COPOLYMERS, THEIR PREPARATION AND USE

Abstract

This invention relates to copolymers which consist essentially of [-ether-phenyl-ether-phenyl-carbonyl-phenyl-]and [ether-phenyl-phenyl-ether-phenyl-carbonyl-phenyl-] repeat units, as well as end units, which have reduced melting temperature (Tm) compared to prior art copolymers including such repeat units. The copolymers of the invention exhibit crystallinity and have similar glass transition temperatures to the prior art polymers.

Claims

1. A copolymer consisting essentially of repeat units of formula I:
—O—Ph—O—Ph—CO—Ph—  I and repeat units of formula II: ##STR00012## and end units, wherein the molar ratio of repeat units of formula Ito repeat units of formula II is from 55:45 to 95:5; and wherein the repeat units of formula I consist essentially of 50 to 90 molar % of repeat units of formula III: ##STR00013## and 10 to 50% by molar % of repeat units which are of formula IV, of formula V or of a mixture thereof; wherein the repeat unit of formula IV is: ##STR00014## and the repeat unit of formula V is: ##STR00015##

2. A copolymer according to claim 1 wherein the molar ratio of repeat units of formula Ito repeat units of formula II is from 60:40 to 90:10.

3. A copolymer according to claim 1 wherein the repeat units of formula I consist essentially of 65 to 90% molar % of repeat units of formula III in combination with 10 to 35 molar % of repeat units which are of formula IV, of formula V, or of a mixture thereof.

4. A copolymer according to claim 3 wherein the repeat units of formula I consist essentially of 80 to 90% molar % of repeat units of formula III in combination with 10 to 20 molar % of repeat units which are of formula IV, of formula V, or of a mixture thereof.

5. A copolymer according to claim 1 wherein the molar ratio of repeat units of formula I to repeat units of formula II is from 90:10 to 80:20 and wherein the repeat units of formula I consist essentially of 80 to 90% molar % of repeat units of formula III in combination with 10 to 20 molar % of repeat units which are of formula IV, of formula V, or of a mixture thereof.

6. A copolymer according to claim 1 wherein the copolymer does not include repeat units of formula IV.

7. A copolymer according to claim 1 wherein the copolymer does not include repeat units of formula V.

8. A copolymer according to claim 1 wherein the end units are the same as the repeat units of the copolymer but terminated with a terminal —OH or —F moiety.

9. A copolymer according to claim 1 wherein the end units include ##STR00016## as end units in addition to end units which are the same as the repeat units of the copolymer but terminated with a terminal —OH or —F moiety.

10. A process for producing a copolymer according to claim 1, the process comprising polycondensing 4,4′-difluorobenzophenone with a mixture of dihydroxy compounds consisting of 1,4-dihydroxybenzene, 4,4′-dihydroxydiphenyl and at least one of 1,3-dihydroxybenzene and 1,2-dihydroxybenzene; wherein the dihydroxy compounds are in the molar proportions required to provide the copolymer of the first aspect of the invention; wherein the molar ratio (4,4′-difluorobenzophenone)/(dihydroxy compounds) is from 1.005 to 1.05; and wherein the polycondensation is carried out in an aromatic sulfone solvent in the presence of particulate sodium carbonate and potassium carbonate.

11. A process according to claim 10 wherein the polycondensation is stopped with a lithium salt and wherein the copolymer is end-capped by addition of further 4,4′-difluorobenzophenone.

12. A process according to claim 10, wherein either a) after polycondensation, an additive is added to a reaction mixture and stirred for at least five minutes; and optionally, wherein the additive is a polyaryletherketone, PAEK, the PAEK having a melting temperature of at least 20° C. above a melting temperature of the copolymer, as determined by Differential Scanning calorimetry, wherein the PAEK comprises 0.1% to 10% by total weight of the reaction mixture; or b) after a purification step, an additive is added to the copolymer in a melt-compounding process to form a composition; and optionally, wherein the additive is a polyaryletherketone, PAEK, the PAEK having a melting temperature of at least 20° C. above a melting temperature of the copolymer, as determined by Differential Scanning calorimetry, wherein the PAEK comprises 0.1% to 10% by total weight of the composition.

13. An additive manufacturing process comprising extruding a filament of the copolymer of claim 1 through a print-head onto a base plate.

14. A method for manufacturing a three-dimensional component from a powder by selective sintering by means of electromagnetic radiation, wherein the powder comprises, consists essentially of, or consists of a copolymer according to claim 1.

15. A powder comprising, consisting essentially of, or consisting of a copolymer according to claim 1 as a building material for manufacture of a three-dimensional component from the powder by selective sintering of the powder by means of electromagnetic radiation.

16. A moulded or extruded component, comprising, consisting essentially of, or consisting of a copolymer according to claim 1.

17. A method of reducing isothermal crystallisation time, where the isothermal crystallisation time is determined by Differential Scanning calorimetry, the method comprising: a) selecting a copolymer according to claim 1, and selecting a polyaryletherketone, PAEK, the PAEK having a melting temperature at least 20° C. above a melting temperature of the copolymer, and melt processing the copolymer and the PAEK to form a composition, wherein the copolymer comprises 90% to 99.9% by weight of the composition and the PAEK comprises 0.1% to 10% by weight of the composition.

18. A copolymer according to claim 1 wherein the molar ratio of repeat units of formula Ito repeat units of formula II is from 70:30 to 90:10.

19. A copolymer according to claim 1 wherein the molar ratio of repeat units of formula Ito repeat units of formula II is from 80:20 to 90:10.

Description

[0087] Specific embodiments of the invention will now be described.

