolymers may include 38 mol% or less; or 36 mol% or less of repeat units of formula V. The copolymer may include 18 to 42 mol%, preferably 20 to 40 mol%, more preferably 23 to 38 mol% of units of formula V.

The sum of the mol% of units of formula IV and V in the copolymer is suitably at least 95 mol%, is preferably at least 98 mol%, is more preferably at least 99 mol%.

In a most preferred embodiment, the PAEK of the invention is a poly(etheretherketone) PEEK polymer in which the polymer comprises at least 90 mol% of repeat units of formula II, preferably consisting or consisting essentially of a polymer of repeat units of formula II with corresponding end groups from the monomers used to generate the repeat units. For this embodiment of the process, the bisphenol used in the nucleophilic polycondensation process for preparing the PEEK is preferably hydroquinone and the organic dihalide compound is preferably 4,4'-difluorobenzophenone, with diphenylsulfone as the solvent. The further organic dihalide compound added in step c is also preferably 4,4'-difluorobenzophenone, so that the PEEK may be at least partially end-capped with 4,4'-difluorobenzophenone.

Such polymers which comprise at least 90 mol% of repeat units of formula II, preferably consisting or consisting essentially of a polymer of repeat units of formula II with corresponding end groups from the monomers used to generate the repeat units, as referred to herein as PEEK polymers.

The PAEK polymer of the invention may comprise residual impurities of aromatic sulfone solvent, sodium salt and organic dihalide monomer from its formation by nucleophilic polycondensation. In particular, when the PAEK is a PEEK polymer as set out above, the PEEK polymer may comprise residual impurities of aromatic sulfone solvent, particularly diphenylsulfone, sodium salt and organic dihalide monomer, particularly 4,4'-difluorobenzophenone, from its formation by nucleophilic polycondensation.

The PAEK or PEEK may be in a particulate form such as a powder, pellets or granules. The powder may have a maximum dimension as measured by sieving of less than 4.0 mm, preferably less than 3.0 mm, more preferably less than 2.5 mm, but preferably of greater than 0.01 mm,

more preferably of greater than 0.1 mm. The pellets or granules may have a maximum dimension of less than 10mm, preferably less than 7.5 mm, more preferably less than 5.0 mm. The granule maximum dimension may be greater than 1 .0 mm, for instance greater than 2.0 mm. The maximum dimension may suitably be assessed by sieving, so that the values referred to above may be determined according whether the granules pass though or are retained on a sieve of the maximum dimension referred to. The pellets or granules may have an aspect ratio of (maximum dimension) : (minimum dimension) of 5:1 to 1 :1 , preferably 4:1 to 1 :1 , more preferably 3:1 to 1 .1 :1 , even more preferably 2:1 to 1 .1 :1 .

The PAEK or PEEK may be in a form such as a filament.

Preferably PAEK or PEEK has a critical strain energy release rate (as tested in accordance with Example 5) of at least 17.5 Jm -2, preferably at least 17.8 Jm -2, more preferably at least 18.0 Jm-2

Preferably PAEK or PEEK has a stress intensity factor K1c (as tested in accordance with Example 5) of at least 5.000 MPa.√m, more preferably of at least or more than 5.050 MPa.Vm.

The PAEK or PEEK preferably has a melt viscosity (MV) measured at 400°C of at least 0.05 kNsm -2, preferably has a MV of at least 0.10 kNsm -2, more preferably at least 0.15 kNsm -2. The PAEK or PEEK may have a MV of less than 1 .20 kNsm -2, suitably less than 1 .00 kNsm -2. The MV is measured using capillary rheometry operating at 400 °C at a shear rate of 1000 s - using a circular cross-section tungsten carbide die, 0.5 mm (capillary diameter) x 3.175 mm (capillary length). The MV measurement is taken once the polymer has fully melted, which is taken to be 5 minutes after the polymer is loaded into the barrel of the rheometer.

In some embodiments, the PAEK or PEEK may be compounded with one or more filler. The filler may include a fibrous filler or a non-fibrous filler. The filler may include both a fibrous filler and a non-fibrous filler. The fibrous filler may be continuous or discontinuous.

The fibrous filler may be selected from inorganic fibrous materials, non-melting and high-melting organic fibrous materials, such as aramid fibres, and carbon fibre.

The fibrous filler may be selected from glass fibre, carbon fibre, asbestos fibre, silica fibre, alumina fibre, zirconia fibre, boron nitride fibre, silicon nitride fibre, boron fibre, fluorocarbon resin fibre and potassium titanate fibre. Preferred fibrous fillers are glass fibre and carbon fibre. A fibrous filler may comprise nanofibers.

The non-fibrous filler may be selected from mica, silica, talc, hydroxyapatite (or hydroxylapatite), alumina, kaolin, calcium sulfate, calcium carbonate, titanium oxide, titanium dioxide, zinc sulfide, ferrite, clay, glass powder, zinc oxide, nickel carbonate, iron oxide, quartz powder, magnesium

carbonate, fluorocarbon resin, graphite (including graphite nanoplatelets and graphene), carbon black, carbon powder, nanotubes (e.g. carbon nanotubes) and/or barium sulfate. The non-fibrous fillers may be introduced in the form of powder or flaky particles.

Preferably, the filler comprises or is one or more fillers selected from glass fibre, carbon fibre, aramid fibres, carbon black and a fluorocarbon resin. More preferably, the filler comprises or is glass fibre or carbon fibre. Such filler preferably comprises or is glass fibre.

A filled PAEK or PEEK composition as described may include at least 20 wt%, or at least 40 wt% of filler. The filled PAEK or PEEK may include 70 wt% or less or 60 wt% or less of filler.