[0088] Copolymers were prepared as described in Example 1 to 32. In the preparations, the progress of the copolymerisation was monitored by measuring the torque applied to the reaction stirrer. As the copolymer molecular weight (degree of polymerisation) increases, the torque rises. The reaction was terminated, as explained below, when a target torque was reached, or after 60 minutes if the target torque was not reached by then. As the polymer molecular mass increases, so does the solution viscosity in the reaction mixture, resulting in an increase in torque at the reaction stirrer. The target torque was a value which would have been expected to give an MV for PEEK from around 0.15 to around 0.45 kNsm.sup.−2 under similar reaction conditions for preparation of PEEK. Examples 34 and 35 provide details on procedures and tests undertaken on the copolymers of the Examples.

[0089] The copolymers of Examples 1 to 3 are not according to the invention, whereas the copolymers of Examples 4 to 32 are according to the invention.

Example 1—Preparation of 0.5 mol Polyetheretherketone PEEK-PEDEK Copolymer (R.SUB.PEEK.:R.SUB.PEDEK.=90:10)

[0090] A 0.5 litre flanged flask fitted with a ground glass lid, stirrer/stirrer guide, nitrogen inlet and outlet was charged with 4,4′-difluorobenzophenone (111.56 g, 0.511 mol), 1,4-dihydroxybenzene (49.55 g, 0.450 mol), 4,4′-dihydroxydiphenyl (9.31 g, 0.050 mol) and diphenylsulphone (314.94g) and purged with nitrogen for 1 hour. The contents were then heated under a nitrogen blanket to 150° C. to form an almost colourless solution. While maintaining a nitrogen blanket, dried sodium carbonate (53.42 g, 0.504 mol) and potassium carbonate (2.764 g, 0.02 mol), both sieved through a screen with a mesh size of 500 micrometres, were added. The temperature was raised to 180° C. at 1° C./min and held for 100 minutes. The temperature was raised to 200° C. at 0.5° C./min; the temperature was then raised to 305° C. at 1° C./min and held for approximately 60 minutes or until the desired degree of polymerisation was reached as indicated by the torque rise on the stirrer. The reaction mixture was then poured into a foil tray, allowed to cool, milled and washed with 2 litres of acetone and then with warm water at a temperature of 40-50° C. until the conductivity of the waste water was <2 μS. The resulting polymer powder was dried in an air oven for 12 hours at 120° C.

Examples 2 to 3—Preparation of Further PEEK-PEDEK Copolymers

[0091] The procedure described in Example 1 was repeated except that the quantities of 1,4-dihydroxybenzene and 4,4′-dihydroxydiphenyl were varied to provide polyetheretherketone (PEEK)—polyetherdiphenyletherketone (PEDEK) copolymers of ratios of PEEK components relative to PEDEK components as shown in Table 1.

TABLE-US-00001 TABLE 1 Mass of 1,4- Mass of 4,4′- dihydroxybenzene dihydroxydiphenyl Example R.sub.PEEK:R.sub.PEDEK (g) (g) 2 75:25 41.29 23.38 3 60:40 33.03 37.24

Example 4 to 9—Preparation of PEEK-oPEEK-PEDEK Copolymer Including 1,2-dihydroxybenzene as Comonomer (Providing R.SUB.oPEEK .Repeat Units)

[0092] The procedure described in Example 1 was repeated except that 1,2-dihydroxybenzene was used in conjunction with 1,4-dihydroxybenzene with the total ratio of dihydroxybezene to 4,4′-dihydroxydiphenyl being varied to provide polyetheretherketone PEEK-oPEEK-PEDEK copolymers with ratios of PEEK:oPEEK:PEDEK repeat units as set out in Table 2.

TABLE-US-00002 TABLE 2 Mass of 1,4- Mass of 1,2- Mass of 4,4′- Ratio of dihydroxybenzene dihydroxybenzene dihydroxydiphenyl Example R.sub.PEEK:R.sub.oPEEK:R.sub.PEDEK (g) (g) (g) 4 80:10:10 44.04 5.51 9.31 5 60:30:10 33.03 16.52 9.31 6 50:10:40 27.53 5.51 37.24 7 30:30:40 16.52 16.52 37.24 8 65:10:25 35.79 5.51 23.28 9 55:20:25 30.28 11.01 23.28

Examples 10 to 13—Preparation of PEEK-mPEEK-PEDEK Copolymer Including 1,3-dihydroxybenzene Comonomer (Providing R.SUB.mPEEK .Repeat Units)

[0093] The procedure described in Example 1 was repeated except that 1,3-dihydroxybenzene was used in conjunction with 1,4-dihydroxybenzene and the total ratio of dihydroxybezene to 4,4′-dihydroxydiphenyl was varied to provide PEEK-mPEEK-PEDEK copolymers with ratios oPEEK:mPEEK:PEDEK components as set out in Table 3.

TABLE-US-00003 TABLE 3 Mass of 1,4- Mass of 1,3- Mass of 4,4′- Ratio of dihydroxybenzene dihydroxybenzene dihydroxydiphenyl Example R.sub.PEEK:R.sub.mPEEK:R.sub.PEDEK (g) (g) (g) 10 80:10:10 44.04 5.51 9.31 11 50:10:40 27.53 5.51 37.24 12 30:30:40 16.52 16.52 37.24 13 65:10:25 35.79 5.51 23.28

Example 14—Preparation of PEEK-mPEEK-oPEEK-PEDEK copolymer including both 1,3-dihydroxybenzene comonomer (providing R.SUB.mPEEK .repeat units) and 1,2-dihydroxybenzene comonomer (providing R.SUB.oPEEK .repeat units)

[0094] In this Example, both 1,3-dihydroxybenzene and 1,2-dihydroxybenzene comonomers were used in conjunction with 1,4-dihydroxybenzene to provide a PEEK-mPEEK-oPEEK-PEDEK copolymer with:

R.sub.PEEK:R.sub.mPEEK:R.sub.oPEEK:R.sub.PEDEK=65/5/5/25.