The invention also provides an article which comprises, consists essentially of, or consists of a PAEK or PEEK according to the invention or made by the process of the invention. The article may be a film, a stock shape such as a rod, or a machined article. The article may be an injection moulded article, a compression moulded article or an extruded article. The article may be formed using an additive manufacturing technique.

The invention also provides a method for manufacturing a three-dimensional object from a PAEK or PEEK by additive layer manufacturing, wherein the PAEK or PEEK comprises, consists of essentially, or consists of PAEK or PEEK according to the invention or made by the process of the invention.

Additive layer manufacturing techniques include any one or more of filament fusion, laser sintering, powder bed fusion, ThermoMELT™and micro pellet fusion.

The invention also provides a method for manufacturing a three-dimensional object from a powder by selective sintering by means of electromagnetic radiation, wherein the powder comprises, consists of essentially, or consists or PAEK or PEEK according to the invention or made by the process of the invention.

The invention also provides a film or tape formed of a composition comprising or consisting of PAEK according to the invention or made by the process of the invention. The film may be extruded and may have a thickness from 5μm to 100 μm or preferably from 5μm to 50 μm.

The PAEK or PEEK when as a film may have a gel/black speck level of less than 300ppm, preferably less than 250ppm, more preferably less than 200ppm, even more preferably less than 180ppm, when measured in accordance with Example 7.

The present invention also provides a pack comprising the PAEK or PEEK of the invention, preferably in the form of powder, pellets and/or granules.

The pack may include at least 1 kg, suitably at least 5kg, preferably at least 10kg, more preferably at least 14kg of material of the polymeric material. The pack may include 1000kg or less, preferably 500kg or less of the polymeric material. Preferred packs include 10 to 500kg of the polymeric material.

The pack may comprise packaging material (which is intended to be discarded or re-used) and a desired material (which suitably comprises the polymeric material). The packaging material preferably substantially fully encloses the desired material. The packaging material may comprise a first receptacle, for example a flexible receptacle such as a plastics bag in which the desired material is arranged. The first receptacle may be contained within a second receptacle for example in a box such as a cardboard box.

The invention also provides a pipe or sheath formed from a composition comprising or consisting of PAEK or PEEK according to the invention or made by the process of the invention.

The invention also provides a method for forming a pipe or sheath by extrusion of a composition comprising or consisting of PAEK according to the invention or made by the process of the invention.

According to a further aspect there is provided a polymeric material comprising a polyaryletherketone (PAEK),

wherein when said PAEK is dissolved in 1 %w/v aqueous sulphuric acid to prepare a resultant solution, said resultant solution exhibits an absorbance of less than 0.20 at a wavelength of light of 550nm, wherein said preparation of said resultant solution and measurement of its absorbance are carried out in accordance with Example 3.

It has surprisingly been found that the polymeric material has enhanced mechanical properties, colour characteristics and has a lower frequency of gels in comparison with known PAEKs.

The absorbance that a resultant solution, obtained by dissolving PAEK in sulphuric acid, exhibits at a wavelength of light of 550nm when measured in accordance with Example 3 is thought to correspond to the level of carbonyl branching of said PAEK i.e. branching that has occurred via reaction at a carbonyl carbon to form a branch point e.g. a triaryl carbinol. During Example 3 these branch points are converted to stable carbonium ions in the presence of sulphuric acid which gives rise to the absorbance at 550nm exhibited by resultant solutions of PAEKs with such branch points. The inventive polymeric material of the first aspect unexpectedly is thought to comprise lower levels of carbonyl branching than known polymeric materials.

Preferably said resultant solution exhibits an absorbance of less than 0.18, more preferably less than 0.16, even more preferably less than 0.14, most preferably less than 0.12, at a wavelength of light of 550nm when measured in accordance with Example 3. Said resultant solution may

exhibit an absorbance of greater than 0.02, preferably greater than 0.04, more preferably greater than 0.06, at a wavelength of light of 550nm when measured in accordance with Example 3.

In the following discussion of the invention, unless stated to the contrary, the disclosure of alternative values for the upper or lower limit of the permitted range of a parameter, coupled with an indication that one of said values is more highly preferred than the other, is to be construed as an implied statement that each intermediate value of said parameter, lying between the more preferred and the less preferred of said alternatives, is itself preferred to said less preferred value and also to each value lying between said less preferred value and said intermediate value.

References herein such as "in the range x to y" are meant to include the interpretation "from x to y" and so include the values x and y.

The following features are generally applicable to the present invention:

Preferably said PAEK comprises a repeat unit of formula:

wherein t1 and w1 independently represent 0 or 1 and v1 represents 0, 1 or 2.

Preferred PAEKs have a said repeat unit wherein t1 =1 , v1 =0 and w1 =0; t1 =0, v1 =0 and w1 =0; t1 =0, w1 =1 , v1 =2; or t1 =0, v1 =1 and w1 =0. More preferred have a repeat unit wherein t1 =1 , v1 =0 and w1 -0; or t1 =0, v1 =0 and w1 =0. The most preferred has a repeat unit wherein t1 =1 , v1 =0 and w1 =0.

In preferred embodiments, said PAEK is selected from polyetheretherketone, polyetherketone, polyetherketoneetherketoneketone and/or polyetherketoneketone, and/or a copolymer including polyetheretherketone and polyetherdiphenyletherketone. In a more preferred embodiment, said PAEK is selected from polyetherketone and/or polyetheretherketone, and/or a copolymer including polyetheretherketone and polyetherdiphenyletherketone. In an especially preferred embodiment, said PAEK is selected from polyetheretherketone, and/or a copolymer including polyetheretherketone and polyetherdiphenyletherketone.