[0095] A 0.5 litre flanged flask fitted with a ground glass lid, stirrer/stirrer guide, nitrogen inlet and outlet was charged with 4,4′-difluorobenzophenone (111.56 g, 0.511 mol), 1,4-dihydroxybenzene (35.79 g, 0.330 mol), 1,3-dihydroxybenzene (2.75 g, 0.03 mol), 1,2-dihydroxybenzene (2.75 g, 0.03 mol), 4,4′-dihydroxydiphenyl (23.28 g, 0.125 mol) and diphenylsulphone (314.94 g) and purged with nitrogen for 1 hour. The contents were then heated under a nitrogen blanket to 150° C. to form an almost colourless solution. While maintaining a nitrogen blanket, dried sodium carbonate (53.42 g, 0.504 mol) and potassium carbonate (2.764 g, 0.02 mol), both sieved through a screen with a mesh size of 500 micrometres, were added. The temperature was raised to 180° C. at 1° C./min and held for 100 minutes. The temperature was raised to 200° C. at 0.5° C./min; the temperature was then raised to 305° C. at 1° C./min and held for approximately 60 minutes or until the desired MV was reached as indicated by the torque rise on the stirrer. The reaction mixture was then poured into a foil tray, allowed to cool, milled and washed with 2 litres of acetone and then with warm water at a temperature of 40-50° C. until the conductivity of the waste water was <2 μS. The resulting polymer powder was dried in an air oven for 12 hours at 120° C.

Example 15—Preparation of PEEK-PEDEK Copolymer Including 1,2-dihydroxybenzene Comonomer (Providing R.SUB.opEEK .Repeat Units)—Reaction Terminated Using Lithium Salt and the Copolymer End-Capped

[0096] In this Example, 1,2-dihydroxybenzene comonomer was used in conjunction with 1,4-dihydroxybenzene to provide a PEEK-oPEEK-PEDEK copolymer with:

R.sub.PEEK:R.sub.oPEEK:R.sub.PEDEK=65/10/25.

[0097] The reaction was stopped, once a desired torque/MV was reached, using addition of lithium sulphate, followed by use of 4,4′-difluorobenzophenone to provide the copolymer with fluorobenzophenone end units:

##STR00010##

[0098] A 0.5 litre flanged flask fitted with a ground glass lid, stirrer/stirrer guide, nitrogen inlet and outlet was charged with 4,4′-difluorobenzophenone (110.19 g, 0.505 mol), 1,4-dihydroxybenzene (35.79 g, 0.330 mol), 1,2-dihydroxybenzene (5.51 g, 0.05 mol) 4,4′-dihydroxydiphenyl (23.28 g, 0.125 mol) and diphenylsulphone (303.00 g) and purged with nitrogen for 1 hour. The contents were then heated under a nitrogen blanket to 150° C. to form an almost colourless solution. While maintaining a nitrogen blanket, dried sodium carbonate (54.58 g, 0.515 mol) and potassium carbonate (0.35 g, 0.0025 mol), both sieved through a screen with a mesh size of 500 micrometres, were added. The temperature was raised to 270° C. at 1 ° C./min and then held until the desired torque rise was reached, when lithium sulphate (0.96 g, 0.00875 mol) and 4,4′-difluorobenzophenone (1.36 g, 0.00625 mol) were added. The reaction mixture was held at 270° C. for a further 30 minutes. The reaction mixture was then poured into a foil tray, allowed to cool, milled and washed with 2 litres of acetone and then with warm water at a temperature of 40-50° C. until the conductivity of the waste water was <2 μS. The resulting polymer powder was dried in an air oven for 12 hours at 120° C.

Example 16—Preparation of PEEK-mPEEK-PEDEK) Copolymer Including 1,3-dihydroxybenzene Comonomer (Providing R.SUB.mPEEK.)—Reaction Terminated Using Lithium Salt and the Copolymer End-Capped

[0099] In this Example, 1,3-dihydroxybenzene comonomer was used in conjunction with 1,4-dihydroxybenzene to provide a PEEK-mPEEK-PEDEK) copolymer with:

R.sub.PEEK:R.sub.mPEEK:R.sub.PEDEK=65/10/25.

[0100] The reaction was stopped, once a desired torque/MV was reached, using addition of lithium sulphate, followed by use of 4,4′-diflurobenzophenone to provide end-capping of the copolymer with fluorobenzophenone end-capping units:

##STR00011##

[0101] A 0.5 litre flanged flask fitted with a ground glass lid, stirrer/stirrer guide, nitrogen inlet and outlet was charged with 4,4′-difluorobenzophenone (110.19 g, 0.505 mol), 1,4-dihydroxybenzene (35.79 g, 0.330 mol), 1,3-dihydroxybenzene (5.51 g, 0.05 mol) 4,4′-dihydroxydiphenyl (23.28 g, 0.125 mol) and diphenylsulphone (303.00 g) and purged with nitrogen for 1 hour. The contents were then heated under a nitrogen blanket to 150° C. to form an almost colourless solution. While maintaining a nitrogen blanket, dried sodium carbonate (54.58 g, 0.515 mol) and potassium carbonate (0.35 g, 0.0025 mol), both sieved through a screen with a mesh size of 500 micrometres, were added. The temperature was raised to 270° C. at 1° C./min and then held until the desired torque rise was reached, when lithium sulphate (0.96 g, 0.00875 mol) and 4,4′-difluorobenzophenone (1.36 g, 0.00625 mol) were added. The reaction mixture was held at 270° C. for a further 30 minutes. The reaction mixture was then poured into a foil tray, allowed to cool, milled and washed with 2 litres of acetone and then with warm water at a temperature of 40-50° C. until the conductivity of the waste water was <2 μS. The resulting polymer powder was dried in an air oven for 12 hours at 120° C.

Example 17—Differential Scanning Calorimetry of the Copolymers of Examples 1 to 16

[0102] Crystallinity (as reported in Table 2) may be assessed by several methods for example by density, by IR spectroscopy, by X-ray diffraction or by differential scanning calorimetry (DSC). The DSC method was been used to evaluate the crystallinity that developed in the polymers from Examples 1-20 using a Mettler Toledo DSC1 Star system with FRS5 sensor.