Said PAEK suitably includes at least 50 mol%, (e.g. 50-99.8 mol%), preferably at least 60 mol% (e.g. 60-100 mol%), more preferably at least 68 mol% (e.g. 68 to 100 mol%), of repeat units of formula I, especially such units where t1 =1 , v1 =0 and w1 =0. In an especially preferred

embodiment, said PAEK includes at least 90 mol%, preferably at least 95 mol%, more preferably at least 98 mol%, especially at least 99 mol% of repeat units of formula I, especially repeat units of formula I wherein t1 =1 , v1 =0 and w1 =0. Other repeat units in said PAEK may be of formula I; or may include -Ph-Ph- moieties where Ph suitably represents an unsubstituted phenylene moiety (especially wherein both -Ph- moieties are 4,4'-substituted). Other repeat units may include Ph moieties bonded to two moieties selected from carbonyl moieties and ether moieties; and-Ph-Ph- moieties bonded to two ether moieties.

Said PAEK suitably includes at least 50 wt% (e.g. 50-100 wt%) of repeat units of formula I.

Said PAEK may be a copolymer which comprises a first moiety of formula I and a second moiety which includes -Ph-Ph- moieties where Ph represents an unsubstituted phenylene moiety (which suitably includes 4,4'-bonds to adjacent moieties).

In one embodiment, said PAEK may be selected from: a polymer comprising at least 98 mol% and/or comprising at least 98 wt% of a repeat unit of formula I, especially such units wherein t1 =1 , v1 =0 and w1 =0; and a copolymer which includes a repeat unit of formula

-O-Ph-O-Ph-CO-Ph- II

and a repeat unit of formula

-O-Ph-Ph-O-Ph-CO-Ph- III

wherein Ph represents a phenylene moiety.

Said PAEK preferably comprises at least 98 wt% (e.g. 98 to 99.9 wt%) of a repeat unit of formula I or a copolymer which includes repeat units of formulae II and III.

In said copolymer, said repeat units II and III are preferably in the relative molar proportions VI:VII of from 50:50 to 95:5, more preferably from 60:40 to 95:5, even more preferably from 65:35 to 95:5.

The phenylene moieties (Ph) in each repeat unit II and III may independently have 1 ,4- para linkages to atoms to which they are bonded or 1 ,3- meta linkages. Where a phenylene moiety includes 1 ,3- linkages, the moiety will be in the amorphous phase of the polymer. Crystalline phases will include phenylene moieties with 1 ,4- linkages. It is generally preferred for the PAEK to be highly crystalline and, accordingly, the PAEK preferably includes high levels of phenylene moieties with 1 ,4- linkages.

In a preferred embodiment, at least 95%, preferably at least 99%, of the number of phenylene moieties (Ph) in the repeat unit of formula II have 1 ,4-linkages to moieties to which they are bonded. It is especially preferred that each phenylene moiety in the repeat unit of formula II has 1 ,4- linkages to moieties to which it is bonded.

In a preferred embodiment, at least 95%, preferably at least 99%, of the number of phenylene moieties (Ph) in the repeat unit of formula III have 1 ,4-linkages to moieties to which they are bonded. It is especially preferred that each phenylene moiety in the repeat unit of formula III has 1 ,4- linkages to moieties to which it is bonded.

Preferably, the phenylene moieties in the repeat unit of formula II are unsubstituted. Preferably, the phenylene moieties in the repeat unit of formula III are unsubstituted.

Said repeat unit of formula II suitably has the structure:

Said repeat unit of formula III suitably has the structure:

Said copolymer may include at least 50 mol%, preferably at least 60 mol% of repeat units of formula IV. Particular advantageous copolymers may include at least 62mol%, or, especially, at least 64 mol% of repeat units of formula IV. Said copolymer may include less than 90 mol%, suitably 82mol% or less of repeat units of formula IV. Said copolymer may include 58 to 82 mol%, preferably 60 to 80 mol%, more preferably 62 to 77 mol% of units of formula IV.

Said copolymer may include at least 10 mol%, preferably at least 18 mol%, of repeat units of formula V. Said copolymer may include less than 42 mol%, preferably less than 39 mol% of repeat units of formula V. Particularly advantageous copolymers may include 38 mol% or less; or 36 mol% or less of repeat units of formula V. Said copolymer may include 18 to 42 mol%, preferably 20 to 40 mol%, more preferably 23 to 38 mol% of units of formula V.

The sum of the mol% of units of formula IV and V in said copolymer is suitably at least 95 mol%, is preferably at least 98 mol%, is more preferably at least 99 mol%.

Said polymeric material may be in a particulate form such as a powder, pellets or granules. Said powder may have a maximum dimension of less than 4.0mm, preferably less than 3.0mm, more preferably less than 2.5mm, but preferably of greater than 0.01 mm, more preferably of greater than 0.1 mm. Said pellets or granules may have a maximum dimension of less than 10mm, preferably less than 7.5mm, more preferably less than 5.0mm. Said pellets or granules may have an aspect ratio of maximum dimension:minimum dimension of 5:1 to 1 :1 , preferably 4:1 to 1 :1 , more preferably 3:1 to 1 .1 :1 , even more preferably 2:1 to 1 .1 :1 . Said powder, pellets or granules may include at least 95wt%, preferably at least 99wt%, especially about 100wt% of said polymeric material.

Preferably said polymeric material has a critical strain energy release rate (as tested in accordance with example 5) of at least 17.5Jm -2, preferably at least 17.8Jm -2, more preferably at least 18.0KJm -2.

Said polymeric material preferably has a melt viscosity (MV) measured at 400°C of at least 0.05 kNsm -2, preferably has a MV of at least 0.10 kNsm -2, more preferably at least 0.15 kNsm -2. Said polymeric material may have a MV of less than 1 .20 kNsm -2, suitably less than 1.00 kNsm -2. The MV is measured using capillary rheometry operating at 400°C at a shear rate of 1000s 1 using a circular cross-section tungsten carbide die, 0.5mm (capillary diameter) x 3.175mm (capillary length). The MV measurement is taken once the polymer has fully melted, which is taken to be 5 minutes after the polymer is loaded into the barrel of the rheometer.