[0103] The Glass Transition Temperature (Tg), the Melting Temperature (Tm) and Heat of Fusion of Melting (□Hm) for the polymers from Examples 1 to 19 were determined using the following DSC method.

[0104] A dried sample of each polymer was compression moulded into an amorphous film, by heating 7 g of polymer in a mould at 400° C. under a pressure of 50 bar for 2 minutes, then quenching in cold water producing a film of dimensions 120×120 mm, with a thickness in the region of 0.20 mm. An 8 mg plus or minus 3 mg sample of each film was scanned by DSC as follows: [0105] Step 1 Perform and record a preliminary thermal cycle by heating the sample from 50° C. to 400° C. at 20° C. /min. [0106] Step 2 Hold for 5 minutes. [0107] Step 3 Cool at 50° C./min to a point halfway between the Tg.sup.1 and Tm.sup.1 as recorded in the first cycle (Tg.sup.1 is the point of greatest slope obtained during the glass transition on heating in step 1. The Tm.sup.1 was the temperature at which the main peak of the melting endotherm reached a maximum value in step 1). [0108] Step 4 Hold for 3 hours [0109] Step 5 Cool at 50° C./min to 50° C. and hold for 5 minutes [0110] Step 6 Re-heat from 50° C. to 400° C. at 20° C./min, recording the Tg, Tm and □Hm for this second heating endotherm.

[0111] From the DSC trace resulting from the scan in step 6, Tg was obtained as the temperature at which the endotherm slope was a maximum during the glass transition. The Tm was the temperature at which the main peak of the melting endotherm reached a maximum value.

[0112] The heat of fusion for melting (□Hm) was obtained by connecting the two points at which the melting endotherm in step 6 deviated from the relatively straight baseline above the Tg. The integrated area under the endotherm as a function of time yields the enthalpy of the melting transition. The mass normalised heat of fusion is calculated by dividing the enthalpy by the mass of the specimen (J/g). The level of crystallisation (%) is determined by dividing the Heat of Fusion of the specimen by 130 J/g. This value of 130 J/g is the heat of fusion for totally crystalline PEEK, which is used as a reference value for this measurement.

[0113] The results are set out in Table 4 below.

Example 18—Thermal Gravimetric Analysis of Polyaryletherketones of Examples 1 to 16

[0114] The thermal stability of a polymer can be measured by assessment of the temperature by which 5 weight % of the polymer mass is lost (Td5) as the temperature is raised from room temperature to 1000° C. at a constant rate in air. Td5 is suitably measured by means of thermal gravimetric analysis (TGA). The TGA method was used to measure Td5 using a TA instruments TGA Q5000 with tared platinum plans in air. The temperature was raised from room temperature up to 1000° C. at a rate of 50° C. per minute decreasing to 1° C. per minute when 0.1% weight loss from the sample has been detected.

[0115] The Results are set out in table 4 below, with the Examples grouped together with other Examples having the same overall (R.sub.PEEK+R.sub.oPEEK+R.sub.mPEEK):R.sub.PEDEK ratios.

TABLE-US-00004 TABLE 4 Tg Tm Td5 Example Polymer (° C.) (° C.) X % (° C.) 1 PEEK-PEDEK (90/10) 143 332 34 508 4 PEEK-oPEEK-PEDEK (80/10/10) 140 313 30 533 5 PEEK-oPEEK -PEDEK (60/30/10) 142 263 20 523 10 PEEK-mPEEK -PEDEK (80/10/10) 145 310 28 536 2 PEEK-PEDEK (75/25) 151 306 26 537 8 PEEK-oPEEK -PEDEK (65/10/25) 152 281 24 536 15 PEEK-oPEEK -PEDEK (65/10/25) End-capped 152 281 22 533 9 PEEK-oPEEK -PEDEK (55/20/25) 148 263 18 522 13 PEEK-mPEEK -PEDEK (65/10/25) 152 283 25 526 16 PEEK-mPEEK-PEDEK (65/10/25) End-capped 152 281 25 539 14 PEEK-mPEEK-oPEEK-PEDEK (65/05/05/25) 153 278 22 531 3 PEEK-PEDEK (60/40) 152 318 19 543 6 PEEK-oPEEK-PEDEK (50/10/40) 150 307 16 537 7 PEEK-oPEEK-PEDEK (30/30/40) 151 306 13 520 11 PEEK-mPEEK-PEDEK (50/10/40) 150 315 25 537 12 PEEK-mPEEK-PEDEK (30/30/40) 147 305 18 536

[0116] It can be seen from Table 4 that the modification of a PEEK-PEDEK copolymer of a particular R.sub.PEEK:R.sub.PEDEK, by replacement of part of the R.sub.PEEK units with R.sub.mPEEK and/or R.sub.oPEEK units leads to: [0117] i) significant reductions in Tm; [0118] ii) some reductions in Tg; [0119] iii) some reductions in crystallinity, but with significant crystallinity still present; and [0120] iv) little effect on Td5.

[0121] In summary, the invention provides copolymers which include [-ether-phenyl-ether-phenyl-carbonyl-phenyl-] (R.sub.PEEK) and [ether-phenyl-phenyl-ether-phenyl-carbonyl-phenyl-] (R.sub.PEDEK) repeat units, have their melting temperature reduced by partially replacing the para-R.sub.PEEK units by R.sub.oPEEK and/or R.sub.mPEEK units, in which the ether-phenyl-ether moieties are ortho- and meta-rather than para-. The copolymers exhibit crystallinity and have similar glass transition temperatures to the prior art polymers without partial para- replacement. Methods of preparation and uses of the copolymers are also disclosed.