In some embodiments, said polymeric material may further comprise one or more filler. Said filler may include a fibrous filler or a non-fibrous filler. Said filler may include both a fibrous filler and a non-fibrous filler. A said fibrous filler may be continuous or discontinuous.

A said fibrous filler may be selected from inorganic fibrous materials, non-melting and high-melting organic fibrous materials, such as aramid fibres, and carbon fibre.

A said fibrous filler may be selected from glass fibre, carbon fibre, asbestos fibre, silica fibre, alumina fibre, zirconia fibre, boron nitride fibre, silicon nitride fibre, boron fibre, fluorocarbon resin fibre and potassium titanate fibre. Preferred fibrous fillers are glass fibre and carbon fibre. A fibrous filler may comprise nanofibers.

A said non-fibrous filler may be selected from mica, silica, talc, hydroxyapatite (or hydroxylapatite), alumina, kaolin, calcium sulfate, calcium carbonate, titanium oxide, titanium dioxide, zinc sulphide, ferrite, clay, glass powder, zinc oxide, nickel carbonate, iron oxide, quartz powder, magnesium carbonate, fluorocarbon resin, graphite, carbon black, carbon powder, nanotubes (e.g. carbon nanotubes) and/or barium sulphate. The non-fibrous fillers may be introduced in the form of powder or flaky particles.

Preferably, said filler comprises one or more fillers selected from glass fibre, carbon fibre, aramid fibres, carbon black and a fluorocarbon resin. More preferably, said filler comprises glass fibre or carbon fibre. Such filler preferably comprises glass fibre.

The polymeric material as described may include at least 20 wt%, or at least 40 wt% of filler. Said polymeric material may include 70 wt% or less or 60 wt% or less of filler.

The PAEK of the polymeric material may have a polydispersity index (PDI) of less than 2.6, when measured in accordance with Example 4. Preferably said PAEK has a polydispersity index (PDI) of less than 2.5, more preferably less than 2.4, even more preferably less than 2.3, most preferably less than 2.2, when measured in accordance with Example 4.

The polymeric material, wherein said polymeric material is in the form of melt-filtered granules, may have a lightness L* of greater than 56.0, an a* coordinate of greater than 1 .3 but less than 5.0, and a b* coordinate of greaterthan 6.5 but less than 10.0. Preferably said polymeric material has a lightness L* of greater than 58.0, more preferably greater than 59.0, even more preferably greater than 60.0, most preferably greater than 61 .0. Preferably said polymeric material has an a* coordinate of greater than 1 .5 but less than 3.5, more preferably greater than 1 .8 but less than 3.0, even more preferably greater than 2.0 but less than 2.5, most preferably greater than 2.1 but less than 2.4. Preferably said polymeric material has a b* coordinate of greater than 6.7 but less than 9.0, more preferably greater than 7.0 but less than 8.7, even more preferably greater than 7.2 but less than 8.5, most preferably greater than 7.4 but less than 8.4. In a preferred embodiment said polymeric material has a lightness L* of greater than 60.0, an a* coordinate of greater than 2.0 but less than 2.5, and a b* coordinate of greater than 7.2 but less than 8.5. In a more preferred embodiment said polymeric material has a lightness L* of greater than 61 .0, an a* coordinate of greater than 2.1 but less than 2.4, and a b* coordinate of greater than 7.4 but less than 8.4.

The PAEK of the polymeric material may exhibit an absorbance of less than 0.20 at a wavelength of light of 550nm when measured in accordance with Example 3. Preferably said PAEK exhibits an absorbance of less than 0.18, more preferably less than 0.16, even more preferably less than 0.14, most preferably less than 0.12, at a wavelength of light of 550nm when measured in accordance with Example 3. Said PAEK may exhibit an absorbance of greater than 0.02, preferably greater than 0.04, more preferably greater than 0.06, at a wavelength of light of 550nm when measured in accordance with Example 3.

There is further provided an article which comprises, preferably consists essentially of, a polymeric material according to any of the previous aspects or made in the process of the sixth aspect. Said article may be a film, a stock shape such as a rod, or a machined article. Said article may be an injection moulded article, a compression moulded article or an extruded article.

Said film may have a gel/black speck level of less than 300ppm, preferably less than 250ppm, more preferably less than 200ppm, even more preferably less than 180ppm, when measured in accordance with Example 7.

There is also provided a pack comprising a polymeric material, preferably in the form of powder, pellets and/or granules, as described above.

Said pack may include at least 1 kg, suitably at least 5kg, preferably at least 10kg, more preferably at least 14kg of material of said polymeric material. Said pack may include 1000kg or less, preferably 500kg or less of said polymeric material. Preferred packs include 10 to 500kg of said polymeric material.

Said pack may comprise packaging material (which is intended to be discarded or re-used) and a desired material (which suitably comprises said polymeric material). Said packaging material preferably substantially fully encloses said desired material. Said packaging material may comprise a first receptacle, for example a flexible receptacle such as a plastics bag in which said desired material is arranged. The first receptacle may be contained within a second receptacle for example in a box such as a cardboard box.

According to a further aspect there is provided a process for producing a polymeric material comprising a polyaryletherketone (PAEK), the process comprising the following steps:

a. polycondensing one or more bisphenol with one or more dihalobenzenoid compound, in the presence of

i. less than 0.005 molar ratio of potassium carbonate, and

ii. one or more carbonate of an alkali metal other than potassium carbonate,

in a reactor; and

b. isolating the PAEK.