Example 19—Preparation of PEEK-oPEEK-PEDEK Copolymer including 1,2-dihydroxybenzene as Comonomer (Providing R.SUB.oPEEK .Repeat Units)

[0122] The procedure described in Example 1 was repeated except that 1,2-dihydroxybenzene was used in conjunction with 1,4-dihydroxybenzene with the total ratio of dihydroxybezene to 4,4′-dihydroxydiphenyl being varied to provide polyetheretherketone PEEK-oPEEK-PEDEK copolymers with ratios of PEEK:oPEEK:PEDEK repeat units as set out in Table 5.

TABLE-US-00005 TABLE 5 Mass of 1,4- Mass of 1,2- Mass of 4,4′- Ratio of dihydroxybenzene dihydroxybenzene dihydroxydiphenyl Example R.sub.PEEK:R.sub.oPEEK:R.sub.PEDEK (g) (g) (g) 19 65:15:20 35.79 8.26 18.62

TABLE-US-00006 TABLE 6 Tg Tm Td5 Example Polymer (° C.) (° C.) X % (° C.) 19 PEEK-oPEEK-PEDEK 65:15:20 144 281 26 517

[0123] Example 19 provides a polymeric material with significant reduction in Tm compared to PEEK-PEDEK copolymer, some reduction in Tg compared to PEEK-PEDEK copolymer and comparable levels of crystallinity as shown in Table 6.

Example 20 and 21 Preparation of PEEK-oPEEK-PEDEK Copolymer Including 1,2-dihydroxybenzene as Comonomer (Providing R.SUB.oPEEK .Repeat Units) with the Addition of Victrex ST45PF (PEKEKK) at the End of the Reaction

[0124] In Example 20, the procedure described in Example 1 was repeated except that 1,2-dihydroxybenzene was used in conjunction with 1,4-dihydroxybenzene with the total ratio of dihydroxybezene to 4,4′-dihydroxydiphenyl being varied to provide polyetheretherketone PEEK-oPEEK-PEDEK copolymers with ratios of PEEK:oPEEK:PEDEK repeat units as set out in Table 5.

[0125] In Example 21, the polymeric material was made as per example 19, and an additive was added to the polymeric material at the end of the reaction to increase the rate of crystallisation of the polymeric material. Victrex ST45PF at a quantity of 7.59 g (available from Victrex Manufacturing Limited, Victrex Technology Centre, Hillhouse International, Thornton Cleveleys, FY5 4QD, UK) was added to the polymeric material, ten minutes after the torque rise has ceased. After a further ten minutes of stirring, the reaction mixture was then poured into a foil tray and allowed to cool, milled and washed as per the procedure in Example 1. Victrex ST45PF is PEKEKK, polyetherketonetherketoneketone.

TABLE-US-00007 TABLE 7 Mass of 1,4- Mass of 1,2- Mass of 4,4′- Mass of Ratio of dihydroxybenzene dihydroxybenzene dihydroxydiphenyl ST45P F Example R.sub.PEEK:R.sub.oPEEK:R.sub.PEDEK (g) (g) (g) (g) 20 65:15:20 35.79 8.26 18.62 0 21 65:15:20 35.79 8.26 18.62 7.59

[0126] The results are set out in Table 8 below.

TABLE-US-00008 TABLE 8 Tg Tm Tc Example Polymer (° C.) (° C.) (° C.) X % 20 PEEK-oPEEK-PEDEK 65:20:15 145 280 225 26 21 PEEK-oPEEK-PEDEK 144 279 232 23 65:20:15 + 5% wt. ST45PF

[0127] It has been surprisingly found that the additive, Victrex ST45PF results in an increase in the rate of crystallisation as indicated by the increase in Tc. Without being bound by theory, it is believed that the ST45PF powder particles act as a nucleation site and therefore increases the rate of crystallisation of the polymeric material through heterogeneous crystallisation. A benefit of increasing the rate of crystallisation is that the polymeric material may used in a variety of manufacturing methods including those that require fast crystallising properties such as injection moulding.

Example 22

[0128] The procedure described in example 8 was repeated on a larger scale, 450 L jacketed steel vessel.

[0129] Diphenylsulphone (99.6 kg) was charged to the vessel and allowed to melt. When the contents were molten and 140-150° C., agitation was set to 20 rpm and the following materials charged sequentially: 1,4-dihydroxybenzene (11.451 kg, 104.0 moles), 1,2-dihydroxybenzene (2.643 kg, 24.0 moles), 4,4′-dihydroxydiphenyl (5.959, 32.0 moles) and 4,4′-difluorobenzophenone (35.715 kg, 163.7 moles). When the contents temperature was 140-150° C., a mixture of sodium carbonate (17.094 kg, 161.3 moles) and potassium carbonate (1.106 kg, 8.0 moles), pre-sieved through 500 μm mesh, were added to the vessel.

[0130] The agitation rate was increased to 50 rpm and contents temperature raised to 200° C. at 0.3° C. min-1 and then raised to 305° C. at 1° C. min-1. The temperature was maintained at 305° C. until sufficient viscosity was attained. The molten mixture was discharged from the reactor over approximately 45 minutes and the solidified material milled to a coarse powder (<2 mm maximum dimension). The powder was transferred to a column where acetone was percolated through until the leaching solvent no longer yielded a precipitate on addition of water. The product was then washed with deionised water at 50° C. to remove aqueous by-products. Once the conductivity of leachate was measured to be <2 μS using a conductivity probe, the material remaining in the column was discharged and dried in an air circulatory oven at 150° C.

Example 23

[0131] Example 22 was repeated but with a reduced 4,4′-diflurobenzophenone charge of 35.505 kg.

Example 24

[0132] Example 22 was repeated but with diphenylsulphone charge of 76.439 kg.

Example 25

[0133] Example 24 was repeated but at the end of the polymerisation reaction, fine ST 45PF powder (PEKEKK), 2.42 kg, was added to the reaction mixture. The mixture was stirred for a further 30 minutes and then discharged and worked up as previously described for Example 22.