The said molar ratio of potassium carbonate may be defined as:

the number of moles of potassium carbonate used in step a of the process

the total number of moles of bisphenol used in step a of the process

It has surprisingly been found that the process of the further aspect described above provides a PAEK with excellent mechanical and colour properties and contains fewer gels in comparison with known PAEKs.

Preferably step a of the process is carried out in the presence of less than 0.0045 molar ratio of potassium carbonate, more preferably less than 0.0040 molar ratio of potassium carbonate, even more preferably less than 0.0036 molar ratio of potassium carbonate, most preferably less than 0.0032 molar ratio of potassium carbonate. Preferably step a of the process is carried out in the presence of greater than 0.0001 molar ratio of potassium carbonate, more preferably greater than 0.0010 molar ratio of potassium carbonate, even more preferably greater than 0.0020 molar ratio of potassium carbonate, most preferably greater than 0.0025 molar ratio of potassium carbonate. These preferred ranges provide benefits in terms of increased speed of reaction whilst avoiding side reactions that can occur if the rate of reaction is too high.

Said one or more carbonate of an alkali metal other than potassium carbonate may comprise sodium carbonate, sodium bicarbonate, and/or potassium bicarbonate, preferably sodium carbonate.

The total molar ratio of said one or more carbonate of an alkali metal other than potassium carbonate may be at least 0.95, preferably at least 1 .00, more preferably at least 1 .02, most preferably at least 1 .03. The said total molar ratio of said one or more carbonate of an alkali metal other than potassium carbonate is defined as the total number of moles of said one or more carbonate of an alkali metal other than potassium carbonate used in step a of the process divided by the total number of moles of bisphenol used in step a of the process. The total molar ratio of said one or more carbonate of an alkali metal other than potassium carbonate may be less than 1 .15, preferably less than 1 .10, more preferably less than 1 .07, most preferably less than 1 .05.

The total molar ratio of carbonates (i.e. the total number of moles of carbonates used in step a of the process divided by the total number of moles of bisphenol used in step a of the process) is suitably at least 1 .00, preferably at least 1 .02, more preferably at least 1 .03, but preferably at most 1 .10, more preferably at most 1 .06, even more preferably at most 1 .05. The term "carbonates" is intended to encompass carbonate (CO32 ) and bicarbonate (HCO3 ).

Where step a of the process is carried out in the presence of sodium carbonate, the molar ratio of sodium carbonate used in step a of the process may be greater than 0.95, preferably greater than 1 .00, more preferably greater than 1 .01 , most preferably greater than 1.02. The said molar ratio of sodium carbonate is defined as the number of moles of sodium carbonate used in step a of the process divided by the total number of moles of bisphenol used in step a of the process. The molar ratio of sodium carbonate may be less than 1 .15, preferably less than 1 .10, more preferably less than 1 .06, most preferably less than 1 .04.

The molar ratio of carbonates other than sodium carbonate and potassium carbonate used in step a of the process is preferably less than 0.05, more preferably less than 0.01 (again related to the moles of bisphenol used in step a of the process).

Preferably, the only carbonates used in step a of the process are sodium carbonate and potassium carbonate.

Step a of the process may be carried out in the presence of a salt A selected from lithium chloride, calcium chloride, magnesium chloride, lithium bromide, lithium iodide and/or lithium sulphate, preferably lithium chloride. Where step a of the process is carried out in the presence of a salt A, preferably lithium chloride, the molar equivalents of salt A (relative to the moles of potassium carbonate present in step a of the process) may be at least 1 .0 molar equivalents, preferably at least 4.0 molar equivalents, more preferably at least 6.0 molar equivalents, most preferably at least 7.0 molar equivalents. The molar equivalents of salt A may be less than 15.0 molar equivalents, preferably less than 12.0 molar equivalents, more preferably less than 10.0 molar equivalents, most preferably less than 9.0 molar equivalents.

The process is preferably carried out in the presence of a solvent. The solvent may be of formula

where W is a direct link, an oxygen atom or two hydrogen atoms (one attached to each benzene ring) and Z and Z', which may be the same or different, are hydrogen atoms or phenyl groups. Examples of such aromatic sulphones include diphenylsulphone, dibenzothiophen dioxide, phenoxanthin dioxide and 4-phenylsulphonyl biphenyl. Diphenylsulphone is a preferred solvent. Step a of the process is preferably carried out in the presence of diphenylsulphone.

Step a of the process may be carried out in the presence of a substantially equimolar ratio of said one or more bisphenol and said one or more dihalobenzoid compound. Preferably step a of the process is carried out in the presence of a molar ratio of dihalobenzoid compound of at least 1 .00, preferably at least 1 .01 , more preferably at least 1 .02, but preferably at most 1 .07, more preferably at most 1.05, even more preferably at most 1 .04. The said molar ratio of dihalobenzoid compound is defined as the number of moles of dihalobenzoid compound used in step a of the process divided by the total number of moles of bisphenol used in step a of the process.

Said one or more bisphenol may comprise hydroquinone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 1 ,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and/or 1 ,6-dihydroxynaphthalene. Preferably said one or more bisphenol comprises hydroquinone, 4,4'-dihydroxybenzophenone and/or 4, 4'-dihydroxybiphenyl.

Said one or more dihalobenzenoid compound may comprise 4,4'-dichlorobenzophenone, 4-chloro-4'-fluorobenzophenone, 4,4'-difluorobenzophenone, 1 ,4-bis(4'-fluorobenzoyl)benzene) and/or 1 ,3-bis(4'-fluorobenzoyl)benzene. Preferably said one or more dihalobenzenoid compound comprises 4,4'-difluorobenzophenone and/or 1 ,4-bis(4'-fluorobenzoyl)benzene). Most preferably said one or more dihalobenzenoid compound comprises 4,4'-difluorobenzophenone.

Step a of the process is preferably carried out under substantially anhydrous conditions. Step a is preferably carried out with stirring of the contents of the reactor. The contents of the reactor comprise any components that are present in the reactor. Step a of the process may be carried out at a temperature of from 100°C to 390°C, preferably from 120°C to 350°C, more preferably from 130°C to 320°C. Preferably step a of the process is carried out at a temperature that increases to a maximum temperature of greater than 280°C, more preferably greater than 290°C, even more preferably greater than 300°C, but preferably less than 350°C, more preferably less than 330°C, even more preferably less than 320°C. Preferably the temperature increases at a rate of greater than 0.25°C/min, more preferably greater than 0.50°C/min, even more preferably greater than 0.70°C/min, but preferably less than 1 .50°C/min, more preferably less than 1 .25°C/min, even more preferably less than 1 .10°C/min. Preferably, however, prior to reaching the maximum temperature, step a of the process may further comprise one or more periods of time during which the temperature remains constant. For example, step a of the process may further comprise one or more periods of time (e.g. for at least 20 minutes) during which the temperature is constant and within the range 170-210°C; and/or during which the temperature is constant within the range 210 to 240°C.

In step a of the process said one or more bisphenol and said one or more dihalobenzenoid compound are preferably brought into contact with each other prior to contacting said potassium carbonate and said one or more carbonate of an alkali metal other than potassium carbonate. Said one or more bisphenol and said one or more dihalobenzenoid compound are preferably brought into contact with each other in the presence of a solvent, preferably diphenylsulphone.

Preferably in step a, prior to reaching the maximum temperature, greater than 1 .000 molar ratio, more preferably greater than 1 .003 molar ratio, even more preferably greater than 1 .005 molar ratio, but preferably less than 1 .012 molar ratio, more preferably less than 1 .010 molar ratio, even more preferably less than 1 .009 molar ratio, of said one or more dihalobenzenoid compound is brought into contact with said one or more bisphenol.

Preferably in step a, after the maximum temperature is reached, said maximum temperature is maintained until a desired molecular weight of the PAEK has been reached. Said desired molecular weight may be indicated by reaching a desired stirrer torque rise. A relationship can be obtained between the molecular weight of the polymer in solution and the torque experienced by a stirrer motor. This is for a defined mass, polymer concentration and temperature. Based on this relationship, a torque rise can be predicted for a desired molecular weight (number average or weight average molecular weight).

Preferably, once said desired molecular weight of the PAEK has been reached, one or more end-capping agent may be added to the reactor. Said end-capping agent may be selected from one or more of a monohalobenzenoid compound such as 4-fluorobenzophenone or monochlorodiphenylsulphone, a dihalobenzenoid compound such as 4,4'-difluorobenzophenone or dichlorodiphenylsulphone, methyl chloride and/or difluorodiketone. Said end-capping agent is preferably selected from 4,4'-difluorobenzophenone and/or 4-fluorobenzophenone. Said end-capping agent is preferably arranged to react with and replace the OH moieties of said bisphenols where present. Said end-capping agent is preferably arranged to end-cap the PAEK produced in the process. As a result, ends of the PAEK suitably include halogen atoms, preferably fluorine atoms, which suitably help to stabilise the PAEK. Preferably greater than 0.004 molar ratio, more preferably greater than 0.006 molar ratio, even more preferably greater than 0.008 molar ratio, most preferably greater than 0.009 molar ratio of end-capping agent is added to the reactor. Preferably less than 0.040 molar ratio, more preferably less than 0.030 molar ratio, even more preferably less than 0.025 molar ratio, most preferably less than 0.022 molar ratio of end-capping agent is added to the reactor. Said molar ratio of end-capping agent is defined as the number of moles of end-capping agent used in step a of the process divided by the total number of moles of bisphenol used in step a of the process.

Preferably said salt A, preferably lithium chloride, is added to the reactor once said desired molecular weight of PAEK has been reached. Said salt A, preferably lithium chloride, may be added to the reactor before said end-capping agent, at the same time as said end-capping agent or after said end-capping agent. Preferably said salt A, preferably lithium chloride, is added to the reactor before said end-capping agent or at the same time as said end-capping agent.

In a preferred embodiment step a of the process comprises:

a. polycondensing one or more bisphenol with one or more dihalobenzenoid compound, in the presence of

greater than 0.0025 molar ratio but less than 0.0036 mole% of potassium carbonate, and i. greater than 1 .01 molar ratio but less than 1 .06 molar ratio of sodium carbonate, n a reactor;

wherein step a of the process is carried out in the presence of diphenylsulphone;

wherein step a of the process is carried out at a temperature of from 130°C to 320°C, and is carried out at a temperature that increases to a maximum temperature of greater than 290°C but less than 320°C;

wherein prior to reaching said maximum temperature, greater than 1.005 molar ratio, but less than 1 .010 molar ratio of said one or more dihalobenzenoid compound is brought into contact with said one or more bisphenol;

wherein after the maximum temperature is reached, said maximum temperature is maintained until a desired molecular weight of the PAEK has been reached;

wherein once said desired molecular weight of the PAEK has been reached, one or more end-capping agent is added to the reactor;

wherein greater than 0.009 molar ratio but less than 0.025 molar ratio of end-capping agent is added to the reactor;

wherein step a of the process is carried out in the presence of at least 6.0 molar equivalents but less than 10.0 molar equivalents of lithium chloride;

wherein said lithium chloride is added to the reactor once said desired molecular weight of the PAEK has been reached; and

wherein said lithium chloride is added to the reactor before said end-capping agent or at the same time as said end-capping agent.