Example 26

[0134] Example 24 was repeated but with a reduced 4,4′-difluorobenzophenone charge of 35.505 kg.

Example 27

[0135] Example 25 was repeated but with a reduced 4,4′-difluorobenzophenone charge of 35.505 kg.

Example 28 Preparation of 12 kg of Polyaryletherketones of Example 22 with the Addition of Victrex ST45PF (PEKEKK) During Melt Processing

[0136] In Example 28, the polymeric material was made as per Example 22. An additive was then added to the polymeric material during a subsequent melt processing step to increase the rate of crystallisation of the polymeric material. Victrex ST45PF at a quantity of 600 g (available from Victrex Manufacturing Limited, Victrex Technology Centre, Hillhouse International, Thornton Cleveleys, FY5 4QD, UK) was added to 11.4 kg of the polymeric material through separate loss-in-weight feeders into the rear feeding section of a Coperion ZSK25 twin screw extruder with barrel temperatures of 310 to 320° C. The resulting mixture was then extruded into two 4mm diameter laces and allowed to cool on a conveyor belt before being granulated into granules of 2.0-4.0 mm in length.

Example 29 Preparation of 12 kg of Polyaryletherketones of Example 23 with the Addition of Victrex ST45PF (PEKEKK) During Melt Processing

[0137] In Example 29 the polymeric material was made as per Example 23. An additive was then added to the polymeric material during a subsequent melt processing step to increase the rate of crystallisation of the polymeric material. Victrex ST45PF at a quantity of 600 g (available from Victrex Manufacturing Limited, Victrex Technology Centre, Hillhouse International, Thornton Cleveleys, FY5 4QD, UK) was added to 11.4 kg of the polymeric material through separate loss-in-weight feeders into the rear feeding section of a Coperion ZSK25 twin screw extruder with barrel temperatures of 310 to 320° C. The resulting mixture was then extruded into two 4mm diameter laces and allowed to cool on a conveyor belt before being granulated into granules of 2.0-4.0 mm in length.

Example 30 Preparation of 5 kg of Polyaryletherketones of Example 22 with the Addition of Hytrel 5555HS (TPC-ET) During Melt Processing

[0138] In Example 30 the polymeric material was made as per Example 22. An additive was then added to the polymeric material during a subsequent melt processing step to reduce the stiffness and improve the impact performance of the polymeric material. Hytrel 5555HS at a quantity of 500 g (available from Dupont, 974 Centre Road, Wilmington, Del. 19805, USA) was added to 4.5 kg of the polymeric material through separate loss-in-weight feeders into the rear feeding section of a Coperion ZSK25 twin screw extruder with barrel temperatures of 290° C. The resulting mixture was then extruded into two 4 mm diameter laces and allowed to cool on a conveyor belt before being granulated into granules of 2.0-4.0 mm in length.

Example 31 Preparation of 5 kg of Polyaryletherketones of Example 22 with the Addition of Hytrel 5555HS (TPC-ET) During Melt Processing

[0139] In Example 31 the polymeric material was made as per Example 22. An additive was then added to the polymeric material during a subsequent melt processing step to reduce the stiffness and improve the impact performance of the polymeric material. Hytrel 5555HS at a quantity of 1.0 kg (available from Dupont, 974 Centre Road, Wilmington, Del. 19805, USA) was added to 4.0 kg of the polymeric material through separate loss-in-weight feeders into the rear feeding section of a Coperion ZSK25 twin screw extruder with barrel temperatures of 290° C. The resulting mixture was then extruded into two 4 mm diameter laces and allowed to cool on a conveyor belt before being granulated into granules of 2.0-4.0 mm in length.

Example 32 Preparation of 5 kg of Polyaryletherketones of Example 22 with the addition of SiItem 1500 (PEI-siloxane copolymer) and UItem 1000 (PEI) During Melt Processing

[0140] In Example 32 the polymeric material was made as per Example 22. Two additives were then added to the polymeric material during a subsequent melt processing step to reduce the stiffness and improve the impact performance of the polymeric material. SiItem 1500 at a quantity of 500 g and UItem 1000 at a quantity of 250 g (both available from Sabic, SAUDI BASIC INDUSTRIES CORPORATION (HQ), PO Box 5101, Riyadh 11422, Saudi Arabia ( ) was added to 4.25 kg of the polymeric material through separate loss-in-weight feeders into the rear feeding section of a Coperion ZSK25 twin screw extruder with barrel temperatures of 290° C. The resulting mixture was then extruded into two 4 mm diameter laces and allowed to cool on a conveyor belt before being granulated into granules of 2.0-4.0 mm in length.

Example 33 Preparation of 5 kg of Polyaryletherketones of Example 22 with the Addition of SiItem 1500 (PEI-siloxane Copolymer) and UItem 1000 (PEI) During Melt Processing

[0141] In Example 33 the polymeric material was made as per Example 22. Two additives were then added to the polymeric material during a subsequent melt processing step to reduce the stiffness and improve the impact performance of the polymeric material. SiItem 1500 at a quantity of 500 g and UItem 1000 at a quantity of 500 g (both available from Sabic, SAUDI BASIC INDUSTRIES CORPORATION (HQ), PO Box 5101, Riyadh 11422, Saudi Arabia) was added to 4.0 kg of the polymeric material through separate loss-in-weight feeders into the rear feeding section of a Coperion ZSK25 twin screw extruder with barrel temperatures of 290° C. The resulting mixture was then extruded into two 4 mm diameter laces and allowed to cool on a conveyor belt before being granulated into granules of 2.0-4.0 mm in length.

Example 34 Differential Scanning Calorimetry (DSC) on Examples 22, 23, 25, 27, 28 and 29

[0142] A further method of Differential Scanning calorimetry (DSC) was utilised to determine melting temperature (Tm), crystallisation temperature (Tc), glass transition temperature (Tg) and heat of fusion (ΔH) in accordance with ISO 11357 for Examples 22, 23, 25, 27, 28 and 29. Instrument used was TA Instrument Q200.