In said preferred embodiment preferably said one or more bisphenol comprises hydroquinone, 4,4'-dihydroxybenzophenone and/or 4,4'-dihydroxybiphenyl. In said preferred embodiment preferably said one or more dihalobenzenoid compound comprises 4,4'-difluorobenzophenone. In said preferred embodiment preferably said end-capping agent comprises a dihalobenzenoid compound, most preferably 4, 4'-difluorobenzophenone.

The process is preferably for producing a polymeric material of any of the first to fourth aspects.

Preferably the polymeric material according to any of the first to fourth aspects is obtainable by or obtained by the process of the seventh aspect.

According to another aspect of the present invention there is provided a use of the process according to the seventh aspect to provide a PAEK with an increased lightness L*, when measured in accordance with Example 6 and with reference to the 1976 CIE L* a* b* colour space.

Any invention described herein may be combined with any feature of any other invention described herein mutatis mutandis.

It will be appreciated that optional features applicable to one aspect of the invention can be used in any combination, and in any number. Moreover, they can also be used with any of the other aspects of the invention in any combination and in any number. This includes, but is not limited to, the dependent claims from any claim being used as dependent claims for any other claim in the claims of this application.

The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.

Each feature disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

Specific embodiments of the invention will now be described, by way of example, and with reference to the accompanying figures in which:

Figure 1 is a graph showing the absorbance at 550nm of a solution of a number of inventive and comparative PEEKs as tested in accordance with Example 3;

Figure 2 is a graph showing the PDI of a number of inventive and comparative PEEKs as tested in accordance with Example 4;

Figure 3a is a graph showing the critical strain energy release of a number of inventive and comparative PEEKs as tested in accordance with Example 5;

Figure 3b is a graph showing the stress intensity factor K1c of a number of inventive and comparative PEEKs as tested in accordance with Example 5;

Figure 4 is a graph showing the lightness (L*) of a number of discs injection moulded from inventive and comparative PEEK powders as tested in accordance with Example 6;

Figure 5 is a graph showing the lightness (L*) of granules of a number of inventive and comparative PEEKs as tested in accordance with Example 6; and

Figure 6 is a graph showing the gel/black speck content of films extruded from a number of inventive and comparative PEEKs as tested in accordance with Example 7.

The following materials are referred to hereinafter:

PEEK-0.45-P - PEEK powder having a Melt Viscosity of 0.45 kNsm -2 at 400°C obtained from Victrex Manufacturing Ltd.

PEEK-0.45-G - PEEK granules having a Melt Viscosity of 0.45 kNsm -2 at 400°C obtained from Victrex Manufacturing Ltd.

PEEK-0.65-P - PEEK powder having a Melt Viscosity of 0.65 kNsm -2 at 400°C obtained from Victrex Manufacturing Ltd.

PEEK-0.65-G - PEEK granules having a Melt Viscosity of 0.65 kNsm -2 at 400°C obtained from Victrex Manufacturing Ltd.

KT810P - Ketaspire KT810P (TM) PEEK powder sold by Solvay.

KT820 - Ketaspire KT820 (TM) PEEK granules sold by Solvay.

L4000G - Vestakeep (TM) L4000G PEEK granules sold by Evonik Degussa.

5000G - Vestakeep (TM) 5000G PEEK granules sold by Evonik Degussa.

The comparative PEEK samples made by Victrex Manufacturing Limited were made by a process equivalent to that disclosed in Example 3 of EP3049457A.

The comparative samples from the manufacturers Solvay and Evonik Degussa were made by their proprietary processes, the details of which are not known.

Example 1 - Preparation of Polyetheretherketone (PEEK)

The following describes the preparation of PEEK by a process according to the invention on a laboratory scale. 4,4'-difluorobenzophenone (109.84 g, 0.504 mol), hydroquinone (55.06 g, 0.500 mol) and diphenyl sulfone (225.43 g, 1 .033 mol) were weighed into a 0.5 L flask and subjected to an inert nitrogen atmosphere at room temperature overnight. Reactants were then heated to 150°C. During this time the reagents were stirred at 20 rpm for 20 minutes, prior to increasing stirrer speed to 70 rpm for the remainder of the reaction.

Sodium carbonate (54.59 g, 0.515 mol) and potassium carbonate (0.242 g, 1 .75 mmol) were added to the reaction mixture over a two minute time period. The reaction temperature was increased to 312°C at 1 °C min -1. A temperature of 312°C was maintained until the desired stirrer torque rise was observed.

At this point, lithium chloride (0.595 g, 0.014 mol) was added in one portion, and immediately afterwards, 4,4'-difluorobenzophenone (2.18 g, 0.010 mol) was added in one portion in order to control molecular mass. After a further thirty minutes, the opaque off-white coloured crude product was discharged from the vessel onto a metal tray to cool and solidify.

Once cool, the crude product was milled into a coarse powder (< 2 mm maximum dimension). The powder was suspended in acetone in a separating column, and washed with acetone to remove organic impurities, namely diphenyl sulfone solvent. Acetone (~ 1 L) was slowly passed through the column until diphenyl sulfone solvent no longer precipitated out of organic wash on addition of water. The remaining product was then washed with cold deionised water to remove acetone (~ 1 L), prior to hot deionised water (~ 2 L) to remove aqueous by products. Once the conductivity of leachate was measured to be < 2 με using a conductivity probe, the material remaining in the column was dried in an oven overnight, yielding an off-white powder product.