[0143] The heat cycles were: [0144] 1st heat cycle: 50.0° C. to 320.0° C. at 20.0° C., isothermal for 5 minutes [0145] 1st cool cycle*: 320.0° C. to 50.0° C. at 20.0° C., isothermal for 5 minutes [0146] 2nd heat cycle: 50.0° C. to 320.0° C. at 20.0° C., isothermal for 5 minutes

[0147] The Tm was the peak temperature at which the melting endotherm on the 2nd heat scan reached a maximum value.

[0148] The Tc was obtained as the peak temperature of the crystallisation exotherm on the first cool scan.

[0149] Glass transition temperature (Tg), onset and mid-point was determined on the 2nd heat scan. The enthalpy of fusion, ΔH, was determined on the 2nd heat scan and the area was calculated by drawing a linear baseline from just above the Tg (157° C.) to a temperature above the last endotherm.

[0150] The mass normalised heat of fusion is calculated by dividing the enthalpy by the mass of the specimen (J/g). The level of crystallisation (%) is determined by dividing the Heat of Fusion of the specimen by 130 J/g. This value of 130 J/g is the heat of fusion for totally crystalline PEEK, which is used as a reference value for this measurement.

[0151] Table 9 shows the Glass Transition Temperature (Tg), the Melting Temperature (Tm) and Tc which is measured on the cooling cycle and is the temperature at which the crystallisation exotherm reaches a minimum. The Heat of Fusion for melting (ΔHm) was obtained by connecting the two points at which the melting endotherm deviates from the relatively straight baseline. The integrated area under the endotherm as a function of time yields the enthalpy (mJ) of the melting transition: the mass normalised heat of fusion is calculated by dividing the enthalpy by the mass of the specimen (J/g). The level of crystallisation (X(%)) is determined by dividing the Heat of Fusion of the specimen by the Heat of Fusion of a totally crystalline polymer, which for the copolymer is 130 J/g.

[0152] As can be seen, there is a significant reduction in the melting temperature of the copolymer compared to Victrex PEEK 150G and Victrex PEEK 450G. This results in a more processable material at lower temperatures, and also opens up the possibility of using additives in combination with the copolymer that would not be applicable for use in PEEK polymers due to the high processing temperatures needed to process PEEKs.

TABLE-US-00009 TABLE 9 material properties of Examples 22 and 23 and comparative examples from DSC Tg Tm Tc Crystallinity (° C.) (° C.) (° C.) (%) 150G 144 344 301 34.7 Example 22 147 282 222 22 450G 144 343 290 32.8 Example 23 147 278 207 15.9

[0153] Examples 25, 27, 28 and 29 are copolymer compositions with added Victrex ST45PF (Victrex ST45PF is PEKEKK, polyetherketonetherketoneketone). Victrex ST45PF has a melting temperature of around 387° C. By adding ST45PF, the inventors have been able to make polymeric materials with reduced crystallisation times as shown in Table 10. The effect of this is that the compositions crystallise far more quickly than the copolymer on its own. One benefit of increasing the cystallisation rate of the copolymer is that when making parts from the copolymer, moulding cycle times may be increased, thereby increasing the number of parts manufactured per minute.

TABLE-US-00010 TABLE 10 crystallisation behaviour from Examples 25, 27, 28 and 29 Isothermal Crystallisation Tm Tc Crystallinity time at 260° C. (° C.) (° C.) (%) (mins) Example 22 281.5 221.8 22 10 Example 28 283.5 231.7 22.1 6.3 Example 25 280.3 223.4 19.3 4.1 Example 23 278.2 206.9 15.9 22.1 Example 29 279.3 226.7 17 14 Example 27 279.1 214.6 17.2 14

Example 35—Rheometry

[0154] The melt viscosity of the PAEK copolymer may be measured by capillary rheometry using an RH10 capillary rheometer (Malvern Instruments Rosand RH10 capillary rheometer), fitted with a tungsten carbide die, 0.5 mm (capillary diameter)×8.0 mm (capillary length). Approximately 5 grams of the copolymer is dried in an air circulating oven for 3 hours at 150° C. The extruder is allowed to equilibrate to 400° C. The dried polymer is loaded into the heated barrel of the extruder, a brass tip (12 mm long×9.92±0.01 mm diameter) placed on top of the polymer followed by the piston and the screw manually turned until the proof ring of the pressure gauge just engages the piston to help remove any trapped air. The column of polymer is allowed to heat and melt over a period of at least 10 minutes. After the preheat stage the screw was is in motion so that the melted polymer is extruded through the die to form a thin fibre at the desired shear rate, while recording the pressure (P) required to extrude the polymer. The Melt Viscosity is given by the formula

[00003]$\mathrm{Melt}\mathrm{Viscosity}=\frac{P\pi r^4}{8\mathrm{LSA}}{\mathrm{kNsm}}^{-2}$

where P=Pressure/kN m.sup.−2 [0155] L=Length of die/m [0156] S=ram speed/ms.sup.−1 [0157] A=barrel cross-sectional area/m.sup.2 [0158] r=Die radius/m [0159] The relationship between shear rate and the other parameters is given by the equation:

Apparent wall shear rate=4Q/πr.sup.3 [0160] where Q=volumetric flow rate/m.sup.3s.sup.−1=SA.

[0161] Hence, by adjusting the ram speed, S, the viscosity of the molten polymer may be measured at different shear rates, such as at 100, 1000 or 10,000 s.sup.−1 or at intermediate rates.