The process above was scaled up to plant scale (based on 386 kg of hydroquinone) in order to obtain 8 batches of PEEK of varying melt viscosities as shown in Table 1 below and as measured according to Example 2. In addition, a portion of five of the eight batches was melt filtered using a single screw extruder (screw speed of 90-1 10 rpm) and a 20 micrometre pore, 15 x 7 inch (17.8 cm) Capsule PEEK Filter Housing (available from Porvair Filtration Group Ltd). The melt filtration was carried out at a rate of 50 kg/hr with extruder barrel and die temperatures of 350-390°C. Upon extrusion the melt filtered material was cooled and chopped to obtain cylindrical granules of 2.0 to 3.5 mm diameter and 2.0 to 4.0 mm length.

CLAIMS
1 . A process for producing polyaryletherketone, PAEK, the process comprising:
a nucleophilic polycondensation of a bisphenol with an organic dihalide compound in a reaction mixture comprising sodium carbonate and potassium carbonate, in an aromatic sulfone solvent, at a reaction temperature rising to a temperature from 290°C to 320°C immediately prior to;

b addition of a salt to the reaction mixture, wherein the molar ratio of the salt to potassium carbonate is from 6.0 to 10.0;

c addition of further organic dihalide compound to the reaction mixture, simultaneously with or subsequent to step b, wherein the molar ratio of further organic dihalide compound to bisphenol is from 0.009 to 0.035;

d maintenance of the resulting reaction mixture's temperature at from 290°C to 320°C for from 20 to 180 minutes;

e cooling of the resulting reaction mixture and recovery of the PAEK resulting from steps a to d from the reaction mixture;

wherein in step a of the process:

i the molar ratio of sodium carbonate to bisphenol is from 0.95 to 1 .15;

ii the molar ratio of potassium carbonate to sodium carbonate is from 0.0025 to 0.0040; and

iii the molar ratio of organic dihalide compound to bisphenol is from 1 .005 to 1 .010.

2. A process according to claim 1 wherein the aromatic sulfone solvent is diphenylsulfone.

3. A process according to claim 1 or claim 2 wherein the process is for producing a PAEK that is homopolymer polyetheretherketone;

wherein the bisphenol is hydroquinone; and

wherein the organic dihalide compound and the further organic dihalide compound are 4,4'-difluorobenzophenone.

4. A process according to any preceding claim, wherein the salt is an alkali metal salt or a alkaline earth metal salt, and optionally, wherein the salt is selected from lithium chloride, calcium chloride, magnesium chloride, lithium bromide, lithium iodide and/or lithium sulphate.

5. A process according to any preceding claim wherein the salt is lithium chloride or is lithium sulphate.

6. A polyaryletherketone, PAEK, comprising residual impurities of aromatic sulfone solvent, sodium salt and organic dihalide monomer from its formation by nucleophilic polycondensation;

wherein when the PAEK is dissolved in concentrated sulfuric acid to prepare a resultant solution with 1 g of the PAEK per 100ml of the resulting solution, the resultant solution has an absorbance contribution from the PAEK of less than 0.20 at a wavelength of light of 550nm.

7. A PAEK according to claim 6 wherein the PAEK has a polydispersity index PDI = MW/MN, based on polystyrene equivalent molecular masses, of less than 2.5;

wherein Mw = weight average molecular mass and Mn = number average molecular mass.

8. A PAEK according to claim 6 or claim 7 wherein when the PAEK is in the form of a sample with planar surface, injection moulded from the PAEK as a powder,

the planar surface has:

a lightness L* of greater than 65.0;

an a* coordinate of greater than 0.2 but less than 5.0;

a b* coordinate of greater than 5.0 but less than 12.0;

with reference to the 1976 CIE L* a* b* colour space.

9. The PAEK according to any one of claims 6 to 8, wherein the PAEK is homopolymer polyetheretherketone, PEEK, with repeat units consisting of formula II:

-O-Ph-O-Ph-CO-Ph- II

or a copolymer with repeat units consisting repeat units of formula II and repeat units of formula III:

-O-Ph-Ph-O-Ph-CO-Ph- III.

10. A PAEK of any one of claims 6 to 9 wherein the PAEK is homopolymer PEEK.

1 1 . A homopolymer PEEK according to claim 10 wherein the PEEK has an extractable concentration of 0.05 mg/kg or less of residual 4,4'-difluorobenzophenone, when immersed in Miglyol 812 at 175°C for six hours.

12. A homopolymer PEEK according to claim 10 or claim 11 wherein the PEEK has residual diphenylsulfone present as 0.063% or less by weight.

13. A homopolymer PEEK according to any one of claims 10 to 12, wherein the PEEK has a critical strain energy release rate of at least 17.5 Jm -2.

14. An enclosure for a portable electronic device composing a PAEK according to any ons of claims 4 to 7 or comprising a homopolymer PEEK according to any one of claims 10 to 13.

15. A pipe comprising a PAEK according to any one of claims 6 to 9 or composing a homopoiymer PEEK according to any one of claims 10 to 13.

16. A wire wrap comprising a PAEK according to any one of claims 46 to 3 or comprising a homopoiymer PEEK according to any one of claims 10 to 13.

17, A film or a tape comprising or consisting of a PAEK according to any ons of claims 6 to S or comprising a homopoiymer PEEK according to any ons of claims 10 to 13.

18. A device formed moulded or machined from a composition comprising or consisting of a PAEK according to any one of claims 6 to 9 or comprising a homopoiymer PEEK according to any one of claims 10 to 13.

19. The use of a PAEK according to any one of claims 6 to 8 or a homopoiymer PEEK according tc any one of claims 10 to 13 in a component intended to contact food.

20. A pipe or sheath formed from a composition comprising or consisting of PAEK according to any one of claims 6 to 9 or formed from a composition comprising or consisting of a homopoiymer PEEK according to any one of claims 10 to 13.

21. A method for forming a pipe or sheath by extrusion of a composition comprising or consisting of PAEK according to any one of claims 6 to 9 or formed from s composition comprising or consisting of a homopolymer PEEK according to any one of claims 10 to 13.