[0162] FIGS. 1 and 2 show the shear viscosity behaviour of Examples 22 and 23 using the method described above in Example 35. Comparative examples are also shown including comparative shear rheology information for Victrex 150G and Victrex 450G (available from Victrex Manufacturing Limited, Victrex Technology Centre, Thornton Cleveleys, UK). Comparative examples from other PAEK suppliers are also shown (for example KT880 from Solvay Speciality Polymers USA, LLC, 4500 McGinnis Ferry Road, Alpharetta, Ga., USA, and L4000 from Evonik Industries AG, Rellinghauser Straße 1-11, 45128 Essen, Germany). Examples 22 and 23 exhibit flow properties between that of comparative polyetheretherketones

[0163] The low shear rate viscosity (between 0.006 s.sup.−1 and 628.319 s.sup.−1) of polymeric material may be measured using rotational rheometry using a TA Instruments™ Discovery Hybrid Rheometer-2 (DHR-2) rotational rheometer. The rheometer was fitted with an Environmental Test Chamber (ETC), a 25 mm Stainless Steel Parallel Plate and a 25 mm Stainless Steel Stepped Lower ETC Plate. Approximately 1.6 grams of the copolymer was dried in an air circulating oven for 3 hours at 150° C. The extruder was allowed to equilibrate to the testing temperature (typically 300-400° C.).

[0164] The dried copolymer was loaded into a melt ring wrapped around the stepped section on the lower plate and once the temperature of the chamber had returned to the test temperature, a delay of three minutes was sufficient to melt the copolymer, upon which the melt ring was removed. The gap between the two plates was closed at a rate of 200 μm/s until the gap size was 1075 μm. After a further two minutes delay, the excess polymeric material was removed from the gap using a 6 mm trimming tool. Once trimmed, the gap was closed to 1000 μm again at a rate of 200 μm/s before starting the test.

[0165] The Viscosity is given by the formula:

[00004]$\mathrm{Viscosity}\left(\eta \right)=\frac{M{K}_{\sigma }}{{\mathrm{\Omega K}}_y}\mathrm{Pa}.Math.s$

where: [0166] M=torque/Nm.sup.−1 [0167] K.sub.σ=Stress Constant [0168] Ω=Motor angular velocity/rad s.sup.−1 [0169] K.sub.γ=Strain Constant.

[0170] For a parallel plate, the

[00005]$\mathrm{strain}\mathrm{constant}=\frac{r}{h}$

where: [0171] r=radius of the plate/m [0172] h=the gap size/m.

[0173] For a parallel plate the

[00006]$\mathrm{stress}\mathrm{constant}=\frac{2}{\pi r^3}$

where: [0174] r=radius of the plate/m.

[0175] To determine the shear viscosity across a range of shear rates, a dynamic oscillation experiment was performed. The torque is kept at a constant value and the frequency is swept from high to low (typically from 100 Hz to 0.01 Hz) logarithmically at 5 points per decade. The complex viscosity is determined to be:

[00007]$\mathrm{Complex}\mathrm{Viscosity}\left({\eta }^{\star }\right)=\frac{G^{\star }}{\omega }\mathrm{Pa}.Math.s$

where: [0176] G*=Complex Modulus/Pa [0177] ω=Angular Frequency/rad s.sup.−1.

[0178] The complex viscosity can be converted to viscosity via the Cox-Merz rule to give a viscosity as a function of shear rate.

[0179] Cox-Merz Rule for Linear Polymers: η*(ω)=η(γ)@γ=ω

where γ=shear rate/s.sup.−1.

[0180] FIG. 2 shows the rheological properties of Examples 22 and 23, compared with Victrex PEEK 150G, Victrex PEEK 450G and Victrex PEEK 650G (all available from Victrex Manufacturing Limited). Copolymers according to the present invention exhibit similar flow behaviour to known PEEKs.

Example 36—Mechanical Properties

[0181] The mechanical properties of the compositions of Examples 22, 23, 26, 30 and 32 were tested according to ISO standards ISO 527 for tensile properties, ISO 178 for flexural properties, and ISO 180/A for the impact strength properties using the type 1A (ISO 3167) test bars at 23° C.

[0182] Table 11 shows tensile mechanical properties for examples 22, 23 and 26. The copolymer exhibits good tensile strength properties close to that of Victrex PEEK 450G.

TABLE-US-00011 TABLE 11 mechanical properties ISO Tensile ISO Tensile Modulus, (Youngs) Strength, GPa Mpa 450G 3.7 98 Example 22 3.5 90 Example 23 3.4 82 Example 26 3.1 90

[0183] Table 12 shows the mechanical properties for immiscible blends comprising the copolymer and an elastomer, Hytrel 5555HS (TPC-ET). By incorporating a small quantity of Hytrel 5555HS (TPC-ET) into the composition, improved impact resistance has been observed.

TABLE-US-00012 TABLE 12 mechanical properties of compositions of immiscible blends ISO Tensile ISO Tensile ISO Flexural ISO Flexural ISO Notched Modulus, (Youngs) Strength, Modulus, Strength Izod, GPa MPa GPa MPa kJ/m2 Example 22 3.5 89.9 3.3 149.4 2.9 Example 30 3.4 80.8 3.2 136.4 4.6

[0184] Table 13 shows the mechanical properties for immiscible blends comprising the copolymer and elastomers, SiItem and UItem. By incorporating a small quantity of SiItem and UItem into the composition, improved impact resistance has been observed.

TABLE-US-00013 TABLE 13 mechanical properties of compositions of miscible blends ISO Tensile ISO Tensile ISO Flexural ISO Flexural ISO Notched Modulus, (Youngs) Strength, Modulus, Strength Izod, GPa MPa GPa MPa kJ/m2 Example 22 3.5 89.9 3.3 149.4 2.9 Example 32 3.2 72.1 3 134.2 5.5

[0185] 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.

[0186] All features disclosed in this specification (including any accompanying claims and drawings), and/or all 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.

[0187] Each feature disclosed in this specification (including any accompanying claims, 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.

[0188] The invention is not restricted to the details of the foregoing embodiment(s). The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.